Monomer Polymer Research Articles

Deep eutectic supramolecular polymers based HPLC stationary phase: Green synthesis strategy and promising application prospects

BackgroundDeep eutectic solvents (DESs) have been widely and significantly applied in various fields due to their outstanding features such as low cost, easy preparation and good biodegradability. As novel derivatives of DESs, deep eutectic supramolecular polymers (DESPs) combine the macroscopic state of DESs with the covalent interactions of supramolecular polymers, which also possess the properties of DESs as multifunctional materials. Therefore, DESPs are believed to be promising candidates for separation science. However, there are no studies on the application of DESPs as stationary phases for HPLC analysis. ResultsIn this work, a novel DESP based HPLC stationary phase (Poly(DES)@SiO2) was developed for the first time through a green synthesis method by using DES as the polymerization monomer as well as the reaction medium. The results manifest that this novel Poly(DES)@SiO2 column can well interact with analytes through various mechanisms, and realize selective separation of a wide range of structurally similar hydrophilic/hydrophobic substances. More importantly, the separation of hydrophobic analytes on the Poly(DES)@SiO2 column is less time-consuming with fewer organic eluent, although the column efficiency is slightly lower than that of commercial C18 column. Furthermore, the Poly(DES)@SiO2 column exhibits excellent mechanical stability and satisfactory separation repeatability for steroid hormones. Therefore, a reliable method was established for detecting steroid hormones in actual samples with the recoveries ranging from 94.56 % to 103.84 %, which can meet the detection needs of commonly seen steroid hormones in food and the environment. SignificanceIn summary, this work provides some valuable theoretical references for the synthesis of new DESP based stationary phases through a green and facile strategy, and meanwhile, verifies the feasibility of DESP for effective HPLC separations. In addition, the promising application prospect of DESP based stationary phases in the analysis of complex samples has also been demonstrated, expanding the potential application of DES in separation science.

Unveiling the optical and molecular characteristics of aging microplastics derived dissolved organic matter transformed by UV/chlor(am)ine oxidation and its potential for disinfection byproducts formation

The investigations into the existence and behavior of microplastics (MPs) in water environment were widely conducted, while the characteristics of dissolved organic matter derived from MPs (MPs-DOM) during advanced oxidation have garnered comparatively little attention. In this study, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) was employed along with multiple statistical analyses to gain a deeper understanding of the conversion of MPs-DOM in UV/chlor(am)ine advanced oxidation processes (AOPs). The diverse treatments exhibited varying degrees of augmentation in both aging and fragmentation of MPs with the order of UV/Cl2 > UV > UV/NH2Cl. The fragmentation degree of MPs upon two UV-based AOPs (UV-AOPs) was dependent on their monomer chemical structure. The highest TOC values of three MPs-DOM were observed after UV/Cl2 AOP and the lowest after UV/NH2Cl AOP. Polyvinyl chloride (PVC) displayed a greater release of MPs-DOM under varying leaching conditions. UV/Cl₂ AOP favored the reaction with saturated MPs-DOM, while UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating disinfection byproducts (DBPs) formation after chlorination. The precursors generated by UV/Cl₂ AOP owned lower H/C, higher modified aromatic index (AImod), and lower molecular weight (MW) products after chlorination. PVC-DOM with fewer CH₂ groups was more reactive. -H₂O, +O and -CH₂ reactions dominated in PVC-DOM (CHO compounds), while -2H, +O, -CH₂ did in PVC-DOM (CHON compounds). The dominant chlorine addition/substitution reactions occurred in PVC-DOM treated by UV/Cl₂ AOP, identifying 195 Cl-DBPs with 220 precursor-product pairs. Mass difference analyses showed that +2H and +O reactions were the most frequent of the 24 reaction types. Environmental ImplicationMicroplastics derived dissolved organic matters (MPs-DOM) transformed into disinfection byproducts (DBPs) under advanced oxidation processes (AOPs), heightening environmental risks. In this study, Fourier transform ion cyclotron resonance mass spectrometry was employed to gain a deeper understanding of MPs-DOM conversion in UV/chlor(am)ine AOPs. MPs fragmentation and fluorescent components varied with monomer chemistry and polymers. UV/Cl₂ AOP reacted with saturated MPs-DOM. UV/NH₂Cl AOP reduced unsaturated MPs-DOM, alleviating DBPs formation. DBPs precursors generated by UV/Cl₂ AOP owned higher modified aromatic index, lower H/C and molecular weight. Unveiling the MPs-DOM transformation during AOPs can mitigate the negative environmental impacts of MPs and their derivatives.

