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The achievement of photoreversible color switching systems (PCSS) has offered great opportunities for fundamental studies and practical applications. However, the development of PCSS that possessing highly reversible cyclability and on-demand regulation of recoloration process remains a grand challenge. Herein, we report a hydrazine-mediated self-doping strategy for the synthesis of alkaline Ti3+ self-doped TiO2-x nanoparticles, enabling the TiO2-x nanoparticles/methylene blue based PCSS with long photoreversible cyclability and rapid color switching rate. The Ti3+ species as internal sacrificial electron donors significantly improve the photoreductive activity of TiO2-x nanoparticles, which results in fast decoloration rate and long cycling number of the PCSS. Simultaneously, the alkaline property of TiO2-x nanoparticles enhances the oxidation kinetics of the PCSS to dramatically accelerate the recoloration rate. Moreover, the PCSS can be integrated elaborately with biodegradable agarose to form flexible color switching films, which exhibit long-waited on-demand regulation of recoloration rate in a wide range. By taking advantage of photoreversible color switching and time-resolved color changing process, we demonstrate their potential application in self-erasing rewritable paper and transient optical information encryption. This work represents a new strategy for the future development of PCSS and their advanced applications.

A biodegradable amphiphilic liquid polymer was designed to form self-emulsifying nanodroplets in water for delivering poorly soluble drugs. The polymer was composed of multiple short blocks of poly(ethylene glycol) (PEG) and poly(caprolactone) (PCL) connected through acid-labile acetal linkages. With an overall average molecular weight of over 18 kDa, the polymer remained as a viscous liquid under room and physiological temperatures. Dispersing the polymer in an aqueous buffer gave rise to highly stable micelle-like nanodroplets with an average size of approximately 15-20 nm. The nanodroplet dispersions underwent reversible temperature-sensitive aggregation with cloud points ranging from 45 to 50 °C, depending on polymer concentration. Nuclear magnetic resonance (NMR) and dynamic light scattering analyses revealed that while the nanodroplets were stable at pH 7.4 for several days, hydrolysis of the acetal linkages in the polymer backbone was much accelerated under mildly acidic pH 5.0, resulting in the formation of large microdroplets. Nile red (NR), a poorly water-soluble fluorophore, can be solubilized in the nanodroplets, and efficient intracellular delivery of NR was achieved. The hydrophobic indocyanine green (ICG) was also encapsulated in the nanodroplets. Near-infrared (NIR) fluorescence imaging and in vivo biocompatibility of the ICG-loaded nanodroplets were demonstrated in mice. In summary, the self-emulsifying nanodroplets of amphiphilic liquid polymer would be a promising material system for poorly soluble drug delivery and imaging in vivo.

Smart materials that reversibly change color upon light illumination are widely explored for diverse appealing applications. However, light-responsive color switching materials are mainly limited to organic molecules. The synthesis of inorganic counterparts has remained a significant challenge because of their slow light response and poor reversibility. Here, we report a seeded growth strategy for the synthesis of TiO2−x/WO3·0.33H2O hetero-nanoparticles (HNPs) with networked wire-like structure of ∼ 10 nm in diameters that enable the highly reversible light-responsive color switching properties. For the TiO2−x/WO3·0.33H2O HNPs, Ti3+ species self-doped in TiO2−x nanoparticles (NPs) act as efficient sacrificial electron donors (SEDs) and Ti-O-W linkages formed between TiO2−x and WO3·0.33H2O NPs ensure the nanoscale interfacial contact, endowing the HNPs enhanced photoreductive activity and efficient interfacial charge transfer upon ultraviolet (UV) illumination to achieve highly efficient color switching. The TiO2−x/WO3·0.33H2O HNPs exhibits rapid light response ( 180 times). We further demonstrate the applications of TiO2−x/WO3·0.33H2O HNPs in ink-free, light-printable rewritable paper that can be written on freehand or printed on through a photomask using UV light. This work opens an avenue for designing inorganic light-responsive color switching nanomaterials and their smart applications.

