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1.
Proc Natl Acad Sci U S A ; 120(23): e2302858120, 2023 06 06.
Artigo em Inglês | MEDLINE | ID: mdl-37252995

RESUMO

Arabinogalactan (AG) is an essential cell wall component in mycobacterial species, including the deadly human pathogen Mycobacterium tuberculosis. It plays a pivotal role in forming the rigid mycolyl-AG-peptidoglycan core for in vitro growth. AftA is a membrane-bound arabinosyltransferase and a key enzyme involved in AG biosynthesis which bridges the assembly of the arabinan chain to the galactan chain. It is known that AftA catalyzes the transfer of the first arabinofuranosyl residue from the donor decaprenyl-monophosphoryl-arabinose to the mature galactan chain (i.e., priming); however, the priming mechanism remains elusive. Herein, we report the cryo-EM structure of Mtb AftA. The detergent-embedded AftA assembles as a dimer with an interface maintained by both the transmembrane domain (TMD) and the soluble C-terminal domain (CTD) in the periplasm. The structure shows a conserved glycosyltransferase-C fold and two cavities converging at the active site. A metal ion participates in the interaction of TMD and CTD of each AftA molecule. Structural analyses combined with functional mutagenesis suggests a priming mechanism catalyzed by AftA in Mtb AG biosynthesis. Our data further provide a unique perspective into anti-TB drug discovery.


Assuntos
Mycobacterium tuberculosis , Humanos , Galactanos , Pentosiltransferases/genética
2.
Chem Soc Rev ; 53(13): 6917-6959, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38836324

RESUMO

Electrochemical energy conversion and storage are playing an increasingly important role in shaping the sustainable future. Differential electrochemical mass spectrometry (DEMS) offers an operando and cost-effective tool to monitor the evolution of gaseous/volatile intermediates and products during these processes. It can deliver potential-, time-, mass- and space-resolved signals which facilitate the understanding of reaction kinetics. In this review, we show the latest developments and applications of DEMS in various energy-related electrochemical reactions from three distinct perspectives. (I) What is DEMS addresses the working principles and key components of DEMS, highlighting the new and distinct instrumental configurations for different applications. (II) How to use DEMS tackles practical matters including the electrochemical test protocols, quantification of both potential and mass signals, and error analysis. (III) Where to apply DEMS is the focus of this review, dealing with concrete examples and unique values of DEMS studies in both energy conversion applications (CO2 reduction, water electrolysis, carbon corrosion, N-related catalysis, electrosynthesis, fuel cells, photo-electrocatalysis and beyond) and energy storage applications (Li-ion batteries and beyond, metal-air batteries, supercapacitors and flow batteries). The recent development of DEMS-hyphenated techniques and the outlook of the DEMS technique are discussed at the end. As DEMS celebrates its 40th anniversary in 2024, we hope this review can offer electrochemistry researchers a comprehensive understanding of the latest developments of DEMS and will inspire them to tackle emerging scientific questions using DEMS.

3.
Nano Lett ; 24(20): 5929-5936, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38655909

RESUMO

Multiferroic materials provide robust and efficient routes for the control of magnetism by electric fields, which have been diligently sought after for a long time. Construction of two-dimensional (2D) vdW multiferroics is a more exciting endeavor. To date, the nonvolatile manipulation of magnetism through ferroelectric polarization still remains challenging in a 2D vdW heterostructure multiferroic. Here, we report a van der Waals (vdW) heterostructure multiferroic comprising the atomically thin layered antiferromagnet (AFM) CrI3 and ferroelectric (FE) α-In2Se3. We demonstrate anomalously nonreciprocal and nonvolatile electric-field control of magnetization by ferroelectric polarization. The nonreciprocal electric control originates from an intriguing antisymmetric enhancement of interlayer ferromagnetic coupling in the opposite ferroelectric polarization configurations of α-In2Se3. Our work provides numerous possibilities for creating diverse heterostructure multiferroics at the limit of a few atomic layers for multistage magnetic memories and brain-inspired in-memory computing.

