Electrochemistry and electron transport properties of copolymers of electron deficient fluorenes with thiophene

Copolymers of fluoren-9-one and (fluoren-9-ylidene)malononitrile with thiophene have been prepared by the electrochemical polymerization of 2-(2-thienyl)fluoren-9-one, 2,7-di(2-thienyl)fluoren-9-one, and (2,7-di(2-thienyl)fluoren-9-ylidene)malononitrile. 2-(2-Thienyl)fluoren-9-one gave polymer films with low conjugation lengths, indicating poorly defined coupling, while both monomers with two terminal thiophenes gave high quality copolymers. Poly-[2,7-di(2-thienyl)fluoren-9-one] was the most easily p-doped material, and gave the highest p-type conductivity of ca. 0.4 mS cm⁻¹. In contrast poly-[(2,7-di(2-thienyl)fluoren-9-ylidene)malononitrile] was more easily reduced by over 0.5 V (formal potential = −0.60 V versus Ag/AgCl), and exhibited the higher n-type conductivity of ca. 6 μS cm⁻¹. Comparisons between the three copolymers reveal differences in the mechanisms of p-type and n-type conduction, with the former dominated by hole transport along the polymer chains and the latter involving electron hopping between localized sites.     

The effect of compression on electron transport and recombination in plastic TiO2 photoanodes

The compression method was applied for the preparation of plastic TiO₂ porous films on a conductive indium–tin oxide (ITO)-coated polyethylene naphthalate (PEN) substrate at low temperature for the generation of high-efficiency plastic dye-sensitized solar cells (DSCs). The compression parameters, including pressure and time, were varied in order to determine their effect on the photovoltaic performance of the plastic DSCs. The results from electrochemical impedance spectroscopy (EIS) showed that charge transport resistance in the porous TiO₂ films (R_t) gradually decreased when the applied pressure was increased from 0 MPa to 150 MPa, which indicated a better connection between the TiO₂ nanoparticles and electron transport in the TiO₂ films. In addition, a longer press time led to an increased resistance of electron recombination (R_ct) and an increased charge-collection efficiency. After optimization of the compression parameters, the efficiency of energy conversion was increased by approximately 81.6%. In addition, the efficiency of energy conversion was increased by an additional 4.65% under AM1.5 illumination.     

The effect of the series resistance in dye-sensitized solar cells explored by electron transport and back reaction using electrical and optical modulation techniques

The influence of the series resistance on the electron transport and recombination processes in dye-sensitized solar cells (DSC) has been investigated. The series resistances induced by some parts of DSC, such as the transparent conductive oxide (TCO), the electrolyte layer and the counter electrode, influence the performance of DSC. By combining three frequency-domain techniques, specifically electrochemical impedance spectroscopy (EIS), intensity modulated photocurrent spectroscopy (IMPS) and intensity modulated photovoltage spectroscopy (IMVS), we studied the relationship between the series resistance and the dynamic response of DSC. The results show that the series resistance induced by the TCO or counter electrode predominantly affects the electron transport under short circuit conditions and has no significant influence on the recombination under open circuit conditions. However, the resistance related to the electrolyte layer not only limits the carrier transport but also influences the recombination. Possible reasons for the influence of the series resistance on the electron transport and recombination processes in DSC are also discussed.     

Electronic structure and transport properties of carbon nanotube adsorbed with a copper chain

The authors have studied the electronic structure and transport properties of hybrid nanowires made of a copper chain adsorbed on a single-wall carbon nanotube (CNT) using first principle methods. Results have shown that after the adsorption of the Cu chain, the density of states and the transmission coefficients of the CNT (5, 5)/Cu nanowire have been increased, while the band gap of CNT (10, 0)/Cu have been significantly reduced. These results imply that the conductivity of CNTs, either metallic or semiconducting, have been enhanced by the adsorption of a copper chain. These hybrid nanowires with enhanced conductivity may be suitable for nanoelectronics.     

Keggin结构多金属氧酸铵盐的缓蚀性能评价

在室温条件下用液相直接沉淀法合成了6种Keggin结构的磷钨酸铵盐,并进行了IR光谱表征.采用静态、动态挂片失重法研究考察了6种多金属氧酸铵盐在水介质中对20~#钢的缓蚀作用,通过扫描电镜对金属表面成膜或腐蚀情况进行了分析和评价.研究结果表明,Keggin结构磷钨酸铵盐均是碳钢良好的缓蚀剂,有机铵盐的缓蚀性能优于无机铵盐.     

