Multifunctional Poly Research Articles

One step preparation of multifunctional poly (ether sulfone) thin films with potential for wound dressing.

The increasing demand for higher-quality medical care has resulted in the obsolescence of traditional biomaterials. Medical care is currently transitioning from an era depending on single-functional biomaterials to one that is supported by multifunctional and stable biomaterials. Herein, long-lasting multifunctional poly(ether sulfone) thin films (MPFs) containing heparin-mimic groups and a quaternary ammonium compound (QAC) were prepared via semi-interpenetrating polymer network (SIPN) strategy. The MPFs, with rough surface and inner finger-like macrovoid, had better hydrophilicity and anti-protein fouling ability, as revealed by scanning electron microscopy (SEM), atomic force microscope (AFM) and water contact angle (WCA) and protein adsorption tests. The results of platelet adhesion and activation, and clotting time confirmed that the hemocompatibility of the MPFs was significantly improved. From cell culture and germ-culture test, it was noted that the overall trend of human umbilical vein endothelial cell (HUVEC) proliferation was enhanced by a combination of heparin-mimic groups and QAC, whereas the growth of Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was significantly prohibited. In addition, the MPFs were capable of modulating the expression level of basic fibroblast growth factor (bFGF) and transforming growth factor-beta1 (TGF-β1) in fibroblast, which was beneficial to controlling the formation of hypertrophic scar. In summary, the MPFs had potential to be used in the field of wound management and the study might help guide the design of surface structure of wound dressing.

Small-Molecule Inhibitors of Tankyrases as Prospective Therapeutics for Cancer.

Tankyrases are multifunctional poly(adenosine diphosphate-ribose) polymerases that regulate diverse biological processes including telomere maintenance and cellular signaling. These processes are often implicated in a number of human diseases, with cancer being the most prevalent example. Accordingly, tankyrase inhibitors have gained increasing attention as potential therapeutics. Since the discovery of XAV939 and IWR-1 as the first tankyrase inhibitors over two decades ago, tankyrase-targeted drug discovery has made significant progress. This review starts with an introduction of tankyrases, with emphasis placed on their cancer-related functions. Small-molecule inhibitors of tankyrases are subsequently delineated based on their distinct modes of binding to the enzymes. In addition to inhibitors that compete with oxidized nicotinamide adenine dinucleotide (NAD+) for binding to the catalytic domain of tankyrases, non-NAD+-competitive inhibitors are detailed. This is followed by a description of three clinically trialled tankyrase inhibitors. To conclude, some of challenges and prospects in developing tankyrase-targeted cancer therapies are discussed.

In Situ Construction of a Multifunctional Interface Regulator with Amino-Modified Conjugated Diene toward High-Rate and Long-Cycle Silicon Anodes.

Silicon (Si) is deemed to be the next-generation lithium-ion battery anode. However, on account of the poor electronic conductivity of Si materials and the instability of the solid electrolyte interphase layer, the electrochemical performance of Si anodes is far from reaching the application level. In this work, a multifunctional poly(propargylamine) (PPA) interlayer is constructed on the Si surface via a simple in situ polymerization method. Benefiting from the electronic conductivity, ionic conductivity, robust interphase interactions for hydrogen bonding, and stability of multifunctional PPA, the optimized Si@PPA-7% electrode shows improved lithium storage capability. A high capacity of 1316.3 mAh g-1 is retained after 500 cycles at 2.1 A g-1, and 2370.3 mAh g-1 can be delivered at 42 A g-1, which are in stark contrast to the unmodified Si electrode. Furthermore, the rate and cycle capabilities of the LiFePO4//Si@PPA-7% full cell are also obviously better than those of LiFePO4//Si.

