- Novel pyrazolone derivatives and corresponding europium(III) complexes: Synthesis and properties research
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A series of pyrazolone derivatives ligands L1?7 were successfully synthesized and validated by 1H NMR and MS, corresponding europium complexes [EuL1?7(NO3)2]NO3·EtOAc were synthesized. Physico-chemistry properties of title complexes were determined by Elemental analysis, Molar conductance, UV absorption spectra, IR spectra and Thermogravimetric analysis. The title complexes exhibit characteristic red fluorescence of Eu3+. The effect of various substituent groups in ligands on the of title Eu3+ complexes is ordered: Cl > -Br > -OCH3 > -F > -CH3 > -H > -NO2, and [EuL6(NO3)2]NO3·EtOAc containing Cl possesses the strongest fluorescence intensity, so does fluorescence quantum yield. The electrochemical properties indicate that energy gap Eg and LUMO energy level are huge affected by substituent groups, and variation trends of LUMO energy level affected by diverse substituent groups are also different. The prepared title europium complexes have potential application prospects in the fields of photoelectric functional materials and life sciences.
- Li, Dewei,Xiong, Suhao,Guo, Tiantong,Shu, Dehua,Xiao, Haihua,Li, Guizhi,Guo, Dongcai
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- Phenyl group participation in rearrangements during collision-induced dissociation of deprotonated phenoxyacetic acid
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Rationale The identification of trace constituents in biological and environmental samples is frequently based on the fragmentation patterns resulting from the collision-induced dissociation (CID) of gas-phase ions. Credible mechanistic characterization of fragmentation processes, including rearrangements, is required to make reliable assignments for structures of precursor and product ions. Methods Mass spectra were collected using both ion trap and triple quadrupole mass spectrometers operating in the negative ion mode. Precursor ion scans and CID of ions generated in-source were used to establish precursor-product ion relationships. Density functional theory (DFT) computations were performed at the MP2/6-311++G(2d,p)//B3LYP/6-31++G(2d,p) level of theory. Results Product ions at m/z 93 and 107 obtained upon CID of phenoxyacetate were attributed to phenoxide and o-methylphenoxide, respectively. An isotopic labeling experiment and computations showed that the phenoxide ion was formed by intramolecular displacement with formation of an α-lactone and also by a Smiles rearrangement. Rearrangement of phenoxyacetate via the ion-neutral complex formed in the α-lactone displacement pathway gave the isomeric o-hydroxyphenylacetate ion which yielded o-methylphenoxide upon decarboxylation. Computations provided feasible energetics for these pathways. Conclusions Previously unrecognized and energetically favorable rearrangements during the collision-induced fragmentation of phenoxyacetate have been characterized using isotopic labeling and DFT computations. Notably, the phenyl substituent plays an indispensable role in each rearrangement process resulting in multiple pathways for the fragmentation of phenoxyacetate.
- Leblanc, Luc M.,Crowell, Andrew M. J.,Grossert, J. Stuart,White, Robert L.
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- Synthesis and properties of coumarin derivatives and their terbium complexes
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A series of coumarin derivatives obtained from salicylaldehyde and phenol were synthesized. Their corresponding terbium complexes were prepared and characterized by elemental analysis, EDTA titrations, molar conductivity, UVvis spectra, IR spectra, and thermal analysis. The luminescent properties and electrochemical properties of the terbium complexes were also investigated. The results showed that all the terbium complexes exhibited characteristic emissions of terbium ions. The introduction of electron-donating groups can improve the luminescent properties, decrease the HOMO and LUMO energy levels of the terbium complex, while electron-withdrawing groups can weaken the luminescent properties, and increase the HOMO and LUMO energy levels of terbium complex.
- Meng, Defen,Xu, De,Li, Dong,Dai, Ming,Li, Guizhi,Guo, Dongcai
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- Synthesis and Biological Activity of Ethyl 4-Alkyl-2-(2-(substituted phenoxy)acetamido)thiazole-5-carboxylate
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(Chemical Equation Presented) A series of novel ethyl 4-(methyl or trifluoromethyl)-2-(2-(substituted phenoxy)acetamido)thiazole-5-carboxylates 7a, 7b, 7c, 7d, 7e and 8f, 8g, 8h, 8i, 8j, 8k, 8l, 8m, 8n, 8o, 8p, 8q, 8r were synthesized, and their structures were confirmed by IR, 1H-NMR, MS spectra and elemental analysis. The results of preliminary bioassays show that some of the title compounds exhibit moderate to good herbicidal activities. Compared with the fluorine free compounds 7a, 7b, and 7e, the compounds bearing fluorine 8g, 8j, and 8q showed higher herbicidal activities with 70-100% inhibition against Capsella bursa-pastoris, Amaranthus restroflexus, and Eclipta prostrata at the dosage of 150 g/ha, which indicated that the trifluoromethyl on the thiazole ring was beneficial for the herbicidal activity. Furthermore, compounds 8f, 8g, 8h, 8i, 8j, 8k, 8l, 8m, 8n, 8o, 8p, 8q, 8r were tested for fungicidal activity against Pseudoperonospora cubensis at 500 μg/mL. Compounds 8f and 8q showed the best fungicidal activity with more than 80% inhibition.
- Mo, Wenyan,Shi, Yanxia,He, Junbo,Li, Baoju,Peng, Hao,He, Hongwu
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- Electrocatalytic dehalogenation of chloroaromatics on palladium-loaded carbon felt cathode in aqueous medium
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The selective dechlorination of highly toxic chloroaromatic herbicides based on phenoxyacetic acid was successfully achieved under mild experimental conditions in aqueous medium by electrocatalytic reduction at palladium-loaded carbon felts. Such cathode material is in principle available for dechlorination of chloroaromatics having different molecular structure.
- Tsyganok, Andrey I.,Yamanaka, Ichiro,Otsuka, Kiyoshi
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- Optimisation of electrocatalytic dechlorination of 2,4- dichlorophenoxyacetic acid on a roughened silver-palladium cathode
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Electrocatalytic hydrogenolysis (ECH) dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) in an aqueous solution was investigated at room temperature using a roughened silver-palladium cathode (Pd/Ag(r) cathode) in batch-mode electrolysis experiments. The Pd/Ag(r) cathode was prepared by galvanic replacement reaction (GRR) of a roughened silver (Ag(r)) electrode with PdCl2 solution. The effect of preparation conditions on the catalytic activity and stability of the Pd/Ag(r) cathode and of operating parameters on the rate and current efficiency (CE) of the ECH dechlorination reaction were evaluated. In particular, the ECH dechlorination mechanism of 2,4-D was analysed with regard to the dependence of dechlorination efficiency on the different operating parameters. Moreover, preliminary assessments of product selectivity and carbon mass balance of the dechlorination reaction were carried out. The results demonstrate that a moderate GRR time and GRR temperature favoured the catalytic activity and cathode stability and that a basic aqueous solution without ethanol, high 2,4-D concentration, and moderate current density had the most beneficial effects on the dechlorination process. Under the optimised conditions, 25 mM of 2,4-D could be selectively dechlorinated to phenoxyacetic acid with 85% yield and 66% CE at 298 K after 6 h electrolysis. The only products generated during the electrolysis process were phenoxyacetic acid, 2-chlorophenoxyacetic acid, and 4-chlorophenoxyacetic acid.
- Xu, Ying Hua,Cai, Qian Qian,Ma, Hong Xing,He, Yan,Zhang, Hong,Ma, Chun An
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- Synthesis of Aryloxyacetic Acids, Esters, and Hydrazides Assisted by Microwave Irradiation
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Under microwave irradiation on clay a series of transformations of a number of phenols into their aryloxyacetic acids 3 and then their methyl esters 4 and hydrazides 5 has been achieved efficiently in good yields.
- Hamid, Hamida M. Abdel,Ramadan, El Sayed,Hagar, Mohamed,El Ashry, El Sayed H.
