Cationic Bis(hydrosilane)-Coinage Metal Complexes: Synthesis, Characterization, and Use as Catalysts for Outer-Sphere C=O Hydrosilylation Not Involving Metal Hydrides.

The preparation of cationic bis(hydrosilane)-coinage-metal complexes by chloride abstraction from the neutral metal chloride precursors with Na[BArF4] is described. Unlike previously reported hydrosilane-stabilized copper and silver complexes, the presented complexes are cationic and feature two bidentate ortho-(silylphenyl)phosphine ligands. These complexes were fully characterized by NMR spectroscopy and X-ray diffraction analysis, revealing that both Si-H bonds are activated by the Lewis acidic cationic metal center. The new complexes were found to be effective in catalytic carbonyl hydrosilylation, leading to the corresponding silyl ethers under mild conditions without the addition of an external base. Combined mechanistic control experiments and quantum chemical calculations support an ionic outer-sphere mechanism, in which a neutral metal alkoxide species instead of a metal hydride is the key intermediate that interacts with the silylcarboxonium ion to generate the silyl ether.

Graphite Nanoflake-Modified Mo2C with Ameliorated Interfacial Interaction as an Electrocatalyst for Hydrogen Evolution Reaction.

Molybdenum carbide (Mo2C) is anticipated to be a promising electrocatalyst for electrocatalytic hydrogen production due to its low cost, resourceful property, prominent stability, and Pt-like electrocatalytic activity. The rational design of Mo2C-based electrocatalysts is expected to improve hydrogen evolution reaction (HER) performance, especially by constructing ultrasmall Mo2C particles and appropriate interfaces. Herein, composites of molybdenum carbide (Mo2C) quantum dots anchored on graphite nanoflakes (Mo2C/G) were fabricated, which realized a stable overpotential of 136 mV at 10 mA cm-2 for the HER with a small Tafel slope of 76.81 mV dec-1 in alkaline media, and operated stably over 10 h and 2000 cycles. The superior HER performance can be attributed to the fact that graphite nanoflakes could act as a matrix to disperse Mo2C as quantum dots to expose more active sites and guarantee high electronic conductivity and, more importantly, provide ameliorated interfacial interaction between Mo2C and graphite nanoflakes with appropriate hydrogen binding energy and charge density distribution. To further explore which kind of interfacial interaction is more favorable to improve the HER performance, density functional theory calculations and corresponding contrast experiments were also performed, and it was interesting to prove that Mo2C quantum dots anchored to the basal planes of defective graphite nanoflakes exhibit better electrochemical performance than those anchored on the edges.

Exosomes: Potential executors of IL-35 gene-modified adipose-derived mesenchymal stem cells in inhibiting acute rejection after heart transplantation.

Heart transplantation has become the only 'cure' for end-stage heart diseases, but acute allograft rejection is the major obstacle to the survival of patients. Our previous studies showed that IL-35 gene-modified adipose-derived mesenchymal stem cells (IL-35-ASCs) can effectively inhibit graft rejection and prolong the survival of transplanted hearts in mice. This study further explored the mechanism of IL-35-ASCs, especially focusing on the important role of IL-35-ASC-derived exosomes (IL-35-ASCexos) in inhibiting acute rejection. IL-35-ASCs were constructed in vitro and pretreated with IL-35 neutralizing antibody and GW4869 (an inhibitor of neutral sphingomyelinase that impairs exosome biogenesis/release). Then, pretreated IL-35-ASCs and CD4+ T cells were cocultured in Transwell plates, and changes in regulatory T cells (Tregs) and cytokines were detected. Then, IL-35-ASCexos were extracted, identified and analysed, and their immunoregulatory effects on CD4+ T cells were studied through coculture experiments. Finally, IL-35-ASCexos were applied to a mouse heart transplantation model to investigate the therapeutic effects on acute rejection of the allograft. The coculture experiment showed that the IL-35-neutralizing antibody could not completely block the immunosuppressive function of IL-35-ASCs, while GW4869 could effectively reduce their immunoregulatory characteristics. Similar to IL-35-ASCs, IL-35-ASCexos also have powerful immunosuppressive properties, effectively upregulating the Treg ratio in vivo and in vitro and prolonging graft survival. As the main effectors of IL-35-ASCs, these findings highlight the therapeutic potential of IL-35-ASCexos in inhibiting acute cardiac rejection of the allograft. Although the specific mechanism remains unclear and needs to be further explored, IL-35-ASCexos therapy is expected to become a new method to inhibit acute graft rejection.

