Manganese corrole catalyzed selective oxidation of styrene to benzaldehyde: sodium nitrite functions as an oxidant and cocatalyst.

Catalytic oxidation using manganese corrole is a hot topic of contemporary porphyrin chemistry, in which PhIO, TBHP, PhI(OAc)2, KHSO5 and m-CPBA are usually used as oxidants. This article reports the first selective oxidation of styrene to benzaldehyde using a manganese(III) corrole catalyst and sodium nitrite (NaNO2) as oxidant and cocatalyst at room temperature. The yield was 158.1% in air and 96.5% under a nitrogen atmosphere, showing oxygen might be involved in the reaction and that NaNO2 is an oxygen source and cocatalyst in the system. The peripheral electron-withdrawing substituents of the manganese corrole were favorable to the catalytic reaction. Radical inhibition and H218O experiments proved that the catalytic reaction was a free radical and hydrolysis-involved reaction.

[Advances of the Regulation of microRNAs in Follicular Development].

In recent years,microRNAs(miRNAs)have been detected at different stages of follicular development and in different cells of follicles.Extracellular vesicle(EV)-derived miRNAs have also been detected in the follicular fluid of mature follicles.miRNAs participate in the regulation of normal follicular development,and the regulation disorder may lead to the occurrence of some ovarian diseases.In order to further systematically elucidate the regulatory mechanism of miRNAs on follicular development and find suitable EV-derived miRNAs that can predict oocyte development,we reviewed the functions of miRNAs in follicular development from the perspectives of granulosa cell development,oocyte development,and hormone synthesis.

Halogenated Gallium Corroles:DNA Interaction and Photodynamic Antitumor Activity.

A series of halogenated gallium corroles were synthesized and characterized by UV-vis, HRMS, NMR, and FT-IR. The interaction between these gallium corroles and calf thymus DNA had been investigated by spectroscopic methods. These gallium corroles would interact with CT-DNA via an outside binding mode. The photodynamic antitumor activity in vitro of these gallium corroles toward different cell lines had also been tested. 3-Ga displayed low cytotoxicity to normal cells under both light and dark conditions but high phototoxicity to liver cancer cells HepG2. The vitro experiment results showed that 3-Ga could be efficiently absorbed by tumor cells. After light illumination, it may induce reactive oxygen species (ROS) and cause destruction of the mitochondrial membrane potential, which may finally trigger tumor cell apoptosis. Flow cytometry results showed that HepG2 cells were mainly distributed in the sub-G0 phase, which corresponds to cells with highly fragmented DNA or dead cells generally. This suggests that 3-Ga could lead to tumor cell apoptosis after light illumination.

Hydroxy-corrole and its gallium(III) complex as new photosensitizer for photodynamic therapy against breast carcinoma.

Three mono-hydroxy corroles 1-3 and their gallium(III) complexes Ga1-3 were synthesized, and their photodynamic antitumour activities towards breast cancer cells were investigated. All corroles showed excellent cytotoxicity against the MDA-MB-231 and 4T1 cell lines upon light irradiation at 625 nm. Ga3 exhibited excellent phototoxicity and selectivity against MDA-MB-231 cells, with an IC50 of 0.06 ± 0.03 µM and a selective index value of 1338.83 (relative to human normal Huvec cells). The performance of Ga3 was even better than that of the clinical photodynamic therapy drug m-THPC. A preliminary mechanistic investigation revealed that corrole 3 and Ga3 were mainly located in the cytoplasm. Upon irradiation, they could generate intracellular reactive oxygen to destroy the mitochondrial membrane potential and arrest the cell cycle at the sub-G1 phase. Flow cytometry revealed that corrole 3 and Ga3 induced cancer cell apoptosis after photodynamic treatment. Corrole 3 and Ga3 displayed negligible cytotoxicity in the dark. These results suggest that corrole 3 and Ga3 are promising candidates for use in the photodynamic therapy of breast cancer.

[Distribution Characteristics of Antibiotic Resistance Genes and Mobile Genetic Elements in Beijing Vegetable Base Soils].

