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Depletion interactions are thought to significantly contribute to the organization of intracellular structures in the crowded cytosol. The strength of depletion interactions depends on physical parameters such as the depletant number density and the depletant size ratio. Cells are known to dynamically regulate these two parameters by varying the copy number of proteins of a wide distribution of sizes. However, mammalian cells are also known to keep the total protein mass density remarkably constant, to within 0.5% throughout the cell cycle. We thus ask how the strength of depletion interactions varies when the total depletant mass is held fixed, a.k.a. fixed-mass depletion. We answer this question via scaling arguments, as well as by studying depletion effects on networks of reconstituted semiflexible actin in silico and in vitro. We examine the maximum strength of the depletion interaction potential U∗ as a function of q, the size ratio between the depletant and the matter being depleted. We uncover a scaling relation U∗ ∼ qζ for two cases: fixed volume fraction φ and fixed mass density ρ. For fixed volume fraction, we report ζ < 0. For the fixed mass density case, we report ζ > 0, which suggests that the depletion interaction strength increases as the depletant size ratio is increased. To test this prediction, we prepared our filament networks at fixed mass concentrations with varying sizes of the depletant molecule poly(ethylene glycol) (PEG). We characterize the depletion interaction strength in our simulations via the mesh size. In experiments, we observe two distinct actin network morphologies, which we call weakly bundled and strongly bundled. We identify a mass concentration where different PEG depletant sizes lead to weakly bundled or strongly bundled morphologies. For these conditions, we find that the mesh size and intra-bundle spacing between filaments across the different morphologies do not show significant differences, while the dynamic light scattering relaxation time and storage modulus between the two states do show significant differences. Our results demonstrate the ability to tune actin network morphology and mechanics by controlling depletant size and give insights into depletion interaction mechanisms under the fixed-depletant-mass constraint relevant to living cells. [ABSTRACT FROM AUTHOR]

In the interstellar medium, diols and other prebiotic molecules adsorb onto icy mantles surrounding dust grains. Water in the ice may affect the reactivity and photoionization of these diols. Ethylene glycol (EG), 1,2-propylene glycol, and 1,3-propylene glycol clusters with water clusters were used as a proxy to study these interactions. The diol–water clusters were generated in a continuous supersonic molecular beam, photoionized by synchrotron-based vacuum ultraviolet light from the Advanced Light Source, and subsequently detected by reflectron time-of-flight mass spectrometry. The appearance energies for the detected clusters were determined from the mass spectra, collected at increasing photon energy. Clusters of both diol fragments and unfragmented diols with water were detected. The lowest energy geometry optimized conformers for the observed EG–water clusters and EG fragment–water clusters have been visualized using density functional theory (DFT), providing insight into hydrogen bonding networks and how these affect fragmentation and appearance energy. As the number of water molecules clustered around EG fragments (m/z 31 and 32) increased, the appearance energy for the cluster decreased, indicating a stabilization by water. This trend was supported by DFT calculations. Fragment clusters from 1,2-propylene glycol exhibited a similar trend, but with a smaller energy decrease, and no trend was observed from 1,3-propylene glycol. We discuss and suggest that the reactivity and photoionization of diols in the presence of water depend on the size of the diol, the location of the hydroxyl group, and the number of waters clustered around the diol. [ABSTRACT FROM AUTHOR]

Glass formation and reorientational motions are widespread but often-neglected features of deep eutectic solvents although both can be relevant for the technically important ionic conductivity at room temperature. Here, we investigate these properties for two mixtures of ethylene glycol and ZnCl2, which were recently considered superior electrolyte materials for application in zinc-ion batteries. For this purpose, we employed dielectric spectroscopy performed in a broad temperature range, extending from the supercooled state at low temperatures up to the liquid phase around room temperature and beyond. We find evidence for a relaxation process arising from dipolar reorientation dynamics, which reveals the clear signatures of glassy freezing. This freezing also governs the temperature dependence of the ionic dc conductivity. We compare the obtained results with those for deep eutectic solvents that are formed by the same hydrogen-bond donor, ethylene glycol, but by two different salts, choline chloride and lithium triflate. The four materials reveal significantly different ionic and reorientational dynamics. Moreover, we find varying degrees of decoupling of rotational dipolar and translational ionic motions, which can partly be described by a fractional Debye–Stokes–Einstein relation. The typical glass-forming properties of these solvents strongly affect their room-temperature conductivity. [ABSTRACT FROM AUTHOR]

Using deuteron spin-lattice and spin-spin relaxometry, the reorientational dynamics of ethaline (choline chloride/ethylene glycol) and reline (choline chloride/urea) are studied in a component-selective, isotope-edited manner over a wide temperature range, thereby complementing previous work on glyceline (choline chloride/glycerol). Differences in the hydrogen bond propensities effectuate that in reline and glyceline, the choline ions move faster than the hydrogen bond donors, glycerol and urea; in ethaline, the ethylene glycol molecules are reorienting faster. For glyceline and reline, the increase in the corresponding time scale ratio indicates a pronounced strengthening of the glycerol and urea networks upon cooling, while in ethaline, the time scale ratio remains essentially constant. For the three deep eutectic solvents, a comparison of the present component-selective results with the dielectric time constants shows that the latter are primarily sensitive to the dynamics of the respective hydrogen bond donors. In a Walden-type plot, the reorientation rates, selectively determined for the hydrogen bond donors and acceptors, are compared with their conductivity and fluidity, revealing that the dynamics of the choline ions relate most directly to the charge transport. [ABSTRACT FROM AUTHOR]

In this study, multi-walled carbon nanotubes (MWCNTs) were synthesized using the arc discharge method, and gold (Au) , and Au@MWCNT nanoparticles (NPs) were obtained via a rapid and cost-effective chemical reduction method. The performance of these catalysts in ethylene glycol (EG) fuel cells was investigated. According to the Transmission Electron Microscope (TEM) results, the Au particle size was determined to be 3.89 nm, and the MWCNT diameter was found to be 8.21 nm. For EG oxidation, current densities of 33.28 mA/cm2 for Au NPs and 171.28 mA/cm2 for Au@MWCNT NPs were obtained. This result demonstrates that the MWCNT support increased the electrocatalytic activity by a factor of 5.14. Long-term stability tests showed that the MWCNT support exhibited more stable and consistent characteristics and improved CO tolerance. Electrochemical Impedance Spectroscopy (EIS) testing revealed that the MWCNT-supported structure significantly enhanced charge transfer. These findings contribute significantly to the literature by demonstrating the potential for cost-effective production of carbon supported Au NPs, and their application in fuel cells. • MWCNT production using arc-discharge method. • Preparation of Au and Au@MWCNT catalysts and their use in ethylene glycol oxidation studies. • Au@MWCNT exhibits superior electrocatalytic activity towards ethylene glycol oxidation. • Synthesis of more stable catalyst for ethylene glycol oxidation. • Anode catalyst showing high potential for fuel cell applications. [ABSTRACT FROM AUTHOR]

[Display omitted] • Porous PEDOT as the support of PdSn nanoalloy electrocatalyst. • Pd 4 Sn 6 /PEDOT is created and used for the oxidation of ethylene glycol and ethanol. • The interface electronic structure of Pd was modified by introducing Sn and PEDOT. • It shows outstanding electrocatalytic performance and poisoning-tolerance ability. Developing a novel catalyst with lower noble-metal loading and higher catalytic efficiency is significant for promoting the widespread application of direct alcohol fuel cells (DAFCs). In this work, poly(3,4-ethylenedioxythiophene) (PEDOT) supported the PdSn alloy (PdSn/PEDOT) were simply synthesized and their electrocatalytic performance toward the oxidation of ethylene glycol and ethanol (EGOR and EOR) were investigated in alkaline media, respectively. In comparison with other control catalysts, the optimized Pd 4 Sn 6 /PEDOT catalyst exhibits the highest mass activity (7125/4166 mA mg Pd −1) and specific activity (26/15 mA cm−2) towards EGOR/EOR. The mass activity of Pd 4 Sn 6 /PEDOT for EGOR and EOR are 11.9 and 10.9 times higher than commercial Pd/C, respectively. Moreover, chronoamperometry (CA) and successive cyclic voltammetry (CV) tests show that the CO resistance ability and durability of the Pd 4 Sn 6 /PEDOT catalyst were superior to Pd 4 Sn 6 , Pd/PEDOT and commercial Pd/C catalysts, which can be attributed to the d-band center of Pd can be effectively downshifted and the interface strain effect between electrons caused by the conjugated structure between PEDOT groups. This work provides an effective strategy for the development of highly efficient anode catalysts of DAFCs. [ABSTRACT FROM AUTHOR]

