Construction of Covalent Triazine Frameworks with Electronic Donor-Acceptor System for Efficient Photocatalytic C-H Hydroxylation of Imidazole[1,2-α]Pyridine Derivatives.

Covalent triazine frameworks (CTFs) are promising heterogeneous photocatalyst candidates owing to their excellent stability, conjugacy, and tunability. In this study, a series of CTFs decorated with different substituents (H, MeO, and F) were synthesised and utilised as photocatalysts for C-H activation reactions. The corresponding optoelectronic properties could be precisely regulated by the electronic effects of different substituents in the nanopore channels of the CTFs; these CTFs were effective photocatalysts for C-H activation in organic synthesis due to their unique structures and optoelectronic properties. Methoxy-substituted CTF (MeO-CTF) exhibited extraordinary catalytic performance and reusability in C-H functionalization by constructing an electronic donor-acceptor system, achieving the highest yield in the photocatalytic C3-H hydroxylation of 2-phenylimidazole[1,2-α]pyridine. This strategy provides a new scaffold for the rational design of CTFs as efficient photocatalysts for organic synthesis.

Photocatalyzed C3-H Nitrosylation of Imidazo[1,2-a]pyridine under Continuous Flow and External Photocatalyst-, Oxidant-, and Additive-Free Conditions.

This study reports a protocol for the highly regioselective photocatalyzed C-H nitrosylation of imidazo[1,2-a]pyridine scaffolds at the C3 position under a combination of visible-light irradiation and continuous flow without any external photocatalyst. This protocol involves mild and safe conditions and shows good tolerance to air and water along with excellent functional group compatibility and site selectivity, generating various 3-nitrosoimidazo[1,2-a]pyridines in excellent yields under photocatalyst-, oxidant-, and additive-free conditions.Notably, the proposed nitrosylation reaction, which introduces the chromophore NO into imidazo[1,2-a]pyridine scaffolds, occurs efficiently under visible-light irradiation without any additional photocatalyst owing to the intense light-absorption characteristics of the nitrosylation products. This study could guide future studies on the development of green organic-synthesis strategies with a wide variety of potential applications.

Modeling the risk of aquatic species invasion spread through boater movements and river connections.

Aquatic invasive species (AIS) are one of the greatest threats to the functioning of aquatic ecosystems worldwide. Once an invasive species has been introduced to a new region, many governments develop management strategies to reduce further spread. Nevertheless, managing AIS in a new region is challenging because of the vast areas that need protection and limited resources. Spatial heterogeneity in invasion risk is driven by environmental suitability and propagule pressure, which can be used to prioritize locations for surveillance and intervention activities. To better understand invasion risk across aquatic landscapes, we developed a simulation model to estimate the likelihood of a waterbody becoming invaded with an AIS. The model included waterbodies connected via a multilayer network that included boater movements and hydrological connections. In a case study of Minnesota, we used zebra mussels (Dreissena polymorpha) and starry stonewort (Nitellopsis obtusa) as model species. We simulated the impacts of management scenarios developed by stakeholders and created a decision-support tool available through an online application provided as part of the AIS Explorer dashboard. Our baseline model revealed that 89% of new zebra mussel invasions and 84% of new starry stonewort invasions occurred through boater movements, establishing it as a primary pathway of spread and offering insights beyond risk estimates generated by traditional environmental suitability models alone. Our results highlight the critical role of interventions applied to boater movements to reduce AIS dispersal.