Uncovering the Mechanism of Poly(ionic‐liquid)s Multiple Inhibition of Ion Migration for Efficient and Stable Perovskite Solar Cells

AbstractLongevity is a key constraint for hybrid perovskite based photovoltaics. Here it is demonstrated that ion migration‐induced degradation can be eliminated by incorporation of multifunctional poly(ionic‐liquid)s (PILs) additives, resulting in ultrastable perovskite solar cells (PVSCs). The presence of PILs suffices to construct an “ionic polymer network,” providing the functionalities of defect passivation and ion immobilization by concurrently forming a physical barrier and chemical bonding. Compared with the defect passivation effect for the imidazolium‐based PIL (PIL‐Im) case, the quaternary ammonium‐based PIL (PIL‐Am) shows a higher interaction energy with the perovskite due to the stronger electronic coupling ascribed to the additional complexation, which endows the corresponding perovskite with higher migration energy for iodide ions. As a result, the power conversion efficiency (PCE) of anion‐cation‐mixed hybrid n‐i‐p PVSCs with PIL‐Am is remarkably improved from 20.26% to 22.22%. Specifically, the PILs‐modified device perfectly retains its dark current characteristics upon a cooling (−40 °C)–heating (85 °C) process. The unencapsulated PIL‐Am stabilized PVSC maintains 80% of the initial PCE under AM 1.5G light soaking for nearly 1500 h. The corresponding device also displays pronounced stability under thermal stress or realistic operation conditions.

In situ polydopamine functionalized poly-L-lactic acid nanofibers with near-infrared-triggered antibacterial and reactive oxygen species scavenging capability

The development of a new multi-functional poly(L)-lactide (PLLA) nanofibrous scaffold with excellent antibacterial and reactive oxygen species (ROS) scavenging capability is quite important in tissue engineering. In this study, polydopamine (PDA)/PLLA nanofibers were prepared by combining electrospinning and post in-situ polymerization. The post in-situ polymerization of PDA on the PLLA nanofiber enable PDA uniformly distribute on PLLA nanofiber surface. PDA/PLLA nanofibrous composites also achieved stronger mechanical strength, hydrophilicity, good oxidation resistance and enhanced near-infrared photothermal effect. The near-infrared photothermal effect from PDA made the PDA/PLLA a good antibacterial material. The in vitro ROS scavenging ability of the PDA made PDA/PLLA be beneficial to damaged tissue repair. These results indicate that PDA/PLLA nanofibrous scaffold can be used as a tissue engineering scaffold material with versatile biomedical applications.

First evaluation of multifunctional poly(ionic liquid)s as novel strong bases in directional efficient valorization of lignin

A novel multifunctional poly(ionic liquid)s with Brønsted–Lewis dibasic sites, well-defined mesoporous channels, and hydrophobicity show excellent catalytic performance with 21.99 wt% yield of lignin-based monocyclic aromatic compounds.

Highly Reversible Zn Metal Anodes Enabled by Multifunctional Poly(Zinc Acrylate) Protective Coating

Highly Reversible Zn Metal Anodes Enabled by Multifunctional Poly(Zinc Acrylate) Protective Coating

Synthesis of multifunctional poly(carbamoyl ester)s containing dual-cleavable linkages and an AIE luminogen via Passerini-type multicomponent polymerization.

We conducted Passerini-type multicomponent polymerizations (P-MCPs) with various monomers and afforded a series of functional poly(carbamoyl ester)s (PCEs). We demonstrated an efficient, diverse, and facile approach through P-MCPs to produce these novel PCEs with dual-cleavable linkages of ester and disulfide groups and the aggregation-induced emission (AIE) luminogen tetraphenylethylene (TPE).

Breathable Artificial Interphase for Dendrite-Free and Chemo-Resistive Lithium Metal Anode.

A dendrite-free and chemically stabilized lithium metal anode is required for extending battery life and for the application of high energy density coupled with various cathode systems. However, uneven Li metal growth and the active surface in nature accelerate electrolyte dissipation and surface corrosion, resulting in poor cycle efficiency and various safety issues. Here, the authors suggest a thin artificial interphase using a multifunctional poly(styrene-b-butadiene-b-styrene) (SBS) copolymer to inhibit the electrochemical/chemical side reaction during cycling. Based on the physical features, hardness, adhesion, and flexibility, the optimized chemical structure of SBS facilitates durable mechanical strength and interphase integrity against repeated Li electrodeposition/dissolution. The effectiveness of the thin polymer film enables high cycle efficiency through the realization of a dendrite-free structure and a chemo-resistive surface of Li metal. The versatile anode demonstrates an improvement in the electrochemical properties, paired with diverse cathodes of high-capacity lithium cobalt oxide (3.5mAh cm-2 ) and oxygen for advanced Li metal batteries with high energy density.

