Roles of terminal groups of oligomer electrolytes in determining photovoltaic performances of dye-sensitized solar cells

The effect of terminal groups of oligomer electrolytes on the photovoltaic performance of dye-sensitized solar cells (DSSCs) have been systematically investigated to show that the terminal group plays a critical role in determining the concentration of I(3)(-), ionic conductivity, flatband potential and consequently the energy conversion efficiency.     

聚甲基苯基硅氮硅氧烷-鈀络合物结构的X-射线光电子能谱(XPS)研究

<正> 近年来,高分子金属催化剂由于其特殊的高分子效应引起人们广泛关注,目前在国外市场上已有高分子金属催化剂商品供应,它较低分子有机金属催化剂活性更高,选择性更好,并已广泛用于加氢,硅氢加成,转化,醛化,分解,齐聚,聚合和不对称合成等很多反应中,然而对其结构的研究至今报道甚少。     

Electrochemical determination of dopamine and ascorbic acid at a novel gold nanoparticles distributed poly(4-aminothiophenol) modified electrode

A modified electrode is fabricated by embedding gold nanoparticles into a layer of electroactive polymer, poly(4-aminothiophenol) (PAT) on the surface of glassy carbon (GC) electrode. Cyclic voltammetry (CV) is performed to deposit PAT and concomitantly deposit Au nanoparticles. Field emission transmission electron microscopic image of the modified electrode, PAT-Au_nano-ME, indicates the presence of uniformly distributed Au nanoparticles having the sizes of 8-10 nm. Electrochemical behavior of the PAT-Au_nano-ME towards detection of ascorbic acid (AA) and dopamine (DA) is studied using CV. Electrocatalytic determination of DA in the presence of fixed concentration of AA and vice versa, are studied using differential pulse voltammetry (DPV). PAT-Au_nano-ME exhibits two well defined anodic peaks at the potential of 75 and 400 mV for the oxidation of AA and DA, respectively with a potential difference of 325 mV. Further, the simultaneous determination of AA and DA is studied by varying the concentration of AA and DA. PAT-Au_nano-ME exhibits selectivity and sensitivity for the simultaneous determination of AA and DA without fouling by the oxidation products of AA or DA. PAT and Au nanoparticles provide synergic influence on the accurate electrochemical determination of AA or DA from a mixture having any one of the component (AA or DA) in excess. The practical analytical utilities of the PAT-Au_nano-ME are demonstrated by the determination of DA and AA in dopamine hydrochloride injection and human blood serum samples.     

Tris（2,2＇-bipyridyl） Ruthenium（Ⅱ） Doped Silica Film Modified Indium Tin Oxide Electrode and Its Electrochemiluminescent Properties

An approach was reported to synthesize silica hybridized ruthenium bipyridyl complex through amidation reaction by covalent attachment of bis（bipyridyl）-4,4＇-dicarboxy-2,2＇-bipyridyl-ruthenium to （3-aminopropyl）-triethoxysilane. The hybrid complex then was gelatinized through acid catalytic hydrolysis method and a sol-gel modified indium tin oxide electrode was prepared via spin coating technique. As prepared indium tin oxide electrode possesses good stability therein with excellent electrochemiluminescence behavior.     

The video-rate imaging of sub-10 nm plasmonic nanoparticles in a cellular medium free of background scattering

Plasmonic nanoparticles (e.g., gold, silver) have attracted much attention for biological sensing and imaging as promising nanoprobes. Practical biomedical applications demand small gold nanoparticles (Au NPs) with a comparable size to quantum dots and fluorescent proteins. Very small nanoparticles with a size below the Rayleigh limit (usually <30–40 nm) are hard to see by light scattering using a dark-field microscope, especially within a cellular medium. A photothermal microscope is able to detect very small nanoparticles, down to a few nanometers, but the imaging speed is usually too slow (minutes to hours) to image living cell processes. Here an absorption modulated scattering microscopy (AMSM) method is presented, which allows for the imaging of sub-10 nm Au NPs within a cellular medium. The unique physical mechanism of AMSM offers the remarkable ability to remove the light scattering background of the cellular component. In addition to having a sensitivity comparable to that of photothermal microscopy, AMSM has a much higher imaging speed, close to the video rate (20 fps), which allows for the dynamic tracking of small nanoparticles in living cells. This AMSM method might be a valuable tool for living cell imaging, using sub-10 nm Au NPs as biological probes, and thereby unlocking many new applications, such as single molecule labeling and the dynamic tracking of molecular interactions.

An absorption modulated scattering microscopy technique that allows for the imaging of sub-10 nm gold nanoparticles within a cellular scattering medium is presented.     

Synthesis,Separation, and Theoretical Studies of Chiral Biphenyl Lignans (α‐ and β‐DDB)

Two biphenyl lignans, α‐ and β‐DDB ( 1 and 2 , respectively) were efficiently synthesized without contamination by other regio‐isomers. The different yields of the Ullmann coupling reactions for the synthesis of 1 and 2 were rationalized by calculating steric hindrance, stability, entropy change, and heat‐of‐formation values. The enantiomers of 1 and 2 were readily separated by HPLC on a chiral stationary phase. Their configurations were assigned based on the Cotton effect of the authentic natural products.     

