“联用技术及元素形态”国际课程探索与实践*

充分利用线上教学的优势,对化学院本科生开设了“联用技术及元素形态”国际课程,避免了传统教学中组织、协调外籍/外地专家资源过程中必要的各种消耗,极大程度地整合教学资源、改善教学效果。在该课程的探索与实践过程中,学生们对痕量元素形态及基于等离子体质谱的各种联用技术产生了极大的兴趣,激发了他们的主动学习热情;教师之间及师生之间的沟通趋向更简单、更灵活、更实时,为后续线上线下混合式国际课程建设提供了良好的基础和借鉴。     

Deep oxidative desulfurization of benzothiophene and dibenzothiophene with a peroxophosphotungstate–ionic liquid brush assembly

A novel, efficient and reusable heterogeneous catalytic assembly of peroxophosphotungstate held in an ionic liquid brush was synthesized and an extraction and catalytic oxidative desulfurization (ECODS) procedure was developed for a model oil of benzothiophene (BT) and dibenzothiophene (DBT) using 30 wt% hydrogen peroxide as terminal oxidant and methanol as solvent under mild conditions. Several factors that affect sulfur removal were investigated in detail. The highest sulfur removal can reach 100% for BT in 7 h at 70 °C when the molar ratio of H₂O₂, S and catalyst is 10:1:0.025. The sulfur removal for DBT can also reach 100% in 4 h at 50 °C with the same molar ratio of H₂O₂, S and catalyst. The experimental results demonstrate that this ECODS process has no apparent scale‐up effect. The catalyst can be easily recovered (via simple filtration) and recycled five times without a significant decrease in activity. Copyright © 2015 John Wiley & Sons, Ltd.     

An Activatable T1-Weighted MR Contrast Agent: A Noninvasive Tool for Tracking the Vicinal Thiol Motif of Thioredoxin in Live Cells

We have synthesized new magnetic resonance imaging (MRI) T₁ contrast agents (CA1 and CA2) that permit the activatable recognition of the cellular vicinal thiol motifs of the protein thioredoxin. The contrast agents showed MR relaxivities typical of gadolinium complexes with a single water molecule coordinated to a Gd³⁺ center (i.e., ~4.54 mM⁻¹s⁻¹) for both CA1 and CA2 at 60 MHz. The contrast agent CA1 showed a ~140% relaxivity enhancement in the presence of thioredoxin, a finding attributed to a reduction in the flexibility of the molecule after binding to thioredoxin. Support for this rationale, as opposed to one based on preferential binding, came from ¹H-¹⁵N-HSQC NMR spectral studies; these revealed that the binding affinities toward thioredoxin were almost the same for both CA1 and CA2. In the case of CA1, T₁-weighted phantom images of cancer cells (MCF-7, A549) could be generated based on the expression of thioredoxin. We further confirmed thioredoxin expression-dependent changes in the T₁-weighted contrast via knockdown of the expression of the thioredoxin using siRNA-transfected MCF-7 cells. The nontoxic nature of CA1, coupled with its relaxivity features, leads us to suggest that it constitutes a first-in-class MRI T₁ contrast agent that allows for the facile and noninvasive monitoring of vicinal thiol protein motif expression in live cells.     

Stabilizing DNAzymes through Encapsulation in a Metal–Organic Framework

DNAzymes are a promising class of bioinspired catalyst; however, their structural instability limits their potential. Herein, a method to stabilize DNAzymes by encapsulating them in a metal–organic framework (MOF) host is reported. This biomimetic mineralization process makes DNAzymes active under a wider range of conditions. The concept is demonstrated by encapsulating hemin-G-quadruplex (Hemin-G4) into zeolitic imidazolate framework-90 (ZIF-90), which indeed increases the DNAzyme's structural stability. The stabilized DNAzymes show activities in the presence of Exonuclease I, organic solvents, or high temperature. Owing to its elevated stability and heterogeneous nature, it is possible to perform catalysis under continuous-flow conditions, and the DNAzyme can be reactivated in situ by introducing K⁺. Moreover, it is found that the encapsulated DNAzyme maintains its high enantiomer selectivity, demonstrated by the sulfoxidation of thioanisole to (S)-methyl phenyl sulfoxide. This concept of stabilizing DNAzymes expands their potential application in chemical industry.     

On the Interfacial Flow Over Porous Media Composed of Packed Spheres: Part 1-Identification of the Effective Slip Length

Transport in Porous Media - The effective slip length at the interface between pure fluid flow and porous media composed of packed spheres has been accurately characterized. In this study, as the...     

A quantitatively controllable mesoscopic reliability model of an interdependent public transit network considering congestion,time-delay interaction and self-organization effects

Nonlinear Dynamics - This paper establishes a multi-parameter controlling cascading failures (CFs) model for measuring interdependent public transit network (PTN) reliability under mesoscopic...