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Divergent synthesis for precise constructions of cyclic unsymmetrical diaryl disulfides or diselenides and polythiophenes from CF3 -containing 1,3-enynes and S8 was developed when the ortho group is F, Cl, Br, and NO2 on aromatic rings. Meanwhile, disulfides (diselenides) were also quickly constructed when the ortho group is H. These transformations undergo cascade thiophene construction/selective C3-position thiolation process, featuring simple operations, divergent synthesis, broad substrate scope, readily available starting materials, and valuable products. A novel plausible radical annulation process was proposed and validated by DFT calculations for the first time. A series of derivatizations about the thiophene (TBT) and disulfides were also well-represented.

We have rationally designed a new class of alkyne-tethered oximes and applied them in an unprecedented iron-catalyzed radical relay protocol for the rapid assembly of a wide array of structurally new and interesting fused pyridines. This method shows broad substrate scope and good functional-group tolerance and enabled the synthesis of several biologically active molecules. Furthermore, the fused pyridines could be diversely functionalized through various simple transformations, such as cyclization, C-H alkylation, and a click reaction. DFT calculation studies indicate that the reactions involve cascade 1,5-hydrogen atom transfer, 5-exo-dig radical addition, and cyclization processes. Moreover, preliminary biological investigations suggest that some of the fused pyridines exhibit good anti-inflammatory activity by restoring the imbalance of inflammatory homeostasis of macrophages in a lipopolysaccharide-induced model.

An efficient cascade reaction of tryptamine-derived isocyanides with C,N-cyclic azomethine imines is described. The polycyclic pyrrolo[2,3- c ]quinoline derivatives, which benefited from rearrangement process driven by hydrogen bonding, could be directly assembled in moderate to good yields (40-87%) under metal-free and mild conditions. This transformation involved four new heterocyclic rings formations and uniquely, ring opening of indole as well as ring expansion of C,N-cyclic azomethine imine. Both experimental and DFT studies provided guidance on the in-depth insight into the reaction pathways and hydrogen bonding was identified to lower the free energy barrier in transition states. This work constitutes a rare example of tryptamine-derived isocyanide-based cascade reactions, and potentially could be a powerful synthetic strategy for accessing polycyclic analogues involved in natural products.

Considering the ubiquitous nature and ready synthesis of amides, and the great significance of organofluorine-containing species, the cross-coupling of amides and polyfluoroarenes, leading to new carbon-carbon bond-forming methodologies, would find useful applications in synthesis, late-stage functionalization, and rapid generation of molecular diversity. Herein, we present a novel synthesis of α-polyfluoroaryl amines via Sm/SmI

Atomically precise enantiomeric metal clusters are scarce, and copper(I) alkynyl clusters with intense circularly polarized luminescence (CPL) responses have not been reported. A pair of chiral alkynyl ligands, (R/S)-2-diphenyl-2-hydroxylmethylpyrrolidine-1-propyne (abbreviated as R/S-DPM) we successfully prepared and single crystals were characterized of optically pure enantiomeric pair of atomically-precise copper(I) clusters, [Cu14 (R/S-DPM)8 ](PF6 )6 (denoted as R/S-Cu14 ), which feature bright red luminescence and CPL with a high luminescence anisotropy factor (glum ). A dilute solution containing R/S-Cu14 was nonluminescent and CPL inactive at room temperature. Crystallization- and aggregation-induced emission (CIE and AIE, respectively) contribute to the triggering of the CPL of R/S-Cu14 in the crystalline and aggregated states. Their AIE behavior and good biocompatibility indicated applications of these copper(I) clusters in cell imaging in HeLa and NG108-15 cells.

Aim Cryoglobulinaemic glomerulonephritis related to hepatitis B virus (HBV) infection has been rarely reported. The aim of this study was to investigate the clinical features, renal biopsy findings in patients with HBV-associated cryoglobulinaemia. Methods Twelve patients with HBV-associated cryoglobulinaemia were identified in this study. The demographic, clinical, pathological characteristics, treatment and follow-up data were analyzed. Results Renal involvement was characterized by nephrotic range proteinuria with microscopic haematuria in all patients, and impaired renal function in nine patients (75%). Purpuric rash was the main extrarenal manifestation (58.3%). Type II cryoglobulinaemia was presented in three patients and type III in nine patients. Hypocomplementaemia and positive of rheumatoid factors were present in all patients. Membranoproliferative glomerulonephritis (MPGN) was observed in all kidney specimens. Seven patients also had evidence of prominent cryoglobulins thrombi on renal biopsy, but only three patients had HBV antigen deposits in renal tissues. Antiviral and steroids or immunosuppressive agents have been used in most of patients. During follow-up, two patients died, and four reaching end-stage renal disease; three patients had complete remission, and three patients had renal function improved after therapy. Conclusions Nephrotic syndrome with haematuria and renal insufficiency are the main clinical manifestation; cryoglobulinaemic glomerulonephritis are the main renal lesion in patients with HBV-Associated cryoglobulinaemia; half of patients have poor outcome even with antiviral and immunosuppressive therapy. The results of this study indicate that cryoglobulins should be detected in hepatitis B virus-Associated nephropathy in endemic area.

