Nickel-Catalyzed Direct Sulfonylation of Styrenes and Unactivated Aliphatic Alkenes with Sulfonyl Chlorides.

A nickel-catalyzed direct sulfonylation of alkenes with sulfonyl chlorides has been developed using 1,10-phenanthroline-5,6-dione as the ligand. Unactivated alkenes and styrenes including 1,1-, 1,2-disubstituted alkenes can be subjected to the protocol, and a wide range of vinyl sulfones was obtained in high to excellent yields with good functional group compatibility. Notably, the process did not allow the desulfonylation of sulfonyl chloride or chlorosulfonylation of alkenes. Radical-trapping experiment supported that a sulfonyl free-radical was likely produced and triggered subsequent transformation in the process.

Functional Group-driven Competing Mechanism in Electrochemical Reaction and Adsorption/Desorption Processes toward High-capacity Aluminum-Porphyrin Batteries.

Nonaqueous organic aluminum batteries are considered as promising high-safety energy storage devices due to stable ionic liquid electrolytes and Al metals. However, the stability and capacity of organic positive electrodes are limited by their inherent high solubility and low active organic molecules. To address such issues, here porphyrin compounds with rigid molecular structures present stable and reversible capability in electrochemically storing AlCl2+. Comparison between the porphyrin molecules with electron-donating groups (TPP-EDG) and with electron-withdrawing groups (TPP-EWG) suggests that EDG is responsible for increasing both HOMO and LUMO energy levels, resulting in decreased redox potentials. On the other hand, EWG is associated with decreasing both HOMO and LUMO energy levels, leading to promoted redox potentials. EDG and EWG play critical roles in regulating electron density of porphyrin π bond and electrochemical energy storage kinetics behavior. The competitive mechanism between electrochemical redox reaction and de/adsorption processes suggests that TPP-OCH3 delivers the highest specific capacity ~171.8 mAh g-1, approaching a record in the organic Al batteries.

Metal-Free Selective Ortho-C-H Amidation of Hypervalent(III) Iodobezenes with N-Methoxy Amides under Mild Conditions.

A metal-free selective ortho-C-H amidation of aryl iodines(III) with the use of N-methoxy amides as aminating reagents under mild conditions is described here. In the protocol, excellent chemoselectivity and high regioselectivity were obtained. Notably, the iodine substituent rendered the amidation product suitable to be used for further elaboration.

Epigenetics comprehensive experimental course based on the integration of science and education to cultivate students' ability of cutting-edge innovation.

The integration of science and education is an effective way for universities to cultivate students in cutting-edge innovative interests. Epigenetics is the expansion of classical genetics, the corresponding experimental courses of which have not been integrated into the current teaching system. In this paper, by taking advantage of our laboratory's research on the DNA methylation maintenance gene, OsMET1-2 in rice, we have integrated our innovative findings in the education curriculum, and built a comprehensive teaching system on experimentation research, which greatly stimulates the curiosity of the students. Taking the OsMET1-2 mutants and its isogenic wild-type rice plants as experimental materials, this course has successfully demonstrated a causal link between genetic mutation and epigenetic variation, a topic widely interested by the students in learning genetics and epigenetics. Through the practice of this course, students have a deeper understanding of the important role of epigenetic modifications, their scientific research capabilities have been greatly improved, thereby strongly supporting the cultivation of top innovative talents among the students.

Photoredox-Catalyzed Acyl Lactonization of Alkenes with Aldehydes: Synthesis of Acyl Lactones.

An acyl lactonization of alkenes with aldehydes under visible-light photoredox catalysis is described. With the protocol, a broad scope of alkenoic acids and aldehydes could be compatible and good functional group tolerance is obtained. A series of acyl lactones are obtained with isolated yields ranging from 50-95%. Mechanistic studies revealed that the transformation should proceed via a radical chain process.

Copper-Catalyzed Intermolecular C(sp2)-H Amination with Electrophilic O-Benzoyl Hydroxylamines.

A copper-catalyzed intermolecular electrophilic amination of benzamides with O-benzoyl hydroxylamines was achieved with the assistance of an 8-aminoquinolyl group. With this protocol, good compatibility was observed for a variety of aryl amides and heteroaryl amides, and excellent tolerance with various functional groups was achieved. Significantly, the monoaminated product was overwhelmingly delivered under the simple reaction conditions. Preliminary mechanistic investigations suggested that a radical pathway should be excluded and C-H activation be potentially the rate-determining step.

