Cu2+ coordination-induced in situ photo-to-heat on catalytic sites to hydrolyze ß-lactam antibiotics pollutants in waters.

For degradation of ß-lactam antibiotics pollution in waters, the strained ß-lactam ring is the most toxic and resistant moiety to biodegrade and redox-chemically treat among their functional groups. Hydrolytically opening ß-lactam ring with Lewis acid catalysts has long been recognized as a shortcut, but at room temperature, such hydrolysis is too slow to be deployed. Here, we found when Cu2+ was immobilized on imine-linked COF (covalent organic framework) (Cu2+/Py-Bpy-COF, Cu2+ load is 1.43 wt%), as-prepared composite can utilize the light irradiation (wavelength range simulated sunlight) to in situ heat anchored Cu2+ Lewis acid sites through an excellent photothermal conversion to open the ß-lactam ring followed by a desired full-decarboxylation of hydrolysates. Under 1 W/cm2 simulated sunlight, Cu2+/Py-Bpy-COF powders placed in a microfiltration membrane rapidly cause a temperature rising even to ~211.7 °C in 1 min. It can effectively hydrolyze common ß-lactam antibiotics in waters and even antibiotics concentration is as high as 1 mM and it takes less than 10 min. Such photo-heating hydrolysis rate is ~24 times as high as under dark and ~2 times as high as Cu2+ homogenous catalysis. Our strategy significantly decreases the interference from generally coexisting common organics in waters and potential toxicity concerns of residual carboxyl groups in hydrolysates and opens up an accessible way for the settlement of ß-lactam antibiotics pollutants by the only energy source available, the sunlight.

Sex Differences in Myocardial and Vascular Aging.

It is well known that cardiovascular disease manifests differently in women and men. The underlying causes of these differences during the aging lifespan are less well understood. Sex differences in cardiac and vascular phenotypes are seen in childhood and tend to track along distinct trajectories related to dimorphism in genetic factors as well as response to risk exposures and hormonal changes during the life course. These differences underlie sex-specific variation in cardiovascular events later in life, including myocardial infarction, heart failure, ischemic stroke, and peripheral vascular disease. With respect to cardiac phenotypes, females have intrinsically smaller body size-adjusted cardiac volumes and they tend to experience greater age-related wall thickening and myocardial stiffening with aging. With respect to vascular phenotypes, sexual dimorphism in both physiology and pathophysiology are also seen, including overt differences in blood pressure trajectories. The majority of sex differences in myocardial and vascular alterations that manifest with aging seem to follow relatively consistent trajectories from the very early to the very later stages of life. This review aims to synthesize recent cardiovascular aging-related research to highlight clinically relevant studies in diverse female and male populations that can inform approaches to improving the diagnosis, management, and prognosis of cardiovascular disease risks in the aging population at large.

The plasmonic effect of Cu on tuning CO2 reduction activity and selectivity.

Copper (Cu) has been widely used for catalyzing the CO2 reduction reaction (CO2RR), but the plasmonic effect of Cu has rarely been explored for tuning the activity and selectivity of the CO2RR. Herein, we conducted a quantitative analysis on the plasmon-generated photopotential (Ehv) of a Cu nanowire array (NA) photocathode and found that Ehv exclusively reduced the apparent activation energy (Ea) of reducing CO2 to CO without affecting the competitive hydrogen evolution reaction (HER). As a result, the CO production rate was enhanced by 52.6% under plasmon excitation when compared with that under dark conditions. On further incorporation with a polycrystalline Si photovoltaic device, the Cu NA photocathode exhibits good stability in terms of photocurrent and syngas production (CO : H2 = 2 : 1) within 10 h. This work validates the crucial role of the plasmonic effect of Cu on modulating the activity and selectivity of the CO2RR.

Benchmarking State-of-the-Art Large Language Models for Migraine Patient Education: A Comparison of Performances on the Responses to Common Queries.

