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The Journal of Physical Chemistry... Jun 2024This work reports the observation and characterization of heterobinuclear transition-metal main-group metal oxide carbonyl complex anions, RuGeO(CO) ( = 3-5), by...
This work reports the observation and characterization of heterobinuclear transition-metal main-group metal oxide carbonyl complex anions, RuGeO(CO) ( = 3-5), by combining mass-selected photoelectron velocity map imaging spectroscopy and quantum chemistry calculations. The experimentally determined vertical electron detachment energy of RuGeO(CO) surpasses those of RuGeO(CO) and RuGeO(CO), which is attributed to distinctive bonding features. RuGeO(CO) manifests one covalent σ and two Ru-to-Ge dative π bonds, contrasting with the sole covalent σ bond present in RuGeO(CO) and RuGeO(CO). Unpaired spin density distribution analysis reveals a 17-electron configuration at the Ru center in RuGeO(CO) and an 18-electron configuration in RuGeO(CO) and RuGeO(CO). This work closes a gap in the quantitative physicochemical characterization of heteronuclear oxide carbonyl complexes, enhancing our insights into catalytic processes of CO/GeO on the metal surface at the molecular level.
PubMed: 38940497
DOI: 10.1021/acs.jpclett.4c01532 -
International Journal of Molecular... Aug 2024Osteosarcoma (OS) is a highly malignant primary bone neoplasm that is the leading cause of cancer‑associated death in young people. GNE‑477 belongs to the second...
Osteosarcoma (OS) is a highly malignant primary bone neoplasm that is the leading cause of cancer‑associated death in young people. GNE‑477 belongs to the second generation of mTOR inhibitors and possesses promising potential in the treatment of OS but dose tolerance and drug toxicity limit its development and utilization. The present study aimed to prepare a novel HO stimulus‑responsive dodecanoic acid (DA)‑phenylborate ester‑dextran (DA‑B‑DEX) polymeric micelle delivery system for GNE‑477 and evaluate its efficacy. The polymer micelles were characterized by morphology, size and critical micelle concentration. The GNE‑477 loaded DA‑B‑DEX (GNE‑477@DBD) tumor‑targeting drug delivery system was established and the release of GNE‑477 was measured. The cellular uptake of GNE‑477@DBD by three OS cell lines (MG‑63, U2OS and 143B cells) was analyzed utilizing a fluorescent tracer technique. The hydroxylated DA‑B was successfully grafted onto dextran at a grafting rate of 3%, suitable for forming amphiphilic micelles. Following exposure to HO, the DA‑B‑DEX micelles ruptured and released the drug rapidly, leading to increased uptake of GNE‑477@DBD by cells with sustained release of GNE‑477. The experiments, including MTT assay, flow cytometry, western blotting and RT‑qPCR, demonstrated that GNE‑477@DBD inhibited tumor cell viability, arrested cell cycle in G1 phase, induced apoptosis and blocked the PI3K/Akt/mTOR cascade response. , through the observation of mice tumor growth and the results of H&E staining, the GNE‑477@DBD group exhibited more positive therapeutic outcomes than the free drug group with almost no adverse effects on other organs. In conclusion, HO‑responsive DA‑B‑DEX presents a promising delivery system for hydrophobic anti‑tumor drugs for OS therapy.
Topics: Animals; Humans; Micelles; Osteosarcoma; Hydrogen Peroxide; Cell Line, Tumor; Dextrans; Mice; Lauric Acids; Apoptosis; Polymers; Xenograft Model Antitumor Assays; Bone Neoplasms; Mice, Nude; Antineoplastic Agents; Mice, Inbred BALB C; Male; TOR Serine-Threonine Kinases
PubMed: 38940336
DOI: 10.3892/ijmm.2024.5393 -
ACS Nano Jun 2024Lithium-sulfur (Li-S) batteries are promising for next-generation high-energy energy storage systems. However, the slow reaction kinetics render mobile polysulfides...
