[3+1+1+1] Annulation to the Pyridine Structure in Quinoline Molecules Based on DMSO as a Nonadjacent Dual-Methine Synthon: Simple Synthesis of 3-Arylquinolines from Arylaldehydes, Arylamines, and DMSO.

A [3+1+1+1] annulation of arylamines, arylaldehydes, and dimethyl sulfoxide (DMSO) to the pyridine structure in quinolines using DMSO as a nonadjacent dual-methine (═CH-) synthon is disclosed. In this annulation, arylamines provide two carbon atoms and one nitrogen atom, arylaldehydes furnish one carbon atom, and DMSO provides two nonadjacent methines (═CH-) to the pyridine ring in quinoline molecules. This annulation provides a simple approach for the synthesis of 3-arylquinolines from readily available substrates in useful yields. On the basis of the control experiments and the literature, a plausible mechanism is proposed.

Regioselective Synthetic Approach to Higher Alkenes from Lower Alkenes with Sulfoxides in the Fe3+/H2O2 System via Direct Alkylation or Arylation of the Csp2-H Bond on the C═C Bond of Alkenes.

The regioselective synthetic approach to higher alkenes from lower alkenes by using sulfoxides as alkyl or aryl reagents in the Fe3+/H2O2 system has been developed. This reaction realized direct alkylation or arylation of alkenes. In this reaction, sulfoxides afforded one Csp3 or Csp2 atom to the C═C bond of alkenes; one new Csp2-Csp3 bond or Csp2-Csp2 bond was formed. Nearly 40 products including di-, tri-, and tetra-substituted products were regioselectively synthesized. Both aliphatic and aromatic alkenes could participate in this reaction. Moreover, not only dimethyl sulfoxide but also three other sulfoxides can be applied to this reaction, including diethyl, dibenzyl, and diphenyl sulfoxide. The mechanism studies showed that this reaction may experience a coupling process via radical addition-elimination and the Fe3+/H2O2 system made the sulfoxides offered one alkyl or aryl radical to the C═C bond of alkenes.

[Risk factors for postoperative long-term hematuria in patients with benign prostatic hyperplasia].

OBJECTIVE: To explore the risk factors for long-term hematuria after operation in BPH patients. METHODS: We retrospectively analyzed the clinical data on 646 cases of BPH treated by transurethral surgery in Liyang People's Hospital from January 2015 to August 2020. According to the incidence of hematuria at 3 months or longer after surgery, we divided the patients into a hematuria and a non-hematuria group, recorded the related factors, and investigated the independent risk factors for long-term hematuria by univariate and multivariate analyses. RESULTS: Of the 646 BPH patients, 48 were found with and 598 without hematuria after transurethral surgery. Univariate analysis showed that hypertension, diabetes mellitus, residual prostate gland, urinary tract infection, bladder neck contracture, prostate cancer, urethral calculus, urethral stricture, excessive activity and constipation were the influencing factors (P < 0.05), while multivariate logistic regression analysis revealed that hypertension (P < 0.001), diabetes mellitus (P = 0.007), residual prostate gland (P = 0.013), urinary tract infection (P < 0.001), bladder neck contracture (P = 0.032), urethral calculus (P = 0.033) and urethral stricture (P = 0.001) were independent risk factors for long-term hematuria in the BPH patients after surgery. CONCLUSION: Complicated hypertension, diabetes mellitus, residual prostate gland, urinary tract infection, bladder neck contracture, urethral calculus and urethral stricture are independent risk factors for long-term hematuria in BPH patients after transurethral surgery.

Unexpected Annulation between 2-Aminobenzyl Alcohols and Benzaldehydes in the Presence of DMSO: Regioselective Synthesis of Substituted Quinolines.

An unexpected annulation among 2-aminobenzyl alcohols, benzaldehydes, and DMSO to quinolines has been disclosed. For the reported annulation between 2-aminobenzyl alcohols and benzaldehydes, the change of the solvent from toluene to DMSO led to the change of the product from the diheteroatomic cyclic benzoxazines to monoheteroatomic cyclic quinolines. This annulation can be used to synthesize regioselectively different substituted quinolines by the choice of different 2-amino alcohols, aldehydes, and sulfoxides as substrates. Interestingly, introducing substituent groups to the α-position of sulfoxides resulted in the interchange of the positions between benzaldehydes and sulfoxides in the product quinolines. On the basis of the control experiments and literatures, a plausible mechanism for this annulation was proposed.

