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1.
J Org Chem ; 89(18): 13540-13555, 2024 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-39255243

RESUMO

How the factors affecting the formation and transformation of the intermediates in Pd(II)-catalyzed aromatic C-H activation: A comprehensive study with the Pd(II)/LA platform. Using the Pd(II)/Lewis acid (LA)-catalyzed C-H activation of electron-rich acetanilides as a platform, the C-H activation intermediates, including the precomplex η2-intermediate, the agostic hydrogen intermediate, and the palladacycle compound have been well-characterized. This work presents how the catalyst source, substrate, and solvent affect the formation of the η2-intermediate and its equilibrium with the agostic hydrogen intermediate, and the transformation of the agostic hydrogen intermediate to the palladacycle compound through C-H activation. The findings disclosed above are provided as a guideline for the catalyst design of the oxidative olefination of acetanilide with dioxygen, and the catalytic efficiency matched well with the mechanistic findings.

2.
Int J Part Ther ; 14: 100629, 2024 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-39309411

RESUMO

To explore the challenges and future of carbon-ion radiation therapy (CIRT) in breast cancer, we summarized the progress of nonclinical and clinical studies on CIRT for breast cancer in this review. A total of 6 nonclinical studies have been reported, which demonstrated a better effect of Carbon-ion irradiation compared with X-ray in breast cancer cell lines (including triple-negative breast cancer and Human Epidermal Growth Factor Receptor 2-negative breast cancer). Combination with Hh inhibitor, dual tyrosine kinase inhibitor, and PARP inhibitor is promising as demonstrated in the in vitro studies. Approximately 34 patients with breast cancer went through CIRT treatment, as reported in 5 clinical studies. All studies demonstrated promising treatment effects with acceptable and manageable risks. In these studies, a total of 21 patients were reported with post-treatment response assessments, among whom 19 patients (90.48%) reported a response of complete response or partial response. The complete response rate was 66.67%. The time to complete the response ranged from 3 months to 24 months. No adverse events were observed in these studies except for grade 1 acute skin reaction in 14 out of the 21 patients (66.67%). Although the time to respond was longer than expected in some studies, the persistent responses and satisfactory safety profile provided the rationale for further research on this new therapy.

3.
Ann Surg Oncol ; 2024 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-39287903

RESUMO

PURPOSE: This study was designed to evaluate the efficacy of different periurethral structural reconstruction approaches to improve postoperative continence post robot-assisted radical prostatectomy (RARP), which remains a critical concern. METHODS: This study included patients with prostate cancer who received single, combined, and nonreconstruction following RARP from April 2017 to May 2021. Medical details were recorded, and patients were followed up via phone or the outpatient clinic. Continence, potency recovery, and quality of life were evaluated. Continence rate was assessed by daily urinary pads use and was compared between groups with the Kaplan-Meier method. Potency recovery was assessed by the questionnaire score. All variables were further analyzed via univariable and multivariable regression analysis. RESULTS: Sixty patients were included in nonreconstruction group. Fifty-two and 156 patients were included in the single and combined group, respectively. Across early postoperative follow-up period, both single and combined reconstruction group showed higher continence rate (p < 0.05). The combined approach showed an advantage over the single one in improving continence rate (p < 0.05). Univariable and multivariable regression analysis point to the reconstruction approach as an independent factor that affects postoperative continence recovery post RARP. CONCLUSIONS: Periurethral reconstruction approaches were found to be beneficial in promoting early continence recovery after RARP, without compromising preserved neurovascular bundle. Combination of anterior and posterior reconstruction could be more beneficial on continence recovery and should be considered in clinical practice.

4.
Nat Cancer ; 2024 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-39256488

RESUMO

Programmed death 1 blockade (tislelizumab) has been approved for metastatic urothelial carcinoma but not as part of neoadjuvant therapy for muscle-invasive bladder cancer (MIBC). In this multicenter single-arm trial (ChiCTR2000037670), 65 participants with cT2-4aN0M0 MIBC received neoadjuvant gemcitabine-cisplatin plus tislelizumab; 57 of them underwent radical cystectomy (RC). The primary endpoint of pathologic complete response (pCR) rate was 50.9% (29/57, 95% confidence interval (CI) 37.3-64.4%) and the pathologic downstaging (secondary endpoint) rate was 75.4% (43/57, 95% CI 62.2-85.9%) in participants undergoing RC. Genomic and transcriptomic analyses revealed three MIBC molecular subtypes (S): S1 (immune-desert) with activated cell-cycle pathway, S2 (immune-excluded) with activated transforming growth factor-ß pathway and S3 (immune-inflamed) with upregulated interferon-α and interferon-γ response. Post hoc analysis showed pCR rates of 16% (3/19, S1), 77% (10/13, S2) and 80% (12/15, S3) (P = 0.006). In conclusion, neoadjuvant gemcitabine-cisplatin plus tislelizumab for MIBC was compatible with an enhanced pCR rate.

