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31.
Fiedler AT Halfen HL Halfen JA Brunold TC 《Journal of the American Chemical Society》2005,127(6):1675-1689
A combined synthetic/spectroscopic/computational approach has been employed to prepare and characterize a series of Fe(II)-thiolate complexes that model the square-pyramidal [Fe(II)(N(His))(4)(S(Cys))] structure of the reduced active site of superoxide reductases (SORs), a class of enzymes that detoxify superoxide in air-sensitive organisms. The high-spin (S = 2) Fe(II) complexes [(Me(4)cyclam)Fe(SC(6)H(4)-p-OMe)]OTf (2) and [FeL]PF(6) (3) (where Me(4)cyclam = 1,4,8,11-tetramethylcyclam and L is the pentadentate monoanion of 1-thioethyl-4,8,11-trimethylcyclam) were synthesized and subjected to structural, magnetic, and electrochemical characterization. X-ray crystallographic studies confirm that 2 and 3 possess an N(4)S donor set similar to that found for the SOR active site and reveal molecular geometries intermediate between square pyramidal and trigonal bipyramidal for both complexes. Electronic absorption, magnetic circular dichroism (MCD), and variable-temperature variable-field MCD (VTVH-MCD) spectroscopies were utilized, in conjunction with density functional theory (DFT) and semiemperical INDO/S-CI calculations, to probe the ground and excited states of complexes 2 and 3, as well as the previously reported Fe(II) SOR model [(L(8)py(2))Fe(SC(6)H(4)-p-Me)]BF(4) (1) (where L(8)py(2) is a tetradentate pyridyl-appended diazacyclooctane macrocycle). These studies allow for a detailed interpretation of the S-->Fe(II) charge transfer transitions observed in the absorption and MCD spectra of complexes 1-3 and provide significant insights into the nature of Fe(II)-S bonding in complexes with axial thiolate ligation. Of the three models investigated, complex 3 exhibits an absorption spectrum that is particularly similar to the one reported for the reduced SOR enzyme (SOR(red)), suggesting that this model accurately mimics key elements of the electronic structure of the enzyme active site; namely, highly covalent Fe-S pi- and sigma-interactions. These spectral similarities are shown to arise from the fact that 3 contains an alkyl thiolate tethered to the equatorial cyclam ring, resulting in a thiolate orientation that is very similar to the one adopted by the Cys residue in the SOR(red) active site. Possible implications of our results with respect to the electronic structure and reactivity of SOR(red) are discussed. 相似文献
32.
The influence of aryl substituents in dibenzylidene acetone (dba) ligands, for Pd(0) complexes, has been evaluated for Suzuki-Miyaura cross-coupling reactions. Electron-withdrawing substituents such as NO(2) or CF(3) deactivate the catalyst species whereas strongly donating substituents such as OMe increase catalytic activity over that of unsubstituted dba ligands. [reaction: see text] 相似文献
33.
Brel VK Belsky VK Stash AI Zavodnik VE Stang PJ 《Organic & biomolecular chemistry》2003,1(23):4220-4226
Reaction of 1-chloro-4-(diethoxyphosphonyl)alka-2,3-dienes 14,15 with purine and pyrimidine heterocyclic bases in the presence of cesium carbonate afforded new acyclic analogues of nucleotides containing a 1,2-alkadienic skeleton 18-23. Dealkylation of 18-23 furnished phosphonic acids 2a-f. In contrast, alkylation reaction with 1-chloro-4-(diethoxyphosphonyl)octa-2,3-diene 16 led to Z- and E-1,3-alkadienic phosphonates 25a,b and 26a,b. A similar reaction with 1-chloro-4-(diethoxyphosphonyl)-2-methylbuta-2,3-diene 17 led to the elimination of hydrochloride and formation of 4-(diethylphosphonyl)-2-methylbut-1-en-3-yne 24. Molecular structures of new acyclic nucleotides 18 and 2f are determined by X-ray crystallographic analysis. 相似文献
34.
Czechowski F Golonka I Jezierski A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(6):1387-1394
The lignins separated from angiosperm and gymnosperm trees, peat and xylitic brown coal were investigated by quantitative EPR. Observed free radicals in lignins are sensitive to alkaline environment. Gaseous ammonia interacting with solid lignins in resonance cavity shifts quinone-hydroquinone equilibria towards formation of semiquinone anions. Complexation of copper(II) by lignins causes drastic decrease of the semiquinones in the matrices. Formation of lignin-Pb(II) complexes yielded radicals characterised by unusually low g-value (1.9999-2.0003). Monomeric structural units of the investigated lignins were recognised by pyrolysis with in situ methylation by tetramethylammonium hydroxide. Although for the natural lignins the mixture of normal semiquinone signals at g about 2.0034 and signals at g 1.9999 were observed, some monomeric components of lignins (e.g., caffeic acid, pyrogallol) gave pure lines at g = 1.9999. The bacterial oxidative biodegradation of lignin monomeric components and their Pb(II) complexes resulted in increase of the radical signals. 相似文献
35.
The geminal regioselectivity observed in the ene reaction between singlet oxygen and alkenes with anion-stabilizing groups is rationalized on the basis of a perepoxide intermediate, in which in analogy to the nucleophilic attack on protonated epoxides, the perepoxide is opened preferentially at the C---O bond weakened by the substituent. 相似文献
36.
