Recovery of cyanophycin granule polypeptide from activated sludge: carbon source dependence and aggregation-induced luminescence characteristics

In the sewage treatment process,facilitating the conversion of pollutants into value-added resources holds great potential for reducing the amount of greenhouse gas emissions and promoting economic circulation.Cyanophycin granule polypeptide(CGP),a recently discovered high value-added biopolymer present in activated sludge,has provided new avenues for the recovery of resources.However,the mechanisms that regulate CGP synthesis and the characteristics of this biopolymer in activated sludge remain unclear thus far.This study investigated the synthesis of CGP,polyhydroxyalkanoates(PHA),and alginate-like exopolysaccharides(ALE)in various microbial aggregates under different carbon sources feeding conditions.Our results showed that the CGP yields was superior that of PHA and ALE when subjected to identical carbon source feeding conditions.Furthermore,biofilm was more conducive to CGP accumulation than floc sludge.Compared with glucose and methanol,sodium acetate significantly enriched the CGP synthetase-encoding gene(cphAabundance=~17419),resulting in the highest CGP yield(average 107.1 mg/g MLSS)in both biofilm and floc sludge.This study is the first to reported the characteristic fluorescence of CGP(Ex/Em=~360/450 nm)caused by the aggregated luminescence of arginine on the side chains.Overall,this study highlights the potential application of CGP as a fluorescent material and offers insights into CGP recovery from activated sludge in wastewater treatment plants.

Nucleophilic Substitution Polymerization-Induced Emission of 1,3-Dicarbonyl Compounds as a Versatile Approach for Aggregation-Induced Emission Type Non-Traditional Intrinsic Luminescence

Nucleophilic substitution reaction and 1,3-dicarbonyl compounds play significant roles in organic chemistry, and non-traditional intrinsic luminescence (NTIL) has become an emerging research area. Here, we demonstrate the successful nucleophilic substitution polymerization of 1,3-dicarbonyl compounds, including acetylacetone, 3,5-heptanedione, methyl acetoacetate, cyclopentane-1,3-dione, 1,3-indandione, 1-phenyl-1,3-butanedione and dibenzoylmethane, where reactive hydrogens at α position of 1,3-dicarbonyl compounds are involved. Through this base catalyzed nucleophilic substitution polycondensation between 1,3-dicarbonyl compounds and α,α’-dibromo xylene, a series of nonconjugated poly(1,3-dicarbonyl)s have been successfully prepared with high yield (up to >99%) under mild conditions. Investigations reveal that this nucleophilic substitution polycondensation exhibits self-accelerating effect and flexible stoichiometry characteristics, which exhibits advantages over traditional polycondensation methods. This polymerization also exhibits intriguing polymerization-induced emission (PIE) characteristics, where nonconjugated poly(1,3-dicarbonyl)s exhibit intriguing chemical structure dependent aggregation-induced emission (AIE) type NTIL. This work therefore expands the monomer, method, chemical structure and property libraries of polymer chemistry, which may cause inspirations to polymerization methodology, PIE, AIE and NTIL.

A novel BODIPY-based nano-photosensitizer with aggregation-induced emission for cancer photodynamic therapy

The discovery of aggregation induced enmission(AIE)effect provides opportunities for the rapid development of fuorescence imaging-guided photodynamic therapy(PDT).In this work,a boron dipyrromethene(BODIPY)-based photosensitizer(ET-BDP-O)with AIE characteristics was developed,in which the two linear arms of BODIPY group were linked with triphenylamine to form an electron Donor-Acceptor-Donor(D-A-D)architecture while side chain was equipped with triethylene glycol group.ET-BDP-O was able to directly self-assemble into nanoparticles(NPs)without supplement of any other matrices or stabilizers due to its amphiphilic property.The as-prepared ET-BDP-O NPs had an excellent colloid stability with the size of 125 nm.Benefiting from the AIE property,ET-BDP-O NPs could generate strong fluorescence and reactive oxygen species under light-emitting diode light rradiation(60mW/cm^(2)).After inter-nalized in cancer cells,ET-BDP-O NPs were able to emit bright red fuorescence signal for bioimaging.In addition,the cell viability assay demonstrated that the ET-BDP-O NPs exhibited excellent photocytotoxicity against cancer cells,while negligible cytotoicity under dark envi-ronment.Thus,ET-BDP-O NPs might be regarded as a promising photosensitizer for fluores-cence imaging-guided PDT in future.

