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.     

高选择性的硫氰酸根离子电极的研究

研究了水杨醛缩硫脲合铜配合物[Cu(Ⅱ)-HBDT]为中性载体的PVC膜阴离子选择性电极.该电极对硫氰酸根离子呈现出优良的电位响应性能和选择性,并呈现反Hofmeister序列行为.其选择性序列从大到小为:SCN~-,ClO_4~-,Sal~-,I~-,NO_3~-,NO_2~-,Br~-,Cl~-,SO_3~(2-);Ac~-,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)～1.0×10~(-5)mol/L浓度范围内呈近能斯特响应,斜率为-57.0 mV/dec,检测下限为4×10~(-6)mol/L.采用交流阻抗、紫外光谱分析技术研究了阴离子与载体的作用机理,结果表明配合物中心金属原子的结构以及载体本身的结构与电极的响应行为之间有非常密切的构效关系.将该电极用于环境废水中SCN~-的监测,获得满意的结果.

Abstract：

A new highly selective thiocyanate PVC membrane electrode with o-hydroxybenzaldehyde thiocarbohydrazone cupper(Ⅱ)as the neutral carrier is made,which displays an anti-Hofmeister selectivity sequence of SCN~-,ClO_4~-,Sal~-,I~-,NO_3~-,NO_2~-,Br~-,Cl~-,SO_3~(2-);Ac~-,SO_4~(2-).The electrode exhibits a near-Nernstian potential linear range to thiocyanate from 1.0×10~(-1) to 1.0×10~(-5)mol/L with a detection limit of 4×10~(-6) mol/L and a slope of -57.0 mV/dec in pH 5.0 of phosphorate buffer solution at 25 ℃.The response mechanism is discussed in view of the a.c.impedance technique and the UV spectroscopy technique.These deviations 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 has the advantage of simplicity,fast response,fair stability and reproducibility and low detection limit.     

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(英文)

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Hof meister选择性行为,其选择性从大到小次序为:SCN-,I-,Cl O4-,Sal-,Br-,NO2-,Cl-,SO32-,NO3-,SO24-.电极在pH=5.0的磷酸盐缓冲体系中,对SCN-在1.0×10-1～4.0×10-6mol/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2.0×10-6mol/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载体的作用机理,结果表明电极的反Hof meister选择性行为与配合物中心金属原子的结构以及载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.     

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.     

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.     

铜席夫碱配合物中性载体水杨酸根离子电极的研究

报道了以Cu(Ⅱ)配合物为中性载体的PVC膜电极对水杨酸根(Sal-)具有优良的电位响应性能和选择性并呈现出反Hofmeister选择性行为,其选择性从大到小次序为Sal-,ClO4-,SCN-,I-,NO2-,Cl-,F-,Br-,H2PO4-.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3.0×10-6～1.0×10-1 mol/L Sal-,斜率为-58.7 mV/dec(20℃),检测下限为1.5×10-6 mol/L.采用交流阻抗技术研究了电极的响应机理,结果表明,配合物中心金属原子的结构以及载体本身的结构与电极的响应行为之间有非常密切的构效关系.电极可用于药品分析.     

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.     

一类具有特殊曲率性质的(α,β)-度量

在一般的(α,β)-度量F=αφ(s)与Riemann度量α的Ricci曲率之间的关系基础上,证明了一类特殊的(α,β)-度量F=α~2/α+β南,在维数n≥3的流形上,如果F具有速向的Ricci曲率,且β是闭的1-形式,则其Ricci曲率等于零.从而得到如果F=α~2/α+β具有常Ricci曲率,并且β是闭的1-形式,则其Ricci曲率等于零.

Abstract：

We studied an important class of(α,β)-metric on the basis of the relationship of Ricci curvature between G1and a Gi.We verified that if F=α~2/α+β on an n dimension manifold M(n≥3)is of istropic Ricci curvature,i.e.Rmm=(n-1)c(x)F~2,where c(x)is a scalar function on M and β is closed 1-form,then c(x)=0.Hence,we obtained that if F=α~2/α+β is of constant Ricci curvature and β is closed,then c(x)=0.     

