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1.
Nat Commun ; 11(1): 5061, 2020 10 08.
Artigo em Inglês | MEDLINE | ID: mdl-33033262

RESUMO

The interplay between the Yamanaka factors (OCT4, SOX2, KLF4 and c-MYC) and transcriptional/epigenetic co-regulators in somatic cell reprogramming is incompletely understood. Here, we demonstrate that the histone H3 lysine 27 trimethylation (H3K27me3) demethylase JMJD3 plays conflicting roles in mouse reprogramming. On one side, JMJD3 induces the pro-senescence factor Ink4a and degrades the pluripotency regulator PHF20 in a reprogramming factor-independent manner. On the other side, JMJD3 is specifically recruited by KLF4 to reduce H3K27me3 at both enhancers and promoters of epithelial and pluripotency genes. JMJD3 also promotes enhancer-promoter looping through the cohesin loading factor NIPBL and ultimately transcriptional elongation. This competition of forces can be shifted towards improved reprogramming by using early passage fibroblasts or boosting JMJD3's catalytic activity with vitamin C. Our work, thus, establishes a multifaceted role for JMJD3, placing it as a key partner of KLF4 and a scaffold that assists chromatin interactions and activates gene transcription.


Assuntos
Reprogramação Celular , Histona Desmetilases com o Domínio Jumonji/metabolismo , Fatores de Transcrição Kruppel-Like/metabolismo , Células-Tronco Pluripotentes/citologia , Células-Tronco Pluripotentes/metabolismo , Animais , Catálise , Proliferação de Células , Senescência Celular , Desmetilação , Elementos Facilitadores Genéticos/genética , Células Epiteliais/metabolismo , Fibroblastos/citologia , Fibroblastos/metabolismo , Regulação da Expressão Gênica no Desenvolvimento , Genoma , Histonas/metabolismo , Lisina/metabolismo , Camundongos , Modelos Biológicos , Regiões Promotoras Genéticas , Ativação Transcricional/genética
2.
Water Sci Technol ; 82(5): 967-983, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-33031074

RESUMO

An easy-to-use, pollution-free and reusable beaded NiOx(OH)y catalyst for improving hypochlorite oxidation was prepared by impregnating the mixture of persulfate and alkali over alumina and then reduced it with Ni2+. The effects of catalyst preparation conditions and reaction parameters on NaClO conversion rate and Ni2+ dissolution rate were studied. Impregnating the γ-Al2O3 beads in PS/OH- mixed solution with 0.59 M PS and PS/OH- molar ratio of 1.1, and then reducing with 0.8 M Ni2+ solution is the best condition for preparing catalyst. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The best catalytic layer is characterized by high content of chemisorbed oxygen which can be converted into atomic oxygen. The hypochlorite conversion rate increased with the catalyst dosage and reuse times, and decreased with available chlorine, while pH of hypochlorite solution had little effect on the conversion rate. After running stably for 120 h in continuous flow test, the chemisorbed oxygen content in the optimal catalytic layer decreased slightly. Atomic oxygen plays an important role in the decolorization of dye solution by NaClO/NiOx(OH)y system. The oxidant consumption cost of this process is much cheaper than Fenton reagent. The prepared catalyst has great potential in hypochlorite decomposition and wastewater treatment.


Assuntos
Ácido Hipocloroso , Águas Residuárias , Catálise , Oxirredução , Difração de Raios X
3.
Yakugaku Zasshi ; 140(10): 1213-1224, 2020.
Artigo em Japonês | MEDLINE | ID: mdl-32999200

RESUMO

In basic pharmaceutical sciences to achieve drug development, research on the efficient chemical synthesis of small molecules having cyclic skeletons is important. We have been engaged in the development of artificial catalysts for asymmetric ring formation reactions that exclusively synthesize right-handed or left-handed cyclic compounds and have achieved the construction of optically active cyclic skeletons using our original catalysts. The synthesis of biologically active compounds was facilitated through six-membered ring construction by Diels-Alder reaction of Danishefsky diene; however, no asymmetric variant of the reaction has been achieved. We approached this unresolved issue using multi-coordinated lanthanide metals. A new chiral lanthanide catalyst was developed, and the catalytic asymmetric Diels-Alder reaction of Danishefsky diene was realized for the first time. By modifying the chemical structure of Danishefsky diene, we applied the lanthanide catalyst to the syntheses of polycyclic compounds and biologically active compounds. We achieved the asymmetric synthesis of natural products, antibacterial and antimalarial compounds, and an anti-obesity drug lead compound. Moreover, the novel catalyst exhibited higher performance than the previously reported ones. The latest generation of the catalyst can be handled stably in air at room temperature. Furthermore, we succeeded in the development of new catalysts by focusing on the properties of its metal precursors, such as nickel and indium, and achieved the construction of polycyclic skeletons by using these catalysts.


