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1.
Angew Chem Int Ed Engl ; : e202414696, 2024 Sep 21.
Artículo en Inglés | MEDLINE | ID: mdl-39305142

RESUMEN

The facile reaction of the SiPh2-bridged bis-silylene (LSi:)2SiPh2 (L = PhC(NBut)2) with diphenylacetylene affords the unprecedented 1,2,3-trisilacyclopentadiene (LSi)2(PhC)2SiPh2 1 with a hypercoordinate λ4Si-λ3Si double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert N2O to form the bicyclic oxygenation product 2 through O-atom insertion in the Si=Si and Si-Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3-disilacyclopentadiene3, representing the first hypercoordinate example of a cyclosilene with a λ4Si-λ3C double bond. Likewise, reaction of Xyl-NC (Xyl = 2,6-dimethylphenyl), an isocyanide isoelectronic with CO, with1furnishes the related 1,3-disilacyclopentadiene4but with an amidinato silylene pendent attached to the Si=C carbon ring atom.

2.
ACS Nano ; 2024 Sep 23.
Artículo en Inglés | MEDLINE | ID: mdl-39312392

RESUMEN

Urea electrosynthesis by coelectrolysis of NO3- and CO2 (UENC) holds enormous promise for sustainable urea production, while the efficient UENC process relies on the rational design of high-performance catalysts to facilitate the electrocatalytic C-N coupling efficiency and the hydrogenation reaction process. Herein, Fe single atoms supported on MoS2 (Fe1/MoS2) are developed as a highly effective and robust catalyst for UENC. Theoretical calculations and operando spectroscopic measurements reveal a tandem catalysis mechanism of the Fe1-S3 motif and MoS2-edge to jointly promote the UENC process, where the Fe1-S3 motif drives the early C-N coupling and subsequent *CO2NO2-to-*CO2NH2 step. The generated *CO2NH2 is then migrated from the Fe1-S3 motif to the nearby MoS2-edge, which facilitates the *CO2NH2 → *COOHNH2 step for urea formation. Noticeably, Fe1/MoS2 assembled in a flow cell reaches a maximum urea Faraday efficiency of 54.98% with a corresponding urea yield rate of 18.98 mmol h-1 g-1, performing at the top level among all of the UENC catalysts reported to date.

3.
Org Lett ; 2024 Sep 23.
Artículo en Inglés | MEDLINE | ID: mdl-39311499

RESUMEN

S-Alkyl dithiocarbamates, as an important class of sulfur-containing compounds, play pivotal roles in diverse fields, yet methods for the synthesis that start from simple, readily available feedstocks and exhibit mild conditions and structurally diverse products are scarce. In this work, we developed an efficient approach for the synthesis of various S-alkyl dithiocarbamates via visible-light photocatalysis with readily available and structurally diverse alkyl carboxylic acids (primary, secondary, and tertiary acids, amino acids, etc.) and disulfide tetraalkylthiuram as the starting materials. This protocol features high efficiency, mild reaction conditions, a broad substrate scope, and good functional group tolerance. Potential applications are further demonstrated by a sunlight experiment, H2O as a solvent, gram-scale synthesis, and facile synthesis of bioactive molecules.

4.
Materials (Basel) ; 17(17)2024 Sep 07.
Artículo en Inglés | MEDLINE | ID: mdl-39274808

RESUMEN

Water scarcity is a serious threat to the survival and development of mankind. Interfacial solar steam generation (ISSG) can alleviate the global freshwater shortage by converting sustainable solar power into thermal energy for desalination. ISSG possesses many advantages such as high photothermal efficiency, robust durability, and environmental friendliness. However, conventional evaporators suffered from huge heat losses in the evaporation process due to the lack of efficient thermal management. Herein, hydrophilic Tencel yarn is applied to fabricate a three-dimensional double-layer fabric evaporator (DLE) with efficient multi-stage thermal management. DLE enables multiple solar absorptions, promotes cold evaporation, and optimizes thermal management. The airflow was utilized after structure engineering for enhanced energy evaporation efficiency. The evaporation rate can reach 2.86 kg·m-2·h-1 under 1 sun (1 kW·m-2), and 6.26 kg·m-2·h-1 at a wind speed of 3 m·s-1. After a long duration of outdoor operation, the average daily evaporation rate remains stable at over 8.9 kg·m-2, and the removal rate of metal ions in seawater reaches 99%. Overall, DLE with efficient and durable three-dimensional multi-stage thermal management exhibits excellent practicality for solar desalination.

