Glycol Research Articles

Physical insights into the molecular mechanisms governing structural and dynamic properties of choline chloride-based deep eutectic solvents

ABSTRACT The present work studies the influence of the hydrogen bond donor (HBD) rigidity on the dynamic properties of Deep Eutectic Solvents (DES). We performed a series of all-atom molecular dynamics (MD) simulations of mixtures formed by choline chloride (ChlCl) with ethylene-glycol (ETG) or urea (UR) as HBD. The main aim is seeking for physical insights into the main molecular mechanisms that affect the transport properties of DES. We find a slower diffusion of cations occur when UR is the HBD, due to its high rigidity difficulties the overall DES molecular mobility. In other words, a rigid HBD decrease the local mobility. Hence, a flexible HBD enhances the molecular diffusion, promoting the stability of the liquid phase. Besides, we find a partial polarisation of the corresponding HBD due to the electrostatic interaction with the ions. Such behaviour is strongly reminiscent of the charge-screening phenomenon observed in classic electrolytes and could be relevant to the intrinsic stability of DES in the liquid phase at room temperature.

Experimental Investigation of the Enhancement of Heat Transfer Rate in Automobile Radiator Using Low Concentration Hybrid Nanofluids

Engine coolant, also called antifreeze, is essential to a vehicle's performance since it controls engine temperature, keeps the cooling system from freezing in cold weather and prevents corrosion. To increase engine cooling efficiency, this study looks into using low-concentration hybrid nanofluids to accelerate heat transfer rates in automobile radiators. To maximise heat dissipation within the radiator system, the project focuses on the synthesis, characterisation and practical applications of these nanofluids. Through an extensive literature review, various nanoparticles, including metallic and oxide-based particles, were evaluated for their compatibility and effectiveness in enhancing heat transfer. The chosen nanoparticles underwent thorough characterisation for size, shape and surface properties to determine their suitability for dispersion in a base coolant. Reduced Graphene is known for its good thermal conductivity, making it an ideal candidate for enhancing cooling rates in various applications hence keeping this in mind, this experiment compares and investigates the heat transfer rate in the radiator of an automobile with a hybrid combination of Reduced Graphene Oxide (RGO) + Copper Oxide (CuO) with ethylene glycol and distilled water, at volume fractions of 0.001%, 0.005% and 0.01%. The results show a notable increase in the efficiency of the radiator both in terms of pressure drop and effectiveness. A maximum of 9.2 and 1.5 times increase in temperature drop is recorded at 0.001%, a maximum of 12.3 and 2.08 times increase in temperature drop is noted at 0.005% and the highest of 17.9 and 3.03 times increase in temperature drop is tabulated at 0.01% volume fraction of copper oxide and 0.01% the volume fraction of RGO hybrid nanofluid. It can safely be concluded that compared to the sixty experiments conducted, the recommended nanofluid among them would be Ethylene Glycol and Distilled Water + 0.01% concentration of RGO and CuO hybrid as they have exhibited higher pressure drop, effectiveness and reduction in temperature.

Spleen‐Targeted mRNA Nanoparticles for Modulating B Cell Hyperactivation in Rheumatoid Arthritis Therapy

AbstractMessenger RNA (mRNA)‐based therapies have emerged as a revolutionary strategy for treating various diseases. In autoimmune diseases like rheumatoid arthritis (RA), targeted mRNA delivery provides a potential intervention to modulate immune responses. However, achieving specific and efficient in vivo modulation of immune regulators, such as the inhibitory Fc gamma receptor, FcγRIIB, on B cells remains challenging. In this study, lipid polymer nanoparticles (LPNs) formulated with AMB‐POC18 lipidoid and poly(ethylene glycol)‐block‐polylactide (PEG‐PLA) are engineered to deliver FcγRIIB mRNA (mFcγRIIB) specifically to splenic B cells for RA treatment. Protein corona analysis indicated that selective adsorption of complement C3 on the LPNs' surface facilitated their targeted delivery to the spleen, enhancing transfection efficiency in B cells following intravenous administration. In a collagen‐induced arthritis mouse model, mFcγRIIB/LPNs effectively upregulated FcγRIIB expression in splenic B cells, significantly reducing autoimmune responses and alleviating RA symptoms. Further mechanistic studies elucidated that increased FcγRIIB expression suppressed B cell activation via the FcγRIIB/Lyn/SHP‐1 signaling pathway. This work underscored the potential of the spleen‐targeted mRNA delivery system for RA therapy, providing a precise and targeted approach to modulate B cell activity and mitigate autoimmune diseases.

