Organic Cosolvents Research Articles

Effects of Cosolvent on the Intermolecular Interactions between an Analyte and a Gold Nanostar Surface Studied Using SERS.

For surface-enhanced Raman scattering (SERS), reproducible solution-phase results are typically obtained using nanoparticles functionalized with surface-stabilizing molecules that can prevent the adsorption of analyte molecules with surface affinities lower than those of the stabilizing agent. Herein, we investigate the effects of intermolecular interactions between a nonthiolated analyte and cosolvent to facilitate and modulate analyte adsorption to gold nanostars. SERS, extinction spectroscopy, transmission electron microscopy (TEM), and density functional theory (DFT) calculations are employed in this regard. Tetrahydrofuran (THF) is utilized as a cosolvent in water to facilitate the detection of acetylsalicylic acid (aspirin) on anisotropic gold nanoparticles. Intermolecular interactions between the analyte, solvent, and surface are modulated by changing the solution composition to understand how THF facilitates the SERS detection of aspirin in THF-water cosolvents. SERS signals for 5 mM aspirin arise only in the presence of THF at and above 60 mM, while no signal with or without THF below 60 mM is observed. SERS detection of aspirin is hypothesized to depend on THF forming a hydrogen-bonded complex with aspirin that reduces aspirin hydrophobicity, thus stabilizing the acid form of the molecule and allowing it to weakly interact with the gold nanoparticles. The aspirin-THF complex adsorbs to the gold surface through π-orbital overlap between the aromatic ring and gold, where additional THF weakens orbital overlap. Understanding the mechanism by which organic cosolvents facilitate the SERS detection of nonthiolated analytes such as aspirin, in aqueous media, allows other cosolvents, nonthiolated analytes, and other surfaces to obtain a SERS signal in a variety of systems.

Regeneration of conventional and emerging PFAS-selective anion exchange resins used to treat PFAS-contaminated waters

Anion exchange resins (AERs) have emerged as a promising separation technology to remediate PFAS-contaminated waters due to their improved selectivities and capacities in comparison to legacy activated carbon adsorbents. Presently, site managers choose between AER systems employing resins defined as being ‘regenerable’ with relatively low PFAS selectivity, and PFAS-selective resins that are marketed as ‘single-use’ media intended for disposal upon PFAS breakthrough. However, the potential for these highly-selective adsorbents to be regenerated and/or reused remains poorly characterized. This study presents a comprehensive evaluation of the efficacy of various regenerant solution constituents, mixtures, and operational considerations on the regenerability of both ‘regenerable’ and ‘PFAS-selective’ AERs that were loaded during a pilot treatment study of PFAS-contaminated groundwater. Batch screening of regenerant solution constituents found that both classes of resins may be effectively regenerated using combinations of salt brine and organic cosolvent, with high cosolvent fractions being necessary for PFAS-selective AERs. While neither brine-only nor solvent-only regenerant solutions led to effective PFAS desorption, the efficacy of regeneration with brine/cosolvent mixtures varied with salt type and cosolvent composition. Chloride salts outperformed sulfate and bicarbonate salts, cosolvent efficacy depended on the volume fraction and type used, and highly non-polar solutions led to optimal PFAS desorption. Continuous-flow regeneration experiments showed near-complete PFAS desorption from regenerable AERs using 10 bed volumes (BVs) of 70 % methanolic brine solutions, whereas PFAS-selective resins required more bed volumes (30) of brines with higher methanol content (90 %) or a more hydrophobic cosolvent (n-propanol); increasing regenerant empty-bed contact time had minimal effect on PFAS desorption. > 90 % methanol recovery from the resulting waste regenerant mixtures was accomplished with negligible PFAS contamination using distillation, leaving a minimal volume of a PFAS-concentrated still bottoms waste that may be further treated for PFAS destruction. Life cycle analyses revealed that groundwater treatment using PFAS-selective AERs operated in a regenerable mode have lower environmental impacts and costs than systems using conventional regenerable AERs, and lower treatment costs than systems operated using PFAS-selective resins in a single-use mode. Although counterintuitive, these findings stem from the fact that higher cosolvent requirements for regeneration of PFAS-selective resins lead to greater internal recycling of regenerant solutions and much lower volumes of residual waste still bottoms that require off-site incineration or disposal.

