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1.
J Am Chem Soc ; 2024 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-38717282

RESUMO

In this study, we investigated the role of aluminum cations in facilitating hydride transfer during the hydrogenation of imines within the context of Noyori-type metal-ligand cooperative catalysis. We propose a novel model involving aluminum cations directly coordinated with imines to induce activation from the lone pair electron site, a phenomenon termed σ-induced activation. The aluminum metal-hydride amidate complex ("HMn-NAl") exhibits a higher ability of hydride transfer in the hydrogenation of imines compared to its lithium counterpart ("HMn-NLi"). Density functional theory (DFT) calculations uncover that the aluminum cation efficiently polarizes unsaturated bonds through σ-electron-induced activation in the transition state of hydride transfer, thereby enhancing substrate electrophilicity more efficiently. Additionally, upon substrate coordination, aluminum's coordination saturation improves the hydride nucleophilicity of the HMn-NAl complex via the breakage of the Al-H coordination bond.

2.
Chem Commun (Camb) ; 60(44): 5707-5710, 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38738645

RESUMO

A tandem palladium-catalyzed Sonogashira coupling, propargyl-allenyl isomerization, and [2+2] cycloaddition sequence between electron-deficient haloarenes and 1,8-diynylic ethers is developed. The reaction shows good functional tolerance and proceeds under mild conditions to provide a new profile of benzooxepane-fused cyclobutene derivatives in moderate to high yields with high selectivity. The reaction mechanism is validated both by experimental studies and DFT calculations.

3.
J Anal Methods Chem ; 2024: 6599029, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38751858

RESUMO

To isolate gastrodin (GAS), 4-hydroxybenzyl alcohol (4-HBA), and phenolic compounds from Chinese medicine Gastrodia elata Blume, and to explore the binding mode of fatty acid binding protein 4 (FABP4/aP2) that is closely related to macrophage inflammation, we study their anti-inflammatory targets. After the ultrasonic extraction of the main active components with 70% ethanol, three resins and three eluents were selected, and eight phenolic monomers with similar structures, such as gastrodin and 4-hydroxybenzyl alcohol, were isolated from Gastrodia elata by AB-8 macroporous resin and silica gel column chromatography and eluted with the CHCl3-MeOH gradient. Their structures were identified by HPLC and nuclear magnetic resonance (NMR). The FABP4 protein was added to GAS and 4-HBA, and the NMR experiment was performed to observe ligand binding. Finally, according to the spectral information of STD-NMR and molecular docking technology, the interaction between ligands and protein was studied. The fluorescence competition experiment confirmed that both GAS and 4-HBA were in the binding cavity of FABP4. Moreover, 3-phenoxy-2-phenylbenzoic acid (PPA) is a possible inhibitor of FABP4, reducing macrophage-related inflammation and endoplasmic reticulum stress. This work provides a new basis for the anti-inflammatory mechanism of Gastrodia elata, paving the way for the research and development of FABP4 inhibitor drugs.

4.
Nature ; 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38806060

RESUMO

Asymmetric catalysis allows the synthesis of optically active compounds, often requiring the differentiation between two substituents on prochiral substrates1. Despite decades of development of mainly noble metal catalysts, achieving differentiation between substituents with similar steric and electronic properties remains a significant challenge2,3. Here, we introduce a class of earth-abundant manganese catalysts for the asymmetric hydrogenation of dialkyl ketimines to give a range of chiral amine products. These catalysts distinguish between pairs of minimally differentiated alkyl groups bound to the ketimine, such as methyl and ethyl, and even subtler distinctions, like ethyl and n-propyl. The degree of enantioselectivity can be adjusted by modifying the components of the chiral manganese catalyst. This reaction demonstrates a wide substrate scope and achieves a turnover number (TON) of up to 107,800. Our mechanistic studies indicate that the exceptional stereoselectivity arises from the modular assembly of confined chiral catalysts and cooperative non-covalent interactions between the catalyst and the substrate.

