One-Step Syntheses of 3,4-Disubstituted Isochroman-1-ones by the Annulation of Benzoic Acids with Nitroalkenes.

The Rh(III)-catalyzed annulation of benzoic acids with nitroalkenes was disclosed to afford a wide range of 3,4-disubstituted isochroman-1-ones with excellent regioselectivity and high catalytic efficiency. Both aromatic and aliphatic nitroalkenes participated in this cyclization reaction successfully. The synthetic value of 3,4-disubstituted isochroman-1-ones was proven by a series of derivatizations. Furthermore, a reliable mechanism is outlined on the basis of experimental investigations and related precedents.

Regioselective Hydro(deutero)silylation of 1,3-Enynes Enabled by Photoredox/Nickel Dual Catalysis.

In the presence of visible light irradiation, organophoto/nickel dual catalysts, and the mild base K2HPO4, 1,3-enynes react with silanecarboxylic acids to give the corresponding α-silylallenes with high selectivity. In this uniquely decarboxylative hydrosilylation of 1,3-enynes, a silyl radical process is involved and diverse electron-rich and -poor substrates proceed smoothly in moderate to excellent yields. This transformation is particularly synthetically worthwhile when using MeOD as the solvent, which furnishes new access to α-silyldeuteroallenes.

Symmetry breaking and competition effect in phase transitions.

This study is started from a photon-magnon model with a competition effect of the level attraction and repulsion, its Hermiticity is mainly decided by a phase-dependent and asymmetric coupling factor, namelyφ = 0 for Hermitian andϕ=πfor non-Hermitian. Then an extensional study predicts the quantum critical behaviors using an Hermitian and even no-Hermitian photon-spins model with an additional second-order drive. The numerical results firstly indicate that this coupling phaseφcan function the protective effect on quantum phase transitions (QPTs), and the new tricritical points can not only be modulated by this nonlinear drive, but also be influenced by the dissipation and the collective decoherence. Secondly, this competition effect can also induce a reversal of the value of order parameters between the positive and negative. This study can also bring more important results of QPTs toward the issue of symmetry breaking and non-Hermiticity.

[Pollution Characteristics and Source Apportionment of Atmospheric Volatile Organic Compounds in Winter in Kaifeng City].

In order to explore the pollution characteristics and sources of atmospheric volatile organic compounds (VOCs) in winter in Kaifeng City, based on the atmospheric VOCs component data obtained from the online monitoring station of the Kaifeng Ecological and Environmental Bureau (Urban Area) from December 2021 to January 2022, the pollution characteristics of VOCs and secondary organic aerosol formation potential (SOAP) were discussed, and the sources of VOCs were analyzed by using the PMF model. The results showed that the average mass concentration of VOCs in winter in Kaifeng City was (104.71±48.56) µg·m-3, and alkanes (37.7%) had the highest proportion of mass concentrations, followed by that of halohydrocarbons (23.5%), aromatics (16.8%), OVOCs (12.6%), alkenes (6.9%), and alkynes (2.6%). The averaged total SOAP contributed by VOCs was 3.18 µg·m-3, of which aromatics contributed as much as 83.8%, followed by alkanes (11.5%). The largest anthropogenic source of VOCs in winter in Kaifeng City was solvent utilization (17.9%), followed by fuel combustion (15.9%), industrial halohydrocarbon emission (15.8%), motor vehicle emission (14.7%), organic chemical industry (14.5%), and LPG emission (13.3%); solvent utilization contributed 32.2% of the total SOAP, followed by motor vehicle emission (22.8%) and industrial halohydrocarbon emission (18.9%). It was found that reducing VOCs emissions from solvent utilization, motor vehicle emission, and industrial halohydrocarbon emission was important to control the formation of secondary organic aerosols in winter in Kaifeng City.

Synthesis of 2-(2-Nitroalkyl)indoles by Rhodium(III)-Catalyzed C-H Alkylation.