Extraction of polyvinylidene fluoride binder materials for used secondary batteries using supercritical CO2 for an effective battery recycling process

In this study, a polyvinylidene fluoride (PVDF) binder material for secondary batteries was removed using a supercritical CO2 extraction process instead of conventional extraction processes such as leaching and pyrolysis. To determine the optimal process conditions, the phase behavior of the binder in CO2 was studied by measuring the pressure and temperature before the supercritical CO2 extraction. To design an effective extraction process, the extraction time, temperature, and pressure were studied under various experimental conditions using a supercritical extraction system. Various organic cosolvents were used in the experiment to improve the extraction efficiency. According to the experimental result, the optimal extraction conditions were determined to 353.2 K, 10 MPa, and 20 min with dimethylformamide (DMF) cosolvent. Under these process conditions, the removal rate of the binder was 98.8 %. However, there was a significant difference in cell performance such as initial discharge capacity and cycling stability depending on the extraction solvent. Specifically, cycling stability improved in the order of using DMF, NMP, DMSO, and DMAc. The extracted binder material was analyzed by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscope (SEM) to compare the raw and processed materials and evaluate the reusability of the binder material.

Water‐Dispersible BODIPY Multifunctionalized Silicon Oxide Nanoparticles for Glutathione Sensing

AbstractGlutathione (GSH), a thiol containing small peptide, plays pivotal roles in maintaining cellular redox balance, metabolism, detoxification, and scavenging of free radicals. Aberrant GSH levels in cells and tissues are associated with various disorders, underscoring the importance of accurate GSH detection for clinical diagnosis and therapy monitoring. Several molecular probes have been designed as fluorescent‐based GSH sensors. However, their water insolubility and the need of using organic cosolvents hinder their applicability on biological samples. Alternatively, nanomaterials have proven to be highly promising for boosting the precision of treatments and enhancing the accuracy of diagnosing diseases, thanks to their compatibility with biological environments and improved cell uptake. Here, the synthesis and characterization of a boron‐dipyrromethene (BODIPY)‐based probe (PB) are reported, incorporating a fluorescent BODIPY core, chlorine substituents for reaction with GSH, and a linking moiety for conjugation to the surface of silicon oxide nanoparticles (SONPs). Functionalized SONPs with PB are also characterized at the nanoscale using high‐resolution transmission electron microscopy (HR‐TEM), dynamic light scattering (DLS), Zeta potential, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), UV–Vis absorption, and fluorescence spectroscopies, confirming the surface functionalization and water‐dispersibility of functionalized SONPs with PB. GSH sensing is evaluated in aqueous solution, conjugated to SONPs, and in living cells, showing promising potential for ratiometric GSH detection.

Dual Functional Propylene Carbonate Co-Solvent for High Performance Aqueous Zinc-Ion Batteries

