Femtosecond time resolved fluorescence dynamics of a cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene)

A recently synthesized cationic water-soluble poly(fluorenevinylene-co-phenylenevinylene) was studied by means of steady state and femtosecond time resolved upconversion spectroscopy in aqueous and EtOH solutions. Steady state spectroscopic measurements showed that the polymer emits at the blue-green spectral region and that aggregates are formed in concentrated polymer solutions. The fluorescence dynamics of the polymer in concentrated solutions, studied at a range of emission wavelengths, exhibited a wavelength dependent and multiexponential decay, indicating the existence of various decay mechanisms. Specifically, a rapid decay at short emission wavelengths and a slow rise at long wavelengths were observed. Both features reveal an energy transfer process from isolated to aggregated chains. The contribution of the energy transfer process as well as of the isolated chains and the aggregates on the overall fluorescence decay of the polymer was determined. The dependence of the energy transfer rate and efficiency on polymer concentration was also examined.     

Fluorescence blinking, exciton dynamics, and energy transfer domains in single conjugated polymer chains

In order to understand exciton migration and fluorescence intensity fluctuation mechanisms in conjugated polymer single molecules, we studied fluorescence decay dynamics at "on" and "off" fluorescence intensity levels with 20 ps time resolution using MEH-PPV [poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] dispersed in PMMA. Two types of intensity fluctuations were distinguished for single chains of conjugated polymers. Abrupt intensity fluctuations (blinking) were found to be always accompanied by corresponding changes in fluorescence lifetime. On the contrary, during "smooth" intensity fluctuations no lifetime change was observed. Time-resolved data in combination with data on fluorescence emission and excitation anisotropy lead to a picture where a single polymer molecule is seen as consisting of several energy transfer domains. Exciton migration is efficient within a domain and not efficient between domains. Each domain can have several emitting low-energy sites over which the exciton continuously migrates until it decays. Emission of individual domains is often highly polarized. Fluorescence from a domain can be strongly quenched by Forster energy transfer to a quencher (hole polaron) if the domain overlaps with the quenching sphere.     

Exciton diffusion and relaxation in methyl-substituted polyparaphenylene polymer films

Exciton diffusion in ladder-type methyl-substituted polyparaphenylene film and solution was investigated by means of femtosecond pump-probe spectroscopy using a combined approach, analyzing exciton-exciton annihilation, and transient absorption depolarization properties. We show that the different views on the exciton dynamics offered by anisotropy decay and annihilation are required in order to obtain a correct picture of the energy transfer dynamics. Comparison of the exciton diffusion coefficient and exciton diffusion radius obtained for polymer film with the two techniques reveals that there is substantial short-range order in the film. Also in isolated chains there is considerable amount of order, as revealed from only partial anisotropy decay, which shows that only a small fraction of the excitons move to differently oriented polymer segments. It is further concluded that interchain energy transfer is faster than intrachain transfer, mainly as a result of shorter interchain distances between chromophoric units.     

CHLOROPHYLLS IN POLYMERS. I. STATE OF CHLOROPHYLL a IN UNSTRETCHED POLYMER SYSTEMS

Abstract— Model systems for the study of energy transfer processes are useful for the elucidation of the various factors governing the mechanism of energy transfer in photosynthetic systems. Here we describe the characterization of two systems, consisting of chlorophyll a incorporated in anhydrous nitrocellulose and polyvinylalcohol films. First, optical spectroscopy and time-resolved fluorescence techniques are used to characterize the state of the chlorophyll molecules in the films. We find that in nitrocellulose films the state of chlorophyll a depends strongly on the ratio of nitrocellulose to dimeth-ylsulfoxide in the solutions from which the films are cast. The state of chlorophyll a in polyvinylalcohol films does not depend on the amount of polymer originally dissolved in dimethylsulfoxide. In these films the pigment is monomeric at low concentrations of chlorophyll a, but aggregates are formed at much lower concentrations than in nitrocellulose. The latter fact is explained by the existence of pockets in polyvinylalcohol, leading to high local concentrations.
To further test the suitability of the nitrocellulose polymer films as model systems for energy transfer processes, time-resolved fluorescence anisotropy profiles are measured in dependence of the concentration of pigments in the matrix. Fits of the observed decay profiles to the predicted decay show good correspondence, as long as no traps are present. Furthermore, the fitted decay times yield the correct value of the Forster radius R₀ as compared to the value obtained spectroscopically. We thus conclude that the chlorophyll a-nitrocellulose system can be very appropriate for the study of energy transfer processes between photosynthetic pigment, since the pigments are uniformally distributed in the matrix.     

