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Photoactive bile salts with critical micellar concentration in the micromolar range
- Source :
- RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia, instname
- Publication Year :
- 2016
-
Abstract
- The aggregation behavior of bile salts is strongly dependent on the number of hydroxyl groups. Thus, cholic acid (CA), with three hydroxyls, starts forming aggregates at 15 mM, while deoxycholic, chenodeoxycholic or ursodeoxycholic acids, with two hydroxyls, start aggregating at 5-10 mM; for lithocholic acid, with only one hydroxyl group, aggregation is observed at lower concentration (2-3 mM). Here, the singular self-assembling properties of dansyl and naproxen derivatives of CA (3 beta-Dns-CA and 3 beta-NPX-CA, respectively) have been demonstrated on the basis of their photoactive properties. Thus, the emission spectra of 3 beta-Dns-CA registered at increasing concentrations (25-140 mu M) showed a remarkable non-linear enhancement in the emission intensity accompanied by a hypsochromic shift of the maximum and up to a three-fold increase in the singlet lifetime. The inflection point at around 50-70 mu M pointed to the formation of unprecedented assemblies at such low concentrations. In the case of 3 beta-NPX-CA, when the NPX relative triplet lifetime was plotted against concentration, a marked increase (up to two-fold) was observed at 40-70 mu M, indicating the formation of new 3 beta-NPX-CA assemblies at ca. 50 mu M. Additional evidence supporting the formation of new 3 beta-Dns-CA or 3 beta-NPX-CA assemblies at 40-70 mu M was obtained from singlet excited state quenching experiments using iodide. Moreover, to address the potential formation of hybrid assemblies, 1 : 1 mixtures of 3 beta-Dns-CA and 3 beta-NPX-CA (2-60 mu M, total concentration) were subjected to steady-state fluorescence experiments, and their behavior was compared to that of the pure photoactive derivatives. A lower increase in the emission was observed for 3 beta-NPX-CA in the mixture, while a huge increase was experienced by 3 beta-Dns-CA in the same concentration range (up to 60 mu M total). A partial intermolecular energy transfer from NPX to Dns, consistent with their reported singlet energies, was revealed, pointing to the formation of extremely fluorescent hybrid assemblies at 5-10 mu M (total concentration). The morphology of the entities was investigated by means of confocal microscopy. At 90 mu M, 3 beta-Dns-CA showed disperse assemblies in the mu m range.<br />Financial support from the Spanish Government (Grants SEV-2012-0267 and CTQ2012-38754-C03-03) and the Generalitat Valenciana (Prometeo Program) is gratefully acknowledged.
- Subjects :
- DYNAMICS
Light
NANOTUBES
General Physics and Astronomy
02 engineering and technology
010402 general chemistry
Photochemistry
DEOXYCHOLIC-ACID
01 natural sciences
Micelle
TUBULES
Bile Acids and Salts
chemistry.chemical_compound
QUIMICA ORGANICA
Naproxen
MIXED MICELLES
QUIMICA ANALITICA
Organic chemistry
Singlet state
Physical and Theoretical Chemistry
Micelles
CHOLIC-ACID
Quenching (fluorescence)
Deoxycholic acid
Cholic acid
AGGREGATION
BUILD SPECIATION DIAGRAMS
021001 nanoscience & nanotechnology
Photochemical Processes
Fluorescence
0104 chemical sciences
Spectrometry, Fluorescence
chemistry
Critical micelle concentration
Phosphatidylcholines
Hypsochromic shift
0210 nano-technology
Subjects
Details
- ISSN :
- 14639084
- Volume :
- 18
- Issue :
- 18
- Database :
- OpenAIRE
- Journal :
- Physical chemistry chemical physics : PCCP
- Accession number :
- edsair.doi.dedup.....ed3497312384bcdfe993fd6196e3c399