Biomedical subjects

G B Dutt

Publications and source records attributed to G B Dutt.

8 recordsLinked to original sources

PubMed2006

Photoisomerization of a carbocyanine derivative in the reverse phases of a block copolymer: evidence for the existence of water droplets.

In an attempt to understand the nature of water present in the reverse phases of aggregates formed with the triblock copolymer poly(ethylene oxide)(20)-poly(propylene oxide)(70)-poly(ethylene oxide)(20) (P123) and also investigate how these confined environments influence the rates of photoisomerization, fluorescence lifetimes and quantum yields of a carbocyanine derivative--3,3'-diethyloxadicarbocyanine iodide (DODCI)--were measured in these systems over the temperature range of 293-318 K. Three different copolymer-oil-water compositions were chosen such that the mole ratio of water to copolymer (W) spans the range of 50-150. In these systems, butyl acetate was used as the oil or the nonpolar component. It has been noticed that in all three systems the fluorescence decays of DODCI comprise a long component whose contribution is 85-90%, and this has been ascribed to the fraction of solute solubilized in the core region where hydrated poly(ethylene oxide) units are present. A short-decay component is associated with the remaining fraction, and its values match with those measured in water, indicating that the water present in these reverse phases is in the form of droplets. The photoisomerization rate constants of DODCI located in the core regions of the reverse phases are identical in the three systems at a given temperature and similar to the ones obtained in normal phases of P123. The reasons for the observed behavior have been discussed.

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PubMed2006

Polyene photoisomerization rates: are they distinct in aqueous block copolymer micellar solutions and gels?

Photoisomerization of 3,3'-diethyloxadicarbocyanine iodide (DODCI) has been investigated in water, 5% and 30% aqueous triblock copolymer, poly(ethylene oxide)20-poly(propylene oxide)70-poly(ethylene oxide)20 (P123) by measuring the fluorescence quantum yields and lifetimes in the temperature range 293-318 K. Reports available in literature indicate that 5% aqueous P123 exists as micellar solution, whereas 30% aqueous P123 forms gel due to micelle-micelle entanglement. This study has been undertaken to find out how the polyene photoisomerization rates are influenced in the sol and gel phases. It has been observed that 60%-70% of DODCI is located in the palisade layer of the micelles in the sol as well as gel phases and the photoisomerization rate of this component is identical in both the phases at a particular temperature. The remainder of the probe is located in the interfacial region and isomerization rates of this fraction are slower by a factor of 1.4-1.1 in the gel phase compared with the micellar solution. The retardation of the isomerization rate in the gel phase has been explained on the basis of enhancement in the friction experienced by the probe due to micelle-micelle entanglement at the interface. Compared to the isomerization rates in water, the rates of photoisomerization of DODCI located in the palisade layer, interfacial region of micellar solution, and interfacial region of the micelles in the gel phase are slower by factors of 3.5, 1.5-1.9, and 2, respectively. The outcome of this study validates the point that in organized media photoisomerization rates are sensitive to the localized friction, which is not uniform unlike in a homogeneous solution.

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PubMed2005

Comparison of microenvironments of aqueous sodium dodecyl sulfate micelles in the presence of inorganic and organic salts: a time-resolved fluorescence anisotropy approach.

Microenvironments of aqueous sodium dodecyl sulfate (SDS) micelles was examined in the presence of additives such as sodium chloride and p-toluidine hydrochloride (PTHC) by monitoring the fluorescence anisotropy decays of two hydrophobic probes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and coumarin 6 (C6). It has been well-established that SDS micelles undergo a sphere-to-rod transition and that their mean hydrodynamic radius increases from 19 to 100 A upon the addition of 0.0-0.7 M NaCl at 298 K. A similar size and shape transition is induced by PTHC at concentrations that are 20 times lower compared to that of NaCl. This study was undertaken to find out how the microviscosity of the micelles is influenced under these circumstances. It was noticed that the microviscosity of the SDS/NaCl system increased by approximately 45%, whereas there was a less than 10% variation in the microviscosity of the SDS/PTHC system. The large increase in the microviscosity of the former system with salt concentration has been rationalized on the basis of the high concentration of sodium ions in the headgroup region of the micelles and their ability to strongly coordinate with the water present in this region, which decreases the mobility of the probe molecules.

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PubMed2005

Do organic solutes experience specific interactions with ionic liquids?

In an attempt to understand the nature of interactions between organic solutes and room temperature ionic liquids, temperature-dependent rotational relaxation of two structurally similar nondipolar solutes--2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP)--has been examined in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim+][PF6(-)]). Even with the ionic liquid, where the cation and the anion are strongly associated, the solute DPP experiences specific interactions, which is evident from its reorientation times that are 50%-60% longer in relation to DMDPP. It has been noticed that the reorientation times of both the solutes are faster in [bmim+][PF6(-)] than in glycerol, which is also a strongly associated solvent and whose viscosity is similar to the ionic liquid. This observation has been explained by taking into consideration the relative sizes of the solvents. By comparing the ratios of the reorientation times of DPP to DMDPP, in [bmim+][PF6(-)] and glycerol, it has been deduced that the strengths of the interaction between DPP-[bmim+][PF6(-)] and DPP-glycerol are the same.

