Transition-Metal-Free Approach to Acridone Derivatives by TBHP-Promoted Oxidative Annulation of Isatins with Arynes.

A tert-butyl hydroperoxide-promoted oxidative annulation reaction of isatins with 2-(trimethylsilyl)aryl triflates for the convenient synthesis of acridone derivatives has been established. Mechanistic investigation suggested that the reaction may proceed via consecutive Baeyer-Villiger-type rearrangement followed by an intermolecular cyclization. This synthetic approach offers several advantages, including broad substrate scope, good functional group tolerance, and simplicity of operation. Additionally, successful late-stage modification of the obtained compounds was achieved, expanding the application potential of this methodology in organic synthesis.

Rh(III)-Catalyzed Tandem Reaction Access to (Quinazolin-2-yl)methanone Derivatives from 2,1-Benzisoxazoles and α-Azido Ketones.

A Rh(III)-catalyzed tandem reaction for the synthesis of (quinazolin-2-yl)methanone derivatives has been explored from 2,1-benzisoxazoles and α-azido ketones. The transformation involves Rh(III)-catalyzed denitrogenation of α-azido ketones, aza-[4 + 2] cycloaddition, ring opening, and dehydration aromatization processes. Notably, the aza-[4 + 2] cycloaddition of an imine rhodium complex intermediate with 2,1-benzisoxazoles is the key to this reaction.

The contribution of China's emissions to global climate forcing.

Knowledge of the contribution that individual countries have made to global radiative forcing is important to the implementation of the agreement on "common but differentiated responsibilities" reached by the United Nations Framework Convention on Climate Change. Over the past three decades, China has experienced rapid economic development, accompanied by increased emission of greenhouse gases, ozone precursors and aerosols, but the magnitude of the associated radiative forcing has remained unclear. Here we use a global coupled biogeochemistry-climate model and a chemistry and transport model to quantify China's present-day contribution to global radiative forcing due to well-mixed greenhouse gases, short-lived atmospheric climate forcers and land-use-induced regional surface albedo changes. We find that China contributes 10% ± 4% of the current global radiative forcing. China's relative contribution to the positive (warming) component of global radiative forcing, mainly induced by well-mixed greenhouse gases and black carbon aerosols, is 12% ± 2%. Its relative contribution to the negative (cooling) component is 15% ± 6%, dominated by the effect of sulfate and nitrate aerosols. China's strongest contributions are 0.16 ± 0.02 watts per square metre for CO2 from fossil fuel burning, 0.13 ± 0.05 watts per square metre for CH4, -0.11 ± 0.05 watts per square metre for sulfate aerosols, and 0.09 ± 0.06 watts per square metre for black carbon aerosols. China's eventual goal of improving air quality will result in changes in radiative forcing in the coming years: a reduction of sulfur dioxide emissions would drive a faster future warming, unless offset by larger reductions of radiative forcing from well-mixed greenhouse gases and black carbon.

Joint Estimation of Mass and Center of Gravity Position for Distributed Drive Electric Vehicles Using Dual Robust Embedded Cubature Kalman Filter.

The accurate estimation of the mass and center of gravity (CG) position is key to vehicle dynamics modeling. The perturbation of key parameters in vehicle dynamics models can result in a reduction of accurate vehicle control and may even cause serious traffic accidents. A dual robust embedded cubature Kalman filter (RECKF) algorithm, which takes into account unknown measurement noise, is proposed for the joint estimation of mass and CG position. First, the mass parameters are identified based on directly obtained longitudinal forces in the distributed drive electric vehicle tires using the whole vehicle longitudinal dynamics model and the RECKF. Then, the CG is estimated with the RECKF using the mass estimation results and the vertical vehicle model. Finally, different virtual tests show that, compared with the cubature Kalman algorithm, the RECKF reduces the root mean square error of mass and CG by at least 7.4%, and 2.9%, respectively.

New Insight into CO2 Reduction to Formate by In Situ Hydrogen Produced from Hydrothermal Reactions with Iron.