Influence of donor:acceptor ratio on charge transfer dynamics in non-fullerene organic bulk heterojunctions

The donor:acceptor(D:A) blend ratio plays a very important role in affecting the progress of charge transfer and energy transfer in bulk heterojunction(BHJ) orga nic solar cells(OSCs).The proper D:A blend ratio can provide maximized D/A interfacial area for exciton dissociation and appro p riate domain size of the exciton diffusion length,which is beneficial to obtain high-performance OSCs.Here,we comprehensively investigated the relationship between various D:A blend ratios and the charge transfer and energy transfer mechanisms in OSCs based on PBDB-T and non-fullerene acceptor IT-M.Based on various D:A blend ratios,it was found that the ratio of components is a key factor to suppress the formation of triplet states and recombination energy losses.Rational D:A blend ratios can provide appropriate donor/accepter surface for charge transfer which has been powerfully verified by various detailed experimental results from the time-resolved fluorescence measurement and transient absorption(TA) spectroscopy.Optimized coherence length and crystallinity are verified by grazing incident wide-angle X-ray scattering(GIWAXS) measurements.The results are bene ficial to comprehend the effects of various D:A blend ratios on charge transfer and energy transfer dynamics and provides constructive suggestions for rationally designing new materials and feedback for photovoltaic performance optimization in non-fullerene OSCs.     

Quantum yields of luminescent lanthanide chelates and far-red dyes measured by resonance energy transfer.

Luminescent lanthanide chelates have unusual spectroscopic characteristics that make them valuable alternative probes to conventional organic fluorophores. However, fundamental parameters such as their quantum yield, and radiative and nonradiative decay rates have been difficult or impossible to measure. We have developed a simple and robust method based on resonance energy transfer to accurately measure these parameters. In addition, the excitation/emission process in lanthanide chelates involves several steps, and we are able to quantify each step. These include excitation of an organic antenna, transfer of energy from the antenna to lanthanide, and then lanthanide emission. Overall, the parameters show that lanthanide chelates can be efficient long-lived emitters, making them sensitive detection reagents and excellent donors in resonance energy transfer. The method is also shown to be applicable to photophysical characterization of red-emitting dyes, which are difficult to characterize by conventional means.     

Energy transfer in polymers and nitroxide decay during photolysis

When polymeric materials doped with nitroxides of the 2,2,6,6-tetramethylpiperidine type are exposed to light, the nitroxide concentration decreases. The two mechanisms for the decrease of the nitroxide are the reaction of nitroxide with free radicals produced during photolysis of the polymer to form amino ethers and the abstraction of hydrogen atoms by excited-state nitroxides to form hydroxyl amines. Excited-state nitroxides can be formed in two ways: by direct absorption and by energy transfer. In this paper, the effect of energy transfer on the rate of decay of the nitroxide signal is studied, and measurements of nitroxide decay are used to probe energy transfer in crosslinked polymeric coatings. A simple kinetic scheme is used to interpret nitroxide decay during photolysis of both solutions and polymers containing benzophenone. These results are used to show that the slope of the line relating nitroxide decay rate to nitroxide concentration is essentially determined by energy transfer from a coating-based chromophore to nitroxide. The nitroxide decay assay is also used to study the effectiveness of a benzotriazole ultraviolet light absorber as a quencher.     