The alcohols methanol, ethylene glycol and diethylene glycol share many characteristics. The most important is that the compounds themselves are relatively nontoxic but are metabolized, initially by alcohol dehydrogenase, to various toxic intermediates. These compounds are readily available worldwide in commercial products as well as in homemade alcoholic beverages, both of which lead to most of the poisonings, from either unintentional or intentional ingestion. Although relatively infrequent, toxic alcohol poisonings do unfortunately occur in outbreaks and can result in severe morbidity and mortality. These poisonings have traditionally been treated with ethanol since it competes for the active site of alcohol dehydrogenase and decreases the formation of toxic metabolites. Although ethanol can be an effective antidote, there are substantial practical problems with its use. Therefore fomepizole, a potent competitive inhibitor of alcohol dehydrogenase, was developed for a hopefully better treatment for metabolically toxic alcohol poisonings. Fomepizole has few side effects and is easy to use in practice and it may obviate the need for haemodialysis in some, but not all, patients. Hence, fomepizole has largely replaced ethanol as the toxic alcohol antidote in many countries. Nevertheless, ethanol remains an important alternative because access to fomepizole can be limited, the cost may appear excessive or the physician may prefer ethanol due to experience. [ABSTRACT FROM AUTHOR]

Elemental sulfur has shown to be a promising alternative feedstock for development of novel polymeric materials with high sulfur content. However, the utilization of inverse vulcanized polymers is restricted by the limitation of functional comonomers suitable for an inverse vulcanization. Control over properties and structure of inverse vulcanized polymers still poses a challenge to current research due to the dynamic nature of sulfur‐sulfur bonds and high temperature of inverse vulcanization reactions. In here, we report for the first time the inverse vulcanization of norbornenyl pentafluorophenyl ester (NB‐PFPE), allowing for post‐modification of inverse vulcanized polymers via amidation of reactive PFP esters to yield high sulfur content polymers under mild conditions. Amidation of the precursor material with three functional primary amines (α‐amino‐ω‐methoxy polyethylene glycol, aminopropyl trimethoxy silane, allylamine) was investigated. The resulting materials were applicable as sulfur containing poly(ethylene glycol) nanoparticles in aqueous environment. Cross‐linked mercury adsorbents, sulfur surface coatings, and high‐sulfur content networks with predictable thermal properties were achievable using aminopropyl trimethoxy silane and allylamine for post‐polymerization modification, respectively. With the broad range of different amines available and applicable for post‐polymerization modification, the versatility of poly(sulfur‐random‐NB‐PFPE) as a platform precursor polymer for novel specialized sulfur containing materials was showcased. [ABSTRACT FROM AUTHOR]

Objective: The Hu sheep is a renowned breed known for its high reproductive rate. It is in estrus all year round, and its breeding population is gradually expanding. However, the current techniques for cryopreserving semen have limited effectiveness, which hinders the continuous development of this species. The purpose of this study is to explore the effects of different penetrating cryoprotectants (CPAs) and egg yolk (EY) concentrations on the cryopreservation of Hu ram semen to determine the most effective combination. Methods: In this study, the effects of glycerol (GLY), ethylene glycol (EG), dimethylacetamide, dimethyl sulfoxide, different proportions of GLY and EG, EY on sperm quality after thawing were investigated by detecting sperm total motility (TM), progressive motility (PM), straight-line velocity, curvilinear velocity, average path velocity, amplitude of lateral head displacement, wobble movement coefficient, average motion degree, functional integrity (plasma membrane integrity, acrosome integrity) and reactive oxygen species (ROS) level. Results: When GLY and EG were added together, compared to other concentration groups, 6% GLY significantly (p<0.05) increased TM, PM, plasma membrane integrity, and acrosome integrity of thawed sperm. Additionally, it significantly (p<0.05) decreased the ROS level of sperm. In this study, the TM, PM, and membrane integrity of the 6% EG were significantly (p<0.05) higher than those of the control, 1% GLY+5% EG and 6% GLY+6% EG groups. Compared to other concentration groups, 20% EY significantly (p<0.05) improved the TM, PM, and plasma membrane integrity of thawed sperm. However, the integrity of the acrosome increased with the higher concentration of EY. Conclusion: In conclusion, the post-thawed Hu ram semen diluted with a diluent containing 6% GLY and 20% EY exhibited higher quality compared to the other groups. [ABSTRACT FROM AUTHOR]

Sulforaphane‐loaded nanoparticles (NP‐SF) were prepared in this study to improve their biological effects. Based on propylene glycol alginate and zein as wall materials and anthocyanin and CaCl2 as crosslinking agents, the NPs were encapsulated by the crosslinking method and freeze‐dried. With the increasing contents of anthocyanin and Ca2+, the encapsulation efficiency and loading capacity of NP‐SF were both increased. In vitro simulated digestion experiments showed controlled release of SF from the NPs. The pharmacokinetics confirmed that NP‐SF exerted a slower release effect in rats, with improved SF bioavailability and protective effects on liver injury induced by N‐diethylnitrosamine in mice. NP‐SF reduced serum indicators of liver injury, increased the activities of antioxidant enzymes and GSH levels, and reduced malondialdehyde levels in the liver. In addition, SF activated the Keap1/Nrf2 signaling pathway and upregulated the expression of the Nrf2 downstream genes NQO1 and heme oxidase 1. High doses of NP‐SF, in particular, had a higher therapeutic effect. In conclusion, encapsulation enhanced the biological activity of SF and promoted physiological function. [ABSTRACT FROM AUTHOR]

• Experimental investigations on the solubility of Propylene and DME in PAG oil. • The form of NRTL and Heil interaction parameters was key to high model accuracy. • Two novel empirical correlations were proposed. • Single coefficient correlation: compact, explicit and robust to low amount of data. • DME most soluble refrigerant followed by Propylene and Propane. This work experimentally investigated the solubility of Propylene and Dimethyl Ether (DME) in polyalkylene glycol (PAG) oil. The solubility experimental data were used to fit different local composition models from the literature, the Wilson and Heil equations, and the Non-Random Two-Liquid (NRTL) model. Two new empirical correlations were proposed to decrease the deviation between experiments and the models. The first correlation used six fitting coefficients and resulted in an average deviation of 1.2 % for Propylene and 2.8 % for DME. The second empirical correlation was proposed with a single solubility coefficient (SSC) and a compact form, which allows solubility to be determined explicitly. The correlation resulted in average deviations from experimental data of 1.6 % for Propylene and 2.5 % for DME. Moreover, the SSC correlation showed performance robustness against the decrease of available data points. The correlation was used to compare the solubility of Propylene and DME with the solubility of Propane. At the same conditions, Propane showed the lowest solubility while DME resulted in the most soluble refrigerant. [ABSTRACT FROM AUTHOR]

