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.

China's response to a national land-system sustainability emergency.

China has responded to a national land-system sustainability emergency via an integrated portfolio of large-scale programmes. Here we review 16 sustainability programmes, which invested US$378.5 billion (in 2015 US$), covered 623.9 million hectares of land and involved over 500 million people, mostly since 1998. We find overwhelmingly that the interventions improved the sustainability of China's rural land systems, but the impacts are nuanced and adverse outcomes have occurred. We identify some key characteristics of programme success, potential risks to their durability, and future research needs. We suggest directions for China and other nations as they progress towards the Sustainable Development Goals of the United Nations' Agenda 2030.

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.

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.

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.

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.

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).

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.

Reexamining the relationship between urbanization and pollutant emissions in China based on the STIRPAT model.

Understanding the relationship between urbanization and pollutant emissions in China is of great significance to realizing sustainable development. Previous studies focused on the relationship between urbanization and air pollutants in China. However, the relationship between urbanization and industrial or domestic pollutants remains unclear. In this paper, we used the stochastic impacts by regression on population, affluence, and technology (STIRPAT) model to examine whether an environmental Kuznets curve (EKC) relationship exists between urbanization and pollutant emissions, including industrial wastewater, industrial SO2, industrial soot (dust), and domestic garbage based on panel data for 277 prefecture-level cities in China from 2003 to 2015. We found that industrial soot (dust) emissions and domestic garbage increased by 83.0% and 43.5%, respectively, whereas industrial wastewater discharge and SO2 emissions decreased by 7.4% and 10.5%, respectively. The identified inverted U-shaped relationship between the urbanization ratio (i.e., percentage of the population living in urban areas) and industrial pollutants supports the EKC hypothesis. However, the domestic garbage volume increased with increasing urbanization ratio. In the future, more attention should be paid to the prevention and control of domestic pollution. In addition, small and medium-sized cities should reduce pollutant emissions and determine effective ways to achieve sustainable development.

Visible-light Promoted Atom Transfer Radical Addition-Elimination (ATRE) Reaction for the Synthesis of Fluoroalkylated Alkenes Using DMA as Electron-Donor.

Here, we describe a mild, catalyst-free and operationally-simple strategy for the direct fluoroalkylation of olefins driven by the photochemical activity of an electron donor-acceptor (EDA) complex between DMA and fluoroalkyl iodides. The significant advantages of this photochemical transformation are high efficiency, excellent functional group tolerance, and synthetic simplicity, thus providing a facile route for further application in pharmaceuticals and life sciences.

Biphasic effects of autophagy on decompression bubble-induced endothelial injury.

Endothelial dysfunction induced by bubbles plays an important role in decompression sickness (DCS), but the mechanism of which has not been clear. The present study was to investigate the role of autophagy in bubble-induced endothelial injury. Human umbilical vein endothelial cells (HUVECs) were treated with bubbles, autophagy markers and endothelial injury indices were determined, and relationship strengths were quantified. Effects of autophagy inhibitor 3-methyladenine (3-MA) were observed. Bubble contact for 1, 5, 10, 20 or 30 minutes induced significant autophagy with increases in LC3-II/I ratio and Beclin-1, and a decrease in P62, which correlated with bubble contact duration. Apoptosis rate, cytochrome C and cleaved caspase-3 increased, and cell viability decreased following bubble contact for 10, 20 or 30 minutes, but not for 1 or 5 minutes. Injuries in HUVECs were correlated with LC3-II/I ratio and partially reversed by 3-MA in 10, 20 or 30 minutes contact, but worsened in 1 or 5 minutes. Bubble pre-conditioning for 1 minutes resulted in increased cell viability and decreased apoptosis rate compared with no pre-conditioning, and 30-minutes pre-conditioning induced opposing changes, all of which were inhibited by 3-MA. In conclusion, autophagy was involved and played a biphasic role in bubble-induced endothelial injury.

The extent of temporary water bodies increased in the drylands of northern China: a multiscale analysis based on MODIS data.

Understanding the dynamics of temporary water bodies (TWBs) is crucial for sustainable development in the drylands of northern China (DNC). Our objective was to quantify the dynamics of TWBs in the DNC between 2000 and 2015. First, we extracted TWBs in the DNC from 2000 to 2015 using the modified normalized difference water index based on Moderate Resolution Imaging Spectroradiometer data. Then, we examined the spatiotemporal patterns of TWBs in the DNC at multiple scales, ranging from the entire region to basins. We found that the area of TWBs increased significantly in the DNC (5.97 thousand km2 in 2000 to 9.92 thousand km2 in 2015) at an annual growth rate of 4.41%. The Heilongjiang Basin had the largest increase in TWBs (848 km2 in 2000 to 3230 km2 in 2015), with an annual growth rate of 23.41%. Such growth was mainly attributed to changes in precipitation in the DNC. We also found that approximately 1/3 of the increase in TWBs was distributed over grasslands and barren lands, which provide valuable water resources that may improve biodiversity and ecosystem services in the DNC. Thus, we suggest that effective measures are needed to manage TWBs to achieve sustainable development in the DNC.

Visible-Light-Induced Direct Difluoroalkylation of Uracils, Pyridinones, and Coumarins.

