Intramolecular Charge Transfer Effect Research Articles

Benzo[1,2-b:6,5-b’]dithiophene-4,5-diamine: A New Fluorescent Probe for the High-Sensitivity and Real-Time Visual Monitoring of Phosgene

The detection of highly toxic chemicals such as phosgene is crucial for addressing the severe threats to human health and public safety posed by terrorist attacks and industrial mishaps. However, timely and precise monitoring of phosgene at a low cost remains a significant challenge. This work is the first to report a novel fluorescent system based on the Intramolecular Charge Transfer (ICT) effect, which can rapidly detect phosgene in both solution and gas phases with high sensitivity by integrating a benzo[1,2-b:6,5-b’]dithiophene-4,5-diamine (BDTA) probe. Among existing detecting methods, this fluorescent system stands out as it can respond to phosgene within a mere 30 s and has a detection limit as low as 0.16 μM in solution. Furthermore, the sensing mechanism was rigorously validated through high-resolution mass spectrometry (HRMS) and density functional theory (DFT) calculations. As a result, this fluorescent probing system for phosgene can be effectively adapted for real-time, high-sensitivity sensing and used as a test strip for visual monitoring without the need for specific equipment, which will also provide a new strategy for the fluorescent detection of other toxic materials.

Twisted Cucurbit[14]uril‐based Supramolecular Self‐Assembly Induces Fluorescence Emission of Dye Molecules for Multi‐Channel Cell Imaging

In this study, a supramolecular fluorescent material was constructed by using double‐cavity twisted cucurbit[14]uril (tQ[14]) and positively charged Astrazon Pink FG (APFG) based on the non‐covalent host‐guest interaction for the first time. The thermodynamic parameters of the APFG@tQ[14] in aqueous solution were determined by isothermal titration calorimetry (ITC), the results indicated that the spontaneous assembly of APFG@tQ[14] is mainly driven by enthalpy. The intramolecular charge transfer (ICT) effect induced the APFG@tQ[14] probe to emit a strong orange‐red fluorescence. Due to its good optical properties and low toxicity, APFG@tQ[14] was successfully applied to multi‐channel imaging of HK2 cells. This demonstrates the great potential of APFG@tQ[14] in labeling and tracking living cells.

A Facile and Efficient Synthesis of BODIPY-Based Fluorescent Probes for Selective Detection of Hydrazine.

A facile and ratiometric BODIPY-based fluorescent probe 4 was developed for the selective detection of hydrazine in solution phase. The BODIPY-based fluorophores 3 and 4 were easily prepared in high yields from the L-proline catalyzed reaction between α/β-formyl BODIPY 1 a/1 b and 3-cyanoacetylindole 2. Use of easily accessible substrates, benign solvent, catalytic amount of L-proline and high product yields are the advantageous features of the developed protocol. Prepared BODIPYs 3 (536 nm) and 4 (567 nm) showed bathochromic shifts (36-67 nm) in UV-Visible absorption maxima when compared to parent BODIPY (500 nm) in dichloromethane (DCM). The stable and economical BODIPY-based probe 4 exhibited rapid response and remarkable selectivity towards hydrazine when compared to other commonly occurring analytes. At low concentration, the BODIPY probe 4 (10 μΜ) is non-fluorescent, however, a significant enhancement in fluorescent (turn-on) was observed with the increasing concentration of hydrazine (0-100 μΜ). This change in fluorescent behaviour may be ascribed to intramolecular charge transfer (ICT) effect as supported by density functional theory (DFT) calculations. With a 4.3 μM detection limit, the BODIPY probe 4 was also found to be useful in detecting hydrazine in real environmental samples.

A novel mitochondrial-targeted fluorescent probe for ratiometric imaging of nitric oxide in cells and zebrafish.

