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1.
Angew Chem Int Ed Engl ; : e202412707, 2024 Aug 13.
Artigo em Inglês | MEDLINE | ID: mdl-39136931

RESUMO

Photo-driven cross-coupling of o-arylenediamines and alcohols has emerged as an alternative for the synthesis of bio-active benzimidazoles. However, tackling the key problem related to efficient adsorption and activation of both coupling partners over photocatalysts towards activity enhancement remains a challenge. Here, we demonstrate an efficient interface synergy strategy by coupling exposed oxygen vacancies (VO) and Pd Lewis acid sites for benzimidazole and hydrogen (H2) coproduction over Pd-loaded TiO2 nanospheres with the highest photoredox activity compared to previous works so far. The results show that the introduction of VO optimizes the energy band structure and supplies coordinatively unsaturated sites for adsorbing and activating ethanol molecules, affording acetaldehyde active intermediates. Pd acts as a Lewis acid site, enhancing the adsorption of alkaline amine moleculesvia Lewis acid-base pair interactions and driving the condensation process. Furthermore, VO and Pd synergistically promote interfacial charge transfer and separation. This work offers new insightful guidance for the rational design of semiconductor-based photocatalysts with interface synergy at the molecular level towards the high-performance coproduction of renewable fuels and value-added feedstocks.

2.
Health Econ ; 2024 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-38937927

RESUMO

Federal authorities banned nursing home visitation in the early days of the coronavirus disease 2019 (COVID-19) pandemic. However, there was growing concern that physical isolation may have unintended harms on nursing home residents. Thus, nursing homes and policymakers faced a tradeoff between minimizing COVID-19 outbreaks and limiting the unintended harms. Between June 2020 and January 2021, 17 states implemented Essential Caregiver policies (ECPs) allowing nursing home visitation by designated family members or friends under controlled circumstances. Using the Nursing Home COVID-19 Public File and other relevant data, we analyze the effects of ECPs on deaths among nursing home residents. We exploit variation in the existence of ECPs across states and over time, finding that these policies effectively reduce both non-COVID-19 and COVID-19 deaths, resulting in a decrease in total deaths. These effects are larger for states that implemented policies mandatorily or without restrictions, indicating a dose-response relationship. These policies reduce non-COVID-19 deaths in facilities with higher quality or staffing levels, while reducing COVID-19 deaths in facilities with lower quality or staffing levels. Our findings support the use and expansion of ECPs to balance resident safety and the need for social interaction and informal care during future pandemics.

3.
Angew Chem Int Ed Engl ; 63(34): e202407791, 2024 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-38860734

RESUMO

Light-driven photoredox catalysis presents a promising approach for the activation and conversion of methane (CH4) into high value-added chemicals under ambient conditions. However, the high C-H bond dissociation energy of CH4 and the absence of well-defined C-H activation sites on catalysts significantly limit the highly efficient conversion of CH4 toward multicarbon (C2+) hydrocarbons, particularly ethylene (C2H4). Herein, we demonstrate a bimetallic design of Ag nanoparticles (NPs) and Pd single atoms (SAs) on ZnO for the cascade conversion of CH4 into C2H4 with the highest production rate compared with previous works. Mechanistic studies reveal that the synergistic effect of Ag NPs and Pd SAs, upon effecting key bond-breaking and -forming events, lowers the overall energy barrier of the activation process of both CH4 and the resulting C2H6, constituting a truly synergistic catalytic system to facilitate the C2H4 generation. This work offers a novel perspective on the advancement of photocatalytic directional CH4 conversion toward high value-added C2+ hydrocarbons through the subtle design of bimetallic cascade catalyst strategy.

