Thermo-Responsive Hydrogels Coupled with Photothermal Agents for Biomedical Applications.

Intelligent hydrogels are materials with abilities to change their chemical nature or physical structure in response to external stimuli showing promising potential in multitudinous applications. Especially, photo-thermo coupled responsive hydrogels that are prepared by encapsulating photothermal agents into thermo-responsive hydrogel matrix exhibit more attractive advantages in biomedical applications owing to their spatiotemporal control and precise therapy. This work summarizes the latest progress of the photo-thermo coupled responsive hydrogel in biomedical applications. Three major elements of the photo-thermo coupled responsive hydrogel, i.e., thermo-responsive hydrogel matrix, photothermal agents, and construction methods are introduced. Furthermore, the recent developments of these hydrogels for biomedical applications are described with some selected examples. Finally, the challenges and future perspectives for photo-thermo coupled responsive hydrogels are outlined.

The application of post-denitrification fixed biofilm reactor for polishing secondary effluent: Nitrate removal, soluble microbial products and micropollutants biotransformation.

This study was conducted to comprehensively evaluate the role of hydraulic retention time (HRT) on simultaneous removal of nitrate and micropollutants (MPs) in secondary effluent from wastewater treatment plants in post-denitrification fixed biofilm reactor (PDFBR). Results showed that PDFBR was favorable for nitrate removal (above 94%). Prolonged HRT promoted the bio-utilization of nonaromatic soluble microbial products with low molecular weight and reduced biomass production. MPs was partially removed in PDFBRs (below 48%). Microbial diversity increased along the extending of HRT and thus partially enhanced MPs removal. Batch experiments showed that changing HRT had no direct impact on the biodegradation rates of the selected MPs. Correlation analysis revealed that Dechloromonas, Terrimonas, and Phreatobacter were reasonable for simultaneous removal of MPs and nitrate. The abundance of nosZ gene had a rapid decrease under extreme HRT. This study provides insights into polishing nitrate and MPs from secondary effluent in a denitrifying biofilm system.

Ball-Milled Silicon with Amorphous Al2O3/C Hybrid Coating Embedded in Graphene/Graphite Nanosheets with a Boosted Lithium Storage Capability.

Electrochemical active silicon has attracted great attention as anodes for lithium-ion batteries owing to a high theoretical capacity of 4200 mA h g-1. In this work, ball-milled silicon particles with submicron size were strategically modified with a hybrid coating of amorphous alumina and carbon, which simultaneously embedded in a porous framework of in situ exfoliated graphene/graphite nanosheets (GGN). The composite exhibits an enhanced electrochemical performance, including high cycling stability and superior rate capability. An initial discharge capacity of 1294 mA h g-1 and a reversible charge capacity of 1044 mA h g-1 at 0.2 A g-1 can be achieved with a high initial Coulombic efficiency of up to ca. 81%. Additionally, the composite can remain 902 mA h g-1 after 100 discharge/charge cycles, accounting for a high retention of about 86%. This silicon composite is a promising anode material for high performance lithium-ion batteries with a high energy density, and the facile one-pot fabrication route is low cost and scalable, with a great prospect for practical application.

Silver-decorated MXene nanosheets as a radical initiator for polymerization and multifunctional hydrogels.

Silver nanoparticle-decorated multilayered titanium carbide MXene (Ag/Ti3C2Tx) itself is capable of initiating the polymerization of a variety of acrylic monomers, due to it being able to generate hydroxyl radicals via the pseudo-Fenton reaction. Furthermore, double-network hydrogel Ag/Ti3C2Tx@gelatin/PAAm is synthesized by a one-pot procedure and displays a good near-infrared light-triggered shape-memory performance.

Dual-recognition membrane Adsorbers combining hydrophobic charge-induction chromatography with surface imprinting via multicomponent reaction.