Crosslinking by Click Chemistry of Hyaluronan Graft Copolymers Involving Resorcinol-Based Cinnamate Derivatives Leading to Gel-like Materials.

The well-known "click chemistry" reaction copper(I)-catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC) was used to transform under very mild conditions hyaluronan-based graft copolymers HA(270)-FA-Pg into the crosslinked derivatives HA(270)-FA-TEGERA-CL and HA(270)-FA-HEGERA-CL. In particular, medium molecular weight (i.e., 270 kDa) hyaluronic acid (HA) grafted at various extents (i.e., 10, 20, and 40%) with fluorogenic ferulic acid (FA) residue bonding propargyl groups were used in the CuAAC reaction with novel azido-terminated crosslinking agents Tri(Ethylene Glycol) Ethyl Resorcinol Acrylate (TEGERA) and Hexa(Ethylene Glycol) Ethyl Resorcinol Acrylate (HEGERA). The resulting HA(270)-FA-TEGERA-CL and HA(270)-FA-HEGERA-CL materials were characterized from the point of view of their structure by performing NMR studies. Moreover, the swelling behavior and rheological features were assessed employing TGA and DSC analysis to evaluate the potential gel-like properties of the resulting crosslinked materials. Despite the 3D crosslinked structure, HA(270)-FA-TEGERA-CL and HA(270)-FA-HEGERA-CL frameworks showed adequate swelling performance, the required shear thinning behavior, and coefficient of friction values close to those of the main commercial HA solutions used as viscosupplements (i.e., 0.20 at 10 mm/s). Furthermore, the presence of a crosslinked structure guaranteed a longer residence time. Indeed, HA(270)-FA-TEGERA-CL-40 and HA(270)-FA-HEGERA-CL-40 after 48 h showed a four times greater enzymatic resistance than the commercial viscosupplements. Based on the promising obtained results, the crosslinked materials are proposed for their potential applicability as novel viscosupplements.

A Tandem-Locked Fluorescent Probe Activated by Hypoxia and a Viscous Environment for Precise Intraoperative Imaging of Tumor and Instant Assessment of Ferroptosis-Mediated Therapy.

Noninvasive fluorescence detection of tumor-associated biomarker dynamics provides immediate insights into tumor biology, which are essential for assessing the efficacy of therapeutic interventions, adapting treatment strategies, and achieving personalized diagnosis and therapy evaluation. However, due to the absence of a single biomarker that effectively reflects tumor development and progression, the currently available optical diagnostic agents that rely on "always-on" or single pathological activation frequently show nonspecific fluorescence responses and limited tumor accumulation, which inevitably compromises the accuracy and reliability of tumor imaging. Herein, based on intramolecular charge transfer (ICT) and twisted intramolecular charge-transfer (TICT) hybrid mechanisms, we report a tandem-locked probe, NTVI-Biotin, for simultaneously specific imaging-guided tumor resection and ferroptosis-mediated tumor ablation evaluation under the coactivation of nitro reductase (NTR)/viscosity. The dual-stimulus-responsive design strategy ensures that NTVI-Biotin exclusively activates near-infrared (NIR) fluorescence signals upon interaction with both NTR and elevated viscosity levels through triggering ICT on while inhibiting the TICT process. Meanwhile, functionalization with a tumor-targeting hydrophilic biotin-poly(ethylene glycol) moiety enhances tumor accumulation. The probe's dual-response and tumor-targeting design minimizes nonspecific tissue activation, allowing for precise tumor identification and lesion removal with a superior tumor-to-normal tissue (T/N > 6) ratio. More importantly, NTVI-Biotin was capable of evaluating ferroptosis-mediated chemotherapeutics by real-time monitoring of the alternations of NTR/viscosity levels. The results reveal that the increased tumor signals of NTVI-Biotin following the combination of ferroptosis and chemotherapy correlate well with the tumor growth inhibition, demonstrating the potential of NTVI-Biotin to assess therapeutic efficacy.

