Preparation of Ag nanoparticle-decorated poly(m-phenylenediamine) microparticles and their application for hydrogen peroxide detection

The chemical oxidation polymerization of m-phenylenediamine (MPD) by ammonium persulfate (APS) at room temperature results in the formation of poly(m-phenylenediamine) (PMPD) microparticles. The subsequent treatment of such microparticles with an aqueous AgNO(3) solution produces Ag nanoparticle (AgNP)-decorated PMPD microparticles. It was found that as-formed AgNPs exhibited remarkable catalytic performance toward the reduction of hydrogen peroxide (H(2)O(2)). The enzymeless H(2)O(2) sensor constructed with such composites showed a fast amperometric response time of less than 5 s, and the corresponding linear range and detection limit were estimated to be from 0.1 to 30 mM and 4.7 μM, respectively, at a signal-to-noise ratio of 3.     

Displacement solid-phase extraction on mercapto-functionalized magnetite microspheres for inductively coupled plasma mass spectrometric determination of trace noble metals

A flow injection online displacement solid-phase extraction (DSPE) via magnetic immobilization of mercapto-functionalized magnetite microspheres onto the inner walls of a knotted reactor (KR) coupled with inductively coupled plasma mass spectrometry was developed for selective preconcentration and determination of trace noble metals (Ru, Rh, Pd, Pt, Ir and Au) in complex matrices. Online DSPE of 2.7 mL aqueous solution gave the enhancement factors of 32-46 for the six noble metals in comparison with direct nebulization of aqueous sample solution, and the detection limits (3 s) of 2.1 ng L(-1) for Ru, 1.9 ng L(-1) for Rh, 2.5 ng L(-1) for Pd, 1.8 ng L(-1) for Ir, 1.9 ng L(-1) for Pt and 1.7 ng L(-1) for Au. The sample throughput of the developed method was about 20 samples h(-1), and the relative standard deviation for eleven replicate determinations of the noble metals at the 30 ng L(-1) level ranged from 1.2% to 2.1%. The recoveries of Ru, Rh, Pd, Pt, Ir and Au still maintained 90% even after successive 140 cycles of DSPE. The developed method was successfully applied to selective determination of trace Ru, Rh, Pd, Pt, Ir and Au in complex matrices.     

Chiral separation and determination of ofloxacin enantiomers by ionic liquid-assisted ligand-exchange chromatography

A simple and accurate method for the separation and determination of ofloxacin enantiomers was developed by ionic liquid-assisted ligand-exchange high performance liquid chromatography. Both achiral and chiral ionic liquids were tested for their efficiency of ofloxacin enantiomeric separation. The effects of ligands, concentration of metal ion, organic modifier, pH of the mobile phase, and temperature were also investigated and evaluated. Optimal conditions were obtained on a conventional C(18) column, where the mobile phase consisted of methanol/water (20 : 80, v/v) (containing 4.0 mmol L(-1) amino acid ionic liquid and 3.0 mmol L(-1) copper sulfate) at a flow rate of 0.5 mL min(-1). Under this condition, the ofloxacin enantiomers could be baseline separated within 14 minutes; the proposed method was used to analyze different commercial ofloxacin medicines.     

Tuning the relative concentration ratio of bulk defects to surface defects in TiO2 nanocrystals leads to high photocatalytic efficiency

TiO(2) nanocrystals with tunable bulk/surface defects were synthesized and characterized with TEM, XRD, BET, positron annihilation, and photocurrent measurements. The effect of defects on photocatalytic activity was studied. It was found for the first time that decreasing the relative concentration ratio of bulk defects to surface defects in TiO(2) nanocrystals could significantly improve the separation efficiency of photogenerated electrons and holes, thus significantly enhancing the photocatalytic efficiency.     

Organization of bacteriochlorophylls in individual chlorosomes from Chlorobaculum tepidum studied by 2-dimensional polarization fluorescence microscopy

Chlorosomes are the largest and most efficient natural light-harvesting systems and contain supramolecular assemblies of bacteriochlorophylls that are organized without proteins. Despite a recent structure determination for chlorosomes from Chlorobaculum tepidum (Ganapathy Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 8525), the issue of a possible large structural disorder is still discussed controversially. We have studied individual chlorosomes prepared under very carefully controlled growth condition by a novel 2-dimensional polarization single molecule imaging technique giving polarization information for both fluorescence excitation and emission simultaneously. Contrary to the existing literature data, the polarization degree or modulation depth (M) for both excitation (absorption) and emission (fluorescence) showed extremely narrow distributions. The fluorescence was always highly polarized with M ≈ 0.77, independent of the excitation wavelength. Moreover, the fluorescence spectra of individual chlorosomes were identical within the error limits. These results lead us to conclude that all chlorosomes possess the same type of internal organization in terms of the arrangement of the bacteriochlorophyll c transition dipole moments and their total excitonic transition dipole possess a cylindrical symmetry in agreement with the previously suggested concentric multitubular chlorophyll aggregate organization (Ganapathy Proc. Natl. Acad. Sci. U.S.A. 2009, 106, 8525).     

