Humidity‐Triggered Self‐Healing of Microporous Polyelectrolyte Multilayer Coatings for Hydrophobic Drug Delivery

Layer‐by‐layer (LbL) self‐assemblies have inherent potential as dynamic coatings because of the sensitivity of their building blocks to external stimuli. Here, humidity serves as a feasible trigger to activate the self‐healing of a microporous polyethylenimine/poly(acrylic acid) multilayer film. Microporous structures within the polyelectrolyte multilayer (PEM) film are created by acid treatment, followed by freeze‐drying to remove water. The self‐healing of these micropores can be triggered at 100% relative humidity, under which condition the mobility of the polyelectrolytes is activated. Based on this, a facile and versatile method is suggested for directly integrating hydrophobic drugs into PEM films for surface‐mediated drug delivery. The high porosity of microporous film enables the highest loading (≈303.5 μg cm^?2 for a 15‐bilayered film) of triclosan to be a one‐shot process via wicking action and subsequent solvent removal, thus dramatically streamlining the processes and reducing complexities compared to the existing LbL strategies. The self‐healing of a drug‐loaded microporous PEM film significantly reduces the diffusion coefficient of triclosan, which is favorable for the long‐term sustained release of the drug. The dynamic properties of this polymeric coating provide great potential for its use as a delivery platform for hydrophobic drugs in a wide variety of biomedical applications.     

Enhanced Photocurrent Production by Photosystem I Multilayer Assemblies

The long‐term success of photosynthetic organisms has resulted in their global superabundance, which is sustained by their widespread, continual mass‐production of the integral proteins that photocatalyze the chemical processes of natural photosynthesis. Here, a fast, general method to assemble multilayer films composed of one such photocatalytic protein complex, Photosystem I (PSI), onto a variety of substrates is reported. The resulting films, akin to the stacked thylakoid structures of leaves, consist of a protein matrix that is permeable to electrochemical mediators and contain a high concentration of photoelectrochemically active redox centers. These multilayer assemblies vastly outperform previously reported monolayer films of PSI in terms of photocurrent production when incorporated into an electrochemical system, and it is shown that these photocatalytic properties increase with the film thickness. These results demonstrate how the assembly of micron‐thick coatings of PSI on non‐biological substrates yields a biohybrid ensemble that manifests the photocatalytic activity of the film’s individual protein constituents, and represent significant progress toward affordable, biologically‐inspired renewable energy conversion platforms.     

Layer‐by‐Layer Assembly of Light‐Responsive Polymeric Multilayer Systems

Layer‐by‐Layer (LbL) assembly is a simple and highly versatile method to modify surfaces and fabricate robust and highly‐ordered nanostructured coatings over almost any type of substrate. Such versatility enables the incorporation of a plethora of building blocks, including materials exhibiting switchable properties, in a single device through a multitude of complementary intermolecular interactions. Switchable materials may undergo reversible physicochemical changes in response to a variety of external triggers. Although most of the works in the literature have been focusing on stimuli‐responsive materials that are sensitive to common triggers such as pH, ionic strength, or temperature, much less has been discussed on LbL systems which are sensitive to non‐invasive and easily controlled light stimulus, despite its unique potential. This review provides a deep overview of the recent progresses achieved in the design and fabrication of light‐responsive LbL polymeric multilayer systems, their potential future challenges and opportunities, and possible applications. Many examples are given on light‐responsive polymeric multilayer assemblies built from metal nanoparticles, functional dyes, and metal oxides. Such stimuli‐responsive functional materials, and combinations among them, may lead to novel and highly promising nanostructured smart functional systems well‐suited for a wide range of research fields, including biomedicine and biotechnology.     