A catalytic approach for the dehydrogenative upgradation of crude glycerol to lactate and hydrogen generation.

The ambiguous nature of non-innocent ligand catalysts provides an excellent strategy for developing an efficient catalyst system featuring extended applicability in sustainable catalysis. In this study, we unveil the catalytic activity of an NNN-Ru catalyst for lactic acid synthesis from a mixture of glycerol, ethylene glycol, and methanol. The developed strategy was also implemented to synthesize lactate (up to 80% yield) with good selectivity via the dehydrogenative upgradation of a crude glycerol and ethylene glycol mixture. As an extended utility, the method was utilized for lactate synthesis from triglyceride directly with hydrogen gas generation.

In Situ Crosslinked Biodegradable Hydrogels Based on Poly(Ethylene Glycol) and Poly(ε-Lysine) for Medical Application.

Hydrogels have emerged as promising biomaterials due to their excellent performance; however, their biocompatibility, biodegradability, and absorbability still require improvement to support a broader range of medical applications. This paper presents a new biofunctionalized hydrogel based on in situ crosslinking between maleimide-terminated four-arm-poly(ethylene glycol) (4-arm-PEG-Mal) and poly(ε-lysine) (ε-PL). The PEG/ε-PL hydrogels, named LG-n, were rapidly formed via amine/maleimide reaction by mixing 4-arm-PEG-Mal and ε-PL under physiological conditions. The corresponding dry gels (DLG-n) were obtained through a freeze-drying technique. 1H NMR, FT-IR, and SEM were utilized to confirm the structures of 4-arm-PEG-Mal and LG-n (or DLG-n), and the effects of solid content on the physicochemical properties of the hydrogels were investigated. Although high solid content could increase the swelling ratio, all LG-n samples exhibited a low equilibrium swelling ratio of less than 30%. LG-7, which contained moderate solid content, exhibited optimal compression properties characterized by a compressive fracture strength of 45.2 kPa and a deformation of 69.5%. Compression cycle tests revealed that LG-n demonstrated good anti-fatigue performance. In vitro degradation studies confirmed the biodegradability of LG-n, with the degradation rate primarily governing the drug (ceftibuten) release efficiency, leading to a sustained release duration of four weeks. Cytotoxicity tests, cell survival morphology observation, live/dead assays, and hemolysis tests indicated that LG-n exhibited excellent cytocompatibility and low hemolysis rates (<5%). Furthermore, the broad-spectrum antibacterial activity of LG-n was verified by an inhibition zone method. In conclusion, the developed LG-n hydrogels hold promising applications in the medical field, particularly as drug sustained-release carriers and wound dressings.

Single-Step Synthesis of Highly Sensitive 19F MRI Tracers by Gradient Copolymerization-Induced Self-Assembly.