Sub-stoichiometric MoO3−x nanostructures with plasmonic absorption via creating oxygen vacancies have attracted extensive attentions for many intriguing applications. However, the synthesis of one-dimensional (1D) plasmonic MoO3−x nanostructures with widely tunable plasmonic absorption has remained a significant challenge because of their serious morphological destruction and phase change with increasing the concentration of oxygen vacancies. Here we demonstrate a surface-ligand protected reduction strategy for the synthesis of 1D MoO3−x nanobelts with tunable plasmonic absorption in a wide wavelength range from 200 to 2,500 nm. Polyethylene glycol (PEG-400) is used as both the reductant to produce oxygen vacancies and the surface protected ligands to maintain 1D morphology during the formation process of MoO3−x nanobelts, enabling the widely tunable plasmonic absorption. Owing to their broad plasmonic absorption and unique 1D nanostructure, we further demonstrate the application of 1D MoO3−x nanobelts as photothermal film for interfacial solar evaporator. The surface-ligand protected reduction strategy provides a new avenue for the developing plasmonic semiconductor oxides with maintained particle morphology and thus enriching their wide applications.

Lightweight, broad-band, and highly efficient microwave-absorbing materials (MAMs) with tunable electromagnetic properties are in high demand. However, the absorption properties are limited by the simple loss mechanism in commonly used absorbing materials. Here, we tested the microwave-absorbing properties of Fe-NiS2/NiS/poly(vinylidene fluoride) (PVDF) in the frequency range of 2-18 GHz. For the 2.5% Fe-NiS2/NiS/PVDF with the filling content of 20 wt %, the maximum reflection loss can reach -61.72 dB at 14.88 GHz, and the bandwidth can reach 3.8 GHz with the reflection loss value below -10 dB. Loss mechanisms of different composites were analyzed on the basis of their magnetic and dielectric properties using both experimental and computational methods. The results indicate that strong microwave absorption property is achieved through a balancing of dielectric loss and magnetic loss. These findings present a new strategy for the future design of MAMs.

The reversible photocatalytic color switching systems (PCSSs) driven by semiconductor nanoparticles have attracted considerable attention because of their wide applications. However, the developed semiconductor nanoparticles with photoreductive activity are mainly limited to TiO2-based photocatalysts, which greatly hinder their broad applications. Here we report a cocapping ligand-assisted strategy for the development of photoreductive BiOCl ultrathin nanosheets with abundant oxygen vacancies. Both the cocapping ligands and oxygen vacancies in BiOCl ultrathin nanosheets act as sacrificial electron donors to efficiently scavenge the photogenerated holes, endowing the BiOCl ultrathin nanosheets high photoreductive activity and thus enabling the photocatalytic color switching of redox dyes, such as methylene blue (MB) and neutral red. By successfully integrating the BiOCl ultrathin nanosheet/MB/H2O color switching system with poly(vinyl alcohol) hydrogel to fabricate a twistable gel film and simultaneously solving the dye-leaching issue of the gel film in a water environment, we further demonstrate its application in a colorimetric oxygen indicator for food packaging, exhibiting high sensitivity to monitor oxygen leakage by the naked eye. We believe the work opens a new avenue for designing photoreductive semiconductor nanomaterials to enrich the PCSSs and their applications.

Supramolecular self-assembly is an effective method for constructing complex ordered aggregates with specific functions by noncovalent bonding. However, silver nanoclusters (NCs) have rarely been e...

The harsh operating conditions and time-consuming fabrication process of the photoelectrode modification process have limited the potential applications of photoelectrochemical (PEC) sensors. To overcome these drawbacks, this study introduced a unique split-type PEC biosensor for microRNA-21 (miRNA-21) detection. Specifically, a Ti

Smart color switching materials that can change color with a fast response and a high reversibility have attracted increasing attention in color-on-demand applications. However, most of them can only respond to a single stimulus from their external environment, which dramatically limits their broad applications. To address this problem, we report a new strategy in developing a dual pH-/photo-responsive color switching system by coupling the pH-dependent and redox-driven color switchable neutral red (NR) with photoreductive TiO

