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Nanosizing confers unique functions in materials such as graphene and quantum dots. Here, we present two nanoscale-covalent organic frameworks (nano-COFs) that exhibit exceptionally high activity for photocatalytic hydrogen production that results from their size and morphology. Compared to bulk analogues, the downsizing of COFs crystals using surfactants provides greatly improved water dispersibility and light-harvesting properties. One of these nano-COFs shows a hydrogen evolution rate of 392.0 mmol g−1 h−1 (33.3 μmol h−1), which is one of the highest mass-normalized rates reported for a COF or any other organic photocatalysts. A reverse concentration-dependent photocatalytic phenomenon is observed, whereby a higher photocatalytic activity is found at a lower catalyst concentration. These materials also show a molecule-like excitonic nature, as studied by photoluminescence and transient absorption spectroscopy, which is again a function of their nanoscale dimensions. This charts a new path to highly efficient organic photocatalysts for solar fuel production.Nanosizing covalent organic frameworks using surfactants provides greatly improved water dispersibility and light-harvesting properties, leading to dramatically enhanced photocatalytic hydrogen production performance. Here the authors observe a reverse concentration-dependent photocatalytic phenomeno, whereby a higher photocatalytic activity is found at a lower catalyst concentration. [ABSTRACT FROM AUTHOR]

Introduction: There is growing evidence within the healthcare sector that employee investigations can harm individuals involved in the process, an organization's culture and the delivery of its services. Methods: This paper details an intervention developed by an NHS Wales organization to reduce the number of its employee investigations through an organization-wide focus that promoted a 'last resort' approach and introduced the concept of 'avoidable employee harm'. A range of associated improvement initiatives were developed to support behavior change among those responsible for determining whether an employee investigation should be initiated. Results: Over a 13-month period, organizational records showed an annual reduction of 71% in investigation cases post-intervention, resulting in an estimated 3,308 sickness days averted annually and total estimated annual savings of £738,133 (based on direct savings and costs averted). This indicates that the organization has started to embrace the "last resort" approach to using employee investigations to address work place issues. The programme was supported with training for those responsible for commissioning and leading the organization's employee investigations. Analysis of survey data from those who attended training workshops to support the programme indicated that participants showed an increased awareness of the employee investigation process post-workshop and an understanding of the concept of avoidable employee harm. Discussion: The programme is congruent with the Healthy Healthcare concept, as the study illustrates how its practices and processes have a beneficial impact on staff, as well as potentially on patients. This study highlights wider issues for consideration, including the: (1) the role of Human Resources (HR), (2) taking a multi-disciplinary approach, (3) culture and practice, (4) the responsibility of the wider HR profession. [ABSTRACT FROM AUTHOR]

The Dark Energy Spectroscopic Instrument Milky Way Survey (DESI MWS) will explore the assembly history of the Milky Way by characterizing remnants of ancient dwarf galaxy accretion events and improving constraints on the distribution of dark matter in the outer halo. We present mock catalogues that reproduce the selection criteria of MWS and the format of the final MWS data set. These catalogues can be used to test methods for quantifying the properties of stellar halo substructure and reconstructing the Milky Way's accretion history with the MWS data, including the effects of halo-to-halo variance. The mock catalogues are based on a phase-space kernel expansion technique applied to star particles in the Auriga suite of six high-resolution lambda-cold dark matter magnetohydrodynamic zoom-in simulations. They include photometric properties (and associated errors) used in DESI target selection and the outputs of the MWS spectral analysis pipeline (radial velocity, metallicity, surface gravity, and temperature). They also include information from the underlying simulation, such as the total gravitational potential and information on the progenitors of accreted halo stars. We discuss how the subset of halo stars observable by MWS in these simulations corresponds to their true content and properties. These mock Milky Ways have rich accretion histories, resulting in a large number of substructures that span the whole stellar halo out to large distances and have substantial overlap in the space of orbital energy and angular momentum. [ABSTRACT FROM AUTHOR]

Addressing the global fossil energy crisis necessitates the efficient utilization of sustainable energy sources. Hydrogen, a green fuel, can be generated using sunlight, water, and a photocatalyst. Employing sensitizers holds promise for enhancing photocatalyst performance, enabling high rates of hydrogen evolution through increased visible light absorption. However, sifting through millions of diverse molecules to identify suitable dyes for specific photocatalysts poses a significant challenge. In this study, we integrate genetic algorithm and geometry-frequency-noncovalent extended tight binding methods to efficiently screen 2.6 million potential sensitizers with a D–π–A–π–AA structure within a short timeframe. Subsequently, these optimized sensitizers are rigorously reassessed by using DFT/TDDFT methods, elucidating why they may serve as superior dyes compared to the reference dye WS5F, particularly in terms of light absorption, driving force, binding energy, etc. Additionally, our methodology uncovers molecular motifs of particular interest, including the furan π-bridge and the double cyano anchoring acceptor, which are prevalent in the most promising set of molecules. The developed genetic algorithm workflow and dye design principles can be extended to various compelling projects, such as dye-sensitized solar cells, organic photovoltaics, photo-induced redox reactions, pharmaceuticals, and beyond. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are useful synthetic materials that are built by the programmed assembly of metal nodes and organic linkers1. The success of MOFs results from the isoreticular principle2, which allows families of structurally analogous frameworks to be built in a predictable way. This relies on directional coordinate covalent bonding to define the framework geometry. However, isoreticular strategies do not translate to other common crystalline solids, such as organic salts3–5, in which the intermolecular ionic bonding is less directional. Here we show that chemical knowledge can be combined with computational crystal-structure prediction6 (CSP) to design porous organic ammonium halide salts that contain no metals. The nodes in these salt frameworks are tightly packed ionic clusters that direct the materials to crystallize in specific ways, as demonstrated by the presence of well-defined spikes of low-energy, low-density isoreticular structures on the predicted lattice energy landscapes7,8. These energy landscapes allow us to select combinations of cations and anions that will form thermodynamically stable, porous salt frameworks with channel sizes, functionalities and geometries that can be predicted a priori. Some of these porous salts adsorb molecular guests such as iodine in quantities that exceed those of most MOFs, and this could be useful for applications such as radio-iodine capture9–12. More generally, the synthesis of these salts is scalable, involving simple acid–base neutralization, and the strategy makes it possible to create a family of non-metal organic frameworks that combine high ionic charge density with permanent porosity.The use of computational crystal-structure prediction has enabled the targeted assembly of frameworks of porous organic ammonium halide salts that have many of the qualities of metal–organic frameworks despite containing no metal. [ABSTRACT FROM AUTHOR]

