Water-Soluble Polymers with Appending Porphyrins as Bioinspired Catalysts for the Hydrogen Evolution Reaction

Molecular design to improve catalyst performance is significant but challenging. In enzymes, residue groups that are close to reaction centers play critical roles in regulating activities. Using this bioinspired strategy, three water-soluble polymers were designed with appending Co porphyrins and different side-chain groups to mimic enzyme reaction centers and activity-controlling residue groups, respectively. With these polymers, high hydrogen evolution efficiency was achieved in neutral aqueous media for electro- (turnover frequency >2.3×10⁴ s⁻¹) and photocatalysis (turnover number >2.7×10⁴). Porphyrin units are surrounded and protected by polymer chains, and more importantly, the activity can be tuned with different side-chain groups. Therefore, instead of revising molecular structures that is difficult from both design and synthesis points of view, polymers can be used to improve molecular solubility and stability and simultaneously regulate activity by using side-chain groups.     

Mechanistic Study of Unprecedented Highly Regioselective Hydrocyanation of Terminal Alkynes: Insight into the Origins of the Regioselectivity and Ligand Effects

Density functional theory (DFT) calculations were performed to gain insight into the mechanism of the nickel-catalyzed hydrocyanation of terminal alkynes with Zn(CN)₂ and water to exclusively generate the branched nitrile with excellent Markovnikov selectivity. After precatalyst activation to give the LNi(0) active species, the transformation proceeds via the following steps: (1) oxidative addition of H₂O to the LNi(0) provides the intermediate LNi(II)H(OH); (2) ligand exchange of LNi(II)H(OH) with Zn(CN)₂ gives the intermediate LNi(II)H(CN); (3) alkyne insertion to the LNi(II)H(CN) forms the alkenyl nickel complex, followed by the reductive elimination step reaching the final product. This mechanism is kinetically and thermodynamically more favorable than that of the experimental proposed ones. On the basis of the experimental observations, more water molecules cannot further improve the reaction as it has also been rationalized. Furthermore, the origin of the high regioselectivity of the product, the variable effectiveness of the metal mediator as function of ligands, as well as the high yield of the alkyl-substituted alkynes substrates, is analyzed in detail. © 2019 Wiley Periodicals, Inc.     

Anisotropic charge carrier transport of optoelectronic functional selenium-containing organic semiconductor materials

Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials.     

基于手机光线传感器为检测器的简易光度计的自组装设计

By using light sensors of the cellphone, we build a simple photometer which can be used in quantitative analysis experiments. We have performed 5 replicate measurements of iron with phenanthroline to verify reproducibility and stability. We find the absorbance of the sample has a good linear relationship with the concentrations of iron with a R² value around 0.999 and the RSD of 2.81%. The result is 4.94 μg·mL^-1 with spectrophotometer and 5.11 μg·mL^-1 with our photometer. The photometer is simple, convenient, accurate and realistic by using a phone as detector, which can replace the traditional spectrophotometer in the laboratory class. The students can enhance their understanding of the structure and principle of spectrophotometer by the DIY photometer experiment.     

手性环丙烯构建策略用于对映选择性合成偕二氟亚甲基三元环化合物

作为最小的不饱和环状分子,环丙烯独特的刚性结构和多变的反应活性吸引了化学家的研究兴趣.自1922年Demjanov[1]报道了环丙烯化合物的首例合成以来,现已发展了一系列环丙烯的合成方法.手性环丙烯的合成是通过炔烃和重氮化合物的[2+1]不对称环加成反应.根据底物的不同,这些不对称环加成反应可以分为四类:(a)末端炔烃和单取代重氮化合物的反应,(b)末端炔烃和双取代重氮化合物的反应,(c)非末端炔烃和双取代重氮化合物的反应,(d)非末端炔烃和单取代重氮化合物的反应.在这四类反应中,末端炔烃和单取代重氮化合物的不对称反应相对容易进行.1992年,Doyle和Müller等[2]报道了手性铑催化剂[Rh2(5R-MEPY)4]促进的末端炔烃和重氮醋酸酯之间的不对称环丙烯基化反应(Scheme 1a).随后各种手性催化剂包括[Rh2(OAc)-(DPTI)3][3]、Ir(salen)衍生物[4]和[Co(3,5-diMes-Chen-Phyrin)][5]等被先后报道用于末端炔烃和单取代重氮化合物的不对称[2+1]环加成反应.     