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- Dechlorination of 2,4-dichlorophenoxyacetic acid using biochar-supported nano-palladium/iron: Preparation, characterization, and influencing factors
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In the present study, peanut shell, a green waste raw material, was used to prepare biochar (BC) and to obtain BC-supported nano-palladium/iron (BC-nPd/Fe) composites for removing 2,4-dichlorophenoxyacetic acid (2,4-D) from water. Characterization analysis demonstrated that nPd/Fe particles were well dispersed on the BC surface with weakened magnetic properties. The average particle diameter and specific surface area of nPd/Fe were 101.3 nm and 6.7 m2 g?1, whereas the corresponding values of the BC-nPd/Fe materials were 88.8 nm and 14.8 m2 g?1, respectively. Several factors were found to influence the dechlorination of 2,4-D, including the weight ratio of BC to Fe, Pd loading ratio, initial solution pH, 2,4-D concentration, and reaction temperature. Dechlorination results indicated that the 2,4-D removal and phenoxyacetic acid (PA) generation rates were 44.1% and 20.1%, respectively, in the nPd/Fe system, and 100.0% and 92.1%, respectively, in the BC-nPd/Fe system. The dechlorination of 2,4-D was well described by the pseudo-first-order kinetic model (R2 > 0.97), and the observed rate constants kobs were 0.0042 min (nPd/Fe) and 0.0578 min (BC-nPd/Fe), respectively. The reaction mechanism indicated that the dechlorination hydrogenation was the main process to remove 2,4-D from water in the BC-nPd/Fe system. In addition, BC inhibited the formation of a passivation layer on the particle surface during the reaction, thus maintaining the high reactivity of BC-nPd/Fe. The easy preparation technique, high 2,4-D dechlorination capacity, and mild reaction conditions suggest that BC-nPd/Fe may be a promising alternative composite to remove 2,4-D from water.
- Zhou, Hongyi,Huang, Ning,Zhao, Yongkang,Baig, Shams Ali,Xiang, Junchao
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- Discovery of 1,3-diethyl-7-methyl-8-(phenoxymethyl)-xanthine derivatives as novel adenosine A1and A2Areceptor antagonists
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Based on a previous report that a series of 8-(phenoxymethyl)-xanthines may be promising leads for the design of A1adenosine receptor antagonists, selected novel and known 1,3-diethyl-7-methyl-8-(phenoxymethyl)-xanthine and 1,3,7-trimethyl-8-(phenoxymethyl)-xanthine analogs were synthesized and evaluated for their A1and A2Aadenosine receptor affinity. Generally, the study compounds exhibited affinity for both the A1and A2Aadenosine receptors. Replacement of the 1,3-dimethyl-substition with a 1,3-diethyl-substition pattern increased A1and A2Abinding affinity. Overall it was found that para-substitution on the phenoxymethyl side-chain of the 1,3-diethyl-xanthines decreased A1affinity except for the 4-Br analog (4f) exhibiting the best A1affinity in the submicromolar range. On the other hand A2Aaffinity for the 1,3-diethyl-xanthines were increased with para-substitution and the 4-OCH3(4b) analog showed the best A2Aaffinity with a Kivalue of 237?nM. The 1,3-diethyl-substituted analogs (4a, and 4f) behaved as A1adenosine receptor antagonists in GTP shift assays performed with rat whole brain membranes expressing A1adenosine receptors. This study concludes that para-substituted 1,3-diethyl-7-methyl-8-(phenoxymethyl)-xanthine analogs represent novel A1and A2Aadenosine receptor antagonists that are appropriate for the design of therapies for neurodegenerative disorders such as Parkinson's and Alzheimer's disease.
- Harmse, Rozanne,van der Walt, Mietha M.,Petzer, Jacobus P.,Terre'Blanche, Gisella
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- Design, docking, synthesis, and characterization of novel N'(2-phenoxyacetyl) nicotinohydrazide and N'(2-phenoxyacetyl)isonicotinohydrazide derivatives as anti-inflammatory and analgesic agents
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Inflammation is the complex biological response of vascular tissues, which is partly determined by prostaglandins (PLA2). The cyclooxygenase (COX) enzyme exists in two isoforms: COX-1 and COX-2 and by the action of this, the PGs are produced. Besides, nonsteroidal anti-inflammatory drugs (NSAIDs) are therapeutic agents useful in the treatment of inflammation. Encouraged by this, the new derivatives of N'(2-phenoxyacetyl)nicotinohydrazide 9(a-e) and N'(2-phenoxyacetyl)isonicotinohydrazide 10(a-e) were designed, synthesized, characterized, and identified as remarkable anti-inflammatory and analgesic agents. These compounds were prepared in a series of steps starting with different phenol derivatives. Among the series, compound (10e) showed the highest IC50 value for COX-1 inhibition, whereas compounds (9e) and (10e) exhibited the highest COX-2SI. Further, molecular Docking Studies have been performed for the potent compound to check the three-dimensional geometrical view of the ligand binding to the targeted enzymes.
- Al-Ostoot, Fares Hezam,Khanum, Shaukath Ara,M, Pallavi H,Vivek, Hamse Kameshwar
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- Synthesis, characterization and pharmacological activity of phenoxy acetic acid and Pyrazinium chlorochromate
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This study describes the synthesis and antibacterial, antifungal activity of phenoxy acetic acid and pyrazinium chlorochromate. The compounds were characterized by infrared and ultra violet visible spectral data. These compounds were reviewed for antibacterial and antifungal activity against Streptococcus, Entrococcus, Bacillus cereus, Proteus vulgaris, Mycobacterium tuberculosis, Azotobacter, E. coli, Pseudomonas aeruginosa, Candida albicans, A. Niger, Fusarium and Trichoderma by disc diffusion method.
- Anbarasu,Ilavenil
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- Synthesis and biological evaluation of isoflavone amide derivatives with antihyperlipidemic and preadipocyte antiproliferative activities
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A series of isoflavone amides were designed with isoflavone in place of the scaffold of 2-arylbenzoxazole as cholesterol ester transfer protein (CETP) inhibitors. Twelve new compounds were synthesized, and their inhibitory activities of CETP and preadipocyte proliferation were assayed. The hypolipidemic potency of the most effective compound HY-2c was further tested in vivo by hamster. The results indicate that HY-2c exhibited favorable antihyperlipidemic and preadipocyte antiproliferative activities.
- Wang, Wenbin,He, Yi,Xu, Pei,You, Qidong,Xiao, Hong,Xiang, Hua
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- Enhanced electrocatalytic hydrodechlorination of 2,4-dichlorophenoxyacetic acid by a Pd-Co3O4/Ni foam electrode
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A new Pd-Co3O4/Ni foam electrode was synthesized by a facile two-step method comprising co-electrodeposition and calcination. Compared with Ni foam-supported Pd electrodes obtained by electrodeposition or chemical deposition, the new Pd-Co3O4/Ni foam electrode exhibited greatly enhanced catalytic hydrodechlorination activity. The introduction of Co3O4 reduced the amount of Pd required. For the same degree of dechlorination of 2,4-D, only 25% of the Pd was required in the Pd-Co3O4/Ni foam electrode compared with the Ni foam electrode prepared by chemical deposition. Various characterizations indicated that Co3O4 on the surface of the Ni foam enhanced catalytic performance through accelerated generation of atomic H?. In addition, the good distribution of macropores, providing a larger specific surface area and lower electron transfer impedance, enabled more adsorption of atomic.
- Liu, Qiuxiang,Shen, Yanting,Song, Shuang,He, Zhiqiao
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- Electrochemical methoxymethylation of alcohols-a new, green and safe approach for the preparation of MOM ethers and other acetals
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A new, green, safe, cost-effective and highly efficient electrochemical approach for the methoxymethylation of alcohols and phenols was successfully developed. The methodology was also applied to the synthesis of substituted acetals.
- Luo, Xiya,Ma, Xiaofeng,Lebreux, Frédéric,Markó, István E.,Lam, Kevin
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- Effective catalytic hydrodechlorination of chlorophenoxyacetic acids over Pd/graphitic carbon nitride
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Catalytic hydrodechlorination (HDC) of chlorophenoxyacetic acids was performed over Pd/graphitic carbon nitride (Pd/g-C3N4) catalysts in the present work. A series of Pd/g-C3N4 catalysts were prepared by a deposition-precipitation method, and characterized by X-ray diffraction (XRD), N2 adsorption-desorption, transmission electron microscopy (TEM), CO chemisorption and X-ray photoelectron spectroscopy (XPS). The Pd/g-C3N4 catalysts showed excellent activity to convert dichlorophenoxyacetic acid (2,4-D) into phenoxyacetic acid (PA) and the catalytic activity was correlated with the ratio of Pd2+/(Pd0 + Pd2+) and Pd particle size. In addition, HDC of 2,4-D over Pd/g-C3N4 catalyst followed the Langmuir-Hinshelwood model, indicating an adsorption-controlled mechanism. Other chlorophenoxyacetic acids, such as 2-chlorophenoxyacetic acid (2-CPA), 4-chlorophenoxyacetic acid (4-CPA) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) could also be completely dechlorinated to PA over Pd/g-C3N4 catalysts.