Free radical copolymerization kinetics of bio-based dibutyl itaconate and n-butyl acrylate

The free radical copolymerization of dibutyl itaconate (DBI), a monomer derived from renewable resources, and n-butyl acrylate (BA) is investigated to explore the potential of incorporating itaconate monomers into commercial acrylic resins to enhance the sustainability of coating materials. Batch experiments were conducted at 50 °C and 80 °C, varying initial monomer and initiator concentrations as well as monomer compositions, with proton NMR and size exclusion chromatography used to analyze monomer conversion profiles and polymer molar mass distributions (MMDs). The data were analyzed using a kinetic model developed to guide the experimental studies and estimate key kinetic parameters controlling copolymer composition, polymerization rate and polymer MMDs. The use of the more reactive BA as comonomer significantly increases the conversion and molar mass of the resulting copolymer. Furthermore, semi-batch operating conditions similar to current industrial practice can incorporate a substantial fraction of DBI into acrylic copolymer resins, thus enhancing their sustainability profile.

Preparation of PAMgA/GL/GO antifreeze conductive hydrogel for wearable strain sensor based on physically cross-linked network

Conductive hydrogels have promising prospects in wearable strain sensor applications. However, the complex and diverse application scenarios put forward higher requirements on the conductivity, anti-freezing, tensile, self-healing, adhesion, and moisture retention properties of the conductive hydrogel. In this study, a polymagnesium acrylate/glycerol/graphene oxide (PAMgA/GL/GO) conductive hydrogel is prepared by free radical polymerization method, with magnesium acrylate (AMgA) as the polymer monomer, glycerol (GL) as the antifreeze filler, and graphene oxide (GO) as the conductive filler. Adding GL not only enhances the antifreeze properties of the composite hydrogels but also improves the moisture retention. The addition of GO increases the conductivity and the gauge factor (GF) of the composite hydrogels. When the GO content is 0.6 wt.%, the PAMgA/GL/GO conductive hydrogel demonstrates excellent properties of antifreeze, conductivity, self-healing, adhesion, and sensitivity. These excellent properties make it suitable as a wearable strain sensor for accurately monitoring human joint movements and subtle physiological signals.

Ultrathin membranes comprising polymers of intrinsic microporosity oligomers for high-performance organic solvent nanofiltration

Microporous organic polymers (MOPs) featuring chemically rigid backbones and permanent micropores are desirable for fabricating molecular selective membranes towards organics separation. However, coordinating facile film processing with high micropore persistence remains a challenge. In this paper, a low molecular weight polymers of intrinsic microporosity was rationally designed by precisely controlling the stoichiometric equilibrium of polymerization monomer. The polymers of intrinsic microporosity oligomers combine rigid and contorted structures with the aqueous solution processability, promoting the formation of 25-nm-thick polyacrylamide nanofilms with enhanced microporosity via support-free interfacial polymerization (SFIP). The resulting composite membranes have superior retention of small molecular solutes and high nonpolar and polar solvent permeances. Experiment and simulation results show that their excellent separation performance is due to substantially open and interconnected microporosity formed in the polymer networks based on rigid and contorted diamines as well as reduced film thickness. This study provides a new sight for using MOPs to construct high-microporosity membranes for precise and rapid molecular sieving.