Direct non-radiative energy transfer studies of interdiffusion latex films: Strategies for data analysis

We are interested in studying polymer diffusion across an interface by direct non-radiative energy transfer. In this paper we examine different approaches and techniques to analyze fluorescence decay data in such systems. One type of technique is used to calculate a parameter f_m characterizing the extent of mixing. A second technique allows the concentration profile of the acceptor dyes at the interface to be evaluated. The third technique introduces the diffusion model into the decay profile analysis and yields the diffusion coefficient of the polymers. We found that when characterizing the extent of interdiffusion using the fraction parameter f_m, ignorance of the detailed concentration gradient does not introduce significant error. The evaluation of diffusion coefficients is a complicated task due to the broad distribution of polymer molecules in latex films.     

Quantifying growth of symmetric and asymmetric lipid bilayer domains

Here, we examine by atomic force microscopy (AFM) the kinetics and morphology of lipid domain growth during lipid phase separation by rapid thermal cooling of fully mixed two-component supported lipid bilayers. At the undercooled temperatures chosen, symmetric 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC)-rich domains favored slower reaction-limited growth whereas asymmetric galactosylceramide (GalCer)-rich domains favored faster diffusion-limited growth, indicated by shape factors and kinetic exponents. Because kinetically limited conditions could be accessed, we were able to estimate the activation energy barrier (approximately 16kT) and lateral diffusion coefficient (approximately 0.20 microm2/s) of lipid molecular addition to a growing domain. We discuss these results with respect to transition states, obstructed diffusion, and the necessity for coordinating growth in both leaflets in a symmetric lipid domain.     

Self-diffusion coefficients of organic solvents in linear and branched high density polyethylene particles measured by PFG NMR

Pulsed field gradient nuclear magnetic resonance （PFG NMR） has been performed to study the diffusion of organic solvents into semicrystalline polyethylene particles. Self-diffusion coefficients in different domains of the sample can be extracted through a bi- exponential fit to the echo intensity attenuation, which allows the precise determination of the tortuosity of the polyethylene particles. Further exploration comes from the measurements with branched polyethylene particles and it was found that the diffusion in polymer phase contributed significantly to the slow component of the exponential decay curve. 2007 Jing Dai Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

SITE-TO-SITE DIFFUSION IN PROTEINS AS OBSERVED BY ENERGY TRANSFER AND FREQUENCY-DOMAIN FLUOROMETRY *

Abstract We report measurements of the site-to-site diffusion coefficients in proteins and model compounds, which were measured using time-dependent energy transfer and frequency-domain fluorometry. The possibility of measuring these diffusion coefficients were shown from simulations, which demonstrate that donor (D)-to-acceptor (A) diffusion alters the donor frequency response, and that this effect is observable in the presence of a distribution of donor-to-acceptor distances. For decay times typical of tryptophan fluorescence, the simulations indicate that D-A diffusion coefficients can be measured ranging from ^?7 to ^?5 cm²/s. This possibility was verified by studies of a methylenechain linked D-A pair in solutions of varying viscosity. The D-A diffusion was also measured for two labeled peptides and two proteins, melittin and troponin I. In most cases we used global analysis of data sets obtained with varying amounts of collisional quenchers to vary the donor decay time. Unfolding of troponin I results in more rapid D-A diffusion, whereas for melittin more rapid diffusion was observed in the α-helical state but over a limited range of distances.     

Monitoring Diffusion of Reptating Polymer Chains by a Direct Energy Transfer Method: A Monte Carlo Simulation

A kinetic Monte Carlo method was used to simulate the diffusion of reptating polymer chains across an interface. A time‐resolved fluorescence technique in conjunction with a direct energy transfer method was used to measure the extent of diffusion of dye‐labeled reptating polymer chains. The diffusion of donor‐ and acceptor‐labeled polymer chains between adjacent compartments was randomly generated. The fluorescence decay profiles of donor molecules were simulated at several diffusion steps to produce mixing of the polymer chains. Mixing ratios of donor‐ and acceptor‐labeled polymer chains in compartments were measured at various stages (snapshots) of diffusion. It was observed that for a given molecular weight, the average interpenetration contour length was found to be proportional to the mixing ratio. Monte Carlo analysis showed that the curvilinear diffusion coefficient is inversely proportional to the weight of polymer chains during diffusion.     

