Mechanistic Investigation on the Regioselectivity of Electrochemical Co(II)-Catalyzed [2 + 2 + 2] Cycloaddition of Terminal Acetylenes.

In this paper, the regioselectivity of electrochemical Co(II)-catalyzed [2 + 2 + 2] cycloaddition of terminal alkynes was investigated using density functional theory. We explored in detail the energy profiles for both 1,2,4- and 1,3,5-regioselectivity pathways and revealed the origin of the regioselectivity. Two kinds of conformational isomers derived from the different coordination modes of alkynes with cobaltacyclopentadiene have been found, which were formed through electrochemically mediated redox processes. The regioselectivity of the reaction depends on the two coordination modes. When the Co(II) center attacks α-C of the third alkyne, while ß2-C in cyclopentadiene bonds to ß-C of the alkyne, the reaction favors the formation of 1,2,4-products. In contrast, when the Co(II) center connects to ß-C of the alkyne, it forms only the 1,3,5-products via [4 + 2] cycloaddition because of the steric repulsion between the bulky ligand on Co(II) and the phenyl group in the alkyne.

[Characteristics of Silent Alpha Thalassemia Gene in Child-Bearing Adults in Guangdong].

OBJECTIVE: To investigate characteristics of silent alpha thalassemia genes in child-bearing adults in Guangdong, in order to provide data for the prevention and control of hemoglobin H disease. METHODS: A total of 8 752 cases were collected from January 2016 to December 2020. Gap-PCR was used to detect the deletional of α-thalassemia mutations (-α3.7, -α4.2), while PCR reverse dot blot hybridization assay (RDB) was used to detect the non-deletional α-thalassemia mutations (Hb CS, Hb QS and Hb Westmead). RESULTS: Among 8 752 subjects, 717 cases of silent α-thalassemia were detected, the detection rate was 8.19%, including 555 cases of deletional α-thalassemia (77.41%) and 162 cases of non-deletional α-thalassemia 22.59%. The mean corpuscular volume (MCV) of deletional silent α-thalassemia was (82.09±4.10) fl, and mean corpuscular hemoglobin (MCH) was (27.03±1.37) pg, which both were over the diagnostic cut-off value for thalassemia. The MCV of non-deletional silent α-thalassemia was (81.07±4.93) fl, and MCH was (26.77±2.20) pg. According to the diagnostic criteria, if using MCV<82 fl or (and) MCH<27 pg as a positive criteria for screening thalassemia in the childbearing age, the screening sensitivity was 53.14% and different in different genotype, among which ααQS/αα was 100%, -α3.7/αα, -α4.2/αα, ααCS/αα and ααWS/αα was 62.15%, 63.41%, 44.83% and 39.62%, respectively. Namely, nearly half the carriers of such mutations might have escaped detection as a result of their screening strategy. CONCLUSION: When a couple is preparing for pregnancy, if one of them has been determined to be mild α-thalassemia or hemoglobin H disease, other half is necessary to carry out silent α thalassemia detection to prevent the birth of children with hemoglobin H disease even if MCV>82 fl and MCH>27 pg.

[Assessment of Emission Reduction Potential of CO2 Capture, Geological Utilization, and Storage in Cement Industry of China].

