Acid In Dimethyl Sulfoxide Research Articles

Highly efficient and straightforward conversion of sugarcane bagasse into high value-added chemicals using carbonaceous catalyst in deep eutectic solvent

The conversion of biomass to 5-hydroxymethylfurfural (HMF), 2,5-diformylfuran (DFF), levulinic acid (LA), formic acid (FA), and other platform chemicals is attracting more attention. In this work, the catalysts were prepared from sugarcane bagasse with H2SO4 (BG-H2SO4) and with p-TsOH (BG-TsOH) containing –SO3H, –COOH, and –OH groups on the surface and used for the conversion of sugarcane bagasse into these valuable compounds. The cellulose was extracted from the sugarcane bagasse by an acetate-based ionic liquid and used as a starting material for this conversion. After investigation, the optimal conditions were BG-H2SO4 (50 mg), MnCl2.4H2O (1 mmol), and [DMSO][ChCl] deep eutectic solvent (10 mmol) at 120 °C for 10 h. The highest yields of valuable products were 17.59 % of HMF, 15.92 % of DFF, 20.02 % of FA, and 41.09 % of LA. Catalytic performance was compared to traditional methods using sulfuric acid in dimethyl sulfoxide (DMSO) or 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid. The BG-H2SO4 catalyst could be recovered and reused four times. Based on the study, the combination of BG-H2SO4, MnCl2.4H2O, and [DMSO][ChCl] demonstrated an efficient and sustainable reaction medium for biomass conversion. Our work will help the scientific community apply revolutionary technologies to sustainably create sophisticated materials with high technological application.

Architecture of the rings of 5-arylidenerhodanine derivatives versus P-gp inhibition.

5-Arylidene derivatives of rhodanine show various biological activities. The new crystal structures of five derivatives investigated towards ABCB1 efflux pump modulation are reported, namely, 2-[5-([1,1'-biphenyl]-4-ylmethylidene]-4-oxo-2-thioxothiazolidin-3-yl)acetic acid dimethyl sulfoxide monosolvate, C18H13NO3S2·C2H6OS (1), 4-[5-([1,1'-biphenyl]-4-ylmethylidene]-4-oxo-2-thioxothiazolidin-3-yl)butanoic acid, C20H17NO3S2 (2), 5-[4-(benzyloxy)benzylidene]-2-thioxothiazolidin-4-one, C17H13NO2S2 (3), 4-{5-[4-(benzyloxy)benzylidene]-4-oxo-2-thioxothiazolidin-3-yl}butanoic acid, C21H19NO4S2 (4), and 5-[4-(diphenylamino)benzylidene]-2-thioxothiazolidin-4-one, C22H16N2OS2 (5). Compounds 1 and 3-5 crystallize in the triclinic space group P-1, while 2 crystallizes in the monoclinic space group P21/n, where the biphenyl moiety is observed in two positions (A and B). Two molecules are present in the asymmetric unit of 5 and, for the other four compounds, there is only one molecule; moreover, 1 crystallizes with one dimethyl sulfoxide molecule. The packing of the molecules containing a carboxyl group (1, 2 and 4) is determined by O-H...O hydrogen bonds, while in the other two compounds (3 and 5), the packing is determined by N-H...O hydrogen bonds. Additionally, induced-fit docking studies have been performed for the active compounds to investigate their putative binding mode inside the human glycoprotein P (P-gp) binding pocket.

Aquatic Diatoms-Inspired Universal Adhesive Coacervates Triggered by Water.

Adhesives with strong underwater adhesion performance are urgently needed in diverse areas. However, designing adhesives with long-term stability to diverse materials underwater in a facile way is challenging. Here, inspired by aquatic diatoms, a series of novel biomimetic universal adhesives is reported that shows tunable performance with robust and long-lasting stable underwater adhesion to various substrates, including wet biological tissues. The versatile and robust wet-contact adhesives are pre-polymerized by N-[tris(hydroxymethyl)methyl]acrylamide, n-butyl acrylate, and methylacrylic acid in dimethyl sulfoxide and spontaneously coacervated in water triggered by solvent exchange. The synergistic interaction between hydrogen bonding and hydrophobic interaction allows the hydrogels with instant and strong adhesion to various substrate surfaces. The slowly formed covalent bonds enhance cohesion and adhesion strength in hours. The spatial and timescale-dependent adhesion mechanism endows the adhesives with strong and long-lasting stable underwater adhesion to be coupled with fault-tolerant convenient surgical operations.

