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  • NMR  (86)
  • Springer  (86)
  • Blackwell Publishing Ltd
  • 1995-1999  (86)
  • 1940-1944
  • 1997  (42)
  • 1996  (44)
  • 1943
  • 1940
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  • 1995-1999  (86)
  • 1940-1944
Year
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of chemical crystallography 26 (1996), S. 807-814 
    ISSN: 1572-8854
    Keywords: NMR ; polymorphism ; racemate ; conglomerate ; enantiomer ; N-aryl(alkyl)-N′-1-(propan-2-ol)ureas
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract NMR spectroscopy and single-crystal X-ray analysis have been used to characterize polymorphism of the racemate of the N-phenyl-N′-[1-(3-(phenyl-4-piperazinyl)propan-2-ol)urea displaying an analgesic activity. The crystal structures of the monoclinic form,R m witha=4.788(1),b=9.432(7),c=40.791(5) Å, β=90.93(1)°, space groupP21/n,Z=4 and of the orthorhombic form,R o witha=10.948(3),b=8.896(3),c=38.857(6) Å, space groupPbca,Z=8, have been determined. In addition, the crystal structure of an enantiomer orthorhombic,E o, isolated from a conglomerate, witha=4.787(3),b=9.461(2),c=40.809(10) Å, space groupP212121, Z=4, has also been determined. The three conformations have been compared when the molecules have the same relative configurations.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 25 (1996), S. 179-189 
    ISSN: 1572-8927
    Keywords: Intramolecular hydrogen bond ; solvent effect ; dipole moment ; IR ; UV ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Solvent effect on intramolecular hydrogen bond in 8-quinolinol N-oxide has been studied by IR, UV,1H NMR and13C NMR spectroscopy, dipole moment measurements and quantum-mechanical calculations. The solute-solvent interactions are of local character and they vary considerably over the range of solvent under study. The results suggest that formation complexes with solvent molecules weaken the intramolecular hydrogen bond in 8-quinolinol N-oxide.
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  • 3
    ISSN: 1572-8854
    Keywords: Carbohydrate ; NMR ; X-ray analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The synthesis, NMR spectra and crystal structure of 4,6-O-ethylidene-2,3-di-O-methanesulfonyl-α-d-glucopyranosyl chloride are reported. The chloro substituted carbohydrate, C10H17ClO9S2, crystallizes in the monoclinic space group.,P21, witha=10.124(4),b=9.517(4),c=18.058(8) Å and β=105.18(1)°. FinalR=0.0434. There are two independent molecules in the asymmetric unit with conformations that differ around the mesyl (−S(O)2CH3) groups.
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  • 4
    Electronic Resource
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    Springer
    Journal of solution chemistry 25 (1996), S. 1029-1039 
    ISSN: 1572-8927
    Keywords: 18-Crown-6 ; barium ; methanol ; exchange kinetics ; bimolecular mechanism ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Exchange kinetics of Ba2+-18-crown-6 complex in deuterated methanol solution was studied by proton NMR line-shape analysis of a series of solutions containing equal population of free and complexed 18-crown-6, but varying concentration of the macrocycle, at various temperatures. From −33 to 37°C, the predominant mechanism for the exchange of the ligand between the two sites is a bimolecular pathway which is characterized by the following activation parameters:E a=47±2 kJ-mol−1; ΔH ≠=45±2 kJ-mol−1; ΔS ≠=−8±4 J-mol−1-K−1. However, the contribution of a dissociative mechanism with activation parametersE a=36±5 kJ-mol−1, ΔH ≠=33±5 kJ-mol−1 and ΔS ≠=104±18 J-mol−1-K−1 becomes more important at higher temperatures.
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  • 5
    ISSN: 1572-8927
    Keywords: Hydrogen-1 ; carbon-13 ; nitrogen-15 ; NMR ; lutetium(III) ; isothiocyanate ; complexation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A direct, low-temperature hydrogen-1, carbon-13, and nitrogen-15 nuclear magnetic resonance study of lutetium(III)-isothiocyanate complex formation in aqueous solvent mixtures has been completed. At −100°C to −120°C in water-acetone-Freon mixtures, ligand exchange is slowed sufficiently to permit the observation of separate1H,13C, and15N NMR signals for coordinated and free water and isothiocyanate ions. In the13C and15N spectra of NCS−, resonance signals for five complexes are observed over the range of concentrations studied. The13C chemical shifts of complexed NCS− varied from −0.5 ppm to −3 ppm from that of free anion. For the same complexes, the15N chemical shifts from free anion were about −11 ppm to −15 ppm. The magnitude and sign of the15N chemical shifts identified the nitrogen atom as the binding site in NCS−. The concentration dependence of the13C and15N signal areas, and estimates of the fraction of anion bound at each NCS−:Lu3+ mole ratio, were consistent with the formation of [(H2O)5Lu(NCS)]2+ through [(H2O)Lu(NCS)5]2−. Although proton and/or ligand exchange and the resulting bulk-coordinated signal overlap prevented accurate hydration number measurements, a good qualitative correlation of the water1H NMR spectral results with those of13C and15N was possible.
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  • 6
    ISSN: 1572-8773
    Keywords: BET ; biosorption ; cadmium ; cobalt ; copper ; Freundlich ; NMR ; Scatchard ; Ulva lactuca ; zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The metabolism-independent metal binding characteristics of Ulva lactuca were investigated using both freeze-dried thalli and cell walls stripped of intracellular material by incubation in Triton-X followed by methanol. Biosorption of Cd, Zn, Cu and Co by freeze-dried thallus was concentration-dependent and followed Freundlich and Langmuir isotherms. The Freundlich plot suggested that freeze-dried U. lactuca had the greatest binding affinity for Cu compared with Cd, Zn and Co. The BET (Brunauer–Emmett–Teller) plot, which indicates a more complex form of adsorption, and the Scatchard plot were not adequate models for Cu adsorption. The Scatchard plot of Cd suggested that two Cd binding sites were available on the freeze-dried thallus, with the second, lower affinity site only becoming available at Cd loading capacities greater than 4.9mmol g dry wt. Cd nuclear magnetic resonance (NMR) studies confirmed that two binding sites were available for Cd on the freeze-dried algal powder, though only one was available on the cell wall, and that the affinity of the binding sites was greater for Cu than for Cd. The results of the NMR experiments suggested that Cd binds to oxygen-containing functional groups in the algal powder and on the cell wall. It is proposed that sulphate or hydroxyl groups attached to polysaccharide subunits are possible sites.
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  • 7
    ISSN: 1572-8773
    Keywords: iron ; siderophore ; Yersinia enterocolitica ; structure ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Clinical isolates of Yersinia enterocolitca, which belong to mouse-lethal serotypes, produce the siderophore yersiniophore. Siderophore production was shown to be iron regulated and to reach maximum production in late log phase. Yersiniophore is a fluorescent siderophore with maximum excitation at 270 nm and a major emission peak at 428 nm. Absorption maxima were seen at 210 and 250 nm with a low broad peak from 280 to 320 nm. Purification of unchelated yersiniophore for structural analysis was made difficult by low yields (1–2 mg mg-1), and susceptibility to acid hydrolysis, oxidation and possibly polymerization. Yersinophore was therefore purified as an Al3+ chelate, which was found to be stable in solution for several weeks. To purify Al3+-yersiniophore, unchelated yersiniophore was first extracted from culture supernatants with dichloromethane, concentrated by rotary evaporation and adsorbed to a DEAE-sephacel column. Al3+-yersiniophore was eluted with 0.01 m AlCl3 and further purified by HPLC. The structure was established by a combination of elemental analysis, high resolution mass spectrometry and two-dimensional NMR experiments. Yersiniophore is a phenolate-thiazole siderophore with the formula C21H24N3O4S3Al and a molecular weight of 505.07404 when chelated to Al3+. The structure of yersiniophore was determined to be closely related to the structures of pyochelin, produced by Pseudomonas aeruginosa, and anguibactin, produced by Vibrio anguillarum.
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  • 8
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    Cellulose 4 (1997), S. 99-107 
    ISSN: 1572-882X
    Keywords: sodium hydroxide ; mercerization ; NMR ; chemical shift
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Low molecular weight cellulose (degree of polymerization = ca 15) was dissolved in 4-- 30% NaOD/D2O, and relationships between 1H- and 13C-chemical shifts of the cellulose and NaOD concentrations were studied in terms of the dissociation of three hydroxyl groups of cellulose in aqueous NaOH solutions. All C---H proton resonances were shifted upfield linearly with an increase in the NaOD concentration, indicating that all C---H protons of cellulose undergo the electron-shielding effect by NaOH. On the other hand, the shifting patterns of carbon resonances varied among the six carbons: C1 and C4 carbons undergo the electron-shielding effect, whereas C2, C3, C5, and C6 carbons experience the electron-deshielding effect by NaOH. Changes in 13C-chemical shifts of cellulose carbons in 4--30% NaOD/D2O indicate that C3---OH has the highest resistance to dissociation in aqueous NaOH of the three hydroxyl groups of an anhydroglucose residue. It is plausible, at least from the aspects of 13C-chemical shifts, that cellulose molecules dissolving in 20--30% NaOH behave differently from those swollen in 20--30% NaOH as alkali- cellulose
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  • 9
    ISSN: 1572-8927
    Keywords: Carbon-13 ; nitrogen-15 ; NMR ; europium-nitrate complexes ; europium-isothiocyanate complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A direct, low-temperature nuclear magnetic resonance spectroscopic study of europium(III)-nitrate contact ion-pairing has been completed, and preliminary results for europium(III)-isothiocyanate have been obtained. In water-acetone-Freon mixtures, at −110°C to −120°C, four15N NMR signals are observed for coordinated nitrate ion. Area evaluations of the signals and their concentration dependence indicate the formation of Eu(NO3)2+, Eu(NO3) 2 1+ , and two higher complexes, possibly the tetra-, with either the penta-or hexanitrato. This correlates well with similar15N NMR results obtained for Ce(III), Pr(III), Nd(III), and Sm(III). As a result of a higher dielectric constant, complex formation is significantly less in water-methanol mixtures, wheein only three complexes form with Eu(NO3) 2 1+ dominating at the highest anion concentrations. Competitive complexing experiments in water-methanol also were made by35Cl NMR chemical shift and linewidth measurements, as well as15N NMR. Initial experiments with the Eu3+-NCS− system show four coordinated anion signals, displaced from the bulk anion peak by about −250 ppm and −2,500 ppm in the13C and15N NMR spectra, respectively. Area evaluations are consistent with the presence of Eu(NCS)2+ through Eu(NCS) 4 1- in these solutions. A consideration of the chemical shifts identified the nitrogen atom as the site of binding in the NCS−. A discussion of these preliminary results, as well as those for several other metal-ions, will be presented.
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  • 10
    ISSN: 1572-882X
    Keywords: microcrystalline cellulose ; tablet ; water ; spin- lattice relaxation time ; spin-spin relaxation time ; NMR ; microfibril
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Medical tablet forming ability of microcrystalline cellulose (MCC) was investigated in relation to the mobility of water molecules in MCC particles. For this purpose, the spin-lattice relaxation time T1 of water in the system was measured by 1H-NMR. Over a wide range of water contents (0.02 ≤ H2O/cellulose (g/g) ≤ 1.79), two different T1 (T1,l and T1,s) values were observed for water in each MCC sample. Below the equilibrium water content, water having these two different T1 values exchange with each other in an MCC particle reaching an equilibrium state within a given time scale (equilibrium constant K). The T1,l, T1,s and K values for water in MCC, estimated at the equilibrium water content, showed fairly good correlations with the hardness of the tablets made by the MCC samples. Sample with a shorter T1, or larger K tended to have a stronger tablet forming ability. In the spin-spin relaxation time T2 measurements for protons in an MCC/D2O system, two T2 components originating from the glassy cellulose solid (T2,G) and the swelling region (T2,l) were observed. It was found that the mole fraction xL of protons with T2,L in the system exhibits a clear linear correlation with K. From these results, a structural model for the distribution of water in MCC particles was propoed by taking the surface of each microfibril and the disordered region within the microfibril into consideration
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  • 11
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    Monatshefte für Chemie 127 (1996), S. 219-225 
    ISSN: 1434-4475
    Keywords: 4-Phosphoranylidene-5(4H)-oxazolones ; Phosphorus ylides ; 5(4H)-Oxazolone enolate ion equivalent ; 5-(4H)-Oxazolones ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung 4-Phosphoranyliden-5(4H)-oxazolone, eine sehr wenig bekannte Gruppe der Phosphor-ylide, wurden auf einfache Weise nach einem neuen Eintopfverfahren mit guten Ausbeuten hergestellt. Als Ausgangsverbindungen wurden 4-unsubtituierte-5-(4H)-Oxazolone (1) eingesetzt, die unter der Einwirkung von Addukten wie Ph3P-Br2, Bu3P-Br2, Ph3P-CCl4 oder Ph3P-CBr4 in Anwesenheit von Triethylamin in CH2Cl2 bei Zimmertemperatur die Titelverbindungen liefern. Die spektroskopischen Eigenschaften der Ylide werden berichtet und diskutiert.
