Simultaneous determination of dopamine and ascorbic acid at an in-site functionalized self-assembled monolayer on gold electrode

The in-site functionalization of 4-aminothiophenol (4-ATP) self-assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4'-mercapto-N-phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0 x 10-6 - 1.25 x 10-4 M and 8.0 x 10-6 - 1.3 x 10-4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3sigma) for DA and AA were found to be 1.2 x 10-6 M and 2.4 x 10-6 M, respectively.

Facile syntheses and characterization of hyperbranched poly(ester-amide)s from commercially available aliphatic carboxylic anhydride and multihydroxyl primary amine

A new method for synthesis of novel hyperbranched poly(ester-amide)s from commercially available AA' and CBx type monomers has been developed on the basis of a series of model reactions. The hyperbranched poly(ester-amide)s with multihydroxyl end groups are prepared by thermal polycondensation of carboxyl anhydrides (AA') and multihydroxyl primary amine (CBx) without any catalyst and solvent. The reaction mechanism in the initial stage of polymerization was investigated with in situ H-1 NMR. In the initial stage of the reaction, primary amino groups of 2-amino-2-ethyl-1,3-propanediol (AEPO) or tris(hydroxymethyl)aminomethane (THAM) react rapidly with anhydride, forming an intermediate which can be considered as a new AB(x) type monomer. Further self-polycondensation reactions of the AB. molecules produce hyperbranched polymers. Analysis using H-1 and C-13 NMR spectroscopy revealed the degree of branching of the resulting polymers ranging from 0.36 to 0.55. These hyperbranched poly(ester-amide)s contain configurational isomers observed by C-13 and DEPT C-13 NMR spectroscopy, possess high molecular weights with broad distributions and display glass-transition temperatures (T(g)s) between 7 and 96 degreesC.

A novel method to construct a third-generation biosensor: self-assembling gold nanoparticles on thiol-functionalized poly(styrene-co-acrylic acid) nanospheres

A novel method for fabrication of horseradish peroxidase (HRP) biosensor has been developed by self-assembling gold nanoparticles on thiol-functionalized poly(styrene-co-acrylic acid) (St-co-AA) nanospheres. At first, a cleaned gold electrode was immersed in thiol-functionalized poly(St-co-AA) nanosphere latex prepared by emulsifier-free emulsion polymerization of St with AA and function with dithioglycol to assemble the nanospheres, then gold nanoparticles were chemisorbed onto the thiol groups. Finally, horseradish peroxi- dase was immobilized on the surface of the gold nanoparticles. The sensor displayed an excellent electrocatalytical response to reduction of H2O2 without the aid of an electron mediator. The sensor was highly sensitive to hydrogen peroxide with a detection limit of 4.0 mumol l(-1), and the linear range was from 10.0 mumol l(-1) to 7.0 mmol l(-1). The biosensor retained more than 97.8% of its original activity after 60 days of use. Moreover, the Studied biosensor exhibited good current repeatability and good fabrication reproducibility.

Enthalpy/entropy compensation: Influence of DNA flanking sequence on the binding of 7-amino actinomycin D to its primary binding site in short DNA duplexes

The effect of the context of the flanking sequence on ligand binding to DNA oligonucleotides that contain consensus binding sites was investigated for the binding of the intercalator 7-amino actinomycin D. Seven self-complementary DNA oligomers each containing a centrally located primary binding site, 5'-A-G-C-T-3', flanked on either side by the sequences (AT)(n) or (AA)(n) (with n = 2, 3, 4) and AA(AT)(2), were studied. For different flanking sequences, (AA)(n)-series or (AT)(n)-series, differential fluorescence enhancements of the ligand due to binding were observed. Thermodynamic studies indicated that the flanking sequences not only affected DNA stability and secondary structure but also modulated ligand binding to the primary binding site. The magnitude of the ligand binding affinity to the primary site was inversely related to the sequence dependent stability. The enthalpy of ligand binding was directly measured by isothermal titration calorimetry, and this made it possible to parse the binding free energy into its energetic and entropic terms.

Effect of DNA flanking sequence on charge transport in short DNA duplexes

Several factors can influence charge transport (CT)-mediated DNA, such as sequence, distance, base stacking, base pair mismatch, conformation, tether length, etc. However, the DNA context effect or how flanking sequences influence redox active drugs in the DNA CT reaction and later in DNA enzymatic repair and synthesis is still not well understood. The set of seven DNA molecules in this study have been characterized well for the study of flanking sequence effects. These DNA duplexes are formed from self-complementary strands and contain the common central four-base sequence 5'-A-G-C-T-3', flanked on both sides by either (AT)(n) or (AA)(n) (n = 2, 3, or 4) or AA(AT)(2). UV-vis, fluorescence, UV melting, circular dichroism, and cyclic voltammetry experiments were used to study the flanking sequence effect on CT-mediated DNA by using daunomycin or adriamycin cross-linked with these seven DNA molecules. Our results showed that charge transport was related to the flanking sequence, DNA melting free energy, and ionic strength. For (AA)(n) or (AT)(n) species of the same length, (AA)(n) series were more stable and more efficient CT was observed through the (AA)(n) series. The same trend was observed for (AA)(n) and (AT)(n) series at different ionic strengths, further supporting the idea that flanking sequence can result in different base stacking and modulate charge transport through these seven DNA molecules.