The identification of complex pre-biotic molecules using millimetre and submillimetre telescopes allows us to understand how the basic building blocks of life are formed in the universe. In the interstellar medium, ethylene glycol (⁠|$({\rm CH}_2{\rm OH})_{2}$|⁠) is the simplest sugar alcohol molecule, and it is the reduced alcohol of the simplest sugar-like molecule, glycolaldehyde (⁠|${\rm CH}_{2}{\rm OHCHO}$|⁠). We present the detection of the rotational emission lines of |$aGg^{\prime }$| conformer of ethylene glycol (⁠|$({\rm CH}_2{\rm OH})_{2}$|⁠) towards the hot molecular core G358.93–0.03 MM1 using the Atacama Large Millimeter/Submillimeter Array. The estimated column density of |$aGg^{\prime }$| - |$({\rm CH}_2{\rm OH})_{2}$| towards the G358.93–0.03 MM1 is (4.5 |$\pm 0.1)\times 10^{16}$| cm |$^{-2}$| with an excitation temperature of 155 |$\pm$| 35 K. The abundance of |$aGg^{\prime }$| - |$({\rm CH}_2{\rm OH})_{2}$| with respect to |${\rm H}_{2}$| is (1.4 |$\pm 0.5)\times 10^{-8}$|⁠. Similarly, the abundances of |$aGg^{\prime }$| - |$({\rm CH}_2{\rm OH})_{2}$| with respect to |${\rm CH}_{2}{\rm OHCHO}$| and |${\rm CH}_{3}{\rm OH}$| are 3.1 |$\pm$| 0.5 and (6.1 |$\pm 0.3)\times 10^{-3}$|⁠. We compare the estimated abundance of |$aGg^{\prime }$| - |$({\rm CH}_2{\rm OH})_{2}$| with the existing three-phase warm-up chemical model abundance of |$({\rm CH}_2{\rm OH})_{2}$|⁠ , and we notice the observed abundance and modelled abundance are nearly similar. We discuss the possible formation pathways of |$aGg^{\prime }$| - |$({\rm CH}_2{\rm OH})_{2}$| towards the hot molecular cores, and we find that |$aGg^{\prime }$| - |$({\rm CH}_2{\rm OH})_{2}$| is probably created via the recombination of two |${\rm CH}_{2}{\rm OH}$| radicals on the grain surface of G358.93–0.03 MM1. [ABSTRACT FROM AUTHOR]

Polycarboxylate superplasticizers (PCEs) have been extensively used in the areas of construction and building; however, the application limitation of PCEs has emerged owing to their sensitivity to clay. In this work, three anticlay PCEs were synthesized by introducing acrylamide (AM), methacryloxyethyltrimethyl ammonium chloride (DMC), or 3-[2-(methacryloyloxy) ethyl] dimethylammonio-propane-1-sulfonate (DMAPS) into the polycarboxylate copolymer of ethylene glycol monovinyl polyethylene glycol ether (EPEG) and acrylic acid (AA), denoted as A-PCE, D-PCE, and S-PCE, respectively. The structures of these superplasticizers were characterized by gel permeation chromatography (GPC) and Fourier-transform infrared spectroscopy (FTIR). Compared with the common polycarboxylate superplasticizers (O-PCEs), the resultant anticlay PCEs showed better dispersion as far as the fluidity of cement paste and mortar were concerned. With the content of 0.5% per weight sodium bentonite in place of cement, these anticlay PCEs exhibited better clay resistance than O-PCE. In addition, the compressive strengths of mortar and concrete by the addition of A-PCE, D-PCE, or S-PCE were slightly higher than those of O-PCE. Total organic carbon (TOC) revealed that the sensitivity of A-PCE, D-PCE, and S-PCE to clay was lower than that of O-PCE. X-ray diffraction (XRD) proved that the layer spacing of clay increased after treatment with superplasticizer. In combination of adsorption determination with XRD analysis, a possible mechanism was proposed. Unlike the PEG side chains inserting into the clay layers for O-PCE, the cations in functional groups entered the clay layers through cation exchange for anticlay PCEs preferentially. [ABSTRACT FROM AUTHOR]

Mixtures of polyglycerol polyglycidyl ether (PGPE) and poly(ethylene glycol) diglycidyl ether (PEGDGE) with different molar ratios were cured with imine-containing phenolic hardeners prepared by the reactions of vanillin with ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, and a polyetheramine (JEFFAMINE® ED-600) to produce bio-based epoxy cured products. Fourier-transform infrared spectroscopy (FT-IR) of the cured products revealed that the curing reaction of the epoxy and phenolic hydroxy groups was almost complete. The cross-linking density, glass transition temperature, and mechanical strength of the cured products decreased with decreasing the PGPE/PEGDGE ratio and increasing the oligoalkyleneoxy chain length of the phenolic hardeners. All cured products were healed three times at 100 °C under 2 MPa for 2 h. The healing efficiency, in terms of tensile strength, increased with decreasing PGPE/PEGDGE ratio and increasing oligoalkyleneoxy chain length. The polyetheramine-based cured product with the lowest PGPE/PEGDGE ratio exhibited the highest healing efficiency (94–97%), which only slightly decreased following repeated healing treatments. [ABSTRACT FROM AUTHOR]

A novel methodology to obtain 3D printable BiVO 4 precursor scaffolds (3DM-BiVO 4) via robocasting, showing excellent periodicity, shape retention, and mechanical stability, is disclosed for the first time. The ceramic pastes (solids at 70 wt.-%) comprised of BiVO 4 precursor, SiO 2 NPs, and a solution of deionized water: ethylene glycol (volume ratio 1:2, DI water: EG) exhibited enhanced rheology for the 3D printing of self-supported structures (3DM-BiVO 4). The thermal treatment induced a monoclinic scheelite phase, and the ethylene glycol contributed to achieving a unique square flake-like particle morphology. 3DM-BiVO 4 scaffolds were used as reusable monolithic photocatalysts, showing 72% acetaminophen mineralization at 240 min and pH = 9. This innovative approach opens avenues for designing 3D printable ceramic pastes, offering potential applications in tailoring-made monolithic photocatalyst fabrication by using SiO 2 NPs as an inorganic binder. [Display omitted] • 3D printable BiVO4 pastes by DIW using SiO2NP as a ceramic binder and DI water:ethylene glycol as solvents. • 3DM-BiVO4 scaffolds with periodicity, excellent shape retention, mechanical stability, and self-supporting were achieved. • Ethylene glycol promotes morphologies of square flake-like particles comprised of small peanut-like BiVO4 particles. • 3DM-BiVO4 exhibited good photocatalytic activity for acetaminophen mineralization. • 3DM-BiVO4 photocatalyst can be easily recovered and reused several times. [ABSTRACT FROM AUTHOR]

A novel magnetic molecular-imprinted polymer (MMIP) was used to selectively extract folic acid directly from real samples. Folic acid was used as template molecule, Fe3O4/SiO2-3-triethoxysilyl-propyl-acrylamide as functional monomer, azobisisobutyronitrile as initiation, ethylene glycol dimethacrylate as crosslinker agent, and acrylamide as the secondary monomer in a mixed ethanol-water solvent. The effect of different parameters on the extraction efficiency was studied, and the optimum conditions were established as follows: the concentrations of crosslinking and template were fixed at 0.05 and 0.06 g, absorption percentage was 96.5, pH was adjusted to 8, and extraction time was 8 h with a temperature of 25 °C. By examining the effect of pH, we tried to investigate the effect of the amide groups that present in MMIP and its intermolecular hydrogen interaction with folic acid. After optimising the effective parameters in polymer synthesis and adsorption rate, a magnetic imprinting dispersive solid-phase extraction method combined with fluorescence spectrophotometry at λem = 367 nm (MMIP-DSPE-FL) was constructed for sensitive determination of folic acid in tomato samples. The limit of quantification (LOQ) and limit of detection (LOD) values were 30.00 ± 0.01 μg L−1 and 10.00 ± 0.03 μg L−1, respectively, after the MMIP-DSPE preconcentration. Three tomato samples were analysed to give recoveries in the range of 80.2–81.6%, with relative standard deviation values below 0.6% (n = 3). The prepared MMIP-DSPE showed high selectivity toward folic acid, which could be used six times without changing adsorption capacity. The adsorption isotherm of the folic acid-imprinted polymer pursued the Langmuir model (RL = 0.029), and the kinetics model followed pseudo-first-order (R 2 = 0.9974). [ABSTRACT FROM AUTHOR]