Amphiphilic gradient copolymers are promising alternatives to block copolymers for self-assembled nanomaterials due to their straightforward synthesis via statistical copolymerization of monomers with different reactivities and hydrophilicity. By carefully selecting monomers, nanoparticles can be synthesized in a single step through gradient copolymerization-induced self-assembly (gPISA). We synthesized highly sensitive 19F MRI nanotracers via aqueous dispersion gPISA of hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMA) with core-forming N,N-(2,2,2-trifluoroethyl)acrylamide (TFEAM). The PPEGMA-grad-PTFEAM nanoparticles were optimized to achieve spherical morphology and exceptional 19F MRI performance. Noncytotoxicity was confirmed in Panc-1 cells. In vitro 19F MR relaxometry and imaging demonstrated their diagnostic imaging potential. Notably, these gradient copolymer nanotracers outperformed block copolymer analogs in 19F MRI performance due to their gradient architecture, enhancing 19F relaxivity. The synthetic versatility and superior 19F MRI performance of gradient copolymers highlight their potential in advanced diagnostic imaging applications.

A comparative study of mono ethylene glycol economic production via different techniques

Mono-ethylene glycol (MEG) is a high-volume chemical intermediate used as a raw material for a variety of chemical products. It could also be used as a hydrate inhibitor in natural gas. Recently, the importance of MEG has been increased due to its usage as a supporting emulsifier in diesel engines to reduce NOx and soot emissions, in addition to its usage as an additive to dual fuel diesel engines. The increase consumption of MEG in wide range of applications leads to the search for the most efficient, environmental friendly and cost effective technique to produce more quantities of it. MEG is most commonly manufactured via the hydration of ethylene oxide (EO). In this work, two different technologies of EO hydration to produce MEG are compared; the direct hydration of EO with water and the indirect hydration through the usage of ethylene carbonate (EC) as an intermediate. Comparative economic and environmental impact assessments were performed based on plant-scale simulations (per 600,000 tons per year of MEG produced) of the two hydration technologies using Aspen HYSYS version 11 simulation software. Economic analysis showed that the utilities’ energy consumption for direct hydration process is significantly higher than for indirect hydration by 279 megawatts. On the other hand, the environmental impact assessments showed that GHG emissions from natural gas power generation from utilities from direct hydration are three times greater than GHG emissions from indirect hydration. This leads to indirect hydration of ethylene oxide through ethylene carbonate formation being considered economically and environmentally preferable compared to the direct hydration process of ethylene oxide.

Comprehensive analysis and validation of TP73 as a biomarker for calcium oxalate nephrolithiasis using machine learning and in vivo and in vitro experiments.

Calcium oxalate (CaOx) nephrolithiasis constitutes approximately 75% of nephrolithiasis cases, resulting from the supersaturation and deposition of CaOx crystals in renal tissues. Despite their prevalence, precise biomarkers for CaOx nephrolithiasis are lacking. With advances in high-throughput sequencing, we aimed to identify biomarkers of CaOx nephrolithiasis by combining twoCaOx nephrolithiasis datasets (GSE73680 and GSE117518). Utilizing weighted gene co-expression network analysis (WGCNA) and four machine learning, we identified six hub genes (DLK2, BHLHA15, C12orf5, ICMT, LOXHD1, and TP73) as potential biomarkers. Additionally, CIBERSORT immune infiltration analysis suggested that these core genes may influence immune cell recruitment and infiltration in CaOx nephrolithiasis. Then, TP73 emerged as a significant hub gene in CaOx nephrolithiasis via receiver operating characteristic (ROC) analysis (AUC = 0.885). Furthermore, the role of TP73 was validated in CaOx nephrolithiasis rat models induced by 1% ethylene glycol, as well as clinical samples and renal tubular epithelial cell models treated with 1mM oxalate. Immunohistochemistry, RNA-Sequencing, and RT-qPCR experiments demonstrated an increased expression of TP73 in CaOx nephrolithiasis rat models and clinical samples. After transfection with TP73 lentivirus, CCK-8 assays suggested that TP73 could inhibit the proliferation of HK-2 and NRK-52E cells. In oxalate-induced cell models, dihydroethidium staining and flow cytometry apoptosis assays indicated that TP73 could enhance ROS levels and cell apoptosis. In summary, our study preliminarily identified TP73 as a diagnostic biomarker and elucidated the promoting role of TP73 in CaOx nephrolithiasis, providing a deeper understanding of the clinical diagnosis and pathogenesis.

