Triazole-based deubiquitylase (DUB)-resistant ubiquitin (Ub) probes have recently emerged as effective tools for the discovery of Ub chain-specific interactors in proteomic studies, but their structural diversity is limited. A new family of DUB-resistant Ub probes is reported based on isopeptide-N-ethylated dimeric or polymeric Ub chains, which can be efficiently prepared by a one-pot, ubiquitin-activating enzyme (E1)-catalyzed condensation reaction of recombinant Ub precursors to give various homotypic and even branched Ub probes at multi-milligram scale. Proteomic studies using label-free quantitative (LFQ) MS indicated that the isopeptide-N-ethylated Ub probes may complement the triazole-based probes in the study of Ub interactome. Our study highlights the utility of modern protein synthetic chemistry to develop structurally and new families of tool molecules needed for proteomic studies. 相似文献
A novel Pd0-catalyzed asymmetric [4+3] annulation reaction of two readily accessible starting materials has been developed for building seven-membered heterocyclic architectures. The potential [3+2] side pathway could be suppressed though fine tuning of the conditions. A broad scope of cycloaddition donors and acceptors participated in the transformation with excellent chemo-, regio-, diastereo-, and enantioselectivtities, leading to valuable tetrahydroazepines and benzo[b]oxepines. 相似文献
Phosphazene base,t-BuP2,was employed to catalyze the proton transfer polymerization(PTP)of 2-hydroxyethyl acrylate(HEA),and PTP was further combined with ring-opening polymerization(ROP)to exploit a new type of hybrid copolymerization.The studies on homopolymerization showed that t-BuP2 was a particularly efficient catalyst for the polymerization of HEA at room temperature,giving an excellent monomer conversion.Throughout the polymerization,transesterification reactions were unavoidable,which increased the randomness in the structures of the resulting polymers.The studies on copolymerization showed that t-BuP2 could simultaneously catalyze the hybrid copolymerization via the combination of PTP and ROP at 25°C.During copolymerization,HEA not only provided hydroxyl groups to initiate the ROP ofε-caprolactone(CL)but also participated in the polymerization as a monomer for PTP.The copolymer composition was approximately equal to the feed ratio,demonstrating the possibility to adjust the polymeric structure by simply changing the monomer feed ratio.This copolymerization reaction provides a simple method for synthesizing degradable functional copolymers from commercially available materials.Hence,it is important not only in polymer chemistry but also in environmental and biomedical engineering. 相似文献
The main objective of the present numerical analysis is to predict the nonlinear frequency ratios associated with the nonlinear free vibration response of porous composite plates at microscale in the presence of different microstructural gradient tensors. To achieve this end, by taking cubic-type elements into account, isogeometric models of porous composite microplates are obtained with and without a central cutout and relevant to various porosity patterns of distribution along the plate thickness. The established unconventional models have the capability to capture the effects of various unconventional gradient tensors continuity on the basis of a refined shear deformable plate formulation. For the simply supported microsized uniform porous functionally graded material (U-PFGM) plate having the oscillation amplitude equal to the plate thickness, it is revealed that the rotation gradient tensor causes to reduce the frequency ratio about 0.73%, the dilatation gradient tensor causes to reduce it about 1.93%, and the deviatoric stretch gradient tensor leads to a decrease of it about 5.19%. On the other hand, for the clamped microsized U-PFGM plate having the oscillation amplitude equal to the plate thickness, these percentages are equal to 0.62%, 1.64%, and 4.40%, respectively. Accordingly, it is found that by changing the boundary conditions from clamped to simply supported, the effect of microsize on the reduction of frequency ratio decreases a bit.
Let Mn denote the partial maximum of a strictly stationary sequence (Xn). Suppose that some of the random variables of (Xn) can be observed and let [(M)\tilde]n\tilde M_n
stand for the maximum of observed random variables from the set {X1, ..., Xn}. In this paper, the almost sure limit theorems related to random vector ([(M)\tilde]n\tilde M_n
, Mn) are considered in terms of i.i.d. case. The related results are also extended to weakly dependent stationary Gaussian sequence as its covariance function satisfies
some regular conditions. 相似文献
A chiral secondary amine phosphoramide was developed and identified as a powerful catalyst for the Mukaiyama–Michael addition of fluorinated enol silyl ethers to tetrasubstituted olefins. The resulting products are obtained with high enantioselectivities and contain a quaternary carbon stereocenter bearing either a difluoroalkyl or monofluoroalkyl group. 相似文献