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Polymer-assisted nanoparticulate contrast-enhancing materials

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science china chemistry 2010年第3期53卷 479-486页

作者： DING Yin1,3,HU Yong2,WU Wei1 & JIANG XiQun1 1laboratory of Mesoscopic chemistry and Department of Polymer science and engineering,College of chemistry & chemical engineering,nanjing university,nanjing 210093,china 2National laboratory of Solid State Microstructure,Department of Material science and engineering,nanjing university,nanjing 210093,china 3.ey laboratory of analytical chemistry for life science,ministry of education,school of chemistry and chemical engineering,nanjing university,nanjing 210093,china laboratory of Mesoscopic chemistry and Department of Polymer science and engineering College of Chemistry & Chemical Engineering Nanjing University Nanjing China Key laboratory of analytical chemistry for life science Ministry of Education School of Chemistry and Chemical Engineering Nanjing University Nanjing China National laboratory of Solid State Microstructure Department of Material Science and Engineering Nanjing University Nanjing China

The application of nanotechnology in medicine research has significant potential in modern biomedical research,disease diagnosis and *** fluorophore-based detection techniques have been widely used as imaging and signal transduction tools for the detection of trace levels of *** photosensitivity of the fluorophores,however,limits their application in such complex environments as living bio-systems where degradation or photobleaching *** nanoparticles have unique and stable optical,electrical,magnetic and catalytic properties because of their various shapes,sizes and *** potential of the nanoparticles as novel imaging agents has been studied as a possible solution to this *** modification of inorganic nanoparticles could enhance their biostability in physiological conditions and ability of targeting bioactive molecules.

关键词： contrast agent cell image gold nanoparticles iron oxide nanoparticles carbon nanotubes polymeric-inorganic hybrid nanoparticles

Magnetic particles and cadmium sulfide nanoparticles tagging for signal-amplifying detection of nucleic acids

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science china chemistry 2011年第8期54卷 1304-1310页

作者： DONG XiaoYa, ZHAO WeiWei, XU JingJuan & CHEN HongYuan State Key laboratory of analytical chemistry for life science school of chemistry and chemical engineering, nanjing university, nanjing 210093, china State Key laboratory of analytical chemistry for life science school of chemistry and chemical engineering Nanjing University Nanjing China

A versatile DNA recognition system using cadmium sulfide nanoparticles (CdS NPs) as labels was proposed for ultrasensitive detection of specific sequence DNA based on target recycling. This strategy utilized the magnetic particles (MNPs) for the immobilization of linker DNA and CdS NPs and the subsequent target DNA hybridization. Using the unique characteristic of nicking endonuclease for cutting one specific strand of double strand DNA (ds DNA), the linker DNA could be transected and the target DNA could be liberated for re-hybridization and hence the amount of released CdS NPs was enhanced. Due to the advantage of the MNPs and signal amplification from the target recycling, the analyte DNA could be detected by the square-wave stripping voltammetry (SWV) in a wide linear range from 0.4 fM to 100 fM with the detection limit down to 0.08 fM. The proposed DNA detection strategy possesses high sensitivity, satisfactory reproducibility and excellent stability, which might have potential in other DNA biological assays.

关键词： CdS nanoparticles square wave stripping voltammetry nicking endonuclease electrochemical DNA assay

Binaphthyl-bridged bis-imidazolinium salts as N-heterocyclic carbene ligand precursors in the palladium-catalyzed Heck reaction

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science china chemistry 2011年第6期54卷 951-956页

作者： WU Hui, JIN Can, HUANG GuoLi, WANG LianJun, JIANG JuLi & WANG Leyong Key laboratory of Mesoscopic chemistry of ministry of education school of chemistry and chemical engineering, nanjing university, nanjing 210093, china Key laboratory of Mesoscopic chemistry of ministry of education school of chemistry and chemical engineering Nanjing University Nanjing China

Two new bis-imidazolinium salts (4a, 4b) have been synthesized as precursors of N-heterocyclic carbenes (NHCs) from the commercially available (R)-2,2′-dihydroxy-1,1′-binaphthalene. The two bis-imidazolinium salts were used as efficient precursor of NHC ancillary ligands in the palladium-catalyzed Heck reaction. Good to excellent yields and high stereoselectivities were obtained with ethyl acrylate, acrylonitrile, and acrylamide as starting materials. The structure of bis-imidazolinium salt 4b was further characterized by single crystal X-ray diffraction analysis.