Polyhydroxyurethane (PHU) with free secondary amine groups was synthesized by reacting poly(ethylene glycol)bis-cyclic carbonate with triethylenetetramine. PHU was mixed with varying amounts of gelatin (GE) and crosslinked by reacting them with either poly(ethylene glycol)glycidyl ether (PEGDE) or 1,4-butanediol diglycidyl ether (BDDE). The tensile strength and fluid handling capacity of the monolayer films obtained from different formulations of PHU, GE, PEGDE, or BDDE were evaluated. To further improve the tensile strength of dressings via increasing the crosslinking of the networks, varying amounts of epoxidized graphene oxide (EGO) were utilized as an auxiliary crosslinking agent. The improved tensile strength of up to 140% was recorded for these samples. Additionally, the membranes containing EGO were able to absorb near-infrared light. The resulting hyperthermia effect (increasing temperature up to about 63 within 15 min) could efficiently kill bacteria (100% killing). The free secondary amine groups on the PHU backbone also reduced the silver ions loaded into the dressings, and resulting silver nanoparticles (Ag NPs) showed acceptable antibacterial activity against E.coli (53% killing) and S.aureus (78% killing). It was also found that the antibacterial activity of AgNPs-containing samples was further improved after incorporating EGO due to the knife-killing effect of EGO nanoplates. [ABSTRACT FROM AUTHOR]

Novel elastomers are made by reaction of hydroxyl‐terminated polyacrylic ester (HyTemp) with polyethylene glycol (PEG, number of ethylene glycol units 1, 3, 6, 9) based cross‐linkers. The influence of the cross‐linker length, the HyTemp/cross‐linker (w/w) ratio and the cross‐linking accelerator trifluoromethanesulfonate scandium salt (ScTFMS) on the structure and the properties of the materials are studied. The cross‐linker length has not influence on the glass transition (Tg) of the products because of the presence of the flexible PEG units that cancels out the cross‐linking effect associated to a shift to higher Tg. A two‐domain structure is seen by the presence of a dual Tg in samples cured with ScTFMS. Mathematical analysis of the modulated differential scanning calorimetry curves offers for the first time the possibility to identify/confirm structural differences in complex three‐dimensional polymeric structures. Scanning electron microscopy and swelling experiments in ethyl acetate respectively reveal an increase in the pore size (1.13 to 5.48 nm) and in the absorption ability of the elastomers cured with different types and quantities of PEG cross‐linker. The new elastomeric materials are exhibiting a rubbery state over a wide temperature range and absorptivity for the potential recovery of pollutants in soil and/or water. [ABSTRACT FROM AUTHOR]

In this study, polyurethane (PU) hydrogels were synthesized via mercapto curing reaction to elucidate the effect of molecular interactions between isocyanate and soft segments on the properties of hydrogels. Further, the mesh size, mechanical properties, hydrophilicity, and biological properties of the PU hydrogels were determined. In the isocyanate series, the structural regularity and rigidity of 4,4′‐dicyclohexylmethane diisocyanate (HMDI) favored the formation of hydrogel materials with small mesh size, high modulus, and low water absorption. In contrast, l‐lysine diisocyanate (LDI) favored the materials with large mesh size, low modulus, and good hydrophilicity. In the soft‐segment series, the strong hydrogen bonds of polycarbonate diol (PCDL) favored the formation of materials with small mesh size, dense cross‐link points, and high modulus, whereas weak hydrogen bonds of polytetrahydrofuran ether glycol (PTMG) favored the hydrogel materials with small mesh size, few crosslink points, and low modulus. PU hydrogels exhibit excellent cytocompatibility, anti‐cell adhesion, and anti‐inflammatory properties. Therefore, this study offers valuable insights into understanding the chain structure and macroscopic properties, thus contributing to preparing PU hydrogels with varying performances, as desired. [ABSTRACT FROM AUTHOR]

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Inadequate ionic conductivity and freezing of the electrolyte are considered one of the main problems in low-temperature electrochemical energy storage. Mixing two or more solvents can reduce the overall freezing point of the solution and also increase the ionic conductivity at low temperatures. Therefore, using the co-solvent method to prepare electrolytes is crucial for preventing electrolyte freezing and improving ion conductivity. In this paper, ethylene glycol (EG) was used as a low-temperature co-solvent and an electrolyte with a freezing point lower than − 80 ℃ was obtained by the introduction of a volume fraction of 20% ethylene glycol in 4.5 mol L−1 LiCl aqueous solution. The resulting electrolyte exhibited high ionic conductivity (1.143 mS·cm−1) at − 60 ℃ and low viscosity (1.391 mPa·s) at 20 ℃. The molecular dynamics (MD) simulations and FITR results indicate that hydrogen bonds can be effectively formed between ethylene glycol and water molecules, which facilitate the electrolyte to operate at low temperatures. Additionally, the supercapacitor was able to operate better even at − 60 °C by introducing ethylene glycol into the electrolyte. [ABSTRACT FROM AUTHOR]

BACKGROUND: The production of value‐added chemicals from pyrolysis oil or its fractions is of great significance for the valorization of biomass. Diols, including ethylene glycol (EG) and 1,2‐propylene glycol (1,2‐PG), are important bulk chemicals with widespread industrial applications. Here we investigated the production of diols from pyrolysis oil water‐soluble fraction (WS) using a hybrid catalyst (Ni + H2WO4). RESULTS: Firstly, levoglucosan, glycolaldehyde and acetol, three main components in WS, were respectively selected as the single model compound, and their respective conversions into diols were investigated at different temperatures for different reaction times. The result showed the optimum reaction temperature and time were 180 °C and 2 h respectively, under which a EG yield of 53.8% and 1,2‐PG yield of 5.2% were obtained from levoglucosan conversion, a EG yield of 98.6% was obtained from glycolaldehyde conversion, and a 1,2‐PG yield of 98.5% was obtained from acetol conversion. The reaction pathway of levoglucosan conversion was analyzed. Secondly, the model mixture of levoglucosan, glycolaldehyde and acetol was used to simulate the real WS, and their conversion was investigated at different ratios of H2WO4 to Ni. The result showed the optimum catalyst composition was 0.15 g H2WO4 and 0.3 g Ni, under which a EG yield of 76.4% and 1,2‐PG yield of 38.4% were obtained. Thirdly, the real original WS was converted under the optimum reaction conditions and the result only gave a EG yield of 19.1% and 1,2‐PG yield of 25.8% (based on the carbon moles of main substrates), which were much less than the two yields of model mixture. That was related to the presences of other types of chemicals in original WS. After the original WS being adsorbed by activated carbon, the yields of EG and 1,2‐PG could be increased to 39.2% and 37.9%, respectively. CONCLUSION: The presences of certain other types of chemicals (such as acids, furans, phenolics and cyclopentanones) in original WS inhibited the production of diols. The activated carbon adsorption could efficiently remove most of furans, phenolics and cyclopentanones in original WS and increased significantly the diols yields. © 2024 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

Karl Fischer titration (KF) measures the water content in organic and inorganic compounds. Water reacts with a titrant solution containing iodine and a sulphurous monoalkyl ester to produce a monoalkyl sulphate ester and HI. In volumetric titrators, a burette injects the titrant directly into a cell while coulometric titrators generate titrant in situ. Regardless of the volume of the sample, volumetric titration is limited to 100 mg, while coulometric titration is best suited for >2mg. KF is fast (<2min), considered accurate (±5%), and precise (<1%). However, factors such as humidity, non‐standard analytes (hexane, isopropanol, ethylene glycol), tritrant composition, and temperature compromise its repeatability: the % sample standard deviation, s (n=4), varied from 2% to 60% (s¯=22%,nconditions=19). This high variability is, in part, due to the experimental design that included samples and conditions ill‐suited for the technique. However, even for the tests for which KF is suitable, s¯>10%. Certain compounds react with the titrant, which increases the variability. The main sources of error affecting the analysis are ambient moisture, pH, solvent, sample handling, and titration speed. As of 2023, the Web of Science has indexed 1332 articles with Karl Fischer as a key word (Topic), but more than 3600 mentioning the technique (All fields). A bibliometric analysis classifies these contributions into five clusters: spectroscopy, stability, temperature, solubility, and mixtures. [ABSTRACT FROM AUTHOR]