Assuntos
Compostos Heterocíclicos/síntese química , Compostos Policíclicos/síntese química , Alcenos/química , Antibacterianos/síntese química , Fármacos Antiobesidade/síntese química , Antimaláricos/síntese química , Produtos Biológicos/síntese química , Catálise , Reação de Cicloadição , Desenvolvimento de Medicamentos , Índio , Elementos da Série dos Lantanídeos/química , Níquel , Estereoisomerismo
4.
Yakugaku Zasshi ; 140(10): 1225-1233, 2020.
Artigo em Japonês | MEDLINE | ID: mdl-32999201

RESUMO

This article describes our stereoselective and site-selective chemical methods for exploiting cationic heterocycles as electron-withdrawing groups (EWGs). We envisioned that the phosphoramide N-H proton of a pyridyl phosphoramide 3 would be activated by the cationic pyridinium moiety that is formed upon protonation. The resulting imide-like N-H proton and the acidic pyridinium proton of the pyridinium phosphoramide 3⋅HX cooperate together, making 3⋅HX a highly acidic dual Brønsted acid. The catalytic ability of 3⋅HX was demonstrated in the development of the first asymmetric Diels-Alder reaction between 1-amide dienes and maleimides. Focusing on the activation of N-bromosuccinimide (NBS) because of its structural similarity to maleimides, the enantioselective bromolactonization of trisubstituted olefinic acids was accomplished utilizing pyridyl phosphoramide 3f as a Brønsted base catalyst bearing an acidic N-H proton. Lastly, our strategy for the site-selective acylation of polyol compounds is described. In our system, a pyridine aldoxime ester 10, used as a mild acylating reagent, was activated by a catalytic amount of Lewis acid via the inductive effect of the cationic pyridinium moiety. The resulting metal complex preferentially attracted the alcohol with a Lewis basic site, thereby facilitating selective acylation via a template effect. This metal-template-driven strategy allowed for the site-selective acylation of diverse α-hydroxyamides, including unprotected N-glycolyl aminosugars.


Assuntos
Cátions/química , Cátions/síntese química , Química Orgânica/métodos , Desenvolvimento de Medicamentos/métodos , Elétrons , Compostos Heterocíclicos/química , Compostos Heterocíclicos/síntese química , Acilação , Amidas/química , Catálise , Complexos de Coordenação/química , Reação de Cicloadição , Ésteres/química , Compostos de Pralidoxima/química , Estereoisomerismo
5.
Mol Cell ; 80(1): 127-139.e6, 2020 10 01.
Artigo em Inglês | MEDLINE | ID: mdl-33007253

RESUMO

Human spliceosomes contain numerous proteins absent in yeast, whose functions remain largely unknown. Here we report a 3D cryo-EM structure of the human spliceosomal C complex at 3.4 Å core resolution and 4.5-5.7 Å at its periphery, and aided by protein crosslinking we determine its molecular architecture. Our structure provides additional insights into the spliceosome's architecture between the catalytic steps of splicing, and how proteins aid formation of the spliceosome's catalytically active RNP (ribonucleoprotein) conformation. It reveals the spatial organization of the metazoan-specific proteins PPWD1, WDR70, FRG1, and CIR1 in human C complexes, indicating they stabilize functionally important protein domains and RNA structures rearranged/repositioned during the Bact to C transition. Structural comparisons with human Bact, C∗, and P complexes reveal an intricate cascade of RNP rearrangements during splicing catalysis, with intermediate RNP conformations not found in yeast, and additionally elucidate the structural basis for the sequential recruitment of metazoan-specific spliceosomal proteins.