- Jiang, Fang,Tan, Wenhui,Chen, Huan,Tan, Ling,Liu, Jingliang
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- Kinetically controlled acylation of 6-APA catalyzed by penicillin acylase from Streptomyces lavendulae: effect of reaction conditions in the enzymatic synthesis of penicillin V
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Enzymatic synthesis of penicillin V (penV) by acylation of 6-aminopenicillanic acid (6-APA) was carried out using methyl phenoxyacetate (MPOA) as activated acyl donor and soluble penicillin acylase from Streptomyces lavendulae (SlPVA) as biocatalyst. The effect of different reaction conditions on penV synthesis was investigated, such as enzyme concentration, pH, molar ratio of 6-APA to MPOA, as well as presence of DMSO as water-miscible co-solvent at different concentrations. Time-course profiles of all reactions followed the typical pattern of kinetically controlled synthesis (KCS) of β-lactam antibiotics: penV concentration reached a maximum (highest yield or Ymax) and then decreased gradually. Such maximum was higher at pH 7.0, observing that final penV concentration was abruptly reduced when basic pH values were employed in the reaction. Under the selected conditions (100 mM Tris/HCl buffer pH 7.0, 30 °C, 2.7percent (v/v) DMSO, 20 mM MPOA, 0.3 UI/ml of SlPVA), Ymax was enhanced by increasing the substrate molar ratio (6-APA to MPOA) up to 5, reaching a maximum of 94.5percent and a S/H value of 16.4 (ratio of synthetic activity to hydrolytic activity). As a consequence, the use of an excess of 6-APA as nucleophile has allowed us to obtain some of the highest Ymax and S/H values among those reported in literature for KCS of β-lactam antibiotics. Although many penicillin G acylases (PGAs) have been described in kinetically controlled acylations, SlPVA should be considered as a different enzyme in the biocatalytic tool-box for novel potential synthetic processes, mainly due to its different substrate specificity compared to PGAs.
- Arroyo, Miguel,García-Martín, Alberto,Hormigo, Daniel,López-Conejo, María Teresa,Saborido, Ana,Serrano-Aguirre, Lara,de la Mata, Isabel
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- Electrochemical reductive dechlorination of 2,4-dichlorophenoxyacetic acid using a palladium/nickel foam electrode
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The electrochemical reductive dechlorination of 2,4-dichlorophenoxyacetic acid (2,4-D) in an aqueous solution was investigated at ambient temperature using a palladium/nickel foam (Pd/Ni foam) electrode in batch mode experiments. The catalytic electrode prepared using the standard chemical deposition method was further characterized using X-ray diffraction and scanning electron microscopy. It was observed that the reaction followed a pseudo-first-order kinetics model, the magnetic agitator-supported system could achieve 87% removal of 2,4-D within 4 h, which is 16% higher than the efficiency obtained under a nitrogen atmosphere. No organic intermediates other than phenoxyacetic (PA), o-chlorophenoxyacetic acid (o-CPA) and p-chlorophenoxyacetic acid (p-CPA) were observed to be generated during the reaction. The dechlorination efficiency depended on several factors including the current density, the palladium loading and the initial concentrations of the supporting NaCl electrolyte and the 2,4-D. The palladium loading and the NaCl concentration had a greater effect on the dechlorination kinetics of 2,4-D. Furthermore, the efficiencies of dechlorination and PA formation could be improved by optimizing the reaction system by modifying the ventilation conditions.
- Zhu, Kairan,Baig, Shams Ali,Xu, Jiang,Sheng, Tiantian,Xu, Xinhua
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- Synthesis and luminescence properties of novel 8-hydroxyquinoline derivatives and their Eu(III) complexes
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Six novel 8-hydroxyquinoline derivatives were synthesized using 2-methyl-8-hydroxyquinoline and para-substituted phenol as the main starting materials, and were characterized by 1H nuclear magnetic resonance (NMR), mass spectrometry (MS), ultraviolet (UV) light analysis and infra-red (IR) light analysis. Their complexes with Eu(III) were also prepared and characterized by elemental analysis, molar conductivity, UV light analysis, IR light analysis, and thermogravimetric–differential thermal analysis (TG–DTA). The results showed that the ligand coordinated well with Eu(III) ions and had excellent thermal stability. The structure of the target complex was EuY1–6(NO3)3.2H2O. The luminescence properties of the target complexes were investigated, the results indicated that all target complexes had favorable luminescence properties and that the introduction of an electron-donating group could enhance the luminescence intensity of the corresponding complexes, but the addition of an electron-withdrawing group had the opposite effect. Among all the target complexes, the methoxy-substituted complex (–OCH3) had the highest fluorescence intensity and the nitro-substituted complex (–NO2) had the weakest fluorescence intensity. The results showed that 8-hydroxyquinoline derivatives had good energy transfer efficiency for the Eu(III) ion. All the target complexes had a relatively high fluorescence quantum yield. The fluorescence quantum yield of the complex EuY3(NO3)3.2H2O was highest among all target complexes and was up to 0.628. Because of excellent luminescence properties and thermal stabilities of the Eu(III) complexes, they could be used as promising candidate luminescent materials.
- Wu, Yongqiang,Guo, Tiantong,Shu, Dehua,Zhang, Wu,Luan, Fangfei,Shi, Ling,Guo, Dongcai
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- Rapid and complete hydrodechlorination of 2,4-dichlorophenoxyacetic acid catalyzed by Pd/TiO2 with H2 in deionized water
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Pd/TiO2 catalyzes rapid and complete hydrodechlorination of 2,4-dichlorophenoxyacetic acid dissolved in H2O with H2 to phenoxyacetic acid with a high turnover number of Pd at 303 K.
- Yamanaka, Ichiro,Nishikawa, Koji,Otsuka, Kiyoshi
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- Synthesis, Characterization and Properties of Novel Coumarin Derivatives and Their Europium Complexes
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Seven novel coumarin derivatives derived from salicylaldehyde and phenol were synthesized and characterized by 1H NMR and 13C NMR spectra, mass spectra, infrared spectra and elemental analysis. Their corresponding Eu(III) complexes having general formula EuL1-7(NO3)3·2H2O were successfully prepared and characterized by elemental analysis, EDTA titrimetric, molar conductivity, UV-Vis, FT-IR and thermal performance studies. The luminescence properties, fluorescence quantum yields and the electrochemical properties of the title complexes were investigated. The results showed that the title complexes exhibited characteristic emissions of europium ions and possessed relatively good fluorescence quantum yields. The luminescence intensity of the complex with bromine-substituted group is the strongest among all the title complexes. The introduction of electron-withdrawing groups can increase the luminescence properties and fluorescence quantum yields, decrease the HOMO and LUMO energy levels of the title europium complexes, but electron-withdrawing group conversely. And these title complexes may possibly be useful for studying in luminescent materials field.
- Yan, Dong,Li, Dong,Cheng, Guang,Yang, Zehui,Shi, Ling,Guo, Dongcai
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- Selective electrochemical dehalogenation of 2,4-dichlorophenoxyacetic acid in MeCN at room temperature
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2,4-Dichlorophenoxyacetic acid (commercial pesticide 2,4-D) can be dechlorinated by electrochemical reduction at different carbon materials under mild conditions to give phenoxyacetic acid with 80% selectivity at 75% conversion of 2,4-D (current efficiency 10~14%).
- Tsyganok, Andrey,Otsuka, Kiyoshi,Yamanaka, Ichiro,Plekhanov, Vasilii,Kulikov, Sergei
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- Design, synthesis, biological evaluation and structure-activity relationship study of quinazolin-4(3H)-one derivatives as novel USP7 inhibitors
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Recent research has indicated that the abnormal expression of the deubiquitinase USP7 induces tumorigenesis via multiple cell pathways, and in particular, the p53-MDM2-USP7 pathway is well understood. USP7 is emerging as a promising target for cancer therapy. However, there are limited reports on USP7 inhibitors. Here we report design, synthesis and biological evaluation of novel quinazolin-4(3H)-one derivatives as potent USP7 inhibitors. Our results indicated that the compounds C9 and C19 exhibited the greatest potency against the USP7 catalytic domain, with IC50 values of 4.86 μM and 1.537 μM, respectively. Ub-AMC assays further confirmed IC50 values of 5.048 μM for C9 and 0.595 μM for C19. MTT assays indicated that gastric cancer MGC-803 cells were more sensitive to these compounds than BGC-823 cells. Flow cytometry analysis revealed that C9 restricted cancer cell growth at the G0/G1 and S phases and inhibited the proliferation and clone formation of MGC-803 cells. Further biochemical experiments indicated that C9 decreased the MDM2 protein level and increased the levels of the tumour suppressors p53 and p21 in a dose-dependent manner. Docking studies predicted that solvent exposure of the side chains of C9 and C19 would uniquely form hydrogen bonds with Met407 of USP7. Additionally, C9 exhibited a remarkable anticancer effect in a zebrafish gastric cancer MGC-803 cell model. Our results demonstrated that quinazolin-4(3H)-one derivatives were suitable as leads for the development of novel USP7 inhibitors and especially for anti-gastric cancer drugs.