5.
Front Neurol ; 15: 1310026, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38654741

RESUMO

Background: The association between benign paroxysmal positional vertigo (BPPV) and various mental disorders is still controversial. This study used the Mendelian randomization (MR) method to clarify the correlation between BPPV and seven mental disorders (bipolar disorder, depression, anxiety disorder, schizophrenia, suicidality, neuroticism, and mood swings) to aid in the exploration of BPPV complications and prevention and early treatment of mental disorders. Methods: The datasets for BPPV and seven mental disorders were obtained from genome-wide association studies (GWASs). Two-sample MR was used to analyze the correlation between exposure (BPPV) and various outcomes (bipolar disorder, depression, anxiety disorder, schizophrenia, suicidality, neuroticism, and mood swings). A reverse MR study was also performed. The inverse variance weighting (IVW) method, the MR-Egger method, the simple mode method, the weighted mode method, and the weighted median method were selected. Results: The MR analysis and the reverse MR analysis results did not reveal significant associations between BPPV and bipolar disorder, depression, anxiety disorder, schizophrenia, suicidal tendencies, neuroticism, and mood swings. Interestingly, neuroticism (IVW: OR = 1.142, 95% CI: 1.059-1.231, P = 0.001; P-MR-PRESSO adjustment = 0.0002) and mood swings (IVW: OR = 3.119, 95% CI: 1.652-5.884, P = 0.0004) may have a significant association with BPPV. After MR-PRESSO adjustment, there was no horizontal pleiotropy or heterogeneity, and a significant association between neuroticism, mood swings, and BPPV has still been suggested. Conclusion: We conducted MR analysis on genetic data from European populations and discovered a causal relationship between BPPV and the seven mental disorders. Our research findings suggest that BPPV may not have a significant causal relationship with bipolar disorder, depression, anxiety disorder, schizophrenia, or suicidal tendencies. However, neuroticism and mood swings may be risk factors for BPPV.

6.
Front Optoelectron ; 17(1): 12, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38689035

RESUMO

Since their inception, frequency combs generated in microresonators, known as microcombs, have sparked significant scientific interests. Among the various applications leveraging microcombs, soliton microcombs are often preferred due to their inherent mode-locking capability. However, this choice introduces additional system complexity because an initialization process is required. Meanwhile, despite the theoretical understanding of the dynamics of other comb states, their practical potential, particularly in applications like sensing where simplicity is valued, remains largely untapped. Here, we demonstrate controllable generation of sub-combs that bypasses the need for accessing bistable regime. And in a graphene-sensitized microresonator, the sub-comb heterodynes produce stable, accurate microwave signals for high-precision gas detection. By exploring the formation dynamics of sub-combs, we achieved 2 MHz harmonic comb-to-comb beat notes with a signal-to-noise ratio (SNR) greater than 50 dB and phase noise as low as - 82 dBc/Hz at 1 MHz offset. The graphene sensitization on the intracavity probes results in exceptional frequency responsiveness to the adsorption of gas molecules on the graphene of microcavity surface, enabling detect limits down to the parts per billion (ppb) level. This synergy between graphene and sub-comb formation dynamics in a microcavity structure showcases the feasibility of utilizing microcombs in an incoherent state prior to soliton locking. It may mark a significant step toward the development of easy-to-operate, systemically simple, compact, and high-performance photonic sensors.

7.
Talanta ; 274: 126002, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38613948

RESUMO

Developing probes for simultaneous diagnosis and killing of cancer cells is crucial, yet challenging. This article presents the design and synthesis of a novel Rhodamine B fluorescence probe. The design strategy involves utilizing an anticancer drug (Melphalan) to bind with a fluorescent group (HRhod-OH), forming HRhod-MeL, which is non-fluorescent. However, when exposed to the high levels of reactive oxygen species (ROS) of cancer cells, HRhod-MeL transforms into a red-emitting Photocage (Rhod-MeL), and selectively accumulates in the mitochondria of cancer cells, where, when activated with green light (556 nm), anti-cancer drugs released. The Photocage improve the efficacy of anti-cancer drugs and enables the precise diagnosis and killing of cancer cells. Therefore, the prepared Photocage can detect cancer cells and release anticancer drugs in situ, which provides a new method for the development of prodrugs.


