Opposite ESIPT characteristic of two AIE-active isomers with different linkage sites

In this work, we report two isomers composed of 1-phenyl-1H-phenanthro[9,10-d]imidazole (PI), hydroxyl and tetraphenylethylene (TPE), abbreviated as m-PITPE and p-PITPE. It is found that they exhibit similar aggregation-induced emission (AIE) behavior but totally different excited-state intramolecular proton transfer (ESIPT) characteristic, as a result of the different linkage sites of PI on TPE moiety. Theoretical calculations and their different experimental responses to F^? demonstrate that only the para-linkage isomer displays ESIPT. In m-PITPE with meta-linkage, the electron cloud distribution only locates at the TPE part in the singlet excited (S₁) states, which results in the localized excited state without ESIPT characteristic.     

杭州市2017年冬季一次重灰霾过程中PM2.5水溶性离子特征、来源及成因分析

利用在线监测仪测量了杭州市一次重灰霾过程（2017年12月29日至2018年1月3日）中PM_2.5主要水溶性离子（Cl^-、SO₄^2-、NO₃^-、NH₄⁺、Na⁺、Ga²⁺、Mg²⁺）及主要气态污染物（SO₂、NO₂、O₃、NO、CO、HCl、NH₃、HNO₂、HNO₃）的小时浓度。结合混合受体模型和国控监测分析,研究了2017年12月30-31日重灰霾事件的污染特征、来源和成因。研究结果表明：PM_2.5浓度高达318 μg·m^-3; NO₃^-/SO₄^2-最大值为2.68,说明移动源污染是杭州市PM_2.5形成的重要来源; PM_2.5/CO最高达到0.19,说明二次细颗粒物对PM_2.5贡献很大;NO₃^-、SO₄^2-、NH₄⁺的浓度总和占PM_2.5平均浓度的64.3%,说明二次无机细颗粒物是杭州重灰霾形成的重要原因,且NO₃^-的贡献最大,占33.5%。混合受体模型分析显示,杭州市重灰霾污染的潜在源区主要位于安徽、江苏、河南、山东四省交界处,以及安徽省中东部、蚌埠、芜湖等工业污染较为严重的城市。夹杂着大量污染物的北方干冷空气远距离传输叠加部分局地源是杭州此次重雾霾形成的根本原因。因此,为了改善杭州市空气质量,不仅需控制当地的污染物排放,而且还需对整个长三角地区甚至跨区域采取大气联防联控策略。     

Quantitative structure‐retention relationships of the chromatographic retentions of phthalic acid ester contaminants in foods

The harmful health effects caused by phthalic acid esters have been supported from the increasing scientific evidence, developing the efficient methodologies to monitor the levels of phthalic acid esters in various foods become especially important from the aspects of human exposure assessment and their migration mechanistic understanding. In this study, quantitative structure‐retention relationship studies on both the gas and liquid chromatographic retention times of 23 phthalic acid esters were performed by genetic function approximation, and the optimal quantitative structure‐retention relationship models (r² > 0.980, r²_CV > 0.960, and r²_pred > 0.865) passed the statistical tests of cross‐validation, randomization, external prediction, Roy′ r_m² metrics, Golbraikh‐Tropsha′ criteria and applicability domain. The established predictive models elucidate the structural requirements for the retention of phthalic acid esters over different chromatographic columns, which were finally used to predict the retention times of 11 new phthalic acid esters. Hopefully, this work could provide useful guidelines for better understanding and accurate prediction of the retention behavior of undetermined phthalic acid esters when lacking standard samples or under poor experimental conditions, and make the simultaneous identification and quantification of numerous phthalic acid esters possible.     

