3-Dimensional dendritic macromolecules

The past year has witnessed the continuing evolution of the field of dendritic macromolecules and other novel 3-dimensional materials. While the rate of publication continues to be high, a perceivable shift in subject matter can be observed. Many key papers are now appearing which deal directly with the structure and properties of dendrimers, as well as their application in a number of advanced technologies.     

Luminescence spectral properties of dendritic oligothiophenesilane macromolecules

The luminescence spectral properties of oligothiophenesilane dendrite macromolecules were studied. It was found that the chromophores responsible for the formation of the absorption and luminescence spectra were dendrimer fragments separated by silicon atoms; all the chromophores are equally involved in the formation of the absorption spectra of dendritic macromolecules of the zero, first, second, and third generations. It was shown that for dendrites of the first, second, and third generations, the luminescence spectrum is mainly formed by the chromophore fragments lying in the internal layers of the dendritic macromolecule due to the induction resonance energy transfer of electronic excitation from peripheral to internal chromophore fragments. The conclusion was drawn that synthesis of dendritic macromolecules with internal chromophore fragments possessing a high quantum yield of fluorescence can give actively luminescing nanosized objects with the molar extinction coefficient proportional to the number of fragments ɛ_max ≈ 10⁶ l/(mol cm). These compounds can find wide application in transducers for converting various types of ionizing radiation into optical radiation in electroluminescent devices.     

Soft effective interactions between weakly charged polyelectrolyte chains

We apply extensive molecular dynamics simulations and analytical considerations in order to study the conformations and the effective interactions between weakly charged, flexible polyelectrolyte chains in salt-free conditions. We focus on charging fractions lying below 20%, for which case there is no Manning condensation of counterions and the latter can be thus partitioned in two states: those that are trapped within the region of the flexible chain and the ones that are free in the solution. We examine the partition of counterions in these two states, the chain sizes and the monomer distributions for various chain lengths, finding that the monomer density follows a Gaussian shape. We calculate the effective interaction between the centers of mass of two interacting chains, under the assumption that the chains can be modeled as two overlapping Gaussian charge profiles. The analytical calculations are compared with measurements from molecular dynamics simulations. Good quantitative agreement is found for charging fractions below 10%, where the chains assume coil-like configurations, whereas deviations develop for charge fraction of 20%, in which case a conformational transition of the chain towards a rodlike configuration starts to take place.     

Encapsulation of nanoparticles using linear–dendritic macromolecules

Benzyl alcohol and Rose Bengal were loaded and entrapped using linear–dendritic macromolecules by two procedures. In the first procedure, benzyl alcohol was attached to the end functional groups of linear–dendritic macromolecules by ester bonds to afford linear–dendritic–host conjugates. In the second procedure, entrapment was based on physical interactions between Rose Bengal and linear–dendritic macromolecules; this procedure is known as complexation method. Loading and binding capacity of different linear–dendritic macromolecules was investigated using ¹H nuclear magnetic resonance (NMR) and UV spectroscopy methods. It was found the loading or binding capacity of linear–dendritic macromolecules depends on their generation, so that higher generations have higher loading or binding capacity. Diameter of nanocarriers was investigated using dynamic light scattering (DLS) experiments, and it was between 16 and 50 nm for different nanocarriers. Release of guest molecules from nanocarriers was evaluated at pH 1, 7.4, and 10. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hybrid linear dendritic macromolecules: From synthesis to applications

Linear‐dendritic copolymers are intriguing macromolecules, which offer challenge and fascination as purely synthetic objects at the crossroad of organic and polymer chemistry and as promising materials for diverse advanced applications. This review traces their discovery and highlights the synthetic strategies used for their construction. The ambivalent character of the linear‐dendritic architecture opens numerous avenues towards emerging and potential applications. Specific solution properties enable the construction of nanometer‐sized nanoreactors for reactions in environmentally friendly media, and the creation of “nanosponges” for selective passive binding of fluorescent pH‐indicators for environmental or biomonitoring. Another structure–property relationship is used for noncovalent and site‐specific modification of glycoproteins, which leads to the formation of “semiartificial” enzymes with enhanced and broadened catalytic activity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5295–5314, 2008     

