Layer‐by‐Layer Hydrogen‐Bonded Polymer Films: From Fundamentals to Applications

Recent years have seen increasing interest in the construction of nanoscopically layered materials involving aqueous‐based sequential assembly of polymers on solid substrates. In the booming research area of layer‐by‐layer (LbL) assembly of oppositely charged polymers, self‐assembly driven by hydrogen bond formation emerges as a powerful technique. Hydrogen‐bonded (HB) LbL materials open new opportunities for LbL films, which are more difficult to produce than their electrostatically assembled counterparts. Specifically, the new properties associated with HB assembly include: 1) the ease of producing films responsive to environmental pH at mild pH values, 2) numerous possibilities for converting HB films into single‐ or two‐component ultrathin hydrogel materials, and 3) the inclusion of polymers with low glass transition temperatures (e.g., poly(ethylene oxide)) within ultrathin films. These properties can lead to new applications for HB LbL films, such as pH‐ and/or temperature‐responsive drug delivery systems, materials with tunable mechanical properties, release films dissolvable under physiological conditions, and proton‐exchange membranes for fuel cells. In this report, we discuss the recent developments in the synthesis of LbL materials based on HB assembly, the study of their structure–property relationships, and the prospective applications of HB LbL constructs in biotechnology and biomedicine.     

层层自组装法制备肝素微囊及其性能研究

以海藻酸钙微核为模板,采用带正电荷的聚稀丙基铵盐酸盐(PAH)和带负电荷的肝素钠(HEP),通过层层自组装(Layer-by-layer,LbL)技术构建具有多层膜结构和抗凝血活性的药物微囊.采用荧光倒置显微镜、SEM、动态光散射仪、Zeta电位仪和抗凝血仪等进行表征.结果表明,制备的海藻酸钙微核粒径约为1.5μm,尺寸均匀、分散性佳;以ALG为模板制得的LbL微囊具备典型的核壳式结构;Zeta电位检测表明,随包膜层数的增加,微囊的电位呈正负交替的变化趋势;通过体外凝血时间(PT、APtt、TT)检测微囊抗凝血活性,比较了分别以PAH和HEP作为最外层时的生物活性,其中以HEP为最外层的显著增强了材料的抗凝血性能,同时随着组装层数的增加,也提高了微囊的抗凝血性能.     

Graphene–Graphene Oxide Floating Gate Transistor Memory

A novel transparent, flexible, graphene channel floating‐gate transistor memory (FGTM) device is fabricated using a graphene oxide (GO) charge trapping layer on a plastic substrate. The GO layer, which bears ammonium groups (NH₃⁺), is prepared at the interface between the crosslinked PVP (cPVP) tunneling dielectric and the Al₂O₃ blocking dielectric layers. Important design rules are proposed for a high‐performance graphene memory device: i) precise doping of the graphene channel, and ii) chemical functionalization of the GO charge trapping layer. How to control memory characteristics by graphene doping is systematically explained, and the optimal conditions for the best performance of the memory devices are found. Note that precise control over the doping of the graphene channel maximizes the conductance difference at a zero gate voltage, which reduces the device power consumption. The proposed optimization via graphene doping can be applied to any graphene channel transistor‐type memory device. Additionally, the positively charged GO (GO–NH₃⁺) interacts electrostatically with hydroxyl groups of both UV‐treated Al₂O₃ and PVP layers, which enhances the interfacial adhesion, and thus the mechanical stability of the device during bending. The resulting graphene–graphene oxide FGTMs exhibit excellent memory characteristics, including a large memory window (11.7 V), fast switching speed (1 μs), cyclic endurance (200 cycles), stable retention (10⁵ s), and good mechanical stability (1000 cycles).     