The distribution characteristics of antibiotic resistance genes (ARGs) and mobile genetic elements (MGEs) in five vegetable base soils from Beijing, China, were assessed. The composition of ARGs and MGEs in soil samples were analyzed by HT-qPCR. We detected 92-121 ARGs and 4-6 MGEs. The ARGs and MGEs in vegetable base soils from different districts were separated from each other. The dominant ARGs shared by vegetable bases were oprD, acrA-04, and acrA-05 of a multidrug, mphA-01 of MLSB, and ß-Lactamase fox5, vanC-03 of vancomycin. The shared MGE among the five vegetable base soils was intI1. A total of seven antibiotics were detected in the soil of several vegetable bases. The dominant antibiotics included enoxacin (ENR), norfloxacin (NOR), oxytetracycline (OTC), and sulfamethoxazole (SMX). The numbers and abundance of antibiotics in the soil of vegetable bases from the Shunyi district were the highest, followed by those from Tongzhou and Changping. Correlation analysis showed that there was a significant positive correlation between the abundance of ARGs and the abundance of antibiotics in the soil of vegetable bases (P<0.05). These results provide basic theoretical data for controlling the transmission of ARGs.

Photodynamic antitumor activity of Ru(ii) complexes of imidazo-phenanthroline conjugated hydroxybenzoic acid as tumor targeting photosensitizers.

Two novel Ru(ii) polypyridyl complexes bearing imidazo-phenanthroline conjugated hydroxybenzoic acid groups were designed to enhance the tumor targeting ability as photosensitizers for photodynamic therapy. [Ru(bpy)2(phcpip)] (ClO4)2 (Ru-1) and [Ru(bpy)2(ohcpip)] (ClO4)2 (Ru-2) (bpy = 2,2'-bipyridine; phcpip = 2-(3-carboxyl-4-hydroxyphenyl) imidazo [4,5-f]phenanthroline; ohcpip = 2-(2-hydroxyl-3-carboxyphenyl) imidazo [4,5-f] [1,10] phenanthroline) were synthesized and their photodynamic antitumor activities were investigated. Both complexes displayed high photocytotoxicity toward cancerous cell lines HepG2, A549, MCF-7, and MDA-MB-231, but low photocytotoxicity toward normal cell lines GES-1 and Huvec. They were mainly localized at the nucleus of HepG2 cells after 24 h incubation, arrested the cell cycle at the G2/M phase and induced cancer cell apoptosis through reactive oxygen species (ROS) mediated pathways. Tumor targeting of the complexes is attributed to stronger molecular binding to DNA.

[Microbial Community Structure and the Distribution of Antibiotic Resistance Genes in Soil Contaminated by Sulfamethoxazole].

A pot experiment was carried out to simulate soil contaminated by sulfamethoxazole at different concentrations. The community structure of soil microorganisms was investigated using Illumina high-throughput sequencing, and 64 subtypes of antibiotic resistance genes (ARGs) resistant to six classes of antibiotic were also analyzed by PCR and droplet digital PCR. The results showed that soil contamination with sulfamethoxazole had no significant effect on fungal diversity after 120 days (P>0.05) whereas bacterial diversity was significantly reduced (P<0.05). The microbial community structure of the contaminated soil changed significantly, with the dominant bacterial and fungal genera being significantly different from the control soil. Sulfamethoxazole contamination resulted in an increase in ARG diversity, and the abundance of the sulfonamide resistance gene sul1 increased significantly (P<0.05). However, the abundance of the sulfonamide resistance gene sul2, the quinolone resistance genes floR and cmlA1, and the tetracycline resistance genes tet(34), tetG2, tetG1,tetM, and tetA/P did not show significant changes in the contaminated soil (P>0.05).

DNA interaction and photodynamic antitumor activity of transition metal mono-hydroxyl corrole.

