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  • Analytical Chemistry and Spectroscopy  (2.202)
  • 1995-1999  (2.202)
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  • 1
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 20 (1997), S. 482-486 
    ISSN: 0935-6304
    Schlagwort(e): Volatile benzene alkyl derivatives ; Simple distillation ; Purge and trap ; Capillary gas chromatograph-mass spectrometry ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Simple distillation was used to prepare aqueous environmental samples (especially those with high content of accompanying dissolved and suspended organic and inorganic matter) for determination of benzene, toluene, ethylbenzene, and xylenes (BTEX) by means of purge and trap (PT) coupled to gas chromatography-mass spectrometry (GC-MS). The PT step was carried out with a laboratory-built device in which alalytes desorbed from a Primary trap (macrotrap) are focused in a microtrap (also with sorbent) and moisture is removed from purge gases by a Nafion tube (walls selectively permeable to water vapor). Recoveries, if only the first 10 ml distillate was collected, were of the order of 40% at optimum distillation parameters. At a probability level of 95% recoveries were independent of concentration in a studied concentration range of 0.50-30 ppb. Enrichment factors for distillation were of the order off 20. Real samples, i.e., raw and treated waste water were analyzedc for BTEX content by the developed medthod.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. S114 
    ISSN: 0749-1581
    Schlagwort(e): electron paramagnetic resonance ; adriamycin ; metal chelation ; coordination structure ; iron ; free radical ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: EPR and Mössbauer studies demonstrate that iron chelation by adriamycin is complex, with several different chelation structures. At physiological pH in aqueous solution, three different EPR spectra are observed: a spectrum at g = 4.2 of Fe3+ in a rhombic crystal field (type 1); a spectrum at g = 2.01 with symmetric Gaussian lineshape linewidth 225 G (1 G = 10-4 T), suggestive of Fe3+ bound in an octahedral crystal field (type 2); and a broad spectrum centered at g = 2.0 suggestive of ferromagnetically coupled Fe3+ (type 3). The type 1 and 2 spectra are observed at adriamycin/Fe3+ ratios 〉4, the type 3 spectrum is observed at ratios 〈4 and at ratios 〈2 an increasing amount of Fe3+ gives rise to EPR silent iron(III) hydroxide polymers. At 4 K the type 1 and 2 complexes exhibit a broad doublet Mössbauer signal with an isomer shift δ = 0.56 (1) mm s-1 and quadrupole splitting δEQ = 0.74 (1) mm s-1. The type 3 complex gives rise to a sextet signal with isomer shift ΔEq = 0.47 (1) mm s-1 and hyperfine splitting HF = 476 (1) kG with exhibits superparamagnetic relaxation behavior with a blocking temperature of 23 K, consistent with a microcrystal size of 25 Å. Cu2+ binds to adriamycin at adriamycin/Cu2+ ratios 〉4:1 giving rise to an EPR spectrum with axial symmetry g∥ = 2.26, g⊥ = 2.066, A∥ = 188 G, while 2:1 complexes exhibit a single Gaussian line at g = 2.09 indicative of exchange-coupled Cu2+. The exchange-coupled Cu2+ and ferromagnetically coupled Fe3+ complexes can be explained by the formation of stacked 2:1 adriamycin-metal polymers. On titration of adriamycin with Fe3+-nitrilotriacetate a different spectrum is observed at g = 4.3 and its intensity plateaus at an adriamycin/iron ratio of 2. The iron adriamycin complexes cycle to reduce molecular oxygen and this cycle has been hypothesized to be a mechanism mediating the therapeutic and toxic effects of the drug. Both EPR and Mössbauer experiments demonstrate that the type 1 and 2 chelates reduce their Fe3+ to Fe2+ while the type 3 chelate does not. Therefore, the stoichiometry and method of complex preparation can profoundly effect the properties of these complexes.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 30 (1995), S. 432-437 
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The positional isomers of mono[(Z)-9-octadecenoyl] glycerol, di[(Z)-12-octadecadienoyl] glycerol were derivatized with nicotinic acid chloride hydrochloride. The resulting nicotinoyl derivatives were examined by gas chromatography/mass spectrometry. In their electron impact mass spectra, each methylene group and double bond of the alkyl chain is reflected by a fragmentation pattern in the high mass region. This is caused by radical-induced cleavage of the alkyl chains following random hydrogen abstraction by the pyridine nucleus. An accurate determination of double bond positions in mono- and diacylglycerols is possible by characteristic spacings between abundant diagnostic ions in this fragmentation pattern.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 4
    ISSN: 0935-6304
    Schlagwort(e): Capillary gas chromatography ; Time-of-flight mass spectrometry ; Hyphenated analytical techniques ; REMPI laser ionization ; Selective ionization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Analysis of environmental samples usually requires time consuming sample preparation and clean-up procedures prior to instrumental detection. Faster analysis requires an enhanced instrumental selectivity in order to reduce the necessary clean-up effort. In this context we present a novel concept for coupling gas chromartography/mass spectrometry (GC-MS) with high resolution UV spectoscopy to increase selectivity. We use UV-laser induced, resonance-enhanced multi-photon ionization (REMPI)as a compound specifie ion source for time-of-flight mass spectrometry (TOFMS). The REMPI ionization involves the UV absorption spectroscopy into the ionization process as an aditional analytical dimension. The heart of the GC-REMPI-TOFMS coupling is a specially designed valve, which repetitively (20 Hz) expands the chromatographic eluent as short supersonic jet gas pulses (≈ 150 μs duration) into the vacuum of the mass specrtrometer. The sample molecules are cooled down to temperatures of 10-40 K within the jet expansion. Under these conditions, UV absorption spectriscopy (i.e. REMPi spectroscopy) becomes highly compound selective, even able to distinguish isomeric compounds. The ions formed by REMPI ionization are mass analyzed in the TOFMS. Thus the GC-REMPI-TOFMS coupling presented here is actually a three-dimensional analytical instrument, providing gas chromatographic (retention time) as well as mass spectrometric (molecular mass) and UV -spectroscopic (excitation laser wavelength) selectivity. In combination with gas phase sampling and concentration techniques for semi-volatile organic air pollutants based, e.g., on silicone rubber traps the GC-LAMS technique can be a powerful tool for fast environmental target analysis, e.g. for industrial emission control purposes.
    Zusätzliches Material: 11 Ill.
    Materialart: Digitale Medien
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  • 5
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 435-441 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The groove binding dye Hoechst 33258 was investigated both in aqueous solution and in the adsorbed form on silver colloids and island films. Fourier transform Raman, resonance Raman and surface enhanced resonance Raman spectra were used together with the results of a normal coordinate analysis for a comprehensive assignment of the rich vibrational spectrum. Relative band intensities in the SERRS spectra indicate that the molecule is adsorbed with its long axis oriented along the silver surface and with the planes of the benzimidazole rings approximately parallel to the surface. The molecule is bound to the surface as a cation protonated at a piperazine nitrogen atom and is desorbed on complete deprotonation.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 493-494 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1315-1320 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Matrix-assisted laser desorption/ionization (MALDI) was used for several small proteins (such as insulin) and for peptides. It was found that the detection efficiencies of MALDI for the insulin B chain and the insulin A chain are drastically different. Similar phenomena were also observed for various types of peptides. The positive-ion signal of MALDI in detecting proteins or peptides was found to be greatly enhanced by the presence of a basic amino acid in their chains. The experimental results indicate that this enhancement may arise from proton transfer in solution by an acid-base reaction between the protein/peptide and matrix molecule. This pre-protonated mechanism provides a low energy barrier for the ionization of peptides in a MALDI process, and greatly reduces the energy threshold of MALDI. Matrix effects on the ionization mechanism are discussed.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 449-453 
    ISSN: 0935-6304
    Schlagwort(e): Capillary electrophoresis ; experimental design ; cyclodextrin ; chiral separation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Orthogonal design and uniform design were used for the optimization of separation of enantiomers using 2,6-di-O-methyl-β-cyclodextrin (DM-β-CD) as a chiral selector by capillary zone electrophoresis. The concentration of DM-β-CD, buffer pH, running voltage, and capillary temperature were selected as variable parameters, their different effects on peak resolution were studied by the design methods. It was concluded that orthogonal design offers a rapid and efficient means for testing the importance of individual parameters and for determining the optimum operating conditions. However, for a large number of both factors and levels, uniform design is more efficient. The effect of addition of methanol and citric acid buffer on the separation of enantiomers was also examined.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 2 (1996), S. 301-309 
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Femtosecond pump-probe experiments are used to study the photophysics and photochemistry of heme proteins on ultrafast time scales. Using electronic relaxation measurements combined with reaction-driven coherence signals, we determine that, after the photoexcitation of myoglobin (Mb)NO, the bond-breaking time is on the order of the electronic dephasing time (∼ 20 fs) and the electronic ground state of deoxy Mb appears on a time scale of 80 ± 30 fs. This latter time scale is linked to the Fe-His bond compression (TFe-His/2 ∼ 75 fs), which is initiated by the photolytic depletion of electron density from the antibonding dz2 orbital. The subsequent depression of the dx2-y2 orbital energy, and its population as the iron moves out of plane, leads to the formation of the S = 2 electronic ground state and drives the doming of the heme (Tdome/4 ∼ 100 fs). Thus, the initial stage of heme doming is completed in TFe-His/2 + Tdome/4 ∼ 180 fs. Samples of hemoglobin (Hb)NO display a strong coherent Fe-His stretching vibration at 230 cm-1, which appears immediately (∼ 200 fs) after photodissociation. The data also show a lower-frequency component at 95 cm-1, which we assign to heme doming. The reaction driven coherence of HbNO is observed to be much stronger than the impulsively stimulated Raman coherence of Hb, as might be expected, based on the large relative displacement between reactant and product equilibrium position. The Raman coherence of deoxy Mb is also studied as a function of temperature. As the temperature decreases from 290 to 10 K, the amplitude of the 370 cm-1 mode increases while the amplitude of the 220 cm-1 Fe-His stretching mode decreases. Finally, we report preliminary observations of the first Raman coherences in samples of another heme protein, cytochrome P450. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 527-534 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ultra-fast pulsed laser measurements in the time domain have several advantages over traditional frequency-domain spectroscopy. For example, very low frequency modes are more easily probed, fluorescent samples can be studied and vibrational modes that are directly coupled to chemical reactions are revealed. This study demonstrated some of these advantages using heme protein samples. Low-frequency modes are observed in deoxymyoglobin (deoxyMb), fluorescence rejection is demonstrated with metMb and product-state vibrational coherence is revealed with MbNO.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 11
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 363-372 
    ISSN: 0886-9383
    Schlagwort(e): PLS regression ; orthogonal expansion ; optimization ; Lagrange multipliers ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A simple iteration algorithm that is faster and less memory-intensive than the NIPALS iteration algorithm for PLS regression is presented. The iteration algorithm is obtained by treating the orthogonal expansion or decomposition of a matrix X as an extremum problem subject to normalization and orthogonality constraint conditions and then solving the problem by use of the method of Lagrange multipliers. The main idea in this method is to find the transformation vector r. The latent variable t is expressed exactly as the linear combination of X-variables with the vector r so that the final regression coefficients can be conveniently provided. In the algorithm the recursion of the orthogonal projection is needed, which is derived by use of a matrix inverse formula. Algorithms are established from the equation for calculating the vector r that are suitable for dealing with three cases of large data sets. The first case is when the number of objects is very large, the number of variables is relatively small and the number of Y-variables is equal to or greater than the number of X-variables. The second case is when the number of objects is very large, the number of variables is relatively small and the number of X-variables is greater than the number of Y-variables. The last case is when the number of variables, either X- or Y-variables, or both, is very large and the number of objects is small.