Objective To study structure-specific solubilization effect of Sulfobutyl ether-β-cyclodextrin (SBE-β-CD) on Remdesivir (RDV) and to understand the experimental clathration with the aid of quantum mechanics (QM), molecular docking and molecular dynamics (MD) calculations. Methods The experiment was carried out by phase solubility method at various pH and temperatures, while the concentration of Remdesivir in the solution was determined by HPLC. The complexation mechanism and the pH dependence of drug loading were investigated following a novel procedure combining QM, MD and molecular docking, based on accurate pKa predictions. Results The phase solubility and solubilization effect of RDV in SBE-β-CD were explored kinetically and thermodynamically for each assessed condition. An optimal drug / SBE-β-CD feeding molar ratio was determined stoichiometrically for RDV solubility in pH1.7 solution. The supersaturated solubility was examined over time after pH of the solution was adjusted from 1.7 to 3.5. A possible hypothesis was raised to elucidate the experimentally observed stabilization of supersaturation based on the proposed RDV Cation A /SBE-β-CD pocket conformations. Conclusion The computational explorations conformed to the experimentally determined phase solubilization and well elucidated the mechanism of macroscopic clathration between RDV and SBE-β-CD from the perspective of microscopic molecular calculations. Graphical Abstract

The dynamic dual-stimuli-responsive surface wrinkles on a bilayer film with high bistability are unattainable and attractive for the applications of smart windows and optical displays. Here, we report a new strategy in developing moisture and temperature dual-responsive surface wrinkles on the polyvinyl alcohol/polydimethylsiloxane (PVA/PDMS) bilayer film by rationally designing the modulus changes of the PVA skin layer upon moisture and temperature. By optimizing the thickness of the PVA layer to 4.5 μm, the as-prepared surface wrinkles show long-awaited properties, such as fast response time, excellent reversibility without degradation of optical contrast, and high light transmittance modulation, which greatly outperforms the reported surface wrinkles. Moreover, the surface wrinkles on the bilayer film remain highly bistable without additional energy consumption for more than five months in ambient room conditions both in the opaque and transparent states. These promising dual-stimuli-responsive surface wrinkles on bilayer films hold great promises for various applications triggered by moisture and temperature, such as smart windows and rewritable optical displays.

The fast and reversible switching of plasmonic color holds great promise for many applications, while its realization has been mainly limited to solution phases, achieving solid-state plasmonic color-switching has remained a significant challenge owing to the lack of strategies in dynamically controlling the nanoparticle separation and their plasmonic coupling. Herein, we report a novel strategy to fabricate plasmonic color-switchable silver nanoparticle (AgNP) films. Using poly(acrylic acid) (PAA) as the capping ligand and sodium borate as the salt, the borate hydrolyzes rapidly in response to moisture and produces OH- ions, which subsequently deprotonate the PAA on AgNPs, change the surface charge, and enable reversible tuning of the plasmonic coupling among adjacent AgNPs to exhibit plasmonic color-switching. Such plasmonic films can be printed as high-resolution invisible patterns, which can be readily revealed with high contrast by exposure to trace amounts of water vapor.

Creating polymeric biomaterials with antifouling surface properties that persist after mechanical abrasion is a significant challenge. We report a simple but effective approach based on nanocomposites consisting of a bulk biocompatible polymer, polycaprolactone (PCL), admixed with a minute fraction (1–3 wt %) of nanoparticles consisting of a hyaluronic acid (HA)-PCL graft copolymer (HA-g-PCL). In a nonaqueous solvent such as chloroform, the HA-PCL graft copolymer adopts a reverse-micelle-like structure with a shell dominated by PCL chains, allowing it to be mixed well with high-molecular-weight PCL in the same solvent and cast into a nanocomposite film. Upon exposure to aqueous buffer, the HA-g-PCL nanoparticles reveal the hydrophilic chains of HA to face the outside, conferring a hydrophilic “slimy” or “artificial mucus” layer to the bulk PCL film that resists protein and cell adhesion, without altering bulk mechanical properties. After mechanical abrasion, the nanoparticles replenish the newly exposed m...

Self-powered electrochromic devices (ECDs) without an external power supply have been attracting extensive attention owing to their great potential in diverse electronic areas. However, conventional self-powered ECDs generally suffer from a complicated configuration, inflexibility, and poor color switching properties. Here, we develop a flexible self-powered quasi-solid-state ECD with a simplified bilayer film configuration based on a cathodic Prussian blue film and an ionic hydrogel film, in which an aluminum wire acts as both the conductive circuit and anode material. Owing to the elaborate bilayer structure and unique ionic hydrogel film, the self-powered ECD exhibits a high color switching speed, high reversibility and a tunable coloration rate on demand. Impressively, the ECD possesses the capability of “reviving” its color switching properties after repeated cycling, which significantly extends its lifetime. Taking advantage of the outstanding color switching properties, simple fabrication process, and straightforward operation, we demonstrated the practical applications of self-powered ECDs in optical information encryption and decryption. These findings may open up a new way to design self-powered ECDs with new functions and thus explore new applications.