Development of modified and multifunctional poly(glycerol sebacate) (PGS)-based biomaterials for biomedical applications

In the recent decade, Poly (glycerol sebacate) (PGS) has received tremendous attention in versatile biomedical fields because of its superior elasticity, excellent biocompatibility, and biodegradability. Conventionally, PGS comprised of glycerol and sebacic acid is prepared via a two-step polymerization, where synthesis parameters such as curing time and temperature, and feeding ratio of the reagents can be readily tailored to improve the performance for the ultimate use. However, such tweaks are no longer able to catch the high demand of intended biomedical applications. As such, a series of modification strategies and construction modalities have been developed to extend traditional PGS with a wider range of physicochemical, mechanical, and biological properties for unmet biomedical needs. Herein, we present a comprehensive literature review of these advanced modification approaches ranging from hydrophilization, functionalization, and mechanical reinforcement. Moreover, various PGS-related constructions used in biomedical applications are highlighted, including hard tissue engineering, soft tissue engineering, and drug delivery and device design. From the perspective of potential clinical use, challenges and limitations of current PGS-based biomaterials, and their future development are also discussed in this review.

Rationally designed novel multifunctional poly(ionic liquid)s for ultra-selective valorization of Yiwu lignite to monocyclic aromatic compounds

The selective valorization of lignite into monocyclic aromatic compounds (MCACs) is extremely challenging due to its chemical inertness and geometrical complexity. The catalytic efficiency of lignite valorization into MCACs over solid acids is significantly reduced by the presence of H2O resulting in the leaching and deactivation of acid sites. Moreover, the precise fabrication of poly(ionic liquid)s (PILs) containing Brønsted-Lewis acidic sites, well-defined mesoporous channels, and hydrophobicity remains a considerable challenge. Herein, a novel hydrophobic mesoporous PILs with strong Brønsted-Lewis acid sites was successfully constructed by a synergistic regulation-induced copolymerization strategy for the first time. More exotically, the resultant multifunctional PILs was found to be ultra-efficient catalyst for the selective valorization of Yiwu lignite (YL) into MCACs with 23.5 wt.% yield, which is the highest yield reported for lignite catalytic valorization by precious metal-free catalysts under mild conditions. The co-catalysis mechanisms of YL valorization into MCACs over the multifunctional PILs are confirmed by characterization methods and the synergistic catalysis mechanisms are as follows: (1) hydrophobic micro-environment: the hydrophobic micro-environment created by hydrophobic block is favorable for preventing the leaching and deactivation of Brønsted-Lewis acid sites; (2) mesoporous confinement: the well-defined mesoporous channels strengthen the adsorption amount of H2 and increases the concentration of substrates; (3) synergistic catalytic active hydrogen transfer of Brønsted-Lewis acid sites: Brønsted-Lewis acid sites synergistically promote H2 heterolysis to the mobile H+ and immobile H−, and then the resulting mobile H+ transfers to oxygen atom in lignite to produce MCACs via C–O bond cleavage. This work not only sheds some light on developing the multifunctional solid acid catalysts, but also demonstrates an efficient catalyzing method to produce lignite-based MCACs by co-catalysis of Brønsted-Lewis acidic sites, mesoporous confinement, and hydrophobic micro-environment.