Nitric oxide (NO) is a key signaling molecule that regulates energy metabolism, apoptosis, and antioxidant balance within mitochondria. It is closely associated with the development of cardiovascular diseases, neurodegenerative diseases, and cancer. Therefore, developing fluorescent probes capable of accurately detecting NO levels in mitochondria is essential for understanding disease mechanisms and clinical diagnostics. In this study, we developed a novel fluorescent probe based on the isophorone fluorophore. This probe achieves high sensitivity and specific ratiometric detection of NO in mitochondria by regulating the intramolecular charge transfer (ICT) effect. The probe emits red fluorescence before reacting with NO, and the addition of NO triggers an amine-NO addition reaction that inhibits the ICT effect, resulting in a color change to yellow-green fluorescence. This ratiometric fluorescence response provides a new method for quantitatively detecting NO. Additionally, the probe has a significant Stokes shift and good ratiometric wavelength separation, enhancing detection accuracy. It localizes explicitly to mitochondria, directly reflecting changes in mitochondrial NO concentration. Experiments in HeLa cells and zebrafish models have demonstrated the potential application of the probe in diagnosing and studying NO-related diseases. This provides new strategies and tools for researching the biological functions of NO and the early diagnosis of related diseases.

Robust Fluorescent Nanoprobe for Rapid Evaluation of the Selenium Supplementation Effect and Imaging.

At present, an increasing number of people pay more attention to selenium-enriched food, but the quality of the selenium-enriched food varies. Therefore, there is an urgent need to develop a new tool to assess the effects of selenium supplementation in foods by rapidly detecting the levels of the metabolite selenium selenocysteine (Sec). In this work, a fluorescent nanoprobe CS-Sec was designed, synthesized, and characterized for Sec detection and imaging in living biosystems, which exhibited the advantages of good biocompatibility, excellent water solubility, high sensitivity, high selectivity, and rapid response (2.5 min) for Sec detection and imaging in vitro and in vivo and evaluation of selenium supplementation in selenium-rich foods. Specifically, CS-Sec was constructed by grafting alkyne groups on organic small-molecule fluorescent probes with azide groups on azido chitosan by click chemistry. A 2,4-dinitrophenyl ether (DNB) with a strong intramolecular charge transfer (ICT) effect was selected as a response group and fluorescence-quenching group, which had excellent chemical specificity toward Sec. In addition, CS-Sec has high selectivity and sensitivity toward Sec over other analytes, and an excellent limit of detection (LOD) is as low as 15 nM. Impressively, CS-Sec has been successfully used to detect and image the concentration of Sec in living HepG2 cells and mouse models with exciting results, indicating that the newly constructed CS-Sec can provide a robust molecule tool for the rapid evaluation of the selenium supplementation effect and imaging in the future.

Construction of carbazole-conjugated dual-emission fluorescent covalent organic framework for distinguishing p-nitroaniline/p-nitrophenol and adsorbing nitroanilines/nitrophenols

Nitroanilines (NAs) and nitrophenols (NPs), crucial industrial raw materials, are extensively utilized across various sectors. However, the environmental pollution and health hazards stemming from their usage are significant, necessitating urgent monitoring and removal to address environmental and safety concerns. The challenge is further compounded by the presence of NAs/NPs isomers, making the selective analysis of specific isomers crucial. In response, a new post-modified fluorescent covalent organic framework (COF) termed COF@CB, exhibiting dual-emission fluorescence, was synthesized. This synthesis involved coupling a high-crystallinity fluorescent COF (COF-TTDB) with carbazole-9-ethanol (CB) via a “Williamson” reaction. COF@CB featured exceptional dual-emission fluorescence, a high specific surface area (919.4 m2·g−1), superior thermal stability, and abundant active sites. These attributes enabled COF@CB to function as a ratiometric fluorescence sensor capable of simultaneous detection and adsorption. The distinct number and arrangement of hydrogen bond sites in NAs/NPs isomers influenced the intramolecular charge transfer (ICT) effects on COF@CB, thereby enabling the COF@CB-ratiometric fluorescence sensor to distinguish and selectively detect p-NA/p-NP from isomers. Analysis of actual water samples further underscored the sensor's effectiveness in detecting p-NA/p-NP. Furthermore, the presence of multiple active sites on the COF@CB-ratiometric fluorescence sensor facilitated the adsorption of NAs/NPs, promoting the removal of them from actual samples.

