Search results for "nuclear magnetic resonance"
showing 10 items of 1743 documents
Double-quantum nutations in a two-level spin system
1986
The transient oscillatory behavior of the nonlinear response of a two-level electron-spin system is experimentally investigated in a sample of glassy silica with ${E}_{1}^{\mathcal{'}}$ centers (S=(1/2)) at microwave frequency at T=4.2 K. The transient regime, excited by an intense step-modulated radiation tuned to double-quantum (DQ) resonance, is monitored by revealing the second-harmonic (SH) wave radiated by the spins undergoing DQ transitions. Time- and frequency-domain results show that the emitted SH wave has two components: the former, which vanishes at the DQ resonance, exhibits an overdamped transient regime, the latter consists of damped oscillations at a frequency which depends …
1H,13C and17O NMR spectroscopic study of four bicyclo [3.1.1]heptenes (derivatives of α-pinene) and four bicyclo[3.1.1]heptanes (derivatives of β-pin…
1992
Four derivatives of 2, 6, 6-trimethylbicyclo[3.1.1]hept-2-ene (α-pinene) and four derivatives of 2-methylene-6, 6-dimethylbicyclo[3.1.1]heptane (β-pinene) were synthesized and their 1H, 13C and 17O NMR spectra were measured, analysed and assigned. The 1H NMR spectral parameters were obtained by computer-aided analyses of the very complex multi-spin, second-order spectra. Some of the 13C NMR chemical shift assignments of these compounds reported in the literature should be changed, based on these accurate 1H NMR spectral analyses and carbon-proton chemical shift correlated spectra (COSY). The new assignments are supported by the 1J(C, H) values, which show a strong dependence on the bond ang…
Molecular dynamics of solid polymers as revealed by deuteron NMR
1983
Pulsed deuteron NMR spectroscopy is described, which has recently been developed to become a powerful tool for studying molecular dynamics in solid polymers. It is shown that by analyzing the line shapes of2H absorption spectra and spectra obtained via solid echo and spin alignment, respectively, both type and timescale of rotational motions can be determined over an extraordinary wide range of characteristic frequencies, approximately 10 MHz to 1 Hz. By applying these techniques to selectively deuterated polymers, motional mechanisms involving different segments of the monomer unit can be monitored. In addition, motional heterogeneities in glassy polymers can be detected. The information a…
Saccharide modified silica particles by enzymatic grafting
1997
The surface of silica particles has been chemically modified with oligo- or poly-(α,1→4)-D-glucopyranose (amylose) chains of various length by covalently attaching maltoheptaose derivatives to the solid support and enzymatic polymerization of glucose-1-phosphate with a potato phosphorylase as catalyst. The characterization of the products by solid-state NMR spectroscopy showed an interesting dependence of the linewidth with the grafting density of the glucan chains. The modified silica particles showed chiral discrimination in liquid chromatography.
Deuteron n.m.r. in relation to the glass transition in polymers
1985
Abstract 2H n.m.r. is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare 2H spin alignment echo spectra of chain deuterated polystyrene with models for restricted rotational Brownian motion. Molecular motion in the polystyrene-toluene system has been investigated by analysing 2H n.m.r. of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into ‘solid’ and ‘liquid’ components where the respective average correlation times differ by more than 5 decades.
Water-Soluble Poly(vinylferrocene)-b-Poly(ethylene oxide) Diblock and Miktoarm Star Polymers
2012
We describe the synthesis of water-soluble diblock and miktoarm star polymers consisting of poly(vinylferrocene) (PVFc) and poly(ethylene oxide) (PEO) blocks. First, end-functionalized poly(vinylferrocene) was generated by end-capping the living carbanionic PVFc chains with benzyl glycidyl ether (BGE) or ethoxy ethyl glycidyl ether (EEGE). Acidic hydrolysis of the EEGE-terminated PVFc partially oxidized the PVFc backbone. However, the dihydroxyl end-functional PVFc was obtained in quantitative yields by hydrogenolysis of the BGE-terminated PVFc. A series of block copolymers and AB2 miktoarm star copolymers was obtained in a second polymerization step, utilizing the respective end-functional…
Monomer Sequence Distribution Monitoring in Living Carbanionic Copolymerization by Real-Time 1H NMR Spectroscopy
2013
Detailed understanding of the monomer sequence distribution in carbanionic copolymerization was achieved by direct online monitoring of copolymerizations in an NMR tube. Obtaining detailed knowledge of the changing monomer concentration in stock during the reaction, this technique permits to determine the incorporation probability for each monomer at every position of the polymer chain. An in situ kinetic study of two different carbanionic copolymerizations has been carried out. On the one hand, the copolymerization of the structurally similar, protected hydroxystyrene derivatives, p-(1-ethoxy ethoxy)styrene (pEES) and 4-tert-butoxystyrene (tBuOS), and on the other hand the copolymerization…
Oxidation-responsive polyether block copolymers lead to non-ionic polymer surfactants with multiple amine N-oxides
2019
Block copolymers consisting of a nonpolar poly(propylene oxide) block and a poly(glycidyl amine) block were prepared by anionic ring-opening polymerization (AROP). The tertiary amine groups of the block copolymers were quantitively transformed into the corresponding zwitterionic amine N-oxides, as confirmed by 1H NMR and 15N NMR spectroscopy. This leads to strongly amphiphilic polyether block copolymers with multiple N-oxides. Full oxidation of the amine groups was also possible in situ in an emulsion, demonstrating the oxidation-responsive character of this new class of non-ionic polymeric surfactants.
Solid state NMR - A tool for studying molecular motion in polymers
1986
After an introduction describing the development of 1H, 2H, and 13C solid state NMR two sections on 13C and 2H NMR, respectively, outline the physical background as related with molecular motion. Some representative examples demonstrate the potential of recent NMR techniques in polymer dynamics studies.
Investigation of the glass transition and melting of polymers by nuclear magnetic resonance
2007
Investigations of the glass transition and melting of partially crystalline polymers by nuclear magnetic resonance provide valuable information on the nature of noncrystalline regions. The broad line NMR signal was separated into a narrow component and a broad component by using a new method which does not imply the ambiguity usually present. From the intensity of the narrow component the mobile fraction was determined. This fraction was extrapolated to “infinite” temperature. By subtracting the mobile fraction from the noncrystalline fraction, the noncrystalline rigid fraction was obtained. Comparison of the measured second moments of the two components of the NMR line with calculated seco…