N,N'-二(5-溴亚水杨基)-2,6-吡啶二氨铜(Ⅱ)配合物为载体的高选择性硫氰酸根离子电极的研制

首次研究以N,N'-二(5-溴亚水杨基)-2,6-吡啶二氨铜(Ⅱ)配合物为载体的PVC膜电极,其对硫氰酸根离子(SCN-)具有优良的电位响应特性并呈现出反Hofmeister选择性行为,其选择性从大到小次序为:SCN~-,I~-,ClO_4~-,Sal~-,Br~-,NO_2~-,Cl~-,SO_3~(2-),NO_3~-,SO_4~(2-).电极在Ph=5.0的磷酸盐缓冲体系中,对SCN~-在1.0×10~(-1)～4.0×10~(-6)mol/L浓度范围内呈近能斯特响应,斜率为58.5 Mv/dec(25℃),检测下限为2.0×10~(-6)mol/L.采用交流阻抗技术和紫外可见光谱技术初步研究了阴离子与栽体的作用机理,结果表明电极的反Hofmeister选择性行为与配合物中心金属原子的结构以及栽体本身的结构有非常密切的构效关系.该电极具有制备简单、响应快、重现性好、检测限低等优点.将电极应用于实验室废水和人的尿液样品分析,结果令人满意.

Abstract：

A new highly selective thiocyanate electrode based on N,N'-bis(5-bromosalicylidene)-2,6-pyridinediamine copper(Ⅱ)complex[Cu(Ⅱ)-BBSPD]as the neutral carrier is described.The electrode has an anti-Hofmeister selectivity sequence:SCN~-,I~-,ClO_4~-,Sal~-,Br~-,NO_2~-,Cl~-,SO_3~(2-),NO_3~-,SO_4~(2-) and a near-Nernstian potential linear range for thiocyanate from 1.0×10~(-1) to 4.0×10~(-6)mol/L with a detection limit of 2.0 × 10~(-6) mol/L and a slope of 58.5 Mv/decade in Ph=5.0 of phosphorate buffer solution at 25℃.The response mechanism was discussed on the basis of the results from AC impedance measurement and UV spectroscopy.The anti-Hofmeister behaviour of the electrode was found to result from the direct interaction between the central metal and the analyte ion and steric effect associated with the structure of the carrier.The electrode had the advantages of simplicity,fast response,fair stability and reproducibility,and low detection limit.Application of the electrode to the determination of thiocyanate in wasted water samples from a laboratory and in human urine samples yielded satisfactory results.     

以新型双穴位配合物为中性载体的硫氰酸根离子选择性电极的研究

研制了基于N,N'-双(2-水杨醛缩氨基苯基)1,3-丙二酸二酰胺合铜(Ⅱ)[Cu(Ⅱ)-BSAPM]为中性载体的子选择性电极.实验表明,以[Cu(Ⅱ)-BSAPM]为中性载体的电极对硫氰酸根(SCN~-)具有良好的电位响应特且呈现反Hofmeister行为,其选择性序列从大到小为: SCN~-,Sal~-,I~-,ClO_4~-,NO_3~-,Br~-,NO_2-,Cl~-,SO_32SO_4~(2-).在Ph=4.0的磷酸盐缓冲体系中,电极电位呈现近能斯特响应,线性响应范围为1.0×10~(-6)～1.0×1mol/L,斜率为-55.9 Mv/dec(25℃),检测下限为8.0×10~(-7)mol/L.采用交流阻抗技术及紫外可见光谱技术了电极的响应机理,并将该电极用于实验室废水中SCN~-检测,其结果令人满意.