To reveal the nature of CO2 reduction to formate with high efficiency by in situ hydrogen produced from hydrothermal reactions with iron, DFT calculations were used. A reaction pathway was proposed in which the formate was produced through the key intermediate species, namely iron hydride, produced in situ in the process of hydrogen gas production. In the in situ hydrogenation of CO2, the charge of H in the iron hydride was -0.135, and the Fe-H bond distance was approximately 1.537 Å. A C-H bond was formed as a transition state during the attack of Hδ- on Cδ+. Finally, a HCOO species was formed. The distance of the C-H bond was 1.107 Å. The calculated free energy barrier was 16.43 kcal/mol. This study may provide new insight into CO2 reduction to formate in hydrothermal reactions with metal.

Robust Inter-Vehicle Distance Measurement Using Cooperative Vehicle Localization.

Precise localization is critical to safety for connected and automated vehicles (CAV). The global navigation satellite system is the most common vehicle positioning method and has been widely studied to improve localization accuracy. In addition to single-vehicle localization, some recently developed CAV applications require accurate measurement of the inter-vehicle distance (IVD). Thus, this paper proposes a cooperative localization framework that shares the absolute position or pseudorange by using V2X communication devices to estimate the IVD. Four IVD estimation methods are presented: Absolute Position Differencing (APD), Pseudorange Differencing (PD), Single Differencing (SD) and Double Differencing (DD). Several static and dynamic experiments are conducted to evaluate and compare their measurement accuracy. The results show that the proposed methods may have different performances under different conditions. The DD shows the superior performance among the four methods if the uncorrelated errors are small or negligible (static experiment or dynamic experiment with open-sky conditions). When multi-path errors emerge due to the blocked GPS signal, the PD method using the original pseudorange is more effective because the uncorrelated errors cannot be eliminated by the differential technique.

Climate warming increases spring phenological differences among temperate trees.

Climate warming has substantially advanced spring leaf flushing, but winter chilling and photoperiod co-determine the leaf flushing process in ways that vary among species. As a result, the interspecific differences in spring phenology (IDSP) are expected to change with climate warming, which may, in turn, induce negative or positive ecological consequences. However, the temporal change of IDSP at large spatiotemporal scales remains unclear. In this study, we analyzed long-term in-situ observations (1951-2016) of six, coexisting temperate tree species from 305 sites across Central Europe and found that phenological ranking did not change when comparing the rapidly warming period 1984-2016 to the marginally warming period 1951-1983. However, the advance of leaf flushing was significantly larger in early-flushing species EFS (6.7 ± 0.3 days) than in late-flushing species LFS (5.9 ± 0.2 days) between the two periods, indicating extended IDSP. This IDSP extension could not be explained by differences in temperature sensitivity between EFS and LFS; however, climatic warming-induced heat accumulation effects on leaf flushing, which were linked to a greater heat requirement and higher photoperiod sensitivity in LFS, drove the shifts in IDSP. Continued climate warming is expected to further extend IDSP across temperate trees, with associated implications for ecosystem function.

Scaling Effects on Chlorophyll Content Estimations with RGB Camera Mounted on a UAV Platform Using Machine-Learning Methods.

Timely monitoring and precise estimation of the leaf chlorophyll contents of maize are crucial for agricultural practices. The scale effects are very important as the calculated vegetation index (VI) were crucial for the quantitative remote sensing. In this study, the scale effects were investigated by analyzing the linear relationships between VI calculated from red-green-blue (RGB) images from unmanned aerial vehicles (UAV) and ground leaf chlorophyll contents of maize measured using SPAD-502. The scale impacts were assessed by applying different flight altitudes and the highest coefficient of determination (R2) can reach 0.85. We found that the VI from images acquired from flight altitude of 50 m was better to estimate the leaf chlorophyll contents using the DJI UAV platform with this specific camera (5472 × 3648 pixels). Moreover, three machine-learning (ML) methods including backpropagation neural network (BP), support vector machine (SVM), and random forest (RF) were applied for the grid-based chlorophyll content estimation based on the common VI. The average values of the root mean square error (RMSE) of chlorophyll content estimations using ML methods were 3.85, 3.11, and 2.90 for BP, SVM, and RF, respectively. Similarly, the mean absolute error (MAE) were 2.947, 2.460, and 2.389, for BP, SVM, and RF, respectively. Thus, the ML methods had relative high precision in chlorophyll content estimations using VI; in particular, the RF performed better than BP and SVM. Our findings suggest that the integrated ML methods with RGB images of this camera acquired at a flight altitude of 50 m (spatial resolution 0.018 m) can be perfectly applied for estimations of leaf chlorophyll content in agriculture.