UNSTRUCTURED: Migraine, a frequent and highly disabling disorder, necessitates enhanced education of individuals with migraine to mitigate this global burden. The rapidly evolving field of large language models (LLMs) presents a promising avenue for assisting in migraine patient education. This study aims to assess the potential of LLMs in this context by evaluating the accuracy of responses from five leading LLMs, including OpenAI's ChatGPT 3.5 and 4.0, Google Bard, Meta Llama2, and Anthropic Claude2, in addressing 30 commonly asked migraine-related queries. We found that LLMs demonstrated varied levels of accuracy. ChatGPT-4.0 provided 96.7% appropriate responses, while other chatbots provided 83.3% to 90% appropriate responses (Pearson's chi-squared test, P=0.481). Additionally, Google Bard had a 'poor' rating proportion of 6.7%, other LLMs had 3.3% (Pearson's chi-squared test, P=0.961). This study underscores the potential of LLMs to accurately address common migraine-related queries. Such findings could advance AI-assisted education for individuals with migraine, providing insights for a holistic approach to migraine management.

Light-Regulated Nucleation for Growing Highly Uniform Single-Crystalline Microrods.

We report a light-irradiation method to control the synchronous nucleation of a donor-acceptor (D-A) fluorophore for growing highly uniform single-crystalline microrods, which is in sharp contrast to the prevailing methods of restricting spontaneous nucleation and additionally adding seeds. The D-A fluorophore was observed to undergo photoinduced electron transfer to CrCl3, leading to the generation of HCl and the subsequent protonation of the D-A fluorophore. By intensifying photoirradiation or prolonging its duration, the concentration of protonated D-A fluorophores can be rapidly increased to a high supersaturation level. This results in the formation of a controlled number of nuclei in a synchronous manner, which in turn kickstart the epitaxial growth of protonated D-A fluorophores towards uniform single-crystalline microrods of controlled sizes. The light-regulated synchronous nucleation and uniform growth of microrods are a unique phenomenon that can only be achieved by specific Lewis acids, making it a novel probing method for sensitively detecting strong Lewis acids such as chromium chloride.

Fabrication of Two-Dimensional Platelets with Heat-Resistant Luminescence and Large Two-Photon Absorption Cross Sections via Cooperative Solution/Solid Self-Assembly.

The combination of solution self-assembly, which enables primary morphological control, and solid self-assembly, which enables the creation of novel properties, can lead to the formation of new functional materials that cannot be obtained using either technique alone. Herein, we report a cooperative solution/solid self-assembly strategy to fabricate novel two-dimensional (2D) platelets. Precursor 2D platelets with preorganized packing structure, shape, and size are formed via the living self-assembly of a donor-acceptor fluorophore and volatile coformer (i.e., propanol) in solution phase. After high-temperature annealing, propanol is released from the precursor platelets, and new continuous intermolecular hydrogen bonds are formed. The new 2D platelets formed retain the controllable morphologies originally defined by the solution phase living self-assembly but exhibit remarkable heat-resistant luminescence up to 200 °C and high two-photon absorption cross sections (i.e., >19,000 GM at 760 nm laser excitation).

Transition from Sequential to Concerted Proton-Coupled Electron Transfer of Water Oxidation on Semiconductor Photoanodes.

Accelerating proton transfer has been demonstrated as key to boosting water oxidation on semiconductor photoanodes. Herein, we study proton-coupled electron transfer (PCET) of water oxidation on five typical photoanodes [i.e., α-Fe2O3, BiVO4, TiO2, plasmonic Au/TiO2, and nickel-iron oxyhydroxide (Ni1-xFexOOH)-modified silicon (Si)] by combining the rate law analysis of H2O molecules with the H/D kinetic isotope effect (KIE) and operando spectroscopic studies. An unexpected and universal half-order kinetics is observed for the rate law analysis of H2O, referring to a sequential proton-electron transfer pathway, which is the rate-limiting factor that causes the sluggish water oxidation performance. Surface modification of the Ni1-xFexOOH electrocatalyst is observed to break this limitation and exhibits a normal first-order kinetics accompanied by much enhanced H/D KIE values, facilitating the turnover frequency of water oxidation by 1 order of magnitude. It is the first time that Ni1-xFexOOH is found to be a PCET modulator. The rate law analysis illustrates an effective strategy for modulating PCET kinetics of water oxidation on semiconductor surfaces.