    Zusätzliches Material: 4 Tab.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 643-646 
    ISSN: 0935-6304
    Schlagwort(e): Enantioselective gas chromatography ; Polysiloxane-anchored chiral crown ether stationary phase ; Chirasil-man-18C6-25 ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 13
    ISSN: 1075-4261
    Schlagwort(e): brown pigment stone ; PAGE ; mid-IR spectroscopy ; far IR spectroscopy ; FT-Raman ; bezoar ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Spectroscopic studies of various types of gallstones carried out in China are reviewed. Three basic classes of gallstones are surveyed: cholesterol stones, brown pigment stones, and black pigment stones. The emphasis of this review is on brown gallstones. The primary spectroscopic methods used in the studies surveyed are Fourier transform infrared absorption and Fourier transform Raman scattering. Chemical components studied in gallstones include cholesterol, bile pigments, glycoproteins, proteins, bilirubin metal complexes, and salts of calcium and other metals. Further studies are needed characterize the relationship of these components to more complex features of gallstones. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 371-380, 1997
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1516-1521 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Electrospray ionization of four structurally diverse natural products, actinomycin D, digitoxin, reserpine and quercetin was investigated. Specific attention was paid to the molecular ions formed under typical reversed-phase high-performance liquid chromatography (RP-HPLC) conditions. The response characteristics of [M + H]+, [M + NH4]+ and [M + Na]+ Ions, observed upon addition of formic acid, ammonium formate and sodium acetate were studied. It was found that the highest response for these molecular ions was obtained with proton, ammonium and sodium ion concentrations of approximately 10-3 ∼ 10-4 M. This critical concentration appears to be correlated with the equilibrium between the thermodynamically controlled molecular ions in solution and electrospray produced gas-phase ions. Gas-phase ion reactions in the ion transfer region were investigated for digitoxin, and the mechanism of gas-phase ion formation is briefly discussed.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 570-572 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: The formation of singly charged oligomers and multiply charged monomers has been studied under different conditions with matrix-assisted laser desorption/ionization and it has been found that the concentration of analyte in matrix solution, as well as the matrix and substrate used, are factors that influence this process. The concentration of analyte in the matrix solution has a strong influence on the formation of singly charged oligomers. When α-cyano-4-hydroxycinnamic acid is used as matrix, more doubly charged monomeric molecular ions are observed than when sinapinic acid is used. By using a nitrocellulose membrane instead of a silver plate as substrate, we find more multiply charged monomers and dimers in the spectra, especially in the case of high mass proteins, such as albumin. It seems that the formation of multiply charged monomers and oligomers is influenced by the overall amount of charge that the sample carries.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 155-160 
    ISSN: 0935-6304
    Schlagwort(e): Solid phase microextraction (SPME) ; Headspace analysis ; Gastight syringe ; Water analysis ; Volatile organic compounds (VOCs) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Headspace solid phase microextraction (headspace SPME) has been demonstrated to be an excellent solvent-free sampling method. One of the major factors contributing to the success of headspace SPME is the concentrating effect of the fiber coating toward organic compounds. The affinity of the fiber coating toward very volatile analytes, such as chloromethane, may, however, not be large enough for detection at the parts per trillion concentration level. Static headspace analysis, on the other hand, is very effective for these very volatile compounds. As analyte volatility decreases, the sensitivity of static headspace analysis drops. The complementary nature of these two sampling methods can be exploited by combining the SPME device with a gastight syringe. The sensitivity of the new sampling device is better than that of SPME for very volatile compounds or that of static headspace analysis for less volatile compounds. This new method can sample a wide range of compounds from chloromethane (b.p. -24°C) to bromoform (b.p. 149°C) with estimated limits of detection at the low parts per trillion level.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 291-297 
    ISSN: 0935-6304
    Schlagwort(e): Gradient ; liquid chromatography ; micro-HPLC ; mixer ; electrospray mass spectrometry ; cytochrome c ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---This paper describes a new method for gradient elution at low flow rate. By adjusting the solvent composition flowing into a dynamic mixer, we can program the concentration of solvent, B, inside a dynamic mixer to form a time-resolved solvent gradient delivered to the column. The input gradient is related to the output gradient by the equation, Bin = Bout + τ × dBout/dt, in which τ is the gradient response time constant at specified flow rate, and Bin and Bout are input and output concentration of solvent B, respectively.
    Zusätzliches Material: 8 Ill.
    Materialart: Digitale Medien
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  • 18
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. S154 
    ISSN: 0749-1581
    Schlagwort(e): EPR spin trapping ; 6,6,-dimethyl-3,4,5,6-tetrahydropyridine N-oxide ; 6-alkoxyl-2,2-dimethylpiperidine-1-oxyl ; aminoxyl (nitroxide) ; conformation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The addition reactions of CH3(CH2)3O·, (CH3)2CHCH2O·, (CH3)2CHCH2CH2O·, (CH3)3CO· and (CH3)2C(CN)O· radicals to a novel six-membered cyclic nitrone, 6,6-dimethyl-3,4,5,6-tetrahydropyridine N-oxide (M2PyO), generate the corresponding 6-alkoxyl-2,2-dimethylpiperidine-1-oxyl aminoxyl (nitroxide) spin adducts. In benzene solution at room temperature, the preferential conformation of these spin adducts appears to be the anomeric conformer with the alkoxyl group in the axial position according to EPR spectroscopic conformational analysis of these aminoxyls. The anomeric effect in these aminoxyls might be the combination of electrostatic and molecular orbital interactions.
    Zusätzliches Material: 4 Ill.
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  • 19
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 18 (1995), S. 579-581 
    ISSN: 0935-6304
    Schlagwort(e): Deactivation ; Packed column SFC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Residual adsorptive activity of reversed phase (RP) column packings used in supercritical fluid chromatography (SFC) can be significantly reduced by a dynamic in-situ silanization with diphenyltetramethyldisilazane (DPTMDS). RP-materials thus deactivated were characterized both chromatographically and by solid-phase 29Si NMR.
    Zusätzliches Material: 3 Ill.
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  • 20
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 666-670 
    ISSN: 0935-6304
    Schlagwort(e): Capillary electrochromatography ; mixed packing technique ; electroosmotic flow ; retention mechanism ; fast analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Mixed packing capillary electrochromatography (MP CEC) with the stationary phase comprising a physical mixture of strong cation exchange (SCX) phase and octadecysilyl (ODS) phase was developed. With the existence of a sulfonic acid group on the surface of SCX, not only could the electroosmotic flow (EOF) remain high at low pH, but also the hydrophilicity of the stationary phase was increased greatly, leading to broad adaptable ranges of both pH and organic modifier concentration in the mobile phase. At the same time, with the coexistence of C18 on the surface of ODS, both the retention and the resolution of samples were improved. Accordingly, MP CEC combined the advantages of both SCX and ODS columns. Effects of operation parameters on EOF and the capacity factors of solutes as well as the retention mechanism of such a column were studied systematically. In addition, MP CEC columns were used in the analysis of strong polar solutes as well as for the high speed separation of acidic, basic, and neutral compounds in a single run.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 21
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Novel cystathionine metabolities, cystathionine sulfoxide and NAc-cystathionine sulfoxide, were identified in the urine of a patient with cystathioninuria using liquid chromatography/mass spectrometry with an atmospheric pressure chemical ionization interface system. NAc-cystathionine sulfoxide was discovered as a new metabolite of cystathionine in the urine of a cystathioninuric patient. The concentrations of cystathionine sulfoxide and NAc-cystathionine sulfoxide in this urine were also determined for the first time using this method, and were 28.69 ± 0.44 and 10.51 ± 0.49 mg g-1 creatinine, respectively. Neither compound was detected in the urine of healthy subjects.
    Zusätzliches Material: 6 Ill.
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  • 22
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 30 (1995), S. 1768-1771 
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 23
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 119-127 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Two-step laser mass spectrometry (L2MS) was applied to study the chemical nature of adsorbates on aerosol particles which were collected from different sites, e.g. in the countryside, in an industrial zone, by a downtown road, and in a tunnel. The method combines infrared laser desorption from the particle surfaces followed by ultraviolet laser post-ionization of the desorbed neutral molecules. Because of the high sensitivity and optical selectivity of L2MS, virtually no sample preparation is needed, and mass spectra can be recorded in a very short time. Qualitative and quantitative comparisons of polycyclic aromatic hydrocarbons in different sampling areas were carried out. By scanning the ionization laser wavelength, two-dimensional UV/MS spectra can be generated for better identification of the adsorbed species.
    Zusätzliches Material: 7 Ill.
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  • 24
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 1 (1995), S. 365-373 
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Fourier transform infrared spectroscopy was used to investigate, without any destructive interference, interactions of the cryoprotective agents, glycerol and dimethyl sulfoxide with Bradyrhizobium japonicum. The intracellular spectrum of glycerol, obtained by subtracting the spectrum of control bacteria from that of glycerol-treated bacteria, showed no differences in infrared features compared to that of pure glycerol. This was not the case when dimethyl sulfoxide treatment was used. The intracellular spectrum displayed important modifications compared to that of the pure chemical. Spectral analysis showed that glycerol and dimethyl sulfoxide uptake required only a few minutes. Moreover, the infrared features resulting from the presence of pure glycerol, in bacteria, were still existent for up to 2 or 3 hours after thawing process. The deconvoluted Amide I and Amide II bands of bacterial proteins reflected important changes in secondary structure after treatment of bacteria with dimethyl sulfoxide (increase in β-sheet and loss of random coil content). In contrast to glycerol, the cryoprotective action of dimethyl sulfoxide probably involves interactions with a wide range of intrabacterial species. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 25
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 565-568 
    ISSN: 0935-6304
    Schlagwort(e): capillary gas chromatography ; precalculation of retention indices ; boiling points ; two- and multidimensional taxonomic groups of organic compounds ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---It was shown that reciprocally unambiguous conformity between GC retention indices (at least for the commonly used standard nonpolar polydimethylsiloxane liquid phases) and boiling points of organic compounds is typical not only within one-dimensional taxonomic groups (homologous series and/or groups of congeners), but also within two- and multidimensional taxonomic groups (with simultaneous variations of some structural fragments). In all cases, this conformity is described by three-parameter non-linear equations log RI = a log Tb + b (n1 + Σ ki ni) + c, where n1 is the serial number of homologue within corresponding series and ni is the number of other structural fragments in the molecules. The coefficients ki in this equation reflect the relative alterations of molecular polarizabilities and may be estimated as ratios of refractions ki = RD(X)/RD(CH2), where X are variable structural fragments within a group of congeners, RD(CH2) = 4.647 cm3mol-1. The approach under discussion permits precalculation of the retention indices of any organic compounds with known boiling points. The precision of proposed method of RI precalculation is comparable with the contemporary level of interlaboratory reproducibility of experimental RI determination with standard nonpolar liquid phases (5-10 i.u.).
