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An organocatalyzed asymmetric Mannich reaction of pyrazoleamides and cyclic trifluoromethyl ketimines with a chiral bifunctional amine-squaramide as the catalyst was developed. A wide range of trifluoromethyl dihydroquinazolinone derivatives bearing adjacent quaternary and tertiary stereogenic centers were readily obtained in good to excellent yields (up to 99%) with high diastereo- and enantioselectivities (up to 99% ee and >20 : 1 dr). The large scale experiment and transformation of the product have also been demonstrated.
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The asymmetric Neber reaction of 3-O-sulfonyl ketoxime, in situ generated from isatin ketoxime and sulfonyl chloride, for the synthesis of chiral spirocyclic oxindole compounds is reported. With the developed protocol, a range of chiral spirooxindole 2H-azirines could be obtained in good to excellent yields and up to a 92 : 8 enantiomeric ratio by using (DHQD)2PHAL as the catalyst. This methodology is the only example of the catalytic asymmetric construction of spirooxindole 2H-azirine compounds.
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Azirinas/química , Azirinas/síntese química , Compostos de Espiro/química , Catálise , Técnicas de Química Sintética , EstereoisomerismoRESUMO
A base-mediated Neber reaction of enaminopyrazolones, which are the tautomers of 4-acyloxime-2-pyrazolin-5-ones, with sulfonyl chlorides was achieved. With this developed approach, a range of spiro-fused 2H-azirine-pyrazolones were obtained in good yields under mild conditions. A preliminary trial of a catalytic asymmetric version of the Neber reaction was conducted and gave promising enantioselectivity.
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An organocatalyzed direct asymmetric vinylogous Michael addition reaction of α,ß-unsaturated γ-butyrolactam to 2-enoylpyridines has been developed with a chiral bifunctional amine-squaramide as the catalyst. This approach provides easy access to a series of optically active α,ß-unsaturated γ-substituted butyrolactams in high yields (up to 99%) with excellent diastereoselectivities (up to >99 : 1) and enantioselectivities (up to >99% ee).
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For the first time, a catalytic asymmetric Henry reaction of 1H-pyrrole-2,3-diones was achieved with a chiral bifunctional amine-thiourea as a catalyst possessing multiple hydrogen-bond donors. With this developed method, a range of 3-hydroxy-3-nitromethyl-1H-pyrrol-2(3H)-ones bearing quaternary stereocenters were obtained in acceptable yield (up to 75%) and enantioselectivity (up to 73% ee).
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Enantioselective Michael/cyclization cascade reactions of 3-hydroxyoxindoles/3-aminooxindoles with α,ß-unsaturated acyl phosphonates by using a cinchonine derived squaramide as the catalyst were developed. A broad range of spirocyclic oxindole-γ-lactones/lactams could be obtained in moderate to excellent yields (up to 98%) with good to excellent diastereo- and enantioselectivities (up to >99:1 dr and 97% ee) under mild conditions. This work represents the first example about the α,ß-unsaturated acyl phosphonates for the asymmetric construction of spirocyclic oxindoles.
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Environmentally friendly waste management (EFWM) is a safer way of waste disposal that can foster a cleaner environment for both farms and their surroundings. It may lessen land, air, and water pollution, as well as moderate ecological footprints, and aid in sustainable agricultural development, which has become one of the major concerns of the modern era. To achieve these outcomes, incentives and control mechanisms initiated by the government may alter farmers' behavior. The study involved a review of relevant literature and the conduct of interviews with 499 pig breeders to evaluate the impacts of government incentives and control mechanisms on fostering the adoption of environmentally friendly waste management practices by farmers. A theoretical framework based on existing studies is proposed, utilizing a structural equation modeling (SEM) approach to analyze the data and illustrate the relationships among incentives and control mechanisms. The results show that: (i) overall the impacts of incentive mechanisms were stronger and more effective than those of control mechanisms. Among them, subsidy policy and discount policy were the most influential for farmers' adoption behavior. However, penalty and disincentive policy also impacted the outcome variables; (ii) a significant relationship was observed among regulatory, disincentive, and subsidy policies and a moderate relationship among penalty, insurance, and discount policies. However, bonus-community service and social critic policies did not show any significant relationship with any other variables. The research findings can assist the Chinese government in gaining a comprehensive understanding of the impacts of two crucial mechanisms and promoting the adoption of environmentally friendly practices by farmers. The government should highlight and strengthen the importance of social obligations and orientation, as well as providing monetary support at the rural level to improve farmers' ability to adapt to environmentally friendly waste management practices.