A Delivery System for Self‐Healing Inorganic Films

Multilayer composites that utilize polymeric and brittle inorganic films are essential components for extending the lifetimes and exploiting the flexibility of many electronic devices. However, crack formation within the brittle inorganic layers that arise from defects as well as the flexing of these multilayer composite materials allows the influx of atmospheric water, a major source of device degradation. Thus, a composite material that can initiate self‐healing upon the influx of environmental water through defects or stress‐induced cracks would find potential applications in multilayer composite materials for permeation barriers. In the present study, the reactive metal oxide precursor TiCl₄ is encapsulated within the pores of a degradable polymer, poly(lactic acid) (PLA). Electrospun PLA fibers are found to be reactive to atmospheric water leading to the hydrolysis of the degradable polymer shell and subsequent release of the reactive metal oxide precursor. Release of the reactive TiCl₄ from the pores results in hydrolysis of the metal oxide precursor, forming solid titanium oxides at the surface of the fibers. The efficacy of this self‐healing delivery system is also demonstrated by the integration of these reactive fibers in the polymer planarization layer, poly(methyl methacrylate), of a multilayer film, upon which an alumina barrier layer is deposited. The introduction of nanocracks in the alumina barrier layer lead to the release of the metal oxide precursor from the pores of the fibers and the formation of titanium dioxide nanoparticles within the crack and upon the thin film surface. In this study the first delivery system that may find utility for the self‐healing of multilayer barrier films through the site‐specific delivery of metal oxide nanoparticles through smart reactive composite fibers is established.     

Macroscopic Properties of Biomimetic Ceramics Are Governed by the Molecular Recognition at the Bioorganic–Inorganic Interface

Bioinspired materials design aims for high‐performing composite materials based on natural biomineralization processes and biomineral architectures. A key component to the research is the bioorganic–inorganic interface, one of the most crucial parameters for controlling the material properties. In this study, genetically engineered phages expressing an inorganic‐binding peptide for the molecular recognition of a ceramic material is exploited to generate thin film multilayer assemblies, with the phage template as minority component. The bioorganic–inorganic interface in the ceramic (zinc oxide, ZnO) multilayer systems is strengthened by the ZnO‐binding motif HSSHH of a peptide to increase Young's modulus and hardness. Applying a point‐mutated version of the peptide, DSSHH, which modulates the interface forces, shows an increased fracture toughness without deteriorating the Young's modulus and the hardness. Molecular matching of the organic phase and its modulation in order to form a specific interface is shown to be important in controlling material properties like in natural biominerals. With this tool in hand, it is not only possible to imitate the structure of biominerals but also to genetically control the molecular recognition of bioorganic molecules to induce macroscopic effects in synthetic composite materials.     

Noise-free anodization profiles of multi-layer structures using an evaporated silicon monoxide mask

In recent years, the anodization process has been developed into an analytical tool for the assessment of multilayer structures. This is usually achieved by using a constant current supply and monitoring the growth of the oxide layer, through the multilayer, by measuring the increase in the voltage developed across the anodization cell. In this paper, it is described how a silicon monoxide film has been used as the masking material in order to overcome the problem of electrical breakdown of the mask. This enables noise free anodization profiles to be obtained from multilayer structures.     

New layer transfers obtained by the SmartCut process

The SmartCut process was first developed to obtain silicon-on-insulator (SOI) materials. Now an industrial process, the main Unibond SOI-structure trends are reported in this paper. Many material combinations can be achieved by this process, because it appears to enable the generic development of new structures. Several of the new structures combining different materials and different bonding layers are described. These include SiGe and strained-Si films onto an oxidized Si wafer, silicon-on-insulating multilayer (SOIM) structures, and InP or 4H-SiC film transfers onto low-cost substrates via metallic or even refractory conductive-film bonding layers. More recently, an original bonding process based on mark patterning, wafer bonding, and layer transfer has been proposed to obtain structures in which the relative crystalline-axis orientations of both the film and the substrate can be controlled accurately. In this case, a SmartCut process that includes a mark-patterning step appears well suited for precise control of axis orientations. A procedure is described to obtain an ultra-thin Si film bonded onto a Si wafer. An example of a pure screw-dislocation network achieved by the mark patterning, bonding, and layer-transfer process is reported in this paper. The results have important implications for nanostructure development.     

Nanostructured Crystalline Comb Polymer of Perylenebisimide by Directed Self‐Assembly: Poly(4‐vinylpyridine)‐pentadecylphenol Perylenebisimide

Well defined nanostructured polymeric supramolecular assemblies are formed when an asymmetric perylenebisimide substituted with ethylhexyl chains on one end and functionalized with 3‐pentadecylphenol at the other termini ( PDP‐UPBI ) is complexed with poly(4‐vinylpyridine) (P4VP) via a non‐covalent specific interaction such as hydrogen‐bonding. The resulting P4VP(PDP‐UPBI) _n complexes are fully solution processable. The bulk structure and morphologies of the supramolecular film studied using small angle and wide angle X‐ray scattering reveals highly crystalline nature of the complex. Thin film morphology of the 1:1 complex analyzed using transmission electron microscopy shows uniform lamellar structures in the domain range of 5–10 nm. A clear trend of improved electrical parameters in P4VP(PDP‐UPBI) system compared to pristine ( PDP‐UPBI ) is observed from space charge limited current measurements. In short, a simple and facile method to obtain spatially defined organization of n‐type semiconductor perylenebisimide molecules using hydrogen bonding interactions with P4VP as the structural motif is showcased herein.     

