Coassembly of exfoliated Ni–In LDHs nanosheets with DNA and infrared emissivity study

The biomolecule–inorganic hybrid materials are potential candidates for low infrared emissivity materials due to the combined functionalities of the biomolecules and the inorganic components. In this study, we describe a facile approach to fabricate DNA/layered double hydroxides (LDHs) nanohybrid by coassembly of exfoliated Ni–In LDHs nanosheets with DNA. In the assembly progress, exfoliated LDHs nanosheets and DNA with different initial DNA/LDHs mass ratio were mixed together, and the DNA intercalated LDHs nanohybrid was obtained only when the input DNA/LDHs mass ratio is ≤0.3 mg/mg. The structure and morphology of as-fabricated hybrid materials were characterized by X-ray diffraction (XRD), UV–Vis absorption spectra, Fourier transform infrared (FT-IR) spectra, thermogravimetry (TG), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicate that the reassembled product has layered structures incorporated with DNA biomolecule. The nanohybrid with expanding LDHs structure of d ₀₀₃ = 2.6 nm confirms the intercalation of DNA molecules into the LDHs interlayer. The helix chain oriented parallel to the basal plane of host layer forming ordered sandwich structure. The infrared emissivity value of the DNA/LDHs nanohybrid was then investigated. It was found that the infrared emissivity values were significantly reduced by coassembly of exfoliated LDHs nanosheets with DNA, which may be attributed to the synergistic effect and interfacial interaction between the DNA biomolecule and inorganic LDHs layers reinforced by the construction of ordered sandwich structure.     

多元LDHs/EVA纳米复合材料的制备及性能研究

以氯化镁(MgCl2.6H2O)、氯化铝(AlCl3.6H2O)、氯化锌(ZnCl2)、氯化铁(FeCl3.6H2O)和碳酸钠(Na2CO3)为原料,采用共沉淀法制备了二元MgAl-CO3LDHs、三元MgAlZn-CO3LDHs和四元MgAlZnFe-CO3LDHs无机纳米粉体,用聚乙二醇(PEG)对3种LDHs进行原位改性,采用熔融共混法制备了EVA/LDHs纳米复合材料,并对LDHs和纳米复合材料进行了透视电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、热重分析(TG)、力学性能、燃烧性能等测试。结果表明加入LDHs纳米粉体后,虽然对复合材料的力学性能有一定的影响,但对复合材料的阻燃效果有着明显的改善;而且随着LDHs元数的增加,复合材料的阻燃效果得到明显提高;当四元MgAlZnFe-CO3LDHs的添加量为15%时,复合材料即可自熄。     

The construction and characterization of layered double hydroxides as delivery vehicles for podophyllotoxins

The aim of this study was to construct PPT-LDH nanohybrids and compare their tumor inhibition effects with that of free PPT. Anticancer drug podophyllotoxin (PPT) was encapsulated in the galleries of Mg-Al layered double hydroxides (LDHs) by a two-step approach. Tyrosine (Tyr) was first incorporated into the interlayer space by co-precipitation with LDH, prop-opening the layers of Mg-Al/LDH and creating an interlayer environment inviting drug molecules. PPT was subsequently intercalated into the resulting material lamella by an ion exchange process. The intermediate and final products, which can be termed drug-inorganic nanocomposites, have been characterized by powder X-ray diffraction (XRD), UV-VIS spectrophotometer, transmission electron microscopy (TEM) and in cell culture. Our results demonstrate that the interlayer spacing distance of the PPT-LDH nanohybrids (34% w/w of drug/material) is 18.2 A. LDHs do not harm normal cells (293T) based on toxicity tests. Ex-vivo anticancer experiments reveal that the PPT-LDH nanohybrids have higher tumor suppression effects than intercalated PPT. We conclude that the higher tumor inhibition effects of PPT-LDH hybrids result from the inorganic drug delivery vehicle, LDHs.     