2-Iodoxybenzoic Acid–Dimethyl Sulfoxide (IBX-DMSO)-Promoted Oxidative Aromatization of Spiro[2.5]octa-4,7-dien-6-one

AbstractA 2-iodoxybenzoic acid (IBX)–dimethyl sulfoxide (IBX-DMSO)-promoted oxidative aromatization of spiro[2.5]octa-4,7-dien-6-ones has been developed. A series of substrates with various substitutions were transformed into oxidative aromatization products in good to excellent yields. This oxidative aromatization features environmentally friendly reagents, high efficiency, a broad substrate scope, broad functional-group tolerance, and mild reaction conditions.

Thermodynamic and volumetric properties of hydroxamic acids in dimethylsulfoxide at T = (298.15 to 313.15) K

Physical properties, such as density, (ρ) and refractive index, (n) of three hydroxamic acids (N-phenylbenzo-, N-phenyl-4-methyl-3-nitrobenzo-, and N-phenyl-4-nitrobenzo-) were measured in dimethyl sulfoxide (DMSO) as a function of concentrations at T = (298.15, 303.15, 308.15, and 313.15) K . The apparent molar volumes (Vϕ0), limiting apparent molar volumes (Vϕ0) at infinite dilution, slope (SV*) and Hepler's constant (∂2Vϕ0∂T2) are calculated from the experimental values of densities (ρ) by applying the Masson's equation. The apparent molar expansibilities at infinite dilution (ϕ0E), molar volumes (V), thermal expansion coefficient (α2) and the excess molar volumes (VE) are also computed. The precise refractive indices (n) data have been used to evaluate the steric parameters viz. molar refractions (RM), polarizability (α) and excess molar refraction (RME) of these molecules. It is inferred from these results that the above mentioned drugs act as structure-making compound due to hydrophobic hydration of the molecules in the drug.

Electrochemical and spectral investigation of copper (II) complexes with various hydroxynicotinic acids in dimethylsulfoxide

• Cyclic voltammetry of various hydroxynicotinic acid (OHNA) ligands in dimethylsulfoxide. • Cyclic voltammetry of copper (II) complexes with various hydroxynicotinic acids in dimethylsulfoxide. • UV-Visible spectroscopy of various hydroxynicotinic acid (OHNA) ligands. • UV-Visible spectroscopy of copper (II) complexes with various hydroxynicotinic acids. • FT-IR spectroscopy of various hydroxynicotinic acids and their complexes. Herein reported the spectral and electrochemical properties of various hydroxynicotinic acids (OHNAs) viz; 2-, 3-, 4-, 5-, and 6-hydroxynicotinic acids and their copper(II) complexes were investigated in 1:2 (metal: ligand) molar ratio in dimethylsulfoxide by using cyclic voltammetry (CV). All cyclic voltammetric waves in OHNA-copper (II) complexes exhibits to OHNA-ligand based electrochemical reactions because of the similarities of the cyclic voltammograms between the OHNAs ligand and copper (II) complexes. The electrochemical behavior of copper(II) complexes with OHNAs ligand have shown that the reduction potential (Epc) shift toward less negative potential, while the oxidation peak potential (Epa) becomes more negative as compared to the used respective ligand clearly indicating that the reduction becomes easier on complexation. The FT-IR and electronic absorption spectroscopy of the hydroxynicotinic acids and their complexes have also been recorded in water/DMSO.

Sulfation of arabinogalactan with sulfamic acid under homogeneous conditions in dimethylsulfoxide medium.

