Bifunctional Chiral Electrocatalysts Enable Enantioselective α-Alkylation of Aldehydes.

Herein, we describe an innovative approach to the asymmetric electrochemical α-alkylation of aldehydes facilitated by a newly designed bifunctional chiral electrocatalyst. The highly efficient bifunctional chiral electrocatalyst combines a chiral aminocatalyst with a redox mediator. It plays a dual role as a redox mediator for electrooxidation, while simultaneously providing remarkable asymmetric induction for the stereoselective α-alkylation of aldehydes. Additionally, this novel catalyst exhibits enhanced catalytic activity and excellent stereoselective control comparable to conventional catalytic systems. As a result, this strategy provides a new avenue for versatile asymmetric electrochemistry. The electrooxidation of diverse phenols enables the C-H/C-H oxidative α-alkylation of aldehydes in a highly chemo- and stereoselective fashion. Detailed mechanistic studies by control experiments and cyclic voltammetry analysis demonstrate possible reaction pathways and the origin of enantio-induction.

[Blind area and layout optimization of parks based on the spatial supply-demand evaluation in Taiyuan City, China]. / åŸºäºŽä¾›éœ€å‡è¡¡çš„å¤ªåŽŸå¸‚å ¬å›­æœåŠ¡ç›²åŒºåŠä¼˜åŒ–å¸ƒå±€.

It is of great practical significance to identify service blind area, scientifically select park construction areas, and clarify the priority of parks' construction based on the co-ordination of supply-demand evaluation. With the urban parks within the Taiyuan Ring Expressway as the research subjects, we estimated the accessibility range and the service pressure of each park by using the application programming interface of Gaode map route planning and point of interest data to characterize their supply and demand levels. We identified the service blind areas of parks by overlay analysis, and used the location-allocation (LA) model to purposefully supply park green space. Results showed that the accessibility coverage rates of the parks by walking and bicycling within 15 minutes were 35.6% and 71.7%, respectively, indicating insufficient supply capacity of parks. The areas with large potential demand for park green space in Taiyuan were mainly concentrated in the business district of Qinxian-Changfeng Street and the Shuangta business district within Dongzhong ring road, which existed the obviously invisible blind areas. Finally, we proposed new park green space site selection proposal based on LA model. Optimization results indicated that the coverage rates of walking and bicycling within 15 minutes increased to 46.7% and 81.0%, respectively, and that the service pressure of parks was relieved. We combined the leisure demands of urban residents and the distribution of urban parks by utilizing network big data, which could promote the scientific nature and accuracy of the optimizing site selection and provide scientific method and theory basis for urban park construction.

[Spatiotemporal Distribution Characteristics of Co-pollution of PM2.5 and Ozone over BTH with Surrounding Area from 2015 to 2021].

PM2.5 and ozone co-pollution, which are harmful to not only human health but also the social economy, has become the pivotal issue in air pollution prevention and synergistic control, especially in Beijing-Tianjin-Hebei and its surrounding areas and "2+26" cities. It is necessary to analyze the correlation between PM2.5 and ozone concentration and explore the mechanism of PM2.5 and ozone co-pollution. In order to study the characteristics of PM2.5 and ozone co-pollution in Beijing-Tianjin-Hebei with its surrounding area, ArcGIS and SPSS software were used to analyze the correlation between air quality data and meteorological data of the "2+26" cities in Beijing-Tianjin-Hebei and its surrounding areas from 2015 to 2021. The results indicated:① PM2.5 pollution constantly decreased from 2015 to 2021, and the pollution was concentrated in the central and southern parts of the region; ozone pollution showed a trend of fluctuation and presented a pattern of "low in the southwest and high in the northeast" spatially. In terms of seasonal variation, PM2.5concentration was mainly in the order of winter>spring ≈ autumn>summer, and O3-8h concentration was in the order of summer>spring>autumn>winter. ② In the research area, days with PM2.5 exceeding the standard continued to decline, whereas days with ozone exceeding the standard fluctuated, and days with co-pollution decreased significantly; there was a strong positive correlation between PM2.5 and ozone concentration in summer, with the highest correlation coefficient of 0.52, and a strong negative correlation in winter. ③ Comparing the meteorological conditions of typical cities during the ozone pollution period with that of the co-pollution period, the co-pollution occurred under the temperature range of 23.7-26.5℃, humidity of 48%-65%, and S-SE wind direction.

