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  • Articles  (31)
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  • Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics  (31)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of wood science 46 (2000), S. 130-136 
    ISSN: 1611-4663
    Keywords: Lignin-carbohydrate complexes ; NMR ; 13C tracer ; Coniferin ; Ketal linkage
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In the present study the specifically13C-enriched lignin precursors of biosynthesis (i.e., coniferin-[side chainα−13C], coniferin-[side chain-β−13C] and coniferin-[side chain-γ−13C]) were synthesized and administered exogeneously to ginkgo shoots (Ginkgo biloba L.) to obtain13C-enriched lignin-carbohydrate complexes (LCCs). The specifically13C-enriched LCCs were isolated from the newly formed xylem of ginkgo shoots administered with the13C-enriched precursors and degraded by enzymes. Lignin-rich fractions, so called enzyme-degraded LCCs (EDLCCs), were obtained. By determining their13C-NMR spectra, information related to the chemical structure of lignin building units and linkages between phenylpropane units of lignin and carbohydrates were obtained. It was found that these precursors were incorporated in natural lignin successfully. Three lignin-carbohydrates linkages (i.e., ether type, ester type, ketal type) were found at the C α -position of the side chain of phenylpropane units in ginkgo LCC. No lignin-carbohydrate bond at the Cβ- or Cγ-position of the lignin side chain was observed in the13C-NMR spectra of the13C-enriched LCCs. This fact indicates that a specific13C tracer technique can be useful in NMR study of the chemical structure of LCCs.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of cluster science 9 (1998), S. 321-328 
    ISSN: 1572-8862
    Keywords: NMR ; tin(II)chloride ; insertion ; platinum ; platinum–tin bond
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The first 119Sn NMR evidence for the presence of direct platinum–tin bond in solution has been obtained for PtCl(SnCl3)(bdpp) complex (bdpp = (2S,4S)-2,4-bis(diphenylphosphino)pentane). Various PtCl2(L2) complexes (L2 = heterobidentate P−P, P−O, P−N, P−S chelating ligands) have been reacted with tin(II)chloride resulting in the formation of the corresponding PtCl(SnCl3)(L2) derivatives. Tin(II)chloride has been inserted into the Pt−Cl bond transto the harder donor atom of the L2 ligand.
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  • 3
    ISSN: 1435-1536
    Keywords: Key words Interaction ; anionic surfactant ; polyvinylpyrrolidone ; ESR ; 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  The interaction between anionic surfactants and polyvinylpyrrolidone (PVP) are investigated using 13C NMR, ESR spectroscopy and surface tension measurements at the air/water interface. The behavior of single-chained surfactant, sodium dodecyl sulphonate (AS), is compared with that of the double-chained surfactant, sodium bis(2-ethylhexyl) phosphate (NaDEHP). The results showed that a surfactant–polymer complex of “necklace and head structure” is formed in AS aqueous solutions in the presence of PVP due to the hydrophobic interaction between PVP and AS. The AS micelles nucleate on the polymer hydrophobic sites, and the mobility of the AS head groups is not affected. But, for NaDEHP surfactant, it was found that PVP is little effective in influencing the monomer–micelle equilibrium and no surfactant– polymer complex formed in the NaDEHP aqueous solution.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 5
    Electronic Resource
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    Springer
    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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  • 6
    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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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    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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  • 9
    ISSN: 0959-8103
    Keywords: polyhydroxyalkanoate ; copolyester ; microstructure ; NMR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The sequence structures of bacterially synthesized copoly(3-hydroxyalkanoates), isolated from the sludge developed in the anaerobic-aerobic waste-water treatment process containing propionate as a carbon source, were analysed by 13C NMR spectroscopy. These copolyesters were composed of four different monomer units, 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxy-2-methylbutyrate and 3-hydroxy-2-methylvalerate. By using water/acetone mixed solvent, one of the copolyester samples was fractionated into fractions by differences in average molecular weights as well as in monomer compositions. The carbonyl carbon resonances, split due to differences in diad sequences, were analysed on the basis of Bernoullian statistics. It is suggested that these copolyesters were mixtures of random copolymers with different monomer compositions.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 40 (1996), S. 63-71 
    ISSN: 0959-8103
    Keywords: NMR ; relaxation ; rubber ; vulcanisation ; epoxidisation ; additives ; mobility ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Proton spin-lattice relaxations in the laboratory and rotating frames, together with transverse relaxation (free induction decay), have been measured for natural and epoxidised rubber, plus a series of vulcanised samples. The data have been analysed by fitting procedures to give characteristic times which are discussed in terms of the mobility of the various parts of the samples, and of their compositions (including the effects of paraffin wax and oil additives). Interpretation has been aided by recording free induction decays following a period of spin-locking. Carbon-13 magic-angle spinning spectra have also been measured.
