Photocatalytic Self‐Doped SnO2−x Nanocrystals Drive Visible‐Light‐Responsive Color Switching

Visible‐light‐responsive reversible color‐switching systems are attractive to many applications because visible light has superior penetration and causes far less damage to organic molecules than UV. Herein, we report that self‐doping of SnO_2−x nanocrystals with Sn²⁺ red‐shifts their absorption to the visible region and simultaneously produces oxygen vacancies, which can effectively scavenge photogenerated holes and thus enable the color switching of redox dyes using visible light. Wavelength‐selective switching can also be achieved by coupling the photocatalytic activity of the SnO_2−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 on using a visible laser pen or projection printing through a photomask. This discovery represents a big step forward towards practical applications, especially in areas in which safety issues and photodamage by UV light are of concern.     

Ultrastretchable,Tough, and Notch‐Insensitive Hydrogels Formed with Spherical Polymer Brush Crosslinker

Spherical polymer brushes, poly(acrylic acid) (PAA)‐grafted polystyrene nanoparticle (PAA@PS), are employed as the macro‐crosslinker to prepare PAA hydrogels. Benefitting from the innumerable hydrogen bonds between highly entangled PAA chains both in bulk and on the polymer brush, the PAA/PAA@PS hydrogels combine desirable stretchability, toughness, and notch‐insensitivity. The uniaxial tensile tests show a very high fracture elongation up to 9.1 × 10³% while the fracture toughness reaches 3.0 MJ m⁻³ and the maximum swelling ratio of the hydrogel can be 2.0 × 10³ as well. After being loaded with silver nanoparticles, the PAA/PAA@PS hydrogels are employed as a recyclable catalyst successfully.     

Immunoassay of plasmonic gold‐nanoparticle clusters: Plasmon coupling effects for Parkinson biomarker detection

A simple signal‐on plasmonic optical assay for the detection of the Parkinson biomarker using gold‐nanoparticle clusters (AuNCs) for signal amplification is presented. This approach is based on the improvement of the optical density (OD) change of the plasmonic band of a localized surface plasmon resonance (LSPR) Au nanoparticle (AuNP) sensor interface using Au NCs conjugated antibodies. The amplification results in a 260‐fold improvement in concentration detection, from 1,000 ng/mL (unlabeled antibody) to 3.8 ng/mL (antibody‐conjugated AuNCs). The sensitivity enhancement can be ascribed to the further plasmonic coupling between the antibody‐conjugated AuNCs and the AuNPs on the LSPR interface and the enhanced amount of target molecule bound to the bioassay. This AuNCs‐assisted signal amplification strategy allows for improving the sensitivity of the plasmon‐based bioassays and can be extended to other optical‐based diagnostic technologies. Importantly, the simple detecting procedure and protocol assembly make it competitive with other existing sensing technologies such as ELISA, allowing for practical usage in clinical diagnostics.     

Thermochromic Color Switching to Temperature Controlled Volatile Memory and Counter Operations with Metal–Organic Complexes and Hybrid Gels

Temperature is often not considered as a precision stimulus for artificial chemical systems in contrast to the host–guest interactions related to many natural processes. Similarly, mimicking multi‐state volatile memory operations using a single molecular system with temperature as a precision stimulus is highly laborious. Here we demonstrate how a mixture of iron(II) chloride and bipyridine can be used as a reversible color‐to‐colorless thermochromic switch and logic operators. The generality of the approach was illustrated using Co^II and Ni^II salts that resulted in color‐to‐color transitions. DMSO gels of these systems, exhibited reversible opaque‐transparency switching. More importantly, optically readable multi‐state volatile memory with temperature as a precision input has been demonstrated. The stored data is volatile and is lost instantaneously upon withdrawal or change of temperature. Simultaneous read‐out at multiple wavelengths results in single‐input/multi‐output sequential logic operations such as data accumulators (counters) leading to volatile memory states. The present system provides access to thermoresponsive materials wherein temperature can be used as a precision stimulus.     