Abstract：

A new PVC membrane electrode based on N,N -bis(2-salicylaldehyde-amino phenyl) malondia-mide copper(Ⅱ) [Cu(Ⅱ)-BSAPM] as neutral carrier is described. The results show that the electrode based on [Cu(Ⅱ)-BSAPM] displays an excellent potentiometric response to thiocyanate ion and an anti-Hofmeister selectivity sequence in the following order: SCN~-,Sal~-,I~-,ClO~-_4,NO~-_3,Br~-,NO~-_2,Cl~-,SO_2~-3,SO~(2-)_4. The electrode exhibits near Nernstian potential linear range of 1.0×10~(-6)-1.0~×10~(-1)mol/L with a detection limit of 8.0×10~(-7)mol/L and a slope of -55.9 Mv/dec in Ph=4.0 phosphorate buffer solution at 25℃. The response mechanism is discussed in view of the A. C. Impedance technique and the UV spectroscopy. Applied to wastewater analysis in laboratory, the electrode gave satisfactory results.     

基于季铵化聚乙烯吡啶和纳米铂固定血红蛋白的过氧化氢生物传感器的研究

将血红蛋白和季铵化聚乙烯吡啶按一定比例混合,滴涂在表面修饰了纳米铂的玻碳电极上,成功制备了性能良好的过氧化氢传感器.通过采用循环伏安法(CV)和计时电流法考察了该传感器的电化学性质.最佳实验条件下,其峰电流值与H_2O_2浓度在3.5×10~(-6)～3.15×10~(-3)mol/L成良好的线性关系,检测下限为1.5×10~(-6)mol/L(S/N=3),相关系数为0.999 2.实验证明该电极对过氧化氢具有响应快,灵敏度高、线性范围宽和稳定性好的性能.

Abstract：

A highly efficient H_2O_2 biosensor was fabricated based on the mixture of hemoglobin (Hb) and quaternized poly(4-vinyl pyridine) (QPVP) and nano-Pt modified glassy carbon electrode.The electro-chemical characteristics of the biosensor were studied by cyclic voltammetry (CV) and chronoamperome-try.Under optimized conditions, the biosensor exhibited a dynamic range of 3.5 × 10~(-6) to 3.15 × 10~(-3) mol/L to H_2O_2 with a detection limit of 1.5×10~(-6) mol/L and a correlation coefficient of 0.999 2.Moreo-ver, the biosensor exhibited high sensitivity to H_2O_2, good repeatability, selectivity and stability.     

The positive function of selenium supplementation on reducing nitrate accumulation in hydroponic lettuce (Lactuca sativa L.)

High nitrate(NO_3~- ) in vegetables, especially in leaf vegetables poses threaten to human health. Selenium(Se) is an important element for maintaining human health, and exogenous Se application during vegetable and crop production is an effective way to prevent Se deficiency in human bodies. Exogenous Se shows positive function on plant growth and nutrition uptake under abiotic and/or biotic stresses. However, the influence of exogenous Se on NO_3~- accumulation in hydroponic vegetables is still not clear. In the present study, hydroponic lettuce plants were subjected to six different concentrations(0, 0.1, 0.5, 5, 10 and 50 μmol L–1) of Se as Na2 Se O3. The effects of Se on NO_3~- content, plant growth, and photosynthetic capacity of lettuce(Lactuca sativa L.) were investigated. The results showed that exogenous Se positively decreased NO_3~- content and this effect was concentration-dependent. The lowest NO_3~- content was obtained under 0.5 μmol L–1 Se treatment. The application of Se enhanced photosynthetic capacity by increasing the photosynthesis rate(Pn), stomatal conductance(Cs) and the transpiration efficiency(Tr) of lettuce. The transportation and assimilation of NO_3~- and activities of nitrogen metabolism enzymes in lettuce were also analysed. The NO_3~- efflux in the lettuce roots was markedly increased, but the efflux of NO_3~- from the root to the shoot was decreased after treated with exogenous Se. Moreover, Se application stimulated NO_3~- assimilation by enhancing nitrate reductase(NR), nitrite reductase(Ni R), glutamine synthetase(GS) and glutamate synthase enzyme(GOGAT) activities. These results provide direct evidence that exogenous Se shows positive function on decreasing NO_3~- accumulation via regulating the transport and enhancing activities of nitrogen metabolism enzyme in lettuce. We suggested that 0.5 μmol L–1 Se can be used to reduce NO_3~- content and increase hydroponic lettuce yield.     