Visible-Light Photoredox-Catalyzed Sulfonyl Lactonization of Alkenoic Acids with Sulfonyl Chlorides for Sulfonyl Lactone Synthesis.

A visible-light photoredox-catalyzed sulfonyl lactonization of unsaturated carboxylic acids with sulfonyl chlorides is described. This reaction features good functional group tolerance and a broad substrate scope, providing a simple and efficient protocol to access a wide range of sulfonyl lactones in high to excellent yields. Preliminary mechanistic investigations suggested that a free-radical pathway should be involved in the process.

Production of 1,3-propanediol and lactic acid from crude glycerol by a microbial consortium from intertidal sludge.

OBJECTIVES: To select a microbial consortium from intertidal sludge and evaluate its ability to convert crude glycerol from biodisel to high value-added products such as 1,3-propanediol (1,3-PDO) and lactic acid (LA). RESULTS: A microbial consortium named CJD-S was selected from intertidal sludge and exhibited excellent performance for the conversion of crude glycerol to 1,3-PDO and LA. The composition of CJD-S was determined to be 85.99% Enterobacteriaceae and 13.75% Enterococcaceae by 16S rRNA gene amplicon high-throughput sequencing. In fed-batch fermentation with crude glycerol under nonsterile conditions, the highest concentrations of 1,3-PDO and LA were 41.47 g/L and 45.86 g/L, respectively. CONCLUSIONS: The selected microbial consortium, CJD-S, effectively converted crude glycerol to 1,3-PDO and LA under nonsterile conditions and can contribute to the sustainable development of the biodiesel industry.

A review on energy chemistry of fast-charging anodes.

With the impetus to accelerate worldwide market adoption of electrical vehicles and afford consumer electronics with better user experience, advancing fast-charging technology is an inevitable trend. However, current high-energy lithium-ion batteries are unable to support ultrafast power input without any adverse consequences, with the capacity fade and safety concerns of the mainstream graphite-based anodes being the key technological barrier. The aim of this review is to summarise the fundamentals, challenges, and solutions to enable graphite anodes that are capable of high-rate charging. First, we explore the complicated yet intriguing graphite-electrolyte interface during intercalation based on existing theories. Second, we analyse the key dilemmas facing fast-charging graphite anodes. Finally, some promising strategies proposed during the past few years are highlighted so as to outline current trends and future perspectives in this field.

Nucleation and Growth Mechanism of Anion-Derived Solid Electrolyte Interphase in Rechargeable Batteries.

Solid electrolyte interphase (SEI) has been widely employed to describe the new phase formed between anode and electrolyte in working batteries. Significant advances have been achieved on the structure and composition of SEI as well as on the possible ion transport mechanism. However, the nucleation and growth mechanism of SEI catches little attention, which requires the establishment of isothermal electrochemical crystallization theory. Herein we explore the virgin territory of electrochemically crystallized SEI. By using potentiostatic method to regulate the decomposition of anions, an anion-derived SEI forms on graphite surface at atomic scale. After fitting the cur-rent-time transients with Laviron theory and Avrami formula, we conclude that the formation of anion-derived interface is surface reaction controlled and obeys the two-dimensional (2D) progressive nucleation and growth model. Atomic force microscope (AFM) images emphasize the conclusion, which reveals the mystery of isothermal electrochemical crystallization of SEI.

Inhibiting Solvent Co-Intercalation in a Graphite Anode by a Localized High-Concentration Electrolyte in Fast-Charging Batteries.

Lithium-ion batteries with routine carbonate electrolytes cannot exhibit satisfactory fast-charging performance and lithium plating is widely observed at low temperatures. Herein we demonstrate that a localized high-concentration electrolyte consisting of 1.5 M lithium bis(fluorosulfonyl)imide in dimethoxyethane with bis(2,2,2-trifluoroethyl) ether as the diluent, enables fast-charging of working batteries. A uniform and robust solid electrolyte interphase (SEI) can be achieved on graphite surface through the preferential decomposition of anions. The established SEI can significantly inhibit ether solvent co-intercalation into graphite and achieve highly reversible Li+ intercalation/de-intercalation. The graphite | Li cells exhibit fast-charging potential (340 mAh g-1 at 0.2 C and 220 mAh g-1 at 4 C), excellent cycling stability (ca. 85.5 % initial capacity retention for 200 cycles at 4 C), and impressive low-temperature performance.

