DMSO Solvent Research Articles

Molecular interactions of diphenyldiselenide in DMSO and varied weight % of ethanol in DMSO solvent media at different compositions and temperatures (288.15 to 318.15)K

In the present work, volumetric, rheological, and thermodynamic analysis has been carried out for varied compositions of diphenyldiselenide in dimethyl sulfoxide/(5–25)% w/w of ethanol in dimethyl sulfoxide at seven distinct temperatures varying from 288.15 K to 318.15 K and ambient pressure (0.1 MPa). Through the acquired density data, the volumetric parameters such as apparent molar volume (Vϕ), limiting apparent molar volume (Voϕ), transfer molar volumes (Vϕ,tro), limiting apparent molar expansivity (Eϕo), thermal expansion coefficient (α), and Hepler’s constant (2c) were estimated. By the use of viscosity data, (viscosity A and B coefficients), viscosity B-coefficient of transfer (Btr), change in viscosity B-coefficient with temperature and thermodynamic properties (Δμ10,Δμ20, ΔH20 and TΔS20) were inferred. These parameters have aided in scrutinizing the various feasible interactions existing in the studied systems. From the explored results, we predicted that ion-hydrophillic / hydrophilic-hydrophillic interactions are predominant in the studied systems. Furthermore, through the positive sign of Hepler’s constant and negative sign of change in viscosity B-coefficient with temperature values, we have inferred that diphenyldiselenide behaves as structure maker in dimethyl sulfoxide/(5–25)% w/w of ethanol in dimethyl sulfoxide.

DFT study of the stabilization preconditions of the indoline spiropyrans with a cationic substituent

The computational modeling results are presented in the defining points of the isomerization process of the spiropyrans with cationic vinyl-3H-indolium substituent in the positions 6' and 8' of the 2H-chromene moiety taking into account DMSO solvent. The role of effective conjugation is revealed, that determines the significant difference in the behavior of the studied systems, based on the data of NBO energetic analysis and the atomic charge transfer analysis. The model shows that the interaction between an anion and a cation in these compounds has predominantly electrostatic nature without chemical bonds in the NBO terms

Fabrication of Cellulose Nanofiltration Membranes by Reusing a Binary Solvent of EMIMAc Ionic Liquid and DMSO

Fabrication of Cellulose Nanofiltration Membranes by Reusing a Binary Solvent of EMIMAc Ionic Liquid and DMSO

DMSO-Assisted K3PO4-Catalyzed Cooperative Metal-Free, Base-Free Etherification of Chloroheteroarenes at Low Temperature.

Etherification of chloroheteroarenes performed at low temperatures under metal-free, ligand-free and base-free that is promoted by the cooperative effect of DMSO (solvent) as a promoter and K3PO4 providing the catalytic surface (rather than a base). The protocol exhibits good substrate scope under mild reaction conditions and has also been explored mechanistically.

Non‐approximative Kinetics of Triplet‐Triplet Annihilation at Room Temperature: Solvent Effects on Delayed Fluorescence

AbstractThe molecular processes taking place during triplet‐triplet annihilation (TTA) in solvents at room temperature are examined in detail. Special attention is paid to modelling of the nonlinear kinetic reactions. Using time‐ and spectrally resolved spectroscopy of DPA and Pt/Pd‐OEP based sensitizer and annihilators, it is shown how the kinetic of parameters, such as the triplet energy transfer (TET) and TTA of the rate‐reactions, can be simulated, measured and fitted, without approximations, using a numerical scheme. Studies of DPA in the solvents DMSO, THF and toluene at room temperature revealed that viscosity/diffusion together with the excited triplet lifetime of the annihilator are the most crucial parameters for high TTA induced delayed fluorescence. From an analysis of the experimentally determined rates an efficiency of 16–40 % was determined for the combined TET and TTA processes using THF, DMSO and toluene as solvents. (DPA=9,10‐diphenylanthracene, OEP=2,3,7,8,12,13,17,18‐octaethyl‐21H,23H‐porphyrin)

Finding the Right Solvent: A Novel Screening Protocol for Identifying Environmentally Friendly and Cost-Effective Options for Benzenesulfonamide.