A porphyrin-based colorimetric and near infrared fluorescent probe for reversible and rapid detection of diethyl chlorophosphate

Given the extremely high toxicity of nerve agents, developing methods for their detection with high sensitivity and specificity is of great significance. In this study, we present single pyridyl-porphyrin (TPPyP) as an effective fluorescent probe for the reversible and rapid detection of the nerve agent simulant diethyl chlorophosphate (DCP). The probe demonstrates excellent spectral properties, with DCP rapidly reacting with the pyridine and pyrrole groups on TPPyP, leading to an enhanced intramolecular charge transfer (ICT) effect. This results in a distinct color change from pink to bright green, accompanied by a gradual disappearance of red fluorescence, all occurring within 35 seconds. Furthermore, the probe can be retrieved from the detection solution by introducing triethylamine, allowing for reversible detection of DCP. Additionally, TPPyP-loaded filter paper serves as a convenient tool for visualizing gaseous DCP. In solution, the probe exhibits sensitive detection capabilities, and when applied to DCP vapor detection, the filter paper shows a color transition and a reduction in red fluorescence that can be quantitatively analyzed using a smartphone application. The green-to-red ratio (G/R) correlates linearly with DCP concentrations in the range of 0–14 ppm, showcasing the probe's potential for field applications. Selectivity and anti-interference tests reveal that only DCP affects the probe's response, confirming its robustness against common interferents. Overall, this TPPyP-based probe offers a rapid, sensitive, and portable solution for detecting nerve agents, with promising implications for environmental monitoring.

An AIE-TICT fluorescence probe cascade responsive to H2S, polarity and viscosity to track microenvironment changes in cellular model of ischemia-reperfusion injury

BackgroundIschemia-reperfusion injury is a common cause of cardiovascular and cerebrovascular diseases. The reoxygenation during reperfusion leads to an overproduction of reactive oxygen species (ROS). As an antioxidant, H2S can scavenge ROS to inhibit oxidative stress and inflammatory reaction, thus attenuating ischemia-reperfusion injury. In this process, the changes of cellular microenvironment (polarity or viscosity) have not been fully discussed. In order to real-time track the changes of cellular microenvironment during the treatment of ischemia-reperfusion injury with H2S. It is necessary to develop highly selective and sensitive probes that can cascade response to hydrogen sulfide and cellular microenvironment. ResultsWe designed and synthesized a fluorescent probe TPEC-DNBS which can produce cascade response to H2S and microenvironment. An intermediate TPEC-OH is produced after highly selective and sensitive response to H2S, which can further respond to polarity and viscosity. In addition, due to the aggregation-induced emission (AIE) and twisted intramolecular charge transfer (TICT) effects, polarity can promote the fluorescence emission wavelength and intensity of TPEC-OH to produce double response characteristics, and its change trend (from weak green fluorescence at low polarity to strong red fluorescence at high polarity) is opposite to that of traditional polar probes (from strong green fluorescence at low polarity to weak red fluorescence at high polarity). Viscosity can only induce the change of fluorescence intensity. By constructing the cardiomyocyte model and hepatocyte model of ischemia-reperfusion, we further prove that after ischemia-reperfusion injury, the cells are in an environment of low polarity, and the microenvironment can be recovered after H2S treatment. SignificanceAn AIE-TICT fluorescence probe capable of cascading responses to H2S, polarity and viscosity was constructed by using tetraphenylethylene and coumarin moieties. This probe provides a more intuitive and convenient condition for real-time tracking the changes of cellular microenvironment (polarity or viscosity) before and after H2S treatment of ischemia-reperfusion injury.

Dipole Moment Modulation of Terminal Groups Enables Asymmetric Acceptors Featuring Medium Bandgap for Efficient and Stable Ternary Organic Solar Cells.