5.
Sci Total Environ ; 953: 175980, 2024 Nov 25.
Artículo en Inglés | MEDLINE | ID: mdl-39236823

RESUMEN

Assessing the bioaccessibility and bioavailability of cadmium (Cd) is crucial for effective evaluation of the exposure risk associated with intake of Cd-contaminated rice. However, limited studies have investigated the influence of gut microbiota on these two significant factors. In this study, we utilized in vitro gastrointestinal simulators, specifically the RIVM-M (with human gut microbial communities) and the RIVM model (without gut microbial communities), to determine the bioaccessibility of Cd in rice. Additionally, we employed the Caco-2 cell model to assess bioavailability. Our findings provide compelling evidence that gut microbiota significantly reduces Cd bioaccessibility and bioavailability (p<0.05). Notably, strong in vivo-in vitro correlations (IVIVC) were observed between the in vitro bioaccessibilities and bioavailabilities, as compared to the results obtained from an in vivo mouse bioassay (R2 = 0.63-0.65 and 0.45-0.70, respectively). Minerals such as copper (Cu) and iron (Fe) in the food matrix were found to be negatively correlated with Cd bioaccessibility in rice. Furthermore, the results obtained from the toxicokinetic (TK) model revealed that the predicted urinary Cd levels in the Chinese population, based on dietary Cd intake adjusted by in vitro bioaccessibility from the RIVM-M model, were consistent with the actual measured levels (p > 0.05). These results indicated that the RIVM-M model represents a potent approach for measuring Cd bioaccessibility and underscore the crucial role of gut microbiota in the digestion and absorption process of Cd. The implementation of these in vitro methods holds promise for reducing uncertainties in dietary exposure assessment.


Asunto(s)
Disponibilidad Biológica , Cadmio , Microbioma Gastrointestinal , Oryza , Oryza/metabolismo , Cadmio/metabolismo , Humanos , Animales , Ratones , Células CACO-2 , Contaminación de Alimentos/análisis , Contaminantes del Suelo/metabolismo , Contaminantes del Suelo/análisis
6.
Radiol Case Rep ; 19(11): 5365-5369, 2024 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-39280743

RESUMEN

Pseudolipoma of Glisson's capsule is a rare, benign subcapsular liver lesion that typically occurs in older adult men. It comprises degenerated fat tissue that likely originates from detached mesothelial appendages or degenerated liver lipomas. We report the case of a 58-year-old female patient with a gastric malignant tumor after admission. No lesions were found in the liver capsule before surgery. During postoperative reviews from 2015 to 2018, new dense, fatty lesions were found under the liver capsule, and highly unusually, the lesions moved under the liver capsule over time. To the best of our knowledge, only 1 other case has been reported of a pseudolipoma of Glisson's capsule that migrated over time. This supports the hypothesis that migrating mesothelial attachments form Glisson capsule pseudolipomas. This case report aims to review liver capsule anatomy, explain why the liver is particularly susceptible to this phenomenon, and present information to aid the diagnosis of fat-containing hepatic lesions by providing a unique perspective on certain pathologies affecting the liver.

7.
Environ Sci Ecotechnol ; 22: 100479, 2024 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-39286480

RESUMEN

Environmental assessments are critical for ensuring the sustainable development of human civilization. The integration of artificial intelligence (AI) in these assessments has shown great promise, yet the "black box" nature of AI models often undermines trust due to the lack of transparency in their decision-making processes, even when these models demonstrate high accuracy. To address this challenge, we evaluated the performance of a transformer model against other AI approaches, utilizing extensive multivariate and spatiotemporal environmental datasets encompassing both natural and anthropogenic indicators. We further explored the application of saliency maps as a novel explainability tool in multi-source AI-driven environmental assessments, enabling the identification of individual indicators' contributions to the model's predictions. We find that the transformer model outperforms others, achieving an accuracy of about 98% and an area under the receiver operating characteristic curve (AUC) of 0.891. Regionally, the environmental assessment values are predominantly classified as level II or III in the central and southwestern study areas, level IV in the northern region, and level V in the western region. Through explainability analysis, we identify that water hardness, total dissolved solids, and arsenic concentrations are the most influential indicators in the model. Our AI-driven environmental assessment model is accurate and explainable, offering actionable insights for targeted environmental management. Furthermore, this study advances the application of AI in environmental science by presenting a robust, explainable model that bridges the gap between machine learning and environmental governance, enhancing both understanding and trust in AI-assisted environmental assessments.