4.
Small ; 20(28): e2310749, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38308118

RESUMO

The unfavorable morphology and high crystallization temperature (Tc) of inorganic perovskites pose a significant challenge to their widespread application in photovoltaics. In this study, an effective approach is proposed to enhance the morphology of cesium lead triiodide (CsPbI3) while lowering its Tc. By introducing dimethylammonium acetate into the perovskite precursor solution, a rapid nucleation stage is facilitated, and significantly enhances the crystal growth of the intermediate phase at low annealing temperatures, followed by a slow crystal growth stage at higher annealing temperatures. This results in a uniform and dense morphology in CsPbI3 perovskite films with enhanced crystallinity, simultaneously reducing the Tc from 200 to 150 °C. Applying this approach in positive-intrinsic-negative (p-i-n) inverted cells yields a high power conversion efficiency of 19.23%. Importantly, these cells exhibit significantly enhanced stability, even under stress at 85 °C.

5.
Chembiochem ; : e202400458, 2024 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-39037928

RESUMO

Asymmetric hydrogenation of alkene moieties is important for the synthesis of chiral molecules, but achieving high stereoselectivity remains a challenge. Biocatalysis using ene-reductases (EReds) offers a viable solution. However, the need for NAD(P)H cofactors limits large-scale applications. Here, we explored an electrochemical alternative for recycling flavin-containing EReds using methyl viologen as a mediator. For this, we built a bio-electrocatalytic setup with an H-type glass reactor cell, proton exchange membrane, and carbon cloth electrode. Experimental results confirm the mediator's electrochemical reduction and enzymatic consumption. Optimization showed increased product concentration at longer reaction times with better reproducibility within 4-6 h. We tested two enzymes, Pentaerythritol Tetranitrate Reductase (PETNR) and the Thermostable Old Yellow Enzyme (TOYE), using different alkene substrates. TOYE showed higher productivity for the reduction of 2-cyclohexen-1-one (1.20 mM h-1), 2-methyl-2-cyclohexen-1-one (1.40 mM h-1) and 2-methyl-2-pentanal (0.40 mM h-1), with enantiomeric excesses ranging from 11% to 99%. PETNR outperformed TOYE in terms of enantioselectivity for the reduction of 2-methyl-2-pentanal (ee 59±7% (S)). Notably, TOYE achieved promising results also in reducing ketoisophorone, a challenging substrate, with similar enantiomeric excess compared to published values using NADH.

6.
Acc Chem Res ; 56(5): 561-572, 2023 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-36795591

RESUMO

ConspectusSingle-atom catalysts (SACs) offer unique advantages such as high (noble) metal utilization through maximum possible dispersion, large metal-support contact areas, and oxidation states usually unattainable in classic nanoparticle catalysis. In addition, SACs can serve as models for determining active sites, a simultaneously desired as well as elusive target in the field of heterogeneous catalysis. Due to the complexity of heterogeneous catalysts bearing a variety of different sites on metal particles and the respective support as well as at their interface, studies of intrinsic activities and selectivities remain largely inconclusive. While SACs could close this gap, many supported SACs remain intrinsically ill-defined due to complexities arising from the variety of different adsorption sites for atomically dispersed metals, hampering the establishment of meaningful structure-activity correlations. In addition to overcoming this limitation, well-defined SACs could even be utilized to shed light on fundamental phenomena in catalysis that remain ambiguous when studies are obscured by the complexity of heterogeneous catalysts.In this Account, we describe approaches to break down the complexity of supported single-atom catalysts through the careful choice of oxide supports with specific binding motives as well as the adsorption of well-defined ligands such as ionic liquids on single metal sites. An example of molecularly defined oxide supports is polyoxometalates (POMs), which are metal oxo clusters with precisely known composition and structure. POMs exhibit a limited number of sites to anchor atomically dispersed metals such as Pt, Pd, and Rh. Polyoxometalate-supported single-atom catalysts (POM-SACs) thus represent ideal systems for the in situ spectroscopic study of single atom sites during reactions as, in principle, all sites are identical and thus equally active in catalytic reactions. We have utilized this benefit in studies of the mechanism of CO and alcohol oxidation reactions as well as the hydro(deoxy)genation of various biomass-derived compounds. More so, the redox properties of polyoxometalates can be finely tuned by changing the composition of the support while keeping the geometry of the single-atom active site largely constant. We further developed soluble analogues of heterogeneous POM-SACs, opening the door to advanced liquid-phase nuclear magnetic resonance (NMR) and UV-vis techniques but, in particular, to electrospray ionization mass spectrometry (ESI-MS) which proves powerful in determining catalytic intermediates as well as their gas-phase reactivity. Employing this technique, we were able to resolve some of the long-standing questions about hydrogen spillover, demonstrating the broad utility of studies on defined model catalysts.

