The last decade of research in the physical sciences has seen a dramatic increase in the study of nanoscale materials. Today, "nanoscience" has emerged as a multidisciplinary effort, wherein obtaining a fundamental understanding of the optical, electrical, magnetic, and mechanical properties of nanostructures promises to deliver the next generation of functional materials for a wide range of applications. While this range of efforts is extremely broad, much of the work has focused on "hard" materials, such as Buckyballs, carbon nanotubes, metals, semiconductors, and organic or inorganic dielectrics. Meanwhile, the soft materials of current interest typically include conducting or emissive polymers for "plastic electronics" applications. Despite the continued interest in these established areas of nanoscience, new classes of soft nanomaterials are being developed from more traditional polymeric constructs. Specifically, nanostructured hydrogels are emerging as a promising group of materials for multiple biotechnology applications as the need for advanced materials in the post-genomic era grows. This review will present some of the recent advances in the marriage between water-swellable networks and nanoscience.

Soft nanotechnology with soft nanoparticles.

Over the past century, hydrogels have emerged as effective materials for an immense variety of applications. The unique network structure of hydrogels enables very high levels of hydrophilicity and biocompatibility, while at the same time exhibiting the soft physical properties associated with living tissue, making them ideal biomaterials. Stimulus-responsive hydrogels have been especially impactful, allowing for unprecedented levels of control over material properties in response to external cues. This enhanced control has enabled groundbreaking advances in healthcare, allowing for more effective treatment of a vast array of diseases and improved approaches for tissue engineering and wound healing. In this extensive review, we identify and discuss the multitude of response modalities that have been developed, including temperature, pH, chemical, light, electro, and shear-sensitive hydrogels. We discuss the theoretical analysis of hydrogel properties and the mechanisms used to create these responses, highlighting both the pioneering and most recent work in all of these fields. Finally, we review the many current and proposed applications of these hydrogels in medicine and industry.

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Stimulus-responsive hydrogels: Theory, modern advances, and applications

Self-cleaning materials have gained considerable attention for both their unique properties and practical applications in energy and environmental areas. Recent examples of many TiO2-derived materials have been illustrated to understand the fundamental principles of self-cleaning hydrophilic and hydrophobic surfaces. Various models including those proposed by Wenzel, Cassie-Baxter and Miwa-Hashimoto are discussed to explain the mechanism of self-cleaning. Examples of semiconductor surfaces exhibiting the simultaneous occurrence of superhydrophilic and superhydrophobic domains on the same surface are illustrated, which can have various advanced applications in microfluidics, printing, photovoltaic, biomedical devices, anti-bacterial surfaces and water purification. Several strategies to improve the efficiency of photocatalytic self-cleaning property have been discussed including doping with metals and non-metals, formation of hetero-junctions between TiO2 and other low bandgap semiconductors, and fabrication of graphene based semiconductor nano-composites. Different mechanisms such as band-gap narrowing, formation of localized energy levels within the bandgap and formation of intrinsic defects such as oxygen vacancies have been suggested to account for the improved activity of doped TiO2 photocatalysts. Various preparation routes for developing efficient superhydrophilic–superhydrophobic patterns have been reviewed. In addition, reversible photo-controlled surfaces with tuneable hydrophilic/hydrophobic properties and its technological applications are discussed. Examples of antireflective surfaces exhibiting self-cleaning properties for the applications in solar cells and flat panel displays have also been provided. Discussion is provided on TiO2 based self-cleaning materials exhibiting hydrophilic and underwater superoleophobic properties and their utilities in water management, antifouling applications and separation of oil in water emulsions are discussed. In addition, ISO testing methods (ISO 27448: 2009, ISO 10678: 2010 and ISO 27447: 2009) for analysing self-cleaning activity and antibacterial action have also been discussed. Rapid photocatalytic self-cleaning testing methods using various photocatalytic activity indicator inks such as resazurin (Rz), basic blue 66 (BB66) and acid violet 7(AV7) for a broad range of materials such as commercial paints, tiles and glasses are also described. Various commercial products such as glass, tiles, fabrics, cement and paint materials developed based on the principle of photo-induced hydrophilic conversion of TiO2 surfaces have also been provided. The wide ranges of practical applications of self-cleaning photocatalytic materials suggest further development to improve their efficiency and utilities. It was concluded that a rational fabrication of multifunctional photocatalytic materials by integrating biological inspired structures with tunable wettability would be favorable to address a number of existing environmental concerns.

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Self-Cleaning Applications of TiO2 by Photo-Induced Hydrophilicity and Photocatalysis

Modification of polyethersulfone membranes – A review of methods

Oil/water separation, especially emulsified oil/water mixture separation, has become a widespread concern because of the severe fouling problem caused by the easy adsorption of oil droplets onto the surfaces of filtration membranes. Many strategies have been employed to eliminate the fouling problem, but it remains a challenge and impedes the development of membrane technology. In this short review, we discuss the recent development of membrane technology for emulsified oil/water separation. As shown in the image, in addition to polymer- and ceramic-dominated traditional membranes, nanomaterial-based membranes have recently demonstrated their superiority and have achieved high performance.

