Poly(ethylene Glycol) Methyl Ether Methacrylate Research Articles

Redox-Responsive "Catch and Release" Cryogels: A Versatile Platform for Capture and Release of Proteins and Cells.

Macroporous cryogels are attractive scaffolds for biomedical applications, such as biomolecular immobilization, diagnostic sensing, and tissue engineering. In this study, thiol-reactive redox-responsive cryogels with a porous structure are prepared using photopolymerization of a pyridyl disulfide poly(ethylene glycol) methacrylate (PDS-PEG-MA) monomer. Reactive cryogels are produced using PDS-PEG-MA and hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) monomers, along with a PEG-based cross-linker and photoinitiator. Functionalization of cryogels using a fluorescent dye via the disulfide-thiol exchange reactions is demonstrated, followed by release under reducing conditions. For ligand-mediated protein immobilization, first, thiol-containing biotin or mannose is conjugated onto the cryogels. Subsequently, fluorescent dye-labeled proteins streptavidin and concanavalin A (ConA) are immobilized via ligand-mediated conjugation. Furthermore, we demonstrate that the mannose-decorated cryogel could capture ConA selectively from a mixture of lectins. The efficiency of protein immobilization could be easily tuned by changing the ratio of the thiol-sensitive moiety in the scaffold. Finally, an integrin-binding cell adhesive peptide is attached to cryogels to achieve successful attachment, and the on-demand detachment of integrin-receptor-rich fibroblast cells is demonstrated. Redox-responsive cryogels can serve as potential scaffolds for a variety of biomedical applications because of their facile synthesis and modification.

High toughness, ultra-sensitive, and extreme environment resistant fabric temperature sensors based on supramolecular-polymer dual network ionic conductive elastomers

Liquid-free ionic conductive elastomers (ICEs) show great potential for next-gen wearable electronics, free from issues like solvent evaporation and freezing. However, crafting ICEs with both strength and temperature sensitivity remains a significant challenge. In this study, a supramolecular gel based on 1,3:2,4-bis (3,4-dimethylbenzene methylene) sorbitol (DMBS) is selected as the first network, and poly(ethylene glycol) methyl ether methacrylate (PEGMA) copolymerized with diallyl dimethyl bis (trifluoromethyl sulfonyl)imide (DADMATFSI) is added as the second network, with the addition of lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI). The supramolecular-polymer dual network ion-conductive elastomer SP-DN-LiTFSI is created. The elastomer exhibits exceptional mechanical characteristics, including a maximum tensile stress of 1591.1 kPa and an impressive strain of 2361 %. Additionally, it demonstrates an extraordinarily high toughness of 33.121 MJ m−3. Moreover, this elastomer-based temperature sensor is responsive to external stimuli, such as blowing, and boasts an outstanding temperature sensing coefficient (S) of 0.114 °C−1 within the range of 30–60 °C. Remarkably, it can discern even the slightest temperature variations as low as 0.5 °C within the typical human body temperature range. This work represents an innovative integration of a dual network structure and two strategies for elastomer fabrication. It provides a novel approach for developing highly sensitive wearable temperature measurement devices that exhibit exceptional resistance to mechanical wear.

Harnessing disulfide and transesterification bond exchange reactions for recyclable and reprocessable 3D-printed vitrimers

Two new vitrimeric materials have been studied for potential additive manufacturing applications such as 3D-printing. A monomer containing disulfide bonds and β-hydroxyesters was easily synthesized from two low-cost and commercially available reagents. Another disulfide-containing monomer was synthesized for comparison purposes. Materials were prepared through a UV-light radical polymerization of methacrylates. The addition of two reactive diluents such as poly(ethylene glycol) methyl ether methacrylate (PEGMA) and ethylene glycol phenyl ether methacrylate (EGPMA) was necessary to achieve a suitable viscosity for the curing as well as for their printability. The curing process was controlled by FTIR. Thermomechanical properties were investigated by means of DMTA analysis revealing near-ambient Tg values. Stress relaxation tests revealed that both materials were capable to relax the 63% of the initial stress in less than 10 min at 110 °C. The recyclability of the materials was achieved, and the mechanical and thermomechanical properties of the recycled samples were compared to the virgin ones revealing a great recovery of the initial properties. Finally, Digital Light Processing (DLP) technique was used to print complex structures with high resolution highlighting the great potential of these vitrimeric materials in 3D printing.