Chlorogenic acid inhibits osteosarcoma carcinogenesis via suppressing the STAT3/Snail pathway.

Chlorogenic acid (CA) is a polyphenol compound that possesses anticancer effects on several types of tumors. However, there are few previous studies concerning the protective effects of CA on osteosarcoma. The current study aimed to examine the toxicity of CA to osteosarcoma cells and to explore the potential mechanisms. Cell growth was evaluated using cell counting kit-8 assay and Western blot analysis of proliferating cell nuclear antigen (PCNA). Apoptosis was assessed by flow cytometry analysis using flow cytometry and caspase-3/7 activity assay. The expression changes of the signal transducer and activator of transcription 3 (STAT3)/Snail pathway were detected by Western blot analysis. We found that CA dose-dependently inhibited cell viability and PCNA expression in osteosarcoma cells. Meanwhile, CA treatment increased the apoptotic rate and caspase-3/7 activity in osteosarcoma cells in a concentration-dependent manner. We found that CA concentration-dependently inhibited the activation of the STAT3/Snail pathway in osteosarcoma cells. Inhibition of the STAT3/Snail pathway by si-STAT3 retarded the growth and induced apoptosis of osteosarcoma cells. Mechanistically, activation of the STAT3/Snail pathway by pcDNA-STAT3 reversed the effects of CA on osteosarcoma cell growth and apoptosis. In conclusion, CA inhibited osteosarcoma carcinogenesis by suppressing osteosarcoma cell growth and inducing apoptosis, which was involved in inactivation of the STAT3/Snail pathway. Therefore, our study suggested that CA might have good therapy prospects in osteosarcoma therapy.

Shortened temperature-relevant period of spring leaf-out in temperate-zone trees.

Temperature during a particular period prior to spring leaf-out, the temperature-relevant period (TRP), is a strong determinant of the leaf-out date in temperate-zone trees. Climatic warming has substantially advanced leaf-out dates in temperate biomes worldwide, but its effect on the beginning and length of the TRP has not yet been explored, despite its direct relevance for phenology modeling. Using 1,551 species-site combinations of long-term (1951-2016) in situ observations on six tree species (namely, Aesculus hippocastanum, Alnus glutinosa, Betula pendula, Fagus sylvatica, Fraxinus excelsior, and Quercus robur) in central Europe, we found that the advancing leaf-out was accompanied by a shortening of the TRP. On average across all species and sites, the length of the TRP significantly decreased by 23% (p < .05), from 60 ± 4 days during 1951-1965 to 47 ± 4 days during 2002-2016. Importantly, the average start date of the TRP did not vary significantly over the study period (March 2-5, DOY = 61-64), which could be explained by sufficient chilling over the study period in the regions considered. The advanced leaf-out date with unchanged beginning of the TRP can be explained by the faster accumulation of the required heat due to climatic warming, which overcompensated for the retarding effect of shortening daylength on bud development. This study shows that climate warming has not yet affected the mean TRP starting date in the study region, implying that phenology modules in global land surface models might be reliable assuming a fixed TRP starting date at least for the temperate central Europe. Field warming experiments do, however, remain necessary to test to what extent the length of TRP will continue to shorten and whether the starting date will remain stable under future climate conditions.

Advanced Estimation Techniques for Vehicle System Dynamic State: A Survey.