7.
Org Biomol Chem ; 22(13): 2620-2629, 2024 03 27.
Artigo em Inglês | MEDLINE | ID: mdl-38451121

RESUMO

Mechanochemical reactions achieved by processes such as milling and grinding are promising alternatives to traditional solution-based chemistry. This approach not only eliminates the need for large amounts of solvents, thereby reducing waste generation, but also finds applications in chemical and materials synthesis. The focus of this study is on the synthesis of quinazolinone derivatives by ball milling, in particular evodiamine and rutaecarpine analogues. These compounds are of interest due to their diverse bioactivities, including potential anticancer properties. The study examines the reactions carried out under ball milling conditions, emphasizing their efficiency in terms of shorter reaction times and reduced environmental impact compared to conventional methods. The ball milling reaction of evodiamine and rutaecarpine analogues resulted in yields of 63-78% and 22-61%, respectively. In addition, these compounds were tested for their cytotoxic activity, and evodiamine exhibited an IC50 of 0.75 ± 0.04 µg mL-1 against the Ca9-22 cell line. At its core, this research represents a new means to synthesise these compounds, providing a more environmentally friendly and sustainable alternative to traditional approaches.


Assuntos
Alcaloides Indólicos , Quinazolinonas , Quinazolinas/química
8.
BMC Psychiatry ; 24(1): 365, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38750479

RESUMO

OBJECTIVES: This study aims to evaluate the safety and efficacy of escitalopram and sertraline in post-stroke depression (PSD) patients, to provide more reliable therapeutics for cardiovascular and psychiatric clinical practice. METHODS: We recruited 60 patients (aged 40-89 years old) with an ICD-10 diagnosis of PSD, who were then randomly assigned to two groups and treated with flexible doses of escitalopram (10 to 20 mg/day, n = 30) or sertraline (50 to 200 mg/day, n = 30) for consecutive 8 weeks, respectively. The 24-item Hamilton Depression Rating Scale (HAMD-24), the 14-item Hamilton Anxiety Rating Scale (HAMA-14), the Treatment Emergent Symptom Scale (TESS), the Montreal Cognitive Assessment Scale (MOCA), and the Activity of Daily Living scale (ADL) were used to assess patients before, during, and after treatment for depression, anxiety, adverse effects, cognitive function, and daily living activities. Repeated measures ANOVA, the Mann-Whitney U test, the chi-square test (χ2), or Fisher's exact test was employed to assess baseline demographics, response rate, adverse effects rate, and changes in other clinical variables. RESULTS: Significant reduction in HAMD-24 and HAMA-14 scores was evaluated at baseline, as well as 1, 3, 4, 6, and 8 weeks of drug intervention (p < 0.01). There was a significant group difference in post-treatment HAMD-24 scores (p < 0.05), but no difference was observed in HAMA-14 scores (p > 0.05). Further analysis showed a significant variance in the HAMD-24 scores between the two groups at the end of the first week (p < 0.01). The incidence of adverse effects in both patient groups was mild, but there was a statistically significant difference between the two groups (p < 0.05). The improvement in cognitive function and the recovery of daily living abilities were comparable between both groups (p > 0.05). CONCLUSION: Escitalopram and sertraline showed comparable efficacy for anxiety symptoms, cognitive function, and daily living abilities in PSD patients. In addition, escitalopram was more appropriate for alleviating depressive symptoms. To validate the conclusion, trials with a larger sample size are in demand in the future. The registration number is ChiCTR1800017373.


