Photochemical reactions in organized assemblies. 44. Surfactant and hydrophobic derivatives of trans-stilbenes as probes of vesicle and micelle solubilization sites. Studies using fluorescence and photoisomerization as probes

Suddaby, Brian R.; Brown, P. E.; Russell, John; Whitten, David G.

doi:10.1021/ja00306a005

Cited by 43 publications

(20 citation statements)

References 29 publications

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“…Enhancements of the reaction rates have been described for cations and tetraphenylporphyrins [109], chlorophylles [110] and for amines with OPA [111]. Photochemical reactions are also modified in the presence of different micellar media [112][113][114][115][116].…”

Section: Properties Leading To Applicationsmentioning

confidence: 99%

Luminescence in organized media and supramolecular interactions:physicochemical aspects and applications

Lerner¹,

Martín²

2000

Analusis

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Introduction Molecular luminescence of analytes in organized media or in supramolecular complexes of cyclodextrinsThe photophysical and photochemical behaviour of molecules complexed to cyclodextrins (CD) is generally different from their behaviour in solution. The first observations in the field were qualitative and were related to the increased stabilisation of labile molecules, mostly drugs, against photodegradation when complexed to natural cyclodextrins [1]. Complexation by CD's was then the preferred subject for those involved in supramolecular chemistry and drug vectorisation techniques [2] as well as in separation techniques [3][4][5]. Stabilization of a molecule against photochemical degradation is still very important in the field of pharmaceutical sciences. A recent example is the stabilisation of promazine as an inclusion complex with β-cyclodextrin [6]. Other photochemists were attracted quite early to this field of research and initiated studies, which were mostly photophysical in nature [7,8]. The key observation was that the formation of supramolecular complexes of analytes with cyclodextrins (CDs) resulted in an increase of their fluorescence quantum yield or even in the appearance of room temperature phosphorescence (RTP) [9][10][11][12]. This enhancement has been used to increase the sensitivity and the selectivity in both luminescence and chromatographic techniques [13-15].We will not say more about RTP with CDs as the subject will be developed in another contribution in the same issue of this Journal. However RTP is also observed in the solubilization of analytes in micellar colloïdal solutions and this field will be reviewed hereunder.These properties have been used to develop analytical techniques, which combine the selectivity of complexation with an enhanced emission [16][17][18][19]. In this way an improvement in the detection limits is obtained in many separation techniques such as HPLC, capillary electrophoresis (CE) or planar chromatography. Furthermore these molecular interactions allow to reveal or to stabilize new molecular forms or to turn species which are normally non-emitting into luminescent ones. All these aspects are reviewed hereunder after a short summary on the nature of the intermolecular interactions, which lie at the heart of these effects. Nature of the interactions between an analyte and a CD or a micelleWithout going into a thorough analysis of the origin of the interactions which exist between molecules in dense media which concern us here, it seems useful to recall the most important factors which should be taken into account when any type of luminescence, fluorescence or phosphorescence is involved.

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Section: Properties Leading To Applicationsmentioning

confidence: 99%

Luminescence in organized media and supramolecular interactions:physicochemical aspects and applications

Lerner¹,

Martín²

2000

Analusis

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“…(Fig. 2A), it is much more easily detectable when trans-stilbene or its amphiphilic derivatives are incorporated into anionic assemblies such as micelles or bilayer vesicles (21)(22)(23)(24). The amplification in quenching sensitivity from solution to anionic detergent (sodium lauryl sulfate) micelles (K SV ϭ 2 ϫ 10 3 ) (Fig.…”

mentioning

confidence: 99%

“…The absorption and fluorescence spectra of MPS-PPV in dilute aqueous solution are similar to those of trans-stilbene and its derivatives, but shifted to longer wavelength because of the extended conjugation in the polymer. It is well established that excited states of trans-stilbene and related molecules are readily quenched by electron-deficient aromatic compounds in both dynamic and static processes (21)(22)(23)(24). (Fig.…”

mentioning

confidence: 99%

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

Chen

McBranch

Wang

et al. 1999

Proc. Natl. Acad. Sci. U.S.A.

