Integrated Evaporator for Efficient Solar-Driven Interfacial Steam Generation.

Solar-driven interfacial steam generation is a promising technique for clean water production because it can minimize thermal loss by localizing solar-to-heat conversion at the air/liquid interface. Here we report an integrated solar evaporator by partially growing 2D polypyrrole microsheets within a melamine foam through chemical vapor polymerization. These microsheets can induce multiple light reflections within the foam, enable omnidirectional light absorption, provide abundant surfaces to promote heat transfer, and achieve spatially defined hydrophobicity to facilitate vapor escape. Meanwhile, the inherent hydrophilicity of the bottom part of the foam promotes spontaneous upward water transport and suppresses heat loss. The composite foam exhibits an excellent apparent evaporation rate of ∼2 kg/(m2·h) and solar-to-vapor efficiency of ∼91%. The combined advantages of large surface area, high efficiency, low cost, all-weather application, excellent durability, and scalable manufacturing make our integrated design promising for fabricating large-scale solar steam generation systems that are suitable for practical clean water production.

Space-Confined Seeded Growth of Black Silver Nanostructures for Solar Steam Generation.

Plasmonic metal nanostructures have attracted considerable attention for solar energy harvesting due to their capability in photothermal conversion. However, the narrow resonant band of the conventional plasmonic nanoparticles greatly limits their application as only a small fraction of the solar energy can be utilized. Herein, a unique confined seeded growth strategy is developed to synthesize black silver nanostructures with broadband absorption in the visible and near-infrared spectrum. Through this novel strategy, assemblages of silver nanoparticles with widely distributed interparticle distances are generated in rod-shaped tubular spaces, leading to strong random plasmonic coupling and accordingly broadband absorption for significantly improved utilization of solar energy. With excellent efficiency in converting solar energy to heat, the resulting black Ag nanostructures can be made into thin films floating at the air/water interface for efficient generation of clean water steam through localized interfacial heating.

A target-triggered strand displacement reaction cycle: the design and application in adenosine triphosphate sensing.

A strand displacement reaction (SDR) system that runs solely on oligonucleotides has been developed for the amplification detection of adenosine triphosphate (ATP). It involves a target-induced SDR and an entropy-driven catalytic cycle of two SDRs with five oligonucleotides, denoted as substrate, fuel, catalyst, C-1, and C-2. Catalyst, released from the ATP aptamer-catalyst duplex by ATP molecule, catalyzes the SDRs to finally form the substrate-fuel duplex. All of the intermediates in the catalytic SDR processes have been identified by polyacrylamide gel electrophoresis (PAGE) analysis. The introduction of ATP into the SDR system will induce the ATP aptamer to form G-quadruplex conformation so as to release catalyst and trigger the SDR cycle. When the substrate and C-2 oligonucleotides were labeled with a carboxyfluorescein (FAM) fluorophore and a 4-([4-(dimethylamino)phenyl]azo)benzoic acid (DABCYL) quencher, this SDR catalytic system exhibited a "turn-on" response for ATP. The condition for detecting ATP, such as Mg²âº concentration, has been optimized to afford a detection limit of 20 nM. This work provides an enzyme-free biosensing strategy and has potential application in aptamer-based biosensing.

Fabrication of superhydrophobic three-dimensionally ordered macroporous polytetrafluoroethylene films and its application.

Three-dimensionally ordered macroporous (3DOM) polytetrafluoroethylene (PTFE) has hardly been prepared due to the poor solubility in most of solvents and high melting temperature of PTFE raw material. In this work, monodispersed polystyrene (PS) microspheres and PTFE latex particles were controlled to simultaneously deposit from water. After the deposits were calcinated at 400 °C, a self-supported superhydrophobic 3DOM PTFE film with a static water contact angle of 154° was successfully fabricated. The pore size can be tunable from 1.5 to 3 µm, depending on the size of PS microspheres. The prepared 3DOM PTFE film were used as micromolds and microreactors to prepare poly(methyl methacrylate) (PMMA) particles and TiO2 macroporous material, respectively. This work provides a facile method to fabricate 3DOM PTFE materials.

Synthesis of anisotropic polymer/inorganic particles via asymmetric swelling-dissolving process.