The anterolateral system (ALS) is a major ascending pathway from the spinal cord that projects to multiple brain areas and underlies the perception of pain, itch, and skin temperature. Despite its importance, our understanding of this system has been hampered by the considerable functional and molecular diversity of its constituent cells. Here, we use fluorescence-activated cell sorting to isolate ALS neurons belonging to the Phox2a-lineage for single-nucleus RNA sequencing. We reveal five distinct clusters of ALS neurons (ALS1-5) and document their laminar distribution in the spinal cord using in situ hybridization. We identify three clusters of neurons located predominantly in laminae I-III of the dorsal horn (ALS1-3) and two clusters with cell bodies located in deeper laminae (ALS4 and ALS5). Our findings reveal the transcriptional logic that underlies ALS neuronal diversity in the adult mouse and uncover the molecular identity of two previously identified classes of projection neurons. We also show that these molecular signatures can be used to target groups of ALS neurons using retrograde viral tracing. Overall, our findings provide a valuable resource for studying somatosensory biology and targeting subclasses of ALS neurons. [ABSTRACT FROM AUTHOR]

The solar‐driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo‐generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed‐linker strategy to build a donor‐acceptor‐acceptor (D–A–A) type covalent organic framework (COF) photocatalyst, FS‐OHOMe‐COF. The FS‐OHOMe‐COF structure features extended π–π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS‐OHOMe‐COF has a low exciton binding energy, long excited‐state lifetime and high photo‐stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h−1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment. [ABSTRACT FROM AUTHOR]

The solar‐driven photocatalytic production of hydrogen peroxide (H2O2) from water and oxygen using semiconductor catalysts offers a promising approach for converting solar energy into storable chemical energy. However, the efficiency of photocatalytic H2O2 production is often restricted by the low photo‐generated charge separation, slow surface reactions and inadequate stability. Here, we developed a mixed‐linker strategy to build a donor‐acceptor‐acceptor (D–A–A) type covalent organic framework (COF) photocatalyst, FS‐OHOMe‐COF. The FS‐OHOMe‐COF structure features extended π–π conjugation that improves charge mobility, while the introduction of sulfone units not only as active sites facilitates surface reactions with water but also bolsters stability through increased interlayer forces. The resulting FS‐OHOMe‐COF has a low exciton binding energy, long excited‐state lifetime and high photo‐stability that leads to high performance for photocatalytic H2O2 production (up to 1.0 mM h−1) with an H2O2 output of 19 mM after 72 hours of irradiation. Furthermore, the catalyst demonstrates high stability, which sustained activity over 192 hours of photocatalytic experiment. [ABSTRACT FROM AUTHOR]

The United Arab Emirates (UAE) joined the BRICS‐led New Development Bank (NDB) as part of its first expansion in terms of membership. Questions regarding the interests and rationale of the UAE in joining the Bank, on the one hand, and the NDB's logic in granting membership to the UAE, on the other, immediately jump out. This article sheds light on the BRICS' cautious move away from exceptionality via the expanded NDB in the context of its membership criteria and approach. It does so by also highlighting the UAE's exceptionality, with a focus on the combination of fiscal resources and strategic geography, in the context of shifting global distributions of power. It finds that the UAE's membership in the NDB dovetails with its memberships in other MDBs, which, in turn, are part of the country's ambition to be seen as a globally influential actor. In turn, the NDB was attracted to the UAE fiscal acumen, credit rating and its carefully cultivated culture of cutting‐edge, sustainable, infrastructure and connectivity projects, as well as innovation. [ABSTRACT FROM AUTHOR]

Robotic automation is proving itself indispensable in the modern Chemistry laboratory, but adoption is slowed down by the technical challenges of implementing such systems. This paper reports on a novel adaptive gripper mechanism that can easily and reliably grasp cylindrical and prismatic objects of various sizes with limited clearance required. The proposed design exploits the inherent compliance of a cable that is driven to fully envelope the target object. The cable is run through a rigid finger, allowing the loop to be placed around objects with minimal clearance required and to provide support for the object once the grip is complete. Thanks to the compliant nature of the mechanism, the gripper requires minimal control effort to complete a gasping task. A prototype of the gripper has been designed and built for chemistry automation tasks, where it showed very high grasp reliability with ≤ 1 % grasp failures. [ABSTRACT FROM AUTHOR]

