Anthracene Fluorescence Research Articles

Synthesis and photophysical properties of 3-aryl-2-cyanoacrylamides: Design of a turn-on fluorescent probe for cyanide ion detection

Three 3-aryl-2-cyanoacrylamide derivatives were synthesised in 71−79 % yields from cheap reagents and mild reaction conditions using the Et3N-mediated Knoevenagel condensation of fluorescent arylaldehydes (e.g., triphenylamine and anthracene) with cyanoacetamide. These dyes' photophysical properties and anions-recognizing behaviour were studied, revealing that the 9-anthracenyl derivative can "turn on" fluorescence in cyanide presence, with high selectivity and a detection limit (LOD) of 710 nM. Initially, there is fluorescence quenching by the energy transfer (ET) from the anthracene ring to the 2-cyanoacrylamide moiety due to the non-coplanarity of these fragments and, upon the cyanide addition to Cβ of the receptor unit, the intrinsic fluorescence of anthracene is restored. HRMS and NMR experiments and TD-DFT calculations were performed to confirm the detection mechanism and fluorescence properties of the design chemodosimeter; fluorescent test paper was also used to detect cyanide in an aqueous medium.

Fluorescence and Photophysical Properties of Anthracene and Phenanthrene in Water.

Polyaromatic hydrocarbons (PAHs) are widely spread pollutants in the environment, including soil and water. Anthracene (anth) and phenanthrene (phen) pose severe health impacts on human lives due to their carcinogenic nature by increasing cancer risk to the skin, lungs, and bladder. Fluorescence spectroscopy is a promising , efficient and straightforward tool for characterizing these trace PAHs in water. Therefore, the current work provides a detailed insight into the fluorescence properties of anth and phen in water. The fluorescence EEMs (excitation-emission matrices) of anth showed emissions at 380nm, 400nm, and 425nm with single excitation at 250nm, whereas phen showed two emissions < 380nm, at 350nm and 365 with single excitation at 250nm. Then the theoretical EX/EM wavelengths were calculated by DFT and CIS-B3LYP for these compounds in water. The environmental effect of pH variation on fluorescence EEM shows a significant difference in fluorescence intensity without changing in peak locations, with highest fluorescence intensity at neutral pH than acidic and alkaline. Furthermore, the theoretical pH effect was described for the first time by simulating the protonated (+ 1), deprotonated (-1) and neutral molecules in water at the DFT level of theory. The variation in simulated oscillator strengths was similar in trend with the experimental fluorescence intensity of these compounds. The HOMO-LUMO were calculated to obtain the energy gap, molecular softness, molecular hardness, electronic potential and electrophilicity of anth and phen. To find the fluorophore contribution, the fluorescence of homogeneous mixture of both isomers was analyzed, which showed an enhanced fluorescence intensity of anth by 12-20%, whereas a decrease of 9-14% was observed in phen. This study describes that the fluorescence technique could be a fast and easy method to distinguish and identify PAHs isomers (anth and phen) in water.

Proton-coupled energy transfer in molecular triads.

We experimentally discovered and theoretically analyzed a photochemical mechanism, which we term proton-coupled energy transfer (PCEnT). A series of anthracene-phenol-pyridine triads formed a local excited anthracene state after light excitation at a wavelength of ~400 nanometers (nm), which led to fluorescence around 550 nm from the phenol-pyridine unit. Direct excitation of phenol-pyridine would have required ~330-nm light, but the coupled proton transfer within the phenol-pyridine unit lowered its excited-state energy so that it could accept excitation energy from anthracene. Singlet-singlet energy transfer thus occurred despite the lack of spectral overlap between the anthracene fluorescence and the phenol-pyridine absorption. Moreover, theoretical calculations indicated negligible charge transfer between the anthracene and phenol-pyridine units. We construe PCEnT as an elementary reaction of possible relevance to biological systems and future photonic devices.

Generation of Long-Lived Photoinduced Charge Separation in a Supramolecular Toroidal Assembly.