    Notes: Summary 4-Phosphoranylidene-5(4H)-oxazolones (2), a hardly known class of phosphorus ylides, were readily prepared from 4-unsubstituted-5-(4H)-oxazolones (1) by treatment with Ph3P-Br2, Bu3P-Br2, Ph3P-CCl4, or Ph3P-CBr4 adducts in the presence of triethylamine in CH2Cl2 at room temperature in a novel, efficient one-pot procedure. The spectroscopic properties of the ylides are reported and discussed.
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  • 12
    ISSN: 1434-4475
    Keywords: Cyclopentadienylruthenium(II) complexes ; Diphosphazane ligands ; Crystal structures ; IR ; Raman ; NMR ; UV/VIS ; Mass spectra ; Hydrogen bridging bonds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This synthetic and structural work describes a series of half-sandwich cyclopentadienylruthenium(II) complexes containing the diphosphazane ligands [(C6H5)2P]2NR (R=H:Hdppa,1a;R=CH3:dppma,1b;R=C2H5:dppea,1c;R=Li:Lidppa,1d). Treatment of1a, d with CpRuCl(PPh3)2 (Cp=η5-C5H5, Ph=C6H5,2) in a molar ratio of 1:1 in boiling aromatic hydrocarbons affords the neutral complexes CpRuCl(Hdppa) (3) and CpRu(dppa)PPh3 (6). The ionic complexes [CpRu(Ph2P-NR-(PPh2)PPh3)Cl (R=CH3:4a;R=C2H5:4b) are formed by the reaction of1b,c with2. One pot reactions of1a–c with2 in the presence of NH4PF6 in boiling CH3OH give only the ionic compounds [CpRu(Ph2P-NR-PPh2)(PPh3)]PF6 (R=H, CH3, C2H5;5a–c). The sulfur dioxide and hydride complexes [CpRu(Hdppa)η1-SO2]Cl (7) and CpRu(H)Hdppa (8) are obtained by the interaction of3 with SO2 or NaOCH3. All compounds are characterized as far as possible by IR, Raman,31P{1H} NMR,1H NMR,13C{1H} NMR, FD mass spectra, and their conductivity in CH2Cl2 solution. The X-ray crystal structures of3 and5a reveal that the P(1)-N(1)-P(2) angle of the coordinated ligand1a in both complexes is reduced to about 100° in comparison to free uncoordinated1a (119°). This small angle leads to a short P(1)–P(2) bond distance of 259.4 pm in3 and 254.3 pm in5a. The molecules of3 are connected by intermolecular (NH...Cl) hydrogen bridging bonds forming chains along thez axis of the unit cell. The crystals of5a contain two independent pairs of ions in the unit cell (Z=8). In5a no hydrogen bonds exist between the NH-groups and the PF 6 − anions.
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  • 13
    ISSN: 1434-4475
    Keywords: Diphenylphosphanyl substituted 5-fluoro-uracils ; X-ray structure determination ; Tautomerism ; NMR ; Vibrational and mass spectra
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary 5-Fluoro-uracil (1) reacts with chloro-diphenylphosphane to 5-fluoro-N(1), N(3)-bis(diphenylphosphanyl)uracil (3) which was characterized by X-ray crystallography, IR, and mass spectra.19F,31P{1H},13C{1H}, and1H NMR spectra indicate that3 rearranges inTHF solution to some extent to the tautomeric 5-fluoro-O(2), O(4)-bis(diphenylphosphanyl)uracil (4). If the solvent contains traces of water, Ph2P(O)-PPh2 (6) and uracil derivatives are formed by hydrolysis.
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  • 14
    ISSN: 1434-4475
    Keywords: Aminyl radicals ; ESR ; NMR ; Pyrazoles ; Triarylaminium cation radicals
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die substituierten 3-Anilino-1,5-diphenylpyrazole1a–i wurden mit Pb(OAc)4 in Benzol oder CH2Cl2 oxidiert. Die intermediären Aminylradikale3f–i wurden ESR-spektroskopisch bei der Oxidation der im Anilinrest methylsubstituierten Pyrazole1f–i nachgewiesen. Die ESR-spektroskopisch nach Oxidation der Pyrazole1a–e beobachteten Radikalintermediate interpretieren wir als Kationradikale6a–e. Diese werden durch Weiteroxidation der Dimeren4a–e gebildet, deren Struktur durch NMR-Untersuchungen und15N-Markierung bewiesen wurde.
    Notes: Summary Substituted 3-anilino-1,5-diphenylpyrazoles1a–i were oxidized with Pb(OAc)4 in benzene or CH2Cl2 solution. The ESR measurements confirmed the formation of aminyl radicals3f–i frompara-CH3 substituted pyrazoles1f–i. The radical intermediates from unsubstituted pyrazoles1a–e were assigned to triarylaminium cation radicals These were generated by consecutive oxidation of the dimeric products4a–e whose structure was proven by NMR spectroscopy and15N labeling.
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  • 15
    ISSN: 1434-4475
    Keywords: NMR ; Thia crown ethers ; Conformation ; Molecular mechanics calculation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Aus Tetrachlorbrenzcatechin-bisallylether (1) und Schwefeldichlorid wurden neben der 1,10-Dithia-dibenzo-18-krone-64 die 9- und 10-Ring-Derivate2 und3 erhalten. In der 10-Ring-Verbindung wurde erstmaligMarkovnikov- undanti-Markovnikov-Konstitution der β-Chlor-thio-Gruppierung in einem Thiamakrocyclus nebeneinander vorgefunden. Das isolierte Diastereomere von3 zeigt bei Temperaturen unter −50 °C zwei Konformere. Die Signalzuordnung war mit homo-und heteronuklearen COSY- sowie mit phasensensitiven NOESY-Spektren möglich. Mit Hilfe molekülmechanischer Rechnungen konnten aus den13C-NMR-Verschiebungen und den vicinalen H,H-Kopplungskonstanten die Vorzugskonformeren und die relative Konfiguration bestimmt werden.
    Notes: Summary Addition of sulfur dichloride to tetrachlorocatechol-bisallylether (1) yields the 9- and 10-ring thia crown ether derivatives2 and3, respectively, together with the dithia-18-crown-6-ether4. The 10-membered ring compound3 represents the first thia macrocycle containing bothMarkovnikov andanti-Markovnikov constitution of the β-chloro-thio structural segments in the same molecule. By1H and13C NMR spectroscopy, equal amounts of two preferred conformers of the only isolated diastereomer of3 were observed at temperatures below −50°C. The signals were assigned to these conformers using COSY, HETCOR, and phase sensitive NOESY spectra at low temperatures. The preferred conformations and the relative configuration were determined using the different effects of γ gauche -and γ anti -positions in13C NMR chemical shifts and analyzing vicinal3 J H,H coupling constants. These results were confirmed by molecular mechanics calculations.
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  • 16
    ISSN: 0948-5023
    Keywords: Sialidase ; NMR ; Protein modelling ; Molecular dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The success of knowledge-based homology modelling is critically dependent on the predictive potency of the program structure-based calculations, which attempt to translate homologous sequences into three-dimensional structures, and on the actual relevance of the crystal structure for the protein topology. As quality control, experimental data for selected parameters of the protein′s conformation are required. Using the crystal structure of the sialidase of Salmonella typhimurium as framework for model building of the homologous enzyme from Clostridium perfringens, a set of energy-minimised conformers is derived. These proteins present e.g. Tyr, Trp and His residues with an assessable area on the surface, since the side chains of these amino acid residues are responsive to chemically induced dynamic nuclear polarization (CIDNP), monitored by NMR. Hence, as first lesson, a comparative analysis for model-derived and experimentally determined values can be performed. The second lesson of this study concerns the notable impact of single amino acid substitutions (Tyr/Phe, Cys/Ser) on the surface accessibility of the CIDNP-reactive amino acid side chains in mutant forms of the sialidase. Corroborating the predictions from the theoretical calculations, the spectra of the engineered mutants reveal marked and non-uniform alterations. Thus, the effect of apparently rather conservative amino acid substitutions on a distinct conformational aspect of this protein, even at distant sites, should not be underestimated.
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  • 17
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    Catalysis letters 38 (1996), S. 115-121 
    ISSN: 1572-879X
    Keywords: NMR ; acid catalysis ; pentene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 13C NMR study of “conjunct polymerisation” of 1-pentene in 95% sulfuric acid demonstrated that this is a carbenium ion reaction, where the esters are the precursors of carbenium ions. In the first step of the reaction a complicated mixture of primary and secondary mono- and dipentyl esters is formed. In an excess of the acid the esters are decomposed yielding aliphatic carbenium ions, which are then involved in secondary reactions resulting in the final products. Similar to heterogeneous catalysis on zeolites, the steady state concentration of the aliphatic carbenium ions during the reaction is, however, too low for their direct detection by NMR.
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  • 18
    ISSN: 1572-879X
    Keywords: MCM-41 synthesis ; alkali-free gel ; n-heptane cracking ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract MCM-41 mesoporous molecular sieve materials are synthesised using aqueous ammonia solution to adjust the pH of the reactant gel. Highly ordered MCM-41 with Si/Al ratio as low as 14 was obtained and characterised by27A1 MAS NMR, XRD, N2-adsorption, benzene sorption, and NH3-TPD measurements. The acidity of MCM-41 materials obtained in this system was conveniently generated through straightforward calcination of the as-synthesised sample. More mild acidic sites generated could be due to the avoidance of the multiple calcination procedure and/or the trace sodium species which are the poisons to Brønsted acid. The catalytic activities forn-heptane cracking and isomerization ofm-xylene were investigated, and these were in accordance with the known properties of MCM-41.
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  • 19
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    Catalysis letters 41 (1996), S. 47-53 
    ISSN: 1572-879X
    Keywords: CuZSM-5 ; lanthanum ; DeNOx ; XRD ; NMR ; XPS ; ISS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of high temperature steam treatment on the activity and selectiv ity of CuZSM-5 catalysts for the selective catalytic reduction of NO with propene have been examined. Loss of activity and selectivity on steam treatment is due to framework dealumination of the zeolite, which causes migration of Cu out of the zeolite pores to the external surface. Pre-exchange of the zeolite with La3+ cations inhibits the dealumination, preventing migration of Cu to the surface and allowing the catalyst to retain high activity and N2 selectivity after steam treatment. The deactivation of the catalysts was monitored using X-ray powder diffraction, magic angle spinning27Al and29Si nuclear magnetic resonance, X-ray photoelectron spectroscopy and ion scattering spectroscopy.
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  • 20
    ISSN: 1432-1890
    Keywords: Key words External pH ; NMR ; Phosphate ; Polyphosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Comparative in vivo 31P-NMR analyses of mycorrhizal and nonmycorrhizal roots of Pinus sylvestris and the fungus of Suillus bovinus in pure culture were used to investigate alterations in phosphate metabolism due to changes in external pH in the range 3.5–8.5. All control samples maintained a constant pH in both cytoplasm and vacuole. Mycorrhizal roots and pure fungus, but not nonmycorrhizal roots, transformed accumulated inorganic phosphate into mobile polyphosphate with a medium chain length. Phosphate uptake rates and polyphosphate accumulation responded differently to external pH. In all cases, maximal phosphate uptake occurred at an external pH close to 5.5. At an external pH of 8.5, both roots and fungus showed a distinct lag in phosphate uptake, which was abolished when the external pH was lowered to 7.5. An irreversible effect on phosphate uptake as a consequence of variation in external pH was also observed. The central role of the fungus in regulating mycorrhizal phosphate metabolism is discussed.
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  • 21
    ISSN: 0948-5023
    Keywords: Keywords: Thiocrown ether ; NMR ; Ag(I) complexes ; Molecular Dynamic simulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The preferred conformations and the complexional behaviour of mn-12S2O2 were studied by means of both NMR spectroscopy and molecular modelling. Furthermore, the AgI complexes of this ligand mn-12S2O2 were also studied by molecular mechanical calculations.