Aggregation-induced emission polymer systems with circularly polarized luminescence

Functional materials with circularly polarized luminescence(CPL)have attracted tremendous attention due to their promising applications in three-dimensional dis-plays,chiral recognition and catalysis,photoelectronic devices,contrast imaging,information encryption,and otherfields.Among various CPL-active materials,poly-meric systems with aggregation-induced emission(AIE)have emerged as excellent candidates because of their efficient aggregate-statefluorescence,large solid-state dissymmetry factor,excellent processibility,diversified self-assembly behaviors,and readily switchable CPL properties.This review summarizes and discusses the recent progress as well as future perspective of diverse AIE polymer systems with CPL,including CPL-active covalent AIE polymers,CPL-active supramolecular AIE polymers,and AIEgen/polymer composites with CPL.According to the loca-tion or introduction method of AIEgen in polymer structures,this review further divides CPL-active covalent AIE polymers into three categories,including polymers with AIEgen in main chains,polymers with AIEgen in side chains,and CPL-active polymers with clusterization-triggered emission.CPL-active supramolecular AIE polymers are discussed based on the driving force for the formation of supramolecular polymers,including host–guest interactions,metal coordination,and other non-covalent interactions.Moreover,examples on the construction of CPL-active AIEgen/polymer composites by physically mixing AIEgens with chi-ral(supra)polymers are also presented.This review is anticipated to provide readers with an overall view on the design strategies of CPL-active AIE polymers,and facil-itate further research on the development of CPL materials and AIE polymers with advanced applications.

Novel strategy of multidimensional information encryption via multi-color carbon dots aggregation-induced emission

Carbon dots(CDs)with aggregation-induced emission(AIE)have sparked significant interest in multidimensional anti-counterfeiting due to their exceptional fluorescence properties.However,the preparation of AIE CDs with multicolor solid-state fluorescence remains a formidable challenge due to its complicated construction.In the present work,a novel class of multicolor AIE CDs(M-CDs)were fabricated using selected precursor(salicylic acid,thiosalicylic acid,and 2,2'-dithiodibenzoic acid),with an eco-friendly,low-cost one-pot solvothermal method.In the dilute organic solution,M-CDs manifested blue emission,but upon aggregation in the presence of water,the red,yellow,green,and blue emissions were displayed due to the AIE effect.Structural analysis,coupled with theoretical calculations,revealed that the increase in the size of sp2 domains would lower the Eg and cause a red-shift emission wavelength.Significantly,the continuous emission of M-CDs from blue to red can be utilized as ink for multimode printing,enabling the creation of a variety of school badges and quick response codes.These findings hold promising implications for multi-information encryption applications.

A supramolecular self-assembly material based on cucurbituril and cationic TPE as ultra-sensitive probe of energetic pentazolate salts

The successful synthesis of the pentazolate anion(cyclo-N-5)has been a great breakthrough in the field of energetic materials.However,the detection methods for these energetic materials based on the pentazolate anion are quite rare.Herein,two fluorescent probes for cyclo-N-5anion were designed.Sensor 1(TPE2N)was synthesized with a tetraphenylethylene functionalized by two cationic groups which can generate strong electrostatic interactions with pentazolate anion and result in specific fluorescent changes.Sensor 2 was designed based on sensor 1 and supramolecular cucurbit[7]uril(CB[7]).The unique structural features of CB[7]provide sites for the interaction between the cations and N-5anion in its cavity,which would generate a platform for the detection and enhance the recognition performance.Isothermal titration calorimetry(ITC)experiment and fluorescence titration experiment indicate the binding molar ratio between sensor 1 with CB[7]is 1:2.Both sensors display typical aggregation-induced emission(AIE)features and good water-solubility.The sensors demonstrate excellent sensitivity to pentazole hydrazine salt with high enhancement constant(sensor 1:1.34×10^(6);sensor 2:3.78×10^(6))and low limit of detection(LOD:sensor 1=4.33μM;sensor 2=1.54μM).The formation of an AIE-based supramolecular sensor effectively improves the sensitivity to N-5anion.In addition,the probes also have good selectivity of N-5anion salts.The research would shed some light on the design of novel fluorescent sensors to detect pentazolate-based molecules and provides an example of supramolecular chemistry combined with fluorescent probes.