Controlling Temporally and Spatially Homogeneous Temperature Distribution of Paper Substrates by Biogenic Phase Change Hybrid Material Coatings

AbstractHere the performance of phase change material (PCM)‐coated paper made from unbleached kraft pulp is introduced. The applied PCM consists of a mixture of ethylene glycol distearate (EGDS), a well‐known PCM wax material, and a fully substituted cellulose stearoyl ester (CSE). Transfer of the PCM material onto/into paper is achieved by spray as well as blade coating of EGDS + CSE mixture. It is shown that the kind of coating method used does not interfere with observed PCM properties. The significantly higher melt viscosity of the EGDS + CSE blends ensures that the EGDS wax is not bleeding out of the paper, which avoids the use of further encapsulation processes. The PCM behavior, as observed by thermal load measurements, and the thermal buffering of the coated paper is a function of the applied mass of the PCM material applied. The thermal retention exhibited a quasi‐isothermal behavior at ≈65 °C with EGDS + CSE coatings. These effects can offset fluctuations in temperature, and the PCM papers can be employed to achieve a more uniform temperature setting. PCM‐modified papers are therefore interesting candidates for paper‐based packaging or for use in paper‐based sensors, where overheating can strongly affect reliability of results.

Comparative efficacy of Knema retusa extract delivery via PEG-b-PCL, niosome, and their combination against Acanthamoeba triangularis genotype T4: characterization, inhibition, anti-adhesion, and cytotoxic activity.

Acanthamoeba spp. is a waterborne, opportunistic protozoan that can cause amebic keratitis and granulomatous amebic encephalitis. Knema retusa is a native tree in Malaysia, and its extracts possess a broad range of biological activities. Niosomes are non-ionic surfactant-based vesicle formations and suggest a future targeted drug delivery system. Copolymer micelle (poly(ethylene glycol)-block-poly(ɛ-caprolactone); PEG-b-PCL) is also a key constituent of niosome and supports high stability and drug efficacy. To establish Knema retusa extract (KRe) loading in diverse nanocarriers via niosome, PEG-b-PCL micelle, and their combination and to study the effect of all types of nanoparticles (NPs) on Acanthamoeba viability, adherent ability, elimination of adherence, and cytotoxicity. In this study, we characterized niosomes, PEG-b-PCL, and their combination loaded with KRe and tested the effect of these NPs on Acanthamoeba triangularis stages. KRe-loaded PEG-b-PCL, KRe-loaded niosome, and KRe-loaded PEG-b-PCL plus niosome were synthesized and characterized regarding particle size and charge, yield, encapsulation efficiency (EE), and drug loading content (DLC). The effect of these KRe-loaded NPs on trophozoite and cystic forms of A.triangularis was assessed through assays of minimal inhibitory concentration (MIC), using trypan blue exclusion to determine the viability. The effect of KRe-loaded NPs was also determined on A.triangularis trophozoite for 24-72 h. Additionally, the anti-adhesion activity of the KRe-loaded niosome on trophozoites was also performed on a 96-well plate. Cytotoxicity activity of KRe-loaded NPs was assessed on VERO and HaCaT cells using MTT assay. KRe-loaded niosome demonstrated a higher yielded (87.93 ±6.03%) at 286nm UV-Vis detection and exhibited a larger size (199.3 ±29.98 nm) and DLC (19.63±1.84%) compared to KRe-loaded PEG-b-PCL (45.2 ±10.07 nm and 2.15±0.25%). The EE (%) of KRe-loaded niosome was 63.67 ±4.04, which was significantly lower than that of the combination of PEG-b-PCL and niosome (79.67±2.08). However, the particle charge of these NPs was similar (-28.2 ±3.68 mV and -28.5 ±4.88, respectively). Additionally, KRe-loaded niosome and KRe-loaded PEG-b-PCL plus niosome exhibited a lower MIC at 24 h (0.25 mg/mL), inhibiting 90-100% of Acanthamoeba trophozoites which lasted 72 h. KRe-loaded niosome affected adherence by around 40-60% at 0.125-0.25 mg/mL and removed Acanthamoeba adhesion on the surface by about 90% at 0.5 mg/mL. Cell viability of VERO and HaCaT cells treated with 0.125 mg/mL of KRe-loaded niosome and KRe-loaded PEG-b-PCL plus niosome exceeded 80%. Indeed, niosome and niosome plus PEG-b-PCL were suitable nanocarrier-loaded KRe, and they had a greater nanoparticle property to test with high activities against A. triangularis on the reduction of adherence ability and demonstration of its low toxicity to VERO and HaCaT cells.

