Encapsulating Au‐Fe3O4 Nanodots into AIE‐active Supramolecular Assemblies: Ambient Visible‐light Harvesting “Dip‐Strip” Photocatalyst for C−C/C−N Bond Formation Reactions

The present study demonstrates the development of a supramolecular porous ensemble consisting of hetero‐oligophenylene derivative 6 and Au‐Fe₃O₄ nanodots. Supramolecular assemblies of AIE‐active hetero‐oligophenylene derivative 6 served as reactors for the generation of Au‐Fe₃O₄ nanodots. The as prepared supramolecular ensemble functioned as an efficient recyclable photocatalytic system for C(sp²)?H bond activation of anilines for the construction of quinoline carboxylates. Interestingly, the “dip catalyst” prepared by depositing PTh‐co‐PANI‐6: Au‐Fe₃O₄ nanodots on a filter paper served as a recyclable strip (up to 10 cycles) for C?C/C?N bond formation reaction.     

Synthesis and Characteristics of Organic Red‐Emissive Materials Based on Phenanthro[9,10‐d]imidazole

Red emission is one of the three primary colors that are essential for the realization of full‐color displays and solid‐state lightings. A high solid‐state efficiency is a crucial factor for the applications in organic light‐emitting diodes (OLEDs). In this work, two new donor‐acceptor‐donor type phenanthro[9,10‐d]imidazole (PIM)‐based derivatives, (2Z,2′Z)‐2,2′‐(1,4‐phenylene)bis(3‐(4‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)phenyl)acrylonitrile) ( PIDSB ) and 2,3‐bis(4′‐(1‐phenyl‐1H‐phenanthro[9,10‐d]imidazol‐2‐yl)‐[1,1′‐biphenyl]‐4‐yl)fumaronitrile ( PIDPh ), are designed and synthesized. Both of them possess high thermal stabilities. PIDPh shows typical characteristics of aggregation‐induced emission enhancement, while PIDSB displays an aggregation‐caused quenching effect. They both exhibit significant red‐shifted emissions compared with PIM owing to intramolecular charge transfer. In the film state, the emission peaks of PIDSB and PIDPh are located at 538 nm and 605 nm with high photoluminescent quantum yields of 63.82 % and 41.26 %, respectively. The non‐doped OLED using PIDPh as the active layer shows the maximum external quantum efficiency of 2.06 % with a very low efficiency roll‐off, and exhibits the electroluminescent peak at 640 nm with a Commission Internationale de l′Éclairage coordinate of (0.617,0.396), meeting well the criteria of red OLEDs.     

Luminescent Solar Concentrators Based on Renewable Polyester Matrices

This study reports for the first time the use of bio‐based alternatives for PMMA as host matrix for luminescent solar concentrators (LSCs). Notably, two types of renewable polyesters were synthesized in varying molar ratios via a two‐step melt‐polycondensation reaction with dibutyl tin oxide as catalyst. The first is a homopolymer of diethyl 2,3:4,5‐di‐O‐methylene galactarate (GxMe) and isosorbide (IGPn), and the second is a random copolymer of GxMe with 1,3‐propanediol and dimethyl terephthalate (GTPn). The two polyesters were found to be optically transparent, totally amorphous with a T_g higher than 45 °C and temperature resistance comparable to PMMA. Lumogen Red (LR) and an aggregation‐induced emission (AIE) fluorophore, TPETPAFN, were utilized as fluorophores and the derived thin polymer films (25 μm) were found highly homogeneous, especially for those prepared from GTPn, possibly due to the presence of compatibilizing terephthalate units in the matrix composition and the higher molecular weight. The spectroscopic characterization and the optical efficiency determination (η_opt) evidenced LSCs performances similar or superior to those collected from LR/PMMA thin films. Noteworthy, η_opt of 7.7 % and 7.1 % were recorded for the GTPn‐based matrix containing LR and TPETPAFN, respectively, thus definitely supporting the bio‐based polyesters as renewable and highly fluorophore‐compatible matrices for high‐performance LSCs.     

Bio‐orthogonal AIE Dots Based on Polyyne‐Bridged Red‐emissive AIEgen for Tumor Metabolic Labeling and Targeted Imaging

In this work, we aim to develop cancer cell‐targeting AIE dots based on a polyyne‐bridged red‐emissive AIEgen, 2TPE‐4E, through the combination of metabolic engineering and bio‐orthogonal reactions. Azide groups on a tumor were efficiently produced by intravenous injection of Ac4ManNAz and glycol‐metabolic engineering. These bio‐orthogonal azide groups could facilitate the specific targeting of DBCO‐AIE dots to the tumor cells undergoing metal‐free click reaction in vivo. The efficiency of this targeting strategy could be further improved with the development of new bio‐orthogonal chemical groups with higher reactivity and a large amount of AIEgens could be delivered to the tumor for diagnosis.     

