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1.
Chin J Integr Med ; 30(6): 489-498, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38801641

RESUMEN

OBJECTIVE: To describe the treatment patterns and survival status of advanced gastric cancer (AGC) in China in the past two decades, and objectively evaluate the impact of standardized Chinese medicine (CM) treatment on the survival of AGC patients. METHODS: This multicenter registry designed and propensity score analysis study described the diagnosis characteristics, treatment-pattern development and survival status of AGC from 10 hospitals in China between January 1, 2000 and July 31, 2021. Overall survival (OS) was evaluated between non-CM cohort (standard medical treatment) and CM cohort (integrated standard CM treatment ≥3 months). Propensity score matching (PSM) and inverse probability of treatment weighting (IPTW) were performed to adjust any difference in average outcomes for bias. RESULTS: A total of 2,001 patients histologically confirmed locally advanced and/or metastasis stomach and gastroesophageal junction adenocarcinoma were enrolled. Among them, 1,607 received systemic chemotherapy, 215 (10.74%) accepted molecular targeted therapy, 44 (2.2%) received checkpoint inhibitor therapy, and 769 (38.43%) received CM. Two-drug regimen was the main choice for first-line treatment, with fluoropyrimidine plus platinum as the most common regimen (530 cases, 60.09%). While 45.71% (16 cases) of patients with HER2 amplification received trastuzumab in first-line. The application of apatinib increased (33.33%) in third-line. The application of checkpoint inhibitors has increased since 2020. COX analysis showed that Lauren mixed type (P=0.017), cycles of first-line treatment >6 (P=0.000), CM (P=0.000), palliative gastrectomy (P=0.000), trastuzumab (P=0.011), and apatinib (P=0.008) were independent prognostic factors for the OS of AGC. After PSM and IPTW, the median OS of CM cohort and non-CM cohort was 18.17 and 12.45 months, respectively (P<0.001). CONCLUSIONS: In real-world practice for AGC in China, therapy choices consisted with guidelines. Two-drug regimen was the main first-line choice. Standardized CM treatment was an independent prognostic factor and could prolong the OS of Chinese patients with AGC. (Registration No. NCT02781285).


Asunto(s)
Medicina Tradicional China , Neoplasias Gástricas , Humanos , Neoplasias Gástricas/tratamiento farmacológico , Neoplasias Gástricas/mortalidad , Neoplasias Gástricas/patología , Neoplasias Gástricas/terapia , Masculino , Femenino , Persona de Mediana Edad , Análisis de Supervivencia , Medicina Tradicional China/métodos , Anciano , China/epidemiología , Puntaje de Propensión , Adulto
2.
Crit Rev Food Sci Nutr ; : 1-15, 2024 Mar 23.
Artículo en Inglés | MEDLINE | ID: mdl-38520155

RESUMEN

Microfluidics is revolutionizing the production of microparticles and nanoparticles, offering precise control over dimensions and internal structure. This technology facilitates the creation of colloidal delivery systems capable of encapsulating and releasing nutraceuticals. Nutraceuticals, often derived from food-grade ingredients, can be used for developing functional foods. This review focuses on the principles and applications of microfluidic systems in crafting colloidal delivery systems for nutraceuticals. It explores the foundational principles behind the development of microfluidic devices for nutraceutical encapsulation and delivery. Additionally, it examines the prospects and challenges with using microfluidics for functional food development. Microfluidic systems can be employed to form emulsions, liposomes, microgels and microspheres, by manipulating minute volumes of fluids flowing within microchannels. This versatility can enhance the dispersibility, stability, and bioavailability of nutraceuticals. However, challenges as scaling up production, fabrication complexity, and microchannel clogging hinder the widespread application of microfluidic technologies. In conclusion, this review highlights the potential role of microfluidics in design and fabrication of nutraceutical delivery systems. At present, this technology is most suitable for exploring the role of specific delivery system features (such as particle size, composition and morphology) on the stability and bioavailability of nutraceuticals, rather than for large-scale production of nutraceutical delivery systems.

