Interfacial Synthesis of a Monolayered Fluorescent Two-Dimensional Polymer through Dynamic Imine Chemistry

A fluorescent monolayered two-dimensional polymer (2DP) containing both tetraphenylethylene (TPE) and imine linkages is synthesized at air-water interface using the Langmuir-Blodgett method. We designed TPE-based monomers with long distances between the TPE and the imine linkages to avoid the charge transfer and therefore keep the fluorescence. A monolayered 2DP provided with more than 104 μm² in domain size and around 0.8 nm thickness was obtained through a successive Schiff base reaction at air-water interface. The nanostructures and fluorescent property of 2DP films were characterized by optical microscopy, SEM, TEM, AFM and fluorescence spectrum. Most importantly, the tip-enhanced Raman spectroscopy (TERS) was utilized here to confirm the success of the polycondensation of monolayered 2DP.     

A note on 3‐partite graphs without 4‐cycles

Let $C_4$ be a cycle of order 4. Write $ex\left(n,n,n,C_4\right)$ for the maximum number of edges in a balanced 3‐partite graph whose vertex set consists of three parts, each has $n$ vertices that have no subgraph isomorphic to $C_4$. In this paper, we show that $ex\left(n,n,n,C_4\right)\ge \frac{3}{2}n\left(p+1\right)$, where $n=\frac{p\left(p?1\right)}{2}$ and $p$ is a prime number. Note that $ex\left(n,n,n,C_4\right)\le \left(\frac{3\sqrt{2}}{2}+o\left(1\right)\right)n^{\frac{3}{2}}$ from Tait and Timmons's works. Since for every integer $m$, one can find a prime $p$ such that $m\le p\le \left(1+o\left(1\right)\right)m$, we obtain that $\underset{n\to \infty }{\lim }\frac{ex\left(n,n,n,C_4\right)}{\frac{3\sqrt{2}}{2}{n}^{\frac{3}{2}}}=1$.     

Enhancing hydrogen evolution of MoS2 basal planes by combining single-boron catalyst and compressive strain

MoS₂ is a promising candidate for hydrogen evolution reaction (HER), while its active sites are mainly distributed on the edge sites rather than the basal plane sites. Herein, a strategy to overcome the inertness of the MoS₂ basal surface and achieve high HER activity by combining single-boron catalyst and compressive strain was reported through density functional theory (DFT) computations. The ab initio molecular dynamics (AIMD) simulation on B@MoS₂ suggests high thermodynamic and kinetic stability. We found that the rather strong adsorption of hydrogen by B@MoS₂ can be alleviated by stress engineering. The optimal stress of −7% can achieve a nearly zero value of ΔG_H (~ −0.084 eV), which is close to that of the ideal Pt–SACs for HER. The novel HER activity is attributed to (i) the B– doping brings the active site to the basal plane of MoS₂ and reduces the band-gap, thereby increasing the conductivity; (ii) the compressive stress regulates the number of charge transfer between (H)–(B)–(MoS₂), weakening the adsorption energy of hydrogen on B@MoS₂. Moreover, we constructed a SiN/B@MoS₂ heterojunction, which introduces an 8.6% compressive stress for B@MoS₂ and yields an ideal ΔGH. This work provides an effective means to achieve high intrinsic HER activity for MoS₂.     

Ce掺杂CrSi2电子结构和光学性质的第一性原理研究

采用基于密度泛函理论的第一性原理计算方法，对未掺杂及Ce掺杂CrSi2的电子结构和光学性质进行理论计算。计算结果表明，未掺杂CrSi2是间接带隙半导体，其禁带宽度为0.392 eV，掺杂Ce元素，仍然是间接半导体，带隙宽度下降为0.031eV。未掺杂CrSi2在费米能级附近主要由Cr-5d、Si-3p态贡献。Ce掺杂后在费米能级附近主要由Cr-5d轨道，Ce-4f轨道，C-2p，Si-3p轨道贡献，掺杂后电导率提高。未掺杂CrSi2有两个介电峰，掺杂后，只有一个介电峰。未掺杂CrSi2，在能量为6.008处吸收系数达到最大值，掺杂后在能量为5.009eV处，吸收系数达到最大值。     

密度泛函理论研究MN@H_2O (M=Ga,Ge, In,Sn, Sb; N=M,Al)团簇的特性

采用密度泛函理论的B3LYP, B3P86, B1B95, P3PW91和PBE1PBE方法结合SDD, LANL2DZ和CEP-121G基组计算了d~(10)组态二聚物MN(M=Ga, Ge, In, Sn和Sb; N=M和Al)的几何结构.采用B3P86/SDD进一步研究了MN@H_2O团簇的几何结构及吸附能.结果表明,水分子结合在二聚物M_2上时,对二聚物影响较大,对水分子自身影响较小.将M_2中Ga, Ge, In, Sn或Sb替换一个原子为Al时,水分子在GeAl和SnAl上的吸附能变化较大,而在GaAl, InAl和SbAl上吸附能变化较小.另外, H_2O吸附在Ga, Ge, In, Sn和Sb上时,与吸附在Al上时,吸附能的变化不大.     

Magnetite nanoparticles−based hydroxyl radical scavenging activity assay of antioxidants using N,N-dimethyl-p-phenylenediamine probe

Excessive amounts of reactive oxygen species (ROS), unless counterbalanced by antioxidants, can cause cellular damage under oxidative stress conditions; therefore, antioxidative defenses against ROS must be measured. With the development of nanotechnology, nanoparticles have found numerous applications in science, health, and industries. Magnetite nanoparticles (Fe ₃ O ₄ :MNPs) have attracted attention because of their peroxidase-like activity. In this study, hydroxyl radicals (•OH) generated by MNPs-catalyzed degradation of H ₂ O ₂ converted the N,N-dimethyl-p-phenylenediamine (DMPD) probe into its colored DMPD•+ radical cation, which gave an absorbance maximum at λ = 553 nm. In the presence of antioxidants, •OH was partly scavenged by antioxidants and produced less DMPD• ⁺ , causing a decrease in the 553 nm-absorbance. Antioxidant concentrations were calculated with the aid of absorbance differences between the reference and sample solutions. The linear working ranges and trolox equivalent antioxidant capacity coefficients of different classes of antioxidants were determined by applying the developed method. In addition, binary and ternary mixtures of antioxidants were tested to observe the additivity of absorbances of mixture constituents. The method was applied to real samples such as orange juice and green tea. Student t-test, F tests, and the Spearman’s rank correlation coefficient were used for statistical comparisons.     

Chemical-Reductant-Free Electrochemical Deuteration Reaction using Deuterium Oxide

We report a method for the electrochemical deuteration of α,β-unsaturated carbonyl compounds under catalyst- and external-reductant-free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O₂ evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.