聚苯并双噁唑酰亚胺的热分解动力学研究

采用二步法合成了以2,6-二(对-氨基苯)苯[1,2-d;5,4-d’]二噁唑和1,4-二(3,4-二苯氧基)苯四甲酸二酐(HQDPA)为单体的聚苯并双噁唑酰亚胺.该聚酰亚胺的预聚体聚酰胺酸的黏度为1.70 dL/g,经过热环化后能够生成浅黄色的聚酰亚胺薄膜.通过热重分析法研究了聚苯并双噁唑酰亚胺在N2气氛中的热降解机理.采用Flynn-Wall-Ozawa和Friedman法计算了聚苯并双噁唑酰亚胺热降解表观活化能,分别为356.36kJ/mol和370.54 kJ/mol,平均值为363.45 kJ/mol;反应级数为4.22,指前因子为6.44×1016s-1.采用Coast-Redfern法和Phadnis-Deshpande法研究了聚苯并双噁唑酰亚胺的热降解固相反应机理,认为该聚酰亚胺的热降解机理属于反曲线(A3)机理,是成核和增长模式(Avrami equation 2方程)控制的热降解反应,积分形式为g(X)=[-ln(1-X)]3.     

Sugar-derived cyclic imines: one-pot synthesis and direct functionalization

A simple method for the synthesis of sugar-derived imines by a Schwartz's reagent reduction of easily available sugar lactams has been described. A direct addition of nucleophiles to the generated in situ cyclic imines and subsequent deprotection of hydroxyl function allows to convert sugar lactams in polyhydroxylated pyrrolidines and piperidines.     

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.     

Nature of Alkali- and Coinage-Metal Bonds versus Hydrogen Bonds

We have quantum chemically studied the structure and nature of alkali- and coinage-metal bonds (M-bonds) versus that of hydrogen bonds between A−M and B⁻ in archetypal [A−M⋅⋅⋅B]⁻ model systems (A, B=F, Cl and M=H, Li, Na, Cu, Ag, Au), using relativistic density functional theory at ZORA-BP86-D3/TZ2P. We find that coinage-metal bonds are stronger than alkali-metal bonds which are stronger than the corresponding hydrogen bonds. Our main purpose is to understand how and why the structure, stability and nature of such bonds are affected if the monovalent central atom H of hydrogen bonds is replaced by an isoelectronic alkali- or coinage-metal atom. To this end, we have analyzed the bonds between A−M and B⁻ using the activation strain model, quantitative Kohn-Sham molecular orbital (MO) theory, energy decomposition analysis (EDA), and Voronoi deformation density (VDD) analysis of the charge distribution.     

An infrared small target detection algorithm based on high-speed local contrast method

Small-target detection in infrared imagery with a complex background is always an important task in remote sensing fields. It is important to improve the detection capabilities such as detection rate, false alarm rate, and speed. However, current algorithms usually improve one or two of the detection capabilities while sacrificing the other. In this letter, an Infrared (IR) small target detection algorithm with two layers inspired by Human Visual System (HVS) is proposed to balance those detection capabilities. The first layer uses high speed simplified local contrast method to select significant information. And the second layer uses machine learning classifier to separate targets from background clutters. Experimental results show the proposed algorithm pursue good performance in detection rate, false alarm rate and speed simultaneously.     

Dielectric relaxation of chlorinated polyvinyl chloride (CPVC) stabilized with cyanoguanidine

Dielectric spectra of CPVC stabilized with cyanoguanidine were studied in the temperature range 300–450 K and frequency range 10 kHz to 1 MHz. In these conditions, only one clear dielectric relaxation band (α-type) associated with dipolar polarization was observed. Dielectric losses was found to directly proportional to the number of dipoles (N) which reflects the orientational distribution of polymer chains in the amorphous region, at which dielectric losses concerned. Calculations of the dielectric modulus M′(T) at low temperature indicate that there is a role of the electrode polarization in the relaxation process. Dielectric loss data were used to calculate the activation enthalpy by two different methods, the obtained value was 450 kJ/mol.     