Synthesis, optical and morphological characterization of soluble main chain 1,3,4-oxadiazole copolyarylethers—potential candidates for solar cells applications as electron acceptors

New copoly(arylether)s containing substituted terphenyl, quinquephenyl, fluorene and anthracene moieties with aromatic 1,3,4-oxadiazole units were prepared and the resulting copolymers are soluble in common organic solvents. Investigation of their optical properties revealed that they emit blue and yellow light. Moreover, their photovoltaic response was studied in blends with poly(3-hexylthiophene) (P3HT) as the electron donor. Despite the low power conversion efficiencies it was shown that photo-induced electron transfer does take place and the performances are higher than a single layer P3HT device. In addition, an anthracene-fluorene-oxadiazole main chain copolymer (PAFOXD) was also examined in a single layer photovoltaic device and gave one of the highest reported open-circuit voltage (V_oc) values in the literature (0.89 V). Finally, a detailed morphological study of the blends and the PAFOXD surface using the atomic force microscopy (AFM) technique, revealed the effect of solvent selection to the preparation of thin films exhibiting the desired performance characteristics.     

Photoelectronic and transport properties of polypyrrole doped with a dianionic dye

Polypyrrole (PPy) doped with dodecylsulfate (DS) and an organic dye (indigo carmine, IC) was electrochemically prepared and characterized by Raman spectroscopy and X-ray diffraction (XRD). The photoelectrochemical properties of PPy-DS and PPy-DS-IC in contact with an electrolytic solution containing a redox couple were studied using the theories for the semiconductor ∣ electrolyte interface. Results indicate that the system containing IC presents a higher photocurrent density under polychromatic illumination and faster response time when compared with PPy-DS. This fact was assigned to the formation of molecular-scale paths in PPy-DS-IC. The IC molecules lying perpendicularly between PPy chains, as confirmed by the X-ray analysis, could facilitate the mass transport at the interface and increase the ordering degree to provide better electronic charge transfer in the bulk. Although the photoelectrochemical devices presented here do not present all the properties of inorganic-based devices, we discuss some strategies to enhance the photoelectrochemical properties and response time of conducting polymers used in these type of systems.     

Preparation and surface- active properties of new amphipathic compounds with two phosphate groups and two long- chain alkyl groups

New compounds bearing two dihydrogen phosphate groups and two long- chain alkyl groups (octyl or decyl) were prepared in good yields by the reaction of 1,ω-bis(alkyloxymethyl)- oligo (ethylene glycol)s with polyphosphoric acid. Amphipathic di- or tetrasodium phosphates were obtained by neutralization of the free acids with sodium hydroxide, and their surface- active properties in water were measured. Almost all these di- or tetrasodium phosphates showed good water solubility. Their abilities to form micelles and to lower surface tension were fairly good as compared with general monoalkyl phosphates consisting of one longer alkyl chain and one hydrophilic group. The foaming property of aqueous solutions of the tetrasodium salts was different from that of the disodium salts. The former showed very low foaming ability.     

用分子动力学模拟研究阳离子链长对离子液体输运特性的影响

阐述了用分子动力学（molecular dynamics,MD）模拟方法研究在T=303K条件下[mmim][TFSA]、[emim][TFSA]、[bmim][TFSA]、[C6 mim] [TFSA]和[C8mim] [TFSA]5种离子液体的输运特性.模拟力场采用修正后的OPLS力场.根据模拟轨迹计算得到5种离子液体的密度值.根据均方位移（MSD）的斜率计算得到的离子液体阴阳离子自扩散系数.采用Nernst-Einstein （NE）方程计算得到离子液体摩尔导电率.这些模拟结果与实验值很吻合.离子液体的自扩散系数和电导率随着阳离子链长的增长而变小,主要原因是阳离子链长增长使离子液体中的氢键作用和范德华作用变强.计算所得离子液体摩尔导电率略大于实验测量值则归因于离子关联运动的结果.     

THF hydrate crystal growth inhibition with small anionic organic compounds and their synergistic properties with the kinetic hydrate inhibitor poly(N-vinylcaprolactam)

Small, cationic tetraalkylammonium ions (particularly for alkyl=butyl or pentyl) are known to inhibit tetrahydrofuran (THF) and natural gas hydrate crystal growth and have been used as synergists for commercial kinetic hydrate inhibitor polymers (KHIs), such as N-vinylcaprolactam polymers, for a number of years. The ability for small, organic anionic molecules to inhibit (THF) hydrate crystal growth and their potential as KHI synergists in blends with poly(N-vinylcaprolactam) have been investigated. Several series of sodium alkyl carboxylates, sulphates and sulphonates were synthesised. It was found that none of these molecules were capable of inhibiting THF hydrate crystal growth as well as the best tetraalkylammonium salts. Alkyl carboxylates appeared to be more effective as inhibitors than the sulphonates or sulphates. The most effective anionic THF hydrate crystal growth inhibitors had butyl or pentyl groups, with alkyl branching at the tail (i.e. iso- rather than n-isomers) being advantageous. Anionic carboxylate molecules, particularly with isopentyl or isobutyl groups, showed some kinetic inhibition synergy with poly(N-vinylcaprolactam) lowering the onset and catastrophic hydrate formation temperatures in high pressure (78 bar) constant cooling experiments with Structure II hydrates by 1–2 °C when dosed at 2500 ppm compared with using 2500 ppm polymer alone. This synergism was however less than the best tetraalkylammonium salts (alkyl=n-butyl or n-pentyl) at the same test conditions. Sodium butyl sulphonate and sodium 4-methylpentanoate did not prevent hydrate agglomeration with 3.6% brine and decane at 25% water cut in stirred sapphire cells when dosed at 20,000 ppm based on the aqueous phase, whereas 10,000–20,000 ppm active material of several commercially available anti-agglomerants gave fine transportable slurries and no hydrate deposits at the same conditions.     