5.
J Environ Manage ; 370: 122390, 2024 Sep 06.
Artigo em Inglês | MEDLINE | ID: mdl-39243647

RESUMO

The establishment of S-scheme heterojunctions represents an effective strategy for enhancing the transfer and separation of charge carriers, thereby bolstering redox capacities and consequently benefiting subsequent photocatalytic reactions. In this study, the pristine Bi7O9I3 underwent a facile vulcanization process to in-situ produce various composites. Systematical characterizations confirmed the simultaneous generation of Bi7O9I3/Bi2S3 (BI-BS) heterojunctions with surface oxygen vacancies (OVs). Under visible light, these BI-BS composites exhibited improved NO removal efficiencies with reduced NO2 generation compared to bare Bi7O9I3. Particularly, the best candidate BI-BS2 possesses the highest NO removal (43.02%) and lowest NO2 generation (5.44%) among all tested samples. The improvement was primarily attributed to synergetic effects of heterojunction and surface OVs, including enhanced charge separation, heightened light responsiveness, and improved generation of reactive oxygen-containing species through an S-scheme mode. Furthermore, the Density Functional Theory (DFT) calculations had demonstrated that the establishment of BI-BS heterojunctions with surface OVs not only optimized the electronic structure to facilitate the transfer and separation of charge carriers, but also significantly enhanced the adsorption of NO, H2O, and O2 molecules, ultimately favoring the generation of NO3- species. These as-synthesized composites indicated sufficient structural stability and hold potential for the photocatalytic removal of NO at ppb levels.

6.
Nat Commun ; 15(1): 8012, 2024 Sep 13.
Artigo em Inglês | MEDLINE | ID: mdl-39271682

RESUMO

Pronounced spatial disparities in heatwave trends are bound up with a diversity of atmospheric signals with complex variations, including different phases and wavenumbers. However, assessing their relationships quantitatively remains a challenging problem. Here, we use a network-searching approach to identify the strengths of heatwave-related atmospheric teleconnections (AT) with ERA5 reanalysis data. This way, we quantify the close links between heatwave intensity and AT in the Northern Hemisphere. Approximately half of the interannual variability of heatwaves is explained and nearly 80% of the zonally asymmetric trend signs are estimated correctly by the AT changes in the mid-latitudes. We also uncover that the likelihood of extremely hot summers has increased sharply by a factor of 4.5 after 2000 over areas with enhanced AT, but remained almost unchanged over the areas with attenuated AT. Furthermore, reproducing Eastern European heatwave trends among various models of the Coupled Model Intercomparison Project Phase 6 largely depends on the simulated Eurasian AT changes, highlighting the potentially significant impact of AT shifts on the simulation and projection of heatwaves.

7.
Heliyon ; 10(14): e34065, 2024 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-39108911

RESUMO

Synchronization in complex networks is a ubiquitous and important phenomenon with implications in various fields. Excessive synchronization may lead to undesired consequences, making desynchronization techniques essential. Exploiting the Proximal Policy Optimization algorithm, this work studies reinforcement learning-based pinning control strategies for synchronization suppression in global coupling networks and two types of irregular coupling networks: the Watts-Strogatz small-world networks and the Barabási-Albert scale-free networks. We investigate the impact of the ratio of controlled nodes and the role of key nodes selected by the LeaderRank algorithm on the performance of synchronization suppression. Numerical results demonstrate the effectiveness of the reinforcement learning-based pinning control strategy in different coupling schemes of the complex networks, revealing a critical ratio of the pinned nodes and the superior performance of a newly proposed hybrid pinning strategy. The results provide valuable insights for suppressing and optimizing network synchronization behavior efficiently.

