用淋洗法修复张士灌区CdPb污染沉积物的研究

采用淋洗法,以组成为0.5m ol·L-1C aC l2和0.1m ol·L-1H C l的复合药剂作为淋洗剂处理沈阳张士灌区C d、Pb污染沉积物(C d39m g·kg-1,Pb1250m g·kg-1),在pH=1.0、反应时间30m in、淋洗剂液固比3∶1、搅拌速度500r·m in-1、温度25℃的条件下,复合淋洗剂对C d和Pb的去除率分别达到70.8%和29.3%。粒级分析表明,沉积物中C d和Pb主要存在于细粒部分,因此,分级处理能够减少处理量,降低成本。一定酸度下C l-的络合作用可能是复合淋洗剂的主要强化淋洗机制。

Effect of acetylation on the properties of corn starch

Acetylated corn starches with different degrees of substitution (DS 0.85, DS 1.78, DS 2.89) were synthesized by the reaction of corn starch with acetic anhydride in the presence of acetic acid under varying reaction temperatures. The product was characterized by FTIR spectroscopy, H-1 NMR, X-ray diffraction and contact angle measurement. Acid-base titration and H-1 NMR methods were employed to determine the degree of substitution of product. FTIR spectroscopic analysis showed that the characteristic absorption intensities of esterified starch increased with increase in the degree of substitution, and the characterized peak of hydroxyl group almost disappeared in the spectrum of DS 2.89 acetylated starch. The detailed chemical microstructure of native starch and acetylated starch was confirmed by H-1 NMR, C-13 NMR and C-13-(1) H-1 COSY spectra.

Solution-processable highly efficient yellow- and red-emitting phosphorescent organic light emitting devices from a small molecule bipolar host and iridium complexes

A bipolar transport compound, 2,5-bis(4-(9-(2-ethylhexyl)-9H-carbazol-3-yl) phenyl)-1,3,4-oxadiazole (CzOXD), incorporating both electron-and hole-transport functionalities, was synthesized and fully characterized by H-1 NMR, C-13 NMR, elemental analysis and mass spectrometry. Its thermal, electrochemical, electronic absorption and photoluminescent properties were studied

Nanoparticle-amplified Surface Plasmon Resonance Study of Protein Conformational Change at Interface

This paper reports the study of protein conformational change by Au nanoparticles (AUNPs)-amplified surface plasmon resonance (SPR) spectroscopy. Taking cytochrome c (Cyt c) as an example, this paper gives a detailed description of the construction of metal-protein-metal sandwich nanostructure consisting of an Au film underlayer, a cytochrome c intermediate layer and an AuNPs upper layer. The incorporation of AuNPs into SPR biosensing results in increased SPR sensitivity to protein conformational change as demonstrated by acid denaturation of Cyt c. It suggests the conformational change of surface-confined Cyt c leads to the distance and electromagnetic coupling variations of Au film-AuNPs.

Band Gap Tunable, Donor-Acceptor-Donor Charge-Transfer Heteroquinoid-Based Chromophores: Near Infrared Photoluminescence and Electroluminescence

A series of D-pi-A-pi-D type of near-infrared (NIR) fluorescent compounds based on benzobis(thia diazole) and its selenium analogues were synthesized and fully characterized by H-1 and C-13 NMR, high-resolution mass spectrometry, and elemental analysis. The absorption fluorescence, and electrochemical properties were also studied. Photoluminescence of these chromophores ranges from 900 to 1600 nm and their band gaps are between 1.19 and 0.56 eV.

Rapid label-free detection of metal-induced Alzheimer's amyloid beta peptide aggregation by electrochemical method

Amyloid beta peptide plays a critical role in the pathogenesis of Alzheimer's disease (AD). Metal ions are highly enriched in cerebral amyloid deposits in AD and are proposed to be able to mediate A beta conformation. Therefore, a rapid, low-cost, and sensitive detection of metal-induced A beta aggregation and their relation to AD is clearly needed for the clinical diagnosis and treatment. In this report, we study metal-induced A beta aggregation by a rapid, label-free electrochemical method and monitor both the aggregation kinetics and the morphology in the absence or presence of Zn (II) and Cu (II).

