Nature of the catalytically labile oxygen at the active site of xanthine oxidase

In this paper we report the results of molybdenum K-edge X-ray absorption studies performed on the oxidized active site of xanthine oxidase at pH 6 and 10. These results indicate that the active site possesses one terminal oxygen ligand (Mo=O), two thiolate ligands (Mo-S), one terminal sulfido ligand (Mo=S), and one Mo-OH moiety. EXAFS analysis demonstrates that the Mo-OH bond shortens from 1.97 A at pH 6 to 1.75 A at pH 10, which is consistent with the generation of a Mo-O- moiety. This study provides convincing structural evidence that the catalytic oxygen donor at the oxidized active site of xanthine oxidase is Mo-OH rather than the Mo-OH2 ligation previously suggested by X-ray crystallography. These results support a mechanism initiated by base-assisted nucleophilic attack of the substrate by Mo-OH.     

Temperature dependence of a first order diffusion-retarded chemical reaction in catalytically active membranes

A method is described to determine the activation energy of the intrinsic reaction rate constant of a diffusion-retarded first order chemical reaction in a catalytically active membrane from measurements of the temperature dependence of the apparent reaction rate constant. At the same time, the activation energy of the diffusion coefficient of substrate within the membrane phase is obtained. The method is tested by studying the hydrolysis of sucrose catalyzed by H⁺ counterions of a strong-acid cation exchange membrane.     

A dendritic active site: catalysis of the Henry reaction

[reaction: see text] Dendrimers containing an encapsulated tertiary amine were prepared by coupling tris(2-aminoethyl)amine with dendritic branches derived from L-lysine. These dendrimers were used as catalysts in the Henry (nitroaldol) reaction between 4-nitrobenzaldehyde and nitroethane, and their catalytic performance was compared with that of triethylamine. Attachment of the dendritic shell alters the rate of reaction and influences the syn:anti ratio of products. It is proposed that the dendritic shell generates an encapsulated catalytically active site, mimicking the behavior of a protein superstructure.     

Ab initio structure of the active site of phosphotriesterase

This research exploits two recent developments to obtain a fundamental understanding of the metalloenzyme active site using the bimetallic enzyme phosphotriesterase as an example of this class. First is the theoretical prediction that the structure and spectroscopy of a native metalloenzyme active site is qualitatively determined by the supermolecule complex of the metal(s) and the first shell of ligands with proper charge states including waters directly bonded to ionic ligands. The second is the development of an effective potential for representing the molecular environment interacting with an all-electron active site in the quantum Hamiltonian. The GAMESS suite of electronic structure codes has implemented this new methodology, effective fragment potentials (EFP), to make theoretical calculations on structure, spectroscopy, and reactivity tractable for systems involving hundreds of atoms. Since there are transition metal cations at the active site of these enzymes, the all-electron part of the complex is calculated with relativistic compact effective potentials (CEP) and their concomitant basis sets. A realistic representation of the active site with its protein environment can be obtained using a combination of the CEP and EFP. This presentation will determine the inherent electronic and structural characteristics of phosphotriesterase using ab initio quantum mechanical methods. A single X-ray structure for the Zn-Zn enzyme is leveraged to obtain the structure of the Cd-Cd enzyme and to examine the consequences of protonating the active site.     

Structural features of catalytically active oligoorganometallosiloxanes

Copper- and (copper, aluminum)-containing organosiloxanes were studied by spectroscopic methods. It was found that in organometallosiloxanes (OMS) with an increased content of copper (Si/Cu=1 ∶ 1) Cu atoms are rather uniformly distributed in the siloxane matrix. All compounds under study are complexes characterized byd-d-transitions in copper ions with a constant coordination number of the metal atom. The intensity of thed-d-transition band increases as the copper content increases. ESR studies demonstrated that in the compounds under consideration, a change from mononuclear paramegnetic centers to clusters, in which copper ions are linked by strong spin-exchange interactions, occurs as the copper content increases. The catalytic activity of the above-mentioned compounds in isomerization reactions of 3,4-dichlorobutene-1 was studied. It was found that copper atoms serve as catalytic centers. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1946–1949, October, 1998.     

