含双吸电子基团的三苯胺染料在太阳电池中的应用

合成了两种具有不同共轭链长度的双吸电子基团的三苯胺类染料TPAR3和TPAR6, 研究了它们的光物理与光电化学性质, 并将它们用作TiO2纳米晶电极的光敏化剂引入太阳电池. 结果表明, 与含有乙烯基共轭桥的染料TPAR3相比, 含有丁二烯基共轭桥的染料TPAR6在甲醇溶液和TiO2膜上的最大吸收均发生一定程度的红移和宽化; 但TPAR6表现出比TPAR3差的光电性能, 主要是因为前者更易发生顺反异构化, 电子不能够顺利地从染料激发态注入到TiO2导带中, 光电流的产生得到抑制. 考察了基于TPAR3的太阳电池在电解液中加入不同浓度的硫氰酸胍(GT)对光电性能的影响, 发现在GT浓度为0.100 mol·L-1时效率达到最大(4.02%).     

Heavy Metal Resistances and Chromium Removal of a Novel Cr(VI)-Reducing Pseudomonad Strain Isolated from Circulating Cooling Water of Iron and Steel Plant

Three bacterial isolates, GT2, GT3, and GT7, were isolated from the sludge and water of a circulating cooling system of iron and steel plant by screening on Cr(VI)-containing plates. Three isolates were characterized as the members of the genus Pseudomonas on the basis of phenotypic characteristics and 16S rRNA sequence analysis. All isolates were capable of resisting multiple antibiotics and heavy metals. GT7 was most resistant to Cr(VI), with a minimum inhibitory concentration (MIC) of 6.5 mmol L^?1. GT7 displayed varied rates of Cr(VI) reduction in M2 broth, which was dependent on pH, initial Cr(VI) concentration, and inoculating dose. Total chromium analysis revealed that GT7 could remove a part of chromium from the media, and the maximum rate of chromium removal was up to 40.8 %. The Cr(VI) reductase activity of GT7 was mainly associated with the soluble fraction of cell-free extracts and reached optimum at pH 6.0～8.0. The reductase activity was apparently enhanced by external electron donors and Cu(II), whereas it was seriously inhibited by Hg(II), Cd(II), and Zn(II). The reductase showed a K _m of 74 μmol L^?1 of Cr(VI) and a V _max of 0.86 μmol of Cr(VI) min^?1 mg^?1 of protein. The results suggested that GT7 could be a promising candidate for in situ bioremediation of Cr(VI).     

Isolation and identification of cyclic oligomers of the poly(ethylene terephthalate)–poly(ethylene isophthalate) copolymer

New cyclic oligomers of the copolymer of poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI) were isolated and identified. A condensation polymerization was carried out at a high temperature, and the solid‐state polymerization that followed yielded the high molecular weight polymer. The oligomers were extracted from the high molecular weight PET–PEI copolymer and separated with preparative high performance liquid chromatography techniques. Their chemical structures and properties were analyzed and determined by ¹H NMR, differential scanning calorimetry, and mass spectroscopy. The oligomers observed at early retention times were a cyclic dimer and cyclic trimers and consisted of [GT]₃, [GI]₂, [GI]₃, [GT]₂[GI]₁, and [GT]₁[GI]₂. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 881–889, 2003     

Polyoxometalate cobalt–gatifloxacin complex with DNA binding and antibacterial activity

An unusual inorganic–organic antibacterial complex based on polyoxometalates (POMs) and the cobalt–gatifloxacin (GT), [Co^II(C₁₉FH₂₂N₃O₄)₃][C₁₉FH₂₃N₃O₄][HSiW₁₂O₄₀]·23H₂O (1), has been synthesized. Single-crystal structural analysis shows that 1 represents for the first time an unusual tripodal coordination style with three GT molecules coordinating to cobalt(II) by six carboxylate and hydroxyl oxygens. The biological activity of 1 has been evaluated by investigating its binding ability to calf thymus DNA (CT-DNA). UV spectrum study of 1 has shown that it can bind to CT-DNA by intercalation. The DNA-binding constant K_b was 9.6?×?10⁴?M?L^?1, higher than that of pure GT, 3.8?×?10^4?M?L^?1. Furthermore, the antibacterial activities of 1 were tested against Staphylococcus aureus and Escherichia coli, respectively, and have shown slightly lower antibacterial activity than that of free GT at the same mass concentration. If the GT component in the complexes was controlled at the same molar concentration, 1 generates the biggest antibacterial area during the Kirby–Bauer disc diffusion detection. This result indicates that the integration of heteropolyanions and GT exhibits synergistic effects on the antibacterial activity, which paves a new way to design low-cost antibacterial compound by the introduction of POMs.     

