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21.
Simon A. Butler Gillian W. Harris David S. Moss Beatrice A. Gorinsky Margaret J. Adams Sheila Gover 《Journal of chemical crystallography》1994,24(1):1-3
We report the estimation of random errors in the refinement of the rigid body displacements of the -helices of the enzyme 6-phosphogluconate dehydrogenase. Least-squares refinement of the TLS parameters of the helices has been carried out using X-ray reflection data of 2.1 Å resolution, resulting in anR-factor of 19.5%. Standard deviations were estimated from the normal matrix. The results show that the translational mean-square displacements of nearly all the helices are significant at this resolution. However the libration parameters are only significant when the helices have at least four turns. Screw-rotation tensor values cannot be determined at this resolution. 相似文献
22.
Given any family of graphsP, theP chromatic number
p
(G) of a graphG is the smallest number of classes into whichV(G) can be partitioned such that each class induces a subgraph inP. We study this for hereditary familiesP of two broad types: the graphs containing no subgraph of a fixed graphH, and the graphs that are disjoint unions of subgraphs ofH. We generalize results on ordinary chromatic number and we computeP chromatic number for special choices ofP on special classes of graphs.Research supported in part by ONR Grant N00014-85K0570 and by a grant from the University of Illinois Research Board. 相似文献
23.
Alan Cooper Michelle Lovatt Margaret A. Nutley 《Journal of inclusion phenomena and macrocyclic chemistry》1996,25(1-3):85-88
The energetics of interaction of a range of cyclodextrins with folded and unfolded proteins has been examined by sensitive microcalorimetry techniques. Weak interaction with exposed amino acid residues promotes unfolding and dissociation of proteins. The possibility that such interactions may facilitate the use of cyclodextrins as chaperone-mimics in the refolding of denatured protein has been explored with the enzyme phosphoglycerate kinase. Up to 40% regain of activity can be achieved in some cases. 相似文献
24.
25.
Sorin Staicu Ilie G Dinulescu Filip Chiraleu Margaret Avram 《Journal of organometallic chemistry》1976,113(4):C69-C72
Coupling of diarylacetylenes with alkenes in the presence of dichlorobis(benzonitrile)palladium gives chloro(syn-1-chloro-anti-1-aryl-syn-3-alkyl)-π-allylpalladium complexes. 相似文献
26.
Experimentally observed product quantum state distributions across a wide range of abstraction reactions at suprathreshold collision energies have shown a strong bias against product internal energy. Only a fraction, sometimes quite a small fraction, of the energetically accessible product quantum states are populated. Picconatto et al. [J. Chem. Phys. 114, 1663 (2001)] noted a simple mathematical relationship between the highest-energy rovibrational states observed and the kinematics of the reaction system. They proposed a reaction model based on reaction kinematics that quantitatively explains this behavior. The model is in excellent agreement with measured quantum state distributions. The assumptions of the model invoke detailed characteristics of reactive trajectories at suprathreshold collision energies. Here we test those assumptions using quasiclassical trajectory calculations for the abstraction reactions H+HCl-->H2+Cl, D+HCl-->HD+Cl, and H+DCl-->HD+Cl. Trajectories were run on a potential-energy surface calculated with a London-Eyring-Polyani-Sato function with a localized 3-center term (LEPS-3C) previously shown to accurately reproduce experimentally observed product state distributions for the H+HCl abstraction reaction. The trajectories sample collision energies near threshold and also substantially above it. Although the trajectories demonstrate some aspects of the model, they show that it is not valid. However, the inadequacy of the proposed model does not invalidate the apparent kinematic basis of the observed energy constraint. The present results show that there must be some other molecular behavior rooted in the reaction kinematics that is the explanation and the source of the constraint. 相似文献
27.
John Fielden Patrick T. Gunning De-Liang Long Margaret Nutley Arkady Ellern Paul Kgerler Leroy Cronin 《Polyhedron》2006,25(18):3474-3480
The coordination chemistry of the tetradentate pyridyl N-donor ligand cis-3,5-bis-[2-pyridinyleneamin]-trans-hydroxycyclohexane (DDOP) has been investigated with zinc(II) nitrate and triflate. The resulting complexes, [Zn(DDOP)(H2O)(NO3)](NO3) (1), and [Zn(DDOP)(H2O)(OTf)](OTf) (2) differ not only in their counterions, but also the arrangement of the axial ligands and their solid state hydrogen bonded networks. Isothermal titration calorimetry was used to assess the difference in binding properties exhibited by the two zinc complexes at physiological pH in an aqueous environment. A series of coordinating amino acids were found to preferentially bind to the mononuclear zinc triflate (1) complex over the corresponding nitrate (2) assembly, with histidine exhibiting a two centre binding mode. 相似文献
28.
