PubMed Health⌕ Search

Biomedical subjects

Hirotaka Ihara

Publications and source records attributed to Hirotaka Ihara.

14 recordsLinked to original sources
PubMed2006

Enhancement of molecular-shape selectivity in high-performance liquid chromatography through multi-anchoring of comb-shaped polymer on silica.

Poly(octadecylacrylate) having plural trimethoxysilyl groups in the side chain (co-ODA(n)) was newly synthesized and immobilized onto silica through these groups. The liquid chromatographic behavior of silica-supported co-ODA(n) (Sil-co-ODA(n)) was investigated and compared with that of Sil-ODA(n), in which poly(octadecylacrylate) was immobilized through a terminal trimethoxy group at one side of the polymer main chain. Sil-co-ODA(n) showed higher selectivity for molecular shape, especially molecular planarity of PAHs than Sil-ODA(n).

Acrylates↗
PubMed2006

Retention mechanism of L-glutamide-derived noncrystalline stationary phases in reversed-phase high-performance liquid chromatography and application for separation of nucleic acid constituents.

Double alkylated L-glutamide-derived noncrystalline stationary phases Sil-DSG and Sil-DBG have been prepared by coupling N',N''-dioctadecyl-N-[4-carboxybutanoyl]-L-glutamide (DSG) and N',N'',-dibutyl-N-[4-carboxybutanoyl]-L-glutamide (DBG) with aminopropylated silica (Sil-APS). TEM observations of DSG and DBG showed that lipid DSG can aggregate in organic solvents (methanol, chloroform, toluene, etc.) and self-assembled nano fibers are observed while such fibrous aggregations are not observed for DBG. The resulting chromatographic data have been provided information about its selective interaction with guest molecules (PAHs) in RP-HPLC. We have observed that the carbonyl groups in Sil-DSG exist in ordered state by forming a condensing thin layer over silica surface while DBG cannot form such an ordered state due to its lower order of short alkyl chain. The ordered carbonyl groups present in Sil-DSG promotes multiple carbonyl pi-benzene pi interactions with guest PAHs isomers which enhance the selectivity for these compounds. The contribution of pi-pi interactions was also supported by the substantial effects on the selectivity of benzene and nitrobenzenes. The effect of pi-electron containing solvent on the retention behavior of the PAHs was also studied. The selectivity for nucleic acid constituents, i.e. nucleosides and its bases were also evaluated by Sil-DSG and the selectivity for these compounds on Sil-DSG was compared with the selectivity of conventional polymeric ODS phase. It has been found that Sil-DSG provided higher selectivity for nucleic acid constituents than polymeric ODS and that HPLC packing materials can be efficiently employed for routine analysis of these compounds. The effect of methanol content on the separation behavior of nucleosides was also studied.

Chromatography, High Pressure Liquid↗
PubMed2005

Molecular shape selectivity through multiple carbonyl-pi interactions with noncrystalline solid phase for RP-HPLC.

A new approach for the synthesis of double-alkylated L-glutamide-derived stationary phases to use in RP-HPLC is described. TEM observation of lipid distearylglutamide (DSG) showed the formation of fibrous aggregates in methanol or in chloroform through intermolecular hydrogen bonding among the amide moieties while dibutylglutamide (DBG) cannot aggregate in aqueous or organic media due to its lower order of short alkyl chain. DSG and DBG were covalently bonded to silica via amino-propyl linkages. Lipid membrane analogues (e.g., DSG) attached to the silica surface have been found in noncrystalline and solid states and can form supramolecular assemblies with specific properties based on their highly ordered structures in aqueous and organic media. 13C CP/MAS NMR and suspension (in methanol)-state 1H NMR, elemental analysis, and DSC measurements were used to characterize Sil-DSG and were compared with the three other octadecyl phases, i.e., monomeric C18, polymeric C18, and silica grafted poly(octadecyl acrylate) Sil-ODA25. The chromatographic behavior of the new RP material was investigated using detailed retention studies of planar and nonplanar polyaromatic hydrocarbons (PAHs) and nonpolar aromatic positional isomers. Aspects of shape selectivity were also evaluated with Standard Reference Materials 869a, Column Selectivity Test Mixture for Liquid Chromatography. Detailed chromatographic study revealed that Sil-DSG showed extremely enhanced molecular shape selectivity compared with the other phases investigated. The higher molecular shape selectivity obtained by Sil-DSG can be explained by a carbonyl pi (present in lipid-grafted stationary phases)-benzene pi (present in guest PAHs) interaction mechanism, and these interactions are more effective for ordered carbonyl groups.