Synthesis and characterisation of novel imidazolium-based ionic liquid crystals with a p-nitroazobenzene moiety

A novel series of compounds with different counter anions, i.e. 1-{[4-(4-nitrophenylazo)phenyloxy]}alkyl-3-methyl-1H-imidazol-3-ium bromide salts (C-n , n=3, 6, 10) and tetrafluoroborate salts (D-n , n=3, 6, 10), were synthesised by the incorporation of an imidazolium group into paraffin side chain-terminated 4-nitroazobenzene derivatives. Their chemical structures were determined by H-1 NMR, C-13 NMR, UV spectroscopy and elemental analysis.

Electrochemistry of Microperoxidase-11 (MP-11) on Glassy Carbon Electrode Modified with Chitosan

In this paper, microperoxidase-11 (MP-11) was immobilized on glassy carbon electrode surface modified with chitosan by physical adsorption. The direct electrochemistry and the electrocatalytic behaviours to O-2 and the H2O2 of MP-11 on glassy carbon electrode modified with chitosan were characterized by cyclic voltammetry. The results indicate that MP-11 on modified electrode displays a quasi-reversible electrochemical process coupled with proton transfer in the phosphate buffer solutions(pH = 7.12). Direct electrochemical reaction of MP-11 on modified electrode has been realized. MP-11 on modified electrode can catalyze reduction for O-2 and H2O2. Both of the catalytic reductions are surface-controlled electrochemical process.

Synthesis, photophysical and electrophosphorescent properties of mononuclear Pt(II) complexes with arylamine functionalized cyclometalating ligands

Four cyclometalated Pt(II) complexes, i.e., [(L-2)PtCl] (1b), [(L-3)PtCl] (1c), [(L-2)PtC CC6H5] (2b) and [(L-3)PtC CC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2'-bipyridine and HL3 = 4-[p(-N,N'-dibutyl-N'-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2'-bipyridine), have been synthesized and verified by H-1 NMR, C-13 NMR and X-ray crystallography. Unlike previously reported complexes [(L-1)PtCl] (1a) and [(L-1)PtC CC6H5] (2a) (HL1 = 4,6-diphenyl-2,2'-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer ((MLCT)-M-1) (d pi(Pt) -> pi*(L)) transitions (epsilon similar to 2 x 10(4) dm(3) mol (1) cm (1)) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c.

Copolymerizations of ethylene with alpha-olefin-omega-ols by highly active vanadium(III) catalysts bearing [N,O] bidentate chelated ligands

The copolymerizations of ethylene with polar hydroxyl monomers such as 10-undecen-1-ol, 5-hexen-1-ol and 3-buten-1-ol were investigated by the vanadium(III) catalysts bearing bidentate [N,O] ligands (1, [PhN=C(CH3)CHC(Ph)O]VCl2(THF)(2): 2, [PhN=CHC6H4O]VCl2(THF)(2); 3, [PhN=CHC(Ph)CHO]VCl2(THF)(2)). The polar monomers were pretreated by alkylaluminum before the polymerization. High catalytic activities and efficient comonomer incorporations can be easily obtained by changing monomer masking reagents and polymerization conditions in the presence of diethylaluminium chloride as a cocatalyst. The longer the spacer group, the higher the incorporation of the monomer. Under the mild conditions, the incorporation level of 10-undecen-1-ol reached 13.9 mol% in the resultant copolymers was obtained. The reactivity ratios of copolymerization (r(1) = 41.4, r(2) = 0.02, r(1)r(2) = 0.83) were evaluated by Fineman-Ross method. According to C-13 NMR spectra, polar units were located both on the main chain and at the chain end.

