State absorption enhancement

The discussion in this chapter is limited to cyanine-like NIR conjugated molecules, and further, is limited to discussing their two-photon absorption spectra with little emphasis on their excited state absorption properties. In principle, if the quantum mechanical states are known, the ultrafast nonlinear refraction may also be determined, but that is outside the scope of this chapter. The extent to which the results discussed here can be transferred to describe the nonlinear optical properties of other classes of molecules is debatable, but there are certain results that are clear. Designing molecules with large transition dipole moments that take advantage of intermediate state resonance and double resonance enhancements are definitely important approaches to obtain large two-photon absorption cross sections. 

Heavy atom enhancement of intersystem crossing has been used to determine the mechanism of acridine photoreduction in ethanol.115 It was found that addition of sodium iodide decreased the fluorescence intensity and the rate of disappearance of acridine to the same extent, confirming that the singlet state is responsible for photoreduction. From the increase in triplet state absorption upon addition of iodide it was found that Of for acridine was 0.76. Thus the short singlet lifetime (0.8 nsec) of acridine is due to rapid inter-system crossing to unreactive triplet states. 

The common bile salts in humans are glycine and taurine conjugates of sodium deoxycho-late (NaDOC) and sodium chenodeoxycholate (CDOC), dihydroxy bile salts, and sodium cholate (NaC, the trihydroxy bile salt). The ability of bile salts to increase transmucosal transport of solutes has been frequently stated [62,81,82]. Generally, the more hydrophobic dihydroxy bile salts act as more effective absorption enhancers in comparison to trihydroxy bile salts. For example, Gullikson et al. [83] have reported that the absorption of inulin, dextran, and albumin in the perfused rat jejunum was enhanced with dihydroxy but not with trihydroxy bile salts. 

Fig. 29. Two molecules with excellent effective two-photon absorption cross-sections. The increased values (6670x10 50 cm4s/photon for the molecule on the left and 8180xl0 5° cm4s/photon for the one on the right) in comparison with similar molecules of Table 6 indicates that they are enhanced by excited state absorption. The molecule on the right has a large potential for optical limiting in the wavelength range from 675 to 800 nm...

The photophysical properties of the self-assembled dimer [54]2 have been studied in detail with various spectroscopic and computational methods [53,54], In the lowest excited singlet (Si) state, the excitation delocalizes over the two macrocycles, and the non-radiative decay is enhanced by dimerization. By contrast, the exciton interaction is very weak in the lowest excited triplet (Ti) state. In the excited-state absorption spectrum recorded in 1-decane, two sharp bands at 658 and 694 nm are observed, which can be attributed to the Q bands of the Tx self-assembled phthalocyanine dimer. 

Figure 11.4. Effect of spin state populations (indicated by the relative thickness of the lines) on NMR signal intensity, (a) Larger than normal excess in lower state, giving enhanced absorption (b) normal slight excess in lower state, giving normal signal intensity (c) saturation, giving zero signal and (d) inverted population (excess in upper state), giving net emission.

Midazolam, Triazolam, and Flurazepam The feasibility of intranasal administration of midazolam, flurazepam, and triazolam has been studied and compared with oral absorption in dogs. There was a 3.4-fold increase in the Cmax after nasal administration, from 5.5-8.7ng/mL to 17.4-30.0 ng/mL. The mean tm showed comparable values for both routes. The Tnmx obtained after nasal administration of midazolam was found to be 15 min, as compared with the 15-45 min observed for oral dosing, while the Cmax after nasal administration was 6.5-20.3 ng/mL, as compared with 3.0-8.6ng/mL observed for the oral route. Like midazolam and triazolam, flurazepam also showed a shorter half-life, 15 min, as compared with 15 15 min with oral administration. The Cmax for oral administration was 0.14-0.59 ng/mL after nasal administration it was in the range of 2.6-11.1 ng/mL, a 16.4-fold increase. Since the gastrointestinal tract at bedtime is likely to be in the fed state, causing a twofold decrease in the absorption of midazolam and triazolam, the nasal route may be a better option for the treatment of amnesia, since these drugs cross the nasal mucosa effectively without the use of an absorption enhancer, as shown in these studies [108],... 

Mulder (1968) described photogeneration in anthracene by a surface-enhanced exciton model. Figures 27 and 28 show the photogeneration efficiency and singlet state absorption coefficient. According to Mulder, when the exciton diffusion length l and the absorption depth, //a, are much less than the thickness, the photogeneration efficiency is... 