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An objective understanding of the current situation and influencing factors of rural green development in China is an important prerequisite for effective formulation making of green development policies. Based on the panel data of 31 provinces of China from the year 1997 to 2017, this paper constructs and measures the rural green development efficiency (RGDE) based on Driving-Force, Pressure, State, Influence, Response (DPSIR) model and super-efficiency slacks-based measure (SBM) model. The results show that, the overall RGDE in China is fluctuating and rising from 1997 to 2017, and there are some differences between and within regions. The RGDE in developed areas is higher than that in developing areas, and coastal areas are higher than that in inland areas. The entire country, eastern, central, and western regions show σ convergence, which indicates that the RGDE is getting better, but there is no absolute ß convergence, that means there is no "catch-up effect" between regions, but the gradient divergence showed central > eastern > western. At the same time, there is no conditional ß convergence; the initial RGDE has a positive impact on the growth rate of RGDE, and the financial self-sufficiency rate promotes the growth of RGDE of the whole country and the western region, but inhibits the improvement of RGDE of the eastern region. The per capita GDP, mechanization degree, and agricultural industrial structure in rural areas did not promote the growth of RGDE. Based on the results, this paper puts forward some policy suggestions, such as promoting the classified implementation of rural green development policies, strengthening the top-level design, optimizing the existing agricultural mechanism and system, and guiding and standardizing the farmers' green production behavior.
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Eficiência , Planejamento Social , Agricultura , China , Humanos , IndústriasRESUMO
Organocatalytic asymmetric dearomatization of 3-nitroindoles and 3-nitrobenzothiophenes by reaction with ethyl 4-mercapto-2-butenoate has been developed. A range of chiral tetrahydrothiopheneindolines and tetrahydrothiophenebenzothiophenes bearing three contiguous stereocenters are obtained in high yields with good diastereoselectivities and excellent enantioselectivities. This is the first example of thiol-triggered catalytic asymmetric dearomatization of 3-nitroindoles and 3-nitrobenzothiophenes.
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Objective:To assess the levels of self-compassion, psychological resilience, and academic adjustment of undergraduate students in a military medical university, and analyze their influencing factors and interactions.Methods:A total of 341 undergraduate students were selected by convenience and purposive sampling in a military medical university from April to May, 2022 for surveys with the General Information Questionnaire, the Chinese version of the Self-Compassion Scale, the Chinese version of the Connor-Davidson Resilience Scale, and the Academic Adjustment Scale for College Students. The collected data were analyzed through univariable analysis and multiple linear regression analysis to determine the influencing factors. AMOS 23.0 was used for path analysis.Results:The scores of self-compassion, psychological resilience, and academic adjustment of the students were at slightly high levels, with a significant positive correlation between one and another ( r s=0.580-0.611, all P<0.001). The influencing factors included professional identity, the level of received support, grade, time spent in student clubs, and the plan of postgraduate study (all P<0.05). The standardized direct effect of self-compassion on academic adjustment was 0.285 ( P=0.001), and the sum of the standardized mediating effects of psychological resilience and professional identity on self-compassion and academic adjustment was 0.314 ( P=0.001). The total mediating effect accounted for 52.42% of the total effect. Conclusions:The levels of self-compassion, psychological resilience, and academic adjustment of undergraduate students in the military medical university are influenced by multiple factors. Relevant departments should pay attention to specific populations and take targeted measures to increase the students' self-compassion, psychological resilience, and academic adjustment.