Enzyme microcapsules with substrate selective permeability constructed via layer-by-layer polyelectrolyte self-assembly

Polyelectrolyte multilayer microcapsules with entrapped horseradish peroxidase (HRP) have been prepared via a layer-by-layer (LbL) self-assembly strategy of polycation and polyanion on CaCO₃ microparticles as templates. Preparation conditions have been studied and optimized. Within the investigated ranges, use of buffer solutions with lower pH value or lower ionic strength in the buffer solution for polyelectrolyte self-assembly has resulted in thinner polyelectrolyte film and higher permeability of the microcapsules. For dissolving the CaCO₃ templates, use of weakly acidic (pH 4.0) buffer solution in place of routinely used EDTA reagent has improved the catalytic activity of microcapsules. The HRP-containing microcapsules have exhibited catalytic activity to pyrogallol as substrate, while the catalytic activity to 2,2′-azino-bis(3-ethylbenz-thiazoline-6-sulfonic acid) (ABTS) was severely suppressed. No less than 90% of the maximum enzymatic activity to pyrogallol has remained after 30 days. Promising prospects in various biocatalysis applications have been expected for the enzyme microcapsules, due to their selective permeability, stability and reusability.     

Controllable Bipolar Doping of Graphene with 2D Molecular Dopants

The fine control of graphene doping levels over a wide energy range remains a challenging issue for the electronic applications of graphene. Here, the controllable doping of chemical vapor deposited graphene, which provides a wide range of energy levels (shifts up to ± 0.5 eV), is demonstrated through physical contact with chemically versatile graphene oxide (GO) sheets, a 2D dopant that can be solution‐processed. GO sheets are a p‐type dopant due to their abundance of electron‐withdrawing functional groups. To expand the energy window of GO‐doped graphene, the GO surface is chemically modified with electron‐donating ethylene diamine molecules. The amine‐functionalized GO sheets exhibit strong n‐type doping behaviors. In addition, the particular physicochemical characteristics of the GO sheets, namely their sheet sizes, number of layers, and degree of oxidation and amine functionality, are systematically varied to finely tune their energy levels. Finally, the tailor‐made GO sheet dopants are applied into graphene‐based electronic devices, which are found to exhibit improved device performances. These results demonstrate the potential of GO sheet dopants in many graphene‐based electronics applications.     

Biocompatible Smart Microcapsules Based on Chitosan‐Poly(vinyl alcohol) Copolymers for Cultivation of Animal Cells

In this study, two novel chitosan‐graft‐poly(vinyl alcohol) copolymers are synthesized and used as water‐soluble at physiological conditions polycations for preparation of smart microcapsules. The microcapsules provide growth and proliferation of eight mammalian cell lines, including hybridoma and tumor cells, at long‐term cell cultivation in vitro. The microcapsules are stable in cell culture medium but can be dissolved by changing pH value of the medium (up to 8.0–8.2), thus making possible a simple release of the entrapped cells. Monoclonal antibody production by encapsulated hybridoma cells is demonstrated. Cultivation of tumor cells within the microcapsules allows the formation of 3D multicellular spheroids, which can be proposed as an in vitro model for anticancer drug screening.     

Microstructure and mechanical properties of silk from different components of the Antheraea pernyi cocoon

Silk fibres from different components of the Antheraea pernyi silkworm cocoon, namely peduncle, outer floss, and cocoon shells (outermost layer and pelade layer) were studied in detail to gain insights into the structure–property–function relationship. Among the fibres from different components, peduncle fibres are the softest with the largest viscoelastic lag, which may reduce the oscillation amplitude when a cocoon hangs on a twig. Fibres from the outermost layer are the toughest and have the largest breaking energy. Outer floss fibres have the highest content of sericin (about 11.98%) but their hardness and elasticity are intermediate. Pelade fibres are shape – preservable and stable with superior hardness and elasticity. The understanding of the properties of different silk fibres is essential for understanding their respective roles in the function of a silk cocoon and will also inspire new designs of protective materials under stringent environmental conditions.     

