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1.
J Am Chem Soc ; 146(30): 20937-20944, 2024 Jul 31.
Artículo en Inglés | MEDLINE | ID: mdl-38979882

RESUMEN

Amidst burgeoning interest, atomically precise copper nanoclusters (Cu NCs) have emerged as a remarkable class of nanomaterials distinguished by their unparalleled reactivity. Nonetheless, the synthesis of hydride-free Cu NCs and their role as stable catalysts remain infrequently explored. Here, we introduce a facile synthetic approach to fabricate a hydride-free [Cu7(SC5H9)7(PPh3)3] (Cu7) NC and delineate its photophysical properties intertwined with their structural configuration. Moreover, the utilization of its photophysical properties in a photoinduced C-C coupling reaction demonstrates remarkable specificity toward cross-coupling products with high yields. The combined experimental and theoretical investigation reveals a nonradical mechanistic pathway distinct from its counterparts, offering promising prospects for designing hydride-free Cu NC catalysts in the future and unveiling the selectivity of the hydride-free [Cu7(SC5H9)7(PPh3)3] NC in photoinduced Sonogashira C-C coupling through a polar reaction pathway.

2.
iScience ; 27(6): 109828, 2024 Jun 21.
Artículo en Inglés | MEDLINE | ID: mdl-38799586

RESUMEN

We have purified Peptidase M84 from Bacillus altitudinis in an effort to isolate anticancer proteases from environmental microbial isolates. This metallo-protease had no discernible impact on normal cell survival, but it specifically induced apoptosis in ovarian cancer cells. PAR-1, a GPCR which is reported to be overexpressed in ovarian cancer cells, was identified as a target of Peptidase M84. We observed that Peptidase M84 induced PAR-1 overexpression along with activating its downstream signaling effectors NF-κB and MAPK to promote excessive reactive oxygen species (ROS) generation. This evoked apoptotic death of the ovarian cancer cells through the intrinsic route. In in vivo set-up, weekly intraperitoneal administration of Peptidase M84 in syngeneic mice significantly diminished ascites accumulation, increasing murine survival rates by 60%. Collectively, our findings suggested that Peptidase M84 triggered PAR-1-mediated oxidative stress to act as an apoptosis inducer. This established Peptidase M84 as a drug candidate for receptor mediated targeted-therapy of ovarian cancer.

3.
J Trace Elem Med Biol ; 84: 127429, 2024 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-38493666

RESUMEN

BACKGROUND: Colorectal cancer (CRC) is a growing public health problem. Several clinical studies have shown a potentially protective effect of selenium (Se), but the reports are inconsistent. The objective of the study was to examine the evidence for relation between serum/tissue Se status and CRC. METHOD AND MATERIALS: In this Systematic Review and Meta-Analysis, we searched Cochrane Library, EBSCOhost, EMBASE, ProQuest, PubMed/MEDLINE, Scopus, and Web of Science for studies reporting serum/plasma/whole blood/tissue Se concentrations in CRC patients and controls for articles published till August 2023. Meta-analysis was performed, and study quality, heterogeneity, and small study effects were assessed. Based on a random effects model, summary mean differences in serum levels of Se between CRC patients and healthy controls, and Se levels between malignant and matched non-malignant tissue specimens were assessed. RESULTS: After initial screening, a total of 24 studies (18 serum and 6 tissue studies) with a pooled total of 2640 participants were included in the meta-analysis. CRC patients had significantly lower serum Se levels than healthy controls, being the difference between the two equal to 3.73 µg/dl (95% CI: 6.85-0.61). However, the heterogeneity was very high, I2= 99% (p < 0.01). Our meta-analysis showed higher Se levels in CRC cancerous specimens than in matched healthy colon tissue: the increase was equal to 0.07 µg/g wet tissue weight (95% CI: 0.06-0.09; p= 0.02). CONCLUSIONS: CRC patients have lower serum and higher colon cancerous tissue Se levels. Some factors, such as Se levels in different tumor grades of CRC need to be further considered for a more conclusive association between Se levels and risk of CRC.


