Showing papers on "Benzoic acid published in 2018"

Cobalt-Catalyzed Coupling of Benzoic Acid C-H Bonds with Alkynes, Styrenes, and 1,3-Dienes.

Abstract: A method for cobalt-catalyzed, carboxylate-directed functionalization of arene C-H bonds is reported. Alkynes, styrenes, and 1,3-dienes can be coupled with benzoic acids to provide cyclic products in good yields. The reactions proceed in the presence of a cobalt(II) hexafluoroacetylacetonate catalyst, (TMS)2 NH base, Ce(SO4 )2 cooxidant, and oxygen oxidant.

Theoretical insight into the adsorption of aromatic compounds on graphene oxide

Abstract: In this work, adsorption of aromatic compounds (ACs) on graphene oxide (GO) was systematically investigated. Bisphenol A, nitrobenzene, phenol, benzoic acid, and salicylic acid were employed as representatives of ACs. Experimental isotherm analysis indicated that the order of adsorption capacity is nitrobenzene > BPA > phenol > salicylic acid > benzoic acid. To examine which mechanism (including π–π, hydrogen bond, vdW, and hydrophobic interactions) governed the adsorption capacity, the π-stacking ability, hydrogen bond interaction energy, polarizability, and interaction intensity of ACs with water were examined using molecular dynamics simulations and density functional theory calculations. The results showed that the adsorption capacity was mainly guided by the π-stacking ability of ACs. Hydrophobic, GO–AC hydrogen bond, van der Waals, and electrostatic interactions may contribute to the adsorption of ACs on GO, but are not important in regulating the adsorption capacity. Local configurations of ACs adsorbed on GO were captured, and two patterns for multilayer adsorption were observed. Further analysis suggested that upon adsorbing on GO, the translational motion of ACs in water will be suppressed; however, the solvent accessible surface area will be increased, which may increase the bio-accessibility of ACs.

Mechanistic Insight into Asymmetric Hetero-Michael Addition of α,β-Unsaturated Carboxylic Acids Catalyzed by Multifunctional Thioureas

Abstract: Carboxylic acids and their corresponding carboxylate anions are generally utilized as Bronsted acids/bases and oxygen nucleophiles in organic synthesis. However, a few asymmetric reactions have used carboxylic acids as electrophiles. Although chiral thioureas bearing both arylboronic acid and tertiary amine were found to promote the aza-Michael addition of BnONH2 to α,β-unsaturated carboxylic acids with moderate to good enantioselectivities, the reaction mechanism remains to be clarified. Detailed investigation of the reaction using spectroscopic analysis and kinetic studies identified tetrahedral borate complexes, comprising two carboxylate anions, as reaction intermediates. We realized a dramatic improvement in product enantioselectivity with the addition of 1 equiv of benzoic acid. In this aza-Michael reaction, the boronic acid not only activates the carboxylate ligand as a Lewis acid, together with the thiourea NH-protons, but also functions as a Bronsted base through a benzoyloxy anion to activate th...

Molecular Vise Approach to Create Metal-Binding Sites in MOFs and Detection of Biomarkers.

Abstract: We report a new approach to create metal-binding site in a series of metal-organic frameworks (MOFs), where tetratopic carboxylate linker, 4',4'',4''',4''''-methanetetrayltetrabiphenyl-4-carboxylic acid, is partially replaced by a tritopic carboxylate linker, tris(4-carboxybiphenyl)amine, in combination with monotopic linkers, formic acid, trifluoroacetic acid, benzoic acid, isonicotinic acid, 4-chlorobenzoic acid, and 4-nitrobenzoic acid, respectively. The distance between these paired-up linkers can be precisely controlled, ranging from 5.4 to 10.8 A, where a variety of metals, Mg2+ , Al3+ , Cr3+ , Mn2+ , Fe3+ , Co2+ , Ni2+ , Cu2+ , Zn2+ , Ag+ , Cd2+ and Pb2+ , can be placed in. The distribution of these metal-binding sites across a single crystal is visualized by 3D tomography of laser scanning confocal microscopy with a resolution of 10 nm. The binding affinity between the metal and its binding-site in MOF can be varied in a large range (observed binding constants, Kobs from 1.56×102 to 1.70×104 L mol-1 ), in aqueous solution. The fluorescence of these crystals can be used to detect biomarkers, such as cysteine, homocysteine and glutathione, with ultrahigh sensitivity and without the interference of urine, through the dissociation of metal ions from their binding sites.

