Synthesis and Characterization of Layered Double Hydroxides and Their Potential as Nonviral Gene Delivery Vehicles

Layered double hydroxides (LDHs) exhibit characteristic anion-exchange chemistry making them ideal carriers of negatively charged molecules like deoxyribonucleic acid (DNA). In this study, hydrotalcite (Mg−Al) and hydrotalcite-like compounds (Mg−Fe, Zn−Al, and Zn−Fe), also known as LDHs, were evaluated for their potential application as a carrier of DNA. LDHs were prepared by coprecipitation at low supersaturation and characterized by Powder X-ray diffraction (XRD), infrared (IR), Raman, and inductively coupled plasma—optical emission spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). XRD patterns showed strong and sharp diffraction peaks for the (003) and (006) planes indicating well-ordered crystalline materials. TEM images yielded irregular circular to hexagonal-shaped particles of 50–250 nm in size. Varying degrees of DNA binding was observed for all the compounds, and nuclease digestion studies revealed that the LDHs afford some degree of protection to the bound DNA. Minimal toxicity was observed in human embryonic kidney (HEK293), cervical cancer (HeLa) and hepatocellular carcinoma (HepG2) cell lines with most showing a cell viability in excess of 80 %. All LDH complexes promoted significant levels of luciferase gene expression, with the DNA:Mg−Al LDHs proving to be the most efficient in all cell lines.     

Layered Double Hydroxides as Catalytic Materials: Recent Development

This report surveys the recent development of layered double hydroxides (LDHs) as catalytic materials, which have attracted considerable attention in the past decade. A major challenge in the rapidly growing field is to improve the functionalities of these materials. Therefore, this article is mainly focused on the lately reported design and synthesis strategies for LDH materials and their catalytic applications as actual catalysts, catalyst precursors and catalyst supports.     

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.     

Single-atom Catalysts Based on Layered Double Hydroxides

Single-atom catalysts(SACs) have attracted much attention for their superior catalytic performance in various fields. It has been widely accepted that the selection of appropriate substrates is crucial to the fabrication and application of SACs. Layered double hydroxides(LDHs) have been developed as one of the promising substrates for single-atoms due to their unique adjustable supramolecular structures. In this review, we comprehensively sort out the research of SACs based on LDHs. By analyzing the characteristics of LDHs and the single-atoms, respectively, the preparation strategies of SACs by using LDHs are summarized. Their applications as efficient catalysts in electrocatalysis, photocatalysis and thermal catalysis are then discussed. Finally, we summarize the opportunities and challenges for the rational design and application expansion of SACs based on LDHs in the future.     

铜镁铝三元水滑石的姜-泰勒效应

采用密度泛函理论(DFT),用CASTEP程序模块,对类水滑石(CuxMg3-xAl-LDHs,x=0-3)周期性模型进行几何全优化,通过分析各体系的结构参数、电子排布、氢键、Mulliken电荷布居、结合能,总结出体系中的姜-泰勒效应和结构稳定性规律.结果表明,姜-泰勒效应不仅存在于d轨道未排满的Cu2+中,在p轨道未排满的Mg2+中也可能存在,且未饱和的d、p轨道共同影响着金属离子姜-泰勒畸变的大小.在CuxMg3-xAl-LDHs(x=0-3)中,铝八面体和镁八面体分别以稳定的拉长的八面体形式存在.而随着Cu2+的增加,铜八面体逐渐从压扁的八面体向稳定的拉长的八面体形式转变,体系获得了逐渐增多的姜-泰勒稳定化能.总体上,随着Cu2+的增加,体系中姜-泰勒效应导致的畸变使主客体间的氢键和静电作用力均有减弱趋势,且体系的结合能绝对值逐渐减小,故体系稳定性下降.这有助于从理论上进一步认识含铜水滑石的姜-泰勒效应.     

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。     

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.     