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BACKGROUND@#There is little published evidence about the role of non-alcoholic fatty liver disease (NAFLD) in the progression from prehypertension to hypertension. This study was conducted to investigate the association of NAFLD and its severity with the risk of hypertension developing from prehypertension.@*METHODS@#The study cohort comprised 25,433 participants from the Kailuan study with prehypertension at baseline; those with excessive alcohol consumption and other liver diseases were excluded. NAFLD was diagnosed by ultrasonography and stratified as mild, moderate, or severe. Univariable and multivariable Cox proportional hazard regression was used to calculate the hazard ratios (HRs) and 95% confidence intervals (CIs) of incident hypertension according to the presence and 3 categories of severity of NAFLD.@*RESULTS@#During a median of 12.6 years of follow-up, 10,638 participants progressed to hypertension from prehypertension. After adjusting for multiple risk factors, patients with prehypertension and NAFLD had a 15% higher risk of incident hypertension than those without NAFLD (HR = 1.15, 95% CI 1.10-1.21). Moreover, the severity of NAFLD was associated with the incidence of hypertension, which was higher in patients with more severe NAFLD (HR = 1.15 [95% CI 1.10-1.21] in the mild NAFLD group; HR = 1.15 [95% CI 1.07-1.24] in the moderate NAFLD group; and HR = 1.20 [95% CI 1.03-1.41] in the severe NAFLD group). Subgroup analysis indicated that age and baseline systolic blood pressure may modify this association.@*CONCLUSIONS@#NAFLD is an independent risk factor for hypertension in patients with prehypertension. The risk of incident hypertension increases with the severity of NAFLD.
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Humanos , Hepatopatia Gordurosa não Alcoólica/complicações , Pré-Hipertensão/diagnóstico , Fatores de Risco , Hipertensão , IncidênciaRESUMO
Objective:To explore the efficacy and safety of endoscopic injection of polidocanol combined with low-dose tissue glue occlusion in the treatment of F3 esophageal varices in liver cirrhosis.Methods:Retrospective analysis was made on 42 patients with cirrhosis type F3 esophageal varices admitted to the Affiliated Hospital of Zunyi Medical University from January 2020 to June 2021. According to different treatment methods, they were divided into the observation group and the control group, with 21 cases in each group. The observation group received endoscopic injection of polidocanol combined with low-dose tissue glue occlusion, while the control group received endoscopic injection of polidocanol. The differences in the effectiveness (remission rate of varices) and safety (incidence of intraoperative bleeding and postoperative rebleeding, incidence of ectopic embolism, incidence of esophageal ulcer, incidence of esophageal perforation, incidence of esophageal stricture) of the two groups of patients were compared.Results:The total effective rate of relieving esophageal varices in the observation group was significantly better than that in the control group [95.2%(20/21) vs 61.9%(13/21), χ 2=6.929, P=0.008]. There were no cases of ectopic embolism in both groups; The intraoperative bleeding rate in the observation group was 4.8% (1/21), significantly lower than the 38.1% (8/21) in the control group (χ 2=6.929, P=0.008); There was no statistically significant difference in postoperative rebleeding rates between the two groups [33.3%(7/21) vs 23.8%(5/21), χ 2=0.467, P=0.495]; The incidence of esophageal ulcers in the observation group was higher than that in the control group [23.8%(5/21) vs 0, χ 2=5.676, P=0.017], mainly caused by glue discharge ulcers; There were no cases of esophageal perforation and esophageal stricture in both groups. Conclusions:Endoscopic injection of polidocanol combined with low-dose tissue glue occlusion for the treatment of F3 esophageal varices in liver cirrhosis is safe, can greatly reduce the occurrence of intraoperative bleeding, and has a better one-time variceal eradication effect.
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CONCLUSIONS: The perineural vascular plexus is a reliable indicator for the detection of the horizontal segment of the facial nerve in surgery for otologists and neurologists. OBJECTIVE: To evaluate the validity and reliability of the perineural vascular plexus for locating the facial nerve in microsurgery of the ear to avoid iatrogenic facial paralysis. PATIENTS AND METHODS: Our study group comprised 311 patients who underwent tympanoplasty or facial nerve decompression from July 2002 to July 2005. The validity of using the perineural vascular plexus to locate the facial nerve was observed and assessed. RESULTS: The perineural vascular plexus was well differentiated on the horizontal mesotympanic segment of the nerve in 95.8% of patients. The 95% confidence interval was 93.6-98.0%.