Conjugated polymers are promising materials for photocatalytic hydrogen evolution. However, most reported materials are not solution‐processible, limiting their potential for large‐scale application, for example as solution cast films. Flexible side‐chains are commonly introduced to provide solubility, but these often impart unfavorable properties, such as hydrophobicity, which lowers photocatalytic activity. Here, computational predictions are employed to aid in the design of chloroform soluble polymer photocatalysts that show increased planarity through favorable intramolecular interactions. Using this approach, three conjugated polymer photocatalysts with identical poly(benzene‐dibenzo[b,d]thiophene sulfone) backbones but different solubilizing side‐chains on the benzene‐ring are explored, i.e., tri(ethylene glycol), n‐decyloxy, and n‐dodecyl. These side‐chain variations significantly alterr the properties of the polymers, specifically energy levels, optical gap, and wettability. The hydrophobic n‐decyloxy functionalized polymer has a sacrificial hydrogen evolution rate of 17.0 µmol h−1 in suspension, while the hydrophilic tri(ethylene glycol) functionalized polymer is almost three times more active (45.4 µmol h−1). Conversely, no hydrogen evolution is observed for the purely alkyl side‐chain (n‐dodecyl) containing polymer due to the side‐chain induced torsion of the backbone. A thin‐film of the most active polymer exhibits a promising area‐normalized sacrificial hydrogen evolution rate of 7.4 ± 0.3 mmol h−1 m−2 under visible light irradiation. [ABSTRACT FROM AUTHOR]

In terms of institutional positioning, the quartet of Indo‐Pacific states – Australia, India, Japan, and the United States – firmly endorse ASEAN. 'ASEAN centrality' is clearly highlighted in all Quad statements. Yet, the Quad presents an organizational and substantive challenge to the core institutional model of ASEAN. This competitive dynamic, with respect to style of associational methods (the how) as opposed to organizational purpose (the why), has not received the scholarly attention it deserves. If the literature does focus on the comparative approaches of ASEAN and the Quad, the prism is for the most part targeted on the differences with respect to the engagement with China. Our analysis is different and emphasizes the contrast between two types of institutional informality exhibited by ASEAN and the Quad. By situating our analysis in the context of contested informality, we point out that both ASEAN and the Quad are signposts showing that the foundational privilege of formal international organizations is under stress, albeit from a wide range of institutional designs. Only by detailing and evaluating the critical divergence in modes of informality can an appreciation of the nature and impact of the contest between ASEAN and the Quad be fully understood. [ABSTRACT FROM AUTHOR]

Chirality was traditionally considered a binary property of periodic lattices and crystals. However, the classes of two‐dimensional lattices modulo rigid motion form a continuous space, which was recently parametrized by three geographic‐style coordinates. The four non‐oblique Bravais classes of two‐dimensional lattices form low‐dimensional singular subspaces in the full continuous space. Now, the deviations of a lattice from its higher symmetry neighbors can be continuously quantified by real‐valued distances satisfying metric axioms. This article analyzes these and newer G‐chiral distances for millions of two‐dimensional lattices that are extracted from thousands of available two‐dimensional materials and real crystal structures in the Cambridge Structural Database. [ABSTRACT FROM AUTHOR]

Crystalline porous organic salts (CPOS) are a subclass of molecular crystals. The low solubility of CPOS and their building blocks limits the choice of crystallisation solvents to water or polar alcohols, hindering the isolation, scale‐up, and scope of the porous material. In this work, high throughput screening was used to expand the solvent scope, resulting in the identification of a new porous salt, CPOS‐7, formed from tetrakis(4‐sulfophenyl)methane (TSPM) and tetrakis(4‐aminophenyl)methane (TAPM). CPOS‐7 does not form with standard solvents for CPOS, rather a hydrated phase (Hydrate2920) previously reported is isolated. Initial attempts to translate the crystallisation to batch led to challenges with loss of crystallinity and Hydrate2920 forming favorably in the presence of excess water. Using acetic acid as a dehydrating agent hindered formation of Hydrate2920 and furthermore allowed for direct conversion to CPOS‐7. To allow for direct formation of CPOS‐7 in high crystallinity flow chemistry was used for the first time to circumvent the issues found in batch. CPOS‐7 and Hydrate2920 were shown to have promise for water and CO2 capture, with CPOS‐7 having a CO2 uptake of 4.3 mmol/g at 195 K, making it one of the most porous CPOS reported to date. [ABSTRACT FROM AUTHOR]

The observations from the Dark Energy Spectroscopic Instrument (DESI) will significantly increase the numbers of known extremely metal-poor stars by a factor of ∼10, improving the sample statistics to study the early chemical evolution of the Milky Way and the nature of the first stars. In this paper we report follow-up observations with high signal-to-noise ratio of nine metal-poor stars identified during the DESI commissioning with the Optical System for Imaging and Low-Resolution Integrated Spectroscopy (OSIRIS) instrument on the 10.4 m Gran Telescopio Canarias. The analysis of the data using a well-vetted methodology confirms the quality of the DESI spectra and the performance of the pipelines developed for the data reduction and analysis of DESI data. [ABSTRACT FROM AUTHOR]

