One-pot Solvent-free Synthesis Research Articles

Sustainable one-pot solvent-free enzymatic synthesis of capric acid-rich structured lipids to enhance the nutritional value of grape seed oil

Grape seed oil (GSO) is a valuable resource for the pharmaceutical, cosmetic, and food industries due to its fatty acid composition, which provides anti-inflammatory, cardioprotective, antimicrobial, and anticancer properties. GSO is also recognized for its sensory attributes and serves as an essential component in our dietary intake, providing vital fatty acids for metabolic reactions. The enzymatic synthesis of structured lipids (SL) using GSO was investigated in this study. The SL was created by incorporating medium chain fatty acids (capric acid – C10) at the sn-1 and sn-3 positions and long chain fatty acids in the internal position of the triacylglycerols (TAG). GSO was selected based on its composition rich in unsaturated fatty acids, mainly linoleic acid. The acidolysis reactions were catalyzed by an immobilized commercial lipase Lipozyme TLIM®. The incorporation degree of C10 into GSO reached 36%. Health lipid indices were calculated to determine the C10 incorporation effect on the improvement of nutritional quality of oil. The SL showed lower oxidative stability index (OSI) values than the original oil and higher degree of fatty acid (DFA) values. The simpler, solvent-free method not only enhances the health benefits of oils but also gives valuable properties to GSO, making it an even more attractive option for food industries.

One-pot synthesis of alginate-antimicrobial peptide nanogel.

Nanosized alginate-based particles (NAPs) were obtained in a one-pot solvent-free synthesis procedure, achieving the design of a biocompatible nanocarrier for the encapsulation of IbM6 antimicrobial peptide (IbM6). IbM6 is integrated in the nascent nanosized hydrogel self-assembly guided by electrostatic interactions and by weak interactions, typical of soft matter. The formation of the nanogel is a dynamic and complex process, which presents an interesting temporal evolution. In this work, we optimized the synthesis conditions of IbM6-NAPs based on small-angle X-ray scattering (SAXS) measurements and evaluated its time evolution over several weeks by sensing the IbM6 environment in IbM6-NAPs from photochemical experiments. Fluorescence deactivation experiments revealed that the accessibility of different quenchers to the IbM6 peptide embedded in NAPs is dependent on the aging time of the alginate network. Lifetimes measurements indicate that the deactivation paths of the excited state of the IbM6 in the nanoaggregates are reduced when compared with those exhibited by the peptide in aqueous solution, and are also dependent on the aging time of the nanosized alginate network. Finally, the entrapment of IbM6 in NAPs hinders the degradation of the peptide by trypsin, increasing its antimicrobial activity against Escherichia coli K-12 in simulated operation conditions.

Catalytic One-pot Solvent Free Synthesis, Biological Activity, and Docking Study of New Series of 1, 3-thiazolidine-4-one Derivatives Derived from 2- (P-tolyl) Benzoxazol-5-amine.

In this study, a simple triethylammonium salt of phosphoric acid (triethylammonium dihydrogen phosphate) (4) in the liquid state was utilized as an inexpensive, efficient one-pot three components, solvent-free synthesis of thiazolidine-4-one derivatives, with good to excellent yields. Techniques such as FT-IR, 1H-NMR, 13C-NMR, 13C-NMR-DEPT-135, and MS. were used for the structural elucidation. The high biotic efficiency of the newly obtained compounds was confirmed by in vitro antimicrobial action against Gram-positive (S. Aureus), Gram-negative bacteria (P. Aeruginosa and E. Coli) and antifungal activity (C. Albicans) via microplate titer dilution technique. Finally, a molecular docking study was performed with a resolved crystal structure of S. Aureus D-alanine alanyl carrier protein ligase (PDB ID: 7VHV). This investigation aimed to synthesize a new series of thiazolidine-4-one derivatives combined with benzoxazole moiety. Ionic liquid assistance one-pot solvent-free synthesis method used to synthesize a new series of thiazolidine-4-one derivative 10(a-e). Structural identification of new synthesis and biological evaluation via techniques of (IR, 1H-NMR, 13C-NMR, 13C-NMR-DEPT-135, and MS). Ionic liquid is utilized as an inexpensive, efficient one-pot three-component solvent-free synthesis of thiazolidine-4-one derivatives with good to excellent yields. Most of the synthesized compounds showed high biological and anti-fungal activity, in line with the docking study against mentioned microorganism and crystal structure of PDB (ID: 7VHV), respectively.

