Trace determination of zirconium using anodic adsorptive voltammetry at a carbon paste electrode modified with multi-walled carbon nanotubes

A carbon paste electrode modified with multi-walled carbon nanotubes （MWCNT） was prepared and the determination of ultra trace amount of zirconium based on the anodic adsorptive voltammetry of the zirconium-calcium-alizarin red S mix-polynuclear complex is described in this paper for the first time. The results showed that the sensitivity and the selectivity of the method are excellent. The second derivative linear scan voltammograms of the complex were recorded by polarographic analyzer from 200 to 1200 mV （vs. SCE） and it was found that the complex can be adsorbed on the surface of the electrode, yielding a peak at about 840 mV, corresponding to the oxidation of ARS in the complex. The peak current increases linearly with Zr （IV） concentration in the range of 6.0×10^-12--6.0×10^-11 mol. L^-1 （accumulation time 120 s）, 6.0×10^-11--2.0×10^-9 mol. L-1 （accumulation time 90 s） and 2.0×10^-9--1.0×10^-7 mol. L^-1 （accumulation time 60 s） and the detection limit （S/N = 3） is 2.0×10^-12 mol. L^-1 （accumulation time 180 s）. The procedure has been successfully applied to the determination of zirconium in the ore samples.     

Effect of total aluminum concentration on the formation and transformation of nanosized Al13 and Al30 in hydrolytic polymeric aluminum aqueous solutions

Influence of total aluminum concentration （CAIT） on the generation and transformation of nanosized AI13 and AI30 in hydrolytic polyaluminum aqueous solutions was investigated using high field 27AI NMR and time-developed AI-Ferron complex colorimetry. When prepared at the optimal basicity （B） of Al13 generation and 80℃, the All3 species in polyaluminum solution tends to further polymerize and convert to AI30 and higher polymers when CAI; 〉0.2 mol· L^-1, but Al13 does not convert to AI30 quantificationally, as the formation of Alu from Al13 and AI30 is accelerated in the same way. The conversion rate of All3 is accelerated by the increase in CAIT. When CAlT 〉0.75 mol·.L^-1, Al13 content decreases rapidly, and AI30 content increases continuously and becomes the dominant nanometer polynuclear aluminum species. AIm is one of prerequisites of Al13 conversion to AI30. When CAI; increases and B reduces, the polymerization rate between Al13 and Aim increases, and at the same time, the dissociation reaction rate of All3 and AI30 by H^＋ also increases. The latter becomes the dominant reaction in polyaluminum solution with low B value, so AI30 decreases with the increasing CAlT. The hydrolytic polyaluminum solution with Al13 content beyond 80% can only be prepared under the condition of CAlT〈0.5 mol· L^-1 and optimal B value.     

Spectrofluorimetric determination of artemisinin with pyronine B as the substrate for horseradish peroxidase

Enzyme-catalytic fluorescence determination of artemisinin （qinghaosu, QHS） was developed using pyronine B （PB） as substrate of horseradish peroxidase （HRP）. The interaction between HRP and QHS was an enzyme-substrate model. The catalytic characteristic of HRP in the oxidation reaction, in which the fluorescence of PB was decreased in the presence of QHS, was studied. The steady-state catalytic rate depended upon enzyme and substrate concentrations, and the Michaelis-Menten parameters Km, Vmax and Kcat were 8.4×10^-5mol·L^-1, 7.4×10^-6mol·L^-1s^-1 and 50.23s^-1. The catalytic activity of enzyme was inhibited in the presence of deactivated agents and at high temperature, respectively. Under optimum conditions, linear relationship between fluorescence intensity change （F0-F） of pyronine B and concen- tration of QHS was in the range of 1.41×10^-7-1.27×10^-6mol·L^-1. The detection limit （3σ） was determined to be 2.7×10^-8mol·L^-1. The proposed method was applied to the concentration determination of QHS in the media of plasma or urine samples.     