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  • 22
    ISSN: 1432-1327
    Keywords: Key words Vanadium ; Erythrocyte ; NMR ; Oxidative stress ; Diabetes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The action of vanadate on intact human erythrocytes was studied by 1H spin echo and 51V NMR spectroscopy as a model for the behaviour of vanadium(V) complexes in experimental diabetes. Vanadate is reduced by the intact erythrocyte at the expense of intracellular glutathione which rapidly depletes from the intracellular volume. Using the blocking agent 4,4′-diisothio-cyanatostilbene-2,2′-disulfonic acid (DIDS), which specifically blocks the anion transporter, vanadate reduction could be inhibited and glutathione depletion arrested. Thus, for the reaction with the intact cell to occur, vanadium(V) must cross the cell wall, possibly via the anion transporter. Nitrofurantoin was used to inhibit glutathione reductase in the erythrocyte suspensions. Under these conditions, treatment of the cells with vanadate induced glutathione oxidation prior to depletion. A study of the reaction of vanadate with haemolysate indicates that, without the influence of the membrane, rapid oxidation of glutathione to glutathione disulfide by the vanadyl cation occurs with no glutathione depletion, and that under these conditions vanadate reduction is incomplete. This study generates a model for the behaviour of vanadium complexes in vivo, providing a basis for the rational design and synthesis of new vanadium-based agents as insulin mimics. In essence, vanadium is transported across the membrane as vanadate(V), is reduced in situ by glutathione, and becomes complexed to a wide range of intracellular binding sites. Exchange reactions between glutathione and sulfhydryl groups present on haemoglobin and membrane lead to the depletion of glutathione from the cytosol.
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  • 23
    ISSN: 1432-1327
    Keywords: Key words Solution structure ; Paramagnetic biomolecules ; NMR ; Cytochrome c
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The availability of NOE constraints and of the relative solution structure of a paramagnetic protein permits the use of pseudocontact shifts as further structural constraints. We have developed a strategy based on: (1) determination of the χ tensor anisotropy parameters from the starting structure; (2) recalculation of a new structure by using NOE and pseudocontact shift constraints simultaneously; (3) redetermination of the χ tensor anisotropy parameters from the new structure, and so on until self-consistency. The system investigated is the cyanide derivative of a variant of the oxidized Saccharomyces cerevisiae iso-1-cytochrome c containing the Met80Ala mutation. The structure has been substantially refined. It is shown that the analysis of the deviation of the experimental pseudocontact shifts from those calculated using the starting structure may be unsound, as may the simple structure refinement based on the pseudocontact shift constraints only.
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  • 24
    ISSN: 1432-1327
    Keywords: Key words Ferredoxin ; Iron-sulfur clusters ; NMR ; Hyperfine shifts ; Magnetic interactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The oxidized Fe7S8 ferredoxin from Bacillus schlegelii, containing both [Fe3S4]+ and [Fe4S4]2+ clusters, has been investigated by 1H NMR spectroscopy. An extensive sequence-specific assignment of the hyperfine-shifted resonances has been obtained by making use of a computer-generated structural model. The pattern and the temperature dependence of the hyperfine shifts of the β-CH2 protons of the cysteines coordinating the [Fe3S4]+ cluster are rationalized in terms of magnetic interactions between the iron ions. The same approach holds for the hyperfine coupling with 57Fe. It is shown that the magnetic interactions are more asymmetric in Fe7S8 ferredoxins than in Fe3S4 ferredoxins. The NMR non-observability of the β-CH2 protons of coordinated cysteines in the one-electron-reduced form has been discussed.
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  • 25
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    European biophysics journal 24 (1996), S. 293-299 
    ISSN: 1432-1017
    Keywords: Phase transition ; NMR ; DSC ; X-ray diffraction ; Bonnet Transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Ternary systems of palmitoyl-oleoyl-phosphatidylcholine (POPC) and the non-ionic surfactant C12EO2 (di-ethylene-oxide-mono-dodecyl-ether) in water have been studied with optical microscopy, NMR, DSC and X-rays from ambient temperatures to 45 °C. Below 29 °C the system is in the lamellar liquid crystalline state. Between 30 and 32 °C it transforms into a cubic Ia3d structure which converts into the cubic Pn3m phase at 39 °C. The transitions are fully reversible. An epitaxial relationship between all three phases was found, which is an elegant and convenient way to rearrange molecules from lamellar bilayers to a network of curved surfaces. The la3d (Q230) to Pn3m (Q224) transition occurs without measurable enthalpy change. This, together with the metric relation of 1.60 between the cubic lattice constants is strong evidence for a Bonnet transformation, where the structural changes occur without change in curvature. The potential significance of the cubic phases as intermediate structures for biological processes, e. g. transport across a bilayer or fusion of membranes, are discussed.
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  • 26
    ISSN: 1432-1017
    Keywords: Protein denaturation ; Folding ; NMR ; Resonance assignments ; 15N labelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Virtually complete sequence specific 1H and 15N resonance assignments are presented for acid denatured reduced E. coli glutaredoxin 3. The sequential resonance assignments of the backbone rely on the combined use of 3D F1-decoupled ROESY-15N-HSQC and 3D 15N-HSQC-(TOCSY-NOESY)-15N-HSQC using a single uniformly 15N labelled protein sample. The sidechain resonances were assigned from a 3D TOCSY-15N-HSQC and a homonouclear TOCSY spectrum. The presented assignment strategy works in the absence of chemical exchange peaks with signals from the native conformation and without 13C/15N double labelling. Chemical shifts, 3J(αH, NH) coupling constants and NOEs indicate extensive conformational averaging of both backbone and side chains in agreement with a random coil conformation. The only secondary structure element persisting at pH 3.5 appears to be a short helical segment comprising residues 37 to 40.
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  • 27
    ISSN: 1432-1017
    Keywords: Key words Melittin ; Permeability ; Cholesterol ; Lipid-protein interaction ; Fluorescence ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract Melittin, an amphiphathic peptide, affects the permeability of vesicles. This can be demonstrated using the dye release technique. Calcein, a fluorescent marker, is trapped in large unilamellar 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) vesicles and melittin-induced leakage of the dye can be monitored directly by increasing fluorescence intensity. First, we characterized the effect of increasing cholesterol content in the membrane on melittin-induced leakage and our results reveal that cholesterol inhibits the lytic activity of the peptide. Using intrinsic fluorescence of the single tryptophan of melittin and 2H-NMR of headgroup deuterated phosphatidylcholine, we demonstrated that the affinity of melittin for phosphatidylcholine vesicles is reduced in the presence of cholesterol; this is associated with the tighter lipid packing of the cholesterol-containing bilayer. This reduced binding is responsible for the reduced melittin-induced leakage from cholesterol-containing membranes. The pathway of release was determined to be an all-or-none mechanism. Finally, we investigated the possibility of achieving specific membrane targeting with melittin, when vesicles of different lipid composition are simultaneously present. Melittin incubated together with vesicles made of pure POPC and POPC containing 30(mol)% cholesterol can empty nearly all the cholesterol-free vesicles while the cholesterol-containing vesicles remain almost intact. Owing to the preferential interaction of melittin with the pure POPC vesicles, we were able to achieve controlled release of encapsulated material from a specific vesicle population.
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  • 28
    ISSN: 1432-1017
    Keywords: Key words Calmodulin ; MARCKS ; Calcium binding ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The myristoylated alanine-rich C kinase substrate (MARCKS) and the MARCKS-related protein (MRP) are members of a distinct family of protein ki-nase C (PKC) substrates that bind calmodulin (CaM) in a manner regulated by Ca2+ and phosphorylation by PKC. The CaM binding region overlaps with the PKC phosphorylation sites, suggesting a potential coupling between Ca2+-CaM signalling and PKC-mediated phosphorylation cascades. We have studied Ca2+ binding of CaM complexed with CaM binding peptides from MARCKS and MRP using flow dialysis, NMR and circular dichroism (CD) spectroscopy. The wild-type MARCKS and MRP peptides induced significant increases in the Ca2+ affinity of CaM (pCa 6.1 and 5.8, respectively, compared to 5.2, for CaM in the absence of bound peptides), whereas a modified MARCKS peptide, in which the four serine residues susceptible to phosphorylation in the wild-type sequence have been replaced with aspartate residues to mimic phosphorylation, had smaller effect (pCa 5.6). These results are consistent with the notions that phosphorylation of MARCKS reduces its binding affinity for CaM and that the CaM binding affinity of the peptides is coupled to the Ca2+ affinity of CaM. All three MARCKS/MRP peptides perturbed the backbone NMR resonances of residues in both the N- and C-terminal domains of CaM and, in addition, the wild-type MARCKS and the MRP peptides induced strong positive cooperativity in Ca2+ binding by CaM, suggesting that the peptides interact with the amino- and carboxy-terminal domains of CaM simultaneously. NMR analysis of the Ca2+-CaM-MRP peptide complex, as well as CD measurements of Ca2+-CaM in the presence and absence of MARCKS/MRP peptides suggest that the peptide bound to CaM is non-helical, in contrast to the α-helical conformation found in the CaM binding regions of myosin light-chain kinase and CaM-dependent protein kinase II. The adaptation of the CaM molecule for binding the peptide requires disruption of its central helical linker between residues Lys-75 and Glu-82.
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  • 29
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    European biophysics journal 26 (1997), S. 299-306 
    ISSN: 1432-1017
    Keywords: Key words Ion binding ; Circular dichroism spectroscopy ; NMR ; Divalent cations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The effects of binding calcium ions to the double helical forms of gramicidin present in methanol solution were examined using circular dichroism (CD) and nuclear magnetic resonance (NMR) spectroscopies. It was found that calcium ions principally alter the relative composition of the equilibrium mixture of gramicidin conformers present in the solvent. In the absence of calcium, both parallel and antiparallel double helices are present. However, the addition of small amounts of Ca2+ shifts the equilibrium towards the left-handed parallel double helical form. This conformational change prevents monovalent cations (caesiums) from binding to the gramicidin double helix, and even converts the shorter, wider anti-parallel double helical form normally produced in the presence of caesium into the longer, narrower parallel double helical form. Furthermore, a temperature study showed that calcium ions tend to stabilize this form relative to the ion-free forms. The conformation of gramicidin is further changed, becoming a disordered structure, when the concentration of Ca2+ is raised. Thus, the binding of divalent calcium ions has a number of dramatic effects on the conformations of gramicidin present in solution.
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  • 30
    ISSN: 1432-1017
    Keywords: NMR ; Dynamics ; Src-homology domain ; Secondary structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Physics
    Notes: Abstract The SH2 domain from Fyn tyrosine kinase, corresponding to residues 155–270 of the human enzyme, was expressed as a GST-fusion protein in a pGEX-E. coli system. After thrombin cleavage and removal of GST, the protein was studied by heteronuclear NMR. Two different phosphotyrosyl-peptides were synthesized and added to the SH2 domain. One peptide corresponded to the regulatory C-terminal tail region of Fyn. Sequence-specific assignment of NMR spectra was achieved using a combination of1H-15N-correlated 2D HSQC,15N-edited 3D TOCSY-HMQC, and15N-edited 3D NOESY-HMQC spectra. By analysis of the α-proton chemical shifts and NOE intensities, the positions of secondary structural elements were determined and found to correspond closely to that seen in the crystal structure of the, homologous, Src-SH2 domain. To investigate the internal dynamics of the protein backbone, T1 and T2 relaxation parameters were measured on the free protein, as well as on both peptide complexes. Analytical ultracentrifugation and dynamic light scattering were employed to measure the effect of concentration and peptide-binding on self-association. The results suggest that, at NMR-sample concentrations, the free protein is present in at least dimeric form. Phosphopeptide binding and lower concentration significantly, but not completely, shift the equilibrium towards monomers. The possible role of this protein association in the regulation of the Src-family tyrosine kinases is discussed.
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  • 31
    ISSN: 1432-1327
    Keywords: Key words Cytochrome c3 ; Mutagenesis ; Redox-Bohr ; NMR ; EPR ; Cooperativity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  Reduction of the haems in tetrahaem cytochromes c 3 is a cooperative process, i.e., reduction of each of the haems depends on the redox states of the other haems. Furthermore, electron transfer is coupled to proton transfer (redox-Bohr effect). Two of its haems and a strictly conserved nearby phenylalanine residue, F20, in Desulfovibrio vulgaris (Hildenborough) cytochrome c 3 form a structural motif that is present in all cytochromes c 3 and also in cytochrome c oxidase. A putative role for this phenylalanine residue in the cooperativity of haem reduction was investigated. Therefore, this phenylalanine was replaced, with genetic techniques, by isoleucine and tyrosine in D. vulgaris (Hildenborough) cytochrome c 3. Cyclic voltammetry studies revealed a small increase (30 mV) in one of the macroscopic redox potentials in the mutated cytochromes. EPR showed that the main alterations occurred in the vicinity of haem I, the haem closest to residue 20 and one of the haems responsible for positive cooperativities in electron transfer of D. vulgaris cytochrome c 3. NMR studies of F20I cytochrome c 3 demonstrated that the haem core architecture is maintained and that the more affected haem proton groups are those near the mutation site. NMR redox titrations of this mutated protein gave evidence for only small changes in the relative redox potentials of the haems. However, electron/electron and proton/electron cooperativity are maintained, indicating that this aromatic residue has no essential role in these processes. Furthermore, chemical modification of the N-terminal amino group of cytochrome c 3 backbone, which is also very close to haem I, had no effect on the network of cooperativities.
