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1.
Nanomaterials (Basel) ; 14(17)2024 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-39269037

RESUMO

The scaling of bulk Si-based transistors has reached its limits, while novel architectures such as FinFETs and GAAFETs face challenges in sub-10 nm nodes due to complex fabrication processes and severe drain-induced barrier lowering (DIBL) effects. An effective strategy to avoid short-channel effects (SCEs) is the integration of low-dimensional materials into novel device architectures, leveraging the coupling between multiple gates to achieve efficient electrostatic control of the channel. We employed TCAD simulations to model multi-gate FETs based on various dimensional systems and comprehensively investigated electric fields, potentials, current densities, and electron densities within the devices. Through continuous parameter scaling and extracting the sub-threshold swing (SS) and DIBL from the electrical outputs, we offered optimal MoS2 layer numbers and single-walled carbon nanotube (SWCNT) diameters, as well as designed structures for multi-gate FETs based on monolayer MoS2, identifying dual-gate transistors as suitable for high-speed switching applications. Comparing the switching performance of two device types at the same node revealed CNT's advantages as a channel material in mitigating SCEs at sub-3 nm nodes. We validated the performance enhancement of 2D materials in the novel device architecture and reduced the complexity of the related experimental processes. Consequently, our research provides crucial insights for designing next-generation high-performance transistors based on low-dimensional materials at the scaling limit.

2.
Chemistry ; : e202402572, 2024 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-39167364

RESUMO

Encapsulation of transition metals represents a crucial method for modifying the electronic structure and regulating the reactivity of fullerene, thereby expanding its applications. Herein, we present calculations with density functional theory methods to investigate the mechanisms of the Diels-Alder (DA) reactions of cyclopentadiene and La@C60 or Gd@C60 as well as their tricationic derivatives. Our findings indicate that the encapsulation of La and Gd into the C60 cage is thermodynamically favorable. The DA reactions are favored by the presence of La and Gd, with lower barriers, though the regioselectivity, favoring 6-6 bonds in the fullerene, is not affected. The effect of external electric fields has been also considered.

3.
Cell Rep Med ; 5(8): 101686, 2024 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-39168104

RESUMO

Resistance to PD-1 blockade in onco-immunotherapy greatly limits its clinical application. T cell immunoglobulin and mucin domain containing-3 (Tim-3), a promising immune checkpoint target, is cleaved by ADAM10/17 to produce its soluble form (sTim-3) in humans, potentially becoming involved in anti-PD-1 resistance. Herein, serum sTim-3 upregulation was observed in non-small cell lung cancer (NSCLC) and various digestive tumors. Notably, serum sTim-3 is further upregulated in non-responding patients undergoing anti-PD-1 therapy for NSCLC and anti-PD-1-resistant cholangiocarcinoma patients. Furthermore, sTim-3 overexpression facilitates tumor progression and confers anti-PD-1 resistance in multiple tumor mouse models. Mechanistically, sTim-3 induces terminal T cell exhaustion and attenuates CD8+ T cell response to PD-1 blockade through carcinoembryonic antigen-related cell adhesion molecule 1 (CEACAM-1). Moreover, the ADAM10 inhibitor GI254023X, which blocks sTim-3 production, reduces tumor progression in Tim-3 humanized mice and reverses anti-PD-1 resistance in human tumor-infiltrating lymphocytes (TILs). Overall, human sTim-3 holds great predictive and therapeutic potential in onco-immunotherapy.


Assuntos
Biomarcadores Tumorais , Linfócitos T CD8-Positivos , Resistencia a Medicamentos Antineoplásicos , Receptor Celular 2 do Vírus da Hepatite A , Receptor de Morte Celular Programada 1 , Receptor Celular 2 do Vírus da Hepatite A/metabolismo , Receptor Celular 2 do Vírus da Hepatite A/antagonistas & inibidores , Humanos , Animais , Linfócitos T CD8-Positivos/imunologia , Linfócitos T CD8-Positivos/metabolismo , Linfócitos T CD8-Positivos/efeitos dos fármacos , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Camundongos , Receptor de Morte Celular Programada 1/antagonistas & inibidores , Receptor de Morte Celular Programada 1/metabolismo , Receptor de Morte Celular Programada 1/imunologia , Prognóstico , Biomarcadores Tumorais/metabolismo , Inibidores de Checkpoint Imunológico/farmacologia , Inibidores de Checkpoint Imunológico/uso terapêutico , Linhagem Celular Tumoral , Feminino , Masculino , Neoplasias Pulmonares/imunologia , Neoplasias Pulmonares/tratamento farmacológico , Neoplasias Pulmonares/patologia , Neoplasias Pulmonares/metabolismo , Carcinoma Pulmonar de Células não Pequenas/imunologia , Carcinoma Pulmonar de Células não Pequenas/tratamento farmacológico , Carcinoma Pulmonar de Células não Pequenas/patologia , Carcinoma Pulmonar de Células não Pequenas/metabolismo , Proteína ADAM10/metabolismo , Camundongos Endogâmicos C57BL , Exaustão das Células T
4.
ACS Energy Lett ; 9(8): 4127-4135, 2024 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-39144815