Molecular Docking, In silico ADMET Study and Synthesis of Quinoline Derivatives as Dihydrofolate Reductase (DHFR) Inhibitors: A Solvent-free One-pot Green Approach Through Sonochemistry

Background: Quinoline derivatives have evinced their biological importance in targeting bacteria by inhibiting Dihydrofolate reductase. H2SO4 was successfully applied as an acid catalyst for a green, efficient, and one-pot solvent-free synthesis of quinoline derivatives using sonochemistry approach from various aromatic amines and glycerol with affording yield up to 96% within 6-10 min. Objective: In this study, the synthesis, characterization, and biological assessment of fifteen quinoline derivatives (1-15) as potential DHFR inhibitors were carried out. The target compounds were docked to study the molecular interactions and binding affinities with the 1DLS enzyme. Methods: The synthesized molecules were characterized using IR, MASS, and 1H and 13C NMR. The Insilico molecular docking study was carried out through target Human Dihydrofolate Reductase (DHFR) retrieved from a protein data bank having PDB ID: 1DLS and the antimicrobial activity of all synthesized compounds were tested against Human Dihydrofolate Reductase(DHFR) enzyme by using in-vitro DHFR assay kit. Results: The molecular docking results revealed that compounds 2 and 6 have the lowest binding energy and good binding affinity with the DHFR enzyme. In-silico ADMET predictions revealed that all bestscored compounds had good absorption and drug-like properties for potential use as DHFR inhibitors to treat bacterial infection. The in vitro studies revealed that compounds 2 and 6 show potent DFHR inhibitory activity against gram-positive and gram-negative with IC50 = 12.05 ± 1.55 μM and 10.04 ± 0.73 μM, respectively. While compounds 12, 13, and 15 exhibited moderate antimicrobial activity through DHFR inhibition with IC50= 16.33 ± 0.73 μM, 17.02 ± 1.55 μM, and 18.04 ± 1.05 μM, respectively. Conclusion: This environmentally benign sonochemistry-based approach for synthesizing quinoline derivatives could be affordable for large-scale production and become a potential lead candidate for developing a new quinoline-based antimicrobial agent.

One-pot solvent-free sequential synthesis of high-density polycycloalkanes fuels from lignin-derivatives over laminated NbOPO4 catalyst

Upgrading lignocellulose biomass to renewable fuels is essential to achieve carbon neutrality. However, the multiple synthetic, and purification steps as well as the employment of solvents in the production of renewable fuel inhibit the overall yields and cause the waste of energy and resources. Herein, a new catalytic strategy for one-pot solvent-free sequential synthesis (OSS) of perhydrofluorene and dicyclohexylmethane was developed from lignin-derivatives. A two-dimensional layered nanosheet niobium phosphate (NbOPO4-IB) catalyst was fabricated to efficiently integrate the alkylation of phenol and benzyl alcohol and sequential hydrodeoxygenation with a cocatalyst of Ru/C. The high crystalline NbOPO4 phase and the lamellar morphology contributes to the large specific surface area to expose more active sites, especially more Brønsted acid sites. The NbOPO4-IB catalyst with a suitable Brønsted/Lewis acid ratio of 1.49 favors the selectivity of fuel precursors benzyl phenol in the alkylation and also provides the appropriate acid strength to promote hydrodeoxygenation activity. NbOPO4-IB also shows good reusability. Excessive phenol plays a vital role in promoting the alkylation reaction by dissolving the intermediates, and then into cyclohexane to enhance the H2 dissolution in the hydrodeoxygenation. A possible mechanism of OSS from lignin-derivatives into polycycloalkanes over the cocatalysts was proposed.