8.
J Clin Psychiatry ; 85(3)2024 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-39145682

RESUMO

Abstract.Background: There is growing evidence that understanding the role of sleep disturbance in bipolar disorder (BD) and major depressive disorder (MDD) is helpful when studying the high heterogeneity of patients across psychiatric disorders.Objective: The present study was designed to investigate the transdiagnostic role of sleep disturbance measured by polysomnography (PSG) in differentiating from MDD with BD.Methods: A total of 256 patients with MDD and 107 first-episode and never medicated patients with BD using the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, criteria were recruited. All patients completed 1 night of PSG recording, and the changes in objective sleep structure parameters were determined by PSG analysis.Results: We showed that patients with MDD had statistically longer rapid eye movement (REM) latency, a higher percentage of stage N2 sleep, and lower percentages of stage N3 sleep and REM sleep than those with BD after controlling for confounding factors (all P < .05). Moreover, using the logistic regression analysis, we identified that REM latency was associated with BD diagnosis among the PSG sleep features. The cutoff value for PSG characteristics to differentiate BD from MDD was 261 in REM latency (sensitivity: 41.4% and specificity: 84.1%).Conclusions: Our findings suggest that PSG-measured sleep abnormalities, such as reduced REM latency, may be a diagnostic differentiating factor between MDD and BD, indicating their roles in identifying homogeneous transdiagnostic subtypes across psychiatric disorders.


Assuntos
Transtorno Bipolar , Transtorno Depressivo Maior , Polissonografia , Humanos , Transtorno Depressivo Maior/diagnóstico , Transtorno Depressivo Maior/fisiopatologia , Transtorno Bipolar/diagnóstico , Transtorno Bipolar/fisiopatologia , Feminino , Masculino , Adulto , Diagnóstico Diferencial , Pessoa de Meia-Idade , Transtornos do Sono-Vigília/diagnóstico , Transtornos do Sono-Vigília/fisiopatologia , Sono REM/fisiologia , Adulto Jovem , Fases do Sono/fisiologia
9.
iScience ; 27(8): 110427, 2024 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-39161960

RESUMO

Prostate cancer (PCa) is one of the most prevalent urogenital malignancies. Bone metastasis from PCa reduces patient survival rates significantly. There currently exists no effective treatment for bone metastatic PCa, and the underlying mechanisms remain unclear. This study performed transcriptomic screening on PCa bone metastasis specimens and intersection analysis in public databases and identified SERPINH1 as a potential target for treatment. SERPINH1 was found to be upregulated in PCa bone metastases and with poor prognosis, high Gleason score, and advanced metastatic status. SERPINH1 induced PCa cells' bone metastasis in vivo, promoted their proliferation, and mitigated apoptosis. Mechanistically, SERPINH1 bound to P62, reducing TRIM21-mediated K63-linked ubiquitination degradation of P62 and promoting proliferation and resistance to apoptosis of PCa. This study suggests the regulation of ubiquitination degradation of P62 by SERPINH1 that promotes PCa bone metastasis and can be considered as a potential target for treatment of bone metastatic PCa.

10.
Int J Mol Sci ; 25(14)2024 Jul 18.
Artigo em Inglês | MEDLINE | ID: mdl-39063097

RESUMO

The association between high-density lipoprotein cholesterol (HDL-C) and cardiovascular disease (CVD) is controversial. HDL-C is one content type of high-density lipoprotein (HDL). HDL consists of diverse proteins and lipids and can be classified into different subclasses based on size, shape, charge, and density, and can change dynamically in disease states. Therefore, HDL-C levels alone cannot represent HDLs' cardioprotective role. In this review, we summarized the methods for separating HDL subclasses, the studies on the association between HDL subclasses and cardiovascular risk (CVR), and the impact of lipid-modifying medications and nonpharmacological approaches (exercise training, dietary omega fatty acids, and low-density lipoprotein apheresis) on HDL subclasses. As HDL is a natural nanoplatform, recombinant HDLs (rHDLs) have been used as a delivery system in vivo by loading small interfering RNA, drugs, contrast agents, etc. Therefore, we further reviewed the HDL subclasses used in rHDLs and their advantages and disadvantages. This review would provide recommendations and guidance for future studies on HDL subclasses' cardioprotective roles.