4.
Int. j. morphol ; 42(3): 692-697, jun. 2024. ilus
Artigo em Inglês | LILACS | ID: biblio-1564635

RESUMO

SUMMARY: To measure and study the anatomical morphological data of the lumbar 5 to sacral 1 intervertebral space with the aid of CT and design an anatomical anterior lumbosacral 3D printed integrated interbody fusion for the treatment of degenerative lumbosacral spine diseases. 100 adults (50 of each sex) who underwent CT examination of the lumbar spine in our hospital were selected, and their lumbar 5 to sacral 1 intervertebral space anatomical data were measured, including the anterior lumbar convexity angle, different sagittal and coronal heights, and the sagittal and coronal diameters of the superior and inferior endplates. The measured data were also statistically analyzed, and morphological design and study of the 3D printed integrated fusion device in the anterior lumbosacral spine was performed by applying computer software. When comparing the coronal and sagittal diameters of the superior and inferior endplates from lumbar 5 to sacral 1, the differences were statistically greater in men than in women (P0.001). When comparing the height at different positions in the median sagittal plane, both males and females showed an anterior high and posterior low pattern. In the coronal plane, both males and females showed the highest height in the middle position (P0.001). CT can measure the anatomical data of the lumbosacral spinal hiatus more accurately. The 3D-printed anterior integrated fusion device of the lumbosacral spine designed according to the analysis of the data results is more in line with the anatomical structure of the lumbosacral spine, fits well with the superior and inferior endplates, and effectively restores the height and anterior convexity angle of the lumbosacral space.


El objetivo de este trabajo fue medir y estudiar los datos morfológicos anatómicos del espacio intervertebral lumbar 5 a sacro 1 con la ayuda de TC y diseñar una fusión intersomática integrada anatómica lumbosacra anterior impresa en 3D para el tratamiento de enfermedades degenerativas de la columna lumbosacra. Se seleccionaron en nuestro hospital 100 adultos (50 de cada sexo) que se sometieron a un examen de TC de la columna lumbar y se midieron los datos anatómicos del espacio intervertebral lumbar 5 al sacro 1, incluyendo el ángulo de la convexidad lumbar anterior, diferentes alturas sagital y coronal, y los diámetros sagital y coronal de las placas terminales superior e inferior. Los datos medidos también se analizaron estadísticamente y se realizó el diseño morfológico y el estudio del dispositivo de fusión integrado impreso en 3D en la columna lumbosacra anterior mediante la aplicación de software informático. Al comparar los diámetros coronal y sagital de las placas terminales superior e inferior desde lumbar 5 hasta sacro 1, las diferencias fueron estadísticamente mayores en hombres que en mujeres (P 0,001). Al comparar la altura en diferentes posiciones en el plano mediano, tanto hombres como mujeres mostraron un patrón anterior alto y posterior bajo. En el plano coronal, tanto hombres como mujeres mostraron la altura más alta en la posición media (P0,001). La TC puede medir los datos anatómicos del hiato espinal lumbosacro con mayor precisión. El dispositivo de fusión anterior integrado impreso en 3D de la columna lumbosacra diseñado de acuerdo con el análisis de los resultados de los datos está más en línea con la estructura anatómica de la columna lumbosacra, se adapta bien a las placas terminales superior e inferior y restaura eficazmente la altura y la parte anterior del ángulo de convexidad del espacio lumbosacro.


Assuntos
Humanos , Masculino , Feminino , Adolescente , Adulto , Adulto Jovem , Impressão Tridimensional , Vértebras Lombares/diagnóstico por imagem , Coluna Vertebral , Tomografia Computadorizada Espiral , Vértebras Lombares/anatomia & histologia
5.
Health Serv Res ; 2024 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-38804024

