Glycolate Research Articles

High‐Efficiency Dimethyl Adipate Hydrogenation for 1,6‐Hexanediol Synthesis Over the Cu/SiO2 Nanoparticles with Reasonably Modulations of Pore Structure and Dispersion via Surface‐Assisted Method

AbstractSurfactant‐assisted co‐precipitation for catalyst preparation is an excellent potential preparation method for enhanced metal‐support interactions and abundant oxygen vacancy. Cu/SiO2 catalysts were prepared containing either glycolic acid ethoxylate lauryl ether (BRIJ35, B5), polyethylene oxide‐polypropylene oxide‐polyethylene oxide (P123 P3), or no surfactant. After further treatment with surfactants, the 1,6‐hexanediol selectivity was significantly increased, especially for P123 surfactant. The Cu/SiO2‐P3 catalyst showed good performance, which may be related to more surface basic amount, the larger dispersion of the Cu and abundant oxygen vacancy. Abundant Ovac may facilitate the hydrogenation of DMA by weakening the C=O bond. After the Cu/SiO2 catalyst was treated with surfactant, the micropores disappeared and SBET of the catalyst increased. Among them, Cu/SiO2‐P3 had the largest specific surface area (312.6 m2 g−1).

Overexpression of the β-Subunit of Acid Ceramidase in the Epidermis of Mice Provokes Atopic Dermatitis-like Skin Symptoms.

We previously reported that a pathogenic abnormality in the barrier and water-holding functions of the stratum corneum (SC) in the skin of patients with atopic dermatitis (AD) is mainly attributable to significantly decreased levels of total ceramides in the SC. That decrease is mediated by the abnormal expression of a novel ceramide-reducing enzyme, sphingomyelin/glucosylceramide deacylase (SGDase), which is the β-subunit (ASAH1b) of acid ceramidase. In this study, we determined whether mice overexpressing ASAH1b in their epidermis develop AD-like skin symptoms. We generated transgenic (TG) mice overexpressing ASAH1b, regulated by the involucrin promoter, to localize its expression in the upper epidermis. After hair removal using a depilatory cream containing glycolic acid, the TG mice without any visible skin inflammation at 8 weeks of age had increased levels of ASAH1b and decreased levels of SC ceramide, with disrupted barrier functions measured by trans-epidermal water loss compared to the wild-type (WT) mice. Interestingly, enzymatic assays revealed that SGDase activity was not detectable in the skin of the TG mice compared to WT mice. Immunological staining revealed that there was an increased expression level of IL-33 in the epidermis and an accumulation of macrophages in the dermis of TG mice compared to WT mice, which are phenotypic characteristics of AD, that were exacerbated by tape-stripping of the skin. In the skin of the TG mice, the mRNA levels of IL-5, CCL11, IL-22, CXCL10, and IFNγ were significantly upregulated compared to the WT mice, and tape-stripping significantly increased the mRNA levels of IL-4, IL-33, CXCL1, CXCL12, TLR9, and CD163 compared to WT mice. These findings strongly indicate that the skin of the depilatory cream-treated TG mice exists in an atopic dry skin condition that is highly sensitive to various environmental stimuli. The sum of our results suggests that ASAH1b itself, even in the absence of its enzymatic activity, is a major etiologic factor for atopic dry skin symptoms via an unknown mechanism.

Photoelectrochemical Oxidation of Glycerol over g-C3N4 Nanosheets Coupled with Metal-Assisted Hybrid Carbon Quantum Dots