Cellular toxicity of inorganic hydroxide nanoparticles

Layered double hydroxides (LDHs), anionic clays, have attracted increasing interest as nanovehicles for delivering genes, drugs, and bio-active molecules into cells. However, no attempts have been made to evaluate the potential undesirable effects of LDH nanoparticles. The cytotoxicity of LDHs with different chemical compositions (ZnAl- and MgAl-LDH) was systematically evaluated in various cell types, such as human normal cells, carcinoma cells, and red blood cells, by measuring cell viability, cell proliferation, membrane damage, and hemolytic effect. No significant cytotoxic effects could be seen in both cases, but ZnAl-LDH was determined to be slightly more toxic than MgAl-LDH in terms of membrane damage and hemolysis induction. It is, therefore, expected that LDHs could be promising candidates for novel inorganic drug delivery carriers.     

Cobalt-based layered double hydroxides as oxygen evolving electrocatalysts in neutral eletrolyte

Co–M (M= Co, Ni, Fe, Mn) layered double hydroxides (LDHs) were successfully fabricated by a hexamethylenetetramine (HMT) pyrolysis method. Composite electrodes were made using a self-assembly fashion at inorganic/organic surface binder-free and were used to catalyze oxygen evolution reaction. Water oxidation can take place in neutral electrolyte operating with modest overpotential. The doping of other transitional metal cations affords mix valences and thus more intimate electronic interactions for reversible chemisorption of dioxygen molecules. The application of employing LDH materials in water oxidation process bodes well to facilitate future hydrogen utilization.     

Non-classical crystal growth of inorganic and organic materials

Abstract

Investigation of the early stage morphologies of some organic and inorganic systems has established that their crystal growth does not always follow the classical route established 120 years ago. The classical theory assumes that a highly symmetric crystal develops from the nucleation and repeated attachment of atoms, molecules or ions to a single nucleus. In instances where surfactants or polymers are introduced, the crystal growth is often found, however, to follow a ‘reversed crystal growth’ route. This non-classical growth route is initiated by organic molecules adsorbed onto the surface of the nanocrystallites in the early stages of growth. In the reversed route, these nanocrystallites form large disordered aggregates followed by surface crystallisation to create a thin, highly crystalline, dense shell and, finally, an extension of the crystallisation from the surface to the core. Although systems following a non-classical crystal growth route have been known for many years, their formation mechanisms have a much shorter history. Discovery of the reversed crystal growth route in several hollow, core–shell and twin crystal type morphologies not only assists in the designing of materials for industrial applications but also helps to understand the interactions between organic and inorganic components. This review highlights recent research relating to organic and inorganic systems whose growth follows the reversed crystal growth route.     

应用DNA模版自组装CdS纳米线

近年来,由于具有双螺旋补偿结构,DNA分子作为智能模版被广泛应用于设计棒状或管状类的纳米结构.本文报道了应用DNA双螺旋模版将CdS纳米粒子自组装为CdS纳米线.制备的CdS纳米线由几根纳米线紧密缠绕在一起,也呈螺旋形结构,该结构在无机材料中是很少见的.该结构形成的主要原因归功于CdS纳米粒子和DNA分子间的强烈静电互作用,由于含自由基的CdS纳米粒子带负电荷,而氨基的DNA核酸根带正电荷.研究结果表明应用DNA模版制备纳米线是一种简便、高效的技术和方法.同时,DNA模版法也为从底上制备纳米级的材料和物体提供了广阔的空间.     

Nanoscale DNA tetrahedra improve biomolecular recognition on patterned surfaces

The bottom-up approach of DNA nano-biotechnology can create biomaterials with defined properties relevant for a wide range of applications. This report describes nanoscale DNA tetrahedra that are beneficial to the field of biosensing and the targeted immobilization of biochemical receptors on substrate surfaces. The DNA nanostructures act as immobilization agents that are able to present individual molecules at a defined nanoscale distance to the solvent thereby improving biomolecular recognition of analytes. The tetrahedral display devices are self-assembled from four oligonucleotides. Three of the four tetrahedron vertices are equipped with disulfide groups to enable oriented binding to gold surfaces. The fourth vertex at the top of the bound tetrahedron presents the biomolecular receptor to the solvent. In assays testing the molecular accessibility via DNA hybridization and protein capturing, tetrahedron-tethered receptors outperformed conventional immobilization approaches with regard to specificity and amount of captured polypeptide by a factor of up to seven. The bottom-up strategy of creating DNA tetrahedrons is also compatible with the top-down route of nanopatterning of inorganic substrates, as demonstrated by the specific coating of micro- to nanoscale gold squares amid surrounding blank or poly(ethylene glycol)-passivated glass surfaces. DNA tetrahedra can create biofunctionalized surfaces of rationally designed properties that are of relevance in analytical chemistry, cell biology, and single-molecule biophysics.     