RESUMO

OBJECTIVE: Medicaid-funded long-term services and supports are increasingly provided through home- and community-based services (HCBS) to promote continued community living. While an emerging body of evidence examines the direct benefits and costs of HCBS, there may also be unexplored synergies with Medicare-funded post-acute care (PAC). This study aimed to provide empirical evidence on how the use of Medicaid HCBS influences Medicare PAC utilization among the dually enrolled. DATA SOURCES: National Medicare claims, Medicaid claims, nursing home assessment data, and home health assessment data from 2016 to 2018. STUDY DESIGN: We estimated the relationship between prior Medicaid HCBS use and PAC (skilled nursing facilities [SNF] or home health) utilization in a national sample of duals with qualifying index hospitalizations. We used inverse probability weights to create balanced samples on observed characteristics and estimated multivariable regression with hospital fixed effects and extensive controls. We also conducted stratified analyses for key subgroups. DATA EXTRACTION METHODS: The primary sample included 887,598 hospital discharges from community-dwelling duals who had an eligible index hospitalization between April 1, 2016, and September 30, 2018. PRINCIPAL FINDINGS: We found HCBS use was associated with a 9 percentage-point increase in the use of home health relative to SNF, conditional on using PAC, and a meaningful reduction in length of stay for those using SNF. In addition, in our primary sample, we found HCBS use to be associated with an overall increase in PAC use, given that the absolute increase in home health use was larger than the absolute decrease in SNF use. In other words, the use of Medicaid-funded HCBS was associated with a shift in Medicare-funded PAC use toward home-based settings. CONCLUSION: Our findings indicate potential synergies between Medicaid-funded HCBS and increased use of home-based PAC, suggesting policymakers should cautiously consider these dynamics in HCBS expansion efforts.

6.
ACS Appl Mater Interfaces ; 16(2): 2554-2563, 2024 Jan 17.
Artigo em Inglês | MEDLINE | ID: mdl-38166372

RESUMO

Flexible pressure sensors have been widely concerned because of their great application potential in the fields of electronic skin, human-computer interaction, health detection, and so on. In this paper, a flexible pressure sensor is designed, with polydimethylsiloxane (PDMS) films with protruding structure as elastic substrate and poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS)/cellulose nanocrystals (CNC) as conductive-sensitive material. The flexible pressure sensor has a wide linear detection range (0-100 kPa), outstanding sensitivity (2.32 kPa-1), and stability of more than 2000 cycles. The sensor has been proven to be able to detect a wide range of human movements (finger bending, elbow bending, etc.) and small movements (breathing, pulse, etc.). In addition, the pressure sensor array can detect the pressure distribution and judge the shape of the object. A smart wristband equipped with four flexible pressure sensors is designed. Among them, the k-nearest neighbor (KNN) algorithm is used to classify sensor data to achieve high accuracy (99.52%) recognition of seven kinds of wrist posture. This work provides a new opportunity to fabricate simple, flexible pressure sensors with potential applications in the next-generation electronic skin, health detection, and intelligent robotics.


Assuntos
Postura , Punho , Humanos , Movimento (Física) , Movimento , Dimetilpolisiloxanos
7.
Nat Genet ; 55(12): 2243-2254, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-38036791

RESUMO

Broomcorn millet (Panicum miliaceum L.) is an orphan crop with the potential to improve cereal production and quality, and ensure food security. Here we present the genetic variations, population structure and diversity of a diverse worldwide collection of 516 broomcorn millet genomes. Population analysis indicated that the domesticated broomcorn millet originated from its wild progenitor in China. We then constructed a graph-based pangenome of broomcorn millet based on long-read de novo genome assemblies of 32 representative accessions. Our analysis revealed that the structural variations were highly associated with transposable elements, which influenced gene expression when located in the coding or regulatory regions. We also identified 139 loci associated with 31 key domestication and agronomic traits, including candidate genes and superior haplotypes, such as LG1, for panicle architecture. Thus, the study's findings provide foundational resources for developing genomics-assisted breeding programs in broomcorn millet.


Assuntos
Panicum , Panicum/genética , Panicum/química , Domesticação , Melhoramento Vegetal , Fenótipo , Genômica
8.
Angew Chem Int Ed Engl ; 62(41): e202311731, 2023 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-37632151

RESUMO

Solar-driven CO2 reduction integrated with C-C/C-X bond-forming organic synthesis represents a substantially untapped opportunity to simultaneously tackle carbon neutrality and create an atom-/redox-economical chemical synthesis. Herein, we demonstrate the first cooperative photoredox catalysis of efficient and tunable CO2 reduction to syngas, paired with direct alkylation/arylation of unactivated allylic sp3 C-H bonds for accessing allylic C-C products, over SiO2 -supported single Ni atoms-decorated CdS quantum dots (QDs). Our protocol not only bypasses additional oxidant/reductant and pre-functionalization of organic substrates, affording a broad of allylic C-C products with moderate to excellent yields, but also produces syngas with tunable CO/H2 ratios (1 : 2-5 : 1). Such win-win coupling catalysis highlights the high atom-, step- and redox-economy, and good durability, illuminating the tantalizing possibility of a renewable sunlight-driven chemical feedstocks manufacturing industry.