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  • 32
    ISSN: 1432-1327
    Keywords: Key words Cooperativity ; Cytochrome c3 ; NMR ; Paramagnetic ; Redox-Bohr
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The thermodynamic model of five interacting charge centres (four haems and an ionisable centre), which was used in the characterisation of the thermodynamic properties of Desulfovibrio vulgaris (Hildenborough) cytochrome c 3 (c 3DvH), is now used to reevaluate the thermodynamic properties in Desulfovibrio vulgaris (Miyazaki F) cytochrome c 3 (c 3DvM) on the basis of published data (Park, J.-S., Ohmura, T., Kano, K., Sagara, T., Niki, K., Kyogoku, Y. and Akutsu, H. (1996) Biochim. Biophys. Acta 1293, 45–54). Contrary to the assertion of Park et al. (1996), the pH dependence of the proton chemical shifts of haem methyls in c 3DvM in several stages of oxidation is well described by the model, which involves both homotropic (e–/e–) and heterotropic (e–/H+) cooperativity. This shows that the pH dependence observed for c 3DvM is not significantly more complicated than that observed for c 3DvH. Since the parameters which we now obtain for c 3DvM are generated with the same model as those from c 3DvH, albeit using less precise data, it is possible to make a preliminary comparison of the thermodynamic properties of these two proteins and of their role in energy transduction. The extrinsic dipolar shifts generated for each methyl group by each of the four haems in c 3DvM are also determined. A novel method for approximating the magnetic susceptibility tensors is used: the orientations of the principal axes of the tensors have been shown to be closely related to the geometry of the axial ligands, which is available from the X-ray structure of c 3DvM, and the components of the tensors are extrapolated from EPR g values. The inclusion of the calculated haem extrinsic contributions clearly describes the pH dependence of the haem methyls in the core of the protein, close to other haems. This description is most remarkable in the case of the haem methyl 21CH3 II I, for which the "unusual pH dependence" commented on by Park et al. (1996) is easily explained using the thermodynamic parameters determined by our model together with the calculated extrinsic dipolar shifts, thus providing a test of the analysis.
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  • 33
    ISSN: 1432-1327
    Keywords: Key words Aminopeptidase ; Streptomyces ; Dinuclear ; NMR ; Co2+ ; Cu2+
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  Streptomyces griseus aminopeptidase has been characterized to have a dinuclear active site and to follow a dinuclear hydrolytic mechanism by means of activity assay, optical, and NMR spectroscopy. A sequential binding of Co2+ to the dinuclear sites in 20 mM Mes buffer at pH 6.1 has also been established. The results from these studies suggest that the two metal sites have a five-coordination sphere, with at least one coordinated His each. A di-Cu2+-substituted derivative of the enzyme has been prepared which exhibits a 1H NMR spectrum with sharp hyperfine-shifted signals, again indicating the presence of a dinuclear active site. This 1H NMR spectrum with sharp hyperfine-shifted features represents a first of its kind for a di-Cu2+ center in metalloproteins.
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  • 34
    ISSN: 1432-1327
    Keywords: Key words Multihaem cytochromes ; Cytochrome c551.5 ; Cytochrome c3 ; Sulfate-reducing bacteria ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  The trihaem cytochrome c 551.5, formerly known as cytochrome c 7, from the organism Desulfuromonas acetoxidans, has been studied in the reduced state by 2D proton NMR. The haem proton resonances were assigned, and several nuclear Overhauser enhancements (NOEs) between resonances arising from different haems were detected and assigned. The relative orientations of the three haems were calculated by fitting both the intensities of the interhaem NOEs and the magnitudes of the ring current shifts of the haem resonances, following the strategy previously used by the authors to reassess the X-ray structure of the haem core in tetrahaem cytochrome c 3 from Desulfumicrobium baculatum. It is concluded that, although the comparison of the protein sequence with those of the tetrahaem cytochromes c 3 shows that in cytochrome c 551.5 about 40% of the sequence is deleted, including the region involved in the attachment of the second of the four haems, this does not induce any significant rearrangement of the remaining three haems other than a slight decrease in the iron-iron distance between two of the haems, namely those corresponding to haems I and IV of cytochrome c 3.
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  • 35
    ISSN: 1432-1327
    Keywords: Key words Cytochrome c6 ; Anabaena PCC 7119 ; EPR ; NMR ; Redox-Bohr
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract  A soluble monoheme c–type cytochrome c 6 has been isolated from the cyanobacterium Anabaena PCC 7119. It is a basic protein, with a molecular mass of 9.7 kDa, which accepts electrons from Anabaena ferredoxin in the ferredoxin-NADP+reductase-dependent NADPH cytochrome c reductase activity assay. The turnover of the reaction has an optimum pH at 7.5. Flavodoxin can also replace ferredoxin in this assay, but with only 20% efficiency. Plastocyanin from Anabaena PCC 7119, as well as the c 6 cytochromes from the green algae Chlorella fusca and Monoraphidium braunii are also shown to accept electrons from Anabaena ferredoxin. The reduction potential of cytochrome c 6 at pH 6.7 was determined to be 338 mV and is pH dependent, with pK a ox=8.4±0.1 and pK a red≈9.5. The ferric and ferrous cytochrome forms and their pH equilibria have been studied using visible, EPR and 1H-NMR spectroscopies. The amino acid sequence and the visible and NMR spectroscopic data indicate that the heme iron has a methionine-histidine axial coordination in the pH range 5–11. However, the EPR data for the ferricytochrome are complex and show that in this pH range five distinct forms are present. Between pH 5 and 9 the spectrum is dominated by two rhombic species, with g–values at 2.94, 2.29, 1.43 and at 2.84, 2.34, 1.56, which interconvert with a pK a of 8.4. The NMR data also show a main interconversion between two cytochrome forms at this pH, which coincides with that determined from the pH dependence of the reduction potential. Both these forms were associated with a methionine-histidine heme-iron coordination by correlation with the visible and NMR spectral data, although having crystal field parameters atypical for this type of coordination. Anabaena cytochrome c 6 is one more example of a heme protein for which the widely used crystal field analysis of the EPR data (truth diagram) fails to unequivocally determine the type of heme-iron ligation.
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  • 36
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    Journal of thermal analysis and calorimetry 50 (1997), S. 625-632 
    ISSN: 1572-8943
    Keywords: DSC ; NMR ; 8-quinolinol compounds ; TG-DTG ; stability ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Solid M-Ox compounds, whereM represents Mg(II), Zn(II), Pb(II) and NbO(III), and Ox is 8-quinolinol, have been prepared. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR) and infrared absorption spectra (IR) have been used to characterize and to study the thermal stability and thermal decomposition of these compounds.
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  • 37
    ISSN: 1573-4919
    Keywords: vanadate effects ; glycolysis ; intracellular sodium ; NMR ; perfused rat hearts ; ischemia-reperfusion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Medicine
    Notes: Abstract Vanadium compounds have been shown to cause a variety of biological and metabolic effects including inhibition of certain enzymes, alteration of contractile function, and as an insulin like regulator of glucose metabolism. However, the influence of vanadium on metabolic and ionic changes in hearts remains to be understood. In this study we have examined the influence of vanadate on glucose metabolism and sodium transport in isolated perfused rat hearts. Hearts were perfused with 10 mM glucose and varying vanadate concentrations (0.7‐100 μM) while changes in high energy phosphates (ATP and phosphocreatine (PCr)), intracellular pH, and intracellular sodium were monitored using 31P and 23Na NMR spectroscopy. Tissue lactate, glycogen, and (Na+, K+)-ATPase activity were also measured using biochemical assays. Under baseline conditions, vanadate increased tissue glycogen levels two fold and reduced (Na+, K+)-ATPase activity. Significant decreases in ATP and PCr were observed in the presence of vanadate, with little change in intracellular pH. These changes under baseline conditions were less severe when the hearts were perfused with glucose, palmitate and b-hydroxybutyrate. During ischemia vanadate did not limit the rise in intracellular sodium, but slowed sodium recovery on reperfusion. The presence of vanadate during ischemia resulted in attenuation of acidosis, and reduced lactate accumulation. Reperfusion in the presence of vanadate resulted in a slower ATP recovery, while intracellular pH and PCr recovery was not affected. These results indicate that vanadate alters glucose utilization and (Na+, K+)-ATPase activity and thereby influences the response of the myocardium to an ischemic insult.
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  • 38
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    Journal of computer aided molecular design 10 (1996), S. 89-99 
    ISSN: 1573-4951
    Keywords: Conformation ; Molecular dynamics ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Proctolin (Arg-Tyr-Leu-Pro-Thr) was the first insect neuropeptide to be chemically characterised. It plays an essential role in insect neurophysiology and is involved in muscular contraction and neuromodulation. Elements of secondary structure in solution have been studied by comparing data obtained from NMR and molecular dynamics simulations. Different secondary structural requirements are associated with agonist and antagonist activities. A favoured conformation of proctolin has an inverse γ-turn, comprising an intramolecular hydrogen bond near the C-terminal end between Thr NH and Leu CO. Antagonists have a more compact structure resembling a ‘paperclip’ loop, containing an intramolecular hydrogen bond between Tyr NH and Pro CO, possibly stabilised by a salt bridge between the N- and C-terminal groups. A cyclic analogue retains antagonist activity and resembles a β-bulge loop, also comprising intramolecular hydrogen bonds between Tyr NH and Pro CO and Thr CO. These models may offer feasible starting points for designing novel compounds with proctolinergic activity.
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  • 39
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    Journal of sol gel science and technology 6 (1996), S. 139-149 
    ISSN: 1573-4846
    Keywords: titanosiloxanes ; siloxanes ; hydrolysis ; condensation ; structural units ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The structural units in diphenylsilanediol/titanium-isopropoxide solutions with molar ratio Si:Ti between 1:0.1 and 1:5 were examined by means of 29Si and 17O NMR. The main component in solutions with molar ratio Si/Ti=1:0.1 is the chain-like octaphenyltetrasiloxanediol. With increasing Ti-isopropoxide content (1:0.25–1:05) Si−O−Ti units of the spirocyclic titanosiloxane Ti[O5Si4(C6H5)8]2 prevail in the solutions accompanied by the chain-like tetrasiloxanediol. The 29Si NMR spectra of 1:1 solutions indicate a lot of different Si containing building units with chemical shifts mainly between-40 and-46 ppm. The signals with a chemical shift between-40 and-46 ppm are probably caused by Si atoms which are connected via oxygen bridges directly (Si−O−Ti) or indirectly (Si−O−Si−O−Ti) with titanium. Contrary to the 1:1 solutions only one or two different species with Si−O−Ti units are present in high Ti-alkoxide containing solutions (1:5). 29Si and 17O NMR results reveal a quick hydrolysis of the Ti−O−Si bonds to titanium-oxo-hydroxo-polymers and phenylsiloxanediols or their isopropyl esters after the addition of water to the solutions. This separation into species only containing either Ti−O−Ti or Si−O−Si bonds can entail a decreased homogeneity of the reaction products on a molecular level.
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  • 40
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    Journal of sol gel science and technology 6 (1996), S. 279-285 
    ISSN: 1573-4846
    Keywords: sol-gel process ; siloxane cross-linking ; gelation ; NMR ; SANS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We have studied by 29Si NMR and small angle neutron scattering the cross-linking by formation of siloxane bridges of two amino-epoxy-silane molecules at different concentration in acidic water. We relate our observations to the fact that one of the studied systems never gels, while the second one displays a concentration threshold for gelation that is accounted for by percolation theory.
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  • 41
    ISSN: 1573-4943
    Keywords: Thrombin receptor peptide ; NMR ; conformation ; bioactivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The conformational properties of the pentapeptide Ser-Phe-Leu-Leu-Arg (P5), a human thrombin receptor-derived sequence forming part of a tethered ligand which activates the thrombin receptor, and its more active amide derivative Ser-Phe-Leu-Leu-Arg-NH2 (P5-NH2), have been studied by proton NMR spectroscopy in dimethylsulfoxide. Measurements of nuclear Overhauser effects, performed using two-dimensional rotating frame nuclear Overhauser (ROESY) and one-dimensional nuclear Overhauser enhancement (NOE) spectroscopy, revealed that P5 exists mainly in an extended conformation. However, proton–proton 1D-NOEs between Phe CαH and Ser CαH, Leu3 CαH and Leu3 NH, and Leu4 CαH and Leu4 NH, as well as between the Ser and Arg sidechains, also implicated a minor conformer for P5 having a curved backbone and a near-cyclic structure. In contrast to P5, measurements of NOEs and ROEs for P5-NH2 revealed a more stabilized cyclic structure which may account for its higher biological potency. Thus strong interresidue sequential NH (i)–NH (i + 1) interactions, as well as C-terminal carboxamide to N-terminal side-chain interactions, i.e., Arg CONH2 to Phe ring and Arg CONH2 to Ser $$C_\alpha /C_{\beta \beta '} $$ , observed at lower levels of the ROESY spectrum, supported a curved backbone structure for SFLLR-NH2. Since the higher potaency P5-NH2 analogue adopts predominantly a cyclic structure, a cyclic bioactive conformation for thrombin receptor agonist peptides is suggested.
