聚合物层状组装膜

介绍了近几年来我们研究组在层状组装膜的构筑以及功能化研究方面取得的一些最新进展.包括结合表面溶胶-凝胶技术与静电层状组装技术,实现了二阶非线性基团在层状组装多层膜中的非对称排列,制备了具有二阶非线性效应的膜材料;采用室温压印技术,发展了一种简便、经济和具有普适性的层状组装聚合物膜图案化方法;以轻度交联的聚合物微凝胶为构筑基元,制备了具有高负载量的聚合物层状组装膜;发展了一种基于离子剥离技术的层状组装自支持膜制备方法;基于层状组装技术,制备了具有超疏水和抗反射功能的涂层.     

聚电解质层层自组装纳滤膜*

层层自组装技术能够方便地对膜的微观结构和组成进行调控,已在制备复合型纳滤膜方面取得了迅速的发展。本文综述了近年来用于聚电解质层层自组装纳滤膜的制备方法,种类以及影响因素。介绍了静态层层交替沉积、压力驱动自组装和电场强化自组装等三种制备方法;归纳了均聚型、共聚型和有机/无机杂化型等三类用于层层自组装纳滤膜的聚电解质的特点;讨论了聚电解质的荷电性、电荷密度和电离程度等因素对其自组装膜分离性能的影响。总结了聚电解质自组装纳滤膜在水处理和有机溶剂中物质的分离等方面的应用。同时,对提高聚电解质自组装纳滤膜的组装效率,分离性能和发展方向提出了设想和建议。     

Fabrication and Catalytic Properties of Films Based on Metal Ion-ligand Interaction between K_2PdCl_4 and 3-Amino-3-(4-pyridinyl)-propionitrile

This work presents a highly active and reusable heterogeneous film catalytic assembly for hydrogenation reduction of aromatic nitro compounds. The multilayer structures of PEI-(K2PdCl4-P1)n-film(PEI = polyethylenmine, P1 = 3-amino-3-(4-pyridinyl)-propionitrile) bound to quartz slides were fabricated by layer-by-layer(LbL) self-assembly method. Various characterization techniques including X-ray photoelectron spectroscopy(XPS), inductively coupled plasma OES spectrometer(ICP), UV-vis spectroscopy and atomic force microscopy(AFM) were employed to reveal the growth process of the resulting LbL multilayers in detail. Subsequent in situ reduction by H2 produced Pd nanoparticles embedded in such films were used as catalyst for the hydrogenation of nitroarenes. The catalytic performance test shows that the thin film catalyst can be applied to the hydrogenation reaction of various substituted nitroaromatics, and exhibits good catalytic activity and good catalyst stability. It is worth mentioning that our catalytic films can be easily removed from the reaction system in any time during the reaction, and the catalytic activity could be fully recovered when reused directly in another catalytic cycle for five times.     

Reversible Layer‐by‐Layer Deposition on Solid Substrates Inspired by Mussel Byssus Cuticle

The protective coating on mussel (Mytilus galloprovincialis) byssus has attracted considerable research interest because of its excellent mechanical properties such as hardness and extensibility. These special properties are known to be highly related with specific interactions between mussel foot protein‐1 and metal ions. In particular, the complexation between catechols in mfp‐1 and iron(III) has been identified as a key interaction. This finding has given opportunities for pursuing promising applications. Herein, we report that emulating the properties of the mussel byssus cuticle provides an important platform for developing reversible layer‐by‐layer (LbL) deposition, an advanced technique for surface modification. LbL films were constructed on solid substrates by sequential immersion of substrates into solutions containing iron(III) and catecholic compounds. The thickness of the LbL films was effectively controlled by increasing the immersion steps, and the reversibility of the LbL deposition was demonstrated by addition of a chelating agent.     

Dynamic sequential layer-by-layer deposition method for fast and region-selective multilayer thin film fabrication

We present a newly devised technique, the dynamic layer-by-layer (LbL) deposition method, that is designed to take advantage of the LbL deposition method and fluidic devices. Polyelectrolyte solutions are sequentially injected through the fluidic LbL deposition device to quickly build well-defined multilayer films on a selected region with a linear increase in the material deposited. Multilayer film fabrication by this new method on a specific region was proven to be fast and effective. The effects on film quality of the processing parameters such as concentration of polyelectrolytes, flow rate, and contact time were investigated. A half-tethered self-standing film on a substrate was fabricated to demonstrate the effectiveness and the region-selective deposition capability of the devised dynamic LbL deposition method.     