Photoreversible color switching materials (PCSMs) are promising for applications in optical information storage and security features. However, conventional inorganic PCSMs such as semiconductor oxides generally suffer from slow color switching speed and limited reversibility. Here we report a fast light-responsive color switching and high reversible inorganic PCSM based on oxygen vacancies BiOBr ultrathin nanosheets. Owing to the unique 2D ultrathin structure and oxygen vacancies, the BiOBr ultrathin nanosheets possess high photoreductive activity and fast charge separation and transfer efficiency under ultraviolet (UV) illumination to initiate color changing from light yellow to brown black. Importantly, UV illumination induced oxygen vacancies during color switching process act as self-accelerating charge separation centers to further boost the photoreversible color switching. By integrating BiOBr ultrathin nanosheets with agarose as matrix, the freestanding BiOBr ultrathin nanosheets/agarose nanocomposite film exhibit outstanding photoreversible color switching properties, including coloration in 1 min under UV illumination, decoloration in 15 min in ambient air, and high reversibility (≥100 cycles). Moreover, we demonstrate the application of nanocomposite films in time-sensitive, self-erasing rewritable paper with long-awaited positive imaging mode and black color. This work presents the possibility of developing high-efficient inorganic PCSMs that could be significantly broad their practical applications.

Photoreversible color switching that can change colors with fast response and high stability is urgently desired in color-on-demand applications. Yet, developing such materials has long been a significant challenge. In this work, a strategy based on the integration of TiO2 nanoparticle (NP) photocatalytic color switching of redox dyes and poly(vinyl alcohol) gel matrix could produce robust and flexible photochromic gels (FPGs) that exhibit fast light-responsive time and high photoreversible stability. Benefited by the soft network structures and monomeric form of redox dyes in the FPG maintained by poly(vinyl alcohol) and ethylene glycol molecules, as well as enhanced photoreductive activity of TiO2 NPs modified by both surface ligands and oxygen vacancies, the FPG exhibits long photoreversible switching cycles (≥50 times), decoloration in a short period of less than 8 s upon UV illumination, and recoloration in 16 min in ambient air and rapidly in 140 s upon near-infrared light illumination. Consequently...

Dynamic manipulation of optical properties through the reversible assembly of plasmonic nanoparticles offers great opportunities for practical applications in many fields. The previous success, however, has been limited to Au nanoparticles. Reversible assembly and plasmonic tuning of Ag nanoparticles (AgNPs) have remained a significant challenge due to difficulty in finding an appropriate surface agent that can effectively stabilize the particle surface and control their interactions. Here, we overcome the challenge by developing a limited-ligand-protection (LLP) strategy for introducing poly(acrylic acid) with precisely controlled coverage to the AgNP surface to not only sufficiently stabilize the nanoparticles but also enable effective control over the surface charge and particle interaction through pH variation. The as-synthesized AgNPs can be reversibly assembled and disassembled and accordingly display broadly tunable coupling of plasmonic properties. Compared to the Au-based system, the success in the reversible assembly of AgNPs represents a significant step toward practical applications such as colorimetric pressure sensing because they offer many advantages, including broader spectral tuning range, higher color contrast, a one-pot process, and low materials and production cost. This work also highlights LLP as a new avenue for controlling the interparticle forces, their reversible assembly, and dynamic coupling of physical properties.

Visible light-responsive reversible color switching systems are attractive to many applications since visible light has superior penetration and causes far less damages to organic molecules than UV. Here we report that self-doping of Sn2+ in SnO2-x nanocrystals red shifts their absorption to visible region and simultaneously produces oxygen vacancies, which can effectively scavenge photogenerated holes and thus enable color switching of redox dyes using visible light. Wavelength selective switching can also be achieved by coupling the photocatalytic activity of the SnO2-x NCs with the color switching kinetics of different redox dyes. The fast light response enables the further fabrication of a solid film that can be repeatedly written freehand using a visible laser pen or projection printing through a photomask. This discovery represents a big step forward towards practical applications, especially in areas with concerns on the safety and photodamage issues of UV light.