- Li, Peng,Liu, Ying,Yang, Hua,Liu, Hong-Min
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- Synthesis and luminescence properties of pyrazolone derivatives and their terbium complexes
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Seven novel pyrazolone derivatives were synthesized and characterized by 1H NMR and 13C NMR spectra, mass spectra, infrared spectra and elemental analysis. Their terbium complexes were prepared and characterized by elemental analysis, EDTA titrimetric analysis, UV/vis spectra, infrared spectra and molar conductivity, as well as thermal analysis. The fluorescence properties and fluorescence quantum yields of the complexes were investigated at room temperature. The results indicated that pyrazolone derivatives had good energy-transfer efficiency for the terbium ion. All the terbium complexes emitted green fluorescence characteristic of terbium ions, possessed strong fluorescence intensity, and showed relatively high fluorescence quantum yields. Cyclic voltammograms of the terbium complexes were studied and the highest occupied molecular orbital (HOMO) and lowest occupied molecular orbital (LUMO) energy levels of these complexes were estimated.
- Xiao, Haihua,Jiang, Xi,Li, Dong,Wu, Limin,Zhang, Wu,Guo, Dongcai
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- Diradicals Photogeneration from Chloroaryl-Substituted Carboxylic Acids
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With the aim of generating new, thermally inaccessible diradicals, potentially able to induce a double-strand DNA cleavage, the photochemistry of a set of chloroaryl-substituted carboxylic acids in polar media was investigated. The photoheterolytic cleavage of the Ar?Cl bond occurred in each case to form the corresponding triplet phenyl cations. Under basic conditions, the photorelease of the chloride anion was accompanied by an intramolecular electron-transfer from the carboxylate group to the aromatic radical cationic site to give a diradical species. This latter intermediate could then undergo CO2 loss in a structure-dependent fashion, according to the stability of the resulting diradical, or abstract a hydrogen atom from the medium. In aqueous environment at physiological pH (pH=7.3), both a phenyl cation and a diradical chemistry was observed. The mechanistic scenario and the role of the various intermediates (aryl cations and diradicals) involved in the process was supported by computational analysis.
- Di Terlizzi, Lorenzo,Protti, Stefano,Ravelli, Davide,Fagnoni, Maurizio
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- Polycarboxylated compounds and compositions containing same
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Methods of selectively modifying lignin, polycarboxylated products thereof, and methods of deriving aromatic compounds therefrom. The methods comprise electrochemically oxidizing lignin using stable nitroxyl radicals to selectively oxidize primary hydroxyls on β-O-4 phenylpropanoid units to corresponding carboxylic acids while leaving the secondary hydroxyls unchanged. The oxidation results in polycarboxylated lignin in the form of a polymeric β-hydroxy acid. The polymeric β-hydroxy acid has a high loading of carboxylic acid and can be isolated in acid form, deprotonated, and/or converted to a salt. The β-hydroxy acid, anion, or salt can also be subjected to acidolysis to generate various aromatic monomers or oligomers. The initial oxidation of lignin to the polycarboxylated form renders the lignin more susceptible to acidolysis and thereby enhances the yield of aromatic monomers and oligomers obtained through acidolysis.
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- Juvenile hormone mimics with phenyl ether and amide functionality to be insect growth regulators (IGRs): synthesis, characterization, computational and biological study
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A series of substituted phenyl ethers derivatives as juvenile hormone (JH) mimics (V1-V8) have been synthesized. Substituted phenoxyacetic acid and amino acid ethyl ester hydrochloride were prepared using NaOH, SOCl2. DCC method has been used for amide linkage. The structure of prepared compounds has been confirmed by Fourier Transform Infra-Red (FT-IR), Electrospray ionization-Mass spectrometry (ESI-MS), Proton and Carbon-13 nuclear magnetic resonance (1H-NMR, 13C-NMR) spectroscopic techniques. Biological efficacy of synthesized analogs has been carried out under laboratory conditions. Galleria mellonella (honey bee pest) has been chosen as testing insect. Juvenile hormone (JH) activity of synthesized compounds has been tested at different concentrations and compared with the standard juvenile hormone analogs (JHAs) pyriproxyfen (M1) and fenoxycarb (M2) against the fifth larval instar of G. mellonella. Compound ethyl 2-[2-(4-methylphenoxy)aminoacetyl]-3-phenyl-propanoate (V6) exhibited better activity among all the synthesized compounds (V1-V8) with LC50 and LC90 values of 0.11 mg/mL and 0.56 mg/mL respectively. Compounds showed insect growth regulating (IGR) activity at lower concentrations. In silico screening of all synthesized compounds with the W-cavity of juvenile hormone-binding protein (JHBP) of insect G. mellonella has been carried out. Chemical reactivity of synthesized series has been studied using DFT/B3LYP/6-311 + G(d,2p) method. Non-toxic behavior of molecules has also been observed from ADMET (Absorption, Distribution, Metabolism, Excretion, and Toxicity) study using discovery studio client 3.0. Communicated by Ramaswamy H. Sarma.
- Awasthi, Pamita,Devi, Vandna
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- (Trifluoromethylselenyl)methylchalcogenyl as Emerging Fluorinated Groups: Synthesis under Photoredox Catalysis and Determination of the Lipophilicity
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The synthesis of molecules bearing (trifluoromethylselenyl)methylchalcogenyl groups is described via an efficient two-step strategy based on a metal-free photoredox catalyzed decarboxylative trifluoromethylselenolation with good yields up to 88 %, which raised to 98 % in flow chemistry conditions. The flow methods allowed also to scale up the reaction. The mechanism of this key reaction was studied. The physicochemical characterization of these emerging groups was performed by determining their Hansch–Leo lipophilicity parameters with high values up to 2.24. This reaction was also extended to perfluoroalkylselenolation with yields up to 95 %. Finally, this method was successfully applied to the functionalization of relevant bioactive molecules such as tocopherol or estrone derivatives.
- Grollier, Kevin,De Zordo-Banliat, Arnaud,Bourdreux, Flavien,Pegot, Bruce,Dagousset, Guillaume,Magnier, Emmanuel,Billard, Thierry
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supporting information
p. 6028 - 6033
(2021/03/15)
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- Modulation of DNA damage response by targeting ATM kinase using newly synthesized di-phenoxy acetamide (DPA) analogs to induce anti-neoplasia
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Background: Imbalance and instability in the structure of the DNA have become major characteristics of cancer. In response to DNA damage, DNA damage response (DDR) protein, ataxia telangiectasia mutated (ATM), plays a pivotal role in the modulation of regulatory regions responsible for inhibition of apoptosis, thereby neoplastic progression. Methods: A new series of DPA (7a–t) were synthesized, characterized. Anti-proliferative studies to identify the lead compound were carried out by LDH and MTT assay. Apoptosis/DNA damage was measured through FACS, Annexin-v staining, TUNEL and Comet assay. Elucidation of molecular mechanism through immunoblot and further validation of the drug effect through in vivo approaches. Results: Initial in vitro anti-proliferative screening of Compounds DPA (7a–t) against multiple cancer cell lines identified Compound DPA (7n) as a potent cytotoxic molecule with IC50 value of 4.3?μM. Down the line, in vitro and in vivo evaluation of Compound DPA (7n) inferred that it has apoptotic inducing potentiality. Further, evaluation of molecular mechanism inferred that Compound DPA (7n) effectively modulates ATM phosphorylation only, eventually altering downstream signalling pathways. Conclusions: Compound DPA (7n) emerged as a potent proapoptotic and anti-neoplastic agent by inhibiting ATM kinase activity both in vitro and in vivo. The conferring results ascertain that the drug could be developed as a new ATM kinase inhibitor with anti-cancer capacity. Graphic abstract: [Figure not available: see fulltext.]
