Glycol Research Articles

Data-Driven Framework for the Prediction of PEGDA Hydrogel Mechanics.

Poly(ethylene glycol) diacrylate (PEGDA) hydrogels are biocompatible and photo-cross-linkable, with accessible values of elastic modulus ranging from kPa to MPa, leading to their wide use in biomedical and soft material applications. However, PEGDA gels possess complex microstructures, limiting the use of standard polymer theories to describe them. As a result, we lack a foundational understanding of how to relate their composition, processing, and mechanical properties. To address this need, we use a data-driven approach to develop an empirical predictive framework based on high-quality data obtained from uniaxial compression tests and validated using prior data found in the literature. The developed framework accurately predicts the hydrogel shear modulus and the strain-stiffening coefficient using only synthesis parameters, such as the molecular weight and initial concentration of PEGDA, as inputs. These results provide simple and reliable experimental guidelines for precisely controlling both the low-strain and high-strain mechanical responses of PEGDA hydrogels, thereby facilitating their design for various applications.

Biological Condensate Growth: Examining the Impact of Solute Crowder on Size Expansion.

Biological condensation refers to the formation of micrometer-sized or smaller condensates by biological macromolecules, a process often influenced by the crowded cellular environment. Poly(ethylene glycol) (PEG) is commonly used to mimic cellular crowding, and its ability to reduce the critical nucleation concentration has been well established. However, its impact on condensate size has been less explored. This study investigates how PEG affects the size of condensates formed between protein TNP1 and DNA. Our experimental findings show that PEG molecules increase condensate size. Notably, at equal mass concentrations of PEG400, PEG3350, and PEG10000, longer PEG molecules have a much greater effect on condensate expansion. Computational simulations further reveal that longer PEG molecules enhance protein-DNA condensation more effectively and contribute to shaping the condensates into regular forms. Overall, our study provides key insights into how crowding factors influence the size and shape of colloidal growth.

Diastereoselective Polypseudorotaxane Formation with Planar Chiral Pillar[5]arenes via Co-crystallization Processes.

As the number of chiral ring molecules in chiral polyrotaxane increases, the number of possible stereoisomers exponentially increases. Consequently, the selective synthesis of a specific stereoisomer becomes much more challenging. To address this problem, we co-crystallized poly(ethylene glycol) and a diastereomeric ring molecule, pillar[5]arene, in the solid state. The co-crystallization formed polypseudorotaxanes with a high diastereomeric excess (ca. 88% de), meaning that polypseudorotaxanes containing (S, pS) stereoisomer pillar[5]arene rings were synthesized selectively. By contrast, in a solution and evaporation systems, the selectivity remained low (ca. 10% de). The results suggested that the packing effect by the co-crystallization contributed to the denser assembly of ring molecules on the polymeric chain, resulting in the diastereoselective formation. High diastereoselectivity was also observed even in higher-molecular-weight poly(ethylene glycol)s. These selectivities arose from the cooperative effects of the ring molecules on the polymeric chain, which were supported by calculating the stabilization energy.

Diastereoselective Polypseudorotaxane Formation with Planar Chiral Pillar[5]arenes via Co‐crystallization Processes

As the number of chiral ring molecules in chiral polyrotaxane increases, the number of possible stereoisomers exponentially increases. Consequently, the selective synthesis of a specific stereoisomer becomes much more challenging. To address this problem, we co‐crystallized poly(ethylene glycol) and a diastereomeric ring molecule, pillar[5]arene, in the solid state. The co‐crystallization formed polypseudorotaxanes with a high diastereomeric excess (ca. 88% de), meaning that polypseudorotaxanes containing (S, pS) stereoisomer pillar[5]arene rings were synthesized selectively. By contrast, in a solution and evaporation systems, the selectivity remained low (ca. 10% de). The results suggested that the packing effect by the co‐crystallization contributed to the denser assembly of ring molecules on the polymeric chain, resulting in the diastereoselective formation. High diastereoselectivity was also observed even in higher‐molecular‐weight poly(ethylene glycol)s. These selectivities arose from the cooperative effects of the ring molecules on the polymeric chain, which were supported by calculating the stabilization energy.