In order to improve handling stability performance and active safety of a ground vehicle, a large number of advanced vehicle dynamics control systems-such as the direct yaw control system and active front steering system, and in particular the advanced driver assistance systems-towards connected and automated driving vehicles have recently been developed and applied. However, the practical effects and potential performance of vehicle active safety dynamics control systems heavily depend on real-time knowledge of fundamental vehicle state information, which is difficult to measure directly in a standard car because of both technical and economic reasons. This paper presents a comprehensive technical survey of the development and recent research advances in vehicle system dynamic state estimation. Different aspects of estimation strategies and methodologies in recent literature are classified into two main categories-the model-based estimation approach and the data-driven-based estimation approach. Each category is further divided into several sub-categories from the perspectives of estimation-oriented vehicle models, estimations, sensor configurations, and involved estimation techniques. The principal features of the most popular methodologies are summarized, and the pros and cons of these methodologies are also highlighted and discussed. Finally, future research directions in this field are provided.

Cesium carbonate-promoted synthesis of aryl methyl sulfides using S-methylisothiourea sulfate under transition-metal-free conditions.

In the presence of cesium carbonate, an efficient synthesis of aryl methyl sulfides by the reactions of aryl halides with commercially available S-methylisothiourea sulfate is developed. This odourless and highly crystalline solid can be used as the substitute for malodorous methanethiol. The gram-scale reaction also proceeds smoothly without the use of column chromatography separation. Similarly, 2-(dimethylamino)ethylthio and cyclopropylmethylthio groups can be easily introduced into the aromatic rings from the corresponding S-[2-(dimethylamino)ethyl]isothiourea dihydrochloride and S-cyclopropylmethylisothiourea hydrobromide. The possible reaction mechanism is proposed. It is believed that this route to aryl alkyl sulfides is well competitive with currently known methods due to its wide substrate scope, excellent yields, easy operation and transition-metal-free conditions.

Detection and attribution of vegetation greening trend in China over the last 30 years.

The reliable detection and attribution of changes in vegetation growth is a prerequisite for the development of strategies for the sustainable management of ecosystems. This is an extraordinary challenge. To our knowledge, this study is the first to comprehensively detect and attribute a greening trend in China over the last three decades. We use three different satellite-derived Leaf Area Index (LAI) datasets for detection as well as five different process-based ecosystem models for attribution. Rising atmospheric CO2 concentration and nitrogen deposition are identified as the most likely causes of the greening trend in China, explaining 85% and 41% of the average growing-season LAI trend (LAIGS) estimated by satellite datasets (average trend of 0.0070 yr(-1), ranging from 0.0035 yr(-1) to 0.0127 yr(-1)), respectively. The contribution of nitrogen deposition is more clearly seen in southern China than in the north of the country. Models disagree about the contribution of climate change alone to the trend in LAIGS at the country scale (one model shows a significant increasing trend, whereas two others show significant decreasing trends). However, the models generally agree on the negative impacts of climate change in north China and Inner Mongolia and the positive impact in the Qinghai-Xizang plateau. Provincial forest area change tends to be significantly correlated with the trend of LAIGS (P < 0.05), and marginally significantly (P = 0.07) correlated with the residual of LAIGS trend, calculated as the trend observed by satellite minus that estimated by models through considering the effects of climate change, rising CO2 concentration and nitrogen deposition, across different provinces. This result highlights the important role of China's afforestation program in explaining the spatial patterns of trend in vegetation growth.

Efficient approach to 2-hydroxy-2,3-dihydrofuran derivatives and its application for the synthesis of novel 4-(1H-pyrazol-4-yl)pyridazines.

A highly efficient method for the synthesis of 2-hydroxy-2,3-dihydrofuran derivatives from 1,4-enediones and phenacyl pyridinium halides via a domino reaction has been developed. This is a simple and beneficial strategy for the construction of 2-hydroxy-2,3-dihydrofuran compounds from readily available starting materials under mild conditions. Moreover, the application of this reaction provides a straightforward and practical route for the synthesis of the novel 4-(1H-pyrazol-4-yl)pyridazine skeleton.

Stereoselective synthesis of 2,8-dioxabicyclo[3.3.1]nonane derivatives via a sequential Michael addition/bicyclization reaction.