Modelo del riesgo de la invasión de especies acuáticas dispersadas por movimiento de botes y conexiones entre ríos Resumen Las especies acuáticas invasoras (EAI) son una de las principales amenazas para el funcionamiento de los ecosistemas acuáticos a nivel mundial. Una vez que una especie invasora ha sido introducida a una nueva región, muchos gobiernos desarrollan estrategias de manejo para disminuir la dispersión. Sin embargo, el manejo de las especies acuáticas invasoras en una nueva región se complica debido a las amplias áreas que necesitan protección y los recursos limitados. La heterogeneidad espacial de un riesgo de invasión es causada por la idoneidad ambiental y la presión de propágulo, que puede usarse para priorizar la ubicación de las actividades de vigilancia e intervención. Desarrollamos una simulación para estimar la probabilidad de que un cuerpo de agua sea invadido por EAI para tener un mejor entendimiento del riesgo de invasión en los paisajes acuáticos. El modelo incluyó cuencas conectadas a través de una red multicapa que incluía movimiento de botes y conexiones hidrológicas. Usamos como especies modelo a Dreissena polymorpha y a Nitellopsis obtusa en un estudio de caso en Minnesota. Simulamos el impacto de los escenarios de manejo desarrollado por los actores y creamos una herramienta de decisiones por medio de una aplicación en línea proporcionada como parte del tablero del Explorer de EAI. Nuestro modelo de línea base reveló que el 89% de las invasiones nuevas de D. polymorpha y el 84% de las de N. obtusa ocurrieron debido al movimiento de los botes, lo que lo estableció como una vía primaria de dispersión y nos proporcionó información más allá de las estimaciones de riesgo generadas por los modelos tradicionales de idoneidad ambiental. Nuestros resultados resaltan el papel crítico de las intervenciones aplicadas al movimiento de los botes para reducir la dispersión de especies acuáticas invasoras.

Modulating the Oxygen Reduction Reaction Performance via Precisely Tuned Reactive Sites in Porphyrin-Based Covalent Organic Frameworks.

Covalent organic frameworks (COFs) have emerged as promising electrocatalysts due to their controllable architectures, highly exposed molecular active sites, and ordered structures. In this study, a series of porphyrin-based COFs (TAPP-x-COF) with various transition metals (Co, Ni, Fe) were synthesized via a facile post-metallization strategy under solvothermal synthesis. The resulting porphyrin-based COFs showed oxygen reduction reaction (ORR) activity with a trend in Co > Fe > Ni. Among them, TAPP-Co-COF exhibited the best ORR activity (E1/2 = 0.66 V and jL = 4.82 mA cm-2) in alkaline media, which is comparable to those of Pt/C under the same conditions. Furthermore, TAPP-Co-COF was employed as a cathode in a Zn-air battery, demonstrating a high power density of 103.73 mW cm-2 and robust cycling stability. This work presents a simple method for using COFs as a smart platform to fabricate efficient electrocatalysts.

Past climate cooling promoted global dispersal of amphipods from Tian Shan montane lakes to circumboreal lakes.

Climate changes have substantial impacts on the geographic distribution of montane lakes and evolutionary dynamics of cold-adapted species. Past climate cooling is hypothesized to have promoted the dispersal of cold-adapted species via montane lakes, while future climate warming is thought to constrain their distributions. We test this hypothesis by using phylogeographic analysis and niche modeling of the Holarctic crustacean Gammarus lacustris with global sampling comprised of 567 sequenced individuals and 3180 occurrence records. We found that the species arose in Tian Shan in Central Asia and dispersed into montane lakes along the Alps, Himalayas, Tibet, East Asia, and the North American Rocky Mountain ranges, with accelerated diversification rates outside Tian Shan. Climatically suitable regions for geographic lineages of G. lacustris were larger during cooling periods (LGM), but smaller during warming periods (Mid-Holocene). In the future (2070) scenario, potential distributions in the Himalayas, North Tibet, South Tibet and North America are predicted to expand, whereas ranges in East Asia, Europe and Tian Shan will decline. Our results suggest that Mid-Miocene-to-Pleistocene continuous cooling promoted multiple independent dispersal events out of Tian Shan due to increased availability of montane lakes via "budding" of lineages. Montane lakes are conduits through which cold-adapted amphipods globally dispersed, dominating circumboreal lakes. However, future climate warming is likely to force organisms to shift upward in altitude and northward in latitude, leading to a future change in local populations. These findings highlight the importance of conservation of montane lakes, especially in the context of climate change.

