Dendrimers In Solution Research Articles

Polar and Electrooptical Properties of [60]Fullerene-Containing Poly(benzyl ether) Dendrimers in Solution

[60]Fulleropyrrolidine-containing poly(benzyl ether) dendrimers 1−4 were synthesized via 1,3-dipolar cycloaddition of amino acid and aldehyde derivatives and [60]fullerene. Their dielectric and electrooptical (Kerr effect) solution properties were studied and compared with poly(propyleneimine) dendrimers, namely DAB-dendr-(alkyl chain)n and DAB-dendr-(CN)n, and with known symmetrical and non-symmetrical poly(benzyl ether) dendrimers carrying benzyl groups ([Gx]-[C]-[Gx]) or benzyl and cyanobenzyl groups (CNn-[Gx]-[C]-[Gx+1]), respectively. It was shown that 1−4 display similar polar and electrooptical characteristics independent of their dendrimer generation. This is in contrast to the reference dendrimers for which a strong dependence of total dipole moment on dendrimer generation was observed.

Starlike dendrimers in solutions: Structural properties and internal dynamics

We measured the shape and the internal dynamics of starlike dendrimers under good solvent conditions with small-angle neutron scattering and neutron spin-echo (NSE) spectroscopy, respectively. Architectural parameters such as the spacer length and generation were varied in a systematic manner. Structural changes occurring in the dendrimers as a function of these parameters are discussed, i.e., in terms of the fractal dimension and deviations of the radius of gyration from the Gaussian value. A first cumulant evaluation of the NSE spectra for each scattering vector q separately yields the length scale dependent relaxation rates. We observe a local minimum in the normalized relaxation rates Omega(q)q(3) on length scales corresponding to the overall dendrimer dimension. The dynamics is discussed within a Rouse-Zimm approach generalized to the case of starlike dendrimers of arbitrary geometry. The model allows an identification of the modes contributing to the relaxation of the dendrimer in the q and time range of the NSE experiment. The local minimum is due to collective breathing motions of (parts of) the dendrons relative to each other. Shape fluctuations are not observed.

Evaluation of polyamidoamine (PAMAM) dendrimers as drug carriers of anti-bacterial drugs using sulfamethoxazole (SMZ) as a model drug

Sulfamethoxazole (SMZ), a sulfonamide with well-known anti-bacterial properties, is not freely soluble in water and causes problems in its clinical applications. In the present study we investigated the potential of ethylenediamine (EDA) core polyamidoamine (PAMAM) dendrimers as drug carriers of SMZ by aqueous solubility, in vitro release as well as anti-bacterial activity studies. Results showed that the aqueous solubility of SMZ was approximately proportional to dendrimer concentration (a 40-fold increase in solubility in 10 mg/ml G3 PAMAM dendrimer solutions compared with that in double-distilled water at 37 °C). The in vitro release of SMZ in the presence of PAMAM dendrimers was significantly slower compared to pure SMZ dissolved in ethanol. Microbiology studies showed that PAMAM dendrimers could increase the anti-bacterial activity of SMZ (a 4- or 8-fold increase in the anti-bacterial activity of SMZ in dendrimer solution compared to pure SMZ dissolved in dimethylsulfoxide (DMSO) or 0.01 M NaOH solution). The in vitro release behavior and anti-bacterial activity studies indicated that PAMAM dendrimers might be considered as potential drug carriers of sulfonamides with a sustained release behavior under suitable conditions.

Effect of PAMAM Dendrimer Size and pH on the Electrostatic Binding of Metal Complexes Using Cyclic Voltammetry

Cyclic voltammetry was employed to investigate the extent of electrostatic binding for metal complexes such as ferrocyanide, [Fe(CN)6]4-, to full generations of polyamidoamine (PAMAM) dendrimers (G1.0−G5.0) as a function of size and pH. Addition of dendrimer solutions to metal complexes caused a large net positive shift in E1/2 and reduced peak currents that varied with the size of the dendrimer. Binding ratios, K4-/K3-, calculated from the potential shifts changed from a ratio of five with small dendrimers (G1.0−G3.0) to 10 for G4.0 and G5.0, consistent with known structural changes in PAMAM dendrimers. Conditional binding constants for [Fe(CN)6]4-, calculated from the diffusion-limited oxidation currents, also increased from G3.0 (8.8 × 104 M-1) to G4.0 (31 × 104 M-1). At pH 5, the binding ratios increased dramatically at all generations, suggesting that the interior amine sites in the dendrimer are easily accessible to metal complexes and that dendrimers show some charge selectivity.