Assuntos
Antineoplásicos , Liberação Controlada de Fármacos , Corantes Fluorescentes , Pró-Fármacos , Rodaminas , Pró-Fármacos/química , Pró-Fármacos/farmacologia , Pró-Fármacos/síntese química , Humanos , Antineoplásicos/farmacologia , Antineoplásicos/química , Antineoplásicos/síntese química , Rodaminas/química , Corantes Fluorescentes/química , Corantes Fluorescentes/síntese química , Espécies Reativas de Oxigênio/metabolismo , Espécies Reativas de Oxigênio/análise , Desenho de Fármacos , Luz , Linhagem Celular Tumoral
8.
Int J Mol Sci ; 25(8)2024 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-38674153

RESUMO

Anti-inflammatory drugs have become the second-largest class of common drugs after anti-infective drugs in animal clinical care worldwide and are often combined with other drugs to treat fever and viral diseases caused by various factors. In our previous study, a novel serine protease inhibitor-encoding gene (MDSPI16) with improved anti-inflammatory activity was selected from a constructed suppressive subducted hybridization library of housefly larvae. This protein could easily induce an immune response in animals and had a short half-life, which limited its wide application in the clinic. Thus, in this study, mPEG-succinimidyl propionate (mPEG-SPA, Mw = 5 kDa) was used to molecularly modify the MDSPI16 protein, and the modified product mPEG-SPA-MDSPI16, which strongly inhibited elastase production, was purified. It had good stability and safety, low immunogenicity, and a long half-life, and the IC50 for elastase was 86 nM. mPEG-SPA-MDSPI16 effectively inhibited the expression of neutrophil elastase and decreased ROS levels. Moreover, mPEG-SPA-MDSPI16 exerted anti-inflammatory effects by inhibiting activation of the NF-κB signaling pathway and the MAPK signaling pathway in neutrophils. It also exerted therapeutic effects on a lipopolysaccharide (LPS)-induced acute lung injury (ALI) mouse model. In summary, mPEG-SPA-MDSPI16 is a novel anti-inflammatory protein modified with PEG that has the advantages of safety, nontoxicity, improved stability, and strong anti-inflammatory activity in vivo and in vitro and is expected to become an effective anti-inflammatory drug.


Assuntos
Lesão Pulmonar Aguda , Lipopolissacarídeos , Inibidores de Serina Proteinase , Animais , Lesão Pulmonar Aguda/tratamento farmacológico , Lesão Pulmonar Aguda/induzido quimicamente , Camundongos , Inibidores de Serina Proteinase/farmacologia , Inibidores de Serina Proteinase/química , Inibidores de Serina Proteinase/uso terapêutico , Anti-Inflamatórios/farmacologia , Anti-Inflamatórios/química , Anti-Inflamatórios/uso terapêutico , Polietilenoglicóis/química , Polietilenoglicóis/farmacologia , NF-kappa B/metabolismo , Masculino , Elastase de Leucócito/metabolismo , Humanos , Transdução de Sinais/efeitos dos fármacos , Proteínas Recombinantes de Fusão/farmacologia , Modelos Animais de Doenças
9.
J Colloid Interface Sci ; 667: 460-469, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38643743

RESUMO

Electrochemical nitrogen reduction (eNRR) is a cost-effective and environmentally sustainable approach for ammonia production. MoS2, as a typical layered transition metal compound, holds significant potential as an electrocatalyst for the eNRR. Nevertheless, it suffers from a limited number of active sites and low electron transfer efficiency. In this study, we constructed a heterostructure by depositing SnO2 (an n-type semiconductor) nanoparticles on MoS2 (a p-type semiconductor). This unique interfacial structure not only generates abundant interfacial contacts but also facilitates the transfer of electrons from SnO2 to MoS2, leading to the formation of an interfacial electric field. Theoretical calculations demonstrate that this electric field increases the number of active electrons, facilitating N2 adsorption and NN bond activation. Moreover, it increases the degree of orbital overlap between N2 and SnO2/MoS2, effectively reducing the energy barrier of the rate-determining step. Benefiting from the interfacial electric field effect, the SnO2/MoS2 catalyst exhibits significant catalytic activity and selectivity towards eNRR, with an ammonia yield of 47.1 µg h-1 mg-1 and a Faraday efficiency of 19.3 %, surpassing those reported for the majority of MoS2- and SnO2-based catalysts.