Design of Photoactive Covalent Organic Frameworks as Heterogeneous Catalyst for Preparation of Thiophosphinates from Phosphine Oxides and Thiols.

Two new covalent organic frameworks (COFs) were synthesized from 4,4',4'',4'''-(pyrene-1,3,6,8-tetrayl)tetraaniline and 2,5-dimethoxyterephthalaldehyde (Py-DMTA-COF) or 2',5'-dimethoxy-[1,1':4',1''-terphenyl]-4,4''-dicarbaldehyde (Py-DMTPDA-COF) under solvothermal conditions. These two COFs were further facilely developed as efficient photocatalytic platforms for the synthesis of thiophosphinates. Py-DMTA-COF exhibited better photocatalytic activity, broad substrate applicability, and excellent recycling capacity for the preparation of thiophosphinates from P(O)H compounds and thiols compared to Py-DMTPDA-COF. This methodology was further extended to the seamless gram-scale production of target phosphorothioate derivatives. The results demonstrate that COFs can provide a robust platform for developing metal-free, base-free, highly efficient, and reusable heterogeneous photocatalysts for organic transformations.

The NIH public access policy did not harm biomedical journals.

The United States National Institutes of Health (NIH) imposed a public access policy on all publications for which the research was supported by their grants; the policy was drafted in 2004 and took effect in 2008. The policy is now 11 years old, yet no analysis has been presented to assess whether in fact this largest-scale US-based public access policy affected the vitality of the scholarly publishing enterprise, as manifested in changed mortality or natality rates of biomedical journals. We show here that implementation of the NIH policy was associated with slightly elevated mortality rates and mildly depressed natality rates of biomedical journals, but that birth rates so exceeded death rates that numbers of biomedical journals continued to rise, even in the face of the implementation of such a sweeping public access policy.

Covalent Organic Frameworks with Tailored Functionalities for Modulating Surface Potentials in Triboelectric Nanogenerators.

Designing materials with high triboelectric is an efficient way of improving output performance of triboelectric nanogenerators (TENGs). Herein, we synthesized a series of covalent organic frameworks (COFs) with similar skeletons but various functional groups ranging between electron-donating and electron-withdrawing. These COFs form an ideal platform for clarifying the contribution of each group to TENG performance because the pore wall is perturbed in a predesigned manner. Kelvin probe force microscopy and computational data suggest that surface potentials and electron affinities of COFs can be improved by introducing electron-donating or withdrawing groups, with the highest values observed for fluorinated COF. The TENG with fluorinated COF delivered an output voltage and current of 420 V and 64 µA, respectively, which are comparable to other reported materials. This strategy can be used to efficiently screen suitable frameworks as TENG materials with excellent output performance.

A multi-faceted comparative perspective on elevational beta-diversity: the patterns and their causes.

The observed patterns and underlying mechanisms of elevational beta-diversity have been explored intensively, but multi-dimensional comparative studies remain scarce. Herein, across distinct beta-diversity components, dimensions and species groups, we designed a multi-faceted comparative framework aiming to reveal the general rules in the observed patterns and underlying causes of elevational beta-diversity. We have found that: first, the turnover process dominated altitudinal patterns of species beta-diversity (ßsim > ßsne), whereas the nestedness process appeared relatively more important for elevational trait dissimilarity (ßfuncsim < ßfuncsne); second, the taxonomic turnover was relative higher than its phylogenetic and functional analogues (ßsim > ßphylosim/ßfuncsim), conversely, nestedness-resultant trait dissimilarity tended to be higher than the taxonomic and phylogenetic measures (ßfuncsne > ßsne/ßphylosne); and third, as elevational distance increased, the contradicting dynamics of environmental filtering and limiting similarity have jointly led the elevational patterns of beta-diversity, especially at taxonomic dimension. Based on these findings, we infer that the species turnover among phylogenetic relatives sharing similar functional attributes appears to be the main cause of shaping the altitudinal patterns of multi-dimensional beta-diversity. Owing to the methodological limitation in the randomization approach, currently, it remains extremely challenging to distinguish the influence of the neutral process from the offset between opposing niche-based processes. Despite the complexities and uncertainties during species assembling, with a multi-dimensional comparative perspective, this work offers us several important commonalities of elevational beta-diversity dynamics.