Assuntos
Atividades Cotidianas , Escitalopram , Sertralina , Acidente Vascular Cerebral , Humanos , Sertralina/uso terapêutico , Sertralina/efeitos adversos , Masculino , Idoso , Feminino , Pessoa de Meia-Idade , Acidente Vascular Cerebral/complicações , Acidente Vascular Cerebral/tratamento farmacológico , Adulto , Idoso de 80 Anos ou mais , Escitalopram/uso terapêutico , Escitalopram/efeitos adversos , Depressão/tratamento farmacológico , Depressão/etiologia , Resultado do Tratamento , Inibidores Seletivos de Recaptação de Serotonina/uso terapêutico , Inibidores Seletivos de Recaptação de Serotonina/efeitos adversos , Escalas de Graduação Psiquiátrica , Antidepressivos/uso terapêutico , Antidepressivos/efeitos adversos , Citalopram/uso terapêutico , Citalopram/efeitos adversos
9.
Environ Toxicol ; 39(1): 299-313, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37705323

RESUMO

Increased neddylation benefits the survival of several types of cancer cells. The inhibition of neddylation has the potential to exert anticancer effects but is rarely assessed in oral cancer cells. This study aimed to investigate the antiproliferation potential of a neddylation inhibitor MLN4924 (pevonedistat) for oral cancer cells. MLN4924 inhibited the cell viability of oral cancer cells more than that of normal oral cells (HGF-1) with 100% viability, that is, IC50 values of oral cancer cells (CAL 27, OC-2, and Ca9-22) are 1.8, 1.4, and 1.9 µM. MLN4924 caused apoptotic changes such as the subG1 accumulation, activation of annexin V, pancaspase, and caspases 3/8/9 of oral cancer cells at a greater rate than in normal oral cells. MLN4924 induced greater oxidative stress in oral cancer cells compared to normal cells by upregulating reactive oxygen species and mitochondrial superoxide and depleting the mitochondrial membrane potential and glutathione. In oral cancer cells, preferential inductions also occurred for DNA damage (γH2AX and 8-oxo-2'-deoxyguanosine). Therefore, this investigation demonstrates that MLN4924 is a potential anti-oral-cancer agent showing preferential inhibition of apoptosis and promotion of DNA damage with fewer cytotoxic effects on normal cells.


Assuntos
Apoptose , Neoplasias Bucais , Humanos , Proliferação de Células , Linhagem Celular Tumoral , Neoplasias Bucais/metabolismo
10.
Int J Mol Sci ; 25(4)2024 Feb 10.
Artigo em Inglês | MEDLINE | ID: mdl-38396816

RESUMO

Focal adhesions (FAs) play a crucial role in cell spreading and adhesion, and their autophagic degradation is an emerging area of interest. This study investigates the role of Thrombospondin Type 1 Domain-Containing Protein 1 (THSD1) in regulating autophagy and FA stability in brain endothelial cells, shedding light on its potential implications for cerebrovascular diseases. Our research reveals a physical interaction between THSD1 and FAs. Depletion of THSD1 significantly reduces FA numbers, impairing cell spreading and adhesion. The loss of THSD1 also induces autophagy independently of changes in mTOR and AMPK activation, implying that THSD1 primarily governs FA dynamics rather than serving as a global regulator of nutrient and energy status. Mechanistically, THSD1 negatively regulates Beclin 1, a central autophagy regulator, at FAs through interactions with focal adhesion kinase (FAK). THSD1 inactivation diminishes FAK activity and relieves its inhibitory phosphorylation on Beclin 1. This, in turn, promotes the complex formation between Beclin 1 and ATG14, a critical event for the activation of the autophagy cascade. In summary, our findings identify THSD1 as a novel regulator of autophagy that degrades FAs in brain endothelial cells. This underscores the distinctive nature of THSD1-mediated, cargo-directed autophagy and its potential relevance to vascular diseases due to the loss of endothelial FAs. Investigating the underlying mechanisms of THSD1-mediated pathways holds promise for discovering novel therapeutic targets in vascular diseases.


Assuntos
Adesões Focais , Trombospondinas , Doenças Vasculares , Humanos , Autofagia , Proteína Beclina-1/metabolismo , Células Endoteliais/metabolismo , Proteína-Tirosina Quinases de Adesão Focal/metabolismo , Adesões Focais/metabolismo , Fosforilação , Doenças Vasculares/metabolismo , Trombospondinas/metabolismo
11.
Angew Chem Int Ed Engl ; : e202408504, 2024 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-38884612

RESUMO

The photocatalytic conversion of biomass and plastic waste provides opportunities for sustainable fuel and chemical production. Heterogeneous photocatalysts, typically composed of semiconductors with distinctive redox properties in their conduction band (CB) and valence band (VB), facilitate both the oxidative and reductive valorization of organic feedstocks. This article provides a comprehensive overview of recent advancements in the photorefinery of biomass and plastics from the perspective of the redox properties of photocatalysts. We explore the roles of the VB and CB in enhancing the value-added conversion of biomass and plastics via various pathways. Our aim is to bridge the gap between photocatalytic mechanisms and renewable carbon feedstock valorization, inspiring further development in photocatalytic refinery of biomass and plastics.