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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 41 (1996), S. 135-149 
    ISSN: 0959-8103
    Keywords: telechelic polyimides ; nadimide ; endo/exo isomerization ; NMR ; HPLC ; thermomechanical properties ; α and β transitions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyimides were synthesized by polycondensation of nadic anhydride monoester (NE), hexafluoroisopropylidene-2,2-bis (phthalic acid anhydride) (6HFDA) and Cardo diamine in aprotic/polar medium. After examining the microstructure and the composition of systems with a polymerization index n̄ = 2.075 and 5.18 by high performance liquid chromatography (HPLC) and nuclear magnetic resonance (NMR) spectroscopy (1H and 13C), their thermomechanical properties were investigated. The rheology curves obtained in the temperature range 50-400°C showed the presence of an α transition (glass transition temperature Tg) and a sub-glass β transition. The temperature of the maximum of the loss modulus G″ of these two transitions varied in the domain of molar mass M̄n studied.The effect of endo/exo isomerization of the nadimide extremities on the values of the glass transition temperature has also been shown. When the percentage of exo isomer of a given polymer increased, the glass transition temperature Tg increased by 50°C.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 6 (1995), S. 291-295 
    ISSN: 1042-7147
    Keywords: film formation ; latex ; vinyl acetate ; glass transition temperature ; differential scanning calorimetry ; VeoVa ; NMR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The physical forces causing deformation of latex particles during the film formation process have been witley studied. However, the forces resisting particle deformation are still poorly characterized. It is clear that the extent of particle deformation is dependent on the viscoelastic nature of the polymer. In an emulsion, the latex particles will normally contain water, surfactants and “free” monomers which lead to plasticization of the polymer. Although this effect has been recognized, so far it has been studied only on films that had been dried and then partially or completely swollen by water.In this work, plasticization of the emulsion polymers by water and co-solvent has been quantified via differential scanning calorimetry investigation directly on the aqueous latex dispersions. More specifically, the plasticizing effect of water on VeoVa/vinyl acetate copolymer latices and its influence on minimum film-forming temperature (MFFT) has been studied. A linear correlation has been found between Tg and MFFT for the wet latices. This new direct method should help to improve our understanding of the forces resisting latex film formation.Additionally, the homogeneous distribution of the hydrophobic and hydrophilic monomers (VeoVa and vinyl acetate respectively) in the latex particles was verified via a 13C-NMR (nuclear magnetic resonance) study performed directly on the latices. This study confirmed that no significant core/shell type of morphology had influenced latex film formation.
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  • 13
    ISSN: 0959-8103
    Keywords: NMR ; pulsed-field gradient ; heteronuclear multiple bond correlation ; block copolymers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The utility of pulsed-field gradient (PFG)-heteronuclear multiple bond correlation (HMBC) 2D NMR experiments for characterizing polymer structure is demonstrated. Heteronuclear multiple quantum coherence (HMQC) and HMBC indirect detection experiments provide correlations indicating the presence of one-bond and two-or three-bond connectivities, respectively; this information is vital for polymer structure determination. When HMBC methods are combined with PFG techniques artifacts are eliminated which normally limit the utility of HMBC. The elimination of these artifacts lowers the detection limit by almost two orders of magnitude, making it feasible to detect signals from the small number of repeat units bonded to defect structures, chain ends, branch points and block junctions, despite the presence of much larger resonances from the main-chain repeat units. Spectra of poly(isobutylene-b-butadiene) diblocks and poly(isoprene-b-styrene) diblocks are used to illustrate these advantages.
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  • 14
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    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 33 (1994), S. 335-339 
    ISSN: 0959-8103
    Keywords: poly(ether sulphones) ; PES ; NMR ; CPMAS ; polymerisation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The synthesis of poly(ether sulphone) using the ‘carbonate’ route based on the reaction of 4,4′-dihydroxydiphenylsulphone, 4,4-dichlorodiphenylsulphone and potassium carbonate dispersed in diphenylsulphone has been studied by 13C CPMAS NMR spectroscopy. In the initial reaction the half potassium salt of 4,4′-dihydroxydiphenylsulphone is formed. No evidence for a stable full salt was found at any time during the polymerisation cycle and no appreciable oligomer formation took place before the polymerisation itself took place.