In this work, an asymmetric swelling-dissolving process of original submicrometer-sized decentered sulfonated polystyrene/silica (SPS/silica) particles in a ternary mixed solvent (water/ethanol/heptane) was first reported. Actinia-like and porous snowman-like SPS/silica composite particles are fabricated through tuning the composition of the ternary mixed solvent. Actinia-like particles, with a silica core embedded in a "blooming" SPS matrix, are obtained when the composition of the mixed solvent is 5 g/5 g/0.1 g (water/ethanol/heptane). If the amount of heptane in the mixed solvent is doubled, then porous snowman-like particles are produced. The TEM and SEM images show that silica particles are exposed in these two anisotropic SPS/silica composite particles compared with the original decentered SPS/silica particles. Considering the particles morphology and the swelling and dissolving performance of SPS in different solvents, the formation of the new-shaped anisotropic SPS/silica composite particles should be attributed to an asymmetric swelling-dissolving process; that is, the swelling-dissolving rate of SPS coating around the protruding silica part is faster than the other part of the composite particles. The anisotropic swelling-dissolving property of polymer/inorganic composite particles inspires a facile way to the fabrication of new composite particles.

Morphological control of multihollow polymer latex particles through a controlled phase separation in the seeded emulsion polymerization.

In this work, we first reported that the phase separation can take place both inside and outside of a multihollow-structured cross-linked seed microspheres swollen by styrene monomers in water during the radiation-induced seeded emulsion polymerization. The phase separation process in these two opposite directions will determine the morphology of final latex particles. First, sulfonated cross-linked polystyrene (SCPS) seed microspheres were swollen by styrene in water. Water will permeate into the SCPS seed microspheres during the swelling process, forced by the osmotic pressure produced by the strong hydrophilicity of the sulfonic acid groups. New aqueous phases are created and stabilized by the hydrophilic -SO3H groups, resulting in a multihollow structure of swollen SCPS seed microspheres. When the polymerization of styrene is induced by (60)Co γ-ray radiation, the phase separation of newly formed polystyrene phase will occur at the seed microsphere-water interface inside and/or outside of the SCPS seed microspheres through adjusting the diameter of seed microsphere, the content of cross-link agent, and the sulfonation degree of SCPS seed microspheres. As a result, SCPS latex particles with a variety of special morphologies, such as spherical multihollow, plum-like, and walnut-like latex particles were obtained. The results of this study provide not only a simple and interesting way to design and synthesize multihollow polymer latex particles with controllable surface morphologies but also a better understanding on phase separation mechanism during the swelling and polymerization of monomers in cross-linked amphiphilic polymer networks.

Formation of cagelike sulfonated polystyrene microspheres via swelling-osmosis process and loading of CdS nanoparticles.

In this report, we studied the formation mechanism of cagelike polymer microspheres fabricated conveniently and efficiently through a swelling-osmosis process of sulfonated polystyrene (SPS) microspheres in a ternary mixed solvent (water/ethanol/heptane). The scanning electron microscopy and transmission electron microscopy observations indicated that the morphology of the final cagelike SPS microspheres is mainly controlled by the composition of the mixed solvent and the swelling temperature. Considering the solubility parameters of related reagents and the low interface tension of heptane and the aqueous solution of ethanol (only 6.9 mN/m), we confirm that the porogen procedure starts from the swelling of SPS microspheres by heptane, followed by the osmosis process of water molecules into the swollen SPS microspheres forced by the strong hydrophilicity of -SO3H group. The water molecules permeated into SPS microspheres will aggregate into water pools, which form the pores after the microspheres are dried. These prepared cagelike SPS microspheres are further served as the scaffold for the in situ generated CdS nanoparticles under γ-ray radiation. The CdS/SPS composite microspheres show good fluorescence performance. This work shows that the cagelike SPS microspheres have a wide industrial application prospect due to their economical and efficient preparation and loading nanoparticles.

Fabrication and morphology of spongelike polymer material based on cross-linked sulfonated polystyrene particles.

A novel spongelike polymer material has been fabricated by γ-ray induced polymerization of methylmethacrylate (MMA) in an emulsion containing cross-linked sulfonated polystyrene (CSP) particles. Scanning electron microscopy (SEM) images reveal that the spongelike structure is made up of interlinked nanosized PMMA particles with micrometer-sized CSP-PMMA particles embedded inside. The nitrogen adsorption isotherm discloses that the spongelike material has a high specific surface area of 29 m(2)/g and a narrow pore size distribution of 60-120 nm. The formation mechanism is discussed in this paper, which indicates that the key steps to form the spongelike material include a Pickering emulsion stabilized by the CSP particles, followed by the swelling process of MMA into these particles. This approach offers a more convenient alternative to prepare polymeric spongelike material without any etching procedure.

