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181.
Human serum albumin (HSA) is a very important multi-domain transporter protein in the circulatory system responsible for carriage of various kinds of ligands within the physiological system. HSA is also known to undergo conformational transformation at different pH(s) and temperatures. In this report we have studied the binding interactions of a photosensitizing drug, protoporphyrin IX (PPIX) with various conformers of HSA at different temperatures using picosecond time-resolved fluorescence spectroscopy. Also, using dynamic light scattering (DLS) and circular dichroism (CD) spectroscopy we have followed the structural transition of various conformers of HSA at different temperatures. Ensuring the intact binding of PPIX to various conformers of HSA at different temperatures as revealed through time-resolved fluorescence anisotropy decay and significant spectral overlap of emission of Trp214 residue (donor) in domain-IIA and absorption of PPIX (acceptor) bound to domain-IB of HSA, we have applied F?rster's resonance energy transfer (FRET) technique to determine the interdomain separation under various environmental conditions. The alkali-induced conformer of HSA shows almost no change in donor-acceptor distance in contrast to the native and acid-induced conformers of HSA, which show a decrease in distance with increase in temperature. Through this study the non-covalently bound PPIX is shown to be an efficient FRET probe in reporting the different temperature-induced folded states of HSA in buffer solutions of widely differing pH values. 相似文献
182.
Cho H Shaw WJ Parvanov V Schenter GK Karkamkar A Hess NJ Mundy C Kathmann S Sears J Lipton AS Ellis PD Autrey ST 《The journal of physical chemistry. A》2008,112(18):4277-4283
Variable temperature 2H NMR experiments on the orthorhombic phase of selectively deuterated NH3BH3 spanning the static to fast exchange limits of the borane and amine motions are reported. New values of the electric field gradient (EFG) tensor parameters have been obtained from the static 2H spectra of V(zz) = 1.652 (+/-0.082) x 10(21) V/m(2) and eta = 0.00 +/- 0.05 for the borane hydrogens and V(zz) = 2.883 (+/-0.144) x 10(21) V/m(2) and eta = 0.00 +/- 0.05 for the amine hydrogens. The molecular symmetry inferred from the observation of equal EFG tensors for the three borane hydrogens and likewise for the three amine hydrogens is in sharp contrast with the C(s) symmetry derived from diffraction studies. The origin of the apparent discrepancy has been investigated using molecular dynamics methods in combination with electronic structure calculations of NMR parameters, bond lengths, and bond angles. The computation of parameters from a statistical ensemble rather than from a single set of atomic Cartesian coordinates gives values that are in close quantitative agreement with the 2H NMR electric field gradient tensor measurements and are more consistent with the molecular symmetry revealed by the NMR spectra. 相似文献
183.
Silly F Shaw AQ Castell MR Briggs GA 《Chemical communications (Cambridge, England)》2008,(16):1907-1909
The mixing of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) and 1,3,5-triazine-2,4,6-triamine (melamine) at room temperature in a ratio of 3 : 4 on Au(111) leads to the formation of a new chiral "pinwheel" structure. 相似文献
184.
The neutral imino-semiquinone, 4,6-di-tert-butyl-2-tert-butylimino-semiquinone (isqH.), can be prepared by a conproportionation of the parent aminophenol and iminoquinone compounds. The neutral radical species has been characterized in the solid state by X-ray diffraction and in solution by EPR and UV-vis absorption spectroscopy. The stability of the open-shell radical is derived from the basicity of the tert-butylimino group and the intramolecular hydrogen bond. 相似文献
185.
Cheng XL Ma SC Yu JD Yang SY Xiao XY Hu JY Lu Y Shaw PC But PP Lin RC 《Chemical & pharmaceutical bulletin》2008,56(7):982-984
Two new unusual natural pigments were first isolated from the whole herbs of Selaginella tamariscina. The structure of selaginellin A (1) was established as (R,S)-4-[(4'-hydroxy-3-((4-hydroxyphenyl)ethynyl)biphenyl-2-yl)(4-hydroxyphenyl)methylene]-2,5-cyclohexadien-1-one and selaginellin B (2) as (R,S)-4-[(4'-methoxy-4-(methyl)-3-((4-methoxyphenyl)ethynyl)biphenyl-2-yl)(4-methoxyphenyl)methylene]-2,5-cyclohexadien-1-one, along with four known biflavonoids, amentoflavone (3), hinokiflavone (4), heveaflavone (5), and 7'-O-methylamentoflavone (6). Their chemical structures were elucidated by spectral analysis of electrospray ionization mass spectroscopy (ESI-MS), one-dimensional nuclear magnetic resonance spectroscopy (1D-NMR) and two-dimensional-nuclear magnetic resonance spectroscopy (2D-NMR) including (1)H-NMR, (13)C-NMR, distortionless enhancement by polarization transfer (DEPT) and heteronuclear multiple bond coherence (HMBC), and single-crystal X-ray diffraction techniques. 相似文献
186.