Living Self-Assembly of Metastable and Stable Two-Dimensional Platelets from a Single Small Molecule.

This study reports the design of a donor-acceptor (D-A) molecule with two fluorene units on each side of a benzothiadiazole moiety, which allows multiple intermolecular interactions to compete with one another so as to induce the evolution of the metastable 2D platelets to the stable 2D platelets during the self-assembly of the D-A molecule. Importantly, the living seeded self-assembly of metastable and stable 2D structures with precisely controlled sizes can be conveniently achieved using an appropriate supersaturated level of a solution of the D-A molecule as the seeded growth medium that can temporarily hold the almost-proceeding spontaneous nucleation from competing with the seeded growth. The stable 2D platelets with smaller area sizes exhibit higher sensitivity to gaseous dimethyl sulfide, illustrating that the novel living self-assembly method provides more available functional structures with controlled sizes for practical applications. The key finding of this study is that the new living methodology is separated into two independent processes: the elaborate molecular design for various crystalline structures as seeds and the application of a supersaturated solution with appropriate levels as the growth medium to grow the uniform structures with controlled sizes; this would make convenient and possible the living seeded self-assembly of rich 1D, 2D, and 3D architectures.

Strong Spin Polarization Effect of Atomically Dispersed Metal Site Boosts the Selective Photocatalytic Nitrobenzene Hydrogenation to Aniline over Graphitic Carbon Nitride.

Atomically dispersed catalysts (ADCs) with a well-defined structure are theoretically desirable for a high-selectivity photocatalytic reaction. However, achieving high product selectivity remains a practical challenge for ADCs-based photocatalysts. Herein, we reveal a spin polarization effect on achieving high product selectivity (95.0%) toward the photocatalytic nitrobenzene (PhNO2) hydrogenation to aniline (PhNH2) on atomically dispersed Fe site-loaded graphitic carbon nitride (Fe/g-C3N4). In combination with the Gibbs free energy diagram and electronic structure analysis, the origin of the photocatalytic performance is attributed not only to the strong metal-support interaction between the Fe site and g-C3N4, but more importantly to the strong spin polarization effect that promotes the potential-determining step (PDS) of *PhNO to *PhNOH. This work could be helpful for the design of ADCs-based photocatalysts in view of the spin polarization effect.

Single-Atom Nickel on Carbon Nitride Photocatalyst Achieves Semihydrogenation of Alkynes with Water Protons via Monovalent Nickel.

Prospects in light-driven water activation have prompted rapid progress in hydrogenation reactions. We describe a Ni2+ -N4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with water supplying protons, powered by visible-light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes in D2 O with excellent deuterium incorporation. Under visible-light irradiation, evolution of a four-coordinate Ni2+ species into a three-coordinate Ni+ species was spectroscopically identified. In combination with theoretical calculations, the photo-evolved Ni+ is posited as HO-Ni+ -N2 with an uncoordinated, protonated pyridinic nitrogen, formed by coupled Ni2+ reduction and water dissociation. The paired Ni-N prompts hydrogen liberation from water, and it renders desorption of alkene preferred over further hydrogenation to alkane, ensuring excellent semihydrogenation selectivity.

Unprecedented Small Molecule-Based Uniform Two-Dimensional Platelets with Tailorable Shapes and Sizes.

Fabrication of uniform two-dimensional (2D) structures from small molecules remains a formidable challenge for living self-assembly despite its great success in producing uniform one-dimensional (1D) structures. Here, we report the construction of unprecedented uniform 2D platelets with tailorable shapes and controlled sizes by creating new nuclei from a donor-acceptor (D-A) molecule and 1-hexanol to initiate 2D living self-assembly. We demonstrate that the D-A molecule undergoes 1-hexanol-induced twisting to form continuous alternative hydrogen bonds in-between under electrostatic attraction, which in turn forms a new nucleus. This connection architecture of the new nucleus allows to simultaneously regulate the growth rate of 1 in two dimensions to generate 2D platelets of distinct shapes through simply varying the amount of 1-hexanol relative to hexane. Furthermore, the living nature of the new nucleus enables seeded growth of complex concentric multiblock 2D heteroplatelets by sequential and alternative addition of different D-A molecules. Interestingly, the resulting 2D platelets obtained by such living self-assembly exhibit enhanced photostability compared to those obtained by conventional self-assembly without the involvement of 1-hexanol.

