Bioinspired Collective Total Synthesis of (±)-Rhynchines A-E.

Herein, we present the first racemic total synthesis of the structurally complex monoterpene indole alkaloids rhynchines A-E, starting from commercially available methyl nicotinate and 3-(2-bromoethyl)-1H-indole. The success of our synthesis is attributed to the utilization of a bioinspired synthetic strategy, which facilitated the rapid construction of the pentacyclic core skeleton of the target molecules through biomimetic skeletal rearrangement and late-stage C-H oxidative cyclization. Additionally, silica-gel-promoted tautomerization played a crucial role as a strategic element in the chemical synthesis of rhynchines A and B.

Bioinspired Total Synthesis of Cephalotaxus Diterpenoids and Their Structural Analogues.

Herein, we present a unified chemical synthesis of three subgroups of cephalotaxus diterpenoids. Key to the success lies in adopting a synthetic strategy that is inspired by biosynthesis but is opposite in nature. By employing selective one-carbon introduction and ring expansion operations, we have successfully converted cephalotane-type C18 dinorditerpenoids (using cephanolide B as a starting material) into troponoid-type C19 norditerpenoids and intact cephalotane-type C20 diterpenoids. This synthetic approach has enabled us to synthesize cephinoid H, 13-oxo-cephinoid H, 7-oxo-cephinoid H, fortalpinoid C, 7-epi-fortalpinoid C, cephanolide E, and 13-epi-cephanolide E. Furthermore, through the development of an intermolecular asymmetric Michael reaction between ß-oxo esters and ß-substituted enones, we have achieved the enantioselective synthesis of advanced intermediates within our synthetic sequence, thus formally realizing the asymmetric total synthesis of the cephalotaxus diterpenoids family.

Total Synthesis of Metaphanine and Oxoepistephamiersine.

Herein, we report a concise and divergent synthesis of the complex hasubanan alkaloids metaphanine and oxoepistephamiersine from commercially available and inexpensive cyclohexanedione monoethylene acetal. Our synthesis features a palladium-catalyzed cascade cyclization reaction to set the tricyclic carbon framework of the desired molecules, a regioselective Baeyer-Villiger oxidation followed by a MeNH2 triggered skeletal reorganization cascade to construct the benzannulated aza[4.4.3]propellane, and a strategically late-stage regio-/diastereoselective oxidative annulation of sp3 C-H bond to form the challenging THF ring system and hemiketal moiety in a single step. In addition, a highly enantioselective alkylation of cyclohexanedione monoethylene acetal paved the way for the asymmetric synthesis of target molecular.

[Clinical features of invasive candidiasis and risk factors for Candida bloodstream infection in children: a multicenter study in Urumqi, China].

OBJECTIVE: To investigate the clinical features of invasive candidiasis in children and the risk factors for Candida bloodstream infection. METHODS: A retrospective study was performed on 134 children with invasive candidiasis and hospitalized in 5 tertiary hospitals in Urumqi, China, between January 2010 and December 2015. The Candida species distribution was investigated. The clinical data were compared between the patients with and without Candida bloodstream infection. The risk factors for Candida bloodstream infection were investigated using multivariate logistic regression analysis. RESULTS: A total of 134 Candida strains were isolated from 134 children with invasive candidiasis, and non-albicans Candida (NAC) accounted for 53.0%. The incidence of invasive candidiasis in the PICU and other pediatric wards were 41.8% and 48.5% respectively. Sixty-eight patients (50.7%) had Candida bloodstream infection, and 45 patients (33.6%) had Candida urinary tract infection. There were significant differences in age, rate of use of broad-spectrum antibiotics, and incidence rates of chronic renal insufficiency, heart failure, urinary catheterization, and NAC infection between the patients with and without Candida bloodstream infection (P<0.05). The multivariate logistic regression analysis showed that younger age (1-24 months) (OR=6.027) and NAC infection (OR=1.020) were the independent risk factors for Candida bloodstream infection. CONCLUSIONS: The incidence of invasive candidiasis is similar between the PICU and other pediatric wards. NAC is the most common species of invasive candidiasis. Candida bloodstream infection is the most common invasive infection. Younger age (1-24 months) and NAC infection are the risk factors for Candida bloodstream infection.

[Time series analysis of Enterobacter cloacae nosocomial infections in children hospitalized in the pediatric intensive care unit].

OBJECTIVE: To characterize the time distribution of the incidence of Enterobacter cloacae nosocomial infections in children hospitalized in the pediatric intensive care unit (PICU) of the First Affiliated Hospital of Xinjiang Medical University. METHODS: The clinical data of children with Enterobacter cloacae nosocomial infections in the PICU of the First Affiliated Hospital of Xinjiang Medical University between January 2010 and December 2013 were collected. The monthly number of cases of Enterobacter cloacae nosocomial infections was recorded, and time series analysis was performed using SPSS 21.0 software. The obtained prediction model was verified using the data from January to June in 2014. RESULTS: A total of 157 cases of Enterobacter cloacae nosocomial infections were reported in the PICU between January 2010 and December 2013, including 33 cases in 2010, 35 cases in 2011, 37 cases in 2012, and 52 cases in 2013. Time series analysis of the monthly number of cases of nosocomial infections reveals a fitted curve with a clear pattern of seasonal variation (R2=0.702, Ljung-Box Q(18)=36.021, P=0.004), with peaks in May, June, and July. The verification using the data from January to June in 2014 showed small differences between the predicted values and the actual values. CONCLUSIONS: In the PICU of the First Affiliated Hospital of Xinjiang Medical University, the incidence of Enterobacter cloacae nosocomial infections is high in May, June, and July every year. The prediction model is accurate and can provide a reference for infection prevention.

Functional Polymorphisms in COX-2 Gene Are Correlated with the Risk of Oral Cancer.

BACKGROUND: This meta-analysis investigated the association between functional COX-2 gene polymorphisms and the risk of oral cancer. METHODS: Several electronic databases were searched for published studies using combinations of keywords related to COX-2 gene polymorphisms and oral cancer. After selection of relevant studies, following strict inclusion and exclusion criteria, data was performed using STATA 12.0 software. RESULTS: We retrieved 83 studies from database search using specific search terms. After multiple rounds of selection and elimination, 7 studies were finally identified as suitable to be included in our present meta-analysis, based on their relevance and data integrity. These 7 studies contained a combined total of 2,296 oral cancer patients and 3,647 healthy controls. Our findings demonstrated that +837 T > C (rs5275) polymorphism in COX-2 showed statistically significant differences in gene frequencies in case and control groups in allele model and dominant model. Similar results were obtained with COX-2 gene polymorphism 765 G > C (rs20417). On the other hand, 1195 A > G (rs689466) polymorphism in COX-2 did not confer susceptibility to oral cancers. CONCLUSION: Based on our results, COX-2 gene polymorphisms, +837 T > C (rs5275) and -765G > C (rs20417), showed clear links with oral cancer susceptibility, and the 1195A > G (rs689466) polymorphism did not show such a correlation.