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Frontiers of Chemical Science and Engineering 2008年第3期2卷 253-256页

作者： Dongmei ZHU Fei WANG Cuiling GAO Zheng XU State Key Laboratory of coordination Chemistry Laboratory of Solid State Microstructures Department of ChemistryNanjing UniversityNanjing 210093China

This paper reports an easy and effective way to fabricate polystyrene/poly(N-isopropylacrylamide)(PS/PNIPAM)core-shell particles and PNIPAM hollow *** main point of the method is to take advantage of the hydrophobic interaction between initiator and PS *** hydrophobic azodiisobutyronitriles automatically concentrate around the PS particles and initiate polymerization of N-isopropylacrylamide(NIPAM)and the crosslinkermethylene bisacrylamide(MBA),which dissolve in the aqueous phase,at the surface of the PS ***,PNIPAM adheres to the PS particles to form a coreshell structure as a result of their hydrophobic *** interaction is due to the unique property of PNIPAM,namely,its ability to transition from hydrophilic to hydrophobic when the temperature rises to 32℃.Furthermore,the hollow PNIPAM spheres were obtained by etching the PS core with chloroform.

关键词： Poly(N-isopropylacrylamide) Polystyrene core-shell polymer incentive sensitive polymer hydrophobic interaction

Synthesis of Novel 1,4-Bissulfonamide Ligands for Enantioselective Addition of Diethylzinc to Aldehydes

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Chinese Journal of Chemistry 2011年第8期29卷 1697-1702页

作者：杨明华孙江涛朱成建 Department of Chemistry Lishui University Lishui Zhejiang 323000 China School of Chemistry and Chemical Engineering State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangsu 210093 China

Several novel chiral sulfonamide ligands based on （1R,2S,4R,5S）-1,4-diamino-2,5-dimethylcyclohexane skele- ton have been synthesized and their application in the enantioselective addition of diethylzinc to aldehydes was in- vestigated in the presence of Ti（Oipr）4. The effect of ligands, temperature and the loading amount of ligands was studied. Under optimized conditions, enantioselective addition of diethylzinc with various aryl aldehydes and aliphatic aldehydes proceeded smoothly and afforded chiral secondary alcohols in up to 88% ee.

关键词： asymmetric catalysis chiral sulfonamide diethylzinc aldehyde

EQUILIBRIUM CONSTANT OF ADDUCTIVE REACTION BETWEEN BIS-(O, O′-DICYCLOHEXYLDITH-IOPHOSPHATO) NICKEL(Ⅱ) AND BENZYL-AMINE AND CRYSTAL STRUCTURE OF ADDUCTS Ni[(C_6H_(11)O)_2PS_2]_2·2NH_2CH_2C_6H_5

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Chinese Science Bulletin 1992年第8期37卷 657-661页

作者：游效曾徐正徐昕林建华俞运鹏林墀昌刘世雄 coordination Chemistry Institute Nanjing UniversityNanjing 210008 PRC Institute of Structural Chemistry Fuzhou University Fuzhou 350002PRC

Ⅰ. INTRODUCTIONEsters of dithiophosphoric acid are a kind of excellent extractant for separating Co-Ni and Co-Mn. It was found that Co（Ⅱ） is easy to oxidize and to form the stable six-coordinated octahedral complex Co[（RO）2PS2] during extraction process. And it made back-extraction process very difficult. It was found that pydridine is able to cause substitute-reduction reaction with Co[（RO）2 PS2]3 and to form Co[（RO）2PS2]2·2Py. It is

关键词： dithiophosphate equilibrium constant crystal structure.

Synthesis and thermal behavior of [Li(thf)3(μ-Cl)La{N(SiMe3)2}3] and its investigation as spin-coating precursor for lanthanum-based layer formation

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Journal of Rare Earths 2018年第5期36卷 537-543页

作者： Andrea PreuB Elaheh Pousaneh Julian Noll Tobias Rüffer Alexaner Jakob Lutz Mertens Michael Mehring Heinrich Lang Technische Universitat Chemnitz Faculty of Natural Sciences Institute of Chemistry Inorganic Chemistry 09107 Chemnitz Germany Technische Universitat Chemnitz Faculty of Natural Sciences Institute of Chemistry Coordination Chemistry 09107 Chemnitz Germany