Multifunctional poly(vinyl alcohol) films using cellulose nanocrystals/oregano and cellulose nanocrystals/cinnamon Pickering emulsions: Effect of oil type and concentration

Poly (vinyl alcohol) (PVA) films with high transparency, UV-barrier, antioxidant, and antimicrobial properties were prepared using oregano essential oil (OEO) and cinnamon essential oil (CEO) Pickering emulsions. The effect of Pickering emulsion type and concentration on the PVA film properties was studied. Cellulose nanocrystals (CNCs) were used as a natural stabilizer to prepare OEO and CEO Pickering emulsions. Both emulsions showed spherical droplets with diameters of 155–291 nm, zeta potential of −36.2 to −49.6 mV, minimum inhibition concentration of 6.25–12.5 μL/mL, and inhibition zone of 40–65 mm, depending on oil type. Morphology and FTIR analysis showed that OEO and CEO Pickering emulsions were compatible with the PVA matrix. The UV-transmittance of PVA films decreased from 77.3% to 30.4% and 2.0% without sacrificing the transparency after adding OEO and CEO Pickering emulsions, respectively. Antimicrobial results showed that E. coli was more sensitive to CEO, while S. aureus was sensitive to OEO Pickering emulsion. PVA/CEO film displayed higher properties than PVA/OEO film.

Multifunctional poly(vinylidene fluoride) and styrene butadiene rubber blend magneto-responsive nanocomposites based on hybrid graphene oxide and Fe3O4: synthesis, preparation and characterization

Two materials were used, like graphene oxide nanosheets (GOn) and ferromagnetic nanoparticles (Fe3O4), to attenuate the electromagnetic (EM) properties in blend hybrid nanocomposites based on styrene-butadiene rubber (SBR) and polyvinylidene difluoride (PVDF) as the matrix. The rationale behind using either a ferroelectric or a ferromagnetic nanofillers as Fe3O4 in combination with intrinsically conducting nanofillers (graphene oxide) at different weight ratios (3.75:1.25; 2.5:2.5 and 1.25:3.75), is to induce both electrical and magnetic dipoles in the hybrid nanocomposite system and characterization to determine the effect of nanofillers hybridization in improving the structural, mechanical, dielectric/electrical, magnetic and thermal properties of a polymer blend (PVDF-SBR) for electromagnetic interference (EMI) shielding application. Due to the synergy between both nanofillers, it was found that Young’s modulus of the nanocomposite containing 5 wt% of the hybrid nanofiller was significantly improved (87%), while the strain at yield remained constant due to the low particle content and the rubbery effect of the SBR copolymer. In addition, the degradation temperature of the matrix was shifted from 464 to 472 °C with the addition of 2.5:2.5 of GOn:Fe3O4. Finally, the hybrid reinforcement also had a positive effect on the electrical and magnetic properties of the nanocomposites with an improvement that exceeds 30%. By careful selection of synthetic techniques and understanding/exploiting the unique physics of the polymeric nanocomposites in such materials, novel functional polymer-inorganic nanocomposites can be designed and fabricated for new interests in magneto applications such as superparamagnetism, electromagnetic wave absorption, and electromagnetic interference shielding. This study opens new avenues to design flexible and lightweight electromagnetic interference shielding materials by careful selection of functional nanoparticles.

Multifunctional poly(methacrylate ester)s-based terpolymer cryogels with basic amino groups: Correlation of elasticity and structural properties with composition

Dual-responsive cryogel-structured materials open up a whole new field of bio-applications. Either dimethylaminoethyl methacrylate (DMAEMA) as a carrier of basic amino groups or glycidyl methacrylate (GMA) as a carrier of epoxy rings was introduced into hydroxypropyl methacrylate (HPMA) skeleton. pH/thermo-responsive cationic terpolymer cryogels were successfully prepared by varying the feeding DMAEMA/GMA mol percent ratio from 80/0 to 0/80. The presence of GMA imparts hydrophobic character that reduces swelling and provides additional crosslinks leading to a significant increase in the flexibility. Reducing the polymerization temperature below the freezing point of the solvent resulted in harder and non-brittle cryogels. Up to 48% reduction in hydration was observed for terpolymer cryogels containing 70 mol% DMAEMA upon increasing pH of bathing medium from 2.1 to 8.0. This trend confirmed pH-modulated swelling of amine-containing terpolymer gels, and pH-dependent transition point was found to be 7.7. Oscillating swelling/deswelling in response to pH cycles was studied. The water transport was strongly affected by incorporation of hydrophobic component GMA and protonation of amine functional groups. The swelling mechanism was shifted from anomalous to diffusion controlled with increasing GMA and overall swelling processes followed Schott second order dynamic equation. Lower equilibrium volume swelling at constant temperature was achieved by increasing GMA content of the terpolymers. In low temperature range, while DMAEMA-rich terpolymer gels were swollen, swelling decreased significantly when the gels were enriched in GMA and the temperature was raised above 55 °C. Regardless of salt type and Na+ or K+ hydrated ion radii, a significant difference was observed in salt-sensitive swelling in dilute salt solution (below about 10−3 M), which is controlled by the amount of DMAEMA in terpolymer structure. This study would provide novel ideas for the design of (meth)acrylate ester-based cationic terpolymer cryogels and elucidate the relationship between the gel matrix and their special swelling behavior.

