Photoinduced inverse vulcanization.

The inverse vulcanization (IV) of elemental sulfur to generate sulfur-rich functional polymers has attracted much recent attention. However, the harsh reaction conditions required, even with metal catalysts, constrains the range of feasible crosslinkers. We report here a photoinduced IV that enables reaction at ambient temperatures, greatly broadening the scope for both substrates and products. These conditions enable volatile and gaseous alkenes and alkynes to be used in IV, leading to sustainable alternatives for environmentally harmful plastics that were hitherto inaccessible. Density functional theory calculations reveal different energy barriers for thermal, catalytic and photoinduced IV processes. This protocol circumvents the long curing times that are common in IV, generates no H2S by-products, and produces high-molecular-weight polymers (up to 460,000 g mol-1) with almost 100% atom economy. This photoinduced IV strategy advances both the fundamental chemistry of IV and its potential industrial application to generate materials from waste feedstocks.

Laser-assisted hatching zona thinning does not improve the pregnancy outcomes of poor-quality blastocysts in frozen-thawed embryo transfer cycle: a retrospective cohort study.

It had been suggested, after facilitating the hatching process, improved pregnancy outcomes could be attained in embryos with thick and hard zona. This study aimed to determine the effect of zona thinning on pregnancy outcomes in poor-quality frozen-thawed blastocysts. This retrospective study included 230 women (≤ 40 years) who underwent frozen embryo transfer of poor-quality blastocysts (scored < 3BB). In total, 105 patients were in the assisted hatching group in which the zona was thinned by laser before transfer and 125 patients were in the control group in which the blastocysts were non-manipulated. Patients' demographics, cycle characteristics, and pregnancy outcomes were compared between the assisted hatching group and the control group. Further, regression analysis was applied to test the correlation between assisted hatching and live birth. All parameters in the patients' demographic characteristics and the cycle's characteristics were not significantly different between two groups. As for pregnancy outcomes, the second trimester pregnancy loss was significantly higher in the assisted hatching group (P = 0.035). Other pregnancy outcomes, including implantation rate, clinical pregnancy rate, biochemical miscarriage rate, the first trimester pregnancy loss, ongoing pregnancy rate, and live birth rate were comparable between two groups. The logistic regression analysis demonstrated no association between live birth and assisted hatching (univariate, OR = 0.787, P > 0.05; multivariate, OR = 0.652, P > 0.05), and the area under the receiver operating characteristic curve of the regression model was almost 0.7. It suggested that zona thinning may not be supposed to perform on poor-quality, frozen-thawed blastocysts. The indications of assisted hatching were still needed to further investigate.

Association of vertebral endplate microstructure with bone strength in men and women.

Epidemiological and biomechanical evidence indicates that the risk of vertebral fracture differs between men and women, and that vertebral fracture frequently involves failure of the endplate region. The goal of this study was to compare the bone microstructure of the endplate region-defined as the (bony) vertebral endplate and underlying subchondral trabecular bone-between sexes and to determine whether any such sex differences are associated with vertebral strength. The bone density (volume fraction, apparent density and tissue mineral density) of the superior-most 2 mm of the vertebra, and the bone density and trabecular architecture of the next 5 mm were quantified using micro-computed tomography in human T8 (12 female, 16 male) and L1 (13 female, 12 male) vertebrae. Average density of the vertebra (integral bone mineral density (BMD)) was determined by quantitative computed tomography and compressive strength by mechanical testing. Few differences were found between male and female vertebrae in the density of the endplate region; none were found in trabecular architecture. However, whereas endplate volume fraction was positively correlated with integral BMD in male vertebrae (r = 0.654, p < .001), no correlation was found in the female vertebrae (r = 0.157, p = .455). Accounting for the density of the endplate region improved predictions of vertebral strength (p < .034) and eliminated sex-specificity in the strength prediction that was based on integral BMD alone. These results suggest that the density of the endplate region influences vertebral fracture and that non-invasive assessment of this region's density can contribute to predictions of vertebral strength in men and women.

Notch signaling via regulation of RB and p-AKT but not PIK3CG contributes to MIA PaCa-2 cell growth and migration to affect pancreatic carcinogenesis.

