担载型铱催化剂上CO吸附量热和红外光谱研究

分别对Al2O3和SiO2担载的不同含量铱(Ir)催化剂进行了H2程序升温还原、CO微量吸附量热和红外研究.结果表明,还原后,Ir/Al2O3上存在金属态Ir0和氧化态Irδ 两种物种,CO在催化剂表面主要以线式和孪生吸附态存在,测量的CO吸附热为两种吸附形式的平均吸附热.提高还原温度和Ir担载量,Ir/Al2O3表面CO线式吸附物种的比例增加,从而导致CO吸附热值的升高.而在Ir/SiO2上Ir物种主要为金属态Ir0,CO吸附都以线式吸附为主,在所考察的条件下CO吸附热随Ir担载量和还原温度的变化不明显。     

The anharmonic effect study of coupled Morse oscillators for the unimolecular reaction

The importance of anharmonic effect in dissociation of molecular systems especially clusters has been noted. In this paper, we shall study the effect of coupled anharmonic oscillator of the standard bilinear form (SBF) Morse oscillator (MO) potential on unimolecular reaction. We shall use the systematic theoretical approach, YL method, proposed by Yao and Lin (YAO L, et. al. J Phys Chem A, 2007, 111(29): 6722-6729), which can evaluate anharmonic effects on the rate constants based on the transition state theory. In treating the anharmonic effect with the Morse oscillator potential on unimolecular reactions under collision-free conditions by using the RRKM (Rice-Ramsperger-Kassel-Marcus) theory, the in-verse Laplace transformation of the partition functions was used to obtain the total amount of state and density of state by using the first-order and the second-order approximations of the saddle-point method. To demonstrate the anharmonic effect of the SBF Morse model, we choose some model systems and a real reaction as examples.     

Syntheses and structures of half-sandwich iridium(III) and rhodium(III) complexes with organochalcogen (S, Se) ligands bearing N-methylimidazole and their use as catalysts for norbornene polymerization

The organochalcogen ligands derived from 3-methyl-imidazole-2-thione/selone groups, Mbit, Mbis, Ebit and Ebis [Mbit = 1,1'-methylenebis(3-methyl-imidazole-2-thione); Mbis = 1,1'-methylenebis(3-methyl-imidazole-2-selone), Ebit = 1,1'-(1,2-ethanediyl)bis(3-methyl-imidazole-2-thione), Ebis = 1,1'-(1,2-ethanediyl)bis(3-methyl-imidazole-2-selone)] have been synthesized and characterized. Reactions of [Cp*Ir(micro-Cl)Cl]2 and [Cp*Rh(micro-Cl)Cl]2 (Cp* = eta5-pentamethylcyclopentadienyl) with Mbit, Mbis, Ebit and Ebis result in the formation of the complexes [Cp*Ir(Mbit)Cl]Cl 1a x Cl), [Cp*Ir(Mbis)Cl]Cl (3a x Cl), [Cp*Ir(Ebit)Cl]Cl (1b x Cl), [Cp*Ir(Ebis)Cl]Cl (2a x Cl), [Cp*Rh(Mbit)Cl]Cl (2b x Cl), Cp*Rh(Mbis)Cl][Cp*RhCl(3)] (3b x[Cp*RhCl(3)]), [Cp*Rh(Ebit)Cl]Cl (4a x Cl) and [Cp*Rh(Ebis)Cl]Cl (4b x Cl), respectively. All compounds have been characterized by elemental analysis, NMR and IR spectra. The molecular structures of 1b, 2b, 3a, 3b and 4a have been determined by X-ray crystallography. After activation with methylaluminoxane (MAO), the iridium complexes exhibit moderate activities for the vinyl polymerization of norbornene.     

DNA tile based self-assembly: building complex nanoarchitectures.

DNA tile based self-assembly provides an attractive route to create nanoarchitectures of programmable patterns. It also offers excellent scaffolds for directed self-assembly of nanometer-scale materials, ranging from nanoparticles to proteins, with potential applications in constructing nanoelectronic/nanophotonic devices and protein/ligand nanoarrays. This Review first summarizes the currently available DNA tile toolboxes and further emphasizes recent developments toward self-assembling DNA nanostructures with increasing complexity. Exciting progress using DNA tiles for directed self-assembly of other nanometer scale components is also discussed.     