Preparation and characterization of poly(ethylene glycol)-b-poly(tert-butyl methacrylate) micelles as potential nanocarriers for donepezil

Polymeric micelles were prepared for the delivery of donepezil, a leading Alzheimer’s disease drug, to enhance its transport across the blood–brain barrier (BBB). Poly(ethylene glycol)-b-poly(tert-butyl methacrylate) amphiphilic block copolymers were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The polymers were characterized by gel permeation chromatography and nuclear magnetic resonance spectroscopy. Empty and donepezil loaded polymer micelles were formed using the dialysis method and characterized by dynamic light scattering and transmission electron microscopy. Drug loading efficiency and release behavior were monitored using UV/Vis spectroscopy, and cytotoxicity was evaluated via colorimetric tests and impedance measurements. Additionally, the permeability of the nanocarriers across an in vitro BBB culture model was assessed. Drug-loaded micelles demonstrated similar permeability to free donepezil but offered sustained release and improved stability. This micellar delivery system holds significant potential for improving therapeutic outcomes in Alzheimer’s treatment by enhancing donepezil’s delivery across the BBB. Improved BBB permeability and sustained drug release could lead to more effective concentration of the drug in the brain, potentially reducing peripheral cholinergic side effects, such as nausea and vomiting, often observed with traditional donepezil administration. This could result in better patient compliance and improved cognitive outcomes, making this nanocarrier system a promising alternative for Alzheimer’s therapy.

Enhancing the Mechanical Strength of a Photocurable 3D Printing Material Using Potassium Titanate Additives for Craniofacial Applications.

Photopolymerization-based three-dimensional (3D) printing techniques such as stereolithography (SLA) attract considerable attention owing to their superior resolution, low cost, and relatively high printing speed. However, the lack of studies on improving the mechanical properties of 3D materials highlights the importance of delving deeper into additive manufacturing research. These materials possess considerable potential in the medical field, particularly for applications such as anatomical models, medical devices, and implants. In this study, we investigated the enhancement of mechanical strength in 3D-printed photopolymers through the incorporation of potassium titanate powder (K2Ti8O17), with a particular focus on potential applications in medical devices. The mechanical strength of the photopolymer containing potassium titanate was analyzed by measuring its flexural strength, hardness, and tensile strength. Additionally, poly(ethylene glycol) (PEG) was used as a stabilizer to optimize the dispersion of potassium titanate in the photopolymer. The flexural strengths of the printed specimens were in the range of 15-39 MPa (Megapascals), while the measured surface hardness and tensile strength were in the range of 41-80 HDD (Hardness shore D) and 2.3-15 MPa, respectively. Furthermore, the output resolution was investigated by testing it with a line-patterned structure. The 3D-printing photopolymer without PEG stabilizers produced line patterns with a thickness of 0.3 mm, whereas the 3D-printed resin containing a PEG stabilizer produced line patterns with a thickness of 0.2 mm. These findings demonstrate that the composite materials not only exhibit improved mechanical performance but also allow for high-resolution printing. Furthermore, this composite material was successfully utilized to print implants for pre-surgical inspection. This process ensures the precision and quality of medical device production, emphasizing the material's practical value in advanced medical applications.