Summary results of the 2014-2015 DARPA Chikungunya challenge.

BACKGROUND: Emerging pathogens such as Zika, chikungunya, Ebola, and dengue viruses are serious threats to national and global health security. Accurate forecasts of emerging epidemics and their severity are critical to minimizing subsequent mortality, morbidity, and economic loss. The recent introduction of chikungunya and Zika virus to the Americas underscores the need for better methods for disease surveillance and forecasting. METHODS: To explore the suitability of current approaches to forecasting emerging diseases, the Defense Advanced Research Projects Agency (DARPA) launched the 2014-2015 DARPA Chikungunya Challenge to forecast the number of cases and spread of chikungunya disease in the Americas. Challenge participants (n=38 during final evaluation) provided predictions of chikungunya epidemics across the Americas for a six-month period, from September 1, 2014 to February 16, 2015, to be evaluated by comparison with incidence data reported to the Pan American Health Organization (PAHO). This manuscript presents an overview of the challenge and a summary of the approaches used by the winners. RESULTS: Participant submissions were evaluated by a team of non-competing government subject matter experts based on numerical accuracy and methodology. Although this manuscript does not include in-depth analyses of the results, cursory analyses suggest that simpler models appear to outperform more complex approaches that included, for example, demographic information and transportation dynamics, due to the reporting biases, which can be implicitly captured in statistical models. Mosquito-dynamics, population specific information, and dengue-specific information correlated best with prediction accuracy. CONCLUSION: We conclude that with careful consideration and understanding of the relative advantages and disadvantages of particular methods, implementation of an effective prediction system is feasible. However, there is a need to improve the quality of the data in order to more accurately predict the course of epidemics.

Ru/Cu Photoredox or Cu/Ag Catalyzed C4-H Sulfonylation of 1-Naphthylamides at Room Temperature.

A mild and efficient protocol for C4-H sulfonylation of 1-naphthylamine derivatives with sodium sulfinates has been described. This C4 sulfonylation proceeded smoothly at room temperature under Ru/Cu photoredox catalysis or Cu/Ag cocatalysis and could tolerate various functional groups. In addition, control experiments suggested that this C4-H sulfonylation reaction might proceed via a single-electron-transfer process.

Impacts of Niche Breadth and Dispersal Ability on Macroevolutionary Patterns.

We describe a spatially explicit simulation experiment designed to assess relative impacts of macroecological traits on patterns of biological diversification under changing environmental conditions. Using a simulation framework, we assessed impacts of species' niche breadth (i.e., the range of their abiotic tolerances) and dispersal ability on resulting patterns of speciation and extinction and evaluated how these traits, in conjunction with environmental change, shape biological diversification. Simulation results supported both niche breadth and dispersal ability as important drivers of diversification in the face of environmental change, and suggested that the rate of environmental change influences how species interact with the extrinsic environment to generate diversity. Niche breadth had greater effects on speciation and extinction than dispersal ability when climate changed rapidly, whereas dispersal ability effects were elevated when climate changed slowly. Our simulations provide a bottom-up perspective on the generation and maintenance of diversity under climate change, offering a better understanding of potential interactions between species' intrinsic macroecological characteristics and a dynamic extrinsic environment in the process of biological diversification.

Ecological approaches in veterinary epidemiology: mapping the risk of bat-borne rabies using vegetation indices and night-time light satellite imagery.