This study puts forth a novel terminal group design to develop medium-band gap Y-series acceptors beyond conventional side-chain engineering. We focused on the strategical integration of an electron-donating methoxy group and an electron-withdrawing halogen atom at benzene-fused terminal groups. This combination precisely modulated the dipole moment and electron density of terminal groups, effectively attenuating intramolecular charge transfer effect, and widening the band gap of acceptors. The incorporation of these terminal groups yielded two asymmetric acceptors, named BTP-2FClO and BTP-2FBrO, both of which exhibited open-circuit voltage (Voc) as high as 0.96 V in binary devices, representing the highest VOCs among the asymmetric Y-series small molecule acceptors. More importantly, both BTP-2FClO and BTP-2FBrO exhibit modest aggregation behaviors and molecular crystallinity, making them suitable as a third component to mitigate excess aggregation of the PM6 : BTP-eC9 blend and optimize the devices' morphology. As a result, the optimized BTP-2FClO-based ternary organic solar cells (OSCs) achieved a remarkable power conversion efficiency (PCE) of 919.34 %, positioning it among the highest-performing OSCs. Our study highlights the molecular design importance on manipulating dipole moments and electron density in developing medium-band gap acceptors, and offers a highly efficient third component for high-performance ternary OSCs.

Regulating the Twisted Intramolecular Charge Transfer and Anti-heavy Atom Effect at Supramolecular Level for Favorable Photosensitizing Activity in Water.

Photosensitizing assemblies based on twisted intramolecular charge transfer (TICT) active donor-acceptor-donor (D-A-D) system BrTPA-Qx having bromine atoms at the periphery have been developed. Through strategic incorporation of bromine atoms at the para-position to the nitrogen-carbon bonds of phenyl rings at the periphery, halogen-halogen interactions are induced in BrTPA-Qx nanoassemblies in H2O:DMSO (99:1) solution. Hence, the anti-heavy atom effect is induced, and the limitations of TICT (dark excited state) and heavy atom effect (triplet deactivation via radiative decay) could be overcome. Because of TICT and anti-heavy atom effect, supramolecular BrTPA-Qx nanoassemblies demonstrate high efficiency in promoting activation of aerial oxygen via electron and energy transfer pathways in aqueous media. The significant influence of the stabilized TICT state and anti-heavy-atom effect in controlling the ROS generation was validated through in-depth solvent-dependent photophysical studies and investigations of the structure-activity relationship in several model compounds. The notable photosensitizing activity of BrTPA-Qx nanoassemblies is manifested in their ability to efficiently catalyze the oxidative coupling of benzylamine (via type I and type II mechanisms), Knoevenagel condensation of aromatic aldehydes (type II), and oxidative hydroxylation of arylboronic acids (type I) under mild conditions.

Effect of Peripheral Functionalization of Pt(II) Porphyrin(2.1.2.1) on Singlet Oxygen Generation.

Four structurally bent porphyrin(2.1.2.1) Pt(II) complexes have been obtained and verified well. Main absorbance of Pt(II) porphyrin(2.1.2.1) displayed a significant red-shift compared to that of porphyrin(1.1.1.1) Pt(II) molecules. 1O2 study indicated that electron-withdrawing group and intramolecular charge transfer effect synergistically endowed Pt(II) porphyrin(2.1.2.1) with good singlet oxygen-sensitizing capacity under blue LED light irradiation. This work presents a simple synthesis way to develop a new series of efficient porphyrinoid singlet oxygen photosensitizers for PDT through molecular engineering.

Thermo-controlled Water Microenvironment Inducing Fluorescence Enhancement of Chalcone Nanohydrogels for Mitochondrial Temperature Sensing.