Assuntos
Fatores de Processamento de RNA/química , Fatores de Processamento de RNA/metabolismo , Spliceossomos/metabolismo , Animais , Catálise , Células HeLa , Humanos , Íntrons/genética , Modelos Moleculares , Complexos Multiproteicos/metabolismo , Complexos Multiproteicos/ultraestrutura , Ligação Proteica , Estabilidade Proteica , RNA/química , RNA/metabolismo , Ribonucleoproteínas/metabolismo , Saccharomyces cerevisiae/metabolismo , Especificidade da Espécie , Fatores de Tempo
6.
Water Sci Technol ; 82(7): 1454-1466, 2020 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-33079723

RESUMO

Tannins are recalcitrant polyphenolic molecules that resist microbial attack. Their main environmental damage is due to their low biodegradability. This work aims to investigate the photo-catalytic degradation of two commercial tannin extracts, chestnut (hydrolysable tannin) and mimosa (condensed tannin). The experiments were carried out under UV-light irradiation in a continuous-flow reactor using titanium dioxide (TiO2) immobilized on cellulosic fibers. It was highlighted that photo-catalytic degradation is unfavourable in acidic medium and when the pH is too high (pH above 12); it reaches its maximum efficiency at pH 7.5 (99 and 97% for chestnut and mimosa, respectively). Nearly complete degradation of tannins requires an irradiation period of 6 h. The process efficiency is inversely affected by the concentration of tannins essentially above 75 mg/L for chestnut and 60 mg/L for mimosa. Above 240 mL/min, any increase in feed flow negatively affects the performance of the process. Furthermore, a significant decrease of treatment efficiency was seen when increasing the concentration of ethanol and salts in the medium. Obtained results suggest that UV-light irradiation in a continuous-flow photo-reactor using immobilized TiO2 may be considered as an adequate process for the treatment of water containing recalcitrant tannin molecules.


Assuntos
Taninos , Titânio , Catálise , Raios Ultravioleta
7.
Sci Total Environ ; 741: 140394, 2020 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-32886989

RESUMO

The photocatalytic activity of two bio-based polymer photocatalysts [poly(ethylene terephthalate)-TiO2 (PET-TiO2) and poly(L-lactic acid)-graphene oxide-TiO2 (PLLA-GO-TiO2)] towards Tamoxifen (TAM), Cyclophosphamide (CP), Cytarabine (CYT) and 5-Fluorouracil (5-FLU) removal was explored and compared. The highest photocatalytic activity for the degradation of the cytostatic drugs was accomplished by PET-TiO2. Among the contaminants, TAM was the most easily removed, requiring 90 min for complete elimination, while CP showed the highest resistance to photocatalysis, not being completely removed after 6 h. Liquid chromatography coupled with high-resolution mass spectrometry analysis was employed for the identification of several transformation products (TPs) and potential pathways were proposed. A total of seventy (70) TPs including thirty-four (34) novel ones detected in AOPs were identified. The ecotoxicity of the mixture of the cytostatic drugs and TPs formed during the photocatalytic treatment was evaluated using Daphnia magna assay and was associated with the occurrence of specific TPs during the treatment process. The follow-up ECOSAR (Ecological Structure Activity Relationship) analysis further elucidated that only minor chemical transformations, such as the hydroxylation or the oxidative opening of an aromatic ring system, could hamper the adverse effects of cytostatic drugs in aquatic species. Such a comparative study on the mixture toxicity of cytostatics and their TPs is presented for the first time.


Assuntos
Citostáticos , Poluentes Químicos da Água/análise , Animais , Catálise , Ciclofosfamida , Fotólise , Titânio
8.
Water Sci Technol ; 82(4): 695-703, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32970622

RESUMO

The current work investigates the removal of two hazardous macrolide molecules, spiramycin and tylosin, by photodegradation under external UV-light irradiation conditions in a slurry photoreactor using titanium dioxide as a catalyst. The kinetics of degradation and effects of main process parameters such as catalyst dosage, initial macrolide concentration, light intensity and stirring rate on the degradation rate of pollutants have been examined in detail in order to obtain the optimum operational conditions. It was found that the process followed a pseudo first-order kinetics according to the Langmuir-Hinshelwood model. The optimum conditions for the degradation of spiramycin and tylosin were low compound concentration, 1 g L-1 of catalyst dosage, 100 W m-2 light intensity and 560 rpm stirring rate. Then, a maximum removal (more than 90%) was obtained after 300 min of irradiation time. Furthermore, results show that the selection of optimized operational parameters leads to satisfactory total organic carbon removal rate (up to 51%) and biochemical oxygen demand to chemical oxygen demand ratio (∼1) confirming the good potential of this technique to remove complex macrolides from aqueous solutions.