Immunomodulating polyorganophosphazene-arginine layered liposome antibiotic delivery vehicle against pulmonary tuberculosis

Tuberculosis (TB) is an infectious disease that leads to high mortality and remains challenging because of the poor treatment efficiency and side effects. The multifunctional poly(organo)phosphazene with arginine to overcome the challenges via immunomodulating properties. Polymer grafted liposomes enhance the delivery of both drugs in the tuberculosis-infected alveolar macrophages. It also effectively triggers macrophage cell proliferation, nitric oxide production and activates innate responses against pathogens. The thin-film method was used to prepare three different liposome designs. And, suitable liposome formulation was selected for coating by the arginine-g-PCPP polymer. The breakdown of ester bonds under the acidic condition helps to drug releases inside the cell. In the endosomal pH condition, the release of RIF and IZN was 73 and 80%. The neutral pH release of RIF and IZN was 57 and 62%. PGL drug delivery system will improve the antibacterial activity against both gram-positive and gram-negative bacteria. Dual drug-loaded PGL shows a higher inhibitory of Mycobacterium at 2 mg/mL. It was four times less concentrated compared to the single drug-loaded PGL. It also accelerates macrophage cell proliferation via m-CSF and CAT-1. Our results indicate that PGL can deliver dual drugs to the TB-infected macrophage and modulate the immune system against TB pathogens.

A straightforward fabrication of solid-state lithium secondary batteries based on multi-functional poly(arylene ether sulfone)-g-poly(ethylene glycol) material

Lithium ion conductive poly(arylene ether sulfone)-g-poly(ethylene glycol) (PAES-g-PEG) is synthesized for the application of solid state electrolyte membrane and electrode binder. The solid polymer electrolyte (SPE) system prepared from PAES-g-PEG and 1-butyl-1-methylpyrrollidum bis(fluoromethane sulfonyl) (PYR-1,4-TFSI) ionic liquid illustrates high ion conductivity of 8.48 × 10−4 S cm−1 and low interfacial resistance at room temperature, along with excellent thermal and mechanical stability (degradation temperature > 180 °C and tensile strength > 0.8 MPa). As the PAES-g-PEG containing lithium bis (fluoromethane sulfonyl) (LiTFSI) salt exhibits not only such high conductivity of 2.11 × 10−4 S cm−1 but also excellent adhesive strength (>23 MPa), it plays an important role as a binder for the electrode. As the active electrode materials such as LiCoO2 (LCO) and LiNi0.6Mn0.2Co0.2O2 (NMC 622) are quite well compatible with PAES-g-PEG, the battery cells fabricated by binding the synthesized SPE and cathode layer show excellent cell performance of 139.01 mAh g−1 (LCO) and 158.15 mAh g−1 (NMC 622) at 0.1C. When this multi-functional PAES-g-PEG material is applied to the lithium sulfur battery system, the resulting cell discharge capacity is even higher than 925 mAh g−1 at 0.1C with long term cyclic stability.