Carbon quantum dots (CDs) are the most promising candidates of the carbon family with a size of less than 10nm. They owned superior properties such as high solubility in aqueous medium, low toxicity, biocompatibility, stable photoluminescence, spectral convertor, and act as electron reservoirs. These properties make CDs suitable for photo-electrochemical catalytic applications. Low quantum yield and activity in the visible light spectrum of CDs may restrict their applicability. To address this issue, doping and surface passivation of CDs is the only approach to improve their physicochemical characteristics, visible light absorption, and quantum yield by altering their size and structure. Metals are electron-efficient entities and act as electron donors. As a result, when metal ions are doped into CDs, the charge density and charge transition between the core of the CDs and the metal ions increases. This results in a greater improvement in the physicochemical properties of CDs as compared to non-metal doping[1]. Metal-assisted CDs i.e. hybrid CDs tend to modulate energy band positions, change the electronic structure, increase quantum yield, and generate new emissive traps in CDs. The photoluminescence property of CDs can be enhanced due to the surface plasmonic resonance (SPR) effects of metal nanoparticles (NPs). Hybrid CDs also show better catalytic performance as compared to the pristine CDs. It helps to enhance the active sites on the CDs surface to facilitate catalytic performance.By keeping these properties, the hybrid CDs were effectively utilized in the field of dye decolorization, degradation of water pollutants, storage materials, and as a sensor[2][3]. The photo-assisted electrochemical glycerol valorization is one of the prominent methods for producing value-added chemicals such as glycolic acid. However, it is a challenge to achieve high yield and selectivity of products. This research investigated the fabrication of heterojunction of g-C3N4 (CN) with CDs and Bi-assisted CDs (BiCD) as a sustainable photoactive material. The heterojunction was obtained by incorporating CDs and BiCD (5wt.% each) onto CN nanosheets by in-situ thermal polymerization treatment and named CDCN and BiCDCN. The prepared composite was analyzed by structural (XRD), functional (XPS) microscopic (FESEM, FETEM) spectroscopic (UV-Vis, PL, TRPL, EDS), and photoelectrochemical characterization techniques.The band gap of CN was obtained as 2.78 eV which was reduced to 2.69 eV for CDCN and 2.62eV for BiCDCN, increasing the absorbance in the visible light zone. The existence of CDs and BiCDs was confirmed by, FETEM investigation (Fig.1a). The XPS analysis of the composite revealed the presence of Bi 4f chemical state of bismuth metal. The calculated TRPL lifetime was 0.28ns for BiCDCN and 2.51 ns for CDCN which was lower than that of CN (9.31 ns) suggesting the rapid electron transfer ability of BiCDCN. In the presence of light and glycerol, the composite BiCDCN had the maximum photocurrent density of 12 mA/cm2, followed by CDCN (1.6 mA/cm2) and CN (1.3 mA/cm2) at 1.2 V. The photoelectrochemical oxidation of glycerol was performed at 0.8V for 3h. The detected products were glycolic acid, glyceric, glyoxylic acid, and oxalic acid. The addition of CD to CN increased the glycerol conversion and yield of glycolic acid & glyoxylic acid significantly. The composite exhibited 43% selectivity towards glycolic acid and 34% for glyoxylic acid. The glycerol conversion and yield of these two products were further enhanced by Bi doping. BiCDCN had a total glycerol conversion of 21%, followed by CDCN at 5.7% and CN at 3.8%. The BiCDCN had the highest yield of glycolic acid at 8.9 % and that for CDCN was 2.4 % and 1.2 % for CN (Fig.1b). The glyoxylic acid yield was 7.2%, 2.2%, and 0.8% for BiCDCN, CDCN, and CN, respectively. Figure 1

Electrochemical Conversion of Low-Cost Glycerol to Valuable Products

Over the last years, biodiesel production, a renewable fuel derived from biomass, has significantly increased, reaching an output of 40 million tons annually. This surge in production has resulted in excessive glycerol production, as a byproduct, accounting for 10 wt.% of biodiesel production. By 2025, it is predicted that glycerol production will amount to 6.3 million tons.1 However, the low demand for glycerol not only causes high disposal costs for this waste byproduct but also poses a threat to the ecosystem. Consequently, the valorization of glycerol is crucial for enhancing the biodiesel industry's economic viability and environmental sustainability.Among all the techniques for the valorization of glycerol, such as catalytic oxidation, dehydration, and hydrogenolysis, the electrochemical oxidation of glycerol stands out for its cost-effectiveness, simplicity, and eco-friendliness. The glycerol electrooxidation reaction (GOR) can yield a wide range of valuable chemicals, such as C3 products (glyceraldehyde, lactic acid, glyceric acid, tartronic acid), C2 products (glycolic acid, oxalic acid, acetic acid), and C1 products (formic acid). Among all the products, C3 products have notably higher economic value compared to others. In particular, glyceric acid stood out by having a price of over 200 folds of glycerol and having the highest worldwide demand among all the GOR products.2 However, a significant technical challenge lies in developing a highly selective catalyst for C3 products showing high activity, and stability. Thus far, most of the catalyst developed for GOR includes noble metals or their alloys, which limits their usage in realistic systems due to their high cost and scarcity.3 Therefore, developing a cost-effective catalyst with high selectivity, activity, and stability is necessary to make the valorization of glycerol economically viable.In this work, we demonstrate a bimetallic catalyst that, despite its low noble metal content, achieves high selectivity towards glyceric acid, along with notable catalytic activity and stability. Our analysis focuses on the impact of noble metal amount on activity and stability, and parametric analysis to improve the selectivity of C3 products. Furthermore, we outline the reasons for the discrepancies in the quantification of GOR products, especially in applying H-NMR analysis, and discuss the methods to improve the precision in GOR product analysis.