关键词： N-heterocyclic carbenes Heck reaction palladium imidazolinium salts

One-dimensional metal phosphonates based on 6-phosphononicotinic acid:A structural and magnetic study

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science china chemistry 2010年第10期53卷 2112-2117页

作者： WANG PengFei, DUAN Yan & ZHENG LiMin State Key laboratory of Coordination chemistry Coordination chemistry Institute, school of chemistry and chemical engineering, nanjing university, nanjing 210093, china State Key laboratory of Coordination chemistry Coordination chemistry Institute School of Chemistry and Chemical Engineering Nanjing University Nanjing China

The reactions of 6-phosphononicotinic acid (pnaH3) and metal salts result in three new compounds, namely, M(pnaH)-(H2O)3·H2O [M = Co(Ⅱ) (1), Ni(Ⅱ) (2), Zn(Ⅱ) (3)]. These compounds are isostructural and contain 21 helical chains made up of corner-sharing {MO5N} octahedra and {PO3C} tetrahedra. The chains are further connected by extensive hydrogen bonds to form a three-dimensional supramolecular structure. Magnetic studies reveal that dominant antiferromagnetic interactions are mediated in both 1 and 2. Interestingly the dehydrated compound 1 shows metamagnetic behavior at low temperature.

关键词： carboxylate-phosphonate coordination polymer magnetic property metamagnetism

Syntheses,crystal structures and properties of three novel coordination polymers with tripodal imidazole-containing ligands and benzenetetracarboxylate

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science china chemistry 2010年第10期53卷 2164-2169页

作者： SU Zhi, FAN Jian & SUN WeiYin State Key laboratory of Coordination chemistry nanjing National laboratory of Microstructures Coordination chemistry Institute, school of chemistry and chemical engineering, nanjing university, nanjing 210093, china State Key laboratory of Coordination chemistry nanjing National laboratory of Microstructures Coordination chemistry Institute School of Chemistry and Chemical Engineering Nanjing University Nanjing China

Three novel coordination polymers, [Ni2(tib)2(btec)]·2H2O (1), [Co2(tib)2(btec)]·2H2O (2) and [Zn4(tib)2(btec)Cl4]·2H2O (3), have been synthesized by using mixed ligands of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2,4,5-benzenetetracarboxylic acid (H4btec) under hydrothermal conditions. Complexes 1 and 2 have the same structure and are rare three-dimensional (3D) self-penetrating (3,4,5)-connected nets, while complex 3 is an unprecedented (3,4)-connected 3D net. The different structures of 1 (2) and 3 are ascribed to the distinct coordination geometry of the metal centers. The thermal stability and photoluminescence property of the complexes were investigated.

关键词： coordination polymer self-penetration crystal structure thermal stability photoluminescence property

Rhodamine B doped silica nanoparticle labels for protein microarray detection

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science china chemistry 2010年第4期53卷 747-751页

作者： WANG Ying1, LI ZhongHui1, ZHONG WenYing2, LI Hui2, XU DanKe1 & CHEN HongYuan1 1Key laboratory of analytical chemistry for life science, ministry of education school of chemistry and chemical engineering, nanjing university, nanjing 210093, china 2Department of analytical chemistry, china Pharmaceutical university, nanjing 210009, china Key laboratory of analytical chemistry for life science Ministry of Education school of chemistry and chemical engineering Nanjing University Nanjing China Department of analytical chemistry China Pharmaceutical University Nanjing China

A core-shell Rhodamine B-doped SiO2 nanoparticle was synthesized and its fluorescent intensity was found to be 1000 times higher than that of individual Rhodamine B molecule. The doped nanoparticles were further conjugated with streptavidin and the resulting nanoparticles were used in the detection of reverse-phase protein microarrays, in which human IgG of various concentrations was first immobilized on aldehyde-modified glass slides and then biotinlyated goat anti human IgG as well as the labeled nanoparticles were sequentially conjugated. The calibration curve is linear over the range from 800 fg to 500 pg and the limit of detection is 100 fg, which is 8 times lower than that of streptavidin-labeled Cy3 fluorescent dyes. The dyedoped SiO2 nanoparticles show potentials for the protein array detection.