The lanthanum（Ⅲ） complex [Li（thf）3（μ-CI）La{N（SiMe3）2}3]（3） was obtained by the reaction of LaCl3 with three equiv of Li[N（SiMe3）2]3 in a tetrahydrofuran solution. The molecular structure of 3 in the solid state was characterized by a tetracoordinated anionic lanthanide（Ⅲ） amide in form of an adduct with LiCl（thf）3 as evidenced by single crystal X-ray structure analysis. In order to study the suitability of 3 as a precursor for the deposition of La2O3/LiLaSiO4 by thin layer deposition techniques,its thermal behavior was investigated by thermogravimetry（TG） and TG-MS-coupled studies. TG studies show a two-step decomposition process, whereby volatile decomposition products can be detected during the second decomposition step. TG measurements under an atmosphere of oxygen produced La2O3, Calcination processes of 3 under ambient atmosphere for 10 h at 1000 ℃ gave La2O3 and LiLaSiO4,which was confirmed by PXRD studies. Metal-organic 3 was applied as spin-coating precursor for La2O3 thin film formation giving the as-deposited layers nearly crack-free.

关键词： Lanthanum Amide Thermogravimetry Solid state structure Spin-coating Rare earths

Synthesis, Photophysical Properties of Tribranched Chromophores Based on 1,3,5-Triazine Core and Different Electro-donating End-groups

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Chinese Journal of Chemistry 2011年第10期29卷 2129-2133页

作者：刘莉黄维史界平吕昌贵崔一平陆国元 Department of Chemistry State Key Laboratory of Coordination Chemistry Nanjing University Nanjing jiangsu 210093 China Advanced Photonics Center Southeast University Nanjing Jiangsu 210096 China

Three two-photon absorption （TPA） tribranched chromophores were successfully prepared, in which 1,3,5-triazine is been as electron deficient core, 1,4-phenylenedivinylene as conjugated bridge, 3,4-ethylenedioxy- thiophene （EDOT）（T1）, N-methylpyrrole （T2） or triphenylamine （T3） as electron-donating end-groups. Their pho- tophysical properties were studied by absorption, one- and two-photon fluorescence and TPA cross-section deter- mination. The nonlinear transmission （NLT） measurement in femtoseconds （fs） regime at 800 nm indicates that TPA cross-section σ2 values of T1, T2 and T3 with extended π-conjugated bridge are much larger than the corresponding chromophore T4 with a short length bridge, and TPA cross-section of T1 with end-groups EDOT exhibits a remarkable enhancement compared with T2 and T3 having the same length It-system. The chromophores T1, T2 and T3 show also remarkable up-converted luminescence and optical limiting activity.

关键词： chromophore triazine 3,4-ethylenedioxythiophene two-photon absorption photophysics Homer- Wadsworth-Emmons reaction

Selective Synthesis of [2＋2] Macrocyclic Schiff Bases from Chiral 1,4-Diamines

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Chinese Journal of Chemistry 2007年第3期25卷 343-345页

作者：诸海滨胡大华董华泽李根喜苟少华 Department of Chemistry and Chemical Engineering State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangsu 210093 China Department of Biochemistry Nanjing University Nanjing Jiangsu 210093 China

[2＋2] macrocyclic Schiff bases of three kinds have been synthesized from chiral 1,4-diamines by use of different methods. Macrocyclic Schiff bases 1a-1c have been selectively obtained based on a non-templated dilution method from chiral 1,4-diamines a-c and dialdehyde DA1, whereas macrocycles 2a-2c have been selectively produced from reaction of diamines a-c and dialdehyde DA2 in the presence of boric acid as templates. Macrocyclic Schiff bases 3a-3c have been afforded in high selectivity from diamines a-c and dialdehyde DA3 by means of sodium-template. All the titled compounds have been confirmed by ^1H NMR and ESI-MS analyses.

关键词： 1,4-diamine macrocycle Schiff base template

Regioselective Ring-opening Reaction of 1,2-Epoxides with Arylselenol under Solvent-free Conditions and Application to the Synthesis of 1,3-Oxazolidin-2-ones

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Chinese Journal of Chemistry 2006年第5期24卷 669-673页

作者：杨明华袁朝英潘毅朱成建 State Key Laboratory of coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing Jiangsu 210093 China Department of Chemistry Lishui College Lishui Zhejiang 323000 China

Regioselective ring-opening reactions of 1,2-epoxides with ArSeH catalyzed by Ti（O^tPr）4 under solvent-free conditions were investigated. A variety of β-hydroxyselenides were obtained in excellent yields of 90%-97% and regioselectivities by a simple, atom economic and environment-friendly procedure. Several N-tosyl- 1,3-oxazolidin-2-ones were prepared starting from the corresponding 1,2-epoxides and ArSeH by a one-pot three-step procedure.