Dual responsive drug-loaded nanomotor based on zwitterionic materials for the treatment of peritoneal metastatic cancer

Innovative treatments for peritoneal metastatic cancer have attracted widespread attention from researchers. Here, we propose a drug-loaded nanomotor (PSBMA/l-Arg/DOX, PLD) based on zwitterionic materials for the treatment of peritoneal metastatic cancer through intraperitoneal injection. Zwitterionic polymer nanocarriers (PSBMA NPs) are obtained by radical polymerization with zwitterionic SBMA as the polymerization monomer and N,N’-Bis(acryloyl)cystamine (BAC) as the cross-linking agent. The zwitterionic substrate of this nanomotor has the ability to resist non-specific protein adsorption in ascites. The loaded l-arginine enables the nanomotor to have the ability to chemotaxis towards high concentrations of ROS/iNOS in tumors and be catalyzed to produce NO, achieving deep penetration into tumor tissue. Furthermore, the disulfide bond (SS) carried by the crosslinking agent used in the preparation of the nanomotor can respond to the high expression of reducing glutathione in the tumor microenvironment and undergo degradation, releasing a large amount of loaded drug DOX. Cell and animal disease model experiments confirme the good therapeutic effect of this drug-loaded nanomotor, providing new therapeutic concepts and strategies for the treatment of peritoneal metastatic cancer.

Polymers Containing Diethylsiloxane Segment and Active Functional Group by Ring-Opening Polymerization of Hexaethylcyclotrisiloxane under the Catalysis of Linear Chlorinated Phosphazene Acid.

Linear chlorinated phosphazene acid is prepared using PCl5 and NH4Cl as raw materials. Using hexaethylcyclotrisiloxane as the monomer, 1,1,3,3-tetramethyldisiloxane or 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as the end-capping agent, and linear chlorinated phosphazene acid as the catalyst, polydiethylsiloxane oligomers terminated with active Si-H or Si-CH=CH2 groups have been prepared. Using hexaethylcyclotrisiloxane and 1,3,5,7-octamethylcyclotetrasiloxane as comonomers, 1,1,3,3-tetramethyldisiloxane or hexamethyldisiloxane as the end-capping agent, or using hexaethylcyclotrisiloxane and octamethylcyclotetrasiloxane as comonomers, 1,1,3,3-tetramethyldisiloxane as the end-capping agent, copolymers containing active Si-H bonds and dimethylsiloxane segments have been prepared under the catalysis of linear chlorinated phosphazene acid. The effects of catalyst dosage, reaction temperature, reaction time, end-capping agent, and polymerization monomer dosage on polymer yield and structure were investigated. Using 300 ppm of linear chlorinated phosphazene acid, oligomers and copolymers containing an active Si-H bond and diethylsiloxane segment were prepared under mild conditions. The molecular weight of the obtained polymers was close to their designed values, but their PDI values were small. The highest yield of α, ω-bisdimethylsiloxyl-terminated PDES oligomers reached 93%. Using oligomers and copolymers containing Si-H bonds and diethylsiloxane segments as crosslinkers, a silicone gel containing diethylsiloxane segments was prepared by hydrosilylation reaction. With the introduction of a diethylsiloxane segment, the glass transition temperature of the silicone gel decreased relative to that of the PDMS oligomer, but the temperature at 5% weight loss in nitrogen atmosphere decreased from 347 °C to 312 °C. The mechanism of the ring-opening polymerization of hexaethylcyclotrisiloxane catalyzed by linear chlorinated phosphazene acid is also discussed.

Programmable light‐driven soft actuator enabled by structurally anisotropic liquid crystalline network

AbstractThe design and fabrication of advanced soft actuators with programmable actuation are highly desirable in constructing intelligent soft robots. In this work, a programmable light‐driven liquid crystalline network (LCN)‐based soft actuator was judiciously designed and prepared by constructing structural anisotropy across the thickness of the film. A three‐dimensional (3D) deformable LCN actuator was realized by polymerization‐induced phase separation of small‐molar‐weight monomers and polymer networks. The resultant anisotropic LCN displays anisotropic microscale nanoporous architecture across the thickness in addition to uniform alignment at the molecular scale. The actuation behaviors of LCN film are tunable by adjusting the size and distribution of nanopores in LCN bulk via changing polymerization conditions and monomer components. More importantly, the nanoporous LCN film can be harnessed as a promising template to achieve diverse light responsiveness by changing the photothermal dyes via a feasible washing and refilling process, demonstrating a reprogrammable light‐driven soft actuator.