Counterion distribution and many-body interaction in charged dendrimer solutions

Coarse-grained molecular dynamics simulations are performed to study the structural formation, counterion distribution and effective interaction on charged dendrimers in an aqueous solution. In particular, the many-body effects in triplet systems are clarified. The conformation of a dendrimer molecule depends on the size of counterions, and the counterion distribution can be scaled by the gyration radius of a dendrimer molecule. Two-body and three-body interactions have been numerically investigated, and the results indicate both similarities and differences between dendrimer solutions and other soft colloidal systems, such as star polymer solutions.

Hydrodynamic properties of rigid pyridine-containing poly(phenylene) dendrimers in solutions

The hydrodynamic properties of pyridine-containing polyphenylene dendrimers of the third and fourth generations in chloroform are studied by photon correlation spectroscopy and viscometry. It has been demonstrated that the hydrodynamic characteristics of these macromolecules in dilute solutions are similar to those of nondraining spheres. The hydrodynamic radius of these dendrimers is shown to be proportional to their molecular mass to a power of 1/3. It has been established that the macromolecules of the dendrimers under examination in solutions conserve the conformation and size over a wide temperature range. The detailed analysis of hydrodynamic data allowed a conclusion concerning an extremely low content of the polymer inside the equivalent sphere for the above dendrimers in solutions. The compounds of interest may be referred to as rigid dendritic systems.

Structure, phase behavior, and inhomogeneous fluid properties of binary dendrimer mixtures

The effective pair potentials between different kinds of dendrimers in solution can be well approximated by appropriate Gaussian functions. We find that in binary dendrimer mixtures the range and strength of the effective interactions depend strongly upon the specific dendrimer architecture. We consider two different types of dendrimer mixtures, employing the Gaussian effective pair potentials, to determine the bulk fluid structure and phase behavior. Using a simple mean field density functional theory (DFT) we find good agreement between theory and simulation results for the bulk fluid structure. Depending on the mixture, we find bulk fluid-fluid phase separation (macrophase separation) or microphase separation, i.e., a transition to a state characterized by undamped periodic concentration fluctuations. We also determine the inhomogeneous fluid structure for confinement in spherical cavities. Again, we find good agreement between the DFT and simulation results. For the dendrimer mixture exhibiting microphase separation, we observe a rather striking pattern formation under confinement.

Removal of Lead from Contaminated Soils Using Poly(amidoamine) Dendrimers

This study investigated the feasibility of using selected dendrimers for the removal of lead (Pb2+) from three contaminated soils. Lead removal was tested in a fixed-bed column setup, where a prescribed dendrimer solution was passed through a lead-loaded soil bed. Effects of dendrimer generation, concentration, type of the terminal groups, solution pH, and soil type were investigated. In all cases, lower pH increased the removal, lower-generation dendrimers were more effective than higher-generation dendrimers based on the same dose, whereas the effect of terminal groups was minimal. The removal was more effective for sandy soil than for clay soil. A sequential extraction experiment indicated that dendrimer treatment removed primarily (>82%) carbonate-bound Pb2+ cations. Approximately 95% of the spent dendrimers was recovered by nanofiltration, followed by acid regeneration. Approximately 96% of the Pb2+ cations in the solution can be retained by nanofiltration, and ∼94% of the retained Pb2+ cations can b...

The spatial structure of dendritic macromolecules

A low-resolutionab initioshape determination was performed from small-angle neutron and X-ray scattering (SANS and SAXS) curves from solutions of polycarbosilane dendrimers with the three-functional and the four-functional branching centre of the fourth, fifth, sixth, seventh and eighth generations. In all cases, anisometric dendrimer shapes were obtained. The overall shapes of the dendrimers with the three- and four-functional branching centres were oblate ellipsoids of revolution and triaxial ellipsoids, respectively. The restored bead models revealed a pronounced heterogeneity within the dendrimer structure. The density deficit was observed in the central part and close to the periphery of the dendrimers. The fraction of the overall volume of the dendrimers available for solvent penetration was about 0.2–0.3. These results may help in the design of new practical applications of dendrimer macromolecules.

Polyamidoamine dendrimers used as solubility enhancers of ketoprofen

Ketoprofen is a non-steroidal anti-inflammatory drug which is not freely soluble in water and creates gastrointestinal problems. In the present study we investigated the potential of polyamidoamine (PAMAM) dendrimers to increase the solubility of ketoprofen. The effect of variables, such as pH condition, concentration and generation of dendrimer, has been investigated. The experimental results showed that the solubility of ketoprofen in the dendrimer solutions was proportional to dendrimer concentration. Under suitable conditions PAMAM dendrimers can be highly effective used to enhance the solubility of ketoprofen.