Occurrence of sulfonamide antibiotics in sewage treatment plants

The occurrence of sulfonamide antibiotics （SAs） was investigated in the six sewage treatment plants （STPs） of Beijing, China. Of the 13 objective antibiotics, suIfamethoxazole, suIfapyrldine, suIfamerazine, sulfadiazine and suIfamethizol were detected in the influents with the average concentrations of 1.2 ± 0.45, 0.29 ± 0.25, 0.048 ± 0.012, 0.35 ± 0.52 and 0.33 ± 0.21 μg·L^-1, respectively, and those in the effluents were 1.4 ± 0.74, 0.22 ± 0.19, 0.021 ± 0.008, 0.22 ± 0.21and 0.01± 0 μg·L^-1, respectively. SuIfamethoxazole was the predominant compound detected, and was found in all wastewater samples with the other two compounds sulfapyridine and suIfamerazine. It should be noted that suIfadiazine was first reported in wastewatera, and the concentration levels of all detected compounds except for suIfamethizol （detected once in the effluent samples） in the influents were observed to be similar to those in the effluents. From the dsts in this study, it can be found that suIfamethoxazole, suIfapyridine, suIfamerazine and suIfadiazine could be partly removed in anoxic and aerobic treatment unit and vice versa in anaerobic process, which led to their low or even negative removal rates in the effluents. The increase on the concentrations of suIfamethoxazole and suIfapyridine in the effluents was found probably due to the biotransformation of their acetylated forms in anaerobic treatment unit. In addition, it was observed that the biodegradation of suIfamethoxazole and suIfapyridine could partly occur during the anoxic and aerobic process, while suIfamerazine was partly eliminated in the anaerobic and anoxic units.     

Effect of TiO_2 on the viscosity and structure of low-fluoride slag used for electroslag remelting of Ti-containing steels

The viscosity of CaF_2–CaO–Al_2O_3–MgO–(TiO_2) slag was measured using a rotating crucible viscometer. Raman spectroscopy analysis was performed to correlate the viscosity to slag structure. The viscosity of the slag was found to decrease with increasing TiO_2 content in the slag from 0 to 9.73wt%. The activation energy decreased from 95.16 kJ /mol to 79.40 kJ /mol with increasing TiO_2 content in the slag. The introduction of TiO_2 into the slag played a destructive role in Al–O–Al structural units and Q~4 units by forming simpler structural units of Q~2 and Ti_2O_6~(4-) chain. The amount of Al–O–Al significantly decreased with increasing TiO_2 content. The relative fraction of Q~4 units in the [AlO_4]~(5-)-tetrahedral units shows a decreasing trend, whereas the relative fraction of Q~2 units and Ti_2O_6~(4-) chain increases with increasing TiO_2 content accordingly. Consequently, the polymerization degree of the slag decreases with increasing TiO_2 content. The variation in slag structure is consistent with the change in measured viscosity.     

Effect of TiO<Subscript>2</Subscript> on the viscosity and structure of low-fluoride slag used for electroslag remelting of Ti-containing steels

The viscosity of CaF₂-CaO-Al₂O₃-MgO-(TiO₂) slag was measured using a rotating crucible viscometer. Raman spectroscopy analysis was performed to correlate the viscosity to slag structure. The viscosity of the slag was found to decrease with increasing TiO₂ content in the slag from 0 to 9.73wt%. The activation energy decreased from 95.16 kJ/mol to 79.40 kJ/mol with increasing TiO₂ content in the slag. The introduction of TiO₂ into the slag played a destructive role in Al-O-Al structural units and Q4 units by forming simpler structural units of Q2 and Ti₂O₆4- chain. The amount of Al-O-Al significantly decreased with increasing TiO₂ content. The relative fraction of Q4 units in the[AlO₄]5--tetrahedral units shows a decreasing trend, whereas the relative fraction of Q2 units and Ti₂O₆4- chain increases with increasing TiO₂ content accordingly. Consequently, the polymerization degree of the slag decreases with increasing TiO₂ content. The variation in slag structure is consistent with the change in measured viscosity.     

Stress corrosion cracking of X80 pipeline steel exposed to high pH solutions with different concentrations of bicarbonate

Susceptibilities to stress corrosion cracking (SCC) of X80 pipeline steel in high pH solutions with various concentrations of HCO₃? at a passive potential of ?0.2 V vs. SCE were investigated by slow strain rate tensile (SSRT) test. The SCC mechanism and the effect of HCO₃? were discussed with the aid of electrochemical techniques. It is indicated that X80 steel shows enhanced susceptibility to SCC with the concentration of HCO₃? increasing from 0.15 to 1.00 mol/L, and the susceptibility can be evaluated in terms of current density at ?0.2 V vs. SCE. The SCC behavior is controlled by the dissolution-based mechanism in these circumstances. Increasing the concentration of HCO₃? not only increases the risk of rupture of passive films but also promotes the anodic dissolution of crack tips. Besides, little susceptibility to SCC is found in dilute solution containing 0.05 mol/L HCO₃? for X80 steel. This can be attributed to the inhibited repassivation of passive films, manifesting as a more intensive dissolution in the non-crack tip areas than at the crack tips.     