Inhibition of terminal C[sbnd]C bonds cleavage drives high selectivity of n-alkane hydroisomerization

Herein we develop a solvent-free one-pot synthesis strategy to simultaneously modify the size effect of metal sites and structural acidity on bifunctional catalysts to in-situ grow platinum nanoparticles (Pt-NPs ∼ 1 nm and ∼ 20 nm) of disparate sizes in the molecular sieve framework without relying on any ligand assistance, causing skeletal defects while exhibiting excellent catalytic performance in n-alkane hydroisomerization. It maintains almost 100 % isomerization selectivity at conversions below 90 %, with performance far superior to that of the conventional catalysts (Pt-NPs ∼ 1 nm). The reason for high selectivity and high liquid yields was revealed by structural characterizations and density functional theory calculations, i.e., the inhibition of terminal CC bond cleavage over n-dodecane chains adsorbed on the defect-containing catalysts and the higher energy barrier of transition state for producing gaseous small molecules, while the size of Pt-NPs may not be the main factor in determining the performance of n-alkane hydroisomerization.

A Simple and Efficient One-Pot Solvent-Free Synthesis of Quinazoline Derivatives Catalyzed by Wet Zinc Ferrite in Air Atmosphere

A Simple and Efficient One-Pot Solvent-Free Synthesis of Quinazoline Derivatives Catalyzed by Wet Zinc Ferrite in Air Atmosphere

AlCl3@ZnO nanostructured material: an efficient green catalyst for the one-pot solvent-free synthesis of 1,4-dihydropyridines.

AlCl3-loaded ZnO nanoparticles have been explored as an efficient catalyst for 1,4-dihydropyridine synthesis under ambient temperature and solvent-free conditions. For this purpose, ZnO nanoparticles were synthesized by a simple solution-based precipitation technique using a stoichiometric amount of zinc sulfate and oxalic acid. The AlCl3@ZnO nanocrystalline catalyst was prepared by loading 20% AlCl3 on ZnO nanoparticles by a simple wet-impregnation technique. This catalyst efficiently performed Hantzsch pyridine reactions with various aromatic aldehydes, ethyl acetoacetate and ammonium acetate. The nanostructured AlCl3-loaded ZnO catalyst was characterized by UV-DRS, XRD, FESEM, EDS, FETEM-STEM-EDS and XPS techniques. The comprehensive characterization reveals the formation of AlCl3-loaded ZnO catalysts with an average particle size of 70-80 nm. The loading of AlCl3 on the ZnO surface was confirmed by minor shifts in the XPS and XRD peaks. FETEM-STEM-EDS also indicates reasonable AlCl3 loading on ZnO nanoparticles. The 20% AlCl3-loaded ZnO nanocatalyst (AlCl3@ZnO) confers 92% yield for the synthesis of 1,4-dihydropyridine under solvent-free and ambient temperature conditions. The synthesized 1,4-dihydropyridines were characterized by 1H-NMR, 13C-NMR, HRMS and FT-IR spectroscopic techniques. The reported catalyst is highly efficient, environmentally friendly and could become an alternative to homogenous and heterogenous catalytic reactions.