Poly(ethylene Glycol) Methyl Ether Methacrylate-Based Injectable Hydrogels: Swelling, Rheological, and In Vitro Biocompatibility Properties with ATDC5 Chondrogenic Lineage.

Here, we present the synthesis of a series of chemical homopolymeric and copolymeric injectable hydrogels based on polyethylene glycol methyl ether methacrylate (PEGMEM) alone or with 2-dimethylamino ethyl methacrylate (DMAEM). The objective of this study was to investigate how the modification of hydrogel components influences the swelling, rheological attributes, and in vitro biocompatibility of the hydrogels. The hydrogels' networks were formed via free radical polymerization, as assured by 1H nuclear magnetic resonance spectroscopy (1H NMR). The swelling of the hydrogels directly correlated with the monomer and the catalyst amounts, in addition to the molecular weight of the monomer. Rheological analysis revealed that most of the synthesized hydrogels had viscoelastic and shear-thinning properties. The storage modulus and the viscosity increased by increasing the monomer and the crosslinker fraction but decreased by increasing the catalyst. MTT analysis showed no potential toxicity of the homopolymeric hydrogels, whereas the copolymeric hydrogels were toxic only at high DMEAM concentrations. The crosslinker polyethylene glycol dimethacrylate (PEGDMA) induced inflammation in ATDC5 cells, as detected by the significant increase in nitric oxide synthase type II activity. The results suggest a range of highly tunable homopolymeric and copolymeric hydrogels as candidates for cartilage regeneration.

Emulsion copolymerization of vinyl chloride with poly (ethylene glycol) methyl ether methacrylate

ABSTRACT In this work, we reported a novel emulsion copolymerization of vinyl chloride monomer (VCM) with amphipathic monomer poly (ethylene glycol) methyl ether methacrylate (PEGMA) by using sodium dodecyl sulfate (SDS) as emulsifier and K2S2O8/NaHSO3 as redox initiator. Owing to the multifunctionality of PEGMA that can serve as co-monomer and ‘emulsifier’, the emulsion copolymerization is achieved successfully and the interesting results demonstrate quite different features such as:(1) the stable P[(VC)-co-(PEGMA)] latex is obtained only when the mass ratio of PEGMA > 10% (to total monomer mass), (2) a small amount of ionic emulsifier SDS is required to achieve a stable latex, and (3) the mechanism of the micellar formation is different from the typical emulsion polymerization. Unexpectedly, the obtained copolymer formed high content of gel fraction which is mainly caused by the chain transfer reaction of the PVC growth chain radical to the hydrogen atom of the methylene from alkoxy (-OCH 2CH 2-) of the PEGMA oligomer chain. However, it could be inhibited effectively by the addition of chain transfer agent 2-mercaptoethanol (2-MCE). Subsequently, the properties of as-obtained P[(VC)-co-(PEGMA)] copolymer are evaluated carefully and it exhibited unique features such as self-plasticization, lower T g (decreased from 83.1 to 59.6 °C), higher heat resistance (increased from 270 to 290 °C), hydrophilic, and high transparent in comparison to pure PVC. These outstanding features of the P[(VC)-co-(PEGMA)] copolymer offered a potential route for the functional modifications of PVC and broadened its further use.

Polymeric Hydrogels for Intervertebral Disc Replacement/Integration: Playing with the Chemical Composition for Tuning Shear Behavior and Hydrophilicity.

Damages to the intervertebral disc (IVD) due to improper loading or degeneration result in back pain, which is a common disease affecting an increasing number of patients. Different strategies for IVD remediation have been developed, from surgical treatment to disc replacement, by using both metallic and non-metallic materials. Hydrogels are very attractive materials due to their ability to simulate the properties of many soft tissues; moreover, their chemical composition can be varied in order to assure performances similar to the natural disc. In particular, for the replacement of the IVD outer ring, namely, the anulus fibrosus, the shear properties are of paramount importance. In this work, we produced hydrogels through the photo-induced crosslinking of different mixtures composed of two hydrophilic monofunctional and difunctional polymers, namely, poly(ethyleneglycol) methyl ether methacrylate (PEGMEMA) and poly(ethyleneglycol) dimethacrylate (PEGDMA), together with a hydrophobic molecule, i.e., tert-butyl acrylate (tBA). By changing the ratio among the precursors, we demonstrated the tunability of both the shear properties and hydrophilicity. The structural properties of hydrogels were studied by solid-state nuclear magnetic resonance (NMR). These experiments provided insights on both the structure and molecular dynamics of polymeric networks and, together with information obtained by differential scanning calorimetry (DSC), allowed for correlating the physical properties of the hydrogels with their chemical composition.