Assuntos
Doenças Cardiovasculares , Lipoproteínas HDL , Humanos , Doenças Cardiovasculares/prevenção & controle , Lipoproteínas HDL/metabolismo , Lipoproteínas HDL/uso terapêutico , Lipoproteínas HDL/classificação , Animais , HDL-Colesterol/metabolismo , HDL-Colesterol/sangue
11.
J Immunother Cancer ; 12(7)2024 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-39067875

RESUMO

BACKGROUND: This study comprehensively investigates the association between the expression of nicotinamide N-methyltransferase (NNMT) and clinical outcomes of urothelial bladder cancer (UBC), as well as the molecular mechanisms by which NNMT in cancer-associated fibroblast (CAF) modulates tumor progression and immunotherapy resistance in UBC. METHODS: Single-cell transcriptomic analyses, immunohistochemical and immunofluorescence assays were performed on bladder cancer samples to validate the relationship between NNMT expression and clinical outcomes. A series of experiments, including chromatin immunoprecipitation assay, liquid chromatography tandem mass spectrometry assay, and CRISPR‒Cas9 (Clustered Regularly Interspaced Short Palindromic Repeats and CRISPR-associated protein 9) knockout, together with in vivo models, have been established to determine the molecular functions of NNMT in CAFs in UBC. RESULTS: We demonstrated that elevated expression of the nicotinamide adenine dinucleotide (NAD+) metabolism enzyme NNMT in CAFs (NNMT+ CAFs) was significantly associated with non-response to programmed death-ligand 1 (PD-L1) blockade immunotherapy in patients with UBC and predicted the unfavorable prognosis of UBC in two independent large cohorts. Targeting NNMT using the inhibitor 5-Amino-1-methylquinolinium iodide significantly reduced tumor growth and enhanced the apoptotic effects of the anti-PD-L1 antibody in UBC mouse models. Mechanistically, NNMT+ CAFs recruit tumor-associated macrophages via epigenetic reprogramming of serum amyloid A (SAA) to drive tumor cell proliferation and confer resistance to programmed death-1/PD-L1 blockade immunotherapy. CONCLUSIONS: NNMT+ CAFs were significantly associated with non-response to PD-L1 blockade immunotherapy in patients with UBC. Elevated NNMT, specifically in CAFs, upregulates SAA expression and enhances the recruitment and differentiation of macrophages in the tumor microenvironment, thereby directly or indirectly promoting tumor progression and conferring resistance to immunotherapies in bladder cancer.


Assuntos
Fibroblastos Associados a Câncer , Imunoterapia , Macrófagos , Nicotinamida N-Metiltransferase , Neoplasias da Bexiga Urinária , Neoplasias da Bexiga Urinária/patologia , Neoplasias da Bexiga Urinária/imunologia , Neoplasias da Bexiga Urinária/genética , Humanos , Fibroblastos Associados a Câncer/metabolismo , Camundongos , Animais , Nicotinamida N-Metiltransferase/metabolismo , Imunoterapia/métodos , Macrófagos/metabolismo , Macrófagos/imunologia , NAD/metabolismo , Resistencia a Medicamentos Antineoplásicos , Feminino , Progressão da Doença , Masculino , Macrófagos Associados a Tumor/metabolismo , Macrófagos Associados a Tumor/imunologia
12.
Appl Opt ; 63(12): 3212-3218, 2024 Apr 20.
Artigo em Inglês | MEDLINE | ID: mdl-38856469

RESUMO

In this paper, a broadband terahertz metasurface dedicated to cross-polarization conversion was designed, fabricated, and assessed. The metasurface, comprising two nested double-split rings, features an inherent insensitivity to the angle of incidence. Simulations reveal that the converter achieves a >99% polarization conversion efficiency across the 90-140 GHz range. Moreover, it maintains a >90% polarization conversion ratio (PCR), even at a 50° incidence angle. The sample, featuring 50×70 arrays, was fabricated, and the relevant experimental results align closely with the simulated outcomes. The metasurface characteristics can markedly enhance the performance of cross-polarization converters operating in the terahertz range.