纯相钙铝层状双氢氧化物对磷的吸附特性

采用乙醇辅助液相共沉淀法制备了纯相Ca-Al-LDH层状双金属氢氧化物,考察了Ca-Al-LDH的投加量、吸附时间、pH值、无机电解质(Na₂CO₃ ,KCl ,Na₂SO₄,KNO₃)和温度等因素对磷吸附的影响,结果表明,纯相Ca-Al-LDH对磷酸根离子具有很好的吸附性能,最大饱和吸附量可达160.78 mg/g,当pH值为5.1、温度为45 ℃、吸附时间为600 min、LDH投加量为0.6 g/L、磷初始浓度为80 mg/L时,磷的去除率高达95.88%;无机阴离子会抑制磷在吸附剂上的吸附,当Cl^-浓度从2.5 g/L升高到25 g/L时,Ca-Al-LDH对磷酸盐的最大饱和吸附量从69.96 mg/g降至53.18 mg/g,降低了23.99%;当SO₄^2-浓度从2.5 g/L升高到25 g/L时,Ca-Al-LDH对磷酸盐的最大饱和吸附量降低了24.79%,其它无机阴离子对磷在吸附剂上的吸附也有一定的影响。 Ca-Al-LDH对水中磷的吸附符合二级动力学方程和Langmuir等温模型。 采用扫描电子显微镜、傅里叶变换红外光谱仪和X射线衍射仪等技术手段对制备的纯相Ca-Al-LDH及其吸附磷酸根后的产物进行表征,揭示了Ca-Al-LDH对磷酸根的吸附可能是静电吸引、化学吸附和阴离子插层等过程协同作用的吸附机理。     

镍铁水滑石电催化氧析出研究进展

氧析出反应(Oxygen evolution reaction, OER)是电解水制氢、二氧化碳还原、二次金属-空气电池等能源储存和转化技术中的关键半反应。镍铁水滑石类材料(NiFe layered double hydroxide, NiFe-LDH)具有独特的层状结构、优异的催化性能和成本低廉等优点,是一类极具潜力的OER催化材料。但电导率低、活性位点暴露不充分等缺点也限制了其催化性能的进一步提高。本文综述了包括引入缺陷、片层剥离、元素掺杂、表面修饰和原位生长等针对NiFe-LDH的改性方法,这些方法能有效提升反应活性位点数量、增强导电性并促进反应动力学过程。最后,讨论了对NiFe-LDH改性中存在的问题以及对后续研究的展望。     

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。     

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.     

层状水滑石对吡啶二甲酸异构阴离子的选择性插层行为

本文采用焙烧复原法研究了镁铝水滑石与吡啶二甲酸异构阴离子单体及其混合体的插层反应，实验发现镁铝水滑石对吡啶二甲酸异构阴离子存在着明显的选择性，有机酸异构体优先进入层间的顺序是：2,3-吡啶二甲酸>2,5-吡啶二甲酸>2,4-吡啶二甲酸>3,5-吡啶二甲酸>3,4-吡啶二甲酸>2,6-吡啶二甲酸。利用XRD、IR和TG测试技术对样品进行了表征，同时采用Gaussian-98软件包中ab initio 分子轨道法（HF/6-31G）计算了吡啶二甲酸异构阴离子的分子结构，理论结合实验探讨了阴离子在水滑石层间可能的空间构型，分析了其结构与插层行为的关系。研究表明镁铝水滑石层状材料插层过程中具有分子识别能力，可用于分离有机异构阴离子。     

