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Biomedical subjects

K D Shimizu

Publications and source records attributed to K D Shimizu.

8 recordsLinked to original sources

Molecules with shape memory based on restricted rotation.

[reaction--see text] Diimide 1 and octaimide 2 both adopt two stable conformations at room temperature as a result of restricted rotation about two C(aryl)-N(imide) single bonds, a compact "folded" and an open "unfolded" structure. Predictable ratios of folded and unfolded rotamers can be achieved by heating in solvents of appropriate polarity as measured by the Reichardt's parameter (E(T30)). On cooling to room temperature, the resulting conformational changes are "locked in" as restricted rotation is reestablished.

Journal Article↗

Characterization of molecularly imprinted polymers with the Langmuir-Freundlich isotherm.

The majority of binding models that have been applied to molecularly imprinted polymers (MIPs) have been homogeneous models. MIPs, on the other hand, are heterogeneous materials containing binding sites with a wide array of binding affinities and selectivities. Demonstrated is that the binding behavior of MIPs can be accurately modeled by the heterogeneous Langmuir-Freundlich (LF) isotherm. The applicability of the LF isotherm to MIPs was demonstrated using five representative MIPs from the literature, including both homogeneous and heterogeneous MIPs. Previously, such comparisons required the use of several different binding models and analyses, including the Langmuir model, the Freundlich model, and numerical approximation techniques. In contrast, the LF model enabled direct comparisons of the binding characteristics of MIPs that have very different underlying distributions and were measured under different conditions. The binding parameters can be calculated directly using the LF fitting coefficients that yield a measure of the total number of binding sites, mean binding affinity, and heterogeneity. Alternatively, solution of the Langmuir adsorption integral for the LF model enabled direct calculation of the corresponding affinity spectrum from the LF fitting coefficients from a simple algebraic expression, yielding a measure of the number of binding sites with respect to association constant Finally, the ability of the LF isotherm to model MIPs suggests that a unimodal heterogeneous distribution is an accurate approximation of the distribution found in homogeneous and heterogeneous MIPs.

Adsorption↗

Moleculary imprinted polymers with metalloporphyrin-based molecular recognition sites coassembled with methacrylic acid.

A diastereoselective molecularly imprinted polymer (MIP) for (-)-cinchonidine, PPM(CD), was prepared by the combined use of methacrylic acid and vinyl-substituted zinc(II) porphyrin as functional monomers. Compared to MIPs using only methacrylic acid or zinc porphyrin as a functional monomer, PM(CD) and PP(CD), respectively, PPM(CD) showed higher binding ability for (-)-cinchonidine in chromatographic tests using the MIP-packed columns. Scatchard analysis gave a higher association constant of PPM(CD) for (-)-cinchonidine (1.14 x 10(7) M(-1)) than those of PP(CD) (1.45 x 10(6) M(-1)) and PM(CD) (6.78 x 10(6) M(-1)). The affinity distribution of binding sites estimated by affinity spectrum analysis showed a higher percentage of high-affinity sites and a lower percentage of low-affinity sites in PPM(CD). The MIPs containing a zinc(II) porphyrin in the binding sites, PPM(CD) and PP(CD), showed fluorescence quenching according to the binding of (-)-cinchonidine, and the quenching was significant in the low-concentration range, suggesting that the high-affinity binding sites contain the porphyrin residue. The correlation of the relative fluorescence intensity against log of (-)-cinchonidine concentrations showed a linear relationship. These results revealed that the MIP having highly specific binding sites was assembled by the two functional monomers, vinyl-substituted zinc(II) porphyrin and methacrylic acid, and they cooperatively worked to yield the specific binding. In addition, the zinc(II) porphyrin-based MIPs appeared to act as fluorescence sensor selectively responded by binding events of the template molecule.

Binding Sites↗

Steps to demarcate the effects of chromophore aggregation and planarization in poly(phenyleneethynylene)s. 1. Rotationally interrupted conjugation in the excited states of 1,4-bis(phenylethynyl)benzene.

A series of photophysical measurements and semiempirical calculations were carried out with 1,4-bis(phenylethynyl)benzene in search of evidence on the effects of phenyl group rotation and chromophore aggregation of oligo- and poly(phenyleneethynylene)s. It is suggested that planarization gives rise to relatively modest shifts of ca. 20-30 nm, which preserve the vibronic structure of the monomer and retain a high emission quantum yield. In contrast, it is proposed that aggregation gives rise to larger shifts and loss of vibronic structure.

Journal Article↗

A rigid trans-spanning dinitrile ligand.

A rigid dinitrile ligand was synthesized from two xanthene units condensed to a naphthalene-1,4,5,8-diimide spacer. The rigidity and C shape of the ligand gave exclusively trans complexes with Pd(II), Ag(I), and Au(I). Evidence for complexation, coordination geometry, and stoichiometry was provided by a combination of 1H NMR, 19F NMR, and IR spectroscopy. The AuBF4 and PdCl2 complexes were shown to have a 1:1 (metal-to-ligand) stoichiometry and the AgBF4 complex was shown to have a 1:2 stoichiometry in solution. The preorganization of the dinitrile ligand resulted in complexes much more stable than their monodentate counterparts.

Gold↗

Synthesis and assembly of self-complementary calix[4]arenes.

A calix[4]arene was designed to reversibly dimerize and form an egg-shaped enclosure. Adhesive interactions in the assembly were provided by four self-associating ureas, which form a cyclic array containing 16 hydrogen bonds. The synthesis was completed in four steps from the previously described O,O',O",O"'-tetrabenzylcalix[4]arene. Evidence for dimerization of the calixarene tetraurea was provided by H NMR, mass spectrometry, and the observation of encapsulated molecules. The resulting cavity was of sufficient size to capture guests such as ethyl benzene and p-xylene.

Benzene↗