9.
Chem Soc Rev ; 52(15): 5013-5050, 2023 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-37431250

RESUMO

The ubiquity of solid-liquid interfaces in nature and the significant role of their atomic-scale structure in determining interfacial properties have led to intensive research. Particularly in electrocatalysis, however, a molecular-level picture that clearly describes the dynamic interfacial structures and organizations with their correlation to preferred reaction pathways in electrochemical reactions remains poorly understood. In this review, CO2 electroreduction reaction (CO2RR) is spatially and temporally understood as a result of intricate interactions at the interface, in which the interfacial features are highly relevant. We start with the discussion of current understandings and model development associated with the charged electrochemical interface as well as its dynamic landscape. We further highlight the interactive dynamics from the interfacial field, catalyst surface charges and various gradients in electrolyte and interfacial water structures at interfaces under CO2RR working conditions, with emphasis on the interfacial-structure dependence of catalytic reactivity/selectivity. Significantly, a probing energy-dependent "in situ characterization map" for dynamic interfaces based on various complementary in situ/operando techniques is proposed, aiming to present a comprehensive picture of interfacial electrocatalysis and to provide a more unified research framework. Moreover, recent milestones in both experimental and theoretical aspects to establish the correct profile of electrochemical interfaces are stressed. Finally, we present key scientific challenges with related perspectives toward future opportunities for this exciting frontier.

10.
Angew Chem Int Ed Engl ; 62(29): e202304306, 2023 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-37208951

RESUMO

Benzimidazoles are a versatile class of scaffolds with important biological activities, whereas their synthesis in a lower-cost and more efficient manner remains a challenge. Here, we demonstrate a conceptually new radical route for the high-performance photoredox coupling of alcohols and diamines to synthesize benzimidazoles along with stoichiometric hydrogen (H2 ) over Pd-decorated ultrathin ZnO nanosheets (Pd/ZnO NSs). The mechanistic study reveals the unique advantage of ZnO NSs over other supports and particularly that the features of Pd nanoparticles in facilitating the cleavage of the α-C-H bond of alcohols and adsorbing subsequently-generated C-centered radicals hold the key to turning on the reaction. This work highlights a new insight into radical-induced efficient benzimidazole synthesis pairing with H2 evolution by rationally designing semiconductor-based photoredox systems.

11.
Research (Wash D C) ; 6: 0073, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36930756

RESUMO

Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis. Here, we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catalysis toward the oxidation of 1-phenylethanol to acetophenone/2,3-diphenyl-2,3-butanediol (pinacol) integrated with the reduction of protons to H2. The strong interaction and typical type-I band-position alignment between CdS quantum dots and ZnS quantum dots result in efficient separation and transfer of electron-hole pairs, thus distinctly enhancing the coupled photocatalyzed-redox activity and stability. The optimal ZnS-CdS hybrid also delivers a superior performance for various aromatic alcohol coupling photoredox reaction, and the ratio of electrons and holes consumed in such redox reaction is close to 1.0, indicating a high atom economy of cooperative coupling catalysis. In addition, by recycling the scattered light in the near field of a SiO2 sphere, the SiO2-supported ZnS-CdS (denoted as ZnS-CdS/SiO2) catalyst can further achieve a 3.5-fold higher yield than ZnS-CdS hybrid. Mechanistic research clarifies that the oxidation of 1-phenylethanol proceeds through the pivotal radical intermediates of •C(CH3)(OH)Ph. This work is expected to promote the rational design of semiconductor quantum dots-based heterostructured catalysts for coupling photoredox catalysis in organic synthesis and clean fuels production.