Layer-by-layer assembly as a versatile bottom-up nanofabrication technique for exploratory research and realistic application

The layer-by-layer (LbL) adsorption technique offers an easy and inexpensive process for multilayer formation and allows a variety of materials to be incorporated within the film structures. Therefore, the LbL assembly method can be regarded as a versatile bottom-up nanofabrication technique. Research fields concerned with LbL assembly have developed rapidly but some important physicochemical aspects remain uninvestigated. In this review, we will introduce several examples from physicochemical investigations regarding the basics of this method to advanced research aimed at practical applications. These are selected mostly from recent reports and should stimulate many physical chemists and chemical physicists in the further development of LbL assembly. In order to further understand the mechanism of the LbL assembly process, theoretical work, including thermodynamics calculations, has been conducted. Additionally, the use of molecular dynamics simulation has been proposed. Recently, many kinds of physicochemical molecular interactions, including hydrogen bonding, charge transfer interactions, and stereo-complex formation, have been used. The combination of the LbL method with other fabrication techniques such as spin-coating, spraying, and photolithography has also been extensively researched. These improvements have enabled preparation of LbL films composed of various materials contained in well-designed nanostructures. The resulting structures can be used to investigate basic physicochemical phenomena where relative distances between interacting groups is of great importance. Similarly, LbL structures prepared by such advanced techniques are used widely for development of functional systems for physical applications from photovoltaic devices and field effect transistors to biochemical applications including nano-sized reactors and drug delivery systems.     

Assembly of ultrathin polymer multilayer films by click chemistry

Layer-by-layer (LbL) assembly is a versatile and robust technique for fabricating tailored thin films of diverse composition. Herein we report a new method of covalent coupling, click chemistry, to facilitate the LbL assembly of thin films. Linear film growth was observed using both UV-vis and FTIR spectroscopy, and film thicknesses were determined by ellipsometry and atomic force microscopy. The assembled films are shown to be stable in a wide pH range. This technique offers the potential to enable the synthesis of new types of stable and responsive LbL films from a variety of polymers.     

Metal ion reactive thin films using spray electrostatic LbL assembly

By using the spray-layer-by-layer (Spray-LbL) technique, the number of metal counterions trapped within LbL coatings is significantly increased by kinetically freezing the film short of equilibrium, potentially limiting interchain penetration and forcing chains to remain extrinsically compensated to a much greater degree than observed in the traditional dipped LbL technique. The basis for the enhanced entrapment of metal ions such as Cu2+, Fe2+, and Ag+ is addressed, including the equilibrium driving force for extrinsic compensation by soft versus hard metal ions and the impact of Spray-LbL on the kinetics of polymer-ion complexation. These polymer-bound metal-ion coatings are also demonstrated to be effective treatments for air filtration, functionalizing existing filters with the ability to strongly bind toxic industrial compounds such as ammonia or cyanide gases, as well as chemical warfare agent simulants such as chloroethyl ethyl sulfide. On the basis of results reported here, future work could extend this method to include other toxic soft-base ligands such as carbon monoxide, benzene, or organophosphate nerve agents.     

Surface-imprinted nanostructured layer-by-layer film for molecular recognition of theophylline derivatives

In this article we report the introduction of the cooperativity of various specific interactions combined with photo-cross-linking of the interlayers to yield binding sites that can realize better selectivity and imprinting efficiency of a surface molecularly imprinted LbL film (SMILbL), thus providing a new approach toward fabrication of nanostructured molecularly imprinted thin films. It involves preassembly of poly(acrylic acid) (PAA) conjugated of the theophylline residue template via a disulfide bridge, denoted as PAAtheo 15, in solution, and layer-by-layer (LbL) assembly of PAAtheo 15 and a positively charged photoreactive diazo resin (DAR) to form multilayer thin film with designed architecture. After photo-cross-linking of the film and template removal, binding sites specific to 7-(beta-hydroxyethyl)theophylline (Theo-ol) molecules are introduced within the film. Binding assay demonstrates that the SMILbL has a high selectivity of SMILbL to Theo-ol over caffeine. A control experiment demonstrates that the selectivity of SMILbL derives from nanostructured recognition sites among the layers. The imprinting amount per unit mass of the film can be 1 order of magnitude larger than that of the conventional bulk molecular imprinting systems. As this concept of construction SMILbL can be easily extended to the other molecules by the following similar protocol: its applications in building many other different molecular recognition systems are greatly anticipated.     