Synthesis and characterization of ß-CD-coated polystyrene microspheres by γ-ray radiation emulsion polymerization.

Polystyrene (PS) microspheres coated with ß-cyclodextrin (ß-CD) were fabricated via γ-ray-induced emulsion polymerization in a ternary system of styrene/ß-CD/water (St/ß-CD/water). The solid inclusion complex of St and ß-CD particles formed at the St droplets-water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that ß-CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of ß-CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the ß-CD content even to 36°. Thus, this work provides a new and one-pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization.

One-pot synthesis of colloidal nanobowls and hybrid multipod-like nanoparticles by radiation miniemulsion polymerization.

A facile approach is proposed to one-pot synthesis of two kinds of nanoparticles: a new type of PS nanobowls (a hole appearing at the bottom of nanobowl) and PS/silica hybrid multipod-like nanoparticles. The two type of nanoparticles generated together during polymerization could be separated easily by centrifugation. Furthermore, the structure of nanobowls could be easily controlled by the weight ratio of monomer/silica. In addition, we find that the multipod-like nanoparticles play important roles in hydrophobic properties. The water contact angle increased from 24.0° to 143.3° after coated with the multipod-like nanoparticles.

Novel walnut-like multihollow polymer particles: synthesis and morphology control.

Novel walnut-like multihollow polymer particles were first prepared by gamma-ray radiation emulsion polymerization using cross-linked and sulfonated polystyrene spheres (CSPs) as the template. The formation process was studied in detail, and the morphology of walnut-like multihollow polystyrene particles could be controlled by the content of cross-linking agent, sulfonation time of CSP particles, and the weight ratio of monomer/CSP. In addition, an application of walnut multihollow polymer particles on bonding Ag nanoparticles onto the surface was achieved, which could be extended to other noble metal nanoparticles and could have a wide range of potential applications, such as catalysts, sensors, solar cells, and photonic crystals.

Biodegradable nano-organosilica gene carrier for high-efficiency gene transfection.

Finding and exploiting safe and high-efficiency gene carriers have always been critical tasks for gene therapy. In this work, novel GSH-triggered degradable organosilica nanoparticles grafted with guanidinated-fluorinated α-polylysine (o-SiNP-GF) are prepared to be studied as gene carriers. The organosilica matrix of o-SiNP-GF is synthesized through the hydrolysis and condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSPTS). The o-SiNP-GF nanoparticles have a size of about 20 nm. They possess a positive zeta potential of 42 mV in PBS (pH 7.4) and can be disintegrated in the presence of GSH. The cytotoxicity and DNA-binding ability of o-SiNP-GF, as well as in vitro gene transfection performance of DNA/o-SiNP-GF complexes, have been investigated using enhanced green fluorescent protein plasmid (pEGFP) as the DNA model. MTT assay shows that the cytotoxicity of o-SiNP-GF is very low even at a concentration up to 800 µg mL-1. The o-SiNP-GF nanoparticles can effectively bind to pEGFP through a complex coacervation method. The in vitro transfection efficiency of pEGFP/o-SiNP-GF complexes in 293T cells is up to 94.7% at the N/P ratio of 10, much higher than that of pEGFP/PEI complexes. Luciferase gene and fibroblast growth factor (FGF2) gene are also used as the DNA models to study the in vivo gene transfection performance of the o-SiNP-GF carrier by bioluminescence imaging and the evaluation of the healing rate of a mouse wound, respectively. Compared with naked DNA and DNA/PEI complexes, DNA/o-SiNP-GF complexes show much higher in vivo transfection efficiency. This work not only provides a way to prepare novel GSH-triggered degradable organosilica nanoparticles of size less than 50 nm, but also proves that the modification of guanidinated-fluorinated α-polylysine is an effective method to improve the efficiency of gene carriers.

The morphological control of anisotropic polystyrene/silica hybrid particles prepared by radiation miniemulsion polymerization.

Novel anisotropic hybrid particles with various morphologies have been synthesized by radiation miniemulsion polymerization for the first time.

Fabrication of inverse-opal lysozyme-imprinted polydopamine/polypyrrole microspheres with near-infrared-light-controlled release property.