Assuntos
Poluentes Químicos da Água , Purificação da Água , Catálise , Cinética , Macrolídeos , Fotólise , Titânio , Raios Ultravioleta
9.
Water Sci Technol ; 82(4): 704-714, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32970623

RESUMO

The radical generation properties of hydrogen peroxide and persulfate for phenol degradation were investigated under microwave irradiation using copper-doped silicon carbide (Cu/SiC) composites as catalyst. The results showed that 90% and 70% of phenol and total organic carbon (TOC), respectively, were removed within 7 min. Microwave activation of hydrogen peroxide and sodium persulfate in terms of thermal effects and accelerated electron transfer was analyzed by degradation kinetics and X-ray photoelectron spectroscopy (XPS). The microwave activation of Na2S2O8 demonstrated that the hot spots promote decomposition of persulfate more rapidly and the rate of persulfate decomposition was more than three times the activation rate of a normal heating method. There is a synergistic effect between Cu and microwave radiation, which is highlighted by the H2O2 activation; ·OH was generated due to the redox cycle between Cu(I)/Cu(II) and was responsible for phenol degradation using H2O2. High performance liquid chromatography (HPLC) analysis indicated that hydroxylation and sulfate radicals addition of phenol were the initial oxidation reaction steps of hydrogen peroxide and persulfate, respectively, followed by further oxidation to form short-chain carboxylic acids.


Assuntos
Peróxido de Hidrogênio , Fenol , Compostos Inorgânicos de Carbono , Catálise , Micro-Ondas , Oxirredução , Compostos de Silício
10.
Mater Sci Eng C Mater Biol Appl ; 117: 111330, 2020 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-32919683

RESUMO

Nanomotors, multimetallic systems are biologically inspired self-propelled tiny engines able to perform difficult tasks of transporting cargos from one end to another in presence of hydrogen peroxide fuel. Nanomotors can revolutionize the drug delivery system at the desired target by converting chemical energy into mechanical energy. Nanomotors exhibit unique properties like moving at higher speed, self-propulsion and drilling into the complex cellular environment. The review focuses on fuel dependent and fuel-free nanomotors with their propulsion mechanism. Further, the review highlights the method of fabrication, biohybrid nanomotors, toxicities along with their application in the field of active drug delivery, diabetes, precise surgery, ischemic stroke therapy, diagnosis and treatment of coronavirus, microwave hyperthermia, zika virus detection, anti-bacterial activity, water treatment and sensing and challenges lying at the forefront in the development of these tiny nanomachines. Hydrogen peroxide is toxic to mankind; biohybrid motors give an extra edge of eliminating hydrogen peroxide as fuel for self-propulsion, this can be used for smart drug delivery by reducing toxicities as compared to artificial nanomotors. Cost-effective fabrication of nanomotors will extend their applications in commercial sector overcoming limitations like scale-up and regulatory approval. In near future, nanomotors will diversify in fields of restoring conductivity of electronic medical devices, 3D printing and theranostics.


Assuntos
Assistência à Saúde , Nanotecnologia , Pesquisa Biomédica , Catálise , Infecções por Coronavirus/terapia , Humanos , Pandemias , Pneumonia Viral/terapia , Impressão Tridimensional
11.
Water Sci Technol ; 82(3): 454-467, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32960791

RESUMO

Many attempts have been made to improve the photocatalytic performance of immobilized photocatalysts for large-scale applications by modification of the photocatalyst properties. In this work, immobilized bilayer photocatalyst composed of titanium dioxide (TiO2) and chitosan-montmorillonite (CS-MT) were prepared in a layer-by-layer arrangement supported on glass substrate. This arrangement allows a simultaneous occurrence of adsorption and photocatalysis processes of pollutants, whereby each layer could be independently modified and controlled to acquire the desired degree of occurring processes. It was found that the addition of MT clay within the CS composite sub-layer improved the mechanical strength of CS, reduced its swelling and shifted its absorption threshold to higher wavelengths. In addition, the band gap energy of the photocatalyst was also reduced to 2.93 eV. The immobilized TiO2/CS-MT exhibited methyl orange (MO) decolourization rate of 0.071 min-1 under light irradiation, which is better than the single TiO2 due to the synergistic processes of adsorption by CS-MT and photocatalysis by TiO2 layer. The MO dye took 6 h to achieve complete mineralization and produced sulfate and nitrate ions as the by-products. Furthermore, the immobilized TiO2/CS-MT could be reused for at least ten cycles of application without significant loss of its activity.