The cement industry faces great pressure from the targets of carbon peak and carbon neutrality. CO2capture, geological utilization, and storage(CCUS) technology is crucial for CO2 mitigation in large-scale fossil-based industries. An integrated techno-economic assessment model of CCUS was improved here to assess the potential of CCUS retrofits in the cement industry in China, and the cost curve or supply curve of CCUS in the cement industry was obtained. The model set up ten scenarios from four aspects:source-sink matching distance, capture rate, CCUS technology, and technical level. The cement enterprise screening, site screening, techno-economic evaluation, and source-sink matching of CCUS were completed to answer some key problems in realizing low-carbon development via CCUS, such as enterprise inventory, storage site, emission reduction scale, and cost range. Under the scenario of 250 km matching distance, 85% net capture rate, CO2-enhanced water recovery technology, and current technical level, 44% of cement enterprises reduced carbon emission via CCUS, the cumulative capacity reached 625 million tons per year, and the levelized cost was 290-1838 yuan·t-1. The projects with a levelized cost of fewer than 600 yuan·t-1 accounted for 77% and could reduce CO2 emission by 564 million tons annually. The projects whose levelized cost was less than 400 yuan·t-1 could reduce CO2 by 199 million tons per year. When the coupling of CO2-enhanced oil recovery and CO2-enhanced water recovery technology was considered, the levelized cost was 27% lower. When the cement capacity was less than 530 million tons per year, the additional cost of cement production was 95-300 yuan·t-1. Under technological progress to 2030, the levelized cost will be reduced by 9%-15%. The regions with early demonstration advantages of full-chain CO2-enhanced water recovery technology were Xinjiang, Inner Mongolia, Ningxia, Henan, and Hebei. Additionally, the areas suitable for cement CCUS cluster included Ordos Basin, Junggar Basin, Bohai Bay Basin, and Songliao Basin. It is technically feasible for the cement industry to deploy full-chain CCUS projects, and low-cost projects have an early demonstration opportunity. These results can provide a quantitative reference for the low-carbon development of the cement industry and the commercial deployment of CCUS in cement production.

Factors associated with quality of life in Chinese people with psoriasis: a cross-sectional study.

BACKGROUND: The ultimate goal of medical care is to eradicate disease and restore normality to a person's life. Quality of life (QOL) is a concern as dermatologists and researchers strive to find better drug treatments. However, there have been few reports on the factors associated with QOL among Chinese people with psoriasis. METHODS: A total of 185 people with psoriasis were surveyed to assess their sociodemographic status, disease-related information, psychosocial status, and QOL. The questionnaires included a sociodemographic questionnaire, the Athens Insomnia Scale, the Hospital Anxiety and Depression Scale, the Perceived Social Support Scale, the Psychosocial Adaptation Questionnaire of Chronic Skin Disease and the Dermatology Life Quality Index. Multiple stepwise regression and path analysis were used to study the factors associated with QOL among Chinese people with psoriasis and to analyse the relationship between them. RESULTS: The results showed that the presence of anxiety/depression, lesion area, sleep disorders, psychosocial adaptation, and sex could jointly predict 62.1% of the variance in QOL among Chinese people with psoriasis. According to previous theories and the literature, a path model was established for five variables. Four internal variables could be effectively explained. The values of the explanatory variables were 62.1% (F(1056) = 61.020, p = 0.000) for QOL, 71.8% (F(2433) = 117.370, p = 0.000) for anxiety/depression, 44.0% (F(660) = 36.935, p = 0.000) for sleep disorders, and 66.9% (F(6886) = 93.556, p = 0.000) for psychosocial adaptation. The path analysis confirmed that 9 paths were consistent with the predicted path, and 3 paths were not confirmed. CONCLUSION: To improve QOL among Chinese people with psoriasis, attention should be given to the presence of anxiety/depression, lesion area, sleep disorders, psychosocial adaptation and sex differences. Therefore, health care programs for psoriasis should include physical, psychological and social aspects.

[Multi-dimensional Analysis of the Synergistic Effect of Pollution Reduction and Carbon Reduction in Tianjin Based on the STIRPAT Model].

Based on the STIRPAT model, this study quantitatively analyzed the synergistic effect of pollution reduction and carbon reduction in Tianjin from three dimensions:total emission, emission reduction, and synergy coefficient. The results showed that the main emission sources of air pollutants and greenhouse gases in Tianjin were industrial sources, and the Pearson correlation coefficient of air pollutants and greenhouse gases was 0.984. The total population, urbanization rate, gross regional product, energy intensity, and carbon dioxide emission intensity were important factors affecting the synergistic effect of pollution reduction and carbon reduction in Tianjin. In 2011 and 2012, Tianjin's air pollutants and greenhouse gas emissions increased synergistically, and the synergistic effect coefficients were 0.18 and 0.17, respectively. From 2013 to 2014 and from 2018 to 2023, the air pollutant emission reduction and greenhouse gas emission increased, the synergistic effect coefficient was less than 0, and the pollution reduction and carbon reduction had no synergistic effect. In 2015-2017 and 2024-2060, air pollutants and greenhouse gas emissions were predicted to be reduced at the same time, with a synergistic effect coefficient ranging from 2.74 to 8.76. Tianjin had the conditions to enter the synergistic stage of pollution reduction and carbon reduction in 2024. The most important things for Tianjin to do to promote the synergy of pollution reduction and carbon reduction were to strictly control the total amount of greenhouse gas emissions, continue to promote the reduction in energy intensity and carbon dioxide emission intensity, and reasonably control the total population, urbanization rate, and regional GDP.