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  • 42
    ISSN: 1573-501X
    Keywords: combinatorial library ; hydrophobic collapse ; NMR ; n-substituted glycines ; structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Synthesis and screening of combinatorial librariesfor pharmaceutical lead discovery is a rapidlyexpanding field. Oligo-N-substituted glycines (NSGs)were one of the earliest sources of moleculardiversity in combinatorial libraries. In one of thefirst demonstrations of the power of combinatorialchemistry, two NSG trimers, CHIR-2279 and CHIR-4531,were identified as nM ligands for two 7-transmembraneG-protein-coupled receptors. The NMR characterizationof these two lead compounds was undertaken to verifycovalent connectivity and to determine solutionconformations, if any. The sequential chemical shiftassignments were performed using a new strategy forassigning 1H and 13C resonances of NSGs. The conformational preferences were then determined inboth an aqueous co-solvent system and an organicsolvent to probe the effects of hydrophobic collapse. NSGs are expected to be more flexible than peptidesdue to the tertiary amide, with both cis andtrans amide bond conformations being accessible. Solution NMR studies indicate that although CHIR-2279and CHIR-4531 have identical backbones and termini,and very similar side chains, they do not display thesame solution conformational characteristics.
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  • 43
    ISSN: 1573-4943
    Keywords: Interleukin-5 ; carboxy-terminal truncations ; NMR ; protein stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The C-terminal region of interleukin-5 has previously been suggested to be important for biological activity [Mackenzieet al., (1991),Mol. Immunol. 28, 155–158; Kodamaet al. (1991),Biochem. Biophys. Res. Commun. 178, 514–519]. We have investigated this region by making a series of truncation mutants. The proteins were expressed inEscherichia coli, purified from inclusion bodies, and were able to refold with the disulfide homodimeric topology typical of interleukin-5. Analysis of the truncated carboxy-terminal proteins in an interleukin-5-dependent proliferation assay on TF-1 cells showed a rapid loss of activity as the C-terminal was shortened by more than two amino acids. This loss of biological activity correlated with a drop in binding affinity to both theα chain of the receptor and the high-affinity complex consisting of theα andβ subunits. Analysis of the proteins by1H-NMR showed that the truncated mutants have higher exchange rates with solvent, indicating a less rigid structure. The carboxy-terminal region is therefore necessary to maintain the stability of the four-helix bundle and to orient correctly the important residues of the fourth helix. Inspection of the structure determined by X-ray crystallography shows that Trp-110 acts as the major residue in anchoring the fourth helix.
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  • 44
    ISSN: 1573-4943
    Keywords: Cytochrome c ; assignments ; ferrocytochrome c ; NMR ; 1H NMR ; 13C NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Yeast iso-1 cytochrome c is a naturally occurring protein that possesses an unusually reactive Cysl02 that imbues iso-1 with a complicated solution chemistry which includes spontaneous dimerization and poorly characterized redox reactions. For this reason previous studies of this typical member of the c-type cytochromes have been relegated to variant proteins in which the 102 position has been mutated, with most common changes involving serine and threonine. However, we have determined sequential 1H resonance assignments for the wild-type native protein because it is the actual participant in yeast mitochondrial electron transfer processes and because the wild-type native protein should be the fundamental assignment basis. In addition to 1H resonance assignments for 97 of 106 amino acids, we have also provided an extensive database of long-range NOEs. Comparison of these NOEs and a chemical shift index based upon α-H resonances has lead to identification of solution secondary structural elements that are consistent with the solid-state crystal structure. Although there is currently no efficient expression system that would facilitate isotope labeling of iso-1 cytochrome c, we tried to assess the usefulness of future heteronuclear experiments by using natural-abundance 1H/13C HMQC experiments to unambiguously assign 35 α-C resonances.
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  • 45
    ISSN: 1573-9171
    Keywords: sodium alkyls ; lithium alkyls ; NMR ; synthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract 1H,23Na, and7Li NMR spectra of 2-ethyl hexylsodiurn, 2-ethylhexyllithium, and isobutyllithium obtained in the reaction of the corresponding alkyl chlorides and metals have been recorded. The1H N MR signal for the protons of the CH2Na group is shifted upheld compared with that for the protons of the CH2Li group (doublets at δ -0.88 and δ -0.83, respectively). The composition of the products of reaction of 2-ethylhexyl chloride with sodium depends on the form of the metal reagent employed. The use of sodium balls with diameter up to 2 mm results in the formation of products containing ionic chlorine (30–50 % with respect to Na); the reaction with the dispersion proceeds faster and the reaction product is chlorine-free. The23Na NMR spectra of these substances are also different, which is explained by the formation of 2-ethylhexylsodium complexes with NaCl in the former case.
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  • 46
    ISSN: 1573-4986
    Keywords: O-acetyl GM3 ; equine erythrocytes ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Novel mono-O-acetylated GM3s, one containing 9-O-acetylN-glycolyl neuraminic acid and another containing 6′-O-acetyl galactose, were isolated as a mixture from equine erythrocytes, and the structures were characterized by one- and two-dimensional proton nuclear magnetic resonance (NMR) and fast atom bombardment-mass spectrometry (FAB-MS). The position of theO-acetyl residue was identified by the downfield shift of the methylene protons at C-9 ofN-glycolyl neuraminic acid (9-O-Ac GM3) and C-6 of galactose (6′-O-Ac GM3) in the NMR spectrum, in comparison to the respective non-acetylated counterparts. To confirm the presence of 6′-O-Ac GM3, theO-acetylated GM3 mixture was desialylated withArthrobacter neuraminidase, giving 6-O-acetyl galactosyl glucosylceramide, the structure of which was estimated by NMR and FAB-MS, together with non-acetylated lactosylceramide with a ratio of 1:1.
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  • 47
    ISSN: 1573-4986
    Keywords: gangliosides ; N-glycolyl-neuraminic acid ; NMR ; conformation ; nOe
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The conformational properties of the oligosaccharide chain of GM1 ganglioside containingN-glycolyl-neuraminic acid, β-Gal-(1-3)-β-GalNAc-(1-4)-[α-Neu5Gc-(2-3)]-β-Gal-(1-4)-β-Glc-(1-1)-Cer, were studied through NMR nuclear Overhauser effect investigations on the monomeric ganglioside in dimethylsulfoxide, and on mixed micelles of ganglioside and dodecylphosphocholine in water. Several interresidual contacts for the trisaccharide core-β-GalNAc-(1-4)-[α-Neu5Gc-(2-3)]-β-Gal-were found to fix the relative orientitation of the three saccharides, while the glycosidic linkage of the terminal β-Gal-was found to be quite mobile as the β-Gal-(1-3)-β-GalNAc-disaccharide exists in different conformations. These results are similar to those found for two GM1 gangliosides containingN-acetyl-neuraminic acid and neuraminic acid [1].
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  • 48
    ISSN: 1573-4986
    Keywords: Chemically induced dynamic nuclear polarization (CIDNP) ; carbohydrate-protein interaction ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The side chains of tyrosine, tryptophan and histidine are able to produce CIDNP (Chemically Induced Dynamic Nuclear Polarization) signals after laser irradiation in the presence of a suitable radical pair-generating dye. Elicitation of such a response in proteins implies surface accessibility of the respective groups to the light-absorbing dye. In principle, this technique allows the monitoring of the effect of ligand binding to a receptor and of site-directed mutagenesis on conformational aspects of any protein if CIDNP-reactive amino acids are involved. The application of this method in glycosciences can provide insights into the protein-carbohydrate interaction process, as illustrated in this initial model study for several N-acetyl-glucosamine-binding lectins of increasing structural complexity as well as for a wild type bacterial sialidase and its mutants. Experimentally, the shape and intensity of CIDNP signals are determined in the absence and in the presence of specific glycoligands. When the carbohydrate is bound, CIDNP signals of side chain protons of tyrosine, tryptophan or histidine residues can be broadened and of reduced intensity. This is the case for hevein, pseudo-hevein, the four hevein domains-containing lectin wheat germ agglutinin (WGA) and the cloned B-domain of WGA 1 (domB) representing one hevein domain. This response indicates either a spatial protection by the ligand or a ligand-induced positioning of formerly surface-exposed side chains into the protein’s interior part, thereby precluding interaction with the photo-activated dye. Some signals of protons from the reactive side chains can even disappear when the lectin-ligand complexes are monitored. The ligand binding, however, can apparently also induce a conformational change in a related lectin that causes the appearance of a new signal, as seen for Urtica dioica agglutinin (UDA) which consists of two hevein domains. Additionally, the three CIDNP-reactive amino acids are used as sensors for the detection of conformational changes caused by pH variations or by deliberate amino acid exchanges, as determined for the isolectins hevein and pseudo-hevein as well as for the cloned small sialidase of Clostridium perfringens and two of its mutants. Therefore, CIDNP has proven to be an excellent tool for protein-carbohydrate binding studies and can be established in glycosciences as a third biophysical method beside X-ray-crystallography and high-resolution multidimensional NMR studies which provides reliable information of certain structural aspects of carbohydrate-binding proteins in solution.
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  • 49
    ISSN: 1573-4986
    Keywords: glycopeptide ; NMR ; proteoglycan ; serglycin ; secondary structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract We present complete1H NMR assignments for two synthetic glycopeptides representative of the carbohydrateprotein linkage region of serglycin proteoglycans. The peptides are: Ser(Galp-Xylp)-Gly-Ser-Gly-Ser(Galp-Xylp)-Gly and, Ser(Galp-Xylp)-Gly-Ser(Galp-Xylp)-Gly-Ser(Galp-Xylp)-Gly. A number of 2D NMR spectra together with a 3D NOESY-TOCSY spectrum were acquired at 600 MHz to complete the assignments of the glycopeptides dissolved in water with 40% trifluoroethanol. Preliminary analysis of the NMR data suggests folded structures for the glycopeptides.
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  • 50
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    Journal of porous materials 4 (1997), S. 245-251 
    ISSN: 1573-4854
    Keywords: fly ash ; zeolite Y ; ageing ; seeding ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Zeolite Y was selectively synthesised by treating Tarong fly ash in a hydrothermal system. The effects of ageing and seeding on the formation of the resultant phases, crystallisation kinetics, and gel chemistry of Si and Al were investigated. Most of the Si and Al components in the Tarong fly ash could be effectively transformed into zeolite Y in the presence of seeds but not the mineral phase, like mullite. The maximum crystallinity of zeolite Y obtained was 72%. The cation-exchange capacity (CEC) of the fly ash was 0.08 mmol/g but increased to 3.2 mmol/g after a proper treatment. Crystallisation of zeolite materials from fly ash is quite different from that of normal zeolite synthesis because the sources of Si and Al are relatively less reactive and other cation ions (e.g., K+, Mg2+) are present in fly ash. Zeolite P is a competitive phase present in the resulting products that could be eliminated by employing the seeding method. NMR study demonstrated that ageing plays an important role in enhancing the hydrothermal condition during which both Si and Al in fly ash dissolved into a basic solution and reacted to form ring-like structures, and further to zeolite materials. Seeding can selectively induce the formation of zeolite Y and eliminate the processes of induction and nucleation.
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  • 51
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    Glycoconjugate journal 13 (1996), S. 487-494 
    ISSN: 1573-4986
    Keywords: Blood group A glycosphingolipids ; monoclonal antibody ; NMR ; mass spectrometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, the antibody 3G9-A was assayed for activity against human erythrocyte glycosphingolipids. The antibody was found to recognize glycosphingolipid components from blood group A erythrocytes but not glycosphingolipids from blood group B or O erythrocytes. Subsequent investigation revealed that the glycosphingolipid components recognized by the antibody were also recognized by a blood group A specific monoclonal antibody. The structures of two of the isolated active glycosphingolipid components were structurally characterized using proteon nuclear magnetic resonance (1H NMR) and gas chromatography-mass spectrometry (GC-MS) techniques and were found to consist of two blood group A glycosphingolipids; the type 2 chain Ab and type 3 chain Aa glycosphingolipids. Subsequent analysis of the remaining active components by GC-MS and immunostaining techniques revealed that all of the active components were blood group A glycosphingolipids. Furthermore, structural studies of the active components suggested that the epitope of the antibody consisted of the group A trisaccharide, GalNAcα1,3(Fucα1,2)Gal.