Two C═C Bond Participation in Annulation to Pyridines Based on DMF as the Nonadjacent N and C Atom Donors.

Two C═C bond participation in annulation to pyridines using N,N-dimethylformamide (DMF) as the N1 and C4 synthons has been carried out. In this reaction, DMF contributed one N atom and one C atom to two disconnected positions of pyridine ring, with no need for an additional nitrogen source. Two C═C bonds in two molecules of substituted styrenes offered four carbon atoms in the presence of iodine and persulfate. With the optimized conditions in hand, both symmetric and unsymmetric diaryl-substituted pyridines were obtained in useful yields. On the basis of relevant literature and a series of control experimental results, a possible mechanism was proposed in this work, which may demonstrate how DMF provides both N1 and C4 sources.

Metal-Free-Catalyzed Synthesis of Allyl Nitriles via Csp2-Csp3 Coupling between Olefins and Azobis (Alkyl-carbonitrile).

The metal-free-catalyzed synthesis of allyl nitriles from Csp2-Csp3 coupling between olefins and azobis was carried out. Key on this work was that the synthesis of allyl nitriles directly using olefin as a starting material was considered to be more efficient and economical than the alkyne, alkynyl carboxylic acid, or cinnamic acid used in previous works. Moreover, in this reaction, iodine served as the sole promoter, azobis served as a cyanation reagent, and N2 was the only nontoxic byproduct that could avoid the utilization of metal catalysts and virulent nitrile reagents and generation of toxic wastes. With an optimum condition in hand, more than 30 examples of desired products including aromatic and aliphatic nitriles have been synthesized in good to excellent yields. Based on control experiments and literature data, a plausible mechanism of cyanation was proposed.

Transition-Metal-Free Oxidative Decarboxylative Cross Coupling of α,ß-Unsaturated Carboxylic Acids with Cyclic Ethers under Air Conditions: Mild Synthesis of α-Oxyalkyl Ketones.

A novel K2S2O8-promoted decarboxylative cross coupling of α,ß-unsaturated carboxylic acids with cyclic ethers was developed under aerobic conditions. The present protocol, which includes C-C and C═O bond formation in one step through addition, oxidation, and decarboxylation processes, leads to the desired ketone products in moderate to excellent yields. In addition, mechanism studies showed that the transformation process undergoes a radical pathway via a direct activation of the α-sp3 C-H bond of oxygen of the cyclic ether.

Transition Metal-Free α-Csp3-H Methylenation of Ketones to Form C═C Bond Using Dimethyl Sulfoxide as Carbon Source.

A direct α-Csp3-H methylenation of arylketones to form C═C bond using dimethyl sulfoxide as one-carbon source is achieved under transition metal-free reaction condition. Various aryl ketone derivatives react readily with DMSO, producing the α,ß-unsaturated carbonyl compounds in yields of 42 to 90%. This method features a transition metal-free reaction condition, wide substrate scope and using DMSO as novel one-carbon source to form C═C bond, thus providing an efficient and expeditious approach to an important class of α,ß-unsaturated carbonyl compounds. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.

Fruit and vegetable intake and breast cancer prognosis: a meta-analysis of prospective cohort studies.

The effect of fruit and vegetable intake on breast cancer prognosis is controversial. Thus, a meta-analysis was carried out to explore their associations. A comprehensive search was conducted in PubMed, Web of Science, OVID, ProQuest and Chinese databases from inception to April 2016. The summary hazard ratios (HR) and 95 % CI were estimated using a random effects model if substantial heterogeneity existed and using a fixed effects model if not. Subgroup analyses and sensitivity analyses were also performed. In total, twelve studies comprising 41 185 participants were included in the meta-analysis. Comparing the highest with the lowest, the summary HR for all-cause mortality were 1·01 (95 % CI 0·72, 1·42) for fruits and vegetables combined, 0·96 (95 % CI 0·83, 1·12) for total vegetable intake, 0·99 (95 % CI 0·89, 1·11) for cruciferous vegetable intake and 0·88 (95 % CI 0·74, 1·05) for fruit intake; those for breast cancer-specific mortality were 1·05 (95 % CI 0·77, 1·43) for total vegetable intake and 0·94 (95 % CI 0·69, 1·26) for fruit intake; and those for breast cancer recurrence were 0·89 (95 % CI 0·53, 1·50) for total vegetable intake and 0·98 (95 % CI 0·76, 1·26) for cruciferous vegetable intake. This meta-analysis found no significant associations between fruit and vegetable intake and breast cancer prognosis.