Rabies remains a disease of significant public health concern. In the Americas, bats are an important source of rabies for pets, livestock, and humans. For effective rabies control and prevention, identifying potential areas for disease occurrence is critical to guide future research, inform public health policies, and design interventions. To anticipate zoonotic infectious diseases distribution at coarse scale, veterinary epidemiology needs to advance via exploring current geographic ecology tools and data using a biological approach. We analyzed bat-borne rabies reports in Chile from 2002 to 2012 to establish associations between rabies occurrence and environmental factors to generate an ecological niche model (ENM). The main rabies reservoir in Chile is the bat species Tadarida brasiliensis; we mapped 726 occurrences of rabies virus variant AgV4 in this bat species and integrated them with contemporary Normalized Difference Vegetation Index (NDVI) data from the Moderate Resolution Imaging Spectroradiometer (MODIS). The correct prediction of areas with rabies in bats and the reliable anticipation of human rabies in our study illustrate the usefulness of ENM for mapping rabies and other zoonotic pathogens. Additionally, we highlight critical issues with selection of environmental variables, methods for model validation, and consideration of sampling bias. Indeed, models with weak or incorrect validation approaches should be interpreted with caution. In conclusion, ecological niche modeling applications for mapping disease risk at coarse geographic scales have a promising future, especially with refinement and enrichment of models with additional information, such as night-time light data, which increased substantially the model's ability to anticipate human rabies.

Global Mpox spread due to increased air travel.

Mpox is an emerging, infectious disease that has caused outbreaks in at least 91 countries from May to August 2022. We assessed the link between international air travel patterns and Mpox transmission risk, and the relationship between the translocation of Mpox and human mobility dynamics after travel restrictions due to the COVID-19 pandemic had been lifted. Our three novel observations were that: i) more people traveled internationally after the removal of travel restrictions in the summer of 2022 compared to pre-pandemic levels; ii) countries with a high concentration of global air travel have the most recorded Mpox cases; and iii) Mpox transmission includes a number of previously nonendemic regions. These results suggest that international airports should be a primary location for monitoring the risk of emerging communicable diseases. Findings highlight the need for global collaboration concerning proactive measures emphasizing realtime surveillance.

Ecological niche conservatism spurs diversification in response to climate change.

Lengthy debate has surrounded the theoretical and empirical science of whether climatic niche evolution is related to increased or decreased rates of biological diversification. Because species can persist for thousands to millions of years, these questions cross broad scales of time and space. Thus, short-term experiments may not provide comprehensive understanding of the system, leading to the emergence of contrasting opinions: niche evolution may increase diversity by allowing species to explore and colonize new geographic areas across which they could speciate; or, niche conservatism might augment biodiversity by supporting isolation of populations that may then undergo allopatric speciation. Here, we use a simulation approach to test how biological diversification responds to different rates and modes of niche evolution. We find that niche conservatism promotes biological diversification, whereas labile niches-whether adapting to the conditions available or changing randomly-generally led to slower diversification rates. These novel results provide a framework for understanding how Earth-life interactions produced such a diverse biota.

Investigating the impact of climatic and environmental factors on HFRS prevalence in Anhui Province, China, using satellite and reanalysis data.

