Reversible Change in Performances of Polymer Networks via Invertible Architecture-Transformation of Cross-Links.

A polymer nanoparticle network using single-chain nanoparticles (SCNPs) as cross-links is designed. The experimental and theoretical study shows that incorporating SCNPs in polymer networks leads to smaller mesh size, faster terminal relaxation time, and reduced fluctuation among cross-links, resulting in a significant increase in shear storage modulus, and enhancement in tensile stress. Notably, the reversible single-chain collapse of SCNPs under thermal stimulation enables the polymer network to undergo coherent changes between two topological states, thereby exhibiting reversible transformations between soft and stiff states. This approach and finding can effectively tailor the mechanical properties of polymer networks, potentially leading to the development of intelligent, responsive materials.

Remarkable untangled dynamics behavior of multicyclic branched polystyrenes.

A typical multicyclic branched-topology polystyrene (c-BPS) with high molecular weight (30 K ≤ Mw MALLS ≤ 300 K g mol-1) and narrow dispersity (1.2 ≤ D ≤ 1.3) was efficiently synthesized by combining atom transfer radical polymerization (ATRP) and atom transfer radical coupling (ATRC) techniques. The topological constraints imposed by the presence of cyclic units and branch points had a marked influence on the entanglement behaviors of the polymer chains in solution. Therefore, c-BPS possesses the lowest loss modulus (G'') and viscosity (η), the highest diffusion coefficient (D0), the largest mesh size (ξ) and the fastest terminal relaxation (TR), compared with branched and linear precursors.

Laser irradiation method to prepare polyethylene porous fiber membrane with ultrahigh xylene gas filtration capacity.

In recent years, volatile organic compound (VOC) gases have caused potential harm to people's health. This study reveals the preparation of polyethylene porous fiber membrane with excellent low-concentration VOCs filtration performance via laser irradiation technology. A neodymium-doped yttrium aluminum garnet (Nd:YAG) pulsed laser beam was used to scan the laser-sensitive low-density polyethylene/carbon black (LDPE/CB) fibers prepared by nanolayer coextrusion in the air. The controllable thermal energy generated by laser irradiation makes the surface of the fiber membrane to produce a porous carbon layer in situ. Laser power and scanning speed are important parameters for controlling laser-induced carbonization. The results indicate that the rich "fluffy" carbon structures on the surface of the porous fiber membrane can efficiently adsorb xylene gas. This study can provide a positive reference for the large-scale preparation of polyolefin porous fiber membrane with VOCs filtration by simple and efficient laser irradiation method.

High Performance and Flexible Polyvinylpyrrolidone/Ag/Ag2Te Ternary Composite Film for Thermoelectric Power Generator.

In this work, polyvinylpyrrolidone (PVP) coated Ag-rich Ag2Te nanowires (NWs) were synthesized by a wet chemical method using PVP coated Te NWs as templates, and a flexible PVP/Ag/Ag2Te ternary composite film on a nylon membrane was prepared by vacuum assisted filtration, followed by heat treatment. TEM and STEM observations of the focused ion beam prepared sample reveal that the composite film shows a porous network-like structure and that the Ag and Ag2Te exist as nanoparticles and NWs, respectively, both bonded with PVP. The Ag nanoparticles are formed by separation of the Ag-rich Ag2Te NWs during the heat treatment. For the composite film starting from a Ag/Te initial molar ratio of 6:1, a high power factor of 216.5 µW/mK2 is achieved at 300 K, and it increases to 370.1 µW/mK2 at 393 K. Bending tests demonstrate excellent flexibility of the hybrid film. A thermoelectric (TE) prototype composed of five legs of the hybrid film is assembled, and a maximum output power of 469 nW is obtained at a temperature gradient of 39.6 K, corresponding to a maximum power density of 341 µW/cm2. This work provides an effective route to a composite film with high TE performance and excellent flexibility for wearable TE generators.

Nanolayer coextrusion: An efficient and environmentally friendly micro/nanofiber fabrication technique.