Dropout is a ubiquitous psychotherapy outcome in clinical practice and treatment research alike, yet it remains a poorly understood problem. Contemporary dropout research is dominated by models of prediction that lack a strong theoretical foundation, often drawing on data from clinical trials that report on dropout in an inconsistent and incomplete fashion. In this article, we assert that dropout is a critical treatment outcome that is worthy of investigation as a mechanistic process. After briefly describing the scope of the dropout problem, we discuss the many factors that limit the field's present understanding of dropout. We then articulate and illustrate a transdiagnostic conceptual framework for examining psychotherapy dropout in contemporary research, concluding with recommendations for future research. With a more comprehensive understanding of the factors affecting retention, research efforts can shift toward investigating key processes underlying treatment dropout, thus, boosting prediction and informing strategies to mitigate dropout in clinical practice. [ABSTRACT FROM AUTHOR]

In the context of the revitalized scholarly interest in small and middle powers, we employ a relational network approach to study the role of non-major powers as bridges and hubs. Contrary to prominent conceptions that centre on preconceived country groupings or states' variable attributes, such as the size of their territory, economy, or armed forces, our study foregrounds the influence that states gain from their position in international networks. We begin by developing an ideal-typical theory of bridges and hubs. We then employ these concepts to discuss empirical examples, examining the extent to which our cases embody these ideal types. Our approach sheds light on the rationale for geostrategic relocation and how states can use networks to gain influence in world politics. [ABSTRACT FROM AUTHOR]

Laser cavity-solitons can appear in a microresonator-filtered laser when judiciously balancing the slow nonlinearities of the system. Under certain conditions, such optical states can be made to self-emerge and recover spontaneously, and the understanding of their robustness is critical for practical applications. Here, we study the formation of a bonded state comprising a soliton and a blue-detuned continuous wave, whose coexistence is mediated by dispersion in the nonlinear refractive index. Our real-time dispersive Fourier transform measurements, supported by comprehensive theoretical analysis, reveal the presence of an elastic bonding between the two states, resulting in an enhancement of the soliton's robustness. Cavity-solitons in microresonator-filtered fibre lasers are robust states with self-recovery capabilities that emerge when a delicate balance of energy-dependent nonlinearities is achieved. In this work, the authors make use of the dispersive Fourier transform to understand the dynamics leading to a soliton bonded with a quasi-continuous wave. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure‐property predictions to generate energy‐structure‐function (ESF) maps for a series of triptycene‐based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low‐energy HOF (TH5‐A) with a remarkably low density of 0.374 g cm−3 and three‐dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5‐A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g−1, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date. [ABSTRACT FROM AUTHOR]

Hydrogen‐bonded organic frameworks (HOFs) with low densities and high porosities are rare and challenging to design because most molecules have a strong energetic preference for close packing. Crystal structure prediction (CSP) can rank the crystal packings available to an organic molecule based on their relative lattice energies. This has become a powerful tool for the a priori design of porous molecular crystals. Previously, we combined CSP with structure‐property predictions to generate energy‐structure‐function (ESF) maps for a series of triptycene‐based molecules with quinoxaline groups. From these ESF maps, triptycene trisquinoxalinedione (TH5) was predicted to form a previously unknown low‐energy HOF (TH5‐A) with a remarkably low density of 0.374 g cm−3 and three‐dimensional (3D) pores. Here, we demonstrate the reliability of those ESF maps by discovering this TH5‐A polymorph experimentally. This material has a high accessible surface area of 3,284 m2 g−1, as measured by nitrogen adsorption, making it one of the most porous HOFs reported to date. [ABSTRACT FROM AUTHOR]

Background: Cognitive and behavioraIn this sample of 42 adults with depression,l change procedures have been hypothesized to be key drivers of the therapeutic benefits clients experience in cognitive behavioral therapy (CBT). However, the extent to which these procedures operate through the same or different pathways in bringing about change is unclear. We evaluated whether cognitive or behavioral therapeutic procedures produce distinct coping skills using data from a randomized comparison of cognitive-only and behavioral-only treatments for depression. Methods: Among 42 clients who participated in 8 weeks of cognitive-only or behavioral-only depression treatments, we examined treatment differences in cognitive and behavioral skills. Our analyses focused on overall skillfulness across both domains (i.e., skill strength) as well as the difference in cognitive versus behavioral skills (i.e., skill differentiation). Results: Cognitive and behavioral treatments yielded similar skill strength, but differed in skill differentiation, with more cognitive skill emerging in cognitive treatment and more behavioral skill in the behavioral treatment. Conclusions: Though both approaches produce similar skill gains, cognitive and behavioral therapeutic strategies do appear to translate into a greater development of the skills that were targeted in treatment. [ABSTRACT FROM AUTHOR]