Assuntos
Bentonita , Quitosana , Compostos Azo , Catálise , Fotólise , Titânio
12.
Water Sci Technol ; 82(3): 481-491, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32960793

RESUMO

Iron oxyhydroxides as important catalysts and environmental mineral materials have drawn significant interest for their potential applications in the field of wastewater treatment. In this work, we investigated the influence of nonionic surfactant Brij30 or glucose (0.01 wt%) on the formation of iron precipitates in iron(III) chloride solutions for 3 days at 40, 60 and 80 °C. The results showed that the presence of glucose or Brij30 could promote the nanospindle-akaganéite formation and the akaganéite with a length of 300-500 nm obtained at 60 °C was the optimal catalyst for organic photocatalysis degradation. Further, we investigated the capacity of C60 akaganéite for degradation removal of methyl orange (MO) under the action of hydrogen peroxide (H2O2) addition and/or UV irradiation, and in the presence of different radical scavengers at pH 4.5. We also researched the effects of various levels of H2O2 and catalyst, and the reaction pH values. It was found that akaganéites could remove almost 100% of MO under 100 mg·L-1 of catalyst and H2O2 at pH 4.5. Akaganéite maintained 86% of MO removal capacity after four successive cycles. Our results can be used as a reference for the synthesis of environmentally functional material and the application in photocatalytic degradation of organic pollutant.


Assuntos
Compostos Férricos , Peróxido de Hidrogênio , Compostos Azo , Catálise
13.
Water Sci Technol ; 82(3): 565-576, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32960800

RESUMO

The heterogeneous electro-Fenton process degradation of Yellow 2G from wastewater was studied using a batch reactor. The COD of the wastewater used in treatment experiments was 163 mg O2·L-1 and the BOD5 was 17 mg O2·L-1 (hardly biodegradable). The treatment of the wastewater at different current densities (2.5 mA·cm-2-12.5 mA·cm-2), solution pH (3 and 6.6), reaction times (5-25 min), electrolyte nature (NaCl, Na2SO4) and electrolyte concentrations (0.15 g·L-1-1 g·L-1) was investigated. According to the results, the heterogeneous electro-Fenton process was suitable for the decolorization of wastewater containing Yellow 2G. The optimum conditions were current density of 12.5 mA·cm-2, initial pH of the wastewater neutral, 25 min of electrolysis treatment using an additive steel electrode as a source of catalysis and in the presence of 1 g NaCl·L-1. We obtained easily biodegradable water with a mineralization rate equal to 85% and non-toxicity confirmed by the pea grain germination test.


Assuntos
Aço , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade , Catálise , Eletrodos , Peróxido de Hidrogênio , Oxirredução , Pirazóis
14.
Water Sci Technol ; 82(3): 603-614, 2020 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-32960803

RESUMO

This study presents a comparison of three methods for TiO2-N synthesis that were applied in the photocatalytic oxidation of the fluoroquinolones (FQs) ciprofloxacin, ofloxacin, and lomefloxacin in aqueous solution. The TiO2-N bandgap is small enough to allow the use of solar energy in the photocatalytic oxidation (PCO) reactions. The TiO2 doped by a sol-gel method with titanium butoxide (TiO2-N-BUT) and titanium isopropoxide (TiO2-N-PROP) as the precursor were effective as the TiO2 (P25) impregnation with urea (TiO2-N-P25) to degrade the FQs. The FQ degradation was higher by 74, 65, and 91%, respectively for TiO2-N-BUT, TiO2-N-PROP, and TiO2-N (load 50 mg L-1, 20 min of reaction under 28 W UV-ASolar). The TiO2-P25 with urea showed the best performance in FQ degradation. The reaction intermediates might present modifications in their acceptor groups by PCO and, because of that the antimicrobial activity dropped as the reaction time increased. Reactions with TiO2-N-P25 (100 mg L-1) and TiO2-N-BUT (100 mg L-1) achieved ≥ 80% of antimicrobial activity removal from the mixed FQ solution (Cciprofloxacin = 100 µg L-1; Cofloxacin = 100 µg L-1; Clomefloxacin = 100 µg L-1) after 40 min of reaction, for both for Escherichia coli and Bacillus subtilis.