Lithium-sulfur (Li-S) batteries are promising for next-generation high-energy energy storage systems. However, the slow reaction kinetics render mobile polysulfides hardly controlled, yielding shuttling effects and eventually damaging Li metal anodes. To improve the cyclability of Li-S batteries, high-efficiency catalysts are desired to accelerate polysulfide conversion and suppress the shuttling effect. Herein, we studied a doping system with NiP and NiB as the end members and found a B-doped NiP catalyst that demonstrates high activity for Li-S batteries. As anionic dopants, B demonstrates an interesting reverse electron transfer to P and tunes the electronic structure of NiP dramatically. The resultant B-doped NiP exhibits short Ni-B bonds and strong Ni-S interaction, and the electron donation of B to P further enhances the adsorption of polysulfide on catalysts. The S-S bonds of polysulfides were activated appropriately, therefore decreasing a low energy barrier for conversion reactions.
PubMed: 38940334
DOI: 10.1021/acsnano.4c03315 -
Angewandte Chemie (International Ed. in... Jun 2024The continuous electrolyte decomposition and uncontrolled dendrite growth caused by the unstable solid electrolyte interphase (SEI) have largely hindered the development...
The continuous electrolyte decomposition and uncontrolled dendrite growth caused by the unstable solid electrolyte interphase (SEI) have largely hindered the development of Li metal batteries. Here, we demonstrate that tuning the facet of current collector can regulate the composition of SEI and the subsequent Li deposition behavior using single-crystal Cu foils as an ideal platform. The theoretical and experimental studies reveal that the (100) facet of Cu possesses strong adsorption to anions, guiding more anions to participate preferentially in the inner Helmholtz plane and further promoting the formation of the stable inorganic-rich SEI. Consequently, the single-crystal Cu foils with a single [100] orientation (s-Cu(100)) achieve the dendrite-free Li deposition with enhanced Li plating/stripping reversibility. Moreover, the Li anode deposited on s-Cu(100) can stabilize the operation of an Ah-level pouch cell (350 Wh kg-1) with a low negative/positive capacity ratio (~2) and lean electrolyte (2.4 g Ah-1) for 150 cycles. Impressively, this strategy demonstrates universality in a series of electrolytes employed different anions. This work provides new insights into the correlation between the SEI and current collector, opening a universal avenue towards high-performance Li metal batteries.
PubMed: 38940290
DOI: 10.1002/anie.202407064 -
Advanced Materials (Deerfield Beach,... Jun 2024Sulfurized polyacrylonitrile (SPAN) has recently emerged as a promising cathode for high-energy Li metal batteries owing to its high capacity, extended cycle life, and...
Sulfurized polyacrylonitrile (SPAN) has recently emerged as a promising cathode for high-energy Li metal batteries owing to its high capacity, extended cycle life, and liberty from costly transition metals. As the high capacities of both Li metal and SPAN lead to relatively small electrode weights, the weight and specific energy density of Li/SPAN batteries are particularly sensitive to electrolyte weight, highlighting the importance of minimizing electrolyte density. In addition, the large volume changes of Li metal anode and SPAN cathode require inorganic-rich interphases that can guarantee intactness and protectivity throughout long cycles. This work addresses these crucial aspects with an electrolyte design in which lightweight dibutyl ether (DBE) is used as diluent for concentrated LiFSI-triethyl phosphate (TEP) solution. The designed electrolyte (d = 1.04 g mL) is 40-50% lighter than conventional localized high-concentration electrolytes (LHCEs), leading to 12-20% extra energy density at the cell level. Besides, the use of DBE introduces substantial solvent-diluent affinity, resulting in a unique solvation structure with strengthened capability to form favorable anion-derived inorganic-rich interphases, minimize electrolyte consumption, and improve cell cyclability. Our electrolyte also exhibits lower volatility than carbonate electrolytes and offers enhanced protection to both Li metal anode and SPAN cathode under thermal abuse. This article is protected by copyright. All rights reserved.