Aim: To identify distinct HbA1c trajectories in people with type 2 diabetes (T2D) starting second‐line glucose‐lowering therapy. Materials and Methods: DISCOVER was a 3‐year observational study of individuals with T2D beginning second‐line glucose‐lowering therapy. Data were collected at initiation of second‐line treatment (baseline) and at 6, 12, 24 and 36 months. Latent class growth modelling was used to identify groups with distinct HbA1c trajectories. Results: After exclusions, 9295 participants were assessed. Four distinct HbA1c trajectories were identified. Mean HbA1c levels decreased between baseline and 6 months in all groups; 72.4% of participants showed stable good levels of glycaemic control over the remainder of follow‐up, 18.0% showed stable moderate levels of glycaemic control and 2.9% showed stable poor levels of glycaemic control. Only 6.7% of participants showed highly improved glycaemic control at month 6 and stable control over the rest of follow‐up. For all groups, dual oral therapy use decreased over time, compensated for by the increasing use of other treatment regimens. Use of injectable agents increased over time in groups with moderate and poor glycaemic control. Logistic regression models suggested that participants from high‐income countries were more probable to be in the stable good trajectory group. Conclusions: Most people receiving second‐line glucose‐lowering treatment in this global cohort achieved stable good or highly improved long‐term glycaemic control. One‐fifth of participants showed moderate or poor glycaemic control during follow‐up. Further large‐scale studies are required to characterize possible factors associated with patterns of glycaemic control to inform personalized diabetes treatment. [ABSTRACT FROM AUTHOR]

Deep Gaussian processes (DGPs) upgrade ordinary GPs through functional composition, in which intermediate GP layers warp the original inputs, providing flexibility to model nonstationary dynamics. Two DGP regimes have emerged in recent literature. A "big data" regime, prevalent in machine learning, favors approximate, optimization-based inference for fast, high-fidelity prediction. A "small data" regime, preferred for computer surrogate modeling, deploys posterior integration for enhanced uncertainty quantification (UQ). We aim to bridge this gap by expanding the capabilities of Bayesian DGP posterior inference through the incorporation of the Vecchia approximation, allowing linear computational scaling without compromising accuracy or UQ. We are motivated by surrogate modeling of simulation campaigns with upwards of 100,000 runs—a size too large for previous fully-Bayesian implementations—and demonstrate prediction and UQ superior to that of "big data" competitors. All methods are implemented in the deepgp package on CRAN. for this article are available online. [ABSTRACT FROM AUTHOR]

Background Carbapenem-resistant Acinetobacter baumannii infections are difficult to treat and are a significant public health threat due to intrinsic/acquired resistance and limited treatment options. Methods A retrospective, observational cohort study in patients receiving cefiderocol via Shionogi's early access program for Acinetobacter spp infections (1 April 2020–30 April 2021; 27 sites; Italy, Spain, Germany, France). Primary outcome was clinical success, defined as clinical resolution of infection at day 14 or day 28 survival. Results Overall, 147 patients were included. Primary infection sites were respiratory (65.3%) and bloodstream (unknown source [15.6%]; catheter-related [10.9%]); 24.5% of patients had polymicrobial infection. Of 136 patients in intensive care (92.5%), 85.3% (116/136) received mechanical ventilation. Septic shock (55.6% [70/126]) and coronavirus disease 2019 (COVID-19) (81.6%) were prevalent. Prior to cefiderocol, 85.0% of patients received gram-negative treatment, 61.2% received ≥2 antimicrobials, and most received colistin (58.5%; median duration, 11.5 days). Cefiderocol monotherapy was used in 30.6% of patients. Clinical success rate was 53.1% and was higher in patients without septic shock (62.5%), without COVID-19 (77.8%), and with lower Sequential Organ Failure Assessment (SOFA) scores (quartile 1 [median, 3; range, 0–5]: 82.9%). Day 28 survival was 44.9% and was higher in patients without septic shock (60.7%), without COVID-19 (59.3%), with lower SOFA score (quartile 1: 82.9%), and receiving first-line cefiderocol (68.2% [15/22]). Resolution of infection at day 14 occurred in 39.5% of patients. Conclusions Despite use in complex patients with limited treatment options and high septic shock/COVID-19 rates, cefiderocol treatment was associated with an overall clinical success rate of 53%. [ABSTRACT FROM AUTHOR]

Background: Eliminating racial/ethnic disparities in physical activity remains a challenge in the United States. South Asian immigrants in the United States have particularly low physical activity levels, and evidence suggests that social context may be important. This study examined associations between personal social networks and moderate to vigorous leisure-time physical activity (MVPA) among South Asians in the United States. Methods: We used cross-sectional data (2014–2017) from 689 South Asians (aged 43–85 y) who participated in the Mediators of Atherosclerosis in South Asians Living in America study. Self-reported physical activity and egocentric network data were collected from participants about their network members. Regression models were used to determine associations between social network characteristics and participants' MVPA. Results: Participants were on average 59 years old (SD = 9) and reported 1335 metabolic equivalent minutes per week of MVPA (interquartile range = 735, 2212). Having network members who exercised or who were exercise partners associated with increased MVPA in men (β coefficient = 241 MET min/wk [95% confidence interval, 63 to 419] and β = 520 MET min/wk [95% confidence interval, 322 to 718], respectively). For women, the association was only significant if the exercise partner was a spouse. Conclusion: Physical activity interventions utilizing network members as exercise partners may have potential in South Asians but must consider gender differences. [ABSTRACT FROM AUTHOR]