Assuntos
Anti-Infecciosos , Titânio , Catálise , Fluoroquinolonas
15.
J Environ Sci (China) ; 97: 110-119, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32933726

RESUMO

FeVO4/CeO2 was applied in the electro-Fenton (EF) degradation of Methyl Orange (MO) as a model of wastewater pollution. The results of the characterization techniques indicate that FeVO4 with triclinic structure and face-centered cubic fluorite CeO2 maintained their structures during the nanocomposite synthesis. The effect of applied current intensity, initial pollutant concentration, initial pH, and catalyst weight was investigated. The MO removal reached 96.31% and chemical oxygen demand (COD) removal 70% for 60 min of the reaction. The presence of CeO2 in the nanocomposite plays a key role in H2O2 electro-generation as a significant factor in the electro-Fenton (EF) system. The metal leaching from FeVO4/CeO2 was negligible (cerium 4.1%, iron 4.3%, and vanadium 1.7%), which indicates that the active species in the nanocomposite are strongly interacting with each other and are stable. The performance of the nanocatalyst in real wastewaters, salty, and binary systems was acceptable and the pollutions were removed efficiently. The synergistic effect between V, Fe, and Ce could be account as the reason for the respectable function of FeVO4/CeO2. The electron transfer proceeds via Haber-Weiss mechanism. A degradation pathway was proposed through by-products analysis using gas chromatography-mass spectrometry (GC-MS) technique. The pseudo-first-order kinetic model described the obtained experimental results (R2 = 0.9906). The electro-Fenton system efficiency was improved by adding persulfate. The nanocomposite preserved almost its efficiency after six cycles. The obtained results demonstrate that the synergistic catalyst (FeVO4/CeO2) has the capability to introduce as a promising replacement of conventional catalysts in the electro-Fenton processes with brilliant proficiency.


Assuntos
Nanocompostos , Poluentes Químicos da Água/análise , Catálise , Peróxido de Hidrogênio , Ferro , Oxirredução , Águas Residuárias
16.
J Environ Sci (China) ; 97: 75-84, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32933742

RESUMO

The catalytic ozonation treatment of secondary biochemical effluent for papermaking wastewater by Ag-doped nickel ferrite was investigated. Ag-doped catalysts prepared by sol-gel method were characterized, illustrating that Ag entirely entered the crystalline of NiFe2O4 and changed the surface properties. The addition of catalyst enhanced the removal efficiency of chemical oxygen demand and total organic carbon. The results of gas chromatography-mass spectrometer, ultraviolet light absorbance at 254 nm and three-dimensional fluorescence excitation-emission matrix suggested that aromatic compounds were efficiently degraded and toxic substances, such as dibutyl phthalate. In addition, the radical scavenging experiments confirmed the hydroxyl radicals acted as the main reactive oxygen species and the surface properties of catalysts played an important role in the reaction. Overall, this work validated potential applications of Ag-doped NiFe2O4 catalyzed ozonation process of biologically recalcitrant wastewater.


Assuntos
Ozônio , Poluentes Químicos da Água/análise , Catálise , Prata , Águas Residuárias
17.
Nat Commun ; 11(1): 4722, 2020 09 18.
Artigo em Inglês | MEDLINE | ID: mdl-32948764

RESUMO

Precisely controlled deuterium labeling at specific sites of N-alkyl drugs is crucial in drug-development as over 50% of the top-selling drugs contain N-alkyl groups, in which it is very challenging to selectively replace protons with deuterium atoms. With the goal of achieving controllable isotope-labeling in N-alkylated amines, we herein rationally design photocatalytic water-splitting to furnish [H] or [D] and isotope alkanol-oxidation by photoexcited electron-hole pairs on a polymeric semiconductor. The controlled installation of N-CH3, -CDH2, -CD2H, -CD3, and -13CH3 groups into pharmaceutical amines thus has been demonstrated by tuning isotopic water and methanol. More than 50 examples with a wide range of functionalities are presented, demonstrating the universal applicability and mildness of this strategy. Gram-scale production has been realized, paving the way for the practical photosynthesis of pharmaceuticals.