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  • 15
    ISSN: 1042-7147
    Keywords: Hydrogel ; Thermoreversible Sol-gel transition ; NMR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: The sol-gel transition mechanism of a thermoreversible hydrogel composed of a copolymer comprising poly(N-isopropylacrylamide) and poly(ethylene glycol) (PNIPAAm-PEG) was studied by NMR. The 1H- and 13C-NMR spectra measured on a PNIPAAm-PEG solution in 99.9% D2O showed a remarkable line width broadening of the PNIPAAm block of more than that of the PEG block, during thermally induced hydrogel formation. This result suggested that the mobility of the PNIPAAm block is more restricted than that of the PEG block during gelation. A crosslinked polymer network formation was ascertained by a sudden reduction in the spin-lattice relaxation time (T1) of the residual HDO proton during gelation. The temperature dependency of the T1 values for the PNIPAAm and PEG blocks revealed that the microscopic condition of the PNIPAAm block in water was drastically changed during gelation, while that of the PEG block was unchanged. The experimental results from NMR supported the following gelation mechanism; that an aggregation of PNIPAAm blocks in the separate copolymers caused by hydrophobic interaction forms crosslinking points to give an infinite three-dimensional network structure. The hydrated PEG chains in the copolymers provide the network with a swelling property in water, and prevent the aggregation from causing a macroscopic phase separation.
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  • 16
    Electronic Resource
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    Springer
    Colloid & polymer science 271 (1993), S. 1129-1133 
    ISSN: 1435-1536
    Keywords: NMR ; surfactant ; hydroxypropylmethyl cellulose ; sodiumdodecyl sulphate ; interaction
    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 interaction between the nonionic water soluble polysaccharide hydroxypropylmethyl cellulose (HPMC) and the low molecular weight amphiphile sodiumdodecyl sulphate (SDS) has been studied by NMR1H-chemical shift measurements and by self-diffusion NMR measurements. The polymer concentration has been kept sufficiently dilute to avoid coil overlap and the SDS composition range goes from zero up to well above the normal CMC point. Although a different fraction was used, the present results agree well with previous results for the same system obtained by techniques other than NMR and show very clear break points that can be related to the polymer surfactant interaction. Furthermore, it can be inferred from the chemical shift measurements that the structure of the micellar clusters are similar whether polymer is present or not. From a combination of chemical shift and self diffusion measurements it is also found that neither the size nor the shape of the clusters seem to change significantly in the composition interval investigated.
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  • 17
    Electronic Resource
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    New York, NY : Wiley-Blackwell
    Polymers for Advanced Technologies 4 (1993), S. 164-171 
    ISSN: 1042-7147
    Keywords: Polyelectrolytes ; Glass transition ; Conductivity ; NMR ; Dielectric ; Relaxation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Ionene glasses are considered as being a new class of materials. Their properties have been investigated in detail by thermoanalytical, solid state NMR, and dielectric techniques. The segmental dynamics of these cationic polyelectrolytes, labeled in chosen positions, have been studied with solid state 2H-NMR. Below the glass transition the quaternized ammonium groups in the polymer backbone are essentially static, due to strong Coulomb interactions. The glass transition in these materials is characterized by the softening of a network formed by the N+-cations. However, both the low molecular weight counterions and the organic chain segments linking the ammonium groups are already mobile below Tg. The dynamics of the organic segments in the glassy state can be described as motion between fixed ends. Ionic conductivity in the glassy state is based on thermally activated anion transport. The influence of the flexibility of the organic chain segments and of the type of the anion on the conductivity are discussed. A simple analytic expression is proposed to describe the conductivity behavior in the low frequency limit.
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  • 18
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    Colloid & polymer science 270 (1992), S. 747-752 
    ISSN: 1435-1536
    Keywords: FTIR ; amorphousorientation ; entropicelasticity ; NMR ; spin-spin ; relaxation ; solidecho ; hardelasticpolypropylene
    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 variation of amorphous orientation and crystalline regularity of hard elastic polypropylene (HEPP) films during cyclic deformation and stress relaxation processes were studied using a FTIR spectrometer. The result proves entropic elasticity and shows the orientational hysteresis in the amorphous region or within the microfibrils, and also shows that the amorphous orientation increases, but that the crystalline regularity decreases with the increase of extension rate. Three spin-spin relaxation timesT 2f,T 2m, andT 2s and associated mass fractionsF f,F m, andF s of HEPP fibers were measured with a solid echo of NMR method at different elongations and after relaxation or recovery for a long time A new possible interpretation was proposed that, while the microfibrils are formed in HEPP, the medium decay component should be ascribed to inner molecules of the microfibrils, and the slow decay component to the surface molecules of the microfibrils. According to this interpretation, the results implied that subfibrillation is the main process when HEPP is stretched up to 15% strain, and that at above 15% strain thinning and lengthening of the microfibrils become the main process. Thickening of the microfibrils was found in the recovery and relaxation processes.