Efficiencies of artificial photosynthetic and photocatalytic systems depend on their ability to generate long-lived charge-separated (CS) states in photoinduced electron transfer (PET) reactions. PET, in most cases, is followed by an ultrafast back electron transfer, which severely reduces lifetime and quantum yield of CS states. Generation of a long-lived CS state is an important goal in the study of PET reactions. Herein, we report that this goal is achieved using a hierarchically self-assembled anthracene-methyl viologen donor-acceptor system. Anthracene linked to two β-cyclodextrin molecules (CD-AN-CD) and methyl viologen linked to two adamantane units (AD-MV2+-AD) form an inclusion complex in water, which further self-assembled into well-defined toroidal nanostructures. The fluorescence of anthracene is highly quenched in the self-assembled system because of PET from anthracene to methyl viologen. Irradiation of the aqueous toroidal solution led to formation of a long-lived CS state. Rational mechanisms for the formation of the toroidal nanostructures and long-lived photoinduced charge separation are presented in the paper.

Fabrication and Characterization of Anthracene Doped P-terphenyl Thin Films By Spin Coating Technique; Investigation of Fluorescence Properties.

Thin films of p-terphenyl luminophors doped by varying amounts of anthracene were prepared by using spin coating technique. The morphological, structural, and photophysical investigation of thin films of p-terphenyl as a function of anthracene concentration is studied by using scanning electron microscopy (SEM), X-ray diffraction (XRD), fluorescence spectroscopy and fluorescence microscopy. The results of XRD and SEM studies indicated that the doped p-terphenyl thin film is homogeneous as compared with a bare p-terphenyl thin film. The fluorescence spectroscopy results indicate complete quenching of p-terphenyl fluorescence and simultaneous sensitization of blue anthracene like emission towards the red side of the spectrum with maximum intensity at 410 nm. The blue intense emission of anthracene seen in fluorescence microscopy images is in agreement with observed fluorescence spectral results. A suitable mechanism of excitation energy transfer (EET) from p-terphenyl to anthracene molecules is proposed and discussed on the basis of energy level diagram. The efficient EET is believed to occur by the orientation of phenyl rings of p-terphenyl in excited state. As the concentration of doped anthracene increases, the fluorescence intensity of doped p-terphenyl and Full Width at Half Maximum (FWHM) found to be increased. The p-terphenyl film containing 0.65 moles of anthracene is of FWHM as low as 28.51 nm. Such narrow band blue emitting doped luminophors are of demand in light emitting diodes (OLED) and scintillation applications.

A multifunctional β-cyclodextrin-conjugate photodelivering nitric oxide with fluorescence reporting

This contribution reports the design, synthesis and photochemical properties of a novel cationic, water soluble, β-cyclodextrin (βCD) conjugate integrating an anthracene moiety and a nitroaniline derivative within the primary side of the βCD scaffold. Photoinduced energy transfer between the anthracene and the nitroaniline chromophores effectively suppresses the fluorescence of the anthracene unit. Excitation with visible light triggers the release of nitric oxide (NO) from the nitroaniline chromophore, accompanied to the concomitant revival of the anthracene fluorescence, which acts as an optical reporter for detecting the amount of the NO released. Furthermore, the anthracene moiety photogenerates singlet oxygen (1O2) sequentially to NO release. The conjugate is also able to accommodate hydrophobic guests within the βCD cavity, as proven by using naphthalene as a model compound. In view of the key role NO and 1O2 play as anticancer and antibacterial species, the present βCD derivative represents an intriguing candidate for further studies in biopharmaceutical research addressed to multimodal therapeutic applications.