The Rh(III)-catalyzed addition of the indole C2-H bond to nitroalkenes under an ambient atmosphere is disclosed, providing direct access to a wide range of 2-(2-nitroalkyl)indoles (33 examples) with excellent chemo- and regioselectivity. In addition, pyrrole derivatives also successfully participated in this Friedel-Crafts alkylation reaction. Representative nitroalkane products could be converted into structurally diverse and valuable indole derivatives. Furthermore, a series of control experiments were conducted, and a plausible mechanism was proposed.

[Differences in PM2.5 Components Between Urban and Rural Sites During Heavy Haze Event in Northern Henan Province].

In recent years, the Beijing-Tianjin-Hebei region and its surrounding areas have experienced multiple haze pollution processes. Owing to the limitation of observational instruments, there has not been a comparative study of haze pollution between urban and rural areas in northern Henan province. A series of high-time-resolution instruments were used during a regional heavy pollution process (January 12-25, 2018) at two urban sites and three rural sites. The results showed that SO42-, NO-3, and NH+4 (SNA) were the components with the highest proportion in PM2.5 at the five sites during the haze event with a range of 53%-63%, of which nitrate was the most important, accounting for 24%-32%, followed by sulfate, ranging from 13%-17%. Compared with urban sites, rural sites were more affected by organic matter, especially at night. With the aggravation of pollution, the proportion of SNA increased, reaching 67% during periods of heavy pollution. When the area was affected by the air mass transported from the south, the proportion of NO-3 in PM2.5 increased, and when the area was affected by the air transport in the north, the proportions of SO42- and organic matter increased. Ammonium nitrate was the most important component that led to the decrease in atmospheric visibility during the haze process. Moreover, the contributions of ammonium nitrate and ammonium sulfate at the urban sites were higher than those at the rural sites. To summarize, there were significant differences in PM2.5 components between the urban and rural sites. Urban areas need to continue to strengthen the reduction in gaseous precursors, and rural areas need to pay attention to the sources of carbonaceous aerosol.

Effects of hypoxia and reoxygenation on oxidative stress, histological structure, and apoptosis in a new hypoxia-tolerant variety of blunt snout bream (Megalobrama amblycephala).

A new hypoxia-tolerant variety of blunt snout bream was obtained by successive breeding of the wild population, which markedly improved hypoxia tolerance. In this study, the hypoxia-tolerant variety was exposed to hypoxia (2.0 mg O2·L-1) for 4, 7 days. The contents of blood biochemical indicators including the number of red blood cells (RBC), total cholesterol (T-CHO), total protein (TP), triglyceride (TG), glucose (GLU), and lactic acid (LD) increased significantly (P < 0.05) under hypoxia. The glycogen content in the liver and muscle decreased significantly (P < 0.05) and the LD content in the brain, muscle and liver increased significantly (P < 0.05) under hypoxia. The levels of oxidative stress-related indicators i.e., superoxide dismutase (SOD), malondialdehyde (MDA), glutathione (GSH), catalase (CAT), and total antioxidant capacity (T-AOC) also changed significantly (P < 0.05) in the heart, liver, and intestine of the new variety under hypoxia. Additionally, hypoxia has caused injuries to the heart, liver, and intestine, but it shows amazing repair ability during reoxygenation. The apoptotic cells and apoptosis rate in the heart, liver, and intestine increased under hypoxia. Under hypoxia, the expression of the B-cell lymphomas 2 (Bcl-2) gene in the heart, liver, and intestine was significantly (P < 0.05) down-regulated, while the expression of the BCL2-associated agonist of cell death (Bad) gene was significantly (P < 0.05) up-regulated. These results are of great significance for enriching the basic data of blunt snout bream new variety in response to hypoxia and promoting the healthy development of its culture industry.

First deliveries of felines by transcervical transfer of in vitro-cultured embryos.