3.
Updates Surg ; 2024 Mar 04.
Artículo en Inglés | MEDLINE | ID: mdl-38438686

RESUMEN

With the emergence of novel variants, Omicron variant caused a different clinical picture than the previous variants and little evidence was reported regarding perioperative outcomes after Omicron variants. The aim of the study was to evaluate the postoperative outcomes of gastrointestinal cancer patients following Omicron variants infection and also to determine the timing of surgery after infection recovery. A total of 124 patients who underwent gastrointestinal cancer surgery with prior SARS-CoV-2 infection between December 2022 and February 2023 were retrospectively reviewed. 174 cases underwent the same operation during December 2018 and February 2019 as control group. SARS-CoV-2-infected patients were further categorized into three groups based on infected time (1-3 weeks; 4-6 weeks; and ≥ 7 weeks). 90.3% of SARS-CoV-2-infected patients had mild symptoms. The COVID-19 vaccination rate was 71.0%, with a full vaccination rate of 48.4%. There were no significant differences in 30-day morbidity and mortality. There was also no significant difference in pulmonary complications, cardiovascular complications, and surgical complications between the three different diagnosis time groups. In conclusion, reducing waiting time for elective surgery was safe for gastrointestinal cancer patients in the context of an increased transmissibility and milder illness severity with Omicron variant.

4.
Angew Chem Int Ed Engl ; 63(14): e202319472, 2024 Apr 02.
Artículo en Inglés | MEDLINE | ID: mdl-38320964

RESUMEN

Herein, we propose an oxygen-containing species coordination strategy to boost CO2 electroreduction in the presence of O2. A two-dimensional (2D) conjugated metal-covalent organic framework (MCOF), denoted as NiPc-Salen(Co)2-COF that is composed of the Ni-phthalocyanine (NiPc) unit with well-defined Ni-N4-O sites and the salen(Co)2 moiety with binuclear Co-N2O2 sites, is developed and synthesized for enhancing the CO2RR under aerobic condition. In the presence of O2, one of the Co sites in the NiPc-Salen(Co)2-COF that coordinated with the intermediate of *OOH from ORR could decrease the energy barrier of the activation of CO2 molecules and stabilize the key intermediate *COOH of the CO2RR over the adjacent Co center. Besides, the oxygen species axially coordinated Ni-N4-O sites can favor in reducing the energy barrier of the intermediate *COOH formation for the CO2RR. Thus, NiPc-Salen(Co)2-COF exhibits high oxygen-tolerant CO2RR performance and achieves outstanding CO Faradaic efficiency (FECO) of 97.2 % at -1.0 V vs. the reversible hydrogen electrode (RHE) and a high CO partial current density of 40.3 mA cm-2 at -1.1 V in the presence of 0.5 % O2, which is superior to that in pure CO2 feed gas (FECO=94.8 %, jCO=19.9 mA cm-2). Notably, the NiPc-Salen(Co)2-COF achieves an industrial-level current density of 128.3 mA cm-2 in the flow-cell reactor with 0.5 % O2 at -0.8 V, which is higher than that in pure CO2 atmosphere (jCO=104.8 mA cm-2). It is worth noting that an excellent FECO of 86.8 % is still achieved in the presence of 5 % O2 at -1.0 V. This work provides an effective strategy to enable the CO2RR under O2 atmosphere by utilizing the *OOH intermediates of ORR to boost CO2 electroreduction.