Molecular detection and phylogenetic analysis of tick-borne encephalitis virus in ticks in northeastern China.

Tick-borne encephalitis virus (TBEV) is an important causative agent that causes neurological infections in humans and animals. In recent years, only few epidemiological surveys on TBEV have been conducted in China. The purpose of this study was to determine the prevalence and subtype of TBEV in ticks in northeastern (NE) China. A total of 3799 questing ticks were collected in NE China between April 2015 and June 2016. Ticks were pooled and tested for TBEV RNA using semi-nested reverse transcriptase-polymerase chain reaction. Positive pools were used to isolate the virus and amplify complete sequences, followed by sequence identity and phylogenetic analysis. TBEV RNA was detected in Ixodes persulcatus ticks at a total prevalence of 2.9% (6/143; 95% confidence interval: 1.2%-5.9%). Three TBEV strains were isolated (JL-T75, HLB-T74, and DXAL-T83) and showed 93.9%-99.1% nucleotide identities and 97.1%-99.5% amino acid identities in Far Eastern (FE) TBEV subtypes, and 82.9%-87.6% nucleotide identities and 92.9%-96.4% amino acid identities in other subtypes. For polyprotein, the JL-T75, HLB-T74, and DXAL-T83 strains showed 29, 50, and 55 amino acid residues, respectively, different from those in the TBEV vaccine (Senzhang) strain in China. Phylogenetic analysis revealed that these viruses were clustered in the FE-TBEV branch but formed distinct clades depending on the natural foci. The results of this study suggest that the FE-TBEV subtype is still endemic in I. persulcatus ticks in NE China, and the viruses in different natural foci in NE China are more likely to have genetic differences.

Digital image correlation based on the pre-deformation assist strategy and an optimized checkerboard-like speckle pattern for large deformation measurement.

Large deformation measurement is one of the main issues faced by the digital image correlation method, and the specially designed speckle pattern offers a promising solution. This Letter suggests an extremely simple method to fabricate an optimized speckle pattern for large deformation problems. It demonstrates a more effective large deformation initial estimation capability and measurement accuracy when combined with the pre-deformation assist strategy. A series of simulated and real experiments are used to test the effectiveness of the proposed method, and the results reveal that it performs significantly better than the traditional method in large deformation problems.

In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal-Organic Frameworks (MOFs) Interfaces.

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal-organic frameworks (MOFs, NH2 -MIL-125 and MIL-125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon-excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti8 O8 (OH)4 cluster) of the MOF structure, and the plasmon-excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4-benzenedicarboxylate-NH2 ). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular-level manipulation of interface charge transfer on plasmonic photocatalysts.

Photocatalytic Oxo-Amination of Aryl Cyclopropanes through an Unusual SN2-Like Ring-Opening Pathway: Won >99% ee.

One-pot oxo-amination of unactivated cyclopropanes with safe, green dioxygen as an oxidant and low-cost amines as nitrogen sources has generated interest since this can directly result in uniform ß-located difunctional units. Formation of the three-electron cation radical followed by the nucleophilic attack of amines to open the strained ring of cyclopropanes catalyzed by classic noble-complex photocatalysts was a promising strategy. However, this ring-opening pathway could not maintain the entire second-order nucleophilic substitution (SN2) conversion, which generally led to unsatisfactory enantioselectivity (enantiomeric excess (ee) value ∼60%). Here, we demonstrate that for such a one-step oxo-amination of cyclopropanes with benign dioxygen and pyrazoles, a highly uniform inversion of configuration could be first accomplished through a TiO2 photocatalyst. This strategy features low-cost, semiheterogeneous photocatalysis and environmentally friendly reaction conditions, without using any sacrificial reagent or additive. Importantly, our protocol not only provides a relatively broad substrate scope tolerant to a certain range of substituted cyclopropanes and pyrazoles, resulting in various ß-amino ketone products (∼50 examples) with excellent conversions and yields, but also retains excellent enantioselectivity (ee value ∼99%). A concerted SN2 ring opening raised from an oxetane cation intermediate rather than a conventional three-electron cation radical prior to attaching to dioxygen was proposed.