Heat revolution on photophysical properties and electroluminescent performance of Ir(ppy)3-doped bipolar host of oxadiazole derivatives attaching with inert group of tert-butyl moiety

Two bipolar materials,2,5-bis(2-(9H-carbazole-9-yl)phenyl)-1,3,4-oxadiazole(o-CzOXD)and 2,5-bis(2-(3',6'-di-tert-butyl-9H-carbazole-9-yl)phenyl)-1,3,4-oxadiazole(tBu-o-CzOXD),were synthesized according to reported methods.In parallel study,it was demonstrated that introduction of inert tert-butyl group improved material thermal stability,even though this modification only had a slight influence to the photophysical and electrochemical properties of these materials.A comparative study focusing on effects of heat treatment was carried out on the quartz glass substrates with vacuum deposited films containing one of the bipolar host doped with 6 wt%fac-tris(2-phenylpyridinato-N,C2’)iridium(Ir(ppy)3).Results show that when the two samples were heated,the absorption,emission,and photo images of the host:dopant system changed,with the o-CzOXD suffering more severe degradation under high temperature,which is consistent with their thermal stability.In addition,it was proved that the high temperature-annealed host:dopant system can enhance the emission of the dopant.This finding was used as a guideline to improve our device performance.We fabricated two types of phosphorescent organic light-emitting devices(PhOLEDs),one was based on o-CzOXD,the other was based on tBu-o-CzOXD.They had analogous structure.We investigated the effect of heat on device performance by selectively annealing.Although these two freshly prepared devices exhibited similar performance,when annealed at 90°C for 10 min,the OLEDs based on tBu-o-CzOXD showed significant performance enhancement,which can be attributed to the observation that annealing Ir(ppy)3 doped host can change film morphology and enhance the dopant emission.The maximum efficiencies of the freshly prepared tBu-o-CzOXD device were 25.8 cd A-1,23.1lm W-1,and 9.3%;whereas those for annealed device were 47.0 cd A-1,42.2 lm W-1,and 13.4%.     

Effects of Cl/Br substitution of antimony octahedra on photoluminescence and a new engineering strategy for performance optimization

Organic-inorganic metal halides have garnered extensive attention due to their versatile structures as well as fascinating optical properties, among which especially antimony halides are the focus of recent research. Herein, we design a series of novel zero-dimensional (0D) antimony halides of (C₁₃H₁₄N₃)₃SbCl_6–xBr_x (x = 0, 3, 6) with bright and tunable broadband emissions from yellow (576 nm) to orange (600 nm), which are attributed to the triplet self-trapped excitons (STEs) of the six-coordinated [SbX₆]^3– (X = Cl^? or Br^?) units. The role of halogens on their specific ³P₁→¹S₀ transition is determined, wherein Cl/Br transmutation reveals a common law modulating photoluminescence behaviors. Furthermore, a new two-step compound technology is innovatively developed for performance optimization, enabling by incorporating the pristine antimony halides into polymethyl methacrylate (PMMA) with high transparency and strong moisture resistance. The composites (C₁₃H₁₄N₃)₃SbCl_6–xBr_x/PMMA (x = 0, 3, 6) were fabricated through a demanding technology that significantly improve the processability and water stability of antimony halides while maintaining high photoluminescence quantum yields. This work not only proposes a method for halogen substitutions to tune emission, but also opens up a feasible research avenue for performance optimization in the multifunctional luminescence materials.     