Study on the viscoelastic behavior of SEEPS block copolymer based on a modified BSW model

Studies on the viscoelastic behavior of styrene[ethylene-（ethylene-propylene）] -styrene block copolymer （SEEPS） were carried out, and some characteristic viscoelastic parameters were calculated. The longest relaxation time was obtained through simulating the relaxation spectrum on the basis of a modified Baumgaertel-SchausbergerWinter （mBSW） model. The results revealed that there exists a “second plateau” in the low frequency region of the master curves. The reason for this phenomenon is attributed to the entanglement of macromolecular chains. It is suggested that the hard blocks, polystyrene, act as entanglement points, resulting in a topology restraint to the movement of macromolecular chains. Meanwhile, it is found that the horizontal shift factors （aT） vs temperature in the master curve could be fitted to the WiUiams-Landel-Ferry （WLF） equation and Arrhenius equation respectively and the flow activation energy （Ea） is 127.88 kJ/mol. In addition, the plateau modulus （GN） and entanglement molecule weight （Me） were calculated.     

Interaction between poly（amidoamine） dendrimers and DNA studied by spectroscopic methods

The interaction between amino-terminated, and ethylenedtamine core poly（amtdoamine） （PAMAM） dendrimers and herring sperm DNA was investigated by various spectroscopic methods including UV spectroscopy, fluorescence spectroscopy, microscopic FTIR- and circular dichroism （CD-） spectroscopy. Ethidium bromide （EB） is used as a nucleic acid probe for this study. Experimental results show that PAMAM dendrimers can form stable complexes with DNA and the dendrimers bind to DNA sufficiently strong which cannot be displaced by EB, and we also found that the formation of the complexes can cause the conformation change of the DNA secondary structure. According to the Scatchard analysis, the association constant of PAMAM to DNA is calculated to be 2.53×10^4 mol/L^-1.     

Electrosynthesis of poly（o-phenylenediamine） in ionic liquid and its properties

Ionic liquid 1-ethyl-3-methylimidazolium bromide (EMIMBr) and N-methylimidazolium tetrafluorobo-rate (HMIMBF4) have been used as solvent and electrolyte for the electropolymerization of o-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It was found that monomer was more easily oxidized in ionic liquid than acidic aqueous solution,and oxidative potential was reduced by 0.725 and 0.455 V,respectively. Electrode modified with poly(o-phenylenediamine) (PPD) has obvi-ous electrochemical activity in acid solution (pH 1-4). The apparent diffusion coefficient (Dapp) of PPD film is measured by chronocoulometry and chronoamperometry. The polymer structure is measured by UV and IR. IR spectrometry reveals that poly(o-phenylenediamine) has phenazine ring structure. The heat stability of polymer is observed from thermogravimetry.     

Electrochemical Behavior and Determination of Trifluoperazine at Decanethiol Self-Assembled Monolayer Modified Gold Electrodes

0　IntroductionTrifluoperazine is a derivative of phenothiazine. It hasneuroleptic and antidepressive actions, hence has beenwidely used in the treatment of psychotic patients[1]. As it hassuch function and application, trifluoperazine’s characteristicsand detection methods were studied by means of spectropho tometry[2], capillary zone electrophoresis[3], titrimetry[4],fluorometry[5], high performance liquid chromatographyetc[6]. Because of the electroactivity of trifluoperaz…     

高灵敏度的硫酸根离子选择性电极

以2-氨基口白啶与SO₂^-4缔合物为电活性物质，以邻苯二甲酸二丁酯(DBP)为增塑剂，制作PVC膜硫酸根离子选择性电极.实验结果表明，电极对硫酸根离子具有良好的选择性和较高的灵敏度，其线性响应范围为5.0×10^-7～1.0×10^-1mol·L^-1.用该电极测定水中的硫酸根离子含量，结果令人满意.     