Unpaired 3d Electrons on Atomically Dispersed Cobalt Centres in Coordination Polymers Regulate both Oxygen Reduction Reaction (ORR) Activity and Selectivity for Use in Zinc–Air Batteries

Reversible oxygen conversion is important for various green energy technologies. Herein we synthesize a series of bimetallic coordination polymers by varying the Ni/Co ratio and using HITP (HITP=2,3,6,7,10,11‐hexaiminotriphenylene) as the ligand, to interrogate the role of metal centres in modulating the activity of the oxygen reduction reaction (ORR). Co₃HITP₂ and Ni₃HITP₂ are compared. Unpaired 3d electrons in Co₃HITP₂ result in less coplanarity but more radical character. Thus, despite of a reduced crystallinity and conductivity, the best ORR activity, comparable to 20 % Pt/C, is obtained for Co₃HITP₂, showing the 3d orbital configuration of the metal centre promotes ORR. Experimental and DFT studies show a transition of ORR pathway from four‐electron for Co₃HITP₂ to two‐electron for Ni₃HITP₂. Rechargeable zinc–air batteries using Co₃HITP₂ as the air cathode catalyst demonstrate excellent energy efficiency and stability.     

Behaviour of silicon ointment for power-cable insulation under external heating

Journal of Thermal Analysis and Calorimetry - The burning process and typical fire parameters of power-cable silicon ointment were explored experimentally using a cone calorimeter, and the effects...     

Comparison of the active components of Aster tataricus from different regions and related processed products by ultra‐high performance liquid chromatography with tandem mass spectrometry

We investigated crude Aster tataricus, vinegar‐processed Aster tataricus, honey‐processed Aster tataricus, and steamed Aster tataricus as a case study and developed a comprehensive strategy integrating quantitative analysis and chemical pattern recognition methods for the evaluation and differentiation of Aster tataricus from different regions, as well as related processed products. In the study, 15 batches of raw Aster tataricus collected from seven provinces were analyzed. A sensitive and rapid ultra‐high performance liquid chromatography with tandem mass spectrometry method for simultaneous determination of 15 compounds was established to evaluate the quality of raw and processed Aster tataricus. Furthermore, multivariate statistical techniques were applied to compare the differences among Aster tataricus samples. As a result, the herbs collected from seven provinces were divided into two categories, and chlorogenic acid was the most important component distinguishing between the regions. Moreover, all of the raw and processed samples were classified by partial least squares discriminant analysis based on the 15 analyzed compounds. Results showed that raw Aster tataricus, vinegar‐processed Aster tataricus, honey‐processed Aster tataricus, and steamed Aster tataricus were clustered in four different areas. Shionone, chlorogenic acid and kaempferol were the significant constituents differentiating the raw and differently processed Aster tataricus samples.     

Transformations of N-arylpropiolamides to indoline-2,3-diones and acids via C≡C triple bond oxidative cleavage and C(sp^2)–H functionalization

A new palladium-catalyzed oxidative conversion of N-arylpropiolamides and H2O to various indoline-2,3-diones and acids through the C≡C triple bond cleavage and C(sp2)–H functionalization is described,which is promoted by a cooperative action of catalytic CuBr2,2,2,6,6-tetramethyl-1-piperidinyloxy(TEMPO)and O2.The method provides a practical tool for transformations of alkynes by means of a C–H functionalization strategy,which enables the formation of one C–C bond and multiple C–O bonds in a single reaction with high substrates compatibility and excellent functional group tolerance.