Sulfation of larch wood arabinogalactan (AG) with sulfamic acid in dimethylsulfoxide (DMSO) medium in the presence of urea was studied for the first time. The use of DMSO as a solvent instead of more toxic 1,4-dioxane allows to sulfate AG under homogeneous conditions. The sulfated AG with a high sulfur content (12.0–12.5 wt %) was produced by sulfation at a temperature of 85–90 °C, the molar ratio of AG / sulfating agent equal to 1:0.85 during 2–3 h. The introduction of sulfate groups into the structure of arabinogalactan was confirmed by the appearance of new absorption bands in FTIR and FT Raman spectra, characteristic for the vibrations of the sulfate groups. It was proved by 13C NMR spectroscopy that the predominant substitution of the primary hydroxyl groups at C6 carbon atoms of the terminal galactose units of main and side chains of arabinogalactan takes place. Simultaneously, the hydroxyl groups associated with C2 and C4 carbon atoms of galactose unit of the main chain are only partially sulfated. According to results of GPC study, the sulfated AG is characterized by a narrow molecular weight distribution with an average molecular weight of 18.8 kDa and a polydispersity of 1.3.Supplementary InformationThe online version contains supplementary material available at 10.1007/s00226-021-01341-2.

Starch Formates: Synthesis and Modification.

Starch can be efficiently converted into the corresponding formates homogeneously using N-formyl imidazole obtained by the reaction of 1,1′-carbonyldiimidazole and formic acid in dimethyl sulfoxide as a solvent. Starch formates are soluble in polar aprotic solvents, not susceptible against hydrolysis, and not meltable. Thermoplastics could be generated by conversion of starch formates with long-chain fatty acids exemplified by the conversion with lauroyl chloride in N,N-dimethylacetamide, leading to mixed starch laurate formates. The mixed esters show melting temperatures mainly dependent on the amount of laurate ester moieties.

Crystal structure and Hirshfeld surface analysis of 2-[(2-oxo-2H-chromen-4-yl)-oxy]acetic acid dimethyl sulfoxide monosolvate.

The title compound, C11H8O5·(CH3)2SO, is a new coumarin derivative. The asymmetric unit contains two coumarin mol-ecules (A and B) and two di-methyl-sulfoxide solvent mol-ecules (A and B). The dihedral angle between the pyran and benzene rings in the chromene moiety is 3.56 (2)° for mol-ecule A and 1.83 (2)° for mol-ecule B. In mol-ecule A, the dimethyl sulfoxide sulfur atom is disordered over two positions with a refined occupancy ratio of 0.782 (5):0.218 (5). In the crystal, mol-ecules are linked by O-H⋯O hydrogen bonds, forming chains running along the c-axis direction. The chains are linked by C-H⋯O hydrogen bonds, forming layers parallel to the ac plane. In addition, there are also C-H⋯π and π-π inter-actions present within the layers. The inter-molecular contacts in the crystal have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots, which indicate that the most important contributions to the packing are from H⋯H (33.9%) and O⋯H/H⋯O (41.2%) contacts.

Mechanisms and kinetics of non-isothermal polymerization of N,N′-bismaleimide-4,4′-diphenylmethane with barbituric acid in dimethyl sulfoxide

Mechanisms and kinetics of non-isothermal polymerization of N,N′-bismaleimide-4,4′-diphenylmethane (BMI) with barbituric acid (BTA) in dimethyl sulfoxide (DMSO) were investigated. The polymerization of BMI with BTA in DMSO was characterized by using differential scanning calorimeter (DSC), electron spin resonance (ESR) and 1H-NMR techniques. The polymerization was primarily governed by the Michael addition reaction and aza- Michael addition reaction mechanisms. By contrast, free radical polymerization mechanism of BMI/BTA could be ruled out in DMSO medium. Model-free (isoconversional) method in combination with model-fitting method were used to determine triplet kinetic parameters for the polymerization of BMI with BTA in DMSO. Average activation energy (Eα) and pre-exponential factor (Aα) were ca. 51 kJ mol−1 and 1.33 × 106 min−1 in the fractional conversion (α) range 0.1–0.9, respectively. The polymerization of BMI with BTA was primarily reaction-controlled [f(α) = (1 − α)].