12.
Angew Chem Int Ed Engl ; 62(22): e202303054, 2023 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-36988009

RESUMO

Photocatalytic epoxide alcoholysis through C-O bond cleavage and formation has emerged as an alternative to synthesizing anti-tumoral pharmaceuticals and fine chemicals. However, the lack of crucial evidence to interpret the interaction between reactants and photocatalyst surface makes it challenging for photocatalytic epoxide alcoholysis with both high activity and regioselectivity. In this work, we report the hierarchical ZnIn2 S4 @CdS photocatalyst for epoxide alcoholysis with high regioselectivity nearly 100 %. Mechanistic studies unveil that the precise activation switch on exposed Zn acid sites for C-O bond polarization and cleavage has a critical significance for achieving efficient photocatalytic performance. Furthermore, the establishment of Z-scheme heterojunction facilitates the interface charge separation and transfer. Remarkably, the underlying regioselective photocatalytic reaction pathway has been distinctly revealed.

13.
ACS Nano ; 16(10): 17444-17453, 2022 10 25.
Artigo em Inglês | MEDLINE | ID: mdl-36170635

RESUMO

Semiconductor-based photoredox catalysis brings an innovative strategy for sustainable organic transformation (e.g., C-C/C-X bond formation), via radical coupling under mild conditions. However, since semiconductors interact with photogenerated radicals unselectively, the precise control of selectivity for such organic synthesis by steering radical conversion is extremely challenging. Here, by the judicious design of a structurally well-defined and atomically dispersed cocatalyst over semiconductor quantum dots, we demonstrate the precise selectivity switch on high-performance selective heterogeneous coupling photosynthesis of a C-C bond or a C-N bond along with hydrogen production over the Ni-oxo cluster and single Pd atom-decorated CdS quantum dots crafted onto the SiO2 support. Mechanistic studies unveil that the Ph(•CH)NH2 and PhCH2NH2•+ act as dominant radical intermediates for such divergent organic synthesis of C-C coupled vicinal diamines and C-N coupled imines, as respectively enabled by Ni-oxo clusters assisted radical-radical coupling and single Pd atom-assisted radical addition-elimination. This work overcomes the pervasive difficulties of selectivity regulation in semiconductor-based photochemical synthesis, highlighting a vista of utilizing atomically dispersed cocatalysts as active sites to maneuver unselective radical conversion by engineering quantum dots toward selective heterogeneous photosynthesis.


Assuntos
Pontos Quânticos , Pontos Quânticos/química , Dióxido de Silício , Semicondutores , Fotossíntese , Hidrogênio , Diaminas , Iminas
14.
ACS Phys Chem Au ; 2(3): 216-224, 2022 May 25.
Artigo em Inglês | MEDLINE | ID: mdl-36855572

RESUMO

Simultaneously utilizing photogenerated electrons and holes in one photocatalytic system to synthesize value-added chemicals and clean hydrogen (H2) energy meets the development requirements of green chemistry. Herein, we report a binary material of CdS/BiVO4 combining one-dimensional (1D) CdS nanorods (NRs) with two-dimensional (2D) BiVO4 nanosheets (NSs) constructed through a facile electrostatic self-assembly procedure for the selectively photocatalytic oxidation of aromatic alcohols integrated with H2 production, which exhibits significantly enhanced photocatalytic performance. Within 2 h, the conversion of aromatic alcohols over CdS/BiVO4-25 was approximately 9-fold and 40-fold higher than that over pure CdS and BiVO4, respectively. The remarkably improved photoactivity of CdS/BiVO4 hybrids is mainly ascribed to the Z-scheme charge separation mechanism in the 1D/2D heterostructure derived from the interface contact between CdS and BiVO4, which not only facilitates the separation and transfer of charge carriers, but also maintains the strong reducibility of photogenerated electrons and strong oxidizability of photogenerated holes. It is anticipated that this work will further stimulate interest in the rational design of 1D/2D Z-scheme heterostructure photocatalysts for the selective fine chemical synthesis integrated with H2 evolution.

