The excellent potential of organic polymeric materials in the biomedical field could be exploited if their interfacial problem could be fully resolved. A necessary prerequisite to this purpose often involves the simple but effective synthesis of a bioactive surface to endow polymer surfaces with high reactivity toward efficient biomolecules conjugation and a bioinert surface to prevent nonspecific adsorption of nontarget biomolecules. Although the corresponding research has been an important topic, actually few strategies could pave the way to comprehensively and simply tackle both of the bioactive and bioinert surfaces preparation issues. Herein we report an extremely simple and integrative bifunctional method that could efficiently tailor an organic material surface toward both bioactive and bioinert functions. This method is based on the use of an amides-initiated photochemical reaction in a confined space, which depending on the type of solutes used, results in the incorporation of primary amine groups or surface carbon radicals on an inert polymer surface. The grafted amine group could be used as a highly reactive site for biomolecule conjugation, and the surface carbon radical could be used to initiate radical graft polymerization of antifouling polymer brushes. We expect this simple but powerful method could provide a general resolution to solve the interfacial problem of organic substrate, offering a low-cost practical approach for real biomedical applications.

The use of antimicrobial materials, for example, silver nanoparticles, has been a cause for concern because they often exert an adverse effect on environmental and safety during their preparation and use. In this study, we report a class of green antimicrobial coating based on a supramolecular assembly of a protein extracted from daily food, without the addition of any other hazardous agents. It is found that a self-assembled nanofilm by mere hen egg white lysozyme has durable in vitro and in vivo broad-spectrum antimicrobial efficacy against Gram-positive/negative and fungi. Such enhanced antimicrobial capability over native lysozyme is attributed to a synergistic combination of positive charge and hydrophobic amino acid residues enriched on polymeric aggregates in the lysozyme nanofilm. Accompanied with high antimicrobial activity, this protein-based PTL material simultaneously exhibits the integration of multiple functions including antifouling, antibiofilm, blood compatibility, and low cytotoxicity due to the existence of surface hydration effect. Moreover, the bioinspired adhesion mediated by the amyloid structure contained in the nanofilm induces robust transfer and self-adhesion of the material onto virtually arbitrary substrates by a simple one-step aqueous coating or solvent-free printing in 1 min, thereby allowing an ultrafast route into practical implications for surface-functionalized commodity and biomedical devices. Our results demonstrate that the application of pure proteinaceous substance may afford a cost-effective green biomaterial that has high antimicrobial activity and low environmental impact.Keywords: antimicrobial; biocompatibility; lysozyme; protein phase transition; surface coating;

AbstractMacromolecular crystallization has many implications in biological and materials science. Similar to the crystallization of other molecules, macromolecular crystallization conventionally considers a critical nucleus, followed by crystallographic packing of macromolecules to drive further crystal growth. Herein, we discover a distinctive macromolecular crystallization pathway by developing the concept of a macromolecular mesocrystal. This nonclassical polymer crystallization occurs through the mesoscale self-assembly of (bio)macromolecular nanocrystals. The new concept for macromolecular crystallization presented herein is fundamental and relevant to many fields, including materials science, chemistry, biomimetics, nanoscience, and structural biology.

The paper summarizes and discusses the recent advances of proteins as functional interlayers in organic field-effect transistors (OFETs). Specific focus is given on the proteins integrated into the device structure, either to act as dielectric materials or to perform as the functional interlayer between the dielectric and the organic semiconductor (OSC). The main emphasis is give to the location and the specific effect of protein layers in the structure of OFETs. Besides, the possibility of amyloid serving as useful building blocks for OFET is discussed.A series of studies suggested that some natural proteins can actually simplify the fabrication process, reduce the costs and enhance the performance of the devices when they were used as dielectric layer, dielectric/semiconductor interlayer, and top gate in organic field-effect transistors (OFETs).

Based on a concept of a smooth and steady landing of fragile objects without destruction via a soft cushion, we have developed a model for the soft landing of deformable lipid giant unilamellar vesicles (GUVs) on solid surfaces. The foundation for a successful soft landing is a solid substrate with a two-layer coating, including a bottom layer of positively charged lysozymes and an upper lipid membrane layer. We came to a clear conclusion that anionic GUVs when sedimented on a surface, the vesicle rupture occurs upon the direct contact with the positively charged lysozyme layer due to the strong coulombic interactions. In contrast, certain separation distances was achieved by the insertion of a soft lipid membrane cushion between the charged GUVs and the lysozyme layer, which attenuated the coulombic force and created a mild buffer zone, ensuring the robust capture of GUVs on the substrate without their rupture. The non-covalent bonding facilitated a fully reversible stimuli-responsive capture/release of GUVs from the biomimetic solid surface, which has never been demonstrated before due to the extreme fragility of GUVs. Moreover, the controllable capture/release of cells has been proven to be of vital importance in biotechnology, and similarity the present approach to capture/release cells is expected to open the previously inaccessible avenues of research.