Fabrication of Supported AuPt Alloy Nanocrystals with Enhanced Electrocatalytic Activity for Formic Acid Oxidation through Conversion Chemistry of Layer‐Deposited Pt2+ on Au Nanocrystals

The exploitation of nanoconfined conversion of Au‐ and Pt‐containing binary nanocrystals for developing a controllable synthesis of surfactant‐free AuPt nanocrystals with enhanced formic acid oxidation (FAO) activity is reported, which can be stably and evenly immobilized on various support materials to diversify and optimize their electrocatalytic performance. In this study, an atomic layer of Pt²⁺ species is discovered to be spontaneously deposited in situ on the Au nanocrystal generated from a reverse‐microemulsion solution. The resulting Au/Pt²⁺ nanocrystal thermally transforms into a reduced AuPt alloy nanocrystal during the subsequent solid‐state conversion process within the SiO₂ nanosphere. The alloy nanocrystals can be isolated from SiO₂ in a surfactant‐free form and then dispersedly loaded on the carbon sphere surface, allowing for the production of a supported electrocatalyst that exhibits much higher FAO activity than commercial Pt/C catalysts. Furthermore, by involving Fe₃O₄ nanocrystals in the conversion process, the AuPt alloy nanocrystals can be grown on the oxide surface, improving the durability of supported metal catalysts, and then uniformly loaded on a reduced graphene oxide (RGO) layer with high electroconductivity. This produces electrocatalytic AuPt/Fe₃O₄/RGO nanocomposites whose catalyst‐oxide‐graphene triple‐junction structure provides improved electrocatalytic properties in terms of both activity and durability in catalyzing FAO.     

Thermoplasmonic‐Triggered Release of Loads from DNA‐Modified Hydrogel Microcapsules Functionalized with Au Nanoparticles or Au Nanorods

Microcapsules consisting of hydrogel shells cross‐linked by glucosamine–boronate ester complexes and duplex nucleic acids, loaded with dyes or drugs and functionalized with Au nanoparticles (Au NPs) or Au nanorods (Au NRs), are developed. Irradiation of Au NPs or Au NRs results in the thermoplasmonic heating of the microcapsules, and the dissociation of the nucleic acid cross‐linkers. The separation of duplex nucleic acid cross‐linkers leads to low‐stiffness hydrogel shells, allowing the release of loads. Switching off the light‐induced plasmonic heating results in the regeneration of stiff hydrogel shells protecting the microcapsules, leading to the blockage of release processes. The thermoplasmonic release of tetramethylrhodamine‐dextran, Texas Red‐dextran, doxorubicin‐dextran (DOX‐D), or camptothecin‐carboxymethylcellulose (CPT‐CMC) from the microcapsules is introduced. By loading the microcapsules with two different drugs (DOX‐D and CPT‐CMC), the light‐controlled dose release is demonstrated. Cellular experiments show efficient permeation of Au NPs/DOX‐D or Au NRs/DOX‐D microcapsules into MDA‐MB‐231 cancer cells and inefficient uptake by MCF‐10A epithelial breast cells. Cytotoxicity experiments reveal selective thermoplasmon‐induced cytotoxicity of the microcapsules toward MDA‐MB‐231 cancer cells as compared to MCF‐10A cells. Also, selective cytotoxicity towards MDA‐MB‐231 cancer cells upon irradiation of the Au NPs‐ and Au NRs‐functionalized microcapsules at λ = 532 or 910 nm is demonstrated.     