13.
ACS Nano ; 18(28): 18560-18571, 2024 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-38941591

RESUMO

High-performance thermal interface materials (TIMs) are highly desired for high-power electronic devices to accelerate heat dissipation. However, the inherent trade-off conflict between achieving high thermal conductivity and excellent compliance of filler-enhanced TIMs results in the unsatisfactory interfacial heat transfer efficiency of existing TIM solutions. Here, we report the graphene fiber (GF)-based elastic TIM with metal-level thermal conductivity via mechanical-electric dual-field synergistic alignment engineering. Compared with state-of-the-art carbon fiber (CF), GF features both superb high thermal conductivity of ∼1200 W m-1 K-1 and outstanding flexibility. Under dual-field synergistic alignment regulation, GFs are vertically aligned with excellent orientation (0.88) and high array density (33.5 mg cm-2), forming continuous thermally conductive pathways. Even at a low filler content of ∼17 wt %, GF-based TIM demonstrates extraordinarily high through-plane thermal conductivity of up to 82.4 W m-1 K-1, exceeding most CF-based TIMs and even comparable to commonly used soft indium foil. Benefiting from the low stiffness of GF, GF-based TIM shows a lower compressive modulus down to 0.57 MPa, an excellent resilience rate of 95% after compressive cycles, and diminished contact thermal resistance as low as 7.4 K mm2 W-1. Our results provide a superb paradigm for the directed assembly of thermally conductive and flexible GFs to achieve scalable and high-performance TIMs, overcoming the long-standing bottleneck of mechanical-thermal mismatch in TIM design.

14.
Int J Surg ; 110(9): 5641-5651, 2024 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-38788195

RESUMO

OBJECTIVE: Most bladder cancers are nonmuscle invasive bladder cancer (NMIBC), and transurethral resection of bladder tumors (TURBT) is the standard treatment. However, postoperative recurrence remains a significant challenge, and the influence of bladder tumor location on prognosis is still unclear. This study aims to investigate how tumor location affects the prognosis of NMIBC patients undergoing TURBT and to identify the optimal surgical approach. METHODS: A multicenter study was conducted, which included Chinese NMIBC data from 15 hospitals (1996-2019) and data from 17 registries of the Surveillance, Epidemiology, and End Results database (SEER) (2000-2020). Patients initially diagnosed with NMIBC and undergoing TURBT or partial cystectomy were analyzed, with cases lost to follow-up or with missing data excluded. The study investigated the overall survival (OS), disease-specific survival (DSS), and recurrence-free survival (RFS) among patients with different tumor locations. Kaplan-Meier, Cox regression, and propensity score matching methods were employed to explore the association between tumor location and prognosis. Stratified populations were analyzed to minimize bias. RESULTS: This study included 118 477 NMIBC patients and highlighted tumor location as a crucial factor impacting post-TURBT prognosis. Both anterior wall and dome tumors independently predicted adverse outcomes in two cohorts. For anterior wall tumors, the Chinese cohort showed hazard ratios (HR) for OS of 4.35 ( P <0.0001); RFS of 2.21 ( P <0.0001); SEER cohort OS HR of 1.10 ( P =0.0001); DSS HR of 1.13 ( P =0.0183). Dome tumors displayed similar trends [Chinese NMIBC cohort OS HR of 7.91 ( P <0.0001); RFS HR of 2.12 ( P <0.0001); SEER OS HR of 1.05 ( P =0.0087); DSS HR of 1.14 ( P =0.0006)]. Partial cystectomy significantly improved the survival of dome tumor patients compared to standard TURBT treatment ( P <0.01). CONCLUSION: This study reveals the significant impact of tumor location in NMIBC patients on the outcomes of TURBT treatment, with tumors in the anterior wall and bladder dome showing poor post-TURBT prognosis. Compared to TURBT treatment, partial cystectomy improves the prognosis for bladder dome tumors. This study provides guidance for personalized treatment and prognosis management for NMIBC patients.


Assuntos
Cistectomia , Programa de SEER , Neoplasias da Bexiga Urinária , Humanos , Neoplasias da Bexiga Urinária/cirurgia , Neoplasias da Bexiga Urinária/patologia , Neoplasias da Bexiga Urinária/mortalidade , Masculino , Feminino , Pessoa de Meia-Idade , Idoso , Prognóstico , China/epidemiologia , Estudos de Coortes , Sistema de Registros , Estudos Retrospectivos , Recidiva Local de Neoplasia/patologia , Recidiva Local de Neoplasia/epidemiologia , Pontuação de Propensão , População do Leste Asiático
15.
Anal Chim Acta ; 1311: 342734, 2024 Jul 04.
Artigo em Inglês | MEDLINE | ID: mdl-38816163