Attempts to theoretically address the problems involved in transferring linear gradient elution methods have been somewhat ad hoc due to the simplifying assumptions usually made in conventional gradient elution theory. Until now, all equations based on the k* parameter of linear gradient elution theory used as the basis for predicting the separation selectivity have not explicitly included the effect of the dwell volume (VD). Using an exact equation for predicting k*, that is, one which fully accounts in an a priori fashion for VD, we find a set of simple yet exact equations which unequivocally must be satisfied to transfer an optimized linear gradient elution method from one system (column or instrument or both) to another. These relationships absolutely mandate that a change in the instrument dwell volume requires a proportional change in the column volume; in turn, a change in the column volume requires a proportional change in the flow rate and/or gradient time to maintain a constant gradient steepness. Although we are not the first to suggest these guidelines, this work provides a complete theoretical foundation for these exact guidelines for the maintenance of gradient selectivity for the case of transferring a linear gradient elution method between different columns packed with the same particles and/or between different instruments. 相似文献
37.
Love JC Urbach AR Prentiss MG Whitesides GM 《Journal of the American Chemical Society》2003,125(42):12696-12697
Metallic rods with submicron diameters that contain disklike ferromagnetic sections self-assemble into highly stable, hexagonally close-packed arrays of rods. The rods were fabricated by electrodeposition in porous alumina membranes and comprised alternating sections of gold and nickel. The thicknesses of the ferromagnetic nickel sections were approximately one-half the diameter of the rods (400 nm); this geometry orients the "easy" axis of magnetization perpendicular to the long axis of the rod. After magnetization of the rods with a rare-earth magnet, followed by sonication of the suspension, the rods spontaneously assembled into three-dimensional (3D) bundles that, on average, contained 15-30 rods. A macroscopic model of the rods suggests that the most stable orientation of the magnetic dipoles for rods in a defect-free, hexagonally close-packed arrangement is in concentric rings with the dipoles oriented head-to-tail. This configuration minimizes the energy of the bundle and does not generate a net dipole for the structure. This work provides a simple demonstration that magnetic interactions between ferromagnetic objects can direct and stabilize the formation of ordered, 3D structures by self-assembly. 相似文献
38.
Adam Bange Jian Tu Xiaoshan Zhu Chong Ahn H. Brian Halsall William R. Heineman 《Electroanalysis》2007,19(21):2202-2207
A microbead based sandwich immunoassay for MS2 bacteriophage was developed using an interdigitated array (IDA) electrode with nanoscale dimensions (220 nm electrode width, 620 nm gap). The IDA was fabricated using an electron beam lithographic lift‐off technique. After an antibody‐assisted capture of MS2 using paramagnetic microbeads, a β‐galactosidase labeled secondary antibody was used to convert p‐aminophenyl‐β‐D ‐galactopyranoside (PAPG) into the redox active p‐aminophenol (PAP). Amperometric detection of PAP with IDA electrodes at +300 and ?200 mV vs. a Ag/AgCl reference electrode was used to measure the result, detecting MS2 concentrations as low as 10 ng/mL. 相似文献
39.
Darian E Hnizdo V Fedorowicz A Singh H Demchuk E 《Journal of computational chemistry》2005,26(7):651-660
A method of statistical estimation is applied to the problem of evaluating the absolute entropy of internal rotation in a molecule with two torsional degrees of freedom. The configurational part of the entropy is obtained as that of the joint probability density of an arbitrary form represented by a two-dimensional Fourier series, the coefficients of which are statistically estimated using a sample of the torsional angles of the molecule obtained by a stochastic simulation. The internal rotors in the molecule are assumed to be attached to a common frame, and their reduced moments of inertia are initially calculated as functions of the two torsional angles, but averaged over all the remaining internal degrees of freedom using the stochastic-simulation sample of the atomic configurations of the molecule. The torsional-angle dependence of the reduced moments of inertia can be also averaged out, and the absolute internal-rotation entropy of the molecule is obtained in a good approximation as the sum of the configurational entropy and a kinetic contribution fully determined by the averaged reduced moments of inertia. The method is illustrated using Monte Carlo simulations of isomers of stilbene and halogenated derivatives of propane. The two torsional angles in cis-stilbene are found to be much more strongly correlated than those in trans-stilbene, while the degree of the angular correlation in propane increases strongly on substitution of hydrogen atoms with chlorine. 相似文献
40.
Gudiksen KL Gitlin I Yang J Urbach AR Moustakas DT Whitesides GM 《Journal of the American Chemical Society》2005,127(13):4707-4714
This study compares the folding of two polypeptides--bovine carbonic anhydrase (BCA) and peracetylated BCA (BCA-Ac(18))--having the same sequence of amino acids but differing by 18 formal units of charge, from a solution containing denaturing concentrations of sodium dodecyl sulfate (SDS). Acetylation of BCA with acetic anhydride converts all 18 lysine-epsilon-NH(3)(+) groups to lysine-epsilon-NHCOCH(3) groups and generates BCA-Ac(18). Both BCA and BCA-Ac(18) are catalytically active, and circular dichroism spectroscopy (CD) suggests that they have similar secondary and tertiary structures. SDS at concentrations above approximately 10 mM denatured both proteins. When the SDS was removed by dialysis, both proteins were regenerated in native form. This study suggests that large differences in the net charge of the polypeptide have no significant influence on the structure, the ability to refold, or the rate of refolding of this protein from solutions containing SDS. This study reinforces the idea that charged residues on the surface of BCA do not guide protein folding and raises the broader question of why proteins have charged residues on their surface, outside of the region of the active site. 相似文献