Origins of Stereospecificity and Divergent Reactivity of Pd-Catalyzed Cross Coupling with α,α-Disubstituted Alkenyl Hydrazones.

This article presents an exploration of stereospecificity and divergent reactivity of Pd-catalyzed α,α-disubstituted alkenyl hydrazones to synthesize 1,4-dienes in the Z configuration and vinylcyclopropane. We calculated the energy profiles of four α,α-disubstituted alkenyl hydrazones. The results show that the energy profiles of the whole catalytic cycle are basically the same before the syn-carbopalladation step. Subsequent syn-ß-C elimination yields skipping dienes, or direct ß-H elimination yields vinylcyclopropane. Current theoretical calculations reveal that the stereospecificity and the divergent reactivity of reactions result from the competition between syn-ß-C elimination and ß-H elimination. The C-C bond rotation and subsequent syn-ß-C elimination step control the stereospecificity of the reaction by changing the olefin stereostructure from E to Z configuration. The steric factor of α-substituted groups mediates the transformation between syn-ß-C elimination and ß-H elimination. The results are of great significance for the scientific design of substrates to achieve accurate synthesis of target products.

Inhibition of BRD4 triggers cellular senescence through suppressing aurora kinases in oesophageal cancer cells.

Oesophageal cancer is one of the most frequent solid malignancies and the leading cause of cancer-related death around the world. It is urgent to develop novel therapy strategies to improve patient outcomes. Acetylation modification of histones has been extensively studied in epigenetics. BRD4, a reader of acetylated histone and non-histone proteins, has involved in tumorigenesis. It has emerged as a promising target for cancer therapy. BRD4 inhibitors, such as JQ1, have exerted efficacious anti-proliferation activities in diverse cancers. However, the effects of JQ1 on oesophageal cancer are still not fully described. Here, we demonstrate that JQ1 suppresses cell growth and triggers cellular senescence in KYSE450 cells. Mechanistically, JQ1 up-regulates p21 level and decreases cyclin D1 resulting in G1 cycle arrest. The inhibitory effects of JQ1 on KYSE450 cells are independent on apoptosis. It activates cellular senescence by increasing SA-ß-gal activity. BRD4 knockdown by shRNA recapitulates cellular senescence. We also display that administration of JQ1 decreases recruitment of BRD4 on the promoter of aurora kinases A and B. Inhibitors targeting at AURKA/B phenocopy JQ1 treatment in KYSE450 cells. These results identify a novel action manner of BRD4 in oesophageal cancer, which strengthens JQ1 as a candidate drug in oesophageal cancer chemotherapy.

Enhancement of light aromatics from catalytic fast pyrolysis of cellulose over bifunctional hierarchical HZSM-5 modified by hydrogen fluoride and nickel/hydrogen fluoride.

Pore structure and accessible active sites of HZSM-5 (Z5) are the key factors for its catalysis. The bifunctional hierarchical Z5 were prepared with leaching agent HF and loading Ni, and their performance for catalytic fast pyrolysis (CFP) of cellulose was investigated in a drop tube quartz reactor. Z5 modified with 0.5 mol/L HF (0.5F-Z5) showed excellent light aromatics (LAs) yield, which can be attributed to the enhancement in the small mesopores (2-10 nm) and the decrease of Brønsted acid sites during dealumination. Simultaneously, the loading of a 1 wt% Ni produced more LAs than 0.5F-Z5, due to the improvement in deoxidation/hydrogenation reactions. The highest LAs yield (31.3%) was obtained over 1%Ni-0.5 mol/LHF-Z5, which increased by 44.9% compared to the parent Z5. In addition, the reaction routes over different active centers and acid-catalyzed reactions were analyzed, based upon the composition of bio-oils and catalyst characterization.