Single particle versus ensemble average: from power-law intermittency of a single quantum dot to quasistretched exponential fluorescence decay of an ensemble

Light-induced diffusion-controlled electron transfer is proposed as an underlying mechanism for the intermittency (power law and breakdown) of a single quantum dot and ensemble-averaged fluorescence decay. The intensity decay can be approximated to a stretched exponential expression. The physical links to the free energy gap, reorganization energy, electronic coupling, and diffusion correlation times are discussed. A procedure is described for extracting these molecular-based parameters from experiments and is demonstrated with examples using existing data.     

Orientational dynamics of water confined on a nanometer length scale in reverse micelles

The time-resolved orientational anisotropies of the OD hydroxyl stretch of dilute HOD in H(2)O confined on a nanometer length scale in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles are studied using ultrafast infrared polarization and spectrally resolved pump-probe spectroscopy, and the results are compared to the same experiments on bulk water. The orientational anisotropy data for three water nanopool sizes (4.0, 2.4, and 1.7 nm) can be fitted well with biexponential decays. The biexponential decays are analyzed using a wobbling-in-a-cone model that involves fast orientational diffusion within a cone followed by slower, full orientational relaxation. The data provide the cone angles, the diffusion constants for motion within the cones, and the final diffusion constants as a function of the nanopool size. The two processes can be interpreted as a local angular fluctuation of the OD and a global hydrogen bond network rearrangement process. The trend in the relative amplitudes of the long and short exponential decays suggest an increasing rigidity as the nanopool size decreases. The trend in the long decay constants indicates a longer hydrogen bond network rearrangement time with decreasing reverse micelle size. The anisotropy measurements for the reverse micelles studied extrapolate to approximately 0.33 rather than the ideal value of 0.4, suggesting the presence of an initial inertial component in the anisotropy decay that is too fast to resolve. The very fast decay component is consistent with initial inertial orientational motion that is seen in published molecular-dynamics simulations of water in AOT reverse micelles. The angle over which the inertial orientational motion occurs is determined. The results are in semiquantitative agreement with the molecular-dynamics simulations.     

The determination of the Förster distance (R0) for phenanthrene and anthracene derivatives in poly(methyl methacrylate) films

Experiments that employ direct resonance energy transfer (DET) to obtain information about distances or domain sizes in polymer systems require independent information about the magnitude of the characteristic (F?rster) energy transfer distance R(0). Values of R(0) are relatively straightforward to obtain by the traditional spectral overlap method (R(0)(SO)) for dyes in fluid solution, but are much more difficult to obtain for dyes in rigid polymer films. Here one can obtain a value for R(0) as a fitting parameter (R(0)(FF)) for donor fluorescence decay experiments for samples containing a random distribution of donor and acceptor dyes in the polymer film. In previous experiments from our group, we needed values of R(0) for various phenanthrene (Phe, donor) and anthracene (An, acceptor) derivatives. In this paper, we describe experiments which determine R(0) values by both methods for a series of Phe-An donor-acceptor pairs in poly(methyl methacrylate) and polystyrene films. Both the location of substituents on the donor and acceptor as well as the choice of the medium had an effect on the measured R(0), which varied between 2.0 and 2.6 nm. We also ascertained that there is some unknown factor, also prevalent in the work of others, which results in the F?rster radius being larger when determined by the F?rster fit method than by the method of spectral overlap.     

Coupled single-particle growth and kinetics modeling for styrene polymerization over silica-supported metallocene catalyst

A comprehensive mathematical model for styrene stereoregular polymerization was carried out. This model was generated by coupling the single particle growth model (SPGM) with kinetics model, to predict the effect of intraparticle mass transfer resistance and initial catalyst size on the polymerization kinetics. SPGM was derived based on a modified multigrain model (MMGM) to calculate the spatial-time evolution of styrene concentration under intraparticle mass transfer limitations. Then, the SPGM was solved simultaneously with kinetics model to estimate the polymerization rate and molecular weight distribution (MWD) under the above mentioned limitations. The results show that a significant radial distribution of styrene concentration across polymer growing. Moreover, the diffusion resistance was most intense at the early step of the polymerization and the effects of the polymerization rate are more strongly. Additionally, it is appear that increasing the initial catalyst size leads to a decrease in the rate of polymerization. For MWD, the model simulation show that the diffusion resistance led to have an increase in the molecular weight within a period of time similar to the one needed in the catalyst decay. The validation of the model with experimental data given a agreement results and shows that the model is able to predict monomer profile, polymerization rate, and MWD of syndiotactic polystyrene.     