A series of iron(III), manganese(III) and copper(III) mono-hydroxyl corrole complexes had been prepared and well characterized by UV-vis, 1H NMR, 19F NMR and HR-MS. These metallocorroles may bind to CT-DNA through external binding mode. Metallocorrole Fe-2c exhibited significant phototoxicity and low toxicity toward A549 tumor cells. While manganese (III) and copper (III) corroles showed hypotoxicity to A549, MCF-7 and HepG-2 tumor cells, whether under dark or illumination conditions. All tested metallocorroles exhibited non-toxicity to human normal cells (GES-1) with or without irradiation at 625 nm. Cell cycle analysis indicated that metallocorrole Fe-2c arrested the cell cycle at G2/M phase and increased the Sub-G1 phase in A549 cell lines. It was mainly localized at mitochondria and could significantly reduce mitochondrial membrane potential after photodynamic treatment, which would further induce tumor cell apoptosis.

Two new eriophyid mite species associated with Clematis terniflora var. mandshurica in China (Acari, Eriophyidae).

Two new eriophyid mite species associated with Clematis terniflora var. mandshurica, namely Aculops jilinensissp. n. and Phyllocoptes ternifloressp. n., are described. Both species infest the tender leaves of host plants, inducing severe curling and blistering.

Chemometrics-enhanced high performance liquid chromatography-diode array detection strategy for simultaneous determination of eight co-eluted compounds in ten kinds of Chinese teas using second-order calibration method based on alternating trilinear decomposition algorithm.

In this work, an attractive chemometrics-enhanced high performance liquid chromatography-diode array detection (HPLC-DAD) strategy was proposed for simultaneous and fast determination of eight co-eluted compounds including gallic acid, caffeine and six catechins in ten kinds of Chinese teas by using second-order calibration method based on alternating trilinear decomposition (ATLD) algorithm. This new strategy proved to be a useful tool for handling the co-eluted peaks, uncalibrated interferences and baseline drifts existing in the process of chromatographic separation, which benefited from the "second-order advantages", making the determination of gallic acid, caffeine and six catechins in tea infusions within 8 min under a simple mobile phase condition. The average recoveries of the analytes on two selected tea samples ranged from 91.7 to 103.1% with standard deviations (SD) ranged from 1.9 to 11.9%. Figures of merit including sensitivity (SEN), selectivity (SEL), root-mean-square error of prediction (RMSEP) and limit of detection (LOD) have been calculated to validate the accuracy of the proposed method. To further confirm the reliability of the method, a multiple reaction monitoring (MRM) method based on LC-MS/MS was employed for comparison and the obtained results of both methods were consistent with each other. Furthermore, as a universal strategy, this new proposed analytical method was applied for the determination of gallic acid, caffeine and catechins in several other kinds of Chinese teas, including different levels and varieties. Finally, based on the quantitative results, principal component analysis (PCA) was used to conduct a cluster analysis for these Chinese teas. The green tea, Oolong tea and Pu-erh raw tea samples were classified successfully. All results demonstrated that the proposed method is accurate, sensitive, fast, universal and ideal for the rapid, routine analysis and discrimination of gallic acid, caffeine and catechins in Chinese tea samples.

[Prevention of Inonotus obliquus polysaccharides for high power microwave radiation induced testicular injury in rats: an experimental research].

OBJECTIVE: To investigate the effect of Inonotus obliquus polysaccharides on testicular injury induced by exposure to high power microwave (HPM) in rats. METHODS: A total of 30 male Wistar rats were randomly divided into 5 groups, i.e., the normal control group, the microwave radiation model group, the treatment group, the new microwave radiation model group, and the prevention group, 6 in each group. All rats, except those in the normal control group, were exposed to microwave at an average power density of 200 mW/cm2 for 6 min. Rats in the control group and the model group were administered with normal saline by gastrogavage, once a day. Rats in the treatment group and the prevention group were given with Inonotus obliquus polysaccharides by gastrogavage, 2 mL each time (400 mg/kg body weight), once a day. All rats were sacrificed on the 11th day.The sperm density and the rate of sperm deformity were determined. Pathological changes of testis were observed by light microscope and transmission electron microscope. RESULTS: Short-term HPM irradiation could significantly reduce the sperm density and increase the sperm deformity rate (P < 0.05). Meanwhile, obvious pathological changes of testes occurred. Compared with the two model groups, the sperm density increased and the sperm deformity rate decreased in the treatment group and the prevention group (P < 0.05). Under the light microscope, injuries of spermatogenic cells and stromal cells, as well as vascular dilatation and congestion were obviously alleviated in the treatment group and the prevention group. Mitochondrial swelling and endoplasmic reticulum expansion shown by ultrastructural observation were also significantly alleviated. Of them, injuries of spermatogenic cells and inflammation response were milder in the treatment group than in the prevention group. CONCLUSIONS: Inonotus obliquus polysaccharides had significant protective effect on microwave radiation induced testicular injury. Better effect was obtained by therapeutic medication than preventive medication.