Self-assemblies of luminescent rare earth compounds in capsules and multilayers

This review addresses luminescent rare earth compounds assembled in microcapsules as well as in planar films fabricated by the layer-by-layer (LbL) technique, the Langmuir–Blodgett (LB) method and in self-assembled monolayers. Chemical precipitation, electrostatic, van der Waals interactions and covalent bonds are involved in the assembly of these compounds. Self-organized ring patterns of rare earth complexes in Langmuir monolayers and on planar surfaces with stripe patterns, as well as fluorescence enhancement due to donor–acceptor pairs, microcavities, enrichment of rare earth compounds, and shell protection against water are described. Recent information on the tuning of luminescence intensity and multicolors by the excitation wavelength and the ratio of rare earth ions, respectively, are also reviewed. Potential applications of luminescent rare earth complex assemblies serving as biological probes, temperature and gas sensors are pointed out.     

Combining layer-by-layer assembly with electrodeposition of silver aggregates for fabricating superhydrophobic surfaces

Taking advantage of the stability and penetrability of layer-by-layer (LbL) films, we develop a novel method to fabricate a branchlike structure of Ag aggregates on the matrix of a LbL polyelectrolyte multilayer by an electrodeposition technique. The morphology of Ag aggregates can be adjusted by electrodeposition time and potential. Moreover, after further chemisorption of a self-assembled monolayer of n-dodecanethiol, the as-prepared surface becomes superhydrophobic with a contact angle as high as 154 degrees and a tilt angle lower than 3 degrees.     

Bifunctional electroactive nanostructured membranes

The advent of techniques based upon the spontaneous assembly of different materials with control over molecular architecture has afforded the fabrication of composite thin films for many nanotechnological applications. The layer-by-layer technique (LbL), in particular, has largely been used in the molecular level processing of nanohybrid systems in the form of multilayers, owing to its low cost and experimental simplicity. In this study we describe the fabrication of a novel, bifunctional film containing platinum nanoparticles/polyamidoamine (PAMAM) dendrimers. Pt nanoparticles were chemically synthesized/stabilized in the presence of PAMAM dendrimers and incorporated in LbL films in conjunction with nickel tetrasulfonated phthalocyanine (NiTsPc). A metallophthalocyanine was chosen because of its well-defined redox activity. Indium tin oxide (ITO)-covered glass plates were used as substrates for film deposition. The nanocomposites displayed high electrocatalytic activity toward dopamine and hydrogen peroxide molecules, two compounds with dissimilar chemical properties.     

X-ray reflectivity measurements of layer-by-layer films at the solid/liquid interface

In this Letter, we present a method for the decoration of layer-by-layer (LbL) structures by heavy metal ions, which allows X-ray reflectivity (XRR) measurements at the solid/water interface. The improved contrast has allowed us to obtain well-structured X-ray reflectivity curves from samples at the liquid/solid interface that can be used for the film structure modeling. The developed technique was also used to follow the formation of complexes between DNA and the LbL multilayer. The XRR data are confirmed by independent null-ellipsometric measurements at the solid/liquid interface on the very same architectures.     

Different binding modes of structurally diverse ligands for human D3DAR

Five different dopamine D3 receptors (D3DARs) models were created considering some suggested binding modes for D3DAR antagonists reported in earlier computational studies. Different hypotheses are justified because of the lack of experimental information about the putative site of interaction and are also due to the variability in scaffolds and size of D3DAR ligands. In this study 114 potent and selective D3DAR antagonists or partial agonists are used as key experimental information to discriminate the most reliable receptor model and to build a docking based 3D quantitative structure-activity relationship model able to indicate the ligand properties and the residues important for activity. The ability of this D3DAR model to discriminate the binding mode of different classes of ligands, showing a good quantitative correlation with their activity, encourages us to use it for screening novel lead compounds.     

Diazulenorubicene as a Non-benzenoid Isomer of peri-Tetracene with Two Sets of 5/7/5 Membered Rings Showing Good Semiconducting Properties

Non-benzenoid polycyclic aromatic hydrocarbons (PAHs) have received a lot of attention because of their unique optical, electronic, and magnetic properties, but their synthesis remains challenging. Herein, we report a non-benzenoid isomer of peri-tetracene, diazulenorubicene (DAR), with two sets of 5/7/5 membered rings synthesized by a (3+2) annulation reaction. Compared with the precursor containing only 5/7 membered rings, the newly formed five membered rings switch the aromaticity of the original heptagon/pentagon from antiaromatic/aromatic to non-aromatic/antiaromatic respectively, modify the intermolecular packing modes, and lower the LUMO levels. Notably, compound 2 b (DAR-TMS) shows p-type semiconducting properties with a hole mobility up to 1.27 cm² V⁻¹ s⁻¹. Moreover, further extension to larger non-benzenoid PAHs with 19 rings was achieved through on-surface chemistry from the DAR derivative with one alkynyl group.     