Electrochemical characteristics of facile prepared carbon nanotubes-ionic liquid gel modified microelectrode and application in bioelectrochemistry

The carbon nanotubes (CNTs) based microelectrode (ME) by modifying CNTs-room temperature ionic liquid (IL) gel at carbon fiber microelectrode (CFME) is easily prepared, which exhibits the typical cyclic voltammogram of ME with sigmoid shape and possesses good stability, high conductivity and enlarged current response and tunable dimension. The direct electron transfer of glucose oxidase has been greatly promoted showing reversible electrochemical behavior even at high scan rate. In addition, the CNTs based ME also exhibits effectively electrocatalytic oxidized ability to biomolecules, e.g. dopamine (DA), ascorbic acid (AA) and dihydronicotinamide adenine dinucleotide. The obvious separation of oxidized peak potential for DA and AA makes it possible to selectively determine DA in presence of AA. These phenomena show that the CNTs based ME has promising potential to detect various species in vivo and in vitro.

Analysis of nephroloxic and carcinogenic aristolochic acids in Aristolochia plants by capillary electrophoresis with electrochemical detection at a carbon fiber microdisk electrode

Aristolochic acids (AAs) are the main bioactive ingredients in the most of Aristolochia plants, which are used to make dietary supplements, slimming pills and Traditional Chinese Medicines (TCMs). Excessive ingestion of AAs can lead to serious nephropathy. Therefore, quantitative analysis and quality control for the plants containing AAs is of great importance. In this paper, capillary electrophoresis (CE) with electrochemical detection (ED) at a 33 mu m carbon fiber microdisk electrode (CFE) has been applied to detect AA-I and AA-II in Aristolochia plants. Under the optimum conditions: detection potential at 1.20 V, 2.0 x 10(-2) mol L-1 phosphate buffer solution (PBS) (pH 10.0), injection time 25 s at a height of 17 cm and separation voltage at 12.5 kV, the AA-I and AA-II were baseline separated within 5 min. Low detection limits for AA-I and AA-II were 4.0 x 10(-8) mol L-1 and 1.0 x 10(-7) mol L-1, respectively. Wide linear ranges were from 4.0 x 10(-8) mol L-1 to 1.9 x 10(-5) mol L-1 and 1.0 X 10(-7) mol L-1 to 5.0 x 10(-5) mol L-1 for AA-I and AA-II, respectively. The proposed method has been successfully applied to analyze AAs contents in plant extracts. The results indicated that the contents of AAs in each part of Aristolochia debilis Sieb. Et Zucc.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Self-assembling gold nanoparticles on thiol-functionalized poly(styrene-co-acrylic acid) nanospheres for fabrication of a mediatorless biosensor

A novel strategy to construct a sensitive mediatorless sensor of H2O2 was described. At first, a cleaned gold electrode was immersed in thiol-functionalized poly(styrene-co-acrylic acid) (St-co-AA) nanosphere latex prepared by emulsifier-free emulsion polymerization St with AA and function with dithioglycol to assemble the nanospheres, then gold nanoparticles were chemisorbed onto the thiol groups and formed monolayers on the surface of poly(St-co-AA) nanospheres. Finally, horseradish peroxidase (HRP) was immobilized on the surface of the gold nanoparticles. The sensor displayed an excellent electrocatalytical response to reduction of H2O2 without the aid of an electron mediator. The biosensor showed a linear range of 8.0 mu mol L-1-7.0 mmol L-1 with a detection limit of 4.0 mu mol L-1. The biosensor retained more than 97.8% of its original activity after 60 days' storage. Moreover, the studied biosensor exhibited good current reproducibility and good fabrication reproducibility.

Multilayer films of carbon nanotubes and redox polymer on screen-printed carbon electrodes for electrocatalysis of ascorbic acid

Multilayer films containing multiwall carbon nanotubes and redox polymer were successfully fabricated on a screen-printed carbon electrode using layer-by-layer (LBL) assembled method. UV-vis spectroscopy, X-ray photoelectron spectroscopy, field-emission scanning electron microscopy and electrochemical method were used to characterize the assembled multilayer films. The multilayer films modified electrodes exhibited good electrocatalytic activity towards the oxidation of ascorbic acid (AA). Compared with the bare electrode, the oxidation peak potential negatively shifted about 350 mV (versus Ag/AgCl). Furthermore, the modified screen-printed carbon electrodes (SPCEs) could be used for the determination of ascorbic acid in real samples.