8.
Heliyon ; 10(18): e37707, 2024 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-39323815

RESUMEN

Background: All-suture anchor (ASA) is a special type of suture anchor. It has been used to repair rotator cuff tears (RCTs). However, mechanical properties and tendon-bone integration at different time postoperatively remains to be unclear. Methods: Mechanical testing and water contact angle measurements were conducted for ASA. In vitro biocompatibility was assessed using rat bone marrow stem cells (BMSCs), including live/dead cell staining and Cell Counting Kit-8 assays. ASA was implanted for rotator cuff repair (ASA group) in a New Zealand White rabbit model of RCTs, and a natural rotator cuff was used as a control (natural group). The animals were sacrificed, and tissue samples were harvested for biomechanical, radiographic, and histological analysis at 4, 8, and 12 weeks postoperatively. Results: ASA was hydrophobic and had a strong mechanical property in vitro. The biocompatibility analysis showed that ASA had no effect on the viability of BMSCs. Mechanical testing in vivo revealed that a gradually improved failure load of ASA group was 118.0 ± 22.53N at 12 weeks postoperatively, which was recovered to the natural group. Micro-CT analysis indicated that an initial decrease in BMD and trabecular quality following ASA implantation, with a slight recovery observed at 12 weeks. Additionally, histological analysis showed the tendon-bone interface gradually integrated in the ASA group. A significant increase in tendon-bone interface scores was found from 4 weeks to 12 weeks. Tendon maturing score also improved in the ASA group, and Type I collagen content recovered to 18.58 ± 4.378 % at 12 weeks and no different from that of the natural group. Conclusion: Rotator cuff repair with ASA in a rabbit model demonstrated the capacity to enhance biomechanical properties and tendon-bone integration.

9.
Colloids Surf B Biointerfaces ; 245: 114219, 2024 Sep 08.
Artículo en Inglés | MEDLINE | ID: mdl-39293290

RESUMEN

Osseointegration is significantly impeded in osteoporotic conditions due to the elevated levels of reactive oxygen species (ROS) and inflammation at the site of injury. To enhance bone regeneration in osteoporotic conditions, a modified polyether ether ketone (PEEK) implants was prepared, denoted as PEEK-PDA-Sr. The implants consisted of mussel adhesion layer with the conjugation of strontium (Sr) ions, which can constantly release Sr ions for up to 3 weeks. PEEK-PDA-Sr demonstrated excellent biocompatibility and effectively regulated intracellular ROS levels and macrophage differentiation. In addition, the PEEK-PDA-Sr facilitated the osteogenesis of bone marrow stromal cells (BMSCs). In the ovariectomized (OVX) rat model of osteoporosis, the PEEK-PDA-Sr exhibited raised osseointegration in the femoral bone defects. The PEEK-PDA-Sr can be used as an immunoregulator with enhanced osseointegration and osteogenesis both in vivo and in vitro, which provides an available approach to treat osteoporotic bone defects.

11.
Sci Rep ; 14(1): 20879, 2024 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-39242594

RESUMEN

Underground cavities have complex spatial structures and geological settings, their arrangement is dense and crisscrossed. The construction system involves multiple work surfaces, levels, and processes. The close integration of construction simulation with actual production conditions is crucial for enhancing the guidance that simulation results provide for practical engineering. Therefore, from the perspective of optimizing construction organization and management, this article comprehensively considers various factors in the construction process, innovatively introduces the principle of production line balance and the concept of rule cycle, and combines technology and management, an underground cavities construction simulation system (UCCSS) is developed. In UCCSS, a hierarchical model is built and calculation are performed on models with different construction methods by modifying the parameters as per the actual engineering characteristics. The simulation results are comprehensively analysed to determine the optimal construction programme. An application case is proposed based on the construction organisation design of the long and parallel diversion tunnels at the CB Hydropower Station. The results show that the system has good practicality and credibility and can provide guidance for the construction organisation design of underground cavities with various features.