RESUMO

Photodynamic therapy (PDT), characterized by high treatment efficiency, absence of drug resistance, minimal trauma, and few side effects, has gradually emerged as a novel and alternative clinical approach compared to traditional surgical resection, chemotherapy and radiation. Whereas, considering the limited diffusion distance and short lifespan of reactive oxygen species (ROS), as well as the hypoxic tumor microenvironment, it is crucial to design photosensitizers (PSs) with suborganelle specific targeting ability and low-oxygen dependence for accurate and highly efficient photodynamic therapy. In this study, we have meticulously designed three PSs, namely CIH, CIBr, and CIPh, based on molecular engineering. Theoretical calculation demonstrate that the three compounds possess good molecular planarity with calculated S1-T1 energy gaps (ΔES1-T1) of 1.04 eV for CIH, 0.92 eV for CIBr, and 0.84 eV for CIPh respectively. Notably, CIPh showcases remarkable dual subcellular targeting capability towards lipid droplets (LDs) and mitochondria owing to the synergistic effect of lipophilicity derived from coumarin's inherent properties combined with electropositivity conferred by indole salt cations. Furthermore, CIPh demonstrates exclusive release of singlet oxygen (1O2)and highly efficient superoxide anion free radicals(O2⦁-) upon light irradiation supported by its smallest S1-T1 energy gap (ΔES1-T1 = 0.84 eV). This leads to compromised integrity of LDs along with mitochondrial membrane potential, resulting in profound apoptosis induction in HepG2 cells. This successful example of molecular engineering guided by density functional theory (DFT) provides valuable experience for the development of more effective PSs with superior dual targeting specificity. It also provides a new idea for the development of advanced PSs with efficient and accurate ROS generation ability towards fluorescence imaging-guided hypoxic tumor therapy.


Assuntos
Gotículas Lipídicas , Mitocôndrias , Fármacos Fotossensibilizantes , Espécies Reativas de Oxigênio , Humanos , Espécies Reativas de Oxigênio/metabolismo , Mitocôndrias/efeitos dos fármacos , Mitocôndrias/metabolismo , Gotículas Lipídicas/química , Gotículas Lipídicas/metabolismo , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/farmacologia , Fotoquimioterapia , Sobrevivência Celular/efeitos dos fármacos
16.
Pest Manag Sci ; 2024 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-38808579

RESUMO

BACKGROUND: Transketolase (TKL, EC 2.2.1.1) is a key enzyme in the pentose phosphate pathway and Calvin cycle, and is expected to act as a herbicidal site-of-action. On the basis of TKL, we designed and synthesized a series of 1-oxy-propionamide-pyrazole-3-carboxylate analogues and evaluated their herbicidal activities. RESULTS: Methyl 1-methyl-5-((1-oxo-1-((4-(trifluoromethyl)phenyl)amino)propan-2-yl)oxy)-1H-pyrazole-3-carboxylate (C23) and methyl 1-methyl-5-((1-oxo-1-((perfluorophenyl)amino)propan-2-yl)oxy)-1H-pyrazole-3-carboxylate (C33) were found to provide better growth-inhibition activities against Digitaria sanguinalis root than those of nicosulfuron, mesotrione and pretilachlor at 200 mg L-1 using the small-cup method. These compounds were also identified as promising compounds in pre-emergence and postemergence herbicidal-activity experiments, with relatively good inhibitory effects toward Amaranthus retroflexus and D. sanguinalis at 150 g ai ha-1. In addition, enzyme inhibition assays and molecular docking studies revealed that C23 and C33 interact favourably with SvTKL (Setaria viridis TKL). CONCLUSION: C23 and C33 are promising lead TKL inhibitors for the optimization of new herbicides. © 2024 Society of Chemical Industry.

17.
Org Biomol Chem ; 22(20): 4089-4095, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38695080

RESUMO

Transition-metal-catalyzed aromatic olefination through direct C-H activation represents an atom and step-economic route for versatile pharmaceutical syntheses, and in many cases, different stoichiometric oxidants are frequently employed for achieving a reasonable catalytic efficiency of the transition metal ions. Herein, we report a Lewis acid promoted Pd(II)-catalyzed acetanilide olefination reaction with atmospheric dioxygen as the oxidant source. The linkage of the Lewis acid to the Pd(II) species through a diacetate bridge significantly improved its catalytic efficiency, and independent kinetic studies on the olefination step revealed that adding the Lewis acid significantly accelerated the olefination rate as well as the C-H activation step. A strong basicity of the internal base in the Pd(II) salt also benefited the olefination reaction plausibly through base-assisted ß-hydride elimination.