Transcervical transplantation of embryos has been wildly used in several species. However, it has not been successful in feline species because of their unique cervix structure combined with poor in vitro culture systems for embryos. In the present study, a simple device to guide the embryo transfer (ET) tube through the cervix and into the uterus was developed. To supply better blastocysts for ET, the in vitro culture system of feline embryos was also optimized. Results showed that 91.67 ± 4.17% of embryos developed to the blastocyst stage in QAU-4 medium compared with 49.17 ± 6.51% in KSOM medium. The total cell number of blastocysts reached 87.1 ± 22.1 in QAU-4 medium compared with 29.8 ± 2.1 in KSOM. Embryoid body formation was also observed in QAU-4 medium. Finally, by the improved technical scheme, CRX (Cone-Rod Homeobox) gene-edited kittens were successfully bred. To date, this is the first report, to our knowledge, of knockout kittens successfully delivered after transcervical ET with a simple transfer tube.

Simulating the Dicke lattice model and quantum phase transitions using an array of coupled resonators.

A proposal for simulating the Dicke-Lattice model in a mechanics-controlled hybrid quantum system is studied here. An array of coupled mechanical resonators (MRs) can homogeneously interact with a group of trapped Bose-Einstein condensates (BECs) via the gradient magnetic field induced by the oscillating resonators. Assisted by the classical dichromatic radio-wave fields, each subsystem with the BEC-MR interaction can mimic the Dicke type spin-phonon interaction, and the whole system is therefore extended to a lattice of Dicke models with the additional adjacent phonon-phonon hopping couplings. In view of this lattice model with theZ2symmetry, its quantum phase transitions behavior can be controlled by this periodic phonon-phonon interactions in the momentum space. This investigation may be considered as a fresh attempt on manipulating the critical behaviors of the collective spins through the external mechanical method.

Recent advances in transition-metal-catalyzed directed C-H alkenylation with maleimides.

Transition-metal-catalyzed directed C-H alkenylation with maleimides has attracted much attention in recent years, as maleimide core moieties are present in various natural products and pharmaceuticals. In addition, these derivatives can be readily modified into biologically important compounds including succinimides, pyrrolidines and γ-lactams. The efficient chelation-assisted inert C-H bond activation strategy provides straightforward access to a wide array of structurally diverse molecules containing maleimide units. This review describes the major progress and mechanistic investigations on Heck-type reaction/cyclization of maleimides with organic molecules until early 2022.

[Pollution Characterization, Source Identification, and Health Risks of Atmospheric Particle-Bound Heavy Metals in PM2.5 in Zhengzhou City: Based on High-resolution Data].

In order to study the pollution characteristics and sources of heavy metals in urban atmospheric PM2.5, 21 elements in atmospheric PM2.5 in Zhengzhou City were detected using an online metal analyzer during July and October 2017 and January and April 2018, and the changes in heavy metal concentrations were analyzed. Heavy metals were traced by enrichment factors, principal component analysis, and potential source function. The US EPA risk assessment model was used to assess their health risks. The results showed that:the concentrations of K, Zn, Mn, Pb, Cu, As, Cr, and Se increased with the increase in pollution level. The results of enrichment factors and principal component analysis showed that the main sources of heavy metals were crust, mixed combustion, industry, and motor vehicles. The characteristic radar charts showed that the pollution dominated by crustal sources mainly occurred in spring and winter, whereas the pollution dominated by mixed combustion sources mainly occurred in winter. Pb, As, and Ni were greatly affected by the transport of a fen nutrient-laden plain, Beijing-Tianjin-Hebei, and southern Henan, whereas Cd was greatly affected by the northwest region of the sampling site. As presented a significant carcinogenic risk in both adults and children, whereas Pb and Sb presented a significant non-carcinogenic risk in children.

Effects of hypoxia and reoxygenation on gill remodeling, apoptosis, and oxidative stress in hypoxia-tolerant new variety blunt snout bream (Megalobrama amblycephala).

