Hydrogen-Bond-Mediated Formation of C-N or C=N Bond during Photocatalytic Reductive Coupling Reaction over CdS Nanosheets.

Reductive amination of carbonyl compounds and nitro compounds represents a straightforward way to attain imines or secondary amines, but it is difficult to control the product selectivity. Herein, we report the selective formation of C-N or C=N bond readily manipulated through a solvent-induced hydrogen bond bridge, facilitating the swift photocatalytic reductive coupling process. The reductive-coupling of nitro compounds with carbonyl compounds using formic acid and sodium formate as the hydrogen donors over CdS nanosheets selectively generates imines with C=N bonds in acetonitrile solvent; while taking methanol as solvent, the C=N bonds are readily hydrogenated to the C-N bonds via hydrogen-bonding activation. Experimental and theoretical study reveals that the building of the hydrogen-bond bridge between the hydroxyl groups in methanol and the N atoms of the C=N motifs in imines facilitates the transfer of hydrogen atoms from CdS surface to the N atoms in imines upon illumination, resulting in the rapid hydrogenation of the C=N bonds to give rise to the secondary amines with C-N bonds. Our method provides a simple way to control product selectivity by altering the solvents in photocatalytic organic transformations.

The impact of oocytes containing smooth endoplasmic reticulum aggregates on assisted reproductive outcomes: a cohort study.

BACKGROUND: The impact of smooth endoplasmic reticulum aggregates (SERa) on assisted reproductive technology (ART) outcomes was still controversial. Our objective is to investigate the impact of the presence of SERa on intracytoplasmic sperm injection (ICSI) outcomes. METHODS: This was a retrospective cohort study. A total of 1,090 fresh ICSI cycles from 944 patients between January 2016 and June 2020 were included. Outcomes from clinical, embryological and neonatal aspects were compared between SERa + and SERa- cycles as well as between SERa + and SERa- oocytes. RESULTS: The total gonadotropin (Gn) dose, number of oocytes retrieved, serum estradiol concentration and number of the available embryo were significantly higher in SERa + cycles than in SERa- cycles (P < 0.05). Comparable two pronuclei (2PN) fertilization rate and poly-pronucleus zygote rate were shown in SERa + and SERa- cycles (P > 0.05), but which were higher in SERa + oocytes than in SERa- oocytes (P < 0.05). No statistical difference in blastocyst formation rate was found in SERa + and SERa- cycles as well as in SERa + and SERa- oocytes (P > 0.05). Good-quality embryo rate was statistically higher in SERa- cycles than in SERa + cycles (P < 0.05), but the difference was comparable between SERa + and SERa- oocytes (P > 0.05). No statistical difference in clinical pregnancy rate, spontaneous abortion rate, live birth rate and premature delivery rate were found in SERa + and SERa- cycles as well as in SERa + and SERa- oocytes (P > 0.05). The implantation rate was comparable in SERa + and SERa- cycles (P > 0.05), but it is higher in the group of only SERa- embryo transfer when compared with the group of mixed SERa + and SERa- embryo transfer (P < 0.05). 159 newborns in SERa + cycles and 140 newborns in SERa- cycles were followed up. Comparable newborn malformation rate was observed between SERa + and SERa- cycles and oocytes (P > 0.05). Logistic regression analysis revealed number of oocytes and total dose of Gn were risk factors for SERa occurrence (aOR = 1.05 and 1.55, P < 0.001). CONCLUSION: Oocyte's SERa is correlated with a number of oocytes retrieved and higher Gn dose, but it does not affect pregnancy outcomes and increase newborn malformation rate.

Risk factors of endometrial cancer in patients with endometrial hyperplasia: implication for clinical treatments.

