Interaction of alkyl chain containing pyrene derivatives with different micellar media: Synthesis and photophysical study.

The present work describes the synthesis and photophysical studies of four newly synthesized alkyl chain containing pyrene derivatives and their applications in micellization process of different types of surfactants e.g. CTAB and SDS. The fluorescent properties of these pyrene derivatives were utilized to understand the micellization process of CTAB and SDS. The length of alkyl chain affects the hydrophobicity of pyrene fluorophore which also affects the sensitivity of fluorophore towards the micellization of CTAB and SDS surfactants. The longest alkyl tail containing, PBBU showed more sensitivity whereas moderate alkyl chain containing, PABU and PBME showed moderate sensitivity and finally PAME contained smallest alkyl tail, showed no sensitivity towards the micellization of CTAB and SDS. The alkyl tail of fluorophore make it more hydrophobic and it could easily bind with the hydrophobic inner core of micelles. In both surfactants, PBBU showed LE emission at ~400 nm and aggregate emission at ~470 nm, whereas, PABU and PBME showed LE emission band at ~400 nm. Before CMC, the aggregates band of PBBU increased with increasing the surfactant concentrations, but after CMC the individual PBBU present into the water medium could binds with the inner core of micelles. Thus PBBU senses the formation of premicellar aggregates of CTAB and SDS. The LE emission of the fluorophore gradually increases while increasing the CTAB and SDS concentrations. The change in fluorescence emission of PABU, PBME and PBBU with increasing concentration of CTAB and SDS were used to calculate the CMC of CTAB and SDS surfactants.

A phenomenological scheme for reversed quartet mechanism of electron spin polarization in covalently linked systems of chromophore and free radical: Determination of magnitude of polarization and application to pyrene-TEMPO linked molecules.

Generation of electron spin polarization (ESP) during the bimolecular quenching of an excited chromophore by a free radical is generally explained by the radical-triplet pair mechanism, which is capable of giving the magnitudes of ESP arising from the quenching of the singlet or the triplet excited chromophore. When the chromophore and the free radical are covalently linked, although there are several mechanisms to explain the observed spin-polarized electron paramagnetic resonance signals under a variety of experimental conditions and in different chromophore-radical systems, there are no schemes that allow quantitative determination of the magnitude of ESP. In this work, we present a phenomenological scheme with this objective. In this scheme, we have incorporated several concepts of the reversed quartet mechanism of Rozenshtein et al. [J. Phys. Chem. A 109, 11144 (2005)] to our phenomenological sequential quenching scheme [V. Rane and R. Das, J. Phys. Chem. A 119, 5515 (2015)] of ESP in covalently linked chromophore-radical systems. This phenomenological reversed quartet scheme is able to explain the observed inversion of ESP with time and can also give a quantitative measure of the absorptive and emissive ESP in such systems. We have applied this scheme to the photophysical quenching of a series of newly synthesized pyrene-TEMPO molecules, where a spacer group of different lengths covalently links the pyrene chromophore and the TEMPO free radical. Given the simplicity of our scheme, reasonable estimates of the magnitudes of the ESP have been obtained in all cases.

Distance-dependent formation of electronic charge-transfer states in the ground states of anthracene and pyrene covalently linked to a TEMPO free radical.

Charge-transfer (CT) electronic states are generally seen in molecules involving interactions between species of low ionization potential and high electron affinity. In this context, the 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) free radical is not considered to be a typical molecule to form charge transfer states with aromatic hydrocarbons. Nevertheless, involvement of such CT states has been invoked in rationalising the spin-dependent photophysical quenching of excited states of aromatic systems by TEMPO during bimolecular collisions. Direct observation of such CT states, however, has been elusive until recently, with our first report on the observation of CT states involving naphthalene and TEMPO moieties covalently linked through a spacer group (Rane et al., J. Fluoresc., 2015, 25, 1351-1361). With a view to demonstrating more systems of CT states involving a TEMPO donor, and establishing a possible dependence on its distance from an acceptor chromophore, we have now extended our investigation to anthracene (An) and pyrene (Py) moieties linked to TEMPO, using two different spacer groups of different lengths. The molecules are An-CH2-O-TEMPO, Py-CH2-O-TEMPO, Py-(CH2)2-O-TEMPO, Py-(CH2)4-O-TEMPO, Py-CH2-CO-O-TEMPO and Py-(CH2)3-CO-O-TEMPO, where a linear alkyl chain containing an ether or an ester moiety constitutes the spacer group. We established the formation of CT states in their ground states by comparing their electronic absorption spectra, steady-state fluorescence spectra and time-resolved fluorescence signals with those of the parent molecules An-CH2-OH, Py-CH2-OH and Py-CH2-COOH. CT bands of appreciable intensity were seen only with An-CH2-O-TEMPO, Py-CH2-O-TEMPO and Py-CH2-CO-O-TEMPO, the molecules with the shortest spacer group. Approximate shapes of the absorption and emission bands of the CT states have been determined. For the rest, very weak bands were seen. Similar trends were seen in their fluorescence lifetimes also. Absorption intensities of the CT bands were found to decrease exponentially with the length of the spacer group. The presence of the ether or the ester moiety in the spacer groups showed little influence on the intensities of the CT bands. Our results are probably the first experimental demonstration of the expected exponential dependence of the efficiency of the formation of CT states on the length of the spacer groups of chromophore-TEMPO linked molecules.

