Spin-orbit charge-transfer intersystem crossing in heavy-atom-free orthogonal covalent boron-dipyrromethene heterodimers.

Boron-dipyrromethene (BODIPY) derivatives are prospective organic-based triplet photosensitizers. Since the triplet generation yield of the parent BODIPY is low, heavy atoms are widely used to improve the triplet yield. However, the dimerization of BODIPYs can also significantly improve their ability to produce triplets.

Ultrafast Charge Separation Driven by Torsional Motion in Orthogonal Boron Dipyrromethene Dimer.

In this work, the photoinduced charge separation (CS) via symmetry breaking in an orthogonal -β-linked boron dipyrromethene (BODIPY) dimer was investigated by polarized transient absorption spectroscopy. The time constant about 0.76 ps of the CS reaction determined in dimethyl sulfoxide is much faster than the solvation dynamics.

Photophyical and photosensitizing properties of BODIPYs substantially changed by alkyl- and phenyl-amino groups on meso carbon.

meso-RNH (R = CH, CH, PhCH, H, and Ph) substituted BODIPY compounds have been prepared to examine their photophysical properties and photosensitizing abilities. We have measured the UV-vis absorption, steady state and time resolved fluorescence, excited triplet state formation using laser flash photolysis, singlet oxygen generation ability using chemical trapping method. The results show that the presence of meso-RNH leads to large blue shift of absorption and emission wavelength, remarkable decrease in fluorescence quantum yield and lifetime values, and significant increase in singlet oxygen formation quantum yield.

Evaluation of fertilization capability of frozen-thawed completely immotile spermatozoa collected from a white bengal tiger after interspecific ICSI with bovine oocytes.

The objective of this study was to evaluate the fertilization capability of White Bengal Tiger frozen-thawed completely immotile spermatozoa after interspecific intracytoplasmic sperm injection (ICSI) with bovine oocytes. The fertilization status of presumptive zygotes was assessed 18 h after ICSI by immunofluorescence staining and confocal microscopy. The fertilization rate was 34.

Halogenated BODIPY photosensitizers: Photophysical processes for generation of excited triplet state, excited singlet state and singlet oxygen.

We have systematically examined the formation of singlet oxygen O(Δ), the excited triplet state (T), and excited singlet state (S) for halogenated BODIPY photosensitizers (halogen = Cl, Br, and I) in eight solvents to understand how halogen atoms and solvent affect these properties. The phosphorescence spectra and lifetimes of singlet oxygen generated by these halogenated BODIPYs have been measured by steady state/time resolved NIR emission, while the formation quantum yield of singlet oxygen (Φ) has been determined by chemical method using diphenylisobenzofuran (DPBF) as the trapping agent. The formation quantum yield Φ of singlet oxygen can be as high as 0.

The excited state behavior of Group IA alkaline-metal phthalocyanines revealed by photoluminescence and singlet oxygen formation.

Group IA alkaline-metal phthalocyanine (Pc) complexes (LiPc, NaPc, KPc, RbPc, CsPc) have been synthesized and purified to study their excited state behavior. Their UV-Vis electronic absorption spectra, fluorescence emission and excitation spectra, fluorescence quantum yields and lifetimes, as well as singlet oxygen formation quantum yields have been measured in DMF. These photophysical properties are compared with that of HPc.

Organo metal halide perovskites effectively photosensitize the production of singlet oxygen (Δ).

Using the steady state and time resolved NIR emission and specific chemical trapping techniques, we show for the first time that metal halide perovskite quantum dots can effectively generate singlet oxygen with a quantum yield of up to 0.34, the highest among nano semiconductor/nano metal singlet oxygen photosensitizers. The mechanism is concluded to be due to energy transfer from triplet excitons to molecular oxygen.

Methylated Unsymmetric BODIPY Compounds: Synthesis, High Fluorescence Quantum Yield and Long Fluorescence Time.

We show that unsymmetric BODIPY compounds with one, two, and three methyl groups can be synthesized easily and efficiently by the unsymmetric reaction method. Their steady state and time-resolved fluorescence properties are examined in solvents of different polarity. These compounds show high fluorescence quantum yields (0.

PET-based bisBODIPY photosensitizers for highly efficient excited triplet state and singlet oxygen generation: tuning photosensitizing ability by dihedral angles.

Herein, four covalent BODIPY heterodimers that differ by dihedral angles were shown to be highly efficient excited triplet state (T) photosensitizers (PSs) for singlet oxygen formation with a quantum yield (Φ) of up to 0.94 as compared to their respective monomers, which had only negligible Φ of ca. 0.