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
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  • 26
    ISSN: 1040-7685
    Schlagwort(e): SPE ; LLE ; C-18 bonded disk ; hydrophobic organic compound ; DOC ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effectiveness of solid phase extraction (SPE) using 90-mm EmporeTM C-18 bonded disks and liquid-liquid extraction (LLE) was compared in extraction of municipal wastewater effluent, as well as distilled and sea water. Both SPE and LLE obtained similar recoveries of polycyclic aromatic hydrocarbons and polychlorinated biphenyls from spiked distilled water. Higher recoveries of chlorinated pesticides were achieved from distilled water than from wastewater effluent by SPE. In addition, SPE yielded higher concentrations of PAHs and LABs from effluent samples than did LLE. Apparently, both SPE and LLE were affected by the presence of abundant dissolved organic carbon in wastewater effluent, but LLE suffered more losses. The condensed packing structure in C-18 disks might allow better extraction of hydrophobic organics from wastewater effluent. Alumina/silica gel clean-up after SPE was necessary to obtain acceptable quantitation results for wastewater effluent. SPE was technically as effective as LLE and superior to LLE, because it used less organic solvent and manpower. Usage of high density glass beads with C-18 disks further improved the efficiency of SPE. Lowering the cost of C-18 disks will make disk SPE more appealing. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
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  • 27
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 224-224 
    ISSN: 0935-6304
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 28
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1386-1390 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: [Leu31, Pro34]-Neuropeptide Y is a thirty-six amino-acid peptide which has a measured relative molecular mass of 4222. Solid-phase synthesis of this peptide resulted in complex crudes of synthesis which were examined by capillary zone electrophoresis (CZE)/electrospray ionization mass spectrometry (ES-MS). The separation efficiency of CZE combined with the mass specificity of mass spectrometry yielded rapid and reliable information on the target peptide and a number of associated side products, which were mainly acetylated peptide sequences having relative molecular masses in the range 2240-4101. Such incomplete or, as they are commonly called, difficult sequences are provoked by problems of swelling and aggregation of the growing peptide chains in the course of synthesis. The use of mass spectrometry is indispensable for obtaining reliable information on the inevitable side products. Initial tuning of the ion source and optimization of the coupling between the CZE system and the mass spectrometer were achieved by performing a number of measurements pertaining to artificially made mixtures of commercial neuropeptides.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 29
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 83-88 
    ISSN: 0935-6304
    Schlagwort(e): Large volume injection ; programmed-temperature vaporizer ; organic acids ; phenols ; derivatization ; trimethylsulfonium hydroxide ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---The combination of on-line methylation using trimethylsulfonium hydroxide with large volume injection of 100 μL was evaluated for the analysis of organic acids and phenols in water. Solvent split injection was applied with complete evaporation of the solvent before analytes were transferred onto the GC column. Despite complete solvent removal, losses were very low compared to conventional splitless injection even for volatile acidic compounds such as propionic acid and phenol. This is explained by intermediate formation of low volatility trimethylsulfonium salts of the analytes which were held in the injector for long evaporation times of up to 10 min, if the evaporation temperature was as low as 10°C. Using a simple liquid/liquid extraction procedure, volatile fatty acids, dicarboxylic acids, benzoic acids and phenols could be detected in 5 mL of water at concentrations of 0.04-0.1 μmol/L with GC/MS in full scan mode. Lactic, pyruvic, and also malonic acids could only be detected at higher levels because of their limited extractability from water as well as their poorer methylation yields. The method provides an easy way to sensitively detect acidic compounds of medium to high volatility in water. It was applied for screening of organic acids and phenols in batch cultures of anaerobic bacteria of which one example is shown.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 30
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 124-127 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 1H NMR ; Vassopressin derivatives ; Chemical exchange ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Proton exchange rates between the solvent H2O and the amidic protons of a nonapeptide (1-desamino-8-D)-argininevasopressin in aqueous solution were determined by using selective nuclear magnetic double-resonance methods. Transverse magnetization, the magnitude of which depends on the chemical exchange rate and the relaxation time T1, is transferred via doubly selective homonuclear Hartmann-Hahn mixing to a scalar coupling partner. With respect to well established two-dimensional experiments, this one-dimensional alternative has two advantages: it is much less time consuming and, as a true benefit, it is even applicable when two signals which are in exchange with the same compound (solvent) are overlapping. The evaluation of amide proton exchange rates in the investigated peptide led to the assumption of an intramolecular hydrogen bond.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 31
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 421-425 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 1H NMR ; peptide T ; HIV ; structure determination ; Hartmann-Hahn transfer ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The conformation of Peptide T in aqueous solution was investigated by means of 1H NMR spectroscopy in one and two dimensions. The data were compared with those obtained previously for the peptide in DMSO solution. While Peptide T forms a β-turn in DMSO, no evidence was found for such a structure in water. Instead, Peptide T exists in aqueous medium in a random coil conformation with an increased tendency to form a stretched chain at the ends of the peptide backbone. This partly populated β-strand was identified mostly by the analysis of atomic distances and coupling constants. To evaluate NMR parameters such as chemical shift and scalar coupling constants in the heavily overcrowded spectral regions, selective homonuclear Hartmann-Hahn transfer was employed, which allows the observation of a distinct multiplet through the excitation of its scalar coupling partner, and subsequent magnetization transfer.
    Zusätzliches Material: 7 Ill.
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  • 32
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 577-580 
    ISSN: 0749-1581
    Schlagwort(e): 1H NMR ; selective pulses ; H,C correlation ; ROE ; glutathione ; 1-O-Methyl-4,6-O-benzylidene-α-D-glucopyranoside ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A 1D H, C correlation ROESY experiment is suggested and applications for signal assignments via through-bond and through-space correlations are demonstrated using glutathione and 1-O-methyl-4,6-O-benzylidene-α-D-glucopyranoside.
    Zusätzliches Material: 4 Ill.
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  • 33
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 245-246 
    ISSN: 0935-6304
    Schlagwort(e): Chloride ; suppressed ion chromatography ; concrete ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 34
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 247-249 
    ISSN: 0935-6304
    Schlagwort(e): High performance liquid chromatography-ultraviolet detection (HPLC-UV) ; Amitraz ; cattle dipping bath ; pesticide ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 35
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 9-14 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Resonance Raman and infrared spectra of the organic superconductor K-(MDT-TTF)2AuI2 were measured to identify the vibrational modes which exhibit strong electron - molecular vibration (EMV) coupling. Excitation wave-length dependence of certain Raman modes was observed and is discussed in connection with the UV - visible absorption spectrum. Raman spectra measured at 77 K revealed a significant enhancement of a low-wavenumber mode attributed to the organic part, while the symmetric AuI2- anion was found to be unaffected at low temperatures.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 36
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Mass Spectrometry Reviews 14 (1995), S. 21-48 
    ISSN: 0277-7037
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 37
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Microcolumn Separations 7 (1995), S. 153-158 
    ISSN: 1040-7685
    Schlagwort(e): silica gel ; PLOT column ; column technology ; gas chromatography ; light hydrocarbons ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: We report a simple method for the preparation of silica PLOT columns using fused silica capillaries. In this method, silica particles were suspended in a methylene chloride/pentane solution containing polymethylhydrosiloxane and passed through the capillary tubing. This caused the silica particles to be dynamically coated on the inner wall of the fused silica capillary. The column was dried and heated, which facilitated the simultaneous deactivation and bonding of a uniform mono-layer of porous silica on the inner wall of the capillary tubing. These columns were used to separate light hydrocarbons, chlorinated hydrocarbons, and aromatic compounds.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 38
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Microcolumn Separations 7 (1995), S. 207-212 
    ISSN: 1040-7685
    Schlagwort(e): charcoal ; active carbon ; PLOT column ; column technology ; gas chromatography ; permanent gases ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The preparation of charcoal porous layer open tabular (PLOT) columns, and their application to the separation of permanent gases and light hydrocarbons are reported. Two types of charcoal, coconut and darco charcoal, were used to prepare columns from fused silica capillaries. The performance of these columns was compared to that of a commercially available carbon molecular sieve PLOT column. The coconut charcoal PLOT column produced good retention and resolution for both permanent gases and light hydrocarbons; all separations were achieved in less than eight minutes under isothermal conditions. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 39
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 573-576 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: The mass spectrometric behavior of some diene-based sex pheromones of lepidopterous insects, under electron impact ionization conditions, was studied with the aid of mass-analyzed ion kinetic energy spectroscopy and high-resolution data. The similarity of the mass spectra of these dienes and their ability to distinguish double bond positional isomers and geometrical isomers was examined by a ‘minimum-maximum’ similarity analysis.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 40
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: We report the measurement of backscattering in-phase dual circular polarization (DCPI) Raman optical activity (ROA) for the simple alanyl peptides L-alanyl-L-alanine ([L-Ala]2), L-alanylglycine (L-Ala-Gly), glycyl-L-alanine (Gly-L-Ala), and L-alanyl-L-alanyl-L-alanine ([L-Ala]3) in aqueous solutions. Empirical correlations between ROA features and the amino acid composition of the peptides are described. It is shown that the sum of the DCPIROA spectra for L-Ala-Gly and Gly-L-Ala is nearly the same as the corresponding ROA spectrum for (L-Ala)2. Additionally, the DCPIROA spectrum for (L-Ala)2 is very close to that of (L-Ala)3, as has been observed previously using backscattering unpolarized incident circular polarization (ICPu) ROA. The ROA contributions of the different L-Ala groups, which occur separately in the two glycyl peptides of alanine and jointly in (L-Ala)2, are described in terms of the extent of vibrational coupling between peptide subunits. From these results, it appears that ROA has a more local sensitivity to vibrational coupling than is found in VCD or electronic circular dichroism. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
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  • 41
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The backscattering in-phase dual circular polarization (DCPI) Raman and Raman optical activity (ROA) for a series of terpene molecules is reported. The selected molecules were studied in three groups of closely related structures and correlations between ROA features and structural elements among molecules within these groups are discussed. One aim of this study was to uncover additional details regarding the sensitivity of ROA to stereostructural features in molecules and to elucidate further the degree of local character of this new stereochemical probe. Another was to compare the backscattering DCPI ROA intensities reported here with those obtained using depolarized right-angle incident circularly polarized (ICP) ROA for some of the same molecules more than a decade ago.
    Zusätzliches Material: 15 Ill.
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  • 42
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 19 (1996), S. 247-256 
    ISSN: 0935-6304
    Schlagwort(e): Gas chromatography with electron capture detection ; Solid phase microextraction ; Organochlorine pesticides ; Water analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: This paper describes the extraction of 20 organochlorine pesticides (OCPs) from water samples using solid-phase microextraction (SPME). Three fused-silica fibers coated or bonded with polydimethylsiloxane (PDMS) of different film thicknesses (20-, 30-, and 100-μm) were evaluated. The extraction time, the effects of stirring and addition of NaCl to the aqueous sample, the linear range and the precision of this technique, and the effect of carryover were examined for 20 analytes and are presented here. A comparison with results using conventional liquid-liquid extraction demonstrate that the SPME technique is well suited as a fast screening technique for OCPs in water samples.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 43
    ISSN: 1075-4261
    Schlagwort(e): protein structure ; cytochrome b5 reductase ; recombinant mutant ; FTIR ; ferredoxin-NADP+ reductase ; thermal denaturation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Fourier-transform infrared (FTIR) spectroscopy was used to study the change of protein structure of NADH-cytochrome b5 reductase in a soluble form. Recombinant mutant cytochrome b5 reductases, serine 127 to proline (S127P), and alanine (S127A) were investigated, where the mutation on Ser-127 to proline is a case found in patients of type II methemoglobinemia. The secondary structure of cytochrome b5 reductase was revealed tentatively by FTIR using resolution enhancement and band-fitting techniques, providing the contents of α-helix (22%), β-sheet (30%), random coil (27%), and β-turn (22%) for the wild-type cytochrome b5 reductase. The mutant enzyme, S127P, was more sensitive to the thermal denaturation than the wild type with increasing β-sheet structures observed at 1624 and 1672 cm-1 during the heat treatment and relatively decreasing in intensities of bands around 1640-1660 cm-1 during heat treatment. The secondary structure of ferredoxin-NADP+ reductase, one of the same family as cytochrome b5 reductase, predicted from FTIR data was similar to that of the wild-type cytochrome b5 reductase but significantly different in the content of β-sheet and was consistent with the X-ray crystallographic data of ferredoxin-NADP+ reductase. The mutation on Ser-127 to proline or alanine in cytochrome b5 reductase caused only a small change (3 or 9%, respectively) in total of α-helix, random coil, and β-turn contents and almost no change in the β-sheet content. These results suggest that the lability of the mutated cytochrome b5 reductases might not result simply from the secondary structural change but from possibly the tertiary structural change, including the peptide side chain positional and the protein-protein interactional changes. © 1997 John Wiley & Sons, Inc. Biospect 3: 215-223, 1997
    Zusätzliches Material: 7 Ill.