RESUMO

Lattice dynamics are critical to photovoltaic material performance, governing dynamic disorder, hot-carrier cooling, charge-carrier recombination, and transport. Soft metal-halide perovskites exhibit particularly intriguing dynamics, with Raman spectra exhibiting an unusually broad low-frequency response whose origin is still much debated. Here, we utilize ultra-low frequency Raman and infrared terahertz time-domain spectroscopies to provide a systematic examination of the vibrational response for a wide range of metal-halide semiconductors: FAPbI3, MAPbI x Br3-x , CsPbBr3, PbI2, Cs2AgBiBr6, Cu2AgBiI6, and AgI. We rule out extrinsic defects, octahedral tilting, cation lone pairs, and "liquid-like" Boson peaks as causes of the debated central Raman peak. Instead, we propose that the central Raman response results from an interplay of the significant broadening of Raman-active, low-energy phonon modes that are strongly amplified by a population component from Bose-Einstein statistics toward low frequency. These findings elucidate the complexities of light interactions with low-energy lattice vibrations in soft metal-halide semiconductors emerging for photovoltaic applications.

5.
Sci Total Environ ; 949: 175101, 2024 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-39074757

RESUMO

Recently, many reagents have been introduced to accelerate the formation of highly reactive intermediate Mn species from permanganate (KMnO4), thereby improving the oxidation activity of KMnO4 towards pollutants. However, most studies have mainly focused on sulfur-containing reducing agents (e.g., bisulfite and sodium sulfite), with little attention paid to nitrogen-containing reducing agents. This study found that hydroxylamine (HA) and hydroxylamine derivatives (HAs) can facilitate KMnO4 in pollutant removal. Taking sulfamethoxazole (SMX) as a target contaminant, the effect of pH, SMX concentration, KMnO4 and HA dosages, and the molar ratio of HA and KMnO4 on the degradation of SMX in the KMnO4/HA process was systematically investigated. Quenching experiments and probe analysis revealed MnO2-catalyzed KMnO4 oxidation, Mn(III) and reactive nitrogen species as the primary active species responsible for SMX oxidation in the KMnO4/HA system. Proposed transformation pathways of SMX in the KMnO4/HA system mainly involve hydroxylation and cleavage reactions. The KMnO4/HA system was more conducive to selective oxidation of SMX, 2,4-dichlorophenol, and several other pollutants, but reluctant to bisphenol S (BPS). Overall, this study proposed an effective system for eliminating pollutants, while providing mechanistic insight into HA-driven KMnO4 activation for environmental remediation.

6.
J Hazard Mater ; 476: 134979, 2024 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-38905982

RESUMO

Spatially confined structure exhibits surprising physics and chemistry properties that significantly impact the thermodynamics and kinetics of oxidation reactions. Herein, porous carbons are rationally designed for tunable nanopore structures (micropores, 4.12 % ∼ 91.64 %) and diverse spatial confinement ability, as indicated by their differential enhancement performances in the Fenton oxidation. Porous carbons can alter the characteristics of the charge transport process for accelerating sustainable electron shuttle between hydrogen peroxide and iron species, and thus exhibit long-term performance (17 cycling tests). The positive spatial confinement for boosting Fenton oxidation (charge transport, mass transfer) occurs in nanochannels < 1 nm, while the diminished effect ranges of 1-1.5 nm, and the adverse effect ranges greater than 1.5 nm. The density functional theory calculation provides further support for certifying the promoted charge transport process and spatial confinement for hydroxyl radical inside the confined nanochannel structure (below 1 nm, especially) by the comparatively large electron cloud and the relatively negative adsorption energy, respectively. Coupling nanochannels with the Fenton oxidation greatly utilize hydrogen peroxide, due to spatial nanoconfinement and selective adsorption towards target contaminants. This strategy of deploying nanochannels in catalyst design can be applied for the elaborate construction of efficient nanostructured catalysts for environmental remediation.