5.
Nat Commun ; 15(1): 1479, 2024 Feb 17.
Artículo en Inglés | MEDLINE | ID: mdl-38368417

RESUMEN

The direct use of flue gas for the electrochemical CO2 reduction reaction is desirable but severely limited by the thermodynamically favorable oxygen reduction reaction. Herein, a photonicswitching unit 1,2-Bis(5'-formyl-2'-methylthien-3'-yl)cyclopentene (DAE) is integrated into a cobalt porphyrin-based covalent organic framework for highly efficient CO2 electrocatalysis under aerobic environment. The DAE moiety in the material can reversibly modulate the O2 activation capacity and electronic conductivity by the framework ring-closing/opening reactions under UV/Vis irradiation. The DAE-based covalent organic framework with ring-closing type shows a high CO Faradaic efficiency of 90.5% with CO partial current density of -20.1 mA cm-2 at -1.0 V vs. reversible hydrogen electrode by co-feeding CO2 and 5% O2. This work presents an oxygen passivation strategy to realize efficient CO2 electroreduction performance by co-feeding of CO2 and O2, which would inspire to design electrocatalysts for the practical CO2 source such as flue gas from power plants or air.

6.
J Agric Food Chem ; 72(9): 4958-4976, 2024 Mar 06.
Artículo en Inglés | MEDLINE | ID: mdl-38381611

RESUMEN

Previously, we found that whey proteins form biomolecular coronas around titanium dioxide (TiO2) nanoparticles. Here, the gastrointestinal fate of whey protein-coated TiO2 nanoparticles and their interactions with gut microbiota were investigated. The antioxidant activity of protein-coated nanoparticles was enhanced after simulated digestion. The structure of the whey proteins was changed after they adsorbed to the surfaces of the TiO2 nanoparticles, which reduced their hydrolysis under simulated gastrointestinal conditions. The presence of protein coronas also regulated the impact of the TiO2 nanoparticles on colonic fermentation, including promoting the production of short-chain fatty acids. Bare TiO2 nanoparticles significantly increased the proportion of harmful bacteria and decreased the proportion of beneficial bacteria, but the presence of protein coronas alleviated this effect. In particular, the proportion of beneficial bacteria, such as Bacteroides and Bifidobacterium, was enhanced for the coated nanoparticles. Our results suggest that the formation of a whey protein corona around TiO2 nanoparticles may have beneficial effects on their behavior within the colon. This study provides valuable new insights into the potential impact of protein coronas on the gastrointestinal fate of inorganic nanoparticles.


Asunto(s)
Nanopartículas , Corona de Proteínas , Proteína de Suero de Leche/metabolismo , Suero Lácteo/metabolismo , Corona de Proteínas/metabolismo , Tracto Gastrointestinal/metabolismo , Nanopartículas/química , Bacterias/metabolismo , Titanio/química
7.
Toxicol Appl Pharmacol ; 483: 116835, 2024 02.
Artículo en Inglés | MEDLINE | ID: mdl-38272317

RESUMEN

Actin-interacting proteins are important molecules for filament assembly and cytoskeletal signaling within vascular endothelium. Disruption in their interactions causes endothelial pathogenesis through redox imbalance. Actin filament redox regulation remains largely unexplored, in the context of pharmacological treatment. This work focused on the peptidyl methionine (M) redox regulation of actin-interacting proteins, aiming at elucidating its role on governing antioxidative signaling and response. Endothelial EA.hy926 cells were subjected to treatment with salvianolic acid B (Sal B) and tert-butyl-hydroperoxide (tBHP) stimulation. Mass spectrometry was employed to characterize redox status of proteins, including actin, myosin-9, kelch-like erythroid-derived cap-n-collar homology-associated protein 1 (Keap1), plastin-3, prelamin-A/C and vimentin. The protein redox landscape revealed distinct stoichiometric ratios or reaction site transitions mediated by M sulfoxide reductase and reactive oxygen species. In comparison with effects of tBHP stimulation, Sal B treatment prevented oxidation at actin M325, myosin-9 M1489/1565, Keap1 M120, plastin-3 M592, prelamin-A/C M187/371/540 and vimentin M344. For Keap1, reaction site was transitioned within its scaffolding region to the actin ring. These protein M oxidation regulations contributed to the Sal B cytoprotective effects on actin filament. Additionally, regarding the Keap1 homo-dimerization region, Sal B preventive roles against M120 oxidation acted as a primary signal driver to activate nuclear factor erythroid 2-related factor 2 (Nrf2). Transcriptional splicing of non-POU domain-containing octamer-binding protein was validated during the Sal B-mediated overexpression of NAD(P)H dehydrogenase [quinone] 1. This molecular redox regulation of actin-interacting proteins provided valuable insights into the phenolic structures of Sal B analogs, showing potential antioxidative effects on vascular endothelium.