关键词： epoxide arylselenol solvent-free reaction titanium isopropoxide 1,3-oxazolidin-2-one

Lanthanide NIR luminescence for telecommunications, bioanalyses and solar energy conversion

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Journal of Rare Earths 2010年第6期28卷 824-842页

作者： Jean-Claude G. Bünzli Svetlana V. Eliseeva cole Polytechnique Fédérale de Lausanne Institute of Chemical Sciences and Engineering WCU Professor Korea University Center for Next Generation Photovoltaic Systems Katholieke Universiteit Leuven Department of Chemistry Laboratory of Coordination Chemistry

Present-day advanced technologies heavily rely on the exciting magnetic and spectroscopic properties of lanthanide ions. In particular, their ability to generate well-characterized and intense near-infrared (NIR) luminescence is exploited in any modern fiber-optic telecommunication network. In this feature article, we first summarize the whereabouts underlying the design of highly luminescent NIR molecular edifices and materials. We then focus on describing the main trends in three applications related to this spectral range: telecommunications, biosciences, and solar energy conversion. In telecommunications, efforts concentrate presently on getting easily processable polymer-based waveguide amplifiers. Upconversion nanophosphors emitting in the visible after NIR excitation are now ubiquitous in many bioanalyses while their application to bio-imaging is still in its early stages; however, highly sensitive NIR-NIR systems start to be at hand for both in vitro and in vivo imaging, as well as dual probes combining magnetic resonance and optical imaging. Finally, both silicon-based and dye-sensitized solar cells benefit from the downconversion and upconversion capabilities of lanthanide ions to harvest UV and NIR solar light and to boost the overall quantum efficiency of these next-generation devices.

关键词： lanthanide luminescence near-infrared luminescence telecommunications bioanalysis solar energy conversion solar cell upconversion downconversion

Studies of copper (Ⅱ) complexes as catalysts for the hydrolysis of DNA

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Chinese Journal of Chemistry 1999年第6期17卷 625-636,5页

作者：任蕤杨频 Institute of coordination Chemistry State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangshu 210093 China Institute Molecular Science Shanxi University Taiyuan Shanxi 030006 China Institute Molecular Science Shanxi University Taiyuan Shanxi 030006 China

Hydrolysis of DNA is an important enzymatic reaction , but it is exceedingly difficult to mimic in the laboratory because of the stability of hydrolysis of DNA. In this paper, the cleavage activity of complexes formed between Cu(Ⅱ) and four different amino acid or amino acid methyl ester on DNA is studied by gel elec-trophoresis. It is found that DNA could be cleaved by Cu(Ⅱ)-L-His and Cu(Ⅱ)-L-His methyl ester complexes and the efficiency of cleavage is largely dependent on the metal ion-to-ligand ratio. Further experiments show that the cleavage of DNA mediated by Cu(Ⅱ)-L-His complexes occurs via a hydrolytic mechanism and the active chemical species that affects DNA cleavage is proposed to be MI2H+ and ML2H22+.

关键词： Copper(Ⅱ) complexes DNA hydrolytic cleavage

DNA Cleavage Promoted by Cu^2＋ Complex of N,N＇-Bis（2-aminoethyl）-2,6-pyridinedicarboxamide

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Chinese Journal of Chemistry 2007年第7期25卷 937-941页

作者：李英盛欣邵莺陆国元 Department of Chemistry State Key Laboratory of Coordination Chemistry Nanjing University Nanjing Jiangsu 210093 China

The interaction of Cu^2＋ complex of N,N＇-bis（2-aminoethyl）-2,6-pyridinedicarboxamide （BAP） with DNA was studied by agarose gel electrophoresis analysis. The results indicate that the BAP-Cu^2＋ complex can promote the cleavage of phosphodiester bond of supercoiled DNA at physiological condition, which is 3.2 × 10^6 times higher than DNA natural degradation. A hydrolytic cleaving mechanism through the cooperation of copper ions and functional amino groups was proposed.

关键词： DNA cleavage phosphodiester bond electrophoresis nuclease model