固液态均荧光发射的四苯乙烯基衍生物的合成

为了打破传统荧光材料的聚集荧光淬灭(ACQ)的应用限制,通过共价键连接聚集诱导发光(AIE)分子与平面ACQ分子,可以构建在溶液中和固态下都具有荧光发射特性的化合物。分别通过多步反应合成了带有烷基硫醚的萘酰亚胺衍生物3和连接炔吡啶的四苯乙烯衍生物7。化合物3和化合物7通过酰胺缩合,合成了一种四苯乙烯-萘酰亚胺二联体化合物8,化合物8兼具ACQ和AIE分子的特性。结果表明:溶液状态下化合物8具有蓝色荧光发射,其最大发射峰位于452 nm,固态下为黄绿色荧光,最大发射峰位于487 nm。利用三氟乙酸对其荧光进行调控能够实现CIE色坐标为(0.33,0.32)的单分子白光发射。

Blue fluorophores comprised of tetraphenylethene and imidazole： aggregation-induced emission and electroluminescence

By melting tetraphenylethene （TPE） and 1,2,4,5-tetraphenyl-lH-imidazole （TPI） units together through different linking positions, three new fluorophores are synthesized, and their optical, electronic and electro- luminescence （EL） properties are fully studied. Owing to the presence of TPE unit（s）, these fluorophores are weak emitters in solutions, but are induced to emit strongly in the aggregated state, presenting typical aggregation-induced emission characteristics. The experimental and computational results reveal that different connection patterns between TPE and TPI could impact the molecular conjugation greatly, leading to varied emission wavelength, fluorescence quantum yield and EL performance in organic light emitting diodes （OLEDs）. The fluorophore built by attaching TPE unit to the 1-position of imidazole ring shows bluest fluorescence, and its EL device emits at deep blue region （445 nm; CIE= （0.16, 0.15））. And the device based on the fluorophore by linking TPE to the 2- position of imidazole ring shows EL at 467 nm （CIE= （0.17, 0.22）） with good efficiencies of 3.17 cd.A ^-1, and 1.77%.

蒽修饰的四苯乙烯衍生物的合成及发光特性研究

四苯乙烯衍生物独特的发光性质使其在成像、传感等众多领域受到了广泛的关注。通过将四苯乙烯与荧光基团蒽相连构筑了化合物4,4′-二(9-蒽甲基氨甲基)四苯基乙烯(TPE-AN),研究表明在四氢呋喃和水的混合体系中随着化合物的聚集,其表现出蒽的单体发射、蒽的激基缔合物发射和四苯乙烯的聚集诱导发光特性。除此之外,TPE-AN表现出可逆的机械变色性能,研磨可导致其发射波长的红移,并伴随着荧光量子产率的下降和荧光寿命的增加,溶剂熏蒸又能使其恢复至初始状态。进一步的研究表明TPE-AN的机械变色特性是由四苯乙烯和蒽单元共同决定的。

Aggregation-induced emission meets magnetic bistability: Synergy between spin crossover and fluorescence in iron(Ⅱ) complexes

Luminescent spin crossover(SCO) materials have attracted significant interest owing to their potential applications in magneto-optical switches. However, the majority of previously reported FeII-based SCO complexes are adversely affected by fluorescence quenching in the solid-state. Here, we have constructed the first mononuclear FeIIcomplex decorated with an aggregation-induced emission(AIE) luminophore(i.e., tetraphenylethylene) that exhibits synergistic SCO and fluorescence behavior. Intriguingly, we obtained two types of crystals in different solvent systems, both displaying distinct magnetic bistability and fluorescence properties. The fluorescence intensity was observed to track the magnetic susceptibility, which confirmed that SCO and solid-state fluorescence operate synergistically. We introduce a novel approach for the construction of luminescent SCO compounds using an AIEgen as a luminophore, which leads to fluorescence emission in the solid-state, thus allowing us to study the synergy between SCO and fluorescence.

Aggregation-induced Emission of Non-conjugated Poly(amido amine)s:Discovering,Luminescent Mechanism Understanding and Bioapplication

It is found that the fluorescence of aliphatic poly（amido amine）s including linear and hyperbranched ones can be dramatically enhanced by simple aggregation of polymer chains, attributing to the formation of a variety of intra- and interchain clusters with shared lone-pair electrons and the restriction of intramolecular motions. Thanks to the combination of strong solid fluorescence and excellent biocompatibility, these non-conjugated polymers become promising candidates for bioimaging such as bacterial detection. This finding not only extends the aggregation-induced emission（AIE） systems from conjugated compounds to non-conjugated materials, which expands the bioapplication range of AIE systems, but also sheds light on the exploration of novel unconventional luminogens.