Controlled electrochemical synthesis of polypyrrole nanoparticle thin film and its redox transition to a highly conductive and stable polypyrrole variant

We demonstrated here a unique method to produce a highly stable and conductive polypyrrole (PPY) nanoparticle film. The procedure entails controlling the redox switching and the electrochemical synthesis of PPY. PPY was synthesized at a very low forming potential or reaction rate in nonaqueous CH2Cl2 solvent to promote the PPY nanoparticle formation. Then its property was further optimized by first electrochemically reducing it at a hydrogen evolution potential in a neutral 0.1 M NaClO4, then in a slightly acidic 0.05 M asparagine electrolyte. The PPY nanoparticle thin film was characterized by AFM, UV-vis and EQCM. The procedures described here have proven to be reproducible. The data provided by the EQCM shows a reversible doping and undoping mechanism of asparagine indicating the presence of a highly conductive PPY variant. Both UV-vis and electrochemical characterization suggest that the PPY film made using our approach has excellent redox activity as well as high stability when characterized in asparagine solution. The reversible doping and undoping of asparagine during redox switching shows great potential of these PPY nanoparticle films as biological membranes for a broad range of biological applications.     

Novel silver‐loaded semi‐interpenetrating polymer network gel films with antibacterial activity

Novel semi‐interpenetrating polymer networks (SIPNs) based on segmented polyurethane‐urea and poly(N‐isopropylacrylamide‐co‐acrylic acid‐co‐butylmethacrylate) (poly(NIPAM‐co‐AA‐BMA)) were synthesized for the fabrication of silver nanoparticles (AgNPs) in the SIPN system that could be useful for wound dressing applications. The obtained SIPN films, after neutralization, showed high swelling in aqueous environments and good mechanical properties in both dry and hydrated states. Analysis of the dried SIPN films by differential scanning calorimetry and dynamic viscoelastic measurements revealed the presence of crosslinked copolymers as well as homopolymers in the SIPN system. The neutralized swollen SIPN film coordinated with the silver ions (Ag⁺) that were incorporated into it. AgNPs were subsequently formed by the reduction of Ag⁺. The formation of AgNPs was characterized by UV‐visible spectroscopy, atomic force microscopy, wide‐angle X‐ray diffraction, and thermogravimetric analysis (TGA). Bactericidal activity tests revealed a distinct zone of microbial inhibition within and around the silver‐doped SIPN films. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4950–4962, 2009     

Metal ion-enriched polyelectrolyte complexes and their utilization in multilayer assembly and catalytic nanocomposite films

The mixing of Ag ion-doped poly(ethyleneimine) (PEI) and poly(acrylic acid) (PAA) produced Ag ion-doped polyelectrolyte complex particles (PECs) in solution. Positively charged Ag ion-doped PECs (Ag ion PECs) with a spherical shape were deposited alternatively with PAA to form a multilayer assembly. The multilayered film containing Ag ion PECs was reduced to generate a composite nanostructure. Metal nanoparticle (NP)-enriched nanocomposite films were formed by an additional process of the postadsorption of precursors on PECs within the nanocomposite films, which resulted in the enhancement of the catalytic and electrical properties of the composite films. Because the films contain PECs that are responsive to changes in pH and most of the NPs are embedded in the PECs, interesting catalytic properties, which are unexpected in a particle-type catalyst, were observed upon pH changes. As a result of the reversible structural changes of the films and the immobilization of the NPs within the films, the film-type catalysts showed enhanced performance and stability during catalytic reactions under various pH conditions, compared to particle-type catalysts.     

Direct detection of DNA using 3D surface enhanced Raman scattering hotspot matrix

Silver nanoparticles (AgNPs) are evaporatively self‐assembled into the 3D surface enhanced Raman scattering (SERS) hotspot matrix with the assistant of glycerol to improve the spectral reproducibility in direct DNA detection. AgNPs and DNA in the glycerol‐stabilized 3D SERS hotspot matrix are found to form flexible sandwich structures through electrostatic interaction where neighboring AgNPs create uniform and homogeneous localized surface plasmon resonance coupling environments for central DNA. Nearly two orders of magnitude extra SERS enhancement, more stable peak frequency and narrower peak full width at half maximum can therefore be obtained in DNA SERS spectra, which ensures highly stable and reproducible SERS signals in direct detection of both single strand DNA and double strand DNA utilizing the 3D SERS hotspot matrix. By normalizing the SERS spectra using phosphate backbone as internal standard, identification of single base variation in oligonucleotides, determination of DNA hybridization events and recognition of chemical modification on bases (hexanethiol‐capped at 5’ end) have been demonstrated experimentally. This proposed 3D SERS hotspot matrix opens a novel perspective in manipulating plasmonic nanoparticles to construct SERS platforms and would make the surface enhanced Raman spectroscopy a more practical and reliable tool in direct DNA detection.     