BACKGROUND: Endometrial hyperplasia (EH) is commonly-seen in the patients with endometrial cancer (EC), we aimed to evaluated the risk factors of EC in patients with EH, to provide evidence to the clinical prevention and treatment of EC. METHODS: This study was a retrospective study design. EH patients confirmed by pathological examinations and treated with hysterectomy in our hospital from June 1, 2018 to February 28, 2021 were included. The clinical characteristics of EC and no-EC patients were compared and analyzed. Logistics regression analyses were conducted to evaluate the risk factors of EC in patients with EH. RESULTS: A total of 228 EH patients were included, the incidence of EC in the EH patients was 31.58%. There were significant differences in the age, BMI, diabetes, hypertension and pathology of EH between EC and no EC groups (all P < 0.05), no significant differences in the hyperlipidemia, preoperative CA125, number of deliveries, menopause and endometrial thickness between EC and no EC groups were found (all P > 0.05). Logistic regression analyses indicated that age > 50 y (OR 3.064, 95% CI 1.945-5.931), BMI ≥ 25 kg/m2 (OR 2.705, 95% CI 1.121-3.889), diabetes (OR 3.049, 95% CI 1.781-5.114), hypertension (OR 2.725, 95% CI 1.108-3.431) and severe hyperplasia (OR 3.181, 95% CI 1.496-4.228) were the risk factors of EC in patients with EH (all P < 0.05). CONCLUSIONS: The risk of EC in EH patients is high, especially for those patients with age > 50 y, BMI ≥ 25 kg/m2, diabetes, hypertension and severe hyperplasia, special attentions should be paid for occurrence of EC and early diagnosis and early treatment are needed for those patients.

Predictive value of age-specific FSH levels for IVF-ET outcome in women with normal ovarian function.

BACKGROUND: Most of infertile women with normal follicle stimulating hormone (FSH) levels and antral follicle count (AFC) at day 2-3 of the period, but poor IVF outcomes may occur when use of routine controlled ovarian stimulation. This paper is to evaluate the predictive value of age-specific FSH levels for IVF-ET outcomes in women with normal ovarian function. METHODS: A total of 1287 women undergoing their first IVF cycles were enrolled in this retrospective study. The FSH levels and AFC of all of the women were within normal ranges (FSH ≤ 12 IU/L;AFC ≥ 5). The patients were grouped by age (younger: < 33 years, medium-aged:33-37years and older:38-41years), and within each age group, the patients were subdivided by the upper limit of the 95 % confidence interval (CI) for mean FSH levels. Patients with FSH levels equal to or greater than the upper 95 % CI of FSH in each age group were included into a premature ovarian aging (POA) subgroup (younger:FSH ≥ 7.84, medium-aged: ≥8.12 and older: FSH ≥ 8.47),the remaining patients in each age group were included into a control subgroup. The outcomes of IVF-ET were compared between the POA subgroup and the control subgroup in each age group. RESULTS: In each age group, the total dose of gonadotropin(Gn) in the POA subgroups were significantly higher than those of the corresponding control subgroups. In the younger and medium-aged groups, women in the POA subgroups had significantly lower oocyte yields, frozen embryos, and higher rates of poor ovarian response(POR) than those in the corresponding control subgroups. When controlling for age, BMI and AFC, the multiple logistic regression analysis indicated the following: In each age group, the total dose of Gn was significantly correlated with POA; the oocyte yield was significantly related to POA only in the younger group; and in the whole age groups, the incidence of POR in the POA group was 2.719 times greater than in the control group (OR = 2.719, 95 % CI [1.598-4.625], P < 0.001). CONCLUSION: Basal FSH levels combined with age (age-specific FSH levels) can be used as a more accurate marker for the ovarian response in women with normal ovarian reserves undergoing IVF-ET, particularly in women ≤37 years old.

Endometriosis fertility index score maybe more accurate for predicting the outcomes of in vitro fertilisation than r-AFS classification in women with endometriosis.

BACKGROUND: Endometriosis is a common disease. The most widely used staging system of endometriosis is the revised American Fertility Society classification (r-AFS classification) which has limited predictive ability for pregnancy after surgery. The endometriosis fertility index (EFI) is used to predict fecundity after endometriosis surgery. This diagnostic accuracy study was designed to compare the predictive value of the EFI with that of the r-AFS classification for IVF outcomes in patients with endometriosis. METHODS: 199 women with endometriosis receiving IVF treatment after surgery were analysis. The EFI score and r-AFS classification in their ability to predict these IVF outcomes were compared in the same population. ROC curves were used to analyse the predictive values of the EFI and r-AFS indices for clinical pregnancy, and their accuracies were evaluated by sensitivity, specificity, and the Youden's index. RESULTS: The Area Under the Curve (AUC) of the EFI score (AUC = 0.641, Standard Error(SE) = 0.039, P = 0.001, 95% CI = 0.564-0.717, cut-off score = 6) was significantly larger than that of the r-AFS classification (AUC = 0.445, SE = 0.041, P = 0.184, and 95% CI = 0.364-0.526). The antral follicle count, oestradiol level on day of hCG, number of oocytes retrieved, number of oocytes fertilised, and number of cleaved embryos in the greater than or equal to 6 EFI score group was greater than that of the lower than or equal to 5 EFI score group, and the dose of gonadotropin of the greater than or equal to 6 EFI score group were less than that in the lower than or equal to 5 EFI score group. Implantation rate, clinical pregnancy rate, and cumulative pregnancy rate in the greater than or equal to 6 EFI score group were higher than in the lower than or equal to 5 EFI score group. CONCLUSIONS: It suggests that the EFI has more predictive power for IVF outcomes in endometriosis patients than the r-AFS classification. The clinical pregnancy rate was higher in patients with EFI greater than or equal to 6 score than with EFI lower than or equal to 5 score.

