Solution‐Processable Hole‐Generation Layer and Electron‐Transporting Layer: Towards High‐Performance,Alternating‐Current‐Driven,Field‐Induced Polymer Electroluminescent Devices

The effect of solution‐processed p‐type doping of hole‐generation layers (HGLs) and electron‐transporting layer (ETLs) are systematically investigated on the performance of solution‐processable alternating current (AC) field‐induced polymer EL (FIPEL) devices in terms of hole‐generation capability of HGLs and electron‐transporting characteristics of ETLs. A variety of p‐type doping conjugated polymers and a series of solution‐processed electron‐transporting small molecules are employed. It is found that the free hole density in p‐type doping HGLs and electron mobility of solution‐processed ETLs are directly related to the device performance, and that the hole‐transporting characteristics of ETLs also play an important role since holes need to be injected from electrode through ETLs to refill the depleted HGLs in the positive half of the AC cycle. As a result, the best FIPEL device exhibits exceptional performance: a low turn‐on voltage of 12 V, a maximum luminance of 20 500 cd m^?2, a maximum current and power efficiency of 110.7 cd A^?1 and 29.3 lm W^?1. To the best of the authors' knowledge, this is the highest report to date among FIPEL devices driven by AC voltage.     

Highly Scalable,Closed‐Loop Synthesis of Drug‐Loaded,Layer‐by‐Layer Nanoparticles

Layer‐by‐layer (LbL) self‐assembly is a versatile technique from which multi­component and stimuli‐responsive nanoscale drug‐carriers can be constructed. Despite the benefits of LbL assembly, the conventional synthetic approach for fabricating LbL nanoparticles requires numerous purification steps that limit scale, yield, efficiency, and potential for clinical translation. In this report, a generalizable method for increasing throughput with LbL assembly is described by using highly scalable, closed‐loop diafiltration to manage intermediate purification steps. This method facilitates highly controlled fabrication of diverse nanoscale LbL formulations smaller than 150 nm composed from solid‐polymer, mesoporous silica, and liposomal vesicles. The technique allows for the deposition of a broad range of polyelectrolytes that included native polysaccharides, linear polypeptides, and synthetic polymers. The cytotoxicity, shelf life, and long‐term storage of LbL nanoparticles produced using this approach are explored. It is found that LbL coated systems can be reliably and rapidly produced: specifically, LbL‐modified liposomes could be lyophilized, stored at room temperature, and reconstituted without compromising drug encapsulation or particle stability, thereby facilitating large scale applications. Overall, this report describes an accessible approach that significantly improves the throughput of nanoscale LbL drug‐carriers that show low toxicity and are amenable to clinically relevant storage conditions.     

Quantum‐Dot‐Functionalized Poly(styrene‐co‐acrylic acid) Microbeads: Step‐Wise Self‐Assembly,Characterization, and Applications for Sub‐femtomolar Electrochemical Detection of DNA Hybridization

A novel nanoparticle label capable of amplifying the electrochemical signal of DNA hybridization is fabricated by functionalizing poly(styrene‐co‐acrylic acid) microbeads with CdTe quantum dots. CdTe‐tagged polybeads are prepared by a layer‐by‐layer self‐assembly of the CdTe quantum dots (diameter = 3.07 nm) and polyelectrolyte on the polybeads (diameter = 323 nm). The self‐assembly procedure is characterized using scanning and transmission electron microscopy, and X‐ray photoelectron, infrared and photoluminescence spectroscopy. The mean quantum‐dot coverage is (9.54 ± 1.2) × 10³ per polybead. The enormous coverage and the unique properties of the quantum dots make the polybeads an effective candidate as a functionalized amplification platform for labelling of DNA or protein. Herein, as an example, the CdTe‐tagged polybeads are attached to DNA probes specific to breast cancer by streptavidin–biotin binding to construct a DNA biosensor. The detection of the DNA hybridization process is achieved by the square‐wave voltammetry of Cd²⁺ after the dissolution of the CdTe tags with HNO₃. The efficient carrier‐bead amplification platform, coupled with the highly sensitive stripping voltammetric measurement, gives rise to a detection limit of 0.52 fmol L^?1 and a dynamic range spanning 5 orders of magnitude. This proposed nanoparticle label is promising, exhibits an efficient amplification performance, and opens new opportunities for ultrasensitive detection of other biorecognition events.     

