Coordinate Bond Breaking Induced by Collapse of Poly(\begin{document}$N$\end{document}-isopropyl acrylamide) as Ligands of a Rare Earth Complex

A novel water-soluble luminescent complex consisting of Eu(ally-dbm)\begin{document}$_3$\end{document}-2Tppo and poly(N-isopropyl acrylamide) (PNIPAM) is synthesized through a series of chemical reactions. The structure of the complex is characterized by TGA, GPC, HNMR, and the thermal-responsive fluorescence of the complex in aqueous solution is investigated. It is found that PNIPAM collapse above the lower critical solution temperature causes the coordination bond breaking, leading to weakening of the fluorescence from Eu\begin{document}$^{3+}$\end{document} and enhancing of the fluorescence from the ligands. When temperature decreases, the fluorescence from Eu\begin{document}$^{3+}$\end{document} is found to boost up and the fluorescence from ligands weakens accordingly. It is deduced from this phenomenon that the ligands re-coordinate with europium ions again along with the temperature decreasing, which is further confirmed by IR measurements. This thermal-responsive fluorescence is of reversibility, which can be used as molecular probes for biological imaging and collapse studying of PNIPAM.     

Biocatalytic Feedback-Controlled Non-Newtonian Fluids

Non-Newtonian fluids are ubiquitous in daily life and industrial applications. Herein, we report an intelligent fluidic system integrating two distinct non-Newtonian rheological properties mediated by an autocatalytic enzyme reaction. Associative polyelectrolytes bearing a small amount of ionic and alkyl groups are engineered: by carefully balancing the charge density and the hydrophobic effect, the polymer solutions demonstrate a unique shear thickening property at low pH while shear thinning at high pH. The urea-urease clock reaction is utilized to program a feedback-induced pH change, leading to a strong upturn of the nonlinear viscoelastic properties. As long as the chemical fuel is supplied, two distinct non-Newtonian states can be achieved with a tunable lifetime span. As a proof of concept, we demonstrate how the physical energy-driven nonequilibrium properties can be manipulated by a chemical-fueled process.     

Electrochemical synthesis of α,α-dihaloacetophenones from terminal alkyne derivatives

By virtue of electrochemistry, a series of α,α-dihaloacetophenones were easily obtained with good to excellent yields. This electrochemical procedure was taken in a divided cell with constant current in aqueous media. The reaction can be carried out smoothly at room temperature under metal and oxidant free condition, which provides an eco-friendly synthesis for the α,α-dihaloacetophenone derivatives.     

基于石墨烯/石墨烯卷轴复合薄膜高灵敏度柔性压力传感器

一维导电材料例如纳米线，大量应用于柔性压力传感器中. 但是一维材料和基底之间接触时相互作用力较弱，使得传感器灵敏度、响应时间、和循环寿命等性能指标有待进一步提高. 针对这些问题，设计了石墨烯/石墨烯卷轴多分子层复合薄膜作为传感器导电层. 石墨烯卷轴具有一维结构，而石墨烯的二维结构可以牢固地固定卷轴，以确保高导电性复合薄膜与基底之间的粘附性，同时整体结构的导电通道得到了增加. 由于一维和二维结构的协同效应，实现了应变灵敏度系数3.5 kPa^-1、 响应时间小于50 ms、能够稳定工作1000次以上的压阻传感器.     

Enhancing electrochemical conversion of lithium polysulfide by 1T-rich MoSe2 nanosheets for high performance lithium–sulfur batteries

The sluggish conversion kinetics and shuttle effect of lithium polysulfides (LiPSs) severely hamper the commercialization of lithium–sulfur batteries. Numerous electrocatalysts have been used to address these issues, amongst which, transition metal dichalcogenides have shown excellent catalytic performance in the study of lithium–sulfur batteries. Note that dichalcogenides in different phases have different catalytic properties, and such catalytic materials in different phases have a prominent impact on the performance of lithium–sulfur batteries. Herein, 1T-phase rich MoSe₂ (T-MoSe₂) nanosheets are synthesized and used to catalyze the conversion of LiPSs. Compared with the 2H-phase rich MoSe₂ (H-MoSe₂) nanosheets, the T-MoSe₂ nanosheets significantly accelerate the liquid phase transformation of LiPSs and the nucleation process of Li₂S. In-situ Raman and X-ray photoelectron spectroscopy (XPS) find that T-MoSe₂ effectively captures LiPSs through the formation of Mo-S and Li-Se bonds, and simultaneously achieves fast catalytic conversion of LiPSs. The lithium–sulfur batteries with T-MoSe₂ functionalized separators display a fantastic rate performance of 770.1 mAh/g at 3 C and wonderful cycling stability, with a capacity decay rate as low as 0.065% during 400 cycles at 1 C. This work offers a novel perspective for the rational design of selenide electrocatalysts in lithium–sulfur chemistry.     