基于单壁碳纳米管修饰电极测定贝诺酯片剂中贝诺酯的含量

运用循环伏安法研究了贝诺酯在单壁碳纳米管修饰电极上的电化学行为。在B-R缓冲溶液(pH5.0)中,贝诺酯于1.10V(vs.SCE)电位处有一个峰形很好的氧化峰。与裸玻碳电极相比,贝诺酯在修饰电极上的电位正移了约30mV,峰电流增加了近5倍。在最佳的实验条件下,贝诺酯的氧化峰电流与其浓度(2.8×10_(-6)~1.4×10~(-4)mol/L)呈现出良好的线性关系,检出限为4.8×10~(-7)mol/L。该方法用于实际样品贝诺酯片剂的检测中,结果令人满意。     

工业废水中酚类污染物的毛细管电泳—安培检测应用研究(英文)

发展了毛细管电泳—安培检测方法,并将这一联用技术应用于苯酚、2,4-二氯苯酚、对硝基苯酚和邻、间、对甲酚的同时分离检测中.考察了氧化还原电位、缓冲溶液酸度、盐度、分离驱动电压及进样时间等因素对分析检测的影响.在优化实验条件下,以Na_2HPO_4-NaOH(pH11.38)为缓冲体系,6种酚类物质能够在25 min内实现基线分离,氧化还原电位0.78 V(versusSCE)下可以定量检测(三电极体系为:直径为300μm的碳圆盘电极、饱和甘汞电极及铂电极).实验结果表明,其线性达3个数量级(S/N=3),检测限达10^(-7)mol/L.本文还尝试把该方法应用于两个实际工业污水的酚类污染物的检测,其回收率为94.0%～107.0%,结果令人满意.因此,该方法可为政府及企业环境检测部门提供一种快速、准确、低廉、无污染、重现性高的质量控制方法.     

Cobalt doped titanate nanotubes: Synthesis and properties

Cobalt oxide doped titanate nanotubes are synthesized with a simple hydrothermal treatment of mixed Co_3O_4 and TiO_2 powders. The formed tubular nanostructure, chemical composition,and the elemental distribution are analyzed using TEM, BET, FTIR, XRD, and XPS. The electrocatalytic activity towards oxygen evolution reactions and photodegradation against Rhodamine B are investigated. It has been found out that the oxygen evolutions starts at 0.8 V and reaches 0.98 mA ·cm~(–1) at 1.4 V vs. SCE. For photodegradation of Rhodamine B, the concentration decreased to 24% after 1 h irradiation using the sample with a mass percentage of 5% cobalt. The results demonstrate that the cobalt oxide doped titanate nanotubes are good candidates as electrocatalysts and photocatalytic materials.     

Electrochemical behavior of adriamycin at a cobalt ion implantation modified electrode

With Co/GCE in 0.005 mol Tris/L/0.05 mol/L NaCl solution (pH 7.1), a sensitive reductive peak of adriamgcin (ADM) was obtained by the linear scan voltammetry. The peak potential is ?0.62 V (vs. SCE). The peak current is proportional to the concentration of ADM. The electrochemical behavior of the system was studied by the linear-sweep and cyclic voltammetry. The experiments showed that the reduction at Co/GCE is a quasi-reversible process with adsorption. According to Laviron’s theory, the electrode reaction rate constant k₀ and the electron transfer coefficient a are determined to be 2.15 s^-1 and 0.62, respectively. The composition of the surface, valence state of elements and depth distribution of elements on the surfaces of Co/GCE were determined by the X-ray photoelectron spectroscopy and Auger electron spectroscopy. The experiments showed that Co was surely implanted into the surface of GCE. The implanted Co element in the form of Co-C catalyzed the reduction of ADM.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Mo添加对金属Ru电催化氧还原性能的影响

以Ru3(CO)12和Mo(CO)6为前驱体,在1,6-己二醇介质中采用低温回流法合成了Ru-Mo催化剂。利用SEM、XRD和旋转圆盘电极(RDE)技术表征了催化剂的物理特征和催化性能。Ru-Mo催化剂呈现以六方结构Rux簇为主相的纳米颗粒特征,同时形成无定形相,聚集颗粒高度分散。在氧气饱和的0.5 mol/L H2SO4溶液中,Ru-Mo催化剂对氧还原的电催化活性和稳定性明显高于Rux簇合物,开路电位为0.91 V(vs.NHE)。