Simultaneous determination of eight flavonoids in propolis using chemometrics-assisted high performance liquid chromatography-diode array detection.

A fast analytical strategy of second-order calibration method based on the alternating trilinear decomposition algorithm (ATLD)-assisted high performance liquid chromatography coupled with a diode array detector (HPLC-DAD) was established for the simultaneous determination of eight flavonoids (rutin, quercetin, luteolin, kaempferol, isorhamnetin, apigenin, galangin and chrysin) in propolis capsules samples. The chromatographic separation was implemented on a Wondasil™ C18 column (250mm×4.6mm, 5µm) within 13min with a binary mobile phase composed of water with 1% formic acid and methanol at a flow rate of 1.0mLmin(-1) after flavonoids were only extracted with methanol by ultrasound extraction for 15min. The baseline problem was overcome by considering background drift as additional compositions or factors as well as the target analytes, and ATLD was employed to handle the overlapping peaks from analytes of interest or from analytes and co-eluting matrix compounds. The linearity was good with the correlation coefficients no less than 0.9947; the limit of detections (LODs) within the range of 3.39-33.05ngmL(-1) were low enough; the accuracy was confirmed by the recoveries ranged from 91.9% to 110.2% and the root-mean-square-error of predictions (RMSEPs) less than 1.1µg/mL. The results indicated that the chromatographic method with the aid of ATLD is efficient, sensitive and cost-effective and can realize the resolution and accurate quantification of flavonoids even in the presence of interferences, thus providing an alternative method for accurate quantification of analytes especially when the complete separation is not easily accomplished. The method was successfully applied to propolis capsules samples and the satisfactory results were obtained.

Interference-free determination of indole-3-acetic acid in two real systems using second-order calibration method coupled with excitation-emission matrix fluorescence.

In this work, a simple and practicable method that combines excitation-emission matrix (EEMs) fluorescence with a second-order calibration method based on parallel factor analysis-alternative least-squares (PARAFAC-ALS) algorithm was developed for the direct interference-free determination of indole-3-acetic acid (IAA) in two real systems, coconut water (CW) and coconut milk (CM). Although the excitation and emission profiles of IAA heavily overlapped with that of unknown interferents in the complex real systems, the actual contents and satisfactory recoveries were still obtained successfully. The contents of IAA in CW and CM were 10.8 ± 0.3 and 4.9 ± 0.2 µg mL(-1), respectively, which were consistent with those reported by LC-MS/MS assays in the reference material. The average spike recoveries of IAA in the validation set based on CW and CM were 102.1 ± 3.2 and 98.0 ± 1.9%, respectively. In addition, routine experiments were performed for establishing the validity of the assay to internationally accepted criteria.

[Histone modifications during spermatogenesis and male infertility].

Many pathological phenomena of male infertility are related to epigenetic changes in male germ cells. Epigenetic regulation during spermatogenesis plays an important role in mitotic/meiotic divisions and spermiogenesis. The histones have various post-translational modifications on different amino acid residues during spermatogenesis. These modifications are crucial to the precise regulation of spermatogenesis. Moreover, the histone-to-protamine transition will occur during spermiogenesis. Many studies have also found that abnormal changes of histone modifications during spermatogenesis may damage the sperm development, leading to male sterility. This article reviews the changes of histone modifications during spermatogenesis, the regulation of the development of male germ cells, and the relationship between histone abnormalities and male sterility.

Simultaneous determination of phenolic antioxidants in edible vegetable oils by HPLC-FLD assisted with second-order calibration based on ATLD algorithm.