In response to the global rise in energy demand, extensive research has spurred the development of batteries with high energy density, affordable cost, and safety. The present Li-ion batteries are attractive due to their high energy density, but their cost and geopolitical accessibility of raw materials, along with safety-related issues, have led researchers to shift their attention towards aqueous batteries.1,2 In aqueous systems, zinc metal has been regarded as the most promising candidate due to its high specific capacity, low redox potential of Zn-metal, environmental friendliness, and low cost. However, challenges such as the dendritic growth of zinc, hydrogen evolution, corrosion, structural degradation and dissolution of oxide cathodes, and poor coulombic efficiencies (CEs) limit their scope. To address these issues, various studies demonstrate the usage of organic co-solvents and additives such as DMSO3, DMC4, etc. at different concentrations in the electrolytes. However, the overall efficiency of the battery performance is hindered due to the large amount requirements of these additives.Along this line, we have studied the electrochemical properties of a hybrid water-highly polar propylene carbonate-based electrolyte, which suppresses water-derived parasitic reactions occurring at both the Zn anode and the V2O5 cathode.5 We have observed a significant enhancement in the battery characteristics, such as high coulombic efficiency and stable capacity, merely by tuning the solvation structure of the electrolyte. Upon a small addition of PC (20 wt.%) in 1M Zn(OTf)2 electrolyte, water molecules solvating Zn2+ ions are replaced by carbonate and triflate anions. The solvated Zn-ion species were further electrochemically reduced to form a ZnF2-rich solid electrolyte interphase (SEI), as demonstrated by post-cycling XPS studies. Moreover, the spectroscopy studies suggest the strong interaction of highly basic carbonyl oxygen of PC with water molecules, which in turn suppresses the dissolution of the cathode, enabling exceptional capacities of ∼300 mAh g−1 over 900 cycles at 1 A g−1. We further demonstrate the significance of the dielectric constant and polarity of an additive or cosolvent in the aqueous zinc ion battery electrolyte by contrasting the performance of cyclic propylene carbonate with acyclic dimethyl carbonate.Reference O. Schmidt, A. Hawkes, A. Gambhir, and I. Staffell, Nature Energy, 2, 1–8 (2017)M. M. Thackeray, C. Wolverton, and E. D. Isaacs, Energy Environ. Sci., 5, 7854–7863 (2012)L. Cao ,D. Li, E. Hu, J. Xu, T. Deng, L. Ma, Y. Wang, X. Q. Yang, and C. Wang, J. Am. Chem. Soc., 142, 21404–21409 (2020)Y. Dong, L. Miao, G. Ma, S. Di, Y. Wang, L. Wang, J. Xua, and N. Zhang, Chem. Sci., 12, 5843–5852 (2021)B. Kakoty, R. Vengarathody, S. Mukherji, V. Ahuja, A. Joseph, C. Narayana, S. Balasubramanian, and P. Senguttuvan, J. Mater. Chem. A, 10, 12597–12607 (2022)

Mixed Crystalline Covalent Heptazine Frameworks with Built-in Heterojunction Structures towards Efficient Photocatalytic Formic Acid Dehydrogenation.

Covalent heptazine frameworks (CHFs) are widely utilized in the recent years as potential photocatalysts. However, their limited conjugated structures, low crystallinity and small surface areas have restricted the practical photocatalysis performance. Along this line, we report herein the synthesis of a kind of mixed crystalline CHF (m-CHF-1) with built-in heterojunction structure, which can efficiently catalyze the formic acid dehydrogenation by visible light driven photocatalysis. The m-CHF-1 is synthesized from 2,5,8-triamino-heptazine and dicyanobenzene (DCB) in the molten salts, in which DCB plays as organic molten co-solvent to promote the rapid and ordered polymerization of 2,5,8-triamino-heptazine. The m-CHF-1 is formed by embedding phenyl-linked heptazine (CHF-Ph) units in the poly(heptazine imide) (PHI) network similar to doping. The CHF-Ph combined with PHI form an effective type II heterojunction structure, which promote the directional transfer of charge carriers. And the integration of CHF-Ph makes m-CHF-1 have smaller exciton binding energy than pure PHI, the charge carriers are more easily dissociated to form free electrons, resulting in higher utilization efficiency of the carriers. The largest hydrogen evolution rate reaches a value of 42.86 mmol h-1 g-1 with a high apparent quantum yield of 24.6 % at 420 nm, which surpasses the majority of other organic photocatalysts.

Water-Dispersible, Magnetically Recyclable Heterogeneous Cobalt Catalyst for C-C and C-N Cross-Coupling Reactions in Aqueous Media.