Maxwell and Kerr effects in solutions of linear dendritic macromolecules

The linear dendritic polymers of the first and second generations have been investigated by the methods of flow birefringence and equilibrium and nonequilibrium electric birefringence. The side dendrons are attached to the polymer backbone through benzamide groups and contain long terminal hexyloxycarbonyl fragments. Optical, dynamic, dipolar, and conformational characteristics of the macromolecules in question have been analyzed in detail. It has been found that the macromolecules of dendritic polymers with dendrons based on L-aspartic acid possess permanent dipole moments and reorient in external electric and hydrodynamic fields according to the large-scale rotation mechanism. The introduction of rigid benzamide fragments substantially increases the equilibrium rigidity, optical anisotropy, and dipole moment of monomer units of dendritic macromolecules. The role of macro-and microform effects in the formation of optical features of the molecules under study is considered in detail.     

The convergent synthesis of poly(glycerol-succinic acid) dendritic macromolecules

The high-yield convergent synthesis of dendrons, dendrimers, and dendritic-linear hybrid macromolecules composed of succinic acid, glycerol, and poly(ethylene glycol) (PEG) is described. This convergent synthesis relies on two orthogonal protecting groups; namely, the benzylidene acetal (bzld) for the protection of the 1,3-hydroxyls of glycerol and the tert-butyldiphenylsilyl (TBDPS) ester for protection of the carboxylic acid of succinic acid. These novel polyester dendritic macromolecules are composed entirely of building blocks known to be biocompatible or degradable in vivo to give natural metabolites. Derivatization of the dendritic periphery with a methacrylate affords a polymer that can be subsequently photo-cross-linked. The three-dimensional cross-linked gels formed by ultraviolet irradiation are optically transparent, with mechanical properties dependent on the initial cross-linkable dendritic macromolecule.     

Hydrodynamic interaction between macromolecules in sedimentation

The sedimentation constant of hard spheres decreases with concentration, due to the effect of backflow and distortion of the hydrodynamic field. For macromolecules at the θ-temperature, this effect of concentration is much smaller than that of equivalent spheres. Pyun and Fixman suggest that intertwinement of macromolecules gives rise to increase of the sedimentation velocity. However, their detailed model of intertwined molecules is unrealistic. An alternative model is proposed by considering a pair of intertwined homologous molecules with N_i and N_j segments respectively, as a single molecule with (N_i + N_j) segments. This model leads to a simple expression for the concentration coefficient in the sedimentation velocity, containing an adaptable parameter, χ_ij, characterising the probability of intertwining. The probability of intertwining is put equal to the probability of intermolecular approach to within a distance of R_int and χ_ij is defined by χ_ij = 2R_int/(R₁ + R_j), with R_i and R_j the friction equivalent molecular radii. From experiments on a number of sharp polystyrene fractions in cyclohexane at T = θ, a value χ_ji = 2.2 is deduced, decreasing with increase of molecular weight. Qualitative agreement is found between experimental results and predictions from the model. Quantitative agreement is not expected in view of uncertainties in the model. In ternary systems, containing molecules of different velocity, probably additional effects operate besides backflow, field distortion and intertwinement.     

Phenylene-ethynylene macrocycles as model systems of interchromophoric interactions in pi-conjugated macromolecules

Unraveling the complex photophysics of macromolecular pi-conjugated systems requires both the development of suitable model systems to access a particular subset of a material's parameter space and the choice of matching spectroscopic techniques. We address the question of the strength of interchromophoric interactions in macromolecular systems by studying the fluorescence depolarization kinetics of a family of prototypical conjugated macrocycles. Shrinking the size of the molecular system decelerates fluorescence depolarization even though the radius of gyration decreases. Although the smaller macrocycles show faster rotational diffusion, the larger compounds exhibit an additional initial depolarization mechanism, attributed to intramolecular interchromophoric energy transfer. Comparison with fragments of the molecule illustrates that the larger macrocycles can be interpreted as bichromophoric systems, whereas the effectively parallel chromophoric elements of the smaller ring are indistinguishable in terms of polarization. The potential role of strong interchromophoric interaction is discussed. The results illustrate a subtle link between interchromophoric arrangement and ultrafast fluorescence depolarization, phenomena, which are often considered in the context of conjugated polymers: chromophoric alignment can potentially counteract the effect of polarization memory loss through energy transfer.     