Efficient Gene Therapy of Pancreatic Cancer via a Peptide Nucleic Acid (PNA)‐Loaded Layered Double Hydroxides (LDH) Nanoplatform

Pancreatic ductal adenocarcinoma (PDAC) is one of the deadliest malignant tumors with extremely poor prognosis due to the later stage diagnosis when surgical resection is no longer applicable. Alternatively, the traditional gene therapy which drives pancreatic cancer cells into an inactive state and inhibiting the proliferation and metastasis, presents potentials to safely inhibit pancreatic cancer progression, but unfortunately has received limited success to date. Here, an efficient gene therapy of pancreatic cancer is shown via a peptide nucleic acid (PNA)‐loaded layered double hydroxides (LDHs) nanoplatform. Compared with the traditional DNA‐ or RNA‐based gene therapies, the gene therapy using PNA features great advantages in recognizing and hybridizing with the target mutant sequences to form PNA–DNA hybrids with significantly enhanced stability due to the absence of electrostatic repulsion, and the constrained flexibility of the polyamide backbone. Moreover, ultrasmall LDHs are engineered to load PNA and the obtained PNA‐loaded LDH platform (LDHs/PNA) is capable of efficiently and selectively targeting the intranuclear mutant sequences thanks to the proton sponge effect. Treatments with LDHs/PNA demonstrate markedly inhibited growth of pancreatic cancer xenografts via a cancer cell proliferation suppression mechanism. The results demonstrate the great potentials of LDHs/PNA as a highly promising gene therapy agent for PDAC.     

Anticancer drug-inorganic nanohybrid and its cellular interaction

An anticancer drug, methotrexate (MTX), has been successfully hybridized with layered double hydroxide (LDH) through co-precipitation route to produce MTX-LDH nanohybrids (MTX-LDH). According to the X-ray diffraction and FT-IR spectroscopy, it was confirmed that MTX molecules are stabilized in the interlayer space of LDHs by electrostatic interaction, maintaining their functional groups and structural integrity. According to the drug release study, the total amount of released MTX from the LDH lattice was determined to be larger under a simulated intracellular lysosomal condition (pH = 4.5) than simulated body fluid one (pH = 7.4). It is, therefore, expected that the MTX molecules in MTX-LDH can be effectively released in lysosomes, since the MTX release could be accelerated via ion-exchange reaction and dissolution of LDH in an acidic lysosomal condition. We also examined the anticancer efficacy of MTX-LDH in human breast adenocarcinoma MCF-7 cells. The cellular uptake of MTX was considerably higher in MTX-LDH-treated cells than in free MTX-treated cells, giving a lower IC50 value for the former than the latter. All the results demonstrated that the MTX-LDH nanohybrid allows the efficient drug delivery in cells, and thus enhances drug efficacy.     

水滑石/钙锌复合热稳定剂对PVC的热稳定作用

本文制备了水滑石/钙锌复合热稳定剂,采用XRD、FT-IR及静态热老化、脱HCl等实验及分析手段,探讨了水滑石对PVC的热稳定机理,研究了水滑石/钙锌复合热稳定剂对PVC的热稳定性能。实验表明,水滑石对PVC热解释放的HCl进行吸附分两个过程,首先层板羟基与HCl反应,然后层间CO32-与Cl-进行交换,可明显改善PVC的热稳定性,使PVC脱HCl的诱导时间提高了1.4倍。     

阻燃抑烟环氧树脂的制备与性能

通过离子交换法将七钼酸根离子插入到含硝酸根的MgAl层状双氢氧化物(NO_3-MgAl LDHs)的层间,得到含钼酸根的MgAl层状双氢氧化物(Mo-MgAl LDHs),并将制得的LDHs加入到环氧树脂(ER)中制成复合材料ER/LDHs。通过热重分析、锥形量热、极限氧指数和烟密度等测试对复合材料的性能进行分析,结果表明,与纯ER相比,ER/LDHs复合材料的最大热释放速率(PHRR)、总的热释放量(THR)和烟密度都降低,氧指数提高,而且ER/Mo-MgAl LDHs复合材料的阻燃抑烟性能要比ER/NO_3-MgAl LDHs的更好;同时,添加少量LDHs可以提高复合材料的力学性能。     