Fe/N/C氧还原催化剂的热稳定性及活性位结构

研制高活性的Fe/N/C氧还原催化剂对于降低燃料电池成本、实现商业化应用有重要意义. 为了实现Fe/N/C催化剂的理性设计,需要深入研究其活性位结构. 本文我们发展一种研究活性位结构的新策略,即以预先合成好的聚间苯二胺基Fe/N/C催化剂(PmPDA-FeNx/C)为起始物,对其在1000~1500 ^oC高温下再次进行热处理并使其失活,通过关联催化剂热处理前后的结构变化与氧还原催化性能来揭示活性位结构. 实验结果表明,随着热处理温度升高,活性中心结构被破坏,铁原子析出团聚并形成纳米颗粒,氮元素挥发损失,导致催化剂失活. XPS分析显示,低结合能含氮物种的含量与催化剂的ORR活性呈良好的正相关性,表明活性中心很可能是由吡啶N和Fe-N物种构成的.     

The structure of catalytically active complexes in copper chloride—dialkyl sulfide—chloroolefin systems

The formation of mixed Cu^I and Cu^II polynuclear complexes with dialkyl sulfide, which are active in the catalytic isomerization of chloroolefins, has been investigated by UV-Vis and ESR spectroscopy. The role of these complexes in catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1395–1401, June, 1996.     

Cobalt spectroscopy and the structure of the active site of carbonic anhydrase

Theoretical models of divalent cobalt bound to the active site of the enzyme, carbonic anhydrase, are constructed to study the effect of the first-shell geometry and coordination number on the experimentally observed visible spectra. Favorable comparisons of the ab initio calculations of the hexa-aquo complex of Co(II) with experimental results provides a test of the method. The d–d spectra variation with pH in the enzyme is found to be determined by the first-shell complex geometry as obtained from energy optimization. The low pH complex is predicted to be predominantly five-coordinate with two waters in the first-shell, whereas the high pH complex is predominantly four-coordinate. Equilibria between the four- and five-coordinate structures at low pH is not indicated by the calculation.     

Real sol-gel synthesis of catalytically active aluminium fluoride

Abstract Amorphous AlF₃ prepared via an anhydrous sol-gel synthesis route exhibits high surface area and Lewis acidity far beyond those known for crystalline AlF₃ phases. Its catalytic properties are comparable to those of SbF₅. Basis of its unusual properties is a sol-gel fluorination with anhydrous HF in organic solvents yielding first a wet Al-F-sol-gel, which can be dried and eventually post-fluorinated. All parts of the synthesis route were thoroughly investigated. The results of these investigations together with detailed analysis of the Al-F-materials obtained are reported and discussed.     

Formation of catalytically active layers on the surface of polymetallic alloys

A new method for the synthesis of catalysts on polymetallic supports via the formation of intermetallic (aluminide) layer on the support surface followed by leaching and stabilization of the layer has been proposed. The intermetallic layer structure and distribution of elements in the layer were studied by scanning electron microscope considering a nickel chromium stainless-steel grid as an example. The morphology and elemental composition of the active phase on the catalyst surface were studied. The complex structure of this phase was found to consist of two types of entities with different composition located on the continuous highly porous substrate. The catalyst sample was tested in deep oxidation of CO and propane and demonstrated high activity. The developed method can be used to obtain new high-performance polymetallic catalysts.     