离子选择电极直接连续测定No_3~--N和NH_4~+-N的研究——Ⅲ 植物分析

提出离子选择电极直接连续测定植物中的 NO_3~-—N 和 NH_4~+—N 的新方法。研究了此法的检测下限、线性范围和共存离子的干扰及消除方法;并成功地用一种提取液同时定量地提取了植物中的 NO_3~-—N 和 NH_4~+—N,分析测定了8种蔬菜和8种树叶中的含量。本法检测下限:NO_3~-:1.26×10~(-6)mol·L~(-1),NH_4~+:4.47×10~(-7)mol·L~(-1)。线性范围:NO_3~-:10~(-1)—10~(-6)mol·L~(-1),NH_4~+:10~(-1)—10~(-7)mol·L~(-1)。干扰离子主要有(?),Br,Cl~-,HCO_3~-,NO_2~-:和 Hg~(2+),Mg~(2+),引起干扰的最低浓度依次为:10~(-7),10~(-6),10~(-4),10~(-3),和10~(-5)mol·L~(-1)。当 Cl~-,NO_2~-,HCO_3~-,浓度等于10~(-3)mol·L~(-1)时,干扰顺序为:(?)>Br~->NO_2~->Cl~->HClO_3~-,而当 Cl~-,NO_2~-,HCO_3~-小于10~(-3)mol·L~(-1)时,则干扰顺序为:I~->Br~->Cl~->HCO_3~(-1)>NO_2~-。在本实验条件下,加入 Ag_2SO_4(1.0×10~(-3)mol·L~(-1)),可消除1000倍的 Cl~-,HCO_3~-,100倍的 NO_2~-,0.1倍 I~-,Br~-,对 NO_3~-的干扰,加入 EDTA(2.0×10~(-2)mol·L~(-1)),可消除10倍的 Mg~(2+),Hg~(2+)对 NH_4~+的干扰,并使阴离子干扰减弱。本法标准样分析结果相对误差 NO_3~-<2.2%,NH_4~+,-2.0%～2.2%;变动系数(n=4)NO_3~-:<1.7%NH_4~+:<1.7%;16种植物样分析结果平均回收率(n=2)NO_3~- 96.5%～103.5%,NH_4~+:96.0%～103.2%。     

流动注射抑制化学发光法测定阿魏酸

基于阿魏酸对鲁米诺-铁氰化钾化学发光体系的抑制作用,建立了阿魏酸的流动注射抑制化学发光分析法,在优化的实验条件下,阿魏酸浓度在4.0×10~(-7)～4.0×10~(-6) mol/L之间时,与化学发光强度减小值呈现良好线性关系,检出限为2.4×10~(-7) mol/L,对1.0×10~(-6) mol/L阿魏酸的相对标准偏差为1.4%(n=9),将其应用于复方当归注射液中阿魏酸含量的测定,结果令人满意.此外,结合化学发光光谱和紫外吸收光谱对抑制化学发光机理进行了初步探讨.

Abstract：

Based on the fact that the chemiluminescence intensity of the luminol- K3Fe(CN)6 system is inhibited in the presence of ferulic acid, a novel flow injection chemiluminescence inhibition method for the determination of ferulic acid was developed. Under the optimum conditions, the decrease in chemiluminescence intensity was linear with ferulic acid concentration in the range from 4. 0 × 10~(-7) to 4.0 × 10~(-6) mol/L.The detection limit was 2.4 × 10~(-7) mol/L and the relative standard deviation was 1.4% for 1.0 × 10~(-6) mol/L ferulic acid (n=9). When applied to the determination of ferulic acid in Fufang Danggui Injection samples, this method gave satisfactory results. Furthermore, combining the chemiluminescence spectra with the UV absorption spectra, the paper presents a brief discussion of their chemiluminescence inhibition mechanisms.     