- Al-Ostoot, Fares Hezam,Sherapura, Ankith,Malojirao, Vikas H.,Thirusangu, Prabhu,Al-Muhimeed, Tahani I.,Khanum, Shaukath Ara,Prabhakar
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p. 1344 - 1360
(2021/06/14)
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- Targeting HIF-1α by newly synthesized Indolephenoxyacetamide (IPA) analogs to induce anti-angiogenesis-mediated solid tumor suppression
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Background: Hypoxic microenvironment is a common feature of solid tumors, which leads to the promotion of cancer. The transcription factor, HIF-1α, expressed under hypoxic conditions stimulates tumor angiogenesis, favoring HIF-1α as a promising anticancer agent. On the other hand, synthetic Indolephenoxyacetamide derivatives are known for their pharmacological potentiality. With this background here, we have synthesized, characterized, and validated the new IPA (8a–n) analogs for anti-tumor activity. Methods: The new series of IPA (8a–n) were synthesized through a multi-step reaction sequence and characterized based on the different spectroscopic analysis FT-IR, 1H, 13C NMR, mass spectra, and elemental analyses. Cell-based screening of IPA (8a–n) was assessed by MTT assay. Anti-angiogenic efficacy of IPA (8k) validated through CAM, Rat corneal, tube formation and migration assay. The underlying molecular mechanism is validated through zymogram and IB studies. The in vivo anti-tumor activity was measured in the DLA solid tumor model. Results: Screening for anti-proliferative studies inferred, IPA (8k) is a lead molecule with an IC50 value of ?5?μM. Anti-angiogenic assays revealed the angiopreventive activity through inhibition of HIF-1α and modulation downstream regulatory genes, VEGF, MMPs, and P53. The results are confirmative in an in vivo solid tumor model. Conclusion: The IPA (8k) is a potent anti-proliferative molecule with anti-angiogenic activity and specifically targets HIF1α, thereby modulates its downstream regulatory genes both in vitro and in vivo. The study provides scope for new target-specific drug development against HIF-1α for the treatment of solid tumors. Graphic abstract: [Figure not available: see fulltext.].
- Al-Ostoot, Fares Hezam,Sherapura, Ankith,V, Vigneshwaran,Basappa, Giridhara,H.K, Vivek,B.T, Prabhakar,Khanum, Shaukath Ara
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p. 1328 - 1343
(2021/05/03)
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- Synthesis and herbicidal activities of aryloxyacetic acid derivatives as HPPD inhibitors
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A series of aryloxyacetic acid derivatives were designed and synthesized as 4-hydoxyphenylpyruvate dioxygenase (HPPD) inhibitors. Preliminary bioassay results reveal that these derivatives are promising Arabidopsis thaliana HPPD (AtHPPD) inhibitors, in particular compounds I12 (Ki = 0.011 μM) and I23 (Ki = 0.012 μM), which exhibit similar activities to that of mesotrione, a commercial HPPD herbicide (Ki = 0.013 μM). Furthermore, the newly synthesized compounds show significant greenhouse herbicidal activities against tested weeds at dosages of 150 g ai/ha. In particular, II4 exhibited high herbicidal activity for pre-emergence treatment that was slightly better than that of mesotrione. In addition, compound II4 was safe for weed control in maize fields at a rate of 150 g ai/ha, and was identified as the most potent candidate for a novel HPPD inhibitor herbicide. The compounds described herein may provide useful guidance for the design of new HPPD inhibiting herbicides and their modification.
- Huang, Hao,Liu, Jian-Min,Shu, Lei,Wang, Man-Man,Yan, Yi-Le,Zhang, Da-Yong,Zhang, Jian-Qiu
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supporting information
p. 233 - 247
(2020/03/27)
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- Shape Similarity by Fractal Dimensionality: An Application in the de novo Design of (?)-Englerin A Mimetics
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Molecular shape and pharmacological function are interconnected. To capture shape, the fractal dimensionality concept was employed, providing a natural similarity measure for the virtual screening of de novo generated small molecules mimicking the structurally complex natural product (?)-englerin A. Two of the top-ranking designs were synthesized and tested for their ability to modulate transient receptor potential (TRP) cation channels which are cellular targets of (?)-englerin A. Intracellular calcium assays and electrophysiological whole-cell measurements of TRPC4 and TRPM8 channels revealed potent inhibitory effects of one of the computer-generated compounds. Four derivatives of this identified hit compound had comparable effects on TRPC4 and TRPM8. The results of this study corroborate the use of fractal dimensionality as an innovative shape-based molecular representation for molecular scaffold-hopping.
- Bauer, Christoph,Byrne, Ryan,Friedrich, Lukas,Gudermann, Thomas,Mederos y Schnitzler, Michael,Schneider, Gisbert,Singh, Inderjeet,Storch, Ursula,Treder, Aaron
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supporting information
(2020/03/24)
-
- Design and synthesis of α-phenoxy-N-sulfonylphenyl acetamides as Trypanosoma brucei Leucyl-tRNA synthetase inhibitors
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Human African trypanosomiasis (HAT), caused by the parasitic protozoa Trypanosoma brucei, is one of the fatal diseases in tropical areas and current medicines are insufficient. Thus, development of new drugs for HAT is urgently needed. Leucyl-tRNA synthetase (LeuRS), a recently clinically validated antimicrobial target, is an attractive target for development of antitrypanosomal drugs. In this work, we report a series of α-phenoxy-N-sulfonylphenyl acetamides as T. brucei LeuRS inhibitors. The most potent compound 28g showed an IC50 of 0.70 μM which was 250-fold more potent than the starting hit compound 1. The structure-activity relationship was also discussed. These acetamides provided a new scaffold and lead compounds for the further development of clinically useful antitrypanosomal agents.
- Xin, Weixiang,Li, Zezhong,Wang, Qing,Du, Jin,Zhu, Mingyan,Zhou, Huchen
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- Sulfuryl Fluoride Mediated Synthesis of Amides and Amidines from Ketoximes via Beckmann Rearrangement
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A metal-free and redox-neutral method for Beckmann rearrangement employing inexpensive and readily available SO2F2 gas is described. The reported transformation proceeds at ambient temperature and is compatible with a wide range of sterically and electronically diverse aromatic, heteroaromatic, aliphatic and lignin-like oximes providing amides in good to excellent yields. The reaction proceeds through the formation of an imidoyl fluoride intermediate that can also be used for the synthesis of amidines.
- Gurjar, Jitendra,Fokin, Valery V.
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supporting information
p. 10402 - 10405
(2020/07/25)
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- Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization
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An electrochemical process has been developed for chemoselective oxidation of primary alcohols in lignin to the corresponding carboxylic acids. The electrochemical oxidation reactions proceed under mildly basic conditions and employ 2,2,6,6-tetramethyl-1-piperidine N-oxyl (TEMPO) and 4-acetamidoO (ACT) as catalytic mediators. Lignin model compounds and related alcohols are used to conduct structure-reactivity studies that provide insights into the origin of the reaction selectivity. The method is applied to the oxidation of lignin extracted from poplar wood chips via a mild acidolysis method, and the reaction affords a novel polyelectrolyte material. Gel permeation chromatography data for the oxidized lignin shows that this material has a molecular weight and molecular weight distribution very similar to that of the extracted lignin, but notable differences are also evident. Base titration reveals a significant increase in the acid content, and the oxidized lignin has much higher water solubility relative to the extracted lignin. Treatment of the oxidized lignin under acidic conditions results in depolymerization of the material into characterized aromatic monomers in nearly 30 wt% yield.
- Rafiee, Mohammad,Alherech, Manar,Karlen, Steven D.,Stahl, Shannon S.
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supporting information
p. 15266 - 15276
(2019/10/19)
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- Design and Synthesis of Novel 4-Hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one Derivatives for Use as Herbicides and Evaluation of Their Mode of Action
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In order to develop a novel herbicide containing the β-triketone motif, a series of 4-hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one derivatives were designed and synthesized. The bioassay results showed that compound II15 had good pre-emergent herbicidal activity even at a dosage of 187.5 g ha-1. Moreover, compound II15 showed a broader spectrum of weed control when compared with a commercial herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), and displayed good crop safety to Triticum aestivum L. and Zea mays Linn. when applied at 375 g ha-1 under pre-emergence conditions, which indicated its great potential as a herbicide. More importantly, studying the molecular mode of action of compound II15 revealed that the novel triketone structure is a proherbicide of its corresponding phenoxyacetic acid auxin herbicide, which has a herbicidal mechanism similar to that of 2,4-D. The present work indicates that the 4-hydroxyl-3-(2-phenoxyacetyl)-pyran-2-one motif may be a potential lead structure for further development of novel auxin-type herbicides.