Hydrogels are of interest for a wide range of applications. The ability to control when the hydrogel degrades can provide beneficial properties such as controlled degradation in the environment or the stimulated release of drugs or cells. Self‐immolative polymers are a class of degradable polymers that undergo complete end‐to‐end depolymerization upon the application of a stimulus. They have been explored for hydrogel development, but the ability to prepare and selectively degrade self‐immolative hydrogels under neutral aqueous conditions has so far been limited. We describe here the preparation of water‐soluble polyglyoxylamides with cross‐linkable pendent azides and their cross‐linking to form hydrogels with 4‐arm poly(ethylene glycol)s having unstrained and strained alkynes using copper‐assisted and strain‐promoted azide‐alkyne click chemistry respectively. The influence of pendent azide density and solution polymer content on the resulting hydrogels was evaluated. A polyglyoxylamide with a 70 : 30 ratio of pendent hydroxyl:azide successfully provided hydrogels with compressive moduli ranging from 1.3–6.3 kPa under copper‐free conditions at 10–20 % (w/w) of polymer in phosphate‐buffered saline. Selective depolymerization and degradation of the hydrogels upon irradiation with light was demonstrated, resulting in reductions in the compressive moduli and the release of depolymerization products that were detected by NMR spectroscopy. [ABSTRACT FROM AUTHOR]

In this study, a series of submicron‐sized functional polymer particles poly(Sty‐co‐MAA) with variable methacrylic acid (MAA) content were prepared by soap‐free emulsion polymerization of styrene (Sty), methacrylic acid (MAA), and ethylene glycol dimethacrylate (EGDMA). The number‐average diameters of polymer particles (Dn) were in the range of 0.11 to 0.19 μm. A decrease in particle size was observed with increasing the molar ratio of MAA comonomer in the recipe. ZnO/poly(Sty‐co‐MAA) hybrid polymer particles were prepared by seeded emulsion copolymerization in presence of zinc oxide nanoparticles (ZnO NPs) as seed particles synthesized using Citrus lemon aqueous leaf extract. Scanning electron microscopy (SEM), transmission electron microsphere (TEM), X‐Ray Diffraction (XRD), and Fourier transformed infra‐red (FT‐IR) analysis were performed to characterize polymer particles. The crystalline size of ZnO NPs and ZnO/poly(Sty‐co‐MAA) hybrid polymer particles calculated from XRD analysis were 20.75 and 29.85 nm, respectively. These hybrid polymer particles were applied as photocatalyst in the photodegradation of methylene blue (MB) dye under UV irradiation, which showed high catalytic activity with degradation efficiency of 85.70 % at room temperature compared to bare ZnO NPs. [ABSTRACT FROM AUTHOR]

AbstractNanosurface-imprinted polymer nanoprobes (Fe3O4@MIP) were prepared by microwave synthesis using Fe3O4 as a nanosubstrate, aspirin as a template, α-methacrylic acid (MAA) as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, and 2,2'-azobisisobutyronitrile (AIBN) as an initiator. Characterization of Fe3O4@MIP revealed that the spectral probe exhibited strong resonance Rayleigh scattering (RRS) for aspirin. With the increase in aspirin concentration, the RRS energy transfer (RRS-ET) was enhanced, and the signal at 370 nm decreased, providing a linear range from 0.25 to 12.5 μmol/L and a detection limit (DL) of 0.08 μmol/L. The developed protocol was used for the determination of aspirin in drugs with recoveries from 93.2 to 102.6. [ABSTRACT FROM AUTHOR]

Deep eutectic solvents (DESs) are gaining rapid prominence in numerous biocatalysis processes due to their green characteristics, biodegradability, low cost, and simple preparation compared to harsh organic solvents and toxic ionic liquids. However, natural enzymes tend to show activity reduction, even inactivation in the presence of many DESs. Here, we present the first rational design approach to achieve enzymes resistant to both DESs and high temperatures. Using the interaction pattern between DESs and BSLA (Bacillus subtilis lipase A, our model enzyme) derived from all-atom molecular dynamics (MD) simulations, we formulated a solvation-guided engineering strategy. This was established after assessing 33 structural, solvation, and energy observables. We rationally designed and experimentally tested 36 single substitutions, of which 28 (a 77.78% success rate) exhibited improvements in at least two DES cosolvents: choline chloride (ChCl) : acetamide, tetrabutylphosphonium bromide (TBPB) : ethylene glycol (EG), and ChCl : EG. Additionally, through stepwise recombination, we identified two robust BSLA variants, D64H/R107L/E171Y and D64H/R142L, showing stability improvements of up to 4.4-fold and 3.2-fold in three DESs and at 50 °C, respectively. Further MD studies demonstrated that (i) the restricted overall structure but fine-tuned local flexibility and (ii) increased water but decreased DES molecules at substituted sites are two main factors contributing to the enhanced multiple DES resistance. Overall, solvation-guided engineering offers an efficient and rational approach for designing lipases tolerant to DES cosolvents and elevated temperatures, with a considerable potential for adaptation to other enzymes. [ABSTRACT FROM AUTHOR]

Green solvent processing of perovskite light‐emitting diodes (PeLEDs) is a necessity for their future commercialization. However, the almost insoluble nature of perovskites in most green solvents strongly impedes the progress of green solvent‐processed PeLEDs. Here, a novel green solvent triethylene glycol (TEG) is used as the processing solvent for perovskites. TEG has better solubility for perovskite precursors than most reported green solvents. Moreover, it is found that the low vapor pressure of TEG solvent and stable precursor solution render a much wider time window for the so‐called antisolvent treatment than that of perovskite precursor solution in commonly dimethyl sulfoxide. High‐quality perovskite film can be readily synthesized with the antisolvent treatment at a time window of 70–100 s, and the resultant green PeLEDs demonstrate nearly identical light‐emitting efficiencies. Together with further interface modification, the optimized green PeLEDs processed with TEG exhibit an external quantum efficiency of 20.4% and a maximal luminance over 38000 cd m−2. It is the first successful attempt to fabricate high‐efficiency PeLEDs utilizing green solvent and is enlightening for the development of high‐performance PeLEDs prepared with eco‐friendly solvents. [ABSTRACT FROM AUTHOR]

The self‐assembly and dynamics of amphiphilic diblock copolymers composed of densely grafted poly(oligo ethylene glycol methacrylate) (POEGMA) and poly(lauryl methacrylate) (PLMA) by means of calorimetry, small‐angle X‐ray scattering (SAXS), and dielectric spectroscopy are investigated. It is reported that the inherent immiscibility between the parent homopolymers, combined with the increased molar mass, results in strong segregation, maintained up to elevated temperatures (i.e., T = 423 K). SAXS reveals that well‐separated POEGMA and PLMA domains self‐assemble into spheres with bicontinuous cubic packing and in lamellar nanostructure in copolymers with respective compositions of 16 and 52 wt.% PLMA. This strong segregation enables the weak crystallization/melting of the short ethylene glycol chains. Additionally, molecular dynamics are investigated through isothermal dielectric and calorimetry measurements. The segmental dynamics (i.e., Tg‐related) of POEGMA and PLMA closely resemble that found in respective homopolymers, implying heterogeneous dynamics. In the glassy state, the local motions of the POEGMA side chains predominantly govern the observed secondary processes in the copolymers. The results on the heterogeneous dynamics in the current amphiphilic diblock copolymers with the densely grafted architecture are compared and contrasted with copolymers having a bottle–brush architecture lacking the amphiphilic nature. [ABSTRACT FROM AUTHOR]

