Search results for "Nuclear magnetic resonance spectroscopy"
showing 10 items of 843 documents
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.
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.
Zum Ligandenaustausch des Ferrocens mit Methyl- und Ethyl-substituierten Naphthalinen
1988
Abstract The replacement of a Cp ligand of ferrocene by each of ten unsymmetrically substituted naphthalenes yields pairs of complex ions [arene-FeCp] + , which have been identified from their 1 H NMR spectra. The influence of the substituent on the ratio of the two isomers, and its temperature dependence implies a complex reaction mechanism involving an η 2 -bound intermediate of the associated naphthalene. The proton resonances of the alkyl groups of the naphthalenes are shifted to lowfield by complexation; this effect decreases with increasing distance from the iron. The resonance shift of the arene protons has a different sign for the complexed (highfield) and the uncomplexed part (lowf…
Zero- to Ultralow-Field NMR Spectroscopy of Small Biomolecules.
2021
Nuclear magnetic resonance (NMR) spectroscopy is a well-established analytical technique used to study chemicals and their transformations. However, high-field NMR spectroscopy necessitates advanced infrastructure, and even cryogen-free benchtop NMR spectrometers cannot be readily assembled from commercially available components. We demonstrate construction of a portable zero-field NMR spectrometer employing a commercially available magnetometer and investigate its applications in analytical chemistry. In particular, J-spectra of small representative biomolecules [13C]-formic acid, [1-13C]-glycine, [2,3-13C]-fumarate, and [1-13C]-d-glucose were acquired, and an approach relying on the prese…
NMR Matrix Technique for Detecting Self Diffusion in Polymers
1979
A technique is discussed where monodisperse small spheres or cylindrical fibers of a polymer are embedded in a matrix of the corresponding fully deuterated polymer. On annealing the sample at a temperature above the glass transition the protonated macromolecules diffuse into the deuterated matrix and vice versa. Since the NMR spectrum depends upon the intermolecular proton proton dipolar coupling, the decrease of this coupling can be used to monitor the diffusion process. For particle diameters d ∼ 10−4 cm and annealing times t ∼ 105 s, extremely small diffusion constants D < d2/t are attainable. The NMR analysis of prospective diffusion experiments with polystyrene is discussed in some det…
13C NMR study of aromatic ring-substituted (E)-3-phenylpropenals and (2E,4E)-5-phenylpenta-2,4-dienals
1990
13C and 1H chemical shifts together with C,H and H,H coupling constants are presented for (E)-3-phenylpropenal, (2E,4E)-5-phenylpenta-2,4-dienal and their o-OCH3- and o-, m- and p-NO2-substituted derivatives. The SCSs calculated for the aldehyde chains show similar effects on the ring carbons, except in the para position where the shorter chain causes a 3.3 ppm deshielding and the longer chain a 1.0 ppm shielding effect. This shift difference is reflected in all the ring-substituted derivatives of the two series of aldehydes, but not in the one-bond C,H coupling constants. The effect of aromatic ring substitution on 2J(C,CHO) seems to be mainly inductive in origin. The importance of the str…
Über tetraaryl-methan-analoga in der gruppe 14
1994
Abstract The title compounds have been synthesized by Grignard reactions or pyrolysis of diplumbanes respectively. The crystal structures of m -Tol 4 Pb and Ph 4 Pb (redetermination) have been determined. All eight compounds (Ph/Tol) 4 (Sn/Pb) are S 4 symmetric and contracted along this unique axis. The 13 C-NMR chemical shifts and the couplings 1 J ( 119 Sn/ 207 Pb 13 C) as well depend additively upon the methyl substituents. The ratios 1 K ( 207 Pb 13 C): 1 K ( 119 Sn 13 C) of the reduced coupling constants are all near to 1.61; a comparison with values from the literature for alkyl, alkenyl and alkinyl substituents is given. The ratio δ( 207 Pb):δ( 119 Sn) results in 2.28. IR (700 dow…