Hydrocarbons fluorescence enhancement

Sodiiun dodecylsulfate, cetyltrimethylam-monium chloride, sodium cholate, -cyclodextrin dansylated amino acids and polycyclic aromatic hydrocarbons > 45-fold 1% in water the greatest enhancement of fluorescence is that of sodium cholate on pyrene [263]... 

In addition, data obtained from infrared, thermal, and fluorescence spectroscopic studies of the outermost layer of skin, stratum corneum (SC), and its components imply enhancer-improved permeation of solutes through the SC is associated with alterations involving the hydrocarbon chains of the SC lipid components. Data obtained from electron microscopy and x-ray diffraction reveals that the disordering of the lamellar packing is also an important mechanism for increased permeation of drugs induced by penetration enhancers (for a recent review, see Ref. 206). 

It is possible, however, that the electrochromic response of some styrylpyridi-nium probes, for example, RH421 (see Fig. 2), is enhanced by a reorientation of the dye molecule as a whole within the membrane. There is a steep gradient in polarity on going from the aqueous environment across the lipid headgroup region and into the hydrocarbon interior of a lipid membrane. Therefore, any small reorientation of a probe within the membrane is likely to lead to a change in its local polarity and hence a solvatochromic shift of its fluorescence excitation spectrum. Such a... 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

Most fluorescent PET molecular sensors, including pH indicators of this type, consist of a fluorophore linked to an amine moiety via a methylene spacer. Photo-induced electron transfer (see Chapter 4, Section 4.3), which takes place from amino groups to aromatic hydrocarbons, causes fluorescence quenching of the latter. When the amino group is protonated (or strongly interacts with a cation), electron transfer is hindered and a very large enhancement of fluorescence is observed. 

Pyrene Carboxaldehyde Probe Studies. Fluorescence spectra of 1-pyrene carboxaldehyde in nonane solutions of sulfonates A and B and In an octane solution of Aerosol OT are compared to the probe spectra in pure hydrocarbon media in Figure 1. Parts (a) and (b) are of sulfonates A and B systems, respectively part (c) is of aerosol OT system. They were constructed at different gain settings and therefore the intensities shown for the individual system are not directly comparable. The fluorescence intensity of 1-pyrene carboxaldehyde in nonane alone is much weaker than in either the sulfonate A or sulfonate B solution. Aerosol OT containing solubilized H.O does not enhance the fluorescence intensity of 1-pyrene carboxardehyde as much as sulfonates A and B, but the band maximum is shifted as expected for this probe in a water-rich medium. 

Pyrene Carboxaldehyde in Calcium Alkarylsulfonates. Our work shows that 1-pyrene carboxaldehyde as a fluorescent probe for the sulfonate systems behaves very much the same as rhodamine B (1 ) and anillnonaphthalene sulfonate (2), whose fluorescence intensities in hydrocarbon media are enhanced in the presence of inverted micelles. However, the intensity Increase observed with AOT was considerably less than that observed with the sulfonates. It is speculated that... 

Wilkinson has recently described a novel approach.113 It has long been known that solvents containing heavy atoms markedly quench the fluorescence of aromatic hydrocarbons, and it has been shown that this effect arises from an enhancement of the rate of intersystem crossing. Thus the ratio of phosphorescence to fluorescence for naphthalene irradiated at 77°K can be increased more than a hundredfold upon addition of some isopropyl iodide to the solvent.114 The same effect has been noted upon changing from hydrocarbon glasses to frozen krypton and xenon matrices.115 Wilkinson found that the decrease in fluorescence intensity from irradiated solutions of anthracene and some of its derivatives upon addition of bromobenzene is attended by an increase in T-T absorption intensity.116 The fluorescence quenching follows the Stern-Volmer law ... 