Attaching naphthalene derivatives onto BODIPY for generating excited triplet state and singlet oxygen: Tuning PET-based photosensitizer by electron donors.

meso-Naphthalene substituted BODIPY compounds were prepared in a facile one pot reaction. The naphthalene functionalization of BODIPY leads up to a 5-fold increase in the formation efficiency of excited triplet state and singlet oxygen in polar solvents. Steady state and time resolved fluorescence, laser flash photolysis, and quantum chemistry methods were used to reveal the mechanism.

Photoinduced Electron Transfer-based Halogen-free Photosensitizers: Covalent meso-Aryl (Phenyl, Naphthyl, Anthryl, and Pyrenyl) as Electron Donors to Effectively Induce the Formation of the Excited Triplet State and Singlet Oxygen for BODIPY Compounds.

Pristine BODIPY compounds have negligible efficiency to generate the excited triplet state and singlet oxygen. In this report, we show that attaching a good electron donor to the BODIPY core can lead to singlet oxygen formation with up to 58 % quantum efficiency. For this purpose, BODIPYs with meso-aryl groups (phenyl, naphthyl, anthryl, and pyrenyl) were synthesized and characterized.

The Fluorescence Properties of Three Rhodamine Dye Analogues: Acridine Red, Pyronin Y and Pyronin B.

The fluorescence spectra, fluorescence quantum yield, and fluorescence lifetime of Acridine Red (AR), Pyronin Y (PYY), and Pyronin B (PYB) in aqueous and organic solvents were measured by steady state fluorescence, time-correlated single photon counting, and electronic absorption methods. The rate constants of radiation and non radiation process (kf and kic) were calculated to elucidate the structural effect on the fluorescence mechanism. The data for each compound are compared with that of the corresponding rhodamine dye.

Intracellular modulation of excited-state dynamics in a chromophore dyad: differential enhancement of photocytotoxicity targeting cancer cells.

The photosensitized generation of reactive oxygen species, and particularly of singlet oxygen [O2 (a(1) Δg )], is the essence of photodynamic action exploited in photodynamic therapy. The ability to switch singlet oxygen generation on/off would be highly valuable, especially when it is linked to a cancer-related cellular parameter. Building on recent findings related to intersystem crossing efficiency, we designed a dimeric BODIPY dye with reduced symmetry, which is ineffective as a photosensitizer unless it is activated by a reaction with intracellular glutathione (GSH).

Synthesis and Photophysics of BF2 -Rigidified Partially Closed Chain Bromotetrapyrroles: Near Infrared Emitters and Photosensitizers.

We report the synthesis, crystallographic, optical, and triplet and singlet oxygen generation properties of a series of BF2 -rigidified partially closed chain bromotetrapyrroles as near infrared emitters and photosensitizers. These novel dyes were efficiently synthesized from a nucleophilic substitution reaction between pyrroles and the 3,5-bromo-substituents on the tetra- and hexabromoBODIPYs and absorb in the near-infrared region (681-754 nm) with high molar extinction coefficients. Their fluorescent emission (708-818 nm) and singlet oxygen generation properties are significantly affected by alkyl substitutions on the two uncoordinated pyrrole units of these dyes and the polarity of solvents.

Spectroscopic insights on selfassembly and excited state interactions between rhodamine and phthalocyanine molecules.

The absorption and fluorescence spectra as well as fluorescence lifetimes of tetrasulfonated zinc phthalocyanine ZnPc(SO3Na)4 were measured in the absence and presence of four rhodamine dyes, Rhodamine B (RB), Ethyl rhodamine B (ERB), Rhodamine 6G (R6G), Rhodamine 110 (R110), and Pyronine B (PYB). The ground state complexes of phthalocyanine-(Rhodamine)2 were observed which exhibit new absorption bands. The binding constants are all very large (0.

Preparation and investigation of CaZr4(PO4)6:Dy(3+) single-phase full-color phosphor.

A novel single-phase full-color phosphor CaZr4(PO4)6:Dy(3+) has been synthesized by a high-temperature solid-state reaction. X-ray powder diffraction (XRD) analysis and FT-IR spectra confirmed the phase formation of CaZr4(PO4)6:Dy(3+) materials. The photoluminescence excitation and emission spectra, the concentration dependence of the emission intensity, decay curves, ultraviolet-visible absorption spectroscopy and Commission International de I(')Eclairage (CIE) of the phosphor were investigated.

