基于层状双金属氢氧化物的电化学生物传感器研究进展

层状双金属氢氧化物（LDHs）具有开放的二维平面结构和良好的生物相容性,是非常适合于将生物酶固定在电极表面用于生物传感器的主体材料。本文介绍了酶在LDHs材料上的固定方法,综述了近年来基于这类二维层状材料的各种电化学生物传感器的研究进展,讨论了不同类型生物传感器的设计原理和电子传递机理,并对LDHs在电化学生物传感领域...     

层板剥离水滑石的制备及影响因素

采用阴离子表面活性剂N-月桂酰基谷氨酸(LG)为插层分子，研究了烷烃-LG-水(O/W)微乳液中烷烃量的变化对插层水滑石层间距的影响，同时研究了烷烃分子大小和水滑石层板阳离子不同对水滑石剥离难易程度的影响。实验表明，随着微乳液中烷烃含量的增加，制备得到了由插层到层板剥离的水滑石，并且烷烃的链长越长，水滑石的剥离越容易实现。层板化学组成对剥离难易程度也有影响，难易程度依次是Mg/Al-LDH，Zn/Al-LDH和Ni/Al-LDH。     

Dispersed Nickel Nanoparticles on Flower‐like Layered Nickel‐Cobalt Double Hydroxides for Non‐enzymic Amperometric Sensing of Glucose

The article describes the preparation of supported nickel nanoparticles (NiNPs) by partial reduction of Ni,Co‐layered double hydroxide (NiCo‐LDH). The nanocomposites were characterized by X‐ray diffraction and their morphology and composition were characterized by scanning electron microscopy and transmission electron microscopy. The electrochemical properties of the nanocomposite were explored by cyclic voltammetry and amperometry, which revealed significant electrocatalytic behavior towards the oxidation of glucose. The resulted non‐enzymatic glucose sensor has a linear response to glucose in the 5.0 μM to 14.8 mM concentration range, a low detection limit of 1.6 μM, high sensitivity, and excellent selectivity.     

镁锡水滑石中的超分子作用

通过构建镁锡水滑石(Mg3Sn-LDHs-yH2O)周期性计算模型,基于密度泛函理论,用CASTEP程序模块,进行模型的几何全优化.对各体系的结构参数、Mulliken电荷布居、态密度(DOS)、逐级水合能等进行分析,探究客体CO320-和H2O的分布形态及其与主体层板的超分子作用.结果表明,[Mg6Sn2(OH)16]4+层间插入客体阴离子CO320-和水分子后,主客体间存在着较强的超分子作用力,主要包括静电和氢键作用,且氢键作用在水合过程中起主导作用,总体上层板-水(L-W)型/层板-阴离子(L-A)型氢键强度要强于阴离子-水(A-W)型/水-水(W-W)型氢键.随着层间水分子的增多,层间距先增大后又稍降低.当y=0、1时,客体所在的平面与主体层板平行,且与两层板的距离基本相等;当y=2、3时,客体以偏向某一层板的形式存在.与层间H2O相比,层间阴离子CO230-对体系态密度的影响更显著,层板与CO320-的总体作用力大于与H2O的总体作用力.随着水分子数的增加,Mg3Sn-LDHs-yH2O体系的逐级水合能绝对值逐渐降低,说明Mg3Sn-LDHs的水合程度不会无限增加,而是具有饱和量.     

Synthesis and Characterization of Layered Double Hydroxides Containing Optically Active Transition Metal Ion

The acetate intercalated layered double hydroxides of Zn and Mn, have been synthesized by chimie douce method. The materials were characterized by XRD, TGA, CHN, IR, XPS, SEM-EDX and UV-visible spectroscopy. The photoluminescence properties was also studied. The optical properties of layered hydroxides are active transition metal ion dependent, particularly d¹⁻¹⁰ system plays an important role. Simultaneously the role of host – guest orientation has been considered the basis of photoluminescence. Acetate ion can be exchanged with iodide and sulphate ions. The decomposed product resulted the pure phase Mn doped zinc oxide are also reported.     

类水滑石材料在核废水处理领域的应用

核能已成为我国能源结构的重要组成部分, 但含放射性物质的废水所带来的危害不容忽视. 如何高效解决核废水污染问题迫在眉睫. 类水滑石材料是一类阴离子型粘土化合物, 因其层板组成及层间阴离子种类的可调控性、 较大的比表面积及粒径和形貌的可调控性等特点已在含放射性核素废水的处理中崭露头角. 本文主要阐述了类水滑石材料对废水中放射性核素的吸附行为及其作用机制, 探讨了存在的问题及可能的解决方法, 并对其发展前景进行了展望.     