7.
Water Res ; 257: 121715, 2024 Jun 15.
Artigo em Inglês | MEDLINE | ID: mdl-38728779

RESUMO

High-valent metal-oxo species (HMOS) have been extensively recognized in advanced oxidation processes (AOPs) owing to their high selectivity and high chemical utilization efficiency. However, the interactions between HMOS and halide ions in sewage wastewater are complicated, leading to ongoing debates on the intrinsic reactive species and impacts on remediation. Herein, we prepared three typical HMOS, including Fe(IV), Mn(V)-nitrilotriacetic acid complex (Mn(V)NTA) and Co(IV) through peroxymonosulfate (PMS) activation and comparatively studied their interactions with Cl- to reveal different reactive chlorine species (RCS) and the effects of HMOS types on RCS generation pathways. Our results show that the presence of Cl- alters the cleavage behavior of the peroxide OO bond in PMS and prohibits the generation of Fe(IV), spontaneously promoting SO4•- production and its subsequent transformation to secondary radicals like Cl• and Cl2•-. The generation and oxidation capacity of Mn(V)NTA was scarcely influenced by Cl-, while Cl- would substantially consume Co(IV) and promote HOCl generation through an oxygen-transfer reaction, evidenced by density functional theory (DFT) and deuterium oxide solvent exchange experiment. The two-electron-transfer standard redox potentials of Fe(IV), Mn(V)NTA and Co(IV) were calculated as 2.43, 2.55 and 2.85 V, respectively. Due to the different reactive species and pathways in the presence of Cl-, the amounts of chlorinated by-products followed the order of Co(II)/PMS > Fe(II)/PMS > Mn(II)NTA/PMS. Thus, this work renovates the knowledge of halide chemistry in HMOS-based systems and sheds light on the impact on the treatment of salinity-containing wastewater.


Assuntos
Oxirredução , Cloretos/química , Cloro/química , Metais/química , Halogenação , Poluentes Químicos da Água/química , Águas Residuárias/química
8.
BMC Womens Health ; 24(1): 293, 2024 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-38760803

RESUMO

Cervical cancer is the fourth most common cancer and the leading cause of mortality among women worldwide. Tumor metastasis is an important cause of poor prognosis. Determining the exact mechanisms of metastasis and potential targeted therapies is urgently needed. Junctional adhesion molecule 3 (JAM3) is an important member of the TJ tight junction (TJ) family, and its biological function in cervical cancer needs to be further clarified. We found that JAM3 was highly expressed in cervical cancer patients with lymph node metastasis and that high expression of JAM3 promoted cervical cancer cell metastasis both in vitro and in vivo. In addition, overexpression of JAM3 induces epithelial-mesenchymal transition (EMT). Moreover, silencing JAM3 suppressed cervical cancer cell migration and invasion in vitro. Finally, JAM3 overexpression activated the HIF-1α/VEGFA pathway. In conclusion, our results suggested that JAM3 promotes cervical cancer cell migration and invasion by activating the HIF-1α/VEGFA pathway. JAM3 may be a promising biomarker and effective therapeutic target for cervical cancer.


Assuntos
Moléculas de Adesão Celular , Movimento Celular , Transição Epitelial-Mesenquimal , Subunidade alfa do Fator 1 Induzível por Hipóxia , Neoplasias do Colo do Útero , Neoplasias do Colo do Útero/patologia , Neoplasias do Colo do Útero/genética , Neoplasias do Colo do Útero/metabolismo , Feminino , Humanos , Subunidade alfa do Fator 1 Induzível por Hipóxia/metabolismo , Moléculas de Adesão Celular/metabolismo , Moléculas de Adesão Celular/genética , Movimento Celular/genética , Linhagem Celular Tumoral , Fator A de Crescimento do Endotélio Vascular/metabolismo , Metástase Linfática/patologia , Animais , Transdução de Sinais , Camundongos , Invasividade Neoplásica
9.
J Hazard Mater ; 471: 134393, 2024 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-38669929

