Fluorescence spectroscopy mechanisms

Ha T, Ting A Y, Liang J, Caldwell W B, Deniz A A, Chemla D S, Schultz P G and Weiss S 1999 Single-molecule fluorescence spectroscopy of enzyme conformational dynamics and cleavage mechanism Proc. Natl Acad. Sc/. USA 96 893-8... 

The most significant differences (i.e. independence) in the analytical methods are provided in the final chromatographic separation and detection step using GC/ MS and LC-FL. GC and reversed-phase LG provide significantly different separation mechanisms for PAHs and thus provide the independence required in the separation. The use of mass spectrometry (MS) for the GC detection and fluorescence spectroscopy for the LG detection provide further independence in the methods, e.g. MS can not differentiate among PAH isomers whereas fluorescence spectroscopy often can. For the GC/MS analyses the 5% phenyl methylpolysiloxane phase has been a commonly used phase for the separation of PAHs however, several important PAH isomers are not completely resolved on this phase, i.e. chrysene and triphenylene, benzo[b]fluoranthene and benzofjjfluoranthene, and diben-z[o,h]anthracene and dibenz[a,c]anthracene. To achieve separation of these isomers, GC/MS analyses were also performed using two other phases with different selectivity, a 50% phenyl methylpolysiloxane phase and a smectic liquid crystalline phase. 

Additional support for this disassembly mechanism was obtained by monitoring the release of the pyrene tail units by fluorescence spectroscopy. The confined proximity of the pyrene units in the dendritic molecule results in formation of excimers. The excimer fluorescence generates a broad band at a wavelength of 470 nm in the emission spectrum of dendron 31 (Fig. 5.25). Upon the release of the pyrene units from the dendritic platform, the 470 nm band disappeared from... 

In the present work, we have examined poly(N-vinylcarbazole) (abbreviated hereafter as PVCz) and pyrene-doped poly(aethyl methacrylate) (PMMA) films by using a tine-resolved fluorescence spectroscopic aethod. Fluorescence spectra and their dynanic behavior of the forner fila were elucidated with a high intensity laser pulse and a streak camera, which nakes it possible to neasure dynaaics just upon laser ablation. This aethod reveals aolecular and electronic aspects of laser ablation phenomena (17). For the latter fila a laser pulse with weak intensity was used for characterizing the ablated and Basked areas. On the basis of these results, we demonstrate a high potential of fluorescence spectroscopy in aolecular studies on laser ablation and consider its mechanism. Experimental... 

Rettig W, Rurack K, Sczepan M (2001) From cyanines to styryl bases - photophysical properties, photochemical mechanisms, and cation sensing abilities of charged and neutral polymethinic dyes. In Valeur B, Brochon JC (eds) New trends in fluorescence spectroscopy applications to chemical and life sciences. Springer, Berlin, pp 125-155... 

Lakowicz JR (2006) Mechanisms and dynamics of fluorescence quenching, Chapter 9. In Principles of fluorescence spectroscopy, 3rd edn. Springer, New York... 

Volume 4 is intended to summarize the principles required for these biomedical applications of time-resolved fluorescence spectroscopy. For this reason, many of the chapters describe the development of red/NIR probes and the mechanisms by which analytes interact with the probes and produce spectral changes. Other chapters describe the unique opportunities of red/NIR fluorescence and the types of instruments suitable for such measurements. Also included is a description of the principles of chemical sensing based on lifetimes, and an overview of the ever-important topic of immunoassays. 

Brown and Bern (26) cinalyzed the elemental composition of four card room dusts using X-ray fluorescence spectroscopy. Two of these were from filter cake material collected in two textile mills from which fine dusts (<20 ym) were separated by mechanical agitation (sonic sifting). The third sample was from filter cake material collected in a textile mill from which dust was removed by hexane washing followed by sonification of the bath, filtration and further sonification. The fourth sample came from dust collected on an electrostatic precipitator in a model card room. Results are shown in Table VI. 

Because the mechanisms of 1-naphtol complexation with HA obtained by using these three techniques exhibit similar pathways, we present the results only from fluorescence spectroscopy. The ratio of fluorescence intensity in the absence (FJ and in the presence (F) of the quencher (HA) over time, as affected by pH and ionic strength, are illustrated in Fig. 16.20. The fluorescence intensity of a fluorophore in the absence of a quencher is directly proportional to its concentration in solution, and therefore time-dependent changes in E can be used to assess the stability of 1-naphtol under different pH and ionic strength. Quenching (FQ) of 1-naphtol fluorescence by humic acid increased with equilibration time from one to seven days. This time-dependent relationship was found to result from weak complexation of... 