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  • 19
    ISSN: 1435-1536
    Keywords: Associative polymers ; NMR ; self-diffusion ; self-assembly
    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 concentration and molecular weight dependence of the self-diffusion coefficient (D self) of associative polymers of HEUR-type in aqueous solution have been investigated using FT-PGSE-NMR technique. The idea of three-dimensional network formation as a result of aggregation of the hydrophobic end-groups of the polymer in junctions is supported through the observed dramatic lowering ofD self with increased concentration. The network-formation efficiency depends on the polymer molecular weight as well as the hydrophobicity of the end-groups. A double logarithmic dependence of the self-diffusion coefficient versus concentration (c) has been observed:D self∝c −a1,a2 . The first exponent,a 1, is valid at low concentration, 〈1% polymer per weight solution, and ranges from 0.5 to 1, whereas the second exponent,a 2, describing systems of higher concentration, ranges from 2 to 2.7.
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  • 20
    ISSN: 1435-1536
    Keywords: Surfactants ; x-raydiffraction ; NMR ; conformation ofpolyethylene oxide
    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 Crystal structure of monodisperse non-ionic surfactants having the general formula C12H25O−(CH2−CH2−O)nH (C12En),n=7,9, 10, 15, 16 and ionic derivatives, C12H25−O−(CH2−CH2−O)n−CH2COONa (C12EnC),n=3,4,5,6,7,9, 12 has been investigated by13C-CP-MAS-NMR and x-ray diffraction. A structural model, in which aliphatic and polyether segments are segregated in bilayers stacking parallel to the elongation direction of the molecules, fits the experimental data for both series. The experimental values of the repeat distance along the stacking directiond(001) are linearly dependent onn and the slope is nearly equal to twice the repeat distance of7/2 helix conformation, which is typical for crystalline polyethyleneoxide. The values ofd(001) agree very well with the values expected for the C12 segment in a planar “zig-zag” conformation, which is tilted with respect to the polyerther segment (7/2 helix conformation) in such a way that both the aliphatic and the polyether regions adopt the mass density of the corresponding crystalline compound. Two additional phases have been detected for C12EnC. One of them is probably characterized by the planar ‘zig-zag” conformation of the polyether chain. The “meader” model, previously proposed in the literature for surfactants containing polyethylene oxide segments is inconsistent with the obtained experimental data.
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  • 21
    ISSN: 1435-1536
    Keywords: Phasediagram ; phospholipids ; calorimetry ; freeze-fracture electronmicroscopy ; NMR ; 31Pdemixing
    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 Differential-scanning-calorimetry, freeze-fracture electron microscopy, and31P-NMR spectroscopy were used to study the lyotropic and thermotropic properties of the system dihexadecylphosphatidylcholine/dihexadecylphosphatidic acid/water/ NaOH in dispersion with excess water at pH=14. The phase diagram showed that both phospholipids are demixed nearly completely in the gel phase. The coexistence of theP β′ and theB β-phase in the mixtures was pointed out in the freeze-fracture electron micrographs by the “ripple structure” (P β′-phase) and by the lamellar structure (B β-phase).
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  • 22
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    Colloid & polymer science 267 (1989), S. 681-686 
    ISSN: 1435-1536
    Keywords: Poly(diethyl siloxane) ; molecularmotions ; NMR ; temperatureinfluence ; differentphases ; chainmobility
    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 Molecular motions in poly(diethyl siloxane) were studied by solid-state29Si-NMR in the temperature range 180–350 K. In this temperature range two solid phasesβ 1 andβ 2, a mesophaseα m, and an amorphous isotropic phase exist. The nature of the chain mobility in the different phases was deduced from the resulting changes in the NMR line-shape governed by anisotropic chemical shift. In the intermediate solid phaseβ 2 its anisotropy is reduced by 25% compared with the low temperature phaseβ 1 due to the onset of oscillations around the chain axis and conformational transitions. In the mesophaseα m the polymer chain rotates about its long axis yielding an axially symmetric chemical shift tensor opposite in sign to that in theβ 1,β 2 phases. The broad transition of the mesophase into the isotropic phase is accompanied by an increase in a narrow Lorentzian line arising from the amorphous phase. The results are compared with previous1H NMR, Raman-spectroscopy and x-ray measurements.
