Engineering J-aggregates for NIR-induced meso-CF_(3)-BODIPY nanoparticles by activated apoptosis mechanism in photothermal therapy

Forming J-aggregates by organic monomer is a fascinating strategy to urge spectroscopic redshift with respect to that of the monomer.Herein,we designed 1,7-diphenyl-substituted meso–CF_(3)-BDP monomer confirmed by X-ray crystallographic analysis.The low-barrier rotation of the–CF_(3)group in meso–CF_(3)-BDP1 significantly enhances the non-radiative efficiency,and the photothermal conversion efficiency(PCE)of the self-assembled nanoparticles(1-NPs:λ_(abs)=746 nm)by J-aggregates was 82%.1-NPs could effectively block cell cycle progression,inhibit cancer cell proliferation and trigger cell apoptosis under low power laser irradiation(0.2 W/cm^(2)).This study proposes an alternate molecular design platform by J-aggregates to promote PCE through the insertion of rotating segment and trigger the cancer cells apoptosis in photothermal therapy at low power laser density.

Synthesis and application of Vis/NIR dialkylaminophenylbuta-1,3-dienyl borondipyrromethene dyes

Mono- and bis-dialkylaminophenylbuta-1,3-dienyl boron-dipyrromethenes(BODIPYs) 1–12 were synthesized in 36%–42% yields by a Knoevenagel-type condensation. The absorption and emission maxima(labs= 614–739 nm; lem= 655–776 nm in CHCl3) of 1–12 covered from the visible to the nearinfrared region. Probe 1 was ratiometric Vis p H probes. Such probe was almost non-fluorescent. Upon the protonation of the tertiary amine function of 1, the strong fluorescence(Φf= 0.97) was released and the florescence intensity was dramatically increased by one thousand folds. The sharp isosbestic points were discovered at 590 nm, which was a ratiometric p H probe.

Synthesis dibromo substituted BOPHY dye for the singlet oxygen generation

A dibromo substituted BOPHY derivative(2) was prepared and found to exhibit photo-sensitization capability. Rapid oxidation of 80% DPBF at the first 6 min was observed suggesting that 2 is a superior photo-sensitizer than methylene blue. The HOMO–LUMO band gap for the lowest energy absorption bands of the BOPHY 1 is smaller than that of PS 2, which is in good agreement with the red shift in the absorption observed between 1 and 2.

A colorimetric chemosensor based on new water-soluble PODIPY dye for Hg^(2+) detection

The phosphorus-containing PODIPY 1 as a chemosensor can detect Hg^(2+) by a color change from pink to violet red without the use of any instrumentation. PODIPY 1 was selective to Hg^(2+)with a remarkable absorption change, and addition of other relevant metal ions caused almost no absorption change. The new PODIPY dye 1 was sensitive to various concentrations of Hg^(2+). The energy gap between the HOMO and LUMO of the metal complex 1–Hg^(2+)is smaller than that of chemosensor 1, which is in good agreement with the red shift in the absorption observed upon treatment of 1 with Hg^(2+). The 1-based test strips were easily fabricated and low-cost, useful in practical and efficient Hg^(2+)test kits.

Near-infrared absorbing(>700 nm)aza-BODIPYs by freezing the rotation of the aryl groups

The typical aza-BODIPYs in the dye family are known for bright fluorescence,excellent stability,and tunable absorption wavelengths.Hence,these dyes are attracting the increasing attention.Aza-BODIPYs having the maxima absorption in the near-infrared(NIR)region(650-900 nm)are very favorable for bioimaging in vivo due to the less photo-damage,deeper tissue penetration,and less interference from background auto-fluorescence by biomolecules in the living systems.Many strategies have been employed to modify the structures of the aza-BODIPY core to provide the NIR absorbing dyes.Among these,the most effective method is the fusion of the aromatic rings in aza-BODIPY system.This review allsidedly summarizes the recent development of ring-fused aza-BODIPY dyes(λ_(abs)>700 nm)focusing on the design,synthesis,and potential applications in the NIR region since 2002.

Development of aryl-containing dipyrrolyldiketone difluoroboron complexes(BONEPYs):Tune the hydrogen bond o-C—H…F for fluoride recognition

Dipyrrolyldiketone difluoroboron complexes(BONEPYs)were synthesized by condensation of the corresponding pyrroles and malonyl chloride followed by treatment with BF3·OEt2.The aryl-substituted pyrrole is introduced to form a cyclic system in order to investigate anion binding studies.In BONEPYs 1-3 the o-H of the aryl group forms hydrogen bonding with F to give a more table complex.In contrast,the intramolecular hydrogen-bonded BONEPY endo-4 is more stable than its exo isomer.While adding F,the hydrogen bonds must be broken first to give 4·(3)F.Owing to the electron-rich group(-OMe),the o-H of the phenyl group can hardly interact with F via hydrogen bonding to give the less stable complex4-(5)F.The energy diffe rences between the different conformations were calculated using DFT methods,which is consistent to the experimental observations.