Asunto(s)
Actinas , Antioxidantes , Benzofuranos , Depsidos , Antioxidantes/farmacología , Antioxidantes/metabolismo , Actinas/metabolismo , Proteína 1 Asociada A ECH Tipo Kelch/metabolismo , Vimentina/metabolismo , Estrés Oxidativo , Metionina , Factor 2 Relacionado con NF-E2/metabolismo , Oxidación-Reducción , Proteínas del Citoesqueleto/metabolismo , Miosinas/metabolismo , Miosinas/farmacología
8.
J Am Chem Soc ; 146(4): 2411-2418, 2024 Jan 31.
Artículo en Inglés | MEDLINE | ID: mdl-38234111

RESUMEN

Nanographene C222, which consists of a planar graphenic plane containing 222 carbon atoms, holds the record as the largest planar nanographene synthesized to date. However, its complete insolubility makes the processing of C222 difficult. Here we addressed this issue by introducing peripheral substituents perpendicular to the graphene plane, effectively disrupting the interlayer stacking and endowing C222 with good solubility. We also found that the electron-withdrawing substituents played a crucial role in the cyclodehydrogenation process, converting the dendritic polyphenylene precursor to C222. After disrupting the interlayer stacking, the introduction of only a few peripheral carboxylic groups allowed C222 to dissolve in phosphate buffer saline, reaching a concentration of up to 0.5 mg/mL. Taking advantage of the good photosensitizing and photothermal properties of the inner C222 core, the resulting water-soluble C222 emerged as a single-component agent for both photothermal and photodynamic tumor therapy, exhibiting an impressive tumor inhibition rate of 96%.


Asunto(s)
Nanopartículas , Neoplasias , Fotoquimioterapia , Humanos , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Terapia Fototérmica , Fotoquimioterapia/métodos , Neoplasias/tratamiento farmacológico
9.
Ultramicroscopy ; 258: 113922, 2024 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-38217895

RESUMEN

The contrast transfer function of direct ptychography methods such as the single side band (SSB) method are single signed, yet these methods still sometimes exhibit contrast reversals, most often where the projected potentials are strong. In thicker samples central focusing often provides the best ptychographic contrast as this leads to defocus variations within the sample canceling out. However focusing away from the entrance surface is often undesirable as this degrades the annular dark field (ADF) signal. Here we discuss how phase wrap asymptotes in the frequency response of SSB ptychography give rise to contrast reversals, without the need for dynamical scattering, and how these can be counteracted by manipulating the phases such that the asymptotes are either shifted to higher frequencies or damped via amplitude modulation. This is what enables post collection defocus correction of contrast reversals. However, the phase offset method of counteracting contrast reversals we introduce here is generally found to be superior to post collection application of defocus, with greater reliability and generally stronger contrast. Importantly, the phase offset method also works for thin and thick samples where central focusing does not. Finally, the independence of the method from focus is useful for optical sectioning involving ptychography, improving interpretability by better disentangling the effects of strong potentials and focus.

