靛蓝胭脂红的光谱电化学研究 II. 靛蓝胭脂红复相电子转移动力学

报道了靛蓝胭脂红在SnO_2透光电极上的复相电子转移动力学参数。由光谱电化学和电化学两种实验方法测定。前一方法为单电位阶跃计时吸收法((SPS/CA)。后一方法为循环伏安法。两种方法的数据处理中均应用了计算机拟合, 较之文献中常规的工作曲线法更为简便、正确。两种方法测定的结果十分一致。进一步的研究表明, 动力学参数值与靛蓝胭脂红的浓度和溶液pH有关, 为靛蓝胭脂红在水溶液中的状态提供了重要信息。     

Neomycin binding to Watson-Hoogsteen (W-H) DNA triplex groove: a model

Neomycin is the most effective aminoglycoside (groove binder) in stabilizing a DNA triple helix. It stabilizes TAT, as well as mixed base DNA triplexes, better than known DNA minor groove binders (which usually destabilize the triplex) and polyamines. Neomycin selectively stabilizes the triplex (in the presence of salt), without any effect on the DNA duplex. (1) Triplex stabilization by neomycin is salt dependent (increased KCl and MgCl(2) concentrations decrease neomycin's effectiveness, at a fixed drug concentration). (2) Triplex stabilization by neomycin is pH dependent (increased pH decreases neomycin's effectiveness, at a fixed drug concentration). (3) CD binding studies indicate approximately 5-7 base triplets/drug apparent binding site, depending upon the structure/sequence of the triplex. (4) Neomycin shows nonintercalative groove binding to the DNA triplex, as evident from viscometric studies. (5) Neomycin shows a preference for stabilization of TAT triplets but can also accommodate CGC(+) triplets. (6) Isothermal titration calorimetry (ITC) studies reveal an association constant of approximately 2 x 10(5) M(-)(1) between neomycin and an intramolecular triplex and a higher K(a) for polydA.2polydT. (7) Binding/modeling studies show a marked preference for neomycin binding to the larger W-H groove. Ring I/II amino groups and ring IV amines are proposed to be involved in the recognition process. (8) The novel selectivity of neomycin is suggested to be a function of its charge and shape complementarity to the triplex W-H groove, making neomycin the first molecule that selectively recognizes a triplex groove over a duplex groove.     

Organosulfur-functionalized Au, Pd, and Au-Pd nanoparticles on 1D silicon nanowire substrates: preparation and XAFS studies

A hybrid preparative method was developed to prepare organosulfur-functionalized Au nanoparticles (NPs) on silicon nanowires (SiNWs) by reacting HAuCl(4) with SiNW in the presence of thiol. A number of organosulfur molecules-dodecanethiol, hexanethiol, 1,6-hexanedithiol, and tiopronin-were used to functionalize the Au surface. Size-selected NPs ranging from 1.6 to 7.5 nm were obtained by varying the S/Au ratio and the concentration of HAuCl(4). This method was further extended to the preparation Pd and Pd-Au bimetallic NPs on SiNWs. The morphology of the metal nanostructures was examined by transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). The local structure and bonding of the SiNW-supported metal nanostructures were studied using X-ray absorption fine structures (XAFS) [including both X-ray near-edge structures (XANES) and extended X-ray absorption fine structures (EXAFS)] at the Au L(3)-, Pd K-, S K-, and Si K-edges. It was also found that the annealing of the thiol-capped Au NPs up to 500 degrees C transforms the surface of the thiol-capped NPs to gold sulfide, as identified using Au L(3)- and S K-edge XANES. We also illustrate that this preparative approach can be used to form size-controllable Au NPs on carbon nanotubes.     

Preconcentration of lanthanides from natural waters with a lipophilic crown ether carboxylic acid

Lipophilic crown ether carboxylic acids such as 2-(sym-dibenzo-16-crown-5-oxy)stearic acid with a cavity size comparable to the ionic radius of rare-earth elements are selective chelation agents for preconcentration and separation of lanthanides from natural waters for NAA. Interfering matrix elements such as sodium and bromine can be simultaneously eliminated during the extraction. The lanthanides can be back-extracted into a dilute acid solution for NAA, thus providing a large preconcentration factor. This two-step extraction method appears suitable for the determination of lanthanides in natural waters and in biological samples.     