Preparation and ferroelectric properties of metal-organic frame lithium ion liquid crystal composites

ABSTRACT Two series of lithium ion liquid-crystalline composites (LCCs) containing metal-organic frame (MOF) materials were fabricated via a self-assembly process by use of poly(4-styrenesulfonic acid) lithium polymers, a cholesteryl-based liquid-crystalline monomer with terminal sulphonic acid group, and Fe-MIL-53_NH2. The chemical structure, chiral smectic C mesophase and ferroelectric property of the LCCs were characterised by various instruments, and the effect of liquid crystal monomer and lithium polymers on the ferroelectric property were investigated. The cholesteryl-based liquid crystal monomer presents a dominant role in the ferroelectric property of the LCCs, in which the asymmetric carbon atoms are responsible for the spontaneous polarisation. For the LCCs, the mechanical properties and porous loading characteristics of liquid crystal polymer are improved by the MOF materials, and the lithium-ion polymer connects the liquid crystal monomer with the MOF by ionic bond and improves the polarity of the material. When the electric field changed from −10 V and 10 V, the maximum residual polarisation strength (Pr) of the LCCs reached 74.82 nC/cm2. Because the LCCs showed excellent ferroelectric and mechanical properties, it has some potentials of application in the field of ferroelectric materials.

Synthesized Crosslinking Suspension Stabilizer for Spacer Fluid in High-Temperature Conditions: Synthesis, Behavior, and Mechanism Research

Summary High-temperature stability of spacer fluid is a vital prerequisite to ensure the safety of cementing operations in deep or ultradeep wells. Faced with this problem, the thermal stability of the suspension agent in the spacer fluid at high temperatures is improved from the aspects of polymerization monomer and molecular chain. A terpolymer SAD was synthesized by free radical polymerization of sodium styrene sulfonate (SSS), acrylamide (AM), and N, N’-diethylacrylamide (DEAA) in aqueous solution. The name of the terpolymer, SAD, is the initial letter composition of the three polymerization monomers. Polyethyleneimine (PEI) can improve the molecular chain structure of SAD by transamidation reaction with the amide group in SAD, so a high temperature suspension agent PSAD (polyethyleneimine + SAD) was obtained by compounding PEI with SAD. The structure and properties of PSAD were characterized by Fourier infrared spectroscopy, hydrogen nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, scanning electron microscopy (SEM), and viscosity test. In addition, the comprehensive properties of the spacer fluid under the action of PSAD are evaluated. The results showed that the crosslinking degree of PSAD gradually increased with the increase in temperature. After aging at 200°C, the decomposition temperature of PSAD was 305°C, which show terrific thermal stability. At the same time, the spacer fluid prepared by PSAD not only has excellent rheological properties in the range of 90 ~ 200°C but also keeps the density difference between the upper and lower parts of the slurry less than 0.02 g/cm3 and the filtration loss of the slurry less than 50 mL.

Selective Electrooxidation of Crude Glycerol to Lactic Acid Coupled With Hydrogen Production at Industrially-Relevant Current Density.

Transforming glycerol (GLY, biodiesel by-product) into lactic acid (LA, biodegradable polymer monomer) through sustainable electrocatalysis presents an effective strategy to reduce biodiesel production costs and consequently enhance its applications. However, current research faces a trade-off between achieving industrially-relevant current density (>300mA cm-2) and high LA selectivity (>80%), limiting technological advancement. Herein, a Au3Ag1 alloy electrocatalyst is developed that demonstrates exceptional LA selectivity (85%) under high current density (>400mA cm-2). The current density can further reach 1022mA cm-2 at 1.2V versus RHE, superior to most previous reports for GLY electrooxidation. It is revealed that the Au3Ag1 alloy can enhance GLY adsorption and reactive oxygen species (OH*) generation, thereby significantly boosting activity. As a proof of concept, a homemade flow electrolyzer is constructed, achieving remarkable LA productivity of 68.9mmolh-1 at the anode, coupled with efficient H2 production of 3.5 Lh-1 at the cathode. To further unveil the practical possibilities of this technology, crude GLY extracted from peanut oil into LA is successfully transformed, while simultaneously producing H2 at the cathode. This work showcases a sustainable method for converting biodiesel waste into high-value products and hydrogen fuel, promoting the broader application of biodiesel.