Hemoglobin‐CdTe‐CaCO3@Polyelectrolytes 3D Architecture: Fabrication,Characterization, and Application in Biosensing

A Hemoglobin‐CdTe‐CaCO₃@polyelectrolyte 3D architecture is synthesized by a stepwise layer‐by‐layer method and is further used to fabricate an electrochemistry biosensor. While the calcium carbonate (CaCO₃) microsphere acts as an effective host for the loading of cadmium telluride (CdTe) quantum dots due to its channel‐like structure, the polyelectrolyte layers further increase the loading amount and help in the formation of a thick and uniform quantum‐dot “shell”, which not only improves the stability of the spheres in water, but also contributes to the fast and effective direct electron transfer between the protein redox center and the macroscopic electrode. The materials are characterized and compared, and the possible mechanism for the direct electrochemistry phenomenon is hypothesized. Our work not only provides a facile and effective route for the preparation of quantum‐dot‐loaded spheres, but also sets an example of how the structure of functional materials can be tuned and related to their applications. In addition, it is one of the few examples of using CaCO₃ microspheres in quantum‐dot loading and biosensing.     

Lubricant‐Infused Nanoparticulate Coatings Assembled by Layer‐by‐Layer Deposition

Omniphobic coatings are designed to repel a wide range of liquids without leaving stains on the surface. A practical coating should exhibit stable repellency, show no interference with color or transparency of the underlying substrate and, ideally, be deposited in a simple process on arbitrarily shaped surfaces. We use layer‐by‐layer (LbL) deposition of negatively charged silica nanoparticles and positively charged polyelectrolytes to create nanoscale surface structures that are further surface‐functionalized with fluorinated silanes and infiltrated with fluorinated oil, forming a smooth, highly repellent coating on surfaces of different materials and shapes. We show that four or more LbL cycles introduce sufficient surface roughness to effectively immobilize the lubricant into the nanoporous coating and provide a stable liquid interface that repels water, low‐surface‐tension liquids and complex fluids. The absence of hierarchical structures and the small size of the silica nanoparticles enables complete transparency of the coating, with light transmittance exceeding that of normal glass. The coating is mechanically robust, maintains its repellency after exposure to continuous flow for several days and prevents adsorption of streptavidin as a model protein. The LbL process is conceptually simple, of low cost, environmentally benign, scalable, automatable and therefore may present an efficient synthetic route to non‐fouling materials.     

Controlled Polarizability of One‐Nanometer‐Thick Oxide Nanosheets for Tailored,High‐κ Nanodielectrics

An important challenge in current microelectronics research is the development of techniques for making smaller, higher‐performance electronic components. In this context, the fabrication and integration of ultrathin high‐κ dielectrics with good insulating properties is an important issue. Here, we report on a rational approach to produce high‐performance nanodielectrics using one‐nanometer‐thick oxide nanosheets as a building block. In titano niobate nanosheets (TiNbO₅, Ti₂NbO₇, Ti₅NbO₁₄), the octahedral distortion inherent to site‐engineering by Nb incorporation results in a giant molecular polarizability, and their multilayer nanofilms exhibit a high dielectric constant (160–320), the largest value seen so far in high‐κ nanofilms with thickness down to 10 nm. Furthermore, these superior high‐κ properties are fairly temperature‐independent with low leakage‐current density (<10^?7 A cm^?2). This work may provide a new recipe for designing nanodielectrics desirable for practical high‐κ devices.     

Evaluation of Digitally Encoded Layer‐by‐layer Coated Microparticles as Cell Carriers

To obtain more biologically relevant data there is a growing interest in the use of living cells for assaying the biological activity of unknown chemical compounds. Density ‘multiplex’ cell‐based assays, where different cell types are mixed in one well and simultaneously investigated upon exposure to a certain compound are beginning to emerge. To be able to identify the cells they should be attached to microscopic carriers that are encoded. This paper investigates how digitally encoded microparticles can be loaded with cells while keeping the digital code in the microcarriers readable. It turns out that coating the surface of the encoded microcarriers with polyelectrolytes using the layer‐by‐layer (LbL) approach provides the microcarriers with a ‘highly functional’ surface. The polyelectrolyte layer allows the growth of the cells, allows the orientation of the cell loaded microcarriers in a magnetic field, and does not hamper the reading of the code. It has further been shown that the cells growing on the polyelectrolyte layer can become transduced by adenoviral particles hosted by the polyelectrolyte layer. It is concluded that the digitally encoded microparticles are promising materials for use in biomedical and pharmaceutical in‐vitro research where cells are used as tools.     