15.
Chem Rev ; 121(21): 13051-13085, 2021 11 10.
Artigo em Inglês | MEDLINE | ID: mdl-34378934

RESUMO

Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as the sole energy input. Following this dual-functional photocatalytic strategy, a dreamlike reaction pathway for constructing C-C/C-X (X = C, N, O, S) bonds from abundant and readily available X-H bond-containing compounds with concomitant release of H2 can be readily fulfilled without the need of external chemical reagents, thus offering a green and fascinating organic synthetic strategy. In this review, we begin by presenting a concise overview on the general background of traditional photocatalytic H2 production and then focus on the fundamental principles of cooperative photoredox coupling of selective organic synthesis and H2 production by simultaneous utilization of photoexcited electrons and holes over semiconductor-based catalysts to meet the economic and sustainability goal. Thereafter, we put dedicated emphasis on recent key progress of cooperative photoredox coupling of H2 production and various selective organic transformations, including selective alcohol oxidation, selective methane conversion, amines oxidative coupling, oxidative cross-coupling, cyclic alkanes dehydrogenation, reforming of lignocellulosic biomass, and so on. Finally, the remaining challenges and future perspectives in this flourishing area have been critically discussed. It is anticipated that this review will provide enlightening guidance on the rational design of such dual-functional photoredox reaction system, thereby stimulating the development of economical and environmentally benign solar fuel generation and organic synthesis of value-added fine chemicals.


Assuntos
Hidrogênio , Semicondutores , Catálise , Técnicas de Química Sintética , Hidrogênio/química , Estresse Oxidativo
16.
Sci Total Environ ; 798: 149268, 2021 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-34333432

RESUMO

Antimicrobial resistance (AMR) has become a public health concern; but antibiotic resistance genes (ARGs) and integrons that link to AMR of Escherichia coli from non-human primates remain largely unknown. This study aimed to investigate antibiotic resistance, emerging environmental pollutants ARGs, and integrons factors (intI1, intI2 and intI3) in 995 E. coli isolates obtained from 50 species of captive non-human primates of 13 zoos in China. Our result showed 83.62% of the E. coli isolates were resistant to at least one antibiotic and 47.94% isolates showed multiple drug resistances (MDR). The E. coli isolates mainly showed resistance to tetracycline (tetracycline 62.71%, doxycycline 61.11%), ß-lactams (ampicillin 54.27%, amoxicillin 52.36%), and sulfonamide (trimethoprim-sulfamethoxazole 36.78%). A total of 423 antibiotic resistance patterns were observed, of which DOX/TET (49 isolates, 4.92%) was the most common pattern. Antibiotic resistance rates among 13 zoos had a significant difference (P < 0.01). We further detected 22 ARGs in the 995 E. coli isolates, of which tetA had the highest occurrence (70.55%). The presence of integrons class 1 and 2 were 24.22% and 1.71%, respectively, while no class 3 integron was found. Significant positive associations were observed among integrons and antibiotics, of which the strongest association was observed for integrons / Gentamicin (OR, 2.642) and integrons / Cefotaxime (OR, 2.512). In addition, cassette arrays were detected in 64 strains of class 1 integron-positive isolates (26.56%) and 10 strains of class 2 integron-positive isolates (58.82%). Eighteen cassette arrays were found within 64 class 1 integron isolates, while 3 cassette arrays were identified within 10 class 2 integron isolates. Our results indicate a high diversity of antibiotic resistance phenotypes in non-human primate E. coli isolates, which carry multiple ARGs and integrons. Corresponding preventive measures should be taken to prevent the spread of integron-mediated ARGs in non-human primates and their living environments in zoos.