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882

863

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The fluorescence of a polyanionic conjugated polymer can be quenched by extremely low concentrations of cationic electron acceptors in aqueous solutions. We report a greater than millionfold amplification of the sensitivity to fluorescence quenching compared with corresponding ''molecular excited states.'' Using a combination of steady-state and ultrafast spectroscopy, we have established that the dramatic quenching results from weak complex formation [polymer (؊) ͞quencher (؉) ], followed by ultrafast electron transfer from excitations on the entire polymer chain to the quencher, with a time constant of 650 fs. Because of the weak complex formation, the quenching can be selectively reversed by using a quencher-recognition diad. We have constructed such a diad and demonstrate that the fluorescence is fully recovered on binding between the recognition site and a specific analyte protein. In both solutions and thin films, this reversible fluorescence quenching provides the basis for a new class of highly sensitive biological and chemical sensors. With the rising awareness of the public vulnerability to chemical and biological terrorism, there is a heightened need for detection techniques that show both high sensitivity and selectivity. Such techniques also would find wide use in medical diagnostics and biomedical research applications. Methods of identifying biological molecules such as the enzyme-linked immunosorbant assay (ELISA) achieve selectivity by using specific antibody͞antigen interactions to anchor the antigen to a substrate, with a subsequent colorimetric change or fluorescence signal on addition of secondary reagents; these techniques can be time-consuming and require multistep procedures. Other approaches have used molecular recognition ligands to link to specific receptor sites on a biological species, usually as a means also of fixing the biomolecule to a substrate or membrane (1-6) It has remained a challenge to incorporate the selectivity offered by ligand͞receptor interactions into a sensor that can be extremely sensitive, robust, and versatile.We have recently explored the photophysical properties of a fluorescent, water-soluble polyanionic conjugated polymer [poly (2-methoxy-5-propyloxy sulfonate phenylene vinylene (MPS-PPV)] (Fig. 1B), one of a larger class of related molecules [poly phenylene vinylene (PPV)] (Fig. 1 A and derivatives) that has been the subject of almost explosive recent interest (7-13). Although much attention has focused on the well known potential for use of PPV derivatives as electronic materials [e.g., electrochemical sensors (14-16) light-emitting diodes (17, 18), and integrated circuits (19,20)], the highly charged backbone of MPS-PPV (with charge density approximating that of polynucleic acids such as DNA and RNA), also makes it a model polymer for understanding the interactions and self-assembly properties of charged biopolymers. In this paper, we report a striking discovery: the use of this fluorescent anionic polymer leads to a greater than million-fold amplificatio...

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“…The photoisomerization in linear polyenes is highly regioselective and is much influenced by substitutent, polarity of the medium [28][29][30][31][32][58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73] and dipolar nature of the excited state [74][75][76][77][78]. Various mechanistic models have been proposed to understand the photoisomerization process of retinyl and related polyenes.…”

Section: Cistrans-photoisomerization Of Diphenylpolyenesmentioning

confidence: 99%

Donor-Acceptor Conjugated Linear Polyenes: A Study of Excited State Intramolecular Charge Transfer, Photoisomerization and Fluorescence Probe Properties

Hota

Singh

2014

J Fluoresc

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Numerous studies of donor-acceptor conjugated linear polyenes have been carried out with the goal to understand the exact nature of the excited state electronic structure and dynamics. In this article we discuss our endeavours with regard to the excited state intramolecular charge transfer, photoisomerization and fluorescence probe properties of various donor-acceptor substituted compounds of diphenylpolyene [Ar(CH = CH) Ar] series and ethenylindoles.

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Photochemical reactions in organized assemblies. 44. Surfactant and hydrophobic derivatives of trans-stilbenes as probes of vesicle and micelle solubilization sites. Studies using fluorescence and photoisomerization as probes

Cited by 43 publications

References 29 publications

Luminescence in organized media and supramolecular interactions:physicochemical aspects and applications

Luminescence in organized media and supramolecular interactions:physicochemical aspects and applications

Highly sensitive biological and chemical sensors based on reversible fluorescence quenching in a conjugated polymer

Donor-Acceptor Conjugated Linear Polyenes: A Study of Excited State Intramolecular Charge Transfer, Photoisomerization and Fluorescence Probe Properties

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