The expanding profile of Chinese international development aid has generated strong academic and policy interests. A growing literature has emerged on Chinese foreign aid's motivations, modalities, and impact. However, a significant lacuna remains in the domestic politics relating to this phenomenon. This gap is especially glaring in public opinion concerning China's growing foreign aid programs. By analyzing empirical data gathered from a variety of sources, including a well-established online forum, social media sites of two influential media organizations, and multi-year surveys of residents of Beijing, this paper presents a nuanced picture of what the Chinese public thinks of Chinese foreign aid and tests two popular explanations of public opposition to foreign aid—perceived budgetary trade-offs and more general dissatisfaction with government policies. [ABSTRACT FROM AUTHOR]

Aims: There is limited research using real‐world data to evaluate protective cardiovascular effects of glucagon‐like peptide‐1 (GLP‐1) agonists among adults with type 2 diabetes (T2D) early in treatment. Materials and Methods: We conducted a retrospective, active comparator cohort study using 2011–2015 administrative claims data to compare cardiovascular disease (CVD) event rates following initiation of exenatide extended‐release (E‐ER), exenatide immediate‐release (E‐IR) or liraglutide in T2D adults who previously received no other antidiabetic medication (ADM) except metformin. The primary outcome was time to first major adverse CVD event (ischaemic heart disease, stroke, congestive heart failure or peripheral arterial disease) after starting GLP‐1. Cox proportional hazards regression was used to model the association between index GLP‐1 and CVD events, adjusting for baseline patient, prescriber and plan characteristics. Primary analyses included all patients with ≥2 prescription fills for the index GLP‐1, regardless of subsequent refill adherence or initiation of other ADM after index date. Results: Compared with liraglutide, neither E‐ER nor E‐IR was associated with risk of composite major CVD events (hazard ratios [HRs] for E‐ER and E‐IR: 1.33 [95% C.I. 0.73–2.39] and 1.30 [0.81–2.09]). No associations were observed between event rates for individual CVD components. The HR for an ischaemic event with E‐IR relative to liraglutide was 1.85 (95% C.I. 0.97–3.53). Adjusting for time‐varying exposure to other ADM and CVD medications after index date produced similar results. Conclusions: Initiating either immediate or extended‐release exenatide rather than liraglutide was not associated with significant differences in CVD risk in this observational real‐world study. [ABSTRACT FROM AUTHOR]

Background/Aims: Recent incidents have raised awareness about how corporate decisions and behaviour can negatively affect the health and wellbeing of healthcare professionals. This article uses a case study to explore the harm that failing to follow human resources procedures can cause to individuals, organisational culture and effectiveness, and make recommendations to improve practice. Methods: Seven experts from a range of professional backgrounds offered opinions on an individual case study involving the misapplication of a human resources policy, considering how it may have deviated from lawful practice and the potential impact this had on both the individual and the organisation. Thematic analysis was carried out on this qualitative feedback to identify superordinate and subordinate themes. Results: The thematic analysis identified four superordinate themes: failure to follow organisational policies; impact on the individual; impact on the organisation; and failure to learn. Conclusions: Poor application of human resources procedures can cause harm to individuals and organisations in a number of different ways. Human resources departments need to actively protect the health and wellbeing of the individual/s involved in investigative procedures, rather than focusing solely on executing the process. [ABSTRACT FROM AUTHOR]

Coastal erosion in Cyrenaica (Eastern Libya) represents a major problem for archaeology and heritage management. The area is rich in archaeological sites, often understudied or not fully documented, but also has extensive stretches of vulnerable eroding coastline. This study demonstrates the extent and impact of erosion via shoreline change assessment at two spatial scales. Firstly, wide area assessment using shorelines extracted from a time-series of medium-resolution Landsat imagery. Secondly, site-specific assessment using recent and historic Very High Resolution (VHR) satellite imagery. In both cases, extracted shorelines at different timesteps were compared using the Digital Shoreline Analysis System (DSAS) tool to quantify rates and magnitudes of shoreline movement. The results show extensive zones of erosion at and around the key ancient harbour sites of Apollonia, Ptolemais and Tocra. They also suggest increased rates of coastal retreat in recent years, which is likely linked to anthropogenic actions such as sand mining and urbanization. Forecasts based on present-day shoreline change rates, coupled with ground-level documentation of the vulnerable shorelines is used to identify archaeological features and structures which will likely be progressively damaged or destroyed over the next 20 years. The ability to actively protect archaeological sites is unclear, but there is a clear need for mitigation in the form of enhanced awareness of environmental problems (e.g. caused by sand mining) and more intensive survey/documentation of sites and areas which will be lost in the coming years. [ABSTRACT FROM AUTHOR]

Hydrogenases are microbial metalloenzymes capable of catalyzing the reversible interconversion between molecular hydrogen and protons with high efficiency, and have great potential in the development of new electrocatalysts for renewable fuel production. Here, we engineered the intact proteinaceous shell of the carboxysome, a self-assembling protein organelle for CO2 fixation in cyanobacteria and proteobacteria, and sequestered heterologously produced [NiFe]-hydrogenases into the carboxysome shell. The protein-based hybrid catalyst produced in E. coli shows substantially improved hydrogen production under both aerobic and anaerobic conditions and enhanced material and functional robustness, compared to unencapsulated [NiFe]-hydrogenases. The catalytically functional nanoreactor as well as the self-assembling and encapsulation strategies provide a framework for engineering new bioinspired electrocatalysts to improve the sustainable production of fuels and chemicals in biotechnological and chemical applications. [ABSTRACT FROM AUTHOR]