Room‐Temperature Metallic Fusion‐Induced Layer‐by‐Layer Assembly for Highly Flexible Electrode Applications

To fabricate flexible electrodes, conventional silver (Ag) nanomaterials have been deposited onto flexible substrates, but the formed electrodes display limited electrical conductivity due to residual bulky organic ligands, and thus postsintering processes are required to improve the electrical conductivity. Herein, an entirely different approach is introduced to produce highly flexible electrodes with bulk metal–like electrical conductivity: the room‐temperature metallic fusion of multilayered silver nanoparticles (NPs). Synthesized tetraoctylammonium thiosulfate (TOAS)‐stabilized Ag NPs are deposited onto flexible substrates by layer‐by‐layer assembly involving a perfect ligand‐exchange reaction between bulky TOAS ligands and small tris(2‐aminoethyl)amine linkers. The introduced small linkers substantially reduce the separation distance between neighboring Ag NPs. This shortened interparticle distance, combined with the low cohesive energy of Ag NPs, strongly induces metallic fusion between the close‐packed Ag NPs at room temperature without additional treatments, resulting in a high electrical conductivity of ≈1.60 × 10⁵ S cm^?1 (bulk Ag: ≈6.30 × 10⁵ S cm^?1). Furthermore, depositing the TOAS–Ag NPs onto cellulose papers through this approach can convert the insulating substrates into highly flexible and conductive papers that can be used as 3D current collectors for energy‐storage devices.     

Multivalent‐Ion‐Mediated Stabilization of Hydrogen‐Bonded Multilayers

Hydrogen‐bonding interactions are an important alternative to electrostatic interactions for assembling multilayer thin films of uncharged components. Herein, a new method is reported for rendering such films stable at pH values close to physiological conditions. Multilayer films based on hydrogen bonding are assembled by the alternate deposition of poly[(styrene sulfonic acid)‐co‐(maleic acid)] (PSSMA) and poly(N‐isopropylacrylamide) (PNiPAAm) at pH 2.5. The use of PSSMA results in multilayers that contain free styrene sulfonate groups, as these moieties do not interact with the PNiPAAm functional groups. Subsequent infiltration of a multivalent ion (Ce⁴⁺ or Fe³⁺) leads to an increase in the total film mass, with little impact on the film morphology, as determined by using atomic force microscopy. To examine the film stability, the resulting films have been exposed to elevated pH (7.1). While there is substantial swelling of the multilayers (25 % and 55 % for Ce⁴⁺‐ and Fe³⁺‐stabilized films, respectively), film loss is negligible. This provides a stark contrast with non‐stabilized films, which disassemble almost immediately upon exposure to pH 7.1. This method represents a simple and effective strategy for stabilizing hydrogen‐bonded structures non‐covalently. Further, the multivalent ions also render the films responsive to changes in the local redox environment, as demonstrated by film disassembly after exposure of Fe³⁺‐treated films to iodide solutions.     

Label‐Free Bioanalysis Based on Low‐Q Whispering Gallery Modes: Rapid Preparation of Microsensors by Means of Layer‐by‐Layer Technology

Low‐Q‐whispering gallery modes (low‐Q‐WGM) can be used for label‐free detection of interactions between biomolecules, measuring their binding and release kinetics or for analysis of changes in the medium in real‐time. The main advantage of the low‐Q‐WGM approach over other label‐free methods is the possibility of measurements in small cavities as the method uses microparticles down to 6 µm as sensors. Commercially available dye‐doped microparticles that are used as low‐Q‐WGM sensors exhibit several drawbacks. Therefore, alternative particle types are developed and optimized as low‐Q‐WGM sensors. First, dye‐doped particles made of different materials are screened. The most critical parameter for WGM performance is the refractive index (RI) of sensor particles. Furthermore, surface roughness of particles, determined by scanning electron microscopy and atomic force microscopy, affects their performance as WGM microsensors. In the second test, fluorescent dyes immobilized on nonfluorescent particles by means of nanometer thick layer‐by‐layer (LbL) films are shown to generate a strong WGM signal. The LbL‐coated particles show remarkably less background fluorescence than dye‐doped particles and are easier to prepare. Finally, this article proposes rapid preparation methods for WGM microparticle sensors based on various parameters such as material type, RI, surface roughness, and number of coated polymer layers.     