Improving the Anti-Tumor Effect of Indoleamine 2,3-Dioxygenase Inhibitor CY1-4 by CY1-4 Nano-Skeleton Drug Delivery System

Background: CY1-4, 9-nitropyridine [2′,3′:4,5] pyrimido [1,2-α] indole -5,11- dione, is an indoleamine 2,3-dioxygenase (IDO) inhibitor and a poorly water-soluble substance. It is very important to increase the solubility of CY1-4 to improve its bioavailability and therapeutic effect. In this study, the mesoporous silica nano-skeleton carrier material Sylysia was selected as the carrier to load CY1-4, and then the CY1-4 nano-skeleton drug delivery system (MSNM@CY1-4) was prepared by coating the hydrophilic polymer material Hydroxypropyl methylcellulose (HPMC) and the lipid material Distearoylphosphatidyl-ethanolamine-poly(ethylene glycol)2000 (DSPE-PEG2000) to improve the anti-tumor effect of CY1-4. Methods: The solubility and dissolution of MSNM@CY1-4 were investigated, and its bioavailability, anti-tumor efficacy, IDO inhibitory ability and immune mechanism were evaluated in vivo. Results: CY1-4 was loaded in MSNM@CY1-4 in an amorphous form, and MSNM@CY1-4 could significantly improve the solubility (up to about 200 times) and dissolution rate of CY1-4. In vivo studies showed that the oral bioavailability of CY1-4 in 20 mg/kg MSNM@CY1-4 was about 23.9-fold more than that in 50 mg/kg CY1-4 suspension. In B16F10 tumor-bearing mice, MSNM@CY1-4 significantly inhibited tumor growth, prolonged survival time, significantly inhibited IDO activity in blood and tumor tissues, and reduced Tregs in tumor tissues and tumor-draining lymph nodes to improve anti-tumor efficacy. Conclusions: The nano-skeleton drug delivery system (MSNM@CY1-4) constructed in this study is a potential drug delivery platform for improving the anti-tumor effect of oral poorly water-soluble CY1-4.

Antimicrobial Biphasic Polymer Coatings Enabled by Fast Diffusion of Active Compounds.

The recent COVID-19 pandemic and the prospect of future global pandemics highlight the long-standing need to passively eliminate viruses and bacteria on surfaces. Conventional antimicrobial surfaces and coatings are typically constrained by a trade-off between antimicrobial efficacy and physical durability. A biphasic polyurethane coating has been developed that breaks this trade-off by incorporating a durability-imparting polycarbonate (PC) discrete phase with a continuous poly(ethylene glycol) (PEG) transport phase that absorbs, stores, and releases antimicrobial active compounds for extended microbial inactivation. The biphasic polymer was shown to absorb carboxylic acid and quaternary ammonium antimicrobial active compounds, maintained their levels after five years of simulated cleaning, and inactivated up to 99.99% of Human Coronavirus 229E and Influenza A H1N1. Furthermore, the levels of antimicrobial active compounds on the biphasic coating could be augmented by cleaning the substrate with a disinfectant. The practicality of biphasic coatings for automotive and commercial aerospace environments was demonstrated by showing control of hardness and stain resistance through biphasic composition, showing environmental durability through heat, humidity, and light exposure, and passing flammability protocols.

Protein-Specific Crowding Accelerates Aging in Protein Condensates.

Macromolecular crowding agents, such as poly(ethylene glycol) (PEG), are often used to mimic cellular cytoplasm in protein assembly studies. Despite the perception that crowding agents have an inert nature, we demonstrate and quantitatively explore the diverse effects of PEG on the phase separation and maturation of protein condensates. We use two model proteins, the FG domain of Nup98 and bovine serum albumin (BSA), which represent an intrinsically disordered protein and a protein with a well-established secondary structure, respectively. PEG expedites the maturation of Nup98, enhancing denser protein packing and fortifying interactions, which hasten beta-sheet formation and subsequent droplet gelation. In contrast to BSA, PEG enhances droplet stability and limits the available solvent for protein solubilization, inducing only minimal changes in the secondary structure, pointing toward a significantly different role of the crowding agent. Strikingly, we detect almost no presence of PEG in Nup droplets, whereas PEG is moderately detectable within BSA droplets. Our findings demonstrate a nuanced interplay between crowding agents and proteins; PEG can accelerate protein maturation in liquid-liquid phase separation systems, but its partitioning and effect on protein structure in droplets is protein specific. This suggests that crowding phenomena are specific to each protein-crowding agent pair.