Researchers have developed many types of nanoscale materials with different properties. Among them, nanofibers have recently attracted increasing interest and attention due to their functional versatility and potential applications in diverse industries, including tapes, filtration, energy generation, and biomedical technologies. Nanolayer coextrusion, a novel polymer melt fiber processing technology, has gradually received attention due to its environmental friendliness, efficiency, simplicity and ability to be mass-produced. Compared with conventional techniques, nanolayer coextruded non-woven nanofibrous mats offer advantages such as a tunable fiber diameter, high porosity, high surface area to volume ratio, and the potential to manufacture composite nanofibers with different components to achieve desired structures and properties. Dozens of thermoplastic polymers have been coextruded for various applications, and the variety of polymers has gradually continued to increase. This review presents an overview of the nanolayer coextrusion technique and its promising advantages and potential applications. We discuss nanolayer coextrusion theory and the parameters (polymer and processing) that significantly affect the fiber morphology and properties. We focus on varied applications of nanolayer coextruded fibers in different fields and conclude by describing the future potential of this novel technology.

Voltage-responsive single-chain polymer nanoparticles via host-guest interaction.

Poly(N-(2-hydroxyethyl)acrylamide) with pendant ß-cyclodextrin was synthesized and intramolecularly crosslinked with bridged bis(ferrocene). This supramolecular nanoparticle can be changed reversibly between a coil and a nanoparticle upon external voltage stimuli.

Supramolecular Nanoparticles via Single-Chain Folding Driven by Ferrous Ions.

Single-chain nanoparticles can be obtained via single-chain folding assisted by intramolecular crosslinking reversibly or irreversibly. Single-chain folding is also an efficient route to simulate biomacromolecules. In present study, poly(N-hydroxyethylacrylamide-co-4'-(propoxy urethane ethyl acrylate)-2,2':6',2''-terpyridine) (P(HEAm-co-EMA-Tpy)) is synthesized via reversible addition fragmentation chain transfer polymerization. Single-chain folding and intramolecular crosslinking of P(HEAm-co-EMA-Tpy) are achieved via metal coordination chemistry. The intramolecular interaction is characterized on ultraviolet/visible spectrophotometer (UV-vis spectroscopy), proton nuclear magnetic resonance ((1)H NMR), and differential scanning calorimetry (DSC). The supramolecular crosslinking mediated by Fe(2+) plays an important role in the intramolecular collapsing of the single-chain and the formation of the nanoparticles. The size and morphology of the nanoparticles can be controlled reversibly via metal coordination chemistry, which can be characterized by dynamic light scattering (DLS), transmission electron microscope (TEM), and atomic force microscope (AFM).

A multifunctional azobenzene-based polymeric adsorbent for effective water remediation.

The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π-π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials.

Highly efficient separation, enrichment, and recovery of peptides by silica-supported polyethylenimine.

Highly efficient and charge-selective adsorption and desorption of peptides at trace level by a solid-phase adsorbent is described. The adsorbent of SiO2@PEI is synthesized by covalent immobilization of branched polyethylenimines (PEI) exclusively on the outer surface of the porous silica particles (∼300 µm). For aqueous peptides (Mw = 600-3000 Da), SiO2@PEI can capture the negatively charged ones and leave the positively charged ones intact, and by adjusting pH of the system peptides with different isoelectric points (pIs) can be well separated. Targeted peptide at low abundance (at least as low as 0.1 mol % with respect to the highest one) can be well separated. The association constants of K > 10(12) M(-1) at pH > pI and K < 10(4) M(-1) at pH < pI are found; that is, selectivity > 10(8) is generally available. Thus, a peptide even at sub-femtomolar level can be extracted and eluted for analysis, and efficient recovery (79-92%) of the peptides is found. The extraction is mainly promoted by multisite electrostatic interaction, and the hydrophilic and cationic properties of PEI at low pH play a unique role in desorption efficiency and selectivity. The unbiased nature of this method renders the adsorbent applicable to the efficient separation of a broad spectrum of peptides, including those with similar pIs.

Design of D-π-A type photoacid generators for high efficiency excitation at 405 nm and 800 nm.