Spectroscopic insights on imidazole substituted phthalocyanine photosensitizers: fluorescence properties, triplet state and singlet oxygen generation.

Imidazole substituted metal phthalocyanine (Pc) complexes were synthesized. UV-vis absorption, steady state and time-resolved fluorescence, as well as laser flash photolysis were used to measure the photophysical and photosensitizing properties. All the imidazole-phthalocyanine conjugates show high ΦT (quantum yield of excited triplet formation), high ΦΔ (singlet oxygen formation yield, >0.

Fluorescence properties of twenty fluorescein derivatives: lifetime, quantum yield, absorption and emission spectra.

The fluorescence lifetime (τf), emission quantum yield (Φf), absorption and emission spectral data of 20 fluorescein derivatives were measured under the same conditions by using time-correlated single photon counting, steady state fluorescence and absorption methods to get comparable data. Based on the results, the factors and mechanism that control the fluorescence properties of the fluorescein dyes are discussed. Both Φf and τf are remarkably dependent on the substitution on either xanthene or phenyl rings, but their ratio (Φf/τf), i.

Self-Assembly and Nanostructures in Organogels Based on a Bolaform Cholesteryl Imide Compound with Conjugated Aromatic Spacer.

The self-assembly of small functional molecules into supramolecular structures is a powerful approach toward the development of new nanoscale materials and devices. As a class of self-assembled materials, low weight molecular organic gelators, organized in special nanoarchitectures through specific non-covalent interactions, has become one of the hot topics in soft matter research due to their scientific values and many potential applications. Here, a bolaform cholesteryl imide compound with conjugated aromatic spacer was designed and synthesized.

Photosensitizer that selectively generates singlet oxygen in nonpolar environments: photophysical mechanism and efficiency for a covalent BODIPY dimer.

Photosensitizers that selectively generate singlet oxygen in non polar/polar microenvironments are highly desirable for photodynamic therapy of tumor but not yet reported. BODIPY (boron-dipyrromethene complexes) covalent dimer 1 is such a photosensitizer that forms singlet oxygen only in hexane, cyclohexane, and toluene significantly but not in polar solvents. Its corresponding monomer is not photoactive in any solvents for forming singlet oxygen.

Noncovalent binding of xanthene and phthalocyanine dyes with graphene sheets: the effect of the molecular structure revealed by a photophysical study.

The fluorescence and absorption properties of several xanthene and phthalocyanine dyes were measured in the presence and absence of chemically derived graphene (CDG) sheets. The interaction of pyronine Y (PYY) with graphene sheets was compared with that of rhodamine 6G (R6G) to reveal the effect of the molecular structure. Although the presence of the perpendicular benzene moiety in a R6G or phthalocyanine molecule does cause the difficulty for forming dye-CDG complex and make CDG less efficient in quenching the fluorescence intensity and shortening the fluorescence lifetime, it does not affect the band position of charge transfer absorption, suggesting that no molecular shape change occurred in a dye molecule caused by the interaction with CDG sheets.

Singlet oxygen generation and triplet excited-state spectra of brominated BODIPY.

The excited triplet-, singlet-, and ground-state properties as well as singlet oxygen generation capability of four brominated BODIPY dyes were measured in toluene with laser flash photolysis, fluorescence spectroscopy, time-correlated single-photon counting, and absorption spectroscopy. The triplet-triplet (T1-Tn) absorption spectra were identified for four dyes 1B, 2B, 4B, and 6B substituted with one, two, four, and six Br atoms, respectively. The triplet quantum yield (ΦT) of a usual BODIPY dye is negligible and has rarely been studied.

Imidazole functionalized magnesium phthalocyanine photosensitizer: modified photophysics, singlet oxygen generation and photooxidation mechanism.

Magnesium phthalocyanine (MgPc) was covalently attached by four imidazole units to form a novel photosensitizer (PS). The photophysical processes within the dyad PS were explored by steady state and time-resolved fluorescence as well as laser flash photolysis. Although the imidazole units caused a 50% decrease in fluorescence quantum yield and a remarkable shortening of fluorescence lifetime of the MgPc moiety, the triplet yield (Φ(T)) is higher and the triplet lifetime becomes longer.

Dual fluorescence of graphene oxide: a time-resolved study.

The fluorescence properties of graphene oxide (GO) was studied by recording the fluorescence lifetime, fluorescence emission, and excitation spectra, as well as UV-visible and near-IR absorption spectra. For the first time, we showed that a blue band (ca. 440 nm) and a long wavelength (LW) band (ca.