Halogen-Bond-Promoted Direct Cross-Coupling of Trifluoromethylated Alkyl Bromides with Coumarins/Quinolinones: Unraveling Trifluoromethyl Effects.

This study introduces a novel approach involving XB-mediated cross-coupling of α-trifluoromethylated alkyl bromides with coumarins and quinolinones under visible light irradiation. Both density functional theory (DFT) calculations and experimental studies converge to suggest that the noncovalent interaction between alkyl bromides and DMAP, intensified by the α-trifluoromethyl group, plays a pivotal role in facilitating this chemoselective reaction.

Dual effects on vegetation from urban expansion in the drylands of northern China: A multiscale investigation using the vegetation disturbance index.

Drylands contribute roughly 40 % of the global net primary productivity and are essential for achieving sustainable development. Investigating the effects on vegetation from urban expansion in drylands within the context of rapid urbanization could help enhance the sustainability of dryland cities. With the use of the drylands of northern China (DNC) as an example, we applied the vegetation disturbance index to investigate the negative and positive effects on vegetation from urban expansion in drylands. The results revealed that the DNC experienced massive and rapid urban expansion from 2000 to 2020. Urban land in the entire DNC increased by 19,646 km2 from 8141 to 27,787 km2, with an annual growth rate of 6.3 %. Urban expansion in the DNC imposed both negative and positive effects on regional vegetation. The area with negative effects reached 7736 km2 and was mainly concentrated in the dry subhumid zones. The area with positive effects amounted to 5011 km2 and was comparable among the dry subhumid, semiarid, and arid zones. Land use/cover change induced by population growth significantly contributed to these negative effects, while the positive effects were largely caused by economic growth. Therefore, it is recommended to strike a balance between urban growth and vegetation conservation to mitigate the adverse effects on vegetation from urban expansion in drylands. Simultaneously, it is imperative to expand urban green spaces and build sustainable and livable ecological cities to facilitate sustainable urban development.

Substantially reducing global PM2.5-related deaths under SDG3.9 requires better air pollution control and healthcare.

The United Nations' Sustainable Development Goal (SDG) 3.9 calls for a substantial reduction in deaths attributable to PM2.5 pollution (DAPP). However, DAPP projections vary greatly and the likelihood of meeting SDG3.9 depends on complex interactions among environmental, socio-economic, and healthcare parameters. We project potential future trends in global DAPP considering the joint effects of each driver (PM2.5 concentration, death rate of diseases, population size, and age structure) and assess the likelihood of achieving SDG3.9 under the Shared Socioeconomic Pathways (SSPs) as quantified by the Scenario Model Intercomparison Project (ScenarioMIP) framework with simulated PM2.5 concentrations from 11 models. We find that a substantial reduction in DAPP would not be achieved under all but the most optimistic scenario settings. Even the development aligned with the Sustainability scenario (SSP1-2.6), in which DAPP was reduced by 19%, still falls just short of achieving a substantial (≥20%) reduction by 2030. Meeting SDG3.9 calls for additional efforts in air pollution control and healthcare to more aggressively reduce DAPP.

Catalyst-free decarboxylative cross-coupling of N-hydroxyphthalimide esters with tert-butyl 2-(trifluoromethyl)acrylate and its application.

Here, we demonstrate a practical method toward the facile synthesis of CF3-containing amino acids through visible light promoted decarboxylative cross-coupling of a redox-active ester with tert-butyl 2-(trifluoromethyl)acrylate. The reaction was driven by the photochemical activity of electron donor-acceptor (EDA) complexes that were formed by the non-covalent interaction between a Hantzsch ester and a redox-active ester. The advantages of this protocol are its synthetic simplicity, rich functional group tolerance, and a cost-effective reaction system.

A Non-Bonding Interaction-Based Fluorescent Probe for Detection of Halogenated Carbonyl Compounds.