Комплексы меди [CuBr2(DMSO-O)3] и [Cu(DMSO-O)4SF6]. Синтез и строение

The dissolution of copper (II) bromide and copper (II) fluoride in the presence of hydrofluoric acid in dimethyl sulfoxide, followed by slow evaporation of the solvent, have synthesized copper complexes [CuBr 2 (DMSO- O ) 3 ] ( 1 ) and [Cu(DMSO- O ) 4 SF 6 ] ( 2 ). They have been structurally characterized. The X-ray diffraction pattern has been obtained at 293 K on an automatic diffractometer D8 Quest Bruker (Mo K α -radiation, λ = 0.71073 Å, graphite monochromator) of crystals 1 [C 6 H 18 O 3 S 3 Br 2 Cu, M 457,74, the monoclinic syngony, the symmetry group P 2 1 /c; cell parameters: a 8.812(6), b 15.335(11), c 12.272(8) Å, α = 90.00 degrees, β = 105.82(3) degrees, γ = 90,00 degrees; V = 1595.5(19)Å 3 ; the crystal size is 0.59 × 0.32 × 0,24 mm; intervals of reflection indexes are –13 ≤ h ≤ 11, –23 ≤ k ≤ 23, –18 ≤ l ≤ 18; total reflections 45529; independent reflections 5832; R int 0.0971; GOOF 1.001; R 1 = 0.0497, wR 2 = 0.1073; residual electron density 0.77/–1.36 e/Å 3 ] and 2 [C 8 H 24 O 4 F 6 S 5 Cu, M 522.11, the triclinic syngony, the symmetry group P –1; cell parameters: a 10.325(18), b 10.428(18), c 10.60(2) Å, α = 77.93(11) degrees, β = 89.49(9) degrees, γ = 68.12(6) degrees; V = 1033(3) Å 3 ; the crystal size is 0.47×0.16×0.13 mm; intervals of reflection indexes are –11 ≤ h ≤ 11, –12 ≤ k ≤ 12, –12 ≤ l ≤ 12; total reflections 9324; independent reflections 3307; R int 0.0709; GOOF 1.029; R 1 = 0.0555, wR 2 = 0.1309; residual electron density 0.64/–0.82 e/Å 3 ], the copper atoms have a distorted square-pyramidal coordination (the trans -OCuO and trans -OCuBr angles are 165.68(11)° and 143.37(10)° ( 1 ); trans -OCuO are 163.8(2), 169.0(2)° ( 2 ); the Cu-Br and Cu-O bond lengths are 2.4681(14) Å and 2.5922(14) Å ( 1 ), 1.944(3)–2.054(3) Å ( 1 ) and 1.940(6)–1.956(5) Å ( 2 ) respectively). Fragment SF 6 in 2 (the FSF trans -angles 178.8(2)–179.7(3)°, cis -angles 88.7(2)–91.0(3)°) linked to the central copper atom (the Cu–F bond length 2.208(6) Å). The structural organization of crystals 1 and 2 is controlled by intermolecular bonds O (DMSO) ∙∙∙H–С (DMSO) (2,57 Å) and Cu–Br∙∙∙H–C (DMSO) (2.89–3.04 Å) ( 1 ), S–F∙∙∙H–C (DMSO) (2.32–2.60 Å) ( 2 ). Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1883471, 1898916; deposit@ccdc.cam.ac.uk; https://www.ccdc.cam.ac.uk).

A Tough and Stiff Hydrogel with Tunable Water Content and Mechanical Properties Based on the Synergistic Effect of Hydrogen Bonding and Hydrophobic Interaction

Hydrogels are usually recognized as soft and weak materials, the poor mechanical properties of which greatly limit their applications as structural elements. Designing of hydrogels with high strength and high modulus has both fundamental and practical significances. Herein we report a series of tough, stiff, and transparent hydrogels facilely prepared by copolymerization of 1-vinylimidazole and methacrylic acid in dimethyl sulfoxide followed by solvent exchange to water. The equilibrated hydrogels with water content of 50–60 wt % possessed excellent mechanical properties, with tensile breaking stress, breaking strain, Young’s modulus, and tearing fracture energy of 1.3–5.4 MPa, 40–330%, 20–170 MPa, and 600–4500 J/m2, respectively. These tough hydrogels were also stable over a wide pH range (2 ≤ pH ≤ 10), resulting from the formation of dense and robust hydrogen bonds between imidazole and carboxylic acid groups. Moreover, the water content and mechanical properties of one gel can be adjusted over a wide r...