12.
Angew Chem Int Ed Engl ; 63(12): e202316925, 2024 Mar 18.
Artigo em Inglês | MEDLINE | ID: mdl-38284505

RESUMO

During multivalent ions insertion processes, intense electrostatic interaction between charge carriers and host makes the high-performance reversible Al3+ storage remains an elusive target. On account of the strong electrostatic repulsion and poor robustness, Prussian Blue analogues (PBAs) suffer severely from the inevitable and large strain and phase change during reversible Al3+ insertion. Herein, we demonstrate an entropy-driven strategy to realize ultralong life aqueous Al-ion batteries (AIBs) based on medium entropy PBAs (ME-PBAs) host. By multiple redox active centers introduction, the intrinsic poor conductivity can be enhanced simultaneously, resulting in outstanding capabilities of electrochemical Al3+ storage. Meanwhile, the co-occupation at metal sites in PBA frameworks can also increase the M-N bond intensity, which is beneficial for constraining the phase change during consecutive Al3+ reversible insertion, to realize an extended lifespan over 10,000 cycles. Based on the calculation at different operation states, the fluctuation of ME-PBA lattice parameters is only 1.2 %. Assembled with MoO3 anodes, the full cells can also deliver outstanding electrochemical properties. The findings highlight that, the entropy regulation strategy could uncover the isochronous constraint on both strain and phase transition for long-term reversible Al3+ storage, providing a promising design for advanced electrode materials for aqueous multivalent ions batteries.

13.
Development ; 147(6)2020 03 16.
Artigo em Inglês | MEDLINE | ID: mdl-32098764

RESUMO

Neocortex development during embryonic stages requires the precise control of mRNA metabolism. Human antigen R (HuR) is a well-studied mRNA-binding protein that regulates mRNA metabolism, and it is highly expressed in the neocortex during developmental stages. Deletion of HuR does not impair neural progenitor cell proliferation or differentiation, but it disturbs the laminar structure of the neocortex. We report that HuR is expressed in postmitotic projection neurons during mouse brain development. Specifically, depletion of HuR in these neurons led to a mislocalization of CDP+ neurons in deeper layers of the cortex. Time-lapse microscopy showed that HuR was required for the promotion of cell motility in migrating neurons. PCR array identified profilin 1 (Pfn1) mRNA as a major binding partner of HuR in neurons. HuR positively mediated the stability of Pfn1 mRNA and influenced actin polymerization. Overexpression of Pfn1 successfully rescued the migration defects of HuR-deleted neurons. Our data reveal a post-transcriptional mechanism that maintains actin dynamics during neuronal migration.


Assuntos
Movimento Celular , Proteína Semelhante a ELAV 1/fisiologia , Neurônios/fisiologia , RNA Mensageiro/metabolismo , Animais , Padronização Corporal/genética , Movimento Celular/genética , Células Cultivadas , Embrião de Mamíferos , Feminino , Células HEK293 , Humanos , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Camundongos Transgênicos , Células-Tronco Neurais/fisiologia , Neurogênese/genética , Gravidez , Profilinas/fisiologia , Processamento Pós-Transcricional do RNA/genética
14.
Small ; 19(40): e2303215, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37269200