- Lei, Kang,Li, Pan,Yang, Xue-Fang,Wang, Shi-Ben,Wang, Xue-Kun,Hua, Xue-Wen,Sun, Bin,Ji, Lu-Sha,Xu, Xiao-Hua
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p. 10489 - 10497
(2019/10/02)
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- Ketoreductase catalyzed stereoselective bioreduction of α-nitro ketones
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We report here the stereoselective bioreduction of α-nitro ketones catalyzed by ketoreductases (KREDs) with publicly known sequences. YGL039w and RasADH/SyADH were able to reduce 23 class I substrates (1-aryl-2-nitro-1-ethanone (1)) and ten class II substrates (1-aryloxy-3-nitro-2-propanone (4)) to furnish both enantiomers of the corresponding β-nitro alcohols, with good-to-excellent conversions (up to >99%) and enantioselectivities (up to >99% ee) being achieved in most cases. To the best of our knowledge, KRED-mediated reduction of class II α-nitro ketones (1-aryloxy-3-nitro-2-propanone (4)) is unprecedented. Select β-nitro alcohols, including the synthetic intermediates of bioactive molecules (R)-tembamide, (S)-tembamide, (S)-moprolol, (S)-toliprolol and (S)-propanolol, were stereoselectively synthesized in preparative scale with 42% to 90% isolated yields, showcasing the practical potential of our developed system in organic synthesis. Finally, the advantage of using KREDs with known sequence was demonstrated by whole-cell catalysis, in which β-nitro alcohol (R)-2k, the key synthetic intermediate of hypoglycemic natural product (R)-tembamide, was produced in a space-time yield of 178 g L?1 d?1 as well as 95% ee by employing the whole cells of a recombinant E. coli strain coexpressing RasADH and glucose dehydrogenase as the biocatalyst.
- Wang, Zexu,Wu, Xiaofan,Li, Zhining,Huang, Zedu,Chen, Fener
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supporting information
p. 3575 - 3580
(2019/04/14)
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- Electrochemical Oxidation of Alcohols and Aldehydes to Carboxylic Acids Catalyzed by 4-Acetamido-TEMPO: An Alternative to "anelli" and "pinnick" Oxidations
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An electrocatalytic method has been developed to oxidize primary alcohols and aldehydes to the corresponding carboxylic acids using 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl (ACT) as a mediator. The method successfully converts benzylic, aliphatic, heterocyclic, and other heteroatom-containing substrates to the corresponding carboxylic acids in aqueous solution at room temperature. The mild conditions enable retention of stereochemistry adjacent to the site of oxidation, as demonstrated in a 40 g-scale synthesis of a precursor to levetiracetam, a medication used to treat epilepsy.
- Rafiee, Mohammad,Konz, Zachary M.,Graaf, Matthew D.,Koolman, Hannes F.,Stahl, Shannon S.
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p. 6738 - 6744
(2018/06/19)
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- Selective conversion of primary amides to esters promoted by KHSO4
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Primary amides, either aliphatic or aromatic, are easily converted to the corresponding esters via reflux in lower primary alcohols in the presence of KHSO4. Secondary amides lead to complicated mixtures under analogous conditions, whereastertiary amides were inert. Use of isopropyl alcohol resulted inthe formation of product atslower rate and lower yieldalong withside products, whereas, use of tertiary alcoholsdid not give successful conversion andallyl and benzyl alcohol provided complex mixtures.
- Sattenapally, Narsimha,Sharma, Jhanvi,Hou, Yuqing
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p. 174 - 183
(2018/09/10)
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- Hydrodehalogenation of Polyhalogenated Aromatics Catalyzed by NiPd Nanoparticles Supported on Nitrogen-Doped Graphene
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Ni30Pd70 nanoparticles supported on nitrogen-doped graphene (NG) acts as a catalyst for the hydrodehalogenation of halogenated aromatics under mild reaction conditions. It reduces mono- or dichloroarenes to the corresponding dehalogenated arenes in >90 % yield in 10 % aqueous isopropanol solvent at or below 50 °C within 5 h. Tests on a variety of substrates containing various functional groups show that the catalyst is selective for reduction of C?Cl and C?Br bonds. In addition, this catalyst completely hydrodehalogenates high-concentration solutions of dioxin, polychlorinated biphenyls, chloroaromatic constituents of the defoliant agent orange, and polybrominated diphenyl ethers in 12 h. The catalyst is reusable and shows no morphological or compositional changes after 5 cycles. This methodology offers a powerful, low-cost, and safe technology for the degradation of polyhalogenated aromatics, and may be useful for preventing proliferation of these toxins in the environment from causing serious health issues.
- Guo, Xuefeng,Yu, Chao,Yin, Zhouyang,Sun, Shouheng,Seto, Christopher T.
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p. 1617 - 1620
(2018/06/15)
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- 3 - (2 - Acetyl) -4 - hydroxy -6 - methyl pyran -2 - ketone derivatives and its application
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The invention relates to a 3 - (2 - acetyl) - 4 - hydroxy - 6 - methyl-pyran - 2 - one derivatives and application. This kind of structure of the compound of the general formula (I), R, R1 Such as defined in the claims. In order to various phenol and chloroethyl acid methyl ester as the raw material, first of all by the substitution, hydrolysis, acylation reaction various phenoxy acetyl chloride, then with 4 - hydroxy - 6 - methyl-pyran - 2 - one condensation borate intermediate, finally through the Fries rearrangement reaction is obtained by the synthesis of 3 - (2 - acetyl) - 4 - hydroxy - 6 - methyl-pyran - 2 - one derivatives. The invention also relates to 3 - (2 - acetyl) - 4 - hydroxy - 6 - methyl-pyran - 2 - one derivatives in the herbicide application. Test results show that the compounds have good herbicidal activity, are a class of novel structure, application prospect of herbicide.
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Paragraph 0017; 0019
(2018/10/11)
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- The Novel 4-Phenyl-2-Phenoxyacetamide Thiazoles modulates the tumor hypoxia leading to the crackdown of neoangiogenesis and evoking the cell death
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Tumor microenvironment is a complex multistep event which involves several hallmarks that transform the normal cell into cancerous cell. Designing the novel antagonistic molecule to reverse the tumor microenvironment with specific target is essential in modern biological studies. The novel 4-phenyl-2-phenoxyacetamide thiazole analogues 8a-ab were synthesized in multistep process, then screened and assessed for cytotoxic and anti-proliferative effects in vitro against multiple cancer cells of different origin such as MCF-7, A549, EAC and DLA cells which revealed that compound 8f with fluoro and methyl substitute has potential cytotoxic efficacy with an average IC50 value of ? 13 μM. The mechanism of cytotoxicity assessed for anti-tumor studies both in ascites and solid tumor models in-vivo inferred the regressed tumor activity. This is due to changes in the cause of tumor microenvironment with crackdown of neovascularization and evoking apoptosis process as assessed by CAM, corneal vascularization and apoptotic hallmarks in 8f treated cells. The molecular gene studies inferred involvement of HIF-1upregulation and stabilization of p53 which are interlinked in signaling as conferred by immunoblot analysis.
- Mohammed, Yasser Hussein Eissa,Malojirao, Vikas H.,Thirusangu, Prabhu,Al-Ghorbani, Mohammed,Prabhakar,Khanum, Shaukath Ara
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p. 1826 - 1839
(2017/11/16)
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- A phenoxy ester preparation method (by machine translation)
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The invention provides a phenoxy ester preparation method, comprises the following steps: the phenol compounds with chlorine suo ester, acid, catalyst in the solvent mixed, one-pot synthesis to carry out the condensation reaction, to obtain the phenoxy carboxylic acid ester compounds; the solvent is DMF, DMSO, DMI and acetone in the one or more; wherein said catalyst is a quaternary ammonium salt or polyethylene glycol. The invention realizes a non-hydrous-phenoxy acetate, anhydrous outputs, anhydrous participation, truly zero waste water discharge, reduce the discharge of waste water, post filtering to salt can, without dehydration, low energy consumption, one-pot synthesis method ensures that the reaction procedure is simple, less equipment investment. And reduces [...] in a hydrolysis reaction, ɑ - chloro carboxylic acid hydrolysis, thereby reducing the consumption of ɑ - chloro carboxylic acid, at the same time effectively avoids the prior art machines or acid pure product of the solid-liquid separation as a result of the losses of the active ingredient, the extraction rate of the active ingredient, the product has high purity, high yield. (by machine translation)
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Paragraph 0044; 0045
(2019/01/08)
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- Preparation method for 2,4-dichlorophenoxyacetic acid
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The invention provides a preparation method for 2,4-dichlorophenoxyacetic acid. The preparation method comprises the following steps: A) reacting halogenated acetic acid with alcohol so as to obtain halogenated acetate, and reacting phenol with alkali to obtain phenolate; B) reacting halogenated acetate with phenolate to obtain phenoxyacetate; C) hydrolyzing phenoxyacetate to obtain phenoxyaceticacid; and D) chlorinating phenoxyacetic acid under the action of a catalyst to obtain 2,4-dichlorophenoxyacetic acid, wherein the catalyst is one or more selected from the group consisting of ferric trichloride, aluminum trichloride, boron trifluoride, niobium pentachloride, trifluoromethanesulfonate, alumina, ferric oxide, boron trioxide, niobium pentoxide, diphenyl ether, diphenyl sulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide. According to the invention, phenolate reacts with halogenated acetate to obtain phenoxyacetate, then phenoxyacetate is hydrolyzed to obtain phenoxyacetic acid, and phenoxyacetic acid is chlorinated under the action of the specific catalyst so as to obtain 2,4-dichlorophenoxyacetic acid. The preparation method of the invention uses the specific catalyst, and has the advantages of good reaction selectivity, few by-products and high yield.
