镧对MC3T3细胞钙激活钾电流及其动力学的影响

利用全细胞膜片钳技术,研究了稀土镧离子对非兴奋性小鼠成骨细胞(MC3T3)钙激活外向钾电流及其激活和失活动力学的影响.结果表明:MC3T3细胞钙激活外向钾电流随着电极内液中游离Ca2+浓度的增加而增加,且具有电压和胞内游离Ca2+依赖性特征.细胞外液中的稀土镧可浓度依赖性地抑制MC3T3细胞钙激活外向钾电流,其半数抑制浓度(EC50)为8.23±1.45μmol/L.50μmol/L氯化镧可使钾电流的激活曲线向正电位方向移动,而使其失活曲线向负电位方向移动,但对激活曲线和失活曲线的斜率因子k值影响都不大.研究表明:抑制钾通道电流,可使细胞膜去极化,细胞的兴奋性增加,从而增加胞外Ca2+向胞内流动,引起胞内Ca2+浓度的增加,由此而诱发一系列的生理和分子生物学事件.这一过程可能是稀土镧影响MC3T3成骨细胞生长和功能的分子作用机制之一.     

镧、钆、镱三种稀土离子诱导背根神经元凋亡及膜上钾电流的比较研究

运用流式细胞仪和膜片钳技术研究La3+,Gd3+,Yb3+三种稀土离子诱导大鼠背根神经元DRG凋亡以及膜上钾离子通道的影响。结果表明:10,100,1000μmol.L-1LaCl3和GdCl3处理DRG神经元96 h,细胞不出现凋亡;YbCl3处理96 h,细胞的凋亡率明显递增。胞外La3+,Gd3+,Yb3+抑制瞬间外向钾电流IA,使IA的激活和失活过程都显著右移,抑制和右移的程度La3+最弱,Gd3+次之,Yb3+最强;胞内的La3+,Gd3+,Yb3+抑制延迟整流钾电流IK,抑制的程度也呈增长趋势。稀土离子在胞内外的结合位点不同;Yb3+较La3+和Gd3+的神经毒性强。     

高氯酸镱对大鼠背根神经元细胞毒性及膜上钾通道的影响

研究了高氯酸镱(Yb(ClO4)3)诱导大鼠背根神经(DRG)元凋亡、引起胞内钙离子浓度变化以及对膜上钾离子通道的影响.急性分离大鼠DRG细胞,用不同浓度的Yb(ClO4)3处理DRG细胞24和96h,采用流式细胞仪和激光共聚焦法,检测细胞的凋亡和细胞内钙离子荧光强度的变化.利用全细胞膜片钳法,记录Yb(ClO4)3对细胞膜上不同钾通道电流的影响.结果表明,10,100,1000μmol/L Yb(ClO4)3处理DRG神经元24h,细胞基本不表现凋亡;处理96h,细胞出现明显的凋亡(P0.05～0.01),尤其是1000μmol/L Yb(ClO4)3,凋亡率达到了(55.23±3.76)%(P0.01).经Yb(ClO4)3孵育的DRG神经元胞内的Ca2+的荧光强度显著增大;Yb(ClO4)3抑制背根神经节纤维和神经元突起的生长.Yb(ClO4)3抑制DRG神经元膜上的钾电流,胞内和胞外的Yb(ClO4)3作用钾通道的部位不同.细胞外液中的Yb(ClO4)3不同程度地阻断了瞬间外向钾电流IA,对延迟整流钾电流几乎没影响;往电极内液中加入同样浓度的Yb(ClO4)3对IA影响很小,却特异性地阻断了延迟整流钾电流IK.10μmol/L Yb(ClO4)3使IA的激活和失活过程都显著右移,延长了瞬间外向钾电流达到峰值的时间和快速失活时间常数,增加神经元的兴奋性.     