10.
Front Oncol ; 14: 1321445, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38434685

RESUMO

Background: Patients with schizophrenia are at a higher risk of developing cancer. However, the causal relationship between schizophrenia and different tumor types remains unclear. Methods: Using a two-sample, two-way Mendelian randomization method, we used publicly available genome-wide association analysis (GWAS) aggregate data to study the causal relationship between schizophrenia and different cancer risk factors. These tumors included lung adenocarcinoma, lung squamous cell carcinoma, small-cell lung cancer, gastric cancer, alcohol-related hepatocellular cancer, tumors involving the lungs, breast, thyroid gland, pancreas, prostate, ovaries and cervix, endometrium, colon and colorectum, and bladder. We used the inverse variance weighting (IVW) method to determine the causal relationship between schizophrenia and different tumor risk factors. In addition, we conducted a sensitivity test to evaluate the effectiveness of the causality. Results: After adjusting for heterogeneity, evidence of a causal relationship between schizophrenia and lung cancer risk was observed (odds ratio [OR]=1.001, 95% confidence interval [CI], 1.000-1.001; P=0.0155). In the sensitivity analysis, the causal effect of schizophrenia on the risk of lung cancer was consistent in both direction and degree. However, no evidence of causality or reverse causality between schizophrenia and other tumors was found. Conclusion: This study elucidated a causal relationship between the genetic predictors of schizophrenia and the risk of lung cancer, thereby providing a basis for the prevention, pathogenesis, and treatment of schizophrenia in patients with lung cancer.

11.
Medicine (Baltimore) ; 103(7): e37209, 2024 Feb 16.
Artigo em Inglês | MEDLINE | ID: mdl-38363938

RESUMO

The recurrence of Meniere disease (MD) strongly affects patient quality of life. Identifying the risk factors for MD is highly important for its prevention and treatment. Previous studies have suggested that alcohol intake may play a role in the development of MD. However, recent studies have shown that the causal relationship between alcohol consumption and MD remains controversial. In this paper, the Mendelian randomization (MR) method was used to determine the causal relationship between alcohol consumption usually consumed with meals and MD, with the aim of providing suggestions for alcohol intake management in individuals with MD and helping in the prevention and treatment of MD. Two-sample MR was used to investigate the causal relationship between alcohol usually taken with meals and MD. We used a dataset from a publicly available large-scale genome-wide association study (GWAS). Inverse variance weighting (IVW), MR-Egger, simple weighting, weighted weighting and the weighted median method were used for analysis. The final results showed that IVW (OR = 0.991, 95% CI: 0.983-0.998, P = .016) results suggested that there was statistical significance, but MR-Egger (OR = 0.978, 95% CI: 0.886-1.080, P = .679), weighted median methods (OR = 0.994, 95% CI: 0.985-1.004, P = .307) and Simple mode (OR = 0.995, 95% CI: 0.980-1.010, P = .566), Weighted mode (OR = 0.995, 95% CI: 0.981-1.010, P = .557) found no significant causal relationship. The results suggest that alcohol usually taken with meals may be negatively correlated with MD.


Assuntos
Doença de Meniere , Humanos , Doença de Meniere/epidemiologia , Doença de Meniere/genética , Estudo de Associação Genômica Ampla , Análise da Randomização Mendeliana , Qualidade de Vida , Etanol , Refeições
12.
BMC Infect Dis ; 23(1): 472, 2023 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-37461013