Highly aqueously stable C60‐polymer nanoparticles with excellent photodynamic property for potential cancer treatment

AbstractFullerenes are a class of carbon nanomaterials that find a wide range of applications in biomedical fields, especially for photodynamic cancer therapy because of its photosensitive effect. However, hydrophobic fullerenes can only be dispersed in organic solvents which hinders their biomedical applications. Here, we report a facile method to prepare highly water‐dispersible fullerene (C60)‐polymer nanoparticles with hydrodynamic sizes of 50–70 nm. Hydrophilic random copolymers containing different ratios of polyethylene glycol methyl ether methacrylate and 2‐aminoethylmethacrylamide were synthesized for conjugating with C60 molecules through efficient nucleophilic Michael addition reaction between amine groups from hydrophilic polymer and carbon‐carbon double bonds from C60. As a result, the amphiphilic C60‐polymer conjugates could be well dispersed and nano‐assembled in water with a C60 concentration as high as 7.8 mg/mL, demonstrating a significant improvement for the solubility of C60 in an aqueous system. Owing to the high C60 content, the C60‐polymer nanoparticles showed a strong photodynamic therapy effect on human lung cancer cells (A549) under light irradiation (450 nm) in both 2D cell culture and 3D spheroid culture, while demonstrating ignorable cytotoxicity under dark. This highly efficient and convenient method to prepare water‐dispersible C60‐polymer conjugates may have a great impact on the future biomedical applications of fullerenes.

Visible-Light Initiated Dispersion Photopolymerization of Styrene.

Polystyrene (PS) particles were synthesized in ethanol/water mixture by dispersion polymerization using visible light irradiation, with either a N-heterocyclic carbene borane-based photoinitiating system (PIS) or a disulfide. With the full PIS and poly(ethylene glycol) methyl ether methacrylate (PEGMA) as stabilizer, the size distributions were broad and the amount of PEGMA had a strong impact on the experiment reproducibility. The addition of a base solved the problem, leading to faster polymerizations, narrower size distributions and larger particles. With the disulfide as sole PIS, bigger and narrowly distributed PS particles were again formed. Quantitative conversion was achieved in each system, with particle size ranging between 100 and 350 nm. The use of poly(N-vinylpyrrolidone) as stabilizer led to significantly larger particles, up to 1.2μm, with narrow size distributions. The production of such large latex particles by photoinitiated polymerizations is unprecedented.

Effect of Polyethylene Glycol Methyl Ether Methacrylate on the Biodegradability of Polyvinyl Alcohol/Starch Blend Films.

Blend copolymers (PVA/S) were grafted with polyethylene glycol methyl methacrylate (PEGMA) with different ratios. Potassium persulfate was used as an initiator. The blend copolymer (PVA/S) was created by combining poly(vinyl alcohol) (PVA) with starch (S) in various ratios. The main idea was to study the effect of different ratios of the used raw materials on the biodegradability of plastic films. The resulting polymers (PVA/S/PEGMA) were analyzed using FTIR spectroscopy to investigate the hydrogen bond interaction between PVA, S, and PEGMA in the mixtures. TGA and SEM analyses were used to characterize the polymers (PVA/S/AA). The biodegradability and mechanical properties of the PVA/S/PEGMA blend films were evaluated. The findings revealed that the mechanical properties of the blend films are highly influenced by PEGMA. The time of degradation of the films immersed in soil and Coca-Cola increases as the contents of PVA and S and the molecular weight (MW) of PEGMA increase in the terpolymer. The M8 sample (PVA/S/PEGMA in the ratio of 3:1:2, respectively) with a MW of 950 g/mol produced the lowest elongation at break (67.5%), whereas M1 (PVA/S/PEGMA in the ratio of 1:1:1, respectively) with a MW of 300 g/mol produced the most (150%). The film's tensile strength and elongation at break were improved by grafting PEGMA onto the blending polymer (PAV-b-S). Tg and Tm increased when the PEGMA MW increased from 300 to 950. Tg (48.4 °C) and Tm (190.9 °C) were the lowest in M1 (300), while Tg (84.8 °C) and Tm (190.9 °C) were greatest in M1 (950) at 209.3 °C. The increased chain and molecular weight of PEGMA account for the increase in Tg and Tm of the copolymers.