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  • 23
    ISSN: 1435-1536
    Keywords: Gel structure ; ageing ; X-ray diffraction ; DSC ; 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 The time dependent changes of the lamellar gel structure in a nonionic O/W cream were studied. It appeared that the changes were connected with alterations in the hydrophilic layers of this lamellar gel structure. The structure of the hydrocarbon layers did not change. The alterations were induced by an increasing hydration of the surfactant molecules on cooling from the preparation temperature to room temperature. Ageing of the cream involves a decrease of the thickness of the hydrophilic layers and a change of the distribution of the surfactant molecules, resulting in, among other things, a decrease of the release rate of a hydrophilic drug. Ageing of the cream can be prevented by using the appropriate amount of starting materials or by the use of polymerizable surfactants. In the former case a cream, from which a drug is slowly released, is obtained. On the other hand, creams containing polymerized surfactants can release drugs at a relatively high rate.
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  • 24
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    Colloid & polymer science 263 (1985), S. 812-817 
    ISSN: 1435-1536
    Keywords: Charge density ; polyacrylamide ; NMR ; DSC ; T g
    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 New methods are suggested for the determination of the charge density of acrylamide/acrylate copolymers.13C nuclear magnetic resonance spectroscopy was used to determine the comonomer ratio by comparing the peak intensities of the methine carbon in acrylamide and acrylate monomers. Results were compared with those obtained by conductometric and potentiometric titration and were found to be in good agreement. Differential scanning calorimetry was employed to determine the glass transition temperatures (T g) of the copolymers. A master curve was established by plottingT g versus charge density of the copolymers previously determined by NMR and conductometric titration. Compositions of poly(acrylamide-co-acrylate) samples can thus be determined by measuring theT g and reading the percent composition directly from the master curve.
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  • 25
    ISSN: 1435-1536
    Keywords: Microemulsions ; diffusion ; NMR ; QELS
    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 Diffusion studies were performed with various methods to obtain some insight into the structure and the dynamical processes of three and four component microemulsions containing p-nonylphenol ethylene oxide adducts which were mixtures of highly branched p-nonyl isomers with well defined distributions of the ethylene oxide chain length. Diffusion coefficients were determined by pulsed field gradient and pulsed field gradient Fourier transform1 H NMR as well as by quasi-elastic light scattering. The combined application of pulsed field gradient NMR and quasi-elastic light scattering gives information about the critical behaviour of the systems whereas pulsed field gradient Fourier transform NMR allows the determination of the diffusion coefficients of the individual constituents. The results suggest that the very complex three and four component microemulsions studied undergo critical concentration fluctuations in a large temperature region from about 15 °C below the lower critical solution temperatures. The deduced critical exponents are in good agreement with theoretical predictions. The aggregates in the three and four component microemulsions show differences in the self diffusion behaviour of their constituents.
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  • 26
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    Colloid & polymer science 262 (1984), S. 667-669 
    ISSN: 1435-1536
    Keywords: surfactants ; NMR ; micelles
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 27
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    Colloid & polymer science 262 (1984), S. 489-496 
    ISSN: 1435-1536
    Keywords: micelle ; NMR ; alkylphosphate
    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 micellization of several monoalkylphoshpates with chain lenghts from 6 to 10 carbons have been investigated by31P and13C NMR spectroscopy with some additional electrical conductivity, density and small angle neutron scattering measurements. The major part of this study was performed on sodium monooctylphosphate. The critical concentration of micellization is 0.14 M, the partial molar volume is 170 cm3/mole in the micellar state. Small angle neutron scattering measurements on a 0.5 molar solution lead to an aggregation number of 43. NMR studies over the whole concentration range show that the pseudophase model holds. The geometry around the polar head is found almost unchanged upon micellization. The frequency denpendence of the31P longitudinal relaxation is interpreted by an isotropic fas motion (τ R=6.5 × 10−11 for the free monomers and by a strongly anisotropic motion withD ‖/D ⊥≈10 andτ 0=(6D)−1 =1.25×10−9 s in the micellar state.