Zwitterionic Conjugated Surfactant Functionalization of Graphene with pH‐Independent Dispersibility: An Efficient Electron Mediator for the Oxygen Evolution Reaction in Acidic Media

The functionalization of graphene has been extensively used as an effective route for modulating the surface property of graphene, and enhancing the dispersion stability of graphene in aqueous solutions via functionalization has been widely investigated to expand its use for various applications across a range of fields. Herein, an effective approach is described for enhancing the dispersibility of graphene in aqueous solutions at different pH levels via non‐covalent zwitterion functionalization. The results show that a surfactant with electron‐deficient carbon atoms in its backbone structure and large π–π interactive area enables strong interactions with graphene, and the zwitterionic side terminal groups of the molecule support the dispersibility of graphene in various pH conditions. Experimental and computational studies confirm that perylene diimide amino N‐oxide (PDI–NO) allows efficient functionalization and pH‐independent dispersion of graphene enabled by hydration repulsion effects induced by PDI–NO. The PDI–NO functionalized graphene is successfully used in the oxygen evolution reaction as an electron mediator for boosting the electrocatalytic activity of a Ru‐based polyoxometalate catalyst in an acidic medium. The proposed strategy is expected to bring significant advances in producing highly dispersible graphene in aqueous medium with pH‐independent stability, thus broadening the application range of graphene.     

Highly Stable Potassium Metal Anodes with Controllable Thickness and Area Capacity

K metal battery is a kind of high-energy-density storage device with economic advantages. However, due to the dendrite growth and difficult processing characteristics, it is difficult to prepare stable K metal anode with thin thickness and fixed area capacity, which severely limits its development. In this work, a multi-functional 3D skeleton (rGCA) is synthesized by simple vacuum filtration and thermal reduction, and K metal anodes with controllable thickness and area capacity (K content) can be fabricated by changing the raw material mass and graphene layer spacing of rGCA. Moreover, the graphene sheet layer of rGCA can relax stress and relieve volume expansion; carbon nanotubes can serve as the fast transport channel of electrons, reducing internal impedance and local current density; Ag nanoparticles can induce the uniform nucleation and deposition of K⁺. The K metal composite anodes (rGCA-K) based on the conductive skeleton can effectively suppress dendrites and exhibit excellent electrochemical performance in symmetric and full cells. The controllable fabrication process of stable K metal anode is expected to help K metal batteries move toward the stage of commercial production.     

Fabrication of graphene thin films based on layer-by-layer self-assembly of functionalized graphene nanosheets

In this study, we present a facile means of fabricating graphene thin films via layer-by-layer (LbL) assembly of charged graphene nanosheets (GS) based on electrostatic interactions. To this end, graphite oxide (GO) obtained from graphite powder using Hummers method is chemically reduced to carboxylic acid-functionalized GS and amine-functionalized GS to perform an alternate LbL deposition between oppositely charged GSs. Specifically, for successful preparation of positively charged GS, GOs are treated with an intermediate acyl-chlorination reaction by thionyl chloride and a subsequent amidation reaction in pyridine, whereby a stable GO dispersibility can be maintained within the polar reaction solvent. As a result, without the aid of additional hybridization with charged nanomaterials or polyelectrolytes, the oppositely charged graphene nanosheets can be electrostatically assembled to form graphene thin films in an aqueous environment, while obtaining controllability over film thickness and transparency. Finally, the electrical property of the assembled graphene thin films can be enhanced through a thermal treatment process. Notably, the introduction of chloride functions during the acyl-chlorination reaction provides the p-doping effect for the assembled graphene thin films, yielding a sheet resistance of 1.4 kΩ/sq with a light transmittance of 80% after thermal treatment. Since the proposed method allows for large-scale production as well as elaborate manipulation of the physical properties of the graphene thin films, it can be potentially utilized in various applications, such as transparent electrodes, flexible displays and highly sensitive biosensors.     

