Search results for "MOLECULE"
showing 10 items of 5162 documents
Dissociation energies within selected configuration interaction and perturbation theory
1993
Abstract Selected configuration interaction (CI) calculations and second-order perturbational theory are used to truncate systematically multireference single and double excitation CI (MRCI) expansions in the calculation of the bond dissociation energies of several systems like the single-bonded LiF molecule or the multiple-bonded N2, NO and O2 diatomic systems. The method is extended to compute the CH bond dissociation energy ofethene C2H4. It is shown how the proposed scheme (perturbation-selected MRCI (MRCI-PS)) is able to reproduce the accuracy of complete MRCI expansions with only a small number of configurations variationally evaluated.
Mesoporous silica-based materials for use in electrochemical enzyme nanobiosensors
2012
Abstract Biology and medicine have seen great advancements in the development of enzyme nanobiosensors capable of characterizing and quantifying biomolecules. We provide an overview of mesoporous silica (MPS)-based enzyme nanobiosensors developed for biological and medical applications, and we describe significant advances in these technologies. We review progress in constructing high-performance electrochemical enzyme biosensors. We also discuss: • MCM-41 and SBA-15-modified and MPS composite electrodes for enzyme biosensing; • incorporation of biorecognition elements into MPS material electrodes for enzyme biosensing; and, • MCM-41 and SBA-15-supported electrocatalytic MPS-based electroch…
Enzymatic and Metabolic Studies on Isolated Nuclei
1957
Publisher Summary In protein synthesis it is important to distinguish between the net synthesis of protein, as measured by an increased amount of protein nitrogen or by the formation of proteins with specific biological properties, such as enzymatically and immunologically active proteins, and exchange reactions, which may be observed in isotope experiments and, which reflect the replacement of an amino acid in a protein molecule with one from its environment. Incorporation of an amino acid into a protein can occur only during net synthesis; both types of reaction occur in similar systems. In true synthesis of protein it is usually difficult to obtain synthesis of a specific entity, especia…
Complexation of C-methyl pyrogallarene with small quaternary and tertiary alkyl ammonium cations
2007
Complexation properties of pyrogallarene 1 towards small quaternary and tertiary alkyl ammonium cations were studied in gas phase, solution and in solid state. In gas phase both dimeric capsules and monomeric 1 : 1 complexes of all cations 2a+–d+ are detected but only in the case of 2a+ is the abundance of the capsule form higher than the monomeric 1 : 1 complex. A similar trend is observed in NMR experiments, which reveal a favourable dimeric complex for 2a+ and a weaker dimeric complex for 2b+ but only monomeric complexes for 2c+ and 2d+. Also in solid state, 2a+ and 2b+ form capsules when crystallized from MeOH while 2c+ and 2d+ form dimeric 1 : 1 complexes. As a reference, hetero-confor…
Two phosphonodehydrotripeptides: Boc0–Gly1–Δ(Z)Phe2–α‐Abu3PO3Me2 and Boc0–Gly1–Δ(Z)Phe2–α‐Nva3PO3Et2
2012
The present paper reports the crystal structures of two short phosphonotripeptides (one in two crystal forms) containing one ΔPhe (dehydrophenylalanine) residue, namely dimethyl (3-{[tert-butoxycarbonylglycyl-α,β-(Z)-dehydrophenylalanyl]amino}propyl)phosphonate, Boc0–Gly1–Δ(Z)Phe2–α-Abu3PO3Me2, C21H32N3O7P, (I), and diethyl (4-{[tert-butoxycarbonylglycyl-α,β-(Z)-dehydrophenylalanyl]amino}butyl)phosphonate, Boc0–Gly1–Δ(Z)Phe2–α-Nva3PO3Et2, as the propan-2-ol monosolvate 0.122-hydrate, C24H38N3O7P·C3H8O·0.122H2O, (II), and the ethanol monosolvate 0.076-hydrate, C24H38N3O7P·C2H6O·0.076H2O, (III). The crystals of (II) and (III) are isomorphous but differ in the type of solvent. The phosphono gr…
Original packing and unusual molecular conformation of the bis(ethylenedithio)tetrathiafulvalene (ET) donors induced by cation–anion interactions in …
2002
The crystal structure of the radical salt ET5[B10I10]·0.8CH2Cl2 has been determined and the packing and molecular conformation of the organic donors are discussed in terms of the C–H⋯I contacts between the ethylene groups of the ET molecules and the iodine atoms of the borane anion [B10I10]2−.
Synthesis of low density poly(ethylene) using nickel iminophosphonamide complexes
2007
Ethylene polymerization using a catalyst derived from the reaction of the phosphorane (Me3Si)2NP(NSiMe3)2 (1) with either Ni(COD)2 or bis(π-allyl)Ni complexes affords branched poly(ethylene) (PE) of variable MW (103−106) depending on conditions. The branched PE of high MW is semicrystalline with Tm < 100 °C. High field 13C NMR spectra reveal the presence of methyl branches (ca. 10−15 per 1000 C atoms), branches longer than six C atoms (15−20 per 1000 C atoms) and trace levels of ethyl, propyl, n-butyl, and sec-butyl branches (total <2 per 1000 C atoms). The branching distribution changes modestly in response to changes in ethylene pressure in a manner consistent with a chain-walking mechani…
Die bestimmung der molekulargewichtsverteilung von nichtkristallisierenden polymeren mit dem elektronenmikroskop, 7. Präparation durch verdampfung de…
1977
A preparation method is described by means of which it is possible to transfer individual molecules of a high molecular weight polymer on a support, in order to determine their mass and therefrom their molecular weight distribution, using our previously published electron microscopic method. The advantages of the new procedure as compared to the previously described freeze-drying are 1 that the range of solvents, which can be used is much larger, and 2 that the preparation is performed by evaporation from a dilute solution, which means that the molecules are distributed statistically on the support. The risk of formation of associates is avoided by keeping the polymer concentration correspo…
Reversible stimulus-responsive Cu(i) iodide pyridine coordination polymer
2015
We present a structurally flexible copper–iodide–pyridine-based coordination polymer showing drastic variations in its electrical conductivity driven by temperature and sorption of acetic acid molecules. The dramatic effect on the electrical conductivity enables the fabrication of a simple and robust device for gas detection. X-ray diffraction studies and DFT calculations allow the rationalisation of these observations.
Studying the role of protein dynamics in an SN2 enzyme reaction using free-energy surfaces and solvent coordinates
2013
Conformational changes are known to be able to drive an enzyme through its catalytic cycle, allowing, for example, substrate binding or product release. However, the influence of protein motions on the chemical step is a controversial issue. One proposal is that the simple equilibrium fluctuations incorporated into transition-state theory are insufficient to account for the catalytic effect of enzymes and that protein motions should be treated dynamically. Here, we propose the use of free-energy surfaces, obtained as a function of both a chemical coordinate and an environmental coordinate, as an efficient way to elucidate the role of protein structure and motions during the reaction. We sho…