A multiple coupling approach to produce high-performance SERS substrates

In this work, large area gold-nanoparticle-cluster pillar array with a gold mirror as high-performance SERS substrate was facilely fabricated by combined use of nanosphere lithography and self-assembly approach.     

[SiMo_2~(Ⅴ)Mo_(10)~(Ⅵ)O_(40)]~(6-)及其钒取代物的量子化学研究

采用SCC－DV－Xα方法对α－Keggin结构硅钼二电子还原态杂多蓝阴离子［SiMo2（V）Mo10（VI）O40］6-和它的混合型钒取代物［SiV2（V）Mo10（VI）O40］6-进行了量子化学计算，获得了轨道能级、费米能级、各原子价电子布居、自由价态密度分析和分子轨道成分等信息．理论分析表明该杂多阴离子中所有原子Si、Mo、V、Oa、Ob、Oc和Od都参与反应，Oc和Od的成键能力较强，化学活性较大，有力地支持了实验结果．中心硅氧四面体结构发生畸变很小，但构成三金属簇的八面体结构都发生了较明显的畸变，其整体仍然保持α－Keggin结构．钒的取代增强了Mo2VO13三金属族中Od的活性．预测这两种杂多阴离子都有被继续还原和取代的趋势，[SiMo2(V)Mo10(VI)O40]6-的趋势更强．     

Determination of Cr(III) and Cr(VI) in environmental waters by derivative flame atomic absorption spectrometry using flow injection on-line preconcentration with double-microcolumn adsorption

The species of Cr(III) and Cr(VI) in water samples were determined by flow injection on-line preconcentration and separation on two-microcolumn system-derivative flame atomic absorption spectrometry during a collaborative analysis for certification. The Cr(III) and Cr(VI) in water samples were retained on two microcolumns with ion exchange resin and were eluted directly to nebulizer by 15% HNO³ and 8% NH⁴NO³, respectively. The characteristic concentration (at the sensitivity grade of 2 mV min^?1 for 1 min of preconcentration time) for Cr(III) and Cr(VI) were 0.130 and 0.0985 μg l^?1, in the order which were 332- and 431-fold better than those of FAAS, and 45- and 47-fold better than those of FI-FAAS, respectively. The relative standard deviations were 3.27% and 3.66% with corresponding detection limits (3σ) of 0.244 and 0.235 μg l^?1, respectively. The linear ranges of determinations for Cr(III) and Cr(VI) were 0～100 μgm l^?1 with correlation coefficients of 0.9984 to 0.9996. The satisfactory recovery of 94.4%～106% for Cr(III) and Cr(VI) could be obtained from water samples.     

First principles study of the structure,electronic state,and stability of CmN2 clusters

Geometric and electronic properties of C_mN₂ (m = 1–14) clusters have been investigated by density functional theory using the hybrid B3LYP functional and the 6‐311G(d) basis set. Harmonic frequencies for these clusters are given to aid in the characterization of the ground states. These results show that C_mN₂ (m = 1–14) clusters form linear structures with D_∞h symmetry. Two N atoms favor to bond at ends in linear isomers. The chains with odd m have triplet ground states whereas the ones with even m have singlet ground states. The calculated HOMO–LUMO gaps and ionization potentials all show that the C_mN₂ (m = 1–14) clusters with even m are more stable than those with odd m, which is consistent with the observed even–odd alternation of the time‐of‐flight signal intensities. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Thermal and mass spectrometric fragmentation of esters of deuterated long chain carboxylic acids

A method combining thermal fragmentation and mass spectrometry for the determination of the position of double bonds in an unsaturated ester is presented. The thermal fragmentation of methyl esters of deuterated long chain carboxylic acids yields a homologous series of olefins plus a homologous series of unsaturated esters. The positions of the deuterium atoms in the original ester are revealed by the deuterium content of its fragments as determined by mass spectrometry. Therefore, the positions of double bonds of a polyunsaturated acid can be determined by pyrolysis after saturation by deuterium. The structures of the unsaturated fragments are ascertained by mass spectrometric method, and the formation of the ion [M – 32] in the mass spectrometric fragmentation of unsaturated methyl esters is studied by means of deuterium labeling.     