Polyelectrolyte Blend Multilayers: A Versatile Route to Engineering Interfaces and Films

The ability to reliably engineer surfaces with nanoscale precision is a rapidly developing field of research with applications ranging from biosensing and biomedical materials to antifouling and corrosion protection. The layer‐by‐layer (LbL) approach is a widely utilized method for engineering surfaces, in part because of the large array of polymeric materials that can be integrated and the diverse range of functionality that these materials afford. Herein, we discuss the LbL deposition of multicomponent ‘blend' solutions to form polyelectrolyte blend multilayer films and coatings. This approach is a versatile platform for enhancing film stability, incorporating a wide range of functional materials, controlling film morphology and material properties, and increasing biological response, thereby expanding the range of potential applications.     

Formation of Thick Porous Anodic Alumina Films and Nanowire Arrays on Silicon Wafers and Glass

A method for the fabrication of thick films of porous anodic alumina on rigid substrates is described. The anodic alumina film was generated by the anodization of an aluminum film evaporated on the substrate. The morphology of the barrier layer between the porous film and the substrate was different from that of anodic films grown on aluminum substrates. The removal of the barrier layer and the electrochemical growth of nanowires within the ordered pores were accomplished without the need to remove the anodic film from the substrate. We fabricated porous anodic alumina samples over large areas (up to 70 cm²), and deposited in them nanowire arrays of various materials. Long nanowires were obtained with lengths of at least 9 μm and aspect ratios as high as 300. Due to their mechanical robustness and the built‐in contact between the conducting substrate and the nanowires, the structures were useful for electrical transport measurements on the arrays. The method was also demonstrated on patterned and non‐planar substrates, further expanding the range of applications of these porous alumina and nanowire assemblies.     

A Three‐Dimensional Nanostructured Array of Protein Nanoparticles

Here a novel technique is reported to construct a three‐dimensional (3D) array of well‐defined and controllable multilayered nanostructures of proteins that is based on alternate layer‐by‐layer assembly of bacterial protein nanoparticles and DNA on a patterned array of gold dots. This is the first report on protein‐based multilayer stacking, which has the following significant advantages over conventional multilayer assemblies: 1) avoiding hazardous chemicals, the multilayer assembly is implemented in aqueous solution under mild temperature and pH conditions over a relatively short period; 2) direct multilayer growth from designated position is possible by controlling the aspect ratio; 3) multicomponent stacking can be easily performed through alternate stacking of different building blocks (in this case protein nanoparticles); and 4) a wide variety of 3D arrays can be constructed using various functionalized protein nanoparticles that are easily prepared through a simple genetic engineering approach. In this study, as a proof of concept, the developed 3D and patterned arrays of protein nanoparticle multilayers are successfully applied to the multiplexed bioassays of breast and colorectal cancer markers.     

Ordering of Disordered Nanowires: Spontaneous Formation of Highly Aligned,Ultralong Ag Nanowire Films at Oil–Water–Air Interface

One‐dimensional nanomaterials and their assemblies attract considerable scientific interest in the physical, chemical, and biological fields because of their potential applications in electronic and optical devices. The interface‐assembly method has become an important route for the self‐assembly of nanoparticles, nanosheets, nanotubes, and nanorods, but the self‐assembly of ultralong nanowires has only been successful using the Langmuir–Blodgett approach. A novel approach for the spontaneous formation of highly aligned, ultralong Ag nanowire films at the oil–water–air interface is described. In this approach, the three‐phase interface directs the movement and self‐assembly process of the ultralong Ag nanowires without the effect of an external force or complex apparatus. The ordered films exhibit intrinsic large electromagnetic fields that are localized in the interstitials between adjacent nanowires. This new three‐phase‐interface approach is proven to be a general route that can be extended to self‐assemble other ultralong nanowires and produce ordered films.     

