Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects

The charge state of the Pd surface is a critical parameter in terms of the ability of Pd nanocrystals to activate O₂ to generate a species that behaves like singlet O₂ both chemically and physically. Motivated by this finding, we designed a metal–semiconductor hybrid system in which Pd nanocrystals enclosed by {100} facets are deposited on TiO₂ supports. Driven by the Schottky junction, the TiO₂ supports can provide electrons for metal catalysts under illumination by appropriate light. Further examination by ultrafast spectroscopy revealed that the plasmonics of Pd may force a large number of electrons to undergo reverse migration from Pd to the conduction band of TiO₂ under strong illumination, thus lowering the electron density of the Pd surface as a side effect. We were therefore able to rationally tailor the charge state of the metal surface and thus modulate the function of Pd nanocrystals in O₂ activation and organic oxidation reactions by simply altering the intensity of light shed on Pd–TiO₂ hybrid structures.     

Anti‐Inflammatory Activity of a Novel Acetylene Isolated from the Roots of Angelica tenuissima Nakai

Three polyacetylenes, one novel and two known, were isolated from the root of Angelica tenuissima. Using ¹H‐ and ¹³C‐NMR, COSY, HMBC, and HMQC, their structures were found to be (3R,8S)‐heptadeca‐1‐en‐4,6‐diyne‐3,8‐diol ( 1 ), falcarindiol ( 2 ), and oplopandiol ( 3 ). Absolute configurations of compound 1 were established using Mosher's esterification. In addition, the polyacetylenes ( 1 – 3 ) were evaluated for their anti‐inflammatory activity. Compounds 1 and 3 showed potent inhibitory activity against lipopolysaccharide‐induced nitric oxide (NO) production in RAW267.7 macrophage cells with IC₅₀ values of 4.31 and 5.06 μm, respectively. Compound 1 strongly inhibited inducible nitric oxide synthase (iNOS) and cyclooxygenase (COX)‐2 in a concentration‐dependent manner.     

Synthesis and Characterization of Copper(II)–Phosphonate Coordination Chain Array of Metallocages

Reaction of CuCl₂ ·2H₂O and 2,4,6‐tris(phosphorylmethyl)mesitylene (H₆tpmm) in H₂O?DMF solution at room temperature afforded green crystals of [Cu₆(H₂tpmm)₃(H₂O)₉]·3H₂O ( 1 ), which were characterized by Fourier transform infrared (FT‐IR), thermogravimetric (TG) analysis, and powder X‐ray diffraction (PXRD). The solid‐state structure of 1 reveals a one‐dimensional chain array of M₄L₂ ‐metallocages constituted by the connection of two kinds of metallocage units, namely MC‐A (phosphonate/water‐bridged) and MC‐B (phosphonate‐bridged only), via μ₂‐O(phosphonate)? Cu bonds in ABAABA order. The tris‐phosphonate ligand H₆tpmm is partially deprotonated to form H₂tpmm^4?, which displays a cis,cis,cis conformation to bridge six Cu(II) centers via two monodentate phosphonate groups in a η ⁰:η ⁰:η ¹‐bonding mode and one tridentate phosphonate group in a μ₄, η ¹:η ¹:η ²‐bondingng mode.     

Separation and identification of compounds in Adinandra nitida by comprehensive two-dimensional liquid chromatography coupled to atmospheric pressure chemical ionization source ion trap tandem mass spectrometry

A comprehensive two-dimensional liquid chromatographic (2D-LC) separation system based on the combination of a CN column and a Merck Chromolith Flash reversed-phase column was developed for the separation of components in Adinandra nitida, one type of traditional Chinese medicine (TCM). The two dimensions were connected by a ten-port, dual-position valve controlled automatically by software written in-house. The effluents were detected by both ultraviolet and atmospheric pressure chemical ionization source ion trap tandem mass spectrometry (MS). The calculated peak capacity of the 2D-LC–MS/MS system was above 1240. More than 57 components were resolved in the methanol extract from Adinandra nitida leaves, and five of these were identified based on their relative retention times, molecular weights and MS/MS spectra.     

Structure and morphology controllable synthesis of Ag/carbon hybrid with ionic liquid as soft-template and their catalytic properties

Ag/carbon hybrids were fabricated by the redox of glucose and silver nitrate (AgNO₃) in the presence of imidazolium ionic liquid ([C₁₄mim]BF₄) under hydrothermal condition. Monodisperse carbon hollow sub-microspheres encapsulating Ag nanoparticles and Ag/carbon cables were selectively prepared by varying the concentration of ionic liquid. Other reaction parameters, such as reaction temperature, reaction time and the mole ratio of silver nitrate to glucose, play important roles in controlling the structures of the products. The products were characterized by XRD, TEM (HRTEM), SEM, energy-dispersive X-ray spectroscopy (EDX), FTIR spectroscopy and a Raman spectrometer. The possible formation mechanism was proposed. The catalytic property of the hybrid in the oxidation of 1-butanol by H₂O₂ was also investigated.     