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  • 44
    ISSN: 1075-4261
    Schlagwort(e): brain microsomal membranes ; fatty acids ; learning behavior ; FTIR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: We measured the Fourier transform infrared spectra of brain microsomal membranes prepared from rats fed under two dietary oil conditions with and without brightness-discrimination learning tasks: one group fed α-linolenate deficient oil (safflower oil) and the other group fed the sufficient oil (perilla oil) from mothers to offspring. The infrared spectra of microsomes under the two dietary conditions without the learning task showed no significant difference in the range 1000-3000 cm-1. Only after the learning task were the infrared spectral differences noted between the microsomal membranes from both groups. Spectral differences were observed mainly in the absorption bands of fatty acid ester at around 1730 cm-1 (sn-2 position), those of phosphate and oligosaccharides in the range of 1050-1100 cm-1, and a band at around 1145 cm-1. The infrared band of fatty acid ester at the sn-2 position in the microsomal membrane shifted to a longer wavenumber position in the perilla oil group than in the safflower oil group, suggesting a difference between both groups in hydrogen bonding of the fatty acid ester with water. A band observed at 1055 cm-1 and a small band at around 1145 cm-1 in the second derivative spectrum decreased in intensity in the perilla oil group after learning task. These bands were assigned mainly to the oligosaccharide C - O bond in hydroxyl groups that might interact with some other membrane components. These results suggest changes in hydration of membrane surface and modification in oligosaccharide environment (removal or modification) of microsomes, which may be correlated in part with dietary oil-induced changes in learning performance. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 281-290, 1997
    Zusätzliches Material: 4 Ill.
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  • 45
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 532-536 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Tandem mass spectrometric (MS/MS) collision-induced dissociation (CID) mass spectra of the molecular ion and main fragment ions in electron ionization of a series of pesticides were recorded using a triple quadrupole mass spectrometer. The fragmentation pathway map of simazine was deduced from the CID mass spectra. The utility of these CID fragmentation ions is demonstrated in the gas chromatography/MS/MS spectrum of carbofuran.
    Zusätzliches Material: 3 Ill.
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  • 46
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A hydride Meisenheimer complex of 2,4,6-trinitrotoluene (TNT) (TNTH-) was synthesized using tetramethylammonium octahydroborate. TNT and TNTH- (as the tetramethylammonium salt) were analyzed by direct exposure probe mass spectrometry using electron impact (EI), chemical ionization (CI) and negative-ion chemical ionization (NCI). For further identification, the ions of the mass spectra were investigated using tandem mass spectrometry with collision-induced dissociation (CID). Although the EI mass spectra of both compounds were similar, the CID mass spectra of the ions at m/z 227 (M+ of TNT) of the two compounds showed large differences in daughter ion abundances. A major difference between the two compounds also appeared in their CI methane mass spectra. Two abundant ions, at m/z 183 and 198, appeared only in the CI mass spectrum of TNNH-. CID parent ion scans showed that the origin of these two ions was not the m/z 227 ion. We suggest that these ions are formed by chemical reactions of the complex on the surface of the heated probe tip, followed by ionization. These reactions, probably a reduction process forming m/z 198 and hydrolysis forming m/z 183, occur preferentially in TNTH-, the already reduced form of TNT. Formation of the ions at m/z 183 and 198 was also observed in the liquid chromatography particle beam CI mass spectrum of TNTH-.
    Zusätzliches Material: 9 Ill.
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  • 47
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Mass Spectrometry Reviews 14 (1995), S. 179-194 
    ISSN: 0277-7037
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: 1,25-dihydroxyvitamin D3 is the active metabolite of vitamin D3, and has been found to play important roles in mineral balance and immunological regulation. Recently, 1,25-dihydroxyvitamin D3 and similar synthetic analogs in development have been found to possess potential therapeutic values in the treatment of proliferative diseases, including leukemia, breast cancer, and psoriasis. Current methods for the analysis of these compounds may either lack the necessary sensitivity (i.e., UV detection) or specificity (i.e., receptor binding assay). In addition, the synthetic analogs developed to date have not been found to uniformly bind with receptors in binding assays, a property that may render them to be difficult for measurement at the trace levels. Methods utilizing mass spectrometry (MS) have been used for either structural identification or quantification. Electron impact ionization has been the technique of choice for structural analysis, whereas newer ionization techniques have been utilized for the quantification of metabolites, often in conjunction with on-line separation. In this review, MS and non-MS based methods for vitamin D analysis will be discussed, with an emphasis on the former. Historical perspectives, the present state, and the future role of MS in vitamin D research will be discussed. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 13 Ill.
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  • 48
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: A gas chromatographic/mass spectrometric method was developed for the simultaneous determination of five synthetic pyrethroid insecticides in soil, moss and fish tissue. These pyrethroids were extracted with hexane-dichloromethane by ultrasonication and cleaned up on Florisil (soil and moss) and mixed acid/base alumina (fish) columns prior to determination by gas chromatography/negative-ion chemical ionization mass spectrometry in selected ion monitoring mode. All the pyrethroids were analyzed simultaneously in a single run on a DB5-MS 15 m capillary column. Recoveries of the pyrethroids from the three matrices at fortification levels of 10, 50 and 100 μg/kg ranged from 80 to 117%. Four determinations were made at each concentration level for each matrix. The practical determination limit of the method was in the range 0.5 to 5 μg/kg depending on the compound. This method was also applied to samples obtained from a contaminated ecosystem.
    Zusätzliches Material: 5 Ill.
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  • 49
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: A fused-silica capillary high-performance liquid chromatography column (i.d. 0.25 mm) packed with octadecylsilane-bonded silica has been used on-line with continuous-flow negative-ion fast-atom bombardment (FAB) mass spectrometry for the separation and structural analysis of series of fatty acids and arachidonic acid metabolites derivatized with 4-aminobenzenesulphonic acid. Negative-ion FAB spectra of the derivatized lipids showed strong [M—H]- pseudomolecular ions. Collision-induced dissociation of these anions produced structurally informative daughter ions, arising from charge-remote fragmentations.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 50
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 18 (1995), S. 443-445 
    ISSN: 0935-6304
    Schlagwort(e): Micellar Electrokinetic Chromatography (MEKC) ; Ionic polymer ; Polycyclic aromatic hydrocarbons (PAHs) ; Alkylphenones ; Fullerenes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 51
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ion-molecule reactions in a pentaquadrupole mass spectrometer are used to generate cluster ions in which neutral pyridine molecules are bound to a linear polyatomic cation, [OCNCO]+. The dimeric adduct, viz. Py1[OCNCO]+Py2 where Py1 and Py2 represent substituted pyridines, formed upon reaction of mass-selected [OCNCO]+ with a mixture of pyridines, has a loosely bound structure, as suggested by triple stage mass spectrometric (MS3) experiments. Dimeric adducts comprised of meta- and/or para-substituted pyridines (unhindered pyridines) display an excellent linear correlation between the fragment ion abundance ratio ln [Py1[OCNCO]+/Py2[OCNCO]+] and the proton affinity difference of the pyridines. On the assumption that the effective temperature of the [OCNCO]+ -bound dimers is similar to that of the corresponding Cl+-bound dimers, [OCNCO]+ affinities of the substituted pyridines relative to pyridine are estimated to be 3-MePy 2.3, 4-MePy 3.2, 3-EtPy 3.5, 4-EtPy 4.1, 3,5-diMePy 4.9 and 3,4-diMePy 5.6 kcal mol-1 (1 kcal = 4.184 kJ). A linear relationship between the relative [OCNCO]+ cation affinity and the relative proton affinity (PA) is derived as relative [OCNCO]+ affinity (kcal mol-1) = 0.96 ΔPA, using the assumed effective temperature of 555 K. Dimers consisting of ortho-substituted pyridines display substantial steric effects between the ortho-substituted alkyl group and the central [OCNCO]+ cation. A set of gas-phase steric parameters (Sk) is determined and steric effects are ordered 2-MePy (-1.39) 〈2,5-diMePy (-3.02) 〈 2,4-diMePy (-3.15) 〈 2,3-diMePy ( -3.29) 〈 2,6-diMePy (-5.09) 〈 2,4,6-triMe (-6.13). A greater steric effect is experienced in the [OCNCO]+ system than in the corresponding Cl+ system, owing to the larger central ion in Py[OCNCO]+ Py. Structural and electronic information regarding the bond angles, bond lengths and charge density distributions in [OCNCO]+, Py[OCNCO]+ and Py[OCNCO]Py+ was obtained from ab initio calculations. The calculations show that [OCNCO]+ is linear with high positive charge densities on the carbon atoms. The calculations also reveal that the Py[OCNCO]+ monomer is a planar ion with the nitrogen atom of pyridine bound to a carbon atom of the [OCNCO]+ cation, and that the Py[OCNCO]Py+ dimer is a symmetrical ion in which the nitrogen atoms on the pyridine molecules bind to the carbon atoms of the central cluster ion, [OCNCO]+.
    Zusätzliches Material: 6 Ill.