Fabrication and properties of a novel superabsorbent composite based on coco peat and poly (acrylic acid) cross‐linked trimethylolpropane trimaleate under ultraviolet irradiation

A series of novel poly(acrylic acid)/coco peat (PAA/CP) superabsorbent composites were prepared via the ultraviolet irradiation copolymerization of acrylic acid monomer (PAA) and coco peat cellulose (CP) in the presence of the cross‐linker trimethylolpropane trimaleate. The physico‐chemical structures of obtained PAA/CP were characterized by Fourier transform infrared spectroscopy, thermogravimetry/derivative thermogravimetry, X‐ray diffraction, and scanning electron microscopy, respectively. The critical parameters of affecting the water absorbency of PAA/CP, including the cross‐linker level, amount of CP and reaction time, were studied in detailed. The experimental results showed that the PAA/CP samples exhibited the maximum swelling value of 523.09 g/g in distilled water and 40.52 g/g in 0.9 wt % NaCl solution. The swelling behaviors of PAA/CP were significantly relied on the concentration of salt solution and the pH of external solution. The effect of ions species on the swelling performance was in the order: Na⁺ > Ca²⁺ > Fe³⁺ , and in pH 2.2 and 7.2 aqueous solutions PAA/CP composites displayed better pH‐responsiveness and reversible on‐off switching characteristics. Urea, as an agrochemical model, was loaded into PAA/CP substrate to supply with nitrogen nutrient. The test of their loading and releasing diffusion performance of urea suggested that the urea loading percentage of PAA/CP was remarkably dependent on the concentration of aqueous urea solutions and the release of urea from loaded PAA/CP samples in water followed a non‐Fickian mechanism. Owing to their considerable good water absorption capacity, slow urea release, economical and environment‐friendly merits, PAA/CP composites could be exploited for the agriculture applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Bright,Multi‐responsive,Sky‐Blue Platinum(II) Phosphors Based on a Tetradentate Chelating Framework

A new class of highly efficient and stable, blue‐phosphorescent Pt^II complexes based on a tetradentate chelating framework has been found to exhibit highly sensitive and reversible responses to multiple external stimuli including temperature, pressure, and UV irradiation with distinct phosphorescent color switching—from blue to red or white. Intermolecular excimer formation is the main origin of this intriguing multi‐response phenomenon. Highly efficient singlet‐oxygen sensitization by the Pt^II compounds yields UV‐light‐induced phosphorescence enhancement and color switching.     

Methanol‐Triggered Vapochromism Coupled with Solid‐State Spin Switching in a Nickel(II)‐Quinonoid Complex

A highly methanol‐selective vapochromic response has been realized in a Ni^II‐quinonoid complex, [Ni(HL^Me)₂] (H₂L^Me=4‐methylamino‐6‐methyliminio‐3‐oxocyclohexa‐1,4‐dien‐1‐olate) which exhibits a reversible structural transformation including a coordination geometrical change between the square‐planar and octahedral structure by the selective uptake of methanol vapor. This was accompanied by a remarkable color change between purple and orange, as well as temperature‐robust spin‐state switching in the solid state under ambient conditions. It is remarkable that the properties are derived by the fine structural modification of the quinonoid ligand such as methyl or ethyl analogues. Such a system has high potential for applications in memory devices as well as chemical sensors and smart responsive materials.     

A new green method for the synthesis of silver nanoparticles and their antibacterial activities against gram‐positive and gram‐negative bacteria

This study aims to evaluate the capability of Ageratum conyzoides and Mikania micrantha extracts to synthesize silver nanoparticles (AgNPs) and their antibacterial capability against gram‐positive and gram‐negative bacteria. Several properties of the synthesized AgNPs, including plasmonic, biomolecule bonding, shape, size, and antibacterial, were investigated. Ultraviolet–visible (UV–vis) spectroscopy was employed for characterizing their plasmonic properties. Functional groups on the produced AgNPs were investigated by Fourier‐transform infrared (FT‐IR) spectroscopy. The size and shape of the AgNPs were identified using the field‐emission scanning electron microscopy (FESEM). Inhibition zone measurement was carried out for evaluating the antibacterial capability. This study showed that the extracts of A. conyzoides and M. micrantha were able reducing agents as evidenced by the formation of the spherical AgNPs. UV–vis spectroscopy, FT‐IR spectroscopy, and FESEM confirmed the physicochemical characteristics of AgNPs. AgNPs that were synthesized using M. micrantha were slightly smaller than those produced using A. conyzoides. In general, the present work establishes that the synthesized AgNPs have antibacterial capability depending on their size and synthesis procedure.     

