Syngas conversion beyond chemical equilibrium by in situ bimolecular reaction

An in situ bimolecular reaction, in which syngas is fed with toluene as a secondary reactant (hereafter Tol in situ methylation), was studied over bifunctional catalysts comprised of methanol synthesis catalyst and H-ZSM-5 in a fixed-bed down-flow reactor at 460 psig. When physically mixed with H-ZSM-5 to form bifunctional catalysts, CrZ_HZ (Cr₂O₃/ZnO + HZSM-5) catalyst showed much higher activity than CZA_HZ (CuO/ZnO/Al₂O₃ + H-ZSM-5) in the Tol in situ methylation, while CrZ catalyst exhibited substantially lower activity than CZA in methanol synthesis. CO conversion to methanol in the Tol in situ methylation was estimated by Bz in situ methylation. The CO conversion to methanol was calculated to be in the range of 11–27 %, while that in methanol synthesis over CrZ was about 5 % at most due to chemical equilibrium limitation. By employing a silicalite-coated H-ZSM-5 (Sil/HZ) in bifunctional catalyst, xylene selectivity and para-xylene yield were much improved in the Tol in situ methylation.     

Doping‐Induced Absorption Bands in P3HT: Polarons and Bipolarons

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p‐type doping (oxidation) of the organic semiconductor poly(3‐ hexylthiophene‐2,5‐diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near‐IR range as well as in the mid‐IR range. In the low‐oxidation regime, two absorption bands related to sub‐gap transitions appear, one in the UV/Vis range and another one in the mid‐IR range. The UV/Vis absorption gradually decreases upon further doping while the mid‐IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p‐type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.     

Chemoenzymatic Synthesis of Glycopeptides with PglB, a Bacterial Oligosaccharyl Transferase from Campylobacter jejuni

The gram-negative bacterium Campylobacter jejuni has a general N-linked glycosylation pathway encoded by the pgl gene cluster. One of the proteins in this cluster, PglB, is thought to be the oligosaccharyl transferase due to its significant homology to Stt3p, a subunit of the yeast oligosaccharyl transferase complex. PglB has been shown to be involved in catalyzing the transfer of an undecaprenyl-linked heptasaccharide to the asparagine side chain of proteins at the Asn-X-Ser/Thr motif. Using a synthetic disaccharide glycan donor (GalNAc-α1,3-bacillosamine-pyrophosphate-undecaprenyl) and a peptide acceptor substrate (KDFNVSKA), we can observe the oligosaccharyl transferase activity of PglB in vitro. Furthermore, the preparation of additional undecaprenyl-linked glycan variants reveals the ability of PglB to transfer a wide variety of saccharides. With the demonstration of PglB activity in vitro, fundamental questions surrounding the mechanism of N-linked glycosylation can now be addressed.     

Spin—rotational relaxation study of molecular reorientation in the presence of internal extended rotational diffusion

Molecular reorientation in the presence of internal rotation is investigated and an analytical expression for the spin—rotational rate of a nucleus attached to the internal rotor is obtained in terms of the internal angular-momentum correlation time. A model of a symmetric-top molecule undergoing anisotropic rotational diffusion is extended to include a modified extended diffusion of internal rotation. The result is applied to liquid toluene and the internal angular-momentum correlation time is evaluated from the ¹³C nuclear spin—rotational relaxation rate of the methyl carbon. A comparison with the previous result on the dipole—dipole relaxation data is made and the consistency of the present theory is discussed.     

Effect of organic vapors and potential-dependent Raman scattering of 2,6-dimethylphenylisocyanide on platinum nanoaggregates

The surface-enhanced Raman scattering characteristics of 2,6-dimethylphenylisocyanide (2,6-DMPI) on Pt nanoaggregates, in ambient and electrochemical environments and in the presence of organic vapors, were examined and compared with those on Au nanoaggregates. Due to the exclusive adsorption via the isocyanide group, the NC stretching band was very susceptible to the measurement conditions although the ring associated bands showed negligible peak shifts. In ambient conditions, the peak shift of the NC stretching vibration on Pt (29 cm(-1)) was one half of that on Au (61 cm(-1)), suggesting that the electron donation capability of the isocyanide group to Au was greater than that to Pt. In the electrochemical environment, the NC stretching peak varied linearly with slopes of ～42 and ～36 cm(-1) V(-1) on Pt and Au, respectively. On the other hand, the NC stretching bands of 2,6-DMPI on Pt red-shifted by as much as 15 and 41 cm(-1), in the presence of acetone and ammonia, respectively, corresponding to the lowering of the surface potential of Pt nanoaggregates from +0.2 to -0.2 and -0.8 V, respectively. On Au nanoaggregates, however, acetone appeared to increase the surface potential of Au from +0.2 to +0.3 V, although ammonia decreased the surface potential from +0.2 to -0.4 V. Acetone must then act as an electron donor when interacting with Pt while it serves as an electron acceptor when interacting with Au, in agreement with an ab initio quantum mechanical calculation.     