Understanding the field enhancement of radiative rates is insufficient to predict how molecular photophysical properties such as enhancement of fluorescence quantum yield will be affected by interactions of the molecule with plasmons. A more detailed model of the photophysics that accounts for non-radiative rates is necessary to deduce effects on photoluminescence (PL) yields. Such a model must include decay pathways present in the absence of metal nanoparticles as well as additional pathtvays such as charge transfer quenching that are associated with the introduction of the metal particles. Schematically, we depict the simplest conceivable model in Figure 19. IB. Note that both the contributions of radiative rate enhancement and the excited state quenching by proximity to the metal surface will depend on distance of the chromophore from the metal assembly. In most circumstances, one expects the optimal distance of the chromophores from the surface to be dictated by the competition between quenching when it is too close and reduction of enhancement when it is too far. The amount of PL will be increased both due to absorption enhancement and emissive rate enhancement. Hence, it is possible to increase PL substantially even for molecules with 100 % fluorescence yield in the absence of metal nanoparticles. 

As noted above, observations of large enhancements of the photoluminescence are insufficient to guarantee utility for application of plasmon-enhanced emission in OLEDs where the excited state is not photogenerated. In principle, increases in photoluminescence observed exfierimentally could be completely due to absorption enhancement. Even observation of reduced excited state lifetimes in conjunction with increased emission is insufficient to prove radiative rate enhancement since the lifetime reduction could be due to excited state quenching by the metallic surface and compensated by large absorption enhancements. 

Figure 19.4C presents data on the phosphorescence decay dynamics on two of the samples in Figure 19.4B, the one without silver and the one having optimum enhancement. These exhibit the characteristic signature of plasmon-enhanced emission, namely that increases in luminescence are accompanied by decreases in excited state lifetime. Ordinarily, radiative rates are fixed by quantum mechanical matrix elements and variation in excited state lifetime is due to changes in nonradiative rates so that increases in lifetime correspond to lower non-radiative rates and increases in luminescence yield. Here, the lifetime is reduced by about a factor of 3 due to increased emissive rate even as the luminescence increases 215 times. These large enhancements cannot be accounted for simply by increase in phosphorescence yield since the yield is greater than 10 % in the absence of silver. It is evident that a substantial fraction of the increase must be accounted for by absorption enhancement. 

Figure 19.5 Schematic diagram showing decomposition of total phosphorescence enhancement of PtOEP on silver films into absorption enhancement E X. ) and emissive rate enhancement E (%.2) based on the photophysical model described in the text and data from steady state and transient spectroscopy of PtOEP films with various thicknesses and excitation wavelengths as labeled. The lines represent the possible combinations that could explain the experimentally observed changes in photoluminescence where each position on the line represents a different choice of fQ, the fraction of the excited states that are quenched nonradiatively by interactions between the molecule and the metallic surface. The blue shaded region on the vertical axis is the range of possibilities allowed by constraints from extinction and excitation spectra as explained in the text. The dotted oval is what we believe to be the most likely decomposition for the 6 nm films characterized in Figure 19.4 as discussed in the text. Reprinted from reference 45 with permission of the American Chemical Society.

The above-mentioned change in absorption for I (H20) (n = 0-4) demonstrates the evolution of diffuse excited states supported by the solvent networks. A schematic energy diagram is illustrated in Figure 5. The slight absorption enhance-... 

The state of hydration of the stratum corneum, which is normally maintained at 10-15%, affects the rate of penetration of chemical substances. By increasing the state of hydration to 50%, the rate of permeation of some chemical substances through the epidermis can be increased up to 10-fold. ° Occlusion has been shown to enhance the pharmacological effect of topically applied hydrocortisone and fluocinolone acetonide " however, percutaneous absorption of drugs is not necessarily increased. The degree of occlusion-induced absorption enhancement appears to increase with increasing lipophilicity of drug substances. 

As pointed out by Baluom and colleagues, absorption enhancers are efficient in small body cavities such as the nasal and the rectum [52], In the fed state, the issues of dilution during gastric mixing would probably obviate the possibility of interaction between the dispersed phase and the small intestine. Using a perfused rat model, the authors showed that a synchronized administration of an absorption enhancer (sodium decanoate) is required for optimal absorption of a poorly absorbed drug (cefazoline) and that levels of the enhancer need to be sustained rather than high. 

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