Co‐templating Ionothermal Synthesis and Crystal Structure of a New Layered Aluminophosphate from a Protic Deep Eutectic Solvent

Protic deep eutectic mixtures are usually composed of organic amine hydrochloride salts and hydrogen bond donors in a specific molar ratio. Ionothermal synthesis of aluminophosphate as an example, herein, was reported for the first time from an urea‐based protic eutectic mixture, consisting of diethylammonium chloride (DEACl) and 1,3‐dimethyl urea (DMU). As a result, a new two dimensional aluminophosphate with 4.8‐network, [CH₃NH₃]₂[(C₂H₅)₂NH₂]Al₃(PO₄)₄, has been successfully synthesized by co‐templating the DEA and methylamine in situ generated from the decomposition of DMU in the absence of HF. Compared to alkyl quaternary ammonium salts with more alkyl‐group connected with N atom, this kind of organic amine salts are more likely as the structure‐directing agents to synthesize aluminophosphates in urea‐based deep eutectic mixtures. It was also found that HF is crucial to the phase selectivity, a known compound with chain‐like structure was obtained with the single methylamine as a structure‐directing agent in the presence of HF. These materials were characterized by powder XRD, SEM, TG‐DSC, ¹³C CP‐MAS NMR and CHN analyses.     

Dry Sintering Meets Wet Silver‐Ion “Soldering”: Charge‐Transfer Plasmon Engineering of Solution‐Assembled Gold Nanodimers From Visible to Near‐Infrared I and II Regions

Achieving highly tunable and localized surface plasmon resonance up to near infrared (NIR) regions is a key target in nanoplasmonics. In particular, a self‐assembly process capable of producing highly uniform and solution‐processable nanomaterials with tailor‐made plasmonic properties is lacking. We herein address this problem through a conjunctive use of wet Ag⁺ soldering and dry thermal sintering to produce nanodimer‐derived structures with precisely engineered charge‐transfer plasmon (CTP). The sintered dimers are water soluble, featuring gradually shifted CTP spanning an 800 nm wavelength range (up to NIR II). Upon silica removal, the products are grafted by DNA to offer surface functionality. This process is also adaptable to DNA‐linked AuNP dimers toward plasmonic meta‐materials via DNA‐guided soldering and sintering.     

Near‐Infrared Fluorescent Probe with New Recognition Moiety for Specific Detection of Tyrosinase Activity: Design,Synthesis, and Application in Living Cells and Zebrafish

Fluorescence imaging of tyrosinase (a cancer biomarker) in living organisms is of great importance for biological studies. However, selective detection of tyrosinase remains a great challenge because current fluorescent probes that contain the 4‐hydroxyphenyl moiety show similar fluorescence responses to both tyrosinase and some reactive oxygen species (ROS), thereby suffering from ROS interference. Herein, a new tyrosinase‐recognition 3‐hydroxybenzyloxy moiety, which exhibits distinct fluorescence responses for tyrosinase and ROS, is proposed. Using the recognition moiety, we develop a near‐infrared fluorescence probe for tyrosinase activity, which effectively eliminates the interference from ROS. The high specificity of the probe was demonstrated by imaging and detecting endogenous tyrosinase activity in live cells and zebrafish and further validated by an enzyme‐linked immunosorbent assay. The probe is expected to be useful for the accurate detection of tyrosinase in complex biosystems.     

Optimizing Optoelectronic Properties of Pyrimidine‐Based TADF Emitters by Changing the Substituent for Organic Light‐Emitting Diodes with External Quantum Efficiency Close to 25 % and Slow Efficiency Roll‐Off

A series of green butterfly‐shaped thermally activated delayed fluorescence (TADF) emitters, namely PXZPM , PXZMePM , and PXZPhPM , are developed by integrating an electron‐donor (D) phenoxazine unit and electron‐acceptor (A) 2‐substituted pyrimidine moiety into one molecule via a phenyl‐bridge π linkage to form a D –π–A–π–D configuration. Changing the substituent at pyrimidine unit in these emitters can finely tune their emissive characteristics, thermal properties, and energy gaps between the singlet and triplet states while maintaining frontier molecular orbital levels, and thereby optimizing their optoelectronic properties. Employing these TADF emitters results in a green fluorescent organic light‐emitting diode (OLED) that exhibits a peak forward‐viewing external quantum efficiency (EQE) close to 25 % and a slow efficiency roll‐off characteristic at high luminance.     