Cyclic voltammetry and scanning electrochemical microscopy studies of the heterogeneous electron transfer reaction of some nitrosoaromatic compounds

The heterogeneous electron transfer reaction for the reduction of some nitroso aromatic derivatives in aqueous-alcoholic medium was studied on both mercury and glassy carbon electrodes (GCE) by using cyclic voltammetry (CV) and scanning electrochemical microscopy techniques (SECM).The nitrosoaromatic derivatives followed a two-electron two-proton mechanism producing a quasi-reversible overall process. This strongly pH dependent mechanism varied from ECCE mechanism at pH < 8.5 to ECEC mechanism at pH > 8.5.The apparent heterogeneous rate constant for the reduction of the nitroso derivatives was calculated using CV or SECM. The rate constant for the electron transfer process depends on the nature of the electrode material. The heterogeneous rate constant on the GCE is almost two orders of magnitude smaller than that on mercury electrode i.e. (3.4 ± 0.3) × 10⁻³ cm s⁻¹ on Hg and (7.0 ± 1.0) × 10⁻⁵ cm s⁻¹ on GCE, for the same nitroso compound and pH.The heterogeneous rate constant values were checked by comparison between experimental and simulated cyclic voltammograms.     

Characterization and electron transport properties of polyaniline nanocomposites containing silver chloride nanoparticles embedded on the gelatin surface

ABSTRACT

Polyaniline (PANI) encapsulating silver chloride nanoparticles embedded on the surface of gelatin nanofibers were prepared. The interaction of PANI/gelatin with AgCl and crystallinity of the composites are characterized by FTIR and XRD. The surface framework of the composites was studied by SEM and TEM. Increase of AgCl has brought out significant increase of DC conductivity of the composites. The hydrophilic GEL acts as a plasticizer in the PANI/GeL-AgCl increases the mobility of charge carriers in the composites which influences the conductivity. Such composites are used in electric devices, sensors, and functional coatings for their high electrical conductivity.     

Characterization and Evaluation of Neuronal Trans-Differentiation with Electrophysiological Properties of Mesenchymal Stem Cells Isolated from Porcine Endometrium

Endometrial stromal cells (EMSCs) obtained from porcine uterus (n = 6) were positive for mesenchymal stem cell markers (CD29, CD44 and CD90), and negative for epithelial marker CD9 and hematopoietic markers CD34, CD45 analyzed by flow cytometry. Further the cells were positive for expression of mesenchymal markers, CD105, CD140b, and CD144 by PCR. Pluripotent markers OCT4, SOX2, and NANOG were positively expressed in EMSCs analyzed by Western blotting and PCR. Further, differentiation into adipocytes and osteocytes was confirmed by cytochemical staining and lineage specific gene expression by quantitative realtime-PCR. Adipocyte (FABP, LPL, AP2) and osteocyte specific genes (ON, BG, RUNX2) in differentiated EMSCs showed significant (p < 0.05) increase in expression compared to undifferentiated control cells. Neurogenic transdifferentiation of EMSCs exhibited distinctive dendritic morphology with axon projections and neuronal specific genes, NFM, NGF, MBP, NES, B3T and MAP2 and proteins, B3T, NFM, NGF, and TRKA were positively expressed in neuronal differentiated cells. Functional analysis of neuronal differentiated EMSCs displayed voltage-dependence and kinetics for transient outward K⁺ currents (I_to), at holding potential of −80 mV, Na⁺ currents and during current clamp, neuronal differentiated EMSCs was more negative than that of control EMSCs. Porcine EMSCs is a suitable model for studying molecular mechanism of transdifferentiation, assessment of electrophysiological properties and their efficiency during in vivo transplantation.     