A cobalt catalyst supported on an iron oxide core, denoted as γ-Fe2O3@PEG@THMAM-Co, has been prepared and characterized by Fourier transform infrared spectroscopy, X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray mapping, thermogravimetry differential thermogravimetry, vibrating sample magnetometry, and inductively coupled plasma. Polyhydroxy end groups in the shell make the catalyst particles dispersible in water, allowing Hiyama, Suzuki, and C-N cross-coupling reactions of aryl iodides and bromides. The catalyst could be recovered by magnetic decantation and reused for at least five successive runs with a negligent decrease in its activity or changes in its morphology. Water as a solvent without requiring additives, surfactants, or organic co-solvents, as well as an abundant and low-cost cobalt catalyst combined with facile recovery, low leaching, and scalability, provides an environmentally and economically attractive alternative to established palladium-catalyzed C-C and C-N coupling reactions.

Regulating solvation structure and enhancing anion-derived solid electrolyte interphase with N, N'-Dimethylpropyleneurea Co-solvent for long-term and dendrite-free Zn metal anodes

Aqueous zinc-ion batteries (ZIBs) are troubled by conventional weak acidic electrolyte, triggering undesirable side reactions and detestable dendrites, thus leading to low Coulombic efficiency (CE) and poor cycle stability. Herein, an organic solvent, N, N′- Dimethylpropyleneurea (DMPU), is introduced as an additive and co-solvent to achieve high-performance ZIBs. As a co-solvent, DMPU can coordinate with Zn2+to replace partial water (H2O) in solvation sheath and limit free H2O activity by H-bond interaction. As an additive, meanwhile, it possesses high Zn absorbability to form a stable inorganic/organic shielding layer for remodeling Zn surface, thus enhancing Zn2+ de-solvation kinetics and restraining unwanted reactions. Distinctly, DMPU regulates non-dendritic Zn plating/stripping behaviors, thus achieving a high CE of 99.3 % and a long cycling life of 2760 h (h) at 2 mA cm−2 and 2 mA h cm−2. The Zn//NaV3O8·1·5H2O (NVO) full cell with DMPU can operate stably for 5850 cycles with a retention of 80.6 % at 3 A g−1. This strategy represents a good point to choose organic co-solvent for practical high-performance ZIBs.

PH-Induced conversion of bolaamphiphilic vesicles to reduction-responsive nanogels for enhanced Nile Red and Rose Bengal delivery

This study details the preparation and investigation of molecular nanogels formed by the self-assembly of bolaamphiphilic dipeptide derivatives containing a reduction-sensitive disulfide unit. The described bolaamphiphiles, featuring amino acid terminal groups, generate cationic vesicles at pH 4, which evolve into gel-like nanoparticles at pH 7. The critical aggregation concentration has been determined, and the nanogels' size and morphology have been characterized through Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM). Circular Dichroism (CD) spectroscopy reveals substantial molecular reconfigurations accompanying the pH shift. These nanogels enhance the in vitro cellular uptake of the lipophilic dye Nile Red and the ionic photosensitizer Rose Bengal into Human colon adenocarcinoma (HT-29) cells, eliminating the need for organic co-solvents in the former case. Fluorescence measurements with Nile Red as a probe indicate the reduction-sensitive disassembly of the nanogels. In photodynamic therapy (PDT) applications, Rose Bengal-loaded nanogels demonstrate notable improvements, with flow cytometry analysis evidencing increased apoptotic activity in the study with HT-29 cells.

Phage-encoded bismuth bicycles enable instant access to targeted bioactive peptides

Genetically encoded libraries play a crucial role in discovering structurally rigid, high-affinity macrocyclic peptide ligands for therapeutic applications. Bicyclic peptides with metal centres like bismuth were recently developed as a new type of constrained peptide with notable affinity, stability and membrane permeability. This study represents the genetic encoding of peptide-bismuth and peptide-arsenic bicycles in phage display. We introduce bismuth tripotassium dicitrate (gastrodenol) as a water-soluble bismuth(III) reagent for phage library modification and in situ bicyclic peptide preparation, eliminating the need for organic co-solvents. Additionally, we explore arsenic(III) as an alternative thiophilic element that is used analogously to our previously introduced bicyclic peptides with a bismuth core. The modification of phage libraries and peptides with these elements is instantaneous and entirely biocompatible, offering an advantage over conventional alkylation-based methods. In a pilot display screening campaign aimed at identifying ligands for the biotin-binding protein streptavidin, we demonstrate the enrichment of bicyclic peptides with dissociation constants two orders of magnitude lower than those of their linear counterparts, underscoring the impact of structural constraint on binding affinity.