TiO2/石墨烯复合材料的光生电荷分离调控与光催化产氢性能研究

半导体光生电荷分离是光催化过程中的关键步骤之一,其效率极大地影响了最终光催化性能.将TiO₂纳米片与石墨烯复合,能够促进TiO₂中光生电子和空穴的分离,从而提高其光催化活性.为了研究光生电荷的分离对TiO₂/石墨烯复合材料光催化性能的影响,通过调控TiO₂纳米片的尺寸来调节TiO₂/石墨烯复合材料中光生电荷分离的能力,然后研究其对TiO₂/石墨烯复合材料光催化性能的影响.合成了一系列不同厚度的TiO₂纳米片,将其与石墨烯复合,并通过光沉积负载Pt纳米颗粒作为助催化剂,用于光催化产氢.实验结果显示,随着TiO₂纳米片厚度减小,其与石墨烯形成的复合结构的光催化性能显著提高.这主要是由于TiO₂纳米片厚度减小时,光生电子沿厚度方向穿过TiO₂纳米片迁移到石墨烯的距离缩短,从而减少了光生电子在迁移过程中与空穴的复合;同时TiO₂纳米片厚度减小使其比表面积增大,使得TiO₂/石墨烯界面面积增大,从而使石墨烯更好地分离出TiO₂中的光生电子,有更多的光生电子到达石墨烯参与催化反应,提高TiO₂/石墨烯复合材料的光催化性能.此研究表明通过控制TiO₂纳米片的尺寸来调控TiO₂/石墨烯复合材料中光生电子和空穴的分离,是显著提高其光催化性能的有效途径.     

氧气氧化铜催化的苯胺邻位叠氮化反应

叠氮取代的苯胺是有机合成中应用广泛的结构单元. 通过C—H键活化策略来制备叠氮基苯胺衍生物往往需要使用当量的剧烈氧化剂, 造成反应的整体原子经济性低, 官能团耐受性差. 本文使用廉价、绿色的氧气作为最终氧化剂, 发展了高效的铜催化苯胺C—H键叠氮化的方法. 该转化具有反应条件温和、区域选择性单一和官能团兼容性广等优点.     

通过增强电荷转移激发态构建激发态下稳定的基于氰基二苯乙烯的E/Z构型

The E/Z isomerization reaction is found extensively in most organic molecules containing double bond unit. This limits their practical application as luminescent materials partly, especially under photoirradiation. Therefore, it is important to obtain E/Z isomers with stable configuration in the excited state after photoirradiation. It is well known that cyanostilbene and its analogues play an important role in the development of organic opto/electronic materials. The substituted cyano group on C＝C double bonds has strong electron-withdrawing ability and large steric hindrance, which benefits the formation of donor-acceptor (D-A) structures and formation of intramolecular charge transfer. In our previous work, we reported a triphenylamine-cyanostilbene molecule (TPNCF) formed by modifying the cyanostilbene structure with triphenylamine, which maintained a stable E/Z configuration as a film and in high polar solvents. According to solvatochromism mechanisms and the results of theoretical calculations, we proposed that the charge transfer (CT) excited state between the triphenylamine donor and cyanostilbene acceptor groups induced the stable configuration of the E- and Z- isomers under photoirradiation. Under irradiation, the E/Z isomerization process occurring at a higher energy locally excited (LE) state was suppressed by a rapid internal conversion process from the LE to CT state. This work inspired us to provide a universal and effective molecular design strategy by modifying D-A substituents on double bonds that can successfully stabilize E/Z isomers. To further confirm that the CT excited state induced stable E- and Z- isomers in the cyanostilbene structure under photoirradiation, we designed and synthesized a donor-acceptor phenoxazine-cyanostilbene molecule (PZNCF) and successfully characterized its two E/Z isomers. In comparison with the reported TPNCF molecule, the in-situ NMR and UV spectra of E- and Z- isomers of PZNCF demonstrated that the E/Z isomerization rate became slower under photoirradiation, which indicated that the stronger electron-donating group of phenoxazine substituted in the cyanostilbene structure induced a more stable E/Z isomer configuration in its excited state. DFT calculations and photophysical results indicated that a stronger CT state was generated in both E- and Z- isomers of PZNCF. This further confirmed our hypothesized mechanism where the stable E/Z configuration can be obtained under photoirradiation by forming a suitable donor-acceptor structure to suppress the E/Z isomerization reaction in the LE state by a rapid internal crossing process from the LE to CT state. This molecular design strategy is of great significance to organic photochemistry and photoelectronics for molecules with double bond units.     