Experimental and computational investigation of reduced graphene oxide nanoplatelets stabilized in poly(styrene sulfonate) sodium salt

The production of large-area interfaces and the use of scalable methods to build up designed nanostructures generating advanced functional properties are of high interest for many materials science applications. Nevertheless, large-area coverage remains a major problem even for pristine graphene, and here we present a hybrid, composite graphene-like material soluble in water that can be exploited in many areas such as energy storage, electrodes fabrication, selective membranes and biosensing. Graphene oxide (GO) was produced by the traditional Hummers’ method being further reduced in the presence of poly(styrene sulfonate) sodium salt (PSS), thus creating stable reduced graphene oxide (rGO) nanoplatelets wrapped by PSS (GPSS). Molecular dynamics simulations were carried out to further clarify the interactions between PSS molecules and rGO nanoplatelets, with calculations supported by Fourier transform infrared spectroscopy analysis. The intermolecular forces between rGO nanoplatelets and PSS lead to the formation of a hybrid material (GPSS) stabilized by van der Waals forces, allowing the fabrication of high-quality layer-by-layer (LbL) films with poly(allylamine hydrochloride) (PAH). Raman and electrical characterizations corroborated the successful modifications in the electronic structures from GO to GPSS after the chemical treatment, resulting in (PAH/GPSS) LbL films four orders of magnitude more conductive than (PAH/GO).     

Biomimetic Extracellular Environment Based on Natural Origin Polyelectrolyte Multilayers

Surface modification of biomaterials is a well‐known approach to enable an adequate biointerface between the implant and the surrounding tissue, dictating the initial acceptance or rejection of the implantable device. Since its discovery in early 1990s layer‐by‐layer (LbL) approaches have become a popular and attractive technique to functionalize the biomaterials surface and also engineering various types of objects such as capsules, hollow tubes, and freestanding membranes in a controllable and versatile manner. Such versatility enables the incorporation of different nanostructured building blocks, including natural biopolymers, which appear as promising biomimetic multilayered systems due to their similarity to human tissues. In this review, the potential of natural origin polymer‐based multilayers is highlighted in hopes of a better understanding of the mechanisms behind its use as building blocks of LbL assembly. A deep overview on the recent progresses achieved in the design, fabrication, and applications of natural origin multilayered films is provided. Such films may lead to novel biomimetic approaches for various biomedical applications, such as tissue engineering, regenerative medicine, implantable devices, cell‐based biosensors, diagnostic systems, and basic cell biology.     

Film Structure of Epitaxial Graphene Oxide on SiC: Insight on the Relationship Between Interlayer Spacing,Water Content,and Intralayer Structure

Chemical oxidation of multilayer graphene grown on silicon carbide yields films exhibiting reproducible characteristics, lateral uniformity, smoothness over large areas, and manageable chemical complexity, thereby opening opportunities to accelerate both fundamental understanding and technological applications of this form of graphene oxide films. Here, we investigate the vertical inter‐layer structure of these ultra‐thin oxide films. X‐ray diffraction, atomic force microscopy, and IR experiments show that the multilayer films exhibit excellent inter‐layer registry, little amount (<10%) of intercalated water, and unexpectedly large interlayer separations of about 9.35 Å. Density functional theory calculations show that the apparent contradiction of “little water but large interlayer spacing in the graphene oxide films” can be explained by considering a multilayer film formed by carbon layers presenting, at the nanoscale, a non‐homogenous oxidation, where non‐oxidized and highly oxidized nano‐domains coexist and where a few water molecules trapped between oxidized regions of the stacked layers are sufficient to account for the observed large inter‐layer separations. This work sheds light on both the vertical and intra‐layer structure of graphene oxide films grown on silicon carbide, and more in general, it provides novel insight on the relationship between inter‐layer spacing, water content, and structure of graphene/graphite oxide materials.     

Single‐ and Double‐Sided Chemical Functionalization of Bilayer Graphene

An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X‐ray photoelectron spectroscopy. Single‐ and double‐sided chemical functionalization are found to give very different results: single‐sided modified bilayers show relatively high mobility (200–600 cm² V^?1 s^?1 at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double‐sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single‐sided modification of bilayers) for sensors and transistors and new graphene‐derivatives materials (through double‐sided modification).     