The aim of the study was to evaluate the pro-apoptotic effects of polysaccharides derived from Lentinus edodes and further elucidated the mechanisms of this action. Our results demonstrated that marked morphological changes of apoptosis were observed after treatment of L. edodes polysaccharides [Lentinan (LTN)]. Moreover, LTN-induced cell apoptosis was characterized by a rapid stimulation of reactive oxygen species production, the loss of mitochondrial membrane potential and an increase in intracellular concentration of Ca(2+) . In addition, the results of the haematoxylin and eosin and TUNEL assay further confirmed that LTN-induced apoptosis in vivo. Furthermore, flow cytometry analysis showed that LTN could arrest the cell cycle at G2/M phase, and immunofluorescence showed LTN caused disruption of microtubule. These results suggest that disruption of cellular microtubule network, arrest of the cell cycle at G2/M phase and induction of apoptosis may be one of the possible mechanisms of anti-tumour effect of LTN.

Purpose To describe the clinical and magnetic resonance (MR) imaging features of primary intracranial hemangiopericytoma (HPC), and to assess the usefulness of minimum apparent diffusion coefficient (MinADC) value of HPC in the differential diagnosis from meningioma. Materials and Methods From 2004 to 2010, fifteen patients with primary intracranial HPC were included. The clinical data, conventional MR findings (n = 15), and diffusion weighted image (DWI) features (n = 10) were retrospectively analyzed. MinADC value of the HPCs (n = 10) was measured on ADC map and was compared with that of meningiomas (n = 37). Results In 15 cases of HPC, isointense signal was detected on both T1-weighted images (T1WI) and T2-weighted images (T2WI) in 11 cases, and heterogeneous signal was demonstrated in 4 cases. Isointensity (n = 9) and iso- and slight hyperintensity (n = 1) were shown on DWI. The mean MinADC value of HPC [(1.116 ± 0.127) × 10−3 mm2/s] was significantly higher than that of meningioma [(0.875 ± 0.104) × 10−3 mm2/s] (P < 0.01). For the differentiation between HPC and meningioma, the critical cutoff MinADC value was 0.991 × 10−3 mm2/s, which provided the best combination of sensitivity (88.9%) and specificity (82.4%). Conclusion MinADC value may be an useful tool for the differentiation between HPC and meningioma. J. Magn. Reson. Imaging 2013;38:1146–1151. © 2013 Wiley Periodicals, Inc.

A tris(2,2-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺)-based electrochemiluminescence (ECL) detection coupled with capillary electrophoresis (CE) method has been established for the sensitive determination of ephedrine for the first time. Under the optimized conditions [ECL detection at 1.15 V, 25 mmol/L phosphate buffer solution (PBS), pH 8.0, as running buffer, separation voltage 12.5 kV, 5 mmol/L Ru(bpy)₃²⁺ with 60 mmol/L PBS, pH 8.5, in the detection cell] linear correlation (r = 0.9987) between ECL intensity and ephedrine concentration was obtained in the range 6.0 × 10⁻⁸-6.0 × 10⁻⁶ g/mL. The detection limit was 4.5 × 10⁻⁹ g/mL (S:N = 3). The developed method was successfully applied to the analysis of ephedrine in human urine and the investigation of its interactions with three proteins, including bovine serum albumin (BSA), cytochrome C (Cyt-C) and myoglobin (Mb). The number of binding sites and the binding constants between ephedrine and BSA, Cyt-C and Mb were 8.52, 12.60, 10.66 and 1.55 × 10⁴ mol/L, 6.58 × 10³ mol/L and 1.59 × 10⁴ mol/L, respectively.

Aim: It has been recognized that renal lesions in patients with diabetes often have other causes of renal damage concomitantly. Renal biopsy is a valuable tool to provide histological evidence. However, the safety in patients with type 2 diabetes receiving renal biopsy is not well evaluated. This study was conducted to monitor the dynamic complications and to evaluate the safety of biopsy in diabetic patients. Methods: A prospective observation was performed on 130 patients with type 2 diabetes and 150 patients not undergoing renal biopsy. The complications were monitored at 4 h, 8 h, 24 h, 48 h and 72 h sequentially after biopsy. Results: Haematoma was observed in 34 (26.15%) patients with diabetes and 50 (33.33%) in controls (P = 0.19). The timing of large haematoma peaked at 4 h. Gross haematuria occurred in 12 (9.23%) diabetic patients and eight (5.33%) controls (P = 0.207). It happened mainly within 8 h. Renal pathological diagnosis showed 96 (73.85%) cases with diabetic nephropathy and 34 (26.15%) cases with non-diabetic renal disease. Conclusion: Renal biopsy in patients with type 2 diabetes is safe. The frequency of complications after renal biopsy in diabetes is no higher than those without diabetes. The complications mostly happened within 8 h, especially within 4 h. Biopsy is also very necessary to rule out other chronic renal diseases in diabetes.

To suppress the shuttle effect and improve the sulfur utilization in lithium–sulfur battery, a novel hollow carbon nitride-based spheres material (HCNx) has been synthesized via polymerization of ethylenediamine and carbon tetrachloride on silica spheres and used as a sulfur host. The rational designed structure of HCNx retards diffusion of lithium polysulfides by both chemisorption and physical confinement. The enhanced conductivity of HCNx improves the utilization of the sulfur. As a result, the S/HCNx exhibits a discharge capacity of 579 mA h g−1 after 500 cycles with a fade rate of 0.076% per cycle at 0.5 C. Even at 2 C, the S/HCNx cathode still exhibits a reversible discharge capacity of 658 mA h g−1.