Introduction: Hemorrhagic Fever with Renal Syndrome (HFRS) is the most commonly diagnosed zoonosis in Asia. Despite taking various preventive measures, HFRS remains prevalent across multiple regions in China. This study aims to investigate the impact of climatic and environmental factors on the prevalence of HFRS in Anhui Province, China, utilizing satellite and reanalysis data. Methods: We collect monthly HFRS data from Anhui Province spanning 2005 to 2019 and integrated MODIS satellite datasets and ERA5 reanalysis data, including variables such as precipitation, temperature, humidity, solar radiation, aerosol optical depth (AOD), and Normalized Difference Vegetation Index (NDVI). Continuous wavelet transform, Spearman correlation analysis, and Poisson regression analysis are employed to assess the association between climatic and environmental factors and HFRS cases. Results: Our findings reveal that HFRS cases predominantly occur during the spring and winter seasons, with the highest peak intensity observed in a 9-year cycle. Notably, the monthly average relative humidity exhibits a Spearman correlation coefficient of 0.404 at a 4-month lag, taking precedence over other contributing factors. Poisson regression analysis elucidates that NDVI at a 2-month lag, mean temperature (T) and solar radiation (SR) at a 4-month lag, precipitation (P), relative humidity (RH), and AOD at a 5-month lag exhibit the most robust explanatory power for HFRS occurrence. Moreover, the developed predictive model exhibiting commendable accuracy. Discussion: This study provides key evidence for understanding how climatic and environmental factors influence the transmission of HFRS at the provincial scale. Insights from this research are critical for formulating effective preventive strategies and serving as a resource for HFRS prevention and control efforts.

Photoactive Covalent Organic Frameworks for Catalyzing Organic Reactions.

Because of their large surface areas, long-range order, π-π stacking interactions and hierarchically integrated building blocks, covalent organic frameworks (COFs) have attracted increasing attention. Recently, COFs have been regarded as promising heterogeneous photocatalysts, owing to their remarkable light-harvesting and energy transition capabilities. The research progress of COFs in photocatalytic organic synthesis is summarized, such as preparation of imines through the oxidation of amines, selective oxidation of sulfides, oxidative hydroxylation of arylboronic acids, C-H bond activation, cyclization, asymmetric organic synthesis and so on. Finally, a perspective of the present challenges of photoactive COFs in organic transformations is given.

Ecological Niche Shifts Affect the Potential Invasive Risk of Rapistrum rugosum (L.) All. in China.

Ecological niche is a key concept that links species distributions. Ecological niche shifts are expected to affect the potential invasive risk of alien species. Rapistrum rugosum is an invasive agricultural weed in many countries. Wild populations of R. rugosum have been recorded in China, representing a great threat to the regional crops. Based on distribution records from different regions and relevant environmental variables, the present study predicted the potential distribution and estimated the invasive risk of R. rugosum in China. Ecological niche shifts strongly affected the potential invasive risk of R. rugosum in China. The two most important variables were annual temperature range (Bio7) and mean temperature of the coldest quarter (Bio11). The total suitable habitat for the species covered an area of 287.53 × 104km2 and was mainly distributed in Southwest, Southeast, and Central China. Australia, Canada, Brazil, the United States, and Argentina accounted for over 90% of the inspection records of R. rugosum from Chinese entry ports during 2015-2018. The intercepted R. rugosum was frequently mixed in Glycine max (L.) Merr., Hordeum vulgare L., linseed, Triticum aestivum L., and Sorghum bicolor (L.) Moench. Moreover, 80% interceptions were recorded from Tianjin, Guangdong, Nanjing, and Chengdu customs. Climatic conditions do not limit the establishment capability of R. rugosum in China. Our results provide a theoretical reference for the development of monitoring and control measures for this invasive weed.

Fluorinated covalent organic frameworks for efficient drug delivery.

In this study, two novel fluorine-functionalized crystalline covalent organic frameworks (COFs), namely DF-TAPB-COF and DF-TATB-COF, were synthesized, and their ordered structure, porosity, suitable pore size, and abundant fluorine groups were expected to serve as effective carriers in drug delivery. The excellent cell viability of DF-TAPB-COF and DF-TATB-COF was verified using MTT assays. Both COFs exhibited very high loading capacities in terms of drug loading performance, in particular the drug loading rate of DF-TAPB-COF for 5-fluorouracil (5-FU) was up to 69%. They also exhibited efficient drug release performance in a simulated body fluid environment. Cell endocytosis experiments demonstrated that DF-TAPB-COF and DF-TATB-COF could be effectively endocytosed by cells. Hence, this study offers new insight into the design and development of COF-based drug carrier systems.