Toward Multifunctional Polymer Hybrid through Tunable Charge Transfer Interaction of Anthracene/Naphthalenediimide

The interaction between building blocks in the polymer hybrids plays an important role in their performance and functions. Herein, a novel multifunctional polymer hybrid with tunable charge transfer (CT) interaction between π‐electron‐poor naphthalenediimide (NDI) containing polyimide (PI) and π‐electron‐rich anthracene (AN) ended polyhedral oligomer silsesquioxane (POSS‐AN) is reported (name the polymer hybrid “PI@POSS‐AN”), in which the presence of CT interaction between NDI and AN and its controllable feature are confirmed by UV−vis and fluorescence spectra. A new absorption band at 500 nm in the visible region appears and the emission maxima of the CT complexes are distinctly red‐shifted to 645 nm, while the fluorescence of NDI (493 nm) and AN (481 nm) are significantly quenched in the polymer hybrids. The resulting hybrid films are transparent and homogeneous, exhibit the enhanced thermal and mechanical performance with the increasing content of POSS‐AN. Thanks to the reversible photodimerization of AN, CT interaction between NDI and AN can be on‐off controlled in situ by UV light and heating, and rewritable fluorescence micro‐patterns with red and green emission can be obtained. In addition, the cross‐linked polymer hybrids possess healability and reprocessing performance.

Albert Coons: harnessing the power of the antibody

Albert Coons: harnessing the power of the antibody

Photon upconversion sensitized by a Ru(II)-pyrenyl chromophore.

The near-visible-to-blue singlet fluorescence of anthracene sensitized by a ruthenium chromophore with a long-lived triplet-excited state, [Ru(5-pyrenyl-1,10-phenanthroline)(3)](PF(6))(2), in acetonitrile was investigated. Low intensity non-coherent green light was used to selectively excite the sensitizer in the presence of micromolar concentrations of anthracene generating anti-Stokes, singlet fluorescence in the latter, even with incident power densities below 500 μW cm(-2). The resultant data are consistent with photon upconversion proceeding from sensitized triplet-triplet annihilation (TTA) of the anthracene acceptor molecules, confirmed through transient absorption spectroscopy as well as static and dynamic photoluminescence experiments. Additionally, quadratic-to-linear incident power regimes for the upconversion process were identified for this composition under monochromatic 488 nm excitation, consistent with a sensitized TTA mechanism ultimately producing the anti-Stokes emission characteristic of anthracene singlet fluorescence.

Enhancement of fluorescence in anthracene by chlorination: Vibronic coupling and transition dipole moment density analysis

The vibronic coupling constants and transition dipole moments for the Franck–Condon and adiabatic S1 states of anthracene, 9-chloroanthracene, and 9,10-dichloroanthracene were calculated and analyzed by using the concept of vibronic coupling density (VCD). The transition dipole moments are also analyzed on the basis of the transition dipole moment density (TDMD). The VCD analyses indicate that the vibronic couplings in the Franck–Condon S1 state come from the side rings of anthracene, and introduction of chlorine atoms reduces the vibronic couplings in the side regions and the reorganization energy. The TDMD analyses indicate that the chlorination enhances the transition dipole moment and that the contribution of the chlorine atom to the transition dipole moment is the largest. Finally, we derived a design principle for anthracene derivatives with a high quantum yield: the same long acceptors should be introduced into the two central carbon atoms in the anthracene’s central ring for the derivative to keep the point group to be D2h.

Anthracene Fluorescence Quenching by a Tetrakis (Ketocarboxamide) Cavitand

Quenching of both fluorescence lifetime and fluorescence intensity of anthracene was investigated in the presence of a newly derived tetrakis (ketocarboxamide) cavitand at various concentrations. Time-correlated single photon counting method was applied for the lifetime measurements. A clear correlation between the fluorescence lifetime of anthracene as a function of cavitand concentration in dimethylformamide solution was observed. The bimolecular collisional quenching constant was derived from the decrease of lifetime. Fluorescence intensity was measured in the emission wavelength region around 400 nm as a result of excitation at 280 nm. Effective quenching was observed in the presence of the cavitand. The obtained Stern-Volmer plot displayed upward curvature. The results did not follow even extended Stern-Volmer behavior, often used to describe deviations from static bimolecular quenching. To explain our results we adopted the Smoluchowski model and obtained a reasonable estimate for the molecular radius of the cavitand in solution.