Serum betaine but not choline is inversely associated with breast cancer risk: a case-control study in China.

PURPOSE: Choline and betaine are important for DNA methylation and synthesis, and may affect tumor carcinogenesis. To our knowledge, no previous study has examined the association between serum choline and betaine and breast cancer risk. This study aimed to examine whether serum choline and betaine were inversely associated with breast cancer risk among Chinese women. METHODS: This hospital-based case-control study consecutively recruited 510 breast cancer cases and 518 frequency-matched (age and residence) controls, and blood samples were available for 500 cases and 500 controls. Serum choline and betaine were assayed by high-performance liquid chromatography-tandem mass spectrometry. Multiple unconditional logistic regression was used to estimate odds ratios (ORs) and 95 % confidence intervals (CIs). RESULTS: An inverse association with breast cancer risk was observed for serum betaine (fourth vs first quartile adjusted OR 0.68, 95 % CI 0.47-0.97) and for the ratio of serum betaine to choline (fourth vs first quartile adjusted OR 0.70, 95 % CI 0.48-1.00), but not for serum choline (fourth vs first quartile adjusted OR 0.80, 95 % CI 0.56-1.15). Serum betaine was inversely associated with breast cancer risk in subjects with below-median dietary folate intake (fourth vs first quartile adjusted OR 0.48, 95 % CI 0.30-0.77). CONCLUSIONS: This study suggested that serum betaine but not choline was inversely associated with breast cancer risk. This result needed to be further confirmed by the prospective studies.

Specific serum carotenoids are inversely associated with breast cancer risk among Chinese women: a case-control study.

Previous epidemiological studies have revealed the anti-cancer effect of dietary circulating carotenoids. However, the protective role of specific individual circulating carotenoids has not been elucidated. The purpose of this study was to examine whether serum carotenoids, including α-carotene, ß-carotene, ß-cryptoxanthin, lycopene and lutein/zeaxanthin, could lower the risk for breast cancer among Chinese women. A total of 521 women with breast cancer and age-matched controls (5-year interval) were selected from three teaching hospitals in Guangzhou, China. Concentrations of α-carotene, ß-carotene, ß-cryptoxanthin, lycopene and lutein/zeaxanthin were measured using HPLC. Unconditional logistic regression models were used to calculate OR and 95% CI using quartiles defined in the control subjects. Significant inverse associations were observed between serum α-carotene, ß-carotene, lycopene, lutein/zeaxanthin and the risk for breast cancer. The multivariate OR for the highest quartile of serum concentration compared with the lowest quartile were 0·44 (95% CI 0·30, 0·65) for α-carotene, 0·27 (95% CI 0·18, 0·40) for ß-carotene, 0·41 (95% CI 0·28, 0·61) for lycopene and 0·26 (95% CI 0·17, 0·38) for lutein/zeaxanthin. However, no significant association was found between serum ß-cryptoxanthin and the risk for breast cancer. Stratified analysis by menopausal status and oestrogen receptor (ER)/progesterone receptor (PR) showed that serum α-carotene, ß-carotene, lycopene and lutein/zeaxanthin were inversely associated with breast cancer risk among premenopausal women and among all subtypes of ER or PR status. The results suggest a protective role of α-carotene, ß-carotene, lycopene and lutein/zeaxanthin, but not ß-cryptoxanthin, in breast cancer risk.

Dietary choline and betaine intake, choline-metabolising genetic polymorphisms and breast cancer risk: a case-control study in China.

Choline and betaine are essential nutrients involved in one-carbon metabolism and have been hypothesised to affect breast cancer risk. Functional polymorphisms in genes encoding choline-related one-carbon metabolism enzymes, including phosphatidylethanolamine N-methyltransferase (PEMT), choline dehydrogenase (CHDH) and betaine-homocysteine methyltransferase (BHMT), have important roles in choline metabolism and may thus interact with dietary choline and betaine intake to modify breast cancer risk. This study aimed to investigate the interactive effect of polymorphisms in PEMT, BHMT and CHDH genes with choline/betaine intake on breast cancer risk among Chinese women. This hospital-based case-control study consecutively recruited 570 cases with histologically confirmed breast cancer and 576 age-matched (5-year interval) controls. Choline and betaine intakes were assessed by a validated FFQ, and genotyping was conducted for PEMT rs7946, CHDH rs9001 and BHMT rs3733890. OR and 95 % CI were estimated using unconditional logistic regression. Compared with the highest quartile of choline intake, the lowest intake quartile showed a significant increased risk of breast cancer. The SNP PEMT rs7946, CHDH rs9001 and BHMT rs3733890 had no overall association with breast cancer, but a significant risk reduction was observed among postmenopausal women with AA genotype of BHMT rs3733890 (OR 0·49; 95 % CI 0·25, 0·98). Significant interactions were observed between choline intake and SNP PEMT rs7946 (P interaction=0·029) and BHMT rs3733890 (P interaction=0·006) in relation to breast cancer risk. Our results suggest that SNP PEMT rs7946 and BHMT rs3733890 may interact with choline intake on breast cancer risk.