RESUMO

In this work, high-performance, light-stimulation healable, and closed-loop recyclable covalent adaptable networks are successfully synthesized from natural lignin-based polyurethane (LPU) Zn2+ coordination structures (LPUxZy). Using an optimized LPU (LPU-20 with a tensile strength of 28.4 ± 3.5 MPa) as the matrix for Zn2+ coordination, LPUs with covalent adaptable coordination networks are obtained that have different amounts of Zn. When the feed amount of ZnCl2 is 9 wt%, the strength of LPU-20Z9 reaches 37.3 ± 3.1 MPa with a toughness of 175.4 ± 4.6 MJ m-3 , which is 1.7 times of that of LPU-20. In addition, Zn2+ has a crucial catalytic effect on "dissociation mechanism" in the exchange reaction of LPU. Moreover, the Zn2+ -based coordination bonds significantly enhance the photothermal conversion capability of lignin. The maximum surface temperature of LPU-20Z9 reaches 118 °C under the near-infrared illumination of 0.8 W m-2 . This allows the LPU-20Z9 to self-heal within 10 min. Due to the catalytic effect of Zn2+ , LPU-20Z9 can be degraded and recovered in ethanol completely. Through the investigation of the mechanisms for exchange reaction and the design of the closed-loop recycling method, this work is expected to provide insight into the development of novel LPUs with high-performance, light-stimulated heal ability, and closed-loop recyclability; which can be applied toward the expanded development of intelligent elastomers.

15.
Chemistry ; 29(67): e202301901, 2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-37874010

RESUMO

Controlling the coordination sphere of heterogeneous single-metal-site catalysts is a powerful strategy for fine-tuning their catalytic properties but is fairly difficult to achieve. To address this problem, we immobilized supramolecular cages where the primary- and secondary coordination sphere are controlled by ligand design. The kinetics of these catalysts were studied in a model reaction, the hydrolysis of ammonia borane, over a temperature range using fast and precise online measurements generating high-precision Arrhenius plots. The results show how catalytic properties can be enhanced by placing a well-defined reaction pocket around the active site. Our fine-tuning yielded a catalyst with such performance that the reaction kinetics are diffusion-controlled rather than chemically controlled.

16.
Theor Appl Genet ; 136(5): 101, 2023 Apr 07.
Artigo em Inglês | MEDLINE | ID: mdl-37027037

RESUMO

KEY MESSAGE: A novel locus for Fusarium crown rot (FCR) resistance was identified on chromosome 1B at 641.36-645.13 Mb using GWAS and could averagely increase 39.66% of FCR resistance in a biparental population. Fusarium crown rot can cause considerable yield losses. Developing and growing resistance cultivars is one of the most effective approaches for controlling this disease. In this study, 361 Chinese wheat landraces were evaluated for FCR resistance, and 27 with the disease index lower than 30.00 showed potential in wheat breeding programs. Using a genome-wide association study approach, putative quantitative trait loci (QTL) for FCR resistance was identified. A total of 21 putative loci on chromosomes 1A, 1B, 2B, 2D, 3B, 3D, 4B, 5A, 5B, 7A, and 7B were significantly associated with FCR resistance. Among these, a major locus Qfcr.sicau.1B-4 was consistently identified among all the trials on chromosome 1B with the physical regions from 641.36 to 645.13 Mb. A polymorphism kompetitive allele-specific polymerase (KASP) marker was developed and used to validate its effect in an F2:3 population consisting of 136 lines. The results showed the presence of this resistance allele could explain up to 39.66% of phenotypic variance compared to its counterparts. In addition, quantitative real-time polymerase chain reaction showed that two candidate genes of Qfcr.sicau.1B-4 were differently expressed after inoculation. Our study provided useful information for improving FCR resistance in wheat.


Assuntos
Fusarium , Estudo de Associação Genômica Ampla , Mapeamento Cromossômico , Triticum/genética , Melhoramento Vegetal , Resistência à Doença/genética , Doenças das Plantas/genética , Fenótipo
17.
Langmuir ; 39(1): 519-532, 2023 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-36562562