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  • 52
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Ion-molecule reactions occurring in a pentaquadrupole mass spectrometer are used to generate and characterize ions in which one or two pyridine molecules are bound by a +CN cation. Cyanide cation binds strongly to the nitrogen atom of pyridine to generate a mono-adduct, which undergoes pyridine exchange reactions and from which one can generate the dipyridine adduct in low abundance. The dimeric ions have two structures, loosely bound and covalently bound, and both fragment to yield the constituent cyanide-bound monomers. In the case of dimers comprised of meta-substituted alkylpyridines, there is a quantitative correlation between relative cyanide cation affinity, as measured using the kinetic method, and literature values of relative proton affinities. These dimers fragment analogously to the corresponding H+- and Cl+- bound dimers, and on this basis are assigned analogous structures, viz. the loosely bound form Py1—+CN—Py2. Semi-empirical molecular orbital calculations show that both pyridines are bound to the carbon atom of the cyanide cation. Making the assumption that the effective temperatures of the activated cyanide-bound dimers are similar to those of the corresponding Cl+- and H+-bound dimers, relative +CN cation affinities are estimated to be 1.5 kcal mol-1 (3-MePy), 1.7 kcal mol-1 (4-MePy), 2.6 kcal mol-1 (3-EtPy), 3.5 kcal mol-1 (3-n-BuPy) and 3.6 kcal mol-1 (3,5-diMePy), all expressed relative to pyridine (1 kcal = 4.184 kJ). A linear relationship between the relative +CN affinity and relative proton affinity (PA) is derived as Δ +CN affinity (kcal mol-1) = 0.78 (ΔPA), with the assumption that the +CN dimer effective temperature is 600 K. The estimated uncertainty is 0.5 kcal mol-1. Relative +CN affinities of pairs of pyridines are smaller by ca. 1 kcal mol-1 than the corresponding Cl+ affinities. Dimers in which one of the pyridines is meta-chlorine- or para-alkyl-substituted have the covalently bound, ring-carbon-substituted structure, in which the +CN group is attached to the pyridine nitrogen and the second pyridine molecule is bound to a ring carbon. The fragmentation of these isomeric dimers yields the corresponding monomers, in addition to other minor ions, but the distribution of the cyanide cation between the two pyridines does not correlate with Cl+ affinity or proton affinity. In the special cases of the 3-methylpyridine-3-n-butylpyridine and the 4-methylpyridine-pyridine cyanide cation adducts, both the loosely bound dimer and the covalently bound adduct are generated and distinguished by their fragmentation behavior. Evidence for the formation of the covalently bound, ring-carbon-substituted structure was also obtained in semi empirical AMI calculations.
    Zusätzliches Material: 5 Ill.
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  • 53
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 18 (1995), S. 725-726 
    ISSN: 0935-6304
    Schlagwort(e): Capillary GC ; Column technology ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 54
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 308-311 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; selective HOHAHA ; coherence transfer ; relaxation time of proton ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A method to implement selective homonuclear Hartmann - Hahn transfer by using two coherent r.f. channels has been developed. This new method does not require complex pulse sequences. When this approach is combined with selective relaxation measurements, the proton relaxation times (T1, T2 and T1p) of individual protons can be determined even when the signals are hidden under other resonances. An example of the use of this method for the analysis of ribonuclease H is given.
    Zusätzliches Material: 5 Ill.
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  • 55
    ISSN: 1075-4261
    Schlagwort(e): doxorubicin ; intercalation ; resonance Raman ; SERRS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: The interactions of doxorubicin and its derivatives, hydroxyrubicin and adriamycinone, with DNA were studied by resonance Raman (RR) and surface-enhanced resonance Raman scattering (SERRS) spectroscopy. The π-π interaction between the chromophore of the drug and DNA base pairs has been shown to downshift the skeletal stretching mode ∼ 1440 cm-1 by 8, 5, and 4 cm-1 for doxorubicin, hydroxyrubicin, and adriamycinone, respectively. The additional effects of intercalation with DNA on the RR and SERRS spectra for hydroxyrubicin are similar to those for doxorubicin. However, different effects are observed for adriamycinone. These results indicate that the sugar moiety is necessary to maintain the maximum van der Waals contact between the chromophore and the DNA base pairs and that the amine group in the amino sugar is more favored than the hydroxyl group. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 307-316, 1997
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 56
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The molecular ion of intact β-endorphinbovine, 1-31 (BE), which was extracted from bovine pituitary, was determined by electrospray ionization mass spectrometry. Liquid secondary ion mass spectrometry determined the molecular masses of three peptides produced by trypsin digestion of BE, and tandem mass spectrometry was used to determine the amino acid sequence of the tryptic peptide BE20-24. These data, in combination, were used to characterize BE in bovine pituitary.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 57
    ISSN: 0935-6304
    Schlagwort(e): Enantiomer separation ; Amino alcohol ; (R)-Mandelic acid ; Ligand exchange chromatography ; Chemiluminescence ; Ruthenium ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 58
    ISSN: 0935-6304
    Schlagwort(e): Ligand-exchange chromatography ; dodecyl-norephedrine ; enantiomeric separation ; amino alcohol ; coating ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Underivatized aliphatic β-amino alcohols with a primary or secondary alcohol moiety were separated into enantiomers by high performance liquid chromatography using octadecylsilanized silica coated with N-n-dodecyl-(1R,2S)-norephedrine as the stationary phase and an aqueous solution containing copper(II) and barbital as the mobile phase.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 59
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 487-489 
    ISSN: 0935-6304
    Schlagwort(e): Carboxymethyl derivatives of amines ; dodecyl-L-hydroxyproline ; chelate ring ; chemiluminescence ; ruthenium complex ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Carboxymethyl derivatives of amines containing a chiral α-carbon were separated into enantiomers by high-performance liquid chromatography using octadecylsilanized silica gel coated with N-n-dodecyl-L-hydroxyproline as the stationary phase and an aqueous solution containing copper(II) as the mobile phase. Detection was by post-column reaction involving derivatization to tertiary amine and chemiluminescence reaction of ruthenium bipyridine complex.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 60
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 315-316 
    ISSN: 0935-6304
    Schlagwort(e): Tertiary amine ; ruthenium ; chemiluminescence ; photochemical oxidation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 61
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1335-1341 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: The behavior of peptides containing multiple tyrosine-O-sulfates in liquid secondary-ion mass spectrometry (LSIMS) has been investigated. In the positive-ion spectra of the peptides containing two tyrosine-O-sulfates, Cionin and CCK-associated C-terminal nonapeptide (CAP-9), the completely desulfated [M+H-2SO3]+ ions formed the base peaks, accompanying the significantly less-intense [M+H]+ and [M+H-SO3]+ ions. In the negative-ion spectra of these peptides, the [M-H]- and [M-H-SO3]- ions gave prominent peaks with significantly weaker [M-H-2SO3]- ions. In the case of a peptide containing three tyrosine-O-sulfates, [Tyr(SO3H)1]CAP-9, the completely desulfated [M+H-3SO3]+ ion again formed the base peak in the positive-ion spectrum. On the other hand, the sulfated tyrosine-containing [M+H]+, [M+H-SO3]+, and [M+H-2SO3]+ ions were of negligible abundance compared to the spectra of peptides containing two tyrosine-O-sulfates. We observed an intriguing ‘ladder fragmentation pattern’ in the negative-ion spectrum of this triply-sulfated peptide. The ladder consisted of the [M-H]-, [M-H-SO3]-, and [M-H-2SO3]- ions, but without the completely desulfated [M-H-3SO3]- ion. These characteristic fragmentation patterns of sulfated tyrosine-containing peptides were considered to bear a close correlation with the inherent acid-lability of a tyrosine-O-sulfate in solution. A possible mechanism has been proposed to explain the fragmentation patterns in the gaseous phase, in which a proton plays a decisive role.
    Zusätzliches Material: 7 Ill.
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  • 62
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1572-1575 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Linear oligogalacturonic acids (1,4-linked α-D-galacturonic acid oligomers), obtained by partial acid hydrolysis of orange polygalacturonides, were studied by negative-ion electrospray ionization mass spectrometry, without prior sample derivatization. After preparative separation using high-resolution anion-exchange chromatography, some fractions enriched in uronic acids were desalted, transferred into a methanol+water solution adjusted to pH 10, and directly submitted to electrospray ionization mass spectrometry in the negative-ion recording mode. Clear molecular mass assignments of the oligomers, covering a degree of polymerization between 4 and 7, were obtained.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 63
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 150-155 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: In this paper we report our studies of reduction phenomena in a high performance liquid chromatography/particle beam interface-mass spectrometer system (HPLC/PB-MS). It is shown that reduction takes place in the ion source of the mass spectrometer, but that the particle beam interface plays an important role in the reduction process since the HPLC mobile phase is involved in the reduction. HPLC flow rate and desolvation-chamber temperature have significant effects on the reduction extent, while ion-source temperature has only a minor effect. All the nitro compounds and sulfoxides tested in this work showed reduction in the system. There was no observed reduction for sulfones. 1,4-Naphthaquinone showed significant reduction, while no reduction was observed for anthraqunone.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
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  • 64
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The mass spectral fragmentations of sixteen new 2-and 4-o-(m- and p-)substituted benzylthiouracils and o-(m- and p-)substituted 2,4-dibenzylthiouracils with NO2 and CI substituents in the benzyl groups were investigated. Fragmentation pathways are proposed on the basis of accurate mass and metastable transitions measurements. The correlation between the abundances of the M+· and the selected fragment ions of investigated compounds is discussed. The data obtained create the basis for distinguishing structural isomers.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 65
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 561-569 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The effects of electronic coherence of doubly or triply degenerate levels are discussed. This coherence will show up in the anisotropy of a pump - probe experiment in which a pump pulse creates the coherence and a probe pulse connects the degenerate levels to a non-degenerate final state. Simple stochastic models for the decay of the anisotropy as a function of pump - probe delay are given, both for molecules with a high symmetry and for symmetric dimers and trimers. The possible role that degenerate level coherence may play in chemical reactions is also discussed. Finally, the stochastic models used to calculate the anisotropy decay are applied towards the calculation of absorption line shapes, Raman scattering and fluorescence.
    Zusätzliches Material: 6 Ill.
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  • 66
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 1 (1995), S. 55-69 
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Fast photovoltage measurements are a valuable tool for the study of trapping of excitation energy, kinetics of charge separation, and relative distances of intermediary acceptors in the photosynthetic reaction center. Recent advances of both, the technique and the data analysis have not been described before. Here, in a first article of this sequence, we describe a theoretical model of the primary photosynthetic reactions and the computer analysis of transient photovoltage as well as of fluorescence data. The model assumes free energy migration between photosynthetic units and takes into account specific effects of high energy excitation like the acceleration of the trapping kinetics, the quenching of the excited state by oxidized reaction centers, and the nonlinear process of exciton-exciton annihilation. Furthermore, the finite duration of the picosecond flashes is considered. The approximations involved in this model are discussed with respect to different functional antenna organizations. In a second article of this sequence we describe the experimental set-up, calibration procedures and the application of the present theory to experimental data. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 67
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 963-967 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: High-pressure Raman spectra of liquid and solid CH4 and CD4 were measured up to 18 and 13 GPa, respectively, at 300 K in a gasketed diamond-anvil cell. On the basis of visual observations under the polarizing microscope and changes in the Raman spectra, it was confirmed that there are only two solid phases (I and VII) for CH4 and CD4 at 300 K up to 18 GPa; no solid-solid phase transition was found around 12 GPa, in contrast to earlier claims. In phase VII, some molecules are orientationally ordered, whereas others are orientationally disordered, just like the low-temperature solid phases II, III, IV and V.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
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  • 68
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 541-546 
    ISSN: 0935-6304
    Schlagwort(e): Solvating gas chromatography ; gas chromatography ; fast separation ; pesticides ; herbicides ; aldehydes ; packed capillary columns ; polymer-encapsulated silica ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---Rapid separations of selected environmentally important polar compounds using polymer-encapsulated silica stationary phases and a carbon dioxide mobile phase under solvating gas chromatography (SGC) conditions are reported. Ten underivatized short chain aldehydes and ten nitrogen-containing herbicides were separated within 1 min and 5 min, respectively, using a 30 cm×250 μm i. d. column packed with diol-bonded, polyethylenimine (PEI)-coated, and hexamethyldisilazane (HMDS)-end-capped silica particles (5 μm, 120 Å). Seven organophosphorus pesticides were resolved in less than 5 min using a 30 cm×250 μm i. d. column packed with polymethylhydrosiloxane-deactivated and SE-54 encapsulated silica particles. Separation numbers per unit time increased with pressure and temperature ramps. Both rapid pressure and temperature programming can be used to increase the speed of SGC. The effects of pressure and temperature on apparent retention factors of solutes with various polarities were investigated using diol-PEI-HMDS silica particles in SGC.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
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  • 69
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 22 (1999), S. 279-282 
    ISSN: 0935-6304
    Schlagwort(e): Solid phase microextraction (SPME) ; SPME/HPLC interface ; C-8 refocusing unit ; explosives analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---No abstract
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
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  • 70
    ISSN: 1075-4261
    Schlagwort(e): black pigment gallstone ; FTIR ; EPR ; nonlinear phenomena ; vibrational mode ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Further spectroscopic studies of gallstones are reviewed with an emphasis on the formation of black pigment gallstones. This type of gallstone appears mainly in Western countries, with only 3% of the cholelithiasis patients in China having black gallstones. Fourier transform infrared absorption and electron paramagnetic resonance are used as spectroscopic probes of gallstones and their metal bilirubinate components. Nonlinear phenomena in gallstone formation were investigated through the appearance of ring structure in gallstones and fractal patterns in the formation in the precipitates of bile salt systems. Although a complete understanding of gallstone formation has not yet been achieved, interesting progress toward this goal has been made recently. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 381-391, 1997
    Zusätzliches Material: 12 Ill.