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%。     

5-溴水杨醛缩邻氨基苯酚金属配合物中性载体水杨酸根离子电极的研究

报道了以5-溴水杨醛缩邻氨基苯酚合钴(Ⅱ)[Co(Ⅱ)-L)金属配合物为中性载体的阴离子选择性电极.该电极对水杨酸根(Sal-)具有优良的电位响应性能和选择性,并呈现反Hofmeister选择性行为,其选择性从大到小依次为Sal-,ClO4-,SCN-,I-,NO3-,HCO3-,Br-,NO2-,SO32-,F-,Cl-,SO42-.在pH为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8.0×10-6～1.0×10-1 mol/L,斜率为-60.3 mV/decade,检测下限为4.0×10-6 mol/L.采用紫外可见光谱技术和交流阻抗技术研究了电极的响应机理,结果表明载体本身的结构与电极的响应性能间有非常密切的关系.电极用于药品分析,其结果令人满意.     

离子色谱法同时测定地表水中4种常见无机阴离子的研究

利用离子色谱法同时快速测定地表水中4种无机阴离子F~-、Cl~-、NO_3~-和SO_4~(2-),其测定曲线的浓度范围:F~-和NO_3~-为0.05～2.00mg/L,Cl~-为0.50～10.00mg/L、SO_4~(2-)为1.00～20.00mg/L;相关系数:0.9997～0.9999;加标回收率:92.0%～108.0%;精密度相对标准偏差:0.94%～1.81%。该方法具有前处理简单、分离效果良好、分析时间较短、灵敏度较高、检出限较低、操作较简便等特点,可用于快速测定环境地表水中F~-、Cl~-、NO_3~-、SO_4~(2-)这4种常见无机阴离子。     

香蕉14-3-3蛋白基因Ma-14-3-3d的克隆及序列分析(英文)

[Objective] The aim of the study is to clone and analyze the gene encoding 14-3-3 protein from banana. [Method] Combined with PCR amplification, RACE (rapid amplification of cDNA ends) technique was employed to clone 14-3-3 gene from banana; then the amplified sequence was sequenced and homologically analyzed. [Result] A new cDNA homologous with 14-3-3 protein genes were obtained by RT-PCR and RACE ( rapid amplification of cDNA ends ) approaches. The full length of this cDNA was 866 bp encoding 197 amino acids. Alignment of deduced amino acid sequence with those from other plants revealed that the cDNA shared high homology with 14-3-3 protein genes from other plants, and was designated as Musa acuminata 14-3-3 gene (Ma-14-3-3d). Phylogenetic analysis reveals that Ma-14-3-3d has closer genetic relationship with those from monocotyledon species than those from other species. [Conclusion] Ma-14-3-3d belongs to the same lineage of 14-3-3 from monocotyledon.     

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.     

利用~(15)N研究玉米-大豆套作体系中氮素利用特征

【目的】明确不同氮水平下玉米-大豆套作系统中氮素利用特征。【方法】通过~(15)N标记试验,研究了2种氮水平和3种种植模式下作物氮素吸收、土壤氮素残留与损失及大豆生物固氮量的影响。【结果】套作系统内(IMS)玉米植株总氮吸收量和~(15)N吸收量显著高于玉米单作(MM);IMS内的大豆总氮吸收量低于大豆单作(MS),而IMS内大豆的~(15)N吸收量较MS显著增加,且IMS内大豆的固氮比例及固氮量较MS显著增加。IMS中玉米和大豆对~(15)NH_4~+总吸收量显著高于~(15)NO_3~-,且其土壤中的~(15)N残留量~(15)NH_4~+均低于~(15)NO_3~-,~(15)N主要残留于0~40 cm土壤中。此外,IMS的~(15)N回收率显著高于各单作,~(15)N损失率低于各单作处理,且IMS的~(15)N回收率~(15)NH_4~+显著高于~(15)NO_3~-,~(15)N残留率~(15)NO_3~-显著高于~(15)NH_4~+,而~(15)N损失率无显著差异。【结论】与相应的单作相比,玉米-大豆套作显著提高了~(15)N回收率、残留率,降低了~(15)N损失率,增强了大豆生物固氮作用,是一种资源高效、环境友好的可持续农业种植模式。     

基于FePz(dtn)4和纳米金固定辣根过氧化物酶生物传感器的研究

在玻碳电极上电沉积四(1,4-二噻英)四氮杂卟啉铁(FePz(dtn)4),将其作为电子媒介体与纳米金结合,利用纳米金的比表面积大,吸附能力强等优点固定辣根过氧化物酶,最后用聚乙烯缩丁醛包埋修饰好的电极,制备了过氧化氢传感器.采用循环伏安法考察了传感器的电化学特性,以-0.25V为工作电位,在pH=6.5,温度为25℃的最佳条件下,其峰电流值与H2O2浓度在3.5×10-6～7.35×10-3mol/L成良好的线性关系,检测下限为1.0×10-6mol/L(S/N=3).该传感器有非常好的稳定性,响应较快、灵敏度较高,且具有良好的选择性.     