RESUMO

Solution pH is one of the primary factors affecting the efficiency of water decontamination. Although the influence of pH on oxidants activation, catalyst activity, and reactive oxygen species have been widely explored, there is still a scarcity of systemic studies on the changes in the oxidation behavior of organic pollutants at different pH levels. Herein, we report the influence laws of pH on the forms, reactivities, active sites, degradation pathways, and products toxicities of organic pollutants. Changes in pH cause the protonation or deprotonation of organic pollutants and further affect their forms and chemistry (e.g., electrostatic force, hydrophobicity, and oxidation potential). The oxidation potential of organic pollutants follows the order: protonated form > pristine form > deprotonated form. Moreover, protonation or deprotonation can modify the active sites and degradation pathways of organic pollutants, wherein deprotonation renders them more susceptible to electrophilic attack, while protonation reduces their activity against electrophilic and nucleophilic attacks. Additionally, pH adjustments can modify the degradation pathway and the toxicity of transformation products. Overall, pH changes can affect the oxidation fate of organic pollutants by altering their structure, which distinguishes it from the effect of pH on oxidants or oxidant activation processes.

10.
Plants (Basel) ; 12(24)2023 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-38140495

RESUMO

Phytophthora capsici, a destructive fungal pathogen, poses a severe threat to pepper (Capsicum annuum L.) crops worldwide, causing blights that can result in substantial yield losses. Traditional control methods often come with environmental concerns or entail substantial time investments. In this research, we investigate an alternative approach involving ferrous sulfate (FeSO4) application to combat P. capsici and promote pepper growth. We found that FeSO4 effectively inhibits the growth of P. capsici in a dose-dependent manner, disrupting mycelial development and diminishing pathogenicity. Importantly, FeSO4 treatment enhances the biomass and resistance of pepper plants, mitigating P. capsici-induced damage. Microbiome analysis demonstrates that FeSO4 significantly influences soil microbial communities, particularly fungi, within the pepper root. Metabolomics data reveal extensive alterations in the redox metabolic processes of P. capsici under FeSO4 treatment, leading to compromised cell membrane permeability and oxidative stress in the pathogen. Our study presents FeSO4 as a promising and cost-effective solution for controlling P. capsici in pepper cultivation while simultaneously promoting plant growth. These findings contribute to a deeper understanding of the intricate interactions between iron, pathogen control, and plant health, offering a potential tool for sustainable pepper production.

11.
Sci Transl Med ; 15(722): eadg6752, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-37967204

RESUMO

T cell immunoglobulin and mucin-containing molecule 3 (Tim-3), expressed in dysfunctional and exhausted T cells, has been widely acknowledged as a promising immune checkpoint target for tumor immunotherapy. Here, using a strategy combining virtual and functional screening, we identified a compound named ML-T7 that targets the FG-CC' cleft of Tim-3, a highly conserved binding site of phosphatidylserine (PtdSer) and carcinoembryonic antigen-related cell adhesion molecule 1 (CEACAM1). ML-T7 enhanced the survival and antitumor activity of primary CD8+ cytotoxic T lymphocytes (CTLs) and human chimeric antigen receptor (CAR) T cells and reduced their exhaustion in vitro and in vivo. In addition, ML-T7 promoted NK cells' killing activity and DC antigen-presenting capacity, consistent with the reported activity of Tim-3. ML-T7 strengthened DCs' functions through both Tim-3 and Tim-4, which is consistent with the fact that Tim-4 contains a similar FG-CC' loop. Intraperitoneal dosing of ML-T7 showed comparable tumor inhibitory effects to the Tim-3 blocking antibody. ML-T7 reduced syngeneic tumor progression in both wild-type and Tim-3 humanized mice and alleviated the immunosuppressive microenvironment. Furthermore, combined ML-T7 and anti-PD-1 therapy had greater therapeutic efficacy than monotherapy in mice, supporting further development of ML-T7 for tumor immunotherapy. Our study demonstrates a potential small molecule for selectively blocking Tim-3 and warrants further study.