Assuntos
Infecções por Escherichia coli , Integrons , Animais , Antibacterianos/farmacologia , Farmacorresistência Bacteriana/genética , Farmacorresistência Bacteriana Múltipla/genética , Escherichia coli/genética , Infecções por Escherichia coli/epidemiologia , Integrons/genética , Testes de Sensibilidade Microbiana , Prevalência , Primatas
17.
Chem Soc Rev ; 50(13): 7539-7586, 2021 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-34002737

RESUMO

Metal phosphides (MPs) with unique and desirable physicochemical properties provide promising potential in practical applications, such as the catalysis, gas/humidity sensor, environmental remediation, and energy storage fields, especially for transition metal phosphides (TMPs) and MPs consisting of group IIIA and IVA metal elements. Most studies, however, on the synthesis of MP nanomaterials still face intractable challenges, encompassing the need for a more thorough understanding of the growth mechanism, strategies for large-scale synthesis of targeted high-quality MPs, and practical achievement of functional applications. This review aims at providing a comprehensive update on the controllable synthetic strategies for MPs from various metal sources. Additionally, different passivation strategies for engineering the structural and electronic properties of MP nanostructures are scrutinized. Then, we showcase the implementable applications of MP-based materials in emerging sustainable catalytic fields including electrocatalysis, photocatalysis, mild thermocatalysis, and related hybrid systems. Finally, we offer a rational perspective on future opportunities and remaining challenges for the development of MPs in the materials science and sustainable catalysis fields.

18.
Angew Chem Int Ed Engl ; 60(39): 21150-21172, 2021 Sep 20.
Artigo em Inglês | MEDLINE | ID: mdl-33908154

RESUMO

Photocatalytic reduction of CO2 to solar fuels and/or fine chemicals is a promising way to increase the energy supply and reduce greenhouse gas emissions. However, the conventional reaction system for CO2 photoreduction with pure H2 O or sacrificial agents usually suffers from low catalytic efficiency, poor stability, or cost-ineffective atom economy. A recent surge of developments, in which photocatalytic CO2 valorization is integrated with selective organic synthesis into one reaction system, indicates an efficient modus operandi that enables sufficient utilization of photogenerated electrons and holes to achieve the goals for sustainable economic and social development. In this Review we discuss current advances in cooperative photoredox reaction systems that integrate CO2 valorization with organics upgrading based on heterogeneous photocatalysis. The applications and virtues of this strategy and the underlying reaction mechanisms are discussed. The ongoing challenges and prospects in this area are critically discussed.

19.
Medicine (Baltimore) ; 100(12): e25093, 2021 Mar 26.
Artigo em Inglês | MEDLINE | ID: mdl-33761671

RESUMO

ABSTRACT: Based on the Thompson classification of intervertebral discs (IVDs), we systematically analyzed gene expression differences between severely degenerated and mildly degenerated IVDs and explored the underlying molecular mechanisms using bioinformatics methods and multichip integration. We used multiomics analysis, includes mRNA microarray and methylation chips, to explore the genetic network and mechanisms of lumbar disc herniation (LDH). Subsequently, the Combat function of the R language SVA package was applied to eliminate heterogeneity between the gene expression data. And the protein-protein interaction (PPI) network, gene ontology (GO), and molecular pathways were used to constructs the mechanisms network. Consequently, we obtained 149 differentially expressed genes. Related molecular pathways are the following: ribosome activity, oxidative phosphorylation, extracellular matrix response. Besides, through PPI network analysis, genes with higher connectivity such as UBA52, RPLP0, RPL3, RPLP2, and RPL27 were also identified, suggesting that they play important regulatory roles in the complex network associated with LDH. Additionally, cg12556991 (RPL27) and cg06852319 (RPLP0) were found to be LDH-related candidate DNA methylation modification sites in the IVDs tissue of LDH patients. In conclusions, ribosome activity, oxidative phosphorylation, and extracellular matrix response may be potential molecular mechanisms underlying LDH, while hub genes involved in UBA52, RPLP0, RPL3, RPLP2, and RPL27, and candidate DNA methylation modification sites of cg12556991and cg06852319 are likely key regulators in the development of LDH.