Developing aggregation-induced emission (AIE)-based hydrogels that exhibit fluorescence enhancement as to thermal properties is an interesting and challenging task. In this work, we employed the fluorophore 2'-hydroxychalcone (HC), fluorescence properties of which are easily influenced by the excited-state intramolecular proton transfer and twisted intramolecular charge transfer (TICT) effects, to develop a novel type of temperature-sensitive polymers, hydroxychalcone-based polymers (HCPs). By controlling the temperature-dependent water microenvironments in HCPs, the intramolecular hydrogen bonds between water and HCPs can be regulated, thereby influencing the TICT process and leading to thermo-induced fluorescence enhancement, which shows a contrary tendency compared to typical AIEgens that always exhibit fluorescence attenuation as the thermal energy accelerates the molecular motion. Following the decoration with triphenylphosphine, the resulting polymer P-HCP assembled into nanohydrogels and served as a fluorescent probe for intracellular mitochondrial temperature sensing.

Symmetrically Fluorinated D-π-A Structured Cyanine Dye for Highly Efficient NIR-II Imaging-Guided Cancer Phototheranostics.

Near-infrared-II (NIR-II) fluorescence imaging-guided photothermal therapy (PTT) represents a cutting-edge approach for precise tumor diagnosis and treatment, providing real-time therapeutic efficacy evaluation. However, a significant challenge lies in the creation of phototheranostic agents that provide robust imaging and efficient photothermal conversion. To address this, a donor-π-acceptor (D-π-A) structure heptamethine cyanine derivative, IR1116, that confers a strong intramolecular charge transfer effect is developed. To enhance its applicability, IR1116 is formulated with DSPE-PEG to create a water-dispersible NIR-II phototheranostic nanoheater, NPIR1116. This nanoheater benefits from the incorporation of an electron-withdrawing group, leading to reduced photooxidation activity and significantly improved photostability. NPIR1116 exhibits strong NIR-II absorption and fluorescence, peaking at 1004 and 1116nm, respectively, as well as a photothermal conversion efficiency of 79% under 1064nm lasers. In vitro and in vivo studies showed the efficacy of NPIR1116 in tumor imaging via NIR-II fluorescence and its ability to effectively induce tumor cell apoptosis under 1064nm laser irradiation. These findings underscore the potential of NPIR1116 in NIR-II fluorescence imaging-guided PTT for tumor treatment, paving the way for further advancements in NIR-II dye development and bioimaging technologies.

Design and synthesis of dicyanoethylene derivatives functionalized with carbazole possessing the properties of obvious aggregation-induced emission and reversible high-contrast mechanofluorochromism

This study devotes to the design, preparation, and examination of two novel D-A structured molecules, designated as CCEDBF and BCCEDBF, which are derived from carbazole unit, dicyanoethylene segment, and dibenzofuran unit. The distinctive D-A molecular architectures and highly twisted spatial configurations of these compounds facilitate pronounced intramolecular charge transfer (ICT) while also imparting robust solid-state luminescence, exhibiting emission efficiencies of 0.518 and 0.739, respectively, and notable aggregation-induced emission (AIE) with AIE factors of 43 and 30. Significantly, both CCEDBF and BCCEDBF demonstrate reversible mechanofluorochromic (MFC) behavior characterized by high fluorescence contrast. Mechanical grinding of the initial powders results in a shift in their emission colors, transitioning from green and yellow-green to yellow and orange-red, respectively, alongside a corresponding shift in emission peaks from 525 nm to 536 nm–558 nm and 597 nm. Powder X-ray diffraction (PXRD) examination of the initially synthesized, mechanically processed, and vaporized samples reveals that the observed fluorescence color change is due to a structural transformation between ordered crystalline and disordered amorphous configurations induced by the application of the external force. The red shift in photoluminescence (PL) spectra post-grinding is attributed to a reduced band gap, driven by factors such as extended π-conjugation length, enhanced planar intramolecular charge transfer (PICT) effect, strengthened π-π interactions and exciton coupling, as well as the increase in the orbitals overlap between neighboring molecular. Moreover, the presence or absence of tert-butyl substituents attaching to the 3- and 6-positions of the carbazole units significantly impacts the photophysical properties of these materials.

