Abstract:The chemistry of trinuclear osmium carbonyl hydrides is a rich area with the three H2Os3(CO)n derivatives (n = 12, 11, 10) all being known stable compounds ultimately obtained from Os3(CO)12 and hydrogen under various conditions. Density functional theory studies on the H2Os3(CO)n systems (n = 12, 11, 10, 9, 8) predict the experimentally observed species for n = 12, 11, and 10. These include a linear structure for H2Os3(CO)12 and triangular structures for H2Os3(CO)11 and H2Os3(CO)10. However, the H2Os3(CO)11 system is predicted to be a fluxional system with the four lowest energy isomers lying within 2 kcal/mol of energy. Three of these H2Os3(CO)11 isomers, all with one terminal hydrogen and one bridging hydrogen, have been observed experimentally by NMR. The lowest energy of these isomers has been isolated and structurally characterized by X-ray crystallography. In contrast to H2Os3(CO)11, the lowest energy H2Os3(CO)10 structure, namely the known structure with an Os=Os edge bridged by both hydrogen atoms and all terminal CO groups, lies ~10 kcal/mol below the next lowest energy isomer. The predicted CO dissociation energies of the H2Os3(CO)n derivatives (n = 12, 11, 10) suggest this H2Os3(CO)10 structure to be the "thermodynamic sink" in the H2Os3(CO)n systems consistent with its synthesis from Os3(CO)12 and H2 at 120 C and atmospheric pressure. The lowest energy structures of the more highly unsaturated H2Os3(CO)n (n = 9, 8) can be derived from this (μ-H)2Os3(CO)10 structure by removal of CO groups from the osmium atom remote to the doubly bridged Os=Os edge of the Os3 triangle with relatively little change in the central (μ-H)2Os3 triangle geometry.

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	1. Metal Triangles versus Metal Chains and Terminal versus Bridging Hydrogen Atoms in Trinuclear Osmium Carbonyl Hydride Chemistry
	Gao Xiaozhen,LI Nan*
	Chemistry 05 January 2014
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	Abstract:The chemistry of trinuclear osmium carbonyl hydrides is a rich area with the three H2Os3(CO)n derivatives (n = 12, 11, 10) all being known stable compounds ultimately obtained from Os3(CO)12 and hydrogen under various conditions. Density functional theory studies on the H2Os3(CO)n systems (n = 12, 11, 10, 9, 8) predict the experimentally observed species for n = 12, 11, and 10. These include a linear structure for H2Os3(CO)12 and triangular structures for H2Os3(CO)11 and H2Os3(CO)10. However, the H2Os3(CO)11 system is predicted to be a fluxional system with the four lowest energy isomers lying within 2 kcal/mol of energy. Three of these H2Os3(CO)11 isomers, all with one terminal hydrogen and one bridging hydrogen, have been observed experimentally by NMR. The lowest energy of these isomers has been isolated and structurally characterized by X-ray crystallography. In contrast to H2Os3(CO)11, the lowest energy H2Os3(CO)10 structure, namely the known structure with an Os=Os edge bridged by both hydrogen atoms and all terminal CO groups, lies ~10 kcal/mol below the next lowest energy isomer. The predicted CO dissociation energies of the H2Os3(CO)n derivatives (n = 12, 11, 10) suggest this H2Os3(CO)10 structure to be the "thermodynamic sink" in the H2Os3(CO)n systems consistent with its synthesis from Os3(CO)12 and H2 at 120 C and atmospheric pressure. The lowest energy structures of the more highly unsaturated H2Os3(CO)n (n = 9, 8) can be derived from this (μ-H)2Os3(CO)10 structure by removal of CO groups from the osmium atom remote to the doubly bridged Os=Os edge of the Os3 triangle with relatively little change in the central (μ-H)2Os3 triangle geometry.
	TO cite this article:Gao Xiaozhen,LI Nan*. Metal Triangles versus Metal Chains and Terminal versus Bridging Hydrogen Atoms in Trinuclear Osmium Carbonyl Hydride Chemistry[OL].[ 5 January 2014] http://en.paper.edu.cn/en_releasepaper/content/4580652