Hydrothermal Synthesis and Structure of a New 3D Lanthanide—Carboxylate Framework,[La（btec）1／2（H2btec）1／2（H2O）]n（H4btec=1,2,4,5—Benzeneteracarboxylic acid）

The title complex, [La(btec)_1/2(H₂btec)_1/2 (H₂O)]_n (H₄btec= 1, 2,4,5‐benzenetetracarboxylic acid) (1) was synthesized by the hydrothermal reaction of 1,2,4,5‐benzenetetracarboxylic dianhydride with La(NO₃)₃·6H₂O in H₂O, and crystallizes in the triclinic system, space group P‐1 with a = 0.64403(3) nm, b = 0.94500(4) nm, c = 0.96380(5) nm, a = 88.535(2)°, β = 100.314(2)°, γ = 76.6470(10)°, V = 1.60968(10) nm³, Z = 2, and final R = 0.0274, R_w = 0.0735. In 1, each La(m) ion is coordinated by eight oxygen atoms from six carboxylate groups and one coordinated water molecule. Two different coordination modes of H₄btec were present in the structure, one of which contains two protonated carboxylate groups to balance the charge.     

Nd-Fe-B alloy-densified agarose gel for expanded bed adsorption of proteins

Novel dense composite adsorbents for expanded bed adsorption of protein have been fabricated by coating 4% agarose gel onto Nd-Fe-B alloy powder by a water-in-oil emulsification method. Two composite matrices, namely Nd-Fe-B alloy-densified agarose (NFBA) gels with different size distributions and densities, NFBA-S (50-165 microm, 1.88 g/ml) and NFBA-L (140-300 microm, 2.04 g/ml), were produced. Lysozyme was used as a model protein to test the adsorption capacity and kinetics for the NFBA gels modified by Cibacron blue 3GA (CB-NFBA gels). Liquid-phase dispersion behavior in the expanded beds was examined by measurements of residence time distributions, and compared with that of Streamline SP (Amersham-Pharmacia Biotech, Sweden). The dependence of axial mixing in the expanded beds on flow velocity, bed expansion degree. settled bed height, and viscosity of liquid phase was investigated. Breakthrough curves of lysozyme in the expanded beds of the CB-NFBA gels were also examined. The dynamic binding capacity at 5% breakthrough was 23.3 mg/ml matrix for the CB-NFBA-S gels, and 16.7 mg/ml matrix for the CB-NFBA-L, at a flow velocity of 220 cm/h. The results indicate that the NFBA gels are promising for expanded bed adsorption of proteins.     

Synthesis of fluorinated imines and carbodiimides from azides via aza-Wittig reaction

The Staudinger reaction of fluoroalkylazides were studied. A series of N-fluoroalkylimines were synthesized via aza-Wittig reaction of N-fluoroalkyliminophosphoranes. The N,N′-difluoroalkylated carbodiimide was also synthesized via the reaction of N-fluoroalkyliminophosphoranes with carbon dioxide or carbon disulfide.     

Highly efficient non-doped blue fluorescent OLEDs with low efficiency roll-off based on hybridized local and charge transfer excited state emitters

Designing a donor–acceptor (D–A) molecule with a hybridized local and charge transfer (HLCT) excited state is a very effective strategy for producing an organic light-emitting diode (OLED) with a high exciton utilization efficiency and external quantum efficiency. Herein, a novel twisting D–π–A fluorescent molecule (triphenylamine–anthracene–phenanthroimidazole; TPAAnPI) is designed and synthesized. The excited state properties of the TPAAnPI investigated through photophysical experiments and density functional theory (DFT) analysis reveal that its fluorescence is due to the HLCT excited state. The optimized non-doped blue OLED using TPAAnPI as a light-emitting layer exhibits a novel blue emission with an electroluminescence (EL) peak at 470 nm, corresponding to the Commission International de L''Eclairage (CIE) coordinates of (0.15, 0.22). A fabricated device termed Device II exhibits a maximum current efficiency of 18.09 cd A⁻¹, power efficiency of 12.35 lm W⁻¹, luminescence of ≈29 900 cd cm⁻², and external quantum efficiency (EQE) of 11.47%, corresponding to a high exciton utilization efficiency of 91%. Its EQE remains as high as 9.70% at a luminescence of 1000 cd m⁻² with a low efficiency roll-off of 15%. These results are among the best for HLCT blue-emitting materials involved in non-doped blue fluorescent OLEDs. The performance of Device II highlights a great industrial application potential for the TPAAnPI molecule.

A new pure fluorescent blue HLCT-emitter was designed and synthesized. Highly efficient non-doped blue OLEDs with low efficiency roll-off were achieved.     

Structural studies of DMβCD/dihalogenated norcarane inclusion complexes

Inclusion complexes of 7,7-dibromonorcarane (1) and 7,7-dichloronorcarane (2) with 2,6-dimethyl--cyclodextrin (DMCD) have been synthesized. Their structures have been studied by chemical analysis, thermal behavior, IR spectra, UV absorptions and¹³C NMR spectra in DMSO solutions. The studies show that the orientation of (1) is different from that of (2) in the DMCD cavity.Presented at the 6th International Symposium on Molecular Recognition and Inclusion, Berlin, Germany, 10–14 September 1990.