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PubMed2005

Effect of "inverse melting transition" of aqueous triblock copolymer solutions on solute rotational dynamics.

Rotational dynamics of two structurally similar hydrophobic solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), has been investigated in 30% wv aqueous solution of triblock copolymer, poly(ethylene oxide)(20)-poly(propylene oxide)(70)-poly(ethylene oxide)(20) as a function of temperature. This study has been undertaken in an attempt to explore how the dynamics of a solute molecule solubilized in a copolymer solution is influenced when it undergoes sol-to-gel transition. It has been observed that the anisotropy decays of both DMDPP and DPP can be described by biexponential functions in the sol as well as in the gel phase. This observation has been rationalized on the basis of the probe molecule undergoing two different kinds of motion rather than being located in two different regions of the micelle. Even in the gel phase, which results as a consequence of micelle-micelle entanglement due to an increase in their volume fraction, the rotational relaxation of the solutes is similar to that observed in the micellar solution. The outcome of this work indicates that even though these gels have very high macroscopic viscosities and hence do not flow, the microenvironments experienced by the solutes are akin to that of a micellar solution.

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PubMed2005

How critical micelle temperature influences rotational diffusion of hydrophobic probes solubilized in aqueous triblock copolymer solutions.

Rotational diffusion of two structurally similar hydrophobic probes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), has been examined in aqueous solutions of poly(ethylene oxide)20-poly(propylene oxide)70-poly(ethylene oxide)20 triblock copolymer as a function of temperature. These studies have been carried out to explore the influence of critical micelle temperature (cmt) on probe dynamics. It has been observed that, below cmt, the anisotropy decays can be adequately described by single-exponential functions with one time constant each for DMDPP and DPP. However, above cmt, biexponential functions with two time constants are needed to satisfactorily fit the anisotropy decays. Another important observation is that both the probes rotate more rapidly below the critical micelle temperature. The dynamics of the probe molecules are akin to that in a homogeneous solution below cmt, whereas above cmt, the rotational diffusion of the probes has been accounted by the two-step model, which is usually employed to explain the results in micelles. A comparison between the microviscosities of these micelles with other nonionic micelles such as Triton X-100 and Brij-35 reveals that the internal environment of the micelles formed with the triblock copolymer is less fluid.

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PubMed2005

Molecular rotation as a tool for exploring specific solute-solvent interactions.

Solute-solvent interactions play an important role in determining the physicochemical properties of liquids and solutions. As a consequence, understanding these interactions has been one of the long-standing problems in physical chemistry. This Minireview describes our approach towards attaining this goal, which is to investigate rotational relaxation of a pair of closely related, medium-sized nondipolar solutes in a set of appropriately chosen solvents. Our studies indicate that solute-solvent hydrogen bonding significantly hinders solute rotation. We have also examined the role of solvent size both in the absence and presence of specific interactions and it has been observed that the size of the solvent has a bearing on solute rotation especially in the absence of specific interactions. Our results point to the fact that only strong solute-solvent hydrogen bonds have the ability to impede the rotation of the solute molecule because, in such a scenario, hydrogen-bonding dynamics and rotational dynamics transpire on comparable time scales. This aspect has been substantiated by measuring the reorientation times of the chosen solutes in solvents such as ethanol and trifluoroethanol, which have distinct hydrogen-bond donating and accepting abilities, and correlating them with solute-solvent interaction strengths. As an alternative treatment, it has been shown that specific interactions between the solute and the solvent can be modeled as dielectric friction with the extended charge distribution model. This approach is not unrealistic considering the fact that specific as well as non-specific interactions are electrostatic by nature and the differences between them are subtle.

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PubMed2004

Is molecular rotation really influenced by subtle changes in molecular shape?

In an attempt to seek out whether the reorientation time of a solute molecule is influenced by marginal changes to its shape, rotational relaxation of four coumarin solutes that are almost identical in size but subtly distinct in shape has been investigated in a viscous nonpolar solvent as a function of temperature. It has been observed that the reorientation times of the four coumarins differ significantly from one another. The four solutes have been treated as asymmetric ellipsoids and Stokes-Einstein-Debye hydrodynamic theory has been employed to calculate the shape factors and boundary condition parameters. The measured reorientation times when normalized by respective shape factors and boundary condition parameters can be scaled on a common curve, which is an indication that ellipsoid based hydrodynamic theory is adequate to model the reorientation times even when the differences in the shapes of the solute molecules are minimal.

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