	2. Poly(amidoamine) dendrimers functionalized titanate nanotubes for amplified luminol electrochemiluminescence
	Shupei Zhang,Lingshan Gong,Mei Fu,Guifang Xu,Shuangyan Lu,Hong Dai
	Chemistry 16 December 2013
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	Abstract:A novel luminol electrochemiluminescent (ECL) sensor platform was constructed by poly(amidoamine) dendrimer (PAAD) functionalized titanate nanotubes (TNTs). Herein, the excellent synergetic effect between PAAD that with the quite open spherical 3 D structures possessing a high density of active groups was propitious to mass transportation and TNTs which possess excellent electronic conductivity promoted the electron transfer at the electrode surface contributed to obviously enhanced availability of electroactive surface capable and electronic conductivity of modified electrode. The effect factors such as the concentration of TNTs, the pH value of buffer solution and electrochemical parameters on ECL intensity of luminol at PAAD/TNTs modified GCE were also studied to obtain a sensitive ECL sensor which presented wide linear response range of luminol and would be further sensitized by hydrogen peroxide (H2O2). Furthermore, base on the quenching effect of superoxide dismutase (SOD) on H2O2-sensitized luminol ECL by the reason of the scavenging effect of SOD on superoxide anion, a sensitive SOD ECL biosensor was then developed and could be useful to reveal the amount of radicals generated which would result to diseases like atherosclerosis, rheumatoid arthritis and some tumours.
	TO cite this article:Shupei Zhang,Lingshan Gong,Mei Fu, et al. Poly(amidoamine) dendrimers functionalized titanate nanotubes for amplified luminol electrochemiluminescence[J].

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	3. Evaluation of uvioresistant effect of naphthopyran derivatives on photo-oxidation of poly(ethylene oxide)
	Guang Wang,Yi He,Kuo Zhang
	Chemistry 11 December 2013
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	Abstract:Naphthopyran and its derivatives were synthesized and used as ultraviolet absorbent in photo-oxidation of poly(ethylene oxide) (PEO). The absorption spectra of naphthopyran before and after irradiation of UV light illustrated that the absorbance of naphthopyran covered a wide range of wavelengths, especially in UV light range. The studies of infrared spectra, differential scanning calorimetric and thermogravimetric analysis proved that the addition of naphthopyran greatly reduced the photo-oxidation speed of PEO.
	TO cite this article:Guang Wang,Yi He,Kuo Zhang. Evaluation of uvioresistant effect of naphthopyran derivatives on photo-oxidation of poly(ethylene oxide)[OL].[11 December 2013] http://en.paper.edu.cn/en_releasepaper/content/4574087


	4. Synthesis, characteristics and adsorption properties of polyphenylene sulfide based strong acid ion exchange fiber
	Dengke Zhang,Huajie Yao,Dongju Zhou,Libo Dai,Jie Zhang,Siguo Yuan
	Chemistry 18 November 2013
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	Abstract:A novel strong acid ion exchange fiber (HO3S-BC-XDC-PPS) was prepared via crosslinking and grafting copolymerization of 1,4-bischloromenthyl benzene (XDC), benzyl chloride (BC) on polyphenylene sulfide (PPS) matrix, as well as following sulfonation reaction. The physicochemical structures and properties of the fibrous ion exchange materials were characterized with FT-IR, SEM, TGA, element analysis and chemical titration, respectively. Compared with the preparation of traditional PP-ST-DVB based ion exchange fibers, the syntheses strategy of PPS based strong acid ion exchange fiber avoided the complicated irradiation grafting process with 60Co or other radiation facilities. Owing to the existing of thioether (Ar-S-Ar) and sulfoxide (-SO-) unit in fibrous matrix, a super-equivalent adsorption phenomenon for Cu(II) ion was observed. The HO3S-BC-XDC-PPS fiber possessed high exchange capacity (about 3.70mmol/g), excellent heat stabilities, and the exchange capacity and desorption rate were not decreased after six adsorption desorption cycles.
	TO cite this article:Dengke Zhang,Huajie Yao,Dongju Zhou, et al. Synthesis, characteristics and adsorption properties of polyphenylene sulfide based strong acid ion exchange fiber[OL].[18 November 2013] http://en.paper.edu.cn/en_releasepaper/content/4569939