一种具有AIE+ESIPT双重属性的席夫碱类荧光探针的合成及在铜离子检测中的应用

设计合成了一种具有聚集诱导发光(AIE)和激发态分子内质子转移(ESIPT)双重属性的席夫碱类荧光探针1。该探针在聚集态下发橙色荧光并表现出较大的斯托克斯(Stokes)位移。实验结果表明,探针1对Cu^(2+)有较高的选择性和灵敏度,检测限为95 nmol/L。Job’s plot曲线分析和质谱结果表明,探针1和Cu^(2+)结合形成1∶1的配合物,阻断了分子原有的ESIPT过程,最终导致荧光淬灭。该探针可用于实际水样中Cu^(2+)的检测。

Aggregation-induced conversion from TADF to phosphorescence of gold(I)complexes with millisecond lifetimes

Long-lived luminescent materials possess wide application prospects in various areas,but their constructions still face a huge challenge,especially the achievement in solution.Manipulating aggregate is an effective method to attain intriguing luminescence,thus it is expected to build long-lived materials in solution.In this work,a series of new gold(I)complexes were developed by employing unique carbazole and phosphine as the ligands,and these resulting systems exhibited rare long lifetimes of milliseconds in the aggregate state.It was well unveiled that these complexes emitted blue thermally activated delayed fluorescence(TADF)with the lifetimes of several microseconds in dilute solution;while orange-red phosphorescence with much longer lifetimes of several milliseconds were achieved in the aggregate state.To our knowledge,this is the first implementation of aggregation-induced conversion from TADF to phosphorescence.Based on their excellent luminescent properties,we successfully applied these complexes in cell imaging and inhibition of cancer cells.

Two-color emissive AIEgens with anti-Kasha property for dual-organelle imaging and phototherapy

Despite the rapid development of probes for targeting single organelle, the construction of robust dual-organelle targeting probes with multicolor emission was rarely reported. Herein, two dual-emissive aggregation-induced emission luminogens(AIEgens)with donor-π-acceptor structures were designed and synthesized, namely QT-1 and QF-2. Both two AIEgens exhibited excitation wavelength-dependence defying the Kasha's rule, and could stain lipid droplets(LDs) and mitochondria in blue and red fluorescence, respectively. Moreover, thanks to the near-infrared emission and abundant reactive oxygen species(ROS) generation efficiency of QT-1, it was chosen as a photodynamic therapy agent to selectively kill cancer cells from normal cells. Upon light irradiation, an obvious decrease of mitochondrial membrane potential(MMP) and serious change of mitochondrial shape in cells were observed, which corresponded to the efficient inhibition of tumor growth in vivo. This work afforded a promising strategy for the construction of multicolor emission by tuning anti-Kasha behaviors and expanding their application in dualorganelle targeting-based phototheranostics.

Fjord-Type AIEgens Based on Inherent Through-Space Conjugation

Through-space conjugation(TSC)is a noncovalently electronic interaction that is emerging as a potential complement to through-bond conjugation(TBC)-based strategies for constructing luminescent materials.However,the design of efficient luminogens based on TSC is currently challenging due to a lack of established structure-property understanding.This is particularly true in the case of luminogens displaying aggregation-induced emission(AIE)effects.In this work,three terphenyl derivatives were prepared,and their photophysical properties were systemically studied.It was found that relative to the corresponding m-and p-linked analogues,the electronic interaction of TBC is weakened while the strength of TSC is commensurately enhanced in the constitutional isomer containing an o-linked fjordtype subunit.Within this set of luminogens,the presence of a fjord-type arrangement promotes a transformation from aggregation-caused quenching to AIE.Further investigations involving congeneric quaterphenyl and pentphenyl isomers support the universality of the fjord-type unit as a framework for synthesizing AIE-active luminogens(AIEgens)with inherent TSC.This work not only provides a novel set of AIEgens but also establishes the utility of TSC in controlling the photophysical properties of nonconventional and twisted luminogens.

Red-emitting tetraphenylethylene derivative with aggregation-induced enhanced emission for luminescent solar concentrators:A combined experimental and density functional theory study

This study examines the use of an aggregation-induced enhanced emission fluorophore(TPE-MRh)to prepare red-emitting luminescent solar concentrators(LSCs)based on poly(methyl methacrylate)(PMMA)and poly(cyclohexyl methacrylate)(PCMA).TPE-MRh is a tetraphenylethylene(TPE)derivative bearing two dimethylamino push groups and a 3-methyl-rhodanine pull moiety,with absorption maxima at around 500 nm and fluorescence peak at 700 nm that strongly increases in solid-state.TPE-MRh displays a typical crystallizationinduced enhanced emission that has been rationalized by modeling the compound behavior in solution and solid-state via density functional theory calculations with the inclusion of the environment.TPE-MRh dispersed into 5×5 cm2 polymer films with a thickness of 25±5μm has revealed a partial fluorescence quenching with fluorophore content.Quantum yields(QYs)below 10%for the 2 wt.%of doping have been addressed to the formation of less emissive micro-sized clusters of fluorophores.PMMA slabs with the same surface size but 3 mm of thickness and 200 ppm of TPE-MRh have provided QY of 36.5%thanks to the attenuation of the detrimental effects of fluorophore aggregation.This feature is reflected in the LSCs performance,with devices achieving the largest power collected by the photovoltaic cell.