10.
J Am Chem Soc ; 146(1): 289-297, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38135454

RESUMEN

Copper (Cu), with the advantage of producing a deep reduction product, is a unique catalyst for the electrochemical reduction of CO2 (CO2RR). Designing a Cu-based catalyst to trigger CO2RR to a multicarbon product and understanding the accurate structure-activity relationship for elucidating reaction mechanisms still remain a challenge. Herein, we demonstrate a rational design of a core-shell structured silica-copper catalyst (p-Cu@m-SiO2) through Cu-Si direct bonding for efficient and selective CO2RR. The Cu-Si interface fulfills the inversion in CO2RR product selectivity. The product ratio of C2H4/CH4 changes from 0.6 to 14.4 after silica modification, and the current density reaches a high of up to 450 mA cm-2. The kinetic isotopic effect, in situ attenuated total reflection Fourier-transform infrared spectra, and density functional theory were applied to elucidate the reaction mechanism. The SiO2 shell stabilizes the *H intermediate by forming Si-O-H and inhibits the hydrogen evolution reaction effectively. Moreover, the direct-bonded Cu-Si interface makes bare Cu sites with larger charge density. Such bare Cu sites and Si-O-H sites stabilized the *CHO and activated the *CO, promoting the coupling of *CHO and *CO intermediates to form C2H4. This work provides a promising strategy for designing Cu-based catalysts with high C2H4 catalytic activity.

11.
J Med Chem ; 66(23): 16330-16341, 2023 12 14.
Artículo en Inglés | MEDLINE | ID: mdl-38093695

RESUMEN

Biosynthetic engineering of bicyclic darobactins, selectively sealing the lateral gate of the outer membrane protein BamA, leads to active analogues, which are up to 128-fold more potent against Gram-negative pathogens compared to native counterparts. Because of their excellent antibacterial activity, darobactins represent one of the most promising new antibiotic classes of the past decades. Here, we present a series of structure-driven biosynthetic modifications of our current frontrunner, darobactin 22 (D22), to investigate modifications at the understudied positions 2, 4, and 5 for their impact on bioactivity. Novel darobactins were found to be highly active against critical pathogens from the WHO priority list. Antibacterial activity data were corroborated by dissociation constants with BamA. The most active derivatives D22 and D69 were subjected to ADMET profiling, showing promising features. We further evaluated D22 and D69 for bioactivity against multidrug-resistant clinical isolates and found them to have strong activity.


Asunto(s)
Antibacterianos , Fenilpropionatos , Antibacterianos/farmacología , Pruebas de Sensibilidad Microbiana
12.
Sci Adv ; 9(49): eadj5777, 2023 Dec 08.
Artículo en Inglés | MEDLINE | ID: mdl-38064550

RESUMEN

Secreted bacterial type III secretion system (T3SS) proteins are essential for successful infection by many human pathogens. Both T3SS translocator SipC and effector SipA are critical for Salmonella infection by subversion of the host cell cytoskeleton, but the precise molecular interplay between them remains unknown. Here, using cryo-electron microscopy, we show that SipA binds along the F-actin grooves with a unique binding pattern. SipA stabilizes F-actin through charged interface residues and appears to prevent inorganic phosphate release through closure of the "back door" of adenosine 5'-triphosphate pocket. We also show that SipC enhances the binding of SipA to F-actin, thus demonstrating that a sequential presence of T3SS proteins in host cells is associated with a sequence of infection events-starting with actin nucleation, filament growth, and stabilization. Together, our data explain the coordinated interplay of a precisely tuned and highly effective mechanism during Salmonella infection and provide a blueprint for interfering with Salmonella effectors acting on actin.


