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31.
Emily K. LuebberingJacob Mick Ranjan K. SinghJohn J. Tanner Ritcha Mehra-ChaudharyLesa J. Beamer 《Journal of molecular biology》2012,423(5):831-846
The α‐d‐phosphohexomutase superfamily comprises enzymes involved in carbohydrate metabolism that are found in all kingdoms of life. Recent biophysical studies have shown for the first time that several of these enzymes exist as dimers in solution, prompting an examination of the oligomeric state of all proteins of known structure in the superfamily (11 different proteins; 31 crystal structures) via computational and experimental analyses. We find that these proteins range in quaternary structure from monomers to tetramers, with 6 of the 11 known structures being likely oligomers. The oligomeric state of these proteins not only is associated in some cases with enzyme subgroup (i.e., substrate specificity) but also appears to depend on domain of life, with the two archaeal proteins existing as higher‐order oligomers. Within the oligomers, three distinct interfaces are observed, one of which is found in both archaeal and bacterial proteins. Normal mode analysis shows that the topological arrangement of the oligomers permits domain 4 of each protomer to move independently as required for catalysis. Our analysis suggests that the advantages associated with protein flexibility in this enzyme family are of sufficient importance to be maintained during the evolution of multiple independent oligomers. This study is one of the first showing that global motions may be conserved not only within protein families but also across members of a superfamily with varying oligomeric structures. 相似文献
32.
A. A. Egorova A. V. Kiselev I. I. Tarasenko P. L. Il’ina G. A. Pankova I. E. Il’ina V. C. Baranov G. P. Vlasov 《Russian Journal of Bioorganic Chemistry》2009,35(4):437-445
The DNA compacting and transfection properties of hyperbranched polylysines whose N-terminal amino groups were modified with histidine and arginine were studied. The histidine-modified hyperbranched polylysines were shown to provide higher efficacy of binding and transfection in comparison with unmodified or hyperbranched arginine-containing polylysines. This fact was explained by the intrinsic endosomolytic activity of the histidine-modified polymers. The dependence between the quantity of the amino acids that modified the terminal lysine residues in the hyperbranched polylysines, the efficacy of their DNA binding, and the transfection activity of the DNA complexes with the corresponding carriers was found. The possibility to increase the transfection activity of the DNA complexes with the hyperbranched polylysines by glycerin or the JTS-1 amphipathic nonapeptide was studied. At the same time, their simultaneous use was found to result in a transfection decrease. 相似文献
33.
Yihui Chen Ana G. Petrovic Marin Roje Gennaro Pescitelli Margaret M. Kayser Yan Yang Nina Berova Gloria Proni 《Chirality》2010,22(1):140-152
This article describes an application of the host‐guest chiral recognition approach called tweezer methodology for the determination of the absolute configuration of 3‐hydroxy‐β‐lactams. These substrates represent challenging cases due to their chemical reactivity, the presence of multiple stereogenic centers and several functional groups which offer various possibilities of binding to the Zn‐porphyrin host. OPLS‐2005, the force field used in this work to predict the interporphyrin twist, modeled correctly the host‐guest complexation mechanism and revealed conformational details of the bound substrates. The computational study also suggested that in cases where an increase in the magnitude of the stereodifferentiation and an intense experimental CD are observed, the bound conformation of the conjugates are hydrogen bonded. The present investigation provides evidence that when the tweezer method is assisted by the OPLS‐2005 based computational approach, it can be successfully applied to the configurational and conformational elucidation of multi‐functional compounds with multiple stereogenic centers. Chirality, 2010. © 2009 Wiley‐Liss, Inc. 相似文献
34.
35.
Cinchonine (Cin) is the primary drug of choice in the treatment of malaria, but its poor solubility has restricted its use via the oral route. Cyclodextrins (CDs) form inclusion complexes with cinchonine to form soluble complexes. This interaction was investigated by solubility studies, electrospray ionization mass spectrometry (ESI-MS), and molecular modeling. ESI-MS evaluated successfully the nature of the solution-phase inclusion complexes. The experimental results showed that not only 1:1, but also stable 2:1 inclusion complexes can be formed between CDs and Cin. Multi-component complexes of beta-CD-Cin-beta-CD (1:1:1), gamma-CD-Cin-gamma-CD (1:1:1), and beta-CD-Cin-gamma-CD (1:1:1) were found in equimolar beta- and gamma-CD mixtures with Cin. The formation of 2:1 and multi-component 1:1:1 non-covalent CD-Cin complexes indicates that beta- and gamma-CD are able to form sandwich-type inclusion complexes with Cin in high concentrations. The phase-solubility diagram showed non-linear type A(p) profile, indicating that more than one cyclodextrin molecule is involved in the complexation of one guest molecule. Molecular modeling calculations have been carried out to rationalize the experimental findings and predict the lowest energy molecular structure of inclusion complex. 相似文献
36.
