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41.
Rivera M Caignan GA Astashkin AV Raitsimring AM Shokhireva TKh Walker FA 《Journal of the American Chemical Society》2002,124(21):6077-6089
The (13)C pulsed ENDOR and NMR study of [meso-(13)C-TPPFe(OCH(3))(OO(t)Bu)](-) performed in this work shows that although the unpaired electron in low-spin ferrihemes containing a ROO(-) ligand resides in a d(pi) orbital at 8 K, the d(xy) electron configuration is favored at physiological temperatures. The variable temperature NMR spectra indicate a dynamic situation in which a heme with a d(pi) electron configuration and planar porphyrinate ring is in equilibrium with a d(xy) electron configuration that has a ruffled porphyrin ring. Because of the similarity in the EPR spectra of the hydroperoxide complexes of heme oxygenase, cytochrome P450, and the model heme complex reported herein, it is possible that these two electron configurations and ring conformations may also exist in equilibrium in the enzymatic systems. The ruffled porphyrinate ring would aid the attack of the terminal oxygen of the hydroperoxide intermediate of heme oxygenase (HO) on the meso-carbon, and the large spin density at the meso-carbons of a d(xy) electron configuration heme suggests the possibility of a radical mechanism for HO. The dynamic equilibrium between the ruffled (d(xy)) and planar (d(pi)) conformers observed in the model complexes also suggests that a flexible heme binding cavity may be an important structural motif for heme oxygenase activity. 相似文献
42.
Mohr F Binfield SA Fettinger JC Vedernikov AN 《The Journal of organic chemistry》2005,70(12):4833-4839
Four-coordinate dichlorocopper(II) complexes derived from di(2-pyridyl)methanes or pyridine itself exhibit high catalytic activity in aziridination of regular olefins with PhINTs in weakly coordinating chloroform in the presence of 1-2 equiv of NaBArF4 (BArF4- = tetra[3,5-di(trifluoromethyl)phenyl]borate). High yields of aziridines exceeding 90% can be obtained with a 1:1 olefin/PhINTs ratio and 1-5 mol % catalyst loading for such reactive olefins as styrene, tri- and tetramethylethylene. For cis-cyclooctene, indene, methyl acrylate, methyl methacrylate, vinyl methyl ketone, tert-butylethylene, and neopentylethylene, as well as for 1-hexene and cyclopentene, yields of corresponding aziridines vary from 44% to 83%. The catalytic activity and efficiency of the reported copper complexes decrease moderately in the absence of NaBArF4. 相似文献
43.
[reaction: see text] The use of a pyridinophane, a macrocycle composed of three pyridines linked, via all ortho positions through CH(2) or CH(2)CH(2) groups, bound to copper, gives good performance (rate and yield) catalyzing the conversion of substituted aliphatic olefins and PhINTs to aziridines. Advantages also derive from using CH(2)Cl(2) solvent and the weakly coordinating anions BAr(4)(-) (Ar = C(6)H(5) or 3,5-C(6)H(3)(CF(3))(2)). Reactions are complete in minutes at 20 degrees C, and yields are almost quantitative for olefins not bearing secondary allylic CH bonds; however, cis-cyclooctene gives only the aziridine despite the allylic hydrogens. 相似文献
44.