This study investigated the solubility of benzenesulfonamide (BSA) as a model compound using experimental and computational methods. New experimental solubility data were collected in the solvents DMSO, DMF, 4FM, and their binary mixtures with water. The predictive model was constructed based on the best-performing regression models trained on available experimental data, and their hyperparameters were optimized using a newly developed Python code. To evaluate the models, a novel scoring function was formulated, considering not only the accuracy but also the bias-variance tradeoff through a learning curve analysis. An ensemble approach was adopted by selecting the top-performing regression models for test and validation subsets. The obtained model accurately back-calculated the experimental data and was used to predict the solubility of BSA in 2067 potential solvents. The analysis of the entire solvent space focused on the identification of solvents with high solubility, a low environmental impact, and affordability, leading to a refined list of potential candidates that meet all three requirements. The proposed procedure has general applicability and can significantly improve the quality and speed of experimental solvent screening.

Effectiveness of Ethanol Extract of Eugenia polyantha Wigh in Inhibiting Streptococcus mutans

Background: Many microorganisms can be found within the oral cavity, including Streptococcus mutans. The introduction of oral bacteria into the bloodstream can lead to the occurrence of bacteremia and subsequent development of systemic diseases. Traditional medicine uses specific ingredients or herbs employed over successive generations and is widely believed to possess medicinal properties. One example is the bay leaf, scientifically known as Eugenia polyantha Wight. Objective. This study aims to determine the effectiveness of bay leaf extract (Eugenia polyantha Wight.) in inhibiting Streptococcus mutans. Materials and Methods: This type of research is an experimental laboratory with Post-test Only Control Group Design. Testing the effectiveness of antibacterial in this study using the diffusion method by diluting bay leaf extract using DMSO solvent into five concentrations, namely 50%, 25%, 12.5%, 6.25%, and 3.125%, with a sample size of 4 for each concentration. Results: The results showed that bay leaf extract concentrations of 50%, 25%, 12.5%, 6.25%, and 3.125% showed a clear zone around the disc paper in Muller Hinton Agar as a medium for the breeding of Streptococcus mutans bacteria. The formation of a clear zone indicates that the ability of bay leaf extract inhibits the growth of Streptococcus mutans with a mean diameter of inhibition of 10.4 ± 0.2944 mm; 8.9 ± 0.7500 mm; 7.1 ± 0.3202 mm; 6.9 ± 0.2944 mm; and 6.4 ± 0.1826 mm. Conclusion: Eugenia polyantha Wight can inhibit the development of Streptococcus mutans. A concentration of 50% is the best in inhibiting the development of Streptococcus mutans based on the growth zone of bacteria.

In Situ Spectroscopic Probing of Oxygen Crossover Effects on Solid Electrolyte Interphase in Aprotic Lithium‐Oxygen Batteries

AbstractThe solid electrolyte interphase (SEI) on lithium metal anodes (LMA) plays a critical role in affording a long lifespan required for aprotic lithium‐oxygen (Li–O2) batteries. Nevertheless, the crossover of oxygen from the cathode to the anode, an inevitable phenomenon for most of the current Li–O2 batteries, and its effects on the formation and operation of SEI on LMA remain less explored. In this work, a mechanistic study of the SEI formation at a model Cu/dimethyl sulfoxide (DMSO) interface in the presence of oxygen is presented. Direct spectroscopic evidence coupled with theoretical calculation reveals that oxygen can alter the SEI formation pathway and result in distinct SEI properties. Specifically, oxygen can inhibit the fission of the C–S bond of DMSO solvent and therefore reduce the formation of unstable SEI components (e.g., C≡C species) and volatile products (e.g., C2H6 and H2). Thus, the SEI formed under oxygen is more uniform and of less voids, and enables improved electrochemical performance of LMA. This work presents new insights into the oxygen crossover effects on SEI chemistry and is beneficial for designing better LMA/electrolyte interface for future Li–O2 batteries.

Unique solvent effect of water in radical cyclization reaction

The radical cyclization reaction in the aqueous environment by Yorimitsu et al. is revisited using the RISM-SCF-cSED method, a hybrid of quantum chemistry and statistical mechanics theory for molecular liquids. The difference between the barrier height of the forward reaction from the intermediate E-rot, the cyclization step, and that of the backward reaction is crucial to the reaction yield. Considering the effect of hydrogen bonding through the RISM theory, we found that the barrier height for the forward reaction is lower, especially in water. In other words, considering microscopic solvation effects clearly shows the difference between water and DMSO solvents, explaining the remarkable acceleration of the reaction in the aqueous environment.