[Analysis of Collision Carcinoma of Larynx Between Moderately Differentiated Squamous Cell Carcinoma and Poorly Differentiated Neuroendocrine Carcinoma from One Case].

A 75-year-old male patient was hospitalized in hoarseness for 2 months. Laryngoscopy showed a mass protruding in right laryngeal chamber and covering the middle part of right vocal cord. Since tumor biopsy showed low differentiation cancer, he received total laryngectomy, and post-operative pathological result found composite carcinoma, which containing medium differentiated squamous cell carcinoma (about 5%) and low differentiated neuroendocrine carcinoma (about 95%). The growth status of tumor indicated it was collision carcinoma. After postoperative regular radiotherapy, no recurrence was found at 6 months of follow-up. The incidence of head and neck collision carcinoma is quite low, and the majority of them occurs in thyroid, which is rare in larynx. The confirmed diagnosis of larynx collision carcinoma is based on postoperative pathological study. The choice of treatment for collision cancer is closely related to the pathological components, the location of the disease and whether there is distant metastasis.

[Proliferation of MicroRNA-365 and E74-like Factor 4 in Cervical Cancer Cells and Its Clinical Significance].

Objective To investigate the expressions,roles,and clinical significance of microRNA-365(miR-365)and E74-like factor 4(ELF4)in cervical cancer. Methods The expressions of miR-365 in normal cervical tissues(n=34),cervical intraepithelial neoplasia 1(CIN 1)(n=31),cervical intraepithelial neoplasia2-3(CIN 2-3)(n=37),squamous cell carcinoma of the cervix(SCC)(n=33),and three cervical cancer cell lines(C33A cells,Hela cells,and SiHa cells)were detected by real-time quantitative polymerase chain reaction(qPCR).Bioinformatic prediction and luciferase reporter gene assay were performed to verify whether ELF4 was a direct target of miR-365.Western blot and immunohistochemistry were used to detect ELF4 expression in cervical cancer cells and in different pathological cervix tissues.CCK8 assay was used to detect the effect of overexpression or inhibition of miR-365 on the proliferation of cervical cancer cells at different time points.The relationships among the miR-365 expression,ELF4 expression,and clinicopathological parameters of cervical cancer were analyzed by correlation analysis. Results qPCR results showed that compared with the normal cervical cell HcerEpic,the expressions of miR-365 in CIN1,CIN2-3,and cervical cancer tissues gradually decreased with the increased pathologic grade,and its expressions also decreased in different cervical cancer cell lines.The luciferase reporter gene assay confirmed that ELF4 was the direct target of miR-365.Western blot showed that the expression of ELF4 increased in all three cervical cancer cell lines compared with normal cervical epidermal cell(P=0.013,P=0.002,P=0.004).Immunohistochemistry showed that ELF4 expression was up-regulated in CIN and cervical cancer tissues.CCK8 assay showed that overexpression of miR-365 inhibited cell proliferation,while inhibition of miR-365 promoted the proliferation of three cervical cancer cells(P<0.05).Further analysis confirmed that there was a negative correlation between the expression levels of miR-365 and ELF4 in CIN2-3 and SCC(r=-0.351,P=0.045;r=-0.349,P=0.035).Clinical analysis showed that the expressions of both miR-365 and ELF4 were correlated with tumor size,pathological grade,and clinical stage in SCC(all P < 0.05).Conclusion The decreased expression of miR-365 in human cervical cancer cells relieves its inhibitory effect on ELF4,which promotes the proliferation of cervical cancer cells and the formation of tumor.

[Rutaecarpine protects against bleomycin-induced pulmonary fibrosis through inhibiting Notch1/eIF3a signaling pathway in rats].