利用碘酰苯(IB)氧化芳构化汉斯酯1,4-二氢吡啶(1,4-DHPs)衍生物的研究

利用碘酰苯(IB)在二氯甲烷中对汉斯酯1,4-二氢吡啶(1,4-DHPs)进行氧化芳构化,反应条件温和,选择性好.操作简单.所得产物均经熔点及~1H NMR验证.

Abstract：

A synthetic method was developed for the oxidative aromatization of Hantzsch 1,4-dihydropyri-dines derivatives by iodoxybenzene in methane dichloride.The reaction proved to be gentle, highly selec-tive and easy to handle.The structures of the products were identified by melt point test and ~1H NMR.     

不同钼水平对生长猪肝脏、肾脏亚硫酸氧化酶活性及尿中SO_3~(2-)、SO_4~(2-)的影响

在生长猪低钼低硒基础饲粮内,分别添加0、10、100ppm钼(钼酸铵),测定了猪肝、肾组织亚硫酸氧化酶活性、尿中SO_3~2-/SO_4~(2-)以及尿中SO_3~(2-)和SO_4~(2-)日排出量。结果初步表明:加钼能提高组织亚硫酸氧化酶活性,减少尿中SO_3~(2-)排出,提高SO_4~(2-)排出,降低尿中SO_2~(2-)/SO_4~(2-)。肝脏亚硫酸氧化酶活性与尿中SO_3~(2-)/SO_4~(2-)和SO_3~(2-)排出呈显著的强负相关,肾脏亚硫酸氧化酶活性与尿中SO_4~(2-)的排出量呈中等正相关。     

新型钴配合物为中性载体的水杨酸根电极研究

研究了基于水杨醛缩邻氨基苯酚合钴(Ⅱ)金属配合物[Co(Ⅱ)-SAAP]为中性载体的PVC膜阴离子电极.该电极对水杨酸根(Sal-)具有优良的电位响应性能和选择性并呈现出反Hofmeister选择性行为,其选择性次序为Sal-＞ClO4-＞SCN-＞I-＞NO2-＞NO3-＞Br-＞Cl-＞SO32-＞SO42-.在pH为5.0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9.0×10-6～1.0×10-1mol/L,斜率为-54.3 mV/dec(20℃),检出下限为5.0×10-6mol/L.采用交流阻抗技术和紫外可见光谱技术研究了电极的响应机理,结果表明配合物中心金属原子的结构以及载体本身的结构与电极的响应行为之间有非常密切的构效关系.该电极具有响应快、重现性好、检出限低、制备简单等优点.将电极用于药品分析,其结果令人满意.     

一类具有迷向Ricci曲率的(α,β)-度量

研究了一类具有迷向Ricci曲率的(α,β)-度量F=(α+β)~2/α,得到这类(α,β)-度量在n(n≥3)维流形上具有迷向Ricci曲率的充分必要条件.从而证明了在n(n≥3)维时,若这类(α,β)-度量具有常的Ricci曲率,则它的Ricci曲率为零.

Abstract：

In this paper,we consider the Finsler metric F =(α+β)~2/α,which has istropic Ricci curvature.We obtain the sufficient and necessary conditions for it to have istropic Ricci curvature on an n-dimension(n ≥ 3)manifold M.Then we prove that if such a Finsler metric on an n-dimension(n ≥3)manifold M has constant Ricci curvature,its Ricci curvature is zero.     

基于Cu2 2,6 双(2 苯并咪唑)吡啶配合物的巯嘌呤荧光分析法

基于配体竞争反应提出了抗癌药物巯嘌呤的荧光分析法.研究发现,在pH=6.8的HEPES缓冲中,Cu2+能与荧光小分子2,6-双(2-苯并咪唑)吡啶(Bbimp)形成非荧光配合物Cu2+-Bbimp,但当抗癌药物巯嘌呤(MP)存在时,由于MP中的巯基(—SH)与Cu2+发生强烈作用而发生配体竞争,游离出的Bbimp的荧光与MP具有函数关系.据此建立了MP的荧光分析方法,线性范围为4.0×10-6～7.0×10-5 mol/L,检测限为3.0×10-7 mol/L.该方法成功用于人体尿样中MP的分析,回收率在96.7%～107.3%之间,相对标准偏差(RSD)小于1.97%.测定结果与药典标准方法一致.