Effect of nanoparticle based mrna delivery on modulation of inflammation in an osteochondral inflammation model

Purpose: In this work we aimed to develop a bovine OA explant model and therapeutic mRNA vehiculated by Nanoparticles. Specifically, modified IL1Ra and IL10 mRNAs and multifunctional poly(amidoamines) nanoparticles.

Multifunctional Additives for High-Energy-Density Lithium-Ion Batteries: Improved Conductive Additive/Binder Networks and Enhanced Electrochemical Properties.

Cylindrical-type cells have been widely adopted by major battery and electric vehicle manufacturers owing to their price competitiveness, safety, and easy expandability. However, placement of electrodes at the core of cylindrical cells is currently restricted because of high electrode curvature and the lack of specialized electrodes and electrode materials. Here, we report the realization of highly flexible high-energy-density electrodes (active material loading of >98.4%) that can be used at the cores of cylindrical cells. The improved properties result from the introduction of a multifunctional poly(melamine-co-formaldehyde) (MF copolymer) additive, which yields a relatively more fluidic and well-dispersed slurry using only 0.08 wt %. MF copolymer-mediated formation of completely wrapped CNT/PVDF networks on LiCoO2 (LCO) and accompanying contact enhancement between LCO and carbon nanotubes (CNTs) resulted in an increase of electrical and mechanical properties of the two types (composites with or without collectors) of electrodes compared with those of additive-free electrodes. Flexibility tests were carried out by rolling electrodes onto cylinder substrates (diameters of ca. 1 and 10 mm); this process resulted in relatively lower resistance changes of the MF copolymer-containing electrodes than for the reference electrodes. In addition, capacity retention after 100 cycles for cells with and without MF copolymers was approximately 10-20% better for the samples with the MF copolymer than for those without. CNT/PVDF networks with MF copolymers were proven to induce a relatively thin and stable cathode electrolyte interface layer accompanying the chemical bond formation during cycling.

Injectable self-healing bioactive antioxidative one-component poly(salicylic acid) hydrogel with strong ultraviolet-shielding for preventing skin light injury

The design and development of one-component temperature-sensitive bioactive hydrogel with multifunctional properties for protecting skin against light injury remain a challenge. Herein, we report a bioactive multifunctional poly(salicylic acid)-F127-poly(salicylic acid) copolymer hydrogel (FPSa) with one-component for potential skin protection applications. The FPSa hydrogel possesses the thermosensitivity (23 °C), injectability, self-healing ability, ultraviolet shielding (shielding the wavelength between 280 and 370 nm), and antioxidation activity (above 70%), and also showed the good cytocompatibility (cell survival rate >90% and hemolysis rate less than 5%) and biodegradability (90% weight loss at 3 days). The in vivo animal model showed that FPSa hydrogel could effectively protect the skin tissue and prevent the ultraviolet induced injury. This study can provide a strategy to design multifunctional bioactive hydrogel with simple composition for disease therapy and regenerative medicine.

Multifunctional poly(ionic liquid)s cross-linked polybenzimidazole membrane with excellent long-term stability for high temperature-proton exchange membranes fuel cells

Novel high temperature-proton exchange membranes (HT-PEMs) are prepared based on norbornene-type PBI (NbPBI) and double bond ionic liquids. For comparison, three ionic liquids are selected to prepare NbPBI-PIL membranes. Herein, the ionic liquids are synthesized into poly(ionic liquid)s (PILs) by in-situ free radical polymerization. Simultaneously, the PILs also react with the norbornene monomer of NbPBI to form a cross-linked network. After acid-base doping, the Br− or Cl− of PILs are successfully replaced with H2PO4− to promote proton transport. Notably, the NbPBI-PIL membranes exhibit high proton conductivity and enhanced phosphoric acid retention, especially the NbPBI-MPIm membrane has a proton conductivity of 0.074 S cm−1 at 170 °C and phosphoric acid retention of 87.2% and 73.8% under 160 °C and 80 °C/40 RH%, respectively. The single-cell with NbPBI-TPAm membrane obtains the highest power density of 385 mW cm−2 at 160 °C and negligible single-cell voltage decay after the 200-h test.