Mechanically controlled FRET to achieve high-contrast fluorescence switching

Organic luminescent materials with the ability to reversibly switch the luminescence when subjected to external stimuli have attracted considerable interest in recent years. However, luminescent materials with mechanochromic and photochromic dualresponsive properties are rarely reported. Hererin, we designed and synthesized a molecule P1 with dipeptide as a spacer to link rhodamine B and spiropyran moieties. P1 exhibited efficient photochromic properties both in solution and solid state. Highcontrast independent fluorescence switch was also realized under the stimulus of external force. Moreover, two-step ring opening reaction and subsequent fluorescence resonance energy transfer process between the donor-acceptor pairs within one single molecule achieved successive color switch by mechanical control. Therefore, this behavior of P1 made it a promising candidate for high-contrast and sensitive optical recording and mechanical sensing system.

Perylenediimide chromophore as an efficient photothermal agent for cancer therapy

Photothermal agents with improved bioavailabilities can generate heat from near-infrared light, which has been efficiently used for in vivo photothermal therapy （PTT） for cancer, with minimum tissue invasion. Strategies for developing organic near-infrared-absorbing molecules for phototfiermal cancer therapy have drawn intensive attention among academic investigators. However, conventional organic nearinfrared-absorbing molecules may not only have complex synthesis procedures, but also easily suffer from photobleaching under light irradiation. These drawbacks might lead to an increase in the synthesis cost, and elicit a risk of side effects in PTF. Thus, it is essential to devise an organic photothermal agent with stable phototbermal capacity, which involves a facile synthesis process. In this study, incorporating a secondary amine group （donor） in the bay regions of perylenediimides （PDls） could lead to a 150-nm bathochromic shift of the absorption maximum. Next, a modification of poly（ethylene glycol） （PEG） at the periphery of the chromophore renders the targeted macromolecule PDI-PEG highly water-soluble, and capable of intense absorption in the near-infrared region. The self-assembled PDl-based nanoparti- des （PDI-NPs） have a size of 55 nm in aqueous solutions. PDI-NPs with excellent photostability possess a high photothermal conversion efficiency of up to 43% ± 2%. Finally, PDI-NPs allow for efficient in vitro and in vivo photothermal cancer therapy. Meanwhile, PDI-NPs exhibit quite low cytotoxicity and no biotoxicity on major organs in vivo. Thus, these easily-manufactured PDI-NPs can serve as extremely stable photothermal agents for efficient photothermal cancer therapy.

Organic dye assemblies with aggregation-induced photophysical changes and their bio-applications

Phototheranostics provide a safe,effective,and noninvasive way for the diagnosis and treatment of contemporary diseases,and organic dyes play a vital role.For example,chemical modification endowed dyes with powerful reactive oxygen species or heat generation ability,favoring for photodynamic therapy and photoacoustic(PA)imaging guided photothermal therapy(PTT)of serious diseases.Therefore,photophysical properties manipulation of dyes has become the focus in current dye chemistry research.The development of aggregate science has made great effort to solve this problem.In recent years,a large number of studies have focused on molecular aggregation behavior and its effect on photophysical performance.The most famous example is the discovery of aggregation-induced emission(AIE)phenomenon.Based on AIE theory,more theories for revealing the relationship between molecular aggregation behavior and photophysical properties were proposed and elucidated.The photophysical property changes caused by dye aggregation have become a unique discipline,guiding the development of molecular science and material science.With the help of molecular self-assembly,controllable aggregation of dyes can be realized,and stable nano-theranostic reagents can be obtained.Furthermore,constructing dye assemblies with various photophysical properties will greatly reduce the cost of theranostic reagents,thus,expanding biomedical applications of organic dyes.Therefore,this review focuses on the photophysical characteristic changes caused by dye aggregation and their biological applications including,fluorescence/phosphorescence/PA imaging as well as photodynamic and PTT.This review will provide guidance for the design of organic dyes,the development of controllable aggregation methods,and the construction of multifunctional phototheranostic reagents.