First Report of Leaf Spot Disease Caused by Alternaria brassicae on Camptotheca acuminata in Sichuan, China.

Camptotheca acuminata (C. acuminata), is belongs to a monotypic genus endemic to southwestern China and listed as the first class national protected plant in China in 1999 (Wen, et al. 2020). Camptothecin, isolated from the wood and bark of C. acuminata Decne, which exhibits clinical effects in various cancer treatments (Pommier, et al. 2006; Kang, et al. 2021). In October 2021, we investigated leaf spot disease occurrence on C. acuminata (FigS1.A) with 80% incidence in Beichuan County, Sichuan Province of China. Leaf symptoms were randomly distributed on the adaxial surfaces and consisted of punctate spots of alternating light gray and dark brown in the early stage of onset (FigS1. B, C). As the disease progressed, these spots expanded irregularly shaped regions of necrotic tissue, and gray-white mildew layers can be seen on the front and back of the lesions in a humid environment. Infected tissues from symptomatic leaves disinfected in 75% ethanol for 45 s, and with 0.1% HgCl2 for 1 min, rinsed then plated on potato dextrose agar (PDA) medium supplemented with ampicillin and carbenicillin (50 µg/ml each). Plates were incubated for 3 days at 25°C. Then prepared by transferring hyphal tips from the edges of these colonies onto fresh PDA medium for subculture. Aerial hyphae had a cotton-like appearance with white to pale gray color (FigS1.D). Conidia were present in long chains, with conidiophores being present in clusters or in isolation (FigS1E), with 1-6 transverse septa, 0-3 oblique and longitudinal septa and an ellipsoidal to obpyriform structure, measuring 10.0-50.9 µm in length and 5.6-11.8 µm in width (n = 20) (FigS1E, G). On the basis of conidial and cultural characteristics, the fungus was consistent with those of members of the Alternaria genus (Simmons, 2008). To confirm this tentative identification, DNA was extracted from isolate XS9, the internal transcribed spacer rDNA regions (ITS), glyceraldehyde-3-phosphate dehydrogenase (GAPDH), translation elongation factor 1-alpha (TEF1), partial RNA polymerase II largest subunit (RPB2) genes were amplified with primers pairs ITS1/ITS4 (White et al.1990), GDF/GDR (Templeton et al.), TEF-728F/TEF-986R (Carbone & Kohn 1999) and RPB2-5F2/RPB2-7cR (Sung et al. 1990; Liu et al. 1999), Bt-2a/Bt-2b (Glass and Donaldson 1995) respectively. The resulting sequences were deposited in GenBank (ITS, OP113690; GAPDH, OP120953; TEF, OP120952; RPB2, OP120954). Further phylogenetic analyses of isolate XS9 revealed it to cluster in the A. brassicae clade with 97% bootstrap support. Pathogenicity identification of isolate XS9 was carried out on the detached leaves. The pure agar plugs (as control) or spraying water on the leaf surface were inoculated on detached leaves, the controls remained healthy after 8 days (FigS1.H-J). but the leaves inoculated with other the mycelium plugs (Fig S1K, L) or the conidia suspension (2×105 conidia/mL) of isolate XS9 was sprayed on the detached leaves (Fig S1M, N), both showed brown necrotic lesions that are similar to the symptoms observed in the field. The pathogen was reisolated and confirmed to be A. brassicae. To our knowledge, this is the first report of leaf spot disease caused by A. brassicae on C. acuminata in China. Leaf spot disease causes the branches and leaves of camptotheca acuminata to wither and even the whole plant to die. To ensure the protection of the irreplaceable species, effective measures should be taken to prevent the spread of the leaf spot disease.

Sustainable electrochemical C(sp3) - H oxygenation using water as the oxygen source.

Electrochemical C(sp3) - H oxygenation of phenols derivatives were accomplished using H2O as the sole oxygen source. Thus, selectively oxidative 4-cresols to 4-acylphenols derivatives proved viable with the aid of indirect electrolysis, through metal- and external oxidant free environmental-friendly and safe electrocatalytic conditions. Advances of this strategy were proved by its ability to transform various sulfonamides with excellent site and regioselectivity. Detailed mechanistic studies allowed to delineate the exact profile of the generation of the oxygenation events.

Asymmetric copper-catalyzed propargylic amination with amine hydrochloride salts.