Assuntos
Aminas/química , Aminas/metabolismo , Luz , Semicondutores , Alquilação , Aminas/farmacologia , Catálise , Deutério , Oxirredução , Preparações Farmacêuticas , Prótons , Água , Difração de Raios X
18.
Nat Commun ; 11(1): 4808, 2020 09 23.
Artigo em Inglês | MEDLINE | ID: mdl-32968058

RESUMO

The creation of artificial enzymes is a key objective of computational protein design. Although de novo enzymes have been successfully designed, these exhibit low catalytic efficiencies, requiring directed evolution to improve activity. Here, we use room-temperature X-ray crystallography to study changes in the conformational ensemble during evolution of the designed Kemp eliminase HG3 (kcat/KM 146 M-1s-1). We observe that catalytic residues are increasingly rigidified, the active site becomes better pre-organized, and its entrance is widened. Based on these observations, we engineer HG4, an efficient biocatalyst (kcat/KM 103,000 M-1s-1) containing key first and second-shell mutations found during evolution. HG4 structures reveal that its active site is pre-organized and rigidified for efficient catalysis. Our results show how directed evolution circumvents challenges inherent to enzyme design by shifting conformational ensembles to favor catalytically-productive sub-states, and suggest improvements to the design methodology that incorporate ensemble modeling of crystallographic data.


Assuntos
Simulação por Computador , Evolução Molecular Direcionada/métodos , Enzimas/química , Evolução Química , Liases/química , Catálise , Domínio Catalítico , Cristalografia por Raios X , Estabilidade Enzimática , Enzimas/genética , Enzimas/metabolismo , Cinética , Liases/genética , Liases/metabolismo , Simulação de Dinâmica Molecular , Mutação , Conformação Proteica , Engenharia de Proteínas
19.
Nat Commun ; 11(1): 4443, 2020 09 07.
Artigo em Inglês | MEDLINE | ID: mdl-32895371

RESUMO

Aryl azole scaffolds are present in a wide range of pharmaceutically relevant molecules. Their ortho-selective metalation at the aryl ring is challenging, due to the competitive metalation of the more acidic heterocycle. Seeking a practical access to a key Active Pharmaceutical Ingredient (API) intermediate currently in development, we investigated the metalation of 1-aryl-1H-1,2,3-triazoles and other related heterocycles with sterically hindered metal-amide bases. We report here a room temperature and highly regioselective ortho-magnesiation of several aryl azoles using a tailored magnesium amide, TMPMgBu (TMP = 2,2,6,6-tetramethylpiperidyl) in hydrocarbon solvents followed by an efficient Pd-catalyzed arylation. This scalable and selective reaction allows variation of the initial substitution pattern of the aryl ring, the nature of the azole moiety, as well as the nature of the electrophile. This versatile method can be applied to the synthesis of bioactive azole derivatives and complements existing metal-mediated ortho-functionalizations.


Assuntos
Azóis/química , Técnicas de Química Sintética/métodos , Estereoisomerismo , Catálise , Estrutura Molecular , Triazóis/química
20.
Chemosphere ; 258: 127384, 2020 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-32947660

RESUMO

As a two-dimensional nanomaterial, bismuth oxybromide (BiOBr) have attracted tremendous interest in the area of visible-light photocatalysis since it can provide the internal electric field (IEF) through z-axis through its unique electronic band structure. However, the insufficient active sites and rapid recombination rate of charged carriers hamper the efficiency of the photocatalysis. To address these two major obstacles, an enticing strategy of constructing heterojunction was established by introducing Bi2O2(OH)(NO3) (BiON) in BiOBr with the same precursor. Through a facile one-pot hydrothermal synthesis, two Sillén-type layered photocatalysts, with intimately constructed ultrathin heterostructure, was synthesized by the co-precipitation method. In this work, the formation of Bismuth-based heterojunction for charge separation is established by the excessive bismuth nitrate, which subsequently participates with the in situ growth of ultrathin hierarchical microspheres. By attenuating the thickness of BiOBr from 20 nm to 8 nm with the aid of BiON, the photogenerated charges could migrate to the active sites through shorter charge diffusion pathway. Also, the BiOBr and BiON act as an active bridge to promote the separation of electron-hole pairs, which also brings out more active sites due to its increased specific surface area. BiON/BiOBr ultrathin hierarchical microspheres exhibited enhanced visible-light photocatalytic activity for decontaminating several types of pollutants. Besides, the activity of as-prepared BiON/BiOBr was further evaluated by inhibiting the growth of kanamycin-resistant bacteria strains. This study presents a novel strategy to incorporate the crystalline bismuth hydrate nitrate into BiOBr to form ultrathin hierarchical microspheres with high surface area for environmental remediation.


Assuntos
Recuperação e Remediação Ambiental , Microesferas , Bismuto/química , Catálise , Luz , Nitratos/química
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