PubMed: 38940263
DOI: 10.1002/adma.202406594 -
Journal of Global Health Jun 2024Diarrhoeal disease disproportionately affects children <5 years in low- and middle-income countries (LMICs). The pathogens responsible for diarrhoea are commonly... (Meta-Analysis)
Meta-Analysis
Lifestraw Family water filters in low- and middle-income countries: a systematic review and meta-analysis to define longer-term public health impact against childhood diarrhoea and inform scale-up.
BACKGROUND
Diarrhoeal disease disproportionately affects children <5 years in low- and middle-income countries (LMICs). The pathogens responsible for diarrhoea are commonly transmitted through faecally-contaminated drinking water. Lifestraw Family point-of-use water filters have been the subject of intervention studies for over a decade and were the first filters evaluated by the World Health Organization in its water treatment evaluation scheme to provide comprehensive protection against many diarrhoea-causing pathogens. This systematic review aimed to: 1) report on aspects related to physical environment and implementation and 2) conduct an updated meta-analysis on Lifestraw Family filter effectiveness against childhood diarrhoea based on studies with ≥12 months of follow-up.
METHODS
We conducted a literature search in November 2022 using MEDLINE, Embase, Cochrane, and CINAHL databases. Inclusion criteria were: 1) RCTs, cluster-RCTs, quasi-experimental, or matched cohort studies on 2) Lifestraw Family 1.0 or 2.0 filters 3) conducted in LMICs 4) that evaluated filter effectiveness against diarrhoea in children <5 and 5) analysed ≥12 months of follow-up data on clinical effectiveness against diarrhoea and were 6) published from 2010 with 7) full-text availability in English. A modified Newcastle-Ottawa Scale was used to assess risk of bias. Relative risk (RR) and 95% confidence intervals (CIs) were extracted and analysed using a random-effects meta-analysis.
RESULTS
We included 6 studies in LMICs involving 4740 children <5. Of the four clinically-effective interventions, common characteristics were access to improved water sources (75%), the 2.0 version of the filter or the 1.0 version with additional water storage (100%), use of behaviour change theory, community engagement, and health messaging (75%), local filter repair-and-replace mechanisms (75%), and specially-trained local interventionists (100%). The meta-analysis showed a 30% reduction in diarrhoea risk in the intervention group (RR = 0.69; 95% CI = 0.52-0.91, P = 0.01).
CONCLUSIONS
Lifestraw Family water filters can be effective interventions to reduce diarrhoea in vulnerable paediatric populations for at least one year, though certain aspects related to physical environment and implementation may increase their public health impact. The findings of this study suggest considerations for scale-up that can be applied in settings in need of longer-term interim solutions until universal access to safe drinking water is achieved.
Topics: Humans; Diarrhea; Developing Countries; Water Purification; Public Health; Filtration; Child, Preschool; Drinking Water; Infant
PubMed: 38939952
DOI: 10.7189/jogh.14.04018 -
Exploration (Beijing, China) Jun 2024COVID-19 is currently pandemic and the detection of SARS-CoV-2 variants in wastewater is causing widespread concern. Herein, cold atmospheric plasma (CAP) is proposed as...
COVID-19 is currently pandemic and the detection of SARS-CoV-2 variants in wastewater is causing widespread concern. Herein, cold atmospheric plasma (CAP) is proposed as a novel wastewater disinfection technology that effectively inactivates SARS-CoV-2 transcription- and replication-competent virus-like particles, coronavirus GX_P2V, pseudotyped SARS-CoV-2 variants, and porcine epidemic diarrhoea virus in a large volume of water within 180 s (inhibition rate > 99%). Further, CAP disinfection did not adversely affect the viability of various human cell lines. It is identified that CAP produced peroxynitrite (ONOO), ozone (O), superoxide anion radicals (O ), and hydrogen peroxide (HO) as the major active substances for coronavirus disinfection. Investigation of the mechanism showed that active substances not only reacted with the coronavirus spike protein and affected its infectivity, but also destroyed the nucleocapsid protein and genome, thus affecting virus replication. This method provides an efficient and environmentally friendly strategy for the elimination of SARS-CoV-2 and other coronaviruses from wastewater.