Determination of emulsion explosives with Span-80 as emulsifier by gas chromatography-mass spectrometry

A novel approach for identification and determination of emulsion explosives with Span-80 (sorbitol mono-oleate) as the emulsifier and their postblast residues by gas chromatography-mass spectrometry (GC-MS) has been developed. 24 kinds of emulsion explosives collected have been processed by transesterification reaction with metholic KOH solution and the emulsifier has turned into methyl esters of fatty acids. From the peak area ratios of their methyl esters, most of these emulsion explosives can be differentiated. In order to detect the postblast residues of emulsion explosives, the sorbitols in the emulsifier Span-80 obtained after transesterification reaction have been further derivatized by silylation reaction with N,O-bis-(trimethylsilyl)trifluoroacetamide (BSTFA) containing 1% trimethylchlorosilane (TMCS) as the derivatizing reagent. The derivatization conditions were optimized and the derivatives were determined by GC-MS. The results showed that the silylation derivatives of sorbitol and it isomers, combined with hydrocarbon compounds and methyl esters of fatty acids, were the characteristic components for identification of the emulsion explosives. The established approach was applied to analyze the postblast residues of emulsion explosives. It has been found that the method was sensitive and specific, especially when detecting the derivatives of sorbitol and its isomers by GC-MS in selecting ion mode. The information of the characteristic components can help probe the origin of the emulsion explosives and providing scientific evidences and clues for solving the crimes of the emulsion explosive explosion.     

反相气相色谱法表征聚丁二烯橡胶的表面性质

采用反相气相色谱技术测定了聚丁二烯橡胶的表面性质。以正己烷、正庚烷、正辛烷、正壬烷作为非极性探针测定其表面色散自由能,以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、乙醚和四氢呋喃作为极性探针测定其路易斯酸碱常数。经计算得出聚丁二烯橡胶在303、313、323、333和343 K的表面色散自由能分别为47.07、46.46、45.85、45.60和45.09 mJ/m2。结果表明,聚丁二烯橡胶表面色散自由能随着温度的升高呈线性降低,路易斯酸常数Ka为0.34,碱常数Kb为1.77,总酸碱作用能力2.11,该聚合物为弱碱性Lewis两性聚合物材料。此外还计算出聚丁二烯橡胶的酸碱作用吸附自由能（~ΔGsa）和吸附焓（~ΔHsa）。     

仿生催化及其在烃类氧化中的应用

从叶绿素及血红素的结构出发,综述金属卟啉仿生催化的特点;重点介绍仿生催化的概念,仿生催化氧化过程与技术以及仿生催化氧化在工业上的应用;总结仿生催化以及该技术的发展现状和前景。     

Preparation,Characterization and Non‐isothermal Kinetics of the Dehydration Process of [Sm(p‐MOBA)3bath]2·4H2O

The new complex of [Sm(p‐MOBA)₃bath]₂·4H₂O (p‐MOBA, p‐methoxybenzoate; bath, 4,7‐diphenyl‐1,10‐phenanthroline) was synthesized and characterized by elemental analysis, molar conductance, IR, UV and XRD patterns. The thermal decomposition of the complex was studied under the non‐isothermal condition by TG‐DTG and IR techniques. The most probable mechanism function of the dehydration process was obtained from the analysis of DSC curves of the complex employing the double extrapolated method on the basis of integral isoconversional non‐linear (NL‐INT) and Tang‐Wanjun integral equations. The integral function of the mechanism was [1? (1?α)^1/2]^1/2 and the corresponding kinetic parameters (activation energy E and the pre‐exponential factor A) were obtained.     

First total synthesis of two new heterocyclic compounds:Bretschneiderazines A and B

Facile synthesis of the two new natural heterocyclic compounds bretschneiderazines A（2） and B（3）,isolated from an extract of the stems of Bretschneidera sinensis,is reported.We employed the cyclization reaction of benzamide by directed lithiation and sequential treatment with sulfur and phosgene as key steps.All new compounds have been fully characterized by means of IR,¹H NMR,¹³C NMR,and HRMS.