Tailorable Thermal Properties Through Reactive Blending Using Orthogonal Chemistries and Layer‐by‐Layer Deposition of Poly(1,3,5‐hexahydro‐1,3,5‐triazine) Networks

The ability to tune both the thermal and mechanical properties of poly(1,3,5‐hexahydro‐1,3,5‐triazine)s (PHTs) is critical to meet the increasingly stringent demands of structural materials. To this end, PHTs are modified during the process of vitrification using a reactive blending technique. Two strategies are employed: (i) the incorporation of a monomer or oligomer that contains amino end groups that are integrated into the network via hemiaminal chemistry and (ii) the incorporation of functional monomers bearing reactive end groups capable of self‐polymerization, as well as insertion by copolymerization with the PHT‐forming reagents to form mixed networks. Both strategies produce homogeneous materials, mitigating any adverse thermal properties of the parent PHT material. Here, a deposition method bringing the PHT technology platform to more diverse, economical and large‐scale applications is also introduced. A unique layer‐by‐layer spray‐coating approach of solutions containing 4,4′‐oxydianiline (ODA) and multifunctional amines obtained by conjugate addition to acrylates is developed, allowing for the preparation of large‐scale PHT‐polymer blend films. The ODA–PHT enables high strength and modulus of the final material, while incorporation of acrylates provide an economical approach to polymer blends with tremendous functional group diversity and will allow for recyclability under mild conditions.     

Porous Nanofilm Biomaterials Via Templated Layer‐by‐Layer Assembly

Hydrogel‐like biomaterials are often too soft to support robust cell adhesion, yet methods to increase mechanical rigidity (e.g., covalent cross‐linking the gel matrix) can compromise bioactivity by suppressing the accessibility or activity of embedded biomolecules. Nanoparticle templating is reported here as a strategy toward porous, layer‐by‐layer assembled, thin polyelectrolyte films of sufficient mechanical rigidity to promote strong initial cell adhesion, and that are capable of high bioactive species loading. Latex nanoparticles are incorporated during layer‐by‐layer assembly, and following 1‐ethyl‐3‐[3‐dimethylaminopropyl]carbodiimide/N‐hydroxysulfosuccinimide (EDC‐NHS) cross‐linking of the polyelectrolyte film, are removed via exposure to tetrahydrofuran (THF). THF exposure results in only a partial reduction in film thickness (as observed by ellipsometry), suggesting the presence of internal pore space. The attachment, spreading, and metabolic activity of pre‐osteoblastic MC3T3‐E1 cells cultured on templated, cross‐linked films are statistically similar to those on non‐templated films, and much greater than those on non‐cross‐linked films. Laser scanning confocal microscopy and quartz crystal microgravimetry indicate a high capacity for bioactive species loading (ca. 10% of film mass) in nanoparticle templated films. Porous nanofilm biomaterials, formed via layer‐by‐layer assembly with nanoparticle templating, promote robust cell adhesion and exhibit high bioactive species loading, and thus appear to be excellent candidates for cell‐contacting applications.     

Percolation‐Controlled Metal/Polyelectrolyte Complexed Films for All‐Solution‐Processable Electrical Conductors

The use of solution‐processable electrically conducting films is imperative for realizing next‐generation flexible and wearable devices in a large‐scale and economically viable way. However, the conventional approach of simply complexing metallic nanoparticles with a polymeric medium leads to a tradeoff between electrical conductivity and material properties. To address this issue, in this study, a novel strategy is presented for fabricating all‐solution‐processable conducting films by means of metal/polyelectrolyte complexation to achieve controlled electrical percolation; this simultaneously imparts superior electrical conductivity and good mechanical properties. A polymeric matrix comprised of polyelectrolyte multilayers is first formed using layer‐by‐layer assembly, and then Ag nanoparticles are gradually synthesized and gradationally distributed inside the polymeric matrix by means of a subsequent procedure of repeated cationic exchange and reduction. During this process, electrical percolation between Ag nanoparticles and networking of electrical pathways is facilitated in the surface region of the complexed film, providing outstanding electrical conductivity only one order of magnitude less than that of metallic Ag. At the same time, the polymer‐rich underlying region imparts strong, yet compliant, binding characteristics to the upper Ag‐containing conducting region while allowing highly flexible mechanical deformations of bending and folding, which consequently makes the system outperform existing materials.     