PubMed: 38939868
DOI: 10.1002/EXP.20230012 -
Chemical Science Jun 2024Alkali metal alkoxides play a pivotal role in nucleophilic alkoxylation reactions, offering pathways for the synthesis of ethers, including the increasingly sought-after...
Alkali metal alkoxides play a pivotal role in nucleophilic alkoxylation reactions, offering pathways for the synthesis of ethers, including the increasingly sought-after trifluoromethyl ethers. However, the synthesis of long-chain perfluoroalkyl ethers remains a substantial challenge in this field. Through the innovative use of triglyme to encapsulate potassium ions, we enhanced the stability of short-lived, longer-chain perfluoroalkoxy anions, thereby facilitating efficient nucleophilic perfluoroalkoxylation reactions. This method provides a new precedent for the halo-perfluoroalkoxylation of -difluoroalkenes and offers a versatile tool for the design of perfluoroalkyl ethers, including those containing complex moieties of heterocycles and drug molecules. We also demonstrated the utility of the resulting halo-perfluoroalkoxyl adducts through various chemical transformations to valuable diverse perfluoroalkyl ethers.
PubMed: 38939153
DOI: 10.1039/d4sc02084g -
Chemical Science Jun 2024Transition-metal compounds (TMCs) have recently become promising candidates as lithium-sulfur (Li-S) battery cathode materials because they have unique adsorption and...
Transition-metal compounds (TMCs) have recently become promising candidates as lithium-sulfur (Li-S) battery cathode materials because they have unique adsorption and catalytic properties. However, the relationship between the anionic species and performance has not been sufficiently revealed. Herein, using FeCoNiX (X = O, S, and P) compounds as examples, we systematically studied the effects of the anion composition of FeCoNiX compounds on the adsorption and catalytic abilities of sulfur cathodes in Li-S batteries. Adsorption tests and density functional theory calculations showed that the adsorption ability toward lithium polysulfides follows the order: FeCoNiP > FeCoNiO > FeCoNiS, while ultraviolet-visible spectroscopy and cyclic voltammetry revealed that the catalytic ability for lithium polysulfide conversion follows the order: FeCoNiP > FeCoNiS > FeCoNiO. These results indicate that FeCoNiP is an excellent polysulfide immobilizer and catalyst that restricts shuttling and improves reaction kinetics. Electrochemical tests further demonstrated that the FeCoNiP cathode delivered superior cycling performance to FeCoNiO or FeCoNiS. In addition, the battery performance order is consistent with that of catalytic ability, which suggests that catalytic ability plays a key influencing role in batteries. This study provides new insight into the use of O-, S-, and P-doped TMCs as functional sulfur carriers.
PubMed: 38939152
DOI: 10.1039/d4sc01628a -
Chemical Science Jun 2024Bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI) is commonly used as an effective dopant to improve the performance of the hole-transporting material (HTM) in...
Bis(trifluoromethane)sulfonimide lithium salt (Li-TFSI) is commonly used as an effective dopant to improve the performance of the hole-transporting material (HTM) in n-i-p perovskite solar cells (PSCs). However, the ultra-hygroscopic and migratory nature of Li-TFSI leads to inferior stability of PSCs. Here, we report on a strategy to regulate the anion unit in Li-TFSI from linear to cyclic, constructing a new dopant, lithium 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide (Li-CYCLIC), for the state-of-the-art poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA). Mechanistic and experimental results reveal that the cyclic anion CYCLIC exhibits stronger interaction with Li and PTAA˙ compared with the linear anion TFSI, thus significantly restraining the moisture absorption and migration of Li and improving the thermodynamic stability of PTAA˙CYCLIC. With this molecular engineering, the resulting PSCs based on Li-CYCLIC obtained an improved efficiency, along with remarkably enhanced stability, retaining 96% of the initial efficiency after over 1150 hours under continuous 1 sun illumination in an N atmosphere, yielding an extrapolated of over 12 000 hours. In a broader context, the proposed strategy of linear-to-cyclic doping provides substantial guidance for the subsequent advancement in the development of effective dopants for photoelectric devices.
PubMed: 38939142
DOI: 10.1039/d4sc02020k