The combination of the molecular imprinting technology and porous materials is a promising way to obtain high-efficient selective adsorption and separation materials for bioactive macromolecules. In this work, we developed a novel approach to prepare near-infrared (NIR)-light-response inverse-opal lysozyme (Lyz)-imprinted polydopamine/polypyrrole (IO-PDA/PPy-MIP) composite microspheres using micron-sized SiO2 colloidal crystal microspheres as the sacrificed template. The pore size of the IO-PDA/PPy-MIP microspheres can be tuned from 200 to 800 nm by the size of silica nanoparticles which self-assemble to form the template SiO2 colloidal crystal microspheres. The IO-PDA/PPy-MIP microspheres show a rapid selective adsorption ability for Lyz due to the inverse-opal macroporous structure. The adsorption capacity exceeds 800 mg/g within 20 min, and the imprinting factor is as high as 24. The bound Lyz molecules can be released rapidly from IO-PDA/PPy-MIP microspheres triggered by the irradiation of NIR laser and remain enough bioactivity to decompose Escherichia coli efficiently. The prepared IO-PDA/PPy-MIP microspheres also exhibit excellent structure stability and good recyclability. The adsorption capacity can remain up to 90% of the initial value after 5 times recycle. This work provides not only a method to prepare novel NIR-light-response inverse-opal macroporous molecularly imprinted microspheres, but also a new perspective on the design of selectively separation materials for the fast, high-efficient recognition and separation of biomacromolecules.

Incorporation of disodium alkyl polyoxyethylene ether sulfosuccinate inside styrene droplets: mechanism and its application for preparation of multihollow polymer spheres.

Emulsion polymerization of styrene was carried out using two kinds of alkyl polyoxyethylene ether sulfosuccinates as surfactant: disodium cetyl polyoxyethylene (25) ether sulfosuccinate (CPS) and octyl-phenol polyoxyethylene (10) ether sulfosuccinate (OPS). In experiments, the incorporation of CPS or OPS inside styrene droplets and polystyrene particles was clearly observed. Based on this phenomenon, multihollow polymer spheres are prepared in a one-step reaction and this strongly supports the proposed incorporation mechanism. CPS is more effective than OPS during the preparation of multiporous spheres. This difference between the two surfactants mainly contributes to the difference of the length of the EO (polyoxyethylene) group, which can determine the affinity among surfactant, styrene, and water molecules.

Emerging Multifunctional NIR Photothermal Therapy Systems Based on Polypyrrole Nanoparticles.

Near-infrared (NIR)-light-triggered therapy platforms are now considered as a new and exciting possibility for clinical nanomedicine applications. As a promising photothermal agent, polypyrrole (PPy) nanoparticles have been extensively studied for the hyperthermia in cancer therapy due to their strong NIR light photothermal effect and excellent biocompatibility. However, the photothermal application of PPy based nanomaterials is still in its preliminary stage. Developing PPy based multifunctional nanomaterials for cancer treatment in vivo should be the future trend and object for cancer therapy. In this review, the synthesis of PPy nanoparticles and their NIR photothermal conversion performance were first discussed, followed by a summary of the recent progress in the design and implementation on the mulitifunctionalization of PPy or PPy based therapeutic platforms, as well as the introduction of their exciting biomedical applications based on the synergy between the photothermal conversion effect and other stimulative responsibilities.

Chitosan-based core-shell structured particles for in vivo sustainable gene transfection.

A core-shell structured chitosan (CS)-based gene vector with a sustainable gene transfection effect was designed and successfully prepared in this study. The pEGFP was first combined with the thiolated and N-alkylated chitosan (TACS). Then, hydroxybutyl chitosan grafted with poly(ethylene glycol) (EG-HBC) was coated on the pEGFP-loaded TACS particles. The prepared pEGFP-loaded TACS@EG-HBC particles have a size of about 200 nm and little cytotoxicity. The in vitro and in vivo gene transfection experiments indicate that the pEGFP-loaded TACS@EG-HBC particles possess a better sustainable gene transfection capacity and a high transfection efficiency, which should be attributed to the biodegradation of the CS-based shell, the thiolation and N-alkylation modification on CS cores, and the grafted PEG chains with better biocompatibility. The in vivo gene expression of the loaded pEGFP can persist up to 60 days. This novel gene vector has a theoretical and practical significance for gene therapy with sustained transfection effect.

Fabrication of fibrous amidoxime-functionalized mesoporous silica microsphere and its selectively adsorption property for Pb(2+) in aqueous solution.

