Microbial electricity generation of diversified carbonaceous electrodes under variable mediators

To evaluate a suitable electrode material for the efficient green energy generation of a bio-fuel cell, carbonaceous based carbon cloth, carbon paper, and carbon felt electrodes were investigated under different mediators. The larger surface area, low resistance, and open network of interwoven fibers of the carbon felt electrode facilitated higher electron transfer from the microbial organisms to the electrode surface than that of other carbonaceous electrodes. Carbon paper electrode exhibited lower fuel cell performances due to its lower roughness and high tortuous nature. The green power generation experiments were also carried out under different mediators such as 2-hydroxy-l,4-naphthoquinone and thionin. The electrons mitigation and power generation was augmented by 2-hydroxy-l,4-naphthoquinone than thionin due to its high solubility, stability, and minimal adsorption characteristic to the electrodes. By the combined efforts of extended electrons generation and transportation, bio-fuel cell performances were extended and endorsed its doable applications in bio-fuel cells.     

Determination of haloacetic acids in water using layered double hydroxides as a sorbent in dispersive solid‐phase extraction followed by liquid chromatography with tandem mass spectrometry

In the present study, highly efficient and simple dispersive solid‐phase extraction procedure for the determination of haloacetic acids in water samples has been established. Three different types of layered double hydroxides were synthesized and used as a sorbent in dispersive solid‐phase extraction. Due to the interesting behavior of layered double hydroxides in an acidic medium (pH?4), the analyte elution step was not needed; the layered double hydroxides are simply dissolved in acid immediately after extraction to release the analytes which are then directly introduced into a liquid chromatography with tandem mass spectrometry system for analysis. Several dispersive solid‐phase extraction parameters were optimized to increase the extraction efficiency of haloacetic acids such as temperature, extraction time and pH. Under optimum conditions, good linearity was achieved over the concentration range of 0.05–100 μg/L with detection limits in the range of 0.006–0.05 μg/L. The relative standard deviations were 0.33–3.64% (n = 6). The proposed method was applied to different water samples collected from a drinking water plant to determine the concentrations of haloacetic acids.     

High-performance liquid chromatography/electrospray ionization tandem mass spectrometry of hydroxylated uroporphyrin and urochlorin derivatives formed by photochemical oxidation of uroporphyrinogen I

Hydroxylated uroporphyrin I and urochlorin I derivatives formed by photochemical oxidation of uroporphyrinogen I were separated by high-performance liquid chromatography and fully characterized by electrospray ionization tandem mass spectrometry. The porphyrins and chlorins were identified by analysis of their product ion spectra with each hydroxylated derivative giving a characteristic collision-induced dissociation fragmentation pattern. The porphyrins and chlorins characterized were meso-hydroxyuroporphyrin I, alpha-hydroxypropionic acid uroporphyrin I, beta-hydroxypropionic acid uroporphyrin I, hydroxyacetic acid uroporphyrin I, trans-7-hydroxy-8-spirolactoneurochlorin I, cis-7-hydroxy-8-spirolactoneurochlorin I and trans- and cis-7,8-dihydroxyurochlorins I.     

Synthetic and X-ray structural and reactivity studies of Cp*RuIV complexes containing bidentate dithiocarbonate, xanthate, carbonate, and phosphinate ligands (Cp* = eta5-C5Me5)

The reaction of [Cp*RuCl2]2 (1; Cp* = eta5-C5Me5) with tetraalkyldithiuram disulfides (R2NC(S)SS(S)CNR2, R = Me, Et), isopropylxanthic disulfide ([iPrOC(S)S]2), and bis(thiophosphoryl) disulfide ([(iPrO)2P(S)S]2) led to the isolation of dark-red crystalline solids of Cp*RuIVCl2(eta2-dithiolate) complexes [dithiolate = S2CNR2, DTCR (2a, R = Me; 2b, R = Et), S2COiPr (3), and S2P(iPrO)2 (4)]. Dichlorido substitution in 2 and 3 with DTCEt and S2COiPr anions yielded RuIV derivatives containing bis(DTC) and mixed DTC-dithiocarbonate ligands. These are the first organoruthenium complexes of such ligands. The reaction of monophosphines with 2a resulted in monochlorido substitution, whereas the analogous reaction with 3 resulted in displacement of both chlorido ligands and reduction of the metal center to RuII. Reduction at Ru was also observed in the reaction of 2a with [CpCr(CO)3]2. Of these complexes, only 2 and 3 are air-stable in the solid state for an extended period. All of the complexes have been spectrally characterized, and selected compounds are also crystallographically characterized.     