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  • 52
    ISSN: 1573-904X
    Keywords: LDL ; LDL models ; synchrotron radiation ; X-ray solution scattering ; NMR ; solvent evaporation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. Drug free and drug loaded protein-free low density lipoprotein (LDL) models consisting mainly of phospholipids, cholesterol, cholesterol esters, and triglycerides in ratios found for physiological LDL have been prepared. Their physicochemical characteristics were compared with those of physiological LDL. Methods. Different characterization methods were used: photon correlation spectroscopy, transmission electron microscopy, X-ray solution scattering, and 1H nuclear magnetic resonance spectroscopy (NMR). Results. Particle sizes are highly dependent on the preparation method and in particular on the homogenization conditions. Electron microscopy indicates that the size distributions of model systems are much broader than those of physiological LDL. The X-ray solution scattering patterns of the model systems display a temperature dependent maximum near 3.8 nm similar to that found in the patterns of physiological LDL. NMR indicates a comparable mobility of the lipid molecules in model particles and in physiological LDL. The influence of drug loading is similar to that found earlier for physiological LDL. In particular, the incorporation of the anti-cancer drug WB 4291 seems to have a fluidizing effect on the lipids in the core region of the particles. Conclusions. The preparation method of LDL model systems is of crucial importance as only the solvent evaporation method yielded systems in the size range of physiological LDL with acceptable high lipid concentrations. The fluidizing influence of temperature and drug incorporation (WB 4291) may be a disadvantage in drug targeting.
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  • 53
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    Pharmaceutical research 13 (1996), S. 535-541 
    ISSN: 1573-904X
    Keywords: bile salt ; phospholipid ; diffusion ; mucin ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The objective of this study is to evaluate the effect of the mucous layer on the transport of the drug-solubilizing bile salt/phosphatidylcholine (BS/PC) aggregates. Methods. The self-diffusion coefficient of BS/PC aggregates in bovine submaxillary mucin (BSM) was measured by Fourier-transform pulsed-field gradient spin-echo (FT-PGSE) 1H NMR spectroscopy. Results. In spite of the complexity of the mixture, the FT-PGSE technique allowed the unambiguous determination of the diffusivity of PC and 1H2HO (HDO, natural abundance in D2O). With a series of BS/ PC total lipid concentrations ranging from 1 to 7 g/dl, a progressive decrease in the effective diffusivity of HDO was observed with an increase in the both the BSM and total lipid concentration. The effective diffusivity of PC decreased with increasing lipid concentrations in the presence of mucin, while in the controls it increased. After correcting the effective diffusivity of PC for the obstruction effect of mucin, the size of the BS/PC mixed micelle was assessed. It appears that PC associates with BSM resulting in a decrease in the available PC for micellization. This reduces the average size of the mixed micelle within the mucous layer. Conclusions. The aggregation state of BS/PC micelle is altered by the presence of mucin which would have a direct impact on the transport of dietary lipid and solubilized drug through the aqueous boundary layer of the intestinal tract.
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  • 54
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    Pharmaceutical research 13 (1996), S. 1815-1820 
    ISSN: 1573-904X
    Keywords: elastase inhibitor ; monocyclic β-lactam ; NMR ; stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The objective was to evaluate the degradation profile of the elastase inhibitor DMP 777 and lay the foundation for formulation development. Methods. The pKa was determined by potentiometric titration in mixed-aqueous solvents. The degradation kinetics were studied as a function of pH, buffer concentration, ionic strength, methanol concentration and temperature using a stability-indicating HPLC assay. The degradation products were identified by LC-MS, NMR, and by comparison with authentic samples. Results. The pKa for the protonated piperazine nitrogen was estimated to be 7.04. The pH-rate profile is described by specific acid-, water-, and specific base-catalyzed pathways. The pH of maximum stability is in the range of 4 to 4.5 where water is the principal catalyst in the reaction. Buffer catalysis, primary salt effects and medium effects were observed. The proposed mechanism for acid catalyzed degradation is the rarely observed AAL1 which involves alkyl-nitrogen heterolysis. The driving force for the reaction appears to lie in the stability of the benzylic carbocation. The proposed mechanism for base catalyzed degradation is BAC2 which involves β-lactam ring opening. The β-lactam ring of DMP 777, a monolactam, appears to be as reactive as that in benzylpenicillin in the k OH controlled region where a similar mechanism of hydrolysis should be operative. A contributing factor to this increased reactivity may lie in the reduced basicity of the β-lactam nitrogen making it a good leaving group. Conclusions. The degradation profile indicates that development of a solution dosage form of DMP 777 with adequate shelf-life stability at room temperature is feasible.
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  • 55
    ISSN: 1573-904X
    Keywords: ionization ; solubilization ; bile salts ; micelles ; NMR ; partition coefficient
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The aqueous solubility and the extent of solubilization and ionization constant in sodium taurodeoxycholate (NaTDC) solutions of a series of benzoic acid and aniline derivatives were measured as a basis to characterize and thereby help predict the nature of the interaction of drugs with bile aggregates. Methods. The aqueous solubility and the solubilization of two series of compounds, 4-alkyl benzoic acids and 4-alkyl anilines, was measured as a function of NaTDC in 0 and 150 mM NaCl. The ionization constants were determined in water and in 50 mM NaTDC at sodium chloride concentrations of 0, 75 and 150 mM by spectrophotometric titration. The diffusion coefficients of NaTDC and the solutes were measured by pulsed-field gradient spin echo NMR spectroscopy. Results. The aqueous solubilities decreased with increasing alkyl chain length in both series, and the aniline derivatives had larger solubilities than the benzoic acid derivatives. The number of moles of solute solubilized per mole of bile salt ranged from 0.17 to 0.31 for the benzoic acid derivatives and from 1.3 to 3.0 for the aniline derivatives. The pKa values of the benzoic acid derivatives in the presence of NaTDC were higher relative to the controls, and the difference in the pKa (ΔpKa,obs) increased with increasing chain length. With the aniline derivatives, the pKa values were also shifted to higher values in NaTDC relative to the control but only in the absence of salt. The presence of the solute caused a decrease in the diffusion coefficient of NaTDC, and the diffusion coefficients of the solutes decreased with increasing alkyl chain length. With the hexyl derivatives, the diffusion coefficient of the solute was smaller than the diffusion coefficient of the bile salt. The chemical shift of the protons attached to carbon 18 and 19 of the bile salt were decreased to a greater extent in the presence of the solutes than the protons attached to carbon 26. Conclusions. Both the solubilization and ionization behavior of solutes were affected by the presence of bile salt aggregates. The surface potential and effective polarity of NaTDC aggregates were found to be dependent on the alkyl chain length for these two homologous series of solutes. The solubilization ratio was largely independent of alkyl chain length, but the unitary partition coefficient was dependent on both the alkyl chain length as well as ionization state. The derivatives reduced the diffusivity of the micelles suggesting the formation of larger sized aggregates and the solutes (hexyl derivatives) appear to favor association with the larger sized aggregates. The phenyl ring of the solutes appears to be oriented parallel to the plane of the steroid frame with preferential positioning near the hydrophobic rings.
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  • 56
    ISSN: 1573-904X
    Keywords: peptide delivery ; conformation ; Caco-2 cells ; membrane permeability ; NMR ; CD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. To determine how restricted conformational flexibility of hexapeptides influences their cellular permeation characteristics. Methods. Linear (Ac-Trp-Ala-Gly-Gly-X-Ala-NH2; X = Asp, Asn, Lys) and cyclic (cyclo[Trp-Ala-Gly-Gly-X-Ala]; X = Asp, Asn, Lys) hexapeptides were synthesized, and their transport characteristics were assessed using the Caco-2 cell culture model. The lipophilicities of the hexapeptides were determined using an immobilized artificial membrane. Diffusion coefficients used to calculate molecular radii were determined by NMR. Two-dimensional NMR spectroscopy, circular dichroism, and molecular dynamic simulations were used to elucidate the most favorable solution structure of the cyclic Asp-containing peptide. Results. The cyclic hexapeptides used in this study were 2−3 times more able to permeate (e.g., Papp = 9.3 ± 0.3 × 10−8 cm/sec, X = Asp) the Caco-2 cell monolayer than were their linear analogs (e.g., Papp = 3.2 ± 0.3 × 10−8 cm/sec, X = Asp). In contrast to the linear hexapeptides, the flux of the cyclic hexapeptides was independent of charge. The cyclic hexapeptides were shown to be more lipophilic than the linear hexapeptides as determined by their retention times on an immobilized phospholipid column. Determination of molecular radii by two different techniques suggests little or no difference in size between the linear and cyclic hexapeptides. Spectroscopic data indicate that the Asp-containing linear hexapeptide exists in a dynamic equilibrium between random coil and β-turn structures while the cyclic Asp-containing hexapeptide exists in a well-defined compact amphophilic structure containing two β-turns. Conclusions. Cyclization of the linear hexapeptides increased their lipophilicities. The increased permeation characteristics of the cyclic hexapeptides as compared to their linear analogs appears to be due to an increase in their flux via the transcellular route because of these increased lipophilicities. Structural analyses of the cyclic Asp-containing hexapeptide suggest that its well-defined solution structure and, specifically the existence of two β-turns, explain its greater lipophilicity.
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  • 57
    ISSN: 1573-904X
    Keywords: cholesterol ; differential scanning calorimetry ; drug delivery ; electron microscopy ; fluorescence quenching ; long circulating liposomes ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. The purpose of this study was to investigate polyethyleneglycol (PEG)-phosphatidylethanolamine (PE) conjugate interaction with cholesterol-phospholipid mixtures in an attempt to explain the effect of cholesterol on liposome circulation time. Methods. Differential scanning calorimetry, NMR, electron microscopy, dynamic light scattering and fluorescence spectroscopy were the major methods used. Results. Studies performed in the absence of cholesterol indicated the formation of three distinct physical states depending on the chain length of PEG in PEG-PE. Mixed micelle formation was observed at concentrations of PEG( 1,000)-DPPE above 7 mol% of lipid. Phase separated lamellae were observed at all concentrations of PEG( 12,000)-DPPE (Bedu-Addo et al. Pharm. Res. 13:710–717 (1996)). Upon incorporation of high concentrations of cholesterol 〉30 mol% into the lipid bilayer, the formation of phase separated lamellae was completely inhibited and the formation of mixed micelles significantly reduced. At high concentrations of PEG( 1,000)-PE, solubilization of the bilayer occurred with preferential solubilization of cholesterol over phosphati-dylcholine. Maximum steric stabilization (surface protection) was observed with low concentrations of short chain PEG-PE and high concentrations of cholesterol. Conclusions. The study provides a physical mechanism for the following observations: the blood circulation time is significantly increased or decreased with liposomes highly enriched with cholesterol or PEG-PE respectively.
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  • 58
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    Pharmaceutical research 14 (1997), S. 676-680 
    ISSN: 1573-904X
    Keywords: ibuprofen ; metabolites ; NMR ; HPLC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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  • 59
    ISSN: 1435-1536
    Keywords: NMR ; nonionic surfactant ; lamellar phase ; shear-induced structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The lamellar phases of two aqueous ethylene oxide surfactants, tetra(ethylene oxide) dodecyl ether and hexa(ethylene oxide) dodecyl ether, have been investigated by deuterium nuclear magnetic resonance spectroscopy during shear. The evolution of the shear-induced NMR line shapes and their dependence on surfactant concentration, shear geometry and shear history is analyzed. Two of three previously described shear-induced states (Diat O, Roux D, Nallet F (1993) J Phys II France 3: 1427–1452), namely the state of aligned lamellae with the layer normal parallel to the velocity gradient, which occurs at low shear rates, and the vesicular state at intermediate shear rates are found and identified by their characteristics NMR line shapes.
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  • 60
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    Colloid & polymer science 274 (1996), S. 191-196 
    ISSN: 1435-1536
    Keywords: Vulcanization ; NMR ; NMR imaging ; vulcametry ; simulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract For the first time, in situ NMR measurements were performed during sulfur vulcanization of unfilled SBR. A vulcanization device was constructed for use in combination with a standard microimaging probe in a vertical bore NMR magnet.1H-linewidth measurements are correlated with cure simulations in a vulcameter to explain the increase of the linewidth during the vulcanization. Inhomogeneous heating conditions in the sample result in an inhomogeneous course of the vulcanization as a function of time. The spatial dependence of this process was monitored by NMR imaging.
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  • 61
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    Colloid & polymer science 275 (1997), S. 67-72 
    ISSN: 1435-1536
    Keywords: Key words Gelatin ; gel formation ; NMR ; viscoelasticity ; circular dichroism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract  Network formation of gelatin gel is known to consist of three-dimensionally cross-linked triple helices among polypeptide chains. The effects of added low molecular weight mono-ols, diols and polyols on the higher-order structure formation of gelatin chains were investigated using the following measurements: melting temperature, viscoelasticity and spin-lattice relaxation time (T 1) of H17 2O of gels, and circular dichroism spectra of diluted gelatin solutions. Furthermore, hydration behaviors of these hydroxy compounds were evaluated from the dynamic hydration numbers (n DHN) derived from T 1 of H17 2O in the solutions. It was found that network structures of gelatin gels containing hydoxy compounds were influenced by the number and position of hydroxyl groups as well as the number of carbon atoms of these coexisting compounds. The effect of hydroxyl groups of hydroxy compounds was considered to stabilize the helices among gelatin chains. Especially, the addition of polyols with large number of hydroxyl groups increased the number of cross-linking junctions in the gel networks, which consist of the aggregation among the helices. On the contrary, the effect of carbon atoms of hydroxy compounds is to disturb the formation of the helices and the aggregation among the helices.