Automated Buildup of Biomimetic Films in Cell Culture Microplates for High‐Throughput Screening of Cellular Behaviors

An automatic method is established for layer‐by‐layer (LbL) assembly of biomimetic coatings in cell culture microplates using a commercial liquid‐handling robot. Highly homogeneous thin films are formed at the bottom of each microwell. The LbL film‐coated microplates are compatible with common cellular assays, using microplate readers and automated microscopes. Cellular adhesion is screened on crosslinked and peptide‐functionalized LbL films and stem cell differentiation in response to increasing doses of bone morphogenetic proteins (2, 4, 7, 9). This method paves the way for future applications of LbL films in cell‐based assays for regenerative medicine and high‐throughput drug screening.     

Monitoring the layer-by-layer self-assembly of graphene and graphene oxide by spectroscopic ellipsometry

Thin films of graphene oxide, graphene and copper (II) phthalocyanine dye have been successfully fabricated by electrostatic layer-by-layer (LbL) assembly approach. We present the first variable angle spectroscopic ellipsometry (VASE) investigation on these graphene-dye hybrid thin films. The thickness evaluation suggested that our LbL assembly process produces highly uniform and reproducible thin films. We demonstrate that the refractive indices of the graphene-dye thin films undergo dramatic variation in the range close to the absorption of the dyes. This investigation provides new insight to the optical properties of graphene containing thin films and shall help to establish an appropriate optical model for graphene-based hybrid materials.     

High Detectivity Graphene‐Silicon Heterojunction Photodetector

A graphene/n‐type silicon (n‐Si) heterojunction has been demonstrated to exhibit strong rectifying behavior and high photoresponsivity, which can be utilized for the development of high‐performance photodetectors. However, graphene/n‐Si heterojunction photodetectors reported previously suffer from relatively low specific detectivity due to large dark current. Here, by introducing a thin interfacial oxide layer, the dark current of graphene/n‐Si heterojunction has been reduced by two orders of magnitude at zero bias. At room temperature, the graphene/n‐Si photodetector with interfacial oxide exhibits a specific detectivity up to 5.77 × 10¹³ cm Hz^1/2 W^‐1 at the peak wavelength of 890 nm in vacuum, which is highest reported detectivity at room temperature for planar graphene/Si heterojunction photodetectors. In addition, the improved graphene/n‐Si heterojunction photodetectors possess high responsivity of 0.73 A W^?1 and high photo‐to‐dark current ratio of ≈10⁷. The current noise spectral density of the graphene/n‐Si photodetector has been characterized under ambient and vacuum conditions, which shows that the dark current can be further suppressed in vacuum. These results demonstrate that graphene/Si heterojunction with interfacial oxide is promising for the development of high detectivity photodetectors.     

Scallop‐Inspired Shell Engineering of Microparticles for Stable and High Volumetric Capacity Battery Anodes

Building stable and efficient electron and ion transport pathways are critically important for energy storage electrode materials and systems. Herein, a scallop‐inspired shell engineering strategy is proposed and demonstrated to confine high volume change silicon microparticles toward the construction of stable and high volumetric capacity binder‐free lithium battery anodes. As for each silicon microparticle, the methodology involves an inner sealed but adaptable overlapped graphene shell, and an outer open hollow shell consisting of interconnected reduced graphene oxide, mimicking the scallop structure. The inner closed shell enables simultaneous stabilization of the interfaces of silicon with both carbon and electrolyte, substantially facilitates efficient and rapid transport of both electrons and lithium ions from/to silicon, the outer open hollow shell creates stable and robust transport paths of both electrons and lithium ions throughout the electrode without any sophisticated additives. The resultant self‐supported electrode has achieved stable cycling with rapidly increased coulombic efficiency in the early stage, superior rate capability, and remarkably high volumetric capacity upon a facile pressing process. The rational design and engineering of graphene shells of the silicon microparticles developed can provide guidance for the development of a wide range of other high capacity but large volume change electrochemically active materials.