类水滑石的制备与改性及其在聚丙烯阻燃中的应用

采用共沉淀法制备了镁铝类水滑石（LDHs）前驱体,加入少量聚磷酸铵（APP）制得APP-LDHs,探讨了不同质量分数APP对LDHs晶体生长的影响;当APP在LDHs前驱浆液中添加量为0.8wt%时,将APP-LDHs与季戊四醇（PER）、硅烷偶联剂KH-550进行球磨混合,制备插层包覆改性的LDHs;通过XRD、FTIR、SEM和TG等对改性前后的LDHs进行了表征;采用极限氧指数（LOI）、垂直燃烧测试（UL-94）、缺口冲击和弯曲实验等方法研究了LDHs改性前后LDHs/聚丙烯（PP）复合材料的阻燃性能及力学性能的差异。研究结果表明：APP的加入,未显著影响LDHs的层板生长,但其层板堆叠受到抑制;SEM观察表明,所制备的LDHs为片状,且经插层包覆改性后的LDHs粉体形貌较为规整,颗粒粒径为100~250 nm;改性LDHs在较高温度下的热稳定性显著优于未改性的LDHs;当PP中加入质量分数为20%的LDHs及改性LDHs时,可抑制PP燃烧时产生的熔滴,并促使LDHs/PP复合材料表面形成炭层;改性LDHs/PP复合材料具有更好的阻燃性能,且其冲击强度、弯曲强度等力学性能下降不明显。     

Nanostructured modified layered double hydroxides (LDHs)-based catalysts: A review on synthesis,characterization, and applications in water remediation by advanced oxidation processes

Layered double hydroxides (LDHs) are emerging catalyst materials with inner layer water molecules and higher anion exchange capacity. They have been extensively used as catalyst materials owing to their high specific surface area, environmental friendliness, lower cost, and non-toxicity. However, the lower surface area and leaching of metal ions from LDHs composites reduce the process efficiency of the catalyst. Modifying the LDHs materials with other materials can improve the surface properties of the composite and enhance the catalytic performance. Herein, this review aims to summarize the recent progress of nanostructured modified LDHs materials, their classification, synthesis, and a detailed discussion on their characterization techniques. Further, this study also discusses the application of nanostructured modified LDHs materials as catalysts in advanced oxidation process (AOPs) for various organic pollutants removal.     

Shaping Colloidal Rutile into Thermally Stable and Porous Mesoscopic Titania Balls

High crystallinity and controlled porosity are advantageous for many applications such as energy conversion and power generation. Despite many efforts in the last decades, the direct synthesis of organic–inorganic composite materials with crystalline transition metal oxides is still a major challenge. In general, molecules serve as inorganic precursors and heat treatment is required to convert as‐synthesized amorphous composites to stable crystalline materials. Herein, an alternative approach to the direct synthesis of crystalline polymer–metal oxide composites by using a spherical polyelectrolyte brush as the template system is presented. Pre‐synthesized electrostatically stabilized rutile nanocrystals that carry a positive surface charge are used as inorganic precursors. In this approach, the strong Coulomb interactions between anionic polyelectrolyte brush chains and cationic crystalline rutile colloids, whose surfaces are not capped and therefore reactive, are the key factors for the organic–inorganic crystalline composite formation. Stepwise calcination first under argon and followed with a second calcination in air lead to the complete removal of the polymer template without collapse and porous rutile balls are obtained. The results suggest that any colloids that carry a surface charge might serve as inorganic precursors when charged templates are used. It is expected that this hierarchical route for structuring oxides at the mesoscale is generally applicable.     

Preparation and intercalation chemistry of magnesium-iron(III) layered double hydroxides containing exchangeable interlayer chloride and nitrate ions

Layered double hydroxides (LDHs) with Mg²⁺ and Fe³⁺ cations in the brucite-like layers and having chloride or nitrate ions in the interlayer region have been prepared and characterized by powder X-ray diffraction (PXRD), elemental analysis and thermal analysis. Thermal decomposition of the LDH-nitrate occurs in two steps, with loss of water followed by simultaneous dehydroxylation of the layers and loss of NO_x/O₂ arising from the nitrate anions. Thermal decomposition of the LDH-chloride involves an additional step, with chloride ions becoming grafted to the layers, prior to loss of HCl. The interlayer anions may be readily replaced by sulfate, thiosulfate, tartrate and vinylbenzenesulfonate ions suggesting that these materials may be useful precursors to Mg-Fe(III) LDHs intercalated with a variety of inorganic and organic anions.     