New sulfonium salts with diphenylamino asymmetrically substituted stilbene as a D-π-A conjugated system have been synthesized. The resulting photoacid generators exhibit a highly efficient acid photogeneration process by either one-photon 405 nm or two-photon 800 nm excitation.

Photochromism-based detection of volatile organic compounds by W-doped TiO2 nanofibers.

W-doped TiO(2) nanofibers with various compositions (W/Ti: 2-8%) were fabricated by the electrospinning method from respective precursor solutions containing tungsten(V) pentaethoxide, titanium tetraisopropoxide (TTIP), and polyvinylpyrrolidone (PVP), followed with calcination at 550 °C. Morphological and structural characteristics of these nanofibers were studied with SEM, XRD and XPS. W-doping inhibited the crystal growth and anatase-to-rutile transformation of TiO(2) nanofibers. W-doped TiO(2) nanofiber mats showed good photocatalytic oxidation abilities for acetone. Obvious color change from white to blue of mats during the photocatalysis process can be detected by naked eyes, which provides a good way in detection of pollutants in indoor air, especially for the volatile organic compounds (VOCs).

Hydrophobic iron oxide and CdSe/ZnS nanocrystal loaded polyglutamate/polyelectrolyte micro- and nanocapsules.

A novel, simple and generic method for the preparation of hydrophobic nanocrystal loaded composite capsules is introduced. Firstly, magnetic Fe(3)O(4) nanocrystals prepared by pyrolysis of fatty acid iron salts in non-aqueous media were successfully incorporated into water-dispersible polyglutamate/polyelectrolyte capsules by combining an ultrasonic protocol and polyelectrolyte layer-by-layer (LBL) assembly. Then, inspired by the similar synthesis mechanism of oxide and semiconductor nanocrystals based on organometallic approaches in non-aqueous media, two kinds of fluorescent semiconductor quantum dots (zinc sulfide-capped cadmium selenide nanocrystals) were chosen as models to explore QD loaded composite capsules. With rhodamine B isothiocyanate (RBITC) tagging PEI as outer layers, fluorescence micrographs and confocal microscopy images indicate that CdSe/ZnS QDs were successfully incorporated into polyglutamate/polyelectrolyte capsules with almost unchanged optical properties and the color of RBITC tagging PEI shell can be changed under different excitation. Color transformation ascribed to spectral conversion of embedded QDs was also observed after the capsules were stored under day light for days. TEM, electron diffraction (ED), and ESEM revealed that the method leads to well-defined nanocrystal loaded composite nanocapsules and is simple and generic.

A facile method for the fabrication of vinyl functionalized hollow silica spheres.

In this paper, we adopt a facile method to prepare vinyl functionalized hollow silica spheres. Vinyl functionalized silica shells were coated on positively charged polystyrene particles by hydrolysis and condensation of vinyltriethoxysilane (VTES), the polystyrene cores were dissolved subsequently in the same medium to form monodispersed vinyl functionalized hollow silica spheres. Neither additional dissolving nor a calcination process is necessary to remove the polystyrene cores. Transmission electron microscopy (TEM), FT-IR analysis, TGA and porosity measurements were used to characterize the monodispersed vinyl functionalized hollow silica spheres.

Preparation and electrochromic property of covalently bonded WO3/polyvinylimidazole core-shell microspheres.

Covalently bonded WO3/polyvinylimidazole (C-WO3/PVI) core-shell microspheres in sizes of 250 nm were prepared. The microstructures of C-WO3/PVI core-shell microspheres were characterized by TEM, IR, and XRD. It is found that the chemical and thermal stabilities of C-WO3/PVI core-shell microspheres are higher than those of pure WO3 nanoparticles and noncovalently bonded WO3/polyvinylimidazole (NC-WO3/PVI) core-shell microspheres. This is attributed to the strengthened interaction of the WO3 nanoparticle core and the PVI shell resulting from the interaction of covalent bonds. The electrochromic device made by the C-WO3/PVI core-shell microspheres was studied. It is suggested that the C-WO3/PVI core-shell microspheres exhibit better electrochromic properties than pure WO3 nanoparticles or NC-WO3/PVI core-shell microspheres.