Highly Segregated Lamello‐Columnar Mesophase Organizations and Fast Charge Carrier Mobility in New Discotic Donor–Acceptor Triads

Four new donor–acceptor triads (D–A–D) based on discotic and arylene mesogens have been synthesized by using Sonogashira coupling and cyclization reactions. This family of triads consists of two side‐on pending triphenylene mesogens, acting as the electron‐donating groups (D), laterally connected through short lipophilic spacers to a central perylenediimide (PI), benzo[ghi]perylenediimide (BI), or coronenediimide (CI) molecular unit, respectively, playing the role of the electron acceptor (A). All D–A–D triads self‐organize to form a lamello‐columnar oblique mesophase, with a highly segregated donor–acceptor (D–A) heterojunction organization, consequent to efficient molecular self‐sorting. The structure consists in the regular alternation of two disrupted rows of triphenylene columns and a continuous row of diimine species. High‐resolution STM images demonstrate that PI‐TP2 forms stable 2D self‐assembly nanostructures with some various degrees of regularity, whereas the other triads do not self‐organize into ordered architectures. The electron‐transport mobility of CI‐TP2, measured by time‐of‐flight at 200 °C in the mesophase, is one order of magnitude higher than the hole mobility. By means of this specific molecular designing idea, we realized and demonstrated for the first time the so‐called p–n heterojunction at the molecular level in which the electron‐rich triphenylene columns act as the hole transient pathways, and the coronenediimide stacks form the electron‐transport channels.     

A Universal equipment for biaxial stretching of polymer films

A biaxial stretching equipment was designed and constructed to enable fundamental studies of the relationship between film processing conditions and structures of oriented film products. With programmable drive motors and scissorlike mechanism, all stretching modes, including uniaxial stretching with constant and free width, simultaneous and sequential biaxial stretching, can be applied to a square-shaped sheet. Parameters related to film stretching manufacturing, such as temperature, draw ratio and stretching speed can be set independently to meet the requirement of different polymers. The force information during stretching is recorded by two miniature tension sensors in two directions independently, which can monitor the mechanical stimulus and stress response. Using this equipment, experiments are conducted to investigate the influence of stretching parameters on the structure of polypropylene films, which provides an effective method to tailor the processing conditions to obtain the films with desired properties.     

Highly Diastereo‐ and Enantioselective Michael Addition of Nitroalkanes to 2‐Enoyl‐Pyridine N‐Oxides Catalyzed by Scandium(III)/Copper(II) Complexes

A C₂‐symmetric Schiff‐base ligand, derived from tridentate‐Schiff‐base, was developed and successfully applied to the asymmetric Michael addition of nitroalkanes to 2‐enoyl‐pyridine N‐oxides. With this newly catalytic system, an unprecedented diastereoselectivity was obtained in the asymmetric Michael addition of nitroalkanes to 2‐enoyl‐pyridine N‐oxides. In addition, a switch in enantioselectivity was achieved by using this newly catalytic system and our previous catalyst. After a facile reduction, the optically active adduct was converted to a biologically active dihydro‐2H‐pyrrol 4 a . Furthermore, a connection of two tridentate‐Schiff‐base subunits proved to be an effective strategy in ligand design.     

Loop formation and stability of self-avoiding polymer chains

Using 3-dimensional Langevin dynamics simulations, we investigated the dynamics of loop formation of chains with excluded volume interactions, and the stability of the formed loop. The mean looping time τ _l scales with chain length N and corresponding scaling exponent α increases linearly with the capture radius scaled by the Kuhn length a/l due to the effect of finite chain length. We also showed that the probability density function of the looping time is well fitted by a single exponential. Finally, we found that the mean unlooping time τ _u hardly depends on chain length N for a given a/l and that the stability of a formed loop is enhanced with increasing a/l.     

Theoretical insights into the mechanism of photocatalytic reduction of CO2 over semiconductor catalysts

Photocatalytic reduction of CO₂ is one important approach to alleviate greenhouse gas emission and energy crisis, which has gained huge attention in the past decades. However, the lack of understanding complex reaction mechanism impedes new catalysts design. It is also very difficult to understand the mechanism by using only experimental approaches. For this concern, theoretical calculations can effectively supplement the experimental deficiency and thus play an important role. Recently theoretical calculations have been performed on adsorption, migration and reduction of CO₂ molecule on the photocatalyst surface, leading to useful information that have contributed greatly to this field. This review summarizes recent advances in first-principles calculations about CO₂ photoreduction over various semiconductor photocatalysts like metal oxides, sulfides and g-C₃N₄. The methods, models, adsorption and reaction pathways have been discussed in detail. The perspective about future investigation on the photocatalytic reduction of CO₂ using first principles calculations is also presented.