多级孔芳香骨架材料的合成及固载硫脲催化剂的研究

合成了一种多级孔芳香骨架材料(PAF-70); 使用由氨基修饰过的单体, 应用该合成策略得到了同样具有窄分布介孔的含有氨基活性位点的PAF材料, 并通过硫脲单体与其氨基活性位点的反应, 将硫脲基团引入PAF-70材料中, 获得了含有硫脲催化位点的材料(PAF-70-thiourea). 氮气吸附-脱附测试结果显示, PAF-70存在孔径分布较窄的介孔, 介孔孔径为3.8 nm, 与模拟计算值(约3.7 nm)吻合. 热重分析结果表明, PAF-70具有很高的热稳定性. PAF-70在大多数溶剂中可以稳定存在, 具有良好的化学稳定性. 将PAF-70-thiourea作为催化剂, 应用在N-溴代琥珀酰亚胺(NBS)氧化醇类的反应中, 其表现出较高的催化活性、 较高的稳定性和广泛的底物适用性. 与含有相同硫脲催化位点的金属有机框架(MOF)材料(IRMOF-3-thiourea)作为催化剂对比, 进一步证实PAFs材料非常适合作为催化有机反应的固载平台.     

Rational Design of a Near-infrared Fluorescent Material with High Solid-state Efficiency,Aggregation-induced Emission and Live Cell Imaging Property

Near-infrared(NIR) fluorescent materials with high photoluminescent quantum yields(PLQYs) have wide application prospects. Therefore, we design and synthesize a D-A type NIR organic molecule, TPATHCNE, in which triphenylamine and thiophene are utilized as the donors and fumaronitrile is applied as the acceptor. We systematically investigate its molecular structure and photophysical property. TPATHCNE shows high T_gof 110℃ and T_d of 385℃ and displays an aggregation-induced emission(AIE) property. A narrow optical bandgap of 1.65 eV is obtained. The non-doped film of TPATHCNE exhibits a high PLQY of 40.3% with an emission peak at 732 nm, which is among the best values of NIR emitters. When TPATHCNE is applied in organic light-emitting diode(OLED), the electroluminescent peak is located at 716 nm with a maximum external quantum efficiency of 0.83%. With the potential in cell imaging, the polystyrene maleic anhydride(PMSA) modified TPATHCNE nanoparticles(NPs) emit strong fluorescence when labeling HeLa cancer cells, suggesting that TPATHCNE can be used as a fluorescent carrier for specific staining or drug delivery for cellular imaging. TPATHCNE NPs fabricated by bovine serum protein(BSA) are cultivated with mononuclear yeast cells, and the intense intracellular red fluorescence indicates that it can be adopted as a specific stain for imaging.     

Classify the Higgs decays with the PFN and ParticleNet at electron–positron colliders

Various Higgs factories are proposed to study the Higgs boson precisely and systematically in a model- independent way. In this study, the Particle Flow Network and ParticleNet techniques are used to classify the Higgs decays into multicategories, and the ultimate goal is to realize an "end-to-end" analysis. A Monte Carlo simulation study is performed to demonstrate the feasibility, and the performance looks rather promising. This result could be the basis of a "one-stop" analysis to measure all the branching fractions of the Higgs decays simultaneously.     

Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand

Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH₂) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S₀ and S₁ states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH₂ can undergo the ESDPT process in the S₁ state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules.     

Piezoelectric Nanogenerator Based on Electrospun Cellulose Acetate/Nanocellulose Crystal Composite Membranes for Energy Harvesting Application

Nanogenerators, as the typical conversion of mechanical energy to electrical energy devices, have great potential in the application of providing sustainable energy sources for powering miniature devices. In this work, cellulose acetate/cellulose nanocrystal(CA/CNC) composite nanofiber membranes were prepared by electrospinning method and then utilized to manufacture a flexible pressure-driven nanogenerator. The addition of CNC not only increased the content of piezoelectric cellulose I crystallization but also strengthened the mechanical deformation of the nanofiber membranes, which could greatly enhance the piezoelectric performance of CA/CNC composite membranes. The CA/CNC composite nanofiber membrane with 20%(mass fraction) of CNC(CA/CNC-20%) showed optimal piezoelectric conversion performance with the output voltage of 1.2 V under the force of 5 N(frequency of 2 Hz). Furthermore, the output voltage of the CA/CNC-20% nanogenerator device exhibited a linear relationship with applied impact force, indicating the great potential in pressure sensors.     

Relationship between the spatial position of the seed and growth mode for single-crystal diamond grown with an enclosed-type holder

The relationship between the spatial position of the diamond seed and growth mode is investigated with an enclosed-type holder for single-crystal diamond growth using the microwave plasma chemical vapor deposition epitaxial method. The results demonstrate that there are three main regions by varying the spatial position of the seed. Due to the plasma concentration occurring at the seed edge, a larger depth is beneficial to transfer the plasma to the holder surface and suppress the polycrystalline diamond rim around the seed edge. However, the plasma density at the edge decreases drastically when the depth is too large, resulting in the growth of a vicinal grain plane and the reduction of surface area. By adopting an appropriate spatial location, the size of single-crystal diamond can be increased from 7 mm × 7 mm × 0.35 mm to 8.6 mm × 8.6 mm × 2.8 mm without the polycrystalline diamond rim.     