The combination of mixed-mode chromatography (MMC) and molecular imprinting technology (MIT) has been proven to be successful for protein separation, but suffered from cumbersome material preparation and limited performance. In this work, a new modification method marrying atom transfer radical polymerization (ATRP) and multicomponent reaction was proposed to simplify the preparation process. Using regenerated cellulose (RC) membrane as the substrate, immunoglobulin G (IgG) as the template protein and tryptamine as the ligand, a dual-recognition membrane adsorbers (MIM) was prepared by mild Ugi four-component reaction (Ugi-4CR) and surface initiated ATRP. Control the ATRP time is the key for surface imprinting. The static IgG uptake and selectivity of UGI membrane were 45 mg/mL and 1.8, respectively, while those of MIM-0.5 were 42.5 mg/mL and 14, indicating that the introduction of molecular imprinting technology significantly improved the selectivity of the membrane to IgG. The MIM-0.5 membrane retains the pH-dependent and salt-tolerant of HCIC. The dynamic flow-through results showed that the MIM-0.5 membrane could effectively separate IgG from IgG/BSA mixed solution with the purity of 88% and retained its bioactivity. This work demonstrated the feasibility of bonding HCIC and MIT to the membrane surface by Ugi-4CR and ATRP.

Poly(siloxane imide) Binder for Silicon-Based Lithium-Ion Battery Anodes via Rigidness/Softness Coupling.

Binders play a crucial role in maintaining mechanical integrity of electrodes in lithium-ion batteries. However, the conventional binders lack proper elasticity, and they are not suitable for high-performance silicon anodes featuring huge volume change during cycling. Herein, a poly(siloxane imide) copolymer (PSI) has been designed, synthesized, and utilized as a binder for silicon-based anodes. A rigidness/softness coupling mechanism is demonstrated by the PSI binder, which can accommodate volume expansion of the silicon anode upon lithiation. The electrochemical performance in terms of cyclic stability and rate capability can be effectively improved with the PSI binder as demonstrated by a silicon nanoparticle anode.

Microporous Binder for the Silicon-Based Lithium-Ion Battery Anode with Exceptional Rate Capability and Improved Cyclic Performance.

Silicon anodes have attracted much attention owing to their high theoretical capacity. Nonetheless, an inevitable and enormous volumetric expansion of silicon in the lithiated state restrained the development of the silicon anode for lithium-ion batteries. Fortunately, the utilization of the high-performance binder is a promising and effective way to overcome such obstacles. Herein, a polymer of intrinsic microporosity (PIM) is applied as the binder for the silicon anode, which is composed of a rigid polymer backbone, an intrinsic porous structure, and active carboxyl groups (PIM-COOH). Compared to the traditional binder, both the long-term stability and rate performance of the electrode using PIM-COOH as the binder are significantly improved. The mechanism responsible for the enhanced performance is investigated. The PIM-COOH binder provides stronger adhesion toward the current collector than the conventional binders. The unique rigid polymer backbone and porous structure of the PIM-COOH binder enable a good capability to withstand the volume change and external stress generated by the Si anode. The porous structure of the PIM-COOH binder enhances lithium-ion transportation compared to the SA binder, which improves rate performance of the silicon anode. This work provides a unique insight into design, synthesis, and utilization of the binders for lithium-ion batteries.

Formation of a thin and continuous MOF membrane with 2-D MOF nanosheets as seeds via layer-by-layer growth.

Current MOF composite membranes usually suffer from unduly thick MOF layers and poor adhesion with the polymer substrate. We prepared a thin MOF film (440 nm) on a polymer support with 2-D MOF nanosheets as seeds via a layer-by-layer growth. These 2-D MOF seeds not only provided bonding between the MOF film and the polymer substrate but also facilitated the formation of a continuous and defect-free MOF membrane, which demonstrated excellent performance in gas separation.

Synthesis, characterization and excellent antibacterial property of cellulose acetate reverse osmosis membrane via a two-step reaction.