Solvent concentration at 50% protein unfolding may reform enzyme stability ranking and process window identification

As water miscible organic co-solvents are often required for enzyme reactions to improve e.g., the solubility of the substrate in the aqueous medium, an enzyme is required which displays high stability in the presence of this co-solvent. Consequently, it is of utmost importance to identify the most suitable enzyme or the appropriate reaction conditions. Until now, the melting temperature is used in general as a measure for stability of enzymes. The experiments here show, that the melting temperature does not correlate to the activity observed in the presence of the solvent. As an alternative parameter, the concentration of the co-solvent at the point of 50% protein unfolding at a specific temperature T in short cU50T\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${c}_{{U}_{50}}^{T}$$\\end{document} is introduced. Analyzing a set of ene reductases, cU50T\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${c}_{{U}_{50}}^{T}$$\\end{document} is shown to indicate the concentration of the co-solvent where also the activity of the enzyme drops fastest. Comparing possible rankings of enzymes according to melting temperature and cU50T\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${c}_{{U}_{50}}^{T}$$\\end{document} reveals a clearly diverging outcome also depending on the specific solvent used. Additionally, plots of cU50\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${c}_{{U}_{50}}$$\\end{document} versus temperature enable a fast identification of possible reaction windows to deduce tolerated solvent concentrations and temperature.

Controlling Interfacial Hydrogen Bonding at a Gold Surface: The Effect of Organic Cosolvents.

Water often serves as both a reactant and solvent in electrocatalytic reactions. Interfacial water networks can affect the transport and kinetics of these reactions, e.g., hydrogen evolution reaction and CO2 reduction reaction. Adding cosolvents that influence the hydrogen-bonding (H-bonding) environment, such as dimethyl sulfoxide (DMSO), has the potential to tune the reactivity of these important electrocatalytic reactions by regulating the interfacial local environment and water network. We investigate interfacial H-bonding networks in water-DMSO cosolvent mixtures on gold surfaces by using surface-enhanced infrared absorption spectroscopy and molecular dynamics simulations. Experiments and simulations show that the gold surface is enriched with dehydrated DMSO molecules and the mixture phase-separates to form water clusters. Simulations show a "buckled" water conformation at the surface, further constraining interfacial H-bonding. The small size of these water clusters and the energetically unfavorable H-bond conformations might inhibit H-bonding with bulk water, suppressing the proton diffusion required for efficient hydrogen evolution reaction processes.

Solvent Replacement Strategies for Processing Pharmaceuticals and Bio-Related Compounds—A Review

An overview of solvent replacement strategies shows that there is great progress in green chemistry for replacing hazardous di-polar aprotic solvents, such as N,N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone (NMP), and 1,4-dioxane (DI), used in processing active industrial ingredients (APIs). In synthetic chemistry, alcohols, carbonates, ethers, eucalyptol, glycols, furans, ketones, cycloalkanones, lactones, pyrrolidinone or solvent mixtures, 2-methyl tetrahydrofuran in methanol, HCl in cyclopentyl methyl ether, or trifluoroacetic acid in propylene carbonate or surfactant water (no organic solvents) are suggested replacement solvents. For the replacement of dichloromethane (DCM) used in chromatography, ethyl acetate ethanol or 2-propanol in heptanes, with or without acetic acid or ammonium hydroxide additives, are suggested, along with methanol acetic acid in ethyl acetate or methyl tert-butyl ether, ethyl acetate in ethanol in cyclohexane, CO2-ethyl acetate, CO2-methanol, CO2-acetone, and CO2-isopropanol. Supercritical CO2 (scCO2) can be used to replace many organic solvents used in processing materials from natural sources. Vegetable, drupe, legume, and seed oils used as co-extractants (mixed with substrate before extraction) can be used to replace the typical organic co-solvents (ethanol, acetone) used in scCO2 extraction. Mixed solvents consisting of a hydrogen bond donor (HBD) solvent and a hydrogen bond acceptor (HBA) are not addressed in GSK or CHEM21 solvent replacement guides. Published data for 100 water-soluble and water-insoluble APIs in mono-solvents show polarity ranges appropriate for the processing of APIs with mixed solvents. When water is used, possible HBA candidate solvents are acetone, acetic acid, acetonitrile, ethanol, methanol, 2-methyl tetrahydrofuran, 2,2,5,5-tetramethyloxolane, dimethylisosorbide, Cyrene, Cygnet 0.0, or diformylxylose. When alcohol is used, possible HBA candidates are cyclopentanone, esters, lactone, eucalytol, MeSesamol, or diformylxylose. HBA—HBA mixed solvents, such as Cyrene—Cygnet 0.0, could provide interesting new combinations. Solubility parameters, Reichardt polarity, Kamlet—Taft parameters, and linear solvation energy relationships provide practical ways for identifying mixed solvents applicable to API systems.