茶碱PVC膜选择性电极的研究

In this Paper, PVC membrane Selective clectrodes are prepared for theophylline which are based on its ion-pair complexes with hexadecylt- rioctylammonium iodide (HTOA) , hexadecyltributyl-ammonium iodide (HTBA), hexadeeyltriophenylphosphonium iodide(HTPP), triphenyloctylphosphonium leoide(TPOP) and tri(p-tolyl) butylphosphonium iodide(TPTBP).The effects of the nature of associate counterions, the plastieizers and their concentrations in the membrane phase have been studied. The electrode based on theophylline-HTOA membrane has a sub-Nernstian response range from 2.0×10~2—6.3×10~(-5)mol/L,with an average slope of 48.0mV/pC. The limit of detection is 8.7×10~(-6)mol/L. The electrode responses were not affected by pH in the range 10-12. The potentiometric selectivity coefficients of various common inorganic and organic ions including those which are similar to theophylline in structure were determined. The Na_2CO_3-Na_2B_4O_7 buffer of pH 11 is selected as the background solution for potentiometric measurements. The electrode was used for determining the theophylline in pharmaceutical preparations with satisfactory results.     

冠醚化合物为载体的PVC膜新型铝离子选择电极研究

研究了基于氮杂冠醚为中性栽体的阳离子选择性电极,该电极在pH为3.0的硝酸缓冲介质中对铝离子有近能斯特响应,其线性范围为8.0×10-5～1.0×10-1 mol/L,检测限为4.0×10-5 mol/L,斜率为20.0 mV/dec.,响应时间为20.0 s.该电极用于EDTA的电位滴定,结果令人满意.     

盐酸文拉法辛离子选择性电极的研制与应用

研究了以盐酸文拉法辛-四苯硼钠为载体、 o-NPOE为增塑剂的对盐酸文拉法辛选择性响应的电极, 该电极在1.0×10-1～8.0×10-6 mol/L范围内呈现能斯特响应, 斜率为58.6 mV/dec, 检测下限为5.2×10-6 mol/L. 可直接用于盐酸文拉法辛胶囊的含量测定, 回收率为98%～101%, 其结果与欧洲药典法一致.     

Effects of different proportions of two Bacillus sp. on the growth performance,small intestinal morphology,caecal microbiota and plasma biochemical profile of Chinese Huainan Partridge Shank chickens

A total of 900 one-d-old Chinese Huainan Partridge Shank chickens were randomly allocated into nine groups with five replicates of 20 each.Birds were fed with basal diet,basal diet supplemented with 150 mg kg~(–1) aureomycin,basal diet supplemented with different proportions of Bacillus licheniformis and Bacillus subtilis,which was 0:1.0×10~6,2.5×10~5:7.5×10~5,3.3×10~5:6.6×10~5,5.0×10~5:5.0×10~5,6.6×10~5:3.3×10~5,7.5×10~5:2.5×10~5 and 1.0×10~6:0,respectively.The duration of the experiment was 56 d.The results indicated that dietary supplementation of 6.6×10~5:3.3×10~5 of B.lichenifornis:B.subtilis improved final body weight,increased the average daily gain,and reduced feed/gain ratio(P0.05).The numbers of total Lactobacillus and Bifidobacterium sp.in the caecum significantly increased,and the numbers of Escherichia coli and Salmonella sp.significantly declined compared to that of the control(P0.05).Intestinal villous height and villous height to crypt depth ratio of the duodenum,jejunum,and ileum were significantly higher than that of the control,and intestinal crypt depth of the duodenum and ileum was significantly lower(P0.05).The total antioxidant capacity,total superoxide dismutase,and glutathione peroxidase ability in plasma significantly improved,while the malondialdehyde concentration in plasma decreased(P0.05).Compared to the control,plasma concentrations of ammonia,uric acid and urea nitrogen and the activity of xanthine oxidase were reduced(P0.05).In conclusion,an inclusion of 6.6×10~5:3.3×10~5 of B.licheniformis:B.subtilis to the diet improved the growth performance,caecal microbiota,plasma biochemical profile,and significantly improved the small intestine morphology,while reducing the mortality rate.