Assuntos
Receptor Celular 2 do Vírus da Hepatite A , Neoplasias , Humanos , Animais , Camundongos , Receptor Celular 2 do Vírus da Hepatite A/metabolismo , Linfócitos T CD8-Positivos , Linfócitos T Citotóxicos/metabolismo , Neoplasias/terapia , Imunoterapia , Microambiente Tumoral
12.
Food Funct ; 2023 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-37779497

RESUMO

Diet is an important source of perfluoroalkyl and polyfluoroalkyl substance (PFAS) exposure, and the dietary inflammatory index (DII) is a tool used to assess the inflammatory potential of an individual's diet. However, limited research has explored the association between the DII and PFAS exposure in humans. This study is the first to analyze the association between the five PFASs and DII using the National Health and Nutrition Examination Survey (NHANES) 2007-2018 database. Additionally, we assessed the interaction between the DII and PFASs regarding oxidative stress and inflammatory markers, including alkaline phosphatase, albumin, neutrophil count, lymphocyte count, total bilirubin, and serum iron based on a previous study. A series of covariates were included in the analysis to reduce the confounding bias. The study included 7773 and 5933 participants based on the different models. The DII was significantly associated with serum perfluorooctanoic acid, perfluorononanoic acid, perfluorooctane sulfonic acid, and sum-PFAS. Some of the food parameters used to calculate the DII also showed associations with special PFAS serum concentrations. Specifically, dietary fiber, n-3 polyunsaturated fatty acids, energy intake, and vitamin D were associated with more than three PFASs. Higher DII levels in participants were linked to a more significant association between bilirubin (the interaction P-value is not significant), alkaline phosphatase, serum iron, neutrophil counts, and some PFASs. In conclusion, this study clarified the association between the three PFASs and DII, highlighting the diverse effects of PFASs on oxidative stress and inflammatory markers across different DII levels.

14.
ACS Nano ; 17(18): 18616-18628, 2023 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-37713681

RESUMO

P2-type layered transition-metal (TM) oxides, NaxTMO2, are highly promising as cathode materials for sodium-ion batteries (SIBs) due to their excellent rate capability and affordability. However, P2-type NaxTMO2 is afflicted by issues such as Na+/vacancy ordering and multiple phase transitions during Na-extraction/insertion, leading to staircase-like voltage profiles. In this study, we employ a combination of high Na content and Li dual-site substitution strategies to enhance the structural stability of a P2-type layered oxide (Na0.80Li0.024[Li0.065Ni0.22Mn0.66]O2). The experimental results reveal that these approaches facilitate the oxidation of Mn ions to a higher valence state, thereby affecting the local environment of both TM and Na ions. The resulting modification in the local structure significantly improves the Na-ion storage capabilities as required for cathode materials in SIBs. Furthermore, it induces a solid-solution reaction and enables nearly zero-strain operation (ΔV = 0.7%) in the Na0.80Li0.024[Li0.065Ni0.22Mn0.66]O2 cathode during cycling. The assembled full cells demonstrate an exceptional rate performance, with a retention rate of 87% at 10 C compared to that of 0.1 C, as well as an ultrastable cycling capability, maintaining a capacity retention of 73% at 2 C after 1000 cycles. These findings offer valuable insights into the electronic and structural chemistry of ultrastable cathode materials with "zero-strain" Na-ion storage.

15.
Cell Rep ; 42(8): 112944, 2023 Aug 29.
Artigo em Inglês | MEDLINE | ID: mdl-37566545

RESUMO

Immune checkpoint blockade (ICB) therapies display clinical efficacy in microsatellite instable (MSI) endometrial cancer (EC) treatment, the key mechanism of which is reversing T cell exhaustion and restoration of anti-tumor immunity. Here, we demonstrate that transcription factor 19 (TCF19), one of the most significantly differentially expressed genes between MSI and microsatellite stable (MSS) patients in The Cancer Genome Atlas (TCGA)-EC cohort, is associated with poor prognosis and immune exhaustion signature. Specifically, TCF19 is significantly elevated in MSI EC, which in turn promotes tripartite motif-containing 14 (TRIM14) transcription and correlates with hyperactive signaling of the TANK-binding kinase 1 (TBK1)-interferon regulatory factor 3 (IRF3)-interferon ß (IFN-ß) pathway. The TCF19-TRIM14 axis promotes tumorigenicity under non-immunological background, and the enhanced downstream secretion of IFN-ß facilitates CD8+ T cell exhaustion through cell differentiation reprogramming. Finally, using humanized models, we show that a combination of TCF19 inhibition and ICB therapy demonstrates more effective anti-tumor responses. Together, our study indicates that targeting TCF19 is a potent strategy for alleviating CD8+ T cell exhaustion and synergizing with ICB in tumor treatment.