Seven new species of the Stenus cirrus group (Coleoptera, Staphylinidae) from Sichuan, Southwest China.

Seven new species of the Stenus cirrus group collected from Sichuan, Southwest China are described: S. cariniventris Tang, Liu Dong, sp. n., S. jiangrixini Tang, Liu Dong, sp. n., S. lineatus Tang, Liu Dong, sp. n., S. emeishanus Tang, Liu Dong, sp. n., S. jiudingshanus Tang, Liu Dong, sp. n., S. xichangensis Tang, Liu Dong, sp. n., S. brevilineatus Tang, Liu Dong, sp. n. The diagnostic characters of the new species are illustrated, and a key to species of the group from Sichuan Province is provided.

The Stenus cirrus group (Coleoptera, Staphylinidae) in Fujian, East China.

Species of the Stenus cirrus group in Fujian Province, East China, are reviewed and two new species are described: S. mangdangshanus sp. n. and S. fujianensis sp. n. The females of S. cooterianus Puthz, 2003 and S. wuyiensis Puthz, 2003 are discovered and illustrated for the first time. The diagnostic characters of the new species are illustrated, and a key to species of the Stenus cirrus group of Fujian Province is provided.

New data on the genus Domene (Coleoptera: Staphylinidae: Paederinae) of mainland China.

Material of the genus Domene Fauvel, 1873 from the Chinese provinces Heilongjiang, Anhui, Zhejiang, Fujian, Guizhou, Sichuan, Shaanxi, Yunnan, Guangdong and Guangxi was examined. Twelve species were identified, seven of them described previously, and five are newly described: D. aqiang Peng and Li, sp. n. (Guangdong: Nanling); D. jiangi Peng and Li, sp. n. (Fujian: Tanshan Park); D. jini Peng and Li, sp. n. (Guangxi: Jiuwan Shan); D. nanlingensis Peng and Li, sp. n. (Guangdong: Nanling); D. tui Peng and Li, sp. n. (Guizhou: Sanchahe). The genus is now represented in mainland China by 21 species. A key to the Domene species of mainland China is provided.

Notes on the Stenus cirrus group of Zhejiang, East China, with descriptions of two new species (Coleoptera, Staphylinidae).

Two new Stenus species of the cirrus group collected from Zhejiang Province, East China, are described, S. wuyanlingus Liu, Tang & Luo, sp. n., S. yuyimingi Liu, Tang & Luo, sp. n. and a new distributional locality for S. ovalis Tang, Li & Zhao, 2005 was discovered. The diagnostic characters of the new species are illustrated, and a key to species of the group from Zhejiang Province is provided.

[Identification of a new 3.8kb deletional α thalassemia and detection of the deletion fragment].

OBJECTIVE: To report the identification of a novel 3.8-kb deletion that caused α thalassemia and establish the method for detecting the deletion fragment. METHODS: Peripheral blood samples were collected from the proband and his mother for analysis of the hematological parameters and routine test for thalassemia genes. For the sample with an inconsistency between the genotyping results and phenotypic analysis results, a specific gap-PCR was employed to identify the rare or novel mutations. RESULTS: A novel 3814-bp deletion causing α thalassemia was found in the proband and his mother, who had genotypes of -α4.2/-α3.8 and αα/-α3.8, respectively. CONCLUSION: We identified a 3.8-kb deletion in the α-globin gene cluster that caused α thalassemia, and this finding enriches the α thalassemia gene mutation spectrum. Specific gap-PCR offers a convenient and efficient means for for detecting this deletion fragment.

Seven new species of the Stenus cirrus group (Coleoptera, Staphylinidae) from Guangxi, South China.