Quinine-Based Polymers Are Versatile and Effective Vehicles for Intracellular pDNA, mRNA, and Cas9 Protein Delivery.

Quinine-based polymers have previously demonstrated promising performance in delivering pDNA in cells owing to their electrostatic as well as the nonelectrostatic interactions with pDNA. Herein, we evaluate whether quinine-based polymers are versatile for delivery of mRNA and Cas9-sgRNA complexes, especially in a serum-rich environment. Both mRNA and the Cas9-sgRNA complex are potent therapeutics that are structurally, chemically, and functionally very different from pDNA. By exploring a family of 7 quinine-based polymers that vary in monomer structure and polymer composition, we tested numerous formulations (42 with pDNA, 96 with mRNA, and 48 with Cas9-sgRNA) for payload-polymer complexation and delivery to compare payload-dependent structure-activity relationships. Several formulations demonstrated performance comparable to or better than the commercially available transfection agent jetPEI. The results of this study demonstrate the potential of quinine-based as a versatile carrier platform for delivering a wide range of nucleic acid therapeutics and serving the drug delivery needs in the field genetic medicine.

Increased stability of polymer dispersions obtained by heterophase radical polymerization of styrene and MMA in the presence of water-insoluble organosilicon macromeres

It is shown that during the copolymerization of methyl methacrylate with the surfactant comonomer α,ω-dipropylmethacrylatep olidimethylsiloxane with the number of repeating dimethylsiloxane units n = 20 (DPMPDMS), strong interfacial adsorption layers are formed on the surface of polymer–monomer particles formed from microdrops, ensuring the stability of particles to various types of influences.

Unraveling the Complexities of Silica Nanoparticle Adsorption onto Polymer Latexes in Pickering Emulsion Polymerization.

Incorporating unmodified silica nanoparticles onto polymer latexes to fabricate aqueous polymer dispersions without relying on electrostatic attraction during the Pickering emulsion polymerization process still faces challenges. For negatively charged silica nanoparticles to successfully adsorb onto polymer latexes, particularly in an anionic initiator emulsion polymerization system, they have remained elusive without the use of auxiliary monomers and cationic initiators. This study investigates various experimental parameters, such as emulsion polymerization temperature, monomer solubility, salt concentration, and cation type, to elucidate the factors influencing the adsorption of unmodified silica nanoparticles in Pickering emulsion polymerization. While poly(methyl methacrylate) (PMMA)/SiO2 hybrid latexes can be obtained under pH conditions of 5-6 and at temperatures of 65 °C or below, the loading rate of silica nanoparticles decreases as the reaction temperature increases, resulting in bare PMMA latexes without silica nanoparticle adsorption at temperatures exceeding 70 °C. Introducing styrene (St) into the monomer mixture with methyl methacrylate in a ratio of up to 10 wt % leads to a gradual decrease in silica nanoparticle loading rate, from 27.3 to 8.2 wt %, attributed to the low solubility of St in water. Furthermore, the presence of sodium ions (Na+) is found to be crucial for silica nanoparticle adsorption onto PMMA latexes, as the sodium ions have a stabilizing effect on both the silica nanoparticles and the silica nanoparticle-armored latexes. These findings highlight the complex nature of Pickering emulsion polymerization in the presence of unmodified silica nanoparticles, demonstrating that the loading rate of silica nanoparticles onto polymer latexes is influenced by various factors. These insights pave the way for developing aqueous polymer dispersions with high silica nanoparticle loading rates onto polymer latexes, which is a desirable trait in the coating industry.