有机阴离子插层LDH在有机溶剂中的分散性能

采用共沉淀法分别制备了以对苯乙烯磺酸根、10-十一烯酸根、α-丙烯基烷基酚聚氧乙烯醚(10)硫酸根(HS-10)插层的层状双金属氢氧化物(LDH),并用X射线衍射、傅里叶红外光谱、元素分析和能谱分析测试技术表征了插层LDH的结构,用激光粒度仪和透射电子显微镜表征了在不同溶剂中LDH的分散尺寸和形貌。 结果表明,HS-10插层LDH在二甲基亚砜中分散性好,并部分剥离。 比较LDH插层剂和溶剂的Hansen溶度参数δ,表明插层剂疏水端的Hansen溶度参数与溶剂的溶度参数越接近,得到的LDH分散液越稳定;而二者Hansen溶度参数δ的极性分量(δ_p)和氢键分量(δ_h)越接近,LDH层板的剥离就越明显。     

LDHs主体层板与卤素阴离子超分子作用的理论研究

构建了LDHs主客体作用模型, 采用混合密度泛函B3LYP方法, 在6-31G(d)水平上进行结构优化和频率分析, 然后分别用6-31G(d)和6-311++G(d, p)基组计算主客体相互作用能, 从几何参数、电荷布居、前线轨道、能量以及热力学参数等角度探讨LDHs主体层板与卤素阴离子(F?, Cl?)间的超分子作用. 计算结果表明, LDHs主体层板复合卤素阴离子是一个自发过程. LDHs主客体间存在着较强的超分子作用, 主要包括静电和氢键作用, 相互作用能分别为?592.45和?444.01 kJ·mol?1. LDHs主体层板与卤素阴离子的前线轨道发生作用, 电子容易从卤素阴离子的HOMO向层板的LUMO转移, 形成的组装产物Mg6Al(OH)14+?F?比Mg6Al(OH)14+?Cl?稳定.     

含Cu水滑石的结构与光催化性能

采用双滴共沉淀法合成出不同投料摩尔比的碳酸根型水滑石, 并用X射线粉末衍射仪(XRD)和傅里叶变换红外光谱仪(FTIR)等对其进行表征, 研究了其结构和性质. 通过考察水滑石层板中金属阳离子比例和种类的变化对光催化的影响, 发现掺入合适比例的Cu阳离子可使水滑石(LDH)的光催化活性有所提高. 同时用n(Cu):n(Mg):n(Al)=2:1:1的LDH对50 mL初始浓度为10 μmol/L的罗丹明B(RhB)溶液进行光催化实验, 发现在13 ℃(通循环水)、 pH=7.84的条件下, 150 mg LDHs对罗丹明B的降解率达到85.2%, 并且光催化降解量所占比重在50%以上. 此外, 探讨了光催化过程的动力学和光催化降解机理, 发现光催化降解过程符合准二级动力学方程.     

Structural Synthon Approach to Predict the Possible Polytypes of Layered Double Hydroxides

The complete universe of possible polytypes of layered double hydroxides (LDH) is predicted on the basis of symmetry arguments. A single [MX₂] (X = OH) layer, also defined as a structural synthon, belongs to the layer group P$\bar{3}$ 2/m1. These layers can be stacked in such a way as to conserve the unique 3‐axis of the layer in the resultant crystal. The different stacking sequences that facilitate symmetry conservation, yield the different possible polytypes of rhombohedral and hexagonal symmetries. More polytypes can be envisaged by including stacking sequences that systematically destroy the principal symmetry elements of the structural synthon. Thereby, stacking sequences that destroy the 3‐axis, while retaining the 2‐axis, yield possible polytypes of monoclinic symmetry. The nitrate‐containing LDH of zinc and aluminum crystallizes in a faulted structure in which, the planar faults are shown to arise on account of stacking sequences whose local symmetry is monoclinic. This approach to polytype prediction expands on an earlier reported method by Bookin and Drits and is very general with important implications for other classes of layered materials.     