A novel pressure-responsive polymer composite film was developed based on Ag@Au composite nanoplates (NPLs) and polyvinylpyrrolidone (PVP) by using Au nanoparticles as concentration reference. The orientation change of Ag@Au NPLs is impelled by the deformation of polymer matrix under pressure, resulting in its localized surface plasmon resonance (LSPR) intensity change of in-plane dipolar peak. The intensity ratio between plasmon peak of Au nanoparticles and in-plane dipolar peak of Ag@Au NPLs relies on the intensity and duration of pressure. By adjusting the viscosity of the polymer, the orientation change of LSPR may respond to a wide range of stresses. This pressure sensitive film can be utilized to record the magnitude and distribution of pressure between two contacting surfaces via optical information.

Hexavalent chromium Cr(VI), a highly toxic oxyanion, widely occurs in drinking water supplies. This study designed and synthesized a new type of highly reductive TiO2 nanocrystals for photochemical Cr(VI) removal, via the thermal hydrolysis of TiCl4 in the presence of diethylene glycol (DEG). Surface analyses and hydroxyl radical measurements suggested that DEG was chemically bonded on TiO2 surface that resulted in an internal hole-scavenging effect and a high electron-releasing capacity, making it advantageous to conventional TiO2 materials. Upon UV irradiation, the synthesized TiO2 photocatalyst exhibited fast Cr(VI) reduction kinetics in diverse water chemical conditions. Fast elimination of Cr(VI) was achieved on a time scale of seconds in drinking water matrices. The removal of Cr(VI) by reductive TiO2 exhibited a three-stage kinetic behavior: an initial fast-reaction phase, a lag phase resulting from surface precipitation of Cr(OH)3(s), and a final reaction phase due to surface regeneration from oxidation-reduction induced ripening process. The lag phase disappeared in acidic conditions that prevented the formation of Cr(OH)3(s). The catalyst exhibited extremely high electron-releasing capacity that can be reused for multiple cycles of Cr(VI) removal in drinking water treatment.

Titania nanocrystals have been investigated for fast color switching through photocatalytic reduction of dyes and hexacyanometalate pigments. Here we reveal that direct binding of sacrificial electron donors (SEDs) to the surface of titania nanocrystals can significantly promote the charge transfer rate by more efficiently scavenging photogenerated holes and releasing more photogenerated electrons for reduction reactions. Using diethylene glycol (DEG) as an example, we show that its binding to the nanoparticle surface, which can be achieved either during or after the nanoparticle formation, greatly enhances the photocatalytic reduction in comparison with the case where free DEG molecules are simply added as external SEDs.

The sensitive and on-site detection of inorganic explosives has raised serious concerns regarding public safety. However, high stability and non-volatility features currently limit their rapid on-site detection. Surface-enhanced Raman spectroscopy (SERS) is emerging as a powerful technique for the trace-level detection of different molecules. Plasmonic Ag nanowires were produced by a hydrothermal synthesis method using polyvinylpyrrolidone (PVP) as a negatively charged stabilizer. Here, we report a rapid detection method for inorganic explosives based on a simple surface swab with a positively charged diethyldithiocarbamate-modified Ag nanowire membrane coupled with SERS. This membrane, serving as an excellent SERS substrate with high uniformity, stability, and reusability, can capture both typical oxidizers in inorganic explosives and organic nitro-explosives, via electrostatic interaction. The detection level of perchlorates (ClO4−), chlorates (ClO3−), nitrates (NO3−), picric acid, and 2,4-dinitrophenol is as high as 2.0, 1.7, 0.1, 45.8, and 36.6 ng, respectively. In addition, simulated typical inorganic explosives such as black powders, firecrackers, and match heads could also be detected. We believe that this membrane represents an attractive alternative for rapid on-site detection of inorganic explosives with high efficiency.