Assuntos
Metilação de DNA/genética , Matriz Extracelular/genética , Deslocamento do Disco Intervertebral/genética , Fosforilação/genética , Proteínas Ribossômicas/genética , Biologia Computacional , Expressão Gênica/genética , Perfilação da Expressão Gênica , Ontologia Genética , Redes Reguladoras de Genes/genética , Humanos , Vértebras Lombares/metabolismo , Análise em Microsséries , Mapas de Interação de Proteínas/genética , RNA Mensageiro/metabolismo , Proteína Ribossômica L3
20.
JAMA Intern Med ; 181(5): 590-597, 2021 05 01.
Artigo em Inglês | MEDLINE | ID: mdl-33587092

RESUMO

Importance: Safety-net hospitals (SNHs) operate under limited financial resources and have had challenges providing high-quality care. Medicaid expansion under the Affordable Care Act led to improvements in hospital finances, but whether this was associated with better hospital quality, particularly among SNHs given their baseline financial constraints, remains unknown. Objective: To compare changes in quality from 2012 to 2018 between SNHs in states that expanded Medicaid vs those in states that did not. Design, Setting, and Participants: Using a difference-in-differences analysis in a cohort study, performance on quality measures was compared between SNHs, defined as those in the highest quartile of uncompensated care in the pre-Medicaid expansion period, in expansion vs nonexpansion states, before and after the implementation of Medicaid expansion. A total of 811 SNHs were included in the analysis, with 316 in nonexpansion states and 495 in expansion states. The study was conducted from January to November 2020. Exposures: Time-varying indicators for Medicaid expansion status. Main Outcomes and Measures: The primary outcome was hospital quality measured by patient-reported experience (Hospital Consumer Assessment of Healthcare Providers and Systems Survey), health care-associated infections (central line-associated bloodstream infections, catheter-associated urinary tract infections, and surgical site infections following colon surgery) and patient outcomes (30-day mortality and readmission rates for acute myocardial infarction, heart failure, and pneumonia). Secondary outcomes included hospital financial measures (uncompensated care and operating margins), adoption of electronic health records, provision of safety-net services (enabling, linguistic/translation, and transportation services), or safety-net service lines (trauma, burn, obstetrics, neonatal intensive, and psychiatric care). Results: In this difference-in-differences analysis of a cohort of 811 SNHs, no differential changes in patient-reported experience, health care-associated infections, readmissions, or mortality were noted, regardless of Medicaid expansion status after the Affordable Care Act. There were modest differential increases between 2012 and 2016 in the adoption of electronic health records (mean [SD]: nonexpansion states, 99.4 [7.4] vs 99.9 [3.8]; expansion states, 94.6 [22.6] vs 100.0 [2.2]; 1.7 percentage points; P = .02) and between 2012 and 2018 in the number of inpatient psychiatric beds (mean [SD]: nonexpansion states, 24.7 [36.0] vs 23.6 [39.0]; expansion states: 29.3 [42.8] vs 31.4 [44.3]; 1.4 beds; P = .02) among SNHs in expansion states, although they were not statistically significant at a threshold adjusted for multiple comparisons. In subgroup analyses comparing SNHs with higher vs lower baseline operating margins, an isolated differential improvement was noted in heart failure readmissions among SNHs with lower baseline operating margins in expansion states (mean [SD], 22.8 [2.1]; -0.53 percentage points; P = .001). Conclusions and Relevance: This difference-in-differences cohort study found that despite reductions in uncompensated care and improvements in operating margins, there appears to be little evidence of quality improvement among SNHs in states that expanded Medicaid compared with those in states that did not.


Assuntos
Medicaid/normas , Provedores de Redes de Segurança/normas , Estudos de Coortes , Humanos , Medicaid/tendências , Avaliação de Resultados em Cuidados de Saúde/métodos , Avaliação de Resultados em Cuidados de Saúde/estatística & dados numéricos , Patient Protection and Affordable Care Act/normas , Patient Protection and Affordable Care Act/tendências , Satisfação do Paciente , Provedores de Redes de Segurança/tendências , Estados Unidos
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