Binding interaction of N-acetylated acridine conjugate with ct-DNA and ß-cyclodextrin: Synthesis and photophysical studies.

In the present work we are reporting the synthesis and binding interaction of a saturated fatty acid containing 9-aminoacridine derivative (AC-PA) with ct-DNA and ß-cyclodextrin (ß-CD). From Steady-state fluorescence experiments this newly synthesized 9-aminoacridine derivative, AC-PA, shows more efficient binding interaction with ct-DNA as compared to the 9-aminoacridine (AC). The extent of interaction of AC-PA and AC with ct-DNA was found out by calculating the fluorescence quenching by using Stern-Volmer quenching equation. The calculated quenching constants of AC-PA and AC are (4.5 ±â€¯0.5) × 103M-1 (3.7 ±â€¯0.5) × 103M-1 respectively. The mechanism of fluorescence quenching of AC-PA and AC, were understand by using Stern-Volmer plots as well as time-resolved fluorescence experiments. The fluorescence quenching of AC-PA and AC by ct-DNA are static in nature and take place by formation of ground state complexes. The binding mode between AC-PA and AC were understood by DNA melting analysis experiment. The DNA melting analysis experiments were reveals that the binding interactions between fluorophores (AC-PA and AC) with ct-DNA are intercalative in nature. The melting temperature and mode of binding intercalative mode of binding between AC-PA and AC were further confirmed by DSC and CD experiments. The steady-state and time-resolved fluorescence parameters of AC-PA are quite sensitive towards the formation of inclusion complexes between AC-PA and ß-CD. Long hydrophobic tail containing acridine conjugate (AC-PA) shows more efficient binding interactions with the ß-CD and the calculated binding constants value of AC-PA is 0.51 × 102M-1. Whereas, the parent molecule, AC not showing any binding interactions with ß-CD.

A Fluorescence Study on Binding Interaction of N-acetylated Dansylamide Conjugates with ß-cyclodextrin, Tween-20 and DPPC Lipid Bilayer Membrane.

The present work describes the photophysical behavior of a saturated fatty acid (palmitic acid) containing N-acetylated dansylamide derivative (DAN-PA) into biologically important organized assembly such as ß-cyclodextrin (ß-CD), Tween-20 (T-20) and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid bilayer membrane. The results were compared by using another N-acetylated dansylamide conjugate having a short hydrophobic tail, DAN-ACYL. Long hydrophobic tail (saturated fatty acid) containing dansylamide conjugate (DAN-PA) shows more efficient binding interactions with the ß-CD as compared to the short tail containing dansylamide derivative (DAN-ACYL). The calculated binding constants values of DAN-PA and DAN-ACYL probes are 1.35 × 102 M -1 and 0.31 × 102 M -1 respectively. The DAP-PA is a sensitive fluorophore for understanding the micellization process in T-20, as compared to the DAN-ACYL because it shows a significant change in fluorescent properties (steady-state and time-resolved both) with changing in T-20 concentrations. The calculated CMC value for T-20 surfactant is 0.07 mM. While the DAN-ACYL does not show any change in the fluorescent properties while changing the T-20 concentrations. Fluorescent parameters like steady-state and time-resolved of DAN-PA are quite sensitive towards the thermo-tropic phase transitional changes into lipid bilayer membrane properties. And the calculated thermo-tropic phase transition temperature by using DAN-PA fluorophore is 42 °C.

Fluorescence of N-acylated dansylamide with a long hydrophobic tail: sensitive response to premicellar aggregation of sodium deoxycholate.

The present work describes the synthesis and photophysical studies of two fluorescent dansylamide derivatives, in which the amine group is acylated by a long hydrophobic chain (a part of a biologically relevant palmitic acid) and by a short hydrophobic tail (a part of acetic acid). The long chain tethered dansyl analogue is successfully utilized in estimating critical micellar concentration (CMC) of bile salts (NaDC, NaC) as well as anionic and cationic surfactants (SDS, CTAB) with the help of enhanced fluorescence intensity facilitated by better solubilization of the molecule in microheterogeneous media. The long chain tethered dansylamide derivative shows significant fluorescence solvatochromism with a red shift (ca. 4000 cm(-1)) from hexane to water. In contrast, the solvatochromism exhibited by the parent/short acyl chain analogue is much less (ca. 2230 cm(-1) from hexane to water) and the fluorescence is not sensitive to micellization. Interestingly, the long chain tethered fluorescent probe shows high sensitivity towards premicellar aggregation of sodium deoxycholate (NaDC) bile salt, through a clear blue shift of emission maxima and concomitant enhancement of fluorescent intensity. Such an observation of fluorescence sensing of premicellar aggregation is unusual.