Spectroscopic and Calorimetric Studies of Molecular Recognitions in a Dendrimer-Surfactant Complex (original) (raw)
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Langmuir, 1997
The structure of a series of poly(amidoamine) dendrimers Gn(C12) generated from a diaminododecane core have been investigated using the photophysical properties of an external dye, nile red. The modified dendrimers Gn(C12) show the ability to host the hydrophobic dye, nile red, in aqueous solution. The ability of Gn(C12) to host nile red has been compared to corresponding amino-core Gn(NH3) and diaminoethanecore Gn(C2) dendrimers of the same generation size. The emission of nile red in aqueous media is significantly enhanced in the presence of Gn(C12) and not at all for Gn(NH3) and Gn(C2). These results imply a strong tendency for the nile red probe to associate with the long methylene chain of the modified dendrimers in aqueous solutions. Moreover, the interactions of these dendrimers with anionic surfactants generate supramolecular assemblies which greatly enhance their ability to accomodate the nile red. Fluorescence polarization and emission as a function of pH were also studied in an effort to elucidate the interaction of the nile red probe with the dendrimer-surfactant assemblies.
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2002
The interactions between poly(amidoamine)dendrimer(generation,4) with octyl end groups and surfactants such as sodium dodecyl sulfate (SDS), dodecyltrimethyl ammonium bromide (DTAB), and hexaoxyethylenedodecyl ether (C 12 E 6 ) in aqueous solutions have been investigated by surface tension, fluorescence spectra of pyrene, and dynamic light scattering measurements. The results of dynamic light scattering and surface tension measurements indicate that the dendrimer molecules are aggregated in the absence and presence of the surfactants and they are adsorbed at the air-water interface, resulting in the remarkable reduction of surface tension of water. From the measurements of pyrene fluorescence spectra it is suggested that the dendrimer-SDS system provides much lower micropolarity environment than those for the dendrimer-DTAB or C 12 E 6 system. The mechanisms for the interactions between the dendrimer and surfactants have been discussed.
Journal of The American Chemical Society, 1990
Fluorescence spectroscopy has been used to characterize the structure of a unique class of anionic macromolecules: starburst dendrimers (SBDs) possessing an external anionic surface. Pyrene was used as a photoluminescence probe to sense various hydrophobic sites in the microheterogeneous architecture offered by poly(amidoamine) starburst dendrimers possessing sodium carboxylated surfaces. A series of IO different "half-generations, n.5" starburst dendrimers, which differ systematically in molecular weight, size, and surface charge density, have been studied. The probe method provides experimental evidence for a structural surface transition between generations 3.5 and 4.5. The same probe method was applied to study how the structural properties of the starburst dendrimers determine their interactions with small ionic amphiphilic molecules. Whereas starburst dendrimers do not noticeably affect the micellization process of an anionic surfactant (sodium dodecyl sulfate, SDS), the association process with a cationic surfactant (dodecyltetrammonium bromide, DTAB) leads to the formation of two different types of SBD-templated surfactant aggregates. Addition of DTAB to aqueous solutions containing the earlier generation (0.5-3.5) SBD leads to the formation of SBD-templated surfactant aggregates that result from noncooperative, random condensation of surfactant molecules on the anionic dendrimer surface. Addition of DTAB to aqueous solutions containing later generation (4.5-9.5) SBDs leads to the formation of SBD-templated surfactant aggregates resulting from initial, noncooperative, random condensation, followed by cooperative condensation of surfactant molecules on the anionic dendrimer surface. The results are shown to be consistent with a change in the morphology of SBDs from an open, branched structure for generations 0.5-3.5 to a closed, increasingly compact surface for generations 4.5-9.5. The dendrimer generation system used in earlier work (see refs la-i) designated the first star-branched species derived from the initiator core as generation 1.0. The present system is preferred wherein that star-branched intermediate is designated generation 0, thus making it consistent with the geometric progression Z = for the number of terminal groups (see .
The Journal of Physical Chemistry B, 1997
The supramolecular structures formed when anionic polyamidoamine starburst dendrimers, in the presence of low concentrations of spin probe surfactants, are added to aqueous solutions of nonlabeled cationic surfactants have been investigated by EPR spectroscopy. In order to obtain an overview of dendrimer/surfactant systems, a variety of spin probe surfactants, differing from one another in chain length, structure, polarity, charge, solubility, and self-aggregating ability, were employed. Computer simulation of the experimental EPR spectra allowed evaluation of mobility and polarity parameters of the spin probes in the supramolecular structures formed in addition to determination of the degree of partitioning of the probe among various supramolecular structures. Depending on the concentrations of both the surfactant and the dendrimer, the dendrimer size, and temperature, the model envisions two types of structures, i.e., primary structures consisting of probe monomers adsorbed on the dendrimer surface and secondary structures consisting of probe monomers adsorbed in surfactant aggregates bound to the dendrimer surface. Depending on the probe concentration and on the probe solubility into the surfactant aggregates, line broadening was observed, which was consistent with spin-spin interactions supporting a model in which more than one probe was inserted in the aggregates. This solubility was enhanced by the presence of dendrimers and by increasing temperature.