Idealized collision model for reactive scattering: Energy dependence of the cross section for CH3I + K → CH3 + Kl

The energy and temperature dependence of the reaction cross section for CH₃I + K → CH₃ + KI have been calculated using the reaction probability obtained from the idealized model of collinear, impulsive interaction between the atoms K and I and between the group CH₃ and I. Calculated values of the cross section agree very closely with the postmaximum data by Gersh and Berastein.     

Comparison of Si-O-C interfacial bonding of alcohols and aldehydes on Si(111) formed from dilute solution with ultraviolet irradiation

Aliphatic alcohols and aldehydes were reacted with the Si(111)-H surface to form Si-O-C interfacial bonds from dilute solution by using ultraviolet light. The resulting monolayers were characterized by using transmission infrared spectroscopy, spectroscopic ellipsometry, and contact angle measurements. The effect of different solvents on monolayer quality is presented. The best monolayers were formed from CH(2)Cl(2). The optimized monolayers were thoroughly characterized to determine the film structure and monolayer stability. The UV-promoted, alcohol-functionalized, and aldehyde-functionalized monolayers are of comparable quality to those previously prepared by other means. Although both molecules are tethered through a Si-O-C bond, the film reactivity is distinctly different with the aldehyde films being more chemically resistant. The differences in chemical reactivity, vibrational spectra, hydrophobicity, and ellipsometric thickness between the alcohol and aldehyde monolayers are attributed to a difference in molecular coverage and monolayer formation.     

Enhanced electrical percolation due to interconnection of three-dimensional pentacene islands in thin films on low surface energy polyimide gate dielectrics

The role of lateral interconnections between three-dimensional pentacene islands on low surface energy polyimide gate dielectrics was investigated by the measurement of the surface coverage dependence of the charge mobility and the use of conducting-probe atomic force microscopy (CP-AFM). From the correlation between the electrical characteristics and the morphological evolution of the three-dimensionally grown pentacene films-based field-effect transistors, we found that during film growth, the formation of interconnections between the three-dimensional pentacene islands that are isolated at the early stage contributes significantly to the enhancement process of charge mobility. The CP-AFM current mapping images of the pentacene films also indicate that the lateral interconnections play an important role in the formation of good electrical percolation pathways between the three-dimensional pentacene islands.     

Group 12 metal complexes of [26]hexaphyrin(1.1.1.1.1.1)

Metalation of meso-hexakis(pentafluorophenyl)-substituted [26]hexaphyrin(1.1.1.1.1.1) (1) has been explored with group 12 metal ions Zn(II), Cd(II), and Hg(II). Zn(II) and Cd(II) ions afforded dinuclear gable-shaped complexes 2 and 3 in good yields, while Hg(II) ion provided bis-Hg(II) and mono-Hg(II) planar complexes (4 and 5) via C-H bond cleavage.     

CD and MCD of CytC3 and taurine dioxygenase: role of the facial triad in alpha-KG-dependent oxygenases

The alpha-ketoglutarate (alpha-KG)-dependent oxygenases are a large and diverse class of mononuclear non-heme iron enzymes that require FeII, alpha-KG, and dioxygen for catalysis with the alpha-KG cosubstrate supplying the additional reducing equivalents for oxygen activation. While these systems exhibit a diverse array of reactivities (i.e., hydroxylation, desaturation, ring closure, etc.), they all share a common structural motif at the FeII active site, termed the 2-His-1-carboxylate facial triad. Recently, a new subclass of alpha-KG-dependent oxygenases has been identified that exhibits novel reactivity, the oxidative halogenation of unactivated carbon centers. These enzymes are also structurally unique in that they do not contain the standard facial triad, as a Cl- ligand is coordinated in place of the carboxylate. An FeII methodology involving CD, MCD, and VTVH MCD spectroscopies was applied to CytC3 to elucidate the active-site structural effects of this perturbation of the coordination sphere. A significant decrease in the affinity of FeII for apo-CytC3 was observed, supporting the necessity of the facial triad for iron coordination to form the resting site. In addition, interesting differences observed in the FeII/alpha-KG complex relative to the cognate complex in other alpha-KG-dependent oxygenases indicate the presence of a distorted 6C site with a weak water ligand. Combined with parallel studies of taurine dioxygenase and past studies of clavaminate synthase, these results define a role of the carboxylate ligand of the facial triad in stabilizing water coordination via a H-bonding interaction between the noncoordinating oxygen of the carboxylate and the coordinated water. These studies provide initial insight into the active-site features that favor chlorination by CytC3 over the hydroxylation reactions occurring in related enzymes.