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  • 71
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 31P NMR ; solid state ; CP/MAS ; crystallographically equivalent nuclei ; 2J(31P, 31P) ; 1J(109/107Ag, 31P) ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Solid-state 31P magic angle spinning (MAS) NMR spectra of Ag[P(m-tolyl)3]2NO3 were investigated as a function of the magic angle spinning frequency. Examination of the 31P MAS NMR spectra obtained at 4.70 and 9.40 T indicates that the two phosphorus nuclei have identical isotropic chemical shifts, that is, they are crystallo-graphically equivalent, δ = 11.2 ppm. However, since the orientation of their respective chemical shift tensors is not coincident, the two phosphorus nuclei are magnetically non-equivalent and exhibit spinning-frequency dependent 31P NMR lineshapes. Analysis of the spinning-frequency dependent 31P MAS NMR spectra at 4.70 and 9.40 T indicates that 2J(31P, 31P) = 140 Hz. This value was confirmed by 2D J-resolved spectroscopy. The determination of an indirect spin-spin coupling constant between two nuclei which constitute an ‘isolated’ spin pair with identical isotropic chemical shifts is not possible in conventional solution-state NMR studies unless a third spin is introduced. The 31P MAS NMR spectra of Ag[P(m-tolyl)3]2NO3 also exhibit resolvable splittings due to 109Ag and 107Ag; 1J(109Ag, 31P) = 517±5 Hz and 1J(107Ag, 31P) = 453 ± 5 Hz. In solution NMR studies these couplings are not always observed because of rapid metal-ligand exchange.
    Zusätzliches Material: 4 Ill.
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  • 72
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 3 (1997), S. 457-467 
    ISSN: 1075-4261
    Schlagwort(e): infrared ; calcium ; amino acid ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: The absorption spectra of 20 amino acids (Gly, Ala, Val, Leu, Ile, Ser, Thr, Asp, Asn, Glu, Gln, Lys, His, Arg, Phe, Trp, Cys, Met, Pro, and hexafluorovaline) and some of their metabolites (α-ketoglutarate, oxalacetate, pyruvate, succinate, citrate, and acetate) were determined in the infrared (IR) region from 1300 to 1700 cm-1 under conditions that are appropriate for biological studies (i.e., in phosphate-buffered D2O solution). The strongest transition in this region is $\nu^{\rm a}_{\rm OCO}$, with an extinction coefficient ∼1 mM-1 cm-1, and an emphasis was made to demonstrate use of this transition for enzymatic assays and to study proteins. To these ends, these relevant features were demonstrated. The value for $\nu^{\rm a}_{\rm OCO}$ is a function of the residue pK: the higher the frequency, the lower the pK of the carboxylic acid. The high extinction of $\nu^{\rm a}_{\rm OCO}$ permits detection of carboxyl groups in parvalbumin, a protein that is rich in Asp and Glu. The IR profiles for the amino acids and their metabolite products are sufficiently characteristic so that IR can be used to monitor enzymatic reactions involving amino acids. We show that transaminase reactions, which interconvert amino and keto acids, can be monitored by IR. © 1997 John Wiley & Sons, Inc. Biospectroscopy 3: 457-467, 1997
    Zusätzliches Material: 10 Ill.
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  • 73
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 21 (1998), S. 498-504 
    ISSN: 0935-6304
    Schlagwort(e): Nonaqueous solvents ; capillary electrophoresis ; charge transfer complexation ; argentation ; silver ion ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: ---This study represents the first application of Ag(I) charge transfer complexation in nonaqueous capillary electrophoresis. This method applies the principles of argentation chromatography to nonaqueous electrophoretic separations and is termed “nonaqueous argentation electrophoresis”. Since the separations are performed in 100% nonaqueous media, the advantages of nonaqueous solvents, such as enhanced solubility and flexibility in selectivity enhancement, compared to an aqueous or mixed hydroorganic solvent, are realized. A variety of compounds were separated. Qualitatively, the separation of eleven sulfonamides in 100% acetonitrile is shown to improve greatly upon the addition of Ag(I). These results also show that nonaqueous argentation electrophoresis provides fast, well-resolved separations of compounds, such as N-containing heterocyclics, that can selectively complex with Ag(I). Migration data and separation selectivities of these compounds by nonaqueous argentation electrophoresis were compared to previous aqueous argentation electrophoresis results. Selectivities were found to be significantly different for the two separation media. Ag(I) complexation provides an effective means of manipulating selectivity in nonaqueous capillary electrophoresis.
    Zusätzliches Material: 9 Ill.
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  • 74
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 493-496 
    ISSN: 0749-1581
    Schlagwort(e): selenium-, silicon- and boron-containing heterocycles ; tricarbonyl(n4-heterodiene) ; tricarbonylmetal ; complexes; 2D NMR; z-filtering; Ψ-BIRD HMQC; ; determination of coupling signs ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The signs of coupling constants [1J(77Se29Si) 〉 0, 2J(77Se13CSiMe) 〉 0,3J(77Se1HSiMe) 〉 0] were determined for pentaorgano-substituted 2,5-dihydro-1,2,5-selenasilaboroles [R3 = Me, la; R3 = C(Me)=CH2, 1b], and also for derivatives in which the surroundings of the selenium atom were changed by forming a pyridine-borane adduct (2), by formation of an Se—AlCl3 adduct (3) and by π-complexation with the transition metal fragments [Fe(CO)3] (4) and [Ru(CO)3] (5). The sign determination was achieved by using various types of 2D heteronuclear shift correlations (HETCOR) with 13C, 29Si or 1H detection (HMQC). Some of these experiments had to be modified by z-filtering or by a Ψ-BIRD pulse sequence. The change in the magnitude of 1J(13C=13C) (la, 58.9 Hz; 4, 33.8 Hz) as a result of π-complexation follows the trend known for diene complexes.
    Zusätzliches Material: 4 Ill.
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  • 75
    ISSN: 0749-1581
    Schlagwort(e): heterocycles ; NMR ; 15N NMR ; 29Si NMR ; Hahn-echo extended INEPT ; ψ-BIRD-HSQC and -HMQC ; 1J(29Si 15N) ; relative signs ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 15N and 29Si NMR data of 2,5-hydro-1,2,5-azasilaborole derivatives and related compounds were determined with emphasis on coupling constants 1J(29Si 15N) which cannot be measured from 15N NMR spectra of most boron-nitrogen compounds. In the case of compounds with an Si—N—H fragment ψ-Bird pulse sequences, combined with HMQC or HSQC, served for 1H detection of the 29Si resonance with preselection of the 15N-1H spin pair. This permitted the measurement of 1J(29Si 15N) and the determination of its absolute sign (〉0). In the absence of an NH group, the coupling constants 1J(29Si 15N) were measured from the 15N satellites in 29Si NMR spectra recorded by using the Hahn-echo extended (HEED) refocused INEPT pulse sequence. Isotope induced chemical shifts 1Δ 15/14N(29Si) were also measured by this technique for all the compounds. The 1J(29Si 15N) values cover the range 8.4-17.0 Hz, depending on the substituents at boron, silicon and nitrogen and on the complexation of the heterocycle.
    Zusätzliches Material: 3 Ill.
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  • 76
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 557-560 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 14N NMR ; 11B NMR ; borazines ; coupling constants 1J(29Si14N),1J(14N11B) ; coupling signs ; 14N electric field gradient ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The nuclear spin relaxation rate of the quadrupolar 14N nuclei in N,N′,N″-tris(trimethylsilyl)borazine (1) is surprisingly slow [T1(14N)=0.1 s]. This allows one to measure 1J(29Si14N) (9.6 Hz) directly from the 29Si NMR spectra and also to compare signs of coupling constants 1J(29Si14N) (〈0) and 3J(14NSiC1H) (〉0) by 2D 29Si/1H HETCOR experiments. Since the transverse relaxation time T2(14N) in 1 is governed by scalar relaxation of the second kind, the magnitude of 1J(14N11B) can be evaluated (23 ± 0.5 Hz). 11B, 14N and 29Si NMR data for N,N′-bis(trimethylsilyl)borazine (2) were also obtained, and 11B and 14N NMR spectra of the parent borazine [HBNH]3 (3), and of [HBNMe]3 (4) were remeasured. Calculation of the tensor components of the 14N electric field gradient shows that eqzz in 1 and in 2 for 14N(Si) is significantly smaller than for other borazines [HBNR]3, e.g. with R=H (3) or Me (4), in agreement with the experimental results.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
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  • 77
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 1H NMR ; Oil shale geoporphyrin ; Iron porphyrin complexes ; Deoxophylloerythroetioporphyrin ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: One- and two-dimensional 1H NMR studies of low-spin iron(III) geoporphyrins derived from the deoxophylloery-throetioporphyrin series (the oil shale source) resulted in an unambiguous assignment of all resonances. Deoxophylloerythroetioporphyrin (DPEP) and its 17-desethyl homologue were isolated from dictyonema shale as vanadyl complexes. They were demetallated and subsequently converted into iron(III) porphyrins under mild conditions. The 17-propionic methyl ester analogue, i.e. deoxophylloerythrin methyl ester, was synthesized for comparative studies. A spectroscopic probe to identify iron(III) isocyclic porphyrins was established. The five-membered isocyclic ring induced considerable asymmetry in the spin density distribution at the 3eπ bonding orbitals, placing the unpaired electron on the dxz orbital located along the N-21 - N-23 axis. The temperature dependence of the hyperfine shift is consistent with the thermal equilibrium between two non-degenerated electronic states (dxz)2(dyz)1↔(dxz)1(dyz)2. The new structural factor generating the asymmetric spin density distribution in low-spin iron(III) porphyrin complex was determined. The hyperfine shift pattern of high-spin iron(III) isocyclic geoporphyrins provided useful probes for their detection in iron geoporphyrin mixtures by 1H NMR prior to their separation. Valuable information is derived from the number of observed signals of meso-protons and characteristic, extremely downfield resonances of isocyclic ring hydrogens. Both features may be useful for the spectral identification of iron(III) porphyrins of the DPEP series from geological materials of relatively low purity.
    Zusätzliches Material: 7 Ill.