Metal-Free and Selective Oxidation of Furfural to Furoic Acid with an N-Heterocyclic Carbene Catalyst

Aerobic oxidation of biomass-derived furfural to furoic acid was studied with an N-heterocyclic carbene as a homogeneous catalyst. Carbene species generated in situ on 1,3-bis(2,4,6-trimethylphenyl) imidazolium chloride with a strong organic base (1,8-diazabicyclo[5.4.0]undec-7-ene) was highly active and selective for the formation of furoic acid in dimethyl sulfoxide at 40 °C. This reaction initiates the formation of a Breslow intermediate between an N-heterocyclic carbene and a furfural molecule and the subsequent activation of molecular O2. While the active carbene catalyst promoted furfural dimerization to afford furoin as a side reaction, furoin was decomposed into the Breslow intermediate and furfural through a reverse reaction, which were then converted quantitatively to furoic acid. Kinetic studies revealed that the apparent activation energy for this furfural oxidation was only 20 kJ mol–1, which is significantly lower than that with a supported Au catalyst (30.4 kJ mol–1). The N-heterocyclic car...

Improved Method for Measuring Lipoxygenase Activity in Barley and Malt

ABSTRACTFor the lipoxygenase (LOX) activity assay, we dissolved the substrate linoleic acid in dimethyl sulfoxide (DMSO) rather than the usual 1% Tween 20. Activity curves with LOXSoybean were established and nine measurements within more than a month showed a standard deviation of the linear slopes of 4.8%. LOX activities in barley and the corresponding malt samples were followed at 10 min time-points for one hour. The activities during the time-course had the tendency to decrease at the end of the extraction time. LOX activity was then converted with the use of a LOXSoybean standard curve into absolute amounts of LOX (LOXeq), assuming the same specific activities for LOX from soybean and the ones from barley and malt, respectively. Furthermore, the protein amounts of all the extracts were determined and, finally, with the LOXeq content and the protein amount, the data were expressed in µg LOXeq/mg protein. The values of the barley samples ranged from 10.7 to 18.2 µg LOXeq/mg protein and the malt samples from 1.1 to 2.5 µg LOXeq/mg protein. As expected, the amount of LOX in malt was over 80% less, than the amount in barley.

Correction to "Theoretical Study on the Acidities of Chiral Phosphoric Acids in Dimethyl Sulfoxide: Hints for Organocatalysis".

Correction to "Theoretical Study on the Acidities of Chiral Phosphoric Acids in Dimethyl Sulfoxide: Hints for Organocatalysis".

Crystal structures of hibiscus acid and hibiscus acid dimethyl ester isolated from Hibiscus sabdariffa (Malvaceae).

The biologically active title compounds have been isolated from Hibiscus sabdariffa plants, hibiscus acid as a dimethyl sulfoxide monosolvate [systematic name: (2S,3R)-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carb-oxy-lic acid dimethyl sulfoxide monosolvate], C6H6O7·C2H6OS, (I), and hibiscus acid dimethyl ester [systematic name: dimethyl (2S,3R)-3-hy-droxy-5-oxo-2,3,4,5-tetra-hydro-furan-2,3-di-carboxyl-ate], C8H10O7, (II). Compound (I) forms a layered structure with alternating layers of lactone and solvent mol-ecules, that include a two-dimensional hydrogen-bonding construct. Compound (II) has two crystallographically independent and conformationally similar mol-ecules per asymmetric unit and forms a one-dimensional hydrogen-bonding construct. The known absolute configuration for both compounds has been confirmed.