Competition for Hydride Between Silicon and Boron: Synthesis and Characterization of a Hydroborane-Stabilized Silylium Ion.

Potent main-group Lewis acids are capable of activating element-hydrogen bonds. To probe the rivalry for hydride between silylium- and borenium-ion centers, a neutral precursor with the hydrosilane and hydroborane units in close proximity on a naphthalene-1,8-diyl platform was designed. Abstraction of one hydride leads to a hydroborane-stabilized silylium ion rather than a hydrosilane-coordinated borenium ion paired with [B(C6 F5 )4 ]- or [HCB11 Cl11 ]- as counteranions. Characterization by multinuclear NMR spectroscopy and X-ray diffraction supported by DFT calculations reveals a cationic, unsymmetrical open three-center, two-electron (3c2e) Si-H-B linkage.

Me CAAC=N- : A Cyclic (Alkyl)(Amino)Carbene Imino Ligand.

A cyclic (alkyl)(amino)carbene (CAAC) has been shown to react with a covalent azide similar to the Staudinger reaction. The reaction of Me CAAC with trimethylsilyl azide afforded the N-silylated 2-iminopyrrolidine (Me CAAC=NSiMe3 ), which was fully characterized. This compound undergoes hydrolysis to afford the 2-iminopyrrolidine and trimethylsiloxane which co-crystallize as a hydrogen-bonded adduct. The N-silylated 2-iminopyrrolidine was used to transfer the novel pyrrolidine-2-iminato ligand onto both main-group and transition-metal centers. The reaction of the tetrabromodiborane bis(dimethyl sulfide) adduct with two equivalents of Me CAAC=NSiMe3 afforded the disubstituted diborane. The reaction of Me CAAC=NSiMe3 with TiCl4 and CpTiCl3 afforded Me CAAC=NTiCl3 and Me CAAC=NTiCl2 Cp, respectively.

The Influence of Spraying Strategy on the Dynamic Response of Polyurea-Coated Metal Plates to Localized Air Blast Loading: Experimental Investigations.

Polyurea has attracted considerable attention owing to its potential applications in protective fields to improve the resistant performance of structures subjected to damage loads resulting from intentional or accidental explosions. However, different spraying strategies of polyurea may lead to significant differences in overall resistance performance of polyurea-coated structures, and the underlying mechanisms have not been clear until now. This study aims to elucidate the influence of spraying strategy, i.e., spraying area, spraying thickness, and spraying interface condition, on the dynamic response of polyurea-coated steel plates under localized air blast loading. Three types of plates manufactured using different spraying strategies were adopted to evaluate their blast-resistant performance. The spraying strategies used were (i) whole-area spraying, (ii) partial-area spraying, and (iii) in-contact backing of polyurea on the rear surfaces of steel plates. In addition, the influence of spraying thickness of polyurea for whole-area sprayed plates was evaluated. The energy absorbing mechanisms of polyurea backing layers were highlighted. The energy absorption of plates was quantitatively analyzed. The results show that the air blast resistances of whole-area sprayed and in-contact backed plates are both superior to, whereas that of partial-area sprayed plates is inferior to, bare steel counterparts. A suitable spraying thickness of polyurea can significantly reduce the damage of the front steel layer, whereas excessive spraying thickness decreases the overall air blast resistance of plates. The polyurea backing layer exhibits favorable performance in absorbing energy under a whole-area spraying condition. This study provides useful guidance for the design of polyurea-coated metal plates in engineering applications.

Inhibition of cardiac allograft rejection in mice using interleukin-35-modified mesenchymal stem cells.