Refining the active site structure of iron-iron hydrogenase using computational infrared spectroscopy

Iron-iron hydrogenases ([FeFe]H2ases) are exceptional natural catalysts for the reduction of protons to dihydrogen. Future biotechnological applications based on these enzymes require a precise understanding of their structures and properties. Although the [FeFe]H2ases have been characterized by single-crystal X-ray crystallography and a range of spectroscopic techniques, ambiguities remain regarding the details of the molecular structures of the spectroscopically observed forms. We use density functional theory (DFT) computations on small-molecule computational models of the [FeFe]H2ase active site to address this problem. Specifically, a series of structural candidates are geometry optimized and their infrared (IR) spectra are simulated using the computed C-O and C-N stretching frequencies and infrared intensities. Structural assignments are made by comparing these spectra to the experimentally determined IR spectra for each form. The H red form is assigned as a mixture of an Fe(I)Fe(I) form with an open site on the distal iron center and either a Fe(I)Fe(I) form in which the distal cyanide has been protonated or a Fe(II)Fe(II) form with a bridging hydride ligand. The Hox form is assigned as a valence-localized Fe(I)Fe(II) redox level with an open site at the distal iron. The Hox(air)(ox) form is assigned as an Fe(II)Fe(II) redox level with OH(-) or OOH(-) bound to the distal iron center that may or may not have an oxygen atom bound to one of the sulfur atoms of the dithiolate linker. Comparisons of the computed IR spectra of the (12)CO and (13)CO inhibited form with the experimental IR spectra show that exogenous CO binds terminally to the distal iron center.     

Studies on catalytically active surface compounds, VIII. On the reaction of VCl4 with aerosil

The preparation and hydrolysis of silica supported vanadium catalysts have been investigated using VCl₄ as a paramagnetic probe. Chemical analysis shows the possibility of the VCl₄ molecule to react one, two, or three hydroxy groups of the surface. The type of reaction is influenced by the temperature of pretreatment of aerosil (TPA). ESR measurements show distortions of the tetrahedral coordination of the (SiO)_nVCl_4–n surface complex, which is strongest for the threefold attachment (n=3) of VCl₄ to the surface. Hydrolysis is accompanied by an increase of the coordination number and leads to highly mobile vanadium species.

---

, VCl₄ . , VCl₄ , . . (SiO)_nVCl_4–n, VCl₄ (n=3). .

     

Highly selective synthesis of catalytically active monodisperse rhodium nanocubes

Monodisperse sub-10 nm Rh nanocubes were synthesized with high selectivity (>85%) by a seedless polyol method. The {100} faces of the Rh NCs were effectively stabilized by chemically adsorbed Br- ions from trimethyl(tetradecyl)ammonium bromide (TTAB). This simple one-step polyol route can be readily applied to the preparation of Pt and Pd nanocubes. Moreover, the organic molecules of PVP and TTAB that encapsulated the Rh nanocubes did not prevent catalytic activity for pyrrole hydrogenation and CO oxidation.     

Shape-selective formation and characterization of catalytically active iridium nanoparticles

Iridium (Ir) nanoparticles (NPs) of variable shapes have been synthesized via the reduction of Ir(III) ions in CTAB micellar media containing alkaline 2,7-DHN under 4h of UV-irradiation. The one-step process generates different shapes, such as nano-spheres, nano-chains, nano-flakes, and nano-needles. The synthesized Ir NPs are stable for more than a month in ambient conditions. The particles' morphology can be tuned by simply changing the surfactant-to-metal ion molar ratios and altering other reaction parameters. The mechanisms of the Ir particle formation and effects of different reaction parameters were studied in detail. The Ir nano-needles serve as a good catalyst for the reduction of organic dye molecules in presence of NaBH(4). The catalysis rate was compared by considering the electron transfer process during the reduction of the dye molecules. The present method would lead to a quick process for the synthesis of other mono-metallic, composite, and semiconductor particles with variable shapes. The Ir NPs will find promising applications in different types of organic and inorganic catalysis reactions, nanoelectronics, and biomedical applications.     