Mitochondrial-Targeting Mesoporous Polydopamine Nanoparticles for Reducing Kidney Injury Caused by Depleted Uranium.

Depleted uranium (DU), when accidentally released from the nuclear industry, can enter the human body and cause kidney damage, as DU induces oxidative damage and apoptosis through mitochondrial pathways and inflammatory reactions. The existing nanoparticles used to treat DU injury have low bioavailability and poor targeting. In this study, mesoporous polydopamine (MPDA), poly-(ethylene glycol) (PEG), and triphenylphosphonium (TPP) are combined to develop a novel mitochondrion-targeting bifunctional nanoparticle, MPDA-PEG-TPP, and confirm that it can protect the kidneys from DU. This study demonstrates the high selectivity of MPDA-PEG-TPP for uranyl in uranyl chelate assays and its promising efficiency in uranyl sequestration from the kidneys, lungs, and femurs, following immediate or delayed administration of MPDA-PEG-TPP nanoparticles. In vitro assays confirm its efficiency in removing reactive oxygen species and targeting the mitochondria. In addition, in vitro and in vivo assays confirm that MPDA-PEG-TPP can reduce mitochondrial dysfunction and ameliorate kidney injury. These results suggest that MPDA-PEG-TPP is a valuable agent for ameliorating the DU-induced kidney injury.

Ruthenium-Substituted Polyoxoanion Serves as Redox Shuttle and Intermediate Stabilizer in Selective Electrooxidation of Ethylene to Ethylene Glycol.

The high carbon intensity of present-day ethylene glycol (EG) production motivates interest in electrifying ethylene oxidation. Noting poor kinetics in prior reports of the organic electrooxidation of small hydrocarbons, we explored the design of mediators that activate and simultaneously stabilize light alkenes. A ruthenium-substituted polyoxometalate (Ru-POM, {Si[Ru(H2O)W11O39]}5-) achieves 82% faradaic efficiency in EG production at 100 mA/cm2 under ambient conditions. Via the union of in situ spectroscopic techniques, electrochemical studies, and density functional theory calculations, we find evidence of a two-step oxidation mechanism: Ru-POM first undergoes electrochemical oxidation to the high valent state, activating ethylene via partial oxidation and forming an intermediate complex; this intermediate complex then migrates to the anode where it undergoes further oxidation to produce EG. The Ru-POM-mediated electrocatalytic system reduces the projected energy consumption required in EG production, requiring 9 GJ per ton of EG (and accompanied by 0.04 ton H2 coproduction), compared to 20-30 GJ/ton in typical prior processes.

Photoelectrochemical Ethylene Glycol Oxidization Coupled with Hydrogen Generation Using Metal Oxide Photoelectrodes.

Photoelectrochemical (PEC) water splitting represents a promising approach for harnessing solar energy and transforming it into storable hydrogen. However, the complicated 4-electron transfer process of water oxidation reaction imposes kinetic limitations on the overall efficiency. Herein, we proposed a strategy by substituting water oxidation with the oxidation of ethylene glycol (EG), which is a hydrolysis byproduct of polyethylene terephthalate (PET) plastic waste. To achieve this, we developed and synthesized BiVO4/NiCo-LDH photoanodes capable of achieving a high Faradaic efficiency (FE) exceeding 85 % for the oxidation of EG to formate in a strongly alkaline environment. The reaction mechanism was further elucidated using in situ FTIR spectroscopy. Additionally, we successfully constructed an unassisted PEC device for EG oxidation and hydrogen generation by pairing the translucent Mo : BiVO4/NiCo-LDH photoanode with a state-of-the-art Cu2O photocathode, resulting in an approximate photocurrent density of 2.3 mA/cm2. Our research not only offers a PEC pathway for converting PET plastics into valuable chemicals but also enables simultaneous hydrogen production.

