The supramolecular chemistry of Ag(i) coordination assemblies continues to attract attention due to their versatile structural diversity and potential physical and chemical functions. This article provides a short review of recent advances in the design and construction of Ag(i) coordination polymers with special emphasis on the Ag(i) ion coordination geometry, ligand functionality, and supramolecular interactions. The potential functions of Ag(i) coordination polymers are briefly summarized.
Thermodynamically stable, but kinetically labile: Trigonal‐prismatic M3L2 metallocages occur in [BF4⊂{Ag3(MsTBim)2}](BF4)2 (1) and [{CuI3⊂[Cu3(MsTBim)2]}2](Cu2I4) (2), the latter with an unprecedented metal‐complex‐host/metal‐complex‐guest arrangement. Large anions such as CF3SO3− or BPh4− have to reside outside the cage facing its “windows”. MsTBim=1,3,5‐tris(benzimidazol‐1‐ylmethyl)‐2,4,6‐trimethylbenzene.
Activation of protein kinase C (PKC) has been implicated in gastric carcinogenesis. Enzastaurin is an oral ATP-competitive inhibitor of the PKCB isozyme. Although enzastaurin was initially advanced to the clinic based on its antiangiogenic activity, it is also known to have a direct effect on a variety of human cancer cells, inducing apoptosis by inhibiting the Akt signal pathway. However, data on enzastaurin for gastric cancer are limited. Therefore, this study was performed to assess the antitumor activity of enzastaurin on gastric cancer cells and to investigate the underlying antitumor mechanisms. Enzastaurin suppressed the proliferation of cultured gastric cancer cells and the growth of gastric carcinoma xenografts. Enzastaurin did not have an effect on gastric cancer cell cycle progression; however, it had a direct apoptosis-inducing effect through the caspase-mediated mitochondrial pathway. Glycogen synthase kinase 3B phosphorylation, a reliable pharmacodynamic marker of enzastaurin activity, and Akt phosphorylation were both decreased after treatment with enzastaurin. Although the p90 ribosomal S6 kinase (Rsk) was also dephosphorylated, Erk phosphorylation was not affected in the enzastaurin-treated gastric cancer cells. Enzastaurin activated Bad, one of the Bcl-2 proapoptotic proteins, through dephosphorylation at Ser 112 , and depletion of Bad activity resulted in resistance to enzastaurin-induced apoptosis and cytotoxicity in gastric cancer cells. These data suggest that enzastaurin induces apoptosis through Rsk-mediated and Badmediated pathways, besides inhibiting the Akt signal cascade. Furthermore, enzastaurin had synergistic or additive effects when combined with 5-fluorouracil, cisplatin, paclitaxel, or irinotecan. These results warrant further clinical investigation of enzastaurin for gastric cancer treatment. [Cancer Res 2008;68(6):1916-26]
Recently, a number of authentication protocols integrated with the Internet of Things (IoT) and cloud computing have been proposed for secure access control on large-scale IoT networks. In this paper, we carefully analyze Amin et al.’s authentication protocol for IoT-enabled devices in distributed cloud computing environment and find that Amin et al.’s protocol is vulnerable to several weaknesses. The main shortcoming of Amin et al.’s protocol is in authentication phase; a malicious cloud server can counterfeit the cloud server chosen by a user, and the control server cannot find this counterfeit. To overcome the shortcomings of Amin et al.’s protocol, we propose an improved protocol. In the registration phase of the improved protocol, the pseudoidentity and real identity of a user or a cloud server are bundled up with the control server’s secret numbers. This measure can effectively prevent impersonation attack. We also compare the improved protocol with several existing authentication protocols in security and computational efficiency.
The two flexible multidentate ligands 1,3-bis(8-thioquinolyl)propane (C3TQ) and 1,4-bis(8-thioquinolyl)butane (C4TQ) were reacted with AgX (X = CF(3)SO(3)(-) or ClO(4)(-)) to give four new complexes: ([Ag(C3TQ)](ClO(4)))(n)() 1, ([Ag(C3TQ)](CF(3)SO(3)))(n)() 2, ([Ag(2)(C4TQ)(CF(3)SO(3))(CH(3)CN)](CF(3)SO(3)))(n)() 3, and ([Ag(C4TQ)](ClO(4)))(n)() 4. All complexes have been characterized by elemental analysis, IR, and (1)H NMR spectroscopy. Single-crystal X-ray analysis showed that chain structures form for all complexes in which the quinoline rings interact via various intra- (1) or intermolecular (2, 3, and 4) pi-pi aromatic stacking interactions, which in the latter cases results in multidimensional structures. Additional weak interactions, such as Ag.O and Ag.S contacts and C-H.O hydrogen bonding, are also present and help form stable, crystalline materials. It was found that the (CH(2))(n) spacers (n = 3 or 4) affect the orientation of the two terminal quinolyl rings, thereby significantly influencing the specific framework structure that forms. If the same ligand is used, on the other hand, then the different counteranions have the greatest effect on the final structure.
Our results provide evidence for an association of a frequent mitochondrial polymorphism with higher fasting glucose and the risk factors of diabetes mellitus.
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