Highly engineerable Schiff base polymer matrix with facile fiber composite manufacturability and hydrothermal recyclability

Researchers have attempted to use Schiff base vitrimer as a matrix resin for preparation of intrinsically recyclable CFRP materials. Because most of the reported Schiff base vitrimer resin systems have high viscosity or are in solid state, solvent is often used during product fabrication to reduce the viscosity and slow down reactions during handling. In this work, a low viscosity Schiff base vitrimer resin is prepared from commercially available diamine, dialdehyde, and bisphenol A epoxy in a solvent-free one-pot synthesis. The obtained crosslinked polymer presents a tensile strength up to 59.6 MPa and an elongation at break up to 7.1%. Moreover, compared with those highly acid-sensitive Schiff base vitrimers in the literature, the vitrimer in this work has excellent chemical resistance toward various solvents. Due to the imine bond exchange reaction, the material exhibits fast stress relaxation at elevated temperatures (>150 °C). By the same thermally induced imine bond exchange reaction, the CFRP prepared from this vitrimer matrix shows unique welding, shape changing, and chemical recycling properties. The CFRP strips can be thermally transformed to a new permanent shape at 180 °C under force, while the welded CFPR strips present a lap shear strength of 8.33 MPa and elongation at break of 2.99%. Hydrolysis of imine linkages is achieved in mild acidic solutions (0.2 M HCl), and the recovered carbon fibers show little damage and are reused to prepare new CFRP. The findings from the study will help to bring Schiff base vitrimer resins from research stage to practical composite applications.

Synthesis and Characterisation of Dicyclohexyl Urea by the improved Green Methodology

The reaction of cyclohexyl amine with urea under solvent-free condition, one-step and one-pot synthesis via transamination for industrial production is studied where, cyclohexyl amine is heated with urea to give desired product DCU in molar yield.

Solvent-free one-pot synthesis of 4-aryl-3,5-dimethyl-1,4,7,8-tetrahydrodipyrazolo[3,4-b:4′,3′-e]pyridines using Fe3O4@SiO2@(BuSO3H)3 catalytic Fe3+ system as selective colorimetric

Solvent-free one-pot synthesis of 4-aryl-3,5-dimethyl-1,4,7,8-tetrahydrodipyrazolo[3,4-b:4′,3′-e]pyridines using Fe3O4@SiO2@(BuSO3H)3 catalytic Fe3+ system as selective colorimetric

One-pot solvent-free synthesis of 1,3,5-trisubstituted 1H-pyrazoles catalyzed by H3[PW12O40]/SiO2 under microwave irradiation

One-pot solvent-free synthesis of 1,3,5-trisubstituted 1H-pyrazoles catalyzed by H3[PW12O40]/SiO2 under microwave irradiation

In silico Study and Solvent-free one-pot Synthesis of Tetrahydropyrimidine derivatives by Mechanochemistry Approach for Targeting Human Neutrophil Elastase against Lung Cancer.

Pyrimidine derivative has evinced its biological importance in targeting lung cancer by inhibiting neutrophil elastase. All THPM derivatives were synthesized by the grindstone method at ambient temperature followed by molecular docking study for efficient binding interaction of THPM compounds by targeting human neutrophil elastase (HNE) (PDB ID: 5A0A) and In-silico ADMET study using PkCSM. Moreover, all synthesized compounds were characterized by spectroscopy techniques and screened for anti-cancer activity using in vitro HNE assay kit. We reported a one-pot solvent-free mechanochemical approach for synthesizing tetrahydropyrimidine (THPM) derivatives from various aromatic aldehydes, ethyl cyanoacetate, and urea followed by in silico study and evaluation against human neutrophil elastase (HNE) for treatment of lung cancer. We calibrated the best molecules that bound to specific targets more efficiently using a molecular docking approach and provided the desired efficacy. In-silico ADMET studies revealed that all best-scored compounds had drug-like characteristics for potential use as human neutrophil elastase inhibitors (HNE) in lung cancer treatment. Additionally, the in vitro studies revealed that compounds 1, 2, and 8 show potent HNE inhibitory activity for lung cancer treatment. In a nutshell, the tetrahydropyrimidine (THPM) scaffold and its derivatives may serve as potential HNE inhibitors for the development of a promising anti-cancer agent.