	5. Photocatalytic Decomposition of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) by Sr-β-Bi2O3 under Visible Light Irradiation
	YIN Lifeng,Bo Fusheng,Dai Yunrong
	Chemistry 16 October 2013
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	Abstract:Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are difficult to remove from the water environment due to their inertness to photolysis, hydrolysis, and biodegradation. In the study, the rapid decomposition of PFOS and PFOA was found in the presence of Sr-β-Bi2O3 as a photocatalyst under visible light irradiation. Compared with nano-TiO2 and direct photolysis, the photocatalysis by Sr-β-Bi2O3 can remove PFOS and PFOA more efficiently. In 1.0 h, about 72.3% of PFOS and 60.1% of PFOA ([PFOS]i = [PFOA]i = 100 μgL-1) can be removed from the aqueous solution under visible light irradiation (λ > 440 nm). The effects of temperature, pH, and initial PFOS/PFOA concentration on the photocatalytic decomposition rates were investigated. Sequentially, the intermediate products were identified as PFO (C8F17), PFHe (C6F13), PFPe (C5F11), PFBu (C4F9), PFPr (C3F7), PFHpS (C7F15SO3), and PFHeS (C6F13SO3). Based on the detection of reactive radicals, photocatalytic reduction by hydrated electron was determined as the major degradation route. The detailed defluorination pathway was also proposed.
	TO cite this article:YIN Lifeng,Bo Fusheng,Dai Yunrong. Photocatalytic Decomposition of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) by Sr-β-Bi2O3 under Visible Light Irradiation[OL].[16 October 2013] http://en.paper.edu.cn/en_releasepaper/content/4564646


	6. Parity Alternation of Silicon-doped Ternary Cationic Carbon Clusters HCnSi2+ (n = 1-9)
	QI Jiayuan
	Chemistry 03 April 2013
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	Abstract:In this paper, we report the design of numerous models for silicon-doped ternary cationic carbon clusters HCnSi2+ (n = 1-9). By means of the B3LYP density functional method, we performed geometry optimization and calculation on vibrational frequency. The ground-state (G-S) isomers of even-n HCnSi2+ (n = 1-9) are found to be structures with the hydrogen atom and a Cn-2Si chain each bonded to a carbon atom of a C2Si ring. The structures of the G-S isomers of odd-n HCnSi2+ (n = 1-9) are "Y" shaped with one silicon atom and the hydrogen atom located at one end of the Cn chain, and another silicon atom located at the other end. The Cn chain (Cn-2 chain for even-n ones) of the G-S isomers of HCnSi2+ (n = 3-9) displays a polyacetylene-like structure. It is found that the G-S isomers of even-n HCnSi2+ (n = 1-9) are more stable than the odd-n ones. The finding is in accord with the relative intensities of HCnSi2+ (n = 1-9) recorded in mass spectrometric investigations. We provide explanations for such a trend of even/odd alternation based on concepts of the bonding character, incremental binding energy, ionization potential, proton affinity, and dissociation channels.
	TO cite this article:QI Jiayuan. Parity Alternation of Silicon-doped Ternary Cationic Carbon Clusters HCnSi2+ (n = 1-9)[J].


	7. Synthesis, Characterization and Reactivity of Lanthanocene Derivatives with the o-Aminobenzamido Dianion Ligand
	SUN Yan,ZHOU Xigeng
	Chemistry 26 March 2013
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	Abstract:A series of new tetranuclear organolanthanide complexes incorporating the o-aminobenzamido dianion ligand, [CpLn(μ-η2:η2-NHC6H4CONH)(μ3-η1:η1:η2- NHC6H4CONH)LnCp(HMPA)}2 (HMPA = OP(NMe2)3; Ln = Yb(1a), Er(1b)), are synthesized by reaction of Cp3Ln with o-aminobenzamide followed by crystallization in a mixed HMPA and toluene solvent. The reactivities of 1 toward isocyanate are also investigated. Treatment of 1 with 4 equiv of PhNCO in toluene gives the unusual dianionic quinazolyldionate (Quo) complexes [Cp2Ln(μ3-η2:η2:η1-Quo)]3Ln(HMPA)2 (Ln = Yb(2a), Er(2b)), indicating that one isocyanate molecule can undergo the tandem reaction with both NH and CONH of 1 to construct a quinazolyldionate skeleton, companying with the elimination of PhNH2. All the new complexes are characterized by elemental analysis and spectroscopic properties, and solid-stated structures of 1a, 1b and 2a are also determined through X-ray analysis.
	TO cite this article:SUN Yan,ZHOU Xigeng. Synthesis, Characterization and Reactivity of Lanthanocene Derivatives with the o-Aminobenzamido Dianion Ligand[OL].[26 March 2013] http://en.paper.edu.cn/en_releasepaper/content/4533473