Column switching-back flushing technique for the analysis of aromatic compounds in gasoline

A simple method, based on the technique of capillary column switching-back flushing, has been developed for the detailed analysis of aromatic compounds in gasoline. The sample was first separated on a 30-m long OV-2330 polar precolumn and then backflushed onto a nonpolar analytical column. The early eluting components from the precolumn and the components of interest (aromatic compounds plus heavier compounds) eluting from the analytical column are all directed to the same flame ionization detection system through a T piece, which permits the quantitative analysis of aromatic hydrocarbons in gasoline by a normalization method using correcting factors. The switching time window of the method is +/-5 s, resulting in easier operation and higher reliability. The reproducibility of the quantitative analysis was < or = 3% RSD for real gasoline samples.     

Coordinative supramolecular assembly of electrochromic thin films

The article is concerned with the layer-by-layer (LbL) assembly of electrochromic films using coordinative interactions between compounds. At first the concepts of coordinative supramolecular assembly are explained and examples are presented. Subsequently electrochromic LbL assemblies prepared upon electrostatic and/or coordinative interactions are briefly discussed. In the focus of the article are films of terpyridine(tpy)-functionalized polyiminoarylene metal ion complexes, which are prepared upon coordinative LbL assembly of the tpy-substituted polyiminoarylenes and metal ions. The films exhibit reversible electrochromic behavior with high contrast and fast response times. It is demonstrated that the electrochromic behavior of the films can be modified by a variation of polymer structure, metal ions, and counterions.     

Anisotropic structure and transport in self-assembled layered polymer-clay nanocomposites

Using the layer-by-layer (LbL) assembly technique, we create a polymer-clay structure from a unique combination of LbL materials: poly(ethylene imine), Laponite clay, and poly(ethylene oxide). This trilayer LbL structure is assembled using a combination of hydrogen bonding and electrostatic interactions. The films were characterized using ellipsometry, profilometry, X-ray photon spectroscopy, atomic force microscopy, scanning electron microscopy, wide-angle X-ray diffraction, grazing-incidence small-angle X-ray scattering, and electrochemical impedance spectroscopy (EIS). We observe a layered, anisotropic structure, which resulted in in-plane ion transport 100 times faster than cross-plane at 0% relative humidity. This study represents a first application of EIS in determining anisotropic ion transport in LbL assemblies and its correlation to structural anisotropy.     

Smoothing of Fast Assembled Layer-by-layer Films by Adjusting Assembly Conditions

To prepare layer-by-layer(LbL) multilayers in time-efficient manners by the dipping method is highly appealing. However, the fast LbL assembly produces multilayers with high surface roughness. In our attempt to smooth the surface morphologies of LbL multilayers obtained by fast assembly(5 s dipping), we studied the influence of the assembly conditions on the surface morphologies. The study shows that by properly adjusting the assembly conditions, such as washing duration, water annealing period, and drying with nitrogen flow, LbL multilayers with enhanced surface smoothness could be obtained through fast LbL assembly.     

Reverse-phase LbL-encapsulation of highly water soluble materials by layer-by-layer polyelectrolyte self-assembly

We report on a novel method for the encapsulation of highly water soluble materials by using layer-by-layer (LbL) polyelectrolyte self-assembly. State of the art polyelectrolyte self-assembly LbL coating and encapsulation methods are only applicable to insoluble or poorly water soluble template materials, because the process is performed in water causing dissolution of the solid template. Our method extends the material spectrum to highly water soluble template materials by using non-ionized polyelectrolytes in an organic phase (reverse-phase) instead of polyelectrolyte salts in an aqueous environment. By using the reverse-phase layer-by-layer (RP-LbL) technique, we have demonstrated the direct encapsulation of proteins, glucose, vitamin C, and inorganic salts in the solid state. Multilayer deposition was proven, layer thickness was determined by AFM, and the advantage of the method to prepare powders of encapsulated materials was demonstrated. The method is simple, robust, and applicable to a broad range of substances with potential applications in several industries.