Synthesis and structure of ruthenium complexes [Ph3PCH2C6H4F-4]2[RuCl6] and [Ph3PCH2C6H4F-4][trans-RuCl4(dmso-S)2

The reaction of (4-fluorobenzyl)triphenylphosphonium chloride with ruthenium(iii) chloride hydrate in the presence of hydrochloric acid in dimethyl sulfoxide affords the complex [Ph3PCH2C6H4F-4]2[RuCl6]. In the absence of hydrochloric acid, the reaction gives the complex [Ph3PCH2C6H4F-4][trans-RuCl4(dmso-S)2]. The structures of the complexes were studied by 1H, 19F, and 31P NMR spectroscopy and X-ray diffraction.

The contraceptive efficacy of intravas injection of Vasalgel\u2122 for adult male rhesus monkeys

BackgroundOptions for male contraception are limited. The purpose of this study was to use a nonhuman primate model to evaluate Vasalgel™, a high molecular weight polymer being developed as a contraceptive device for men.MethodsSixteen adult male rhesus monkeys received intravas injections of Vasalgel, consisting of 25% styrene maleic acid in dimethyl sulfoxide. After a one-week recovery, males were returned to outdoor group housing, which included at least 3 and up to 9 intact, breeding females with a successful reproductive history.ResultsTreated males have had no conceptions since Vasalgel injections. All males were housed with intact females for at least one breeding season and seven have been almost continually housed with females for 2 years. Complications were minor and included one incident of incorrect placement of Vasalgel into the vas deferens and the development of a sperm granuloma in one animal. Three unilateral vasectomies were performed, one was necessary for incorrect placement of Vasalgel, the other two were elective.ConclusionsIntravas injection of Vasalgel in sexually mature adult male rhesus monkeys was effective in preventing conception in a free-living, group environment. Complications were few and similar to those associated with traditional vasectomy.

Synthesis of polyacrylates from limonene by catalytic oxidation and multi-component reaction

A new strategy to obtain polyacrylates from limonene via regioselective catalytic acetoxylation, catalytic isomerization and subsequent Passerini three-component reaction (P-3CR) is described. The acetoxylated limonene derivative, selectively functionalized at the exocyclic double bond, was synthesized by a palladium-catalyzed C-H activation process in the presence of para-benzoquinone (BQ) as reoxidation agent and acetic acid in dimethyl sulfoxide. The obtained product was further saponified and subsequently isomerized under mild conditions into the corresponding aldehyde using a hydrogen-activated palladium catalyst. The resulting aldehyde, acrylic acid and various isocyanides were then used in the Passerini three-component reaction (P-3CR) in order to obtain several acrylate monomers in a straightforward and atom economic process. In subsequent free radical polymerizations using AIBN as thermal initiator, polyacrylates with molecular weights (Mn) up to 30kDa were obtained and carefully characterized by SEC, NMR and DSC analysis.

Ascorbyl palmitate synthesis in an organic solvent system using a Celite-immobilized commercial lipase (Lipolase 100L).

Ascorbyl palmitate was synthesized using a Celite-immobilized commercial lipase (Lipolase 100L) in dimethylsulfoxide (DMSO) as an organic solvent system. Lipase immobilized by surface adsorption onto Celite 545 matrix and subsequently exposed to 1 % glutaraldehyde showed 75 % binding of protein. The Celite-bound lipase was optimally active at 75 °C and pH 8.5 under shaking and showed maximum hydrolytic activity toward p-NPP as a substrate. The bound lipase was found to be stimulated only in the presence of Al3+ and EDTA. All surfactants (Tween-20, Tween-80 and Triton X-100) had an inhibitory effect on lipase activity. The optimization of various reaction conditions of ascorbyl palmitate was achieved considering one factor at a time. The esterification of ascorbic acid and palmitic acid was carried out with 1 M ascorbic acid and 2.5 M palmitic acid in DMSO at 75 °C for 18 h under shaking (120 rpm). Molecular sieves had an important effect on the ester synthesis resulting in an enhanced yield. The by-product (H2O) produced in the reaction was scavenged by the molecular sieves (20 mg/ml) added in the reaction mixture which enhanced the ester yield to 80 %. The characterization of synthesized ester was done through FTIR spectroscopy.