Exploring yeast biodiversity and process conditions for optimizing ethylene glycol conversion into glycolic acid.

Plastics have become an indispensable material in many fields of human activities, with production increasing every year; however, most of the plastic waste is still incinerated or landfilled, and only 10% of the new plastic is recycled even once. Among all plastics, polyethylene terephthalate (PET) is the most produced polyester worldwide; ethylene glycol (EG) is one of the two monomers released by the biorecycling of PET. While most research focuses on bacterial EG metabolism, this work reports the ability of Saccharomyces cerevisiae and nine other common laboratory yeast species not only to consume EG, but also to produce glycolic acid (GA) as the main by-product. A two-step bioconversion of EG to GA by S. cerevisiae was optimized by a design of experiment approach, obtaining 4.51±0.12g l-1 of GA with a conversion of 94.25±1.74% from 6.21±0.04g l-1 EG. To improve the titer, screening of yeast biodiversity identified Scheffersomyces stipitis as the best GA producer, obtaining 23.79±1.19g l-1 of GA (yield 76.68%) in bioreactor fermentation, with a single-step bioprocess. Our findings contribute in laying the ground for EG upcycling strategies with yeasts.

Surface Microfabrication of Lactic Acid–Glycolic Acid Copolymers Using a Gas-Permeable Porous Mold

We attempted to perform surface microfabrication of the bioabsorbable material lactic acid–glycolic acid copolymer (LG-80) using a micro-imprint lithography technique with a gas-permeable porous mold at less than 5 °C. As a result, high-resolution surface micromachining with a height of 1.26 μm and a pitch of 2.97 μm was achieved using a convex sapphire mold with a height of 1.3 μm and a pitch of 3 μm. After processing, the LG-80 exhibited high water repellency, and FT-IR analysis of the surface showed no significant change in its chemical structure, confirming that the surface microfabrication was successful, while retaining the properties of the material. This demonstrated new possibilities for surface microfabrication technology for bioabsorbable materials, which are expected to be applied in the medical and life science fields in products such as surgical implants, tissue regeneration materials, and cell culture scaffold materials. In particular, the use of micro-imprint lithography enables low-cost and high-precision processing, which will be a major step toward the practical application of bioabsorbable materials.

Effects of low-molecular-weight organic acids on the transport of polystyrene nanoplastics: An insight at the structure of organic acids

Plastic nanoparticles are extensively used in various products, leading to inevitable pollution in soil. Understanding their transport in soils where various organic substances exist is crucial. This study examined the impact of low-molecular-weight organic acids (LMWOAs) on the transport of polystyrene nanoplastics (PS-NPs) through saturated quartz sand. The experiments involved three dibasic acids—malonic acid (MA1), malic acid (MA2) and tartaric acid (TA) — and four monobasic acids— formic acid (FA), acetic acid (AA), propanoic acid (PA) and glycolic acid (GA) —under different pH levels (4.0, 5.5, 7.0) and in the presence of cations (Na+, Ca2+). The results demonstrated that in the presence of Na+, dibasic acids significantly enhanced PS-NPs transport, with TA being the most effective, followed by MA2 and MA1. This enhancement is attributed to the adsorption of LMWOAs onto the nanoparticles and sand, creating a more negative ζ-potential, which increases the electrostatic repulsion and decreases the PS-NPs deposition, thereby facilitating the transport. Applying the Derjaguin-Landau-Verwey-Overbeek theory, higher pH levels increased the energy barrier and secondary energy minimum, decreasing PS-NPs deposition. Moreover, dibasic acids significantly enhanced the hydrophilicity of PS-NPs. Conversely, monobasic acids, except for GA, slightly reduced the hydrophilicity of PS-NPs, as indicated by a small increase in the water contact angle, hereby minimally affecting PS-NPs transport. As for GA, although it is a monobasic acid, the additional -OH group in its molecular structure promoted PS-NPs transport, similar to dibasic acids. For example, GA also significantly enhanced the hydrophilicity of PS-NPs. In the presence of Ca2+, the enhancement of PS-NPs transport by LMWOAs was comparable to that with Na+, primarily due to the complex-forming and bridging effects of Ca2+ with the organic acids and PS-NPs. These findings provide important insights into predicting and analyzing the transport behaviors of PS-NPs.