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Paragraph 0050; 0051; 0052; 0053; 0054; 0055
(2018/09/08)
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- Method for synthesizing phenoxyacetic acid derivatives
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The invention relates to a method for synthesizing phenoxyacetic acid derivatives. The method comprises the steps of mixing a salt compound of phenol or cresol and a salt compound of chloroacetic acid, putting the mixture into a solvent for heating reaction, and performing acidification by an inorganic acid to obtain phenoxyacetic acid; and then, dissolving the phenoxyacetic acid in a solvent, adding a catalyst, introducing chlorine gas for heating chlorination reaction, and performing cooling crystallization to obtain a chlorine-substituted phenoxyacetic acid (or methylphenoxyacetic acid) derivative. Compared with the prior art, during the reaction process, the solvent of the reaction system and wastewater are recovered for recycled, so that the method satisfies production balance and cyclic utilization of a closed system, the yield is more than 95%, the product content is more than 98%, the utilization rate of the recycled solvent is greater than 95%, and wastewater emission is reduced by 95% or more in the entire production process.
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Paragraph 0027-0028
(2018/04/21)
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- Isoflavone amide derivatives, their preparation method and medical use
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The invention belongs to the field of medicinal chemistry, and relates to derivatives of isoflavones amides, as well as a preparation method and medical application of derivatives, in particular to the derivatives of the isoflavones amides with the general formula of (I) shown as the specification, the preparation method and the medical application of the derivatives, particularly the application of the derivatives of the isoflavones amides serving as medicaments for preventing or treating hyperlipemia, adiposis or type-II diabetes.
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Paragraph 0077
(2017/08/31)
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- The anti-invasive role of novel synthesized pyridazine hydrazide appended phenoxy acetic acid against neoplastic development targeting matrix metallo proteases
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Neoplastic metastasis is a major process where tumor cells migrate from the primary tumor and colonize at other parts of our body to form secondary tumor. Cancer incidences are rising and novel anti-neoplastic compounds with new mechanism of actions are essential for preventing cancer related deaths. In the current examination, a novel series of pyridazine analogues 6a-l was synthesized and evaluated against metastatic neoplastic cells. Experimental data postulated compound 6j has potential cytotoxic efficacy with prolonged activity against various cancer cells, including A549, HepG2, A498, CaSki and SiHa cells. Moreover, compound 6j arrests the A549 migration and invasions markedly by counteracting matrix metalloproteinase (MMP)-2 and MMP-9 expressions. Also, compound 6j proved its potentiality against Dalton's solid lymphoma progression in-vivo by abridging MVD and MMP expressions. Compound 6j interacts with MMP-2 and MMP-9 by H- bond in-silico, thereby down regulates the MMPs action in tumourigenesis. Altogether, we concluded that compound 6j down regulates MMP-2 and MMP-9 and thereby impairs metastatic cancer cell migration and invasions which can be translated into a potent anti-neoplastic agent.
- Eissa Mohammed, Yasser Hussein,Thirusangu, Prabhu,Zabiulla,Vigneshwaran,B.T, Prabhakar,Khanum, Shaukath Ara
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p. 375 - 386
(2017/09/02)
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- Dissociative reactions of benzonorbornadienes with tetrazines: Scope of leaving groups and mechanistic insights
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Bioorthogonal dissociative reactions boast diverse potential applications in chemical biology and drug delivery. The reaction of benzonorbornadienes with tetrazines to release amines from carbamate leaving groups was recently introduced as a bioorthogonal bond-cleavage reaction. The present study aimed at investigating the scope of leaving groups that are compatible with benzonorbornadienes. Synthesis of several benzonorbornadienes with different releasable groups is reported, and the reaction of these molecules with tetrazine was found to be rapid and afforded high release yields. The tetrazine-induced release of molecules proceeds in a cascade of steps including inverse-electron demand cycloaddition and cycloreversion reactions that form unstable isoindoles/isobenzofuran intermediates and spontaneously eliminate a leaving group of interest. In the case of oxygen-bridged BNBDs at room temperature, we observed the formation of an unproductive byproduct.
- Xu,Galindo-Murillo,Cheatham,Franzini
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supporting information
p. 9855 - 9865
(2017/12/12)
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- A continuous synthesis of phenoxy acetic acid method
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The invention provides a continuous synthetic method of phenoxy acetic acid and belongs to the technical field of preparation of a herbicide 2,4-D intermediate. The method comprises the following steps: simultaneously adding a sodium phenoxide aqueous solution and a sodium chloroacetate aqueous solution into a constant-pressure funnel provided with a heating sleeve to perform mixed reaction, and retaining the mixture in the constant-pressure funnel for 10-15min; overflowing reaction liquid into a 3-mouth flask containing dilute hydrochloric acid or dilute sulfuric acid at 15-20 DEG C; adjusting the pH value to 5-6 by using the dilute hydrochloric acid or dilute sulfuric acid; stirring for 0.8-1.2 hours at room temperature; and performing suction filtration to obtain white crystalline powder namely phenoxy acetic acid. According to the method provided by the invention, the sodium phenoxide aqueous solution and the sodium chloroacetate aqueous solution are simultaneously added into the constant-pressure funnel provided with the heating sleeve to perform reaction, so that the internal pressure can be kept unchanged, inverse suction can be prevented and the liquid in the funnel can flow downwards smoothly to improve the reaction efficiency; and moreover, during the preparation of the sodium chloroacetate solution, a Na2CO3 solution is dropwise added into chloroacetic acid slowly, and the chloroacetic acid is excessive, so that the reaction temperature can be beneficially controlled, and side reactions are reduced.
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Paragraph 0022; 0025; 0026; 0029; 0030; 0033
(2017/08/25)
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- Reactions of peroxide products of ozonolysis of allyl ethers/esters in the AcOH-CH2Cl2 system on treatment with semicarbazide hydrochloride
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Background: A one-pot method for the preparation of the corresponding alkoxy acetic acids by low-temperature ozonolysis of allyl ethers/esters followed by treatment with semicarbazide hydrochloride has been suggested. The reaction occurs via formation of acetoxyhydroperoxide, subsequent reduction of which depends on the process temperature and the nature of the starting substrate. Objective: The article is aimed at the development of one-pot method for obtaining practically important alkoxy acetic acids, because the ozonolytic cleavage of a ?=? double bond is the key step in full syntheses of many biologically active compounds. Methods: We used a low temperature ozonolysis of functionally substituted olefins in the system acetic acid-methylene dichloride followed by reduction of semicarbazide hydrochloride. To create a method we have used available allyl ethers/esters as starting materials. Results: We investigated reaction of the peroxide products of ozonolysis of monoallyl ethers, ester and diallyl ethers in an AcOH/CH2Cl2 mixture on treatment with semicarbazide hydrochloride at various temperatures. We have discovered that the selectivity of reduction of acetoxyhydroperoxide formed at the first stage depends both on the process temperature and on the nature of the starting substrate. A decrease in temperature favors acid hydrolysis and formation of a carboxylic acid. Conclusion: We have proposed a simple and highly efficient one-pot method for the preparation alkoxy acetic acids without isolation of intermediate peroxides.
- Raskil'dina, Gulnara Z.,Legostaeva, Yuliya V.,Garifullina, Liliya R.,Sultanova, Rimma M.,Ishmuratov, Gumer Y.,Zlotskii, Simon S.
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p. 652 - 656
(2017/01/13)
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- Formononetin derivatives and preparation methods and medical application thereof
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The invention relates to the field of pharmaceutical chemistry, and relates to formononetin derivatives and preparation methods and medical application thereof, in particular to formononetin derivatives with the general formula as shown in (I), preparation methods thereof, pharmaceutical compositions containing the compounds and medical application of the derivatives and the pharmaceutical compositions, particularly, application of the derivatives and the pharmaceutical compositions serving as drugs for preventing or treating hyperlipidaemia or obesity or type-II diabetes. Please see the formula in the description.
