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21.
Robert Huber 《Angewandte Chemie (International ed. in English)》1988,27(1):79-88
Proteins may be rigid or flexible to various degrees as required for optimal function. Flexibility of large parts of a protein, which rearrange or move, is particularly interesting and will be discussed in this article. We differentiate between several categories, although the boundaries between them are diffuse: flexibility of peptide segments, order–disorder transitions of spatially contiguous regions, and domain motions. The domains may be flexibly linked to allow rather unrestricted motions or the motions may be constrained to certain modes. The various categories of large-scale flexibility will be illustrated with the following examples: (1) Small protein proteinase inhibitors are rather rigid molecules which provide binding surfaces complementary to their cognate proteases but show also limited segmental flexibility and adaptation. (2) Large plasma proteinase inhibitors exhibit large conformational changes after interaction with proteases probably for regulatory purposes. (3) Pancreatic serine proteases employ a disorder–order transition of their activation domain as a means to regulate enzymic activity. (4) Immunoglobulins show rather unrestricted and also hinged domain motions in different parts of the molecule probably to allow binding to antigens in different arrangements. (5) Citrate synthase adopts open and closed forms by a hinged domain motion to bind substrates and release products and to perform the catalytic condensation reaction, respectively. (6) Riboflavin synthase, a bifunctional multienzyme complex, catalyzes two consecutive reactions by means of two subunits, α and β. The β-subunits form a shell, in which the α-subunits are enclosed. Diffusional motion of the catalytic intermediates is therefore restricted. In addition, rearrangement of the N-terminal segment occurs during the assembly of the β-subunit. In contrast, rigidity is dominant in the structures of the light-harvesting complexes and the photosynthetic reaction centers involved in photosynthetic light reactions. These are large protein–pigment complexes in which the proteins serve as matrices to hold the pigments in the appropriate conformation and relative arrangement. Since motion would contribute to deactivation of the photoexcited states of the pigments and diminish the efficiency of light-energy and electron transfer, the functional role of rigidity is easy to rationalize for these proteins. 相似文献
22.
The hydrogen fluoride dimer (HF)2 is the most completely characterized hydrogen bonded species incorporating a donor molecule and an acceptor molecule. We provide a summary of experimental and theoretical information pertinent to the fundamental and harmonic vibrational frequencies, equilibrium geometry and dissociation energiesD
e andD
0 as well as a brief critical discussion including some new results on the potential function and current best estimates of experimental quantities. 相似文献
23.
Sakae Uemura Haruo Miyoshi Masaya Okano Isao Morishima Toshiro Inubushi 《Journal of organometallic chemistry》1979,165(1):9-19
Treatment of norbornene, norbornadiene, benzonorbornadiene, and chloro- and methoxy-benzonorbornadiene with thallium(III) acetate in methanol affords only the corresponding cis-exo-acetoxythallation adducts in a sharp contrast to oxymercuration of such strained olefins where methoxymercuration prevails. In the cases of substituted benzonorbornadienes the products are obtained as the regioisomeric mixtures, the isomer ratio being determined by 13C NMR. In the cases of 5-norbornene-2,3-dicarboxylic anhydride, 5-norbornene-2-methyl-2,3-dicarboxylic anhydride, and 5-norbornen-2-endo-carboxylic acid, lactonization occurs to give a trans-oxythallation adduct having a lactone ring, no introduction of either methoxy or acetoxy groups being observed. 1H and/or 13C NMR data for several new oxythallation adducts are provided. The alkaline sodium borohydride reduction of adducts in methanol affords mainly the parent olefin together with 10–16% yields of the corresponding exo-alcohol. 相似文献
24.
The microwave acid digestion method was applied to the decomposition of rock samples and optimum conditions were investigated. Samples of 10–100 mg were decomposed by changing the amount and composition of acid, heating time and number of reheating steps and then the concentrations of Si, Fe, Mn, Na, K and Mg in these samples were measured. The concentrations agreed with reported values when 10 mg of sample were decomposed by heating for 60 s with 0.3 ml of concentrated HNO3 and 0.1 ml of concentrated HF. Similarly, 100 mg of sample were also decomposed successfully by heating for 45–110 s with 0.3–1.0 ml of concentrated HNO3 and 0.4–0.7 ml of concentrated HF. It is concluded that the microwave acid digestion method decomposes rock samples with a very short heating time and with small amount of reagents compared with methods using conventional sealed PTFE vessels, which require several hours for the heating step and several millilitres of reagents. 相似文献
25.