A DFT study on the mechanism of hydrosilylation of unsaturated compounds with neutral hydrido(hydrosilylene)tungsten complex

Recently, Tobita et al. reported stoichiometric hydrosilylation reactions of acetone and acetonitrile with neutral hydrido(hydrosilylene)tungsten complexes Cp'(CO)2(H)W=Si(H)[C(SiMe(3))(3)] (Cp' = Cp*, C(5)Me(4)Et). The mechanisms of the hydrosilylation reactions of unsaturated compounds (ketone and nitrile) with the tungsten complexes have been investigated with the B(3)LYP density functional theory method. Four possible reaction mechanisms were studied. The results of the calculations indicate that the hydrosilylation of acetone proceeds via a metal hydride migration mechanism proposed by Tobita et al., while the hydrosilylation of nitrile occurs through a silyl migration mechanism, analogous to the modified Chalk-Harrod mechanism. The [2(sigma)+2(pi)] additions of various CX (CX = C=O or CN) multiple bonds with the Si-H bonds in the neutral complexes have very high barriers although similar additions were found feasible in other related cationic complexes. All the hydrosilylation reactions studied here give stable tungsten-silylene or tungsten-silyl products, which are not easily converted into the starting hydrido(hydrosilylene)tungsten complexes when reacting with a hydrosilane substrate molecule. Therefore, we predict that hydrosilylation of acetonitrile and acetone catalyzed by these tungsten complexes is difficult to achieve.     

Evaluation of various derivatization approaches for gas chromatography-mass spectrometry analysis of buprenorphine and norbuprenorphine

Various chemical derivatization approaches have been adapted for the analysis of buprenorphine and its major metabolite (norbuprenorphine) by GC-MS based methodologies. These approaches included alkylation, acylation, and silylation resulting in the formation of methyl, acetyl, trifluoroacetyl, pentafluoropropionyl, heptafluorobutyryl, and trimethylsilyl derivatives. This study conducted a comprehensive evaluation on the merits of these approaches based on the following criteria: reaction yields and ionization efficiency of the derivatization products; chromatographic characteristics; and cross-contributions to the intensities of ions designating the analytes and the internal standards. Under acidic derivatization conditions, the analytes could form three artifact products. Overall, derivatization by acetyl anhydride resulted in best performance characteristics.     

Syntheses of ladder-type oligonaphthalene derivatives and their photophysical and electrochemical properties

Ladder-type oligophenylene derivatives are important compounds for light-emitting devices. However, the closely related ladder-type oligonaphthalene derivatives have received little attention due to the lack of synthetic accessibility. We hereby report the syntheses of these novel conjugated systems by means of an intramolecular cationic cyclization protocol. Utilizing a one-pot-multiple-component reaction, the acyclic precursors to these ladder-type oligomers up to pentamer can be synthesized from small fragments in just two or three steps. Photophysical and electrochemical studies revealed that the electron delocalization in these compounds is considerably enhanced relative to that found in the regular unplanarized oligonaphthalene derivatives. However, such an effect is much weaker than that found in fully planar rylene derivatives.     

Dilational viscoelasticity of PEO-PPO-PEO triblock copolymer films at the air-water interface in the range of high surface pressures

The dynamic dilational elasticity of adsorbed and spread films of PEO-PPO-PEO triblock copolymers at the air-water interface was measured as a function of surface pressure, surface age, and frequency. At low surface pressures (<10 mN/m), the surface viscoelasticity is identical to that of PEO homopolymer films. The results at higher surface pressures can be explained by the desorption of PPO segments from the interface and then mixing with PEO segments in water. Unlike some recent results, the spread and adsorbed films are not identical. Spread films exhibit a maximum real part of the dynamic surface elasticity of about 20 mN/m and probably begin to dissolve in water at surface pressures above 19 mN/m. However, the surface elasticity of the adsorbed films decreases beyond the maximum, indicating the formation of a loose surface structure.     

Genome mining in Streptomyces coelicolor: molecular cloning and characterization of a new sesquiterpene synthase

The terpene synthase encoded by the SCO5222 (SC7E4.19) gene of Streptomyces coelicolor was cloned by PCR and expressed in Escherichia coli as an N-terminal-His6-tag protein. Incubation of the recombinant protein, SCO5222p, with farnesyl diphosphate (1, FPP) in the presence of Mg(II) gave a new sesquiterpene, (+)-epi-isozizaene (2), whose structure and stereochemistry were determined by a combination of 1H, 13C, COSY, HMQC, HMBC, and NOESY NMR. The steady-state kinetic parameters were kcat 0.049 +/- 0.001 s-1 and a Km (FPP) of 147 +/- 14 nM. Individual incubations of recombinant epi-isozizaene synthase with [1,1-2H2]FPP (1a), (1R)-[1-2H]-FPP (1b), and (1S)-[1-2H]-FPP (1c) and NMR analysis of the resulting deuterated epi-isozizaenes supported an isomerization-cyclization-rearrangement mechanism involving the intermediacy of (3R)-nerolidyl diphosphate (3).