Electrochromic material containing unsymmetrical substituted N,N,N′,N′‐tetraaryl‐1,4‐phenylenediamine: Synthesis and their optical,electrochemical, and electrochromic properties

A novel dibromo compound containing unsymmetrical substituted bi‐triarylamine was synthesized. A conjugated polymer was prepared via the Suzuki coupling from the newly prepared dibromo compound and 9,9‐dioctylfluorene‐2,7‐bis(trimethyleneboronate). The glass transition temperature (T_g) of the conjugated polymer was 140 °C, 10% weight‐loss temperatures (T_d10) in nitrogen was 458 °C, and char yield at 800 °C in nitrogen higher than 64%. Cyclic voltammogram of the polymer film cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at 0.70 and 1.10 V versus Ag/Ag⁺ in acetonitrile solution. The polymer films revealed excellent stability of electrochromic characteristics, with a color change from yellow green of the neutral form to the dark green and blue of oxidized forms at applied potentials ranging from 0 to 1.3 V. The color switching time and bleaching time were 4.25 and 7.22 s for 860 nm and 5.51 s and 6.48 s for 560 nm. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1469–1476, 2010     

Highly redox‐stable and electrochromic aramids with morpholinyl‐substituted triphenylamine units

A novel morpholinyl‐substituted, triphenylamine‐based diamine monomer, namely 4,4′‐diamino‐4″‐(4‐morpholinyl)triphenylamine, was synthesized and polymerized with various aromatic dicarboxylic acids via the phosphorylation polyamidation reaction leading to a series of electroactive aromatic polyamides (aramids). All aramids were readily soluble in polar organic solvents and could be solution cast into tough and flexible films with high thermal stability. Cyclic voltammograms of the aramid films on the indium‐tin oxide‐coated glass substrate exhibited a pair of reversible oxidation waves with very low onset potentials of 0.36 − 0.41 V (vs. Ag/AgCl) in acetonitrile solution. The polymer films showed reversible electrochemical oxidation accompanied by strong color changes with high coloration efficiency, high contrast ratio, and rapid switching time. The optical transmittance change (Δ%T) at 650 nm between the neutral state and the fully oxidized state is up to 90%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1289–1298     

Surface-enhanced Raman nanoparticle beacons based on bioconjugated gold nanocrystals and long range plasmonic coupling

We have developed a new class of surface-enhanced Raman scattering beacons (SERS beacons) that can be turned on and off by long-range plasmonic coupling, induced by biomolecular recognition and binding events. The beacons are based on colloidal gold nanocrystals in two sizes (40 and 60 nm) and are prepared by spectral encoding with a Raman reporter molecule, functionalized with thiolated DNA probes, and stabilized and protected by low molecular weight poly(ethylene glycol)s (PEGs). The results show the SERS signal intensities increase by 40-200-fold when the nanoparticle beacons are activated by plasmonic coupling, much higher than the bright-to-dark intensity ratios reported for traditional molecular beacons. Multivalent gold nanoparticles also have exquisite specificity and are able to recognize single-base mismatches or mutations. This class of SERS nanoparticle beacons has novel mechanisms for molecular detection and signal amplification, and its long-range coupling nature raises new opportunities in developing plasmonic probes to detect proteins, cells, and intact viruses.     