Electronic structure and magnetism in transition metals doped 8-hydroxy-quinoline aluminum

We report the room-temperature ferromagnetism in transition metals (Co, Ni)-doped 8-hydroxy-quinoline aluminum (Alq3) by thermal coevaporation of high purity metal and Alq3 powders. For 5% Co-doped Alq3, a maximum magnetization of approximately 0.33 microB/Co at 10 K was obtained and ferromagnetic behavior was observed up to 300 K. The Co atoms interact chemically with O atoms and provide electrons to Alq3, forming new states acting as electron trap sites. From this, it is suggested that ferromagnetism may be associated with the strong chemical interaction of Co atoms and Alq3 molecules.     

Molecular beam resonant two-photon ionization study of caffeine and its hydrated clusters

We investigated electronically excited states of caffeine and its 1:1 complex with water by using resonant two-photon ionization (R2PI) and UV-UV hole-burning techniques. Strong vibronic coupling between a pair of close-lying pi-pi* and n-pi* transitions is proposed to be responsible for the broad spectral feature observed. By comparing the experimental results with those of theoretical calculations, both the O-bonded and N-bonded forms were suggested to be initially produced for the 1:1 complex. The electronic transitions of the O-bonded complex were blueshifted in the R2PI spectrum. For the N-bonded complex, the excited state undergoes an ultrafast decay process, followed by dissociation on a repulsive potential energy surface, which gives rise to a characteristically anomalous cluster distribution in nanosecond experiments.     

Classification of the hydrogen-bonding species in a series of novel hydrazide based azobenzene derivatives investigated by two-dimensional correlation infrared spectroscopy and molecular modeling

Classification of hydrogen-bonding species in a series of novel hydrazide modified p-methoxyazobenzene derivatives, 4-{n-[4-(4-methoxy-phenylazo)-phenoxy]-alkoxy}-benzoic acid hydrazide (Dn, n = 3, 6, 10) are performed in the present study. Temperature-dependent infrared (IR) spectra of Dn have been measured to investigate the thermal stability of the weak intermolecular interactions, such as hydrogen bonding among hydrazide moieties, pi-pi stacking among aromatic groups, and hydrophobic interaction between alkyl chains. In order to reveal the hydrogen bonding formed between NH, NH2, and CONH groups efficiently, two-dimensional (2D) correlation spectra have been constructed in the thermal sensitive spectral regions of (a) 3500-3100 cm(-1) and (b) 1700-1450 cm(-1), separately, and it have also been constructed between these two spectral regions. Based on the experimental data, the ab initio computational models have been developed to the proposed patterns of hydrogen bonding related to intermolecular interactions in Dn. The intermolecular hydrogen bondings and molecular alignments patterns result from both the experimental data and the computational models are performed for D3, D6, and D10, respectively, in the present study.     

Stabilities,electronic properties of exohedral fluorine and trifluoromethyl derivatives for Td C28 fullerene C28F4–n(CF3)n (n = 0,1,2,3,4)

ABSTRACT: Stability and electronic property calculations are performed systematically based on density functional theory at the B3LYP/6‐31G(d) level for T_d C₂₈ fullerene and exohedral fluorine and trifluoromethyl derivatives C₂₈F_4–n(CF₃)_n (n = 0,1,2,3,4). All the exohedral derivatives that are on the potential energy surfaces are kinetically stable with large HOMO‐LUMO gaps. Further investigations show that binding energies of C₂₈F_4–n(CF₃)_n (n = 0,1,2,3,4) molecules are positive, suggesting they are thermodynamically stable. An analysis of the π‐orbital axis vector indicates the high strain in T_d C₂₈ cage could be greatly released by fluorine and trifluoromethyl decorations. Mulliken charge analysis reveals that adding different electron groups to the T_d C₂₈ cage can cause remarkably different charge populations. In addition, from the ionization potential and electron affinity investigations, the C₂₈F_4–n(CF₃)_n (n = 0,1,2,3,4) molecules manifest weak redox properties. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Directed Electron Delivery from a Pb-Free Halide Perovskite to a Co(II) Molecular Catalyst Boosts CO2 Photoreduction Coupled with Water Oxidation

The development of high-performance photocatalytic systems for CO₂ reduction is appealing to address energy and environmental issues, while it is challenging to avoid using toxic metals and organic sacrificial reagents. We here immobilize a family of cobalt phthalocyanine catalysts on Pb-free halide perovskite Cs₂AgBiBr₆ nanosheets with delicate control on the anchors of the cobalt catalysts. Among them, the molecular hybrid photocatalyst assembled by carboxyl anchors achieves the optimal performance with an electron consumption rate of 300±13 μmol g⁻¹ h⁻¹ for visible-light-driven CO₂-to-CO conversion coupled with water oxidation to O₂, over 8 times of the unmodified Cs₂AgBiBr₆ (36±8 μmol g⁻¹ h⁻¹), also far surpassing the documented systems (<150 μmol g⁻¹ h⁻¹). Besides the improved intrinsic activity, electrochemical, computational, ex-/in situ X-ray photoelectron and X-ray absorption spectroscopic results indicate that the electrons photogenerated at the Bi atoms of Cs₂AgBiBr₆ can be directionally transferred to the cobalt catalyst via the carboxyl anchors which strongly bind to the Bi atoms, substantially facilitating the interfacial electron transfer kinetics and thereby the photocatalysis.