MiRNA and DNA analysis by negative ion electron transfer dissociation and infrared multiple-photon dissociation mass spectrometry

BackgroundThe use of simple and hybrid fragmentation techniques for the identification of molecules in tandem mass spectrometry provides different and complementary information on the structure of molecules. Nevertheless, these techniques have not been as widely explored for oligonucleotides as for peptides or proteins. The analysis of microRNAs (miRNAs) warrants special attention, given their regulatory role and their relationship with several diseases. The application of different fragmentation techniques will be very interesting for their identification. ResultsFour synthetic miRNAs and a DNA sequence were fragmented in an ESI-FT-ICR mass spectrometer using both simple and hybrid fragmentation techniques: CID, nETD followed by CID, IRMPD, and, for the first time, nETD in combination with IRMPD. The main fragmentation channel was base loss. The use of nETD-IRMPD resulted in d/z, a/w, and c/y ions at higher intensities. Moreover, nETD-IRMPD provided high sequence coverage and low internal fragmentation. Native MS analysis revealed that only miR159 and the DNA sequence formed stable dimers under physiological ionic strength. The use of organic co-solvents or additives resulted in a lower sequence coverage due to lesser overall ionization efficiency. NoveltyThis work demonstrates that the combination of nETD and IRMPD for miRNA fragmentation constitutes a suitable alternative to common fragmentation methods. This strategy resulted in efficient fragmentation of [miRNA]5- using low irradiation times and fewer internal fragments while ensuring a high sequence coverage. Moreover, given that such low charge states predominate upon spraying in physiological-like conditions, native MS can be applied for obtaining structural information at the same time.

Performance of Particleboard Made of Agroforestry Residues Bonded with Thermosetting Adhesive Derived from Waste Styrofoam.

This paper investigated the upcycling process of thermoplastic waste polystyrene (WPS) into thermosetting particleboard adhesive using two cross-linkers, namely methylene diphenyl diisocyanate (MDI) and maleic anhydride (MA). The WPS was dissolved in an organic co-solvent. The weight ratio of WPS/co-solvent was 1:9, and 10% of cross-linkers based on the WPS solids content were added subsequently at 60 °C under continuous stirring for 30 min. The adhesive properties, cohesion strength, and thermo-mechanical properties of WPS-based adhesives were examined to investigate the change of thermoplastic WPS to thermosetting adhesives. The bonding strength of WPS-based adhesives was evaluated in particleboard made of sengon (Falcataria moluccana (Miq.) Barneby & J.W. Grimes) wood and rice straw particles at different weight ratios according to the Japanese Industrial Standard (JIS) A 5908:2003. Rheology and Dynamic Mechanical Analysis revealed that modification with MDI and MA resulted in thermosetting properties in WPS-based adhesives by increasing the viscosity at a temperature above 72.7 °C and reaching the maximum storage modulus above 90.8 °C. WPS modified with MDI had a lower activation energy (Ea) value (83.4 kJ/mole) compared to the WPS modified with MA (150.8 kJ/mole), indicating the cross-linking with MDI was much faster compared with MA. Particleboard fabricated from 100% sengon wood particles bonded with WPS modified with MDI fulfilled the minimum requirement of JIS A 5908:2003 for interior applications.