Competitive Non-Radical Nucleophilic Attack Pathways for NH3 Oxidation and H2 O Oxidation on Hematite Photoanodes.

The sluggish H2 O oxidation kinetics on photoanodes severely obstructs the overall solar-to-energy efficiency of photoelectrochemical (PEC) cells. Herein, we find a 10 to 55-fold increase of photocurrent by conducting ammonia oxidation reaction (AOR) on hematite (α-Fe2 O3 ) photoanodes under near-neutral pH (9-11) and moderate applied potentials (1.0-1.4 VRHE ) compared to H2 O oxidation. By rate law analysis and operando spectroscopic studies, we confirm the non-radical nucleophilic attack of NH3 molecules on high-valent surface Fe-O species (e.g., FeIV =O) and Fe-N species that produces NOx - and N2 , respectively, which overwhelms the nucleophilic attack of H2 O on surface FeIV =O and contributes to a high Faradaic efficiency of above 80 % for AOR. This work reveals a novel non-radical nucleophilic attack strategy, which is significantly different from the conventional indirect radical-mediated AOR mechanism, for the rational design of high-performance AOR photoelectrocatalysts.

Association between organ damage and visceral adiposity index in community-dwelling elderly Chinese population: the Northern Shanghai Study.

BACKGROUND: The visceral adiposity index (VAI) is a newly developing indicator about visceral fat function and insulin resistance. This research aims to assess the association between organ damage and VAI in the community-dwelling elderly Chinese population. METHODS: In total, 3363 elderly participants were recruited between June 2014 and August 2019. VAI was used to measure visceral adipose accumulation, and organ damage was measured with standardized methods, including arterial stiffness, lower extremity atherosclerosis, carotid hypertrophy, left ventricular hypertrophy, micro-albuminuria, and chronic kidney disease. RESULTS: According to multivariable linear regression analysis, VAI was related to carotid-femoral pulse wave velocity (cf-PWV; ß = 0.047, P = 0.024), urine albumin to creatinine ratio (UACR; ß = 3.893, P = 0.008), estimated glomerular filtration rate (eGFR; ß = - 0.526, P = 0.003) and loge(ankle-to-brachial index) (ABI; ß = -0.003, P = 0.024). Using multivariable stepwise logistic regression model, higher VAI was found to be significantly related to cf-PWV > 10 m/s (OR 1.44, [95% CI 1.17-1.78]; Pfor trend < 0.001), and chronic kidney disease (CKD; OR 1.54, [95% CI 1.09-2.20]; Pfor trend = 0.015). CONCLUSIONS: Since higher VAI is related to increased risk of arterial stiffness and CKD, it may serve as a useful index for the assessment of arteriosclerosis and CKD in elderly population. TRIAL REGISTRATION: NSS, NCT02368938.

Pseudo-safety in a cohort of patients with COVID-19 discharged home from the emergency department.