Aerobic oxidative C-C bond cleavage and functionalization for the synthesis of value-added chemicals.

The aerobic oxidative cleavage of C-C bonds is an attractive and sustainable route for constructing valuable molecules such as esters, nitriles, and amides. Traditionally homogeneous catalytic systems for C-C bond cleavage required harsh conditions, stoichiometric oxidants, and noble metal catalysts to overcome the thermodynamic and kinetic barriers of C-C bonds, imposing environmental concerns of the transformation. Therefore, developing efficient, low-cost, and environmentally benign methods for C-C bond cleavage is of great importance and a cutting-edge area in modern chemistry. This feature article summarizes the sustainable aerobic oxidative C-C bond cleavage method developed by our group in the past 5 years. Fundamental principles in catalyst design, substrate scope, and mechanism for C-C bond cleavage are also discussed.

The predictive value of endometrial thickness in 3117 fresh IVF/ICSI cycles for ectopic pregnancy.

OBJECTIVES: To evaluate the predictive value of endometrial thickness (EMT) during in vitro fertilization (IVF)/intracytoplasmic sperm injection (ICSI) cycles for ectopic pregnancy (EP). METHODS: A total of 3068 patients with 3117 fresh IVF/ICSI cycles between January 2016 and February 2019 from the Reproductive Medicine Center of Sun Yat-Sen Memorial Hospital were included in this retrospective study. The patients were divided into an EP group (n = 92) and an intrauterine pregnancy (IUP) group (n = 3025). Multiple logistic regression analysis was conducted to evaluate the EP risk factors. Receiver operating characteristic (ROC) curves were used to evaluate the predictive value of the risk factors for EP and calculate the cutoff value of EMT for EP prediction. RESULTS: The incidence rate of EP was 2.95 % (92/3117). After adjustment for other factors in the logistic regression model, the incidence of EP decreased by 55 % with an EMT > 10 mm compared with an EMT ≤ 10 mm (odds ratio 0.450, 95 % confidence interval 0.296-0.684, P < 0.001). The EMT in the EP group was significantly thinner than that in the live birth (n = 2540) and spontaneous abortion (n = 485) groups (p < 0.017). The cutoff value of EMT for EP prediction was 10.65 mm, with a sensitivity of 59 % and a specificity of 63 %. CONCLUSION: A decreased risk of EP was found among the patients with an EMT > 10 mm prior to embryo transfer. A certain EMT is needed to reduce the incidence of EP.

Expression and prognostic value of glutamate dehydrogenase in extrahepatic cholangiocarcinoma patients.

Glutamate dehydrogenase (GDH) produces a precursor to glutathione, an important molecule in maintaining cellular redox balance and the cancerous characteristics of tumor cells through intracellular signaling pathways. However, the underlying molecular mechanisms linking glutamate dehydrogenase and extrahepatic cholangiocarcinoma have not been elucidated yet. Herein, we examined GDH expression levels and evaluated its potential correlations with prognosis. Meanwhile, the therapeutic value of GDH targeting the Smad pathways in extrahepatic cholangiocarcinoma was explored. Immunohistochemical studies revealed that GDH expression level was correlated to CD34 expression, cellular differentiation, the presence or absence of capsular and vascular invasion, lymph node metastasis, neural invasion and patient age. Kaplan-Meier survival analysis and COX proportional hazards models demonstrated that the prognosis was closely associated with GDH expression, CD34 positivity, nerve infiltration and cell differentiation. GDH silencing significantly reduced the proliferation, migratory potential and invasive capability. We also demonstrated that GDH promoted cell proliferation and metastasis potentially through Smad-mediated induction of TGF-ß signaling pathway. Therefore, GDH may be an important prognostic indicator and may provide a new target for novel treatments of extrahepatic cholangiocarcinoma.