Peroxygenase-Catalyzed Allylic Oxidation Unlocks Telescoped Synthesis of (1S,3R)-3-Hydroxycyclohexanecarbonitrile.

The unmatched chemo-, regio-, and stereoselectivity of enzymes renders them powerful catalysts in the synthesis of chiral active pharmaceutical ingredients (APIs). Inspired by the discovery route toward the LPA1-antagonist BMS-986278, access to the API building block (1S,3R)-3-hydroxycyclohexanecarbonitrile was envisaged using an ene reductase (ER) and alcohol dehydrogenase (ADH) to set both stereocenters. Starting from the commercially available cyclohexene-1-nitrile, a C-H oxyfunctionalization step was required to introduce the ketone functional group, yet several chemical allylic oxidation strategies proved unsuccessful. Enzymatic strategies for allylic oxidation are underdeveloped, with few examples on selected substrates with cytochrome P450s and unspecific peroxygenases (UPOs). In this case, UPOs were found to catalyze the desired allylic oxidation with high chemo- and regioselectivity, at substrate loadings of up to 200 mM, without the addition of organic cosolvents, thus enabling the subsequent ER and ADH steps in a three-step one-pot cascade. UPOs even displayed unreported enantioselective oxyfunctionalization and overoxidation of the substituted cyclohexene. After screening of enzyme panels, the final product was obtained at titers of 85% with 97% ee and 99% de, with a substrate loading of 50 mM, the ER being the limiting step. This synthetic approach provides the first example of a three-step, one-pot UPO-ER-ADH cascade and highlights the potential for UPOs to catalyze diverse enantioselective allylic hydroxylations and oxidations that are otherwise difficult to achieve.

Nanophotosensitizing through Space Charge Transfer Assemblies of Pentacenequinone Derivative for 'Metal-free' Photoamidation Reactions.

The present study demonstrates the influence of small portion (20 %) of organic co-solvent (DMSO/THF/ACN/MeOH) in mixed aqueous media (80 % water) in controlling the size, quantum yield and life time of the through space charge transfer assemblies (TSCT) of pentacenequinone derivative (TPy-PCQ-TPy). Among various solvent systems [H2 O : DMSO (8 : 2), H2 O : THF (8 : 2), H2 O : ACN (8 : 2) and H2 O : MeOH (8 : 2)] examined, highly emissive (Φf =12 %) and nano-sized assemblies having long life time (3.11 ns) were formed in H2 O : DMSO (8 : 2) solvent system. The solvent dependent differences in the size and excited state properties of TPy-PCQ-TPy assemblies are reflected in their photosensitizing behaviour in different solvent systems. Backed by excellent photosensitizing properties, TPy-PCQ-TPy assemblies smoothly catalyse the photoamidation reactions between unactivated/activated aldehydes and secondary amine under mild reaction conditions (visible light irradiation, aerial atmosphere, room temperature) in H2 O : DMSO (8 : 2) solvent mixture. The as prepared assemblies of TPy-PCQ-TPy also exhibit high potential to catalyse the oxidation of benzyl alcohols to aromatic aldehydes, thus, generating a possibility to use aromatic alcohols as the starting material in photoamidation reactions. The real time application of TSCT assemblies has also been demonstrated in gram scale transformation of aromatic aldehydes to aromatic amides and photooxidation of benzyl alcohol to aromatic aldehyde.