12.
J Comput Chem ; 2024 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-39240057

RESUMEN

Sulfonyl fluorides hold significant importance as highly valued intermediates in chemical biology due to their optimal balance of biocompatibility with both aqueous stability and protein reactivity. The Cornella group introduced a one-pot strategy for synthesizing aryl sulfonyl fluorides via Bi(III) redox-neutral catalysis, which facilitates the transmetallation and direct insertion of SO2 into the BiC(sp2) bond giving the aryl sulfonyl fluorides. We report herein a comprehensive computational investigation of the redox-neutral Bi(III) catalytic mechanism, disclose the critical role of the Bi(III) catalyst and base (i.e., K3PO4), and uncover the origin of SO2 insertion into the Bi(III)C(sp2) bond. The entire catalysis can be characterized via three stages: (i) transmetallation generating the Bi(III)-phenyl intermediate IM3 facilitated by K3PO4. (ii) SO2 insertion into IM3 leading to the formation of Bi(III)-OSOAr intermediate IM5. (iii) IM5 undergoes S(IV)-oxidation yielding the aryl sulfonyl fluoride product 4 and liberating the Bi(III) catalyst for the next catalytic cycle. Each stage is kinetically and thermodynamically feasible. Moreover, we explored other some small molecules (NO2, CO2, H2O, N2O, etc.) insertion reactions mediated by the Bi(III)-complex, and found that NO2 insertions could be easily achieved due to the low insertion barriers (i.e., 17.5 kcal/mol). Based on the detailed mechanistic study, we further rationally designed additional Bi(III) and Sb(III) catalysts, and found that some of which exhibit promising potential for experimental realization due to their low barriers (<16.4 kcal/mol). In this regard, our study contributes significantly to enhancing current Bi(III)-catalytic systems and paving the way for novel Bi(III)-catalyzed aryl sulfonyl fluoride formation reactions.

13.
Heliyon ; 10(16): e35618, 2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39247291

RESUMEN

Neonicotinoid insecticides (NEOs) are a widely used type of insecticide found globally, leading to broad human exposure. However, there is limited research on how internal exposure levels of NEOs and their metabolites impact in vitro fertilization/intracytoplasmic sperm injection (IVF/ICSI) outcomes. A study was conducted at the Sixth Affiliated Hospital of Sun Yat-sen University between 2017 and 2020 involving 436 women undergoing IVF/ICSI treatment. Data on demographics and clinical history were collected from medical records. The concentrations of 11 NEOs and 4 NEO metabolites in follicular fluid and serum were measured using a salting-out assisted liquid-liquid extraction method and liquid chromatography-tandem mass spectrometry. Our findings indicated that NEOs were prevalent in women with infertility. One NEO metabolite, N-dm-ACE, was detected in all samples with median concentrations of 0.221 ng/mL in follicular fluid and 0.228 ng/mL in serum. The study showed a decrease in the number of retrieved oocytes, mature oocytes, 2 PN zygotes, and high-quality embryos as the number of exposed NEOs in follicular fluid increased. Women in the highest tertile of N-dm-ACE exposure had fewer mature oocytes, 2 PN zygotes, and lower oocyte maturity rates compared to those in the lowest tertile. The findings suggest that exposure to NEOs may negatively impact reproductive outcomes in IVF/ICSI pregnancies, particularly affecting oocyte retrieval and embryo quality. This study highlights the potential adverse effects of environmental NEO exposure on IVF/ICSI outcomes, emphasizing the importance of considering such exposures in preconception care.