Asunto(s)
Actinas , Infecciones por Salmonella , Humanos , Actinas/metabolismo , Microscopía por Crioelectrón , Proteínas Bacterianas/metabolismo , Citoesqueleto de Actina/metabolismo
13.
Cell ; 186(23): 5098-5113.e19, 2023 11 09.
Artículo en Inglés | MEDLINE | ID: mdl-37918395

RESUMEN

Drug-resistant Pseudomonas aeruginosa (PA) poses an emerging threat to human health with urgent need for alternative therapeutic approaches. Here, we deciphered the B cell and antibody response to the virulence-associated type III secretion system (T3SS) in a cohort of patients chronically infected with PA. Single-cell analytics revealed a diverse B cell receptor repertoire directed against the T3SS needle-tip protein PcrV, enabling the production of monoclonal antibodies (mAbs) abrogating T3SS-mediated cytotoxicity. Mechanistic studies involving cryoelectron microscopy identified a surface-exposed C-terminal PcrV epitope as the target of highly neutralizing mAbs with broad activity against drug-resistant PA isolates. These anti-PcrV mAbs were as effective as treatment with conventional antibiotics in vivo. Our study reveals that chronically infected patients represent a source of neutralizing antibodies, which can be exploited as therapeutics against PA.


Asunto(s)
Anticuerpos Antibacterianos , Anticuerpos Neutralizantes , Infecciones por Pseudomonas , Pseudomonas aeruginosa , Humanos , Anticuerpos Antibacterianos/farmacología , Microscopía por Crioelectrón , Inmunoglobulinas/metabolismo , Pseudomonas aeruginosa/efectos de los fármacos , Pseudomonas aeruginosa/fisiología , Infecciones por Pseudomonas/tratamiento farmacológico
14.
BMC Cancer ; 23(1): 1005, 2023 Oct 19.
Artículo en Inglés | MEDLINE | ID: mdl-37858067

RESUMEN

BACKGROUND: SH2 domain containing 1A (SH2D1A) expression has been linked to cancer progression. However, the functions of SH2D1A in hepatocellular carcinoma (HCC) have not been reported. METHODS: The effects of SH2D1A on the proliferation, migration, and invasion of HCC cells and the related pathways were re-explored in cell models with SH2D1A overexpression using the CCK-8, migration and invasion assays and western blotting. The functions and mechanisms of genes co-expressed with SH2D1A were analyzed using gene ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis. The relationship between SH2D1A expression and immune microenvironment features in HCC was explored. RESULTS: Elevated SH2D1A expression promoted cell proliferation, migration, and invasion, which was related to the overexpression of p-Nf-κB and BCL2A1 protein levels in HCC. SH2D1A expression was related to the immune, stromal, and ESTIMATE scores, and the abundance of immune cells, such as B cells, CD8+ T cells, and T cells. SH2D1A expression was significantly related to the expression of immune cell markers, such as PDCD1, CD8A, and CTLA4 in HCC. CONCLUSION: SH2D1A overexpression was found to promote cell growth and metastasis via the Nf-κB signaling pathway and may be related to the immune microenvironment in HCC. The findings indicate that SH2D1A can function as a biomarker in HCC.


Asunto(s)
Carcinoma Hepatocelular , Neoplasias Hepáticas , Proteína Asociada a la Molécula de Señalización de la Activación Linfocitaria , Humanos , Biomarcadores de Tumor/genética , Biomarcadores de Tumor/inmunología , Carcinoma Hepatocelular/genética , Carcinoma Hepatocelular/inmunología , Carcinoma Hepatocelular/patología , Linfocitos T CD8-positivos , Biología Computacional , Neoplasias Hepáticas/genética , Neoplasias Hepáticas/inmunología , Neoplasias Hepáticas/patología , Procesos Neoplásicos , FN-kappa B , Proteína Asociada a la Molécula de Señalización de la Activación Linfocitaria/genética , Proteína Asociada a la Molécula de Señalización de la Activación Linfocitaria/inmunología , Microambiente Tumoral/genética , Microambiente Tumoral/inmunología
15.
Angew Chem Int Ed Engl ; 62(46): e202309820, 2023 Nov 13.
Artículo en Inglés | MEDLINE | ID: mdl-37768737

RESUMEN

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency of CO2 photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through the construction of one-dimensional (1D) pyrene-based covalent organic frameworks (PyTTA-COF). The dual-chain-like edge architectures of 1D PyTTA-COF enable the stabilization of aromatic backbones, thus reducing energy loss during exciton dissociation and thermal relaxation, which provides energetic photoelectron to traverse the energy barrier of imine linkages. As a result, the 1D PyTTA-COF exhibits significantly enhanced CO2 photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding a remarkable CO evolution of 1003 µmol g-1 over an 8-hour period, which surpasses that of the corresponding 2D counterpart by a factor of 59. These findings present a valuable approach to address in-plane charge transfer limitations in imine-based COFs.