镧对心肌细胞钾通道的作用研究

用全细胞膜片钳记录方式研究了La^3^+对大鼠心室肌细胞钾通道的作用机理。对酶解分离的大鼠心室肌细胞施一跃迁电压可引出一非钙依赖性电压去激活的外向钾电流。将10μmol/LLa^3^+加入细胞外液后，非钙依赖性电压去激活的外向钾电流明显减小，这提示在大鼠心室肌细胞钾通道上存在La^3^+结合位点。     

构象转换型传感器对汞、铅、锶离子的同时检测

将核酸构象转换与纳米孔膜技术联用设计了一种新型高灵敏电化学传感器, 实现了对Hg ²⁺, Pb ²⁺和Sr ²⁺的分步同时检测. 使用2种分别能与Hg ²⁺及Pb ²⁺, Sr ²⁺结合的核酸适体, 将其固定在氧化铝纳米孔膜孔道内以阻碍铁氰化钾离子传导. 利用核酸适体包裹目标物时的蜷缩状态与目标物被洗脱剂洗脱后核酸适体的伸展状态之间的构象转换, 控制纳米孔通道的“开”和“关”, 使铁氰化钾溶液的氧化还原电流发生改变. 通过监测铁氰化钾溶液的电信号变化值, 可实现同时检测此3种金属离子的目的. 实验结果表明, 该传感器对3种金属离子具有很高的灵敏度和选择性, 检测的线性范围均为0.051.50 nmol/L, 对Hg ²⁺, Pb ²⁺和Sr ²⁺的检出限分别为0.013, 0.017和0.022 nmol/L(S/N=3).     

稀土掺杂氟化镁钾纳米晶的合成及其光谱特性

采用微乳液法合成了Eu²⁺,Ce³⁺单掺和双掺KMgF₃纳米晶,分析了样品的结构与形态. 结果表明,所合成的样品均为单相,颗粒粒度分布均匀. 讨论了光谱特性并与高温固相法合成的产物作了对比. 研究发现,在KMgF₃纳米晶双掺体系中,由于Eu²⁺和Ce³⁺竞争吸收激发能,只能观察到Ce³⁺的发射带; 而在KMgF3多晶共掺体系中,因为存在Ce³⁺→Eu²⁺能量传递过程,只能观察到Eu²⁺的发射峰.     

胞外高钾对大鼠背根神经元超极化电流的影响

应用全细胞膜片钳技术研究了胞外高钾对大鼠背根神经元（DRG）超极化电流（Ih）的影响．结果表明,Ih随着胞外钾离子浓度的增大而增大,同时随着外加刺激电压的增高而增强．当胞外钾离子浓度[Kext]为4,8和16mmol／L时,半数激活电压V1/2分别为-98±1．9,-106±1．3（p〈0．05）和-110±1．0mV（p〈0．05）,其对应的最大电流的峰值分别为1085±340,1576±409和2124±614pA,与4mmol／L比较,后者分别增长了45％和92％．胞外高钾使,Ih激活曲线显著左移,说明高Kext改变了超极化电流的激活过程．提高细胞外钾离子浓度,可以使早期钾通道（又称快通道）的激活时间常数增大,使晚期钾通道（又称慢通道）激活时间常数减小．当胞外钾离子浓度由4mmol／L升高到8和16mmol／L时,翻转电位右移,但不具有显著性差异．结果提示,细胞外高浓度钾可增强大鼠背根神经元超极化电流,Ih,改变Ih的激活过程,从而提高了神经元的兴奋性,产生不正常的动作电位,对神经细胞产生损伤．     

Cr3+比色荧光探针的合成及细胞成像应用

以2,3,3-三甲基-3H-苯并[e]吲哚和对二甲氨基苯甲醛为原料, 乙醇作溶剂, 在酸性催化条件下, 通过一步反应合成了比色荧光探针B. 在EtOH/HEPES(pH=7.4)体积比为9∶1的混合体系中, 向探针B溶液中加入Cr ³⁺后, 溶液颜色由淡黄色变为紫红色, 说明探针B可以对Cr ³⁺进行裸眼识别. 紫外-可见吸收光谱和荧光发射光谱分析表明, 探针B对Cr ³⁺的选择性好、 灵敏度高且对EDTA有良好的接力识别. 探针B对Cr ³⁺的结合常数K_a=0.28×10 ² mol/L, 检出限为1.90×10 ^-8 mol/L, 该检出限低于世界卫生组织(WHO)规定的饮用水中Cr ³⁺的最大含量(9.60×10 ^-8 mol/L). 利用荧光发射光谱对实际水样中Cr ³⁺的浓度进行了定量检测. 探针B也可应用于对活细胞中Cr ³⁺的检测, 具有较好的应用前景和实用价值.     