Preparation of Polymer-Functionalized Iron Oxide Nanoparticles and Their Biomedical Properties

Superparamagnetic iron oxide nanoparticles with narrow size distributions were successfully prepared in large scale by a facile one‐pot synthetic method in the presence of hydrophilic polymers, such as polyethylene glycol diacid (HOOC‐PEG‐COOH) and poly(acrylic acid) (PAA). The as‐prepared products were investigated in detail by powder X‐ray diffraction (XRD), thermogravimetric analyses (TGA), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS), and vibrating sample magnetometer (VSM). The interaction between polymers and iron oxide nanoparticles was investigated using Fourier transform infrared spectrometry (FT‐IR). The results show that polymers can be attached onto the surface of iron oxide nanoparticle by bridging coordination and monodentate fashion, respectively. The interaction affects iron oxide nanoparticle properties significantly, such as XRD diffraction intensity, hydrodynamic diameter, isoelectric point, and saturation magnetization. Furthermore, the results of in vitro experiments indicated that iron oxide‐PEG‐COOH nanoparticle is more cytotoxic than iron oxide‐PAA nanoparticle due to different coordinating modes.     

pH‐Switchable Bioelectrocatalysis Based on Weak Polyelectrolyte Multilayers

Weak polyelectrolytes poly(allylamine hydrochloride) (PAH) and poly(acrylic acid) (PAA) were assembled into {PAH/PAA}_n layer‐by‐layer films on electrodes. The cyclic voltammetry (CV) response of ferrocenecarboxylic acid (Fc(COOH)) at {PAH/PAA}₅ film electrodes assembled under the specific condition showed pH‐sensitive “on‐off” switching property. This property was further used to control the electrocatalytic oxidation of glucose by glucose oxidase (GOD) with Fc(COOH) as the electron transfer mediator, so that the pH‐switchable bioelectrocatalysis could be realized. The mechanism of pH‐sensitive behavior of the system was explored and believed to originate from the pH‐dependent structure change of the films.     

Electrosynthesis of ambipolar electrochromic polymer films from anthraquinone–triarylamine hybrids

Two ester derivatives featuring anthraquinone as an interior core and terminal electroactive triphenylamine or carbazole groups were prepared by the condensation of 2,6‐dihydroxyanthraquinone with 4‐(diphenylamino)benzoyl chloride and 4‐(9H‐carbazol‐9‐yl)benzoyl chloride, respectively. The electrochemistry and electropolymerization of these monomers were investigated. The polymeric films were built onto ITO/glass surface by repetitive cyclic voltammetry scanning of the monomer solutions containing an electrolyte. The electrogenerated polymer films exhibited reversible electrochemical processes and strong color changes upon electro‐oxidation or electro‐reduction, which can be switched by potential modulation. The remarkable electrochromic behavior of the film was clearly interpreted on the basis of spectroelectrochemical studies, and the electrochromic stability was evaluated by the electrochromic switching studies. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 644–655     

Core-satellites assembly of silver nanoparticles on a single gold nanoparticle via metal ion-mediated complex

We report core-satellites (Au-Ag) coupled plasmonic nanoassemblies based on bottom-up, high-density assembly of molecular-scale silver nanoparticles on a single gold nanoparticle surface, and demonstrate direct observation and quantification of enhanced plasmon coupling (i.e., intensity amplification and apparent spectra shift) in a single particle level. We also explore metal ion sensing capability based on our coupled plasmonic core-satellites, which enabled at least 1000 times better detection limit as compared to that of a single plasmonic nanoparticle. Our results demonstrate and suggest substantial promise for the development of coupled plasmonic nanostructures for ultrasensitive detection of various biological and chemical analytes.     

Plasmonic Switching of the Reaction Pathway: Visible‐Light Irradiation Varies the Reactant Concentration at the Solid–Solution Interface of a Gold–Cobalt Catalyst

Product selectivity of alkyne hydroamination over catalytic Au₂Co alloy nanoparticles (NPs) can be made switchable by a light‐on/light‐off process, yielding imine (cross‐coupling product of aniline and alkyne) under visible‐light irradiation, but 1,4‐diphenylbutadiyne in the dark. The low‐flux light irradiation concentrates aniline on the catalyst, accelerating the catalytic cross‐coupling by several orders of magnitude even at a very low overall aniline concentrations (1.0×10^?3 mol L^?1). A tentative mechanism is that Au₂Co NPs absorb light, generating an intense fringing electromagnetic field and hot electrons. The sharp field‐gradient (plasmonic optical force) can selectively enhance adsorption of light‐polarizable aniline molecules on the catalyst. The light irradiation thereby alters the aniline/alkyne ratio at the NPs surface, switching product selectivity. This represents a new paradigm to modify a catalysis process by light.