Spectrofluorimetric determination of thiols by use of N[P-(2-benzoxazolyl)phenyl]maleimide

The weak fluorescence of N-[P-(2-benzoxazolyl)phenyl]maleimide (BOPM) can be greatly enhanced by thiol-containing compounds. A sensitive and simple spectrofluorimetric method based on the use of BOPM has been developed for the determination of thiols such as cysteine (Cys) and reduced glutathione (GSH). Calibration plots were linear in the concentration range from 0 to 1.6 x 10(-7) mol L(-1) for Cys and 0 to 1.7 x 10(-7) mol L(-1) for GSH. The detection limits (3a) were 2.36 x 10(-10) mol L(-1) for Cys and 1.49 x 10(-10) mol L(-1) for GSH. Many other amino acids (present at 100-fold greater concentrations) did not interfere with the determination. The proposed method has been used for the determination of Cys in protein hydrolysate and cystine electrolyte or GSH in serum, with recoveries of 95.4-103.7%.     

Transition metal coordination polymers with polycarboxylic acid as bridging ligands: Synthesis and structure characterization of [Fe(μ4-bta)0.5(phen)(OH)]<Subscript>n</Subscript>

A new 2D (two-dimensional) coordination polymer, [Fe(μ4-bta)o.5(phen)(OH)]_n (1), has been hydrothermally synthesized with FeCl₃ 6H₂, Na₄bta (h₄bta = 1,2,4,5-benzentetracarboxylic acid), 1,10-phen (1,10-phenanthroline) and H₂O as raw materials. The crystals of the compound belong to monoclinic P2₁/n space group, a = 1.0129(2) nm, b = 0.9265(2) nm, c = 1.5696(3) nm, β=91.37(3)°V=1.4721(5) nm³,Z=3, final R₁=0.0292, wR ₂=0.0798 for 2572 [/>2σ(/)] observed reflections. The result of structure determination shows that in the compound each bta ligand is connected with four Fe³, forming a new μ4-coordination mode. Four deprotonated carboxylic groups of bta link to Fe³ ions alternatively through monodentate and bidentate coordination fashion, constructing 2D layer network. The measurement of variable temperature magnetic susceptibility indicates that there exist antiferromagnetic interactions between Fe³ ions in the compound. The TGA spectrum displays relatively fine thermal stability of the compound. In addition, IR and UV-Vis spectra of compound 1 have also been measured.     

Filter-based microfluidic device as a platform for immunofluorescent assay of microbial cells

A filter-based microfluidic device was combined with immunofluorescent labeling as a platform to rapidly detect microbial cells. The coin-sized device consisted of micro-chambers, micro-channels and filter weirs (gap = 1-2 microm), and was demonstrated to effectively trap and concentrate microbial cells (i.e., Cryptosporidium parvum and Giardia lamblia), which were larger in size than the weir gap. After sample injection, a staining solution containing fluorescently-labeled antibodies was continuously provided into the device (flow rate = 20 microl min(-1)) to flush the microbial cells toward the weirs and to accelerate the fluorescent labeling reaction. Using a staining solution that was 10 to 100 times more dilute than the recommended concentration used in a conventional glass method, those target cells with a fluorescent signal-to-noise ratio of 12 could be microscopically observed at single-cell level within 2 to 5 min prior to secondary washing.     

A graphical evaluation of characteristic polynomials of huckel trees

Characteristic polynomials of acyclic carbon chains (Huckel trees) are treated in a systematic way. Formulas of coefficients (a_k) of the polynomial are obtained in terms of connectivities that were introduced for dealing with moments in a previous paper. Based on the meaning of a_k, a graph-theoretical analysis is given such that a_k can be expressed as a linear combination of binomial factors specified by a set of graphs containing ½k edges. The numerical relationship is disclosed between each binomial factor and its specified graph. This stimulates the proposal of a novel approach for evaluating ak by simply collecting the graph set of defnite edges. The approach is equally applicable for the evaluation of matching polynomials of cyclic systems and extendable to the investigation of general trees.