A novel strategy that combines the chemometrics method with high performance liquid chromatography with fluorescence detector (HPLC-FLD) was developed for the simultaneous determination of seven phenolic antioxidants in six kinds of oil samples. After a simple dilution step, oil samples can be directly injected into the detecting system and the data were measured in a short time with a chromatographic system operating in the gradient elution mode. Since the chromatographic and spectral peaks among interesting analytes and interferences were heavily overlapped, second-order calibration method based on alternating trilinear decomposition (ATLD) algorithm which fully exploiting the second-order advantage was adopted. Successful resolution was obtained in the presence of different matrix interferences in different oil samples, and the developed approach allows the quantification of the antioxidants at levels found in edible vegetable oils, without the necessity of applying either preconcentration or extraction steps, moreover, a column washing is also not required. Meanwhile, the effectiveness and reproducibility of the proposed method were also validated by some statistical parameters like root mean squared error of prediction (RMSEP), limits of detection (LOD) and relative standard deviation (RSD). Then the proposed method was compared with several commonly selected methods in sample preparation, elution time and LOD.

Fast analysis of synthetic antioxidants in edible vegetable oil using trilinear component modeling of liquid chromatography-diode array detection data.

A new chromatographic methodology is presented for fast quantitative analysis of ten synthetic phenolic antioxidants in five kinds of oil samples: propyl gallate (PG), 2,4,5-trihydroxybutyrophenone (THBP), tert-butylhydroquinone (TBHQ), nordihydroguaiaretic acid (NDGA), ethoxyquin (EQ), 3-tert-butyl-4- hydroxyanisole (BHA), octyl gallate (OG), 2,6-di-tert-butyl-4-hydroxymethyphenol (Ionox-100), dodecyl gallate (DG), 3,5-di-tert-butyl-4-hydroxytoluene (BHT). The second-order calibration, with second-order advantage, based on the alternating penalty trilinear decomposition (APTLD) algorithm has shown to be an excellent tool for modeling the three-way data, where overlapping peaks, uncalibrated inteferences, and baseline drift existed, making the fast determination and resolution of the phenolic antioxidants in oils possible. Such extraction procedure in which the antioxidants of interest would be seperated is unnecessary and the ten antioxidants can be eluted within 6 mins. For the validation of the method, linearity, root-mean-square error of prediction (RMSEP) and limit of detection (LOD) have been performed. The average recovery of antioxidants ranges from 94.9 to 106.1% and the ten analytes can be adequately determined with limits of detection of 0.18-5.72 µgm l(-1).

Gene therapy of endometriosis introduced by polymeric micelles with glycolipid-like structure.

To reduce the side effects and improve the lack of clinical treatment countermeasures in endometriosis chemotherapy, a polymeric micelle gene delivery system composed of lipid grafted chitosan micelles (CSO-SA) and the pigment epithelium derived factor (PEDF) was designed. Due to the cationic property, the glycolipid-like micelles could compact the PEDF to form complexes nanoparticles. The complexes nanoparticles with an N/P at 9.6 had 135.6 nm volume average hydrodynamic diameters with a narrow size distribution, and 6.4 ± 0.1 mV surface potential. PEDF can be distributed to endometriotic lesions in a rat model of peritoneal endometriosis mediated by CSO-SA via the intravenous injection. It showed that the CSO-SA/PEDF nanoparticles gene therapy caused decrease in the sizes of the endometriotic lesions and atrophy and degeneration of ectopic endometrium significantly. And it showed no toxicity to the reproductive organs under electron microscope observation. In addition, a reduction in microvessel density labeled by Von Willebrand factor was observed and no decrease in α-Smooth Muscle Actine-positive mature vessels. And the index of apoptotic was increased significantly in endometriotic lesions of CSO-SA/PEDF group. So, glycolipid-like structure micelles mediated PEDF gene delivery system could be used as an effective treatment approach for endometriosis disease.

Flavihumibacter petaseus gen. nov., sp. nov., isolated from soil of a subtropical rainforest.