Arsenic trioxide-induced apoptosis is independent of stress-responsive signaling pathways but sensitive to inhibition of inducible nitric oxide synthase in HepG2 cells

Arsenic trioxide (As(2)O(3)) has been found to be remarkably effective in the treatment of patients with acute promyelocytic leukemia (APL). Although evidences for the proapoptotic activity of As(2)O(3) have been suggested in leukemic and other solid cancer cells, the nature of intracellular mechanisms is far from clear. In the present study, we investigated As(2)O(3) affect on the stress-responsive signaling pathways and pretreatment with antioxidants using HepG2 cells. When treated with micromolar concentrations of As(2)O(3), HepG2 cells became highly apoptotic paralleled with activation of caspase-3 and members of mitogen-activated protein kinases (MAPKs) including extracellular signal-regulated kinase (ERK) and c-jun NH(2)-terminal kinase (JNK) but not p38 MAP kinase. However, inhibition of each kinase activity failed to inhibit apoptosis by As(2)O(3). Addition of n-acetyl cysteine (NAC) or diphenyleneiodonium (DPI) effectively protected cells from apoptosis and significantly lowered As(2)O(3)-induced activation of caspase-3. However, neither NAC nor DPI was able to effect ERK or JNK activation induced by As(2)O(3). Guanidinoethyldisulfide dihydrochloride (GED) and 2-ethyl-2-thiopseudourea (ETU), known inhibitors of the inducible nitric oxide synthase (iNOS), also suppressed the apoptotic activity of As(2)O(3). These results suggest that As2O3 induces caspase-mediated apoptosis involving a mechanism generating oxidative stress. However, activation of some stress-responsive signaling pathways by As(2)O(3) may not be the major determinant in the course of apoptotic processes.     

A series of tetrahomodioxacalix[4]biscrown-n. Syntheses, crystal structures, and metal binding abilities

A series of novel tetrahomodioxacalix[4]biscrowns with crown-2, crown-3, crown-4, crown-5, and crown-6 units were synthesized. Conformations of each product are dependent on the base used and their conformation stabilities. All conformations were proven by NMR spectra and/or X-ray crystal structures. The 1,3-alternate homodioxacalix[4]biscrown-4 (4b) shows the best selectivity for K+, whereas the 1,3-alternate homodioxacalix[4]crown-5 (5) does for Cs+. Those selectivities are attributable to electrostatic interaction between the metal ion and the crown ring, as well as a pi-metal complexation. However, the C-1,2-alternate conformation does not take the metal ions regardless of the crown species as a result of steric hindrance from the methylene bridge of an ArCH2Ar unit.     

Complexation mechanism of olefin with silver ions dissolved in a polymer matrix and its effect on facilitated olefin transport

Remarkable separation performance of olefin/paraffin mixtures was previously reported by facilitated olefin transport through silver-based polymer electrolyte membranes. The mechanism of facilitated olefin transport in solid membranes of AgCF3SO3 dissolved in poly(N-vinyl pyrrolidone) (PVP) is investigated. In silver polymer electrolyte membranes, only free anions are present up to the 2:1 mole ratio of [C=O]:[Ag], and ion pairs start to form at a ratio of 1:1, followed by higher-order ionic aggregates above a ratio of 1:2. At silver concentrations above 3:1, the propylene permeance increases almost linearly with the total silver concentration, unexpectedly, regardless of the silver ionic constituents. It was also found that all the silver constituents, including ion pairs and higher order ionic aggregates, were completely redissolved into free anions under the propylene environment; this suggests that propylene can be a good ligand for the silver cation. From these experimental findings, a new mechanism for the complexation reaction between propylenes and silver salts in silver-polymer electrolytes was proposed. The new mechanism is consistent with the linearity between the propylene permeance and the total silver concentration regardless of the kind of the silver constituents. Therefore, the facilitated propylene transport through silver-polymer electrolytes may be associated mainly with the silver cation weakly coordinated with both carbonyl oxygen atoms and propylene.     

On-channel base stacking in microchip capillary gel electrophoresis for high-sensitivity DNA fragment analysis

We evaluated a novel strategy for high-sensitivity DNA fragment analysis in a conventional glass double-T microfluidic chip. The microchip allows for a DNA on-channel concentration based on base stacking (BS) with a microchip capillary gel electrophoretic (MCGE) separation step in a poly(vinylpyrrolidone) (PVP) sieving matrix. Depending if low conductivity caused a neutralization reaction between the hydroxide ions and the run buffer component Tris+, the stacking of DNA fragments were processed in the microchip. Compared to a conventional MCGE separation with a normal electrokinetic injection, the peak heights of 50-2650-base pair (bp) DNA fragments on the MCGE-BS separation were increased 3.9-8.0-fold. When we applied the MCGE-BS method to the analysis of a clinical sample of bovine theileria after PCR reaction, the peak height intensity of the amplified 816-bp DNA fragment from the 18S rRNA of T. buffeli was enhanced 7.0-fold compared to that of the normal injection method.