Solubility of nicotinic acid in polyamidoamine dendrimer solutions

In the present study we investigated the effect of ethylenediamine (EDA) core polyamidoamine (PAMAM) dendrimers on the aqueous solubility of nicotinic acid. The aqueous solubility of nicotinic acid was measured in the presence of dendrimers at room temperature in distilled water. The effect of variables, such as pH condition, concentration, surface functional group and generation (molecule size) of dendrimer, has been investigated. Results showed that the solubility of nicotinic acid in the dendrimer solutions was proportional to dendrimer concentration, both amine and ester-terminated dendrimers caused the higher increase in nicotinic acid solubility at higher pH conditions. The order in which the dendrimers increased the solubility at a constant pH condition was G4 > G3 > G2 > G1. In addition, at each pH, the solubility of nicotinic acid was greater in the presence of amine-terminated dendrimers compared to the amine ester-terminated dendrimers possessing the same number of surface functional groups. Under suitable conditions PAMAM dendrimers can be highly effective used to enhance the solubility of nicotinic acid.

Dendrimers as Potential Drug Carriers. Part I. Solubilization of Non-Steroidal Anti-Inflammatory Drugs in the Presence of Polyamidoamine Dendrimers

The aqueous solubility of non-steroidal anti-inflammatory drugs (NSAIDs) Ketoprofen, Ibuprofen, Diflunisal and Naproxen were measured in the presence of the ethylenediamine (EDA) core polyamidoamine (PAMAM) dendrimers at 37 °C. The effect of concentration and generation of the PAMAM dendrimers has been investigated. Results showed that the solubility of NSAIDs in the PAMAM dendrimer solutions was approximately proportional to dendrimer concentration; the solubility of NSAIDs in higher generation PAMAM solutions was in fact higher that those in lower ones; the order of increased solubility of NSAIDs in PAMAM dendrimers at a constant dendrimer concentration and generation was Naproxen>Ketoprofen>Ibuprofen>Diflunisal. Under suitable conditions PAMAM dendrimers can be highly effective used to enhance the solubility of NSAIDs.

Equilibrium Structure of Dendrimers: Results and Open Questions

AbstractFor Abstract see ChemInform Abstract in Full Text.

Molecular simulation of dendrimers and their mixtures under shear: Comparison of isothermal-isobaric (NpT) and isothermal-isochoric (NVT) ensemble systems

Flow properties of dendrimers are studied with the aid of nonequilibrium molecular dynamics techniques. Simulations are performed in the NpT ensemble using the NpT-SLLOD algorithm [P. J. Davis and D. J. Evans, J. Chem. Phys. 100, 541 (1994)] and are compared to the results from simulations performed in the NVT ensemble reported earlier [J. T. Bosko, B. D. Todd, and R. J. Sadus, Chem. Phys. 121, 12050 (2004)]. Shear thickening observed at high strain rates vanishes in systems kept under constant pressure. Also the exponents in the power-law dependencies of the viscosity and the normal stress coefficients change. The variations are significant only at high strain rates and do not affect largely microscopic properties such as shape, alignment, or rotation of molecules. The NpT-SLLOD algorithm has been applied to study various systems including dendrimers in solution and their blends with linear chain molecules of the same molecular mass, and some results for these systems are presented.

Control of composition in the multilayer films fabricated from mixed solutions containing two dendrimers

A series of multilayer films were fabricated alternately from poly(4-vinylpyridine) solution and mixed solutions of two carboxyl-terminated dendrimers. UV-Vis absorption spectroscopy was applied to study the composition of the multilayer films. In contrast to mixed solutions of linear polymers, the total amount of dendrimers in multilayer film is independent of the ratio of dendrimers in mixed solution, which is possibly due to the globular conformation of the dendrimer. Furthermore, the ratio of two dendrimers in films is linearly dependent on the ratio of the two dendrimers in solutions, which facilitates control of the composition in multilayer films.