It is demonstrated that complexation between the ferric cation and the Z-chalcone of the naturally occurring anthocyanin malvin takes place in acidic aqueous solutions. The flexible open cavity of the Z-chalcone best fits the steric and electronic requirements of the ferric ion in water. 相似文献
37.
A novel chemical reactor was designed and developed for the continuous high-rate production of uniform capsules. This reactor helps to control precisely the reaction time between the reacting liquids (anion drops and the cation bath, or vice versa), thereby leading to the formation of uniform capsules with walls of identical thickness. In addition, mild tumbling of the capsules during transit through the reactor ensures that every capsule wall is uniformly thick all around. 相似文献
38.
The interaction of dilute mixtures of proteins and ABC triblock methacrylic polyampholytes at different values of pH was investigated turbidimetrically. The onset of interaction was manifested by large changes in turbidity at certain critical pHs which lie close to the isoelectric points of the two interacting components. Protein precipitation yields in protein-polyampholyte binary mixtures followed the corresponding turbidity profiles and varied from 10% to 90%. The synthetic polyampholytes self-aggregate around their isoelectric point. The kinetics of precipitation of one of the same polymer with soybean trypsin inhibitor were studied, with turbidity-based characteristic times (exponential fit) of 2-3 min. The kinetics of precipitation of the protein-polymer mixture are slower than that of pure polymer because a small, but steady, long-term increase in turbidity is observed in the former case. The pH-dependence of the turbidity of binary mixtures of one protein and one synthetic polyampholyte, as well as a tertiary mixture of two proteins and one polyampholyte, were measured 30 min after the pH adjustment. The observations in these experiments along with the measured protein precipitation yields in the binary mixtures and the polyampholyte self-aggregation can be used for polymer removal and recycling. The latter constitutes a significant advantage over the use of homopolyelectrolytes which cannot easily be recycled. (c) 1994 John Wiley & Sons, Inc. 相似文献
39.
The resolution of racemic δ-phenyl-δ-valerolactone by chromatography on cellulose triacetate CTA I results in one of the best separations of optical antipodes observed so far on this chiral stationary phase. The thermodynamics of the stereoselective interaction of the enantiomers of δ-phenly-δ-valerolactone have been studied by chromatography at different temperatures and by direct microcalorimetric investigations of the complexation with CTA I. This analysis suggests that the separation process is mainly controlled thermodynamically and that kinetic effects, if any, play a minor role. Microcalorimetric titration experiments indicate that specific (optimum) complexation sites on CTA I for the stronger retained enantiomer of δ-phenly-δ-valerolactone are rapidly saturated, whereas the first eluted enantiomer seems to interact much less selectively with defined interaction sites on the chiral polymer matrix. © 1993 Wiley-Liss, Inc. 相似文献
40.
Suspended particulate oxides and organic matter interactions in trace metal sorption reactions in a small urban river 总被引:2,自引:0,他引:2
The relative scavenging abilities of suspended particulate oxides (SPOX), and organic matter (SPOM) for Cd, Zn and Cu were evaluated in a small, anthropogenically influenced river. In addition, the factor most important in influencing the sorption density (Ad: metal concentration associated with a given phase divided by the concentration of that geochemical phase in the suspended particulate pool) of each metal to SPOX and SPOM were identified through multiple linear regression analyses from the suite of: pH, temperature, dissolved metal concentration, and the concentration of the other particulate fraction. Results indicate that SPOX-SPOM interactions do occur in trace metal complexation reactions; and interactions are both phase and cation specific. Fe oxides are able to outcompete discrete organic binding sites for Cu and Zn as a relative decrease in the amount of these two cations sorbed to organic matter was observed with increasing particulate Fe oxides. SPOM concentration was identified as being most important in influencing Cu sorption densities associated with the SPOX fraction. Organic matter — oxide complexes are postulated to occur that enhance oxide sorption of Cu such that relatively more Cu is sorbed to particulate oxides with increasing particulate organic matter concentrations. Dissolved concentrations of Cd and Zn were found to be most important in influencing the sorption densities for these two metals associated with the oxides fraction. The sorption behaviour appears to follow Freundlich isotherm behaviour where the amount sorbed is a function of the dissolved concentration. 相似文献