Carrier cascade target delivery of 5-aminolevulinic acid nanoplatform to enhance antitumor efficiency of photodynamic therapy against lung cancer

5-Aminolevulinic acid (5-ALA) is a prodrug of porphyrin IX (PpIX). Disadvantages of 5-ALA include poor stability, rapid elimination, poor bioavailability, and weak cell penetration, which greatly reduce the clinical effect of 5-ALA based photodynamic therapy (PDT). Presently, a novel targeting nanosystem was constructed using gold nanoparticles (AuNPs) as carriers loaded with a CSNIDARAC (CC9)-targeting peptide and 5-ALA via Au-sulphur and ionic bonds, respectively, and then wrapped in polylactic glycolic acid (PLGA) NPs via self-assembly to improve the antitumor effects and reduce the side effect. The successful preparation of ALA/CC9@ AuNPs-PLGA NPs was verified using ultraviolet-visible, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The analyses revealed good sphericity with a particle size of approximately140 nm, Zeta potential of 10.11 mV, and slow-controlled release characteristic in a weak acid environment. Confocal microscopy revealed targeting of NCL-H460 cells by NPs by actively internalising CC9 and avoiding the phagocytic action of RAW264.7 cells, and live fluorescence imaging revealed targeting of tumours in tumour-bearing mice. Compared to free 5-ALA, the nanosystem displayed amplified anticancer activity by increasing production of PpIX and reactive oxygen species to induce mitochondrial pathway apoptosis. Antitumor efficacy was consistently observed in three-dimensionally cultured cells as the loss of integrity of tumour balls. More potent anti-tumour efficacy was demonstrated in xenograft tumour models by decreased growth rate and increased tumour apoptosis. Histological analysis showed that this system was not toxic, with lowered liver toxicity of 5-ALA. Thus, ALA/CC9@AuNPs-PLGA NPs deliver 5-ALA via a carrier cascade, with excellent effects on tumour accumulation and PDT through passive enhanced permeability and retention action and active targeting. This innovative strategy for cancer therapy requires more clinical trials before being implemented.

Influence of diode laser irradiation on microtensile bond strength of etch-and-rinse adhesive to dentin using two different etchants: An in vitro study

Aim: The aim of this study was to evaluate the influence of 970 nm diode laser (DL) irradiation on the microtensile bond strength (µTBS) of etch-and-rinse adhesive (ERA) to dentin using phosphoric acid (PA) or alpha-hydroxy glycolic acid (GA) as etchants. Materials and Methods: A total of 32 human third molars were selected and assigned randomly among two different groups and four subgroups based on etching protocols and DL irradiation: PA, PA-DL, GA, and GA-DL. After tooth preparation and subsequent incremental composite build-up, the samples were stored in distilled water for 24 h at 37°C. µTBS values were obtained using the universal testing machine. The failure modes observed in dentin were categorized as adhesive, cohesive within dentin/resin, or mixed. Statistical Analysis: The data were analyzed using one-way analysis of variance, followed by Tukey’s post hoc test (P ≤ 0.001). Results: GA showed better or similar bond strength values to PA. Furthermore, irradiation of DL increased the µTBS to dentin when both PA or GA are used as etchants. Conclusion: GA can be used as an alternative etchant to PA. DL irradiation stands as a promising approach for elevating the performance of ERA adhesive systems to dentin.

Aspects of glass and hybridization protocols for bonding of fiber posts to root dentine.

This study evaluated bond strength of glass fiber posts to root dentin using push-out (PO) and diametral compression (DC), testing glycolic acid as a conditioner and varying dentin moisture. An additional aim was to test whether DC can be an alternative test to PO for bond strength assessment. Eighty bovine teeth were divided into eight groups (n=10) defined by the use of either 37% glycolic acid or 37% phosphoric acid (PA) on moist or wet dentin before bonding with either Adapter SingleBond/RelyX ARC or One Step Plus/Duo-Link Bisco. Each tooth provided discs with an internal diameter of 2mm, external diameter of 5mm, and height of 2mm, which underwent PO and DC. Finite element analysis (FEA) was carried out on 3D models. When analyzing PO results through linear regression, the highest values of bond strength were observed using glycolic acid on wet dentin in the cervical and middle thirds of the teeth. Analyzing DC results, the only statistical influence on values was the dental thirds. The scatterplot of the DC results and the PO bond strength values indicated no relationship between the results of the two tests (r=0.03; p=0.64). PO test detected more sensitive changes in bond strength values than DC.