Repulsion between oppositely charged macromolecules or particles

The interaction of two oppositely charged surfaces has been investigated using Monte Carlo simulations and approximate analytical methods. When immersed in an aqueous electrolyte containing only monovalent ions, two such surfaces will generally show an attraction at large and intermediate separations. However, if the electrolyte solution contains divalent or multivalent ions, then a repulsion can appear at intermediate separations. The repulsion increases with increasing concentration of the multivalent salt as well as with the valency of the multivalent ion. The addition of a second salt with only monovalent ions magnifies the effect. The repulsion between oppositely charged surfaces is an effect of ion-ion correlations, and it increases with increasing electrostatic coupling and, for example, a lowering of the dielectric permittivity enhances the effect. An apparent charge reversal of the surface neutralized by the multivalent ion is always observed together with a repulsion at large separation, whereas at intermediate separations a repulsion can appear without charge reversal. The effect is hardly observable for a symmetric multivalent salt (e.g., 2:2 or 3:3).     

Hyperbranched‐upon‐dendritic macromolecules as unimolecular hosts for controlled release

Novel amphiphilic hyperbranched‐upon‐dendritic polymers with a dendritic polyester core, a linear poly(ε‐caprolactone) (PCL) inner shell, and a hyperbranched polyglycerol outer shell have been prepared. The structures of the hyperbranched‐upon‐dendritic polymers were characterized by using NMR spectra. The critical aggregating concentrations (CACs) of those amphiphilic hyperbranched‐upon‐dendritic polymers were measured by using pyrene as the polarity probe. To study the encapsulation performances of those hyperbranched‐upon‐dendritic polymers as unimolecular hosts, inter‐molecular encapsulation was carefully prevented by controlling the host concentrations below their CACs and by washing with good organic solvents. The study on encapsulation of two model guest molecules, pyrene and indomethacin, was performed. The amounts of encapsulated molecules were dependent mainly on the size of inner linear shells. About three pyrene molecules or five indomethacin molecules were encapsulated in hyperbranched‐upon‐dendritic polymers with average PCL repeating units of two but different hyperbranched polyglycerol outer shells, whereas about five pyrene molecules or about 12 indomethacin molecules were encapsulated in those with PCL repeating units of nine. The encapsulated molecules could be released in a controlled manner. Thus, the hyperbranched‐upon‐dendritic polymers could be used as unimolecular nanocarriers with controllable molecular encapsulation dosage for controlled release. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4013–4019, 2010     

Excitation energy transfer in branched dendritic macromolecules at low (4 k) temperatures

To understand the mode of energy transport in branched dendritic macromolecules, the optical excitation of a dendritic core (A-DSB) at low temperature (4.2 K) was investigated. Fluorescence depolarization measurements were utilized to probe the energy-transfer processes in the branching center at several different temperatures. We found that the anisotropy decay shows an interesting trend at low temperature where depolarization times decreased and the residual anisotropy value also decreased with decreasing temperature. The very fast anisotropy decay suggests a coherent mechanism of energy transport in these systems at low temperature. The contribution of inhomogeneous broadening is suggested as an important factor in the temperature dependence of the anisotropy decay and residual value. The change in inhomogeneous linewidth is responsible for this type of anisotropy behavior.     

Effect of salt on the inter- and intramolecular hydrophobic interactions of macromolecules

The effect of salt on the structure of a low density lipoprotein (LDL) and on the reversible polymerization of bovine serum albumin (BSA) reduced with 2-mercaptoethanol was investigated by means of ultracentrifugal analysis. The chaotropic anion, e.g., SCN^– and I^–, at 5M completely disrupted the LDL structure and effectively dissociated BSA oligomers at lower concentrations. The parallelism between the anion order of these effects and that of the chaotropic effect suggested that the observed salt effects are primarily based on the disruption of hydrophobic interactions. The cation effectiveness disrupting the LDL structure followed the order of their promoting effect on the water structure, i.e., Li⁺>Na⁺>K⁺>Cs⁺. However, Cs⁺ was most effective in dissociating BSA oligomers, and this was attributed to the -complex formation with the aromatic amino acid side chains which otherwise contribute to the promotion of the intermolecular hydrophobic association.     