Strong Pancake 2e/12c Bond in π-Stacking Phenalenyl Derivatives Avoiding Bond Conversion

The nature of the 2e/12c bond and its conversion to a carbon-carbon single bond in phenalenyl dimers have prompted a great deal of interests recently. In this work, we theoretically investigated a series of π-stacking phenalenyl derivatives with 2e/12c bonding character by density functional theory (DFT) calculations to elucidate origin of this unusual bond conversion. Results show that bond-conversion of the phenalenyl dimer easily occurs at room-temperature both dynamically and thermodynamically. However, bond-conversion of hetero π-stacking adducts, in which the two center carbon atoms were substituted by boron and nitrogen atoms, respectively, is much more difficult, because the 2e/12c bond is stabilized by its charge transfer character. Consequently, the bond-conversion is an endothermic process, albeit with a low conversion barrier. Interestingly, Lewis acid-base interactions would be induced by substitution of the center nitrogen atom to phosphorus atom. The 2e/12c bond is further stabilized by 5.9 kcal mol⁻¹ and its conversion is also thermodynamically unfavorable.     

Evaluation of Charged Defect Energy in Two-Dimensional Semiconductors for Nanoelectronics: The WLZ Extrapolation Method

Defects play a central role in controlling the electronic properties of two-dimensional (2D) materials and realizing the industrialization of 2D electronics. However, the evaluation of charged defects in 2D materials within first-principles calculation is very challenging and has triggered a recent development of the WLZ (Wang, Li, Zhang) extrapolation method. This method lays the foundation of the theoretical evaluation of energies of charged defects in 2D materials within the first-principles framework. Herein, the vital role of defects for advancing 2D electronics is discussed, followed by an introduction of the fundamentals of the WLZ extrapolation method. The ionization energies (IEs) obtained by this method for defects in various 2D semiconductors are then reviewed and summarized. Finally, the unique defect physics in 2D dimensions including the dielectric environment effects, defect ionization process, and carrier transport mechanism captured with the WLZ extrapolation method are presented. As an efficient and reasonable evaluation of charged defects in 2D materials for nanoelectronics and other emerging applications, this work can be of benefit to the community.     

Aqueous-processed insulating polymer/nanocrystal solar cells with effective suppression of the leakage current and carrier recombination

As one of the most environmentally friendly photovoltaic(PV) conversion equipments,aqueousprocessed CdTe nanocrystal solar cells(NC SCs) have attracted great interest in recent years because of their excellent properties such as high charge-carrier mobility and broad absorption.However,two issues including interfacial recombination and leakage current seriously restrict their performance.In this paper,insulating polymer poly(vinyl pyrrolidone)(PVP) is introduced into CdTe NC SCs to solve the problems.The experimental results of transmission electron microscopy(TEM),atomic force micro scopy(AFM) and dark current measurements,etc.,demonstrate the leakage current is effectively suppressed by introducing PVP.Through further designing device structure,the reduction of interfacial recombination after introducing PVP is confirmed.By strategically taking the advantages of PVP properties(e.g.,water solubility and thermostability),the power conversion efficiency of the devices with PVP is enhanced by almost 37% compared to pure CdTe devices.This work demonstrates an effective and low-cost method to fabricate NC SCs via aqueous route.Moreover,it also proves that appropriate content of insulating polymer is of beneficial in promoting the PV performance.     

Modelling heavy-tailedness in count time series

Count data frequently exhibit overdispersion, zero inflation and even heavy-tailedness (the tail probabilities are non-negligible or decrease very slowly) in practical applications. Many models have been proposed for modelling count data with overdispersion and zero inflation, but heavy-tailedness is less considered. The proposed model, a new integer-valued autoregressive process with generalized Poisson-inverse Gaussian innovations, is capable of capturing these features. The generalized Poisson-inverse Gaussian family is very flexible, which includes Poisson distribution, Poisson inverse Gaussian distribution, discrete stable distribution and so on. Stationarity and ergodicity of this model are investigated and the expressions of marginal mean and variance are provided. Conditional maximum likelihood is used for estimating the parameters, and consistency and asymptotic normality for the estimators are presented. Further, we consider the h-step forecast and diagnostics for the proposed model. The proposed model is applied to three real data examples. In the first example, we consider the monthly number of cases of Polio, which validates that the proposed model can take into account count data with excessive zeros. Then, we illustrate the use of the proposed model through an application to the numbers of National Science Foundation fundings. Finally, we apply the proposed model to the numbers of transactions in 5-min intervals for the stock traded at Empire District Electric Company. The second and third examples show that the proposed model has a good performance in modelling heavy-tailed count data.