Study of the structure and transport of asymmetric polyamide membranes for reverse osmosis using the electron spin resonance (ESR) method

The electron spin resonance technique (ESR) was used to study the structure and transport of asymmetric aromatic polyamide membranes. TEMPO (2,2,6,6-tetramethyl-1-piperridinyloxy free radical) was used as a spin probe that was brought into the membrane either by (a) immersion ofthe membranes in aqueous TEMPO solutions, (b) reverse osmosis (RO) experiments with feed solutions involving TEMPO or (c) blending TEMPO in casting solutions. The membranes were further tested for the separation of sodium chloride and TEMPO from water by RO. It was concluded that aromatic polyamide membranes contain water channels in the polymer matrix like cellulose acetate membranes. The presence of such water channels allows aromatic polyamide membranes to be used as RO membranes. The diffusion of organic solutes through the water channels seems much slower in aromatic polyamide membranes than in cellular acetate membranes, which probably causes a higher separation of organic solutes by aromatic polyamide membranes than cellulose acetate membranes. A comparison was made with other RO membranes (cellulose acetate, CA) and ultrafiltration membranes (polyethersulphone, PES). It was observed that the ESR technique can be used to study the structure of OF and RO membranes. The presence of water channels in the polymer matrix seems indispensable for the RO membrane.     

A study on the dependence of the micro-pore configurations on the volatilization and the burn processes of the organic compounds in the matrix of molten carbonate fuel cells

The micro-pore configurations on the matrix surface were studied by SEM. The matrix of molten carbonate fuel cell (MCFC) performance was also improved by the better coordination between the reasonable radius of the micro-pores and the higher porosity of the cell matrix. The many and complicated micro-pore configurations in the cell matrix promoted the volatilization of the organic additives and the burn of polyvinyl butyral (PVB). The smooth volatilization of the organic additives and the complete burn of PVB were the significant factors for the improved MCFC performance. Oxygen diffusion controlled-burn mechanism of PVB in the cell matrix was proposed.     

Evaluation of the Adenocarcinoma-Associated Gene AGR2 and the Intestinal Stem Cell Marker LGR5 as Biomarkers in Colorectal Cancer

We aim to estimate the diagnostic performances of anterior gradient homolog-2 (AGR2) and Leucine-rich repeat-containing-G-protein-coupled receptor 5 (LGR5) in peripheral blood (PB) as mRNA biomarkers in colorectal cancer (CRC) and to explore their prognostic significance. Real-time PCR was used to analyze AGR2 and LGR5 in 54 stages I-IV CRC patients and 19 controls. Both mRNAs were significantly increased in PB from CRC patients compared to controls. The area under the receiver-operating characteristic curves were 0.722 (p = 0.006), 0.376 (p = 0.123) and 0.767 (p = 0.001) for AGR2, LGR5 and combined AGR2/LGR5, respectively. The AGR2/LGR5 assay resulted in 67.4% sensitivity and 94.7% specificity. AGR2 correlated with pT3-pT4 and high-grade tumors. LGR5 correlated with metastasis, R2 resections and high-grade. The progression-free survival (PFS) of patients with high AGR2 was reduced (p = 0.037; HR, 2.32), also in the stage I-III subgroup (p = 0.046). LGR5 indicated a poor prognosis regarding both PFS (p = 0.007; HR, 1.013) and overall survival (p = 0.045; HR, 1.01). High AGR2/LGR5 was associated with poor PFS (p = 0.014; HR, 2.8) by multivariate analysis. Our findings indicate that the assessment of AGR2 and LGR5 in PB might reflect the presence of circulating tumor cells (CTC) and stem cell like CTC in CRC. Increased AGR2 and LGR5 are associated with poor outcomes.     

含Fe~(3+)的酸液对钢铁的腐蚀作用及其抑制

钢铁制品的酸浸去除轧制铁鳞以及换热设备酸洗除锈除垢时有Fe~(3+)产生.通过恒电位法和失重法研究了含Fe~(3+)的酸液对钢铁的腐蚀作用及其抑制,结果表明:Fe~(3+)的存在会促进钢铁的腐蚀,一定结构的硫脲衍生物和阴离子表面活性剂之间存在协同效应,能有效地抑制氢离子放电的阴极过程和Fe~(3+)还原的阴极过程,从而抑制金属的腐蚀.     

地下水中有机污染物的迁移规律及去除方法

本文概述了地下水中有机污染物的迁移弥散理论，介绍了几种去除有机污染物的方法。     

A novel synthesis of polymers with anthracene and dihydroanthracene subunits in the main chain

A new polycondensation method to connect redox-active and chromophoric subunits by forming a C-C bond and leading to a polyhydrocarbon is described. 1,ω-bis(9,10-Dihydro-9-anthry)alkanes with various alkylene spacers can be deprotonated by butyllithium to afford a monoanion in each dihydroanthracene moiety. Alkylation with dielectrophiles such as dibromoalkanes yields soluble polymers with dihydroanthracene units in the main chain. The reaction proceeds regioselectively in the 9,10-position. Aromatization generates a polymer with anthracene units. The molecular weights are determined by GPC up to M?_n = 10 000. To prove the structure and to calibrate the GPC, suitable model compounds were synthesized.