Self-assembled monolayers (SAMs) have been widely employed as etching resists in wet lithography systems to form patterns in which the ordered molecular packing of the SAM regions significantly delays the etchant attack. A generally accepted recognition is that the SAMs ability to resist etching is positively correlated to the quality of the surface-assembled structures, and a more ordered molecular packing would correspond to a better etching resistance. Such a classical belief is debated in the present work by providing an alternative SAM-assisted negative lithography where ordered SAM regions are etched more quickly than their disordered counterparts. This method features a unique photoirradiation-imprinted patterning process that simply consists of two steps: (1) UV irradiation on an OH-terminated SAM-modified gold surface through a photomask and (2) the subsequent immersion of the exposed substrate in an aqueous etching solution of N-bromosuccinimide/pyridine to develop a wet lithographic pattern. The entire experimental process reveals a finding from previous work that the etching rate on the UV-exposed regions with disordered molecular packing could be modulated to be slower than that in the unexposed well-defined SAM regions. Longer irradiation times would also revert the patterns from negative to positive. Thus, by merely using one kind of SAM-modified surface to provide both positive and negative micropatterns on gold layers, one could obtain flexible opportunities for high-resolution micro/nanofabrication resembling photolithography.

It may be hardly believable that inert C–H bonds on a polymeric material surface could be quickly and efficiently transformed into C–OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C–H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C–H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C–H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C–H bonds to C–OSO3– and, subsequently, to C–OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl groups preserve their own reactivity toward other complementary compounds, thus creating a novel base with distinct surface properties. Thanks to this functionalized platform, a wide range of organic, inorganic and metal materials have been attached to conventional organic polymer substrates through the rational engineering of surface molecular templates from small functional groups to macromolecules. It is expected that the proposed novel CPO method and its versatile usages in advanced material applications will offer new opportunities for a variety of scientific communities, especially for those working on surface/interface modulation.Keywords: hydroxylation; organic−inorganic hybrid material; patterning; photochemical reaction; polymer functionalization; Surface modification;

The well-controlled material assembly and patterning on indium tin oxide (ITO) coating layer is of great importance for the practical fabrication of a functional device. Nonetheless, the conventional way to achieve this aim is still mainly based on the combination of photolithography with pattern transfer techniques (e.g., wet/dry etching, μCP) due to the lack of one method that is able to directly afford site-selective ITO surface tailoring and subsequent templating for material assembly. Herein, we reported a novel, fast, and efficient photochemical reaction to accurately tailor the surface property of ITO with light-controlled site-selectivity, thus resulting in direct photoresist-free and etching/contact-free lithographic patterning of building blocks, e.g., ZnO, BaTiO3, CdS, lipid membrane, conductive polymers, colloids, and liquid crystals. The entire process reveals new interfacial chemistry suitable for inorganic metal oxide and its important versatile implications for low-cost fabrication of large-area flat and flexible optical/electronic/biorelated devices.

In Nature, certain organisms can perform microbial corrosion on base metals by oxidation of neutral metallic atoms (H. L. Ehrlich, Appl. Microbiol. Biotechnol., 1997). Herein we describe the first discovery of biological nucleic acids able to catalyze and mediate gold oxidation from neutral Au0 to trivalent Au(III) under certain oxidative environments provided by mild oxidizing reagent N-bromosuccinimide or amino acids. A new biolithography technique for gold patterning is further developed.

In Nature, certain organisms can perform microbial corrosion on base metals by oxidation of neutral metallic atoms (H. L. Ehrlich, Appl. Microbiol. Biotechnol., 1997). Herein we describe the first discovery of biological nucleic acids able to catalyze and mediate gold oxidation from neutral Au0 to trivalent Au(III) under certain oxidative environments provided by mild oxidizing reagent N-bromosuccinimide or amino acids. A new biolithography technique for gold patterning is further developed.