Pancreatic cancer is one of the leading causes of cancer-associated mortality. The understanding of the expression pattern of key protein factors and their function in pancreatic cancer cells is therefore vital for the diagnosis and treatment of this malignancy. The results of the present study reveal that the levels of neurogenic locus notch homolog protein 2 (Notch2) and phosphorylated (p)-SMAD family member 2 decreased, whereas the expression of Notch3 and phosphoinositide-3 kinase catalytic subunit-γ protein increased in human pancreatic cancer tissues compared with tumor-adjacent tissues. Using the human pancreatic cancer MIA PaCa-2 cell line, it was observed that retinoblastoma-associated protein (RB) and p-RB expression were inhibited and p-AKT was upregulated when Notch signaling was activated in MIA PaCa-2 cells. Furthermore, inhibition of phosphoinositide-3 kinase catalytic subunit-γ (PIK3CG) activity by AS-605240 was able to block the growth and migration of MIA PaCa-2 cells. In conclusion, the results of the present study demonstrate that the Notch signal pathway may be involved in pancreatic carcinogenesis by modulating RB and p-AKT. PIK3CG may therefore be a potential target gene for the treatment of pancreatic cancer.

Radical aryl migration enables diversity-oriented synthesis of structurally diverse medium/macro- or bridged-rings.

Medium-sized and medium-bridged rings are attractive structural motifs in natural products and therapeutic agents. Due to the unfavourable entropic and/or enthalpic factors with these ring systems, their efficient construction remains a formidable challenge. To address this problem, we herein disclose a radical-based approach for diversity-oriented synthesis of various benzannulated carbon- and heteroatom-containing 8-11(14)-membered ketone libraries. This strategy involves 1,4- or 1,5-aryl migration triggered by radical azidation, trifluoromethylation, phosphonylation, sulfonylation, or perfluoroalkylation of unactivated alkenes followed by intramolecular ring expansion. Demonstration of this method as a highly flexible tool for the construction of 37 synthetically challenging medium-sized and macrocyclic ring scaffolds including bridged rings with diverse functionalities and skeletons is highlighted. Some of these products showed potent inhibitory activity against the cancer cell or derivative of human embryonic kidney line in preliminary biological studies. The mechanism of this novel strategy is investigated by control experiments and DFT calculations.

Active Components of Fungus Shiraia bambusiscola Can Specifically Induce BGC823 Gastric Cancer Cell Apoptosis.

OBJECTIVE: Gastric cancer is a major health issue worldwide. Using a therapeutic approach, with minor side-effects, is very essential for the treatment of the gastric cancer. Shiraia bambusicola is a parasitic fungus which is widely used in China for curing several diseases with little side-effects. However, the mechanisms are not well understood yet. The aim of this study was to further understand the pharmacological mechanisms of Shiraia bambusicola and investigate whether it can be used for curing gastric cancer. MATERIALS AND METHODS: In this experimental study, we mainly tested the effect of active components extracted from Shiraia bambusicola on BGC823, A549 and HepG2 cells. We used MTT assay to test cell viability. We also analyzed morphologic changes caused by apoptosis using Hoechst 33342 fluorescence staining, as well as cell cycle status and apoptosis ratio using flow-cytometer. In addition, protein expression level was tested by Western-blotting assay. RESULTS: BGC-823 cell proliferation was specifically inhibited by active components of Shiraia bambusicola. Meanwhile, these active components could induce BGC-823 cells apoptosis and retard the cell cycle in S/G2 phase. We also determined that two critical protein markers cleaved Poly(ADP-ribose) polymerase-1 (PARP-1) and FLICE-inhibitory protein (FLIP), involved in apoptosis process, were regulated by these active components. CONCLUSION: These data shed light on the treatment of human gastric cancer and conclude that Shiraia bambusicola can be a good therapeutic candidate for treatment of this malignancy.

Preparation of Thermo-Responsive Poly(ionic liquid)s-Based Nanogels via One-Step Cross-Linking Copolymerization.

