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57Fe Mössbauer spectroscopy is used to study the interactions, geometry, and the coordination characteristics of the Fe-complexes of biopolymers such as chitosan, glucosamine, and chondritin sulfate. In addition, a computational effort is undertaken for predicting the geometries and energies of the metal complexes by the Density Functional Theory (DFT) methods as implemented in the Gaussian 2003 quantum mechanical program. Both experimental and computational results suggest that the structure of the metal complexes resemble closely the structure of the active sites of metalloenzymes in 2+ or 3+ oxidation states and is at least tetracoordinated and can possibly have six ligands. 相似文献
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A. Chandrasekhar Rao B. Natarajan H. Anandhalakshmi 《Journal of Physics and Chemistry of Solids》2007,68(2):305-310
Single crystal EPR studies of Cu(II) incorporated in magnesium rubidium sulphate hexahydrate are carried out at RT and 77 K. Since the hyperfine lines are not resolved at RT, single crystal rotations have been carried out at 77 K. The spin Hamiltonian parameters calculated from the 77 K spectra are: g11=2.133, g22=2.137, g33=2.327, A11=0.01, A22=1.44 and . The impurity ion occupies an interstitial position in this crystal lattice, which is not very common for copper ion. In addition, the low hyperfine coupling constant is explained by considering an admixture of dx2-y2 ground state with dz2 excited state. Bonding parameters, κ=0.254, , α2=0.706, α=0.8406 have also been calculated. The present study has helped to understand the static nature of JT, for which the present system is an example. 相似文献
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CH Oxidation of Ingenanes Enables Potent and Selective Protein Kinase C Isoform Activation
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Dr. Yehua Jin Dr. Chien‐Hung Yeh Dr. Christian A. Kuttruff Dr. Lars Jørgensen Dr. Georg Dünstl Dr. Jakob Felding Dr. Swaminathan R. Natarajan Prof. Dr. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2015,54(47):14044-14048
Ingenol derivatives with varying degrees of oxidation were prepared by two‐phase terpene synthesis. This strategy has allowed access to analogues that cannot be prepared by semisynthesis from natural ingenol. Complex ingenanes resulting from divergent C? H oxidation of a common intermediate were found to interact with protein kinase C in a manner that correlates well with the oxidation state of the ingenane core. Even though previous work on ingenanes has suggested a strong correlation between potential to activate PKCδ and induction of neutrophil oxidative burst, the current study shows that the potential to activate PKCβII is of key importance while interaction with PKCδ is dispensable. Thus, key modifications of the ingenane core allowed PKC isoform selectivity wherein PKCδ‐driven activation of keratinocytes is strongly reduced or even absent while PKCβII‐driven activation of neutrophils is retained. 相似文献
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Natarajan Sathiyamoorthy Venkataramanan Ambigapathy Suvitha Hiroshi Mizuseki Yoshiyuki Kawazoe 《International journal of quantum chemistry》2015,115(21):1515-1525
The study on the absorption of toxic gases such as mustard gas by organic host is essential to the development of inexpensive detection and decontamination equipments. Using quantum chemical methods, we propose cucurbituril as an effective host to capture mustard gas. It was found that stable complexes are formed with the inclusion of the toxic gas molecules inside the cucurbituril cavity, compared with the lateral and exterior interactions. Oxygen mustard has a comparable binding energy with sulfur mustard and hence can be used during experimental investigation. Additionally, during the inclusion complex formation, the presence of heteroatoms helps the guest molecules to undergo a larger structural reorganization to get accommodated inside the cucurbituril macromolecule. Atoms‐in‐molecules analysis shows the existence of strong intermolecular CH…O bonding between the guest molecules and cucurbituril macromolecule. The presence of an intramolecular CH…Cl type of bonding accounts for the higher stabilization of sulfur mustard inside the cucurbituril macromolecule. © 2015 Wiley Periodicals, Inc. 相似文献
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Asialoglycoprotein receptor (ASGPR) is one of the recognition motifs on the surface of hepatocytes, which promote their adhesion to extracellular matrix in liver tissue and appropriate artificial surfaces. ASGPR-mediated adhesion is expected to minimize trans-differentiation of hepatocytes in vitro that is generally observed in integrin-mediated adhesion. The aim of the present study is to verify the role of ASGPR in hepatocyte adhesion and proliferation in scaffolds for hepatic tissue engineering. Scanning Electrochemical Microscopy (SECM) is emerging as a suitable non-invasive analytical tool due to its high sensitivity and capability to correlate the morphology and activity of live cells. HepG2 cells and rat primary hepatocytes cultured in Polyvinyl alcohol (PVA)/Gelatin hydrogel scaffolds with and without galactose (a ligand for ASGPR) modification are studied using SECM. Systematic investigation of live cells cultured for different durations in scaffolds of different compositions (9:1 and 8:2 PVA:Gelatin with and without galactose) reveals significant improvement in cell–cell communication and proliferation on galactose incorporated scaffolds, thereby demonstrating the positive influence of ASGPR-mediated adhesion. In this work, we have also developed a methodology to quantify the respiratory activity and intracellular redox activity of live cells cultured in porous tissue engineering scaffolds. Using this methodology, SECM results are compared with routine cell culture assays viz., MTS ((1-Oxyl-2,2,5,5,-tetramethyl-Δ3-pyrroline-3-methyl) Methanethiosulfonate) and Albumin assays to demonstrate the better sensitivity of SECM. In addition, the present study demonstrates SECM as a reliable and sensitive tool to monitor the activity of live cells cultured in scaffolds for tissue engineering, which could be used on a routine basis. 相似文献
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