The preparation and crystal structure determination of the iron(III) compound of formula [(NH(4))(2)[Fe(2)O(ox)(2)Cl(2)].2H(2)O](n) (1) (ox = oxalate dianion) are reported here. Complex 1 crystallizes in the orthorhombic system, space group Fdd2, with a = 14.956(7) A, b = 23.671(9) A, c = 9.026(4) A, and Z = 8. The structure of complex 1 consists of the chiral anionic three-dimensional network [Fe(2)O(ox)(2)Cl(2)](2-) where the iron(III) ions are connected by single oxo and bisbidentate oxalato groups. The metal-metal separations through these bridging ligands are 3.384(2) and 5.496(2) A, respectively. Ammonium cations and crystallization water molecules are located in the helical pseudohexagonal tunnels defined by iron atoms. The longest iron-iron distance in the pseudohexagonal tunnel is 15.778(2) A whereas the shortest one is 8.734(2) A. The iron atoms are hexacoordinated: a terminal chloro ligand and five oxygen atoms, that of the oxo group and four from two cis coordinated oxalate ligands, build a distorted octahedral environment around the metal atom. The Fe-O(oxo) bond distance [1.825(2) A] is significantly shorter than the Fe(III)-O(ox) [average value 2.103(4) A] and Fe(III)-Cl bond distances [2.314(2) A]. Magnetic susceptibility measurements of 1 in the temperature range 2.0-300 K reveal the occurrence of a susceptibility maximum at 195 K and a transition toward a magnetically ordered state in the lower temperature region with T(c) = 40 K. The strong antiferromagnetic coupling through the oxo bridge (J = -46.4 cm(-1), the Hamiltonian being H = -JS(A).S(B)) accounts for the susceptibility maximum whereas a weak spin canting of approximately 0.3 degrees due to the antisymmetric magnetic exchange within the chiral three-dimensional network is responsible for the magnetic ordering. The values of coercive field (H(c)) and remnant magnetization (M(r)) obtained from the hysteresis loop of 1 at 5 K are 4000 G and 0.016 micro(B). 相似文献
45.
Novel N-acylated-(S)-cysteine derivative-N-(R)-mandelyl-(S)-cysteine (R-NMC), containing additional chiral center, aromatic and polar alpha-substituents in contrast to the traditionally used enantiomerically pure thiols, has been demonstrated to be an efficient SH-reagent for enantiomeric HPLC analysis of primary nonfunctionalized amines and amino alcohols after precolumn derivatization with o-phthalaldehyde. The R-NMC-derived isoindoles as well as adducts formed using traditional SH-reagents had a characteristic absorption maximum at 340 nm with a molar absorbance 6000 M(-1) cm(-1), were stable during the HPLC-analysis and highly fluorescent allowing to detect 1 fmol of amino compound. Using diastereomeric R-NMC all tested amino alcohols were resolved effectively as well as nonfunctionalized amines, some of which were not resolved by a direct method on a chiral phase. Applying traditional enantiomeric N-acetyl-(S)-cysteine (NAC) only some isoindoles formed by aliphatic amino alcohols have been separated satisfactorily. The enhanced selectivity for R-NMC-derived isomers has been achieved, obviously, due to the involvement of the substituents at an extra chiral center into additional intramolecular interactions. 相似文献
46.
Nae FA Saito N Hozumi A Takai O 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1398-1402
Using a molecular fluorine laser at 157 nm wavelength, submicron patterning of organosilane self-assembled monolayers (SAMs) is demonstrated utilizing mask-contact photolithography. An organosilane, namely, octadecyltrimethoxysilane [ODS, CH(3)(CH(2))(17)Si(OCH(3))(3)], SAM is chemisorbed onto Si substrates covered with a 2 nm thick oxide layer and subsequently patterned using the laser. The optical path of the laser beam and the photomask-sample space are evacuated and then backfilled and purged with nitrogen during laser firing. The resulting pattern is investigated using various measurement techniques. The scanning probe microscopy images show that patterns are transferred to the SAM-covered Si substrates and that 500 nm features are successfully photoprinted in this way. 相似文献
47.