Investigating of Carbon Agent Distribution Using Long-Chain Alkyl in Grafted Binder for High-Capacity SiOx/Graphite Anode

A small amount of the conductive carbon agent in lithium-ion battery (LIB) formulation has a significantly impact on the rate capability performance of battery but the distribution problem of the carbon conductive material is issued in the electrode slurry due to its hydrophobic and inert characteristics. To overcome this problem, the use of dispersant agent was proposed in the electrode fabrication process.In this study, the grafting of adhesive acrylamide monomer (AM) and a long-chain alkyl monomer onto carboxymethyl cellulose (CMC) is applied to binder to improve the conductive agent distribution in a high-capacity SiOx/C anode. The long alkyl chain in the monomer of the graft copolymer binder exhibits good dispersibility of the carbon agent and improved conductive matrix compared to the binder with no alkyl monomer. This may be explained by CH-π integration between the alkyl monomer in graft polymer and carbon agent. The high-capacity SiOx/C anode with the long-alkyl chain introduced graft binder is examined in the slurry level with rheology and dispersion stability, in the electrode sheet level with electric resistance, peel-off, and coin-cell level with various electrochemical performance, charge/discharge performance. Keywords: Silicon oxide; Graphite; Carbon agent distribution, long-chain alkyl monomer; Acrylamide; Graft copolymer Figure 1

Electrochemiluminescence enhanced by molecular engineering linear π-conjugated polymer: An ingenious ECL emitter for the construction of exosome sensing platform

Linear π-conjugated polymers (LCPs) with π-electron conjugation system have many remarkable optical characteristics such as fluorescence and electrochemiluminescence (ECL). However, the extremely strong interchain interaction and π-π stacking limit the luminescence efficiency. In this work, 1H-1,2,4-triazole-3,5-diamine was chosen as the polymer monomer and reacted with terephthalaldehyde via simple Schiff base condensation to synthesize LCPs. Subsequently, molecular engineering strategy was adopted to construct zirconium-based LCPs (MLCPs), which not only prevented π-π stacking but also ensured that extended π-coupling was maintained in the LCPs, thus effectively promoting charge transport and achieving strong luminescence. Second, the coreactant polyethyleneimine (PEI) was assembled onto the MLCPs (MLCPs@PEI) to further promote the emission of ECL. To further explore the potential of the obtained MLCPs@PEI as emerging ECL emitter, colorectal cancer exosome was chosen as model biomarker, and an innovative ECL ratiometric system based on MLCPs@PEI and luminol was designed to improve the validity and accuracy of the sensors. This research provides a fresh nanoplatform for exosome detection and broadens the application of LCPs in ECL immunoassay.

Trace organic–inorganic hybrid lead halide perovskite nanocrystals as photocatalysts for PET-RAFT polymerization with high efficiency

Lead halide perovskite has emerged as a new class of materials in photocatalysis due to its promising photocatalytic performance. Here, we introduce organic–inorganic hybrid lead halide perovskite (OIHP) nanocrystals as photocatalysts (PCs) for efficient photoinduced electron/energy transfer–reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. PET-RAFT polymerization is successfully conducted with 0.025 wt% PC loading under blue light (6 mW/cm2, 460 nm), yielding upwards of 90 % monomer conversion and polymer products with narrow dispersity (≤1.20) within 2 h, demonstrating a fast polymerization rate. Moreover, the oxygen resistance of the polymerization process has been demonstrated. Due to the advantages of low PC usage, fast polymerization rate and oxygen tolerance, OIHP mediated PET-RAFT polymerization is expected to be used for large-scale production and industrial applications.