Ultraviolet Irradiation of Permanganate Enhanced the Oxidation of Micropollutants by Producing HO• and Reactive Manganese Species

Abstract: Permanganate was activated by ultraviolet (UV) photolysis at 254 nm, resulting in the efficient degradation of micropollutants. The degradation of four probe molecules (i.e., nitrobenzene, benzoic acid, terephthalic acid, and p-chlorobenzoic acid) and two micropollutants (i.e., gemfibrozil and nalidixic acid) resistant to permanganate oxidation was enhanced by the UV/permanganate system, with pseudo-first-order rate constants (k′) of 0.065–0.678 min–1 under the experimental conditions. Hydroxyl radicals (HO•) and Mn(V) peroxide, which were produced during the activation of permanganate by UV irradiation, were responsible for the enhancement. The quantum yield of HO• was 0.025 ± 0.001 mol Einstein–1 (mol Es–1) in the system. HO• oxidation primarily accounted for the degradation of nitrobenzene and gemfibrozil, while both HO• and Mn(V) were responsible for the degradation of benzoic acid, terephthalic acid, p-chlorobenzoic acid, and nalidixic acid. This study is the first report on the activation of permang...

Ultrasensitive Fluorescence Detection of Peroxymonosulfate Based on a Sulfate Radical-Mediated Aromatic Hydroxylation

Abstract: Recently, peroxymonosulfate (PMS)-based advanced oxidation processes have exhibited broad application prospects in the environment field. Accordingly, a simple, rapid, and ultrasensitive method is highly desired for the specific recognition and accurate quantification of PMS in various aqueous solutions. In this work, SO4•–-induced aromatic hydroxylation was explored, and based on that, for the first time, a novel fluorescence method was developed for the PMS determination using Co2+ as a PMS activator and benzoic acid (BA) as a chemical probe. Through a suite of spectral, chromatographic, and mass spectrometric analyses, SO4•– was proven to be the dominant radical species, and salicylic acid was identified as the fluorescent molecule. As a result, a whole radical chain reaction mechanism for the generation of salicylic acid in the BA/PMS/Co2+ system was proposed. This fluorescence method possessed a rapid reaction equilibrium (<1 min), an ultrahigh sensitivity (detection limit = 10 nM; quantification lim...

Synthesis of Nitroolefins and Nitroarenes under Mild Conditions

Abstract: 1,3-Disulfonic acid imidazolium nitrate {[Dsim]NO3} was prepared and characterized as a new ionic liquid and nitrating agent for the ipso-nitration of various arylboronic acids and nitro-Hunsdiecker reaction of different α,β-unsaturated acids and benzoic acid derivatives, by in situ generation of NO2 to give various nitroarenes and nitroolefins without using any cocatalysts and solvents under mild conditions.

Corrosion Resistance of Mild Steel Coated with Orgainc Material Containing Pyrazol Moiety

Abstract: Pyridine (P1) and benzoic acid (P2) derivatives with pyrazole moieties were synthesized and evaluated as corrosion inhibitors for mild steel in acidic medium. The evaluation was performed by electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, and weight loss measurement. The surface morphologies of the control and steel samples coated with the pyrazole derivatives P1 and P2 were examined by the scanning electron microscopy (SEM), UV-Vis, and X-ray photoelectron spectrocopy (XPS) spectroscopies. Results revealed minor changes on steel surfaces before and after immersion in a 1 M HCl solution. Both derivatives, P1 and P2, showed good inhibition efficiency that is dependent on inhibitor concentration. Both P1 and P2 act as mixed-type inhibitors. The benzoic acid derivative (P2) showed a higher efficiency than P1, which could be attributed to the carboxyl group that is located at the para position to the amino group. This induces a direct electronic resonance between the two groups, the amino and the carboxyl. As a result of this, a higher electron density on the carboxyl group and a stronger bonding to the metal surface occurred. Results also show that, the bonding of both pyrazoles on mild steel surface obey Langmuir adsorption isotherm. Quantum chemical calculations were performed to theoretically define the relationship between the molecular structures and inhibition efficiencies of P1 and P2.