Synthesis, characterization and cytotoxicity evaluation of a novel magnetic nanocomposite with iron oxide deposited on cellulose nanofibers with nickel (Fe3O4@NFC@ONSM-Ni).

A heterogeneous, magnetically recoverable nanocomposite, Fe3O4@NFC@ONSM-Ni(ii) was prepared by immobilization of a novel Ni(ii) Schiff base complex on Fe3O4@NFC nanoparticles followed by treatment with melamine. This trinuclear catalyst has been characterized using several analytical techniques including FT-IR, TEM, Fe-SEM, EDX, DLS, ICP, TGA, VSM, and XRD. It was used as an efficient catalyst for one-pot solvent-free synthesis of 1,4-dihydropyridine and poly-hydro quinoline derivatives through Hantzsch reaction. This catalyst showed remarkable advantage over previously reported catalysts due to suitable conditions, short reaction time, high efficiency and lower catalyst load and timely recovery of the magnetic catalyst. Moreover, the effects of Fe3O4@NFC@ONSM-Ni(ii) nanoparticles on the in vitro proliferation of human leukemia cell line (k562) and human breast cancer cells (MDA-MB-231) were investigated. The results of MTT and Hochest assays suggested that the nanoparticles could effectively inhibit the proliferation of these cancer cells in a time- and concentration-dependent manner.

An efficient (TBA)2S2O8 catalyzed regioselective solvent-free one-pot synthesis of fully substituted pyrazoles

An efficient tetra-n-butyl ammonium peroxydisulphate (TBA)2S2O8 catalyzed a direct one-pot synthesis of fully substituted pyrazoles in excellent yields with high regioselectivity has been described via a three-component cyclocondensation of aldehydes, aryl hydrazines with β-diketones or β-keto esters under solvent-free conditions. The structure of the target compound 4 m was confirmed by X-ray diffraction.

Solvent-free K–CaO/Ca(OH)2 mixed-phase nanocatalytic single-step methanolysis, ethanolysis and aminolysis of Pongamia pinnata triglycerides

In this report, the K–CaO/Ca(OH)2 mixed-phase nanodendrites were prepared and used as a heterogeneous catalyst for the one-pot solvent-free synthesis of methyl esters, ethyl esters and alkyl amides from Pongamia pinnata triglycerides. A modified incipient-wetness chemical impregnation method was used to prepared potassium hydroxide doped CaO, MgO, and ZnO nanocrystallites. The prepared K–CaO/Ca(OH)2 nanocrystallites were found as the most efficient heterogeneous catalyst (4%, w/w) for aminolysis (6:1 M ratio of diethanolamine/oil, 110 °C), methanolysis (9:1 M ratio of methanol/oil at 65 °C) and ethanolysis (9:1 M ratio of ethanol/oil at 75 °C) of Pongamia pinnata oil and took 40 min for the completion (99% yield) of all the reactions. The K–CaO/Ca(OH)2 nanodendrites were found to be efficient at room temperature (25–30 °C) also and reused for 10 reaction cycles. The pseudo-first-order reaction kinetic model was applied and the first-order rate constant was calculated as 0.112 min−1, 0.093 min−1, and 0.118 min−1 for the methanolysis, ethanolysis, and aminolysis of Pongamia pinnata oil, respectively.

A Swift One-Pot Solvent-Free Synthesis of Benzimidazole Derivatives and Their Metal Complexes: Hydrothermal Treatment, Enzymatic Inhibition, and Solubilization Studies

