New PEG-based hydrogel materials have been synthesized by Click chemistry and shown to result in well-defined networks having significantly improved mechanical properties; the selectivity of the azide/acetylene coupling reaction also allows for the incorporation of various additives and functional groups leading to chemical tailoring of the hydrogels.

Unsymmetrical dendrimers, containing both mannose binding units and coumarin fluorescent units, have been prepared using click chemistry and shown to be highly efficient, dual-purpose recognition/detection agents for the inhibition of hemagglutination.

A new strategy for the preparation of functional, multiarm star polymers via nitroxide-mediated "living" radical polymerization has been explored. The generality of this approach to the synthesis of three-dimensional macromolecular architectures allows for the construction of nanoscopically defined materials from a wide range of different homo, block, and random copolymers combining both apolar and polar vinylic repeat units. Functional groups can also be included along the backbone or as peripheral/chain end groups, thereby modulating the reactivity and polarity of defined portions of the stars. This modular approach to the synthesis of three-dimensional macromolecules permits the application of these tailored materials as multifunctional hosts for hydrogen bonding, nanoparticle formation, and as scaffolds for catalytic groups. Examples of applications of the functional stars in catalysis include their use in a Heck-type coupling as well as an enantioselective addition reaction.

The synthesis and characterization of complex dendritic, rigid rod poly-2,7-fluorene homopolymers and copolymers via a macromonomer approach is reported. Several 2,7-dibromofluorene monomers containing benzyl ether dendrons (generations 1, 2, and 3) in the 9,9'-position of the fluorene ring were prepared and employed in condensation polymerizations to yield both homopolymers and copolymers with diethylhexylfluorene. Fluorescence measurements of the materials reveal extensive conjugation along the polymer backbone. The determination of the solid-state PL spectra and quantum efficiencies showed that there is an apparent optimum size of the dendritic side groups with the [G-2]-derivatives showing high reactivity with associated site isolation of the conjugated chain. AFM analysis and DSC results confirmed that the hybrid polymers and copolymers did not show any sign of a microphase-separated morphology. First EL-results demonstrated that the homopolymers have higher turn-on voltages then the corresponding copolymers.

The effect of dendritic substituents on a nonlinear optical chromophore for optical power limiting (OPL) has been investigated. Synthesis and characterization of bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II) with dendritic end groups are described. Polyester dendrimers up to the fourth generation were grown divergently using the anhydride of 2,2-bis(methylol)propionic acid (bis-MPA). The introduction of the dendritic moieties onto the NLO chromophore enables further processing of the materials using polymeric and related techniques. OPL measurements performed at 532, 580, and 630 nm show that the OPL properties improve with increasing size of the dendritic substituent. It is also shown that the addition of the dendrons increase the OPL as compared to the nondecorated bis((4-(phenylethynyl)phenyl)ethynyl)bis-(tributylphosphine)platinum(II). By use of femtosecond z-scan measurements carried out at different pulse-repetition frequencies, it is shown that the two-photon absorption cross section is ∼10 GM. Using pulse repetition frequencies (100 kHz-4.75 MHz) so that the time between the pulses is comparable with the triplet excited lifetime, the z-scans become dominated by excited-state absorption of excited triplet states.

The high efficiency and mild reaction conditions associated with the Cu(I) catalyzed cycloaddition of azides and alkynes were exploited for the covalent layer‐by‐layer synthesis of dendritic thin films on silicon wafers. The preparation of azide and alkyne‐terminated dendrimers based on bisMPA was accomplished by a divergent strategy; combinations of these monodisperse building blocks from the 2nd to the 5th generation were used for construction of the thin films. The layer‐by‐layer self assembly process proceeds under ambient conditions and was monitored by ellipsometry, XPS, and ATR‐IR, which showed extremely regular growth of the dendritic thin films. Film thickness could be accurately controlled by both the size/generation number of the dendrimers as well as the number of layers. In comparison with linear analogues, the growth of the dendritic films was significantly more controlled and defect‐free with each layer being thinner than the corresponding films prepared from the isomeric linear polymers, demonstrating the well‐defined, three‐dimensional nature of the dendritic architecture. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2835–2846, 2007

Highly ordered, porous honeycomb films are prepared by the breath‐figure (BF) technique using dendron‐functionalized star polymers as precursors. By changing the nature of the dendritic end groups, dramatically different porous morphologies can be produced. Three series of star polymers are prepared with both the size of the 2,2‐bis(methoxy)propionic acid (bis‐MPA)‐based dendron end group and the dendron functionality being varied. Star polymers end‐functionalized with acetonide‐protected dendrons (generations 1 to 4) are initially prepared and the acetonide groups subsequently deprotected to yield hydroxyl‐functionalized star polymers. Modification of these hydroxyl groups with pentadecafluorooctanoyl chloride yields a third series of functionalized star polymers. The resulting star polymers have surface groups with very different polarity and by utilizing these star polymers to form honeycomb films by the BF technique, the morphology produced is dramatically different. The star polymers with amphiphilic character afford interconnected porous morphologies with multiple layers of pores. The star polymers with pentadecafluorooctanoyl end groups show highly ordered monolayers of pores with extremely thin walls and represent a new porous morphology that has previously not been reported. The ability to prepare libraries of different dendronized star polymers has given further insights into the BF technique and allows the final porous morphology to be controllably tuned utilizing the functional chain ends and generation number of the dendronized star polymers.

A small mass concentration of poly(benzyl ether) dendrimer added to a low molecular mass polystyrene is found to inhibit the dewetting of a thin (≈50 nm) polystyrene film from an acid-etched silicon substrate. The inhibition effect is found to depend on generation number where the lowest generation (G ) 3) tested was the most effective. Our findings are qualitatively similar to previous observations by Barnes et al. [Macromolecules 2000, 33, 4177-4185.] where the addition of fullerenes ("buckyballs", C60) similarly inhibited the dewetting of thin polystyrene and polybutadiene films. Thus, dewetting inhibition by nanoparticles appears to be a general effect, although certain conditions apparently need to be met for its occurrence. Specifically, a general tendency for the particles to segregate to the solid substrate seems to be required and the interaction between the particles and polymer must not be too unfavorable. The phase boundaries of the dendrimer-polymer mixtures depend on the generation, the higher generation being more miscible in terms of mass fraction. This suggests that the driving force for the dendrimer to segregate to the boundary is varied by changing the generation number, thus giving rise to a dendrimer generational effect on dewetting suppression.