Multiple BODIPY derivatives with 1,3,5-triazine as core: balance between fluorescence and numbers of BODIPY units

The multiple BODIPY derivatives could exhibit higher fluorescence than mono-BODIPY derivatives but also might produce the stronger aggregation-induced quenching effect. It is important to investigate the relationship between fluorescence and numbers of BODIPY units. In this work, series of multiple BODIPY derivatives 2–5 with 1,3,5-triazine as core were designed and synthesized in high yields. A subtle balance between the fluorescence enhancement of multiple BODIPY units and fluorescence quenching based on H-aggregation of multiple BODIPY units was observed for these multiple BODIPY derivatives. Compound 3 bearing two BODIPY units with triazine as core presented the strongest fluorescence emission and highest fluorescence quantum yield. Compound 3 was successfully applied in viscosity measurement, exhibiting the linear relationship between fluorescence intensity (or steady-state emission anisotropy) and viscosity.     

Fluorescence properties of indolenine semi-squarylium dyes

3-Butoxy-4-(1-butyl-3,3-dimethyl-3H-indol-2-ylidenemethyl)-3-cyclobut-1,2-dione exhibited the most intense florescence at fluorescence maxima 536 and 563 nm with fluorescence quantum yield 0.21 among any indolenine semi-squarylium dyes in the crystalline form due to the isolated dimer-type molecular packing and its suitable melting point. This compound showed aggregation-induced emission enhancement.     

BSA-tetraphenylethene derivative conjugates with aggregation-induced emission properties: fluorescent probes for label-free and homogeneous detection of protease and α1-antitrypsin

Herein, BSA-tetraphenylethene derivative conjugates with aggregation-induced emission (AIE) properties were constructed and used as fluorescent probes for label-free detection of protease and α1-antitrypsin. Conjugated AIE probes were formed based on the electrostatic induced assembly between an ammonium cation of quaternized tetraphenylethene salt and carboxyl anion groups of BSA. While water soluble quaternized tetraphenylethene salt showed very low fluorescence in its well-dispersed state, obvious enhancement in the fluorescence of the aggregated tetraphenylethene derivative on the BSA templates was achieved due to the abnormal aggregation-induced emission properties of tetraphenylethene. These BSA-tetraphenylethene derivative conjugates enabled label-free detection of protease. In the presence of trypsin, the BSA templates were enzymatically hydrolyzed and the conjugates decomposed. Therefore the quaternized tetraphenylethene molecules became increasingly isolated from each other. Accordingly, the aggregation to dispersing state change of tetraphenylethene derivative resulted in an obvious decrease in the fluorescence of the conjugates probes and enabled the sensitive and selective detection of trypsin. Furthermore, upon addition of α1-antitrypsin, the enzymatic activity of trypsin was inhibited and the fluorescence was consequently preserved. Sensitive detection of α1-antitrypsin was thus realised. The protein-tetraphenylethene derivative conjugates with aggregation-induced emission properties therefore show great promise for the monitoring of biological processes and cancer diagnostics with simplicity, high sensitivity, and rapid response.     

A highly sensitive “turn-on” fluorescent probe for bovine serum albumin protein detection and quantification based on AIE-active distyrylanthracene derivative

A sulfonated 9,10-distyrylanthracene derivative with aggregation-induced emission (AIE) property is designed and synthesized. It shows a highly sensitive and selective fluorescence enhancement property for bovine serum albumin (BSA) protein detection and quantification. Analysis on the interaction between the probe molecule and BSA reveals the essential role of the hydrophobic cavities of the protein folding structure.     