Nonionic Amphiphilic Copolymers of Poly(poly(ethylene Glycol) Methacrylate) Brushes with Methyl Methacrylate Prepared by Atom Transfer Radical Polymerization as Dry Solid Polymer Electrolytes for Next Generation Li-ion Battery Applications

Nonionic Amphiphilic Copolymers of Poly(poly(ethylene Glycol) Methacrylate) Brushes with Methyl Methacrylate Prepared by Atom Transfer Radical Polymerization as Dry Solid Polymer Electrolytes for Next Generation Li-ion Battery Applications

Printable and Tunable Bioresin with Strategically Decorated Molecular Structures.

As personalized medicine rapidly evolves, there is a critical demand for advanced biocompatible materials surpassing current additive manufacturing capabilities. This study presents a novel printable bioresin engineered with tunable mechanical, thermal, and biocompatibility properties through strategic molecular modifications. The study introduces a new bioresin comprising methyl methacrylate (MMA), ethylene glycol dimethacrylate (EGDMA), and a photoinitiator, which is further enhanced by incorporating high molecular weight polymethyl methacrylate (PMMA) to improve biostability and mechanical performance. The integration of printable PMMA presents several synthesis and processing challenges, necessitating substantial modifications to the 3D printing process. Additionally, the bioresin is functionalized with antibacterial silver oxide and bone-growth-promoting hydroxyapatite at various weight ratios to extend its application further. The results demonstrate the agile printability of the novel bioresin and its potential for transformative impact in biomedical applications, offering a versatile material platform for additive manufacturing-enabled personalized medicine. This work highlights the adaptability of the novel printable bioresin for real-life applications and its capacity for multiscale structural tailoring, potentially achieving properties comparable to native tissues and extending beyond conventional additive manufacturing techniques.

Modular chem‐bio upcycling of waste poly(ethylene terephthalate) to glycolic acid and 2,4‐pyridine dicarboxylic acid

AbstractUpcycling of waste poly(ethylene terephthalate) (PET) into valuable products represents a promising avenue for advancing carbon neutrality and circular economy. Here, we demonstrate a modular strategy for converting waste PET into glycolic acid (GA) and 2,4‐pyridine dicarboxylic acid (2,4‐PDCA), achieving an upcycling process and 45% reduction in greenhouse gas emissions. We conducted comprehensive studies on PET hydrolysis, PET‐derived ethylene glycol (EG) photooxidation, and PET‐derived terephthalic acid (TPA) bioconversion. Utilizing a plasmon‐active CuPt nanoalloy, EG oxidation proceeds at mild conditions with impressive EG conversion (94.78%) and GA yield (71.98%). Two Escherichia coli strains were employed to convert TPA into 2,4‐PDCA, achieved a 91.03% molar yield. This work successfully accomplishes the comprehensive utilization of waste PET through an environmentally friendly and economically viable strategy, leading to a significant reduction in PET plastic pollution while simultaneously generating substantial economic benefits.

New insights into transreaction mechanism between poly (ethylene terephthalate) and bisphenol A polycarbonate in melt

AbstractIn the present study, the macromolecular chain composition of copolymers prepared by the reactive blending of poly(ethylene terephthalate) (PET) and bisphenol A polycarbonate (PC) in the presence of Ti(OBu)4 catalyst was tested using 1H and 13C NMR spectroscopy. The NMR spectra were meticulously analyzed across all regions, revealing unexpected results that provide new insights into the transreaction mechanism occurring between these two polymers in the melt phase. It was found that only two primary reactions occurred: the formation of a bisphenol A terephthalate bond accompanied by the release of ethylene carbonate and the formation of an aliphatic–aromatic ether bond with the release of CO2. The release of ethylene carbonate during the PET‐PC blending led to a loss of ethylene glycol (EG). The kinetics of EG loss and ether bond formation were examined. A new transreaction mechanism for PET‐PC reactive blending is proposed. © 2024 Society of Chemical Industry.