Permeation and separation properties of polyimide membranes to olefins and paraffins

Pure and mixed gas permeation experiments for olefins and paraffins of C₂ and C₃ were carried out for several polyimide and other polymer membranes at pressures up to 8 atm and temperatures from 308 to 423 K. The olefins were more permeable to the corresponding paraffins due to their preferential diffusion based on the difference in their molecular size. Polyimide prepared from 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,4,6-trimethyl-1,3-phenylenediamine (TrMPD) displayed relatively high performance: permeability coefficient to propylene, P_C3H6 = 20–40 Barrer (1 Barrer = 1 × 10⁻¹⁰ cm³(STP)/(cm s cmHg)) and ideal separation factor (permeability ratio of pure propylene and propane). α_id(C₃H₆/C₃H₈) = 11 at 323 K and 2 atm. Polyimide from 6FDA and dimethyl-3,7-diaminodiphenylthiophene-5,5-dioxide (DDBT) displayed low permeability and high permselectivity: P_C3H6 = 0.8 Barrer and α_id(C₃H₆/C₃H₈) = 27 at 323 K and 2 atm. Their performance was much better than that of other polymers such as poly(2,6-dimethyl-1,4-phenyleneoxide). For mixed gas permeation, the separation factor was lower by about 40% than the α_id due to the increase in P_C3H8 caused by coexisting propylene.     

Photocatalytic Hydrogen Production by the Sensitization of Sn(IV)-Porphyrin Embedded in a Nafion Matrix Coated on TiO2

Efficient utilization of visible light for photocatalytic hydrogen production is one of the most important issues to address. This report describes a facile approach to immobilize visible-light sensitizers on TiO₂ surfaces. To effectively utilize the sensitization of Sn(IV) porphyrin species for photocatalytic hydrogen production, perfluorosulfonate polymer (Nafion) matrix coated-TiO₂ was fabricated. Nafion coated-TiO₂ readily adsorbed trans-diaqua[meso-tetrakis(4-pyridinium)porphyrinato]tin(IV) cation [(TPy^HP)Sn(OH₂)₂]⁶⁺ via an ion-exchange process. The uptake of [(TPy^HP)Sn(OH₂)₂]⁶⁺ in an aqueous solution completed within 30 min, as determined by UV-vis spectroscopy. The existence of Sn(IV) porphyrin species embedded in the Nafion matrix coated on TiO₂ was confirmed by zeta potential measurements, UV-vis absorption spectroscopy, TEM combined with energy dispersive X-ray spectroscopy, and thermogravimetric analysis. Sn(IV)-porphyrin cationic species embedded in the Nafion matrix were successfully used as visible-light sensitizer for photochemical hydrogen generation. This photocatalytic system performed 45% better than the uncoated TiO₂ system. In addition, the performance at pH 7 was superior to that at pH 3 or 9. This work revealed that Nafion matrix coated-TiO₂ can efficiently produce hydrogen with a consistent performance by utilizing a freshly supplied cationic Sn(IV)-porphyrin sensitizer in a neutral solution.     

Biosensor based on laccase and an ionic liquid for determination of rosmarinic acid in plant extracts

Novel biosensors based on laccase from Aspergillus oryzae and the ionic liquids (ILs) 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMIPF₆) and 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMIBF₄) were constructed for determination of rosmarinic acid by square-wave voltammetry. The laccase catalyzes the oxidation of rosmarinic acid to the corresponding o-quinone, which is electrochemically reduced back to rosmarinic acid at +0.2 V vs. Ag/AgCl. The biosensor based on BMIPF₆ showed a better performance than that based on BMIBF₄. The best performance was obtained with 50:20:15:15% (w/w/w/w) of the graphite powder:laccase:Nujol:BMIPF₆ composition in 0.1 mol L⁻¹ acetate buffer solution (pH 5.0). The rosmarinic acid concentration was linear in the range of 9.99 × 10⁻⁷ to 6.54 × 10⁻⁵ mol L⁻¹ (r = 0.9996) with a detection limit of 1.88 × 10⁻⁷ mol L⁻¹. The recovery study for rosmarinic acid in plant extract samples gave values from 96.1 to 105.0% and the concentrations determined were in agreement with those obtained using capillary electrophoresis at the 95% confidence level. The BMIPF₆-biosensor demonstrated long-term stability (300 days; 920 determinations) and reproducibility, with a relative standard deviation of 0.56%.     