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  • 62
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    Plant and soil 178 (1996), S. 133-140 
    ISSN: 1573-5036
    Keywords: aluminum toxicity ; ectomycorrhiza ; metabolism ; NMR ; phosphate ; polyphosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Aluminium toxicity may be an important factor in the decline in vitality of many forest trees and the associated ectomycorrhizal fungal flora. In this study, comparative in vivo 31P NMR investigations on Al-adapted and non-Aladapted fungus of Suillus bovinus in pure culture have produced interesting new data. With respect to intracellular compartments, 31P NMR spectroscopy showed the spectra to differ in a peak-6 ppm appearing in the spectra of the A1-adapted fungus indicating terminal phosphate groups of mobile polyphosphate. Thus, in the Al-adapted fungus the average chain length of mobile polyphosphate is considerably shorter than in the non-Al-adapted fungus. A special method of cyclic phosphate supply followed by block averaging of the NMR spectra was used to determine the kinetic behaviour of phosphate uptake, storage and incorporation into polyphosphate at a constant external pH 3.5. While the Al-adapted fungus showed resistance to Al, an irreversible break-down in phosphate metabolism of the non-Al-adapted fungus by exposure to Al was caused. In comparison with the non-Al-adapted fungus supplied by nutrient solutions omitting Al, the Al-adapted fungus showed higher levels in both phosphate uptake and mobile polyphosphate concentration. As a consequence of these results a de-toxification of freely mobile Al-ions into a stable and insoluble complex in the Al-adapted fungus is considered to be due to a capture of intracellular Al by mobile polyphosphate of shorter chain length.
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  • 63
    ISSN: 1573-5036
    Keywords: compost ; manure ; maturity ; NMR ; plant yield ; wheat straw
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Chemical maturity parameters in addition to plant growth limiting factors have been monitored in the course of a 2-month composting experiment. Wheat straw with 5% dry w horse manure was adjusted to C/N= 45 with urea. The pile was rotated and homogeneous samples were taken every four days. The most intense changes in straw fractions occurred in the first 20 days of composting, as suggested by wet chemical analyses, thermogravimetry and 13C NMR spectrometry. Nevertheless, plant response to compost application gave significant changes at between 20–60 days that were not clearly reflected by the above techniques. Glasshouse experiments with a soil treated with compost samples taken at the successive transformation stages suggested no linear correlation between composting time and the potential of compost in improving plant yield. In the samples taken after 20 days in the conditions studied, referred to as postmature composts, the ryegrass yield did not depend on most of the organic matter characteristics, but closely paralleled the concentration of available nitrogen and – to lesser extent – phosphorous in the compost. The probable immobilization of these elements in the course of composting was also suggested by plant response experiments with different doses of compost and the addition or not of mineral solution.
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  • 64
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    Journal of chemical ecology 22 (1996), S. 2209-2219 
    ISSN: 1573-1561
    Keywords: Allelopathy ; aquatic plant ; bioassay ; Nuphar lutea ; alkaloids ; NMR ; nupharolutine ; 6,6′-dihydroxythiobinupharidine ; Nymphaeaceae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Two of the majorNuphar alkaloids, nupharolutine and 6,6′-dihydroxythiobinupharidine, were isolated from the aquatic perennial herbNuphar lutea (L.) Sibth. & Sm., yellow water lily. In a lettuce seedling bioassay of the two pure compounds, the former was inactive and the latter was highly inhibitory of radicle elongation at concentrations greater than 2 ppm. Structures and stereochemistry of the two compounds were confirmed by DEPT,1H-1H COSY,1H-13C COSY, and1H-1H NOESY experiments.
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  • 65
    ISSN: 1435-1528
    Keywords: NMR ; viscometry ; shear flow ; liquid-crystalline polymer ; nematic solvent
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Abstract The flow behavior of a highly concentrated solution of a nematic side-chain liquid crystal polymer in a low molecular mass nematic solvent is investigated by deuterium nuclear magnetic resonance with simultaneous measurement of the shear viscosity in a cone-and-plate NMR viscometer. The director orientation under shear in the magnetic field is determined from the quadrupole splitting of the NMR spectra. The orientation as a function of shear rate is analyzed in terms of the Ericksen-Leslie-Parodi theory, yielding the Leslie coefficients μ 2 and μ 3 and thus the flow alignment parameter λ. From the combined analysis of orientation and viscosity as a function of shear rate a total of four independent viscosity parameters is obtained for the nematic solution. The value determined for the flow-alignment parameter, λ≈0.2, and the analysis of the data based on Brochard's theory show that the polymer is of the non-flow-aligning type and has a slightly prolate shape.
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  • 66
    ISSN: 1572-9001
    Keywords: Scopolamine ; atropine ; scopine ; tropine ; ab initio ; X-ray crystallography ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Ab initio geometry optimizations at the RHF-21G basis set level were calculated forequatorial andaxial N-methyl diastereomers ofO-formyltropine andO-formylscopine esters and other model compounds. These optimized geometries were then utilized as input for single-point energy calculations using the higher level RHF/6-31G* basis set to afford a more precise estimation of the total energies and atomic charges. Ethano bridge “pinching” of theN-protonated tropanyl piperidine moiety pushes the smalleraxial N-proton closer toward the neighboring twoaxial C-H bonds compared with the analogous case for a bulkyaxial N-methyl. Increasedcis 1,3-diaxial interactions in theaxial N-methyl diastereomer destabilize this epimer in favor of theequatorial N-methyl counterpart [e.g., 2.121 kcal/mol lower energy for theequatorial N-methylO-formyltropineN-protonated diastereomer (12) than for theaxial epimer (13)]. Lower pyramidality at nitrogen in the free base maintains the relative stability of theequatorial N-methyl free base diastereomer (14) (1.120 kcal/mol more stable than theaxial free base15). A nonprotonated carbon atom at the apex of a three-membered ring fused to the 6,7-positions of theO-formyltropine skeleton results in severe transannular nonbonding steric interactions involving the neighboringequatorial N-methyl group inN-protonated16 (3.335 kcal/mol less stable than theaxial N-methyl epimer17, where these transannular interactions are reduced due to the smallerequatorial N-H proton). Oxygen atom occupation of the apex of a similar fused three-membered ring retains the same severe transannular nonbonding steric interactions involving the neighboringequatorial N-methyl group inN-protonated18. These transannular interactions now become electrostatically attractive in theN-protonatedaxial N-methyl epimer19 (2.031 kcal/mol more stable than theequatorial epimer). Reduced pyramidality at nitrogen in theO-formylscopine free base reduces the repulsive transannular interaction with the neighboringequatorial N-methyl group compared to that in theN-protonated form. Lowered pyramidality also reduces thecis-1,3-diaxial interactions in theaxial N-methyl epimer, but the nitrogen lone pair is pushed close to the transannular oxygen lone pair as a result (theequatorial N-methyl free base20 is 3.870 kcal/mol more stable than theaxial epimer21). Theseab initio-calculated models ofO-formyltropines andO-formylscopineN-methyl diastereomeric protonated cations and free bases provide stereochemical insight into the relative stabilities of solution-state atropine and scopolamineN-methyl species previously observed by NMR spectroscopic methods.
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  • 67
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    Structural chemistry 8 (1997), S. 217-226 
    ISSN: 1572-9001
    Keywords: NMR ; ab initio calculation ; restricted rotation ; solvent effects ; NBO
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The restricted rotation about the partial C,N double bond in 2-chloro-6-NR2-pyran-4-ones is discussed in the light of NMR spectroscopic data and theoretical calculations.Ab initio calculations at the HF/6-31G* level were carried out using a continuum model to take solvent effects into account. The delocalization ofπ-electron density [described by natural bond orbital analysis (NBO)] was applied to determine the degree of conjugation in the ground state (GS) and in the transition state (TS) for the restricted rotation of the compounds studied. The reason for the different barriers to rotation of the NR2 substituents (pyrrolidino 〉 dimethylamino 〉 morpholidino 〉 piperidino) at the 2-chloro-pyran-4-one ring appears to be the different steric hindrance of the NR2 substituents in the GS for the restricted rotation.
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  • 68
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    Biogeochemistry 36 (1997), S. 89-97 
    ISSN: 1573-515X
    Keywords: dissolved organic carbon ; UV-B ; NMR ; lakes ; rivers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Geosciences
    Notes: Abstract Reductions in the global stratospheric ozone layer arethought to be increasing the amount of ultraviolet B (UV-B) radiationreaching the planet’s surface and may be affecting the chemistry ofdissolved organic carbon (DOC) in surface waters. We studied theabundance of chromophores in DOC collected in four different aquaticenvironments in southwestern Nova Scotia using 13C nuclearmagnetic resonance (13C NMR) spectroscopy. We showed a clearseasonal pattern in the distribution of structural carbon related tolight-sensitive chromophores. There seemed to be little variation in theUV-B related chemical structure of DOC between lakes and streams, thoughwater from a bog pool showed large differences from the other samples. Thesepatterns of potential UV-B reactivity tend to be dampened however, byvariations in DOC concentrations which also occur seasonally.
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  • 69
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    Journal of inclusion phenomena and macrocyclic chemistry 28 (1997), S. 213-221 
    ISSN: 1573-1111
    Keywords: β-Cyclodextrin ; surfactants ; inclusion complexes ; NMR ; surface tension
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The inclusion complexes of β-CD with sodium octylsulfonate (C8As), sodium dodecyl sulfonate (C12As), andsodium hexadecyl sulfonate (C16As) in aqueous solutions havebeen studied by surface tension measurement at the air/water interfaceand 1H NMR spectroscopy at 323 K. At fixed concentrations of the surfactants, the surface tensions firstincrease with the increase of β-CD concentrations,then they attain a maximum. The surface tension curves of the surfactantsin the presence of β-CD are higher than those in the absence ofβ-CD. The values increase with increasing β-CD concentrations foreach surfactant. The apparent critical micelle concentrations (CMC) of thesurfactants vary linearly with β-CD concentrations. A 1H NMR study shows that the signals of theinner H-3 and H-5 of β-CDshift upfield upon addition of the surfactants.The magnitude of the chemicalshift changes (Δδ=δ CDδ obs)varies as a functionof the concentrations of the surfactants. From therelationships between the chemicalshift changes of H-3 or H-5 inside the β-CD cavityand guest/host molar ratios, a 1:1 stoichiometry foreach inclusion complex is assumed. The associationconstants of the inclusion complexes have beendetermined by 1H NMR spectroscopy.
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  • 70
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    World journal of microbiology and biotechnology 13 (1997), S. 305-313 
    ISSN: 1573-0972
    Keywords: NMR ; pcpB ; pcpC ; pentachlorophenol degradation ; Pseudomonas spp
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Eighty-nine bacterial isolates obtained by enrichment from pentachlorophenol (PCP)-contaminated soil samples were tested for PCP dechlorination activity and hybridization to pcpB (encoding PCP-4-monooxygenase) and pcpC (encoding tetrachlorohydroquinone reductive dehalogenase) gene probes synthesized by polymerase chain reaction from Flavobacterium sp. ATCC 39723 genomic DNA. Seven isolates were able to dechlorinate PCP, hybridize to both pcpB and pcpC DNA probes, and mineralize sodium pentachlorophenate (NaPCP) at an initial concentration of 100μg/ml. Although the seven PCP-mineralizing isolates possessed DNA sequences homologous to the Flavobacterium pcpB and pcpC genes, restriction analysis revealed sequence differences between the isolates and the Flavobacterium PCP dechlorination genes. Two isolates, designated UG25 and UG30, with the fastest onset and highest extent of PCP mineralization were selected for further study. Both isolates were tentatively identified as Pseudomonas spp. and exhibited stoichiometric release of Cl− ions as PCP was degraded. The release of Cl− began concomitantly with PCP disappearance from the medium. Both UG25 and UG30 degraded NaPCP at a concentration of 250 μg/ml in a minimal salt medium. Supplementation of the medium with glutamate increased the NaPCP degradation threshold of UG25 to a concentration of 300 μg/ml but did not affect that of UG30. 31P-NMR spectra of UG25 and UG30 cell suspensions exposed to PCP showed lower intracellular ATP levels and a more acidic cytoplasmic pH relative to untreated cells. This de-energization may explain the lack of cell growth in the presence of high PCP concentrations.