NMR-based metabonomic study on the subacute toxicity of aristolochic acid in rats

The subacute toxicity of aristolochic acid (AA) was investigated by H-1 NMR spectroscopic and pattern recognition (PR)-based metabonomic methods. Model toxins were used to enable comparisons of the urinary profiles from rats treated with known toxicants and AA at various time intervals. Urinary H-1 NMR spectra were data-processed and analyzed by pattern recognition method. The result of visual comparison of the spectra showed that AA caused a renal proximal tubular and papillary lesion and a slight hepatic impair. Pattern recognition analysis indicated that the renal proximal tubule lesion was the main damage induced by AA, and the renal toxicity induced by AA was a progressive course with the accumulation of dosage by monitoring the toxicological processes from onset, development and part-recovery. These results were also supported by the conventional clinical biochemical parameters.

Compatibilization of PP/EPDM blends by grafting acrylic acid to polypropylene and epoxidizing the diene in EPDM

In this article, ethylene-propylene-diene-rubber (EPDM) was epoxidized with an in situ formed performic acid to prepare epoxided EPDM (eEPDM). The eEPDM together with the introduction of PP-g-AA was used to compatibilize PP/EPDM blends in a Haake mixer. FTIR results showed that the EPDM had been epoxidized. The reaction between epoxy groups in the eEPDM and carboxylic acid groups in PP-g-AA had taken place, and PP-g-EPDM copolymers were formed in situ. Torque test results showed that the actual temperature and torque values for the compatibilized blends were higher than that of the uncompatibilized blends. Scanning electron microscopy (SEM) observation showed that the dispersed phase domain size of compatibilized blends and the uncompatibilized blends were 0.5 and 1.5 mu m, respectively. The eEPDM together with the introduction of PP-g-AA could compatibilize PP/EPDM blends effectively. Notched Izod impact tests showed that the formation of PP-g-EPDM copolymer improved the impact strength and yielded a tougher PP blend.

预辐射聚丙烯反应挤出接枝丙烯酸的研究

利用电子束(EB)预辐照方法和反应挤出技术制备了聚丙烯接枝丙烯酸共聚物PP-g-AA.采用化学滴定、红外光谱、偏光显微镜(PLM)、DSC和广角X射线衍射(WAXD)对接枝产物进行了表征.研究结果表明,接枝率随辐照剂量增加而增大并逐渐达到平台值,但随单体浓度增大而表现为线性增加,接枝链能起到异相成核作用,从而提高了结晶速率并细化了球晶.同时,熔体流动速率(MFR)和力学性能测试结果表明,预辐射和挤出过程造成了PP严重降解,据此可认为接枝反应主要发生在聚丙烯断裂分子链的末端.

Thermal properties and morphology of noncrosslinking linear low-density polyethylene-grafted acrylic acid

Noncrosslinking linear low-density polyethylene-grafted acrylic acid (LLDPE-g-AA) was prepared by melt-reactive extrusion in our laboratory. The thermal behavior of LLDPE-g-AA was investigated by using differential scanning calorimetry (DSC). Compared with neat linear low-density polyethylene (LLDPE), melting temperature (T-m) of LLDPE-g-AA increased a little, the crystallization temperature (T-c) increased about 4degreesC, and the melting enthalpy (DeltaH(m) ) decreased with an increase in acrylic acid content. Isothermal crystallization kinetics of LLDPE and LLDPE-g-AA samples were carried out by using DSC. The overall crystallization rate of LLDPE was smaller than that of grafted samples. It showed that the grafted acrylic acid monomer onto LLDPE acted as a nucleating agent. Crystal morphologies of LLDPE-g-AA and LLDPE were examined by using SEM. Spherulite sizes of LLDPE-g-AA samples were lower than that of LLDPE.

Effect of the compatibilization of linear low-density polyethylene-g-acrylic acid on the morphology and mechanical properties of poly(butylene terephthalate)/linear low-density polyethylene blends

A poly(butylene terephthalate) (PBT)/linear low-density polyethylene (LLDPE) alloy was prepared with a reactive extrusion method, For improved compatibility of the blending system, LLDPE grafted with acrylic acid (LLDPE-g-AA) by radiation was adopted in place of plain LLDPE. The toughness and extensibility of the PBT/LLDPE-g-AA blends, as characterized by the impact strengths and elongations at break, were much improved in comparison with the toughness and extensibility of the PBT/LLDPE blends at the same compositions. However, there was not much difference in their tensile (or flexural) strengths and moduli. Scanning electron microscopy photographs showed that the domains of PBT/LLDPE-g-AA were much smaller and their dispersions were more homogeneous than the domains and dispersions of the PBT/ T,T PE blends. Compared with the related values of the PBT/LLDPE blends, the contents and melting temperatures of the usual spherulites of PBT in PBT/LLDPE-g-AA decreased.