Migratory Shift in Oxidative Cyclodehydrogenation Reaction of Tetraphenylethylenes Containing Electron‐Rich THDTAP Moiety

Four tetraphenylethylenes ( 2 a – d ) containing an electron‐rich 2,3,4,6‐tetrahydro‐1,6‐dithia‐3a‐azaphenalene (THDTAP) moiety have been synthesized. The 2 a – d show aggregation‐induced emission (AIE) with yellowish green photoluminescence (PL) in THF‐H₂O (v/v, 1:9) solution and in the solid state. Compounds 2 a – d undergo 1,2‐migratory shift in oxidative cyclodehydrogenation reactions to afford the unexpected products 3 a – d which display green PL in CH₂Cl₂ solution and are non‐emissive in the solid state. The PL intensities of 3 a – d are clearly enhanced in the presence of meta‐chloroperoxybenzoic acid (mCPBA) owing to the oxidation of the S‐atoms on the THDTAP moiety. In contrast, the PL of 2 a – d in THF‐H₂O (v/v, 1:9) solution is quenched by adding mCPBA, ascribable to the oxidation of the C=C bond on the ethylene moiety. It is found that the absorption of 3 a – d is distinctly red‐shifted from the UV/Vis region to the NIR region upon acidification, arising from the protonation of the N‐atom on the THDTAP moiety. Furthermore, 3 a – d display nonlinear optical response (NLO) and optical limiting (OL) behaviour which is superior to that of the well‐known OL material C₆₀.     

Water‐soluble Glucosamine‐coated AIE‐Active Fluorescent Organic Nanoparticles: Design,Synthesis and Assembly for Specific Detection of Heparin Based on Carbohydrate–Carbohydrate Interactions

Two water‐soluble carbohydrate‐coated AIE‐activate fluorescent organic nanoparticles TPE3G and TPE4G were designed and synthesized for the detection of heparin. Different from the reported strategy, we not only utilized the general detection mechanism of electrostatic interactions, but also introduced the concept of carbohydrate‐carbohydrate interactions (CCIs) to enrich the detection mechanism of heparin. TPE3G can serve as an efficient “turn‐on” probe with higher selectivity towards heparin than TPE4G . TEM studies revealed that the micro‐aggregated TPE3G was encapsulated with the heparin chain to form a complex self‐assemblied composite and emits strong fluorescence. It is believed that the results illustrated in this study provide a novel strategy based on CCls to design water‐soluble and more efficient bio‐probes for various biological and clinical applications.     

Squaraine Dyes: Interaction with Bovine Serum Albumin to Investigate Supramolecular Adducts with Aggregation‐Induced Emission (AIE) Properties

Bovine serum albumin (BSA)–squaraine supramolecular adducts with aggregation‐induced emission (AIE) properties were prepared and characterized by spectroscopic methods. While squaraine dyes showed a very low fluorescence quantum yield in water, a great enhancement in the fluorescence of the aggregated BSA adducts was achieved due to the abnormal aggregation‐induced emission properties of squaraines. The adducts formation was studied from a kinetic point of view showing unexpected structure–properties relationships.     

多芳基吡咯衍生物的发光性质及其应用

荧光分子在良溶剂中基本不发光或发光较弱,而在聚集状态下发光较强的现象,称为聚集诱导发光(Aggregation-induced emission,AIE)现象,这与传统的聚集导致猝灭(Aggregation-caused quenching,ACQ)现象相反。本文研究了多苯基吡咯衍生物的结构与发光性能的关系。通过比较吡咯衍生物的单晶结构和发光性质发现扭曲的结构可以限制共轭发光基团的分子内旋转(RIR),这是产生AIE现象的主要原因。羧酸化的吡咯衍生物可以对Al³⁺实时、选择性检测。由DMF诱导的三苯基吡咯羧酸衍生物(TPPA)重结晶在固态时出现可控的荧光发射,它具备很好的温度选择性,响应迅速,并可以循环利用,这证明TPPA可以作为一种热响应材料用于温度监控设备中。     

多壁纳米碳管/二氧化硅复合膜中的联吡啶钌电化学发光法测定氧氟沙星的研究与应用

基于氧氟沙星对联吡啶钌(Ru(bpy)_3~(2+))电化学发光的增敏作用,建立了一种以多壁纳米碳管(MWCNTs)/二氧化硅-联吡啶钌复合物修饰的玻碳电极电化学发光检测氧氟沙星的新方法.利用溶胶-凝胶(sol-gel)固定化稳定的优点和纳米碳管的电催化作用,提高了传感器的电流响应.在最佳实验条件下,氧氟沙星浓度在4.0×10~(-6) ～1.0×10~(-4) mol/L范围内与相对发光强度呈线性关系(r~2=0.994 8),检出限(S/N=3)为2.0×10~(-6) mol/L.连续平行测定2.4×10~(-5) mol/L的氧氟沙星溶液 5次,发光强度的RSD为1.8%.     

A novel tris(2,2′-bipyridine)ruthenium(II)/tripropylamine cathodic electrochemiluminescence in acetonitrile for the indirect determination of hydrogen peroxide

A novel tris(2,2′-bipyridine)ruthenium(II) (Ru(bpy)₃²⁺) cathodic electrochemiluminescence (ECL) was generated at −0.78 V at the Pt electrode in acetonitrile (ACN), which suggested that the cathodic ECL differed from conventional cathodic ECL. It was found that tripropylamine (TPrA) could enhance this cathodic ECL and the linear range (log-log plot) was 0.2 μM-0.2 mM. In addition, hydrogen peroxide (H₂O₂) could inhibit the cathodic ECL and was indirectly detected with the linear range of 27-540 μM. The RSD (n = 12) of the ECL intensity in the presence of 135 μM H₂O₂ was 0.87%. This method was also demonstrated for the fast determination of H₂O₂ in disinfectant sample and satisfactory results were obtained.