Recent work by Schmidt and Schuster (1978a, 1980a) has shown that the addition of any of several easily oxidized, fluorescent aromatic hydrocarbons or amines to solutions of [21] results in greatly enhanced chemiluminescence. Moreover, addition of these molecules accelerates the rate of reaction of [21]. The catalyzed reaction is first order in both [21] and aromatic hydrocarbon or amine (which is termed the activator, act). Acetone is still produced quantitatively, and the activator is not consumed in the reaction, but rather serves as a catalyst for the decomposition of the dioxetanone. The kinetic behavior is thus described by the simple rate law (27), where kt is the rate... 

Likewise, the luminescence properties of many analytes can be altered in the presenoe of surfactant aggregates (4,7.,8.). Consequently, addition of micelle-forming surfactants (present either in the LC mobile phase or added post-column) can improve the sensitivity of fluorimetric LC detectors (49,482). Micellar spray reagents have been utilized to enhance the fluorescence densitometric detection of dansylamino acids or polycyclic aromatic hydrocarbons (483). The effect was observed for TLC performed on cellulose or polyamide stationary phases with the micellar spray reagent being either CTAC, SB-12, or NaC (483). More recently, use of nonionic Triton X-100 has been found to improve the HPLC detection of morphine by fluorescence determination after post-column derivatization (486) as well as improve the N-chlorination procedure for the detection of amines, amides, and related compounds on thin-layer chromatograms (488). 

Radiation absorbed by atoms under conditions used in atomic absorption spectrometry may be re-emitted as fluorescence. The fluorescent radiation is characteristic of the atoms which have absorbed the primary radiation and is emitted 1n all directions. It may be monitored in any direction other than in a direct line with radiation from the hollow-cathode lamp which ensures that tha detector will not respond to the primury absorption process nor to unabsorbed radiation from the lamp. The intensity of fluorescent emission is directly proportional to the concentration of the absorbing atoms but it is diminished by collisions between excited atoms and other species within the flame, a process known as quenching. Nitrogen and hydrocarbons enhance quenching, and flames incorporating either should be avoided or their effect modified by dilution with argon. 

Often, experimental studies of lipid systems are based on spectroscopic approaches, which in turn frequently employ probes for enhancement of sensitivity and resolution. For example, in NMR, hydrogen atoms of lipids are replaced with deuterium, and in fluorescence spectroscopy and imaging, native lipid molecules are replaced with lipids in which one of the hydrocarbon chains is linked covalently to a fluorescent marker such as pyrene or diphenylhexatriene. Fluorescent markers allow one to follow numerous cellular processes in real time, such as intracellular trafficking of molecules and formation of domains within a biomembrane, see Fig. 3. The downside is that the probes tend to perturb their environment and affect the thermodynamic state of the system. Experiments have shown, for example, that probes may change the main transition temperature of a lipid membrane, and that the dynamics of probes may deviate considerably from the dynamics of corresponding native molecules (see discussion in Reference 27). Therefore, we wish to pose several questions. What is the range of perturbations induced by the probe How significant are these perturbations actually ... 

Freeman, Crosby, Lawson (13), Kropp, and Windsor 17, 18) had reported that hydrated europium chloride crystals and aqueous solutions of europium salts, respectively, showed considerable enhancement of ion fluorescence and lifetimes upon substitution of H2O by D2O, the latter workers have reported (37) that wet hydrocarbon solutions of the thenoyltrifluoroacetone chelate of europium showed no enhancement of quantum yield and lifetime upon replacing the H2O present by D2O. They suggested that whereas deuteration enhanced the fluorescent properties of the free ions by inhibiting nonradiative deactivation of the Do level, the quantum efficiency of Do luminescence obtained upon direct excitation of this level (JO, 11) is already so high in the fluorinated diketone chelates e.g. thenoyltrifluoroacetone) that deuteration of the environment should have little further enhancing effect. 

In the case of fluorescence, that is, chemienergized by energy transfer, an energy acceptor is chosen that exhibits efficient fluorescence, for example, polycyclic aromatic hydrocarbons and, particularly, 9,10-disubstituted anthracene derivatives. Consequently, in the presence of such fluorescers (FI), the feeble direct chemiluminescence emission intensity is significantly enhanced. Such a phenomenon is commonly referred to as enhanced chemOuminescence (EC). 

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