Spectral and electrochemical detection of protonated triplex formation by a small-molecule anticancer agent

Triplex helical formation has been the focus of considerable interest because of possible applications in developing new molecular biology tools as well as therapeutic agents and the possible relevance of H-DNA structures in biology system. We report here that a small-molecule anticancer agent, coralyne, has binding preference to the less stable protonated triplex d(C+-T)(6):d(A-G)(6).d(C-T)(6) over duplex d(A-G)(6).d(C-T)(6) and shows different spectral and electrochemical characteristics when binding to triplex and duplex DNA, indicating that electrochemical technique can detect the less stable protonated triplex formation.

一种新的拓扑指数用于手性化合物的构效关系研究

为了研究羟酸类和氨基酸类手性化合物的构效关系,本实验引进了手性乘积算法:P=(1-b/a)(1-c/b)(1-a/c)(1-a/d),其中a、b、c和d分别为与分子中手性中心碳原子4个不同连接片断手性eAm指数和分子连接性指数mx的计算值,并考察了所得参数与羟酸类和氨基酸类化合物手性薄层色谱保留指数的相关性。为了评定所得预测模型的稳定性,文中运用了交叉验证法。结果表明,由人工神经网络方法(BP法)所得数学模型比较稳定,且明显优于多元回归分析结果。

Investigation of the hydrolysis of ginsenosides by high performance liquid chromatography-electrospray ionization mass spectrometry

The hydrolysis of ginsenoside standards and the crude extracts of ginseng has been investigated at different pH values (2.4 - 11.2) using high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS). The experimental results indicated that the pH value of aqueous solutions is an important factor in changing the composition of ginsenosides. For (20S)-protopanaxadiol ginsenosides, ginsenosides with a large mass hydrolyzed to form hydrolysates (20S)-Rg(3) and (20R)-Rg(3) at pH 4.3. There were more hydrolyzed products observed at pH 3.3: (20S)-F-2, C-25,26 hydrated ginsenoside "C-Y-1" and "C-Y-2" (MW = 802 Da) accompanied with (20S)-Rg(3), (20R)-Rg(3). At pH 2.4, only (20R)-Rg(3), (20S)-F-2, a small quantity of (20S)-Rg(3) and three C-25,26 hydrated ginsenosides were obtained. For (20S)protopanaxatriol Re, no hydrolysates were observed at pH 4.3; it was hydrolyzed at pH 3.3 to form hydrolysates (20S)-Rg, (20R)Rg(2) and hydrated C-25,26 (MW = 802 Da) and at pH 2.4 only C-25,26 hydrated ginsenosides "C-Y-1" and "C-Y-2" (MW = 802 Da) were left in the solution. Similar hydrolysis reactions could be also observed for the crude extracts of ginseng. It showed that HPLC/ESI-MS is a fast and convenient method to study the hydrolysis of ginseng.

pH-dependent protein conformational changes in albumin : gold nanoparticle bioconjugates: A spectroscopic study

The conformational changes of bovine serum albumin (BSA) in the albumin:gold nanoparticle bioconjugates were investigated in detail by various spectroscopic techniques including UV-vis absorption, fluorescence, circular dichroism, and Fourier transform infrared spectroscopies. Our studies suggested that albumin in the bioconjugates that was prepared by the common adsorption method underwent substantial conformational changes at both secondary and tertiary structure levels. BSA was found to adopt a more flexible conformational state on the boundary surface of gold nanoparticles as a result of the conformational changes in the bioconjugates. The conformational changes at pH 3.8, 7.0, and 9.0, which corresponded to different isomeric forms of albumin, were investigated, respectively, to probe the pH effect on the conformational changes of BSA in the bioconjugates. The results showed that the pH of the medium influenced the changes greatly and that fluorescence and circular dichroism studies further indicated that the changes were larger at higher pH.