Condensation Induced Delamination of Nanoscale Hydrophobic Films

Vapor condensation is a crucial phenomenon governing the efficiency of many processes. In particular, dropwise condensation on hydrophobic thin films (≈100 nm‐thick) has the potential to achieve remarkable heat transfer. However, the lack of durability of these thin films has limited applications for a century. Although degradation due to steam condensation has been described as “blistering,” no satisfactory insight exists capable of elucidating the driving force for film delamination. Here, it is shown that nanoscale pinholes in hydrophobic films are the source of blister formation. By creating artificial pinholes via nanoindentation on thin (30 to 500 nm‐thick) fluorinated hydrophobic films, it is demostrated that water blisters can be initiated at the pinholes during condensation. It is experimentally demonstrated that vapor is transferred to the blister through the nanoscale pinhole, and the driving force for delamination is capillary pressure generated at the pinhole by the pinned liquid–vapor interface. The techniques and insights presented here will inform future work on polymeric thin film and enable their durable design for a variety of applications.     

软X光激光用多层膜反射镜的制备与检测

介绍在制备和检测软Ｘ光激光用多层膜反射镜中听做的研究工作。重点是制备过程，包括基板、镀膜设备、膜厚控制方法，以及经大量实验得出的镀膜工艺条件、给出了利用Ｘ光射线衍射仪所做的周期结构检测结果，以及利用激光等离子体作光源的精密反射率计所作的反射率测量结果。最后，对工作进展和存在的问题做了简略评述。     

Multicompartment Polymer Vesicles with Artificial Organelles for Signal‐Triggered Cascade Reactions Including Cytoskeleton Formation

Organelles, i.e., internal subcompartments of cells, are fundamental to spatially separate cellular processes, while controlled intercompartment communication is essential for signal transduction. Furthermore, dynamic remodeling of the cytoskeleton provides the mechanical basis for cell shape transformations and mobility. In a quest to develop cell‐like smart synthetic materials, exhibiting functional flexibility, a self‐assembled vesicular multicompartment system, comprised of a polymeric membrane (giant unilamellar vesicle, GUV) enveloping polymeric artificial organelles (vesicles, nanoparticles), is herein presented. Such multicompartment assemblies respond to an external stimulus that is transduced through a precise sequence. Stimuli‐triggered communication between two types of internal artificial organelles induces and localizes an enzymatic reaction and allows ion‐channel mediated release from storage vacuoles. Moreover, cytoskeleton formation in the GUVs' lumen can be triggered by addition of ionophores and ions. An additional level of control is achieved by signal‐triggered ionophore translocation from organelles to the outer membrane, triggering cytoskeleton formation. This system is further used to study the diffusion of various cytoskeletal drugs across the synthetic outer membrane, demonstrating potential applicability, e.g., anticancer drug screening. Such multicompartment assemblies represent a robust system harboring many different functionalities and are a considerable leap in the application of cell logics to reactive and smart synthetic materials.     

A General Solvent Selection Strategy for Solution Processed Quantum Dots Targeting High Performance Light‐Emitting Diode

An all‐solution‐processed quantum dots (QDs) light emitting diode (QLED) consists of different layers deposited from various orthogonal solvents. Here, the authors develop a general solvent selection strategy to obtain orthogonal solubility properties as well as high film quality. It is found that a “poor” QDs film morphology with striation defects often occurs when the QDs film is deposited from “bad” solvent. A physical model is presented to rationalize the observed striation defects, and then a general solvent selection strategy is proposed to prevent both surface striation defects and the dissolving of the underlying layers by carefully choosing the “good” solvent for QDs. A compact QDs film can be fabricated without altering the original morphology of underlying functional layers in a QLED device, leading to significant device performance improvement. An external quantum efficiency of 15.45% is achieved in a green QLED with uniform emitting region. This solvent selection strategy provides a general way to deposit high quality films for most of the solution‐processed multilayer optoelectronic devices.     