16.
ACS Appl Mater Interfaces ; 15(31): 37640-37648, 2023 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-37491709

RESUMO

As a new-generation photoelectric material, perovskites have attracted researchers' attention due to their excellent optoelectronic properties. However, the existence of defects inevitably causes structural degradation and restricts their performance, which need to be further improved by post-treatment. At present, post-treatments mostly focus on non-contact treatments, which may constrain the effect since the influence on the perovskites caused by the direct contact is much more straightly. Therefore, we proposed an annealing strategy of straight manipulation in a solvent atmosphere with the assistance of polyimide (PI) tape for the perovskite post-treatment, due to the high heat resistance and less glue residual of this tape. It casts an influence on the perovskite directly, proving the possibility of the straight manipulation by operators, promoting the recrystallization of the perovskite grains and removing the impurity substance. The optimized Pb-free perovskite film exhibits a better X-ray sensitivity of 7.5 × 104 µC Gyair-1 cm-2 and a great detection limit of 47 nGyair s-1, which is comparable to advanced Pb-based perovskite X-ray detectors and all commercial ones. The new annealing strategy provides a facile, effective, and simple method to improve the perovskite quality, exhibiting the potential and harmlessness of the direct contact post-treatment, which paves the way for a broader application of perovskites.

17.
Environ Sci Technol ; 57(29): 10804-10815, 2023 07 25.
Artigo em Inglês | MEDLINE | ID: mdl-37431633

RESUMO

Carbon nanotubes (CNTs) and their derivatives have been widely exploited to activate various oxidants for environmental remediation. However, the intrinsic mechanism of CNTs-driven periodate (PI) activation remains ambiguous, which significantly impedes their scientific progress toward practical application. Here, we found that CNTs can strongly boost PI activation for the oxidation of various phenols. Reactive oxygen species analysis, in situ Raman characterization, galvanic oxidation process experiments, and electrochemical tests revealed that CNTs could activate PI to form high-potential metastable intermediates (CNTs-PI*) rather than produce free radicals and 1O2, thereby facilitating direct electron transfer from the pollutants to PI. Additionally, we analyzed quantitative structure-activity relationships between rate constants of phenols oxidation and double descriptors (e.g., Hammett constants and logarithm of the octanol-water partition coefficient). The adsorption of phenols on CNT surfaces and their electronic properties are critical factors affecting the oxidation process. Besides, in the CNTs/PI system, phenol adsorbed the CNT surfaces was oxidized by the CNTs-PI* complexes, and products were mainly generated via the coupling reaction of phenoxyl radical. Most of the products adsorbed and accumulated on the CNT surfaces realized phenol removal from the bulk solution. Such a unique non-mineralization removal process achieved an extremely high apparent electron utilization efficiency of 378%. The activity evaluation and theoretical calculations of CNT derivatives confirmed that the carbonyl/ketonic functional groups and double-vacancy defects of the CNTs were the primary active sites, where high-oxidation-potential CNTs-PI* were formed. Further, the PI species could achieve a stoichiometric decomposition into iodate, a safe sink of iodine species, without the generation of typical iodinated byproducts. Our discovery provides new mechanistic insight into CNTs-driven PI activation for the green future of environmental remediation.


Assuntos
Nanotubos de Carbono , Nanotubos de Carbono/química , Fenol , Oxirredução , Fenóis
18.
BMC Genomics ; 24(1): 377, 2023 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-37407925

RESUMO

BACKGROUND: Basic leucine zipper (bZIP) proteins are important transcription factors in plants. To study the role of bZIP transcription factors in walnut explant browning, this study used bioinformatics software to analyze walnut bZIP gene family members, along with their transcript levels in different walnut tissues, to evaluate the transcriptional expression of this gene family during the primary culture of walnut explants and to reveal the mechanism of action of walnut bZIP genes in walnut explant browning. RESULTS: The results identified 65 JrbZIP genes in the walnut genome, which were divided into 8 subfamilies and distributed on 16 chromosomes. The results of transcriptome data analysis showed that there were significant differences in the expression of four genes, namely, JrbZIP55, JrbZIP70, JrbZIP72, and JrbZIP88, under both vermiculite and agar culture conditions. There were multiple hormone (salicylic acid, abscisic acid, auxin, and gibberellin) signaling and regulatory elements that are responsive to stress (low temperature, stress, and defense) located in the promoter regions of JrbZIP55, JrbZIP70, JrbZIP72, and JrbZIP88. The walnut JrbZIP55 protein and Arabidopsis bZIP42 protein are highly homologous, and the proteins interacting with Arabidopsis bZIP42 include the AT2G19940 oxidoreductases, which act on aldehyde or oxygen-containing donors. CONCLUSION: It is speculated that JrbZIP55 may participate in the regulation of browning in walnut explants.