四甲基联苯胺显色光度法测定过氧化氢酶活性

基于Fe²⁺-H₂O₂-四甲基联苯胺(tetramethylbenzidine,TMB)显色体系测定过氧化氢酶(CAT)活性。在Fe ²⁺催化作用下过氧化氢与四甲基联苯胺发生显色反应。加入CAT后,A值减小,显然CAT对显色反应具有阻抑作用。在优化实验条件下,CAT活性在0.00~0.10 U·mL^-1之间与△A呈现良好的线性关系:△A=0.0348+19.19 E(U·mL^-1)(r=0.9977),检出限为0.0016 U·mL^-1。采用酶失活样品液作空白,可有效排除样品共存还原性物质的干扰;方法用于健康人体血清CAT活性检测,为广大临床检验工作者提供参考。     

细胞色素C的光谱研究

细胞色素C是吸呼链的1个重要组成部分,位于细胞色素C₁和细胞色素a之间,血红素辅基中的铁原子可交替地处于+3或+2氧化态^[1]。Smith^[2]和Osheroff等^[3]对细胞色素C与细胞色素C₁及a的结合进行了详细的研究。关于细胞色素C与小分子的相互作用,除Corthesy^[4]进行了与ATP的作用,Osheroff^[3]进行了与碳酸根的作用外,与其它小分子的作用以及氧化型、还原型之间的相互转化受介质的影响还未见报道。     

La3+,Sr2+置换对Ca[(Mg1/3Nb2/3)0.6Ti0.4]O3陶瓷微波介电性能的影响

研究了La^3＋，Sr^2＋置换对Ca[（Mg1/3Nb2/3）0.6Ti0.4]O3陶瓷微观结构与微波介电性能的影响。研究结果表明：La^3＋，Sr^2＋置换改性Ca[（Mg1/3Nb2/3）0.6Ti0.4]O3系列陶瓷均形成了单一正交系的钙钛矿结构；随着置换量的增加，La^3＋改性Ca[（Mg1/3Nb2/3）0.6Ti0.4]O3陶瓷的介电常数、介电损耗下降，同时谐振频率温度系数向正的方向移动，而Sr^2＋改性陶瓷则表现出相反的规律，其主要原因在于La^3＋，Sr^2＋置换所引起Ca[（Mg1/3Nb2/3）0.6TiO4]O3陶瓷内部氧八面体结构变化上的差异。     

Electronic and medium effects on the rate of arene C [bond] H activation by cationic Ir(III) complexes

A detailed mechanistic study of arene C [bond] H activation in CH(2)Cl(2) solution by Cp(L)IrMe(X) [L = PMe(3), P(OMe)(3); X = OTf, (CH(2)Cl(2))BAr(f); (BAr(f) = B[3,5-C(6)H(3)(CF(3))(2)](4))(-)] is presented. It was determined that triflate dissociation in Cp(L)IrMe(OTf), to generate tight and/or solvent-separated ion pairs containing a cationic iridium complex, precedes C [bond] H activation. Consistent with the ion-pair hypothesis, the rate of arene activation by Cp(L)IrMe(OTf) is unaffected by added external triflate salts, but the rate is strongly dependent upon the medium. Thus the reactivity of Cp(PMe(3))IrMe(OTf) can be increased by almost 3 orders of magnitude by addition of (n-Hex)(4)NBAr(f), presumably because the added BAr(f) anion exchanges with the OTf anion in the initially formed ion pair, transiently forming a cation/borate ion pair in solution (special salt effect). In contrast, addition of (n-Hex)(4)NBAr(f) to [CpPMe(3)Ir(Me)CH(2)Cl(2)][BAr(f)] does not affect the rate of benzene activation; here there is no initial covalent/ionic pre-equilibrium that can be perturbed with added (n-Hex)(4)NBAr(f). An analysis of the reaction between Cp(PMe(3))IrMe(OTf) and various substituted arenes demonstrated that electron-donating substituents on the arene increase the rate of the C [bond] H activation reaction. The rate of C(6)H(6) activation by [Cp(PMe(3))Ir(Me)CH(2)Cl(2)][BAr(f)] is substantially faster than [Cp(P(OMe)(3))Ir(Me)CH(2)Cl(2)][BAr(f)]. Density functional theory computations suggest that this is due to a less favorable pre-equilibrium for dissociation of the dichloromethane ligand in the trimethyl phosphite complex, rather than to a large electronic effect on the C [bond] H oxidative addition transition state. Because of these combined effects, the overall rate of arene activation is increased by electron-donating substituents on both the substrate and the iridium complex.     