Measuring Erosion of Biodegradable Polymers in Brimonidine Drug Delivery Implants by Quantitative Proton NMR Spectroscopy (q-HNMR)

Erosion of biodegradable polymeric excipients, such as polylactic acid (PLA) and polylactic-co-glycolic acid (PLGA), is generally characterized by microbalance for the remaining mass of PLA and/or PLGA and Gel Permeation Chromatography (GPC) for molecular weight (MW) decrease. For polymer erosion studies of intravitreal sustained release brimonidine implants, however, both microbalance and GPC present several challenges. Mass loss measurement by microbalance does not have specificity for excipient polymers and drug substances. Accuracy of the remaining mass by weighing could also be low due to sample mass loss through retrieval-drying steps, especially at later drug release (DR) time points. When measuring the decrease of polymer MW by GPC, trace amounts of polymeric degradants (oligomers and/or monomers) trapped inside the implants during DR tests may not be measurable due to sensitivity limitations of the GPC detector and column MW range. Previous efforts to measure remained PLGA weight of dexamethasone micro-implants using qNMR with external calibration have been performed, however, these measurements do not account for chemical structure changes (i.e. LA to GA ratio changes from time zero) of PLGA implants during drug release tests. Here, a qNMR method with an internal standard was developed to monitor the following changes in micro-implants during drug release tests: 1. The remaining overall PLA/PLGA mass. 2. The remaining lactic acid (LA), glycolic acid (GA) unit and PLGA's lauryl ester end group percentages. 3. The trace content of PLA/PLGA oligomers as degradants retained in the implants. Unlike microbalance analysis, qNMR has both specificity for drug substance, excipient polymer, and accuracy due to minimal implant loss during sample preparation. Compared to the overall PLA/PLGA remaining mass generally monitored in erosion studies, the percentage of remaining LA, GA, and the ester end group provide more information about the microstructure change (such as hydrophobicity) of PLA/PLGA. Additionally, the qNMR method can complement GPC methods by measuring the change of remaining PLA and PLGA oligomer concentrations in brimonidine implants, with tenfold less sample and no MW cutoff. The qNMR method can be used as a sensitive tool for both polymer excipient characterization and kinetics studies of brimonidine implant erosion.

Glycolic acid and D-lactate-putative products of DJ-1-restore neurodegeneration in FUS - and SOD1-ALS.

Amyotrophic lateral sclerosis (ALS) leads to death within 2-5 yr. Currently, available drugs only slightly prolong survival. We present novel insights into the pathophysiology of Superoxide Dismutase 1 (SOD1)- and in particular Fused In Sarcoma (FUS)-ALS by revealing a supposedly central role of glycolic acid (GA) and D-lactic acid (DL)-both putative products of the Parkinson's disease associated glyoxylase DJ-1. Combined, not single, treatment with GA/DL restored axonal organelle phenotypes of mitochondria and lysosomes in FUS- and SOD1-ALS patient-derived motoneurons (MNs). This was not only accompanied by restoration of mitochondrial membrane potential but even dependent on it. Despite presenting an axonal transport deficiency as well, TDP43 patient-derived MNs did not share mitochondrial depolarization and did not respond to GA/DL treatment. GA and DL also restored cytoplasmic mislocalization of FUS and FUS recruitment to DNA damage sites, recently reported being upstream of the mitochondrial phenotypes in FUS-ALS. Whereas these data point towards the necessity of individualized (gene-) specific therapy stratification, it also suggests common therapeutic targets across different neurodegenerative diseases characterized by mitochondrial depolarization.