16.
J Am Chem Soc ; 145(36): 19856-19865, 2023 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-37653575

RESUMEN

Introducing an external visible-light field would be a promising strategy to improve the activity of the electrocatalytic CO2 reduction reaction (CO2RR), but it still remains a challenge due to the short excited-state lifetime of active sites. Herein, Ru(bpy)3Cl2 struts as powerful photosensitive donors were immobilized into the backbones of Co-porphyrin-based covalent organic frameworks (named Co-Bpy-COF-Rux, x is the molar ratio of Ru and Co species, x = 1/2 and 2/3) via coordination bonds, for the photo-coupled CO2RR to produce CO. The optimal Co-Bpy-COF-Ru1/2 displays a high CO Faradaic efficiency of 96.7% at -0.7 V vs reversible hydrogen electrode (RHE) and a CO partial current density of 16.27 mA cm-2 at -1.1 V vs RHE under the assistance of light, both of which were far surpassing the values observed in the dark. The significantly enhanced activity is mainly attributed to the incorporation of a Ru(bpy)3Cl2 donor with long excited-state lifetime and concomitantly giant built-in electric field in Co-Bpy-COF-Ru1/2, which efficiently accelerate the photo-induced electron transfer from Ru(bpy)3Cl2 to the cobalt-porphyrin under the external light. Thus, the cobalt-porphyrin active sites have a longer excited-state lifetime to lower the rate-determining steps' energy occurring during the actual photo-coupled electrocatalytic CO2RR process. This is the first work of porphyrin-based COFs for photo-coupled CO2RR, opening a new frontier for the construction of efficient photo-coupled electrocatalysts.

17.
J Am Chem Soc ; 145(36): 19885-19893, 2023 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-37651697

RESUMEN

Epitaxial heterostructures of two-dimensional (2D) halide perovskites offer a new platform for studying intriguing structural, optical, and electronic properties. However, difficulties with the stability of Pb- and Sn-based heterostructures have repeatedly slowed the progress. Recently, Pb-free halide double perovskites are gaining a lot of attention due to their superior stability and greater chemical diversity, but they have not been successfully incorporated into epitaxial heterostructures for further investigation. Here, we report epitaxial core-shell heterostructures via growing Pb-free double perovskites (involving combinations of Ag(I)-Bi(III), Ag-Sb, Ag-In, Na-Bi, Na-Sb, and Na-In) around Pb perovskite 2D crystals. Distinct from Pb-Pb and Pb-Sn perovskite heterostructures, growths of the Pb-free shell at 45° on the (100) surface of the lead perovskite core are observed in all Pb-free cases. The in-depth structural analysis carried out with electron diffraction unequivocally demonstrates the growth of the Pb-free shell along the [110] direction of the Pb perovskite, which is likely due to the relatively lower surface energy of the (110) surface. Furthermore, an investigation of anionic interdiffusion across heterostructure interfaces under the influence of heat was carried out. Interestingly, halide anion diffusion in the Pb-free 2D perovskites is found to be significantly suppressed as compared to Pb-based 2D perovskites. The great structural tunability and excellent stability of Pb-free perovskite heterostructures may find uses in electronic and optoelectronic devices in the near future.