团结就是力量,独立才能发光——关于AIE和ACQ效应的科普实验

发光材料在生活中具有诸多的应用,但目前面向公众的有关发光材料尤其是ACQ和AIE分子的发光现象及其光学性能研究的普及实验仍有欠缺。本实验是以科普为目的,分别针对各个年龄段的受众设计了特色性普及实验;同时,本实验也是一个多场景适用性科普实验,分别于线上线下多渠道进行展示。实验步骤简单易行,色彩丰富,发光效果明显。既便于操作,又能极大地让公众了解生活中的发光分子,更重要的是本实验可以有效引导青少年发现、提出并解决科学问题,更有利于实现对青少年一定程度上的研究性思维与方法的培养,具有一定创新性。

Biocompatible organic dots with aggregation-induced emission for in vitro and in vivo fluorescence imaging

Fluorescent probes play a key role in modern biomedical research. As compared to inorganic quantum dots (QDs) composed with heavy metal elements, organic dye-based fluorescent nanoparticles have higher biocompatibility and are richer in variety. However, traditional organic fluorophores tend to quench fluorescence upon aggregation, which is known as aggregation-caused quenching (ACQ) effect that hinders the fabrication of highly emissive fluorescent nanoparticles. In this work, we demonstrate the synthesis of organic fluorescent dots with aggregation-induced emission (AIE) in far-red/near-infrared (FA/NIR) region. A conventional ACQ-characteristic fluorescent dye, 3,4:9,10-tetracarboxylic perylene bisimide (PBI), is converted into an AIE fluorogen through attaching two tetraphenylethylene (TPE) moieties. The fluorescent dots with surface folic acid groups are fabricated from PBI derivative (DTPEPBI), showing specific targeting effect to folate receptor-overexpressed cancer cells. In vivo studies also suggest that the folic acid-functionalized AIE dots preferentially accumulate in the tumor site through enhanced permeability and retention (EPR) effect and folate receptor-mediated active targeting effect. The low cyto-toxicity, good FR/NIR contrast and excellent targeting ability in in vitro/in vivo imaging indicate that the AIE dots have great potentials in advanced bioimaging applications.

Tetraphenylethylene-BODIPY aggregation-induced emission luminogens for near-infrared polymer light-emitting diodes

The aggregation-induced emission(AIE) phenomenon provides a new direction for the development of organic light-emitting devices. Here, we present a new class of emitters based on 4,4-difluoro-4-bora-3 a,4 a-diaza-s-indacene(BODIPY), functionalized at different positions with tetraphenylethylene(TPE), which is one of the most famous AIE luminogens. Thanks to this modification, we were able to tune the photoluminescence of the BODIPY moiety from the green to the near-infrared(NIR)spectral range and achieve PL efficiencies of ~50% in the solid state. Remarkably, we observed an enhancement of the AIE and up to ~100% photoluminescence efficiencies by blending the TPE-substituted BODIPY fluorophores with a poly[(9,9-di-noctylfluorene-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,7-diyl)](F8 BT) matrix. By incorporating these blends in organic lightemitting diodes(OLEDs), we obtained electroluminescence peaked in the range 650–700 nm with up to 1.8% external quantum efficiency and ~2 m W/cm2 radiance, a remarkable result for red/NIR emitting and solution-processed OLEDs.

Frontiers in circularly polarized luminescence:molecular design,self-assembly,nanomaterials,and applications

The research in circularly polarized luminescence has attracted wide interest in recent years.Efforts on one side are directed toward the development of chiral materials with both high luminescence efficiency and dissymmetry factors,and on the other side,are focused on the exploitations of these materials in optoelectronic applications.This review summarizes the recent frontiers(mostly within five years)in the research in circularly polarized luminescence,including the development of chiral emissive materials based on organic small molecules,compounds with aggregation-induced emissions,supramolecular assemblies,liquid crystals and liquids,polymers,metal-ligand coordination complexes and assemblies,metal clusters,inorganic nanomaterials,and photon upconversion systems.In addition,recent applications of related materials in organic light-emitting devices,circularly polarized light detectors,and organic lasers and displays are also discussed.