钴钒水滑石纳米片用于电催化尿素氧化

电解水是一种常用的制氢方法,但高能耗的阳极析氧反应(OER)阻碍了其应用。尿素氧化反应(UOR)具有较低的热力学电势,是最有前景的OER替代反应之一。过渡金属基水滑石具有独特的层状结构和层间阴离子可交换等优点,被认为是性能优异的UOR催化剂,然而目前大多数研究主要聚焦于后过渡金属元素。该研究通过一步法制备了具有前/后过渡金属的CoV-LDHs纳米片。与相同方法制备的Co(OH)₂相比,CoV-LDHs纳米片具有以下优点：1)纳米片结构有利于暴露更多的活性位点。2) V的引入增强了CoV-LDHs的亲水性,提高了其本征电催化动力学。3) Co (3d⁷4s²)和V (3d³4s²)之间的d-电子补偿效应有利于促进尿素的吸附。因此,CoV-LDHs仅需要1.52 V (vs. RHE) 就可以达到10 mA∙cm⁻²的电流密度,比Co(OH)₂低了70 mV,同时CoV-LDHs较低的塔菲尔斜率表明了其较快的反应动力学。此外,CoV-LDHs在连续反应10 h后,驱动电位几乎没有增加,表明其具有良好的稳定性。该研究结果不仅证明了前/后过渡金属之间的d-电子补偿效应可以提高UOR催化性能,还为设计高效的UOR催化剂提供了可行的途径。     

Sorption of Anionic Surfactants on Layered Double Hydroxides

In the present study we investigated the adsorption of sodium dodecyl- and octylsulfate, and sodium dodecyl- and octylbenzenesulfonate, on a layered double hydroxide (LDH) under controlled conditions. The results were compared to those obtained for the adsorption of surfactants on mineral oxides and on LDHs, showing that the behavior of surfactant adsorption on LDHs can be approximately explained by the models proposed for surfactant adsorption on mineral oxides. The electrokinetic potential of the surfactant-adsorbed LDH particles in suspension was measured in order to monitor the variation of this potential as a function of the adsorption. The results showed a characteristic behavior of the surfactant-adsorbed LDH that can be correlated to a rearrangement of the adsorbed layer at concentrations above the CMC. Surfactant sorption was also studied, using SDS and the calcined LDH, showing the regeneration of the calcined material by intercalating the DS anions. Two processes can occur during the removal of surfactants from aqueous solutions by LDHs, depending on the starting material: (i) adsorption itself, when a noncalcined LDH intercalated with a nonexchangeable anion, such as carbonate, is used; and (ii) adsorption and intercalation, which occurs when a calcined LDH, like Mg-Al-CO(3), is used. The potential application of this material for surfactant removal is one of the reasons for the need for a better understanding of the mechanisms involved. As we demonstrate here, LDHs are very efficient in removing surfactants from aqueous solutions. Copyright 2000 Academic Press.     

Layered Double Hydroxides as Rising-Star Adsorbents for Water Purification: A Brief Discussion

Within the frame of this article, briefly but comprehensively, we present the existing knowledge, perspectives, and challenges for the utilization of Layered Double Hydroxides (LDHs) as adsorbents against a plethora of pollutants in aquatic matrixes. The use of LDHs as adsorbents was established by considering their significant physicochemical features, including their textural, structural, morphological, and chemical composition, as well as their method of synthesis, followed by their advantages and disadvantages as remediation media. The utilization of LDHs towards the adsorptive removal of dyes, metals, oxyanions, and emerging pollutants is critically reviewed, while all the reported kinds of interactions that gather the removal are collectively presented. Finally, future perspectives on the topic are discussed. It is expected that this discussion will encourage researchers in the area to seek new ideas for the design, development, and applications of novel LDHs-based nanomaterials as selective adsorbents, and hence to further explore the potential of their utilization also for analytic approaches to detect and monitor various pollutants.     

层状双金属氢氧化物的剥离方法及其应用

层状双金属氢氧化物(LDHs)是由带结构正电荷的片层和层间阴离子有序组装而成的层状无机化合物, 近期其剥离研究受到关注. 剥离后的LDHs纳米片可被看做“无机高分子”, 具有纳米尺度的开放结构, 既可作为理论研究模型, 又可作为新型基元组装功能复合纳米结构或材料, 具有显著的应用潜力. 本文对LDHs的剥离方法、剥离产物的表征方法及其应用研究现状进行了综述, 并对今后的研究方向进行了展望.     

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...