Use of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids as chelate extraction solvent with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione

Possible use of room temperature ionic liquids (RTILs) as chelate extraction solvent was evaluated by using 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF₆]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][PF₆]). These RTILs showed high extraction performance for divalent metal cations with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Htta). The extracted metals were back-extracted into 1 mol dm⁻³ nitric acid quantitatively. Furthermore, the extracted species were estimated as neutral hydrated complexes M(tta)₂(H₂O)_n (n= 1 or 2) for M = Ni, Cu and Pb and anionic complexes M(tta)₃⁻ for M = Mn, Co, Zn and Cd.     

Eu(fod)(3) binding on the (1)H-NMR spectra of some benzo[3n]crown-n and dibenzo[3n+2]crown-n

The complexing of Eu(fod)₃ with macrocyclic ethers, benzo[15]crown-5, benzo[12]crown-4, dibenzo[20]crown-6, dibenzo[23]crown-7 and dibenzo[26]crown-8 was observed on their ¹H-NMR spectra and the selective binding constants at 400 MHz and 305 K in CDCl₃ were reported. The Eu(fod)₃ interaction displayed the selective binding role of oxygen on macrocyclic, H₂COCH₂, backbones with o- or m-dioxyphenyl groups referring the ¹H chemical shifts. The estimated equilibrium constants, K_a of 1:1 ratio of interactions were in accordance with the Eu³⁺ ionic radii to bind the oxygen sites depending on the macrocyclic size and conformation of the ethers. The minimum lanthanide-macrocyclic ether distance displayed the maximum stability so that benzo[3n]crown-n (n=4, 5) group was found to bind the Eu(fod)₃ moderately whilst dibenzo[3n+2]crown-n (n=6-8) oligomer chemical shifts were induced largely since the such Eu³⁺ complexes are more stable with larger ethyleneoxy groups.     

W/Mo-polyoxometalate-derived electrocatalyst for high-efficiency nitrogen fixation

Ammonia is the feedstock chemical for most fertilizers and the alternative of renewable energy carriers. Environmentally benign electrochemical nitrogen reduction reaction (NRR) under mild conditions has been recognized as one of the most attractive strategies for N₂ fixation. Herein, inspired by Mo-based nitrogenase, W/Mo-doping electrocatalysts were developed with mixed-metal polyoxometalate H₃PW₆Mo₆O₄₀ as the precursor for high performance electrocatalytic NRR. Trace amount of Pt was transplanted on the surface of W/Mo@rGO via in situ electroplating treatment to further improve the NRR performance. The resulting Pt-W/Mo@rGO-6 achieves excellent performance for NRR with a high NH₃ yield of 79.2 µg h^?1 mg_cat^?1 due to the multicomponent synergistic effect in the composite catalyst. The Pt-W/Mo@rGO-6 represents the first example of highly efficient NRR electraocatalyst derived from mixed-metal polyoxometalate, which exhibits outstanding stability confirmed by the constant catalytic performance over 24 h chronoamperometric test. This finding opens a new avenue to construct highly efficient NRR electrocatalyst by employing mixed metal polyoxometalate as the precursor under ambient conditions.     

Electrochemical Responses and Sensitivities of Films Based on Multi-Walled Carbon Nanotubes in Aqueous Solutions