Assuntos
Arabidopsis , Juglans , Juglans/genética , Arabidopsis/genética , Perfilação da Expressão Gênica , Transcriptoma , Genes de Plantas , Fatores de Transcrição de Zíper de Leucina Básica/genética , Fatores de Transcrição de Zíper de Leucina Básica/metabolismo , Regulação da Expressão Gênica de Plantas , Filogenia , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo
19.
ACS Omega ; 8(26): 23791-23798, 2023 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-37426225

RESUMO

Organosilicon and organotin compounds have been widely used in many fields, such as organic synthesis, materials science, and biochemistry, because of their unique physical and electronic properties. Recently, two novel compounds containing C-Si or C-Sn bonds have been synthesized. These compounds can be used for late modification of drug-like molecules such as probenecid, duloxetine, and fluoxetine derivatives. However, the detailed reaction mechanisms and the influencing factors that determine selectivity are still unclear. Moreover, several questions remain that are valuable to investigate further, such as (1) the influence of the solvent and the lithium salt on the reaction of the Si/Sn-Zn reagent, (2) the stereoselective functionalization of C-O bonds, and (3) the differences between silylation and stannylation. In the current study, we have explored the above issues with density functional theory and have found that stereoselectivity was most likely caused by the oxidative addition of cobalt to the C-O bond of alkenyl acetate with chelation assistance and that transmetalation was most likely the rate-determining step. For Sn-Zn reagents, the transmetalation was achieved by anion and cation pairs, whereas for Si-Zn reagents, the process was facilitated by Co-Zn complexes.

20.
Oncogene ; 42(31): 2386-2401, 2023 07.
Artigo em Inglês | MEDLINE | ID: mdl-37391593

RESUMO

Splicing factors play a crucial role in the initiation and development of various human cancers. SNRPB, a core spliceosome component, regulates pre-mRNA alternative splicing. However, its function and underlying mechanism in ovarian cancer remain unclear. This study identified SNRPB as a critical driver of ovarian cancer through TCGA and CPTAC database analysis. SNRPB was highly upregulated in fresh frozen ovarian cancer tissues compared with normal fallopian tubes. Immunohistochemistry revealed that SNRPB expression was increased in formalin-fixed, paraffin-embedded ovarian cancer sections and was positively correlated with a poor prognosis for ovarian cancer. Functionally, SNRPB knockdown suppressed ovarian cancer cell proliferation and invasion, and overexpression exerted opposite effects. SNRPB expression increased after cisplatin treatment, and silencing SNRPB sensitized ovarian cancer cells to cisplatin. KEGG pathway analysis revealed that the differentially expressed genes (DEGs) were mainly enriched in DNA replication and homologous recombination, and almost all DEGs related to DNA replication and homologous recombination were downregulated after SNRPB knockdown according to RNA-seq. Exon 3 skipping of the DEGs DNA polymerase alpha 1 (POLA1) and BRCA2 was induced by SNRPB silencing. Exon 3 skipping of POLA1 yielded premature termination codons and led to nonsense-mediated RNA decay (NMD); exon 3 skipping of BRCA2 led to loss of the PALB2 binding domain, which is necessary for homologous recombination, and increased ovarian cancer cell cisplatin sensitivity. POLA1 or BRCA2 knockdown partially impaired the increased malignancy of SNRPB-overexpressing ovarian cancer cells. Moreover, miR-654-5p was found to reduce SNRPB mRNA expression by directly binding to the SNRPB 3'-UTR. Overall, SNRPB was identified as an important oncogenic driver that promotes ovarian cancer progression by repressing exon 3 skipping of POLA1 and BRCA2. Thus, SNRPB is a potential treatment target and prognostic marker for ovarian cancer.


Assuntos
Neoplasias Ovarianas , Humanos , Feminino , Neoplasias Ovarianas/genética , Fatores de Processamento de RNA/genética , Cisplatino/farmacologia , Éxons/genética , Splicing de RNA , Processamento Alternativo , Proteínas Centrais de snRNP/genética , Proteínas Centrais de snRNP/metabolismo , Proteína BRCA2/genética , Proteína BRCA2/metabolismo
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