High consumption of vegetable and fruit colour groups is inversely associated with the risk of colorectal cancer: a case-control study.

The colour of the edible portion of vegetables and fruit reflects the presence of specific micronutrients and phytochemicals. No existing studies have examined the relationship between the intake of vegetable and fruit colour groups and the risk of colorectal cancer. The present study, therefore, aimed to investigate these associations in a Chinese population. A case-control study was conducted between July 2010 and July 2014 in Guangzhou, China, in which 1057 consecutively recruited cases of colorectal cancer were frequency-matched to 1057 controls by age (5-year interval), sex and residence (rural/urban). A validated FFQ was used to collect dietary information during face-to-face interviews. Vegetables and fruit were classified into four groups according to the colour of their primarily edible parts: green; orange/yellow; red/purple; white. Unconditional logistic regression models were used to estimate the OR and 95 % CI. A higher consumption of orange/yellow, red/purple and white vegetables and fruit was inversely associated with the risk of colorectal cancer, with adjusted OR of 0·16 (95 % CI 0·12, 0·22) for orange/yellow, 0·23 (95 % CI 0·17, 0·31) for red/purple and 0·53 (95 % CI 0·40, 0·70) for white vegetables and fruit when the highest and lowest quartiles were compared. Total vegetable intake and total fruit intake have also been found to be inversely associated with colorectal cancer risk. However, the intake of green vegetable and fruit was not associated with colorectal cancer risk. The results of the present study, therefore, suggest that a greater intake of orange/yellow, red/purple and white vegetables and fruit is inversely associated with the risk of colorectal cancer.

Higher intake of carotenoid is associated with a lower risk of colorectal cancer in Chinese adults: a case-control study.

PURPOSE: The associations between specific carotenoid intake and colorectal cancer risk remain inconsistent. The aim of this study was to examine the association between specific dietary carotenoid intake with colorectal cancer risk in Chinese adults. METHOD: From July 2010 to October 2013, 845 eligible colorectal cancer cases and 845 frequency-matched controls (age and sex) completed in-person interviews. A validated food frequency questionnaire was used to estimate dietary intake. Multivariate logistical regression models were used to calculate the odds ratio (OR) and 95% confidence intervals (95% CIs) of colorectal cancer risk after adjusting for various confounders. RESULTS: A strong inverse association was found between ß-cryptoxanthin intake and colorectal cancer risk. Compared with the lowest quartile, the highest quartile intake showed a risk reduction of 77% (OR 0.23, 95% CI 0.17-0.33, P trend < 0.01) after adjustment for various confounding variables. The inverse associations were also observed for α-carotene (OR 0.50, 95% CI 0.37-0.68, P trend < 0.01), ß-carotene (OR 0.67, 95% CI 0.49-0.91, P trend < 0.01), and lycopene (OR 0.51, 95% CI 0.37-0.70, P trend < 0.01). There was no statistically significant association between lutein/zeaxanthin intake and colorectal cancer risk. These findings were consistent across cancer site, sources of controls, and smoking status. The inverse associations between dietary α-carotene, ß-cryptoxanthin, and lycopene intake and colorectal cancer risk were found in both males and females, while inverse associations between ß-carotene intake and colorectal cancer risk were only observed in males. CONCLUSIONS: Consumption of α-carotene, ß-carotene, ß-cryptoxanthin, and lycopene was inversely associated with colorectal cancer risk. No significant association was found between lutein/zeaxanthin intake and colorectal cancer risk.

Oxidative rearrangement of internal alkynes to give one-carbon-shorter ketones via manganese porphyrins catalysis.

Oxidative rearrangement of internal alkynes catalyzed by manganese(III) porphyrin is described, which opens a new access to one-carbon-shorter ketones using molecular oxygen. Under the standard conditions, a variety of alkynes including diarylalkynes and arylalkylalkynes rearranged smoothly to the corresponding ketones in high yields. Based upon experimental observations, a plausible reaction mechanism is proposed.

