Interfacial charge-transfer enhances the dual-function of the porous NiCo2S4@SiO2 heterojunction for high-performance Li-S batteries.

Porous NiCo2S4@SiO2 is employed as the sulfur host. The negatively charged SiO2 can increase the charge density and conductivity of NiCo2S4 and accelerate the conversion of sulfur. The charge transfer effect would in turn reduce the electrostatic repulsion between SiO2 and negatively charged polysulfide, thereby enhancing the adsorption of polysulfides.

Silver-Promoted Direct Phosphorylation of Bulky C(sp2)-H Bond to Build Fully Substituted ß-Phosphonodehydroamino Acids.

A general and practical cross-dehydrogenative coupling protocol between readily available trisubstituted α,ß-dehydro α-amino carboxylic esters and H-phosphites is described. This C(sp2)-H phosphorylation reaction proceeds with absolute Z-selectivity promoted by silver salt in a radical relay manner. The bulky tetrasubstituted ß-phosphonodehydroamino acids were obtained in grams and added new modules to the toolkit for peptide modifications.

Direct Enamido C(sp2 )-H Diphosphorylation Enabled by a PCET-Triggered Double Radical Relay: Access to gem-Bisphosphonates.

Herein we report a novel and straightforward protocol for the construction of valuable gem-BPs by means of proton-coupled electron-transfer (PCET)-triggered enamido C(sp2 )-H diphosphorylation. This reaction represents a rare example of realizing the challenging double C-P bond formation at a single carbon atom, thus providing facile access to a broad variety of structurally diverse bisphosphonates from simple enamides under silver-mediated conditions. Initial mechanistic studies demonstrated that the diphosphorylation involves two rounds of PCET-initiated radical relay process.

Cu-Mediated Expeditious Annulation of Alkyl 3-Aminoacrylates with Aryldiazonium Salts: Access to Alkyl N2-Aryl 1,2,3-Triazole-carboxylates for Druglike Molecular Synthesis.

Alkyl N-aryl 1,2,3-triazole-carboxylates are important molecules or intermediates in medicinal chemistry, but the synthesis of N2-aryl counterparts remains elusive. Herein, we describe a Cu-mediated annulation reaction of alkyl 3-aminoacrylates with aryldiazonium salts, both of which are readily available substrates. Furthermore, alkyl 2-aminoacrylates are also viable substrates. Diverse alkyl N2-aryl 1,2,3-triazole-carboxylates and their analogues can be rapidly prepared under mild conditions. Especially, this protocol allows one to access several druglike variants of carbonic anhydrase inhibitors and celecoxib.

[Establishment and characterization of serial subpopulations with highly metastatic potential via different metastatic routes].

OBJECTIVE: To establish the serial cell lines, derived from the same parental gallbladder cancer cell line GBC-SD, with highly metastatic potential via different routes and characterize their biological behaviors to understand the different metastasis mechanisms via lymph and blood. METHODS: The spleen-liver metastasis model and footpad-inguinal lymph node metastasis model were established. GBC-SD was injected into spleen or footpad of nude mice. Then the highly metastasized subpopulations via lymph and blood were isolated. Their differences in morphology, genetic background, proliferation, migration, invasion and adhesion were revealed by comparing the lymphatic-disseminating and hematogenous-disseminating subpopulations with parental cells. RESULTS: The lymphatic-disseminating and hematogenous-disseminating subpopulations were successfully isolated and designated as GBC-SD/HL and GBC-SD/M3 respectively. They demonstrated the identical genetic background with GBC-SD. In comparison with parental cells, the hematogenous-disseminating subpopulation was morphologically characterized with epithelial-mesenchymal transition (EMT) while it was not shown in the lymphatic-disseminating subpopulation. Furthermore, the hematogenous-disseminating subpopulation showed the strongest migrating capacity but the lymphatic-disseminating subpopulation demonstrated a stronger invasive and adhesive ability. CONCLUSION: The whole parental cell GBC-SD, hematogenous-metastasized subpopulation GBC-SD/M3 and lymphatic-disseminating subpopulation GBC-SD/HL is an ideal tool for metastatic mechanism study of gallbladder cancer. EMT plays an important role in hematogenous metastasis while lymphatic metastasis relies more on enhanced invasiveness and adhesion. It may be a target for interfering the lymphatic metastasis of gallbladder cancer.

Antiallodynic effects of propentofylline Elicited by interrupting spinal glial function in a rat model of bone cancer pain.

The activation of microglia and astrocytes in the spinal cord is involved in the progress of cancer pain. Propentofylline (PPF), a glial modulating agent, alleviates pain hypersensitivity in neuropathic pain models. The present study investigated the potential roles of PPF in a preclinical rat model of bone caner pain established by inoculating Walker 256 cells into the left tibia. At day 9 postinoculation, single administration of PPF (10 µg/10 µl, i.t.) significantly but transiently suppressed mechanical allodynia induced by bone cancer. Repeated application of PPF (10 µg/10 µl, i.t., once daily from days 9 to 12) persistently relieved mechanical allodynia on the side ipsilateral to surgery. Immunohistochemistry and ELISA showed that microglia and astrocytes in the spinal cord were activated, and the production of glia-derived proinflammatory cytokines interleukin-1ß (IL-1ß), IL-6, and tumor necrosis factor-α (TNF-α) markedly increased at day 12 postinoculation in the cancer group. Intrathecal injection of PPF (10 µg/10 µl) significantly inhibited the activation of spinal glial cells and the expression of proinflammatory cytokines. These results suggest that the glial modulating agent PPF has antiallodynic effects on bone cancer pain and has potential utility for clinical treatment of cancer pain.

[Therapeutic feasibility of percutaneous puncture and chemical neurolysis of thoracic sympathetic nerve block in palmar hyperhidrosis under the guidance of computed tomograph].

OBJECTIVE: To explore the therapeutic feasibility of percutaneous puncture and neurolytic thoracic sympathetic nerve block under the guidance of computed tomograph (CT). METHODS: From September 2009 to August 2010, 23 cases with primary palmar hyperhidrosis underwent percutaneous puncture and neurolytic thoracic sympathetic nerve block at our hospital. The puncture of thoracic sympathetic nerve was guided by CT through the gap of T3-4. The screen showed the direction of needle and the location of needle tip at the upper joint of costal head beside T3 body and outside of costal pleura. A mixed injection of 1% lidocaine and 30% iohexol was administered. On CT, lidocaine was found to cover the area where the thoracic sympathetic nerve was located. And after several minutes, the patient's palms turned warm and dry from cool and wet without the onset of Horner's syndrome. Then 2.5 ml of absolute alcohol was injected to block the thoracic sympathetic nerve. RESULTS: CT could guide the needle to the right position. And the injectate spreaded to the site of thoracic sympathetic nerve. At 5 min after anesthetic injection, the palmar temperature raised an average of 2.86°C and the amplitude of pulse rose over 55%. Palmar hyperhidrosis was cured in 19 patients by one attempt and 4 patients required a second block with absolute alcohol. No complication occurred and there were 2 patients with tendency of recurrence during a follow-up period of 8 - 18 months. CONCLUSION: The CT-guided therapy of percutaneous puncture and chemical neurolysis of thoracic sympathetic nerve block is both feasible and efficacious for palmar hyperhidrosis.