In order to improve the antibacterial efficiency and spectrum of cellulose acetate reverse osmosis membrane (CA-RO), both quaternary ammonium and bromoacetyl groups were introduced into cellulose diacetate under mild conditions forming CA-RO with bi-antibacterial groups for seawater desalination. Bromoacetyl bromide and a series of tertiary amine were chosen as the modification agents respectively. The characterization results showed that both two antibacterial groups were successfully introduced with a certain density. The obtaining membrane had a less hydrophilic but more electronegative surface as well as improved mechanical property. The flux values increased firstly and decreased subsequently after twice modifications while the salt rejection rose. The membrane modified with N,N-dimethyloctylamine (DMOA) had the optimal comprehensive performance of flux and salt rejection. The antibacterial testing results indicated that the resulting RO membranes showed high antibacterial efficiency and broad-spectrum. Their bactericidal rates against gram-negative Escherichia coli (E. coli) and gram-positive Staphylococcus aureus (S. aureus) were more than 99.9%.

Direct Non-Oxidative Methane Conversion in a Millisecond Catalytic Wall Reactor.

Direct non-oxidative methane conversion (DNMC) has been recognized as a single-step technology that directly converts methane into olefins and higher hydrocarbons. High reaction temperature and low catalyst durability, resulting from the endothermic reaction and coke deposition, are two main challenges. We show that a millisecond catalytic wall reactor enables stable methane conversion, C2+ selectivity, coke yield, and long-term durability. These effects originate from initiation of the DNMC on a reactor wall and maintenance of the reaction by gas-phase chemistry within the reactor compartment. The results obtained under various temperatures and gas flow rates form a basis for optimizing the process towards lighter C2 or heavier aromatic products. A process simulation was done by Aspen Plus to understand the practical implications of this reactor in DNMC. High carbon and thermal efficiencies and low cost of the reactor materials are realized, indicating the technoeconomic viability of this DNMC technology.

Hierarchical Porous and Zinc-Ion-Crosslinked PIM-1 Nanocomposite as a CO2 Cycloaddition Catalyst with High Efficiency.

CO2 cycloaddition to epoxides is an effective and economical utilization method to alleviate the current excessive CO2 emission situation. The development of catalysts with both high catalytic efficiency and high recyclability is necessary but challenging. In this context, a heterogeneous catalyst was synthesized based on a zinc-ion-crosslinked polymer with intrinsic microporosity (PIM-1). The high microporosity of PIM-1 promoted a high Zn2+ loading rate. Additionally, the relatively stable ionic bond formed between Zn2+ and the PIM-1 framework through electrostatic interaction ensured high loading stability. In the process of CO2 cycloaddition with propylene epoxide, an optimized conversion of 90 % with a turnover frequency as high as 9533 h-1 could be achieved within 0.5 h at 100 °C and 2 MPa. After 15 cycles, the catalytic efficiency did not demonstrate a significant decline, and the catalyst was able to recover most of its activity after Zn2+ reloading. This work thereby provides a strategically designed CO2 conversion catalyst based on an ionic crosslinked polymer with intrinsic microporosity.

Non-leaching antibacterial cellulose triacetate reverse osmosis membrane via covalent immobilization of quaternary ammonium cations.

A novel procedure to fabricate quaternized cellulose triacetate reverse osmosis (QCTA-RO) membranes via the etherification procedure between partially hydrolyzed CTA-RO membrane and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride (CHPTAC) in alkaline solutions (pH=9-11) for different reaction time (1, 2, 3 and 4h) was proposed. The structure and performances of the obtained QCTA-RO membranes were characterized and their antibacterial performances against E. coli and S. aureus were evaluated through colony counting method. The results showed that quaternary amine group was successfully grafted on the surface of membrane via covalently bond without significant damage to morphology, mechanical performance and thermal stability. The permeation flux values increased with prolonging modification time to 3h, while the salt rejection decreased slightly but remained above 92%. QCTA-RO membranes displayed good antibacterial activity against Gram-negative E. coli and Gram-positive S. aureus and their bactericidal rates were 78.7-89.0% and 64.7-76.6% respectively at the optimized modification time of 2-3h.

Silicon Oxycarbide/Carbon Nanohybrids with Tiny Silicon Oxycarbide Particles Embedded in Free Carbon Matrix Based on Photoactive Dental Methacrylates.