Cover Picture: Fabrication and Characterization of Three‐Dimensional Silver‐Coated Polymeric Microstructures (Adv. Funct. Mater. 13/2006)

Kuebler and co‐workers report on p. 1739 a method for preparing conductive and optically reflective silver‐coated polymeric microstructures having virtually any 3D form. Shown are reflection images of a silvered five‐layer simple‐cubic lattice having a period of 2.4 μm (background) and a macroscopic silvered polymer film (inset). To prepare metallopolymeric microstructures, 3D polymeric scaffolds are first created by multiphoton direct laser writing, then functionalized with gold particles, and metallized using nucleated electroless silver deposition. A method is reported for fabricating complex 3D silver‐coated polymeric microstructures. The approach is based on the creation of a crosslinked polymeric microscaffold via patterned multiphoton‐initiated polymerization followed by surface‐nucleated electroless deposition of silver. The conductivity and reflectivity of the resulting silver–polymer composites and the nanoscale morphology of the deposited silver are characterized. Sub‐micrometer thick layers of silver can be controllably deposited onto surfaces, including those of 3D microporous forms without occluding the interior of the structure. The approach is general for silver coating crosslinked polymeric structures based on acrylate, methacrylate, and epoxide resins and provides a new path to complex 3D micrometer‐scale devices with electronic, photonic, and electromechanical function.     

Stiff and Transparent Multilayer Thin Films Prepared Through Hydrogen‐Bonding Layer‐by‐Layer Assembly of Graphene and Polymer

Due to their exceptional orientation of 2D nanofillers, layer‐by‐layer (LbL) assembled polymer/graphene oxide thin films exhibit unmatched mechanical performance relative to any conventionally produced counterparts with similar composition. Unprecedented mechanical property improvement, by replacing graphene oxide with pristine graphene, is demonstrated in this work. Polyvinylpyrrolidone‐stabilized graphene platelets are alternately deposited with poly(acrylic acid) using hydrogen bonding assisted LbL assembly. Transmission electron microscopy imaging and the Halpin‐Tsai model are used to demonstrate, for the first time, that intact graphene can be processed from water to generate polymer nanocomposite thin films with simultaneous parallel‐alignment, high packing density, and exfoliation. A multilayer thin film with only 3.9 vol% of highly exfoliated, and structurally intact graphene, increases the elastic modulus (E) of a polymer multilayer thin film by 322% (from 1.41 to 4.81 GPa), while maintaining visible light transmittance of ≈90%. This is one of the greatest improvements in elastic modulus ever reported for a graphene‐filled polymer nanocomposite with a glassy (E > 1 GPa) matrix. The technique described here provides a powerful new tool to improve nanocomposite properties (mechanical, gas transport, etc.) that can be universally applied to a variety of polymer matrices and 2D nanoplatelets.     

Fabrication of highly transparent self‐cleaning protection films for photovoltaic systems

A moth‐eye anti‐reflective structure was fabricated by hot‐embossing and UV nanoimprint lithography on a solar cell protective film to suppress the reflection of incident light. Moreover, a superhydrophobic surface was developed by reducing the surface energy by forming a hydrophobic self‐assembled monolayer coating on an anti‐reflective structured resin surface. Therefore, the transmittance of incident light was increased by the anti‐reflective structure. As a result, the solar cell efficiency was enhanced and the total accumulated electrical energy generated by a solar cell with a nano‐patterned polymeric film was increased. The efficiency of each solar cell was evaluated by an analysis of its I‐V characteristics using a solar simulator, and the external quantum efficiency according to the wavelength of incident light was analyzed by using an incident photon‐to‐current conversion efficiency system. Finally, the enhancement of the generated power was confirmed by a field test and a power charging experiment. Copyright © 2012 John Wiley & Sons, Ltd.     

Oxidative Inorganic Multilayers for Polypyrrole Film Generation

A controlled nanoscale fabrication of conducting polymer films sets severe requirements for the preparation method and substrate. A new and versatile approach for producing thin polypyrrole films on a variety of surfaces is presented. Purely inorganic thin films are first prepared from poly(metaphosphate) and tetravalent metal ions using a sequential layer‐by‐layer technique. Redox‐active cerium(IV) polyphosphate multilayer and redox‐inactive zirconium(IV) and hafnium(IV) polyphosphate multilayers are prepared. Cerium‐based polyphosphate films grow exponentially with the number of layers but multilayers containing zirconium or hafnium exhibit a linear buildup process. All the studied systems produce relatively smooth films with initial bilayer thickness less than 2 nm. The cerium(IV) containing film is redox‐active, which is shown by its capability to form a polypyrrole layer on its surface by oxidation of pyrrole monomers in the adjacent aqueous solution. This is a general method to produce thin oxidative films of arbitrary size and form on a wide variety of surfaces.