Blunt snout bream plays an important role in freshwater aquaculture in China, but the development of its culture industry has been restricted by increasing hypoxia problem. Through the breeding of wild blunt snout bream populations (F0), a hypoxia-tolerant new variety (F6) was obtained. In this study, the new variety was stressed under low oxygen concentration (2.0 mg·L-1) for 4 and 7 days, the morphological structure of the gill tissue showed a striking change, the interlamellar cell mass (ILCM) volume reduced significantly (P < 0.05), and the lamellar respiratory surface area enlarged significantly (P < 0.05), compared to normoxic controls. After 7 days of oxygen recovery, gill remodeling was completely reversed. Additionally, the TUNEL-positive apoptotic fluorescence signals increased in the gills exposed to hypoxia up to 4 and 7 days; the apoptosis rate also increased significantly (P < 0.05). Under 4 and 7 days of hypoxia stress, the expression of anti-apoptotic gene Bcl-2 in the gills downregulated significantly (P < 0.05), with the significantly (P < 0.05) upregulated expression of pro-apoptotic gene Bad. Furthermore, under hypoxia stress, the activity or content of oxidative stress-related enzymes (superoxide dismutase (SOD), catalase (CAT), malondialdehyde (MDA), and glutathione (GSH)) in gill tissue increased to varying degrees compared to normoxic controls. These results offer a new perspective into the cellular and molecular mechanism of hypoxia-induced gill remodeling in blunt snout bream and a theoretical basis for its hypoxia adaptation mechanism.

[Evolution and Evaluation of O3 and VOCs in Zhengzhou During the National Traditional Games of Ethnic Minorities Period].

During the National Traditional Games of Ethnic Minorities (NTGEM) 2019, air quality in Zhengzhou was analyzed to evaluate the impact of pollution prevention and control measures on Zhengzhou. Ground-observed meteorological and pollutant data as well as the chemical compositions of volatile organic compounds (VOCs) were investigated. The results showed that the six parameters of pollutants in the safeguard period in 2019 indicated a downward trend as compared with that during the same time in 2018, and the average concentrations of PM2.5 and PM10 were decreased by 16.2% and 25.1%, respectively. However, the average concentration of O3 was only reduced by 3.7%. The daily proportions of primary pollutants of O3 increased to 90% during the NTGEM, and the ozone pollution was severe in this period. Meanwhile, the concentration of total volatile organic compounds (TVOCs) in the safeguard period was 26.21×10-9, which was significantly lower than that during the historical period. Six emission sources of the VOCs were identified using PMF model, including vehicle exhaust (28%), LPG evaporation (21%), combustion source (16%), industrial emissions (15%), solvent utilization (15%), and biogenic VOCs (5%). During the NTGEM period, the control of combustion sources and industrial sources was evident.

[Ambient VOCs Characteristics, Ozone Formation Potential, and Source Apportionment of Air Pollution in Spring in Zhengzhou].

Ambient volatile organic compounds (VOCs) were determined by GC 5000 online gas chromatography in the urban site of Zhengzhou from April 15 to May 15, 2018. Based on chemical composition analysis, in this study, the concentrations, ozone formation potential (OFP), and source apportionment were studied. The results show that the averaged volume fraction of VOCs in Zhengzhou during spring was 40.26×10-9, which was 23% higher on polluted days (44.12×10-9) than on non-polluted days (35.82×10-9). The contribution of VOC species to OFP was in the order: alkenes > aromatics > alkanes > alkyne. The five factors identified by the PMF model were liquefied petroleum gas (LPG) volatilization sources (66.05%), motor vehicle exhaust sources (47.39%), industrial solvent sources (37.51%), fuel combustion sources (37.80%), and biogenic sources (11.25%). The contributions of LPG volatilization sources and biogenic sources on polluted days were higher by 22.92% and 68.50% than on non-polluted days, respectively.

Inhibition of DNA repair protein RAD51 affects porcine preimplantation embryo development.