The fluorescent detection of neutral and volatile carbonyl halogenated compounds had not been studied before. We describe here a simple and sensitive turn-on rhodamin fluorescent probe for the selective detection of fluorinated/brominated/chlorinated/iodinated carbonyl compounds. A wide range of linear or cyclic volatile organic halides was detected with a limit of detection as low as 45.6 nM within 1 min. Mechanistic experiments and DFT calculations indicate the reversible formation of a 1:1 complex of sensor and analyst through non-bonding interaction.

Trifluoromethyl Rhodium-Carbynoid in [2+1+2] Cycloadditions.

Trifluoromethyl cationic carbyne (CF3 C+ :) possessing dual carbene-carbocation behavior emulated as trifluoromethyl metal-carbynoid (CF3 C+ =M) has not been explored yet, and its reaction characteristics are unknown. Herein, a novel α-diazotrifluoroethyl sulfonium salt was prepared and used in Rh-catalyzed three-component [2+1+2] cycloadditions for the first time with commercially available N-fused heteroarenes and nitriles, yielding a series of imidazo[1,5-a] N-heterocycles that are of interest in medicinal chemistry, in which the insertion of trifluoromethyl Rh-carbynoid (CF3 C+ =Rh) into C=N bonds of N-fused heteroarenes was involved. This strategy demonstrates synthetic applications in late-stage modification of pharmaceuticals, construction of CD3 -containing N-heterocycles, gram-scale experiments, and synthesis of phosphodiesterase 10A inhibitor analog. These highly valuable and modifiable imidazo[1,5-a] N-heterocycles exhibit good antitumor activity in vitro, thus demonstrating their potential applications in medicinal chemistry.

Backbone N-methylation of peptides: Advances in synthesis and applications in pharmaceutical drug development.

Peptide-based drugs have garnered considerable attention in recent years owing to their increasingly crucial role in the treatment of diverse diseases. However, the limited pharmacokinetic properties of peptides have hindered their full potential. One prominent strategy for enhancing the druggability of peptides is N-methylation, which involves the addition of a methyl group to the nitrogen atom of the peptide backbone. This modification significantly improves the stability, bioavailability, receptor binding affinity and selectivity of peptide drug candidates. In this review, we provide a comprehensive overview of the advancements in synthetic methods for N-methylated peptide synthesis, as well as the associated limitations. Moreover, we explore the versatile effects of N-methylation on various aspects of peptide properties. Furthermore, we emphasize the efforts dedicated to N-methylated peptide pharmaceuticals that have successfully obtained marketing approval.

Synthesis of Alkylated Polyfluorobenzenes through Decarboxylative Giese Addition of Aliphatic N-Hydroxyphthalimide Esters with Polyfluorostyrene.

Polyfluoroaromatic compounds play crucial roles in medicinal and material science. However, the synthesis of alkylated polyfluoroarenes has been relatively underdeveloped. In this study, we devised a novel decarboxylative coupling reaction between aliphatic N-hydroxyphthalimide esters and polyfluorostyrene, leveraging the photochemical activity of electron donor-acceptor (EDA) complexes. This method offers simple reaction conditions, a broad substrate scope, and excellent functional group tolerance. Furthermore, we have demonstrated the practicality of this protocol through late-stage polyfluoroaryl modification of biologically active molecules using readily available carboxylic acids as starting materials, thus providing an important supplement to the current toolbox for accessing alkylated polyfluoroaryl motifs.

The challenge of population aging for mitigating deaths from PM2.5 air pollution in China.