An efficient and general method for the synthesis of difluoroalkylated uracils, pyridinones, and coumarins through visible-light-induced reaction with commercial materials is developed. The strategy proceeds with high efficiency under mild reaction conditions and shows excellent functional group compatibility, even toward bromide and hydroxyl group, thus demonstrates high potent application in a late-stage fluoroalkylation. Moreover, the difluoroalkylated products can be further transformed to a diverse variety of difluoroalkylated heterocycles, including molecules of potential biological activity.

Understanding Land System Change Through Scenario-Based Simulations: A Case Study from the Drylands in Northern China.

The drylands in northern China are expected to face dramatic land system change in the context of socioeconomic development and environmental conservation. Recent studies have addressed changes of land cover with socioeconomic development in the drylands in northern China. However, the changes in land use intensity and the potential role of environmental conservation measures have yet to be adequately examined. Given the importance of land management intensity to the ecological conditions and regional sustainability, our study projected land system change in Hohhot city in the drylands in northern China from 2013 to 2030. Here, land systems are defined as combinations of land cover and land use intensity. Using the CLUMondo model, we simulated land system change in Hohhot under three scenarios: a scenario following historical trends, a scenario with strong socioeconomic and land use planning, and a scenario focused on achieving environmental conservation targets. Our results showed that Hohhot is likely to experience agricultural intensification and urban growth under all three scenarios. The agricultural intensity and the urban growth rate were much higher under the historical trend scenario compared to those with more planning interventions. The dynamics of grasslands depend strongly on projections of livestock and other claims on land resources. In the historical trend scenario, intensively grazed grasslands increase whereas a large amount of the current area of grasslands with livestock converts to forest under the scenario with strong planning. Strong conversion from grasslands with livestock and extensive cropland to semi-natural grasslands was estimated under the conservation scenario. The findings provide an input into discussions about environmental management, planning and sustainable land system design for Hohhot.

Differentiating climate- and human-induced drivers of grassland degradation in the Liao River Basin, China.

Quantitatively distinguishing grassland degradation due to climatic variations from that due to human activities is of great significance to effectively governing degraded grassland and realizing sustainable utilization. The objective of this study was to differentiate these two types of drivers in the Liao River Basin during 1999-2009 using the residual trend (RESTREND) method and to evaluate the applicability of the method in semiarid and semihumid regions. The relationship between the normalized difference vegetation index (NDVI) and each climatic factor was first determined. Then, the primary driver of grassland degradation was identified by calculating the change trend of the normalized residuals between the observed and the predicted NDVI assuming that climate change was the only driver. We found that the RESTREND method can be used to quantitatively and effectively differentiate climate and human drivers of grassland degradation. We also found that the grassland degradation in the Liao River Basin was driven by both natural processes and human activities. The driving factors of grassland degradation varied greatly across the study area, which included regions having different precipitation and altitude. The degradation in the Horqin Sandy Land, with lower altitude, was driven mainly by human activities, whereas that in the Kungl Prairie, with higher altitude and lower precipitation, was caused primarily by climate change. Therefore, the drivers of degradation and local conditions should be considered in an appropriate strategy for grassland management to promote the sustainability of grasslands in the Liao River Basin.

Urban expansion dynamics and natural habitat loss in China: a multiscale landscape perspective.

China's extensive urbanization has resulted in a massive loss of natural habitat, which is threatening the nation's biodiversity and socioeconomic sustainability. A timely and accurate understanding of natural habitat loss caused by urban expansion will allow more informed and effective measures to be taken for the conservation of biodiversity. However, the impact of urban expansion on natural habitats is not well-understood, primarily due to the lack of accurate spatial information regarding urban expansion across China. In this study, we proposed an approach that can be used to accurately summarize the dynamics of urban expansion in China over two recent decades (1992-2012), by integrating data on nighttime light levels, a vegetation index, and land surface temperature. The natural habitat loss during the time period was evaluated at the national, ecoregional, and local scales. The results revealed that China had experienced extremely rapid urban growth from 1992 to 2012 with an average annual growth rate of 8.74%, in contrast with the global average of 3.20%. The massive urban expansion has resulted in significant natural habitat loss in some areas in China. Special attention needs to be paid to the Pearl River Delta, where 25.79% or 1518 km(2) of the natural habitat and 41.99% or 760 km(2) of the local wetlands were lost during 1992-2012. This raises serious concerns about species viability and biodiversity. Effective policies and regulations must be implemented and enforced to sustain regional and national development in the context of rapid urbanization.

Direct olefination of fluorinated benzothiadiazoles: a new entry to optoelectronic materials.

Fluorinated olefin-containing benzothiadiazoles have important applications in optoelectronic materials. Herein, we reported the direct olefination of fluorinated benzothiadiazoles, as catalyzed by palladium. The reaction proceeds under mild reaction conditions and shows high functional-group compatibility. A preliminary study of the properties of the resulting symmetrical and unsymmetrical olefin-containing fluorinated benzothiadiazoles in red-light-emitting dyes has also been conducted.

Direct (het)arylation of fluorinated benzothiadiazoles and benzotriazole with (het)aryl iodides.

A new and controllable method for the preparation of unsymmetrical and symmetrical fluorinated benzothiadiazole (FBT)-arene structures that can be applied in organic optoelectronic materials has been developed. The reaction proceeds under mild reaction conditions with high efficiency and shows excellent functional group compatibility, even toward bromide. Fluorinated benzotriazoles also take part in the 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.

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.