Synthesis of Layered Double Hydroxides with Novel Morphologies

Generally, the hexagonal plate morphology of Mg-Al layered double hydroxides (LDHs) is more favorable, in this article, we report the synthesis of Mg-Al LDHs with unique morphologies, such as ring-like, fiber-like, and sphere-like particles, respectively, using simple traditional coprecipitation method. This synthesis of MgAl-LDHs were carried out with sodium dodecylsulfate together with Na₂-edta, Na₂-edta, and sodium tartrate, respectively, as assistants to favor the precipitation process. The obtained products were characterized by transmission electron microscopy, x-ray diffraction, and FTIR spectroscopy. The studied results confirm that morphology of LDHs might be controlled by a soft-template effect of assistants in traditional coprecipitation method.     

溶胶-凝胶法制备的介体型电流式葡萄糖生物传感器

以戊二醛为交联剂，将葡萄糖氧化酶（GOD）和介体甲苯胺蓝（TBO）通过共价键作用固定于铂电极表面上的溶胶－凝胶薄膜载体上，制成了葡萄糖生物传感器；该功能化薄膜由γ－氨丙基甲基二甲氧基硅烷和四甲氧基硅在稀盐酸催化作用下通过水解－缩聚反应制得；红外光谱证实，GOD和TBO在载体上的固定化是通过交联剂分子上的醛基与GOD、TBO和载体上的氨基反应实现的，共价交联方式有效地避免了酶和介体从载体上的脱落；葡萄糖生物传感器的循环伏安特性表明，TBO能在GOD反应活性中心与铂电极表面之间进行有效的电子传递；葡萄糖生物传感器对底物葡萄糖响应的线性范围是1－8mmol/L，检出限是0．05mmol/L，寿命超过1个月。     

谷氨酸柱撑水滑石超分子结构层柱材料的插层组装

用返混沉淀方法实现了谷氨酸柱撑水滑石超分子结构层柱材料的插层组装,得到结晶度高、晶相单一且谷氨酸在层间有序排列的超分子结构层柱材料.用X射线衍射、原子光谱、元素分析、红外光谱及热重-差热分析表征了超分子结构层柱材料的结构,给出其结构模型.     

Glucose Biosensors Based on Electrodes Modified with Ferrocene Derivatives Intercalated into Mg/Al Layered Double Hydroxides

Two amperometric biosensors based on glassy carbon electrodes (GC) modified with Mg/Al layered double hydroxides (LDHs) containing ferrocene‐carboxylate (Fc? CO₂H) or ferrocene‐sulfonate (Fc? SO₃H), as interlayer anions, and glucose oxidase (GOx) are presented. Amperometric detection of glucose involves the electrochemical oxidation of H₂O₂ mediated by the ferrocene derivative. Optimization of the biosensors construction and of the operative conditions was investigated and is discussed herein. The performances of the two biosensors were evaluated by chronoamperometry, working at low anodic potentials (+0.400 V for Fc? CO₂H and +0.500 V for Fc? SO₃H vs. SCE). The linearity extended up to 1.5 mM and 10.0 mM in batch and in flow conditions, respectively, for both biosensors, whereas the sensitivity was higher for the one based on Fc? CO₂H (4.8±0.3 versus 2.0±0.3 μA mM^?1cm^?2 in batch mode, and 63.9±0.4 versus 25.8±0.4 μA mM^?1cm^?2 in flow mode). The biosensors display rapid response time (less than 20 s), good reproducibility, as well as good operational stability. Glucose can be accurately determined in the presence of the most common interferences that coexist in blood serum if an oxidative membrane containing nanoparticles of MnO₂ is applied on the biosensors' surface.     

新方法合成规则六角片状层状双金属氢氧化物

探索了一种合成规则的层状双金属氢氧化物(简称LDHs)六角纳米片的新方法,该方法基于传统的共沉淀法,并借鉴了尿素法的优点。 系统研究了沉淀剂、反应溶剂、反应时间和沉淀剂滴加速率对最终得到的粒子结晶度和形貌的影响。 研究结果表明,采用NH4OH为沉淀剂,以乙醇/水混合溶液为溶剂得到的LDHs纳米粒子结晶度高,晶型发育完美,呈现规则的六角片状,单分散性良好,粒径介于100~250 nm之间。 乙醇的加入一方面减慢了NH4OH电离出OH-的速率,降低了溶液过饱和度;另一方面,乙醇分子包裹在LDHs粒子周围,其表面的羟基起到了空间位阻作用,阻止粒子之间的团聚。 最佳反应时间既要保证LDHs晶粒的充分发育和成长,又要防止粒子之间的团聚。反应时间较短(1 h)时,晶粒发育不完全,粒子呈现不规则的六角片形;反应时间较长(4 h)时,LDHs粒子出现了六角片状重叠现象;只有当反应时间适中(3 h),LDHs粒子因晶胞生长充分而粒径分布均匀,并呈现规则六角片状。 沉淀剂滴加速率的不同会改变体系的过饱和度,从而影响LDHs粒子的形貌,滴加速率较低(0.025 mL/s)时,得到的粒子形貌规则、单分散性良好,且随着滴加速率的降低,粒子粒径逐渐增大。     