Photothermal immunotherapy represents an effective approach for eliminating both local and metastatic tumors through priming of the tumor‐specific immune response. Cytosolic delivery of double‐stranded DNA via pH‐responsive vehicles is recently verified to activate the cyclic guanosine monophosphate–adenosine monophosphate (GMP‐AMP) synthase‐stimulator of interferon genes (cGAS‐STING) pathway, which is robust in activating both innate and adaptive antitumor immunity. Herein, multifunctional phototheranostics with excellent photothermal conversion capacity, second near‐infrared (NIR‐II) fluorescence, and cGAS‐STING activating capacity are prepared by encapsulating fish testis DNA and conjugated boron dipyrromethene tetramers with poly(lactic‐co‐glycolic acid) and poly(ethylene glycol)‐b‐poly(lactic‐co‐glycolic acid) via a CaCO3‐assisted double emulsion method. The obtained phototheranostics (coined DB4CaP NPs) after intravenous administration gradually accumulate in tumor regions, as shown by NIR‐II fluorescence imaging. Together with local 915 nm laser exposure, primary tumors in mice treated with DB4CaP NPs could be effectively eradicated, with a complete response of 83.3%. Furthermore, such DB4CaP NPs could synergize with anti‐programmed cell death protein 1 immunotherapy to suppress the growth of distant unirradiated and rechallenged tumors through activating the antitumor immune response. This study highlights a promising strategy for eradicating tumors, particularly invisible and unresectable micronodules, through NIR‐II fluorescence imaging‐guided photothermal immunotherapy. [ABSTRACT FROM AUTHOR]

Progress is made in the advancement of efficient and durable electrocatalysts for the ethylene glycol oxidation reaction (EGOR), which is a critical breakthrough in the conversion of waste plastic into high‐value‐added chemicals. Here, an organic ligand‐modified PdNi bimetallenes (PdNi O‐BMs) catalyst is designed and constructed through the one‐pot method. Benefiting from the frizzy and porous surface structure and inorganic–organic hybrid interface modification, PdNi O‐BMs undergo electrocatalytic reforming of ethylene glycol (EG) derived from polyethylene terephthalate (PET) to form formic acid. The unique structural advantages result in high EGOR performance. Meanwhile, the influence of Ni and organic ligand on the catalyst performance is confirmed through density functional theory calculations. This study reveals an advanced strategy for the synthesis of inorganic–organic hybrid bimetallenes, providing a green and sustainable new approach for PET value‐added transformation. [ABSTRACT FROM AUTHOR]

Polymer networks with controlled ratios of neutral and ionic dynamic crosslink points were prepared from ethylene glycol, boric acid, and lithium hydroxide. Both neutral and ionic sites led to the emergence of distinct damping modes separate from the glass transition. This work highlights the potential of polymer networks for multimodal damping spectra through dynamic bond selection. [ABSTRACT FROM AUTHOR]

To synthesize an effective and versatile nano-platform serving as a promising carrier for controlled drug delivery, visible-light-induced diselenide-crosslinked polyurethane micelles were designed and prepared for ROS-triggered on-demand doxorubicin (DOX) release. A rationally designed amphiphilic block copolymer, poly(ethylene glycol)-b-poly(diselenolane diol-co-isophorone diisocyanate)-b-poly(ethylene glycol) (PEG-b-PUSe-b-PEG), which incorporates dangling diselenolane groups within the hydrophobic PU segments, was initially synthesized through the polycondensation reaction. In aqueous media, this type of amphiphilic block copolymer can self-assemble into micellar aggregates and encapsulate DOX within the micellar core, forming DOX-loaded micelles that are subsequently in situ core-crosslinked by diselenides via a visible-light-triggered metathesis reaction of Se-Se bonds. Compared with the non-crosslinked micelles (NCLMs), the as-prepared diselenide-crosslinked micelles (CLMs) exhibited a smaller particle size and improved colloidal stability. In vitro release studies have demonstrated suppressed drug release behavior for CLMs in physiological conditions, as compared to the NCLMs, whereas a burst release of DOX occurred upon exposure to an oxidation environment. Moreover, MTT assay results have revealed that the crosslinked polyurethane micelles displayed no significant cytotoxicity towards HeLa cells. Cellular uptake analyses have suggested the effective internalization of DOX-loaded crosslinked micelles and DOX release within cancer cells. These findings suggest that this kind of ROS-triggered reversibly crosslinked polyurethane micelles hold significant potential as a ROS-responsive drug delivery system. [ABSTRACT FROM AUTHOR]

The production of ethylene glycol (EG) from cellulose has garnered significant attention in recent years as an attractive alternative to fossil fuels due to the potential of cellulose as a renewable and sustainable feedstock. In this work, to the best of our knowledge, a series of low-cost Ni-W bimetallic catalysts supported on glucose/carbon nanotube hybrid carbons were synthesised for the first time and employed to transform cellulose into EG. Two different strategies were combined for the preparation of the carbons: the activation and addition of carbon nanotubes (CNTs) to obtain a hybrid material (AG-CNT). The catalytic conversion process proceeded through cellulose hydrolysis to glucose, followed by glucose retro-aldol condensation to glycolaldehyde and its subsequent hydrogenation to EG. Through the optimisation of the catalyst's properties, particularly the metals' content, a good synergistic effect of C-C bond cleavage and hydrogenation capabilities was assured, resulting in the highly selective production of EG. The balance between Ni and W active sites was confirmed to be a crucial parameter. Thus, total cellulose conversion (100%) was achieved with EG yields of 60–62%, which are amongst the best yields ever reported for the catalytic conversion of cellulose into EG via carbon-supported catalysts. [ABSTRACT FROM AUTHOR]

Bone tissue exhibits self-healing properties; however, not all defects can be repaired without surgical intervention. Bone tissue engineering offers artificial scaffolds, which can act as a temporary matrix for bone regeneration. The aim of this study was to manufacture scaffolds made of poly(lactic acid), poly(ε-caprolactone), poly(propylene fumarate), and poly(ethylene glycol) modified with bioglass, beta tricalcium phosphate (TCP), and/or wollastonite (W) particles. The scaffolds were fabricated using a gel-casting method and observed with optical and scanning electron microscopes. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR), differential scanning calorimetry (DSC), thermogravimetry (TG), wettability, and degradation tests were conducted. The highest content of TCP without W in the composition caused the highest hydrophilicity (water contact angle of 61.9 ± 6.3°), the fastest degradation rate (7% mass loss within 28 days), moderate ability to precipitate CaP after incubation in PBS, and no cytotoxicity for L929 cells. The highest content of W without TCP caused the highest hydrophobicity (water contact angle of 83.4 ± 1.7°), the lowest thermal stability, slower degradation (3% mass loss within 28 days), and did not evoke CaP precipitation. Moreover, some signs of cytotoxicity on day 1 were observed. The samples with both TCP and W showed moderate properties and the best cytocompatibility on day 4. Interestingly, they were covered with typical cauliflower-like hydroxyapatite deposits after incubation in phosphate-buffered saline (PBS), which might be a sign of their excellent bioactivity. [ABSTRACT FROM AUTHOR]