In this study, thermo-responsive polymeric nanogels were facilely prepared via one-step cross-linking copolymerization of ethylene glycol dimethacrylate/divinylbenzene and ionic liquid (IL)-based monomers, 1,n-dialkyl-3,3'-bis-1-vinyl imidazolium bromides ([CnVIm]Br; n = 6, 8, 12) in selective solvents. The results revealed that stable and blue opalescent biimidazolium (BIm)-based nanogel solutions could be obtained without any precipitation when the copolymerizations were conducted in methanol. Most importantly, these novel nanogels were thermo-response, and could reversibly transform to precipitation in methanol with temperature changes. Turbidity analysis and dynamic light scatting (DLS) measurement illustrated that PIL-based nanogel solutions presented the phase transform with upper critical solution temperature (UCST) in the range of 5-25 °C. The nanogels were characterized using Fourier transform infrared (FTIR), thermogravimetric analyses (TGA), and scanning electron microscopy (SEM). In addition, BIm-based nanogels could also be used as highly active catalysts in the cycloaddition reaction of CO2 and epoxides. As a result, our attributes build a robust platform suitable for the preparation of polymeric nanomaterials, as well as CO2 conversion.

Clinical analysis of early and mid-late elevated intraocular pressure after silicone oil injection.

PURPOSE: To discuss the incidence and clinical features of early and mid-late elevated intraocular pressure after pars plana vitrectomy and silicone oil injection, and to evaluate the clinical management of eyes with secondary glaucoma. METHODS: This was an observational consecutive case series of 691 eyes in 679 patients who were treated with pars plana vitrectomy and silicone injection. The diagnostic criteria of early elevated intraocular pressure after silicone oil injection was ≥ 21 mmHg two weeks after surgery, while mid-late elevated intraocular pressure was ≥ 21 mmHg after two weeks. The incidence and clinical management of elevated intraocular pressure were analyzed. RESULTS: In total, 211 of 691 eyes (30.54%) developed elevated intraocular pressure two weeks after pars plana vitrecto my and silicone injection. Of the 211 eyes, 101 eyes (47.87%) had ocular inflammation, 64 eyes (30.33%) showed hyphema, 35 eyes (16.59%) had silicone oil in the anterior chamber, 6 eyes (2.84% ) had excess silicone oil injected, and 5 eyes (2.37%) had rubeosis irides. Eighty three of 691 eyes (12.01%) developed elevated intraocular pressure after two weeks. Of these 83 eyes, 25 eyes (30.12%) had rubeosis irides, 16 eyes (19.27%) had issues related to topic steroid therapy, 13 eyes (15.66%) had a papillary block, silicone oil in the anterior chamber, 10 eyes (12.05%) had a silicone emulsion, 10 eyes (12.05%) had peripheral anterior synchiae, and 9 eyes (10.84%) had silicone oil in the anterior chamber. All eyes with elevated intraocular pressure were treated with antiglaucoma medications and surgeries. CONCLUSION: The reasons for elevated intraocular pressure differed between early and mid-late after pars plana vitrectomy and silicone oil injection. The elevated intraocular pressure can be controlled effectively by immediate diagnosis and proper treatment with medicine and operation.

One-step synthesis of thermosensitive nanogels based on highly cross-linked poly(ionic liquid)s.

A gel for all seasons: Thermosensitive nanogels based on highly cross-linked poly(ionic liquid)s (CLPNs) were prepared in one step by the copolymerization of imidazolium-based monomers with cross-linkers in selective solvents. Reversible nanogel-macrogel transitions of CLPNs in methanol could be achieved by changing the temperature.

[Study on the fluorescence spectra of 7-hydroxyquinoline in dimethyl sulfoxide solution].

7-hydroxyquinoline (7-HQ) is a kind of organic molecule with excited-state proton transfer (ESPT) effect. 7-HQ in ethanol solution causes ESPT reaction under the excitation of ultraviolet light. The fluorescence spectrum of the sample exhibits two bands. In contrast, 7-HQ in dimethyl sulfoxide (DMS) solution does not cause ESPT reaction. The fluorescence spectrum of the sample exhibits a single band. But after the sample was irradiated with a strong UV light, its fluorescence spectrum also exhibits two bands. This phenomenon is reported for the first time in the present paper, and its cause is investigated through the study on the absorption spectra and fluorescence spectra of 7-HQ in ethanol, dimethyl sulfoxide and N, N-dimethyl formamide solution. The conclusion is that the change in the fluorescence spectrum of 7-HQ in DMS solution is due to the fact that 7-HQ causes ESPT reaction which results from the photodecomposition of DMS and the product of water after the solution was irradiated with strong UV light.