Amperometric Glucose Determination by Means of Glucose Oxidase Immobilized on a Cellulose Acetate Film: Dependence on the Immobilization Procedures

Glucose microelectrodes were prepared by immobilizing glucose oxidase onto a cellulose acetate film coating a platinum wire. Hexamethylenediamine (HMDA) and Glutaraldehyde (GA) were employed as spacer and coupling agent, respectively. Sensitivities and linear response ranges were studied as a function of the relative amounts of HMDA and GA. The best sensitivity was found when HMDA and GA were 5% and 2.5% in aqueous solutions, respectively. Taking as a reference the functioning of this biosensor, the roles of HMDA and GA percentages appear to be opposed when the extension of the linear response range is considered. Indeed, an increase of one unit in HMDA percentage (from 5 to 6 %) induces an increase in the extension of the linear response range equal to that obtained with a decrease of one unit of GA percentage (from 2.5 to 1.5%).     

Glucose Biosensor Using Glucose Oxidase Immobilized in Polyaniline

A biosensor for glucose utilizing kinetics of glucose oxidase (EC 1.1.3.4.) was developed. The enzyme was immobilized on polyaniline by covalent bonding, using glutaraldehyde as a bifunctional agent. The system showed a linear response up to 2.2 mM of glucose with a response time of 2.5–4.0 min. In addition, the immobilized enzyme had a higher activity between pH 6.5 and 7.5. The system retained 50% of its activity after 30 d of daily use. The optical absorption spectra of the polyaniline/glucose oxidase electrode after glucose had been added to the buffer solution showed that the absorption band around 800 nm had changed considerably when glucose was allowed to react with the electrode. This optical variation makes polyaniline a very promising polymer for use as a support in optical sensor for clinical application.     

层状双金属氢氧化物的制备及其应用研究

层状双金属氢氧化物是一类新型的无机功能材料,具有特殊的层状结构和优异的物理化学特性,已成为当前研究的热点。介绍了层状双金属氢氧化物的结构与性质,特别分析了层状双金属氢氧化物的制备方法及其在催化材料、吸附材料、生物医药材料、光电功能材料等方面的应用研究进展,并对其在未来的发展方向进行了展望。     

Prussian Blue Modified Amperometric Hg2+ Ion Biosensor Based on Glucose Oxidase Inhibition

In this research a Hg²⁺ ion biosensor was developed by combining Prussian blue (PB) with glucose oxidase (GOx) – an enzyme that can be inhibited by Hg²⁺ ions. An application of PB in the design of Hg²⁺ ion biosensor enabled detecting changes in hydrogen peroxide reduction current at low operational potential of 0.2 vs Ag|AgCl,KCl_sat. The described Hg²⁺ ion biosensor exhibited wide linear range from 27 μM to 247 μM of Hg²⁺ and higher maximal detectable concentration of Hg²⁺ than other GOx inhibition-based biosensors, making it convenient for the analysis of samples with high concentration of Hg²⁺ ions.     

以四硫富瓦烯为电子媒介体的电流式葡萄糖传感器

用四硫富瓦烯作为酶与电极之间的电子传递体，通过Ｎａｆｉｏｎ水溶液把葡萄糖氧化酶固定在Ｎａｆｉｏｎ－ＴＴＦ修饰玻碳电极上，最后在电极上装饰一层Ｎａｆｉｏｎ膜，制备成葡萄糖传感器。Ｎａｆｉｏｎ膜不仅能防止四硫富瓦烯流失，而且能把抗坏血酸、尿酸等电活性物质阻挡在电极外，防止其干扰，同时具有防污性能。通过实验表明ＴＴＦ＾＋１、ＴＴＴ＾＋２都能够氧化葡萄糖氧化酶中的辅酶。该传感器的线性范围为３．０×１０＾－