Dr. Jie Wang Dr. Tian Qin Dr. Tie‐Gen Chen Dr. Laurin Wimmer Jacob T. Edwards Dr. Josep Cornella Benjamin Vokits Dr. Scott A. Shaw Prof. Phil S. Baran 《Angewandte Chemie (International ed. in English)》2016,55(33):9676-9679
A transformation analogous in simplicity and functional group tolerance to the venerable Suzuki cross‐coupling between alkyl‐carboxylic acids and boronic acids is described. This Ni‐catalyzed reaction relies upon the activation of alkyl carboxylic acids as their redox‐active ester derivatives, specifically N‐hydroxy‐tetrachlorophthalimide (TCNHPI), and proceeds in a practical and scalable fashion. The inexpensive nature of the reaction components (NiCl2?6 H2O—$9.5 mol?1, Et3N) coupled to the virtually unlimited commercial catalog of available starting materials bodes well for its rapid adoption. 相似文献
187.
Kumarn S Oelke AJ Shaw DM Longbottom DA Ley SV 《Organic & biomolecular chemistry》2007,5(16):2678-2689
A sequential, organocatalysed asymmetric reaction to access chiral 1,2-oxazines and chiral pyridazines is reported, which proceeds in moderate to good yields and good to excellent enantioselectivities. 相似文献
188.
Sepehri S Feaver A Shaw WJ Howard CJ Zhang Q Autrey T Cao G 《The journal of physical chemistry. B》2007,111(51):14285-14289
Ammonia borane (AB) is of great interest for storing hydrogen, an important issue in the growing field of hydrogen technology. The reaction pathways leading to the thermal decomposition of solid-state AB incorporated in carbon cryogels (CC) have been studied by spectroscopic methods. The time-dependent thermal decomposition was followed by in situ 11B nuclear magnetic resonance (NMR) and showed a significant increase in hydrogen release kinetics for AB in CC compared to neat AB. Both 11B NMR and Fourier transform infrared spectroscopy show a new reaction product, formed in the thermal decomposition of AB in CC scaffold (CC-AB) that is assigned to reactions with surface oxygen groups. The results indicate that incorporation of AB in CC enhances kinetics because of the reactions with residual surface-bound oxygen functional groups. The formation of new products with surface -O-B bonds is consistent with the greater reaction exothermicity observed when hydrogen is released from CC-AB materials. Scanning electron microscopy shows different morphology of AB in CC-AB nanocomposite as compared to neat AB. 相似文献
189.
In this paper we study the Cauchy–Riemann equation in complex projective spaces. Specifically, we use the modified weight function method to study the $\bar\partial$ -Neumann problem on pseudoconvex domains in these spaces. The solutions are used to study function theory on pseudoconvex domains via the $\bar\partial$ -Cauchy problem. We apply our results to prove nonexistence of Lipschitz Levi-flat hypersurfaces in complex projective spaces of dimension at least three, which removes the smoothness requirement used in an earlier paper of Siu. 相似文献
190.
Shaw R Laye RH Jones LF Low DM Talbot-Eeckelaers C Wei Q Milios CJ Teat S Helliwell M Raftery J Evangelisti M Affronte M Collison D Brechin EK McInnes EJ 《Inorganic chemistry》2007,46(12):4968-4978
We report the synthesis, by solvothermal methods, of the tetradecametallic cluster complexes [M14(L)6O6(OMe)18Cl6] (M=FeIII, CrIII) and [V14(L)6O6(OMe)18Cl6-xOx] (L=anion of 1,2,3-triazole or derivative). Crystal structure data are reported for the {M14} complexes [Fe14(C2H2N3)6O6(OMe)18Cl6], [Cr14(bta)6O6(OMe)18Cl6] (btaH=benzotriazole), [V14O6(Me2bta)6(OMe)18Cl6-xOx] [Me2btaH=5,6-Me2-benzotriazole; eight metal sites are VIII, the remainder are disordered between {VIII-Cl}2+ and {VIV=O}2+] and for the distorted [FeIII14O9(OH)(OMe)8(bta)7(MeOH)5(H2O)Cl8] structure that results from non-solvothermal synthetic methods, highlighting the importance of temperature regime in cluster synthesis. Magnetic studies reveal the {Fe14} complexes to have ground state electronic spins of S相似文献