Keith A. Hunter Margaret R. Leonard Peter D. Carpenter J. David Smith 《Colloids and surfaces. A, Physicochemical and engineering aspects》1997,120(1-3):111-121
The kinetics of iron colloid aggregation in estuaries have been simulated with a model estuary in which seawater is continuously pumped into a reservoir initially containing river water. Profiles of colloidal Fe concentration versus salinity produced in this apparatus closely resembled field data for actual estuaries. Synthetic Fe colloids prepared by peptising Fe(OH)3 with humic acid and phosphate showed very similar kinetic behaviour. Aggregation rate was found to be almost independent of velocity shear rate, implying that most aggregations are induced by brownian interparticle collisions. A heterogeneous kinetic model is proposed to explain the kinetic behaviour of Fe colloids during seawater-induced aggregation. This model describes kinetic behaviour in terms of a log-normal distribution of rate constants characterised by a mean value k and a standard deviation γ. Experiments showed that k is linearly related to the rate constant for salinity increase during mixing. This coupling of salinity changes and aggregation rate leads to Fe-salinity profiles that are nearly independent of the rate of salinity change, but which are dependent on γ. 相似文献
29.
Stephen E. Ullrich Esther Azizi Margaret L. Kripke 《Photochemistry and photobiology》1986,43(6):633-638
Abstract— After a single exposure of mice to UV radiation, their ability to generate a contact hypersensitivity (CHS) response to contact sensitizers applied epicutaneously to distant, unirradiated skin is severely impaired. It is not clear, however, if the classic delayed type hypersensitivity (DTH) reponse to exogenous antigens, injected into the subcutaneous (s.c.) space, can also be modulated by UV radiation. We report here that a single exposure of mice to UV radiation suppressed the induction of DTH to both erythrocyte and soluble protein antigens injected s.c., but did not suppress the elicitation of the response. The suppressive effect was abrogated by cyclophosphamide treatment. In addition, antigen-specific suppressor cells were found in the spleens of the mice with a decreased DTH response. Since the ability to mount a DTH response has been linked with the resistance to certain pathogenic microorganisms, we suggest that the suppression of DTH by UV radiation may have the potential to compromise host resistance to such infectious agents. 相似文献
30.
The synthesis of several ABE tricyclic analogues of the alkaloid methyllycaconitine 1 is reported. The analogues contain two key pharmacophores: a homocholine motif formed from a tertiary N-ethyl amine in a 3-azabicyclo[3.3.1]nonane ring system and a 2-(3-methyl-2,5-dioxopyrrolidin-1-ly)benzoate ester 4. The synthesis of the ABE tricyclic analogues of MLA 1 began with selective allylation at C-3 of 3 to produce allyl beta-keto ester 4. Double Mannich reaction of 4 with ethylamine and formaldehyde produced bicyclic amine 5 The C-9 ketone of bicyclic amine 5 was selectively reduced to form bicyclic alcohols 6 and 7 which were subsequently allylated to form dienes 8 and 9. Ring closing metathesis of dienes 8 and 9 afforded tricyclic ethers 11 and 12, respectively, the C-8 ester of which was reduced to a hydroxymethyl group to form ABE tricyclic analogues 13 and 14. Addition of allylmagnesium bromide to the C-9 ketone of 20 afforded dienes 21 and 22, which underwent ring closing metathesis to form tricyclic esters 23 and 24, respectively. Reduction of the C-8 ethyl ester of 23 and 24 to a hydroxymethyl group afforded diols 25 and 26 respectively. The 2-(3-methyl-2,5-dioxopyrrolin-1-ly)benzoate ester was introduced by conversion of alcohols 13, 14, 25 and 26, to the anthranilate esters 16, 17, 27 and 28 using N-(trifluoroacetyl)anthranilic acid 15 followed by fusion with methylsuccinic anhydride to afford the substituted anthranilates 18, 19, 29 and 30 containing the key 2-(3-methyl-2,5-dioxopyrrolidin-1-ly)benzoate ester pharmacophore. 相似文献