1,3,6,8-Tetraethynylpyrene and 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene: Photophysical properties in homogeneous media

The photophysical properties of two new tetra substituted derivatives of pyrene: 1,3,6,8-tetraethynylpyrene (TEP) and 1,3,6,8-tetrakis(trimethylsilylethynyl)pyrene (TEP-TMS) have been studied. Studies were done with respect to mirror image symmetry in the absorption and emission spectra and permissive or forbidden nature of S₀–S₁ transition, solvent sensitivity of the first and third vibronic bands and fluorescence anisotropy. Both the derivatives exhibited a strongly allowed S₀–S₁ transition, high fluorescence quantum yield, shorter fluorescence lifetime compared to pyrene and invariance of the vibronic band intensity ratio to solvent polarity. The behavior of the two pyrene derivatives validates the hypothesis “solvent polarity mediates vibronic coupling and therefore the emission band intensities, for forbidden S₀–S₁ transitions”. The trimethylsilyl derivative (TEP-TMS) was characterized by a strong fluorescence in solid state. The tetraethynyl derivative (TEP) showed high fluorescence anisotropy comparable to the well-known anisotropy probe DPH in glycerol at 0 °C. The fluorescence intensities of TEP and TEP-TMS did not show any significant change in the temperature ranger 0–40 °C for a low viscous solvent like ethanol and in the range 0–60 °C in glycerol. Unlike pyrene, no excimer emission was observed even up to 10⁻³ M for TEP and TEP-TMS.     

Fabrication of Double Emission Enhancement Fluorescent Nanoparticles with Combined PET and AIEE Effects

The major challenge in the fabrication of fluorescent silica nanoparticles (FSNs) based on dye-doped silica nanoparticles (DDSNs) is aggregation-caused fluorescence quenching. Here, we constructed an FSN based on a double emission enhancement (DEE) platform. A thio-reactive fluorescence turn-on molecule, N-butyl-4-(4-maleimidostyryl)-1,8-naphthalimide (CS), was bound to a silane coupling agent, (3-mercaptopropyl)-trimethoxysilane (MPTMS), and the product N-butyl-4-(3-(trimethoxysilyl-propylthio)styryl)-1,8-naphthalimide (CSP) was further used to fabricate a core–shell nanoparticle through the Stöber method. We concluded that the turn-on emission by CSP originated from the photoinduced electron transfer (PET) between the maleimide moiety and the CSP core scaffold, and the second emission enhancement was attributed to the aggregation-induced emission enhancement (AIEE) in CSP when encapsulated inside a core–shell nanoparticle. Thus, FSNs could be obtained through DEE based on a combination of PET and AIEE effects. Systematic investigations verified that the resulting FSNs showed the traditional solvent-independent and photostable optical properties. The results implied that the novel FSNs are suitable as biomarkers in living cells and function as fluorescent visualizing agents for intracellular imaging and drug carriers.     

New cyano-substituted organic dyes containing different electrophilic groups: aggregation-induced emission and large two-photon absorption cross section

Three aggregation-induced emission active dyes (3a–c) were synthesized and their one- and two-photon absorption properties have been investigated. They were all found to be weakly fluorescent in THF solution, while they exhibited dramatic fluorescence enhancement in water/THF mixtures. The solid fluorescence of 3a–c was recorded and their fluorescence quantum efficiency (Φ_F) values were determined to be 8.0%, 8.1%, and 16.4%, respectively. Moreover, the two-photon absorption (2PA) cross-sections (σ) of 3a–c were measured and 3a showed the highest value of 702 GM. The excellent aggregation-induced emission and 2PA properties provide a promising alternative for biophotonic materials.     

基于聚集诱导荧光性质的免标记DNA四链体检测以及凝血酶的传感研究

基于带正电荷硅杂环戊二烯衍生物的聚集诱导荧光性质,利用其与富含G的单链DNA和四链体作用后的荧光强度差别,发展了一种免标记的DNA四链体检测方法,并将该方法应用于凝血酶的荧光分析.     

Synthesis and characterization of fluorescence active G4-quartet and direct evaluation of self-assembly impact on emission

Fluorescence (FL) active 8-aryl guanosine derivatives were prepared and applied for cation mediated self-assembly to form the H-bonded G₈-quadruplexes. The p-cyano (p-CN) and 8-anthracene (8-An) substituted guanosines were identified to give the strongest fluorescence with the formation of G₈-octamers (G₈) both in solution (NMR) and solid state (X-ray). This well-defined G₈-octamer system has provided the first direct evidence on the self-assembled G-quadruplex fluorescence emission with aggregation-induced emission (AIE), which could be applied as the foundation for FL molecular probe design toward G-quadruplex recognition.     