Amino Acid-Based Polymer-Coated Silver Nanoparticles as Insulin Fibril Inhibitors

To explore the impact of polymer-coated silver nanoparticles (PC-AgNPs) on the extent of the insulin aggregation process, herein, we have synthesized three copolymers comprising poly(ethylene glycol) methyl ether methacrylate (PEGMA) and tert-butoxycarbonyl (Boc)-protected amino acid (alanine, leucine, and phenylalanine) containing methacrylate monomers, via reversible addition-fragmentation chain transfer (RAFT) polymerization. After deprotection of the Boc groups, the as-prepared water-soluble copolymers were coated on silver nanoparticles (Ag NPs), and the role of these NPs on insulin aggregation pathways was examined by multifarious spectroscopic and microscopic techniques. The extent of the inhibitory effect against the insulin fibrillation process was found to be related to the surface properties of the NPs, with the highest inhibitory effect detected for phenylalanine-based polymer-coated Ag NPs (PPhe-AgNPs). Using circular dichroism (CD) spectroscopy and Nile red (NR) fluorescence spectroscopy, we investigated the conformational changes and examined the role of hydrophobic interaction in inhibiting the aggregation properties of insulin upon treatment with PC-AgNPs. Furthermore, PC-AgNPs were also able to disintegrate the matured insulin fibrils and efficiently decreased the fibril-induced cytotoxicity, as confirmed by transmission electron microscopy (TEM) and the hemolysis study, respectively. Together, our findings established the novel amino acid-based PC-AgNPs as potent nanomaterials with 77–96% insulin fibril inhibition and marked disaggregation of matured insulin fibrils.

Antioxidant Polymers with Enhanced Neuroprotection Against Insulin Fibrillation.

Lipoic acid (LA) and dihydrolipoic acid (DHLA) are well established antioxidants to scavenge reactive oxygen species (ROS). However, they are carboxylates with ≈4.7pKa making them negatively charged at physiological pH (7.4) reducing their passive diffusion through cell membranes. LA is known to be capable of reducing protein fibrillation. Incorporation of LA and especially DHLA in polymer side chains are scarce. Herein, the first examples of the anti-amyloidogenic effect of LA and DHLA incorporated into the side-chain of a block copolymer with a water-soluble poly(polyethylene glycol methyl ether methacrylate) (PPEGMA) segment are presented. The resultant polymers show improved ROS scavenging activity and improved ability to reduce insulin fibrillation compared to free LA and DHLA. Furthermore, the resultant polymers are also capable of disintegrating preformed insulin firbrils. Interestingly, polymers with dihydro-lipoate moieties showed 93% free radical scavenging activity with 91% anti-fibrillating efficacies for insulin protein confirmed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay and Thioflavin T (ThT) dye binding study, respectively. Further, the antioxidant polymers increase the cell viability against fibrillar insulin aggregates that may be involved in the etiology of several diseases. Overall, this work reveals that antioxidant polymer-based therapeutic agents can serve as a powerful modulation strategy for developing novel drugs in future against amyloid-related disorders.

UV-photopolymerized cellulose acetate-acrylate membranes for lithium-ion battery separator

Cellulose acetate (CA) is attractive for use as a separator in lithium-ion batteries (LIBs). However, the dissolubility in the liquid electrolyte limits its applications. Herein, we would report a cellulose acetate (CA) cross-linked film for the separator of lithium-ion battery. First, methacrylate modified cellulose acetate (M-CA) was prepared by esterification between CA and methylacryloyl chloride. Subsequently, an insoluble polymer membrane was obtained through the UV-induced polymerization of M-CA, poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) and trihydroxymethylpropyl trimethylacrylaye (TMPTMA). The results show that these polymer membranes have good thermal and chemical stability due to the cross-linked polymer matrix. When the amount of TMPTMA is 20% of the molar amount of PEGMEMA, not only has the obtained gel polymer electrolyte (GPE) a suitable ionic conductivity of 4.17 mS cm−1 and an excellent lithium ion transfer number of 0.80, but also it has discharge capacity of the half battery composed of LiFePO4/GPE/Li 120 mAh g−1 at 2 C. This study demonstrated a great possibility that the high-performance and biodegradable GPE could be applied in LIBs. In addition, there are many other methacrylate monomers that can be polymerized with M-CA to prepare various GPEs, which will open a new avenue for the application of CA in GPEs.

