Enhancing the stability and performance of a battery cathode using a non-aqueous electrolyte

For conductive polymers to be considered materials for energy storage, both their electroactivity and stability must be optimized. In this study, a non-aqueous electrolyte (0.2 M LiClO₄ in acetonitrile) was studied for its effect on the charge storage capacity and stability of two materials used in batteries developed in our laboratory, polypyrrole (pPy) and poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2,2′-azino-bis(3-ethylbenzothiaxoline-6-sulfonic acid (ABTS). The results are compared to the performance of these materials in an aqueous electrolyte (0.2 M HCl/aq). Loss of ABTS dopant was eliminated principally due to the low solubility of ABTS in acetonitrile, resulting in cathode materials with improved stability in terms of load cycling and performance.     

A universal approach for continuum solvent pK a calculations: are we there yet?

This paper reviews several pK _a calculation strategies that are commonly used in aqueous acidity predictions. Among those investigated were the direct or absolute method, the proton exchange scheme, and the hybrid cluster–continuum (Pliego and Riveros) and implicit–explicit (Kelly, Cramer and Truhlar) models. Additionally, these protocols are applied in the pK _a calculation of 55 neutral organic and inorganic acids in conjunction with various solvent models, including the CPCM-UAKS/UAHF, IPCM, SM6 and COSMO-RS, with a view to identifying a universal approach for accurate pK _a predictions. The results indicate that the direct method is unsuitable for general pK _a calculations, although moderately accurate results (MAD <3 units) are possible for certain classes of acids, depending on the choice of solvent model. The proton exchange scheme generally delivers good results (MAD <2 units), with CPCM-UAKS giving the best performance. Furthermore, the sensitivity of this approach to the choice of reference acid can be substantially lessened if the solvation energies for ionic species are calculated via the IPCM cluster–continuum approach. Reference-independent hybrid approaches that include explicit water molecules can potentially give reasonably accurate values (MAD generally ~2 units) depending on the solvent model and the number of explicit water molecules added.     

Ultrasound‐assisted dispersive liquid–liquid microextraction coupled with capillary gas chromatography for simultaneous analysis of nine pyrethroids in domestic wastewaters

A simple and rapid ultrasound‐assisted dispersive liquid–liquid microextraction method coupled with GC‐flame ionization detection was developed for simultaneous determination of nine pyrethroids in domestic wastewater samples. An ultrasound‐assisted process was applied to accelerate the formation of the fine cloudy solution using small volume of disperser solvent, which markedly increased the extraction efficiency and reduced the equilibrium time. Various parameters affecting the extraction efficiency were investigated, including the type and volume of extraction solvent and disperser solvent, extraction and ultrasonic time. Good linearity was obtained for all analytes in the range of 0.8–100 μg/L with the correlation coefficient (r²)≥0.998. The recoveries at three spiking levels ranged from 75.3 to 101.2% with the RSD less than 8.7% (n=5). Under the optimum condition, the enrichment factors for the nine pyrethroids ranged from 728‐ to 1725‐fold. This method offered a good alternative for routine analysis due to its simplicity and reliability.     

Microchip electrophoretic separation for the fast diagnosis of Anaplasma phagocytophilum infection in cattle

We report a diagnostic method for Anaplasma phagocytophilum (A. phagocytophilum) infection in cattle using a nested PCR and microchip electrophoresis (ME). A. phagocytophilum causes human granulocytic anaplasmosis and granulocytic ehrlichiosis, which are emerging tick‐borne zoonotic diseases. Nested PCR was used to amplify genomic DNA samples extracted from cattle blood. The amplified PCR products were analyzed under a sieving gel matrix of 0.7% poly(ethyleneoxide) (M_r=8 000 000) in a conventional glass microchip. In the ME assay, A. phagocytophilum was analyzed within 35 s with a relative standard deviation of 1.30% (n=5) using a programmed field strength gradient (PFSG) as follows: 615.3 V/cm for 0–24 s, 66.7 V/cm for 24–34 s, 615.3 V/cm for 34–100 s. The ME‐PFSG assay was clinically validated by comparing the 16S rRNA gene levels obtained by this method with those measured using conventional slab gel electrophoresis performed with ten cattle blood samples suspected of A. phagocytophilum infection. In contrast to slab gel electrophoresis, the proposed ME‐PFSG methodology had increased sensitivity (200–450 pg/μL), a faster analysis time (<35 s), and required a smaller sample volume (～162 fL).     