Small luminescent molecular probe for developing as assay for alkaline phosphatase

Alkaline phosphatase (ALP) is an important biomarker in clinical diagnostics, and the abnormal level of ALP enzyme in serum is closely related to various diseases such as bone metastases, bone or liver cancer, and extrahepatic biliary obstruction. Recognizing the location and expression level of ALP in live cells has a substantial importance in early-stage cancer diagnosis, as well as an important parameter for studying the recovery of the patients after liver transplantation. With the advent of the newer and advanced fluorescence imaging techniques, small-molecule fluorescent probes have become a very powerful tool for mapping the subtle changes in the enzyme expression level in living cells and tissues in real-time. In this account, we provide an overview of recent advances in small-molecule ALP fluorescent probes, mainly during the last few years, including the design strategies and applications for biological applications.     

ZIF-derived mesoporous carbon materials prepared by activation via Na2SiO3 for supercapacitor

Metal organic frameworks (MOFs) derived carbonaceous materials have a wide range of applications in the fields of energy storage, catalysis, adsorption and separation, etc. Especially, zeolitic imidazolate framework-8 (ZIF-8) is an excellent candidate to synthesize porous carbon due to the large surface area and high nitrogen content. However, the dominated microporous structure of ZIF-8-derived carbon significantly hinders ionic mass transfer, limiting the improvement of performance. Herein, MOF-derived mesoporous carbon was prepared using ZIF-8 as carbon precursor and cheap sodium silicate (Na₂SiO₃) as activator. The introduction of Na₂SiO₃ created rich mesoporous structure and increased specific surface area, as well as the effects of pyrolysis temperature and Na₂SiO₃ dosage on performance was also investigated. The obtained ZIF-derived porous carbon exhibits good electrochemical performance with specific capacitance of 263 F/g at 1 A/g and excellent cycle life (96.07% after 10,000 GCD cycles) in supercapacitor. The use of cheap Na₂SiO₃ activator provides a new orientation for the preparation of MOF-derived carbons with rich pores, high surface area, and facilitates the large-scale application of MOF-derived carbons.     

基于3G-ASCX的小型飞行器异常导航信号检测系统设计

传统方法在异常导航信号信噪比较低时对小型飞行器异常导航信号的检测效果不理想。设计并实现了一种基于3G-ASCX的小型飞行器异常导航信号检测系统,硬件设计时着重于ASCX传感器模块、异常导航信号检测模块、主控基站模块、3G/GPRS传输模块的研究,3G/GPRS传输模块的硬件设计中,通过功耗低体积小的CC1100完成异常导航信号的收发,传输过程中通过芯片STC12C5410AD完成电容的平衡转换,选取了MC3486进行电压的转换,最终实现异常信号数据的安全快速传输;软件设计中,系统软件流程设计及异常导航信号检测模块软件设计,最后进行仿真实验,实验结果证明,相比传统系统,所设计系统检测到的小型飞行器异常导航信号同实际测量的异常导航信号具有较高的匹配度,与实际值相比,误差小于1dB,适合推广使用。     

液态丙烯腈低聚物修复聚丙烯腈基碳纤维微孔缺陷

提出一种全新的缺陷修复的方法,即将聚丙烯腈基(PAN)碳纤维T300在液态丙烯腈低聚物(LAN)中浸渍后,再进行预氧化和碳化热处理,可以将T300的拉伸强度提高25%.应用二维小角X射线散射(SAXS)法可以计算出LAN修复缺陷前后T300微孔缺陷的长度(L)、横截面尺寸(lp)、取向角(Beq)、相对体积(Vrel)的变化,结果表明碳纤维的拉伸性能越好,微孔的长度、取向角、相对体积含量越小.T300拉伸性能的提高是由于缺陷修复的结果.应用BET比表面积法、扫描电子显微镜(SEM)表征LAN修复缺陷前后T300的比表面积以及表面形貌的变化,结果表明,T300在LAN中浸渍并经过预氧化和碳化热处理,比表面积变小,表面缺陷明显减少.进一步验证LAN对碳纤维中的微孔缺陷具有修复作用.应用X射线光电子能谱(XPS)法表征LAN修复前后T300表面化学成分的变化,结果表明,LAN修复后含氧官能团(C―OH,C=O,HO―C=O)显著增加,有利于增强碳纤维与树脂基体之间的相互作用,从而提高碳纤维的力学性能.