A self healing model based on polymer-mediated chromophore correlations

Here we present a model of self healing in which correlations between chromophores, as mediated by the polymer, are key to the recovery process. Our model determines the size distribution of the correlation volume using a grand canonical ensemble through a free energy advantage parameter. Choosing a healing rate that is proportional to the number of undamaged molecules in a correlated region, and a decay rate proportional to the intensity normalized to the correlation volume, the ensemble average is shown to correctly predict decay and recovery of the population of disperse orange 11-DO11 (1-amino-2-methylanthraquinone) molecules doped in PMMA polymer as a function of time and concentration as measured with amplified spontaneous emission and linear absorption spectroscopy using only three parameters that apply to the full set of data. Our model also predicts the temperature dependence of the process. One set of parameters should be characteristic of a particular polymer and dopant chromophore combination. Thus, the use of the model in determining these parameters for various materials systems should provide the data needed to test fundamental models of the underlying mechanism responsible for self healing.     

Fragmentation of singly charged adenine induced by neutral fluorine beam impact at 3 keV

The fragmentation scheme of singly charged adenine molecule (H(5)C(5)N(5)(+)) has been studied via neutral fluorine impact at 3 keV. By analyzing in correlation the kinetic energy loss of the scattered projectile F(-) produced in single charge transfer process and the mass of the charged fragments, the excitation energy distribution of the parent adenine molecular ions has been determined for each of the main dissociation channels. Several fragmentation pathways unrevealed in standard mass spectra or in appearance energy measurements are investigated. Regarding the well-known hydrogen cyanide (HCN) loss sequence, we demonstrate that although the loss of a HCN is the dominant decay channel for the parent H(5)C(5)N(5)(+) (m = 135), the decay of the first daughter ion H(4)C(4)N(4)(+) (m = 108) involves not only the HNC (m = 27) loss but also the symmetric breakdown into two dimers of HCN.     

Mass transfer in composite polymer-zeolite catalytic membranes

The incorporation of zeolite-encaged iron-phthalocyanine partial oxidation catalysts into a dense hydrophobic polymer membrane results in a substantial improvement in catalyst performance. The diffusion through these zeolite-filled membranes is described using a two-dimensional model, and it is demonstrated that for a permeability ratio (polymer over catalyst) higher than 10⁴, the diffusion through composite polymer-zeolite membranes can be described by a one-dimensional model. Such a one-dimensional mathematical model was developed and validated with the experimental data, obtained from the time lag measurements on zeolite-filled poly(dimethylsiloxane) polymer membranes. Consequently diffusion through composite catalytic membranes can be predicted using the mass transfer coefficients of pure catalyst and polymer material, and a single tortuosity factor, only dependent on the catalyst loading.     

Diffusion of oriented single molecules with switchable mobility in networks of long unidimensional nanochannels

Single dye molecules incorporated into a mesoporous matrix can act as highly sensitive reporters of their environment. Here, we use single TDI molecules incorporated as guests into hexagonal mesoporous films containing highly structured domains. The dye molecules allow us to map the size of these domains which can extend to over 100 microm. Investigation of the translational and orientational dynamics via single molecule fluorescence techniques gives structural as well as dynamical information about the host material. In an air atmosphere, the guest molecules show no movement but perfect orientation along the pore direction. The diffusion of the TDI molecules can be induced by placing the mesoporous film in a saturated atmosphere of chloroform. In single molecule measurements with very high positioning accuracy (down to 2-3 nm) the movement of molecules could be observed even between neighboring channels. This reveals the presence of defects like dead ends closing the pores or small openings in the silica walls between neighboring channels, where molecules can change from one channel to the next. A statistical analysis demonstrates that the diffusion of TDI in the mesoporous film cannot be described with a 1D-random diffusion but is more complicated due to the presence of adsorption sites in which the TDI molecules can be occasionally trapped.