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991.
Joseph A. Akkara Kris J. Senecal David L. Kaplan 《Journal of polymer science. Part A, Polymer chemistry》1991,29(11):1561-1574
Polymers were synthesized from substituted phenolic and aromatic amine compounds with hydrogen peroxide as the source of an oxidizing agent and horseradish peroxidase enzyme as the catalyst. The polymerization reaction was carried out in a monophasic organic solvent with small amounts of water at room temperature. Conditions for the synthesis of polymers with respect to reaction time and yield were studied with a number of monomers at different concentrations and in solvents with different buffers with pH range of 5.0–7.5. Physical and chemical properties of these homo-and copolymers were determined with respect to melting point, solubility, elemental analysis, molecular weight distribution, infrared absorption (including FTIR), solid-state 13C nuclear magnetic resonance, thermal gravimetric analysis, and differential scanning calorimetry. The enzyme catalyzed reactions produced polymers of molecular weight greater than 400,000 which were further fractionated by differential solubility in solvent mixtures and the molecular weight distribution of the polymer fractions were determined. In general, the polymers synthesized have low solubilities, high melting points, and some degree of branching. 相似文献
992.
Salma Kassem Alan T. L. Lee David A. Leigh Augustinas Markevicius Daniel J. Tetlow Naoyuki Toriumi 《Chemical science》2021,12(6):2065
Peptides attached to a cysteine hydrazide ‘transporter module’ are transported selectively in either direction between two chemically similar sites on a molecular platform, enabled by the discovery of new operating methods for a molecular transporter that functions through ratcheting. Substrate repositioning is achieved using a small-molecule robotic arm controlled by a protonation-mediated rotary switch and attachment/release dynamic covalent chemistry. A polar solvent mixtures were found to favour Z to E isomerization of the doubly-protonated switch, transporting cargo in one direction (arbitrarily defined as ‘forward’) in up to 85% yield, while polar solvent mixtures were unexpectedly found to favour E to Z isomerization enabling transport in the reverse (‘backward’) direction in >98% yield. Transport of the substrates proceeded in a matter of hours (compared to 6 days even for simple cargoes with the original system) without the peptides at any time dissociating from the machine nor exchanging with others in the bulk. Under the new operating conditions, key intermediates of the switch are sufficiently stabilized within the macrocycle formed between switch, arm, substrate and platform that they can be identified and structurally characterized by 1H NMR. The size of the peptide cargo has no significant effect on the rate or efficiency of transport in either direction. The new operating conditions allow detailed physical organic chemistry of the ratcheted transport mechanism to be uncovered, improve efficiency, and enable the transport of more complex cargoes than was previously possible.Peptides are transported in either direction between chemically similar sites on a molecular platform, substrate repositioning is achieved using a cysteine hydrazide transporter module and a small-molecule robotic arm controlled by a rotary switch. 相似文献
993.
Gregory M. Su Han Wang Brandon R. Barnett Jeffrey R. Long David Prendergast Walter S. Drisdell 《Chemical science》2021,12(6):2156
Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework CuI-MFU-4l, which contains coordinatively unsaturated copper(i) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(i) sites in CuI-MFU-4l via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within CuI-MFU-4l. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry. In situ near edge X-ray absorption fine structure spectroscopy directly probes unoccupied states associated with backbonding interactions between the open metal site in a metal–organic framework and various small molecule guests. 相似文献
994.
Grażyna Janowska Teresa Mikołajczyk Dorota Wołowska-Czapnik M. Boguń 《Journal of Thermal Analysis and Calorimetry》2005,82(1):129-135
The paper discusses the thermal properties of alginate fibres made from alginic acid or sodium alginate and from alginates
substituted with divalent metal ions during the fibre-forming stage. Alginate fibres with an addition of silica nanoparticles
have also been examined. The selection of fibre-forming parameters was intended to obtain the best either sorption or strength
properties depending on the specific fibre application. Thermal curves of the fibres under investigations obtained by under
air atmosphere and differential scanning calorimetry (DSC) under neutral gas atmosphere have been interpreted from the view
of physical and chemical changes in the fibre-forming material. Based on thermogravimetric curves, the fibre thermal stability
indices have been determined. It has been found that the addition of silica nanoparticles exerts a positive influence on the
thermal properties of the examined fibres. 相似文献
995.
Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy
Concepción López Rosa M. Claramunt M. Ángeles García José Elguero 《Central European Journal of Chemistry》2004,2(4):660-671
Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by13C and 15N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists. 相似文献
996.
We extend our sol-gel methodology of one-pot sequences of reactions with opposing reagents to an enzyme/metal-complex pair. Sol-gel entrapped lipase and sol-gel entrapped RhCl[P(C(6)H(5))(3)](3) or Rh(2)Co(2)(CO)(12) were used for one-pot esterification and C-C double bond hydrogenation reactions, leading to saturated esters in good yields. When only the enzyme is entrapped, the homogeneous catalysts quench its activity and poison it. Thus, when 10-undecenoic acid and 1-pentanol were subjected in one pot to the entrapped lipase and to homogeneously dissolved RhCl[P(C(6)H(5))(3)](3) under hydrogen pressure, only 7% of the saturated 1-pentyl undecanoate was obtained. The yield jumped 6.5-fold when both the enzyme and the catalyst were immobilized separately in silica sol-gel matrixes. Similar one-pot esterifications and hydrogenations by sol-gel entrapped lipase and heterogenized rhodium complexes were carried out successfully with the saturated nonoic, undecanoic, and lauric acids together with several saturated and unsaturated alcohols. The use of (S)-(-)-2-methylbutanol afforded an optically pure ester. The heterogenized lipase is capable of inducing asymmetry during esterification with a prochiral alcohol. Both the entrapped lipase and the immobilized rhodium catalysts can be recovered simply by filtration and recycled in further runs without loss of catalytic activity. 相似文献
997.
Ermann M Simkovsky NM Roberts SM Parry DM Baxter AD 《Journal of combinatorial chemistry》2002,4(4):352-358
A solid-phase synthesis of substituted cyclic urea derivatives as potential heterocyclic library scaffolds is described. 2-Amino-3-nitropyridine is attached to Wang resin via a carbamate linkage. Reduction of the nitro group was achieved with SnCl(2).2H(2)O. Reductive alkylation with a range of substituted benzaldehydes followed by cyclative cleavage afforded a small library of 3-substituted imidazo[4,5-b]pyridine-2-ones in 33-45% yield and 59-88% purity. Subsequently, this methodology was applied to the synthesis of 3-substituted imidazo[4,5-f]quinolin-2-ones. 相似文献
998.
[reaction: see text] Formamidine ureas display a rich manifold of reactivity. Thiols induce substitution at the carbonyl carbon to give thiolcarbamates; base-mediated alkylation and acylation occurs at the terminal urea nitrogen, and a new fragmentation/acylation pathway has been uncovered with isocyanates. 相似文献
999.
Summary. Phenoxyacetic acid distribution in two-phase systems n-aliphatic hydrocarbon (C5–C8) – water and its dimerization in organic phase were investigated. The values of distribution coefficient (D
HR), distribution constant (K
D), and dimerization constant (K
dim) of acid were obtained. The empirical correlations of these quantities with Hildebrand solubility parameter of organic solvents were established. The influence of pH of the aqueous phase as well as the polarity of the applied organic solvents on phenoxyacetic acid physical chemistry in
the two-phase systems was described. 相似文献
1000.
Ronaldo Santos da Silva Maria Inês Basso Bernardi Antonio Carlos Hernandes 《Journal of Sol-Gel Science and Technology》2007,42(2):173-179
In this work, we have studied the influence of the pH on the synthesis and structural properties of the Ba0.77Ca0.23TiO3 nanopowders synthesized by a modified polymeric precursor method, in order to achieve non-agglomerated powders. Synthesis,
morphology, thermal reactions, crystallite and average particle size of the synthesized powders were investigated through
thermal analysis (DTA/TG), X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM) and Infrared spectroscopy.
In summary, Ba0.77Ca0.23TiO3 nanopowders were synthesized for the first time at a relative low temperature (500 °C). It was also found that the alkalinity
and acidity of the solution presented a great influence on the powder properties. The best results were obtained from solutions
with pH = 8.5 and 11 whose nanopowders presented weakly agglomerate, with homogeneous particle size and a narrow size distribution
(30–40 nm). This behavior could be explained based on the FT-IR results in which it was possible to see the increased of the
chelation in higher pHs. 相似文献