Reduced Overlap Population Analysis for Triosmium Clusters

The use of reduced overlap population (ROP) analysis from EHMO calculations as a means to gauge the presence of metal–metal bonds in triosmium clusters is examined. A number of triosmium clusters containing bridging ligands have been used as test cases, including the bis-ethoxy bridged cluster Os₃(μ-OEt)₂(CO)₁₀, 1b, and some of its group 15 derivatives Os₃(μ-OEt)₂(CO)₉(EPh₃), 2. These latter clusters are newly synthesized and have been characterized completely, including by single-crystal X-ray crystallographic studies. In honour of Professor Dieter Fenske on his 65th birthday.     

Developments in single-drop microextraction

Single-drop microextraction (SDME) has become a very popular liquid-phase microextraction technique because it is inexpensive, easy to operate and nearly solvent-free. Essentially, SDME combines extraction (and conceivably, cleanup) and concentration in a minimum number of steps, and thereafter, direct extract introduction into an analytical system. In this review, in order to encourage further development of SDME, we focus on its recent developments in its various guises. Its applications when used in combination with different analytical techniques, such as gas chromatography, high-performance liquid chromatography, inductively-coupled plasma mass spectrometry, capillary electrophoresis, mass spectrometry and electrothermal atomic absorption spectrometry, are summarized. SDME does have some limitations, and these are also discussed as well. Finally, an outlook on the future of the technique is given.     

Theoretical Modelling and Facile Synthesis of a Highly Active Boron‐Doped Palladium Catalyst for the Oxygen Reduction Reaction

A highly active alternative to Pt electrocatalysts for the oxygen reduction reaction (ORR), which is the cathode‐electrode reaction of fuel cells, is sought for higher fuel‐cell performance. Our theoretical modelling reveals that B‐doped Pd (Pd‐B) weakens the absorption of ORR intermediates with nearly optimal binding energy by lowering the barrier associated with O₂ dissociation, suggesting Pd‐B should be highly active for ORR. In fact, Pd‐B, facile synthesized by an electroless deposition process, exhibits 2.2 times and 8.8 times higher specific activity and 14 times and 35 times less costly than commercial pure Pd and Pt catalysts, respectively. Another computational result is that the surface core level of Pd is negatively shifted by B doping, as confirmed by XPS, and implies that filling the density of states related to the anti‐bonding of oxygen to Pd surfaces with excess electrons from B doping, weakens the O bonding to Pd and boosts the catalytic activity.     

Polymer-coated hollow-fiber microextraction of estrogens in water samples with analysis by gas chromatography-mass spectrometry

A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples.     

Sol-gel-coated oligomers as novel stationary phases for solid-phase microextraction

Amphiphilic and hydrophilic oligomers were synthesized and coated on fused silica capillaries using a sol-gel technique. Sol-gel-coated capillaries were evaluated for the solid-phase microextraction and preconcentration of a wide variety of non-polar and polar analytes. Both types of coatings were stable under high temperature (up to 280 degrees C). The extraction efficiency of the sol-gel coatings was evaluated for the extraction of both non-polar and polar analytes, including organochlorine pesticides, triazine herbicides, estrogens and alkylphenols (APs) and bisphenol-A (BPA). Compared with commercially available solid-phase microextraction (SPME) adsorbents such as poly(dimethylsiloxane)divenylbenzene and polyacrylate, the new materials showed comparable selectivity and sensitivity towards both non-polar and polar analytes. The new coatings gave good linearity and detection limits. For example with triazines, a detection limit of <0.005 microl l(-1), precision from 5.0 to 11.0% (n = 6) and linearity of the calibration plots (0.5 to 50 microl l(-1)) were obtained. The sol-gel coated SPME capillaries were used for the determination of triazine herbicides in reservoir water samples collected in Singapore.