14.
Res Vet Sci ; 178: 105380, 2024 Oct.
Artículo en Inglés | MEDLINE | ID: mdl-39173243

RESUMEN

Blastocystis is a common intestinal protist in humans and animals. Currently, Blastocystis infection in bar-headed geese is unknown. To understand the prevalence and distribution of Blastocystis subtypes in bar-headed geese, fecal samples were collected from 358 bar-headed geese in three regions. The total infection rate of Blastocystis in bar-headed in China was 5.9% (21/358), with 5.0% (6/120) in Aba (Ngawa) Tibetan and Qiang Autonomous Prefect, Sichuan province, 11.8% (14/119) in Maqu county, Gansu province, and 0.8% (1/119) in Caohai, Wei ning county, Guizhou province. The differences in prevalence rates by region were statistically significant. Sequences analyses showed that one known subtype (ST7, n = 16) and one potentially novel ST (n = 5) in bar-headed geese were detected in this study. This is the first report on the prevalence and subtype distribution of Blastocystis in bar-headed geese, which will improve our understanding of the epidemiology and public health implications of Blastocystis infection in wild migratory birds.


Asunto(s)
Infecciones por Blastocystis , Blastocystis , Heces , Gansos , Animales , Infecciones por Blastocystis/epidemiología , Infecciones por Blastocystis/veterinaria , Infecciones por Blastocystis/parasitología , Gansos/parasitología , Blastocystis/aislamiento & purificación , Blastocystis/clasificación , China/epidemiología , Prevalencia , Heces/parasitología , Enfermedades de las Aves de Corral/epidemiología , Enfermedades de las Aves de Corral/parasitología , Filogenia
15.
Mater Horiz ; 2024 Aug 05.
Artículo en Inglés | MEDLINE | ID: mdl-39102285

RESUMEN

Polydimethylsiloxane (PDMS) elastomers with high mechanical and healing properties are developed as smart materials for electrical power systems and electronic devices to address electrical or mechanical damage. However, the challenge is to reconcile the conflicting molecular mechanisms of mechanical and healing properties in the development of PDMS elastomers. This study adopts the "rigid-while-flexible" mutual network structure by copolymerizing the rigid polyimide (PI) with flexible segments with dynamic reversible crosslinking designed on the PDMS backbones. This elastomer (designated PSiPI) exhibits high toughness, tensile strength and elongation at break, as well as excellent healing efficiency and recyclability. Moreover, the PSiPI elastomer also exhibits good insulation and corona damage healing properties. Taking advantage of the recyclability and healing properties of PSiPI elastomers, healable superhydrophobic coatings with contact angles greater than 150° have been prepared by compositing PSiPI elastomers with SiO2. Likewise, combining the elastomer with conductive materials can create a healing flexible conductor. This "rigid-while-flexible" design approach provides important inspiration for the development of high-performance, sustainable and environmentally friendly PDMS elastomers for electrical and electronic applications.

16.
BMC Pediatr ; 24(1): 547, 2024 Aug 24.
Artículo en Inglés | MEDLINE | ID: mdl-39182032

RESUMEN

OBJECTIVE: Patients who carry NUP98::NSD1 or FLT3/ITD mutations are reported to have poor prognosis. Previous studies have confidently reported that the poor outcome in younger AML patients is owning to dual NUP98::NSD1 and FLT3/ITD positivity, with a high overlap for those two genetic lesions. In this study, we assessed the prognostic value of the presence of both NUP98::NSD1 and FLT3/ITD in pediatric AML patients. METHODS: We screened a large cohort of 885 pediatric cases from the COG-National Cancer Institute (NCI) TARGET AML cohort and found 57 AML patients with NUP98 rearrangements. RESULTS: The frequency of NUP98 gene fusion was 10.8% in 529 patients. NUP98::NSD1 fusion was the most common NUP98 rearrangement, with a frequency of 59.6%(34 of 57). NUP98::NSD1 -positive patients who carried FLT3/ITD mutations had a decreased CR1 or CR2 rate than those patients carried FLT3/ITD mutation alone (P = 0.0001). Moreover, patients harboring both NUP98::NSD1 fusion and FLT3/ITD mutation exhibited inferior event-free survival (EFS, P < 0.001) and overall survival (OS, P = 0.004) than patients who were dual negative for these two genetic lesions. The presence of only NUP98::NSD1 fusion had no significant impact on EFS or OS. We also found that cases with high FLT3/ITD AR levels ( > = 0.5) with or without NUP98::NSD1 had inferior prognosis. Multivariate analysis demonstrated that the presence of both NUP98::NSD1 and FLT3/ITD was an independent prognostic factors for EFS (hazard ratio: 3.2, P = 0.001) in patients with pediatric AML. However, there was no obvious correlation with OS (hazard ratio: 1.3, P = 0.618). Stem cell transplantation did not improve the survival rate of cases with NUP98 fusion or NUP98::NSD1 AML in terms of EFS or OS. CONCLUSION: Presence of both NUP98::NSD1 and FLT3/ITD was found to be an independent factor for dismal prognosis in pediatric AML patients. Notably, lack of FLT3/ITD mutations in NUP98::NSD1 -positive patients did not retain its prognostic value.