Synthesis of non-symmetrical alkynylpyridines by chemoselective Sonogashira cross-coupling reactions

4-Bromo-2,3,5-trichloro-6-iodopyridine was studied as a new substrate in chemoselective Sonogashira reactions. This approach provides an efficient access to non-symmetrical mono-, di-, tri- and pentaalkynylated pyridines in good yields. Selected pentaalkynylated pyridines were studied with regard to their UV/Vis- and emission properties showing moderate to high fluorescence quantum yields.     

Hetero-oligophenylene-based AIEE material as a multiple probe for biomolecules and metal ions to construct logic circuits: application in bioelectronics and chemionics

New hetero-oligophenylene derivative (2) was synthesized which exhibits aggregation-induced emission enhancement (AIEE) in H(2)O/THF (80:20). The aggregates serve as a biological probe for three different proteins, that is bovine serum albumin (BSA), cytochrome?c, and lysozyme, and DNA in contrasting modes. Further, among 29 metal ions tested, the contrasting fluorescence behavior of aggregates of 2 is observed with only Pb(2+) and Pd(2+) ions. Multiple output logic circuits based upon the fluorescence behavior between BSA and cytochrome?c and between Pb(2+) and Pd(2+) ions are constructed.     

An aggregation-induced emissive chromophore as a ratiometric fluorescent sensor for cyanide in aqueous media

A para-terphenyl derivative containing a lateral diphenylamino group and two terminal dicyanovinyl groups has been designed and synthesized. This compound displays aggregation-induced emission characteristics and thus shows intense intramolecular charge transfer fluorescence even in the condensed state, including in the aggregates formed in an aqueous solvent system consisting of greater than 99% water and in the solid state. The addition of cyanide to its aggregates in aqueous media induces a large blue shift in fluorescence, enabling ratiometric fluorescence sensing of cyanide anions. In addition, its prompt fluorescence responses to cyanide anions were also observed even in the solid state.     

Spatiotemporal Dynamics of Aggregation-Induced Emission Enhancement Controlled by Optical Manipulation

We present spatiotemporal control of aggregation-induced emission enhancement (AIEE) of a protonated tetraphenylethene derivative by optical manipulation. A single submicrometer-sized aggregate is initially confined by laser irradiation when its fluorescence is hardly detectable. The continuous irradiation of the formed aggregate leads to sudden and rapid growth, resulting in bright yellow fluorescence emission. The fluorescence intensity at the peak wavelength of 540 nm is tremendously enhanced with growth, meaning that AIEE is activated by optical manipulation. Amazingly, the switching on/off of the activation of AIEE is arbitrarily controlled by alternating the laser power. This result means that optical manipulation increases the local concentration, which overcomes the electrostatic repulsion between the protonated molecules, namely, optical manipulation changes the aggregate structure. The dynamics and mechanism in AIEE controlled by optical manipulation will be discussed from the viewpoint of molecular conformation and association depending on the laser power.     

Dual-mode of assembly of anthracene-based imidazolium salts both in non-polar organic solvents and in aqueous solution

Amphiphilic anthracene derivatives showed solvent-polarity-dependent fluorescence. Monomer emission and aggregation-induced emission (AIE) were observed in polar and non-polar organic solvents, respectively. AIE became predominant in aqueous solution in the case of hexafluorophosphate as a counter anion.     

Semi-fused hexaphenyl hexa-peri-hexabenzocoronene: a novel fluorophore from an intramolecular Scholl reaction

A semi-fused hexaphenyl hexabenzocoronene derivative (hexaphenyl-1/2HBC) was discovered and isolated from an intramolecular Scholl reaction of an oligo(ethyleneglycol) substituted hexabiphenylbenzene. This new derivative exhibits blue-shifted λ_em and significantly enhanced fluorescence in dichloromethane compared to the completely cyclized hexaphenyl-HBC derivative.     