Three benzimidazole derivatives, 1-(1H-benzimidazol-2-yl)ethanol (HBE), 1H-benzimidazol-2-yl(diphenyl)methanol (BDM) and 1,2-bis(1H-benzimidazol-2-yl)ethane-1,2-diol (BHBED), have been synthesized following the one-pot rapid green protocol. Complexes of benzimidazole derivatives with six 3d transition metals, Cu(II), Mn(II), Zn(II), Fe(II), Co(II), and Ni(II), have been synthesized by free hydrothermal method. The synthesized products have been characterized by FTIR, 1H, and 13C NMR, and mass spectroscopy, and CHN analysis, and 2:1 ligand to metal stoichiometry has been confirmed. The synthesized ligands and metal complexes have been tested for antioxidant potential (DPPH), inhibitory activity including inhibition of acetylcholinesterase (AChE), butyrylcholinesterase (BChE), lipoxygenase (LOX), α-glucosidase. Micellar solubilization of the metal complexes has been studied in sodium dodecyl sulphate (SDS) by UV-Vis spectroscopy and conductivity. The selected complexes of nickel, zinc and cobalt have demonstrated interaction with SDS, and the value of critical micellar concentration increased in all cases.

One-pot solvent-free synthesis of MgFe2O4 nanoparticles from ferrous sulfate waste

ABSTRACTThis study proposed a one-pot solvent-free method to synthesize magnesium ferrite nanoparticles using ferrous sulfate waste as raw materials and provided a new idea for high-quality use of ferrous sulfate waste and was promising to be applied in industrialization. Magnesium ferrite nanoparticles (MgFe2O4) were successfully synthesized by a solid-reduction method using ferrous sulfate waste, pyrite and Magnesium carbonate as raw materials. X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) method, and superconducting quantum interference device magnetometer were applied to determine the characteristics of obtained samples. The mechanism of synthesizing magnesium ferrite was studied by TGA.

Highly branched and nontoxic plasticizers based on natural cashew shell oil by a facile and sustainable way

Abstract Almost 80% of plasticizers used in polyvinyl chloride (PVC) materials are toxic o-phenyl plasticizers. In order to replace o-phenyl plasticizers in PVC materials, a series of highly branched and nontoxic plasticizers (CHE-4,CHE-8 and CHE-12) based on natural cashew shell oil (CNSL), an agricultural and forestry residue, were synthesized via facile one-pot solvent-free synthesis. The chemical structure, relative molecular mass and thermal stability of the obtained highly branched and nontoxic plasticizers were characterized. The toxicity of CHE-12 was investigated in the low (1000 mg/kg), middle (2000 mg/kg and 3000 mg/kg) and high dose (5000 mg/kg), the results suggested that CHE-12 has toxic doses of 5000 mg/kg and is a non-toxic plasticizer. PVC materials plasticized with CHE-12 showed more excellent thermal stability, plasticizing property and migration stability than dioctyl phthalate (DOP). Microstructure of PVC materials was investigated and the results showed that compatibility of PVC with CHE-12 is better than DOP. The microscopic plasticizing mechanism was also investigated. CHEs were proved to be promising candidates for the chemical conversion of CNSL derivatives into environmentally friendly and non-toxic plasticizers.

One-Pot Solvent-Free Synthesis of N,N-Bis(2-Hydroxyethyl) Alkylamide from Triglycerides Using Zinc-Doped Calcium Oxide Nanospheroids as a Heterogeneous Catalyst

N,N-Bis(2-hydroxyethyl) alkylamide or fatty acid diethanolamides (FADs) were prepared from a variety of triglycerides using diethanolamine in the presence of different transition metal-doped CaO nanocrystalline heterogeneous catalysts. The Zn-doped Cao nanospheroids were found to be the most efficient heterogeneous catalyst, with complete conversion of natural triglycerides to fatty acid diethanolamide in 30 min at 90 °C. The Zn/CaO nanoparticles were recyclable for up to six reaction cycles and showed complete conversion even at room temperature. The amidation reaction of natural triglycerides was found to follow the pseudo-first-order kinetic model, and the first-order rate constant was calculated as 0.171 min–1 for jatropha oil aminolysis. The activation energy (Ea) and pre-exponential factor (A) for the same reaction were found to be 47.8 kJ mol–1 and 4.75 X 108 min-1, respectively.