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Paragraph 0069; 0070; 0071; 0075; 0076; 0077
(2017/04/29)
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- 2,4-dichlorophenoxyacetic acid preparation method
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The invention provides a 2,4-dichlorophenoxyacetic acid preparation method including the following steps: A) providing phenoxyacetic acid; B) mixing hydrochloric acid, an oxidizing agent and the phenoxyacetic acid of the step A), carrying out a chlorination reaction in the presence of a chlorination catalyst, to obtain 2,4-dichlorophenoxyacetic acid, wherein the molar ratio of the phenoxyacetic acid to the hydrochloric acid to the oxidizing agent is 1 to (2-200) to (2-200), and the molar ratio of the hydrochloric acid to the oxidizing agent is 1 to (0.1-10). The 2,4-dichlorophenoxyacetic acid preparation method provided by the invention only needs one-step chlorination reaction, and then the 2,4-dichlorophenoxyacetic acid can be obtained; while the purity and yield of the 2,4-dichlorophenoxyacetic acid are ensured, the production process of the 2,4-dichlorophenoxyacetic acid is simplified. Moreover, the preparation method provided by the invention has no 'three wastes' emissions and achieves greenization of synthesis of the product.
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Paragraph 0080-0081
(2017/03/14)
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- A process for preparing 2,4-dichlorophenoxy acetic acid method
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The invention discloses a method for preparing 2,4-dichlorophenoxyacetic acid. The method comprises the following specific steps of adding chloroacetic acid into a sodium hydroxide solution, stirring, adding phenol and adjusting the pH to 11 with sodium bicarbonate; heating for 40 minutes at 100 DEG C; adding hydrochloric acid to adjust the pH value to 4; finally cooling in an ice-water bath to obtain a solid, washing the obtained solid and drying to obtain phenoxy acetic acid; adding the phenoxy acetic acid into a mixed solution of acetic acid and water, adding iron phthalocyanine and stirring; introducing chlorine to carry out chlorination reaction; reacting for 35-50 minutes until the chlorination reaction is completed to obtain a reaction product; cooling the reaction product and filtering to obtain a solid substance; and finally cooling the solid substance to obtain the finished product 2,4-dichlorophenoxyacetic acid, wherein the molar amount of iron phthalocyanine is 0.1% of phenoxy acetic acid. By the method, the product has the advantages of high quality, high yield and high purity; the preparation process is simple and stable, low in industrial cost and environmental friendly.
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Paragraph 0020; 0021
(2018/02/04)
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- A methyl benzofuranacetic [...] biological probe and its preparation method and application
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The invention discloses a benzofuran quinoline type biological probe and a preparation method thereof, and application of the benzofuran quinoline type biological probe in detecting a G-quadruplex structure and in the mechanism of action of cryptolepine and G-quadruplex, wherein the biological probe is high in fluorescence intensity and excellent in fluorescence property, and can be applied to specially detecting the G-quadruplex structure and researching the mechanism of action of a cryptolepine derivative and the G-quadruplex. The invention relates to the research whether the cryptolepine derivative acts on the telomere G-quadruplex or the C-MYCG-quadruplex in the promoter region, or on other G-quadruplex structures in vivo; the detection method has the advantages of simple, convenient and quick operation, good selectivity and obvious visualization; the shortcomings of unavailable in-vivo detection, high price, high requirement equipment, relatively complex technical operations and the like of other detection methods are overcome.
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Paragraph 0071; 0072
(2017/02/02)
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- DOPAMINE D2 RECEPTOR LIGANDS
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The present invention relates to novel dopamine D2 receptor ligands. The invention further relates to functionally-biased dopamine D2 receptor ligands and the use of these compounds for treating or preventing central nervous system and systemic disorders associated with dysregulation of dopaminergic activity. The present invention relates to novel compounds that modulate dopamine D2 receptors. In particular, compounds of the present invention show functional selectivity at the dopamine D2 receptors and exhibit selectivity downstream of the D2 receptors, on the 0- arrestin pathway and/or on the cAMP pathway.
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Page/Page column 143; 144
(2016/07/05)
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- An Efficient One-Pot Synthesis of 2-(Aryloxyacetyl)cyclohexane-1,3-diones as Herbicidal 4-Hydroxyphenylpyruvate Dioxygenase Inhibitors
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4-Hydroxyphenylpyruvate dioxygenase (EC 1.13.11.27, HPPD) is an important target for new bleaching herbicides discovery. As a continuous work to discover novel crop selective HPPD inhibitor, a series of 2-(aryloxyacetyl)cyclohexane-1,3-diones were rationally designed and synthesized by an efficient one-pot procedure using N,N′-carbonyldiimidazole (CDI), triethylamine, and acetone cyanohydrin in CH2Cl2. A total of 58 triketone compounds were synthesized in good to excellent yields. Some of the triketones displayed potent in vitro Arabidopsis thaliana HPPD (AtHPPD) inhibitory activity. 2-(2-((1-Bromonaphthalen-2-yl)oxy)acetyl)-3-hydroxycyclohex-2-en-1-one, II-13, displayed high, broad-spectrum, and postemergent herbicidal activity at the dosage of 37.5-150 g ai/ha, nearly as potent as mesotrione against some weeds. Furthermore, II-13 showed good crop safety against maize and canola at the rate of 150 g ai/ha, indicating that II-13 might have potential as a herbicide for weed control in maize and canola fields. II-13 is the first HPPD inhibitor showing good crop safety toward canola.
- Wang, Da-Wei,Lin, Hong-Yan,He, Bo,Wu, Feng-Xu,Chen, Tao,Chen, Qiong,Yang, Wen-Chao,Yang, Guang-Fu
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p. 8986 - 8993
(2016/12/09)
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- Degradation of organochlorinated pollutants in water by catalytic hydrodechlorination and photocatalysis
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The degradation of chlorinated herbicides (MCPA and 2,4-D) and 4-chlorophenol (4-CP) by photocatalytic oxidation (PCO) and the combination of catalytic hydrodechlorination (HDC) and photocatalysis, at ambient conditions, has been studied. Commercial TiO2 (P25) and Pd/Al2O3 catalysts were used for PCO and HDC, respectively. MCPA and 2,4-D were transformed upon photo-oxidation to intermediate products and almost total mineralization was achieved. However, in the case of 4-CP, a conversion of only 82% of chloride formation and 87% TOC were obtained. In spite of the fact that the HDC reaction resulted in a total dechlorination of organochlorinated pollutants combined with an important decrease of the effluent ecotoxicity, the percentage of mineralization obtained in the combined process (HDC-PCO) was slightly lower than in the PCO treatment. Thus, the HDC-PCO process is not justified versus a single PCO treatment.
- Diaz, Elena,Cebrian, Marina,Bahamonde, Ana,Faraldos, Marisol,Mohedano, Angel F.,Casas, Jose A.,Rodriguez, Juan J.
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p. 168 - 174
(2016/03/25)
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- Synthesis, evaluation and in silico molecular modeling of pyrroyl-1,3,4-thiadiazole inhibitors of InhA
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Enoyl acyl carrier protein reductase (ENR) is an essential type II fatty acid synthase (FAS-II) pathway enzyme that is an attractive target for designing novel antitubercular agents. Herein, we report sixty-eight novel pyrrolyl substituted aryloxy-1,3,4-thiadiazoles synthesized by three-step optimization processes. Three-dimensional quantitative structure-activity relationships (3D-QSAR) were established for pyrrolyl substituted aryloxy-1,3,4-thiadiazole series of InhA inhibitors using the comparative molecular field analysis (CoMFA). Docking analysis of the crystal structure of ENR performed by using Surflex-Dock in Sybyl-X 2.0 software indicates the occupation of pyrrolyl substituted aryloxy 1,3,4-thiadiazole into hydrophobic pocket of InhA enzyme. Based on docking and database alignment rules, two computational models were established to compare their statistical results. The analysis of 3D contour plots allowed us to investigate the effect of different substituent groups at different positions of the common scaffold. In vitro testing of ligands using biological assays substantiated the efficacy of ligands that were screened through in silico methods.
- Joshi, Shrinivas D.,More, Uttam A.,Koli, Deepshikha,Kulkarni, Manoj S.,Nadagouda, Mallikarjuna N.,Aminabhavi, Tejraj M.
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p. 151 - 167
(2015/03/30)
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- Radical decarboxylative fluorination of aryloxyacetic acids using N-fluorobenzenesulfonimide and a photosensitizer
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Fluorinated methoxy arenes are emerging as important motifs in both agrochemicals and pharmaceuticals. A novel technique for the synthesis of monofluoromethoxy arenes through the direct fluorodecarboxylation of carboxylic acids was developed that uses photosensitizers and N-fluorobenzenesulfonimide (NFSI). Utilization of the oxidatively mild fluorine transfer agent NFSI enabled the synthesis of fluoromethyl ethers that were previously inaccessible with decarboxylative fluorinations performed with Selectfluor. Mechanistic studies are consistent with the photosensitizer effecting oxidation of the aryloxyacetic acid.
- Leung, Joe C. T.,Sammis, Glenn M.
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supporting information
p. 2197 - 2204
(2015/04/14)
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