Effects of essential caregiver policies on COVID-19 and non-COVID-19 deaths in nursing homes.

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.

Spatially and temporally understanding dynamic solid-electrolyte interfaces in carbon dioxide electroreduction.

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.

Bimetallic Single Atom/Nanoparticle Ensemble for Efficient Photochemical Cascade Synthesis of Ethylene from Methane.

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.

Interface Synergy of Exposed Oxygen Vacancy and Pd Lewis Acid Sites Enabling Superior Cooperative Photoredox Synthesis.

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.

Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts.

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.

Efficient and Direct Functionalization of Allylic sp3 C-H Bonds with Concomitant CO2 Reduction.

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.

Exposed Zinc Sites on Hybrid ZnIn2 S4 @CdS Nanocages for Efficient Regioselective Photocatalytic Epoxide Alcoholysis.

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.

New Radical Route and Insight for the Highly Efficient Synthesis of Benzimidazoles Integrated with Hydrogen Evolution.

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.

Nanostructured metal phosphides: from controllable synthesis to sustainable catalysis.

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.

Coupling Strategy for CO2 Valorization Integrated with Organic Synthesis by Heterogeneous Photocatalysis.

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.

Cooperative Syngas Production and C-N Bond Formation in One Photoredox Cycle.

Solar-driven syngas production by CO2 reduction provides a sustainable strategy to produce renewable feedstocks. However, this promising reaction often suffers from tough CO2 activation, sluggish oxidative half-reaction kinetics and undesired by-products. Herein, we report a function-oriented strategy of deliberately constructing black phosphorus quantum dots-ZnIn2 S4 (BP/ZIS) heterostructures for solar-driven CO2 reduction to syngas, paired with selectively oxidative C-N bond formation, in one redox cycle. The optimal BP/ZIS heterostructure features the enhanced charge-carrier separation and enriched active sites for cooperatively photocatalytic syngas production with a tunable ratio of CO/H2 and efficient oxidation of amines to imines with high conversion and selectivity. This prominent catalytic performance arises from the efficient electronic coupling between black phosphorus quantum dots and ZnIn2 S4 , as well as the optimized adsorption strength for key reaction intermediates, as supported by both experimental and theoretical investigations. We also demonstrate a synergistic interplay between CO2 reduction and amine dehydrogenation oxidation, rather than simply collecting these two single half-reactions in this dual-functional photoredox system.

Earth-Abundant MoS2 and Cobalt Phosphate Dual Cocatalysts on 1D CdS Nanowires for Boosting Photocatalytic Hydrogen Production.

Cocatalysts play a significant role in accelerating the catalytic reactions of semiconductor photocatalyst. In particular, a semiconductor assembled with dual cocatalysts, i.e., reduction and oxidation cocatalysts, can obviously enhance the photocatalytic performance because of the synergistic effect of fast consumption of photogenerated electrons and holes simultaneously. However, in most cases, noble metal cocatalysts are employed, which tremendously increases the cost of the photocatalysts and restricts their large-scale applications. Herein, on the platform of one-dimensional (1D) CdS nanowires, we have utilized the earth-abundant dual cocatalysts, MoS2 and cobalt phosphate (Co-Pi), to construct the CdS@MoS2@Co-Pi (CMC) core-shell hybrid photocatalysts. In this dual-cocatalyst system, Co-Pi is in a position to expedite the migration of holes from CdS, while MoS2 acts as an electron transporter as well as active sites to accelerate the surface water reduction reaction. Taking the advantages of the dual-cocatalyst system, the prepared CMC hybrid shows an obvious enhancement of both the photoactivity and photostability toward hydrogen production compared with bare 1D CdS nanowires and binary hybrids (CdS@MoS2 and CdS@Co-Pi). This work highlights the promising prospects for rational utilization of earth-abundant dual cocatalysts to design low-cost and efficient hybrids toward boosting photoredox catalysis.

Broadband Light Harvesting and Unidirectional Electron Flow for Efficient Electron Accumulation for Hydrogen Generation.

The efficiency of solar hydrogen evolution closely depends on the multiple electrons accumulation on the catalytic center for two-electron-involved water reduction. Herein, we report an effective approach to enable broadband light absorption and unidirectional electron flow for efficiently accumulating electrons at active sites for hydrogen evolution by rationally engineering the nanostructure of Pt nanoparticles (NPs), TiO2 , and SiO2 support. In addition to Schottky-junction-driven electron transfer from TiO2 to Pt, Pt NPs also produce hot electrons by recycling the scattered visible and near-infrared (vis-NIR) light of the support. Unidirectional electron flow to active sites is realized by tuning the components spatial distribution. These features collectively accumulate multiple electrons at catalytic Pt sites, thereby affording enhanced activity toward hydrogen evolution under simulated sunlight.

The role of Medicaid home- and community-based services in use of Medicare post-acute care.

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.

PDMS Film-Based Flexible Pressure Sensor Array with Surface Protruding Structure for Human Motion Detection and Wrist Posture Recognition.

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.

Heterostructure-Engineered Semiconductor Quantum Dots toward Photocatalyzed-Redox Cooperative Coupling Reaction.

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.

Pangenome analysis reveals genomic variations associated with domestication traits in broomcorn millet.

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.

Engineering Semiconductor Quantum Dots for Selectivity Switch on High-Performance Heterogeneous Coupling Photosynthesis.

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.

Nanoscale Assembly of CdS/BiVO4 Hybrids for Coupling Selective Fine Chemical Synthesis and Hydrogen Production under Visible Light.

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.

Relative contributions of hospital versus skilled nursing facility quality on patient outcomes.

BACKGROUND: Hospitals and health systems worldwide have adopted value-based payment to improve quality and reduce costs. In the USA, skilled nursing facilities (SNFs) are now financially penalised for higher-than-expected readmission rates. However, the extent to which SNFs contribute to, and should thus be held accountable for, readmission rates is unknown. To compare the relative contributions of hospital and SNF quality on readmission rates while controlling for unobserved patient characteristics. METHODS: Retrospective cohort study of Medicare beneficiaries, 2010-2016. Acute care hospitals and SNFs in the USA. Medicare beneficiaries with two hospitalisations followed by SNF admissions, divided into two groups: (1) patients who went to different hospitals but were discharged to the same SNF after both hospitalisations and (2) patients who went to the same hospital but were discharged to different SNFs. Hospital-level and SNF-level quality, using a lagged measure of 30-day risk-standardised readmission rates (RSRRs). Readmission within 30 days of hospital discharge. RESULTS: There were 140 583 patients who changed hospitals but not SNFs, and 183 232 who changed SNFs but not hospitals. Patients who went to the lowest-performing hospitals (highest RSRR) had a 0.9% higher likelihood of readmission (p=0.005) compared with patients who went to the highest-performing hospitals (lowest RSRR). In contrast, patients who went to the lowest-performing SNFs had a 2% higher likelihood of readmission (p<0.001) compared with patients to went to the highest-performing SNFs. CONCLUSIONS: The association between SNF quality and patient outcomes was larger than the association between hospital quality and patient outcomes among postacute care patients. Holding postacute care providers accountable for their quality may be an effective strategy to improve SNF quality.