Microdisplacement printing

We describe a new patterning technique that employs microcontact printing to replace preformed labile self-assembled monolayers (SAMs) selectively; we call this "microdisplacement printing". We demonstrate that this technique results in ordered molecular regions of both the patterning ("displacing") molecule as well as the remnant labile film, here 1-adamantanethiolate. The existence of the 1-adamantanethiolate SAM before patterning hinders lateral surface diffusion of the patterning molecules, and therefore permits the use of molecules that are otherwise too mobile to pattern by other methods.     

Novel bioinorganic nanostructures based on mesolamellar intercalation or single-molecule wrapping of DNA using organoclay building blocks

Nanosheets or nanoclusters of aminopropyl-functionalized magnesium phyllosilicate (AMP) were prepared in water by exfoliation and used as structural building blocks for the preparation of DNA-based hybrid nanostructures in the form of ordered mesolamellar nanocomposites or highly elongated nanowires, respectively. The former consisted of alternating layers of single sheets of AMP interspaced with intercalated monolayers of intact double-stranded DNA molecules of relatively short length ( approximately 700 base pairs) that were accessible to small molecules such as ethidium bromide. In contrast, the nanowires comprised isolated micrometer-long molecules of lambda-DNA or plasmid DNA that were sheathed in an ultrathin organoclay layer and which were either protected from or remained accessible to endonuclease-mediated clipping depending on the extent of biomolecule wrapping. Both types of hybrid nanostructures showed a marked increase in the DNA melting (denaturation) temperature, indicating significant thermal stabilization of the confined biomolecules. Our results suggest that nanoscale building blocks derived from organically modified inorganic clays could be useful agents for enhancing the chemical, thermal, and mechanical stability of isolated molecules or ensembles of DNA. Such constructs should have increased potential as functional components in bionanotechnology and nonviral gene transfection.     

磺基水杨酸插层Mg/Cu/Zn/Al-LDHs的组装、表征及紫外性能

以共沉淀法制备了磺基水杨酸插层Mg/Cu/Zn/Al-LDHs复合材料, 借助XRD、FT-IR、TG-DTA等手段对样品测试表明, 客体进入LDHs层间, 层间距由0.832 nm扩至1.125 nm, 推测了层间排列模型; EDS分析验证了插层后层板元素组成比接近理论比值, 插层组装仍能保持良好的层状结构, 且客体进入层间因静电和氢键等作用提高了热稳定性; 同时由UV-DRS结果可知, 插层LDHs复合材料对紫外线具有良好的屏蔽和吸收双重作用。     

原位接枝聚合改性LDHs/PCL纳米复合薄膜的制备及氧气阻隔性能

以纳米层状双羟基金属氧化物(LDHs)为引发剂,通过原位聚合的方法在纳米LDHs表面接枝上了聚己内酯(PCL)分子链(LDHs-g-PCL),并将其与纯PCL采用溶液浇筑法制备出LDHs/PCL纳米复合材料,研究了LDHs-g-PCL的化学结构,纳米复合材料的结晶特性、力学性能、阻隔性能等。结果表明,成功制备出化学键合牢固的PCL包覆LDHs;随着LDHs-g-PCL的加入,复合材料的结晶度呈现出逐渐升高的趋势,但异相成核作用效率有一定程度减弱。LDHs-g-PCL的质量分数为10%时,复合材料的拉伸强度和断裂伸长率均达到最大值,相比纯PCL分别提高了31%和37%。LDHs-g-PCL的质量分数为50%时,复合材料对氧气的渗透性达到最低值,相比纯PCL降低程度高达78%,这与层状结构的LDHs显著延长氧气分子在纳米复合材料的曲折渗透路径必不可分。基于Nielsen的相对渗透理论来优化纳米复合材料的渗透模型,结果表明,LDHs/PCL纳米复合材料阻隔性能的提高不仅归结于层状LDHs发挥的阻隔效应,而且更重要的是LDHs-g-PCL加入引起的体积效应。