Nanoparticle forming polyelectrolyte complexes derived from well-defined block copolymers

Polymers can be used in nanoparticle associated formulations to encapsulate cytotoxic drugs (e.g., paclitaxel). Polyelectrolyte complexes (PECs) that form drug associated colloids also have potential to form particulate associated formulations. We used RAFT polymerisation to prepare small families of narrow molecular weight distributed (i) methacrylate block co-polymers comprised of oligomeric ethylene glycol, poly(ethylene glycol) methyl ether methacrylate (PEGMA), and dimethyl amino pendent chains, 2-(dimethylamino) ethyl methacrylate (DMAEMA), and (ii) poly(methacrylic acid), PMAA. These polymers were examined for their ability to form PECs capable of drug encapsulation. Optimal control in RAFT polymerisation was confirmed by the linear increase of molecular weight and the narrow dispersity of the polymers (<1.2) as determined by 1H nuclear magnetic resonance and gel permeation chromatography. Dynamic light scattering and transmission electron microscopy showed formation of well-defined monodispersed nanoparticles with a hydrodynamic diameter of 25 ± 3 nm upon self-assembly of poly(PEGMA0.23-b-DMAEMA0.77)99 and PMAA75. These PECs are highly haemocompatible. Thin film hydration was used to encapsulate two hydrophobic drugs, paclitaxel and carmofur, into spherical nanoparticles. The results show that carmofur was encapsulated markedly more effectively than paclitaxel (72 vs 1.5%).

3 stage filtration system utilizing 3 distinct membranes derived from one single dope solution and finely-tuned phase inversion processes

Wastewater treatment by membrane processes requires at least 3 different membranes with performances falling in the microfiltration, ultrafiltration and nanofiltration ranges. Often, the composition of these membranes varies, and their preparation processes may involve several steps and lengthy or costly post-treatment procedures, for instance to endow the membrane with fouling-resistance property. Here, we intended to explore potential routes to simplify the treatment process. We solely used one single casting solution with the purpose of preparing 3 membranes without any post-treatment, that were then implemented in a 3-stage filtration process. This solution contains polyvinylidene fluoride (PVDF), a copolymer of styrene and polyethylene glycol methyl ether methacrylate (PS-r-PEGMA), and a solvent. 3 phase inversion processes: vapor-induced phase separation (VIPS), liquid-induced phase separation (LIPS) and evaporation-induced phase separation (EIPS) were executed to reach the desired membrane properties. Careful examination of the membrane structure, physical properties and permeability prove that the membranes prepared by VIPS (pore size: 0.4–0.8 µm), LIPS (pore size: 0.008–0.09 µm) and a combination of EIPS and LIPS (pore size: 3–6 nm) were suitable for the rejection of large biofoulants such as microalgae, large and small proteins, respectively, despite the presence of the antifouling copolymer that affected the membrane structure. Next, the 3 membranes were used to treat synthetic wastewater containing a mixture of microalgae, bovine serum albumin (BSA) and lysozyme. The first filtration stage permitted to reject almost entirely the Microalgae (99.3–99.5% rejection), the second filtration stage then removed larger proteins (cumulated “Microalgae/protein” rejection of about 93%) while the last stage rejected a large quantity of the smaller protein. The copolymer was also shown to reduce fouling by a 5-fold factor. Hence, this work demonstrates that a complete set of pressure-driven antifouling membranes for full wastewater treatment may be prepared from one single formulation and by phase inversion only.

Toughening of epoxy thermosets by self-assembled nanostructures of amphiphilic comb-like random copolymers.

Amphiphilic comb-like random copolymers synthesized from poly(ethylene glycol) methyl ether methacrylate (PEGMMA) and stearyl methacrylate (SMA) with PEGMMA contents ranging between 30 wt% and 25 wt% were demonstrated to self-assemble into various well-defined nanostructures, including spherical micelles, wormlike micelles, and vesicle-like nanodomains, in anhydride-cured epoxy thermosets. In addition, the polymer blends of the comb-like random copolymer and poly(stearyl methacrylate) were prepared and incorporated into epoxy thermosets to form irregularly shaped nanodomains. Our research findings indicate that both the comb-like random copolymers and polymer blends are suitable as toughening modifiers for epoxy. When added at a concentration of 5 wt%, both types of modifiers lead to substantial improvements in the tensile toughness (>289%) and fracture toughness of epoxy thermosets, with minor reductions in their elastic modulus (<16%) and glass transition temperature (<6.1 °C). The fracture toughness evaluated in terms of the critical stress intensity factor (KIC) and the strain energy release rate (GIC) increased by more than 67% and 131% for the modified epoxy thermosets containing comb-like random copolymers.