To investigate whether the protection of rutaecarpine against bleomycin-induced pulmonary fibrosis is mediated by inhibiting Notch1/eukaryotic initiation factor 3a (eIF3a) signaling pathway, and whether these effects are related to the synthesis and release of calcitonin gene-related peptide (CGRP) and inhibition of epithelial-mesenchymal transition (EMT) of alveolar epithelial cells, male Sprague-Dawley rats were randomly divided into five groups (n=12), respectively, Control group, bleomycin group, rutaecarpine (100, 300 mg·kg⁻¹) group and capsaicin plus rutaecarpine (300 mg·kg⁻¹) group. Bleomycin (5 mg·kg⁻¹) was used to induce pulmonary fibrosis rat model. Rats were given capsaicin (50 mg·kg⁻¹) by subcutaneous injections 1 days before and 7, 14, 21 days after induce pulmonary fibrosis rat model to deplete endogenous CGRP. At the end of experiments, blood was collected from carotid artery to determinate the plasma levels of CGRP by ELISA. Pulmonary tissue change was observed by HE staining. Masson's trichrome stain was used to demonstration collagen deposition. The collagen I expression in pulmonary tissue was measured by immunohistochemisty. The expression of CGRP, Notch1, eIF3a, collagen I, vimentin, alpha-smooth muscle actin (α-SMA), E-cadherin and zonula occludens-1 (ZO-1) was detected by qPCR or Western blot. Compared with the control group, the pulmonary tissue of the bleomycin group showed significant fibrosis, including significant disturbed alveolar structure, marked thickening of the interalveolar septa and dense interstitial infiltration by inflammatory cells and fibroblasts, and concomitantly with the decrease in plasma CGRP and expression of CGRP. Importantly the expression of E-cadherin and ZO-1 was decreased and expression of Notch1, eIF3a, collagen I, vimentin and α-SMA was increased in bleomycin group (P<0.05 or P<0.01). Compared with the bleomycin group, rutaecarpine (100, 300 mg·kg⁻¹) group significantly reduced bleomycin-induced pulmonary injury concomitantly with the increase in plasma CGRP and expression of CGRP. Importantly the expression of E-cadherin and ZO-1 was increased and expression of Notch1, eIF3a, collagen I, vimentin and α-SMA was decreased by rutaecarpine treatment (P<0.05 or P<0.01). All these effects of rutaecarpine were abolished by capsaicin.These results suggest that rutaecarpine protects against bleomycin-induced pulmonary fibrosis by inhibiting Notch1/eIF3a signaling pathway, alleviating EMT process, which is related to the increased synthesis and release of CGRP.

Selection and characterization of an anaerobic microbial consortium with high adaptation to crude glycerol for 1,3-propanediol production.

Crude glycerol is an ideal feedstock for bioproduction of 1,3-propanediol (1,3-PDO) while pure culture always shows low substrate tolerance and limited productivity. In this study, an anaerobic microbial consortium for conversion of crude glycerol was selected and its 1,3-PDO production capacity was evaluated. The consortium was obtained from anaerobic activated sludge by 19 serial transfers and mainly consisted of 94.64% Clostridiaceae and 4.47% Peptostreptococcaceae. The consortium adapted well with high glycerol concentration of 120 g/L as well as wide substrate concentration fluctuation from 15 to 80 g/L, producing 60.61 and 82.66 g/L 1,3-PDO in the batch and fed-batch fermentation, with the productivity of 3.79 and 3.06 g/(L∙h), respectively, which are among the best results published so far. Furthermore, mini consortia isolated by serial dilution exhibited similar microbial composition but gradually decreasing tolerance to crude glycerol. Four randomly selected Clostridium butyricum displayed different substrate tolerance and insufficient 1,3-PDO production capacity. This work demonstrated that the high adaptation to crude glycerol of the consortium was the collaborative effort of different individuals.

Cardioprotective Effects of Malvidin Against Isoproterenol-Induced Myocardial Infarction in Rats: A Mechanistic Study.

BACKGROUND Malvidin (alvidin-3-glucoside) is a polyphenol that belongs to the class of natural anthocyanin, which is abundantly found in red wines, colored fruits, and the skin of red grapes. Therefore, the current investigation was intended to evaluate the effect of malvidin against myocardial infarction induced by isoproterenol in the rats. MATERIAL AND METHODS The cardioprotective effects was assessed by determining the effect of malvidin on the activities of endogenous antioxidants - catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase (GSH) - and on the levels of lipid peroxidation and serum marker enzymes. The serum levels of IL-6 and TNF-α were also determined using an enzyme-linked immunosorbent assay (ELISA) kit. RESULTS The present study demonstrated a significant cardioprotective effect of malvidin by restoring the defensive activities of endogenous antioxidants - catalase (CAT), superoxide dismutase (SOD), and glutathione peroxidase (GSH) - and by reducing the levels of lipid peroxidation and serum marker enzymes lactate dehydrogenase (LD) and creatine kinase (CK). Malvidin significantly ameliorated the histopathological changes and impaired mitochondria in the cardiac necrosis stimulated with isoproterenol. Additionally, the results also demonstrated that nuclear translocation of Nrf-2 and subsequent HO-1 expression might be associated with nuclear factor kappa B (NF-κB) pathway activation. CONCLUSIONS Our findings suggest that malvidin exerts cardioprotective effects that might be due to possible strong antioxidant and anti-inflammatory activities. Therefore, this study provides the basis for the development of malvidin as a safe and effective treatment of myocardial infarction.