Structure-fluorescence relationship of push-pull 2-phenylbenzothiazole derivatives designed based on the firefly light-emitter

6-Dimethylamino-2-phenylbenzothiazole (1a) mimicking the firefly oxyluciferin structure and the derivatives with an electron-withdrawing substituent on the phenyl group were prepared, and their fluorescence properties were investigated in various solvents. 1a showed solvatochromic fluorescence with good fluorescence quantum yields (Φ_f >0.8). The introduction of an electron-withdrawing group led to a red-shift of the emission maximum. In particular, the derivatives with the 2,2-dicyanoethenyl and (1,3-dihydro-1,3-dioxo-2H-inden-2-ylidene)methyl groups showed near-infrared fluorescence in chloroform. In addition, the derivative with the phenylimine moiety showed efficient solid-state fluorescence, resulted from a molecular arrangement inhibiting intermolecular interactions for quenching the fluorescence state in crystals.     

The convenient fluorescence turn-on detection of heparin with a silole derivative featuring an ammonium group

A new silole derivative with an ammonium group was designed and studied with a view to developing a convenient fluorescence turn-on assay for heparin by taking advantage of the aggregation-induced enhanced emission (AIE) feature of silole (silacyclopentadiene) molecules.     

Crystallization-induced light-emission enhancement of diphenylmethane derivatives

A family of diphenylmethane derivatives has been synthesized and their luminescence properties characterized. While in solution the compounds are weakly emissive, showing no aggregation-induced emission enhancement, the crystals of three dialkyl 5,5′-methylenebis(2-hydroxybenzoate) samples exhibit intense emission. This emission enhancement upon crystallization is ascribed to particular molecular packing, which stiffens the structure of the compounds via hydrogen bonds, preventing consecutive π–π interactions.     

Synthesis of water-soluble N-Acetyl-L-cysteine conjugates of naphtazarin (5,8-Dihydroxy-1,4-naphthoquinone) derivatives

Base-catalytic condensation of N-acetyl-L-cysteine with substituted naphthazarins was first obtained a series of mono-, di-, tri- and tetra-substituted S-aminoacid naphthazarin conjugates bearing alkyl (hydroxy) groups. It was shown that three- and tetra-N-acetyl-L-cysteine naphthazarin derivatives are readily soluble in water.     

Push–Pull Bisnaphthyridylamine Supramolecular Nanoparticles: Polarity-Induced Aggregation and Crystallization-Induced Emission Enhancement and Fluorescence Resonance Energy Transfer

Emissive push–pull-type bisnaphthyridylamine derivatives ( BNA-X : X=Me, Et, Bzl, Ph, BuBr, and BuTEMPO) aggregate in aqueous methanol. Furthermore, a two-step emission and aggregation process is controllable by varying the methanol-to-water ratio. At 2:3 MeOH/H₂O, crystallization-induced emission enhancement (CIEE) occurs via formation of an emissive crystal phase, whereas, at 1:9 MeOH/H₂O, aggregation-induced emission enhancement (AIEE) occurs, induced by emissive supramolecular nanoparticles (NPs). For BNA-Ph , the emission quantum yield was 25 times higher in aqueous methanol than that in pure methanol. Despite the high hydrophobicity of BNA-X (C log P=6.1–8.0), the spherical NPs were monodisperse (polydispersity indices <0.2). Moreover, the emissive NPs exhibited fluorescence resonance energy transfer (FRET) with pyrene; however, for BNA-X bearing the TEMPO radical ( BNA-BuTEMPO ), no FRET was observed because of quenching. In particular, the BNA-BuTEMPO NPs have a slow rotational correlation time (1.3 ns), suggesting applications as magnetic resonance imaging contrast agents with large relaxivity.