Interleukin-35 (IL-35) is a cytokine recently discovered to play a potent immunosuppressive role by intensifying the functions of regulatory T cells and inhibiting the proliferation and functions of T helper 1 and T helper 17 cells. Mesenchymal stem cells (MSCs) have recently emerged as promising candidates for cell-based immune therapy, and our previous study showed that IL-35 gene modification can effectively enhance the therapeutic effect of MSCs in vitro. In this study, we isolated adipose tissue-derived MSCs in vitro and infected them with lentiviral vectors overexpressing the IL-35 gene, thereby creating IL-35-MSCs. Subsequently, IL-35-MSCs were then injected into mice of the allogeneic heterotopic abdominal heart transplant model to determine their effect on allograft rejection. The results showed that IL-35-MSCs could continuously secrete IL-35 in vivo and in vitro, successfully alleviate allograft rejection and prolong graft survival. In addition, compared to MSCs, IL-35-MSCs showed a stronger immunosuppressive ability and further reduced the percentage of Th17 cells, increased the proportion of CD4+ Foxp3+ T cells, and regulated Th1/Th2 balance in heart transplant mice. These findings suggest that IL-35-MSCs have more advantages than MSCs in inhibiting graft rejection and may thus provide a new approach for inducing immune tolerance during transplantation.

Mesenchymal stem cells overexpressing IL-35: a novel immunosuppressive strategy and therapeutic target for inducing transplant tolerance.

Inducing donor-specific immunological tolerance, which avoids the complications of long-term immunosuppression, is an important goal in organ transplantation. Interleukin-35 (IL-35), a cytokine identified in 2007, is mainly secreted by regulatory T cells (Tregs) and is essential for Tregs to exert their maximal immunoregulatory activity in vitro and in vivo. A growing number of studies show that IL-35 plays an important role in autoimmune diseases and infectious diseases. Recent research has shown that IL-35 could effectively alleviate allograft rejection and has the potential to be a novel therapeutic strategy for graft rejection. With increasing study of immunoregulation, cell-based therapy has become a novel approach to attenuate rejection after transplantation. Mesenchymal stem cells (MSCs), which exhibit important properties of multilineage differentiation, tissue repair, and immunoregulation, have recently emerged as attractive candidates for cell-based therapeutics, especially in transplantation. Accumulating evidence demonstrates that the therapeutic abilities of MSCs can be amplified by gene modification. Therefore, researchers have constructed IL-35 gene-modified MSCs and explored their functions and mechanisms in some disease models. In this review, we discuss the potential tolerance-inducing effects of MSCs in transplantation and briefly introduce the immunoregulatory functions of the IL-35 gene-modified MSCs.

Synthesis and Reduction of Sterically Encumbered Mesoionic Carbene-Stabilized Aryldihaloboranes.

Sterically hindered, in situ generated 1,3,4-substituted 1,2,3-triazol-5-ylidene mesoionic carbenes (MICs) were employed to stabilize a number of aryl- and heteroaryldihaloboranes, as well as the first MIC-supported diborane. Reduction of borane adducts of the 1-(2,6-diisopropylphenyl)-3-methyl-4-tert-butyl-1,2,3-triazol-5-ylidene ligand with KC8 in non-coordinating solvents led to intramolecular C-H- and, C-C-activation at an isopropyl residue of the supporting ligand. DFT calculations showed that each of these activation reactions proceeds via a different isomer of a borylene intermediate.

[Diagnosis and treatment of 51 patients with pancreatic islet cell tumors].

OBJECTIVE: To investigate the diagnosis and treatment of pancreatic islet cell tumors. METHODS: Fifty-one patients with islet cell tumors treated in our department from January 1991 to April 2011 were included in this study. The data of clinical features, diagnosis and treatment were retrospectively analyzed. RESULTS: Among the 51 cases, 38 cases showed typical Whipple's triad, and the other 13 cases were non-functional islet cell tumors. In these 13 cases, 5 patients had no specific clinical symptoms, and 8 patients had abdominal distending pain. The positive rates of imaging were: B-ultrasound 43.1%, multi-slice spiral CT 69.8%; MRI 62.5%, endoscopic ultrasonography (EUS) 64.7% (11/17), and intraoperative ultrasound (IOUS) 96.3%, the differences among them were statistically significant (P<0.05). All patients underwent surgical treatment. Postoperative pancreatic leakage happened in 6 cases. Finally all the patients recovered after effective external drainage, anti-infection treatment and nutritional support. CONCLUSIONS: Intraoperative ultrasonography (IOUS) has a higher accuracy in the diagnosis of pancreatic islet cell tumors, compared with preoperative B-ultrasonography, CT, MRI, and endoscopic ultrasound (EUS). The most effective treatment of this disease is surgery.