Asunto(s)
Neoplasias Colorrectales , Selenio , Selenio/sangre , Neoplasias Colorrectales/sangre , Neoplasias Colorrectales/patología , Humanos
4.
Artículo en Inglés | MEDLINE | ID: mdl-38253840

RESUMEN

This study utilized nine anaerobic digesters (ADs) with individual capacities of 10 l to investigate methane (CH4) gas generation from various waste combinations and operating conditions, employing both non-tumbling and tumbling processes with the aid of the Taguchi method. The experimentation encompassed different varieties of fruit waste (FW), raw vegetable waste (RVW), and mixed cooked waste (MCW) at varying proportions (1:1, 1:1.5, and 1:2) and temperatures (35 °C, 40 °C, and 45 °C), along with multiple feed inputs. Additionally, the study assessed the impact of tumbling, examining durations of 0, 10, and 20 min at a speed of 15 rpm. The results yielded substantial insights, revealing coefficient of determination (R2) values of 94.76% and 98.48% for non-tumbling and tumbling processes, respectively. Under the conditions of 40 °C and a 1:1.5 ratio, the average optimal methane (CH4) gas generation in FW without tumbling was determined to be 37.12%. For RVW and MCW at ratios of 1:1.5 and 1:2, respectively, the estimated CH4 values were 26.7% and 26.68% at a temperature of 35 °C. Comparison between tumbling and non-tumbling conditions demonstrated noteworthy improvements in CH4 gas production. For FW, tumbling for 10 and 20 min resulted in 11% and 6% increases in CH4 gas production, respectively. Tumbling also led to substantial boosts in CH4 gas production for RVW, with 31.1% and 47.9% increases after 10 and 20 min, and for MCW, with 25.7% and 12.2% increases after 10 and 20 min, respectively. Tumbling enhances CH4 gas production in anaerobic digesters, promising for waste-to-energy conversion.

5.
Nanoscale ; 16(7): 3583-3590, 2024 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-38268470

RESUMEN

Atomically precise copper nanoclusters (Cu NCs), an emerging class of nanomaterials, have garnered significant attention owing to their versatile core-shell architecture and their potential applications in catalytic reactions. In this study, we present a straightforward synthesis strategy for [Cu29(StBu)12(PPh3)4Cl6H10][BF4] (Cu29) NCs and explore their catalytic activity in the carbonylative C-N coupling reaction involving aromatic amines and N-heteroarenes with dialkyl azodicarboxylates. Through a combination of experimental investigations and density functional theory studies, we elucidate the radical mechanisms at play. The crucial step in the catalytic process is identified as the decomposition of diisopropyl azodicarboxylates on the surface of Cu29 NCs, leading to the generation of oxyacyl radicals and the liberation of nitrogen gas. Subsequently, an oxyacyl radical abstracts a hydrogen atom from aniline, initiating the formation of an aminyl radical. Finally, the aminyl radical reacts with another oxyacyl radical, culminating in the synthesis of the desired carbamate product. This detailed analysis provides insights into the intricate catalytic pathways of Cu29 NCs, shedding light on their potential for catalyzing carbonylative C-N coupling reactions.

6.
J Trace Elem Med Biol ; 82: 127370, 2024 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-38159434

RESUMEN

BACKGROUND: Colorectal cancer (CRC) is the third most commonly diagnosed cancer worldwide and a public health problem. Several clinical studies have shown that copper (Cu) is involved in carcinogenesis, possibly via cuproptosis, a new form of programmed cell death, but the conclusions from published reports are inconsistent. This study aimed at evaluating the potential of Cu dysregulation as a CRC susceptibility factor. METHODS: In this systematic review and meta-analysis, we searched Cochrane Library, EBSCOhost, EMBASE, ProQuest, PubMed/MEDLINE, Scopus, and Web of Science for studies reporting serum Cu concentrations in CRC patients and controls from articles published till June 2023. The studies included reported measurements of serum/plasma/blood Cu levels. Meta-analyses were performed as well as study quality, heterogeneity, and small study effects were assessed. Based on a random effects model, summary standardized mean differences (SMDs) and the corresponding 95% confidence intervals (95% CIs) were applied to compare the levels of Cu between CRC patients and controls. RESULTS: 26 studies with a pooled total of9628 participants and 2578 CRC cases were included. The pooled SMD was equal to 0.85 (95% CIs -0.44; 2.14) showing that the CRC patients had higher mean Cu levels than the control subjects, but the difference was not significant (p = 0.185) and the heterogeneity was very high, I2 = 97.9% (95% CIs: 97.5-98.3%; p < 0.001). CONCLUSION: The pooled results were inconclusive, likely due to discordant results and inaccuracy in reporting data of some studies; further research is needed to establish whether Cu dysregulation might contribute to the CRC risk and whether it might reflect different CRC grades.


Asunto(s)
Neoplasias Colorrectales , Cobre , Humanos
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