Novel films consisting of multi-walled carbon nanotubes (MWCNTs) were fabricated by means of chemical vapor deposition with decomposition of either acetonitrile (ACN) or benzene (BZ) using ferrocene as catalyst. The electrochemical responses of MWCNT-based films towards the ferrocyanide/ferricyanide, [Fe(CN)₆]^3?/4? redox couple were probed by means of cyclic voltammetry and electrochemical impedance spectroscopy at 25.0?±?0.5?°C. Both MWCNT-based films exhibit Nernstian response towards [Fe(CN)₆]^3?/4? with some slight kinetic differences. Namely, heterogeneous electron transfer rate constants lying in ranges of 2.69?×?10^?2?C1.7?×?10^?3 and 9.0?×?10^?3?C2.6?×?10^?3?cm·s^?1 were obtained at v?=?0.05?V·s^?1 for MWCNT_ACN and MWCNT_BZ, respectively. The detection limit of MWCNT_ACN, estimated to be about 4.70?×?10^?7?mol·L^?1 at v?=?0.05?V·s^?1, tends to become slightly poorer with the increase of the scan rate, namely at v?=?0.10?V·s^?1 the detection limit of 1.70?×?10^?6?mol·L^?1 was determined. Slightly poorer response ability was exhibited by MWCNT_BZ; specifically the detection limits of 1.57?×?10^?6 and 4.35?×?10^?6?mol·L^?1 were determined at v?=?0.05 and v?=?0.10?V·s^?1, respectively. The sensitivities of MWCNT_ACN and MWCNT_BZ towards [Fe(CN)₆]^3?/4? were determined as 1.60?×?10^?7 and 1.51?×?10^?7?A·L·mol^?1·cm^?2, respectively. The excellent electrochemical performance of MWCNT_ACN is attributed to the presence of incorporated nitrogen in the nanotube??s structure.     

Solvent effects on the redox potentials of tetraethylammonium hexacyanomanganate(III) and hexacyanoferrate(III)

Tetraethylammonium hexacyanomanganate(III) was studied in formamide, N-methylformamide, methanol, propylenecarbonate, N,N-dimethylthioformamide, N-methylthiopyrrolidinone(2), butyrolactone, acetonitrile, dimethylsulfoxide, N,N-dimethylformamide, N-methylpyrrolidinone(2), nitromethane and tetramethylenesulfone employing polarographic and voltammetric techniques. Reversible or nearly reversible behaviour for the reaction Mn(CN)₆^3?/Mn(CN)₆^2? was observed in most solvents on the stationary platinum electrode. The reaction Mn(CN)₆^3?/Mn(CN)₆^4? was studied on both the dropping mercury electrode and the stationary platinum electrode. Besides the reaction Mn(CN)₆^3?/Mn(CN)₆^4? several anodic waves due to successive reactions of mercury with the cyano-ligand of the complex occurred at the dropping mercury electrode. No redox reaction for (et₄N)₃Mn(CN)₆ was found in nitromethane. The polarographic behaviour of tetraethylammonium hexacyanoferrate(III) was studied in formamide, N-methylformamide, N-methylpyrrolidinone(2) and butyrolactone. The variation of E_1/2 and 1/2 (E_pa+E_pc) values versus bisphenylchromium(I)/bisbiphenylchromium(0) as reference redox system of the processes Mn(CN)₆^3?/Mn(CN)₆^2?, Mn(CN)₆^3?/Mn(CN)₆^4? and Fe(CN)₆^3?/Fe(CN)₆^4? with the nature of the solvent is discussed within the donor-acceptor concept. Correlations between the E_1/2 and 1/2(E_pa+E_pc) values and the acceptor properties of the solvent have been observed. The preparation of tetraethyl- and tetrabutylammonium hexacyanomanganate(III) is described.     

Top–down glycolipidomics: fragmentation analysis of ganglioside oligosaccharide core and ceramide moiety by chip‐nanoelectrospray collision‐induced dissociation MS2–MS6

We developed a straightforward approach for high‐throughput top–down glycolipidomics based on fully automated chip‐nanoelectrospray (nanoESI) high‐capacity ion trap (HCT) multistage mass spectrometry (MSⁿ) by collision‐induced dissociation (CID) in the negative ion mode. The method was optimized and tested on a polysialylated ganglioside fraction (GT1b), which was profiled by MS¹ and sequenced in tandem MS up to MS⁶ in the same experiment. Screening of the fraction in the MS¹ mode indicated the occurrence of six [M ? 2H]^2? ions which, according to calculation, support 13 GT1 variants differing in their relative molecular mass due to dissimilar ceramide (Cer) constitutions. By stepwise CID MS²–MS⁵ on the doubly charged ion at m/z 1077.20 corresponding to a ubiquitous GT1b structure, the complete characterization of its oligosaccharide core including the identification of sialylation sites was achieved. Structure of the lipid moiety was further elucidated by CID MS⁶ analysis carried out using the Y₀ fragment ion, detected in MS⁵, as a precursor. MS⁶ fragmentation resulted in a pattern supporting a single ceramide form having the less common (d20 : 1/18 : 0) configuration. The entire top–down experiment was performed in a high‐throughput regime in less than 3 min of measurement, with an analysis sensitivity situated in the subpicomolar range. Copyright © 2009 John Wiley & Sons, Ltd.     