Colloidal barium-doped TiO2 nanocrystals have been developed that enable the highly reversible light-responsive color switching of redox dyes with excellent cycling performance and high switching rates. Oxygen vacancies resulting from the Ba doping serve as effective sacrificial electron donors (SEDs) to scavenge the holes photogenerated in TiO2 nanocrystals under UV irradiation and subsequently promote the reduction of methylene blue to its colorless leuco form. Effective color switching can therefore be realized without relying on external SEDs, thus greatly increasing the number of switching cycles. Ba doping can also accelerate the recoloration under visible-light irradiation by shifting the absorption edge of TiO2 nanocrystals to a shorter wavelength. Such a system can be further casted into a solid film to produce a rewritable paper on which letters and patters can be repeatedly printed using UV light and then erased by heating; this process can be repeated for many cycles and does not require additional inks.

© 2016 American Chemical Society. Developing efficient photoreversible color switching systems for constructing rewritable paper is of significant practical interest owing to the potential environmental benefits including forest conservation, pollution reduction, and resource sustainability. Here we report that the color change associated with the redox chemistry of nanoparticles of Prussian blue and its analogues could be integrated with the photocatalytic activity of TiO2nanoparticles to construct a class of new photoreversible color switching systems, which can be conveniently utilized for fabricating ink-free, light printable rewritable paper with various working colors. The current system also addresses the phase separation issue of the previous organic dye-based color switching system so that it can be conveniently applied to the surface of conventional paper to produce an ink-free light printable rewritable paper that has the same feel and appearance as the conventional paper. With its additional advantages such as excellent scalability and outstanding rewriting performance (reversibility >80 times, legible time >5 days, and resolution >5 μm), this novel system can serve as an eco-friendly alternative to regular paper in meeting the increasing global needs for environment protection and resource sustainability.

We report a novel photoreversible color switching system based on the photocatalytic activity of TiO2 nanocrystals and the redox-driven color switching property of methylene blue (MB). This system rapidly changes from blue to colorless under UV irradiation and recovers its original blue color under visible light irradiation. We have identified four major competing reactions that contribute to the photoreversible switching, among which two are dominant: the decoloration process is mainly driven by the reduction of MB to leuco MB by photogenerated electrons from TiO2 nanocrystals under UV irradiation, and the recoloration process operates by the TiO2-induced self-catalyzed oxidation of LMB under visible irradiation. Compared with the conventional color switching systems based on photoisomerization of chromophores, our system has not only low toxicity but also significantly improved switching rate and cycling performance. It is envisioned that this photoreversible system may promise unique opportunities for many light-driven actuating or color switching applications.

Supramolecular self-assembly is an effective method to assemble organic and inorganic units into various hierarchical structures with excellent properties and is widely used in material and life science. In this article, the self-assembled hollow-sphere and core-in-hollow-shell nanostructures composed of m-phenylenediamine and a novel Preyssler-type polyoxometalates (POM, K12.5Na1.5[NaP5W30O110]·15H2O (abbreviated as P5W30)) without template were successfully realized by adjusting the non-covalent interactions. For comparison, we also selected o-phenylenediamine and p-phenylenediamine to investigate whether isomerides have different effects on the self-assembly behavior with P5W30. The results indicated that only m-phenylenediamine/P5W30 can form hollow spheres and core-in-hollow-shell structure while o-phenylenediamine/P5W30 and p-phenylenediamine/P5W30 cannot which revealed that the self-assembly process can be regulated via isomer effects. Moreover, the detailed analysis of the formation of hollow spheres and core-in-hollow-shell structure are studied and the mechanism is mainly due to the Ostwald ripening. In addition, m-phenylenediamine/P5W30 composite has a good adsorption capacity for methylene blue (MB) dyes, even in the presence of other dyes such as rhodamine B (RB) and amaranth (AR). Our findings further confirmed that supramolecular self-assembly between organic molecules and POM can unique a distinctive “bottom-up” strategy to construct diversiform structures with functional properties.

Porous TiO2/C nanocomposite shells with high capacity, excellent cycle stability, and rate performance have been prepared. The synthesis involves coating colloidal TiO2 nanoshells with a resorcinol-formaldehyde (RF) layer with controllable thickness through a sol-gel-like process, and calcining the composites at 700 °C in an inert atmosphere to induce crystallization from amorphous TiO2 to anatase and simultaneous carbonization from RF to carbon. The cross-linked RF polymer contributes to the high stability of the shell morphology and the porous nature of the shells. A strong dependence of the capacity on the amount of incorporated carbon has been revealed, allowing the optimization of the electrode structure for high-rate cell performance.