Asunto(s)
Leucemia Mieloide Aguda , Mutación , Proteínas de Complejo Poro Nuclear , Tirosina Quinasa 3 Similar a fms , Humanos , Tirosina Quinasa 3 Similar a fms/genética , Niño , Femenino , Leucemia Mieloide Aguda/genética , Leucemia Mieloide Aguda/mortalidad , Masculino , Pronóstico , Preescolar , Proteínas de Complejo Poro Nuclear/genética , Adolescente , Lactante , Proteínas de Fusión Oncogénica/genética , N-Metiltransferasa de Histona-Lisina/genética , Proteínas Nucleares/genética , Péptidos y Proteínas de Señalización Intracelular/genética
17.
Cell Death Dis ; 15(8): 624, 2024 Aug 27.
Artículo en Inglés | MEDLINE | ID: mdl-39191723

RESUMEN

Osteoporosis (OP) is a disorder of bone remodeling caused by an imbalance between bone resorption by osteoclasts and bone formation by osteoblasts. Therefore, inhibiting excessive osteoclast activity is one of the promising strategies for treating OP. A major transient receptor potential cation channel, known as transient receptor potential ankyrin 1 (TRPA1), was found to alleviate joint pain and cartilage degeneration in osteoarthritis. However, little research has focused on TRPA1 function in OP. As a result, this study aimed to explore the TRPA1 characteristics and its potential therapeutic function during osteoclastogenesis. The TRPA1 expression gradually increased in the osteoclast differentiation process; however, its suppression with small interfering RNA and an inhibitor (HC030031) significantly controlled the osteoclast count and the expression of osteoclast characteristic genes. Its suppression also inhibited endoplasmic reticulum (ER) stress-related pancreatic ER kinase (PERK) pathways. An ER stress inhibitor (thapsigargin) reversed the down-regulated levels of ER stress and osteoclast differentiation by suppressing TRPA1. Transcriptome sequencing results demonstrated that TRPA1 negatively regulated reactive oxygen species (ROS) and significantly increased the expression of an antioxidant gene, SRXN1. The osteoclast differentiation and the levels of ER stress were enhanced with SRXN1 inhibition. Finally, TRPA1 knockdown targeting macrophages by adeno-associated virus-9 could relieve osteoclast differentiation and osteopenia in ovariectomized mice. In summary, silencing TRPA1 restrained osteoclast differentiation through ROS-mediated down-regulation of ER stress via inhibiting PERK pathways. The study also indicated that TRPA1 might become a prospective treatment target for OP.


Asunto(s)
Diferenciación Celular , Estrés del Retículo Endoplásmico , Osteoclastos , Osteogénesis , Osteoporosis , Canal Catiónico TRPA1 , Canal Catiónico TRPA1/metabolismo , Canal Catiónico TRPA1/genética , Animales , Osteoporosis/metabolismo , Osteoporosis/patología , Osteoporosis/genética , Ratones , Osteoclastos/metabolismo , Osteogénesis/efectos de los fármacos , Femenino , Ratones Endogámicos C57BL , Células RAW 264.7 , Especies Reactivas de Oxígeno/metabolismo
18.
Org Lett ; 26(34): 7110-7115, 2024 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-39150722

RESUMEN

We disclose herein an asymmetric synthesis of axially chiral oxazepine-containing bridged biaryls via CPA-catalyzed kinetic asymmetric alcoholysis. Control experiments showed that this CPA-catalyzed alcoholysis was reversible, and lowering the reaction temperature could almost suppress the reversible reaction, thus providing a series of axially chiral oxazepine-containing bridged biaryl compounds in good to excellent enantioselectivities. The gram-scale reactions and facile derivatizations of the enantioenriched products demonstrate the practical utility of this reaction.