Facile synthesis and tunable fluorescent properties of a new D-π-A isocoumarin: Applications in encryption and OLED technology

A facile synthesis of a new D-π-A isocoumarin (ICP-NH2) with only two steps under mild conditions through O-acylation/Wittig/reduction reaction has been established. The readily accessible phosphonium salt precursor 1 and 4-nitrobenzoyl chloride 2 produced intermediate ICP-NO2 in the presence of triethylamine. Subsequently, ICP-NO2 underwent conversion to ICP-NH2 through the reduction of stannous dichloride. ICP-NH2 exhibits enhanced fluorescence overcoming the photo-induced electron transfer (PET) process in ICP-NO2. ICP-NH2 demonstrates a significant change in fluorescence from blue to green in various polar solvents, and DFT analysis confirmed that its solvatochromism is attributed to intramolecular charge transfer (ICT) effect. ICP-NH2 undergoes noticeable acidochromism based on reversible protonation and deprotonation reactions with TFA and TEA, leading to periodic changes in fluorescence from green to dark blue. This phenomenon can be utilized in designing reusable encryption technology. Additionally, ICP-NH2 can be employed in the fabrication of a cyan green OLED device.

Cyano-Substituted Oligo(p-phenylene vinylene) Derivatives with Aggregation-Induced Enhanced Emissions and Mechanofluorochromic Luminescence.

Developing red fluorescence emitters with simple structures via convenient synthetic routes is highly desirable yet challenging. Herein, two novel donor-acceptor-type red emitters, DCFOPV-TPA and SCFOPV-TPA, featuring the intramolecular charge transfer effect were designed by integrating triphenylamine and trifluoromethyl into a CN-substituted oligo(p-phenylene vinylene) backbone. Both chromophores exhibited aggregation-induced enhanced emission and solvatochromic behavior. Moreover, DCFOPV-TPA also displayed reversible mechanofluorochromic properties under external force.

Emission in the Biological Window from AIE-Based Carbazole-Substituted Furan-Based Compounds for Organic Light-Emitting Diodes and Random Lasers.

The emission quenching observed in devices utilizing luminescent materials such as solid thin films is a prevalent issue. Consequently, searching for new organic luminescent compounds exhibiting aggregation-induced emission (AIE) behavior and characterized by relatively simple and cost-effective synthesis is of crucial interest among applications from optoelectronics and organic lasing branches. Herein, we report the optical properties of three furan-based carbazole-substituted compounds, namely, tBuCBzSO2Ph, tBuCBzSPh, and tBuCbzTCF, exhibiting the aforementioned AIE phenomenon. The optical properties of dyes were determined in classical spectroscopic experiments supported by quantum-chemical calculations. The thermal investigations and electrochemical properties of dyes were performed to verify their usefulness in the construction of organic light-emitting diodes (OLEDs). In pursuit of this objective, OLEDs with a different design were fabricated, and their performance was subject to evaluation. In more detail, the different design strategies relying on the utilization of neat-dye films, as well as the preparation of dye-doped poly(9-vinylcarbazole):2-(4-tert-butylphenyl)-5-(4-biphenylyl)-1,3,4-oxadiazole (PVK:PBD) matrices were examined. The analysis that was conducted indicated the superior potential of tBuCBzSPh for optoelectronic applications. Notably, the positive impact of the AIE effect on the emission of the OLEDs and the ability to establish the lasing phenomenon in asymmetric, poly(methyl methacrylate) (PMMA)-doped polymeric slab waveguides were verified. The study showed that the combination of the strong intramolecular charge transfer (ICT) effect with dye aggregation enables the tuning of the emission of the OLED toward the first biological window, making examined dyes promising candidates for biomedical purposes. The same optical region can be attained for laser emission at relatively low pumping conditions, reaching as low as 7.3 kW of optical power for the tBuCBzSO2Ph compound.