A yellow-coloured bacterium, T41(T), was isolated from a soil sample of a subtropical rainforest in Nepal. Cells were Gram-reaction-positive, aerobic, non-motile, short rods. Phylogenetic analysis based on 16S rRNA gene sequences indicated that the strain formed a cluster with Terrimonas ferruginea, Terrimonas lutea, Niabella soli, Flavisolibacter ginsengiterrae, Flavisolibacter ginsengisoli, Niastella yeongjuensis and Niastella koreensis in the phylum Bacteroidetes. The strain showed the highest sequence similarity to the type strain of Terrimonas lutea (93.2 %). The major isoprenoid quinone was MK-7 and the predominant cellular fatty acids (>10 %) were iso-15 : 0 (33.8 %), iso-15 : 1 G (13.3 %) and iso-17 : 0 3-OH (12.9 %). The DNA G+C content was 48.1 mol%. On the basis of phenotypic and phylogenetic data and genomic distinctiveness, strain T41(T) represents a novel species in a new genus in the phylum Bacteroidetes, for which the name Flavihumibacter petaseus gen. nov., sp. nov. is proposed. The type strain of Flavihumibacter petaseus is strain T41(T) (=CGMCC 1.7723(T) =NBRC 106054(T)).

Influence of intercropping and intercropping plus rhizobial inoculation on microbial activity and community composition in rhizosphere of alfalfa (Medicago sativa L.) and Siberian wild rye (Elymus sibiricus L.).

Alfalfa-Siberian wild rye intercropping is the predominant cropping system used to produce forage in China. In this study, the effects of intercropping and intercropping-rhizobial inoculation on soil enzyme activities, microbial biomass and bacterial community composition in the rhizosphere were examined. In both treatments, the yield of alfalfa, microbial biomass and activities of soil urease, invertase and alkaline phosphatase in the alfalfa rhizosphere were markedly increased, whereas there was a slight increase in the yield of Siberian wild rye, few impacts on soil microbial biomass, and decreased enzyme activities (except for urease) in the Siberian wild rye rhizosphere. Terminal restriction fragment length polymorphism (T-RFLP) of 16S rRNA genes indicated that Alphaproteobacteria, Betaproteobacteria, Gammaproteobacteria, Deltaproteobacteria, Firmicutes, Actinobacteria and Bacteroidetes were the major bacterial groups in the rhizosphere of both plants. However, intercropping and rhizobial inoculation induced some shifts in the relative abundance of them. Nitrosomonas and Nitrosospira groups were detected in all treatments by the T-RFLP patterns of ammonia monooxygenase subunit A (amoA) gene, but the relative abundance of Nitrosomonas increased and that of Nitrosospira decreased in the intercropping-rhizobial inoculation treatment. Both treatments tended to increase the diversity of amoA. Conclusively, the two treatments clearly affected soil microbial composition and soil enzyme activities, which might be reflected in changes in yield.

Abdominal acupuncture for insomnia in women: a randomized controlled clinical trial.

A randomized single-blind trial was conducted to evaluate the efficacy of short-term abdominal acupuncture as a novel treatment for insomnia in Chinese women. Forty-four patients between the ages of 22 and 56 were randomly assigned to an acupuncture (n = 23) and a medication group (n = 21). The acupuncture group received abdominal acupuncture once a day for the first three days and once every three days for the remaining 11 days. In addition, every subject in acupuncture group also received a placebo pill once daily. Abdominal acupuncture was administered according to a standardized protocol involving four master and four adjunctive acupoints: Zhongwan (CV 12), Xiawan (CV 10), Guanyuan (CV 4), and Qihai (CV 6); bilateral Shangqu (KI 17), Huaroumen (ST 24), Xiafengshidian, and Qipang. Subjects in the medication group were treated with sham acupuncture at the same time as the acupuncture group and received estazolam once a day. The outcome measure was the Leeds Sleep Evaluation Questionnaire (LSEQ), administered before and after the trial. Subjects who received abdominal acupuncture lowered their LSEQ scores by an average of 26.32 points (95% CI: 37.34, 15.30). After controlling for potential confounding factors, the effect of abdominal acupuncture in relieving insomnia was still statistically significant. Results indicate that short-term abdominal acupuncture is more effective than pharmacological treatment for relieving insomnia in adult women and has few adverse effects.