时间分辨激光光散射测量系统 总被引:1,自引:1,他引:1
自选设计,装配了一套时间分辨的激光光散射测量系统,该系统摄像机,录像机,计算机和自编的软件实现了一体化的数据采集,显示和分析过程,本文给出了该系统的应用实例,球晶的光散射和环氧树脂的固化反应诱导的相分离过程。 相似文献
26.
Pereira J.C.G. Catlow C.R.A. Price G.D. Almeida R.M. 《Journal of Sol-Gel Science and Technology》1997,8(1-3):55-58
Density Functional Theory is used to study water, methanol, ethanol, TMOS, and TEOS molecules and the most important silica
clusters participating in sol-gel processes. Calculated bond lengths, bond angles and electric dipole moments compare well
with experimental data. The energy of these molecules is reported and used to discuss the energetics of the hydrolysis and
condensation reactions. Molecular Dynamics is employed to simulate liquid water, methanol, ethanol, TMOS, TEOS and experimental
sol-gel solutions. Calculated densities and enthalpies of vaporisation compare well with experimental data. Preliminary results
are presented for MD simulations of sol-gel solutions. 相似文献
27.
Amirhossein Nazhand Alessandra Durazzo Massimo Lucarini Maria Alessandra Mobilia Besma Omri 《Natural product research》2020,34(1):110-121
AbstractTaxol is one of the anticancer drugs synthesized naturally in the evergreen Taxus brevifolia forest tree belonging to the yew family (Taxaceae) growing on the Pacific. There are reportedly evidence for treating ovarian, breast and lung cancers through this drug given its unique structural and functional features. Extraction of this drug from yew trees bark is one of the most common ways of producing this drug, but 3000 trees are needed to obtain a kilogram of Taxol. Hence, further attention has recently been attracted to the metabolic engineering strategies, including, engineering cellular metabolism of microorganisms and their optimization. Accordingly, the present paper article was aimed to review recent advances in elevating the production and commercialization of Taxol through metabolic engineering techniques. 相似文献
28.
29.
Fu-Sheng S 《Talanta》1983,30(6):446-448
The conditions for the reaction between phenylarsenazo (PAA) (2-[(2-arsonophenyl)azoj-7-(phenylazo)-1, 8-dihydroxynaphthalene-3,6-disulphonic acid) and chromium(III) have been studied. A blue 1:1 complex is formed at pH 2.2 on heating the reactants at 100 degrees for 15 min. It has maximum absorption at 635 nm and is stable for at least 24 hr. The molar absorptivity is 3.3 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed in the chromium concentration range 0-1.4 mug ml . The reaction has been successfully applied to determination of chromium in alloy steel. 相似文献
30.
The behaviour of gold and elements impeding its x-ray fluorescence spectrometric (XRF) determination, namely zinc, lead and arsenic, was studied during their extraction from hydrochloric acid, nitric acid, and aqua regia solutions using tributyl phosphate as a solid extractant [SE(TBP)]. Extraction of gold from pulps after aqua regia leaching was found to be the most favourable approach for the quantitative and selective recovery of gold. The gold distribution ratio, DAu, is ca. 104 ml g?1. For extraction from hydrochloric acid solutions the DAu value also exceeds 104 in the whole range of gold concentrations studied (10?8?10?4 M), but it decreases substantially with increasing extraction temperature, from 5 × 105 ml g?1 at 20°C to 9 × 103 ml g?1 at 70°C. An anomalously high distribution ratio of lead, DPb ≈ 103 ml g?1, was observed during extraction from hydrochloric solutions in the presence of chlorine. This could be explained by the formation of the chloro complexes of lead(IV). An XRF method for the determination of gold in natural samples was developed, which includes back-extraction of gold from SE(TBP) using a hot 0.025 M thiourea solution, providing a thin sample layer for secondary XRF. For 25 g of sample material the limit of determination is 10 ng g?1 (10?6%). The accuracy of the technique was checked using different reference materials. The results agreed within 10%. 相似文献