Homologous recombination (HR) plays a critical role in facilitating replication fork progression when the polymerase complex encounters a blocking DNA lesion, and it also serves as the primary mechanism for error-free DNA repair of double-stranded breaks. DNA repair protein RAD51 homolog 1 (RAD51) plays a central role in HR. However, the role of RAD51 during porcine early embryo development is unknown. In the present study, we examined whether RAD51 is involved in the regulation of early embryonic development of porcine parthenotes. We found that inhibition of RAD51 delayed cleavage and ceased development before the blastocyst stage. Disrupting RAD51 activity with RNAi or an inhibitor induces sustained DNA damage, as demonstrated by the formation of distinct γH2AX foci in nuclei of four-cell embryos. Inhibiting RAD51 triggers a DNA damage checkpoint by activating the ataxia telangiectasia mutated (ATM)-p53-p21 pathway. Furthermore, RAD51 inhibition caused apoptosis, reactive oxygen species accumulation, abnormal mitochondrial distribution and decreased pluripotent gene expression in blastocysts. Thus, our results indicate that RAD51 is required for proper porcine parthenogenetic activation (PA) embryo development.

An Approach to 3-(Indol-2-yl)succinimide Derivatives by Manganese-Catalyzed C-H Activation.

The manganese-catalyzed addition of C-2 position of indoles to maleimides has been achieved under additive-free conditions. The manganese catalyst exhibits excellent chemo- and regioselectivity, good functional group compatibility, and high catalytic efficiency. The substrate scope can also be extended to maleates, ethyl acrylate, 1,4-dihydro-1,4-epoxynaphthalene, pyrroles, and 2-phenylpyridine, which further demonstrates the universality of this straightforward approach.

[Kinetic cluster and α-divergence-based dynamic myocardial factorial analysis of positron-emission computed tomography images].

OBJECTIVE: We purpose a novel factor analysis method based on kinetic cluster and α-divergence measure for extracting the blood input function and the time-activity curve of the regional tissue from dynamic myocardial positron emission computed tomography(PET) images. METHODS: Dynamic PET images were decomposed into initial factors and factor images by minimizing the α-divergence between the factor model and actual image data. The kinetic clustering as a priori constraint was then incorporated into the model to solve the nonuniqueness problem, and the tissue time-activity curves and the tissue space distributions with physiological significance were generated. RESULTS: The model was applied to the 82RbPET myocardial perfusion simulation data and compared with the traditional model-based least squares measure and the minimal spatial overlap constraint. The experimental results showed that the proposed model performed better than the traditional model in terms of both accuracy and sensitivity. CONCLUSION: This method can select the optimal measure by α value, and incorporate the prior information of the kinetic clustering of PET image pixels to obtain the accurate time-activity curves of the tissue, which has shown good performance in visual evaluation and quantitative evaluation.

[Expression and clinical significance of serine-threonine kinase/mammalian target of rapamycin/p70 S6K signal path- way in oral squamous cell carcinoma].

OBJECTIVE: To investigate the expressions of serine-threonine kinase (Akt)/mammalian target of rapamycin (mTOR)/p70 S6K in oral squamous cell carcinoma (OSCC) and provide references for early diagnosis and prognosis evalua- tion of OSCC. METHODS: A total of 51 cases of OSCC, 10 cases of paracancerous mucosa, and 10 cases of normal oral mucosa were collected. The expressions of Akt/mTOR/p70 S6K in these cases were detected using the SP method of immunohisto- chemistry. The correlation between their expressions in OSCC was also analyzed. RESULTS: The positive expressions ofp-Akt, p-mTOR, and p70 S6K in OSCC were significantly higher than those in normal oral mucosa and paracancerous mucosa. The expressions of p-Akt, p-mTOR, and p70 S6K in OSCC were not correlated with age, gender, and clinical stage; by comparison, these expressions were correlated with lymph node metastasis and pathological grade. Strong positive correlations were also observed between the expressions ofp-Akt, p-mTOR, and p70 S6K in OSCC. CONCLUSION: Akt/mTOR/p70 S6K signaling molecules exhibit active expressions in OSCC and may be implicated in the occurrence and development of OSCC.