Combined Quenching Mechanism of Anthracene Fluorescence by Cetylpyridinium Chloride in Sodium Dodecyl Sulfate Micelles

The Stern-Volmer quenching constant (KSV) for quenching of anthracene fluorescence in sodium dodecyl sulfate (SDS) micelles by pyridinium chloride has been reported previously to be 520M(-1) based on steady state fluorescence measurements. However, such measurements cannot distinguish static versus dynamic contributions to the overall quenching. In the work reported here, the quenching dynamics of anthracene in SDS micelles by cetylpyridinium chloride (CPC), an analogue of pyridinium chloride, were investigated using both steady state and time resolved fluorescence quenching. Concurrent measurement of the decrease in fluorescence intensity and lifetime of anthracene provide a quantitative evaluation of collision induced (i.e. dynamic) versus complex formation (i.e. static) quenching of the anthracene fluorophore. The results reveal that a combined quenching mechanism is operative with approximately equal constants of 249 ± 6M(-1) and 225 ± 12M(-1) for dynamic and static quenching, respectively.

Luminescence kinetics of two-component molecular systems in porous glasses

The kinetics of bimolecular photoreactions accompanied by a characteristic delayed emission of reactant molecules is studied in nanoporous silica glasses upon selective activation of a two-component luminophore system (erythrosine-anthracene) by a short (10 ns) pulse of a Nd3+:YAG laser (532 nm). Time-resolved luminescence signals with different shapes are recorded in different spectral regions. The emission at a wavelength of 430 nm is identified as the sensitized delayed annihilation fluorescence of anthracene. The long-time luminescence in the region of 570 nm consists of thermally induced delayed fluorescence of erythrosine and an emission resulting from heterogeneous annihilation of triplet excitations of erythrosine and anthracene. The effect of pore sizes on the triplet-triplet energy transfer efficiency is determined.

Chiral anthracene fluorescence system using achiral 1-naphthylmethylamine

A chiral anthracene fluorescence system was developed from achiral 2-anthracenecarboxylic acid and 1-naphthylmethylamine. Although chiral functional organic materials are usually prepared using chiral molecules, in this system, a chiral supramolecular organic fluorophore, which exhibited fluorescence in the solid state, was prepared from achiral molecular components.

The Kinetics of Joined Action of Triplet-Triplet Annihilation and First-Order Decay of Molecules in the State in the Case of Nondominant First-Order Process

This paper presents the description of triplet-triplet annihilation in the case of nondominant first-order decay of molecules in the triplet state. The kinetics of the statistical system is influenced by joined action of two processes: the first- and second-order decies. This kinetics can be described with analytical function if the rate parameter of second-order reaction is constant. The approach presented here combines the well-known Smoluchowski formula with the previously published intuitive and non-Fickian models of diffusion-controlled triplet-triplet annihilation. The kinetics of the delayed fluorescence of anthracene is used as a practical example of applicability of the model proposed. The advantages and limits of the proposed model are discussed.

Manipulation of Förster Energy Transfer of Coupled Fluorophores Through Biotransformation by Pseudomonas resinovorans CA10

An alkyne-terminated anthracene and azide-terminated carbazole were joined through a copper-catalyzed cycloaddition to form a joined donor/acceptor pair. The photonic pair exhibited energy transfer when excited at the peak absorbance of carbazole and fluoresced with an anthracene spectral response. The fluorescent behavior was confirmed as Förster energy transfer (FRET). The lysate of Pseudomonas resinovorans CA10, a member of a predominant group of soil microorganisms that can metabolize a host of substrates, was employed to degrade the pair and alter the luminance spectral characteristics. The FRET was diminished and the corresponding, individual fluorescence of carbazole and anthracene returned. This general approach may find applications in single-cell metabolic studies and bioactivity assays.

FRET Between Anthracene and Proflavine Hemisulphate in Micellar Solution and Analytical Application on Determination of Proflavine Hemisulphate

Fluorescence resonance energy transfer (FRET) between anthracene and proflavine hemisulphate is studied in micellar solution of sodium dodecyl sulfate. The fluorescence of anthracene is quenched by proflavine hemisulphate (PF) and quenching is accordance with Stern-Volmer relation. The efficiency of energy transfer found to increase with concentration of proflavine hemisulphate. The value of critical energy transfer distance (R0) calculated by using Foster relation is 19.34 Å and as it is less than 50 Å indicates efficient energy transfer in present system. The optimum conditions for the fluorometric determination of proflavine hemiulphate were studied and the quenching method was successfully applied to estimate the proflavine hemisulphate from the pharmaceutical sample directly.