Estimating the health burden of air pollution against the background of population aging is of great significance for achieving the Sustainable Development Goal 3.9 which aims to substantially reduce the deaths and illnesses from air pollution. Here, we estimated spatiotemporal changes in deaths attributable to PM2.5 air pollution in China from 2000 to 2035 and examined the drivers. The results show that from 2019 to 2035, deaths were projected to decease 15.4% (6.6%-20.7%, 95% CI) and 8.4% (0.6%-13.5%) under the SSP1-2.6 and SSP5-8.5 scenario, respectively, but increase 10.4% (5.1%-20.5%) and 18.1% (13.0%-28.3%) under SSP2-4.5 and SSP3-7.0 scenarios. Population aging will be the leading contributor to increased deaths attributable to PM2.5 air pollution, which will counter the positive gains achieved by improvements in air pollution and healthcare. Region-specific measures are required to mitigate the health burden of air pollution and this requires long-term efforts and mutual cooperation among regions in China.

The supply and demand of water-related ecosystem services in the Asian water tower and its downstream area.

Climate change and human activities can have an impact on the supply and demand of water-related ecosystem services (WRESs) in the Asian water tower (AWT) and its downstream area, which is closely related to the production and livelihoods of billions of people. However, few studies have taken the AWT and its downstream area as a whole to assess the supply-demand relationship of WRESs. This study aims to assess the future trends of the supply-demand relationship of WRESs in the AWT and its downstream area. Here, the supply-demand relationship of WRESs in 2019 was assessed using the Integrated Valuation of Ecosystem Services and Tradeoffs (InVEST) model and socio-economic data. Then, future scenarios were selected under the framework of the Scenario Model Intercomparison Project (ScenarioMIP). Finally, trends in the supply-demand of WRESs were analysed at multiple scales from 2020 to 2050. The study found that the supply-demand imbalance of WRESs in the AWT and its downstream area will continue to intensify. The area with imbalance intensification was 2.38 × 106 km2 (61.7 %). The supply-demand ratio of WRESs will decline significantly under different scenarios (p < 0.05). The main reason for the imbalance intensification in WRESs is the constant growth of human activities, with a relative contribution of 62.8 %. Our findings suggest that in addition to the pursuit of climate mitigation and adaptation, attention should also be paid to the impact of rapid human activity growth on the supply-demand imbalance of WRESs.

Magnetic CoFe2O4 and NiFe2O4 Induced Self-Assembled Graphene Nanoribbon Framework with Excellent Properties for Li-Ion Battery.

A magnetically induced self-assembled graphene nanoribbons (GNRs) method is reported to synthesize MFe2O4/GNRs (M = Co,Ni). It is found that MFe2O4 compounds not only locate on the surface of GNRs but anchor on the interlayers of GNRs in the diameter of less than 5 nm as well. The in situ growth of MFe2O4 and magnetic aggregation at the joints of GNRs act as crosslinking agents to solder GNRs to build a nest structure. Additionally, combining GNRs with MFe2O4 helps to improve the magnetism of the MFe2O4. As an anode material for Li+ ion batteries, MFe2O4/GNRs can provide high reversible capacity and cyclic stability (1432 mAh g-1 for CoFe2O4/GNRs and 1058 mAh g-1 for NiFe2O4 at 0.1 A g-1 over 80 cycles).

Contribution of Tibetan Plateau ecosystems to local and remote precipitation through moisture recycling.

The ecosystems of the Tibetan Plateau (TP) provide multiple important ecosystem services that benefit both local populations and those beyond, such as through climate regulation services on precipitation for East Asia and China. However, the precipitation regulation service of the TP ecosystems for supplying moisture and maintaining precipitation is yet to be evaluated. In this study, we used the moisture recycling framework and a moisture tracking model to quantify the precipitation regulation services of TP ecosystems for their contribution to precipitation. We found TP ecosystems contributed substantially to local and downwind precipitation, with a contribution of 221 mm/year for the TP and neighboring areas through evapotranspiration (ET) (104 mm/year through transpiration), declined to <10 mm/year for eastern China and other surrounding countries. Among ecosystem types, grassland contributed most to precipitation, followed by barren and snow lands, forests, and shrublands. In terms of seasonality, precipitation contribution from TP ecosystems was greater in summer months than in non-summer months for western China, while the opposite was true for eastern China-although the magnitude was much smaller. Over the past two decades, the significant ET increases in TP translated to a widespread increase in precipitation contribution for TP and downwind beneficiary regions from 2000 to 2020. Our study provides a quantitative way to understand the precipitation regulation services of TP ecosystems through moisture recycling, substantiating their key role to maintain precipitation and the water cycle for downwind regions-effectively acting as an ecological safeguard that could be perceived by the public.