The highly enantioselective copper-catalyzed propargylic amination of propargylic esters with amine hydrochloride salts has been realized for the first time using copper salts with chiral N,N,P-ligands. This method features a broad substrate scope and wide functional group tolerance, generating propargylic amines in good to excellent yields with high enantioselectivities (up to 99% ee). The utility of the approach was demonstrated by late-stage functionalization of marketed pharmaceuticals.

Highly enantioselective copper-catalyzed propargylic amination to access N-tethered 1,6-enynes.

A highly enantioselective copper-catalyzed propargylic amination starting from benzylic allylic amines has been developed with a new chiral N,N,P ligand. A series of N-tethered 1,6-enynes were synthesized in good to excellent yields with excellent enantioselectivities. Utilization of transition metal-catalyzed cycloisomerization of 1,6-enynes provides several enantioselectively enriched chiral five-membered N-heterocycles efficiently.

[Scenario Analysis of PM2.5 Concentration Targets and Milestones in China].

Reports of decreasing PM2.5 concentrations in some developed countries and regions, as well as the trends of annual average concentrations of PM2.5 in the 74 key cities of China from 2013 to 2016 were analyzed. The cities were categorized based on PM2.5 concentration ranges and the regions where they are located. The average annual declining rates of PM2.5 concentration were calculated for these categories. Based on previous PM2.5 rates, we proposed different scenarios of decreasing PM2.5 concentration in Chinese cities for the future decades. Future PM2.5 concentration was calculated for each of the Chinese cities, and the milestones for 31 provinces and key areas were analyzed. The results showed that the annual average concentration of PM2.5 in China could meet the national air quality standard by 2025 and drop below 30 µg·m-3 in 2030 under both scenarios. The PM2.5 concentration in Beijing-Tianjin-Hebei and surrounding areas could meet the standards in 2030, and the Yangtze River Delta area in 2025. It will be difficult for Beijing, Tianjin, Hebei, and Henan to meet the standard in 2030. Even in the scenario where measures were intensified in the key areas, the cities failed to meet the PM2.5 concentration standards. In Beijing-Tianjin-Hebei and surrounding areas, the values were close to 40% of the target by 2030. To accelerate the reduction of PM2.5 concentration, extreme efforts will be needed in the highly polluted areas.

[PM2.5 Emission Characteristics and Estimation of Emission Reduction Potential from Typical Industrial Sources in Anyang].

To investigate the characteristics of PM2.5 emissions in Anyang, the PM2.5 emission inventory from industrial sources of Anyang in 2016 was established based on reasonable estimation method and emission factor. The spatial distribution analysis was carried out using Geographic Information System (GIS) technology. Based on the industry's typical ultra-low emission transformation and coal pressure reduction requirements, three scenarios were set to estimate the PM2.5 emission reduction potential of industrial sources from Anyang in 2020. The results show that the total PM2.5 emissions from industrial sources in Anyang was 81071.13 t in 2016. Non-ferrous metallurgy, iron and steel, and building materials industries were the main contributing sources, accounting for 45.43%, 25.74%, and 18.00% of the total emissions, respectively. The emission differences between towns and within Anyang were outstanding. The PM2.5 emissions were mainly concentrated in urban areas, Linzhou City, and Anyang County. The emissions in Anyang City were most prominent, while the emission intensity differences between the four jurisdictions of Anyang City were even greater. In the three different control scenarios, the potential for PM2.5 emission reduction in Anyang in 2020 was estimated to be 398.72, 11623.87, and 14072.27 t, accounting for 0.49%, 14.34%, and 17.22% of the total industrial source emissions in 2016, respectively. It can be concluded that Anyang has a great potential for PM2.5 emission reduction. In addition, ultra-low emission reform and coal pressure reduction can be of great significance for PM2.5 emission reduction in Anyang.

Phosphorescence emission and fine structures observed respectively under ambient conditions and at ca. 55 K in a coordination polymer of lead(ii)-thiophenedicarboxylate.

Under solvothermal conditions, a robust Pb2+-based coordination polymer (CP), [Pb(TDC)]n (1), where H2TDC is thiophenedicarboxylic acid, has been achieved. Structural analysis reveals that 1 crystallizes in the monoclinic space group C2/c, where the Pb2+ ions show quadrangular prism coordination geometry. CP 1 represents a 3D coordination network based on a TDC2- ligand as bridges and quadrangular prismatic PbO8 units as nodes, among which the PbO8 units are extended through edge-sharing to form a 2D layer in the bc plane. Interestingly, CP 1 emitted intense and long-lived orange phosphorescence in the solid state at room temperature, with a quantum yield of 6.7% and a phosphorescence lifetime of 1.78 ms. A fine structure is clearly observed in the phosphorescence emission spectra at temperatures below 55 K. The emission mainly arose from the electron transition within the π-type orbitals of the TDC2- ligand. This study gives a fresh impetus to achieve CP-based long-lived phosphorescent materials under ambient conditions.