An effective ‘salt in dimethyl sulfoxide/water’ electrolyte enables high-voltage supercapacitor operated at −50 °C

Compared with organic electrolytes, aqueous electrolytes exhibit significantly higher ionic conductivity and possess inherent safety features, showcasing unique advantages in supercapacitors. However, challenges remain for low-salt aqueous electrolytes operating at high voltage and low temperature. Herein, we report a low-salt (0.87 m, m means mol kg−1) ‘salt in dimethyl sulfoxide/water’ hybrid electrolyte with non-flammability via hybridizing aqueous electrolyte with an organic co-solvent of dimethyl sulfoxide (hydrogen bond acceptor). As a result, the 0.87 m hybrid electrolyte exhibits enhanced electrochemical stability, a freezing temperature below −50 °C, and an outstanding ionic conductivity of 0.52 mS cm−1 at −50 °C. Dimethyl sulfoxide can anchor water molecules through intermolecular hydrogen bond interaction, effectively reinforcing the stability of water in the hybrid electrolyte. Furthermore, the interaction between dimethyl sulfoxide and water molecules diminishes the involvement of water in the generation of ordered ice crystals, finally facilitating the low-temperature performance of the hybrid electrolyte. When paired with the 0.87 m ‘salt in dimethyl sulfoxide/water’ hybrid electrolyte, the symmetric supercapacitor presents a 2.0 V high operating voltage at 25 °C, and can operate stably at −50 °C. Importantly, the suppressed electrochemical reaction of water at −50 °C further leads to the symmetric supercapacitor operated at a higher voltage of 2.6 V. This modification strategy opens an effective avenue to develop low-salt electrolytes for high-voltage and low-temperature aqueous supercapacitors.

A Green Asymmetric Bicyclic Co-Solvent Molecule for High-Voltage Aqueous Lithium-Ion Batteries.

Hybridizing aqueous electrolytes with organic co-solvents can effectively expand the voltage window of aqueous electrolytes while reducing salt usage, but most reported co-solvents are usually flammable and toxic, hardly achieving compatibility between safety and electrochemical performance. Here, a new non-flammable and non-toxic low-salt-concentration (1.85 m) aqueous electrolyte is reported using the green co-solvent isosorbide dimethyl ether (IDE). Owing to its unique 3D molecular structure, IDE can form a five-membered ring structure by binding the Li ion. The steric hindrance effect from IDE weakens its solvation ability, generating anion-participated solvation structures that produce a robust and uniform LiF-rich solid electrolyte interphase layer while containing elastic IDE-derived organics. Moreover, the multiple O atoms in IDE can effectively regulate the intermolecular hydrogen bonding networks, reducing H2O molecule activity and expanding the electrochemical window. Such unique solvation structures and optimized hydrogen bonding networks enabled by IDE effectively suppress electrode/electrolyte interfacial side reactions, achieving a 4.3 V voltage window. The as-developed Li4Ti5O12(LTO)||LiMn2O4(LMO) full cell delivers outstanding cycling performance over 450 cycles at 2 C. The proposed green hybrid aqueous electrolyte provides a new pathway for developing high-voltage aqueous lithium batteries.

A critical factor in reactive oxygen species (ROS) studies: the need to understand the chemistry of the solvent used: the case of DMSO.

Reactive oxygen species (ROS) play critical roles in normal physiological processes including cellular signaling and immune responses. Various pathological conditions including infections of various types, inflammation, cancer, and respiratory conditions are associated with elevated levels of ROS. Therefore, there is widespread interest in understanding ROS concentrations under various pathophysiological conditions for diagnostic and therapeutic applications including ROS-triggered drug delivery. However, in determining ROS concentration, there are major concerns of inappropriate use of various methods that lead to erroneous results; this has prompted the publication of a consensus paper in Nature Metabolism by a group of ROS experts stating "Unfortunately, the application and interpretation of these measurements are fraught with challenges and limitations. This can lead to misleading claims." Along this line, we have identified an overlooked factor, which can significantly skew the results and results interpretation: the organic co-solvent. DMSO is one of the most widely used organic co-solvents to dissolve a reagent for bioassays. Herein, we describe the rapid oxidation of DMSO by hypochlorite and how this oxidation impacts results of ROS determination in buffer, cell culture media, cell culture, and cell lysates. We hope to use this one example to draw attention to the convoluted roles that DMSO and possibly other organic co-solvents can play and skew experimental results. We also hope to stimulate additional studies to bring more rigor to studying ROS concentration and biology.