RESUMO

BACKGROUND: Patients with malignancy are at a higher risk of developing nosocomial infections. However, limited studies investigated the clinical features and prognostic factors of nosocomial infections due to fungi in cancer patients. Herein, this study aims to investigate the clinical characteristics of in-hospital fungal infections and develop a nomogram to predict the risk of in-hospital death during fungal infection of hospitalized cancer patients. METHODS: This retrospective observational study enrolled cancer patients who experienced in-hospital fungal infections between September 2013 and September 2021. Univariate and multivariate logistic regression analyses were performed to identify independent predictors of in-hospital mortality. Variables demonstrating significant statistical differences in the multivariate analysis were utilized to construct a nomogram for personalized prediction of in-hospital death risk associated with nosocomial fungal infections. The predictive performance of the nomogram was evaluated using receiver operating characteristic (ROC) curves, calibration curves, and decision curve analysis. RESULTS: A total of 216 participants were included in the study, of which 57 experienced in-hospital death. C.albicans was identified as the most prevalent fungal species (68.0%). Respiratory infection accounted for the highest proportion of fungal infections (59.0%), followed by intra-abdominal infection (8.8%). The multivariate regression analysis revealed that Eastern Cooperative Oncology Group Performance Status (ECOG-PS) 3-4 (odds ratio [OR] = 6.08, 95% confidence interval [CI]: 2.04-18.12), pulmonary metastases (OR = 2.76, 95%CI: 1.11-6.85), thrombocytopenia (OR = 2.58, 95%CI: 1.21-5.47), hypoalbuminemia (OR = 2.44, 95%CI: 1.22-4.90), and mechanical ventilation (OR = 2.64, 95%CI: 1.03-6.73) were independent risk factors of in-hospital death. A nomogram based on the identified risk factors was developed to predict the individual probability of in-hospital mortality. The nomogram demonstrated satisfactory performance in terms of classification ability (area under the curve [AUC]: 0.759), calibration ability, and net clinical benefit. CONCLUSIONS: Fungi-related nosocomial infections are prevalent among cancer patients and are associated with poor prognosis. The constructed nomogram provides an invaluable tool for oncologists, enabling them to make timely and informed clinical decisions that offer substantial net clinical benefit to patients.


Assuntos
Infecção Hospitalar , Neoplasias Pulmonares , Humanos , Mortalidade Hospitalar , Nomogramas , Estudos Retrospectivos , Prognóstico
13.
Nat Commun ; 14(1): 3511, 2023 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-37316484

RESUMO

The catalytic asymmetric inverse-electron-demand oxa-Diels-Alder (IODA) reaction is a highly effective synthetic method for creating enantioenriched six-membered oxygen-containing heterocycles. Despite significant effort in this area, simple α,ß-unsaturated aldehydes/ketones and nonpolarized alkenes are seldom utilized as substrates due to their low reactivity and difficulties in achieving enantiocontrol. This report describes an intermolecular asymmetric IODA reaction between α-bromoacroleins and neutral alkenes that is catalyzed by oxazaborolidinium cation 1f. The resulting dihydropyrans are produced in high yields and excellent enantioselectivities over a broad range of substrates. The use of acrolein in the IODA reaction produces 3,4-dihydropyran with an unoccupied C6 position in the ring structure. This unique feature is utilized in the efficient synthesis of (+)-Centrolobine, demonstrating the practical synthetic utility of this reaction. Additionally, the study found that 2,6-trans-tetrahydropyran can undergo efficient epimerization into 2,6-cis-tetrahydropyran under Lewis acidic conditions. This structural core is widespread in natural products.

14.
Chem Sci ; 14(16): 4278-4287, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37123174

RESUMO

Boronic acids have become one of the most prevalent classes of reagents in modern organic synthesis, displaying various reactivity profiles via C-B bond cleavage. Herein, we describe the utilization of a readily available boronic acid as an efficient surrogate of hydroxide upon activation via fluoride complexation. The hitherto unknown aryne induced ring-opening reaction of cyclic sulfides and three-component coupling of fluoro-azaarenes are developed to exemplify the application value. Different from metal hydroxides or water, this novel hydroxy source displays mild activation conditions, great functionality tolerance and structural tunability, which shall engender a new synthetic paradigm and in a broad context offer new blueprints for organoboron chemistry. Detailed computational studies also recognize the fluoride activation mode, provide in-depth insights into the unprecedented mechanistic pathway and elucidate the reactivity difference of ArB(OH) x F y complexes, which fully support the experimental data.