Palladium-Catalyzed Carbon Isotope Exchange on Aliphatic and Benzoic Acid Chlorides.

Abstract: An operationally simple protocol for a palladium-catalyzed 13CO and 14CO exchange with activated aliphatic and benzoic carbonyls is presented. Several 13C and 14C building blocks, natural product derivatives, and pharmaceuticals have been prepared to showcase the method for late-stage carbon isotope incorporation and its functional group compatibility.

Biodegradation of Mordant orange-1 using newly isolated strain Trichoderma harzianum RY44 and its metabolite appraisal

Abstract: Herein, we systematically reported the capability of T. harzianum RY44 for decolorization of Mordant orange-1. The fungi strains were isolated from the Universiti Teknologi Malaysia tropical rain forest. For initial screening, the decolorization was conducted using 50 strains of the fungi for 20 days incubation time and the best performance was selected. Then, the decolorization capability and fungal biomass were evaluated using different dye concentrations, namely, 0, 50, 75 and 100 ppm. Effects of the carbon sources (fructose, glucose, and galactose), nitrogen sources (ammonium nitrate, ammonium sulfate and yeast extract), surfactant (tween 80), aromatic compounds (benzoic acid, catechol and salicylic acid), and pH on the decolorization efficiency were examined. This study has found that the employed carbon sources, nitrogen sources, and aromatic compounds strongly enhance the decolorization efficiency. In addition, increasing the surfactant volume and pH generally decreased the decolorization efficiencies from 19.5 to 9.0% and 81.7 to 60.5%, respectively. In the mechanism philosophy, the present work has found that Mordant orange-1 were initially degraded by T. harzianum RY44 to benzoic acid and finally transformed into salicylic acid.

Screening of a beta-cypermethrin-degrading bacterial strain Brevibacillus parabrevis BCP-09 and its biochemical degradation pathway

Abstract: A novel beta-cypermethrin (Beta-CP)-degrading strain isolated from activated sludge was identified as Brevibacillus parabrevis BCP-09 based on its morphological and physio-biochemical characteristics, and 16S rRNA gene analysis. Strain BCP-09 could effectively degrade Beta-CP at pH 5.0–9.0, 20–40 °C, and 10–500 mg L−1 Beta-CP. Under optimal conditions (pH 7.41, 38.9 °C, 30.9 mg L−1 Beta-CP), 75.87% Beta-CP was degraded within 3 days. Beta-CP degradation (half-life, 33.45 h) and strain BCP-09 growth were respectively described using first-order-kinetic and logistic-kinetic models. Seven metabolites were detected by high-performance liquid chromatography and gas chromatography-mass spectrometry- methyl salicylate, catechol, phthalic acid, salicylic acid, 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid, 3-phenoxybenzaldehyde, and 3-phenoxybenzoic acid (3-PBA). The major Beta-CP metabolite, 3-PBA was further degraded into phenol, benzoic acid, and 4-methylhexanoic acid. BCP-09 also degraded aromatic compounds such as phenol, catechol, and protocatechuic acid. Beta-CP appears to be mainly degraded into 3-PBA, which is continuously degraded into smaller benzene or chain compounds. Thus, strain BCP-09 could form a complete degradation system for Beta-CP and might be considered a promising strain for application in the bioremediation of environments and agricultural products polluted by Beta-CP.

New Findings on Aromatic Compounds' Degradation and Their Metabolic Pathways, the Biosurfactant Production and Motility of the Halophilic Bacterium Halomonas sp. KHS3.

Abstract: The study of the aromatic compounds' degrading ability by halophilic bacteria became an interesting research topic, because of the increasing use of halophiles in bioremediation of saline habitats and effluents. In this work, we focused on the study of aromatic compounds' degradation potential of Halomonas sp. KHS3, a moderately halophilic bacterium isolated from hydrocarbon-contaminated seawater of the Mar del Plata harbour. We demonstrated that H. sp. KHS3 is able to grow using different monoaromatic (salicylic acid, benzoic acid, 4-hydroxybenzoic acid, phthalate) and polyaromatic (naphthalene, fluorene, and phenanthrene) substrates. The ability to degrade benzoic acid and 4-hydroxybenzoic acid was analytically corroborated, and Monod kinetic parameters and yield coefficients for degradation were estimated. Strategies that may enhance substrate bioavailability such as surfactant production and chemotactic responses toward aromatic compounds were confirmed. Genomic sequence analysis of this strain allowed us to identify several genes putatively related to the metabolism of aromatic compounds, being the catechol and protocatechuate branches of β-ketoadipate pathway completely represented. These features suggest that the broad-spectrum xenobiotic degrader H. sp. KHS3 could be employed as a useful biotechnological tool for the cleanup of aromatic compounds-polluted saline habitats or effluents.

