Preparation, electrochemical properties and electrocatalytic activity of Zn-substituted tungstoborate modified electrode.

3-Aminopropyltrimethoxysilane (APTMS) was covalently grafted on a glassy carbon electrode (GCE) by silicon-oxygen bonds formation. The APTMS-modified GCE was used as a suitable charged substrate to fabricate Keggin Zn-substituted tungstoborate (BW11Zn)-consisting monolayer film through layer-by-layer assembly based on the electrostatic attraction. This modification strategy is proven to be a general one suitable for anchoring many kinds of POMs on the APTMS-modified GCE. The APTMS/BW11Zn film obtained on GCE is electrochemically active in acid aqueous solutions and exhibited three pairs of well defined, stable and quasi-reversible cyclic voltammetry peaks in the pH range 0-2. The anodic and cathodic peak currents are linearly proportional to the scan rate in the 200-1000 mV s(-1), indicating a surface confined electrode process. The formal potentials of BW11Zn film, E0 versus saturated calomel electrode (SCE), are -0.27, -0.43, -0.55 V in pH 1 H2SO4 solution and changed linearly with the slope of 44, 63, and 60 mV/pH in the pH range 0-2, respectively. The BW11Zn/APTMS/GC electrode shows good catalytic activity for the reduction of BrO3-, NO2- and H2O2.

[Association between the synovial expression of cyclic citrullinated peptide and susceptibility variants of HLA-DRB1 shared epitope alleles and PADI 4 gene single nucleotide polymorphisms in patients with rheumatoid arthritis].

OBJECTIVE: To analyze the association between the synovial expression of cyclic citrullinated peptide (CCP) and susceptibility variants of HLA-DRB1 shared epitope (SE) alleles and/or peptidylarginine deiminase 4 (PADI4) gene single nucleotide polymorphisms (SNP) in patients with rheumatoid arthritis (RA). METHODS: From October 2008 to December 2011, 53 RA patients and 42 controls were enrolled. The expression of CCP in RA synovial tissues was detected by immunohistochemical assay with 6×His tagged anti-CCP single chain fragment V (ScFv) antibodies generated by pHEN2 phagemid recombinant antibodies display system. PADI4 SNP was genotyped by reverse transcription cDNA sequencing and heterozygote was DNA haplotype was mapped by TA clone sequencing. HLA-DRB1 SE alleles were analyzed by sequence specific primer-polymerase chain reaction (SSP-PCR). RESULTS: The prevalence of synovial CCP expression was significantly different between RA group and the control (76.9% and 11.4% respectively, P < 0.01). The frequencies of 2 SNPs (PADI4_89 G+ and PADI4_104 T+) varied significantly between the groups(P < 0.05). Compared with the major haplotypes, only these two minor alleles were associated with the increased RA susceptibility (OR = 3.67 and 2.53, P < 0.05). SE+ alleles was strongly associated with RA susceptibility (OR = 5.57, P < 0.01). The synovial expression of CCP in RA was strongly associated with SE+ alleles, only 2 minor SNPs (PADI4_89 G+ and PADI4_104T+) and the combination. Serum anti-CCP titers were significantly associated with SE+ alleles, PADI4_104T+, SE+/PADI4_89 G+ and SE+/PADI4_104T+ haplotype. CONCLUSION: The synovial expression of CCP and the generation of anti-CCP antibodies are strongly associated with SE alleles and/or certain PADI4 gene SNP in RA.

[Synthesis, spectroscopy and photocatalytic activity of II B elements substituted tungstoborate heteropoly complexes].

The Keggin II B element-monosubstitiuted heteropoly compounds with the stoichiometry of K7 [BW11 O39 M(H2O)] (M = Zn, Cd) were prepared by one-pot method and characterizated via elemental analyses, FTIR, UV and XRD. The photocatalytic activity of K7 [BW11O39M(H2O)] was tested vis degradation of the model molecule, methyl red (MR). After 60 min irradiation in the presence of K7 [BW11O39M(H2O)] (20 mg x L(-1)), the degradation rate of an aqueous MR (25 micromol X L(-1), pH 2) got to 95%.