The synthesis of a new porous organic cage decorated with isopropyl moieties (CC21) was achieved from the reaction of triformylbenzene and an isopropyl functionalised diamine. Unlike structurally analogous porous organic cages, its synthesis proved challenging due to competitive aminal formation, rationalised using control experiments and computational modelling. The use of an additional amine was found to increase conversion to the desired cage. [ABSTRACT FROM AUTHOR]

Context. Mergers and tidal interactions between massive galaxies and their dwarf satellites are a fundamental prediction of the Lambda-cold dark matter cosmology. These events are thought to provide important observational diagnostics of non-linear structure formation. Stellar streams in the Milky Way and Andromeda are spectacular evidence for ongoing satellite disruption. However, constructing a statistically meaningful sample of tidal streams beyond the Local Group has proven a daunting observational challenge, and the full potential for deepening our understanding of galaxy assembly using stellar streams has yet to be realised. Aims. Here we introduce the Stellar Stream Legacy Survey, a systematic imaging survey of tidal features associated with dwarf galaxy accretion around a sample of ∼3100 nearby galaxies within z ∼ 0.02, including about 940 Milky Way analogues. Methods. Our survey exploits public deep imaging data from the DESI Legacy Imaging Surveys, which reach surface brightness as faint as ∼29 mag arcsec−2 in the r band. As a proof of concept of our survey, we report the detection and broad-band photometry of 24 new stellar streams in the local Universe. Results. We discuss how these observations can yield new constraints on galaxy formation theory through comparison to mock observations from cosmological galaxy simulations. These tests will probe the present-day mass assembly rate of galaxies, the stellar populations and orbits of satellites, the growth of stellar halos, and the resilience of stellar disks to satellite bombardment. [ABSTRACT FROM AUTHOR]

PURPOSE Integrating social care into clinical care requires substantial resources. Use of existing data through a geographic information system (GIS) has the potential to support efficient and effective integration of social care into clinical settings. We conducted a scoping literature review characterizing its use in primary care settings to identify and address social risk factors. METHODS In December 2018, we searched 2 databases and extracted structured data for eligible articles that (1) described the use of GIS in clinical settings to identify and/or intervene on social risks, (2) were published between December 2013 and December 2018, and (3) were based in the United States. Additional studies were identified by examining references. RESULTS Of the 5,574 articles included for review, 18 met study eligibility criteria: 14 (78%) were descriptive studies, 3 (17%) tested an intervention, and 1 (6%) was a theoretical report. All studies used GIS to identify social risks (increase awareness); 3 studies (17%) described interventions to address social risks, primarily by identifying relevant community resources and aligning clinical services to patients' needs. CONCLUSIONS Most studies describe associations between GIS and population health outcomes; however, there is a paucity of literature regarding GIS use to identify and address social risk factors in clinical settings. GIS technology may assist health systems seeking to address population health outcomes through alignment and advocacy; its current application in clinical care delivery is infrequent and largely limited to referring patients to local community resources. [ABSTRACT FROM AUTHOR]

The design of molecular organic photocatalysts for reactions such as water splitting requires consideration of factors that go beyond electronic band gap and thermodynamic driving forces. Here, we carried out a theoretical investigation of three molecular photocatalysts (1–3) that are structurally similar but that show different hydrogen evolution activities (25, 23 & 0 μmol h−1 for 1–3, respectively). We used density functional theory (DFT) and time-dependent DFT calculations to evaluate the molecules' optoelectronic properties, such as ionization potential, electron affinity, and exciton potentials, as well as the interaction between the molecular photocatalysts and an idealized platinum cocatalyst surface. The 'static' picture thus obtained was augmented by probing the nonadiabatic dynamics of the molecules beyond the Born–Oppenheimer approximation, revealing a different picture of exciton recombination and relaxation for molecule 3. Our results suggest that slow exciton recombination, fast relaxation to the lowest-energy excited state, and a shorter charge transfer distance between the photocatalyst and the metal cocatalyst are important features that contribute to the photocatalytic hydrogen evolution activity of 1 and 2, and may partly rationalize the observed inactivity of 3, in addition to its lower light absorption profile. [ABSTRACT FROM AUTHOR]

Radial colour gradients within galaxies arise from gradients of stellar age, metallicity, and dust reddening. Large samples of colour gradients from wide-area imaging surveys can complement smaller integral-field spectroscopy data sets and can be used to constrain galaxy formation models. Here, we measure colour gradients for low-redshift galaxies (z < 0.1) using photometry from the DESI Legacy Imaging Survey DR9. Our sample comprises ∼93 000 galaxies with spectroscopic redshifts and ∼574 000 galaxies with photometric redshifts. We focus on gradients across a radial range 0.5 R eff to R eff, which corresponds to the inner disc of typical late-type systems at low redshift. This region has been the focus of previous statistical studies of colour gradients and has recently been explored by spectroscopic surveys such as MaNGA. We find that the colour gradients of most galaxies in our sample are negative (redder towards the centre), consistent with the literature. We investigate empirical relationships between colour gradient, average g − r and r − z colour, Mr , M ⋆, and sSFR. Trends of gradient strength with Mr (M ⋆) show an inflection around Mr ∼ −21 (⁠|$\log _{10} \, M_\star /\mathrm{M_\odot }\sim 10.5$|⁠). Below this mass, colour gradients become steeper with increasing M ⋆, whereas colour gradients in more massive galaxies become shallower. We find that positive gradients (bluer stars at smaller radii) are typical for galaxies of |$M_{\star }\sim 10^{8}\, \mathrm{M_\odot }$|⁠. We compare our results to age and metallicity gradients in two data sets derived from fits of different stellar population libraries to MaNGA spectra, but find no clear consensus explanation for the trends we observe. Both MaNGA data sets seem to imply a significant contribution from dust reddening, in particular, to explain the flatness of colour gradients along the red sequence. [ABSTRACT FROM AUTHOR]