Management of a patient with cardiac arrest, intestinal ischemia necrosis, multiple fractures, hemorrhagic shock, renal failure, disseminated intravascular coagulation, and thrombosis after severe abdominal crush injury: A case report.

Abdominal crush injury has been widely reported. However, abdominal crush injury cases involving most of the organ systems have seldom been reported. In the present case report, a 58-year-old man was hit in the abdomen by a 4-ton machine tool. The case described a rare combination of cardiac arrest, intestinal ischemia necrosis, multiple fractures, hemorrhagic shock, renal failure, disseminated intravascular coagulation and thrombosis after severe abdominal crush injury. During the treatment, crush syndrome, anemia, electrolyte disorder, pleural effusion, pulmonary emphysema, compartment syndrome, respiratory failure, pulmonary hemorrhage, injury of the right common peroneal nerve and tibial nerve, septum abscess and malnutrition were also observed. Systemic and symptomatic treatments were performed for >3 months, after which the patient was discharged from hospital without any further risk of fatality. The related treatments were also described in detail in the present case report. This case represented one of the most complicated cases among abdominal crush injuries that have been reported, and the treatment experiences reported here will hopefully provide suitable reference points for similar cases.

Discovery of Potential Biomarkers for Postmenopausal Osteoporosis Based on Untargeted GC/LC-MS.

Purpose: As an important public health problem, osteoporosis (OP) in China is also in an upward trend year by year. As a standard method for diagnosing OP, dual-energy X-ray absorptiometry (DXA) cannot analyze the pathological process but only see the results. It is difficult to evaluate the early diagnosis of OP. Our study was carried out through a serum metabolomic study of OP in Chinese postmenopausal women on untargeted gas chromatography (GC)/liquid chromatography (LC)-mass spectrometry (MS) to find possible diagnostic markers. Materials and Methods: 50 Chinese postmenopausal women with osteoporosis and 50 age-matched women were selected as normal controls. We first used untargeted GC/LC-MS to analyze the serum of these participants and then combined it with a large number of multivariate statistical analyses to analyze the data. Finally, based on a multidimensional analysis of the metabolites, the most critical metabolites were considered to be biomarkers of OP in postmenopausal women. Further, biomarkers identified relevant metabolic pathways, followed by a map of metabolic pathways found in the database. Results: We found that there may be metabolic pathway disorders like glucose metabolism, lipid metabolism, and amino acid metabolism in postmenopausal women with OP. 18 differential metabolites are considered to be potential biomarkers of OP in postmenopausal women which are a major factor in metabolism and bone physiological function. Conclusion: These findings can be applied to clinical work through further validation studies. It also shows that metabonomic analysis has great potential in the application of early diagnosis and recurrence monitoring in postmenopausal OP women.

Updating global urbanization projections under the Shared Socioeconomic Pathways.

Urbanization level is an important indicator of socioeconomic development, and projecting its dynamics is fundamental for studies related to global socioeconomic and climate change. This paper aims to update the projections of global urbanization from 2015 to 2100 under the Shared Socioeconomic Pathways by using the logistic fitting model and iteratively identifying reference countries. Based on historical urbanization level database from the World Urbanization Prospects, projected urbanization levels and uncertainties are provided for 204 countries and areas every five years. The 2010-2100 year-by-year projected urbanization levels and uncertainties based on the annual historical data from the World Bank (WB) for 188 of countries and areas are also provided. The projections based on the two datasets were compared and the latter were validated using the historical values of the WB for the years 2010-2018. The updated dataset of urbanization level is relevant for understanding future socioeconomic development, its implications for climate change and policy planning.