Simple Summary: In the last years, many domesticated and wild animal species, as well as local and transboundary breeds, have been threatened with genetic depletion and extinction. The application of conservation strategies to sheep breeds is necessary to safeguard the productive characteristics but also the historical and cultural value that they exert on their territory and inhabitants. Despite many advances that have been made in gamete cryopreservation, in vitro embryo production (IVEP) and juvenile in vitro production (JIVET), the efficiency of these technologies is still low, and the application is restricted in the ovine species. In the present study, a high concentration-rapid exposure (HC-RE) and a low concentration-slow exposure (LC-SE) vitrification protocol, using dimethyl sulfoxide (DMSO) and ethylene glycol (EG) as permeating cryoprotectants (CPAs), were applied to pre-pubertal lamb immature cumulus–oocyte complexes (COCs) and evaluated on nuclear and cytoplasmic parameters after in vitro maturation (IVM). Slightly more encouraging results were observed with the LC-SE vitrification protocol, leading to the hypothesis that low CPA concentrations in association with prolonged exposure times could be more promising to pursue in order to improve pre-pubertal lamb immature COC vitrification. Oocyte vitrification allows for the storing of endangered breed female gametes. Cryoprotectant (CPA) concentration and exposure time should ensure cell protection with minimal toxicity. In the present study, a high concentration-rapid exposure (HC-RE) and a low concentration-slow exposure (LC-SE) vitrification protocol, using dimethyl sulfoxide (DMSO) and ethylene glycol (EG) as permeating CPAs, were evaluated on meiotic competence and bioenergetic-oxidative status of pre-pubertal lamb immature COCs after in vitro maturation (IVM). For each protocol, COCs vitrified through a traditional protocol and fresh ones were used as controls. Both protocols allowed COC morphology preservation after vitrification-warming (V-W) and cumulus expansion after IVM. The maturation rate (7% and 14%) was comparable to the vitrified control (13% and 21%) but not satisfactory compared to fresh ones (58% and 64%; p < 0.001). The rate of mature oocytes displaying a perinuclear/subcortical (P/S) mitochondrial distribution pattern, an index of cytoplasmic maturity, was comparable between vitrified and fresh oocytes. The LC-SE vitrification protocol did not affect quantitative bioenergetic-oxidative parameters compared to both controls whereas HC-RE protocol significantly reduced intracellular reactive oxygen species (ROS) levels, indicating cell viability loss. In conclusion, to improve pre-pubertal lamb immature COC vitrification, the combination of low CPA concentrations with prolonged exposure time could be more promising to investigate further. [ABSTRACT FROM AUTHOR]

Molecularly imprinted polymers (MIPs) are a growing highlight in polymer chemistry. They are chemically and thermally stable, may be used in a variety of environments, and fulfill a wide range of applications. Computer-aided studies of MIPs often involve the use of computational techniques to design, analyze, and optimize the production of MIPs. Limited information is available on the computational study of interactions between the epinephrine (EPI) MIP and its target molecule. A rational design for EPI-MIP preparation was performed in this study. First, density functional theory (DFT) and molecular dynamic (MD) simulation were used for the screening of functional monomers suitable for the design of MIPs of EPI in the presence of a crosslinker and a solvent environment. Among the tested functional monomers, acrylic acid (AA) was the most appropriate monomer for EPI-MIP formulation. The trends observed for five out of six DFT functionals assessed confirmed AA as the suitable monomer. The theoretical optimal molar ratio was 1:4 EPI:AA in the presence of ethylene glycol dimethacrylate (EGDMA) and acetonitrile. The effect of temperature was analyzed at this ratio of EPI:AA on mean square displacement, X-ray diffraction, density distribution, specific volume, radius of gyration, and equilibrium energies. The stability observed for all these parameters is much better, ranging from 338 to 353 K. This temperature may determine the processing and operating temperature range of EPI-MIP development using AA as a functional monomer. For cost-effectiveness and to reduce time used to prepare MIPs in the laboratory, these results could serve as a useful template for designing and developing EPI-MIPs. [ABSTRACT FROM AUTHOR]

Visualizing the network of a solvent‐swollen polymer gel remains problematic. To address this challenge, open transmission electron microscopy (TEM) was applied to thin gel films permeated by a nonvolatile ionic liquid. The targeted physical gels were prepared by cooling concentrated solutions of poly(ethylene glycol) in 1‐ethyl‐3‐methyl imidazolium ethyl sulfate [EMIM][EtSO4]. During the cooling, gelation occurred by a frustrated crystallization of the dissolved polymer, leading to a percolated, solvent‐permeated semicrystalline network in which nanoscale polymer crystals acted as crosslinks. Crystalline features ranging from ~5 to ~200 nm were observed, with the visible network strands dominantly consisting of long curvilinear crystallites of ~15–20 nm diameter. Nascent spherulites irregularly decorated the network, creating a complex structural hierarchy that complicated analyses. Lacking diffraction contrast, TEM did not visualize the many disordered, fully solvated PEG chains present in the voids between crystals. Recognizing that a network's three dimensionality is ambiguous when assessed through two‐dimensional microscopy projections, a small gel region was studied by TEM tomography, revealing a nearly isotropic three‐dimensional arrangement of the curvilinear crystallites, which displayed remarkably uniform cylindrical cross sections. [ABSTRACT FROM AUTHOR]

Controlling the extensional rheological properties of solutions is of great interest for a number of applications, such as printing and coatings, as polymeric additives can modify a fluid's droplet size, formation, and breakup. We have measured the extensional flows of polyacrylamide graft poly(ethylene glycol) amine (PAM‐g‐PEGa) solutions as a function of grafting density. PAM‐g‐PEGa is synthesized with grafting densities of 2.5%, 5.5%, 8%, and 30% and extensional flow was analyzed with drop‐on‐substrate rheology. Flow time scales and profiles are then compared to understand the effects of backbone extension from the addition of side chains. At low grafting densities, the viscous friction from the added side chains is comparable to, and in some cases, counteracts the losses in extensibility to the graft polymer's backbone, leading to increases in the relaxation time of the polymer. At higher grafting densities, the extension of the backbone reduces the relaxation time. By characterizing the effects of the graft density architecture on extensional flows, we are able to fine‐tune and control the breakup dynamics of elastic solutions. [ABSTRACT FROM AUTHOR]

The structural rigidity of thiourea (TU) motifs has made them useful in supramolecular (bio)materials. However, the role of the TU motif in a single system endowing dual noncovalent interactions, i.e., Hydrogen‐bonding (H‐bonding) association and metal‐coordination interaction, to afford nanomedicine is still unexplored. Herein a smart supramolecular polymeric nanomedicine constructed via TU motifs privileged dual noncovalent interactions, toward synergistic chemo/chemodynamic (CT/CDT) cancer therapy is reported. The study first synthesized a six‐arm star‐shaped amphiphilic polymer vehicle containing pendant TU motifs, poly(acylthiourea‐co‐oligo(ethylene glycol) ethyl acrylate)6 (P(TU‐co‐OEGEA)6), followed by addressing both H‐bonding association and metal‐coordination to fabricate supramolecular nanomedicine (e.g., Dox/Cu@P(TU‐co‐OEGEA)6). Structural privilege and functional diversity of TU motifs constitute an outstanding scaffold, not only offering an H‐bonding site to associate doxorubicin (Dox) but also acting as a ligand to coordinate copper (Cu). Thereby, one TU motif can enable dual noncovalent binding modes, triggering multiple curative outcomes. TU/Dox and TU/Cu noncovalent interactions can induce intermolecular configuration, yielding prompted cargo loading and in vivo stability. Moreover, benefiting from pH‐responsive Dox release and Fenton‐like copper redox chemistry, accompanied by Dox‐induced intratumoral H2O2 elevation and prompted •OH generation, synergistic CT/CDT with extraordinary anti‐tumor efficacy is indeed accomplished. This work provides a new paradigm using TU motifs regulated dual supramolecular forces to meet therapeutic goals. [ABSTRACT FROM AUTHOR]

Owing to the intrinsically high safety, low cost, natural abundance, and high energy density of Zn metal, aqueous Zn ion batteries (AZIBs) have become a promising candidate for large‐scale energy conversion and storage. However, the practical application of AZIBs is hampered by the severe Zn dendrites growth and the poor low‐temperature performance due to the elevated freezing point of aqueous electrolyte. Herein, the study proposes a new kind of room‐temperature liquid Zn salt, which is called Zn coordinated ionic liquid (i.e., (EMIM)5Zn(OTF)7), for all‐temperature AZIBs. The aqueous electrolyte containing 0.261 mol kg−1 (EMIM)5Zn(OTF)7 in Ethylene Glycol (EG) / H2O (6:4) exhibits ultralow freezing point below −100 °C. The liquid Zn salt and EG molecules not only modulate the solvation structure of Zn2+ ion, reducing the coordinated H2O in the first solvation sheath, but also suppresses the parasitic side reaction. As a proof of concept, Zn || Zn symmetric cells and Zn || PANI full cells with the designed electrolyte achieve improved cycling stability and can operate under wide temperature (from −40 to 60 °C). Even with high Zn utilization ratio of 40%, long cycle life over 70 times with capacity retention of 80% is achieved. [ABSTRACT FROM AUTHOR]