Membraneless Compartmentalization of Cell-Free Transcription-Translation by Polymer-Assisted Liquid-Liquid Phase Separation.

Living cells use liquid-liquid phase separation (LLPS) to compartmentalize metabolic functions into mesoscopic-sized droplets. Deciphering the mechanisms at play in LLPS is therefore critical to understanding the structuration and functions of cells at the subcellular level. Although observed and achieved to a significant degree of control in vivo, the reconstitution of LLPS integrating advanced biological functions, such as gene expression, has been so far limited in vitro. LLPS of cell-free transcription-translation (TXTL) reactions require multi-step experimental approaches that lack biomimetic and have relatively poor efficacy, thus limiting their usage in cell-free engineered systems such as synthetic cells. Here the polymer-assisted LLPS of TXTL reactions are reported as the single-pot one-step compartmentalization of a model complex metabolic system obtain without using solvents or surfactants. LLPS occurs by adding the biocompatible polymers poly(ethylene glycol), poly(vinyl alcohol), and dextran to a TXTL reaction, that remains highly active. These polymers serve as partitioning agents that localize TXTL in mesoscopic-sized droplets rich in dextran. Cytoplasmic and membrane-interacting proteins are synthesized preferentially inside these droplets, and localize either uniformly or preferentially at the interface, depending on their nature. The LLPS-TXTL system presented in this work is a step toward the design of synthetic membraneless active organelles.

Concurrently Selective Electrosynthesis of Ammonia and Glycolic Acid Over Cathodic Single‐Atom Cobalt and Anodic PdNi Alloying Catalysts

AbstractHerein, an electrocatalytic coupling system for selective ammonia and glycolic acid production over cathodic single‐atom Co (Co─N─C) and anodic PdNi alloying nanoparticles on the carbonized cellulose (PdNi/CBC), respectively are reported. As a cathodic electrocatalyst for nitrate reduction reaction (NtrRR), the Co─N─C displays remarkably high activity, delivering an NH3 yield rate of 20.5 ± 2.7 mg h−1 mgcat.−1 with a Faradaic efficiency (FE) of 95.5 ± 2.8% at −0.5 V (vs RHE). In situ spectroscopy combined with theoretical calculations unveiled the NtrRR mechanism on Co─N4 site. As an anodic electrocatalyst for ethylene glycol oxidation reaction (EGOR), the PdNi/CBC shows a high FE of 96.6 ± 1.7% for glycolic acid (GA) production at 1.6 V (vs RHE) and robust stability of 168 h. Remarkably, a proof of concept experiment of coupling electrocatalytic NtrRR with EGOR demonstrates that only an applied potential of −0.1 V (vs RHE) is required to reach a current density of 10 mA cm−2 for co‐producing ammonia and glycolic acid. As a result, the coupled NtrRR‐EGOR system can achieve an NH3 yield rate of 6.0 ± 0.6 mg h−1 mgcat.−1 and a GA yield rate of 16.8 ± 1.7 mg h−1 mgcat.−1 at −0.7 V (vs RHE).

Highly Sensitive Ethylene Glycol Gas Sensor Based on MIL-68(In)@ZIF-8 Derivative.

Ethylene glycol, as a colorless and tasteless organic compound, is an important industrial raw material but can be hazardous to the environment and human health. Thus, the development of high-performance sensing materials is required for the monitoring of ethylene glycol. In this paper, a method to synthesize In2O3@ZnO using MIL-68(In)@ZIF-8 to serve as a sacrificial template is proposed for testing ethylene glycol sensing capabilities. For verifying an effective improvement in gas-sensitive performance by bimetallic organic skeleton (MOF) synthesized heterojunctions, we performed gas-sensitive tests on In2O3, ZnO, and In2O3@ZnO. In2O3@ZnO has the best sensitivity to ethylene glycol, including ultrahigh response value (20 ppm-200.12), moderate response/recovery time (53/50 s), and excellent selectivity. The construction of heterojunction is the main reason for enhancing the ethylene glycol response of the sensor. On this basis, the gas-sensitive enhancement mechanism of composites is analyzed. The results show that the design method of synthesizing heterojunctions using bis-MOFs proposes a new approach that enhances the properties of ethylene glycol.

