Ratiometric mode with dyads: a breakthrough in dynamic trapping and quantification for redox regulation in living cells

Redox-based post-translational modification of protein thiols has become an attractive strategy in cellular homeostasis and cell signaling.Due to the reductive end of the redox buffer network,the vicinal dithiol-containing proteins(VDPs)maintains an appropriate oxidation-reduction state of proteins through the reversible transformation from vicinal dithiols to disulfide,which is responsible for a variety of     

A Hexagonal Covalent Porphyrin Framework as an Efficient Support for Gold Nanoparticles toward Catalytic Reduction of 4‐Nitrophenol

A hexagonal porphyrin‐based porous organic polymer, namely, CPF‐1, was constructed by 3+2 ketoenamine condensation of the C₂‐symmetric porphyrin diamine 5,15‐bis(4‐aminophenyl)‐10,20‐diphenylporphyrin and 1,3,5‐triformylphloroglucinol. This material exhibits permanent porosity and excellent thermal and chemical stability. CPF‐1 can be employed as a superior supporting substrate to immobilize Au nanoparticles (NPs) as a result of the strong interactions between Au NPs and the CPF support. An Au@CPF‐1 hybrid was synthesized by an interfacial solution infiltration method with NaBH₄ as reducing agent. Au NPs (5 nm) grew on CPF‐1 and were distributed without aggregation. Moreover, Au@CPF‐1 exhibits superior catalytic activity compared to many other reported Au‐based catalysts for the reduction of 4‐nitrophenol in the presence of NaBH₄. In addition, Au@CPF‐1 has excellent stability and recyclability, and it can be reused for three successive reaction cycles without loss of activity. The dense distribution of phenyl rings on the channel walls of the CPF support can reasonably be regarded as the active sites that adsorb the 4‐nitrophenol molecule through hydrogen‐bonding and C?H ??? π interactions, as was confirmed by the X‐ray structure of model compound DAPP‐Benz.     

Asymmetric Michael Addition of Aldimino Esters with Chalcones Catalyzed by Silver/Xing‐Phos: Mechanism‐Oriented Divergent Synthesis of Chiral Pyrrolines

The mechanism‐oriented reaction design for the divergent synthesis of chiral molecules from simple starting materials is highly desirable. In this work, aromatic amide‐derived nonbiarylatropisomer/silver (silver/Xing‐Phos) complex was used to catalyze the Michael addition of glycine aldimino esters to chalcones and successfully applied to the subsequent cyclocondensation to afford substituted cis‐Δ(1)‐pyrroline derivatives with up to 98 % ee. Besides the inherent performance of the chiral Ag/Xing‐Phos catalyst system, it was found that the workup of such reactions played an important role for the stereoselective construction of stereodivergent Δ(1)‐pyrrolines, in which an epimerization of the cis‐Δ(1)‐pyrrolines to the trans‐isomers during was revealed.     

Temperature memory effect and its stability revealed via differential scanning calorimetry in ethylene‐vinyl acetate within glass transition range

In this article, we reveal the temperature memory effect (TME) in a commercial thermoplastic polymer, namely ethylene‐vinyl acetate (EVA), within its glass transition range via a series of differential scanning calorimeter (DSC) tests. In addition, we investigate the influence of heating holding time and also compare the observed TME in current study with that of shape memory alloys (SMAs). It is concluded that the TME via DSC (without any macroscopic shape change) is achievable within the glass transition range of a polymer. Conversely, although the observed TME shares the many similar features as those in SMAs, due to the nature of micro‐Brownian motion in the glass transition of polymers, the resulted TME is strongly affected by the heating holding time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1731–1737     

In‐Depth Understanding of the Chemical Properties of Rarely Explored Carbide Cluster Metallofullerenes: A Case Study of Sc2C2@C3v(8)‐C82 that Reveals a General Rule

The chemical properties of carbide‐cluster metallofullerenes (CCMFs) remain largely unexplored, although several new members of CCMFs have been discovered recently. Herein, we report the reaction between Sc₂C₂@C_3v(8)‐C₈₂, which is viewed as a prototypical CCMF because of its high abundance, and 3‐triphenylmethyl‐5‐oxazolidinone ( 1 ) to afford the corresponding pyrrolidino derivative Sc₂C₂@C_3v(8)‐C₈₂(CH₂)₂NTrt ( 2 ; Trt=triphenylmethyl). Single‐crystal X‐ray crystallography studies of 2 revealed that the reaction takes place at a [6,6]‐bond junction, which is directly over the encapsulated C₂ unit and is far from either of the two scandium atoms. On the basis of theoretical calculations and by considering previously reports, we have found that a hexagonal carbon ring on the cage of Sc₂C₂@C_3v(8)‐C₈₂ is highly reactive toward different reagents due to the overlap of high p‐orbital axis vector (POAV) angles and large LUMO coefficients. We propose that this highly concentrated area of reactivity is generated by the encapsulation of the Sc₂C₂ cluster because this region is absent from the empty fullerene C_3v(8)‐C₈₂. Moreover, the absorption and electrochemical results confirm that derivative 2 is more stable than pristine Sc₂C₂@C_3v(8)‐C₈₂, thus illuminating its potential applications.     

Output feedback regulation of time-delay nonlinear systems with unknown continuous output function and unknown growth rate

Nonlinear Dynamics - This paper is concerned with the global regulation via output feedback for the time-delay nonlinear systems with unknown continuous output function and unknown growth rate....