Crossed-second-order-effects of the isotope shift and hyperfine-structure parameters in the Eu I configuration 4f 7 6s6d

In the Eu I configuration 4f ⁷ 6s6d the isotope shift (IS) and hyperfine-structure (hfs) of the termse ⁶ D ande ¹⁰ D were determined from fourteen transitions (4f ⁷ 6s6d-4f ⁷ 6s6p) with computer supported interference spectroscopy. From the IS of altogether nine levels of 4f ⁷ 6s6d the crossed-second-order-parameterg ₃(4f,6s)=?0.90(6)mK was evaluated. The ratiog ₃/G ₃=?4.4(3)·10^?6 (G ₃: Slater Integral of the fine structure) is of the same size as that from five other independent investigations and one theoretical value. The single electron hfs splitting constantsa _4f ¹⁰ =?1.9(3)mK,a _6s ¹⁰ =391(3)mK, anda _6d ¹² =0.9(3)mK were also evaluated and are compared with those of other Eu 4f ⁷ 6snl configurations.     

Attachment of NH3 clusters to Hg(6P0)

The ultraviolet luminescence from the Hg-photosensitised reaction of ammonia was investigated at pressures up to 10 atmospheres. From a variation of the wavelength distribution on the [NH₃], it was concluded that Hg(6³P₀) can attach clusters of NH₃ molecules to form Hg(NH₃)_n^* with n up to at least 5. The emission profiles of the stabilized complexes with n = 1–4 were determined, and also the profile from unstabilised HgNH₃^* formed in a bimolecular encounter of Hg(6³P₀) with NH₃. Dissociation constants for complexes with n = 2, 3 and 4 were measured.     

Determination of mercury species by the diffusive gradient in thin film technique and liquid chromatography – atomic fluorescence spectrometry after microwave extraction

A diffusive gradient in thin films technique (DGT) was combined with liquid chromatography (LC) and cold vapor atomic fluorescence spectrometry (CV-AFS) for the simultaneous quantification of four mercury species (Hg²⁺, CH₃Hg⁺, C₂H₅Hg⁺, and C₆H₅Hg⁺). After diffusion through an agarose diffusive layer, the mercury species were accumulated in resin gels containing thiol-functionalized ion-exchange resins (Duolite GT73, and Ambersep GT74). A microwave-assisted extraction (MAE) in the presence of 6 M HCl and 5 M HCl (55 °C, 15 min) was used for isolation of mercury species from Ambersep and Duolite resin gels, respectively. The extraction efficiency was higher than 95.0% (RSD 3.5%). The mercury species were separated with a mobile phase containing 6.2% methanol + 0.05% 2-mercaptoethanol + 0.02 M ammonium acetate with a stepwise increase of methanol content up to 80% in the 16th min on a Zorbax C18 reverse phase column. The LODs of DGT–MAE–LC–CV-AFS method were 38 ng L⁻¹ for CH₃Hg⁺, 13 ng L⁻¹ for Hg²⁺, 34 ng L⁻¹ for C₂H₅Hg⁺ and 30 ng L⁻¹ for C₆H₅Hg⁺ for 24 h DGT accumulation at 25 °C.     