Fluorescent imidazole-based chemosensors for the reversible detection of cyanide and mercury ions

Abstract: We report 4-(2-(5-(tert-butyl)-3-formyl-2-hydroxyphenyl)-1H-phenanthro[9,10-d]imidazol-1-yl)benzoic acid 1 and 4-(2-(5-(tert-butyl)-3-formyl-2-hydroxyphenyl)-4,5-diphenyl-1H-imidazol-1-yl)benzoic acid 2 as reversible luminescent sensors for the detection of cyanide and mercury ions. These imidazole derivatives were characterized using spectroscopic techniques and single crystal X-ray crystallography. The compounds showed sensing exclusively towards CN− ions, which resulted in the quenching of fluorescence and a decreased singlet state life time. The detection limit of imidazole derivatives 1 and 2 were found to be 0.8 μM and 1.2 μM respectively, in a CH3CN/H2O system. Job's plot analysis, 1H NMR spectra and LC-MS studies supported the formation of the respective cyanohydrin. This cyanohydrin was further used as a reversible sensor for the detection of Hg2+ ions through metal-assisted elimination. The reversibility and reusability of sensors for the detection of CN− and Hg2+ ions were tested for four consecutive cycles.

Stabilization of NaBH4 in Methanol Using a Catalytic Amount of NaOMe. Reduction of Esters and Lactones at Room Temperature without Solvent-Induced Loss of Hydride

Abstract: Rapid reaction of NaBH4 with MeOH precludes its use as a solvent for large-scale ester reductions. We have now learned that a catalytic amount of NaOMe (5 mol %) stabilizes NaBH4 solutions in methanol at 25 °C and permits the use of these solutions for the reduction of esters to alcohols. The generality of this reduction method was demonstrated using 22 esters including esters of naturally occurring chiral γ-butyrolactone containing dicarboxylic acids. This method permits the chemoselective reductions of esters in the presence of cyano and nitro groups and the reductive cyclization of a pyrrolidinedione ester to a fused five-membered furo[2,3-b]pyrrole and a (-)-crispine A analogue in high optical and chemical yields. Lactones, aliphatic esters, aromatic esters containing electron-withdrawing groups, and heteroaryl esters are reduced more rapidly than aryl esters containing electron-donating groups. The 11B NMR spectrum of the NaOMe-stabilized NaBH4 solutions showed a minor quartet due to monomethoxyborohydride (NaBH3OMe) that persisted up to 18 h at 25 °C. We postulate that NaBH3OMe is probably the active reducing agent. In support of this hypothesis, the activation barrier for hydride transfer from BH3(OMe)- onto benzoic acid methyl ester was calculated as 18.3 kcal/mol.

New Cytotoxic Cyclic Peptide from the Marine Sponge-Associated Nocardiopsis sp. UR67

Abstract: A new cyclic hexapeptide, nocardiotide A (1), together with three known compounds—tryptophan (2), kynurenic acid (3), and 4-amino-3-methoxy benzoic acid (4)—were isolated and identified from the broth culture of Nocardiopsis sp. UR67 strain associated with the marine sponge Callyspongia sp. from the Red Sea. The structure elucidation of the isolated compounds were determined based on detailed spectroscopic data including 1D and 2D nuclear magnetic resonance (NMR) experimental analyses in combination with high resolution electrospray ionization mass spectrometry (HR-ESI-MS), while the absolute stereochemistry of all amino acids components of nocardiotide A (1) was deduced using Marfey’s method. Additionally, ten known metabolites were dereplicated using HR-ESI-MS analysis. Nocardiotide A (1) displayed significant cytotoxic effects towards the murine CT26 colon carcinoma, human HeLa cervix carcinoma, and human MM.1S multiple myeloma cell lines. The results obtained revealed sponge-associated Nocardiopsis as a substantial source of lead natural products with pronounced pharmacological activities.