Fibrous cyano-modified mesoporous SiO2 microspheres with specific surface area of ca. 300 m(2) g(-1) have been successfully fabricated respectively by in-situ synthesis and post-modification methods, based on the hydrolysis of ethyl silicate in the presence of (2-cyanoethyl)triethoxysilane at a certain condition. TEM observations show that the average diameters of the prepared fibrous cyano-modified SiO2 microspheres by these two methods are 68 and 211 nm, respectively. The N2 adsorption-desorption isotherms analysis on the fibrous SiO2 microspheres show sharp peaks in the 10-20 nm range. After the cyano groups transformed to amidoxime groups, the adsorption behavior of the fibrous amidoxime-functionalized mesoporous SiO2 microspheres for Fe(3+), Cu(2+), and Pb(2+) was investigated. The results show that the prepared SiO2 microspheres can selectively adsorb Pb(2+). The maximum equilibrium adsorption capacity for Pb(2+) could reach 284 mg/g. The desorption of Pb(2+) in 2M HNO3 completes within 60 min. The efficiency of the desorption is as high as 96.2%. This work provides the methods to prepare amidoxime-functionalized SiO2 microsphere with high specific surface area and total pore volume, which has the potential to be applied as an efficient adsorbent for specific heavy metal ions.

The preparation, drug loading and in vitro NIR photothermal-controlled release behavior of raspberry-like hollow polypyrrole microspheres.

The combination of NIR photothermal therapy and chemotherapy is considered as the promising technique for future cancer therapy. The key point of this technique is the design and synthesis of photothermal agents with high-efficiency photothermal effects and high chemical drug loading capacity. Herein, submicron-sized raspberry-like hollow-structured polypyrrole microspheres (H-PPy) were facilely prepared through in situ polymerization of pyrrole on monodispersed polystyrene (PS) template microspheres with a diameter of 220 nm, followed by the chemical etching of PS templates. The prepared H-PPy microspheres show rapid and remarkable photothermal effects in water under NIR laser irradiation (808 nm) only for 5 min. Further, a model small molecular drug, (S)-(+)-camptothecin (CPT), was loaded into the void core by a simple dispersion-permeation process through the micro-pores on the raspberry-like PPy shell, with a loading capacity of 0.14 mg/(mg H-PPy). The MTT assay and the in vitro NIR-laser triggered release behavior indicated that pure H-PPy microspheres have good biosafety, but the release of loaded CPT into H-PPy microspheres can be achieved with remarkable spatial/temporal resolution after NIR laser irradiation, which results in excellent synergistic effect of photothermal and chemical ablation on HeLa cells, as proved by fluorescence microscopy. This work provides convenient synthesis of a promising cancer therapy agent with high drug-loading capacity and efficient NIR light photothermal effects, which can perfectly achieve the synergistic NIR photothermal therapy and chemotherapy of PPy microspheres.

Fabrication of High-Performance Magnetic Lysozyme-Imprinted Microsphere and Its NIR-Responsive Controlled Release Property.

The preparation of efficient and practical biomacromolecules imprinted polymer materials is still a challenging task because of the spatial hindrance caused by the large size of template and target molecules in the imprinting and recognition process. Herein, we provided a novel pathway to coat a NIR-light responsive lysozyme-imprinted polydopamine (PDA) layer on a fibrous SiO2 (F-SiO2) microsphere grown up from a magnetic Fe3O4 core nanoparticle. The magnetic core-shell structured lysozyme-imprinted Fe3O4@F-SiO2@PDA microspheres (MIP-lysozyme) can be easily separated by a magnet and have a high saturation adsorption capacity of lysozyme of 700 mg/g within 30 min because of the high surface area of 570 m(2)/g and the mesopore size of 12 nm of the Fe3O4@F-SiO2 support. The MIP-lysozyme microspheres also show an excellent selective adsorption of lysozyme (IF > 4). The binding thermodynamic parameters studied by ITC proves that the lysozyme should be restricted by the well-defined 3D structure of MIP-lysozyme microspheres. The MIP-lysozyme can extract lysozyme efficiently from real egg white. Owing to the efficient NIR light photothermal effect of PDA layer, the MIP-lysozyme microspheres show the controlled release property triggered by NIR laser. The released lysozyme molecules still maintain good bioactivity, which can efficiently decompose E. coli. Therefore, this work provides a novel strategy to build practical NIR-light-responsive MIPs for the extraction and application of biomacromolecules.