A highly specific ferrocene-based fluorescent probe for hypochlorous acid and its application to cell imaging

A highly specific ferrocene-based fluorescent probe, (9-anthryl)ethenylferrocene, has been designed, synthesized and characterized for fluorescence imaging of hypochlorous acid (HOCl) in live cells. The design strategy for the probe is based on the strong quenching effect of electron-donor ferrocene on anthracene fluorescence via an intramolecular charge transfer process, and is accomplished through constructing the conjugated molecule by using a cleavable double bond as a linker. The double bond in the probe reacts selectively with HOCl rather than the other reactive oxygen species (e.g., *OH, *O(2)(-), (1)O(2), and H(2)O(2)) in pH 7.4, accompanied by more than 100-fold fluorescence enhancement. Moreover, the probe is cell membrane permeable, and its applicability has been successfully demonstrated for fluorescence imaging of HOCl in HeLa cells.

Self-assembly, stability quantification, controlled molecular switching, and sensing properties of an anthracene-containing dynamic [2]rotaxane

The preparation of a novel anthracene-containing dynamic [2]rotaxane by a templating self-assembly process between a diamine and a dialdehyde to form a [24]crown-8 macrocyclic diimine, in the presence of a dumbbell containing a secondary dialkylammonium ion center as the template, which has been exploited for its sensing properties. By appealing to the ability of the anthracene ring system--one of the two stoppers associated with the dumbbell--to act as a fluorescent probe, the fluorescence and fluorescence-quenching nature of the dynamic rotaxane in an equilibrium mixture has been investigated and quantified in the presence of external stimuli such as water, acids, salts, and an amine. The stability, as expressed by the hydrolysis of the dynamic rotaxane has been monitored by following: (i) the anthracene fluorescence and (ii) the movements of the signals in the (1)H NMR spectra. The rate of hydrolysis (t(1/2) = 6.9 min) of the dynamic rotaxane in the presence of a small amount (1 equiv.) of acid was found to be very much faster than when the hydrolysis was carried out with a large amount (>100 equiv.) of water, when t(1/2) > 140 min. Furthermore, it has been established that the anthracene fluorescence of the dynamic rotaxane rises with an increasing amount of acid. Two acid sensors have been identified with different operating modes-namely, logarithmic and linear. The combination of different inputs involving water, acids, salts and an amine leads to different fluorescence outputs from the dynamic rotaxane, hence, producing a prototype for expressing molecular logic.

Comportamento fotofísico do antraceno em sistemas micro-heterogêneos argila-surfactantes-íons metálicos

Argilas constituem uma classe de complexos micro-heterogêneos e podem ser utilizados como substrato para adsorção. O seu comportamento de sorção em fase sólida intensificada pela presença de surfactantes, argilas organofílicas, é um importante fenômeno explorado pela tecnologia ambiental para a remoção de compostos orgânicos policíclicos (hidrocarbonetos aromáticos policíclicos, HPA) da água, introduzidos no ambiente por fontes antropogênicas. Este trabalho tem por objetivo estudar o comportamento fotofísico do antraceno, como modelo de HPA, em sistemas micro-heterogêneos argila-surfactantes-íons metálicos (M(II)= Cd(II), Cu(II), Hg(II), Ni(II) e Pb(II); surfactantes: CTACl; SDS; TR-X100). Os estudos foram conduzidos pelo monitoramento na mudança das propriedades de fluorescência estática e na supressão da emissão do antraceno utilizado como sonda fluorescente. Como supressores foram utilizados os cátions metálicos: Cd(II), Cu(II), Hg(II), Ni(II) e Pb(II). O perfil do espectro de fluorescência e os resultados dos ensaios de supressão da fluorescência da sonda permitiram inferir na localização do sítio de solubilização do antraceno nos sistemas micro-heterogêneos estudados e na conseqüente organização dos mesmos.