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The synthesis, preliminary in vivo biological activity, singlet oxygen and fluorescence yields of a series of alkyl ether derivatives of chlorophyll-alpha analogs are described. For short-chain carbon ethers (1-7 carbon units), it was observed that the biological activity increased by increasing the length of the carbon chain, being maximum in compounds with n-hexyl and n-heptyl chains. Related sensitizers prepared by reacting 2-(1-bromoethyl)-2-devinylpyropheophorbide-alpha with (sec)alcohols were found to be less effective. Under similar treatment conditions, photosensitizers containing cis- and trans- 3-hexenyl side chains were ineffective. Thus, both stereochemical and steric factors caused differences in sensitizing activity. In general, pyropheophorbide-alpha analogs were found to be more active than related chlorin e6 derivatives, in which the isocyclic ring (ring "E") was cleaved. Related photosensitizers in the 9-deoxy- series were found to be as effective as the corresponding pyropheophorbide-alpha analogs. The photosensitizers prepared from pyropheophorbide-alpha methyl ester and chlorin e6 trimethyl ester have long wavelength absorption at 660 nm (epsilon 45 000 to 50 000). Reduction of the carbonyl group in the pyropheophorbide-alpha to methylene (ring E) resulted in a blue shift to 648 nm (epsilon 38 000).

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This work investigates the possibility of injecting dilute aqueous solutions of novel surfactants into the Yibal field (Sultanate of Oman). This was accomplished through an experimental protocol based on the following criteria: (i) compatibility of the surfactants with the high-saline reservoir water (~200 g/L); (ii) low interfacial tension (IFT) between crude oil and reservoir water (less than 10 -2 mN m -1 ); and (iii) maintaining the low IFT behavior during the entire surfactant flooding. Novel surfactants selected in this study consist of a series of ether sulfonates and an amphoteric surfactant (6-105). These surfactants were found to be compatible with reservoir water up to 0.1% surfactant concentration, whereas 6-105 and 7-58 showed compatibility within the full range of surfactant concentration investigated (0.001-0.5%). All surfactant systems displayed dynamic IFT behavior, in which ultralow transient minima were observed in the range 10 -4 -10 -3 mN m -1 , followed by an increase in the IFT to equilibrium values in the range 10 -3 -10 -1 mN m -1 . The results also showed that with respect to concentration (0.05-0.5 %) and temperature (45-80°C), AES-205 and 7-58 surfactants exhibit a wide range of applicability, with the IFT remaining below 10 -2 mN m -1 , as required for substantial residual oil recovery. In addition, ultralow IFT were obtained at surfactant concentrations as low as 0.001%, making the use of these surfactants in enhanced oil recovery extremely cost-effective.Paper no. S1524 in JSD 9, 287-293 (Qtr. 3, 2006). KEY WORDS: Compatibility, dynamic interfacial tension, surfactants, ultralow transient interfacial tension.Approximately 60% of the original oil in place (OOIP) will remain in an average oil reservoir after primary and secondary (water flooding in most cases) production. The residual oil is trapped in the reservoir pore structures by capillary forces and cannot be recovered by conventional means. Among the non-conventional techniques (known as enhanced oil recovery [EOR]) used to enhance oil production, surfactant flooding is one of the most appealing methods to enhance oil recovery from depleted reservoirs. In this technique, surfactants are added to the oil/water system to reduce the interfacial tension (IFT) from about 20-30 mN m -1 to less than 10 -2 mN m -1 (1,2). This seems to be a very simple method for recovering residual oil from reservoirs. However, from a technical point of view, there are some adverse conditions that prevent this technique from being successful in the field. The environment of an oil reservoir is often such that surfactants cannot generate this considerable reduction in surface tension as simply as described. One crucial aspect is that the water in these reservoirs is very salty (up to 200 g/L)-salinities above the solubility limits of most conventional surfactants used in EOR. Clearly, the compatibility of surfactants with reservoir brine is essential to avoid plugging of the porous medium, especially in reservoirs of low permeability. The other importa...

The synthesis, photophysical characteristics, in vivo photosensitizing efficacy, human serum albumin (HSA) binding properties, and skin phototoxicity of some stable bacteriochlorins were investigated. The novel bacteriochlorins, obtained from chlorophyll-a, have long-wavelength absorptions in the range lambda max = 734-758 nm. Preferential migration of ethyl over methyl substituents among ketobacteriochlorins obtained in the pinacol-pinacolone rearrangements of vic-dihydroxybacteriochlorins was confirmed by NOE studies. The bacteriochlorins show relatively low fluorescence quantum yields. Among all the bacteriochlorins the triplet states were quenched by ground state molecular oxygen in a relatively similar manner, yielding comparable singlet oxygen quantum yields. In preliminary in vivo studies (DBA/2 mice, transplanted with SMT/F tumors), ketobacteriochlorins were found to be more photodynamically active than the related vic-dihydroxy analogues. Replacement of the methyl ester functionalities with di-tert-butylaspartic acids enhanced the in vivo efficacy. Site specific human serum albumin (HSA) binding studies indicated a direct correlation between the ability of the compound to bind to the diazepam binding site (albumin site II) and the in vivo photosensitizing efficacy.