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  • 71
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    Journal of inclusion phenomena and macrocyclic chemistry 25 (1996), S. 313-325 
    ISSN: 1573-1111
    Keywords: Inclusion complex ; tolbutamide ; permethyl-β-cyclodextrin ; hypoglycemic effect ; glucose level ; NMR ; FT-IR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of a stable inclusion complex between tolbutamide and permethyl-β cyclodextrin was systematically studied. It shows that permethyl-β-CD forms a 1 : 1 complex with tolbutamide. Its molecular structure was elucidated by physicochemical methods including IR and high field NMR analysis. The influence of pennethyl-β-cyclodextrin on the hypoglycemic effect of tolbutamide was evaluated by measuring the blood glucose level. The reduction in plasma glucose was significantly greater when the rabbits were treated with the complex than with tolbutamide alone. The enhancement of the bioavailability of tolbutamide by permethyl-β-cyclodextrin is likely attributed to the molecular inclusion effect.
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  • 72
    ISSN: 1573-1111
    Keywords: Biliar acid ; 2-hydroxypropyl-β-cyclodextrin ; interaction studies ; IR ; NMR ; DSC ; XRD
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction of two biliar acids (chenodeoxycholic acid and cholic acid) with 2-hydroxypropyl-β-cyclodextrin (HPβCD) in solution and in the solid state was studied using different techniques. The formation of an inclusion complex with a 1:1 stoichiometry was suggested by the phase solubility studies. Both differential scanning calorimetry and X-ray diffractometry exhibited the amorphous state of the complex. The inclusion of both biliar acids into the HPβCD cavity was confirmed by the13C-NMR studies. Cholic acid showed a weaker affinity with respect to chenodeoxycholic acid probably owing to the presence of a hydroxyl group onC(12) (12α) close to the complexation site.
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  • 73
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    Journal of inclusion phenomena and macrocyclic chemistry 26 (1996), S. 243-251 
    ISSN: 1573-1111
    Keywords: Crown ethers ; Li+ ion ; mixed-solvent ; complex stability ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Proton NMR spectroscopy was used to study the complexation reaction between lithium ion and 12-crown-4, 15-crown-5 and 18-crown-6 in a number of binary acetonitrile-nitrobenzene mixtures. In all cases the exchange between free and complexed crowns was fast on the NMR time scale and only a single population average1H signal was observed. Formation constants of the resulting 1:1 complexes in different solvent mixtures were determined by computer fitting of the chemical shift-mole ratio data. There is an inverse relationship between the complex stability and the amount of acetonitrile in the mixed solvent. It was found that, in all solvent mixtures used, 15-crown-5 forms the most stable complex with Li+ ion in the series.
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  • 74
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    Journal of inclusion phenomena and macrocyclic chemistry 24 (1996), S. 1-17 
    ISSN: 1573-1111
    Keywords: Calixarene ; inclusion ; structure ; NMR ; dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Despite the proliferation of structural studies on calixarene host-guest compounds, some important structural details remain obscure. In particular, the ubiquitous disorder of the calixt-butyl group often hinders a detailed determination of the non-bonding interactions between host and guest. We propose and develop a synoptic approach in which several complementary characterization techniques (X-ray diffraction and NMR) provide a powerful means of assessing the interplay of structure and dynamics in calixarene-guest compounds. The simplet-butylcalix[4]arene-guest compounds (guest = toluene, nitrobenzene, cyclohexane,n-pentane, l-chlorobutane) are examined with this approach, and new structural and dynamic features are uncovered.
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  • 75
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    Journal of inclusion phenomena and macrocyclic chemistry 26 (1996), S. 209-218 
    ISSN: 1573-1111
    Keywords: Cyclodextrins ; bicyclo[3.3.1]nonanes ; complexation ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation and structure of inclusion complexes of 2,6- and 2,9-substituted bicyclo[3.3.1]nonanes withα- andβ-cyclodextrin (CD) has been investigated by high-resolution1H NMR spectroscopy.α- andβ-CD were found to form 1:1 inclusion complexes and the binding constants were estimated from titration studies. 2D ROESY experiments provided insight into the structure of the complexes.
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  • 76
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    Journal of inclusion phenomena and macrocyclic chemistry 28 (1997), S. 39-49 
    ISSN: 1573-1111
    Keywords: Diaza-18-crown-6 ; DDQ ; charge transfer complexes ; spectrophotometry ; IR ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of charge transfer complexes with 1:1 and 2:1 stoichiometries (acceptor-to-donor) between DDQ and 1,10-diaza-18-crown-6 in chloroform solution was investigated spectrophotometrically. The stepwise formation constants of the resulting complexes were evaluated from the non-linear least-squaresfitting of the absorbance-mole ratio data. The enthalpies and entropiesof the complexation reactions were determined from the temperature dependence of the stepwise formation constants. The resulting 1:1 and 2:1 complexes were isolated in crystalline form and characterized. The results are consistent with the ionic structure of the resulting charge transfer complexes.
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  • 77
    ISSN: 1573-2746
    Keywords: silica gel ; surface modification ; silicon oxynitride ; FTIR ; XPS ; NMR ; porosity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract Mesoporous silica gel has been coated with a thin silicon oxynitridefilm via chemical surface coating. In the first part of the synthesis, achemically bound preceramic polysilazane coating is formed layer by layer onthe pore walls at low temperature, using SiCl4 andNH3 as reagents. In the second part of the synthesis, thepolysilazane coated silica gel is pyrolysed, yielding a chemically bound,thin oxynitride coating. During the synthesis, the evolution of the chemical and morphologicalcomposition has been investigated with several elemental and spectroscopicanalysis techniques as well as with nitrogen porosimetry.
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  • 78
    ISSN: 1573-3904
    Keywords: Molecular modeling ; NMR ; Peptides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The conformations of thermolysin synthetic substrates in H2O/D2O (9/1) and glycerol-d 5 (5 M) are investigated using two-dimensional nuclear magnetic resonance spectroscopy and molecular modeling. The structures obtained from molecular modeling and NMR studies are compared. Comparisons of these structures with bound inhibitor in the active site of thermolysin are also discussed.
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  • 79
    ISSN: 1573-3904
    Keywords: CD ; Endopeptidase ; Micro-environment ; NMR ; Subtilisin BPN′
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary 1H-NMR studies of the bovine insulin S-sulfonated B-chain are reported in H2O/D2O (9/1) and in glycerol-d 5 (5 M) using two-dimensional NMR spectroscopy. The first results show that the oxidized insulin B-chain secondary structure differs from that of native insulin by a loss of the α-helix between the two disulfide bridges and that the glycerol favours the structuring of the peptide.
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  • 80
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    International journal of peptide research and therapeutics 3 (1996), S. 53-60 
    ISSN: 1573-3904
    Keywords: Gramicidin S ; Cyclic peptide ; Synthesis ; Cyclization ; NMR
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simple method is described for the facile synthesis of gramicidin S and six other analogs, using standard solidphase synthetic technology and a single solution-phase cyclization step. The peptides were purified to homogeneity and characterized by plasma desorption time-of-flight mass spectrometry and NMR spectroscopy. Complete 1H NMR assignments for all seven peptides (in aqueous solution) are presented. Unlike previous approaches, the presented method is simple, automatable, rapid (less than three days), high-yielding, requires no side-chain protection during cyclization, and appears to be generally applicable to the preparation of a variety of related head-to-tail cyclic peptides.
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  • 81
    ISSN: 1573-3904
    Keywords: CD ; Endopeptidase ; Micro-environment ; NMR ; Subtilisin BPN′
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    Topics: Chemistry and Pharmacology
    Notes: Abstract H-NMR studies of the bovine insulin S-sulfonatedB-chain are reported in H2O/D2O (9/1) and inglycerol-d5 (5 M) using two-dimensional NMRspectroscopy. The first results show that the oxidizedinsulin B-chain secondary structure differs from thatof native insulin by a loss of the α-helixbetween the two disulfide bridges and that theglycerol favours the structuring of the peptide.
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  • 82
    ISSN: 1573-3904
    Keywords: Molecular modeling ; NMR ; Peptides
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The conformations of thermolysin synthetic substrates inH2O/D2O (9/1) and glycerol-d5 (5 M) are investigated using two-dimensional nuclearmagnetic resonance spectroscopy and molecular modeling. The structuresobtained from molecular modeling and NMR studies are compared. Comparisonsof these structures with bound inhibitor in the active site of thermolysinare also discussed.
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    International journal of peptide research and therapeutics 4 (1997), S. 245-249 
    ISSN: 1573-3904
    Keywords: Folding ; Molecular modelling ; NMR ; Squash trypsin inhibitor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Trypsin inhibitor EETI II, possessing six cysteinesengaged in three disulfide bridges, shares a commonstructural motif with other proteins of differentorigins and functions. To understand the principlesthat govern folding of this largely distributed basicscaffold, mainly composed of a small triple-strandedΒ-sheet, we have studied different stages in thefolding of EETI II. The conformational properties ofa synthetic analogue of EETI II possessing only onenative (15-27) disulfide bridge were investigated withthe combined use of 1H NMR and molecularmodelling. Although two native-like reverse turns wereobserved, formation of Β-sheet could not beevidenced in the one disulfide analogue, while themotif has been shown to be present in a foldingintermediate with two native disulfide bridges (9-21and 15-27). These results suggest that the structuralmotif requires stabilisation by two disulfide bridges
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    International journal of peptide research and therapeutics 4 (1997), S. 29-39 
    ISSN: 1573-3904
    Keywords: NMR ; Hydrogen bond ; Conformational shifts ; TFE
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Temperature coefficients are widely used as an indication of solvent accessibility to amide protons. Low temperature coefficients are related to low accessibility and are often interpreted as evidence for intramolecular hydrogen bonding. Conformational shifts, i.e. the difference between chemical shifts of a particular residue in a structured and in a random-coil conformation, provide information on secondary structure. In particular, negative CHα conformational shifts are often used to delineate the extent of helical stretches. NH conformational shifts show large oscillations within a helix that have been interpreted as the result of helix distortions affecting hydrogen bond lengths. In the ocurse of the study of differnet peptides that adopt a helical structure in the presence of the structure-inducing solvent hexafluoroisopropanol (HFIP), we have found a strong correlation between temperature coefficients and amide conformational shifts. However, contrary to the initial expectations, lower temperature coefficients were associated to amide protons involved in longer, and presumably weaker, hydrogen bonds. The correlation can be explained, however, assuming that, in helical peptides dissolved in HFIP, temperature affects the chemical shift of amide protons mainly by changing the average length of intramolecular hydrogen bonds and changes in solvent accessibility play only a secondary role under these experimental conditions. The pattern of temperature coefficients in helical peptides can therefore be used to identify short or long hydragen bonds causing bending of the helix axis.
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    International journal of peptide research and therapeutics 4 (1997), S. 29-39 
    ISSN: 1573-3904
    Keywords: NMR ; Hydrogen bond ; Conformational shifts ; TFE
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Temperature coefficients are widely used as an indication of solvent accessibility to amide protons. Low temperature coefficients are related to low accessibility and are often interpreted as evidence for intramolecular hydrogen bonding. Conformational shifts, i.e. the difference between chemical shifts of a particular residue in a structured and in a random-coil conformation, provide information on secondary structure. In particular, negative CHα conformational shifts are often used to delineate the extent of helical stretches. NH conformational shifts show large oscillations within a helix that have been interpreted as the result of helix distortions affecting hydrogen bond lengths. In the course of the study of different peptides that adopt a helical structure in the presence of the structure-inducing solvent hexafluoroisopropanol (HFIP), we have found a strong correlation between temperature coefficients and amide conformational shifts. However, contrary to the initial expectations, lower temperature coefficients were associated to amide protons involved in longer, and presumably weaker, hydrogen bonds. The correlation can be explained, however, assuming that, in helical peptides dissolved in HFIP, temperature affects the chemical shift of amide protons mainly by changing the average length of intramolecular hydrogen bonds and changes in solvent accessibility play only a secondary role under these experimental conditions. The pattern of temperature coefficients in helical peptides can therefore be used to identify short or long hydrogen bonds causing bending of the helix axis.
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    International journal of peptide research and therapeutics 4 (1997), S. 245-249 
    ISSN: 1573-3904
    Keywords: Folding ; Molecular modelling ; NMR ; Squash trypsin inhibitor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Trypsin inhibitor EETI II, possessing six cysteines engaged in three disulfide bridges, shares a common structural motif with other proteins of different origins and functions. To understand the principles that govern folding of this largely distributed basic scaffold, mainly composed of a small triple-stranded β-sheet, we have studied different stages in the folding of EETI II. The conformational properties of a synthetic analogue of EETI II possessing only one native (15–27) disulfide bridge were investigated with the combined use of1H NMR and molecular modelling. Although two native-like reverse turns were observed, formation of β-sheet could not be evidenced in the one disulfide analogue, while the motif has been shown to be present in a folding intermediate with two native disulfide bridges (9–21 and 15–27). These results suggest that the structural motif requires stabilisation by two disulfide bridges.
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