Silencing MRP1-4 genes by RNA interference enhances sensitivity of human hepatoma cells to chemotherapy.

AIM: Besides surgical treatment, systematic chemotherapy plays a crucial role in HCC treatment, especially for patients with advanced HCC. However, none of the single-drug-treatment strategies have shown significant survival benefit due to a high incidence rate of chemoresistance. This study was designed to observe the effect of small interfering of RNA (SiRNA) targeting multidrug resistance-related protein 1-4 (MRP1, MRP2, MRP3, and MRP4) in modulating drug resistance of HepG2/ADM and SMMC7721/ADM cells. METHODS: HepG2/Adriamycin (ADM) and SMMC7721/ADM cell lines were developed by exposing parental cells to stepwise increasing concentrations of ADM. MTT assay was used to determine drug sensitivity and half inhibitory concentration (IC50) of drugs was calculated. Flow cytometry was employed to analyze cell cycle distribution. MRP1-4 mRNA expression levels were measured by quantitative real-time PCR (QRT-PCR). Expression of proteins was analyzed by Western blot. The growth curve was draw and the cell apoptosis was also observed. Animal experiment was used to compare the cell growth. RESULTS: MTT assay showed that the values of IC50 and RI of HepG2/ADM and SMMC7721/ADM decreased after siRNA treatment in HepG2/ADM cells and SMMC7721/ADM cells. QRT-PCR analysis demonstrated the MRP1-4 mRNA expression decreased significantly in HepG2/ADM cells and SMMC7721/ADM cells after siRNA transfection. In addition, compared with parental cells, MRP1-4 protein expressions apparently decreased in SMMC7721/ADM and HepG2/ADM cells. Flow cytometry showed significantly elevated apoptosis rate following MRP1-4 siRNA transfection. Animal experiment suggested that silencing MRP1-4 gene in vivo inhibited tumor growth. CONCLUSION: Inhibition of MRP1-4 by small interfering RNA enhanced and selectively restored sensitivity of hepatoma cells to drugs. MRP1-4 siRNA might represent a new therapeutic option for HCC.

Clinical Outcomes of In Vitro Fertilization among Chinese Infertile Couples Treated for Syphilis Infection.

To compare the clinical outcomes of infertile patients with and without syphilis after in vitro fertilization and embryo transfer (IVF-ET), in this case-control study, 320 infertile couples were enrolled and divided into syphilis (n = 160) and control groups (n = 160). The primary IVF outcomes were the clinical pregnancy rate and the birth of a healthy baby. All syphilis patients received the standard anti-syphilis treatment before undergoing IVF/ICSI. Our results showed that the endometrial thickness of the syphilis group was greater than that of the control group following hCG injection (16.9±5.4 vs. 13.0±4.7 mm, P<0.001). The numbers of normally fertilized eggs and normally cleaved fertilized eggs and the implantation rate were 6.8±4.8, 6.3±4.7 and 24.2%, respectively, for the syphilis group and 8.3±4.6, 8.1±4.6 and 34.4%, respectively, for the control group, and these values were significantly different between the groups. The clinical pregnancy rate was lower in the syphilis group compared with that in the control group (43.8% vs. 55.6%, P = 0.03). Lower offspring birth weight was observed in the infected male group compared with those in the infected female (2.7±0.4 vs. 3.0±0.4 kg, P = 0.01) and infected couple groups (2.7±0.4 vs. 3.1±0.5 kg, P = 0.007). Therefore, syphilis infection reduces the clinical pregnancy rate after IVF/ICSI.

Paraneoplastic pemphigus associated with follicular dendritic cell sarcoma: report of a case and review of literature.

Follicular dendritic cell sarcoma (FDCS) is a rare tumor associated with paraneoplastic pemphigus. It is Blame drenchs auxiliary cell tumor which is derived from the peripheral lymphoid tissues. Throughout the world, several patients of paraneoplastic pemphigus associated follicular dendritic cell sarcoma were reported in the literature, but mostly originated from the neck lymph nodes, and extranodal origin of follicular dendritic sarcoma was rarely reported. Also, so far we have found that the malignant degree of all patients diagnosed with malignant tumors have been reported were low and after combined treatment of surgery, radiotherapy and chemotherapy, most of the prognosis was good. However, here we present a patient of paraneoplastic pemphigus associated with follicular dendritic cell sarcoma origined from outside of the lymph nodes and had high tumor malignant degree for its unclear cell boundaries, obvious atypia and mitoses and the patient's state became progressively deteriorate after operation.