Insights into the reaction mechanism of soluble epoxide hydrolase from theoretical active site mutants

Density functional theory calculations of active site mutants are used to gain insights into the reaction mechanism of the soluble epoxide hydrolases (sEHs). The quantum chemical model is based on the X-ray crystal structure of the human soluble epoxide hydrolase. The role of two conserved active site tyrosines is explored through in silico single and double mutations to phenylalanine. Full potential energy curves for hydrolysis of (1S,2S)-beta-methylstyrene oxide are presented. The results indicate that the two active site tyrosines act in concert to lower the activation barrier for the alkylation step. For the wild-type and three different tyrosine mutant models, the regioselectivity of epoxide opening is compared for the substrates (1S,2S)-beta-methylstyrene oxide and (S)-styrene oxide. An additional part of our study focuses on the importance of the catalytic histidine for the alkylation half-reaction. Different models are presented to explore the protonation state of the catalytic histidine in the alkylation step and to evaluate the possibility of an interaction between the nucleophilic aspartate and the catalytic histidine.     

Cationic and neutral diphenyldiazomethanerhodium(I) complexes as catalytically active species in the C-C coupling reaction of olefins and diphenyldiazomethane

Cationic rhodium(I) complexes cis-[Rh(acetone)2(L)(L')]+ (2: L = L'=C8H14; 3: L=C8H14; L'=PiPr3; 4: L=L'=PiPr3), prepared from [RhCl(C8H14)2]2] and isolated as PF6 salts, catalyze the C-C coupling reaction of diphenyldiazomethane with ethene, propene, and styrene. In most cases, a mixture of isomeric olefins and cyclopropanes were obtained which are formally built up by one equivalent of RCH=CH2 (R = H, Me, Ph) and one equivalent of CPh2. The efficiency and selectivity of the catalyst depends significantly on the coordination sphere around the rhodium(I) center. Treatment of 4 with Ph2CN2 in the molar ratio of 1:1 and 1:2 gave the complexes trans-[Rh(PiPr3)2(acetone)(eta1-N2CPh2)]PF6 (8) and trans-[Rh(PiPr3)2(eta1-N2CPh2)2]PF6 (9), of which 8 was characterized by X-ray crystallography. Since 8 and 9 not only react with ethene but also catalyze the reaction of C2H4 and free Ph2CN2, they can be regarded as intermediates (possibly resting states) in the C-C coupling process. The lability of 8 and 9 is illustrated by the reactions with pyridine and NaX (X=Cl, Br, I, N3) which afford the mono(diphenyldiazomethane)rhodium(I) compounds trans-[Rh(PiPr3)2(py)(eta1-N2CPh2)]PF6 (10) and trans-[RhX(eta1-N2CPh2)(PiPr3)2] (11-14), respectively. The catalytic activity of the neutral complexes 11 - 14 is somewhat less than that of the cationic species 8, 9 and decreases in the order Cl > Br> I > N3.     

Preparation and characterization of the catalytically active forms of rare earth oxides

Catalytically active forms of the rare earth oxides Ln₂O₃(Ln = La, Sm, Eu, Dy, Ho, and Yb), Pr₆O₁₁, and CeO₂ have been prepared. The dehydration behavior of the precursors of these oxides has been studied by XRD, TG, DTA, TPD-MS, IR, and adsorption-desorption isotherms of N₂ at −196°C. Thermal analyses show that in most cases the dehydration takes place through an intermediate oxyhydroxide LnO (OH) that decomposes to the respective oxide at around 400°C. Strongly held difficult to remove carbonates were present on the surface, e.g., for Yb₂O₃ it was necessary raise the outgassing temperature to 700°C to achieve carbonate decomposition. At temperatures around 500°C these oxides are well crystallized and have moderate specific surface areas (10–40 m²g⁻¹). As a representative of the series, a detailed study of the dehydration and surface decarbonation of Yb₂O₃ was carried out by means of TPD-MS and infrared spectroscopy.