RESUMO

Twelve kinds of 8-hydroxyquinoline derivatives were synthesized and characterized. The weight loss method was used to evaluate their inhibition efficiencies (IEs) in a 1.0 M HCl solution at 333 K. The results showed that the alkyl chain length, heteroatoms (S, N, and O), and number of benzene rings significantly affect the IE. Herein, the IE of 5-[(dodecylthio)methyl]-8-quinolinol reached 98.71%. Meanwhile, the potentiodynamic polarization results indicated that all 8-hydroxyquinoline derivatives were mixed-type inhibitors. Electrochemical impedance spectroscopy results revealed that 8-hydroxyquinoline derivatives can increase polarization resistance, supporting their adsorption on the N80 steel surface. Moreover, according to density functional theory (DFT), the frontier orbital distribution and quantum chemical parameters (EHOMO, ELUMO, dipole moment µ, etc.) were calculated, and the results confirmed that the substituents of protonated 8-hydroxyquinoline derivatives significantly influenced the frontier orbital distribution. Molecular dynamics simulation illustrated that all protonated 8-hydroxyquinoline derivatives were adsorbed parallel to the Fe(110) surface, and the interaction energy (Eint) evidenced that the molecular size would affect their strength of adsorption on the Fe(110) surface. The linear and nonlinear quantitative structure-activity relationship models were established by linear regression (LR) methods and BP neural networks (NN), respectively. The LR model was established by using Eint and µ, and the coefficient of determination (R2) was 0.934. In addition, the nonlinear NN model was obtained according to IE and all parameters (DFT parameters and Eint). Then, the two calculation inhibition efficiencies (IEcal) were obtained from the LR and NN models, and the R2 values of the linear correlation between the IEcal and the experimental IE were 0.940 and 0.951, respectively. In addition, the IE of the tested inhibitor was 51.86% and the IEcal values predicted by the LR and NN models were 52.68% and 53.06%, respectively. Our results demonstrate that both the LR and NN models have good fits and predictive ability.

18.
Crit Rev Food Sci Nutr ; : 1-19, 2023 May 24.
Artigo em Inglês | MEDLINE | ID: mdl-37222572

RESUMO

Advanced glycation end products (AGEs), the products of non-enzymatic browning reactions between the active carbonyl groups of reducing sugars and the free amines of amino acids, are largely considered oxidative derivatives resulting from diabetic hyperglycemia, which are further recognized as a potential risk for insulin resistance (IR) and type 2 diabetes (T2D). The accumulation of AGEs can trigger numerous negative effects such as oxidative stress, carbonyl stress, inflammation, autophagy dysfunction and imbalance of gut microbiota. Recently, studies have shown that cereal polyphenols have the ability to inhibit the formation of AGEs, thereby preventing and alleviating T2D. In the meanwhile, phenolics compounds could produce different biological effects due to the quantitative structure activity-relationship. This review highlights the effects of cereal polyphenols as a nonpharmacologic intervention in anti-AGEs and alleviating T2D based on the effects of oxidative stress, carbonyl stress, inflammation, autophagy, and gut microbiota, which also provides a new perspective on the etiology and treatment of diabetes.

19.
Crit Rev Food Sci Nutr ; : 1-17, 2023 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-37552798

RESUMO

Citrus polyphenols can modulate gut microbiota and such bi-directional interaction that can yield metabolites such as short-chain fatty acids (SCFAs) to aid in gut homeostasis. Such interaction provides citrus polyphenols with powerful prebiotic potential, contributing to guts' health status and metabolic regulation. Citrus polyphenols encompass unique polymethoxy flavonoids imparting non-polar nature that improve their bioactivities and ability to penetrate the blood-brain barrier. Green extraction technology targeting recovery of these polyphenols has received increasing attention due to its advantages of high extraction yield, short extraction time, low solvent consumption, and environmental friendliness. However, the low bioavailability of citrus polyphenols limits their applications in extraction from citrus by-products. Meanwhile, nano-encapsulation technology may serve as a promising approach to improve citrus polyphenols' bioavailability. As citrus polyphenols encompass multiple hydroxyl groups, they are potential to interact with bio-macromolecules such as proteins and polysaccharides in nano-encapsulated systems that can improve their bioavailability. This multifaceted review provides a research basis for the green and efficient extraction techniques of citrus polyphenols, as well as integrated mechanisms for its anti-inflammation, alleviating metabolic syndrome, and regulating gut homeostasis, which is more capitalized upon using nano-delivery systems as discussed in that review to maximize their health and food applications.

20.
J Org Chem ; 88(24): 17227-17236, 2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-38019169

RESUMO

This study presents a convenient approach to the synthesis of indole- and benzofuran-based benzylic sulfones using unactivated alkynes containing aryl iodides and sodium sulfinates under visible light irradiation. The procedure involves a sequential series of dehalogenation, carbo-cyclization, and radical sulfonylation. Plausible insights into the reaction mechanism are derived from control experiments, leading to the proposal of a radical cascade reaction pathway.

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