15.
Sci Rep ; 13(1): 5187, 2023 03 30.
Artigo em Inglês | MEDLINE | ID: mdl-36997618

RESUMO

We aimed to investigate differences in patients' anxiety and satisfaction between patients undergoing paper-based patient decision aid (PDA) for shared decision-making (SDM) and those receiving computer-based PDA. We retrospectively collected questionnaires before and after SDM. Basic demographic data as well as anxiety, satisfaction, knowledge acquisition, and participation in SDM were recorded. We divided our population into subgroups according to use of paper-based or computer-based PDA. In addition, Pearson correlation analysis was applied to assess the relationships among variables. In total, 304 patients who visited our Division of Nephrology were included in the final analysis. Overall, over half of the patients felt anxiety (n = 217, 71.4%). Near half of the patients felt a reduction in anxiety after SDM (n = 143, 47.0%) and 281 patients (92.4%) were satisfied with the whole process of SDM. When we divided all the patients based on use of paper-based or computer-based PDA, the reduction of anxiety level was greater in the patients who underwent paper-based PDA when compared with that of those who underwent computer-based PDA. However, there was no significant difference in satisfaction between the two groups. Paper-based PDA was as effective as computer-based PDA. Further studies comparing different types of PDA are warranted to fill the knowledge gaps in the literature.


Assuntos
Tomada de Decisões , Satisfação do Paciente , Humanos , Estudos Retrospectivos , Ansiedade , Satisfação Pessoal
16.
Artigo em Inglês | MEDLINE | ID: mdl-36834344

RESUMO

The thermal environment is a crucial part of ecological environments. It is vital to study the distribution and generation of thermal environments for regional sustainable development. Mining area, agricultural area and urban area were taken as the research object, and remote sensing data were used to study the spatiotemporal distribution characteristics of the thermal environment. The relationship between the thermal environment and land use types was analyzed, and the effect of mining and reclamation on the thermal environment was emphasized. The main findings were: (1) the thermal effect zone in the study area was dispersed. The area ratio of the thermal effect zone accounted for 69.70%, 68.52%, 65.85%, 74.20% and 74.66% in the year 2000, 2003, 2009, 2013 and 2018, respectively. The contribution to the overall thermal effect was in the order of agricultural area > mining area > urban area. (2) The proportion of forest and the average grid temperature always showed a significant negative correlation in different scales and had the highest correlation and the greatest influence. (3) The land surface temperature (LST) of opencast areas was higher than the surrounding temperature, and the temperature difference was 3-5 °C. The LST of reclaimed sites was lower than the surrounding temperature, and the temperature difference was -7 to 0 °C. The quantitative study found that reclamation mode, shape and spatial location could affect the cooling effect of the reclaimed site. This study can provide a reference for the mitigation of thermal effects and the identification of influences of mining and reclamation on the thermal environment in the coordinated development of similar regions.


Assuntos
Agricultura , Florestas , Temperatura , Mineração , Telemetria , Monitoramento Ambiental , China
17.
Analyst ; 147(24): 5747-5753, 2022 Dec 05.
Artigo em Inglês | MEDLINE | ID: mdl-36413105

RESUMO

Photosensitizers and enzyme mimics are extensively used in photoelectrochemical (PEC) sensing, but few materials can be used as both photosensitizers and enzyme mimics in PEC sensing. Herein, we report Au nanoclusters (AuNCs) as both photosensitizers and peroxidase mimics for sensitive PEC sensing of Hg2+. It is found that AuNCs can act as photosensitizers to improve the PEC activity of WO3 nanorods; so the WO3/AuNCs composite material can be used as an advanced photosensitive material for PEC detection. AuNCs can also catalyze precipitate formation on the photoelectrode because of their peroxidase mimetic activity, and the interface electron transfer is hindered by the formed precipitate. Thus, the photocurrent of the WO3/AuNCs-based photoelectrode is quenched. When Hg2+ is present, the AuNCs-catalyzed precipitate formation is inhibited by Hg2+ because of the binding of Hg2+ to AuNCs through Hg2+-Au+ interactions. The photocurrent of the WO3/AuNCs-based photoelectrode increases accordingly, enabling "signal on" PEC detection of Hg2+. A broad linear range for Hg2+ detection is achieved between 1.0 pM and 50 nM with a detection limit of 0.2 pM. We have developed an advanced photosensitive material and introduced a simple method for PEC detection of Hg2+.