Seven new species of the Stenus cirrus group collected from Guangxi, South China are described and illustrated: S. hujiayaoi Liu and Tang, sp. n., S. bullatus Liu and Tang, sp. n., S. exesus Liu and Tang, sp. n., S. damingshanus Liu and Tang, sp. n., S. jinxiuensis Liu and Tang, sp. n., S. lianhuashanus Liu and Tang, sp. n., S. hechiensis Liu and Tang, sp. n. The diagnostic characters of the new species are illustrated, and a key to species of the group from Guangxi is provided.

Three new species of the Stenus cirrus group from Guizhou, southwest China (Coleoptera, Staphylinidae).

Three new Stenus species of the cirrus group collected from Guizhou Province, southwest China, are described: S. dashaheensissp. n., S. zhangyuqingisp. n., and S. liuyixiaoisp. n. The diagnostic characters of the new species are illustrated, and a key to species of the group from Guizhou Province is provided.

Is brain damage really involved in the pathogenesis of obstructive sleep apnea?

Obstructive sleep apnea (OSA) syndrome is a surprisingly complex and highly individualized disease, with different factors contributing toward the disease process. Many factors can induce OSA disease, such as hypertrophy uvula, adenoidectomy, tonsil caused by mechanical obstruction of the airway, airway obstruction on obesity cause of decubitus, etc.; in addition, abnormal structure and function of the central nervous system (CNS) is also one of the important factors. This paper examines the relationship of the CNS with the onset of OSA. Evidence has shown that dysfunction of the CNS may be related to the occurrence of OSA. Although modification of the behaviors of the motor neurons may offer a potentially interesting means of controlling the airway, human afferent and motor pathways that regulate eupnea are still poorly understood. Combining some clinical phenomena of patients with cerebral hemorrhage or brain trauma at the temporal lobe, it seems that no close relation with OSA has been observed in clinical work and animal experiments; however, CNS damage at the temporal lobe is involved in the pathogenesis of OSA. This article examines the role of the CNS in the pathogenesis of OSA and its mechanisms. We have summarized previous findings of OSA-related brain damage, which were obtained by brain functional MRI, clinical, and animal experiment data to better understand the roles of the CNS in the pathogenesis of OSA. More specifically, this review summarizes how altered activity of the limbic system and its related structures could be associated with the occurrence of OSA. This conclusion may contribute toward our understanding of nosogenesis and the treatment of OSA.

Cytotoxicity and apoptosis induced by nanobacteria in human breast cancer cells.

BACKGROUND: The existing evidence that nanobacteria (NB) are closely associated with human disease is overwhelming. However, their potential toxicity against cancer cells has not yet been reported. The objective of this study was to investigate the cytotoxic effects of NB and nanohydroxyapatites (nHAPs) against human breast cancer cells and to elucidate the mechanisms of action underlying their cytotoxicity. METHODOLOGY/PRINCIPAL FINDINGS: NB were isolated from calcified placental tissue, and nHAPs were artificially synthesized. The viability of the MDA-MB-231 human breast cancer cell line was tested by using the Kit-8 cell counting kit assay. Apoptosis was examined by transmission electron microscopy and flow cytometry. The endocytosis of NB and nHAPs by MDA-MB-231 cells was initially confirmed by microscopy. Although both NB and nHAPs significantly decreased MDA-MB-231 cell viability and increased the population of apoptotic cells, NB were more potent than nHAPs. After 72 hours, NB also caused ultrastructural changes typical of apoptosis, such as chromatin condensation, nuclear fragmentation, nuclear dissolution, mitochondrial swelling, and the formation of apoptotic bodies. CONCLUSION/SIGNIFICANCE: In MDA-MB-231 human breast cancer cells, NB and nHAPs exerted cytotoxic effects that were associated with the induction of apoptosis. The effects exerted by NB were more potent than those induced by nHAPs. NB cytotoxicity probably emerged from toxic metabolites or protein components, rather than merely the hydroxyapatite shells. NB divided during culturing, and similar to cells undergoing binary fission, many NB particles were observed in culture by transmission electron microscopy, suggesting they are live microorganisms.

Nanobacteria may be linked to calcification in placenta.