Colloidal hollow nanocrystals with controlled hollow interior and shell thickness represent a class of important nanostructured materials, because of their promising applications for nanoreactors, drug delivery, and catalysis. Since the first report in 2004 on the synthesis of CoS and CoO hollow nanocrystals by sulfidation and oxidation of Co nanocrystals, several different kinds of hollow nanocrystals have been prepared by a similar approach that involves the nanoscale Kirkendall effect. In this review, we introduce the application of this well-known classical phenomenon in metallurgy in the synthesis of hollow nanocrystals. We start with a brief introduction to the synthesis of hollow nanocrystals, then discuss the concepts and applications of nanoscale Kirkendall effect for the synthesis of hollow nanocrystals, and finally touch on the extension of the process to the formation of nanotubes. We conclude with a summary and our personal perspectives on the directions in which future work on this field mig...

New biodegradable poly(ester urethane)/soy protein isolate (PEU/SPI) hybrids were prepared by in situ polymerization. The chemical incorporation of the SPI into the backbone chain of the PEU was facilitated by the reaction of the amine functional groups of SPI with methylene diphenyl diisocyanate (MDI). X-ray diffraction results showed that the chemical incorporation of SPI into PEU significantly changed the molecular structure of the PEU. The PEU/SPI hybrids exhibited higher thermal decomposition temperature and significant increase in the modulus compared with that of pure PEU. Microscopic examination of the morphology of PEU/SPI hybrids confirmed very fine and homogeneous SPI dispersion in PEU. The hydrolytic degradation of the PEU in a phosphate buffer solution was accelerated by incorporation of SPI, which was confirmed by water absorption and scanning electron microscopy of the samples after up to 10 weeks immersion in the buffer solution. This study provides a facile and innovative method of controlling the biodegradation rate of pure PEU with the additional advantage of environmentally-benign biodegradation of the hybrid PEU/SPI polymer, making the concept potentially widely applicable.

The photoreversible color switching system holds great promise for applications in display and signage technologies, sensing devices, and security features, because light, in comparison to other stimuli such as heat and electricity, has the advantages of noninvasiveness and easy control of parameters including wavelength, intensity, coverage area, and illumination duration. Here, the recent advances in the design and synthesis of titania nanoparticles for catalytic photoreversible color switching of redox dyes and pigments, along with their applications in ink-free, light-printable rewritable paper and colorimetric oxygen indicators, are reviewed. Specifically, the importance of surface engineering and defect manipulation of titania nanoparticles for the color-switching purpose, by introducing a number of methods including surface binding of sacrificial capping ligands and creating oxygen vacancies through doping of metal ions, is highlighted. Finally, a summary and perspectives on current challenges and future research directions in this field are given.

Summary In this article we review the current research activities on the fabrication of inorganic hollow nanostructures by using self-templating methods. We start with a brief introduction to the traditional template-based methods, including those using hard and soft templates. The concepts and applications of four types of newly developed self-templating approaches are then discussed in detail, including those involving the “surface-protected etching” strategy, Ostwald ripening, the Kirkendall effect, and the galvanic replacement. We finally conclude with a summary and our personal perspectives on the directions in which future work on this field might be focused.

The primary goal of this study is to develop a facile and inexpensive synthesis method for a new biodegradable and biocompatible poly(ester urethane) (PEU)/polyhedral oligomeric silesquioxanes (POSS) nanocomposite via in situ homogeneous solution polymerization reaction into prescribed macromolecular structure and properties including improved biocompatibility, thermal and hydrolytic stability, and stiffness and strength. Cell culture studies, nuclear magnetic resonance spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetry, and dynamic mechanical analysis measurements were used to confirm the structure and property improvements. The results show that the targeted PEU/POSS nanocomposites (which are remarkably different from conventional polymers, polymer nanocomposites and microcomposites) have significant improvements in mechanical properties and degradation resistance at small POSS concentrations (≤6 wt%). The nanocomposites exhibited excellent support for cell growth without any toxicity. POSS concentration did not affect cell adhesion or cell growth, but it significantly changed the surface structure of the PEU into a 3-dimensional matrix with regular pores that may allow cells to better access the growth factors/nutrients, waste exchange, and tissue remodeling. The PEU/POSS nanocomposites were resistant to degradation over a period of six months when exposed to a buffer solution. These desirable characteristics suggest that the nanocomposites may hold great promise for future high-end uses such as in biomedical devices, especially at cardiovascular interfaces.