粘结剂对形貌各异的石墨负极电化学性能的影响

As an important component in electrodes, the choice of an appropriate binder is significant when fabricating lithium-ion batteries (LIBs) with good cycle stability and rate capability, which are used in numerous applications, especially portable electronics and eco-friendly electric vehicles (EVs). Semi-crystalline poly(vinylidene fluoride) (PVDF), which is a traditional and widely used binder, cannot efficiently accommodate the volume changes observed in the anode during the charge-discharge process while binding all the components in the electrode together, which results in increased internal cell resistance, detachment of the electrode components, and capacity fading. Herein, we have investigated a highly polar and elastomeric polyacrylonitrile-butadiene (NBR) rubber for use as a binder in LIBs, which can accommodate graphite particles of different shapes compared to semi-crystalline PVDF. Prior to our electrochemical tests, NBR was analyzed using thermogravimetric analysis (TGA) and X-ray diffraction (XRD), showing good thermal stability and an amorphous morphology. NBR is more conformable to irregular surfaces, which results in the formation of a homogeneous passivation layer on both spherical and flaky graphite particles to effectively suppress any electrolyte side reactions, further allowing more uniform and fast Li ion diffusion at the electrolyte/electrolyte interface. As a result, the electrochemical performance of both spherical and flaky shape graphite electrodes was significantly improved in terms of their first cycle Coulombic efficiency (CE) and cycle stability. With comparative specific capacity, the first cycle CE of the NBR-based spherical and flaky graphite electrodes were 87.0% and 85.5%, compared to 85.3% and 82.6% observed for their corresponding PVDF-based electrodes, respectively. After 1000 discharge-charge cycles at 1C, the capacity retention of the NBR-based graphite electrodes was significantly higher than that of PVDF-based electrodes. This was attributed to the good stability of the solid electrolyte interphase (SEI) formed on the graphite electrodes and the high stretching ability of the elastomeric NBR binder, which help to accommodate the repeated volume fluctuation of graphite observed during long-term charge-discharge cycling. Electrochemical impedance spectroscopy (EIS) and microscopic analysis (SEM and TEM) were carried out to investigate the formation and evolution of the SEI layers formed on the spherical and flaky graphite electrodes. The results show that thin, homogeneous, and stable SEI layers are formed on the surface of both spherical and flaky graphite electrodes prepared using the NBR binder. When compared to the PVDF-based graphite electrodes, the graphite electrodes constructed using NBR showed decreased resistance in the SEI layer and faster charge transfer, thus enhancing the electrode kinetics for Li ion intercalation/deintercalation. Our study shows that the electrochemical performance of spherical and flaky graphite electrodes prepared using the NBR binder is significantly improved, demonstrating that NBR is a promising binder for these electrodes in LIBs.     

Ethylene/1-Hexene Copolymerization with Modified Ziegler-Natta Catalyst

Siloxane compounds were treated with the compounds containing internal donors, such as aromatic ester, phosphate, or 1,3-diether compounds, and the resulting intermediates were further reacted with TiCl₄ to form the modified Ziegler-Natta catalysts for ethylene/1-hexene(E-H) copolymerization. Using the modified Ziegler-Natta catalysts, the effect of the internal donors and the molar ratio of alcohol to magnesium on the catalyst performance was investigated by the orthogonal experiments. The synthetic method of the catalysts was also optimized by choosing the proper way to mix the internal donors. The branch degree, sequence structure, molecular weight, and molecular weight distribution of the copolymer products were determined by Fourier transform infrared spectroscopy(FTIR), carbon-13 nuclear magnetic resonance(¹³C NMR) spectrometry and gel permeation chromatography(GPC). Under the optimum conditions, the catalytic system with tetraethyl orthosilicate and 2,2-dimethoxypropane as the internal donors exhibited the best performance with an activity of 926.74 g copolymer/(g Cat·h^-1). The branch degree, 1-hexene content, and molecular weight distribution of the resulting copolymers reached up to 40 branches/1000C, 5.99% and 5.8, respectively.     

递推-组合法推求j-j耦合光谱项

本文提出了推求等价组态j-j耦合原子光谱项的新方法－－递推－组合法。该法计算过程简单，易于掌握。