18.
Angew Chem Int Ed Engl ; 62(36): e202306822, 2023 Sep 04.
Artículo en Inglés | MEDLINE | ID: mdl-37468435

RESUMEN

We propose an effective highest occupied d-orbital modulation strategy engendered by breaking the coordination symmetry of sites in the atomically precise Cu nanocluster (NC) to switch the product of CO2 electroreduction from HCOOH/CO to higher-valued hydrocarbons. An atomically well-defined Cu6 NC with symmetry-broken Cu-S2 N1 active sites (named Cu6 (MBD)6 , MBD=2-mercaptobenzimidazole) was designed and synthesized by a judicious choice of ligand containing both S and N coordination atoms. Different from the previously reported high HCOOH selectivity of Cu NCs with Cu-S3 sites, the Cu6 (MBD)6 with Cu-S2 N1 coordination structure shows a high Faradaic efficiency toward hydrocarbons of 65.5 % at -1.4 V versus the reversible hydrogen electrode (including 42.5 % CH4 and 23 % C2 H4 ), with the hydrocarbons partial current density of -183.4 mA cm-2 . Theoretical calculations reveal that the symmetry-broken Cu-S2 N1 sites can rearrange the Cu 3d orbitals with d x 2 - y 2 ${d_{x^2 - y^2 } }$ as the highest occupied d-orbital, thus favoring the generation of key intermediate *COOH instead of *OCHO to favor *CO formation, followed by hydrogenation and/or C-C coupling to produce hydrocarbons. This is the first attempt to regulate the coordination mode of Cu atom in Cu NCs for hydrocarbons generation, and provides new inspiration for designing atomically precise NCs for efficient CO2 RR towards highly-valued products.

19.
Waste Manag ; 169: 52-61, 2023 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-37406504

RESUMEN

Poor properties and high concentrations of heavy metals are still major concerns of successful application of animal manure-derived biochar into the environment. This work thus proposed to add chlorine-based additives (Cl-additives, i.e., CaCl2, MgCl2, KCl, NaCl, and PVC, 50 g Cl/ kg) to improve biochar properties and enhance heavy metal volatilization during swine manure pyrolysis. The results showed that the addition of CaCl2 could improve the retention of carbon (C) by up to 13.1% during pyrolysis, whereas other Cl-additives had little effect on it. Moreover, CaCl2 could enhance the aromaticity of biochar, as indicated by lower H/C ratio than raw biochar. Pretreatment with CaCl2, MgCl2 and PVC reduced phosphorus (P) solubility but increased its bioavailability via the formation of chlorapatite (Ca5(PO4)3Cl). The CaCl2 was more effective for enhancing the volatilization efficiency of heavy metals than other Cl-additives, except for Pb that tended to react with the generated Ca5(PO4)3Cl to form more stable and less volatile Pb5(PO4)3Cl. However, high pyrolysis temperature (900℃) was essential for CaCl2 to simultaneously decrease the bioavailability of heavy metals. Our results indicated that co-pyrolysis of swine manure with CaCl2 is a promising strategy to increase C retention, P bioavailability, and volatilization of heavy metals, and, at higher temperature, reduce the bioavailability of biochar-born heavy metals.


Asunto(s)
Cloro , Metales Pesados , Porcinos , Animales , Estiércol , Pirólisis , Cloruro de Calcio , Plomo , Volatilización , Carbón Orgánico
20.
Zookeys ; 1166: 155-173, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-37333901

RESUMEN

The systematics of the potamid freshwater crab Cryptopotamonanacoluthon (Kemp, 1918) is clarified, and its generic position in Sinolapotamon Tai & Sung, 1975, is confirmed based on morphological comparisons, geographical information and phylogenetic analyses. A new species of Sinolapotamon, Sinolapotamoncirratumsp. nov. is described from the Guangxi Zhuang Autonomous Region of China. Sinolapotamoncirratumsp. nov. is distinguished from its congeners by the combination of characters of its carapace, third maxilliped, anterolateral margin, and unique male first gonopod. Phylogenetic analyses based on partial COX1, 16S rRNA and 28S rRNA genes also support the species as new.

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