19.
J Hazard Mater ; 477: 135221, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-39096630

RESUMEN

The co-contamination of soils by microplastics (MPs) and cadmium (Cd), one of the most perilous heavy metals, is emerging as a significant global concern, posing risks to plant productivity and human health. However, there remains a gap in the literature concerning comprehensive evaluations of the combined effects of MPs and Cd on soil-plant-human systems. This review examines the interactions and co-impacts of MPs and Cd in soil-plant-human systems, elucidating their mechanisms and synergistic effects on plant development and health risks. We also review the origins and contamination levels of MPs and Cd, revealing that sewage, atmospheric deposition, and biosolid applications are contributors to the contamination of soil with MPs and Cd. Our meta-analysis demonstrates that MPs significantly (p<0.05) increase the bioavailability of soil Cd and the accumulation of Cd in plant shoots by 6.9 and 9.3 %, respectively. The MPs facilitate Cd desorption from soils through direct adsorption via surface complexation and physical adsorption, as well as indirectly by modifying soil physicochemical properties, such as pH and dissolved organic carbon, and altering soil microbial diversity. These interactions augment the bioavailability of Cd, along with MPs, adversely affect plant growth and its physiological functions. Moreover, the ingestion of MPs and Cd through the food chain significantly enhances the bioaccessibility of Cd and exacerbates histopathological alterations in human tissues, thereby amplifying the associated health risks. This review provides insights into the coexistence of MPs and Cd and their synergistic effects on soil-plant-human systems, emphasizing the need for further research in this critical subject area.


Asunto(s)
Cadmio , Microplásticos , Contaminantes del Suelo , Cadmio/toxicidad , Cadmio/análisis , Contaminantes del Suelo/toxicidad , Contaminantes del Suelo/análisis , Contaminantes del Suelo/metabolismo , Humanos , Microplásticos/toxicidad , Plantas/efectos de los fármacos , Plantas/metabolismo , Suelo/química
20.
ACS Sens ; 9(8): 4069-4078, 2024 Aug 23.
Artículo en Inglés | MEDLINE | ID: mdl-39136380

RESUMEN

Enantioselective recognition is a fundamental property of chiral linkers in chiral metal-organic frameworks (CMOFs). However, clarifying the efficient enantioselective discrimination tailored by achiral linkers remains challenging to explain the chiral recognition mechanism and efficiency. Here, two CMOFs ([Zn2(l-Phe)2(bpa)2]n and [Zn2(l-Phe)2(bpe)2]n) with the completely different enantioselective recognition are synthesized from different nonchiral ligands and the same chiral ligands. The enantioselective recognition of CMOF is undoubtedly related to l-Phe, which differs in the hydrogen bonding to the Trp enantiomer. However, the electrochemical signals are weak and undifferentiated. [Zn2(l-Phe)2(bpe)2]n produces a flattened coplanar conformation with the -C═C- tether in the achiral ligand. The flattened achiral bpee ligand and its surrounding chiral phenylalanine molecules interact through multiple π-π stacking and hydrogen bonding, which together create a chiral sensor that facilitates the recognition of l-Trp. However, [Zn2(l-Phe)2(bpa)2]n produces a stepped conformation due to the -C-C- tether in the achiral ligand; despite the recognition effect of bpea, the recognition is unsatisfactory. Therefore, the chiral recognition of the two CMOFs stems from the synergistic effect between chiral and achiral ligands. This work shows that nonchiral ligands are also crucial in determining enantiomeric discrimination and opens up a new avenue for designing chiral materials.


Asunto(s)
Estructuras Metalorgánicas , Zinc , Estructuras Metalorgánicas/química , Ligandos , Estereoisomerismo , Zinc/química , Técnicas Electroquímicas/métodos , Fenilalanina/química , Fenilalanina/análogos & derivados , Enlace de Hidrógeno
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