Near–Infrared Heptamethine Cyanine Photosensitizers with Efficient Singlet Oxygen Generation for Anticancer Photodynamic Therapy

AbstractNear‐infrared photosensitizers are valuable tools to improve treatment depth in photodynamic therapy (PDT). However, their low singlet oxygen (1O2) generation ability, indicated by low 1O2 quantum yield, presents a formidable challenge for PDT. To overcome this challenge, the heptamethine cyanine was decorated with biocompatible S (Scy7) and Se (Secy7) atom. We observe that Secy7 exhibits a redshift in the main absorption to ~840 nm and an ultra‐efficient 1O2 generation capacity. The emergence of a strong intramolecular charge transfer effect between the Se atom and polymethine chain considerably narrows the energy gap (0.51 eV), and the heavy atom effect of Se strengthens spin–orbit coupling (1.44 cm−1), both of which greatly improved the high triplet state yield (61 %), a state that determines the energy transfer to O2. Therefore, Secy7 demonstrated excellent 1O2 generation capacity, which is ~24.5‐fold that of indocyanine green, ~8.2‐fold that of IR780, and ~1.3‐fold that of methylene blue under low‐power‐density 850 nm irradiation (5 mW cm−2). Secy7 exhibits considerable phototoxicity toward cancer cells buried under 12 mm of tissue. Nanoparticles formed by encapsulating Secy7 within amphiphilic polymers and lecithin, demonstrated promising antitumor and anti‐pulmonary metastatic effects, exhibiting remarkable potential for advancing PDT in deep tissues.

Near-Infrared Heptamethine Cyanine Photosensitizers with Efficient Singlet Oxygen Generation for Anticancer Photodynamic Therapy.

Near-infrared photosensitizers are valuable tools to improve treatment depth in photodynamic therapy (PDT). However, their low singlet oxygen (1O2) generation ability, indicated by low 1O2 quantum yield, presents a formidable challenge for PDT. To overcome this challenge, the heptamethine cyanine was decorated with biocompatible S (Scy7) and Se (Secy7) atom. We observe that Secy7 exhibits a redshift in the main absorption to ~840 nm and an ultra-efficient 1O2 generation capacity. The emergence of a strong intramolecular charge transfer effect between the Se atom and polymethine chain considerably narrows the energy gap (0.51 eV), and the heavy atom effect of Se strengthens spin-orbit coupling (1.44 cm-1), both of which greatly improved the high triplet state yield (61 %), a state that determines the energy transfer to O2. Therefore, Secy7 demonstrated excellent 1O2 generation capacity, which is ~24.5-fold that of indocyanine green, ~8.2-fold that of IR780, and ~1.3-fold that of methylene blue under low-power-density 850 nm irradiation (5 mW cm-2). Secy7 exhibits considerable phototoxicity toward cancer cells buried under 12 mm of tissue. Nanoparticles formed by encapsulating Secy7 within amphiphilic polymers and lecithin, demonstrated promising antitumor and anti-pulmonary metastatic effects, exhibiting remarkable potential for advancing PDT in deep tissues.

An Acid-Responsive Fluorescent Molecule for Erasable Anti-Counterfeiting.

A tetraphenylethylene (TPE) derivative, TPEPhDAT, modified by diaminotriazine (DAT), was prepared by successive Suzuki-Miyaura coupling and ring-closing reactions. This compound exhibits aggregation-induced emission enhancement (AIEE) properties in the DMSO/MeOH system, with a fluorescence emission intensity in the aggregated state that is 5-fold higher than that of its counterpart in a dilute solution. Moreover, the DAT structure of the molecule is a good acceptor of protons; thus, the TPEPhDAT molecule exhibits acid-responsive fluorescence. TPEPhDAT was protonated by trifluoroacetic acid (TFA), leading to fluorescence quenching, which was reversibly restored by treatment with ammonia (on-off switch). Time-dependent density functional theory (TDDFT) computational studies have shown that protonation enhances the electron-withdrawing capacity of the triazine nucleus and reduces the bandgap. The protonated TPEPhDAT conformation became more distorted, and the fluorescence lifetime was attenuated, which may have produced a twisted intramolecular charge transfer (TICT) effect, leading to fluorescence redshift and quenching. MeOH can easily remove the protonated TPEPhDAT, and this acid-induced discoloration and erasable property can be applied in anti-counterfeiting.