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  • 78
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 4 (1998), S. 147-159 
    ISSN: 1075-4261
    Schlagwort(e): protected surface-enhanced resonance Raman spectroscopy ; chlorophyll transformation products ; pheophytins ; geochemical transformations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Protected surface-enhanced resonance Raman spectroscopy (PSERRS) has been used to study a number of chlorophyll transformation products that have been suggested as intermediates in the so-called Treibs hypothesis which describes the transformation of ancient chlorophyll a (chla) in the biosphere into desoxophylloerythroetioporphyrin (DPEP) found in sedimentary environments. Both Soret- and Qy-resonant PSERR spectra have been recorded, providing two-dimensional structural fingerprints containing a number of bands which enable the presence of specific peripheral substituents to be identified. Some of these marker bands can be assigned directly to vibrational modes of the particular substituents. This has allowed further characterization of the vibrational spectrum of chl a; in particular, a vinyl mode has been identified which previously was thought to be Raman silent. © 1998 John Wiley & Sons, Inc. Biospectroscopy 4: 147-159, 1998
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
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  • 79
    ISSN: 1075-4261
    Schlagwort(e): FTIR microspectroscopy ; cervical cancer ; leukocytes ; lymphocytes ; erythrocytes ; semen ; mucins ; fibroblasts ; thrombocytes ; bacteria ; nylon ; Candida albicans ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: FTIR microscopy was applied to the analysis of cell types and other variables present in Pap smears to ascertain the limitations of infrared spectroscopy in the diagnosis of cervical cancer and dysplasia. It was found that leukocytes, and in particular lymphocytes, have spectral features in the phophodiester region (1300-900 cm-1) suggestive of what has previously been described as changes indicative of malignancy. Endocervical cells and fibroblasts have similar spectral features to HeLa cells and consequently could also confound diagnosis. The use of ethanol as a fixative and dehydrating agent results in retention of glycogen in cervical cell types and thus minimizes spectral changes in the glycogen region due to sampling technique. Spectra of seminal fluids exhibit strong bands in the phosphodiester/carbohydrate region; however, sperm contamination should be easily detectable by the presence of a distinctive doublet at 981/968 cm-1. Erythrocyte spectra exhibit a reduction in glycogen band intensity, but can be discerned by a relatively low-intensity νs $PO^{-}_{2}$ band. Endocervical mucin spectra exhibit a reduction in glycogen bands and a very pronounced νs $PO^{-}_{2}$ band, which is similar in intensity to the corresponding band in HeLa cells. Thrombocytes have strong bands in the phosphodiester region, but thrombocytes can be discerned from other cell types by the presence of two small broad bands at 980 and 935 cm-1. Candida albicans is characterized by strong bands in the polysaccharide region which could potentially obscure diagnostic bands if C. albicans is present in large numbers. Spectra of bacteria common to the female genital tract, in general, also have strong absorptions in the polysaccharide region; however, bacterial contamination is usually minimal and would not be expected to obscure cervical cell spectra. Nylon threads and bristles from cervical sampling implements produce characteristic IR profiles which allow for easy identification. Given the number of potential confounding variables associated with cervical cytology, a multivariate statistical or neural network analysis would appear to be necessary before the implementation of FTIR technology in clinical laboratories. © 1998 John Wiley & Sons, Inc. Biospectroscopy 4: 75-91, 1998
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 2 (1996), S. 143-153 
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Fourier-transform infrared (FTIR) microspectroscopy, combined with Principal Component Analysis (PCA), was applied in the study of exfoliated cervical cells from 272 patients. Six spectra were recorded for each patient, and these were visually sorted into two types (type 1 and type 2), based on their profiles. Spectra designated type 1 exhibited a profile characteristic of normal epithelial cells, with intense glycogen bands at 1022 cm-1 and 1150 cm-1, and a pronounced symmetric phosphate stretch at 1078 cm-1. Spectra designated type 2 exhibited features suggestive of dysplastic or malignant transformation, with pronounced symmetric and asymmetric phosphate modes and a reduction in glycogen-band intensity.Of the 272 patients, 68.6% of samples exhibited only type 1 profiles for all six recorded spectra, 29.4% of samples yielded at least one type 2 spectrum in any of the six recorded spectra and 2% of samples were inconclusive. Of the 68.6%, 86% were diagnosed normal by Pap smear with no follow up biopsy ordered, 7% were diagnosed abnormal by biopsy, 5% normal by biopsy and 2% were still inconclusive. For the remaining 29.4% of classified samples, 71% had shown an abnormal Pap result. These 71% were subsequently biopsied, and 87% were confirmed abnormal. The association of type 2 spectra and abnormality was further corroborated by spectra of cultured malignant cells from the HeLa cell line that displayed a profile similar to type 2 spectra in the 1300-950 cm-1 region. PCA decomposition using a reduced data matrix resulted in a score plot that showed general separation of the visually categorised spectra. This study demonstrates the potential of automated FTIR cervical screening technology in the clinical environment. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 9 Ill.
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  • 81
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1007-1011 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: We evaluated the precision, accuracy and linearity of three commercial gas chromatography/combustion isotope ratio mass spectrometry (GC/C-IRMS) instruments in regard to stable carbon isotope ratio measurements of fatty acids with 13C enrichment levels ranging from natural abundance to 924‰, in comparison to measurements by conventional gas isotope ratio mass spectrometry (GIRMS). Memory effect was also evaluated with a fatty acid mixture containing methyl myristate and methyl stearate at natural abundance levels of 13C but methyl palmitate at 13C enrichment levels of 460 or 924‰. At natural abundance, the δ13C values of fatty acids measured by the GC/C-IRMS instruments were reproducible to within 0.34‰ (range: 0.11‰ to 0.32‰) and accurate to -0.38±0.40‰ (mean difference ± standard deviation; range: -0.03±0.25‰ to -0.84±0.39‰). At enrichment levels of 13C (23 to 924‰), the δ13C values were reproducible to within 1.48‰ (range 0.20‰ to 1.00‰) and accurate to -1.11±3.16‰ (range: -1.02±3.23‰ to +4.56±13.42‰). Stable carbon isotope ratio measurements by all three GC/C-IRMS instruments were found to be linear from -30 to 924‰ (r2 〉 0.9999; p ≤ 0.004) in comparison to those measured by GIRMS. Significant memory effect was found in only one system. Based on our data, the GC/C-IRMS instruments can provide linear, precise and accurate stable carbon isotope ratio measurements and require only pico-and nanogram quantities of samples.
    Zusätzliches Material: 1 Ill.
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  • 82
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: The transmission infrared spectra of exfoliated endocervical mucin-producing columnar epithelial cells and the attenuated total reflectance (ATR) infrared spectra of the single-columnar cell layer on the endocervical tissues have been measured and compared with the corresponding infrared spectra of the ectocervical squamous cells and squamous epithelium. The infrared spectra of the exfoliated cervical cells obtained from the present work are comparable with those directly measured from the epithelia on the cervical tissues by ATR technique. The transmission infrared spectra of endocervical columnar epithelial tissue containing some components of the underlying connective tissue have also been measured and compared with the ATR/FTIR (Fourier-transform infrared) spectra of the endocervical columnar epithelial tissue. The effects of the contaminated connective tissue on the infrared spectra of the endocervical columnar epithelial tissue have demonstrated that ATR/FTIR is a more desirable method than the transmission method to obtain meaningful and good-quality infrared spectra of tissue samples, especially samples consisting of thin layers of different types of tissues. Substantial differences in the infrared spectra between the columnar cells and squamous cells on the endocervical and ectocervical tissues, respectively, were evident. The strong glycogen bands in the infrared spectrum of the ectocervical squamous cells are absent in the spectrum of the endocervical columnar cells. This spectral change is similar to that observed in malignant squamous cells. Therefore, if the decrease in the intensity of the glycogen bands is used as the only criterion for the determination of cellular abnormalities in the cervix, the presence of a large number of normal endocervical columnar cells in the cervical specimen would lead to a false result. Consequently, in addition to the glycogen bands, other features in the infrared spectra should be considered for the evaluation of abnormalities in exfoliated cervical epithelial cells. In order to identify the spectral features that are unique to endocervical columnar cells, the infrared spectra of an aqueous solution of glycogen, the mucus from the endocervix, and the connective tissues from both the endocervix and the ectocervix have also been measured and analyzed. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 83
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 30 (1995), S. 1144-1148 
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Consistent with experimental observations, high-level ab initio calculations, at the G2(MP2) level of theory, predict that the XCCY2+ (X, Y = O, S and NH) dications are remarkably stable species in the gas phase. OCCS2+, SCCS2+, HNCCO2+, HNCCS2+ and HNCCNH2+ are calculated to be thermodynamically stable species, whereas OCCO2+ is predicted to lie in a deep potential well, separated from exothermic C—C cleavage by a large barrier. All the doubly charged species are calculated to have a linear skeleton. Despite the inherent strong Coulombic repulsion, these species are characterized by short C≡X or C≡Y triple bonds. Vertical and adiabatic ionization energies of the XCCY+· monocations and the heats of formation of the resulting dications are reported. There are remarkable changes in the structures and stability ordering of isomers on going from the XCCY neutrals to the XCCY+· monocations and to the XCCY2+ dications. The rationalization of these results is discussed.
    Zusätzliches Material: 2 Ill.
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  • 84
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The analysis of oligonucleotides by mass spectrometry should give information on both the molecular mass and sequence. Fast atom bombardment mass spectrometry gives both in one step. Until now glycerol, thioglycerol and triethanolamine have been used as matrices for the analysis of oligonucleotides by fast atom bombardment mass spectrometry (FABMS), but there have been no comparative studies for matrix selection for these specific analytes. In this work, the influence of diethanolamine, glycerol, 1-thioglycerol and triethanolamine on the analysis of unprotected trimer up to heptamer oligoribonucleotides was studied using negative-ion FABMS on a sector-type mass spectrometer. Collision-induced dissociation MS/MS measurements were performed and the fragmentation patterns in MS and MS/MS were compared.
    Zusätzliches Material: 6 Ill.
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  • 85
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 9 (1995), S. 230-231 
    ISSN: 0886-9383
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Materialart: Digitale Medien
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  • 86
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 674-678 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 14N NMR ; nitrogen shielding ; nitrogen chemical shifts ; nitroso compounds ; cyano compounds ; substituent interactions ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The nitrogen NMR shieldings (Δσ, equivalent to  - Δδ on the frequency scale of chemical shifts) of the NO group in nitrosoalkanes are shown to be a sensitive probe to electron-withdrawing effects of substituents and to steric strain effects. The former produce high-field (low-frequency) shifts, which can amount to about 90 ppm, while the latter result in considerable low-field (high-frequency) shifts of the NO nitrogen resonance. The CN nitrogen shieldings show less pronounced low-field (high-frequency) shifts under the influence of electron acceptors. The signs and magnitudes of the observed effects are explained in terms of semi-empirical molecular orbital calculations of the shieldings and molecular mechanics evaluations of strain energies. The overall picture of relationships between the NO and CN nitrogen shieldings and electron charge migration within the molecules concerned is in accord with that obtained in earlier studies of solvent-induced effects on the nitrogen shieldings in alkyl cyanides and nitro compounds.
    Zusätzliches Material: 7 Ill.