The effect of the Co-anion,SCN−, on macrocycle-facilitated selective transport of Cd (II) over Ag (I) in an emulsion membrane

Emulsion membrane systems consisting of (1) an aqueous source phase containing 0.001 M Cd (NO₃)₂ and/or 0.001 M AgNO₃ and varying concentrations of SCN⁻, (2) a toluene membrane containing dicyclohexano-18-crown-6 (DC18C6) (0.02 M) and the surfactant Span 80 (sorbitan monooleate) (3% v/v), and (3) an aqueous receiving phase containing MgS₂O₃ or Mg (NO₃)₂ were studied with respect to the disappearance of Cd (II) and/or Ag (I) from the source phase as a function of time. The transport rate of Cd (II) was highest when a maximum amount of the Cd(II) in the source phase was present as Cd(SCN)₂ ([SCN⁻] =0.4 M). Cadmium(II) was transported over Ag(I), which is present mainly as Ag(SCN)₄³⁻, by 5- and 55-fold in 5 minutes with 0.4 M SCN⁻ in the source phase and 0.3 M S₂O²⁻₃ and 0.3 M NO⁻₃, respectively, in the receiving phase. In these competitive experiments, the total percent of Cd (II) transported was 98 and 84, respectively. The results are explained using the various equilibrium constants for cation-DC18C6, cation-SCN⁻ and cation-S₂O²⁻₃ interactions. These results indicate that rapid transport occurs when a cation is present in the source phase as a neutral complex. Selectivity for neutral species can be designed into these membrane systems when other cations interact with the source-phase anion to form charged species. Emulsion systems like those above were studied with respect to the appearance of Li⁺ in the source phase as a measure of membrane breakage. Maximum membrane stability was obtained when the ionic strengths of the source and receiving phases were equal.     

Nucleophilic substitution reactions of acetylides on substituted tricarbonyl(η6-fluoroarene)chromium and reactions of tricarbonyl[η6-(2-trimethylsilylethynyl)toluene]chromium and tricarbonyl[η6-(p-ethynyl-phenylethynyl)benzene]chromium with dicobalt octacarbonyl

Nucleophilic substitution reactions of various acetylides on substituted tricarbonyl(η⁶-fluoroarene)chromiums were pursued. The reaction presumably underwent a more complicated mechanism rather than the direct substitution on the fluorine-bearing carbon. The organometallic compounds (η⁶-C₆H₃R¹R²R³)Cr(CO)₃ (R¹: CC–C₆H₄CH₃, R²: o-Me, R³: H (5a), R¹: CC–C₆H₄CH₃, R²: o-OMe, R³: H (6a), R¹: CC–C₆H₄CH₃, R²: m-OMe, R³: H (6b), R¹: CCPh, R²: o-Me, R³: o-OMe (8b), R¹: CCPh, R²: m-Me, R³: m-OMe (8c), R¹: CCSiMe₃, R²: o-Me, R³: H (9a), R¹: CC–C₆H₄CCH, R²: H, R³: H (12), R¹: CC–C₆H₄CCH, R²: o-Me, R³: H (13)) as well as the organometallic dimmer [{(η⁶-o-Me-C₆H₄)Cr(CO)₃(di-ethynyl)] (di-ethynyl: CC–C₆H₄CC (14)) have been synthesized from nucleophilic substitution reactions of tricarbonyl(η⁶-fluoroarene)(chromium) compounds with suitable acetylides. The products have been characterized by spectroscopic means. In addition, (8b) and (8c) were characterized by X-ray diffraction studies. Further reactions of (9a) and (12) with appropriate amount of Co₂(CO)₈ yielded μ-alkyne bridged bimetallic complexes, Co₂(CO)₆{μ-Me₃SiCC–(o-tolueneCr(CO)₃} (10) and (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–(benzene)Cr(CO)₃)}(15), respectively. Both (10) and (15) were characterized by spectroscopic means as well as single crystal X-ray crystallography. The core of these molecules is quasi-tetrahedron containing a Co₂C₂ unit. A two-dicobalt-fragments coordinated di-enyls complex, (Co₂(CO)₆)₂{μ-HCC–C₆H₄–CC–H} (17), was synthesized from the reaction of 1,3-diethynylbenzene with Co₂(CO)₈. Crystallographic studies of (17) also show that it exhibits a distorted Co₂C₂ quasi-tetrahedral geometry.