Modulating planarity of cyanine dye to construct highly stable Haggregates for enhanced photothermal therapy

Self-assembly of dyes has become a flexible strategy to modulate their photophysical properties.H-aggregates show great potential to increase heat generation,while the precise designing of H-aggregates as efficient photothermal agents is still challenging.Herein,a quinoline cyanine(QCy)is developed for constructing stable H-aggregated nanoparticles(NPs)to significantly enhance photostability and photothermal conversion efficiency(PCE).With symmetrical rigid planar quinoline structures,QCy has a small and symmetrical dihedral angle(11.9°),which ensures excellent molecular planarity.In aqueous solution,the planar QCy can form closeπ–πmolecular stacking,and fast self-assemble into stable H-aggregates even at low concentrations(1×10−7 M).QCy H-aggregates are sphere-like NPs(QCy NPs)with an average diameter of 120 nm and exhibit high stability.H-aggregation of QCy significantly enhances PCE from 20.1%(non-H-aggregated QCy)to 63.8%(QCy NPs).In addition,the positive charge of quaternarized quinoline provides mitochondrial anchoring ability,which further enhances the photothermal effect.With high PCE and tumor accumulation,QCy NPs in low-doses have been successfully used in photoacoustic imaging-guided tumor photothermal therapy.

An AIE Star Polymer with Enhanced Co-Delivery of Drug and Gene for Synergistic Pest Control

Pesticides,as the most common means of pest managements,have caused a series of problems such as pest resistance and environmental pollution.Aggregation-induced emission(AIE)polymers exhibit great potential in biological applications because their fluorescent intensities significantly enhance in the aggregated state.In this paper,an AIE star polymer including a tetraphenyl ethylene(TPE)core and poly(2-(dimethylamino)ethyl methacrylate)arms is designed and further developed as a multi-functional nanocarrier for agricultural pest control.The nanocarrier shows high water solubility,good size stability and AIE imaging ability.Meanwhile,the twisted AIE core and positively charged polymer arms make the nanocarrier efficiently co-load dinotefuran(DIN)and dsRNA via hydrogen bonds and electrostatic interactions,respectively.The AIE star polymer displays low toxicity and high fluorescence traceability.As a result,the nanocarrier co-loading with DIN and dsRNA exhibits a highly synergistic insecticidal effect with higher pest mortality compared to the separate delivery of DIN and dsRNA.This study develops the AIE star polymer to improve the efficiency of co-delivery of drug and dsRNA and proposes a new strategy toward efficient and synergistic pest control.

Synthesis of water-soluble dye-cored poly(amidoamine) dendrimers for long-term live cell imaging

Hydrophilic dendrimers, especially poly（amidoamine）（PAMAM） dendrimers are widely applied in modifying fluorescent dyes to endow them with water solubility and biocompatibility for biologic fluorescence imaging.Common preparation strategies of fluorescent dendrimers including encapsulating dyes or attaching dyes at periphery of dendrimers might cause uncertain constituent and lower biocompatibility. Here, we have developed a series of watersoluble fluorescent dendrimers with dye as core and fanshaped PAMAM as arms. Carboxylated perylene bisimides（PBI） dye and squarylium indocyanine（SICy） dye were conjugated with PAMAM dendrons by amidation to obtain a series of fluorescent dendrimers with enhanced water-solubility. Two PBI based dendrimers（PBI-G2.5 and PBI-G1.5）were chosen as model compounds for further optical, selfassembly and biological studies. In aqueous environment,PBI-G2.5 exhibited strong fluorescence, small size（~30 nm）and slightly positive surface charge（~2.46 mV）, which are ideal for biomedical applications. In vitro assays demonstrated that PBI-G2.5 nanoparticles accumulated in the cytoplasm of He La cells with rapid cellular uptake. The strong fluorescence in He La cells remained for over 48 h. To conclude, our study provides an effective strategy for preparing water-soluble fluorescent dendrimers towards long-term live cell imaging.