INTRODUCTION: EDs are often the first line of contact with individuals infected with COVID-19 and play a key role in triage. However, there is currently little specific guidance for deciding when patients with COVID-19 require hospitalisation and when they may be safely observed as an outpatient. METHODS: In this retrospective study, we characterised all patients with COVID-19 discharged home from EDs in our US multisite healthcare system from March 2020 to August 2020, focusing on individuals who returned within 2 weeks and required hospital admission. We restricted analyses to first-encounter data that do not depend on laboratory or imaging diagnostics in order to inform point-of-care assessments in resource-limited environments. Vitals and comorbidities were extracted from the electronic health record. We performed ordinal logistic regression analyses to identify predictors of inpatient admission, intensive care and intubation. RESULTS: Of n=923 patients who were COVID-19 positive discharged from the ED, n=107 (11.6%) returned within 2 weeks and were admitted. In a multivariable-adjusted model including n=788 patients with complete risk factor information, history of hypertension increased odds of hospitalisation and severe illness by 1.92-fold (95% CI 1.07 to 3.41), diabetes by 2.20-fold (1.18 to 4.02), chronic lung disease by 2.21-fold (1.22 to 3.92) and fever by 2.89-fold (1.71 to 4.82). Having at least two of these risk factors increased the odds of future hospitalisation by 6.68-fold (3.54 to 12.70). Patients with hypertension, diabetes, chronic lung disease or fever had significantly longer hospital stays (median 5.92 days, 3.08-10.95 vs 3.21, 1.10-5.75, p<0.01) with numerically higher but not significantly different rates of intensive care unit admission (27.02% vs 14.30%, p=0.27) and intubation (12.16% vs 7.14%, p=0.71). DISCUSSION: Patients infected with COVID-19 may appear clinically safe for home convalescence. However, those with hypertension, diabetes, chronic lung disease and fever may in fact be only 'pseudo-safe' and are most at risk for subsequent hospitalisation with more severe illness and longer hospital stays.

Long-Range Exciton Migration in Coassemblies: Achieving High Photostability without Disrupting the Electron Donation of Fluorene Oligomers.

In this work, photostable coassemblies from a nonphotostable fluorene oligomer (the energy donor) and a photostable oligomer (the energy acceptor) are fabricated. Long-range exciton migration over a net distance of about 370 energy-donor molecules to energy acceptors is demonstrated in such coassemblies. The fast and long energy migration allows harvesting of the excitation energy of energy donors by embedding a small number of energy acceptors for photostability enhancement. Importantly, embedding a small number of energy acceptors in coassemblies causes a negligible negative influence on the electron donation of energy donors that are desired in practical applications. The advantages of the coassemblies fabricated, that is, high photostability without disrupting the electron donation of energy donors, are well illustrated in fluorescence detection of trace explosives where prolonged working life and improved detection capacity are achieved.

Does healthy obesity exist in the elderly? Findings from the Northern Shanghai Study.

BACKGROUND AND AIMS: Metabolic unhealthiness and obesity are both associated with an increased risk of cardiovascular disease. We aimed to investigate the significance of metabolic unhealthiness and obesity in organ damages in a community-based elderly cohort. METHODS AND RESULTS: A total of 3325 elderly participants (>65 years old) were recruited in northern Shanghai. Associations of metabolic status and obesity with organ damages were investigated. In all, 1317 (39.6%) participants were metabolically unhealthy and 481 (14.5%) were obese. Compared with metabolically healthy nonobese (MH-nonobese) individuals, metabolically healthy obese subjects had a greater left ventricular mass index (LVMI) and pulse wave velocity (PWV). Metabolically unhealthy subjects, regardless of their obesity status, had greater organ damage parameters including E/Ea, LVMI, PWV, and urine albumin-creatinine ratio (UACR) than MH-nonobese subjects (all P < 0.05). After multivariate adjustments, both metabolic unhealthiness and obesity increased the risk of left ventricular hypertrophy (LVH) (OR 1.31, 95% CI 1.10-1.57 and OR 1.63, 95% CI 1.30-2.04), diastolic dysfunction (OR 1.33, 95% CI 1.06-1.67 and OR 1.51, 95% CI 1.14-1.99), and lower extremity atherosclerosis (OR 1.44, 95% CI 1.11-1.85 and OR 2.01, 95% CI 1.49-2.70). Metabolic unhealthiness was also associated with arterial stiffness, microalbuminuria and chronic kidney disease (all P < 0.05). In a subgroup analysis, metabolic unhealthiness was associated with more organ damages in nonobese subjects, and obesity was associated with LVH and lower extremity atherosclerosis regardless of metabolic status. CONCLUSION: Both obesity and metabolic unhealthiness were associated with organ damages. Metabolic unhealthiness was associated with more organ damages, especially in nonobese individuals. Even healthy obesity was significantly associated with cardiac and vascular impairment. REGISTRATION NUMBER FOR CLINICAL TRIALS: NCT02368938.