Curcuminoid boron difluoride dyes have garnered significant attention in the realm of bioimaging, primarily owing to their excellent photophysicochemical properties. However, the strong hydrophobicity limits their optimal near-infrared (NIR) fluorescence emission, and the synthesis process is complicated. In this study, Curc-TPA, a curcuminoid boron difluoride derivative with a high fluorescence quantum yield, was facilely synthesized and surprisingly exhibited aggregation-induced NIR emission in a dimethyl sulfoxide/water mixture. The compound self-assembled into stable and homogeneous nanoparticles through hydrophobic interaction with the amphiphilic polymer 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-poly(ethylene glycol), which showed enhanced aggregation-induced emission (AIE) capacity in the NIR region. The nanoparticles specifically enriched at the tumor site due to the enhanced penetration and retention effect and exhibited bright fluorescence in vitro and in vivo. Notably, they showed satisfactory hematological compatibility and unobservable cellular and histological toxicity. Therefore, they are of promising clinical significance in the AIE-enhanced NIR fluorescence imaging-visualized precise diagnosis of cancer. [ABSTRACT FROM AUTHOR]

[Display omitted] Lanthanide-doped up-converting nanoparticles (UCNPs) have emerged as promising biomedical tools in recent years. Most research efforts were devoted to the synthesis of inorganic cores with the optimal physicochemical properties. However, the careful design of UCNPs with the adequate surface coating to optimize their biological performance still remains a significant challenge. Here, we propose the functionalization of UCNPs with four distinct types of surface coatings, which were compared in terms of the provided colloidal stability and resistance to degradation in different biological-relevant media, including commonly avoided analysis in acidic lysosomal-mimicking fluids. Moreover, the influence of the type of particle surface coating on cell cytotoxicity and endocytosis/exocytosis was also evaluated. The obtained results demonstrated that the functionalization of UCNPs with poly(isobutylene- alt -maleic anhydride) grafted with dodecylamine (PMA- g -dodecyl) constitutes an outstanding strategy for their subsequent biomedical application, whereas poly(ethylene glycol) (PEG) coating, although suitable for colloidal stability purposes, hinders extensive cell internalization. Conversely, surface coating with small ligand were found not to be suitable, leading to large degradation degrees of UCNPs. The analysis of particle' behavior in different biological media and in vitro conditions here performed pretends to help researchers to improve the design and implementation of UCNPs as theranostic nanotools. [ABSTRACT FROM AUTHOR]

Water‐dispersible fluorescent nano‐/microspheres have been widely used as fluorescent probes in many fields. In this paper, aldehyde‐functionalized fluorescent micelles are synthesized by self‐assembly of end‐modified hyperbranched poly(m‐phenyleneethynylene‐alter‐p‐phenyleneethynylene)(hb‐PMPE). First, hb‐PMPE with ‐Br end‐groups(hb‐PMPE‐Br) is obtained by the polymerization of AB2 monomer PhBr2–C≡C–Ph–C≡CH, then the reaction of hb‐PMPE‐Br with 4‐ethynylbenzaldehyde (EBA) gives end aldehyde‐functionalized hyperbranched polymer hb‐PMPE‐CHO. Hence, hb‐PMPE‐CHO is reacted with aminooxy methoxypolyethylene glycol‐2000 (NH2O‐MPEG2000) to link poly(ethylene glycol) (PEG) chains to the ends of hb‐PMPE‐CHO with partial residual aldehyde end‐groups, resulting in aldehyde‐functionalized amphiphilic polymer hb‐PMPE‐PEG. Fluorescent micelles with aldehyde‐containing fluorescent hb‐PMPE core and PEG shell are obtained by self‐assembling hb‐PMPE‐PEG in water. The micelle diameter is determined by the PEG content in hb‐PMPE‐PEG, which can be controlled by the reaction weight ratio of NH2O‐MPEG2000/hb‐PMPE‐CHO. When the ratio of NH2O‐MPEG2000/hb‐PMPE‐CHO > 0.75/1, micelles with a diameter < 50 nm are obtained. The water dispersion of hb‐PMPE‐PEG‐1/2 micelles (28.9 nm) emits bright green fluorescence with λmax ≈ 490 nm under UV irradiation, and the emission intensity increases with increasing concentration. [ABSTRACT FROM AUTHOR]

Biocompatible, sustainable, and conductive inks are of special interest and are highly valued in the printable bioelectronics. However, the conventional inks, which increase electrical conductivity by mixing metal particles or graphene, can cause long‐term damage when applied to the body and environment. Herein, a method for creating a stable matrix based on a UV‐cross‐linkable polymer to which a conductive polymer can be grafted is investigated to solve the above problems by recycling biomass. Through this, it is possible to achieve high conductivity using only biocompatible and sustainable polymers. Here, conductive inks for printable bioelectronics are developed by grafting polypyrrole on methacrylate‐modified sericin and poly(ethylene glycol) diacrylate (PEGDA). The highest electrical conductivity is achieved by adjusting the ratio of the pyrrole monomers polymerized on each polymer until the conductivity is optimized. Owing to the photoreactive nature of PEGDA, the prepared conductive inks are cross‐linked by UV light, thus giving them easy‐printing properties. The biodegradability, biocompatibility, and electrical properties of the printed patterns are systematically analyzed. This study has significant implications in the field of sustainable and printable bioelectronics as it has developed of a conductive ink with the biocompatibility, biodegradability, and high conductivity that is safer and simpler than conventional methods. [ABSTRACT FROM AUTHOR]

UV‐curable oligomers were synthesized by the reaction of ethylene glycol (EG) or 1,4‐butanediol (BDO) with isophorone diisocyanate (IPDI), and then terminated with hydroxyethyl acrylate (HEA). The chemical structures and molecular weight of the two oligomers were analyzed by Fourier transform infrared spectroscopy (FT‐IR), nuclear magnetic resonance (1H NMR and 13C NMR) and high performance liquid chromatography (HPLC). The obtained UV‐curable oligomers were separately mixed with bisphenol A‐type epoxy acrylate (EA) in different mass ratios. The resulting mixture was then mixed with the active diluent tetrahydrofuran acrylate (THFA) and the photoinitiator ethyl 2,4,6‐trimethylbenzoylphosphonate (TPO‐L) for UV curing. The curing reactions were performed at UV light intensity of 120 mW/cm2. The unsaturation conversion was monitored by real‐time infrared spectroscopy (real‐time FT‐IR). The mechanical properties and coating properties of the UV‐cured products were analyzed. The results showed that the synthesized UV‐curable oligomers had good toughening effect on EA, and the tensile strength of EA was also improved. [ABSTRACT FROM AUTHOR]

Vat photopolymerization 3D printing has proven very successful for the rapid additive manufacturing (AM) of polymeric parts at high resolution. However, the range of materials that can be printed and their resulting properties remains narrow. Herein, we report the successful AM of a series of poly(carbonate‐b‐ester‐b‐carbonate) elastomers, derived from carbon dioxide and bio‐derived ϵ‐decalactone. By employing a highly active and selective Co(II)Mg(II) polymerization catalyst, an ABA triblock copolymer (Mn=6.3 kg mol−1, ÐM=1.26) was synthesized, formulated into resins which were 3D printed using digital light processing (DLP) and a thiol‐ene‐based crosslinking system. A series of elastomeric and degradable thermosets were produced, with varying thiol cross‐linker length and poly(ethylene glycol) content, to produce complex triply periodic geometries at high resolution. Thermomechanical characterization of the materials reveals printing‐induced microphase separation and tunable hydrophilicity. These findings highlight how utilizing DLP can produce sustainable materials from low molar mass polyols quickly and at high resolution. The 3D printing of these functional materials may help to expedite the production of sustainable plastics and elastomers with potential to replace conventional petrochemical‐based options. [ABSTRACT FROM AUTHOR]