Joint effects of folate intake and one-carbon-metabolizing genetic polymorphisms on breast cancer risk: a case-control study in China.

This study aimed to examine the joint effects of folate intake, polymorphisms of 5,10- methylenetetrahydrofolate reductase (MTHFR), methionine synthesis reductase (MTRR) and methionine synthase (MTR) genes and breast cancer risk. A case-control study of 570 consecutively recruited breast cancer cases and 576 controls was conducted in Guangzhou, China. Multifactor dimensionality reduction and logistic regression approach were used to evaluate gene-gene interaction. The covariates were chosen based on comparison of baseline characteristics of cases and controls. Folate intake was found to be inversely associated with breast cancer risk. The MTRRrs162036 GG genotype was associated with a decreased risk of breast cancer [adjusted odds ratio (OR) 0.41, 95% confidence interval (CI) 0.20-0.85]. Compared with the wild-type group (MTRRrs162036 AA with MTRrs1805087 AA) MTRRrs162036 AA with MTRrs1805087 GA + GG was associated with a decreased risk (OR 0.70, 95% CI 0.48-1.03). With the combined MTHFRrs1801131 TT and MTHFRrs1801133 GG genotypes as a reference, MTHFRrs1801131 TT with MTHFRrs1801133 GA + AA was associated with a decreased risk (OR 0.78, 95% CI 0.57 - 1.08) and MTHFRrs1801131 GT + GG with MTHFRrs1801133 GA + AA was associated with an increased risk (OR 1.35, 95% CI 0.88-2.05). The joint impact of MTRRrs162036 and MTRrs1805087, MTHFRrs1801131 and MTHFRrs1801133, folate and MTHFRrs1801133 may contribute to breast cancer risk.

High serum iron level is associated with an increased risk of hypertensive disorders during pregnancy: a meta-analysis of observational studies.

The exact cause of hypertensive disorders in pregnancy (HDP) has not been clearly elucidated. Some researchers have recently investigated the relationship between the serum iron level and the incidence of HDP. However, the results are inconsistent, and these data have not been systematically evaluated. Therefore, we conducted a meta-analysis to evaluate the real association between the serum iron level and the incidence of HDP. We searched for published and ongoing trials in PubMed, EMBASE, Scopus, Web of Science, the Chinese Biomedical Database, CNKI, and the WANFANG database from January 1990 to May 2015 to identify studies that met our predefined criteria. Finally, 26 studies, including 1 cross-sectional study, 23 case-control studies, and 2 prospective nested case-control studies, including 1349 patients and 1119 control participants, were selected for this meta-analysis. The pooled results show that a high serum iron level increased the incidence of HDP (standard mean deviation [SMD], 1.50; 95% confidence interval [CI], 0.94-2.06; P < .0001), especially gestational hypertension (SMD, 3.65; 95% CI, 1.50-5.81; P = .0009) and preeclampsia (SMD, 1.27; 95% CI, 0.76-1.78; P < .0001). No significant difference was seen between the eclampsia groups and the control participants (SMD, 3.34; 95% CI, -0.02 to 6.69; P = .05). The results of this meta-analysis indicate that a high serum iron level is associated with an increased risk of HDP, especially gestational hypertension and preeclampsia.

[Clinical observation on treatment of cerebral infarction-induced broca aphasia by Tiaoshen Fuyin acupuncture therapy combined with language training].

OBJECTIVE: To observe therapeutic effect of Tiaoshen Fuyin acupuncture therapy on cerebral infarction-induced Broca aphasia. METHODS: Sixty cases were randomly divided into an observation group and a control group, 30 cases in each group. The observation group were treated with Tiaoshen Fuyin acupuncture therapy and language training, and the control group with simple language training. For the acupuncture treatment, Sishencong (EX-HN 1), Benshen (GB 13), Shenting (GV 24), Lianquan (CV 23), Xinshu (BL 15), Shentang (BL 44), Shendao (GV 11), Lingtao (HT 4) were selected and language training included training of phonatory organs in mouth, the mouth shape, sound, spoken language expression and practical exchange ability. They were treated for 5 therapeutic courses. Language examination was conducted once each before and after treatment with "Aphasia Battery of Chinese" (ABC method). RESULTS: The therapeutic effect of Tiaoshen Fuyin acupuncture therapy combined with language training was better than that of simple language training. CONCLUSION: Tiaoshen Fuyin acupuncture therapy combined with language training can significantly improve language function and increase life quality in the patient of cerebral infarction-induced Broca aphasia.