High‐Performance Organic Photosynaptic Transistors Using Donor−Acceptor Type and Crosslinked Core−Shell Nanoparticles as a Floating Gate Electret

AbstractPhotosynaptic transistor is considered to be a potential candidate for breaking the von Neumann bottleneck in photo‐communication field. Herein, a series of donor−acceptor type and crosslinked core−shell nanoparticles are designed and applied in phototransistors as a charge‐trapping electret. The outer shell is composed of poly(ethylene glycol) methyl ether methacrylate (PEGMA); while the inner core comprises donors of thiophene and bithiophene (2T) and acceptors of benzothiazole (BT), naphthalenediimide (NDI), and hexafluorobenzene‐naphthalenediimide (FB‐NDI). It is found that the core−shell and donor−acceptor design play an important role in the charge trapping, photoresponse, and the corresponding device performance. Accordingly, the phototransistor comprising the crosslinked core−shell nanoparticles with a donor of 2T and an acceptor of BT (PV2T‐BT) produced the highest memory ratio of 105 over 104 s at a high operating voltage of −40 V. Meanwhile, the same device presented the highest paired‐pulse facilitation ratio of 168% at a medium operating voltage of −1 V, and an ultra‐low energy consumption of 0.0324 fJ at a low operating voltage of −1 µV. The findings in this study provide a new perspective on material design for phototransistor devices.

Covalent Conjugate of Ser-Pro-Cys Tripeptide with PEGylated Comb-Like Polymer as Novel Killer of Human Tumor Cells.

Recently, we detected a previously unknown Ser-Pro-Cys (SPC) tripeptide in the blood serum of multiple sclerosis patients. Its role as a biomarker of the autoimmune disease was suggested, although its origin and real biological activity remained unclear. Here, we created a biocompatible PEGylated comb-like polymer that was used as a platform for covalent immobilization of the SPC, which provided a possibility to explore the biological activity of this tripeptide. This macromolecular conjugate was synthesized via a reaction of the terminal epoxide group of the biocompatible copolymer of dimethyl maleate (DMM) and polyethylene glycol methyl ether methacrylate (PEGMA) with the amino group of the SPC tripeptide. Unexpectedly, the resulting conjugate containing SPC demonstrated anticancer activity in vitro. It possessed pro-apoptotic action toward human tumor cells, while there was no cytotoxic effect of that conjugate toward normal lymphocytes of human peripheral blood. The detected biological effects of the created conjugate inspired us to carry out a thorough study of structural and colloidal-chemical characteristics of this surface-active copolymer containing side PEG chains and a terminal nontoxic synthetic fragment. The copolymer composition, in particular, the content of the peptide fragment, was determined via elemental analysis and NMR spectroscopy. At CMC, it formed polymeric micelle-like structures with a hydrodynamic diameter of 180 ± 60 nm. The conjugation of the peptide fragment to the initial comb-like copolymer caused a change of zeta-potential of the formed micelle-like structures from -0.15 to 0.32 mV. Additional structural modification of the created polymeric nanoplatform was performed via attachment of fluorescein isothiocianate (FITC) dye that permitted monitoring of the behavior of the bioactive SPC-functionalized conjugate in the treated tumor cells. Its penetration into those cells and localization in their cytoplasm were revealed. The principal novelty of this study consists in finding that covalent conjugation of two nontoxic compounds-SPC tripeptide and comb-like PEGylated polymer-led to an unexpected synergy which appeared in the distinct cytotoxic action of the macromolecular complex toward human tumor cells. A potential role of peculiarities of the colloidal-chemical properties of the novel conjugate in its cytotoxic effect are discussed. Thus, synthesized comb-like PEGylated polymers can provide a prospective nanoplatform for drug delivery in anticancer chemotherapy.

Sponges from Plasma Treated Cellulose Nanofibers Grafted with Poly(ethylene glycol)methyl Ether Methacrylate.