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Orelha Média/irrigação sanguínea , Orelha Média/inervação , Nervo Facial/anatomia & histologia , Cuidados Intraoperatórios , Osso Temporal/irrigação sanguínea , Osso Temporal/inervação , Descompressão Cirúrgica , Nervo Facial/cirurgia , Humanos , Microcirculação , Microcirurgia , TimpanoplastiaRESUMO
A method for the enantioselective construction of hydrocarbazole skeletons through dearomative [4 + 2] annulation of 3-nitroindoles with Nazarov reagents is reported. The reactions use multiple hydrogen-bonding bifunctional thiourea as catalyst and are highly diastereo- and enantioselective (up to >20:1 dr and >99% ee). The protocol was demonstrated by preparative-scale experiment and the versatile conversion of the products. The multiple hydrogen-bonding in the catalyst plays a pivotal role in the reactivity and stereoselectivity.
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OBJECTIVE@#To investigate the therapeutic effects of total saponins from Panax notognseng (PNS) combined with cyclophosphamide (CTX) in mice bearing hepatocellular carcinoma H22 cell xenograft.@*METHODS@#We examined the effects of treatment with different concentrations of PNS on H22 cell proliferation for 24 to 72 h in vitro using CCK8 colorimetric assay. Annexin V/PI double fluorescence staining was used to detect the effect of PNS on apoptosis of H22 cells. Mouse models bearing H22 cell xenograft were established and treated with CTX (25 mg/kg), PNS (120, 240 or 480 mg/kg), alone or in combinations. After treatments for consecutive 10 days, the mice were euthanized for examinations of carbon clearance ability of the monocytes and macrophages, splenic lymphocyte proliferation, tumor necrosis factor (TNF-α), interleukin-2 (IL-2), serum hemolysin antibody level, blood indicators, and the tumor inhibition rate.@*RESULTS@#Treatment with PNS concentration-dependently inhibited the proliferation and significantly promoted apoptosis of cultured H22 cells (P < 0.01). In the tumor-bearing mouse models, PNS alone and its combination with CTX both resulted in obvious enhancement of phagocytosis of the monocyte-macrophages, stimulated the proliferation of splenic lymphocytes, promoted the release of TNF-α and IL-2 and the production of serum hemolysin antibody, and increased the number of white blood cells, red blood cells and lymphocytes in the peripheral blood. Treatment with 480 mg/kg PNS combined with CTX resulted in a tumor inhibition rate of 83.28% (P < 0.01) and a life prolonging rate of 131.25% in the mouse models (P < 0.05).@*CONCLUSION@#PNS alone or in combination with CTX can improve the immunity and tumor inhibition rate and prolong the survival time of H22 tumor-bearing mice.
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Animais , Humanos , Camundongos , Carcinoma Hepatocelular/patologia , Ciclofosfamida/uso terapêutico , Proteínas Hemolisinas , Xenoenxertos , Interleucina-2 , Neoplasias Hepáticas/patologia , Panax notoginseng , Saponinas/uso terapêutico , Fator de Necrose Tumoral alfaRESUMO
This paper presents a robust information theoretic (RIT) model to reduce the uncertainties, i.e., missing and noisy labels, in general discriminative data representation tasks. The fundamental pursuit of our model is to simultaneously learn a transformation function and a discriminative classifier that maximize the mutual information of data and their labels in the latent space. In this general paradigm, we, respectively, discuss three types of the RIT implementations with linear subspace embedding, deep transformation, and structured sparse learning. In practice, the RIT and deep RIT are exploited to solve the image categorization task whose performances will be verified on various benchmark data sets. The structured sparse RIT is further applied to a medical image analysis task for brain magnetic resonance image segmentation that allows group-level feature selections on the brain tissues.
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Purpose@#The aim of this study was to examine the behavioral responses of pregnant women during the early stage of Coronavirus Disease 2019 (COVID-19) outbreak. @*Methods@#We recruited 1,099 women to complete an online questionnaire survey from February 10 to February 25, 2020. The subjects were divided into two groups (the pregnant women group and the control group). @*Results@#Concerns about infection: most of the participants watched the COVID-19 news at least once a day. Protective behaviors: the utilization rate of pregnant women (often using various measures) was higher than that of nonpregnant women. Exercise: 30.6% of the pregnant women continued to exercise at home, whereas in the control group, this percentage was 8.4%. Spouse relationship: 38.8% of the subjects’ relationship improved, whereas only 2.3% thought the relationship was getting worse. @*Conclusion@#Pregnant women had some unique behavioral responses different from that of nonpregnant women. It is important to understand the behavioral responses of pregnant women in this network era.