SAPO-34处理方法对吸附性能的影响

以二乙胺为结构导向剂, 在微波条件下合成了SAPO-34分子筛材料, 并分别在空气和氮气氛下1073 K焙烧. 考察了氮气氛下分子筛表面碳改性后对材料表面及水、甲醇和乙醇吸附性能的影响. 结果表明: 碳改性后SAPO-34比表面、孔容下降, 但孔径趋于均一. 与SAPO-34样品相比, 碳改性后SAPO-34吸水量从0.295 g/g降低到0.180 g/g, 甲醇/乙醇的吸附比从1.42提高到2.81.     

用动态光散射跟踪钙-海藻酸水溶液凝胶化

海藻酸(alginate)是一种天然多糖,是直链键合的β-D-甘露糖醛酸(M)和α-L-古洛糖醛酸(G)的无规嵌段共聚物[1].在海藻酸水溶液中加入钙、铜、锌、铅等二价正离子,能够形成凝胶;其中钙-海藻酸凝胶在细胞输送、组织工程等领域受到人们的关注[2,3].影响海藻酸凝胶化的因素包括海藻酸的分子量和分子量分布、M/G值和序列分布、溶液浓度、正离子种类与浓度等[4,5].     

高分辨电感耦合等离子体质谱仪测定中亚山地冰川雪冰中超痕量元素

在超净实验条件下,利用高分辨电感耦合等离子体质谱仪直接测定雪冰样品中浓度在1ng/L~100μg/L之间的多种超痕量元素Al、Fe、Mn、Co、Cu、Zn、Sr、Sb、Cd、CsBa、Tl、Pb和Bi的实验方法进展。在测定过程中灵敏度的变化可通过监测ArAr质谱峰的变化进行校正,并建立了数学校正公式。以1%HNO3为空白溶液获得了各元素的检出限(ng/L)分别为:Al40、Mn6、Fe40、Co2.74、Cu9.6、Zn20、Sr0.03、Sb0.15、Cs0.04、Ba0.4、Tl0.07、Pb0.8和Bi0.05。利用标准参考物质SLRS-4对测试方法的准确度进行了评价。研究了在硝酸含量分别为0.5%、1%、2%和4%时雪冰中超痕量元素质谱信号强度的变化特点。测定结果发现,对于污化层样品,当硝酸的含量为1%时痕量元素的质谱信号强度最大;对于非污化层样品,痕量元素的质谱信号强度在硝酸含量为0.5%时较大,但与硝酸含量为1%时的质谱信号强度相比变化率小于10%。结合中亚山地冰川雪冰中痕量元素浓度差别大的特点,确定硝酸在样品中的含量为1%为合适的酸度。并对卓奥友峰和珠穆朗玛峰雪坑样品进行了分析方法的重复性研究。     

微波作用下高分子咪唑盐催化合成含氟芳香物

高分子咪唑盐1是一种新型高分子相转移催化剂,具有制备简单、稳定性好、催化活性高等特点。TG分析表明,其分解温度可达350℃左右。在微波作用下,采用此高分子咪唑盐相转移催化剂于中等极性的非质子溶剂中成功制备了系列含氟硝基苯类化合物,其收率为72.1%～94.4%,反应时间较常规加热最多可缩短60%以上,拓宽了卤素交换氟化反应溶剂的选择空间。选用中等极性溶剂,反应中还可突出地体现出微波对反应的“非热效应”。     

Transport behavior and efflux of Rg1 in rat pulmonary epithelial cells

The aim of this study was to investigate whether ginsenoside Rg1 could be transported into rat pulmonary epithelial cells and its transport behavior and efflux through the cells. A high-performance liquid chromatography coupled with 2487 UV-vis detector at 203 nm was applied. The mobile phase was 0.05% phosphate-acetonitrile (75:25, v/v). Cells were incubated with Rg1 (100 microg/mL) for a specific time, then lysed and sonicated in methanol to extract intracellular Rg1. Cells incubated with Rg1 and verapamil or KCN were processed by the same method. A 20 microL aliquot of sample was injected into the HPLC system to determine Rg1 concentration. The results showed that Rg1 could be transported into the epithelial cells with peak concentration of 1.28 microg/10(5) cells at 0.5 h. Metabolic inhibitor KCN and P-glycoprotein inhibitor verapamil could increase Rg1 concentration within the cells, indicating that efflux of Rg1 was energy-dependent and P-gp was likely to be involved. This is the first time that the transport behavior and efflux of Rg1 through rat pulmonary epithelial cells has been demonstrated. The phenomenon that Rg1 concentration in the cells decreased whereas that in the medium remained high indicated that a more effective means of drug administration should be found.