A charge reversal nano-assembly prevents hepatic steatosis by resolving inflammation and improving lipid metabolism

Lipid metabolism imbalance combined with over-activated inflammation are two key factors for hepatic stestosis. However, on-demand anchoring inflammation and lipid metabolism disorder for hepatic stestosis treatment has yet to be realized. Here we propose a charge reversal fullerene based nano-assembly to migrate hepatic steatosis via inhibiting macrophage-mediated inflammation and normalizing hepatocellular lipid metabolism in obesity mice. Our nano-assembly (abbreviated as FPPD) is comprised of electropositive polyetherimide (PEI), charge-shielded dimethylmaleic anhydride (DMA), and poly(lactic-co-glycolic acid) (PLGA), which provides hydrophobic chains for self-assembly with anti-oxidative dicarboxy fullerene poly(ethylene glycol) molecule (FP). The obtained FPPD nano-assembly owns a charge reversal ability that switches to a positive charge in an acidic environment that targets the electronegative mitochondria both in pro-inflammatory macrophages and steatosis hepatocytes. We demonstrate that the anti-oxidative and mitochondria-targeting FPPD notably reduces inflammation in macrophages and lipid accumulation in hepatocytes by quenching excessive reactive oxygen species (ROS) and improving mitochondrial function in vitro. Importantly, FPPD nano-assembly reveals a superior anti-hepatic steatosis effect via migrating inflammation and facilitating lipid transport in obesity mice. Overall, the charge reversal nano-assembly reduces over-activated inflammation and promotes lipid metabolism that provides an effectiveness of a multi-target strategy for hepatic steatosis treatment.

Biocompatible hydrogel coating on single living cells through visible light-induced polymerization.

Visible light-mediated photocatalysis leads to the efficient hydrogel coating of individual mammalian cells, functionalized with biocompatible anchor molecules tagged with fluorescein serving as a trifecta: photocatalyst, initiator, and fluorophore. NIH3T3 fibroblast cells are encapsulated within hydrogel shells of poly(ethylene glycol) diacrylate (PEGDA) and N-vinylpyrrolidone without any noticeable decrease in cell viability.

Laboratory, comparative and statistical investigations of MWCNT and ZnO (15:85)/ethylene–glycol hybrid nanorefrigerant for improving thermal conductivity of ethylene glycol

Laboratory, comparative and statistical investigations of MWCNT and ZnO (15:85)/ethylene–glycol hybrid nanorefrigerant for improving thermal conductivity of ethylene glycol

Upcycling of Postconsumer PET Using Serinol: Green Preparation of a New Multifunctional Initiator for PLA

ABSTRACTChemical recycling is attracting more and more interest as it can transform a plastic scrap into a high‐value material. This work shows that the aminolysis of postconsumer poly(ethyleneterephthalate) (PET) with serinol, a nontoxic and biosourced hydroxyamine, leads to a novel multifunctional initiator for poly(lactic acid) (PLA). The reaction was performed at 180°C, without the need of catalysts, and resulted in a substantially complete aminolysis of PET, selectively yielding the corresponding diamide of terephthalic acid (terephthalic acid serinol bis‐amide, TASBA), together with ethylene glycol as the co‐product. TASBA holds four hydroxy groups and was used as multifunctional initiator in the polymerization of lactide to PLA, with 0.1%, 0.5%, and 1% w/w of TASBA with respect to L‐lactide. TASBA led to a multiarm PLA, whose molecular weight and thermal and rheological properties could be tuned with the amount of initiator. The lowest amount of initiator left substantially unaffected the molecular weight and led to higher melt viscosity and to lower crystallinity. Lower molecular weight and melt viscosity were obtained by increasing the amount of TASBA. This work therefore proposes a synergy between the most important polyesters, the most diffused PET and the compostable PLA.

