Synthesis of Fluorescent, Dumbbell-Shaped Polyurethane Homo- and Heterodendrimers and Their Photophysical Properties.

Fluorescent dendrimers have wide applications in biomedical and materials science. Here, we report the synthesis of fluorescent polyurethane homodendrimers and Janus dendrimers, which often pose challenges due to the inherent reactivity of isocyanates. Polyurethane dendrons (G1-G3) were synthesized via a convergent method using a one-pot multicomponent Curtius reaction as a crucial step to establish urethane linkages. The alkyne periphery of the G1-G3 dendrons was modified by a copper catalyzed azide-alkyne click reaction (CuAAC) to form fluorescent dendrons. In the reaction of the surfaces functionalized two different dendrons with a difunctional core, a mixture of three dendrimers consisting of two homodendrimers and a Janus dendrimer were obtained. The Janus dendrimer accounted for a higher proportion in the products' distribution, being as high as 93% for G3. The photophysical properties of Janus dendrimers showed the fluorescence resonance energy transfer (FRET) from one to the other fluorophore of the dendrimer. The FRET observation accompanied by a large Stokes shift make these dendrimers potential candidates for the detection and tracking of interactions between the biomolecules, as well as potential candidates for fluorescence imaging.

Low-generation fluorescent polyurethane dendrimers via late-stage modification using azide-alkyne click chemistry.

Protecting group free one-pot multicomponent Curtius reaction afforded a versatile MN2 type dendron, ensuring late-stage modification of both dendron and dendrimer to afford highly fluorescent symmetrical and unsymmetrical (Janus) polyurethane dendrimers. Fluorescence study of these dendrimers exhibited the Förster resonance energy transfer (FRET) between blue and mint green fluorophores.

A Model for Late-Stage Modification of Polyurethane Dendrimers Using Thiol-Ene Click Chemistry.

Dendritic materials possessing urethane linkage are surprisingly more stable than similar structures having functional groups such as ether, ester, amide, or carbosilane. This generates profound interest in dendritic polyurethanes. Construction of a well-defined polyurethane dendrimer is, however, challenging because of isocyanates' high reactivity. As a model of our ongoing dendrimer-research, herein, we report a protecting group-free one-pot multicomponent Curtius reaction to furnish a robust and versatile AB2-type dendron, which ensures late-stage modification of both the dendron and dendritic macromolecule yielding a surface functionalized polyurethane dendrimer. While 5-hydroxyisophthalic acid, 11-bromoundecanol, and 4-penten-1-ol were utilized in the construction of the dendron, thiol-ene click chemistry was employed for the late-stage modification. Novel dendrons and dendrimers synthesized were characterized by NMR (1D and 2D) and high-resolution MALDI-TOF analysis. This strategy allows an easy late-stage modification of dendritic macromolecules and is highly useful in the synthesis of both symmetrical and unsymmetrical dendrimers (Janus dendrimers).

Capillary electrophoresis of heparin and other glycosaminoglycans using a polyamine running electrolyte.

This study involves the use of polyamines as potential resolving agents for the capillary electrophoresis (CE) of glycosaminoglycans (GAGs), specifically heparin, dermatan sulfate, chondroitin sulfate, over-sulfated chondroitin sulfate (OSCS), and hyaluronan. All of the compounds can be separated from each other with the exception of chondroitin sulfate and hyaluronan. Using optimization software, the final run conditions are found to be 200 mM ethylenediamine and 45.5 mM phosphate as the electrolyte with -14 V applied across a 50 µm ID×24.5 cm fused silica capillary at 15°C. The ion migration order, with OSCS as the last instead of the first peak, is in contrast to previous reports using either a high molarity TRIS or lithium phosphate run buffer with narrower bore capillaries. Total analysis time is 12. 5 min and the relative standard deviation of the heparin migration time is about 2.5% (n=5). The interaction mechanism between selected polyamines and heparin is explored using conductivity measurements in addition to CE experiments to show that an ion-pairing mechanism is likely.

Detection of ozone gas using gold nanoislands and surface plasmon resonance.

Gold nanoislands interact with gaseous ozone to produce a surface plasmon resonance shift, similarly to the interaction of ozone and gold nanoparticles in water. Gold nanoislands are produced by sputtering, which significantly simplifies the synthesis and produces controlled size for the gold nanoislands. The shift of surface plasmon resonance peak was monitored while gold nanoislands were exposed to variable concentration of gaseous ozone. The shift was then correlated with ozone concentration. Our current results indicate sensing gaseous ozone at concentration of as low as 20 microg/L is achievable. Gold nanoislands were reversed to their original wavelength and were able to cycle between the wavelengths as ozone was introduced and removed. Potentially, this system can be useful as a sensor that identifies the presence of ozone at low part-per-billion concentrations of ozone in gaseous media.

Removal of transition metals from motor oil using ion exchange resins.

A variety of polystyrene-divinylbenzene resins functionalized with such groups as SO3H, N(CH2COOH)2, and SH were tested in the slurry batch mode for the removal of transition metals from used motor oil. Naturally occurring materials such as coal and clay were also tested. The N(CH2COOH)2 resin (Chelex 100) and the SH resin (Duolite GT-73) were found effective removing on the average 70 and 78% of metals such as Fe, Pb, Zn, Cu, Ni, and Mn, respectively. About 700 mLs of hot oil when pumped through a 37 × 0.9 cm column packed with the Duolite resin could be demetalized to the extent of about 80% if the column was first washed with hexane.