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Recent progress in developing advanced membranes for emulsified oil/water separation

We have successfully prepared monodispersed thermoresponsive core-shell hydrogel microspheres with a mean diameter of 200-400 nm with poly(N-isopropylacrylamide-co-styrene) [P(NIPAM-co-St)] cores and poly(N-isopropylacrylamide) (PNIPAM) shells. The submicrometer-sized monodispersed P(NIPAM-co-St) core seeds were prepared by using a surfactant-free emulsion polymerization method, and the PNIPAM shell layers were fabricated onto the core seeds by using a seed polymerization method. The particle size, morphology and monodispersity, and thermoresponsive characteristics of the prepared microspheres were experimentally studied. In the preparation of P(NIPAM-co-St) seeds, with increasing the initiator dosage, the mean diameters and the dispersal coefficients were almost at the same levels at first; however, when the initiator dosage increased further to a critical amount, the mean diameters decreased drastically and the monodispersity became worse significantly. With increasing the stirring rate, the particle diameter decreased, and when the stirring rate was larger than 600 rpm, the monodispersity became worse obviously. With increasing the phase ratio, the mean diameter became larger simply, and the monodispersity became worse first and then became better again. With increasing the reaction time, the particle sizes nearly did not change, while the monodispersity gradually became better slightly. For the core-shell microspheres, with increasing the NIPAM dosage in the preparation of the PNIPAM shell layers, the mean diameters became larger simply, the monodispersity became better, and the thermoresponsive swelling ratio of the hydrodynamic diameters increased.

Preparation of submicrometer-sized monodispersed thermoresponsive core-shell hydrogel microspheres.

In this paper, we report on a novel family of monodisperse thermo-sensitive core–shell hydrogel microspheres that is featured with high monodispersity and positively thermo-responsive volume phase transition characteristics with tunable swelling kinetics, i.e., the particle swelling is induced by an increase rather than a decrease in temperature. The microspheres were fabricated in a three-step process. In the first step, monodisperse poly(acrylamide-co-styrene) seeds were prepared by emulsifier-free emulsion polymerization. In the second step, poly(acrylamide) or poly[acrylamide-co-(butyl methacrylate)] shells were fabricated on the microsphere seeds by free radical polymerization. In the third step, the core–shell microspheres with poly- (acrylamide)/poly(acrylic acid) based interpenetrating polymer network (IPN) shells were finished by a method of sequential IPN synthesis. The proposed monodisperse core–shell microspheres provide a new mode of the phase transition behavior for thermo-sensitive “smart” or “intelligent” monodisperse micro-actuators that is highly attractive for targeting drug delivery systems, chemical separations, sensors, and so on.

Positively Thermo-Sensitive Monodisperse Core–Shell Microspheres†

This study reports a simple and effective route for the hydrophilic surface modification of ceramic-supported polyethersulfone membranes by synthesizing a poly(vinyl alcohol)/polyamide composite thin surface layer with an interfacial polymerization method. The fabricated membranes were characterized with XPS, SEM, and contact angle measurements, and the effects of hydrophilic surface modification on the membrane flux and oil rejection in the treatment of oil-in-water (O/W) microemulsions were experimentally studied. All the characterizations and filtration results showed that, the hydrophilic surface modification was achieved successfully and consequently reduced the membrane fouling effectively. The presented route is valuable for developing robust membranes with a low level of membrane fouling in the separation of O/W microemulsions.

Surface Modification of Ceramic-Supported Polyethersulfone Membranes by Interfacial Polymerization for Reduced Membrane Fouling

Water-in-water (w/w) emulsions are attractive microcompartmentalized platforms due to their outstanding biocompatibility. To address the main disadvantage of poor stability that hampers their practical application, here we report a novel type of polymer–protein conjugate emulsifier obtained by Schiff base synthesis to stabilize w/w emulsions. In particular, the proposed mild approach benefits the modification of proteins of suitable size and wettability as particulate emulsifiers retaining their bioactivity. As demonstrated in a model system, the methoxy polyethylene glycol (mPEG)-urease conjugate particles anchor at the w/w interfaces, where they serve as an effective emulsifier-combined-catalyst and catalyze the hydrolysis of urea in water to ammonium carbonate. Our study is unique in that it employs bioactive particles to stabilize w/w emulsions. Considering the characteristics of all-aqueous, compartmental and interfacial biocatalysis of the system, it will open up new possibilities in the life sciences.

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Shu Wang

Papers

Preparation of submicrometer-sized monodispersed thermoresponsive core-shell hydrogel microspheres.

Positively Thermo-Sensitive Monodisperse Core–Shell Microspheres†

Surface Modification of Ceramic-Supported Polyethersulfone Membranes by Interfacial Polymerization for Reduced Membrane Fouling

Polymer–Protein Conjugate Particles with Biocatalytic Activity for Stabilization of Water-in-Water Emulsions

Nano-structure construction of porous membranes by depositing nanoparticles for enhanced surface wettability