A new facile scalable method has been developed to synthesize silicon oxycarbide (SiOC)/carbon nanohybrids using difunctional dental methacrylate monomers as solvent and carbon source and the silane coupling agent as the precursor for SiOC. The content (from 100% to 40% by mass) and structure (ratio of disordered carbon over ordered carbon) of the free carbon matrix have been systematically tuned by varying the mass ratio of methacryloxypropyltrimethoxysilane (MPTMS) over the total mass of the resin monomers from 0.0 to 6.0. Compared to the bare carbon anode, the introduction of MPTMS significantly improves the electrochemical performance as a lithium-ion battery anode. The initial and cycled discharge/charge capacities of the SiOC/C nanohybrid anodes reach maximum with the MPTMS ratio of 0.50, which displays very good rate performance as well. Detailed structures and electrochemical performance as lithium-ion battery anodes have been systematically investigated. The structure-property correlation and corresponding mechanism have been discussed.

Porous titania/carbon hybrid microspheres templated by in situ formed polystyrene colloids.

A new strategy to synthesize hierarchical, porous titania/carbon (TiO2/C) hybrid microspheres via solvothermal reaction in N,N'-dimethyl formamide (DMF) has been developed. In situ formed polystyrene (PS) colloids have been used as templating agent and carbon source, through which TiO2/PS microspheres with a diameter of ca. 1 µm are built by packed TiO2 nanoparticles of tens of nanometers. The TiO2/PS microspheres are converted to TiO2/C microspheres with different amounts of carbon under controlled calcination condition. The mechanism investigation unveils that the introduction of concentrated HCl creates surface tension between PS and DMF, leading to the formation of PS colloids in solution. The solvothermal treatment further promotes the formation of PS colloids and integration of the titania nanoparticles within the PS colloids. The morphology, crystallinity, nature and content of carbon, UV-Vis absorption, carbon doping, pore size distribution, pore volume, and BET surface area of the TiO2 microspheres with different amounts of carbon have been measured. The applications of the TiO2/C hybrid microspheres as photo catalyst for water splitting and lithium-ion battery anode have been demonstrated. Superior photo catalytic activity for hydrogen conversion under both full spectrum and visible light illumination compared to commercial P25 has been observed for the TiO2/C microspheres with 2 wt% of carbon. Besides, the TiO2/C microspheres with 8 wt% of carbon as lithium-ion battery anode showed a much higher capacity than the bare TiO2 microsphere anode. The origin for the enhanced performance as photo catalyst and lithium-ion battery anode is discussed.

Facile Scalable Synthesis of TiO2/Carbon Nanohybrids with Ultrasmall TiO2 Nanoparticles Homogeneously Embedded in Carbon Matrix.

A facile scalable synthesis of TiO2/C nanohybrids inspired by polymeric dental restorative materials has been developed, which creates ultrasmall TiO2 nanoparticles homogeneously embedded in the carbon matrix. The average size of the nanoparticles is tuned between about 1 and 5 nm with the carbon content systematically increased from 0% to 65%. Imaging analysis and a scattering technique have been applied to investigate the morphology of the TiO2 nanoparticles. The composition, nature of carbon matrix, crystallinity, and tap density of the TiO2/C nanohybrids have been studied. The application of the TiO2/C nanohybrids as lithium-ion battery anode is demonstrated. Unusual discharge/charge profiles have been exhibited, where characteristic discharge/charge plateaus of crystalline TiO2 are significantly diminished. The tap density, cyclic capacities, and rate performance at high current densities (10 C, 20 C) of the TiO2/C nanohybrid anodes have been effectively improved compared to the bare carbon anode and the TiO2/C nanohybrids with larger particle size.

A Scalable Method toward Superhydrophilic and Underwater Superoleophobic PVDF Membranes for Effective Oil/Water Emulsion Separation.