Hair-straightening cosmetics containing glyoxylic acid induce crystalline nephropathy

We recently reported the case of a patient who experienced three consecutive episodes of acute kidney injury, all of them following a "Brazilian" hair-straightening treatment. The cream used for the straightening procedure contained glyoxylic acid. To examine possible underlying mechanisms causing kidney injury, four groups of mice were exposed to topical application of (i) the straightening product, (ii) a cream containing 10% glyoxylic acid, (iii) a cream containing 10% glycolic acid or (iv) a control cream. Application of glycolic acid slightly increased urine oxalate excretion, while glyoxylic acid and the straightening product dramatically increased urine oxalate excretion and caused calcium oxalate nephropathy after transcutaneous absorption. Thus, glyoxylic acid was presumptively absorbed through the skin, metabolized to oxalate and promoted crystallization of calcium oxalate in urine. Hence, cosmetic products containing glyoxylic acid may induce acute kidney injury and should be discontinued. Further studies are needed to investigate the metabolism of glycolic acid and glyoxylic acid following topical application.

Selective Electrocatalytic Oxidation of Ethylene Glycol into Glycolic Acid at Coin-Group Electrodes: An Investigation on Catalytic Activity and Selectivity

Selective Electrocatalytic Oxidation of Ethylene Glycol into Glycolic Acid at Coin-Group Electrodes: An Investigation on Catalytic Activity and Selectivity

Reactivity of N terminal histidine of peptides towards excipients/impurity of excipients: A case study of liraglutide excipient compatibility study

The selection of quality excipients is a crucial step in peptide formulation development. Apart from excipient incompatibility, process-related impurities or degradants of an excipient can interact with peptide-active pharmaceutical ingredients, forming the interaction products. The formaldehyde has been reported as an impurity of excipient in polyethylene glycol, glycerol, magnesium stearate, microcrystalline cellulose, mannitol, etc. The peptide contains various amino acids such as histidine, lysine, and arginine having free amine groups. These amine groups act as strong nucleophile and can increase the reactivity of peptides. PLGA is the most widely used biodegradable polymer in sustained-release formulations. The hydrolysis of PLGA generates glycolic acid and lactic acid impurities, which can form the interaction product with the amines of peptides. During the formulation development of Liraglutide, we have found few interaction products. The systematic characterization and mechanistic understanding of these interaction products lead us to imidazopyrimidine, glycolyl, and lactolyl moieties. These interaction products have been characterized thoroughly with the use of LC-HRMS, MS/MS, and hydrogen-deuterium exchange mass studies. The study revealed that the reactivity of N-terminal histidine must be considered for formulation development. Moreover, the quality of excipients with respect to presence of impurities must be considered as critical material attributes.

Effect of the composition of combined solid lipid particles with gefitinib and a photosensitizer on their size, stability and cytotoxic activity

The creation of combined nanomedicines and their controlled release under the influence of photoinduction is an actively developing branch of scientific research. This work is devoted to the development of models of solid lipid nanoparticles for a well-known antitumor drug – gefitinib in combination with a photoindicating agent – a photosensitizer from the phthalocyanine group. Nanoparticles were obtained by several methods: hot homogenization with stearic acid, sesame oil and Tween 80 and by one-step dispersion with copolymers of lactic and glycolic acids and polyvinyl alcohol. In vitro experiments when irradiating particles with a laser in the near-infrared range (about 730 nm) proved the advantage of using combined nanoparticles with gefitinib and a photosensitizer compared to monotherapy, while the activity in terms of IC50 was 5.1-8.7 times higher for gefitinib and 1.5-1.8 times for the photosensitizer.

Enhanced Separation of Americium and Curium in Cyanex301 System by Using Formic Acid and Glycolic Acid as Stripping Chelates

ABSTRACT The distribution equilibria of Am(III) and Cm(III) between the organic phase of bis(2,4,4-trimethylpentyl)dithiophosphonic acid (purified Cyanex301, HA) in xylene and aqueous solutions containing varying concentrations of formic acid or glycolic acid have been investigated aiming at the separation of the two actinides from each other after the groups separation of Am(III)/Cm(III) from Ln(III) ions. The apparent extraction constants for Am(III) and Cm(III) in the Cyanex301-xylene system are determined to be −8.84 and −9.37, respectively, at 0.01 M ionic strength. The specific ion interaction method (SIT) is used to obtain the stability constants of Am(III) and Cm(III) with nitrate and glycolate for calculating the speciation of the ions in extraction at 25°C and I = 0.01 M. The separation of Cm(III) from Am(III) loaded in 0.5 M HA in xylene can be considerably improved by emplying 0.01 to 0.05 M formic acid or glycolic acid as selective stripping reagents favoring complexation with Cm(III). Specifically, with 0.01 M formic acid or glycolic acid in the aqueous phase, the separation factor (SF) for Am(III) over Cm(III) is improved from 3.61 to 5.87 and 5.26, respectively. Hence, both separations of An(III) from Ln(III) and then Am(III) from Cm(III) are achieved by a selective extraction process at first and then a selective stripping process in one simple efficient system using purified Cyanex301 as extractant in organic phase and carboxylic acids as stripping chelates in aqueous.