Design of branched and chiral solvatochromic probes: toward quantifying polarity gradients in dendritic macromolecules

[reaction: see text] A pair of chiral, branched monomer building blocks, consisting of a solvatochromic probe and a spectroscopically inactive volume dummy, has been developed. The probe can selectively be excited, and its fluorescence characteristics provide information about local polarity. Incorporation of these monomers into high-generation polyester dendrimers should enable a detailed investigation of the polarity/density profile in dendritic architectures and ultimately allow for the realization of energy gradients from one chromophore building block only.     

Comparing dendritic and self-assembly strategies to multivalency--RGD peptide-integrin interactions

This paper compares covalent and non-covalent approaches for the organisation of ligand arrays to bind integrins. In the covalent strategy, linear RGD peptides are conjugated to first and second generation dendrons, and using a fluorescence polarisation competition assay, the first generation compound is demonstrated to show the most effective integrin binding, with an EC(50) of 125 μM (375 μM per peptide unit). As such, this dendritic compound is significantly more effective than a monovalent ligand, which does not bind integrin, even at concentrations as high as 1 mM. However, the second generation compound is significantly less effective, demonstrating that there is an optimum ligand density for multivalency in this case. In the non-covalent approach to multivalency, the same RGD peptide is functionalised with a hydrophobic C12 chain, giving rise to a lipopeptide which is demonstrated to be capable of self-assembly. This lipopeptide is capable of effective integrin binding at concentrations of 200 μM. These results therefore demonstrate that covalent (dendritic) and non-covalent (micellar self-assembly) approaches have, in this case, comparable efficiency in terms of achieving multivalent organisation of a ligand array.     

Perturbation expansion of macromolecules with realistic pair interactions in three and four dimensions

We calculated the first-order perturbation expansion of the mean-square end-to-end distance of polymers in three and four space dimensions. The segments of the chain were assumed to interact via a pair potential with a short-range repulsive and an additional attractive part. For a purely repulsive potential, the well-known results of the δ-function-pseudopotential approach are recovered, whereas the inclusion of an attractive part leads to a non-vanishing contribution even for a vanishing binary cluster integral.     

Tunable dendritic ligands of chiral 1,2-diamine and their application in asymmetric transfer hydrogenation

Tunable dendritic N-mono-sulfonyl ligands have been designed and synthesized via direct N-mono-sulfonylization of the chiral dendritic vicinal diamines and their ruthenium complexes demonstrated high catalytic and recyclable activities with comparable enantioselectivities to Noyori–Ikariya’s TsDPEN-Ru in the asymmetric transfer hydrogenation of an extended range of substrates, such as ketones, keto esters, and olefins.     

Interactions between macromolecules and metal nanoparticles in aqueous-saline media

The influence of the concentration of low-molecular-mass salt additives in the reaction medium on the size characteristics of copper nanoparticles in sols formed through the reduction of Cu²⁺ ions in the presence of a cationic polyelectrolyte and nonionogenic polymers with hydrophilic (poly(ethylene oxide) and hydrophobic (poly(N-vinylpyrrolidone)) main chains has been studied. Formation of sols with a narrow size (diameter) distribution of metal nanoparticle indicates the pseudomatrix character of formation of the metal phase under the studied conditions. Effects of the neutral salt and its concentration in the reaction medium on the synthesis of copper sols and on the mean size of metal nanoparticles are related to a change in the nature or character (when oppositely charged polyelectrolyte macromolecules and copper nanoparticles are involved in interaction) of noncovalent interactions stabilizing the macromolecule-nanoparticle complex on passage from the salt-free aqueous medium to the aqueous-saline medium with a sufficiently high concentration of the neutral salt.