Assuntos
Mercúrio , Nanotubos , Fármacos Fotossensibilizantes , Catálise , Peroxidases
18.
Nat Chem ; 14(11): 1233-1241, 2022 11.
Artigo em Inglês | MEDLINE | ID: mdl-36097055

RESUMO

The high efficiency of widely applied Noyori-type hydrogenation catalysts arises from the N-H moiety coordinated to a metal centre, which stabilizes rate-determining transition states through hydrogen-bonding interactions. It was proposed that a higher efficiency could be achieved by substituting an N-M' group (M' = alkali metals) for the N-H moiety using a large excess of metal alkoxides (M'OR); however, such a metal-hydride amidate intermediate has not yet been isolated. Here we present the synthesis, isolation and reactivity of a metal-hydride amidate complex (HMn-NLi). Kinetic studies show that the rate of hydride transfer from HMn-NLi to a ketone is 24-fold higher than that of the corresponding amino metal-hydride complex (HMn-NH). Moreover, the hydrogenation of N-alkyl-substituted aldimines was realized using HMn-NLi as the active catalyst, whereas HMn-NH is much less effective. These results highlight the superiority of M/NM' bifunctional catalysis over the classic M/NH bifunctional catalysis for hydrogenation reactions.


Assuntos
Complexos de Coordenação , Manganês , Cinética , Catálise , Hidrogenação , Complexos de Coordenação/química , Metais
19.
J Phys Chem Lett ; 13(33): 7694-7701, 2022 Aug 25.
Artigo em Inglês | MEDLINE | ID: mdl-35960186

RESUMO

Bicyclo[1.1.0]butane (BCB) derivatives are versatile coupling partners, and various reaction modes for their activation and transformation have been proposed. In this work, three BCB-activation modes in Rh-catalyzed BCB transformations that construct diastereoselective α-quaternary ß-lactones were investigated by density functional theory calculations. Our results show that, compared with C1-C3 insertion and C-C3 oxidative addition, C2-C3 oxidative addition is more favorable. The whole catalytic cycle involves five main steps: C-H activation, oxidative addition, ß-C elimination/reductive elimination, Rh walking, and aldehyde insertion/protonation. Independent gradient model, intrinsic reaction coordinate, distortion-interaction energy, and Laplacian electron-density analyses were carried out to investigate the mode of BCB activation. Our calculation also showed that aldehyde-insertion is the diastereoselectivity determining step, which is controlled by the steric effect between the ligand, methyl group, and aldehyde.


Assuntos
Ródio , Aldeídos , Butanos , Catálise , Oxirredução
20.
Artigo em Inglês | MEDLINE | ID: mdl-35886533

RESUMO

The mine-agriculture-urban compound area formed under the combined effects of natural conditions, mineral resource endowments, and historical development is affected by severe man-made disturbances, and faces a prominent contradiction between economic development and ecological protection. Guiding the future development is an urgent problem in this region. This research used image data, logical reasoning, and empirical analysis, based on social and economic statistics and land-use data, to analyze the typical characteristics and problems of the social-ecological system in the mine-agriculture-urban compound area. Moreover, we identified future directions for the region guided by policy documents and built a philosophy framework for sustainable development and management of the region based on the concept of adaptability. The results showed the following: (1) At present, the output value of the coal industry accounts for 84.10% of the total regional output value, severely disturbing its social-ecological system, which needs to be protected and restored under human guidance and management. (2) The future development of this region depends on the one hand on green mining, and on the other hand, it is necessary to fully tap the potential of arable land and livestock farms to develop efficient and intensive agriculture. (3) The key contents of the social-ecological system management of the mine-agriculture-urban compound area include resolving the contradiction between development and protection, ensuring development, optimizing industrial structure, and safeguarding public interests. In conclusion, this research can expand the connotation and application scope of adaptive management and provide a reference for such areas facing the prominent contradiction between development and protection.


Assuntos
Conservação dos Recursos Naturais , Ecossistema , Agricultura , China , Conservação dos Recursos Naturais/métodos , Desenvolvimento Econômico , Humanos
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