Single proton anti-freezing hydrogel electrolyte with enhanced ion migration number enabling high-performance supercapacitor

Compared with traditional binary ion electrolytes, single-ion electrolytes have higher ion migration number and can avoid concentration polarization. In this work, single proton hydrogel electrolytes were prepared by one-step free radical polymerization of acrylamide and 2-acrylaminoamido-2-methyl-1-propane sulfonic acid in ethylene glycol (EG)/water binary solvent. The electrolyte possesses good mechanical strength and excellent anti-freezing ability. A high conductivity of 1.28 mS cm−1 at −40 °C is achieved by adjusting monomer ratio and EG content. The proton hopping along the ion channel formed by the anionic polymer chain and the Grotthuss transport are responsible for the high conductivity. An extremely high ion migration number of 0.87 is obtained. The fixed anionic group endows the hydrogel electrolyte with good anticorrosion ability. The hydrogel electrolyte assembled supercapacitor (SC) exhibits excellent electrochemical performance in a wide temperature range from −40 °C to 60 °C and can be stored at −30 °C for 10 months without capacitance attenuation. The capacitance retention rate of the SC is as high as 92% after 15,000 cycles at both room temperature and − 40 °C. The single proton hydrogel electrolyte provides a new route for the further development of storage device based proton transport.

Activation of the l-fucose utilization cluster in Campylobacter jejuni induces proteomic changes and enhances Caco-2 cell invasion and fibronectin binding

Most Campylobacter jejuni isolates carry the fucose utilization cluster (Cj0480c-Cj0489) that supports the metabolism of l-fucose and d-arabinose. In this study we quantified l-fucose and d-arabinose metabolism and metabolite production, and the impact on Caco-2 cell interaction and binding to fibronectin, using C. jejuni NCTC11168 and the closely related human isolate C. jejuni strain 286. When cultured with l-fucose and d-arabinose, both isolates showed increased survival and production of acetate, pyruvate and succinate, and the respective signature metabolites lactate and glycolic acid, in line with an overall upregulation of l-fucose cluster proteins. In vitro Caco-2 cell studies and fibronectin-binding experiments showed a trend towards higher invasion and a significantly higher fibronectin binding efficacy of C. jejuni NCTC11168 cells grown with l-fucose and d-arabinose, while no significant differences were found with C. jejuni 286. Both fibronectin binding proteins, CadF and FlpA, were detected in the two isolates, but were not significantly differentially expressed in l-fucose or d-arabinose grown cells. Comparative proteomics analysis linked the C. jejuni NCTC11168 phenotypes uniquely to the more than 135-fold upregulated protein Cj0608, putative TolC-like component MacC, which, together with the detected Cj0606 and Cj0607 proteins, forms the tripartite secretion system MacABC with putative functions in antibiotic resistance, cell envelope stress response and virulence in Gram negative pathogenic bacteria. Further studies are required to elucidate the role of the MacABC system in C. jejuni cell surface structure modulation and virulence.

About alcohol-initiated polymerization of glycolide and separate crystallization of cyclic and linear polyglycolides

Alcohol-initiated polymerizations of glycolide (GL) catalyzed by tin(II) 2-ethylhexanoate (SnOct2) were carried out in bulk with variation of GA/In ratio, temperature and time. Due to a rather strong competition of cyclization polyglycolide (PGA) free of cycles were never obtained. When the cyclic catalysts 2,2-dibutal-2-stanna −1,3-dithiolane (DSTL) or 2-stanna 1,3-dioxo-4,5,6,7 bibenzepane (SnBiph) were used in combination with 1,4-butanediol the influence of cyclization was even stronger. Furthermore, the degrees of polymerization were higher than the GA/alcohol ratio due to rapid polycondensation in the solid state. At 160 °C or below, the matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra indicated separate crystallization of low molar mass cyclic and linear PGAs from the same reaction mixture (also observed for poly(l-lactide)s).