Stilbene derivatives have long been known to undergo “acid-catalyzed” Z → E isomerization, where a strong mineral acid at high concentration is practically necessary. Such severe reaction conditions often cause undesired by-reactions and limit their potential application. Herein, we present a trace mild acid-catalyzed Z → E isomerization found with stilbene derivatives fused with a norbornene moiety. By-reactions, such as the migration of the CC double bond and electrophilic addition reactions, were completely inhibited because of the ring strain caused by the fused norbornene component. Direct photolysis of the E isomers at selected wavelengths led to the E → Z photoisomerization of these stilbene derivatives and thus constituted a unique class of molecular switches orthogonally controllable by light and acid. The catalytic amount of acid could be readily removed, and the Z → E isomerization could be controlled by turning on/off the irradiation of a photoacid, which allowed repeated isomerization in a non-invasive manner. Moreover, the Z isomer produced by photoisomerization could spontaneously self-recover to the E isomer in the presence of a catalytic amount of acid. The kinetics of Z → E isomerization were adjustable by manipulating catalytic factors and, therefore, unprecedented molecular photoswitches with adjustable self-recovery were realized.Quantitative Z → E isomerization was catalyzed by trace mild acids to offer molecular switches orthogonally controllable by acid and light.相似文献
Splenectomy has been reported to improve liver fibrosis in patients with cirrhosis and hypersplenism. However, the mechanisms remain unclear. Tumor necrosis factor superfamily 14 (TNFSF14; also known as LIGHT) is highly expressed in the context of fibrosis and promotes disease progression in patients with fibrotic diseases such as pulmonary and skin fibrosis. Here, we determined whether splenectomy controls the production of LIGHT to improve liver fibrosis. Splenectomy reduced serum LIGHT levels in cirrhotic patients with hypersplenism and a ConA-induced liver fibrosis mouse model. Blocking LIGHT resulted in the downregulation of TGF-β1 in RAW264.7 cells. LIGHT treatment of RAW264.7 and JS1 cells in coculture regulated transforming growth factor-β1 (TGF-β1) expression through the activation of JNK signaling. Small interfering RNA-mediated silencing of lymphotoxin β receptor (LTβR) in macrophages resulted in pronounced decreases in the levels of fibrosis and αSMA in JS1 cells. These results indicated that LIGHT bound to LTβR and drove liver fibrosis in vitro. Blocking TGF-β1 abolished the effect of LIGHT in vitro. Furthermore, the administration of recombinant murine LIGHT protein-induced liver fibrosis with splenectomy, while blocking LIGHT without splenectomy improved liver fibrosis in vivo, revealing that the decrease in fibrosis following splenectomy was directly related to reduced levels of LIGHT. Thus, high levels of LIGHT derived from the spleen and hepatic macrophages activate JNK signaling and lead to increased TGF-β1 production in hepatic macrophages. Splenectomy attenuates liver fibrosis by decreasing the expression of LIGHT.Subject terms: Tumour-necrosis factors, Liver fibrosis, Hepatic stellate cells, Liver cirrhosis, Experimental models of disease相似文献
Zinc molybdate (ZnMoO4), a layer perovskite material, has the advantages of high stability, excellent optical and charge properties. However, its high band gap and high electron–hole recombination efficiency limit its application in the photocatalytic reduction field like hydrogen production. In this study, we used CdS as a co-catalyst and successfully prepared CdS/ZnMoO4 composite photocatalysts with different loadings. The hydrogen evolution rate of CdS/ZnMoO4 reached 530.2 µmol h?1 g?1, which was approximately 11 and 100 times more than rates of pure CdS and ZnMoO4 under the same conditions, respectively. It is the presence of CdS that contributed to this improved performance, which acted as an electron acceptor to separate electrons and holes. Besides, a reasonable mechanism was provided based on photoelectrochemical characterizations. CdS loading greatly improved the hydrogen evolution performance of ZnMoO4 under visible light, providing a direction to improving the performance of perovskite based photocatalysts.
Thermal analysis by classical molecular dynamics simulations is discussed on hand of heat capacity of crystals of 9600 atoms. The differences between quantum mechanical and classical mechanical calculations are shown. Anharmonicity is proven to be an important factor. Finally, it is found that defects contribute to an increase in heat capacity before melting. The energy of conformational gauche defects within the crystal is only about 10% due to internal rotation. The other energy must be generated by cooperative strain. The conclusion is that the next generation of faster computers may permit wider use of molecular dynamics simulations in support of the interpretation of thermal analysis.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthday 相似文献