In this work, cellulose nanofibers (CNF) were surface treated by plasma and grafted with poly(ethylene glycol)methyl ether methacrylate (PEGMMA) for increasing mechanical strength and hydrophobicity. The surface characteristics of the sponges were studied by scanning electron microscopy, micro-computed tomography, and Fourier transform infrared spectroscopy, which demonstrated successful surface modification. Plasma treatment applied to CNF suspension led to advanced defibrillation, and the resulting sponges (CNFpl) exhibited smaller wall thickness than CNF. The grafting of PEGMMA led to an increase in the wall thickness of the sponges and the number of larger pores when compared with the non-grafted counterparts. Sponges with increased hydrophobicity demonstrated by an almost 4 times increase in the water contact angle and better mechanical strength proved by 2.5 times increase in specific compression strength were obtained after PEGMMA grafting of plasma treated CNF. Cells cultivated on both neat and PEGMMA-grafted CNF sponges showed high viability (&gt;99%). Remarkably, CNF grafted with PEGMMA showed better cell viability as compared with the untreated CNF sample; this difference is statistically significant (p &lt; 0.05). In addition, the obtained sponges do not trigger an inflammatory response in macrophages, with TNF-α secretion by cells in contact with CNFpl, CNF-PEGMMA, and CNFpl-PEGMMA samples being lower than that observed for the CNF sample. All these results support the great potential of cellulose nanofibers surface treated by plasma and grafted with PEGMMA for biomedical applications.

Construction of pH-responsive nanoplatform from stable magnetic nanoparticles for targeted drug delivery and intracellular imaging

Currently, developing responsive hydrophobic drug delivery systems centered on magnetic nanoparticles is a promising approach for the efficient delivery of hydrophobic drugs to living cells. Here, an efficacious designed strategy was proposed to construct pH-responsive nanoplatform for targeted hydrophobic drug delivery based on the formation of surface-anchored targeting molecules on the surface of Fe3O4 @C via single electron transfer living radical polymerization (SET-LRP) method. First, we prepared polymer-modified Fe3O4 @C using 4-vinylphenylboronic acid (VB) and polyethylene glycol methyl ether methacrylate (PEGMA) as polymerized monomers and confirmed that Fe3O4 @C-VB-PEGMA had high biocompatibility and low cytotoxicity. Next, we prepared curcumin-containing Fe3O4 @C-VB-PEGMA-Cur nanoplatform with an encapsulation efficiency for Cur as high as 67.7%. Furthermore, the nanoplatform not only displayed pH-responsive release behaviors of Cur under different pH values (pH=7.2, 6.5, 5.4), but also can be effectively targeted into HepG2 cells. More importantly, the nanoplatform also exhibited effectively inhibiting the growth of HepG2 cells and continuously intracellular imaging by the targeted releasing of loaded Cur. It is envisaged that these findings are a step forward in the construction of pH-responsive platform as a tool for clinical hydrophobic drug delivery.

Investigation on Tethered Anion Effects in Solid Polymer Electrolytes for Li-Ion Batteries

Solid polymer electrolytes (SPEs) have been proposed to reduce concentration polarizations within batteries by immobilizing anions to the polymer matrix, which can help stabilize the electrodeposition process and extend Li-ion battery lifetime. Unfortunately, single-ion conducting SPEs continue to suffer from poor conductivity due to coupling with the slow segmental mobility of polymer chains and poor ion pair dissociation. Our group systematically investigated how different tethered anions affect the Li-ion conduction and polymer segmental mobility. Copolymers were synthesized using a common neutral monomer, poly(ethylene glycol) methyl ether methacrylate (PEGMA), with a series of different anionic monomers: 4-styrene sulfonate, 4-styrene phosphonate, 4-styrene TFSI, and methacrylate TFSI. These monomers presented a series of anions of varying strength with the same styrene structure, sulfonate vs. phosphonate vs. TFSI, as well as exploring structural monomer changes for the same TFSI anion, styrene vs. methacrylate, that allows for systematic changing of polymer electrolyte properties. Each copolymer series was further expanded by changing the composition of neutral-to-anionic monomers, ranging from 10-67 mol% anionic. The increased ion exchange capacity of the phosphonate groups led to a high degree of ion aggregation that exhibited hard mechanical properties and very low Li-ion conductivities. Increasing the electron delocalization of the ions from sulfonate to TFSI greatly improved the conductivities and lowered activation energies of ion transport, with methacrylate being slightly better than styrene. Implications of these results will be discussed for next-generation polymer electrolyte design.