Organocatalyzed-Aerobic Oxidation of Arylboronic Acids toward the Synthesis of Phenolic Derivatives

Abstract: An effective organocatalyzed ipso-hydroxylation of arylboronic acids for the preparation of phenol derivatives has been demonstrated. The elucidated phenomenon relies on the catalytic performance of 3-nitropyridine under the influence of sub-stoichiometric quantities of KOtBu employing aerobic conditions in DMSO solvent. This method excludes the excess usage of oxidizing agents and bases by providing a user-friendly synthetic tool for the preparation of phenols. It was acclaimed that the 3-nitropyridine acts as an oxygen transferring agent from in situ generated hydrogen peroxide to boronic acid derivatives to furnish the desired molecules. The required hydrogen peroxide was in situ generated from aerial oxygen by the KOtBu-mediated single electron transfer process. The described process is applicable to a variety of arylboronic acids for the preparation of phenols in good yields with considerable resistance of functional moiety.

A highly efficient, green, and straightforward approach for 2,5-diformylfuran synthesis from carbohydrates using carbonized sugarcane bagasse and KBr

2,5-Diformylfuran (DFF) is an important chemical that is utilized to synthesize several valuable chemicals. Direct preparation of DFF from plentiful and inexpensive carbohydrates in a one-pot approach is highly desired. Here, we report the development of a heterogeneous sulfonated amorphous carbon-derived sugarcane bagasse combined with KBr as a catalyst system to convert fructose to DFF in a short time and high yield in DMSO. Several reaction conditions, such as the effect of metal bromide, the effect of KBr and carbon-based solid acid catalyst loading, the effect of temperature, the effect of solvent, the effect of substrate, reusability test, and scale-up synthesis, have been investigated. The optimized yield of DFF was 90 ± 3% at 140 °C in DMSO solvent for 5 h. The approach has several outstanding features, including high chemo-selectivity, high yield, low cost, and recyclable catalyst.

Detection of melanin influence on skin samples based on Raman spectroscopy and optical coherence tomography dual-modal approach.

Melanoma is responsible for more than half of the deaths related to skin cancer in the last few decades. A dual-modality optical biopsy system with Raman spectroscopy and optical coherence tomography approach was built with the goal of achieving noninvasive skin measurement. To mimic melanoma and evaluate the effect of melanin on skin, models have been created by dissolving synthetic melanin in dimethyl sulfoxide and adding it to fresh skin samples. Compared to the untreated samples, morphological images showed that the imaging depth on melanin-treated skin has been increased from 250 μm to 350 μm due to the optical clearing effect of the DMSO solvent, and Raman analysis revealed that relative spectral intensities of melanin-treated samples were lower in the amide-I and CH2 -deformation bands, and higher in the CH2 -twist and C-C stretch bands. Using machine learning for skin type classification, an accuracy of 89% is achieved.

Synthesis, characterization, and investigation photophysicochemical properties of axially 2-hydroxymethyl-1,4-benzodioxan di-substituted Silicon(IV) phthalocyanine

Phthalocyanines are a derivative of macro heterocyclic compound and the different substituents can be added to phthalocyanine ring according to aim. Thus, they can be used in many industrial and scientific areas. One of these important areas is photodynamic therapy (PDT) treatment of cancer. In this study; Silicon(IV) phthalocyanine was preferred because it easily undergoes chemical modification thanks to its axial position and 2-hydroxymethyl-1,4-benzodioxan was used as a substituent to provide solubility in organic solvents thanks to its alkyl and oxygen groups. As a result, a new compound was synthesized with Silicon(IV) as the central metal atom and a soluble substituent in the axial position. The molecular structure of this newly synthesized substance was characterized by UV–Vis, FT-IR, MALDI TOF MS, and 1H NMR. The substance's photophysical and photochemical characteristics were investigated in both DMSO and DMF solvents. Additionally, singlet oxygen quantum yields were calculated as Φ∆: 0.65 in DMSO and Φ∆: 0.69 in DMF and this new compound produced significant singlet oxygen quantum yields, making it potentially useful as a photosensitizer in photodynamic treatment (PDT) for cancer.

Solvent effect on adsorption of benzylidene oxindole to C20 nanocage: A DFT approach

