Fluorescent dye encapsulated conjugated polymer nanoparticles have been paid significant attention for potential applications in photonics and biophotonics due to their high brightness and better photostability. Bright, photostable, and monodispersed Nile Red (NR) dye encapsulated poly-Nvinylcarbazole (PVK) fluorescent polymer nanoparticles have been prepared to understand the influence of size of particles and the concentration of dye inside the particles on the photophysical properties by using steady-state, timeresolved fluorescence spectroscopy and fluorescence correlation spectroscopy (FCS). Here, we have quantitatively analyzed the hydrodynamic diameter, particle brightness, and population of NR molecules inside the particle with varying the particle size and NR concentration by using fluorescence correlation spectroscopy (FCS). The average fluorescence intensity of a single nanoparticle, i.e., per particle brightness (PPB) value, increases from 80 to 500 kHz, and the number of NR molecules per nanoparticle increases from 5 to 22 by increasing the concentration of NR from 0.5 to 1.8 wt % at the time of nanoparticle preparation. Fluorescence anisotropy study has been undertaken to understand the rotational dynamics of encapsulated NR molecules with varying particle size and NR concentration inside the nanoparticle. The particle brightness and quantum yield are enhanced due to increasing the radiative decay rate. Higher brightness (almost one order of magnitude higher with respect to free dye) and better photostability (15-fold enhancement) of these polymer nanoparticles are found to be efficient for bioimaging purposes.
PCET is reported for free-base meso-(pyridyl)porphyrins, a pure organic system in dichloromethane solution, by employing UV/Vis and fluorescence spectroscopic techniques.
Steady state and time resolved fluorescence quenching behaviors of meso-Tetrakis (pentafluorophenyl) porphyrin (H(2)F(20)TPP) in presence of different aliphatic and aromatic amines have been executed in homogeneous dichloromethane (DCM) solution. At room temperature in DCM, free base (H(2)F(20)TPP) shows fluorescence with two distinct peaks at 640 and 711 nm and natural lifetime tauf=9.8 ns which are very similar to that of meso-tetraphenyl porphyrin (TPP). Unlike TPP, addition of both aliphatic and aromatic amines to a solution containing H(2)F(20)TPP results in an efficient decrease in fluorescence intensity without altering the shape and peak position of fluorescence emission. Upon addition of amines there was no change in optical absorption spectra of H(2)F(20)TPP. The fluorescence quenching rate constants ranged from 1 x 10(9) to 4 x 10(9) s(-1), which are one order below to the diffusion control limit, and temperature dependent quenching rate constants yield the activation energies which are found to be order of 0.1 eV. Femto second transient absorption studies reveal the existence of amine cation radical and porphyrin anion radicals with very short decay time (15 ps). The fluorescence quenching reaction follows Stern-Volmer kinetics. Steady state and time-resolved data are interpreted within general kinetic scheme of Marcus semi-classical model which attributes bimolecular electron transfer process between amines and the lowest excited singlet state of H(2)F(20)TPP. Calculated internal reorganization energies are found to be in between 0.04 and 0.22 ev. Variation of electron transfer rate as function of free energy change (DeltaG(0)) points the ET reactions in the present systems are in Marcus normal region. This is the first example of reductive fluorescence quenching of free base neutral porphyrins in homogeneous organic solvent ever known.
Enhanced reductive fluorescence quenching of meso-tetrakis-5,10,15,20-pentafluorophenyl porphyrin (H2F20TPP) by two different phenols, 4-methoxy phenol (4-MeOPhOH) and 2,6-dimethoxy phenol (2,6-DiMeOPhOH) in the presence of various pyridine bases in dichloromethane solution is studied using steady state and time resolved fluorescence spectroscopic methods by employing time correlated single photon counting (TCSPC) and fluorescence up-conversion techniques. An enhanced quenching behaviour of H2F20TPP is observed when phenols are hydrogen bonded to various pyridine bases. Quenching observed in the steady state and time resolved studies in the nanosecond time domain follows second order kinetics and generates quenching rate constants and hydrogen bond equilibrium constants, the latter of which agree quite closely with those obtained from independent spectroscopic measurements. A significant kinetic deuterium isotope effect is observed, indicating the importance of proton movement in the quenching processes. This quenching effect is attributed to be due to a tri-molecular transition state involving H2F20TPP and a hydrogen bonded phenol complex, in which electron transfer from phenol to excited H2F20TPP is concerted with proton movement from the phenol to hydrogen bonded base. Observed quenching behaviours are rationalized by invoking diffusion controlled proton coupled electron transfer. Fluorescence up-conversion studies in the 100 ps time domain confirm ultrafast PCET for 4-MeOPhOH and base pairs which fall in a non-diffusive regime.
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