	8. Three-component Synthesis of Homoallylic Amines Catalyzed by Phosphomolybdic Acid Supported on Silica Gel
	XIE Zhengfeng,WANG Jide
	Chemistry 11 March 2013
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	Abstract:Phosphomolybdic acid supported on silica gel (PMA/SiO2) has been used for the catalysis of the three-component reactions of aldehydes, amines and allyltributylstannane with acetonitrile as the solvent at room temperature. The experimental parameters were optimized in the three-component reaction system. The obtained results showed the PMA/SiO2 showed its highly efficient nature for catalyzing the three-component reactions. were not found to induce a obvious reduction in the yield of the corresponding allylation reaction, regardless of aromatic aldehydes and amines containing electron-donating or electron-withdrawing groups in the aromatic ring that involve in the three-component reaction with Aromatic amines or aldehydes and allyltributylstannane. Our results indicated that this synthetic process has advantages of high yield, mild reaction conditions, environment benign and easy manipulation.
	TO cite this article:XIE Zhengfeng,WANG Jide. Three-component Synthesis of Homoallylic Amines Catalyzed by Phosphomolybdic Acid Supported on Silica Gel[OL].[11 March 2013] http://en.paper.edu.cn/en_releasepaper/content/4526296


	9. A New Method for the Preparation of the Derivatives of 4-amino-thiophenol in Mild Conditions
	SHANG Hai,REN Zhigang,LANG Jianping,LI Hongxi
	Chemistry 17 February 2013
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	Abstract:A new route to the synthesis of the derivatives of 4-amino-benzenethiol is described. After comparing with several reaction systems, such as CuClO4/NH4SCN, I2/NH4SCN, FeCl3/NH4SCN, DDQ/NH4SCN, BDMS/NH4SCN, a series of aromatic thiocyanate compounds were prepared almost quantitatively from N-methyl-N-R-aniline(R = CH2COOEt, CH(CH3)Ph, CH2CH=CH2, CH2CN) under the system of combination of BDMS/NH4SCN. The resulting aromatic thiocyanate compounds were reduced by Zn/HOAc mild reduing system to produce the corresponding benzenethiols in good to excellent yields.
	TO cite this article:SHANG Hai,REN Zhigang,LANG Jianping, et al. A New Method for the Preparation of the Derivatives of 4-amino-thiophenol in Mild Conditions[OL].[17 February 2013] http://en.paper.edu.cn/en_releasepaper/content/4505882


	10. Bio-based chemicals: a sustainable candidate for new generation of green solvents
	Gu Yanlong
	Chemistry 09 January 2013
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	Abstract:Biomass has exhibited great potential to replace fossil resources for the production of chemicals and fuels. The search for alternative reaction media to replace petroleum-based, volatile and often toxic solvents commonly used in chemical processes is an important objective of significant environmental consequence. Recently, bio-based compounds have been either used entirely as green solvents or utilized as pivotal ingredients for constructing innovative solvents, providing a new generation of green solvents, which are inexpensive, less toxic and bio-compatible. This review presents background and classification of these new media and highlights recent advances in their use in various areas including organic synthesis, biotransformations and separations.
	TO cite this article:Gu Yanlong . Bio-based chemicals: a sustainable candidate for new generation of green solvents[OL].[ 9 January 2013] http://en.paper.edu.cn/en_releasepaper/content/4513564

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