富勒烯结构Si60的从头算研究

采用量子化学从头算方法, 系统地研究了Si60-Ih及其各种降低对称性后的扭曲构型的稳定性. 找到了5个低能量低对称性(对称性分别为T, Ci, C1, CS和C2) Si60的稳定结构. 分析计算结果表明, 典型的低能量Si60结构对应着一些硅原子凸出球外和一些硅原子凹进球内, 部分Si原子间的成键呈sp3杂化方式.     

Local amperometric detection of K+ in aqueous solution using scanning electrochemical microscopy ion-transfer voltammetry

A robust ultramicroelectrode (UME) probe is described for the amperometric determination of K⁺ ions in aqueous solution. The approach is based on ion-transfer voltammetry at the interface between two immiscible electrolyte solutions (ITIES), with a liquid ¦ liquid interface formed between a 1,2-dichloroethane solution, containing dibenzo-18-crown-6, in a glass capillary, which is placed in an aqueous K⁺ salt solution of interest (KCl in this study). The ITIES is externally polarised by applying a potential between silver electrodes in each phase. The UME probe has an inlaid disk geometry, making conventional ultramicroelectrode and scanning electrochemical microscopy (SECM) mass transport models applicable. Limiting current measurements of K⁺ in aqueous solution show a linear dependence on KCl concentration between 1 × 10⁴ and 2.5 × 10³ mol dm³. The K⁺ microprobe is shown to be particularly suitable for use in SECM, for both approach curve and imaging applications.     

MoO3/γ-Al2O3, MoO3/TiO2和MoO3/SiO2的还原性质及表面状态研究

本文以XPS为检测手段研究了浸渍法制备的MoO_3/γ-Al_2O_3、MoO_3/TiO_2和MoO_3/SiO_2三个系列样品的还原性质。用XPS测定还原后与还原前强度比的比值, 实验结果表明阈值后的样品还原后强度比急剧增大, 说明晶相MoO_3从内孔向颗粒外表面大幅度迁移。而单层MoO_3的性质却各不相同, TiO_2上的单层MoO_3还原后部分凝聚, SiO_2上单层则部分迁移, 而γ-Al_2O_3上的单层MoO_3既不迁移也不凝聚, 亦即单层MoO_3的稳定性是Mo(Al)>Mo(Ti)>Mo(Si)。这也是MoO_3与这三个载体表面作用力强弱的顺序。用计算机对Mo3d谱峰解叠, 结果表明, 几乎所有样品还原后都只含有四价和五价钼。Mo(Al)和Mo(Si)体系还原后Mo~Ⅳ的百分数随负载量的增大而增大。我们认为反映了两种载体表面区域的不均匀性。Mo(Ti)体系还原后Mo~Ⅳ百分数在阈值附近出现转折点, 阈值前各点还原性质相同, 说明在应用还原为探测手段时, TiO_2表面表现为均匀的。以Mo~(Ⅳ)百分数衡量时, 三个体系的还原性为Mo(Al)相似文献   

