Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures

A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003     

Observation of a quadrupole plasmon mode for a colloidal solution of gold nanoprisms

The synthesis and optical properties of single crystalline gold nanoprisms have been investigated. A three-step mediated seed growth process in an aqueous solution generated gold nanoprisms with a relatively homogeneous size distribution. The purity of these nanostructures has allowed us to observe a weak quadrupole resonance in addition to a strong dipole resonance associated with these novel structures. The experimental optical spectra agree with discrete dipole approximation calculations that have been modeled from the dimensions of gold nanoprisms produced in this synthesis.     

Dendritic molecular capsules for hydrophobic compounds

Reichardt's dye, a highly solvatochromic dye, was encapsulated within poly (glycerol succinic acid) ([Gn]-PGLSA-OH) dendrimers to investigate the interior environment of these dendritic macromolecules. The absorption maximum for the encapsulated Reichardt's dye in water was indicative of a relatively high dielectric constant present within the dye/dendrimer complex. (1)H NMR of the encapsulated complex showed the presence of aromatic protons from Reichardt's dye along with the aliphatic protons of the dendrimer. Additionally, there were substantial changes in T(1) and T(2) times of the encapsulated dye when compared with the free dye, and (1)H NOESY spectra for the complex showed a significant number of intermolecular NOE cross-peaks. These data reveal the close through-space proximity of the dye to the dendrimer and the restricted motion of the encapsulated dye. To demonstrate the potential use of these macromolecules as drug delivery vehicles, the poorly water-soluble anticancer drug 10-hydroxycamptothecin (10HCPT) was encapsulated within a carboxylated PGLSA dendrimer ([G4]-PGLSA-COONa). Cytotoxicity assays with human breast cancer cells showed a significant reduction of cell viability, demonstrating that 10HCPT retains activity upon encapsulation.     

Signal amplification and detection via a supramolecular allosteric catalyst

The design of a supramolecular allosteric catalyst system for catalytic signal amplification and detection is presented. The catalyst was switched "on" by the introduction of an analyte that also behaves as an allosteric activator. Concentrations of Cl- ions as low as 800 nM were catalytically amplified and detected. The signal was transduced via a pH-sensitive fluorescent probe and observed visually using a laboratory, handheld UV lamp and by spectrophotometry. Furthermore, the allosteric effect was quantified using gas chromatography for a range of Cl- concentrations. This three-part detection scheme involving analyte binding, allosteric catalyst activation, and signal transduction represents a new approach to small-molecule detection.     

DNA-nanotube artificial ion channels

There is considerable interest in developing chemical devices that mimic the function of biological ion channels. We recently described such a device, which consisted of a single conically shaped gold nanotube embedded within a polymeric membrane. This device mimicked one of the key functions of voltage-gated ion channels: the ability to strongly rectify the ionic current flowing through it. The data obtained were interpreted using a simple electrostatic model. While the details are still being debated, it is clear that ion-current-rectification in biological ion channels is more complicated and involves physical movement of an ionically charged portion of the channel in response to a change in the transmembrane potential. We report here artificial ion channels that rectify the ion current flowing through them via this "electromechanical" mechanism. These artificial channels are also based on conical gold nanotubes, but with the critical electromechanical response provided by single-stranded DNA molecules attached to the nanotube walls.     

Substoichiometric determination of traces of palladium by neutron-activation analysis

A highly selective, rapid one-step radiochemical separation procedure for palladium has been developed. It is based on the solvent extraction of palladium diethyldithiocarbamate from a 5M hydrochloric acid solution with a substoichiometric amount of copper diethyldithiocarbamate in chloroform. The separation has been applied to the determination of traces of palladium by neutron-activation analysis, in platinum, the rocks W-1 and PCC-1 and a biological material (kale). Amounts of palladium down to 10(-8) g have been determined.     

The practical synthesis of a novel and highly potent analogue of bryostatin

Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer.     

Efficient trapping of HNO by deoxymyoglobin

Nitrosyl hydride, HNO, also commonly termed nitroxyl, is a transient species that has been implicated in the biological activity of nitric oxide, NO. Herein, we report the first generation of a stable HNO-metal complex by direct trapping of free HNO. Deoxymyoglobin (Mb-Fe(II)) rapidly reacts with HNO produced from the decomposition of methylsulfonylhydroxylamine (MSHA) or Angeli's salt (AS) in aqueous solutions from pH 7 to pH 10, forming an adduct, Mb-HNO. The unique 1H NMR signal of the Fe-bound HNO at 14.8 ppm allows definitive proof of its formation. The generation of Mb-HNO and quantification of various myoglobin byproducts were accomplished by correlation of 1H NMR, UV-vis, and EPR spectroscopies. Typically, the maximum Mb-HNO yield obtained is 60-80%; competitive side reactions with byproducts as well as the further reactivity of the Mb-HNO decrease the overall yield. At pH 10, the observed rate of Mb-HNO generation by trapping HNO from MSHA is close to that for MSHA decomposition; kinetic simulations give a lower limit to the bimolecular rate of trapping as 1.4 x 10(4) M(-1) s(-1). The binding of HNO to deoxymyoglobin is rapid and essentially irreversible, which suggests that the biological activity of nitroxyl may be mediated by its reactivity with ferrous heme proteins such as myoglobin and hemoglobin.