Synthesis of Secondary Trifluoromethylated Alkyl Bromides Using 2-Bromo-3,3,3-trifluoropropene as a Radical Acceptor.

Herein, the first example using commercially available 2-bromo-3,3,3-trifluoropropene (BTP) as a radical acceptor has been reported. Taking advantage of this strategy, a wide range of secondary trifluoromethylated alkyl bromides were synthesized in good to excellent yields with broad functional group tolerance by using redox-active esters as a radical precursor. The practicality of this protocol was further demonstrated by diverse derivations and direct modification of biologically active molecules.

Nickel-Catalyzed Cross-Coupling of Amino-Acid-Derived Alkylzinc Reagents with Alkyl Bromides/Chlorides: Access to Diverse Unnatural Amino Acids.

Unnatural α-amino acids are important synthetic targets in the field of peptide science. Herein we report an efficient, versatile, and straightforward strategy for the synthesis of homophenylalanine derivatives via the nickel-catalyzed Csp3-Csp3 cross-coupling of (fluoro)benzyl bromides/chlorides with natural α-amino-acid-derived alkylzinc reagents. The current protocol features the advantages of a low-cost nickel catalyst system, synthetic convenience, and the tolerance of rich functionality and stereochemistry.

Diazotrifluoroethyl Radical: A CF3-Containing Building Block in [3 + 2] Cycloaddition.

We present herein a visible-light-induced [3 + 2] cycloaddition of a hypervalent iodine(III) reagent with α-ketoacids for the construction of 5-CF3-1,3,4-oxadiazoles that are of importance in medicinal chemistry. The reaction proceeds smoothly without a photocatalyst, metal, or additive under mild conditions. Different from the well-established trifluorodiazoethane (CF3CHN2), the diazotrifluoroethyl radical [CF3C(·)N2], a trifluoroethylcarbyne (CF3CC:) equivalent and an unusual CF3-containing building block, is involved in the present reaction system.

Future global urban water scarcity and potential solutions.

Urbanization and climate change are together exacerbating water scarcity-where water demand exceeds availability-for the world's cities. We quantify global urban water scarcity in 2016 and 2050 under four socioeconomic and climate change scenarios, and explored potential solutions. Here we show the global urban population facing water scarcity is projected to increase from 933 million (one third of global urban population) in 2016 to 1.693-2.373 billion people (one third to nearly half of global urban population) in 2050, with India projected to be most severely affected in terms of growth in water-scarce urban population (increase of 153-422 million people). The number of large cities exposed to water scarcity is projected to increase from 193 to 193-284, including 10-20 megacities. More than two thirds of water-scarce cities can relieve water scarcity by infrastructure investment, but the potentially significant environmental trade-offs associated with large-scale water scarcity solutions must be guarded against.

Visible-Light-Induced Palladium-Catalyzed Selective Defluoroarylation of Trifluoromethylarenes with Arylboronic Acids.

Selective functionalization of inactive C(sp3)-F bonds to prepare medicinally interesting aryldifluoromethylated compounds remains challenging. One promising route is the transition-metal-catalyzed cross-coupling through oxidative addition of the C(sp3)-F bond in trifluoromethylarenes (ArCF3), which are ideal precursors for this process due to their ready availability and low cost. Here, we report an unprecedented excited-state palladium catalysis strategy for selective defluoroarylation of trifluoromethylarenes with arylboronic acids. This visible-light-induced palladium-catalyzed cross-coupling proceeds under mild reaction conditions and allows transformation of a variety of arylboronic acids and ArCF3. Preliminary mechanistic studies reveal that the oxidative addition of the C(sp3)-F bond in ArCF3 to excited-state palladium(0) via a single electron transfer pathway is responsible for the C(sp3)-F bond activation.