Enhancing Thermal Conductivity of Water-Ethylene Glycol Mixtures: A Study on TiO2-Al2O3 Hybrid Nanofluids with Surfactants

This analysis examines the thermal behaviour of 40% ethylene glycol-based TiO2-Al2O3 hybrid nanofluids by synthesizing them and assessing their thermal conductivity as a function of volume concentration and temperature. These hybrid nanofluids, emerging as a promising new class of advanced operating fluids, offer remarkable potential for enhancing heat transfer performance in various thermal engineering applications. Using a two-stage synthesis method, TiO2-Al2O3/40% ethylene glycol nanofluids were prepared across five distinct volume focuses (varying from 0.02% to 0.1%), incorporating Polyvinylpyrrolidone (PVP) as a stabilizing emulsifier. Precise thermal conductivity measurements were conducted over 30 °C to 80 °C, with incremental steps of 10 °C, ensuring comprehensive data collection. The investigation yielded significant findings, notably a substantial maximum thermal conductivity enhancement of 37.44%, observed at 80 °C with a 0.1% volume concentration, demonstrating pronounced sensitivity to elevated temperatures and concentrations. The strategic addition of PVP surfactant resulted in a remarkable 125% improvement in the nanofluid's stability period, although a maximum 5.33% reduction in thermal conductivity. Considering the inadequacy of existing predictive models to capture the observed data accurately, this study proposed developing a high-precision predictive model, achieving an impressive maximum deviation of less than 3%. The research concludes that these hybrid nanofluids, characterized by their exceptional stability and significantly enhanced thermal conductivity, hold immense potential to revolutionize heat transfer applications across various domains of practical thermal engineering. This breakthrough paves the way for developing more efficient, high-performance heat transfer systems, potentially catalysing energy efficiency and thermal management advancements across diverse industrial sectors.

Calcium sensing receptor regulate claudin-14 via PKA-STAT3 pathway in rat model of nephrolithiasis

BackgroundThe calcium-sensitive receptor (CaSR) has been identified as a key factor in the formation of kidney stones. A substantial body of research has illuminated the function of CaSR in stone formation with respect to oxidative stress, epithelial injury, crystal adhesion, and stone-associated proteins. Nevertheless, as a pivotal molecule in renal calcium excretion, its pathway that contributes to stone formation by regulating calcium supersaturation remains underexplored.MethodsAn in vitro rat calcium oxalate kidney stone model was established through the co-cultivation of calcium oxalate monohydrate (COM) with NRK-52E cells, while an in vivo model was constructed using the ethylene glycol method. Subsequently, the level of the CaSR-claudin-14 pathway was determined. To further elucidate the molecular pathway of CaSR-mediated regulation of claudin-14, drugs were selectively added to the in vitro and ex vivo kidney stone models, and the expression of claudin-14 and the levels of stone formation were detected. Moreover, the direct regulation of claudin-14 by CaSR with STAT3 serving as a transcription factor was examined via the dual luciferase assay. Eventually, a Cldn-14 knockout rat model and a model of kidney stone induction by ethylene glycol were generated using CRISPR-Cas9 technology to further clarify the role of claudin-14 in the CaSR-regulated formation of kidney stones.ResultsIn vitro and in vivo observations revealed that calcium oxalate induces high expression of CaSR-claudin-14. Specifically, CaSR regulates claudin-14 expression through phosphorylation modification of STAT3 via protein kinase A (PKA). In vitro, the intervention of PKA and STAT3 reversed the elevated claudin-14 levels and stone formation induced by CaSR. Finally, we generated cldn-14 knockout rats using CRISPR-Cas9 technology and observed that ethylene glycol still induced stone formation in these animals. Nevertheless, the specific activation or inhibition of CaSR demonstrated no notable impact on stone formation.ConclusionThe results of our study indicate that calcium oxalate crystals induce the activation of the pro-stone pathway of CaSR. That is, activated CaSR regulates claudin-14 levels via the PKA-STAT3 pathway, which further promotes calcium salt stone formation. The role of CaSR in the regulation of stone homeostasis is further enriched.