Enhanced Electrochromism with Rapid Growth Layer‐by‐Layer Assembly of Polyelectrolyte Complexes

In this work, a facile method to deposit fast growing electrochromic multilayer films with enhanced electrochemical properties using layer‐by‐layer (LbL) self‐assembly of complex polyelectrolyte is demonstrated. Two linear polymers, poly(acrylic acid) (PAA) and polyethylenimine (PEI), are used to formulate stable complexes under specific pH to prepare polyaniline (PANI)/PAA‐PEI multilayer films via LbL deposition. By introducing polymeric complexes as building blocks, [PANI/PAA‐PEI]_n films grow much faster compared with [PANI/PAA]_n films, which are deposited under the same condition. Unlike the compact [PANI/PAA]_n films, [PANI/PAA‐PEI]_n films exhibit porous structure that is beneficial to the electrochemical process and leads to improved electrochromic properties. An enhanced optical modulation of 30% is achieved with [PANI/PAA‐PEI]₃₀ films at 630 nm compared with the lower optical modulation of 11% measured from [PANI/PAA]₃₀ films. The switching time of [PANI/PAA‐PEI]₃₀ films is only half of that of [PANI/PAA]₃₀ films, which indicates a faster redox process. Utilizing polyelectrolyte complexes as building blocks is a promising approach to prepare fast growing LbL films for high performance electrochemical device applications.     

Tubular Titania Nanostructures via Layer‐by‐Layer Self‐Assembly

Nanostructured titania‐polyelectrolyte composite and pure anatase and rutile titania tubes were successfully prepared by layer‐by‐layer (LbL) deposition of a water‐soluble titania precursor, titanium(IV ) bis(ammonium lactato) dihydroxide (TALH) and the oppositely charged poly(ethylenimine) (PEI) to form multilayer films. The tube structure was produced by depositing inside the cylindrical pores of a polycarbonate (PC) membrane template, followed by calcination at various temperatures. The morphology, structure and crystal phase of the titania tubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and UV‐vis absorbance measurements. The as‐prepared anatase titania tubes exhibit very promising photocatalytic properties, demonstrated by the degradation of the azodye methyl orange (MO) as a model molecule. They are also easily separated from the reaction system by simple filtration or centrifugation, allowing for straightforward recycling. The reported strategy provides a simple and versatile technique to fabricate titania based tubular nanostructures, which could easily be extended to prepare tubular structures of other materials and may find application in catalysis, chemical sensing, and nanodevices.     

Preparation of Protamine–Titania Microcapsules Through Synergy Between Layer‐by‐Layer Assembly and Biomimetic Mineralization

A novel approach combining layer‐by‐layer (LbL) assembly with biomimetic mineralization is proposed to prepare protamine–titiania hybrid microcapsules. More specifically, these microcapsules are fabricated by alternative deposition of positively charged protamine layers and negatively charged titania layers on the surface of CaCO₃ microparticles, followed by dissolution of the CaCO₃ microparticles using EDTA. During the deposition process, the protamine layer induces the hydrolysis and condensation of a titania precursor, to form the titania layer. Thereafter, the negatively charged titania layer allows a new cycle of deposition step of the protamine layer, which ensures a continuous LbL process. The morphology, structure, and chemical composition of the microcapsules are characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, and X‐ray photoelectron spectroscopy. Moreover, these protamine–titania hybrid microcapsules are first employed as the carrier for the immobilization of yeast alcohol dehydrogenase (YADH), and the encapsulated YADH displays enhanced recycling stability. This approach may open a facile, general, and efficient way to prepare organic–inorganic hybrid materials with different compositions and shapes.