Photoelectrochemical Ethylene Glycol Oxidization Coupled with Hydrogen Generation Using Metal Oxide Photoelectrodes

AbstractPhotoelectrochemical (PEC) water splitting represents a promising approach for harnessing solar energy and transforming it into storable hydrogen. However, the complicated 4‐electron transfer process of water oxidation reaction imposes kinetic limitations on the overall efficiency. Herein, we proposed a strategy by substituting water oxidation with the oxidation of ethylene glycol (EG), which is a hydrolysis byproduct of polyethylene terephthalate (PET) plastic waste. To achieve this, we developed and synthesized BiVO4/NiCo‐LDH photoanodes capable of achieving a high Faradaic efficiency (FE) exceeding 85 % for the oxidation of EG to formate in a strongly alkaline environment. The reaction mechanism was further elucidated using in situ FTIR spectroscopy. Additionally, we successfully constructed an unassisted PEC device for EG oxidation and hydrogen generation by pairing the translucent Mo : BiVO4/NiCo‐LDH photoanode with a state‐of‐the‐art Cu2O photocathode, resulting in an approximate photocurrent density of 2.3 mA/cm2. Our research not only offers a PEC pathway for converting PET plastics into valuable chemicals but also enables simultaneous hydrogen production.

Nonlinear model predictive controller of hydrogenation of dimethyl oxalate for ethylene glycol production

Abstract Ethylene glycol (EG) is a valuable commodity organic intermediate that is produced using the catalyzed gas-phase hydrogenation process of dimethyl oxalate (DMO) from syngas. The reactor process is challenging to control because of its nonlinearity and multivariable condition. Thus, this study proposes the application of Neural Wiener model predictive control (NWMPC) for DMO hydrogenation reactor control. The application of empirical-based MPC, such as NWMPC, is still new in DMO hydrogenation reactor control. In order to simulate the process, the DMO hydrogenation reactor is modeled using Aspen Plus and Aspen Dynamic software. The Neural Wiener (NW) model is developed based on state space and neural network modeling using a Linear-Nonlinear (L-N) identification approach. A validation test is also performed to verify the accuracy of the NW model. Based on the test, the model accuracy is acceptable with the coefficient of determination (R2) of 0.965 for EG output mole fraction (first output) and R2 of 0.936 for product temperature (second output). The NWMPC capability is evaluated with a PID controller to handle a setpoint change in EG output mole fraction and reject disturbance in the feed stream flow rate. The control performance results have demonstrated the superior ability of the NWMPC to handle such scenarios better than PID in terms of controller action speed and profile.

Exactly defined molecular weight poly(ethylene glycol) allows for facile identification of PEGylation sites on proteins

PEGylation (the covalent attachment of one or more poly(ethylene glycol) (PEG) units to a therapeutic) is a well-established technique in the pharmaceutical industry to increase blood-residence time and decrease immunogenicity. A challenging aspect of PEGylation is the dispersity of PEGylation agents, which results in batch-to-batch variations and analytical limitations. Herein, we present an approach to overcome these limitations by manufacturing a defined molecular weight (dispersity-free) PEGylation agent. We synthesise a defined molecular weight (Mw), linear 5 kDa methoxy-PEG (mPEG) active ester in an efficient and scalable manner using an iterative liquid-phase approach based on Nanostar Sieving. We then perform a comparative study on the random PEGylation and subsequent characterisation of the protein bovine serum albumin (BSA), using both the defined Mw, dispersity-free mPEG active ester, and a commercially available disperse 5 kDa mPEG active ester. We demonstrate that the defined Mw PEG both allows for facile monitoring of chemical modification reactions during the synthesis of the PEGylation agents, and facilitates straightforward identification of the PEGylated fragments within a PEGylated protein via a simple peptide mapping approach using UPLC-MS.