Small-Angle Neutron Scattering Studies of Charged Carboxyl-Terminated Dendrimers in Solutions

Small-angle neutron scattering was used to characterize the solution behavior of charged carboxylic acid terminated "cascade" dendrimers (Z-Cascade/methane [4]/3-oxo-6-oxa-2-azaheptylidyne/3-oxo-2-azaheptylidyne/propanoic acids) of third (G3) and fifth (G5) generations as a function of dendrimer concentration, pH, and ionic strength. An increase in dendrimer concentration leads to a single broad peak in the scattering profile arising from interdendrimer interaction. The dissociation of terminal carboxylate groups also gives rise to an interdendrimer interaction peak, which could be suppressed by the addition of excess salt. The results of contrast matching measurements indicate the accumulation of an excess concentration of tetramethylammonium counterions around the surface of these highly charged particles, and the thickness of these counterions lies somewhere between 4 and 6 A. This conclusion is consistent with our previous potentiometric titration (Zhang, H.; et al. J. Phys. Chem. B 1997, 101, 3494) and capillary electrophoresis (Huang, Q. R.; et al. J. Phys. Chem. B 2000, 104, 898) data.

Polymetallic Lanthanide Complexes with PAMAM-Naphthalimide Dendritic Ligands: Luminescent Lanthanide Complexes Formed in Solution

Generation 3 PAMAM dendrimers functionalized with 2,3-naphthalimide chromophoric groups on the end branches were synthesized, and the formation of Eu3+ polymetallic complexes was investigated. The luminescence properties of these complexes upon binding were fully characterized. On addition of Eu3+ to the dendrimer solution, lanthanide luminescence appears. The formation of a luminescent species corresponding to a dendrimer:lanthanide ratio of 1:8 was determined by luminescence batch titration and indicated by the maximum of Eu3+ emission. This indicates an overall average coordination number of 7.5 around each lanthanide metal cation. This is the first report of such characterization in the literature. Luminescence lifetimes indicate that the metal cation is well protected from nonradiative deactivation by the dendritic structure. Despite the limited efficiency of the sensitization of Eu3+, the absolute quantum yield being 0.0006, the good protection of the eight lanthanide cations bound in the dendrimer structure and the high absorptivity leads to the red emission from Eu3+ that is easily observed in solution under irradiation with 354 nm UV light.

Poly(amidoamine) dendrimers as ophthalmic vehicles for ocular delivery of pilocarpine nitrate and tropicamide

The purpose of this study was to determine the influence of a controlled incremental increase in size, molecular weight and number of amine, carboxylate and hydroxyl surface groups in several series of poly(amidoamine) (PAMAM) dendrimers for controlled ocular drug delivery. The duration of residence time was evaluated after solubilization of several series of PAMAM dendrimers (generations 1.5 and 2–3.5 and 4) in buffered phosphate solutions containing 2‰ (w/v) of fluorescein. The New Zealand albino rabbit was used as an in vivo model for qualitative and quantitative assessment of ocular tolerance and retention time after a single application of 25 μl of dendrimer solution to the eye. The same model was also used to determine the prolonged miotic or mydriatic activities of dendrimer solutions, some containing pilocarpine nitrate and some tropicamide, respectively. Residence time was longer for the solutions containing dendrimers with carboxylic and hydroxyl surface groups. No prolongation of remanence time was observed when dendrimer concentration (0.25–2%) increased. The remanence time of PAMAM dendrimer solutions on the cornea showed size and molecular weight dependency. This study allowed novel macromolecular carriers to be designed with prolonged drug residence time for the ophthalmic route.

Wavelength dependence of first molecular hyperpolarizability of a dendrimer in solution.

The frequency dependence of the first molecular hyperpolarizability of a dendrimer incorporated with thiophene-stilbene based charge-transfer chromophores is investigated by using a nanosecond 1907 nm laser and a number of wavelengths ranging from 1160 to 1760 nm emitted from an optical parametric amplifier pumped by a 1 kHz 130 fs Ti:sapphire laser. The measured hyperpolarizabilities are compared with those calculated from the charge-transfer absorption spectrum involving a Kramers-Kronig transformation scheme. The Kramers-Kronig transformation analysis provides a satisfactory account of the dispersion of the first molecular hyperpolarizability over the entire excitation wavelength range measured. The Kramers-Kronig technique extends the Oudar-Chemla two-level model previously proposed for the first molecular hyperpolarizability and it can be used in the nonresonance as well as the resonance region where the Oudar-Chemla model fails. The Kramers-Kronig transformation scheme allows a consistent intrinsic hyperpolarizability beta(0) to be obtained from the measured beta(HRS) using different excitation wavelengths for the dendrimer. The comparison of beta(0) for the dendrimer, which contains three chromophores, with that of corresponding monomer chromophore suggests that the chromophores inside the dendrimer are independent. This gives the evidence of the site isolation effect of the dendrimer and substantiates the larger macroscopic optical nonlinearity recently obtained for the dendrimer.

Redox and photoactive dendrimers in solution and on surfaces.

These branching, tree-like molecules may have applications in catalysis, light harvesting, molecular devices, and information storage systems.