AIMS: Placental calcification is a common pathologic condition in obstetrics. To detect the bacteria infection mechanisms for calcification, an experiment was performed to isolate, culture, and identify the nanobacteria in placental calcification. METHOD: Sixteen cases of placental calcification of pregnant women were collected for the purpose of the isolation of nanobacteria, cultivation, and identification of 16S rDNA sequence. RESULT: Under transmission electron microscope, novel oval-shape nanobacteria-like particles (NLP) in extracellular matrix of calcified placenta tissues were found with 50-500 nm in diameter, and among hydroxyapatite crystals aggregation existed. After about 4 weeks of culturing and isolating NLP from these calcified tissues, all calcified placental tissue samples and one adjacent tissue of calcified placental tissue samples showed white granular depositions, which were firmly attached to the bottom of the culture tubes and visible to the naked eyes. In the control group they could not be seen. After PCR was amplified a 1407-bp fragment was obtained and submitted to GenBank after sequencing with accession number JN029830. The 16S rDNA sequence homology between the isolation strain and strain nanobacteria (X98418) was 92% in GenBank. CONCLUSION: For the first time isolated, cultured, and identified nanobacteria in placental calcification indicated that nanobacteria infection is related to placental calcification.

Isolation, cultivation and identification of nanobacteria from placental calcification.

OBJECTIVE: The etiology of placental calcification (PC) is lack of research. To detect the bacterial infection mechanisms for PC, the experiment of isolating, culturing and identifying the nanobacteria in PC was done. METHOD: The calcified placental tissues from 18 confirmed PC cases with normal placental tissue samples from 18 cases were studied by transmission electron microscopy (TEM), special nanobacterial culture methods, and identification of 16S rRNA sequence. RESULT: Under transmission electron microscope (TEM), Nanobacteria-like particles (NLP) in extra-cellular matrix (ECM) of calcified placental tissues were found, they were 50-500 nm in diameter, existed aggregation, among hydroxyapatite (HAP) crystals. Isolation and culture of NLP from the calcified tissues with methods described for nanobacteria were successful. All calcified placental tissue samples showed white granular deposition, which were firmly attached to the bottom of the culture tubes visible to the naked eyes. In the control group they could not be seen. According to 16S rRNA gene sequences analysis and was amplified adopting PCR and obtained 1407 bp fragment. Submit to GenBank after sequencing with accession number JN029830. CONCLUSION: Indicating that nanobacteria infection is related with placental calcification.

Mal-effects of obstructive sleep apnea on the heart.

OBJECTIVE: This study aims to examine the impact of chronic intermittent hypoxia on hearts in patients with obstructive sleep apnea (OSA). METHODS: Two hundred twenty patients were divided into groups based on (1) severity of the disease, (2) years of disease history, and (3) with or without secondary hypertension. All subjects underwent blood pressure measurements, polysomnogram monitoring, and cardiac Doppler ultrasound examinations. RESULTS: The left ventricular ejection fraction (LVEF), fractional shortening (FS), and the ratio of early to late diastolic filling (E/A) in patients with severe OSA were lower than in those with moderate OSA and in healthy controls. The inner diameters of the main pulmonary artery (inD of MPA), the inner diameters of the right cardiac ventricle (inD of RV), and the thickness of anterior wall of the right ventricle (TAW of RV) were increased in patients with severe OSA compared to those with moderate disease and worsened as a function of time with disease. The tissue Doppler imaging-derived Tei index and pulmonary artery systolic pressure were also increased along with the severity of OSA. LVEF and FS in patients who had suffered from OSA for >10 years were decreased compared with those suffering from OSA for a shorter time. LVEF and FS in patients with secondary hypertension were decreased significantly relative to non-hypertensive OSA patients and healthy controls. E/A was decreased in OSA patients whether they had secondary hypertension or not. CONCLUSION: OSA affected the left ventricular diastolic function in the early stage of the disease. Extended exposure to OSA resulted in left ventricular dysfunction with increased hypertension. Right ventricle dysfunction and abnormalities became more severe as the disease progressed.