We report a solution-phase rapid-injection-based route for the synthesis of calcium molybdate (CaMoO4) microstructures with well-defined shape and size. This ternary metal oxide material has been widely used as phosphors, scintillator, and laser materials for a long time because of its attractive luminescence property. Complex three-dimensional structures, mainly doughnut-shaped microparticles with highly controllable size and aspect ratio, can be obtained at 100 °C by controlling the reaction conditions including the concentration of reactants, molar ratio between reactants, molybdenum source, pH, and the volume ratio of the mixed solvents. Other shapes such as spindles, nanosheets, and microspheres can also be produced by pushing the reaction conditions away from those optimal for doughnuts. X-ray diffraction, scanning electron microscopy, transmission electronic microscopy, and X-ray energy dispersive spectrometer were used to characterize the obtained samples. The photoluminescence spectra of the CaMo...

We report the activity for a new tin-polyhedral oligomeric metal silsesquioxane (POMS) catalyst in 1-butanol and 2-butanol model reactions with 4,4'-methylenebis(cyclohexylisocyanate) (H 12 MDI) in toluene and N,N-dimethylformamide (DMF). Kinetic rate constants for varying levels of tin-POMS ranging between 100 ppm and 1000 ppm tin are reported. We observed urethane reactions in toluene to follow second order reaction kinetics, whereas similar reactions in DMF followed first order reaction kinetics. We determined tin-POMS is an efficient catalyst system for urethane reactions and found the new catalyst to be easy to handle, soluble, and very effective for catalyzing urethane reactions. By direct comparison of a model reaction between tin-POMS and dibutyltin dilaurate (DBTDL), tin-POMS was found to be quite similar to DBTDL for urethane catalytic activity. In addition, we show the efficacy for tin-POMS to be an excellent polyurethane reaction catalyst through a model reaction of H 12 MDI with 2000 g/mol poly(e-caprolactone) diol.

Novel biodegradable and biocompatible poly(ester-urethane)s were synthesized by in situ homogeneous solution polymerization of poly(ɛ-caprolactone) diol, dimethylolpropionic acid (DMPA), and methylene diphenyl diisocyanate in acetone followed by solvent exchange with water. The effects of the DMPA content and hard segment content on the properties of the polyurethanes were measured by DSC, TGA, and hydrolytic degradation measurements. The results showed that DMPA had a dramatic effect on the particle size; the particle size decreased rapidly with increasing DMPA content. The hydrolytic degradation test showed that the degradation rate was little affected by the DMPA content in the range investigated, but was observed to be influenced by the hard segment content. Cell toxicity analysis showed that the biodegradable poly(ester-urethane)s synthesized in this study did not exhibit any detectable toxicity to human umbilical vein endothelial cells and mouse embryonic stem cells. Both types of cells can effectively adhere to and spread on the surface of pure poly(ɛ-caprolactone) or poly(ester-urethane)s. The present study demonstrates the feasibility of a facile synthesis of biodegradable polyurethanes and of their aqueous dispersions with prescribed properties for biomedical applications.

World-wide changes in clean fuel regulations have accelerated the research works for reducing sulfur in fluidized catalytic cracking (FCC) gasoline. In this work, NiSO4 and Ni(AC)2 were supported on nano-HZSM-5, Al2O3, and SiO2 supports by impregnation to prepare catalysts modified by NiSO4 and NiO. The catalysts were characterized using X-ray powder diffraction (XRD), nitrogen adsorption (BET), NH3 temperature-programmed desorption (TPD), Fourier transform infrared (FTIR) analysis with adsorbed pyridine, H2 temperature-programmed reduction (TPR), and differential thermogravimetric (DTG) analysis. NH3−TPD shows that the acid sites and acid strength is increased after NiSO4 modification and decreased after Ni(AC)2 modification. FTIR results indicate that most of the increased acidity is Lewis acid. Infrared spectra before and after pyridine adsorption demonstrate that there is a strong interaction between S═O in SO42− and alumina oxides. The interaction makes NiSO4 on the surface of alumina oxides harder t...