The antitumour effects of eudesmin on lung cancer by inducing apoptosis via mitochondria-mediated pathway in the tumour cells.

CONTEXT: Limonoids possess broad range of biological activities, including antitumour, antimicrobial and antioxidant activities, etc. Eudesmin (EDN) is a type of limonoid which also possesses various activities. However, there is no report on the antitumour lung cancer (LC) activities of this compound. OBJECTIVE: The present study investigates the antitumour effects of EDN and its potential molecular mechanisms. MATERIALS AND METHODS: The in vitro antitumour effects of EDN on LC A549 cells were evaluated by using MTT assay. The in vivo antitumour effects were investigated on a xenograft athymic nude mouse model. The mice were administered orally with EDN (10, 20 and 40 mg/kg) once daily for 28 days. Effects of EDN on apoptosis-related or signalling proteins (Bcl-2, Bax, caspase-3, caspase-9, P53, Akt and JNK) were assayed by western blot analysis. RESULTS: EDN showed significant inhibitory effects on the growth of LC A549 cells in vitro with the half maximal inhibitory concentration (IC50) of 18.3 µM. By treating with EDN (10, 20 and 40 µM), expression of caspase-3, caspase-9, Bax, P53 and phosphorylated JNK in A549 cells were significantly upregulated, whereas expression of Bcl-2 and Akt phosphorylation were significantly down-regulated. Interestingly, EDN-induced apoptosis could be attenuated by JNK inhibitor. In addition, in vivo experiments also indicated EDN (10, 20 and 40 mg/kg) had significant antitumour effects (p < 0.01) on nude mice. CONCLUSIONS: Overall, the results indicated that EDN possesses significant antitumour effects on LC and the possible mechanism might be related to induction of mitochondria-mediated apoptosis.

Chemical Components and Pharmacological Activities of Terpene Natural Products from the Genus Paeonia.

Paeonia is the single genus of ca. 33 known species in the family Paeoniaceae, found in Asia, Europe and Western North America. Up to now, more than 180 compounds have been isolated from nine species of the genus Paeonia, including terpenes, phenols, flavonoids, essential oil and tannins. Terpenes, the most abundant naturally occurring compounds, which accounted for about 57% and occurred in almost every species, are responsible for the observed in vivo and in vitro biological activities. This paper aims to give a comprehensive overview of the recent phytochemical and pharmacological knowledge of the terpenes from Paeonia plants, and enlighten further drug discovery research.

Investigation and analysis of the caring attitude and behaviour of nurses in Shanghai, China.

The aim of this study was to investigate and analyse the caring attitude and behaviour of clinical nurses in terms of importance, competency and feasibility. The study used a survey design. Data were collected between January and June 2010. Two hundred and sixty clinical nurses were recruited. The caring attitude and behaviour of the nurses were assessed by using a translated version of the original Caring Nurse-Patient Interaction Scale-Short Scale. The subjects considered operative caring behaviour to be more important than expressive caring behaviour. The nurses felt more competent to practise operative caring behaviour in the clinic, and reported that such care was more feasible. The competency scores were positively correlated with age and work seniority. The feasibility scores for the clinical care dimension were positively correlated with age and work seniority. Nurses with a higher positional title had higher competency and feasibility scores. The results suggest that a rich life experience, accumulation of work experience and better competency might promote caring behaviour in nurses.

Laryngo-tracheobronchial amyloidosis: a case report and review of literature.

AMYLOIDOSIS is a benign process which can have systemic involvement. Though larynx is the common site of localized amyloidosis in the head and neck region,1 it was seldom reported with heterochronous implication of bilateral ventricles. Here we report a case of laryngeal amyloidosis heterochronously localized at bilateral ventricles with tracheobronchial involvement. Combined with our experience we reviewed the literature, and discuss the pertinent managements of this condition.