AbstractIn this paper, one of the selective and potent inhibitors named (E)‐3‐benzylidene‐indoline‐2‐one (I), as against different receptor tyrosine kinase in metastasis, angiogenesis, and tumor growth, is inspected in the gas phase and in solution, at B3LYP/6‐311++G** and B3LYP/AUG‐cc‐pVTZ level of theory. A stimulating issue for this biologically active species is the effect of different media on its stability, structure, and energy gap in intermolecular [4 + 2] adsorption of I (as diene) to C20 (as dienophile) to yield (E)‐3‐benzylidene‐indoline‐2‐one[20]fullerene: Ia complex. In going from gas phase to C6H6, C2H4Cl2, EtOH, MeNO2, DMSO, and H2O solvents, individually, the optimization of complex (Ia) leads to the following: (1) The thermodynamic stability; the adsorption energy difference between liquid and gas phase (∆El–g) and dipole moment (μ) seem proportional to the dielectric constant (ε) of the scrutinized media. (2) The kinetic stability; energy difference (∆EL–H) between the frontier molecular orbitals; FMO in different media is altered in the opposite direction of ε. (3) Despite of popular belief that the endo isomer emerges thermodynamically more stable than its corresponding exo isomer, we suggest formation of kinetically more stable exo isomer because of π–π stacking among the benzyl ring and C20 nanocage. (4) The possibility of hetero [4 + 2] cycloaddition is anticipated by the lowest energy barrier of 3.8 kcal/mol probed for exo transition state (TS) in gas phase, while the highest energy barrier of 7.9 kcal/mol corresponds to the endo TS in water. (5) Due to lack of the repulsion type interaction, the exo [4 + 2] cycloaddition of unstable C20 fullerene with the scrutinized oxindole can be carried out thermally at r.t. and currently hold responsible for the origin of stereoselectivity.

Synthesis of 2-aminobenzoxazoles from elemental sulfur mediated cyclization of 2-aminophenols and aryl isothiocyanates

We report a method for cyclization of substituted 2-aminophenols and aryl isothiocyanates to afford 2-aminobenzoxazoles. Reactions proceeded in the presence of elemental sulfur, potassium carbonate base, and DMSO solvent. The conditions were tolerant of useful functionalities including halogen, nitro, and pyridine groups.

Insights into the photo- and thermal induced intramolecular processes of 2-(hydroxyphenyl)benzoxazoles: Experimental and theoretical aspects

It has been established that 2-(2-carboisopropoxy-3,4-dichloro-6-hydroxyphenyl)benzoxazole exhibits solvatochromic properties due to keto-enol equilibrium through reversible GSIPT processes. The photoinitiated processes occurring in the studied molecules of the 2-(2-hydroxyphenyl)benzoxazole are determined by their isomeric form. In the case of enol forms, photoexcitation leads to ESIPT processes accompanied by fluorescence with an anomalous Stokes shift. While the keto forms exhibit negative T-type photochromism due to reversible Z-E photoisomerization. It was found that the thermal keto-enol equilibrium is completely determined by specific interactions with the solvent. On the reaction pathways associated with the excited state proton transfer and further structural transformations on the S1 potential energy surface, twisted intermediates (TICT state) were found that specify various channels for the deactivation of the excited state. Based on the results obtained, the mechanisms of photoinduced processes in heptane and DMSO are proposed. In strong proton acceptor solvents DMSO and DMF, along with the keto-enol tautomeric rearrangement, an equilibrium of dissociation of HBO molecules with the formation of anionic forms was revealed.

Visualization of latent fingerprints using an AIE-active unsymmetrical azine: 2-Naphthol-pyrrole acrylate conjugate and its fluorescent sensing of Cu2+ and S2− ions, smartphone and logic gate applications

A novel, AIE-active unsymmetrical azine-based probe LH2 was designed and developed by simple condensation of ethyl-α-cyano-5-formyl-2-pyrroleacrylate and 1-(hydrazonomethyl)naphthalene-2-ol. The synthesized probe LH2 was characterized by NMR and mass spectrometric methods. Aggregation-induced emission (AIE) behavior of azine derivative, LH2 was examined in a DMSO-H2O mixture, where the compound displayed a weak emission in pure organic solvent DMSO, and the emission was found to be enhanced at 608 nm on increasing the water fraction owing to the occurrence of restriction of intramolecular rotation (RIR). The aggregation feature of LH2 was supported by DLS and FE-SEM studies. Further, the practical application of aggregates was established by imaging latent fingerprints (LFPs) over a TLC glass slide and other platofrms. In addition, the probe LH2 could selectively detect Cu2+ ions colorimetrically and fluorometrically in DMSO: H2O mixture over the other metal ions. More significantly, the naked eye-detectable color change of LH2 has been fruitfully integrated with an RGB color value app to make it suitable for easy on-site and real-time detection of Cu2+ ions. The LH2-Cu2+ ensemble displayed high selectivity towards S2− ion over other anions via displacement approach and such reversible On-Off-On emission characteristics were utilized for the construction of the IMPLICATION logic gate.