Shape selective alkylation of ethylbenzene with isobutylene over ZSM-12: Effect of acid distribution and morphology

Para-tert-butyl ethylbenzene (p-TBEB) is an important polymer monomer raw material to produce poly (tert-butylstyrene). Achieving relatively high selectivity to p-TBEB (Sp-TBEB) by shape selective alkylation of ethylbenzene with isobutylene is highly attractive, and it is crucial to clarify the major factors affecting Sp-TBEB. Herein, ZSM-12 zeolites with various morphology or acid distribution were synthesized by altering alkalinity or structure directing agent (SDA). Despite different morphology of MTW(70)-M-x series samples using MTEACl as the SDA, they show similar catalytic performance in alkylation of ethylbenzene with isobutylene due to their similar acid distribution. On the other hand, MTW(100)-M-0.06 and MTW(100)-T with various morphology, synthesized with MTEACl and TEAOH as the SDA, respectively, exhibit quite different selectivity to the target product in this reaction. MTW(100)-M-0.06 has much higher STBEB (87 % vs. 70 %) and Sp-TBEB (95 % vs. < 60 %) than MTW(100)-T, which is attributed to that MTW(100)-M-0.06 possesses much more Brønsted acid sites distributed in the micropore channel. This provides a route to improve the selectivity to main product (TBEB, especially p-TBEB) of alkylation of ethylbenzene with isobutylene over ZSM-12 zeolite even other zeolites.

Hydrophobic sisal cellulose paper-based TENG for collecting rain energy and raindrop-based sensor

Hydrophobic Sisal cellulose paper (SCP) was obtained by surface modification of SCP via physical adsorbing polymer and chemical grafting monomer, respectively. The influence of surface modification conditioning on the hydrophobicity, dielectric constant and dipole moment of the SCP was investigated. The results showed that the hydrophobicity and dielectric constant of the modified SCP increased with the concentration and amount of the modifiers. The output electrical performance of the TENGs assembled by the two types of hydrophobic SCP for rain energy collection was compared. The output electrical performance of the chemically modified hydrophobic SCP-TENG is higher than that of the physical modified. The maximum power density of the former reaches 8.2 mW/m2. Furthermore, based on the linear relationship between the output performance (output voltage intensity and output current intensity) of hydrophobic SCP-TENG and the droplet velocity, a raindrop-based sensor based on hydrophobic SCP-TENG was successfully constructed and estimated.

Formulation and In Vitro Assessment of Polymeric pH-Responsive Nanogels of Chitosan for Sustained Delivery of Madecassoside.

Madecassoside, a triterpenoid saponin compound mainly isolated from the gotu kola herb (Centella asiatica), shows an extensive range of biological activities, including antiapoptotic, antioxidant, anti-inflammatory, moisturizing, neuroprotective, and wound healing effects. It has been highly used in the management of eczema, skin wounds, and other diseases. Due to poor oral bioavailability, membrane permeability, and intestinal absorption, the clinical application of the madecassoside is limited. Hence, a drug carrier system is needed that not only sustains the release of the madecassoside but also overcomes the drawbacks associated with its administration. Therefore, the authors prepared novel pH-responsive chitosan-based nanogels for the sustained release of madecassoside. Free radical polymerization technique was used for cross-linking of polymer chitosan and monomer methacrylic acid in the presence of cross-linker N',N'-methylene bis(acrylamide). The decrease in polymer crystallinity after polymerization and development of nanogels was demonstrated by XRD and FTIR analysis. The effects of nanogel contents on polymer volume, sol-gel analysis, swelling, drug loading, and release were investigated. Results indicated that high swelling and maximum release of the drug occurred at pH 7.4 compared to pH 1.2 and 4.6, indicating the excellent pH-sensitive nature of the engineered nanogels. High swelling and drug release were perceived with the integration of a high quantity of chitosan, while a decline was observed with the high integration of N',N'-methylene bis(acrylamide) and methacrylic acid contents. The same effects of nanogel contents were shown for drug loading too. Sol fraction was reduced, while gel fraction was enhanced by increasing the chitosan load, N',N'-methylene bis(acrylamide), and methacrylic acid. The Korsmeyer-Peppas model of kinetics was trailed by all nanogel formulations with non-Fickian diffusion. The results demonstrated that prepared nanogels can be employed for sustained release of the madecassoside.