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Purpose@#The aim of this study was to examine the behavioral responses of pregnant women during the early stage of Coronavirus Disease 2019 (COVID-19) outbreak. @*Methods@#We recruited 1,099 women to complete an online questionnaire survey from February 10 to February 25, 2020. The subjects were divided into two groups (the pregnant women group and the control group). @*Results@#Concerns about infection: most of the participants watched the COVID-19 news at least once a day. Protective behaviors: the utilization rate of pregnant women (often using various measures) was higher than that of nonpregnant women. Exercise: 30.6% of the pregnant women continued to exercise at home, whereas in the control group, this percentage was 8.4%. Spouse relationship: 38.8% of the subjects’ relationship improved, whereas only 2.3% thought the relationship was getting worse. @*Conclusion@#Pregnant women had some unique behavioral responses different from that of nonpregnant women. It is important to understand the behavioral responses of pregnant women in this network era.
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A highly diastereo- and enantioselective [3+2] cycloaddition reaction of N-2,2,2-trifluoroethylisatin ketimines and 3-alkenyl-5-arylfuran-2(3H)-ones was developed with 1 mol% thiourea-tertiary amine as the catalyst. A series of spiro[pyrrolidin-3,2'-oxindoles] bearing four consecutive stereocenters, including two vicinal spiro-quaternary chiral centers, were efficiently obtained with excellent results (up to >99% yield, >20 : 1 dr, and >99% ee).
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Objective: To retrospectively analyze the allergen characteristics and the onset season of allergic rhinitis (AR) patients in Shanghai, China. Methods: From Jan. 1, 2015 to Dec. 31, 2017, 1 570 suspected AR patients were selected from the Department of Otolaryngology/Head and Neck Surgery, Changzheng Hospital, Naval Medical University (Second Military Medical University). One milliliter of serum was extracted from each patient and the specific immunoglobulin E (IgE) levels of 22 kinds of allergens and total IgE levels were detected using allergen specific IgE antibody detection kit (immunoblotting method). The AR patients were divided into 5-16, 17-39, 40-64 and ≥65 years old groups, and the positive rates of allergens were compared. The number of AR patients with one or more positive allergens was recorded every month, and the seasonal distribution of positive allergen was analyzed. Results: Of the 1 570 suspected AR patients, 143 (9.1%) had elevated serum total IgE, and 1 182 (75.3%) had one or more positive allergens, including 491 (41.5%) with single positive allergen and 691 (58.5%) with two or more positive allergens. Among the 22 kinds of allergens, dust mites (including Dermatophagoides pteronyssinus and Dermatophagoides farinae) were the most common allergens (715 cases, 60.5%), followed by penicillin (239 cases, 20.2%) and Chinese parasol (167 cases, 14.1%). Among the 1 182 AR patients, 17-39 years old was the highest proportion (61.0%, 721 cases). The positive rate of dust mites in the 5-16 years old group was significantly higher than those in the 17-39, 40-64 and ≥65 years old groups (all P<0.05). The prevalence peaks of AR were in Apr., May, Jun., Aug., Sep., Oct. and Nov.; and the numbers of AR patients with one or more positive allergens were 175±21, 156±16, 259±31, 172±15, 176±14, 164±4 and 204±32, respectively, which were significantly higher than the average value (97±42) of 36 months from Jan. 1, 2015 to Dec. 31, 2017 (all P<0.05). The positive detection time of dust mites was mainly in May, Jun., Jul., Aug., Sep. and Nov.; and the numbers of dust mite positive AR patients were 64±11, 113±21, 68±18, 76±15, 70±11 and 89±21, respectively, which were significantly higher than the average value (52±32) of the 36 months (all P<0.05). Conclusion: Dust mites are the most common and main allergens of AR patients in Shanghai, China. The proportion is high in AR patients aged 17-39 years old, and the prevalence peaks are from Apr. to Jun. and from Aug. to Nov..