Effects of Trichostatin A on the Histone Deacetylases (HDACs), Intrinsic Apoptotic Pathway, p21/Waf1/Cip1, and p53 in Human Neuroblastoma, Glioblastoma, Hepatocellular Carcinoma, and Colon Cancer Cell Lines

Background: The aberrant and altered patterns of gene expression play an important role in the biology of cancer and tumorigenesis. DNA methylation and histone deacetylation are the most studied epigenetic mechanisms. Histone deacetylase inhibitors (HDACIs) such as valproic acid (VPA) and trichostatin A (TSA) are a group of anticancer compounds for the treatment of solid and hematological cancers. Previously, we reported the effect of two HDACIs, valproic acid (VPA) and TSA, on colon cancer and hepatocellular carcinoma (HCC), respectively. The aim of the current in vitro study is to investigate the effects of TSA on the intrinsic apoptotic pathway, p21/Waf1/Cip1 (p21), p53, and histone deacetylases (HDACs) 1, 2 and 3 in human neuroblastoma LAN-1, glioblastoma GBM-29, HCC SMMC7721, and colon cancer COLO 201 cell lines.
 Materials and methods: In this lab-trial study, all three cell lines were seeded at the density of 3 × 105 cells per well and incubated for 24 hours. Then, the cells were treated with TSA based on IC50 values for 24 hours except in the control groups; the control cells were treated with the equal amounts of the DMSO solvent. Subsequently, cell viability, cell apoptosis and gene expression were determined by three techniques including MTT assay, flow cytometry assay, and qRT-PCR.
 Results: The result of qRT-PCR indicated that TSA could increase the expression levels of Bid, BimEL, Noxa, p21, and p53 genes and decrease those of Bcl-xL, RIP, Mcl-1, XIAP, HDACs 1, 2 and 3 significantly (P < 0.0001) by which it inhibited cell growth and induced significant cell apoptosis in LAN-1, GBM-29, SMMC7721, and COLO 201 cell lines (p value<0.001).
 Conclusion: TSA can affect cell apoptotic via the intrinsic apoptotic pathway in LAN-1, GBM-29, SMMC7721, and COLO 201 cell lines.

Water Content-Controlled Formation and Transformation of Concomitant Pseudopolymorph Coordination Polymers.

Two concomitant pseudopolymorph coordination polymers {[Cd2L2(OAc)4]·2DMSO} n (1) and {[CdL(OAc)2]·2.75H2O} n (2) were synthesized by self-assembly of 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (L) and cadmium acetate in DMSO. Single-crystal X-ray diffraction confirmed that 1D ladder structural motifs exist for pseudopolymorphs 1 and 2 which contain DMSO and water guest molecules, respectively. Our study illustrated the active role of solvent water content in obtaining compound 2. We find that the presence of water as an impurity in the DMSO solvent creates the possibility of formation of concomitant pseudopolymorph coordination polymers which is a unique event. Furthermore, our analyses showed the effect of environmental humidity on the transformation of unstable compound 1. 1D ladder pseudopolymorphic compound 1 could be transformed to guest-free 1D linear compound [CdL(OAc)2(H2O)] n (3') (the powder form of single crystals of 3) through a scarce case of water absorption from air. Also, the crystalline material of coordination polymer 3 was transformed to coordination polymer 2 through the dissolution-recrystallization structural transformation process in DMF or DMSO. Our study clarified that the amount of water in the reaction container can control the formation of one of the compounds 2 or 3. In the presence of a significant amount of water, compound 3 (coordinated water) will be produced, whereas if a small amount of water is present, compound 2 (uncoordinated water) is prepared as an exclusive product.

Theoretical Study on Photothermal Properties of Azobenzene Sulfonate/Magnesium-Aluminum Hydroxide Composite Dye.

The assembly of various azo dyes and pigments with inorganic layered materials could develop new types of intercalation materials. The electronic structures and photothermal properties of composite materials (AbS--LDH) constituted by azobenzene sulfonate anions (AbS-) and Mg-Al layered double hydroxide (LDH) lamella were theoretically studied at the M06-2X/def2-TZVP//M06-2X/6-31G(d,p) level using density functional theory and time-dependent density functional theory. Meanwhile, the influences of LDH lamella on the AbS- in AbS--LDH materials were investigated. The calculated results showed that the addition of LDH lamella could lower the isomerization energy barrier of CAbS- anions (CAbS- stands for cis AbS-). The thermal isomerization mechanisms of AbS--LDH and AbS were related to the conformational change of the azo group, out-of-plane rotation and in-plane inversion. The LDH lamella could reduce the energy gap of the n → π* and π → π* electronic transition and lead to a red-shift in the absorption spectra. When a polar solvent DMSO was applied, the excitation energy of the AbS--LDHs was increased, making its photostability stronger than in nonpolar solvent and solvent-free.