A superhydrophilic and underwater superoleophobic PVDF membrane (PVDFAH) has been prepared by surface-coating of a hydrogel onto the membrane surface, and its superior performance for oil/water emulsion separation has been demonstrated. The coated hydrogel was constructed by an interfacial polymerization based on the thiol-epoxy reaction of pentaerythritol tetrakis (3-mercaptopropionate) (PETMP) with diethylene glycol diglycidyl ether (PEGDGE) and simultaneously tethered on an alkaline-treated commercial PVDF membrane surface via the thio-ene reaction. The PVDFAH membranes can be fabricated in a few minutes under mild conditions and show superhydrophilic and underwater superoleophobic properties for a series of organic solvents. Energy dispersive X-ray (EDX) analysis shows that the hydrogel coating was efficient throughout the pore lumen. The membrane shows superior oil/water emulsion separation performance, including high water permeation, quantitative oil rejection, and robust antifouling performance in a series oil/water emulsions, including that prepared from crude oil. In addition, a 24 h Soxhlet-extraction experiment with ethanol/water solution (50:50, v/v) was conducted to test the tethered hydrogel stability. We see that the membrane maintained the water contact angle below 5°, indicating the covalent tethering stability. This technique shows great promise for scalable fabrication of membrane materials for handling practical oil emulsion purification.

Green facile scalable synthesis of titania/carbon nanocomposites: new use of old dental resins.

A green facile scalable method inspired by polymeric dental restorative composite is developed to synthesize TiO2/carbon nanocomposites for manipulation of the intercalation potential of TiO2 as lithium-ion battery anode. Poorly crystallized TiO2 nanoparticles with average sizes of 4-6 nm are homogeneously embedded in carbon matrix with the TiO2 mass content varied between 28 and 65%. Characteristic discharge/charge plateaus of TiO2 are significantly diminished and voltage continues to change along with proceeding discharge/charge process. The tap density, gravimetric and volumetric capacities, and cyclic and rate performance of the TiO2/C composites are effectively improved.

Surface glycosylation of polysulfone membrane towards a novel complexing membrane for boron removal.

In this study, a novel complexing membrane was synthesized for boron removal from aqueous solution. A glycopolymer, poly(2-gluconamidoethyl methacrylate) (PGAMA), was grafted onto the chloromethylated polysulfone (CMPSF) microporous membrane via surface-initiated ATRP (SIATRP). The glycosylated PSF (GlyPSF) membrane was characterized by attenuated total refection-Flourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscopy (FESEM). It was demonstrated that PGAMA was successfully anchored onto the membrane surface and the grafting yield can be tuned in a wide range up to 5.9 mg/cm(2) by varying the polymerization time. The complexing membrane can adsorb boron rapidly with the equilibrium reached within 2h and has a remarkable high boron adsorption capacity higher than 2.0 mmol/g at optimized conditions. Freundlich, Langmuir, and Dubinin-Radushkevich adsorption isotherms were applied, and the data were best described by Langmuir model. Kinetic data were analyzed, and the data fitted very well to the pseudo-second-order rate expression. The optimal pH for boron uptake is in a wide range of 6-9, and the optimal initial boron concentration is over 300 mg/L. Studies of ionic strength effects indicated the formation of inner-sphere surface complexes. The complexed boron can be leached quantitatively under acid condition.

Direct electrochemistry of hemoglobin entrapped in cyanoethyl cellulose film and its electrocatalysis to nitric oxide.

A water-soluble cyanoethyl cellulose (CEC), homogeneously synthesized in NaOH/urea aqueous solution, was used as an immobilization matrix to entrap proteins and enzymes. Then hemoglobin (Hb) was used as a template to fabricate CEC-Hb biomimetic membranes in which the Hb showed direct electrochemistry on a glass carbon electrode (GCE). The characterizations of CEC-Hb film were demonstrated by ultraviolet-visible (UV-vis) spectra, scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). The electrochemical behaviors of Hb in CEC film have been investigated and a pair of well-defined and quasi-reversible cyclic voltammetric peaks for the protein heme Fe(III)/Fe(II) redox couples was observed at about -0.369 V (vs. SCE). The CEC-Hb film exhibited a good electrocatalytic activity for the reduction of nitric oxide (NO). The amperometric response of the biosensor varied linearly with the NO concentration ranging from 1.1x10(-6) to 1.3x10(-4) mol L(-1). Moreover, the studied biosensor exhibited high sensibility, good reproducibility, and long-term stability. Finally, this method has applied to monitoring the NO release from biologic samples.