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  • 87
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Microcolumn Separations 7 (1995), S. 17-22 
    ISSN: 1040-7685
    Schlagwort(e): enantiomer separation ; capillary electrophoresis ; chiral buffer additives ; proteins ; cyclodextrins ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The direct enantiomeric analysis of six DNP-amino acids by capillary electrophoresis is reported. This study describes a comparison of several chiral buffer additives. Both the natural proteins BSA, AGP, ovomucoid and casein, and the cyclic oligosaccharides α-, β-, and γ-cyclodextrin were used as chiral selectors. For the first time, casein from goat milk was successfully applied for chiral discrimination. The influence of the modifier n-propanol on chiral discrimination is demonstrated with BSA as a buffer additive.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
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  • 88
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 30 (1995), S. 1574-1580 
    ISSN: 1076-5174
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Sulfonylurea herbicides have been studied using negative-ion desorption chemical ionization (DCI) mass spectrometry (MS) and DCI-MS/MS techniques. Both [M — H]- and M-· ions were observed in the DCI mass spectra. The collisionally activated dissociation (CAD) spectra were characteristic of the structure of the herbicides examined. The fragmentation pattern was established based on the tandem mass spectra of the in situ deuterated sulfonylureas and on the comparison of the CAD spectra of sulfonylurea fragment ions with the CAD spectra of the ions derived from saccharin (o-benzoic sulfimide) and methyl 2-(aminosulfonyl)benzoate.
    Zusätzliches Material: 6 Ill.
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  • 89
    ISSN: 0049-8246
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: Soil samples from a potentially contaminated site were prepared and analysed for their copper, nickel and zinc contents by both inductively coupled plasma (ICP) spectrometry and x-ray fluorescence (XRF) spectrometry. Results obtained by XRF spectrometry were either comparable with or slightly higher than those obtained by ICP. However, when the results obtained by the two techniques were compared with the threshold values for contamination by the three metals, then each set of results led to the same conclusion with respect to the categorization of the site. Comparability between the two techniques was thus demonstrated and either may be used to screen soil for phytotoxic metals.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 90
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 367-374 
    ISSN: 0749-1581
    Schlagwort(e): NMR ; 1H NMR ; 13C NMR ; antidepressants ; trimipramine maleate ; nitrogen inversion ; molecular dynamics ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The solution conformations and dynamics of the antidepressant drug trimipramine maleate were investigated by 1H and 13C NMR spectroscopy. Of particular interest was an observed non-equivalence of the N-methyl groups in the aliphatic side-chain of the drug, which is present in both 1H and 13C spectra under a range of aqueous and non-aqueous solvent conditions when the terminal nitrogen is protonated. Although the inequivalence was first observed for the maleate salt, the nature of the counter ion is not a determining factor. The solution concentration of the drug does, however, modulate the observed inequivalence, with the two peaks coalescing at higher drug concentrations. The diastereotopic environments of the two methyl groups arise because of a chiral centre in the aliphatic side-chain. Inversion of the terminal nitrogen produces exchange between the two environments, thereby destroying the inequivalence and leading to a single averaged resonance for the two methyl groups. The energy barrier for the exchange process was determined from variable-temperature NMR experiments to be 16.3 kcal ml-1 (1 kcal = 4.184 kJ). This is higher than would be expected for simple inversion of a tertiary nitrogen, but reflects the fact that inversion can only occur for the small fraction of molecules which are not protonated. The barrier determined from the variable-temperature experiments was in agreement with rates of interchange between the two methyl environments determined from saturation transfer experiments. These rates were measured for a series of different protonation states of the nitrogen, with the rate contant for interchange of environments decreasing with an increasing degree of nitrogen protonation. 13C spin-lattice relaxation times and nuclear Overhauser enhancement effects were also measured to determine the degree of mobility in the aliphatic side-chain of trimipramine maleate.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 91
    Digitale Medien
    Digitale Medien
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 33 (1995), S. 632-638 
    ISSN: 0749-1581
    Schlagwort(e): HMBC ; pulsed field gradients ; H,X long-range coupling constants ; dihedral angle ; angustifolin ; UDP-glucose ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A gradient-selected J-HMBC experiment is presented. Coherence selection with magnetic field gradients results in HMBC spectra in which t1 noise is very low or completely eliminated. This makes it possible to detect unequivocally very small (〈2 Hz) long-range H,X coupling constants. With a slight modification, the HMBC experiment can be used for the quantitative measurement of these couplings. The signal amplitude of spectra with increasing coupling evolution time τ shows the characteristic sin (πJXHτ) dependence. By fitting a sine curve to the experimental data or by performing a 3D J-resolved HMBC experiment, accurate nJXH coupling constants are obtained. This method is especially useful for estimating coupling constants between protons and unprotonated heteronuclei, e.g. quaternary carbons, 15N nuclei in labelled prolines or 31P in organophosphates.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 92
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 18 (1995), S. 477-482 
    ISSN: 0935-6304
    Schlagwort(e): Shape selectivity ; Polycyclic aromatic hydrocarbons ; Isomers ; Coupled columns ; Coal tar ; SRM 1597 ; SRM 869 ; SRM 1647c ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The retention behavior of polycyclic aromatic hydrocarbons (PAHs) in packed-column supercritical fluid chromatography (SFC) is studied for monomeric and polymeric C18 columns. Molecular shape discrimination (shape selectivity) is assessed through the use of Standard Reference Materials (SRMs), adn changes in selectivity are studied as a function of temperature, pressure, and mobile phase composition. Examples of separations of complex PAH isomer mixtures are presented, and guidelines are provided for modification and optimization of shape selectivity in SFC.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 93
    Digitale Medien
    Digitale Medien
    Chichester [u.a.] : Wiley-Blackwell
    Journal of Raman Spectroscopy 26 (1995), S. 427-433 
    ISSN: 0377-0486
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: A series of polyethylene samples were analysed using a micro Raman system. The data were analysed using a commercial partial least-squares package and correlated with the polymer density. A correlation coefficient of up to 0.98 was obtained, depending on the spectral region used. A standard error of prediction of 2.15 kg m-3 was obtained and the densities of ‘blind’ samples were predicted with good accuracy.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 94
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 1330-1330 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 95
    Digitale Medien
    Digitale Medien
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 18 (1995), S. 373-377 
    ISSN: 0935-6304
    Schlagwort(e): Capillary GC ; Equilibrium headspace sampling ; Tenax TA trapping ; Thermal desorption ; TD-GC-MS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Volatile compounds from biodegradable household waste and infected building materials have been studied by dynamic or equilibrium headspace sampling and concentration on Tenax TA followed by thermal desorption and HRGC-MS. Equilibrium headspace sampling was also used to study vegetables stored for 14-18 days at ambient temperature. Over 200 compounds were tentatively identified. The concentration of organic sulfur compounds from garden waste was high enough to contribute to respiratory problems of waste handling personnel. Nitriles, alkyl nitro compounds, and alkyl nitrates were isolated from radish and carrot samples at low concentrations (10-50 ppb). Air monitoring in waste handling working environments may be required to ensure the safety of personnel. Branched aliphatic aldehydes, carboxylic acids, esters, and 2-alkanones were found in the headspace of the infected building materials, indicating that volatile compounds may be useful for detection of microbial growth in buildings.
    Zusätzliches Material: 1 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 96
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: We characterized the particle size distribution and the analyte transmission efficiency of a liquid chromatography/particle beam/mass spectrometry (LC/PB/MS) system as a function of experimental variations normally used to optimize the LC/PB/MS system. The particle size distribution was evaluated using an electrical differential mobility particle sizer (DMPS) and both the DMPS and the mass spectrometer were used to evaluate transmission. The latter results were correlated to provide evidence related to mechanisms which contribute to poor sample transmission. Addition of ammonium acetate buffer did not increase the aerosol particle riean diameter. However, it did lead to significant increases in caffeine transmission efficiency observed in both the DMPS and the mass spectrometer. Our results were interpreted to suggest a possible electrostatic cause for quantitative anomalies in LC/PB/MS rather than simple mass discrimination in the particle beam momentum separator.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 97
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 138-142 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: An AC corona-discharge device was inserted upstream of a thermospray vaporizer tip in a liquid chromatography/particle beam mass spectrometer to neutralize static aerosol charging. Response of a test analyte was measured with or without discharge initiation. If the solvent contained no ammonium acetate buffer, increased analyte signal was associated with the discharge. However, in the presence of ammonium acetate the benefit of AC discharge neutralization was either not observed or was more subtle. This led to the conclusion that the previously observed ammonium acetate “carrier” effect is attributable, at least in part, to neutralization of static electric charges produced spontaneously during the solvent nebulization process. In a second experiment, the pattern of particles issuing from the system momentum separator was examined by aiming the particle beam at a cold target located within a mass spectrometer ion source. Variations in particle density were observed depending on (i) whether or not the aerosol had been neutralized and (ii) the proximity of electron-beam-collimating magnets to the particle beam trajectory. These results are consistent with a hypothesis that electrostatic charging occurs spontaneously during the nebulization process in which an aerosol is formed from the high performance liquid chromatography effluent. Such electrostatic charging introduces a factor likely to degrade system performance by at least two modes: through interactions of the charged aerosol particles (i) with the walls of the aerosol transmission pathway, and, after they are accelerated into a particle beam and introduced into the mass spectrometer, (ii) with the magnets used for electron beam collimation in many mass spectrometer ion sources.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 98
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Biospectroscopy 2 (1996), S. 263-275 
    ISSN: 1075-4261
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: The early development of time-resolved resonance Raman spectroscopy during the late 1970s and beginning of the 1980s is reviewed. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 15 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    New York, NY : Wiley-Blackwell
    Rapid Communications in Mass Spectrometry 9 (1995), S. 221-224 
    ISSN: 0951-4198
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Physik
    Notizen: In order to study sputtering of Van-der-Waals solids by MeV ion impact, films of solid argon condensed onto a metallic substrate at a temperature of 10 K were irradiated by 252Cf fission fragments. The secondary ions emitted from the surface were investigated by a time-of-flight technique. The mass spectra are dominated by a cluster series Arn+ with n ranging from 1 to about 30. Comparatively high absolute ion yields were determined; the yield of Ar+ was 48 ions/impact. The mass line of Ar+ was broadened due to ejection energies of up to 50 eV. The line shape of the cluster ions indicates delayed particle emission. Some of the observed phenomena are not typical for electronic sputtering at MeV energies; they are briefly discussed. These are the first and preliminary results of a systematic exploration of high energy sputtering from solid rare gases.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 100
    ISSN: 1075-4261
    Schlagwort(e): protein secondary structure ; FTIR spectroscopy ; Fourier self-deconvolution ; factor analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Biologie , Physik
    Notizen: Fourier self-deconvolution (FSD) was performed on protein amide I and II Fourier transform infrared (FTIR) spectra to test if the resultant increased band shape variation would lead to improvements in protein secondary structure prediction with our factor analysis based restricted multiple regression (RMR) methods. FTIR spectra of 23 proteins dissolved in H2O were measured and normalized to a constant amide I peak absorbance. The deconvolved spectra were renormalized by area so that the deconvolved spectra sets had the same area as before. Principal component analysis of the deconvolved spectra sets was carried out, which was followed by a selective multiple linear regression (RMR) analysis of the principal component loadings with regard to the fractional components (FC) of secondary structure. As compared to analyses based on the original spectra set, helix and sheet predictions were not noticeably improved by FSD; but, if a very large number of component spectra (16) were retained in the pool to select which loadings to be used in the RMR optimization, better predictions of turn and “other” resulted. The prediction quality varied depending on the deconvolution parameters used. © 1998 John Wiley & Sons, Inc. Biospectroscopy 4: 93-106, 1998
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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