A highly efficient and stereoselective synthesis of coumarin-, 1,3-cyclohexanedione-, and 1,4-naphthoquinone-fused 2,8-dioxabicyclo[3.3.1]nonanes is described. This was achieved via a sequential Michael addition/bicyclization reaction from easily accessible 3-(2-hydroxyphenyl)-1-phenylprop-2-en-1-one derivatives. Three chemical bonds (one C-C bond and two C-O bonds), two six-membered cycles, and two stereogenic centers were formed in a one-pot operation.

AgOTf-catalyzed reactions of naphthols/substituted phenols with 2-hydroxychalcones: facile synthesis of di-aromatic ring-fused [3.3.1]bicyclic compounds.

A simple and efficient method for the synthesis of functionalized di-aromatic ring-fused 2,8-dioxabicyclo[3.3.1]nonane derivatives catalyzed by silver triflate from easily available 2-hydroxychalcones and naphthols/substituted phenols is described. Two six-membered cycles were formed in a one-pot operation. This reaction was probably achieved via a Friedel-Crafts alkylation/bicyclization domino process.

Hydrothermal Reduction of CO2 to Value-Added Products by In Situ Generated Metal Hydrides.

An integrated process by coupling hydrothermal reactions, including CO2 reduction and H2O dissociation with metals, is proposed. The hydrogen could be rapidly produced under hydrothermal conditions, owing to the special characteristics of high temperature water, generating metal hydrides as intermediates. Hydrogen production from the H2O dissociation under hydrothermal conditions is one of the most ideal processes due to its environmentally friendly impact. Recent experimental and theoretical studies on the hydrothermal reduction of CO2 to value-added products by in situ generated metal hydrides are introduced, including the production of formic acid, methanol, methane, and long-chain hydrocarbons. These results indicate that this process holds promise in respect to the conversion of CO2 to useful chemicals and fuels, and for hydrogen storage, which could help alleviate the problems of climate change and energy shortage.

[Temporal and Spatial Characteristics of Net CO2 Emissions and Decoupling Analysis in Yangtze River Economic Belt].

Calculating the fossil energy consumption, revealing the temporal and spatial evolution characteristics of net CO2 emissions, and analyzing the decoupling effect between social development and net CO2 emissions in different regions of the Yangtze River Economic Belt (YREB) is crucial to support the different regions, allowing them to select their individual industrial development and carbon emission reduction path. The results showed that:① from 1999 to 2012, YREB became greener, the CO2 emission of the YREB increased by 2244.23 million tons, and the carbon sink increased by 148.07 million tons during the research period. ② From 2013 to 2018, the area of medium-high carbon sequestration (NPP>800 g·m-2, count for C) increased by 23.25%, compared with that from 1999-2012. ③ A highly decoupling effect between social development and net CO2 emissions was found in the downstream of the YREB. The highest decoupling cities in the upstream, midstream, and downstream accounted for 12%, 34%, and 54% of the highest decoupling cities in the YREB, respectively.

Artificial intelligence reveals dysregulation of osteosarcoma and cuproptosis-related biomarkers, PDHA1, CDKN2A and neutrophils.

At present, the impact of cuproptosis-related genes in the study of osteosarcoma is largely unknown. Genome-wide data of osteosarcoma and controls were downloaded from 3 different databases, and specific diagnostic models associated with cuproptosis in osteosarcoma were constructed by support vector machines with artificial intelligence, random forest trees and LASSO regression. Differential analysis of immune cell infiltration was examined using routine blood data from 25,665 cases. Differential expression was examined using immunohistochemistry and PCR. PDHA1 and CDKN2A were obtained as specific cuproptosis-related biomarkers for osteosarcoma after artificial intelligence analysis. PDHA1, CDKN2A and neutrophils were differentially expressed in OS and control groups. PDHA1 and CDKN2A are significantly dysregulated in OS and are able to serve as biomarkers of OS.

Unexpected C-C bond cleavage: a route to 3,6-diarylpyridazines and 6-arylpyridazin-3-ones from 1,3-dicarbonyl compounds and methyl ketones.

An unexpected C-C bond cleavage has been revealed in the absence of metal. This observation has been exploited to develop an efficient approach toward 3,6-diarylpyridazines and 6-arylpyridazin-3-ones from simple and commercially available 1,3-dicarbonyl compounds and methyl ketones.