Combining fluorescence spectroscopy with fluorescence microscopy, confocal microscopy could be used to elucidate the pathway of siderophore-mediat iron uptake in the fungus Ustilago maydis, and visualize this pathway by providing unique fluorescent microscopic images. Using these techniques, clear images of two independent iron-uptake mechanisms have become visualized as well as their cellular compartment locahzed. 

Fig. 7. Potential mechanisms of actinide (represented by Cm(ni)) interaction with colloids as interpreted from laser fluorescence spectroscopy (TRLFS) experiments. Spectra are taken from Stumpf et al. (2001o, b) and Chung et al. (1998).

Wandruszka et al. (1997) studied the role of selected cations in the formation of pseudomicelles in aqueous HA using fluorescence spectroscopy. Ragle et al. (1997) applied fluorescence techniques to study mechanisms for the interactions of dissolved HA with nonpolar micropollutants. 

Binding of the components in a neutral aqueous solution was confirmed by potentiometric titrations. The feasibility of electron transfer between the components was predicted by cyclic voltammetry and an efficient outer-sphere fast electron transfer was foreseen. Fluorescence spectroscopy measurements showed that the formation of a defined donor-acceptor complex worked even in water at neutral pH. Electron transfer as the quenching mechanism was proved by laser flash photolysis. 

Ha, T., Ting, A. Y., Liang, J., Caldwell, W. B., Deniz, A. A., Chemla, D. S., Schultz, P. G., and Weiss, S (1999a). Single-molecule fluorescence spectroscopy of enzyme conformational dynamics and cleavage mechanism. Proc. Natl. Acad. Sci. USA 96, 893-898. 

Chan, C. "Measurement of OH in Flames using Laser Induced Fluorescence Spectroscopy" Ph.D. thesis, Department of Mechanical Engineering, University of California, Berkeley, 1979. 

To improve topical therapy, it is advantageous to use formulation additives (penetration enhancers) that will reversibly and safely modulate the barrier properties of the skin. Fick s first law of diffusion shows that two potential mechanisms are possible. The two constants that could be altered significantly are the diffusion coefficient in the stratum corneum and the concentration in the outer regions of the stratum corneum. Thus, one of mechanisms of action of an enhancer is for it to insert itself into the bilayer structures and disrupt the packing of the adjacent lipids, thereby, reducing the microviscosity. The diffusion coefficient of the permeant will increase This effect has been observed using ESR and fluorescence spectroscopy [16,17]. 

We have also prepared BLMs from polymerizable surfactants and polymerized them in situ (26). Extents of polymerization have been followed by nanosecond, time-resolved fluorescence spectroscopy and anisotropic measurements (26). Experiments have been initiated for realizing the different biological transport mechanisms in polymerized and partially-polymerized BLMs and for studying their mechanisms by simultaneous electrical and spectroscopic measurements. 

Hydrogen. The reaction of O ( D2) with H2 takes place on the ground state potential surface of water, HiOf Ai). On the basis of trajectory calculations, (Whitlock et al., 1982) it has been suggested that, as is true for the hydrocarbons, parallel mechanisms involving insertion/elimination and direct abstraction govern the course of this reaction. The observation using laser induced fluorescence spectroscopy (Luntz et al., 1979 Smith and Butler, 1980) of a highly excited, non-Boltzmann rotational distribution and a nearly statistical vibrational distribution for v" = 1 and v" = 0 is consistent with the insertion/elimination... 

Metal-free phthalocyanine (H2PC) exists in the a, P, r, and X polymorphic forms. The a,P, and X forms have been characterized by electrochemistry [36a], fluorescence spectroscopy [36b], and optical absorption [36c] and a,p, and t forms by C-NMR spectroscopy [36d], optical absorption, and X-ray powder diffraction [36e]. Figure 19 shows the optical absorption spectra of the four forms. The t form has been further characterized as to particle shape (Types I and II) [36f]. The as-synthesized y9-H2Pc is converted to a-H2Pc by acid pasting and this can be converted to the X or T forms with mechanical milling under specific conditions. The X and r forms convert to the P with thermal, solvent, or extended mechanical treatment. 

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