Journal of Colloid and Interface Science, 2002
The intermolecular dendrimer interactions between poly (amidoamine) dendrimers (SBDs) of different generations (G = 2, 4, and 6) were studied in aqueous solution by EPR and fluorescence depolarization. For the EPR studies a spin probe (TEMPO) was covalently linked to the SBDs, and for the fluorescence depolarization studies a fluorophor (fluorescein) was covalentely linked to the SBDs. The mobility of the TEMPO labeled SBDs was determined by EPR over a range of the concentration of added SBDs (unlabeled SBD of the same generation) from 0.01 to 75% (w/w) in water solutions. The mobility of the TEMPO label was not influenced by added SBD below a concentration of approximately 5%, suggesting that no significant interdendrimer interactions, such as aggregation, occurred. Above a concentration of 30% SBD in water (w/w), the mobility of the TEMPO label decreased dramatically; the effect is mostly attributed to the viscosity increase at such high concentrations. Fluorescence depolarization studies, employing fluorescein-labeled dendrimers are in agreement with the EPR studies.
Amphiphilic Dendrimers as Building Blocks in Supramolecular Assemblies
Journal of the American Chemical Society, 1998
The self-assembly of amphiphilic dendrimers based on poly(propylene imine) dendrimers of five different generations with up to 64 end groups modified with long hydrophobic chains has been studied. At the air-water interface stable monolayers form in which the dendritic surfactants presumably adopt a cylindrical shape; all the chains are aligned perpendicular to the water surface, and the dendritic poly(propylene imine) core faces the aqueous phase. Electron microscopy and dynamic light-scattering measurements performed on aqueous solutions of the amphiphiles at pH) 1 showed the formation of small spherical aggregates with diameters varying between 20 and 200 nm. X-ray diffraction of cast films of these aggregates revealed bilayer thicknesses of 48-54 Å. A phase transition was detected by measuring fluorescence anisotropy. The theoretical volumes of the dendritic amphiphiles were in good agreement with those calculated from the monolayer experiments and X-ray diffraction data. Hence, the amphiphilic dendrimers within the aggregates in solution have the same highly asymmetric conformation as that proposed at the air-water interface. Calculations showed that the shape of the dendritic poly(propylene imine) core in the aggregates is distorted and that the axial ratio (r b :r a) ranges from 1:2.5 for the first generation to approximately 1:8 for the three highest generation of dendrimer. This behavior illustrates the high flexibility of the poly(propylene imine) dendrimers.
Binding properties of polyamidoamine dendrimers
Journal of Applied Polymer Science, 2006
Dendrimers are globular, hyperbranched polymers possessing a high concentration of surface functional groups and internal cavities. These unique features make them good host molecules for small ligands. To reveal relationships between dendrimer size and its encapsulating properties, the interactions of the fourth and the sixth generations of polyamidoamine dendrimers (PAMAM G4 and PAMAM G6) with a fluorescent dye 1‐anilinonaphthalene‐8‐sulfonate (ANS) were studied. Because ANS is a fluorescent molecule and its fluorescence is very sensitive to changes in its microenvironment, it was possible to use spectrofluorometric methods to evaluate the interactions with dendrimers. A double fluorometric titration method was used to estimate a binding constant and the number of binding centers. There were two types of dendrimer binding centers characterized by different affinity towards ANS. For PAMAM G4, the values of Kb and n for low‐affinity and high‐affinity sites equaled to 2.6 × 105, 0.60...
International journal of pharmaceutics, 2012
The equilibrium of the formation of polyamidoamine dendrimer (PAMAM-NH(2) G4) and an oncological drug, 5-fluorouracil (FU) in water at room temperature has been examined. Using calorimetric titration, the number of active sites in the dendrimer combining the drug molecules and the equilibrium constant of the dendrimer-drug complex were estimated. The addition of the drug to the dendrimer active sites is an exothermic process. This process is accompanied by a beneficial change in entropy. The number of drug molecules combined by the polymer was confirmed by means of (1)H NMR spectroscopy. (1)HNMR measurements show that the dendrimer macromolecule binds the drug molecules with superficial protonated or unprotonated amine groups.
The Journal of Physical Chemistry, 1996
The aggregation characteristics of aqueous solutions of a positively charged nitroxide surfactant (CAT16) in the presence and absence of half-generation polyamidoamine starburst dendrimers (n.5-SBDs) have been investigated by electron paramagnetic resonance (EPR). Computer simulation of the EPR spectra allowed the convenient extraction of several parameters that were related to the supramolecular structure of the aggregates formed by CAT16 and SBDs. From examination of the EPR spectra as a function of variation of the concentration of CAT16, the concentration of SBDs, and the ionic strength and application of the EPR parameters available from simulation of the spectra, a paradigm for the structure and dynamics of the aggregates formed by CAT16 in the presence and absence of SBDs under various conditions is deduced. A study of the fluorescence quenching of pyrene in the presence of CAT16 is compared to a previous investigation of the interaction of SBDs with cationic surfactants. It is concluded that at low SBD concentration, for earlier generation SBDs (G < 3.5), whose size is smaller than or comparable to the size of the CAT16 micellar aggregates, the SBDs act as "guests" that bind to the micelles that serve as "hosts". In contrast, at low SBD concentration of the later generation SBD (G > 3.5), the size of the SBD is now larger than that of the micelles so that the latter can serve as "guests" for the former. A bilayer aggregate of the surfactant on the SBD is proposed. Finally, at high concentration of the later generation SBD, it is proposed that because of the large number of sites compared to the number of surfactants, an aggregate in which two or more SBDs are bridged by bilayers is formed by the surfactant and coexists with CAT16 micelles.