Porous materials are the subject of extensive research because of potential applications in areas such as gas adsorption and molecular separations. Until recently, most porous materials were solids, but there is now an emerging class of materials known as porous liquids. The incorporation of intrinsic porosity or cavities in a liquid can result in free‐flowing materials that are capable of gas uptakes that are significantly higher than conventional non‐porous liquids. A handful of porous liquids have also been investigated for gas separations. Until now, the release of gas from porous liquids has relied on molecular displacement (e.g., by adding small solvent molecules), pressure or temperature swings, or sonication. Here, we explore a new method of gas release which involves photoisomerisable porous liquids comprising a photoresponsive MOF dispersed in an ionic liquid. This results in the selective uptake of CO2 over CH4 and allows gas release to be controlled by using UV light. [ABSTRACT FROM AUTHOR]

Aims: To describe glucose‐lowering treatment regimens and glycated haemoglobin (HbA1c) trajectories in individuals with type 2 diabetes (T2D) over 36 months of follow‐up from the start of second‐line therapy. Materials and Methods: This data analysis from the 3‐year, observational DISCOVER study programme included 14 687 participants from 37 countries with T2D initiating second‐line glucose‐lowering therapy. Treatment and HbA1c data were collected at baseline (start of second‐line therapy) and at 6, 12, 24 and 36 months. Treatment regimen changes over follow‐up were analysed using the McNemar test, with carry‐forward imputation for intermediate missing values. Results: A total of 11 592 participants had treatment data at baseline and 36 months, and 11 882 had HbA1c data at baseline. At baseline and 36 months, respectively, rates of oral monotherapy use were 12.1% and 12.4% (P = 0.22), rates of dual oral therapy use were 63.4% and 47.6% (P < 0.0001), rates of ≥ triple oral therapy use were 17.5% and 25.4% (P < 0.0001), and rates of injectable treatment use were 7.0% and 13.7% (P < 0.0001). Use of injectable drugs was most common among participants with an HbA1c level ≥64 mmol/mol (≥8.0%). Overall, 42.9% of participants changed treatment during follow‐up. Mean HbA1c levels at baseline and 6 months were 67 mmol/mol (8.3%) and 55 mmol/mol (7.2%), respectively, remaining stable thereafter. Conclusions: Dual oral therapy was the most common treatment regimen at the start of second‐line treatment, and over half of the participants remained on the same treatment during follow‐up. [ABSTRACT FROM AUTHOR]

This paper develops geographic style maps containing two‐dimensional lattices in all known periodic crystals parameterized by recent complete invariants. Motivated by rigid crystal structures, lattices are considered up to rigid motion and uniform scaling. The resulting space of two‐dimensional lattices is a square with identified edges or a punctured sphere. The new continuous maps show all Bravais classes as low‐dimensional subspaces, visualize hundreds of thousands of lattices of real crystal structures from the Cambridge Structural Database, and motivate the development of continuous and invariant‐based crystallography. [ABSTRACT FROM AUTHOR]

A porous molecular crystal (TSCl) was found to crystallise from dichloromethane and water during the synthesis of tetrakis(4-sulfophenylmethane). Crystal structure prediction (CSP) rationalises the driving force behind the formation of this porous TSCl phase and the intermolecular interactions that direct its formation. Gas sorption analysis showed that TSCl is permanently porous with selective adsorption of CO2 over N2, H2 and CH4 and a maximum CO2 uptake of 74 cm3 g−1 at 195 K. Calculations revealed that TSCl assembles via a combination of weak hydrogen bonds and strong dispersion interactions. This illustrates that CSP can underpin approaches to crystal engineering that do not involve more intuitive directional interactions, such as hydrogen bonding. [ABSTRACT FROM AUTHOR]

The 1969 UN Report "Problems of the Human Environment" was a seminal work that first highlighted environmental problems at a global scale. This report underpinned a series of subsequent international summits and conventions of the 1992 Rio Earth Summit and the subsequent three global conventions on Biodiversity, Climate Change and Desertification. We assessed the report half a century after its publication to track changes in vocabulary and highlight critical lessons that could have been learned. The assessment contains several strengths and weaknesses that are pertinent to modern global-scale analyses. Many issues of that day have declined in importance or been superseded, and several major environmental problems (including climate change and plastic pollution) were not foreseen. Most of the report's predictions proved to be much more conservative than proved by reality (a criticism that has also been levelled at contemporary IPCC reports). The report, however, did forewarn of global pandemics and stimulated thinking on a global scale that led to identification of the current climate crisis. [ABSTRACT FROM AUTHOR]