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  • 28
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    Colloid & polymer science 259 (1981), S. 220-226 
    ISSN: 1435-1536
    Keywords: NMR ; polymers ; molecular motions ; entanglements
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Die Solid-Echo-Technik wurde auf die Bestimmung der restdipolaren und restquadrupolaren Kopplung in Schmelzen von Polyäthylen (PE) und deuteriertem PE angewandt. Die Restkopplung, definiert durch die Wurzel aus dem zweiten Moment, beträgt etwa 1% der entsprechenden Kopplung im festen Zustand. Sie nimmt mit steigendem Molekular-gewicht zu, nimmt aber ab mit steigender Temperatur. Eine theoretische Behandlung von zeitabhängigen Restkopplungen ergibt eine Zerfallzeit, die in PE-Schmelzen etwa 0.1 ms beträgt und die innerhalb der Fehlergrenzen unabhängig von Molekulargewicht und Temperatur ist. Die Restkopplung wird im Zusammenhang mit der Kettenverhakung in PE diskutiert. Experimentell bestimmte Spin-Gitter- und Spin-Spin-Relaxationszeiten werden mit der schnelleren segmentalen Bewegung in PE in Beziehung gebracht.
    Notes: Summary The solid echo technique is applied to determining residual dipolar and quadrupolar couplings in molten polyethylene (PE) and deuterated PE, respectively. The residual coupling defined by the square root of the second moment is about 1% of the corresponding quantity in the solid. It increases with molecular weight, and decreases with rising temperature. A theoretical treatment of time dependent residual couplings yields a decay time that is found experimentally to be about 0.1 ms in molten PE, and independent of molecular weight and temperature within our limits of accuracy. The residual coupling is discussed in relation with chain entanglement in PE. Measurements of the spin-lattice and spin-spin relaxation time are related with the more rapid segmental motion of PE chains.
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  • 29
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    Colloid & polymer science 259 (1981), S. 990-994 
    ISSN: 1435-1536
    Keywords: NMR ; proton spin-spin relaxation ; styrene-butadienestyrene block copolymer ; rubber crosslink density
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Zusammenfassung Zur quantitativen Erfassung der Vernetzung eines Kautschuks ist es wünschenswert, die Vernetzungsdichte des Netzwerks zu bestimmen. Styrol-Butadien-Styrol Blockcopolymere können als Modellnetzwerke für einen Kautschuk mit einheitlichen Netzbogenlängen angesehen werden. Für die Modellnetzwerke wird die Beziehung zwischen der Protonen Spin-Spin-Relaxationszeit und der Vernetzungsdichte bestimmt. Unterhalb eines kritischen Molekulargewichts (M c = 40 000) des Kautschuks, das der Bildung von Verschlaufungen entspricht, ist die Spin-Spin-Relaxationszeit proportional zur Netzbogenlänge; oberhalb des kritischen Wertes ist sie nahezu unabhängig vom Molekulargewicht des Kautschuks.
    Notes: Summary For a quantitative description of rubber crosslinking it is desirable to determine the crosslink density of the network. Styrene-butadiene-styrene block copolymers can be regarded as model networks for a rubber with uniform chain lengths between the crosslinks. For these model networks the relation between the proton spin-spin relaxation time and the crosslink density is determined. Below a critical value for the molecular weight of the rubber segment (M c = 40 000) which corresponds to the formation of entanglements, the relaxation time is proportional to the crosslink spacing. Above the critical value the relaxation time is almost independent of the molecular weight of the rubber.
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  • 30
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    Colloid & polymer science 259 (1981), S. 744-746 
    ISSN: 1435-1536
    Keywords: Thiourea ; NH4OM ; acetaldehyde ; propionaldehyde condensates ; Structure ; NMR ; I.R.
    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: Summary Thiourea-ammonia-acetaldehyde/propionaldehyde condensate has been obtained. A closed chain triazone structure has been established for it with the help of mass and IR spectrometric studies.
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  • 31
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    Colloid & polymer science 259 (1981), S. 741-743 
    ISSN: 1435-1536
    Keywords: Thiourea acetaldehyde condensates ; Thiourea propionaldehyde condensates ; Structure ; NMR ; I.R.
    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: Summary Thiourea reacts with acetaldehyde and propionaldehyde in acidic media to give condensates in solid state. The nature of these condensates has been investigated with the help of mass and IR spectrometric techniques and a closed chain structures proposed for them.
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