Oleg A. Raitman Andrei B. Kharitonov Maya Zayats Eugenii Katz Itamar Willner 《Analytica chimica acta》2004,504(1):101-111
Crosslinked films consisting of the acrylamide-acrylamidophenylboronic acid copolymer that are imprinted with recognition sites for β-nicotinamide adenine dinucleotide (NAD+), β-nicotinamide adenine dinucleotide phosphate NADP+, and their reduced forms (NAD(P)H), are assembled on Au-coated glass supports. The binding of the oxidized cofactors NAD+ or NADP+ or the reduced cofactors NADH or NADPH to the respective imprinted sites results in the swelling of the polymer films through the uptake of water. Surface plasmon resonance (SPR) spectroscopy is employed to follow the binding of the different cofactors to the respective imprinted sites. The imprinted recognition sites reveal selectivity towards the association of the imprinted cofactors. The method enables the analysis of the NAD(P)+ and NAD(P)H cofactors in the concentration range of 1×10−6 to 1×10−3 M. The cofactor-imprinted films associated with the Au-coated glass supports act as active interfaces for the characterization of biocatalyzed transformations that involve the cofactor-dependent enzymes. This is exemplified with the characterization of the biocatalyzed oxidation of lactate to pyruvate in the presence of NAD+ and lactate dehydrogenase using the NADH-imprinted polymer film. 相似文献
48.
Using idealized models for parallel and antiparallel beta sheets, we calculate the linear and two-dimensional infrared spectra of the amide I vibration as a function of size and secondary structure. The model assumes transition-dipole coupling between the amide I oscillators in the sheet and accounts for the anharmonic nature of these oscillators. Using analytical and numerical methods, we show that the nature of the one-quantum vibrational eigenstates, which govern the linear spectrum, is, to a large extent, determined by the symmetry of the system and the relative magnitude of interstrand interactions. We also find that the eigenstates, in particular their trends with system size, depend sensitively on the secondary structure of the sheet. While in practice these differences may be difficult to distinguish in congested linear spectra, we demonstrate that they give rise to promising markers for secondary structure in the two-dimensional spectra. In particular, distinct differences occur between the spectra of parallel and antiparallel beta sheets and between beta hairpins and extended beta sheets. 相似文献
49.
Summary. Parameters of the formalism [1–6] describing spin crossover in the solid state have been defined via molecular potentials in model systems of neutral and ionic complexes. In the first instance Lennard-Jones and electric dipole–dipole potentials have been used whereas in ionic systems Lennard-Jones and electric point-charge potentials have been used. Electric dipole–dipole interaction of neutral complexes brings about
a positive excess energy controlled by the difference of electric dipole moments of HS and LS molecules. Differences of the
order of Δμ = 1–2 D cause an abrupt spin crossover in systems with T1/2 = 100–150 K. Magnetic coupling contributes both to the excess energy and excess entropy, however the overall effect is equivalent
to a modest positive excess energy. Ionic systems in the absence of specific interactions are characterised by very small
excess energies corresponding to practically linear van’t Hoff plots. Detectable positive and negative excess energies in these systems may arise from interactions of ligands belonging
to neighbouring complexes. The HOMO–LUMO overlap in HS–LS pairs can bring about a nontrivial variation of the shape of transition
curves. Examples of regression analysis of experimental transition curves in terms of molecular potentials are given. 相似文献
50.
Joy Chakraborty Brajagopal Samanta Andrei S. Batsanov Joan Ribas M. Salah El Fallah Samiran Mitra 《Structural chemistry》2006,17(4):401-407
A ligand–metal–ligand type co-ordination polymer [Ni (C6H12N4)(NCS)2(H2O)2]
n
has been synthesised under controlled hydrothermal conditions. Here 1,3,5,7-tetraazatricyclo[3.3.1]decane [or hexamethylenetetramine (hmt)] has been used as a μ-(N,N′) bidentate spacer molecule. The prepared polymeric complex has been characterised by elemental and spectral analyses. The structure has been confirmed by a single crystal X-ray diffraction study. Magneto-structural correlation has been drawn from cryomagnetic susceptibility measurements (2–300 K) which unequivocally reflects very weak magnetic spin interactions among the long distant octahedral Ni(II) metal centres mediated by hmt and weak hydrogen bonding interactions between the adjacent zigzag one-dimensional polymeric chains carrying into a two-dimensional infinite polymeric framework. 相似文献