18.
Soft Matter ; 20(23): 4591-4607, 2024 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-38805009

RESUMO

The limitations in previous dissipative particle dynamics (DPD) studies confined simulations to a narrow resin range. This study refines DPD parameter calculation methodology, extending its application to diverse polymer materials. Using a bottom-up approach with molecular dynamics (MD) simulations, we evaluated solubility parameters and bead number density governing nonbonded interactions via the Flory-Huggins parameter and covalent-bonded interactions. Two solubility parameter methods, Hildebrand and Krevelen-Hoftyzer, were compared for DPD simulations. The Hildebrand method, utilizing MD simulations, demonstrates higher consistency and broader applicability in determining solubility parameters for all DPD particles. The DPD/MD curing reaction process was examined in three epoxy systems: DGEBA/4,4'-DDS, DGEBA/MPDA and DGEBA/DETA. Calculations for the curing profile, gelation point, radial distribution function and branch ratio were performed. Compared to MD data for DGEBA/4,4'-DDS, the maximum deviation in secondary reactions between epoxy and amine groups according to DPD simulations with Krevelen-Hoftyzer was 14.8%, while with the Hildebrand method, it was 1.7%. The accuracy of the DPD curing reaction in reproducing the structural properties verifies its expanded application to general polymeric material simulations. The proposed curing DPD simulations, with a short run time and minimal computational resources, contributes to high-throughput screening for optimal resins and investigates mesoscopic inhomogeneous structures in large resin systems.

19.
Small ; 20(34): e2400415, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38698600

RESUMO

Highly flexible and superelastic aerogels at large deformation have become urgent mechanical demands in practical uses, but both properties are usually exclusive. Here a trans-scale porosity design is proposed in graphene nanofibrous aerogels (GNFAs) to break the trade-off between high flexibility and superelasticity. The resulting GNFAs can completely recover after 1000 fatigue cycles at 60% folding strain, and notably maintain excellent structural integrity after 10000 cycles at 90% compressive strain, outperforming most of the reported aerogels. The mechanical robustness is demonstrated to be derived from the trans-scale porous structure, which is composed of hyperbolic micropores and porous nanofibers to enable the large elastic deformation capability. It is further revealed that flexible and superelastic GNFAs exhibit high sensitivity and ultrastability as an electrical sensors to detect tension and flexion deformation. As proof, The GNFA sensor is implemented onto a human finger and achieves the intelligent recognition of sign language with high accuracy by multi-layer artificial neural network. This study proposes a highly flexible and elastic graphene aerogel for wearable human-machine interfaces in sensor technology.

20.
Talanta ; 276: 126281, 2024 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-38788386

RESUMO

In the medical field, changes in interleukin-6 (IL-6) concentration serve as essential biomarkers for monitoring and diagnosing various conditions, including acute inflammatory responses such as those seen in trauma and burns, and chronic illnesses like cancer. This paper detailed a label-free electrochemical aptamer sensor designed for IL-6 quantification. A composite material consisting of Ti3C2Tx and MoS2 was successfully synthesized to fabricate this sensor. The synergistic effect of MoS2's catalytic action on hydrogen peroxide (H2O2), used as a signalling marker, when combined with the exceptional conductivity and large specific surface area of Ti3C2Tx, not only enables an increased loading of MoS2 but also significantly boosts the electrochemical response. The in situ-reduced Au NPs provided stable immobilization sites for DNA aptamers (DNAapt) and facilitated electron transfer, ensuring accurate IL-6 recognition. Under optimal conditions, the aptamer sensor exhibited a wide linear range (5 pg/mL to 100 ng/mL) and a low limit of detection (LOD) of 2.9 pg/mL. Its sensing performance in human serum samples highlights its potential as a promising clinical analysis tool.


Assuntos
Aptâmeros de Nucleotídeos , Técnicas Biossensoriais , Técnicas Eletroquímicas , Interleucina-6 , Nanopartículas Metálicas , Humanos , Aptâmeros de Nucleotídeos/química , Técnicas Biossensoriais/métodos , Dissulfetos/química , Técnicas Eletroquímicas/métodos , Ouro/química , Peróxido de Hidrogênio/química , Interleucina-6/sangue , Interleucina-6/análise , Limite de Detecção , Nanopartículas Metálicas/química , Molibdênio/química , Titânio/química
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