[Efficacy observation on navel-warming therapy combined with western medication for yang-deficiency tympanites].

OBJECTIVE: To observe the effects of navel-warming therapy on clinical efficacy in patients with yang-deficiency tympanites based on regular treatment of western medication. METHODS: One hundred and twenty cases of yang-deficiency tympanites were randomly divided into a navel-warming therapy group and a western medication group, sixty cases in each one. The regular treatment of western medicine was applied in the western medication group, including oral administration of antiviral drug and diuretics as well as intravenous drip of hepatic protector. Based on western medicine treatment, the navel-warming therapy was applied in the navel-warming group. A medical cake was laid on Shenque (CV 8), and then a medical cylinder was placed above the medical cake and ignited. The treatment was given once daily. One month was considered as a treatment session in both groups and totally one session was required. The TCM symptom score, B-ultrasound ascites and temporary use of diuretics before and after treatment were observed in both groups; also the efficacy was evaluated. RESULTS: The total effective rate was 81.7% (49/60) in the navel-warming therapy group, which was superior to 56.7% (34/60) in the western medication group (P < 0.05). After the treatment, the TCM symptom score and ascites were improved in both groups (all P < 0.05), which was more significant in the navel-warming therapy group (all P < 0.05). The temporary use of diuretics was statistically different between the two groups (P < 0.05), indicating the navel-warming therapy group could obviously reduce or stop the use of diuretics. CONCLUSION: Based on regular treatment of western medication, the navel-warming therapy could significantly improve therapeutic efficacy, effectively relieve clinical symptoms and ease ascites.

[Simulation of air pollution characteristics and estimates of environmental capacity in Zibo City].

To develop a new pattern of air pollution control that is based on the integration of "concentration control, total amount control, and quality control", and in the context of developing national (2011-2015 air pollution control plan for key areas) and (Environmental protection plan of Zibo municipality for the "12th Five-Year Plan" period), a simulation of atmospheric dispersion of air pollutants in Zibo City and its peripheral areas is carried out by employing CALPUFF model, and the atmospheric environmental capacity of SO2, NO(x) and PM10 is estimated based on the results of model simulation and using multi-objective linear programming optimization. The results indicates that the air pollution in Zibo City is significantly related to the pollution sources outside of Zibo City, which contributes to the annual average concentration of SO2, NO2 and PM10 in Zibo City by 26.34%, 21.23%, and 14.58% respectively. There is a notable interaction between districts and counties of Zibo municipality, in which the contribution of SO2, NO(x) and PM10 emissions in surrounding counties and districts to the annual average concentrations of SO2, NO2 and PM10 in downtown area are 35.96%, 43.17%, and 17.69% respectively. There is a great variation in spatial sensitivity of air pollutant emission, and the environmental impact of unit pollutant emissions from Zhoucun, Huantai, Zhangdian and Zichuan is greater than that released from other districts/counties. To meet the requirement of (Ambient air quality standard) (GB 3095-2012), the environmental capacities of SO2, NO(x) and PM10 of Zibo City are only 8.03 x 10(4) t, 19.16 x 10(4) t and 3.21 x 10(4) t, respectively. Therefore, it is imperative to implement regional air pollution joint control in Shandong peninsula in order to ensure the achievement of air quality standard in Zibo City.

[Study on recognition of the true or false red wine based on visible-near infrared spectroscopy].

This study selected 90 samples from different brands of red wine. In order to eliminate the impact of spectral curve's baseline, the first derivatives of all of spectral curves were calculated and the principal component analysis was carried out on the first derivative spectra. The result showed that the contribution rate of the first two principal components was over 80 percent. By the first two principal components, all the red wine samples were obviously divided into two classes. Furthermore a 3-layer artificial neural network predictive model was built with the first four principal components as input variables and 100 percent correct prediction rate was gained. The research showed that the visible-near infrared spectroscopy combined with principal component analysis provides an accurate and reliable new method to rapidly and nondestructively recognize the true or false red wines.