Gas chromatography‐mass spectrometric method for the screening and quantification of illicit drugs and their metabolites in human urine using solid‐phase extraction and trimethylsilyl derivatization

A simple and rapid GC‐MS method has been developed for the screening and quantification of many illicit drugs and their metabolites in human urine by using automatic SPE and trimethylsilylation. Sixty illicit drugs, including parent drugs and their metabolites that are possibly abused in Korea, can be monitored by this method. Among them, 24 popularly abused illicit drugs were selected for quantification. Very delicate optimizations were carried out in SPE, trimethylsilylation derivatization, and GC/MS to enable such remarkable achievements. Trimethylsilylated analytes were well separated within 21 min by GC‐MS. In the validation results, the LOD of all the analytes were in the range of 2–75 ng/mL. The LOQ of the quantified analytes were in the range of 5–98 ng/mL. The linearity (r²) of the quantified analytes ranged 0.990–1.000 in each concentration range between 10 and 1000 ng/mL. The mean recoveries ranged from 62 to 126% at three different concentrations of each analyte. The inter‐day and inter‐person accuracies were within ?13.3～14.9%, and ?10.1～13.0%, respectively, and the inter‐day and inter‐person precisions were less than 12.9%. The method was reliable and efficient for the screening and quantification of abused illicit drugs in routine urine analysis.     

Computational design of a self-assembling β-peptide oligomer

The first computationally designed self-assembling oligomer consisting of exclusively β-amino acids (βAAs) is presented. The packing of a β-3(14) helix into coiled-coils of varying stoichiometries as a function of amino acid sequence is examined. β-Peptides with hVal repeating every third residue in the sequence appeared to have a strong propensity to pack into hexameric bundles. The designed sequence was synthesized and characterized with CD spectroscopy, NMR, and analytical ultracentrifugation, suggesting that the peptide adopts a well-folded hexameric structure.     

Synthesis of poly(p‐phenylenediamine‐ co‐o‐aminophenol)/multi‐walled carbon nanotube composites by emulsion polymerization

Organic–inorganic composites composed of electrically conducting copolymer p‐phenylenediamine‐ co‐o‐aminophenol and carboxylic acid functionalized multi‐walled carbon nanotubes [poly(pPD‐co‐oAP)/c‐MWNTs] were prepared via in situ emulsion pathway using sodium dodecyl sulphate (SDS) as an emulsifier and potassium persulphate as an oxidant. Acid functionalized MWNTs were used as cores in the formation of tubular shells of the composites. TEM and FESEM analysis showed that a tubular layer of coated copolymer film of several nanometer thicknesses is present on the c‐MWNTs surfaces. FT‐IR spectra endorsed the formation of composites. TGA results indicated that the decomposition temperatures of composites were higher than the bare copolymer. UV‐visible absorption spectra of diluted colloidal dispersion of composites were similar to those of the bare copolymer. The composites were also confirmed by XRD and XPS. Room‐temperature conductivity increases with an increasing fraction of c‐MWNTs. Copyright © 2009 John Wiley & Sons, Ltd.     

First-principles prediction of the pK(a)s of anti-inflammatory oxicams

The gas- and aqueous-phase acidities of a series of oxicams have been computed by combining M05-2X/6-311+G(3df,2p) gas-phase free energies with solvation free energies from the CPCM-UAKS, COSMO-RS, and SMD solvent models. To facilitate accurate gas-phase calculations, a benchmarking study was further carried out to assess the performance of various density functional theory methods against the high-level composite method G3MP2(+). Oxicams are typically diprotic acids, and several tautomers are possible in each protonation state. The direct thermodynamic cycle and the proton exchange scheme have been employed to compute the microscopic pK(a)s on both solution- and gas-phase equilibrium conformers, and these were combined to yield the macroscopic pK(a) values. Using the direct cycle of pK(a) calculation, the CPCM-UAKS model delivered reasonably accurate results with MAD ~ 1, whereas the SMD and COSMO-RS models' performance was less satisfactory with MAD ~ 3. Comparison with experiment also indicates that direct cycle calculations based on solution conformers generally deliver better accuracy. The proton exchange cycle affords further improvement for all solvent models through systematic error cancellation and therefore provides better reliability for the pK(a) prediction of compounds of these types. The latter approach has been applied to predict the pK(a)s of several recently synthesized oxicam derivatives.     

S-Adenosyl-L-methionine ameliorates TNF��-induced insulin resistance in 3T3-L1 adipocytes

An association between inflammatory processes and the pathogenesis of insulin resistance has been increasingly suggested. The IκB kinase-β (IKK-β)/ nuclear factor-κB (NF-κB) pathway is a molecular mediator of insulin resistance. S-Adenosyl-L-methionine (SAM) has both antioxidative and anti-inflammatory properties. We investigated the effects of SAM on the glucose transport and insulin signaling impaired by the tumor necrosis factor α (TNFα) in 3T3-L1 adipocytes. SAM partially reversed the basal and insulin stimulated glucose transport, which was impaired by TNFα. The TNFα-induced suppression of the tyrosine phosphorylation of the insulin receptor substrate-1 (IRS-1) and Akt in 3T3-L1 adipocytes was also reversed by SAM. In addition, SAM significantly attenuated the TNFα-induced degradation of IκB-α and NF-κB activation. Interestingly, SAM directly inhibited the kinase activity of IKK-β in vitro. These results suggest that SAM can alleviate TNFα mediated-insulin resistance by inhibiting the IKK-β/NF-κB pathway and thus can have a beneficial role in the treatment of type 2 diabetes mellitus.