关键词： Rhodamine B SiO2 nanoparticles protein detection protein microarrays

Two bimetallic W(Ⅳ)-Mn(Ⅱ) complexes based on octacyanometallates:structures and magnetic properties

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science china chemistry 2009年第11期52卷 1801-1807页

作者： LIU BaoLin,XIAO HongPing,SONG You & YOU XiaoZeng State Key laboratory of Coordination chemistry,nanjing National laboratory of Microstructures,school of chemistry and chemical engineering,nanjing university,nanjing 210093,china State Key laboratory of Coordination chemistry Nanjing National Laboratory of Microstructures School of Chemistry and Chemical Engineering Nanjing University Nanjing China

Two cyano-bridged heterobimetallic coordination polymers,[{Mn(dpa)2}2W(CN)8·CH3CN·4H2O]n(1)(dpa = 2,2'-dipyridylamine) and [Mn2(H2O)4{W(CN)8}·3H2O]n(2),have been synthesized and characterized structurally and magnetically.X-ray analysis shows that complex 1 is a one-dimensional(1-D) polymer of W2(CN)4Mn2 square units in which adjacent square fragments are interlinked by sharing [W(CN)8]4-moieties to form an infinite *** 2 is a three-dimensional(3-D) polymer,which shows an unforeseen structure,exhibiting a 3-D open network with a 1-D channel(ca.13.21  × 11.82 ).Fitting of the magnetic properties indicates that both polymers exhibit weakly antiferromagnetic interactions between the adjacent Mn ions.

关键词： cyano-bridged coordination polymer magnetic property manganese(Ⅱ) complex

Tripod molecules build molecular networks and open-dimer capsules by weak interactions

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science china chemistry 2010年第4期53卷 851-857页

作者： HAN Jun1, DENG Chao1, FANG Ru1, LI YiZhi2, WANG Leyong1& PAN Yi2 1Key laboratory of Mesoscopic chemistry, ministry of education school of chemistry and chemical engineering, nanjing university, nanjing 210093, china 2State Key laboratory of Coordination chemistry, nanjing university, nanjing 210093, china Key laboratory of Mesoscopic chemistry Ministry of Education Nanjing University Nanjing China school of chemistry and chemical engineering Nanjing University Nanjing China State Key laboratory of Coordination chemistry Nanjing University Nanjing China

Three tripod molecules, tris(2-methoxy-5-nitrobenzyl)phosphine oxide (1), tris(2-butoxy-3-methyl-5-nitrobenzyl)phosphine oxide (2), and tris(3-nitrobenzyl)amine (TNBA), were synthesized and crystallized. The structures of 1, 2, and their comparison (TNBA) were determined by X-ray crystallography. It is noteworthy that compound 1 interacted with adjacent molecules via π-π stacking and C-H···π interactions to yield an open supramolecular network with the porosity P in 8.9%, whereas compound 2 gathered closely to form an open-dimer capsule by sixfold N-O···π and triple C-H···O interactions, which showed a rare example of a stable in, out-invertomer of phosphine inversion existing in open-dimers. A series of columns were built and arranged side by side by these weak interactions. By contrast, TNBA crystallized to form a 2D network maintained by C-H···O and C-H···πinteractions. It seems minor changes of the chemical structure may cause large differences in the crystal structure and interactions in crystal engineering.

关键词： tripod molecule supramolecular network open-dimer capsule weak interaction

Regioselective aminohalogenation of β-nitrostyrenes using NCS and NBS as nitrogen/halogen sources

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science china chemistry 2010年第1期53卷 140-146页

作者： ZHI SanJun1,2,SUN Hao2,LIN Chen2,ZHANG GuangQian2,LI GuiGen4 & PAN Yi2,3 1 Department of chemistry,Huaiyin Normal university,Huai’an 221003,china 2 school of chemistry and chemical engineering,nanjing university,nanjing 210093,china 3 State Key Lab of Coordination chemistry,nanjing university,nanjing 210093,china 4 Department of chemistry and Biochemistry,Texas Tech university,Lubbock,Texas 79409-1061,USA Department of chemistry Huaiyin Normal University Huai’an China school of chemistry and chemical engineering Nanjing University Nanjing China Department of chemistry and Biochemistry Texas Tech University Lubbock USA State Key Lab of Coordination chemistry Nanjing University Nanjing China

Aminohalogenation reaction of β-nitrostyrenes with N-halosuccinimides(N-chloro and N-bromosuccinimides) has been successfully conducted by using nickel acetate as a catalyst in the presence of potassium carbonate and succinimide as *** reaction was easily performed at room temperature under nitrogen gas protection to give dihalorinaed haloamino products in good to excellent yields(60%-98%).The structure has been confirmed by X-ray crystal structure analysis.

关键词： aminohalogenation vicinal haloamines β-nitrostyrenes NBS NCS