全细胞膜片钳法研究铜对急性分离大鼠海马细胞钾电流的影响

Using the whole cell patch clamp technique, the effect of Cu^2＋on transient outward K^＋current （/to） and delayed rectifier K^＋ current （Idr） was studied in acutely isolated rat hippocampal neurons.Ito and Idr were increased when the concentration of Cu^2＋ was lower than 2 × 10^-5 and 10^-5 tool/L, respectively, and increased ratio was decreased with increasing Cu^2＋concentration in the bath solutions. When the concentration continued to increase to 5× 10^-5 and 2 × 10^- 5 mol/L, the currents were hardly changed, while the concentration was more than 10^-4 and 5 × 10^-5 mol/L, the currents were inhibited remarkably. Cu^2＋ （10^-5 mol/L） did not affect the activation and inactivation process of Ito. The activation curve of Idr was shifted toward positive potential, but 10^-5 mol/L Cu^2＋did not affect slope factor. According to these results, it was considered that Cu^2＋at low concentration in the bath solution could promote Ito and Idr while at high concentration could inhibit them, and change of amplitude was different with different membrane voltage. Conclusion was drawn： Cu^2＋may be involved in the pathophysiologic mechanism of diseases with neuropathological components.     

Effects of lanthanum on calcium-activated K+ currents and its kinetics in MC3T3 cells

Using the whole cell patch-clamp technique,we studied the effects of La3+ on calcium-activated K+ currents and its kinetics of activation and inactivation in non-excitable MC3T3 cells.Our results showed that the calcium-activated outward K+ currents were promoted with increasing concentration of Ca2+ in the pipette solution and a voltage- and Ca2+-dependent manner.La3+ in the bath solution inhibited the currents in a concentration-dependent manner and the inhibition EC50 was 8.23 ± 1.45 μmol/L.At the concentration of 50 μmol/L,La3+ significantly changed the Vh of the activation curve and shifted the activation curve to more positive potentials,but shifted the inactivation curve to more negative potentials.It had no effect on the slope factor k of the activation and inactivation curves.Potassium currents inhibition could induce a series of physiological and molecular biological functions,presumably because of its ability to depolarize the plasma membrane and enhance cell excitability,resulting in increasing Ca2+ influx and cytoplast Ca2+ concentration.This process may be one of the molecular mechanisms by which La3+ affects the cell growth and function of MC3T3 cells.     

Thermal Properties of K（Y1-xYbx）（WO4）2（x=0.098,0.196,0.294） Crystal

Thermal properties of pure KY(WO4)2 and K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystals were investigated.The specific heat and thermal diffusivity of crystals were calculated at a range of 50～300 ℃.The calculated result shows that the specific heat and thermal diffusivity of K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystals were slightly affected by the Yb3+ concentration.The thermal expansion coefficient of K(Y0.804Yb0.196)(WO4)2 crystals along x,y and z axes were determined to be 13.51,4.474 and 16.60×10-6 K-1,respectively.These results suggest the K(Y1-xYbx)(WO4)2(x=0.098,0.196,0.294) crystal as a laser crystal of low-middle power.     

安乃近在蒙脱土修饰电极上的电化学行为及测定

制备了蒙脱土修饰电极,并采用循环伏安法研究了安乃近在该电极上的电化学行为。结果表明,该电极过程是一受扩散控制的不可逆过程。用方波溶出伏安法优化了实验参数,测定了浓度与峰电流Ipa的线性关系,发现Ipa与安乃近浓度在2.0×10-6~8.0×10-5mol.L-1之间呈良好的线性关系,其线性回归方程为:Ipa(μA)=-0.07784-15443.54c(μmol.L-1),r=-0.9993,检出限可达1.12×10-6mol.L-1,回收率为94.0%~108.25%。该方法可用于药物中安乃近含量的测定。     

FeS阳极过程电化学研究

采用高温合成法由光谱纯的Fe和S制备FeS,并应用电位扫描和电位阶跃法研究FeS在0.5mol·L-1H2SO4+0.5mol·L-1K2SO4溶液中的阳极电化学行为.考察酸度对FeS阳极极化的影响,测定阳极过程的传递系数β、交换电流I0和Fe2+在FeS中的固相扩散系数DFe以及不同电极电位下阳极电化学反应活化能ΔEa.