Chromatography, High Pressure Liquid↗
PubMed2005

Dioctadecyl L-glutamide-derived lipid-grafted silica as a novel organic stationary phase for RP-HPLC.

Dialkyl L-glutamide-derived lipids have been found to form supramolecular assemblies and to show specific properties based on their highly ordered structures in aqueous and organic media. To use these unique properties to create molecular recognition systems, dioctadecyl L-glutamide-derived lipid-grafted porous silica particles (Sil-DSG) were newly prepared and used as a stationary phase in reversed phase liquid chromatography. Compared with conventional ODS (octadecylated silica), the Sil-DSG column showed remarkably higher selectivity for polycyclic aromatic hydrocarbons (PAHs). Especially, Sil-DSG recognized the molecular linearity and planarity of PAHs. Suspension state 1H NMR and 13C CP/MAS-NMR spectroscopies showed that the alkyl chains on the Sil-DSG are in gauche form and their mobility is strongly restricted at room temperature. This paper discusses higher selectivity of Sil-DSG with a carbonyl pi-benzene pi interactions.

Chromatography, High Pressure Liquid↗
PubMed2005

Molecular-length and chiral discriminations by beta-structural poly(L-alanine) on silica.

Poly(L-alanine)-grafted porous silica (Sil-Ala22) was prepared by polymerization of N-carboxyanhydride of L-alanine initiated by 3-aminopropylated silica. Its selective interaction with aromatic guest molecules was evaluated by the retention time in liquid chromatography using the column packed with Sil-Ala22. Sil-Ala22 showed a specific selective retention with discriminating molecular shapes, such as molecular length, linearity and planarity. This selectivity can be explained by a multiple pi-pi interaction with the carbonyl groups one dimensionally-aligned on the rigid beta-form structure in the peptide main chain. Chiral separation with Sil-Ala22 was also described.

Chromatography, Liquid↗
PubMed2005

Surface charge controlled magnetic nanoparticles with grafting of poly(4-vinylpyridine).

Poly(4-vinylpyridine)-grafted magnetic nanoparticles were prepared by the "graft to" method. Surface-modified magnetic particles are covered with a hydrophobic layer because it can be dispersed in organic solvents such as methanol, toluene, benzene, and chloroform, but not in water. Surface charge control with magnetic nanoparticles of various isoelectric point was achieved by quaternization of pyridyl groups, and the positively charged particles can be dispersed in water within a wide range of pH.

Crystallization↗
PubMed2004

Helical structures of conjugate polymers created by oxidative polymerization using synthetic lipid assemblies as templates.

The morphology of conjugate polymers (such as poly(ethylenedioxythiophene), poly(pyrrole), and poly(aniline)) can be controlled in their polymerization processes, by applying the concept of the templating method to oxidative polymerization. As oxidative polymerization of these monomers produces cationic intermediates, the anionic assemblies can act as potential templates due to the mutual electrostatic attractive force. Oxidative polymerization of ethylenedioxythiophene (EDOT), pyrrole, and aniline was carried out using helical superstructures of synthetic lipid assemblies as templates. Interestingly, we have found that oxidative polymerization of these monomers results in novel polymeric aggregates, such as a helical-tape structure and an intertwined helical structure, and that both the right-handed and left-handed helical structures can be created by a change in the hydrophilic head groups. This is the first example of helical superstructures composed of conjugate polymers that have been designed utilizing a convenient templating method.

Journal Article↗
PubMed2004

Photosensitized NADH formation system with multilayer TiO2 film.

A TiO(2)/polymer film on a quartz plate fabricated by a layer-by-layer method was employed for NADH production from NAD(+) with lipoamide dehydrogenase and methyl viologen in Tris-HCl buffer on irradiation with UV light, and the ultra thin film prevented from enzyme deactivating effectively.

Buffers↗
PubMed2004

Conformational effect of silica-supported poly(octadecyl acrylate) on molecular-shape selectivity of polycyclic aromatic hydrocarbons in RP-HPLC.

Poly(octadecyl acrylate) with a terminal reactive group was synthesized by radical telomerization in various solvents. The polymers were grafted onto porous silica for use in RP-HPLC, and the molecular recognition ability was investigated along with the selectivity for the structural isomers of polycyclic aromatic hydrocarbons. The mechanism of selectivity was also investigated with differential scanning calorimetry and NMR spectroscopic observations.

Journal Article↗
PubMedDate not supplied

Synthesis and in vitro evaluation of glutamide-containing cationic lipids for gene delivery.

A novel series of cationic amphiphiles based on dialkyl glutamides with cationic pyridinium head group were synthesized as potential gene delivery agents. Four cationic lipids with glutamide as linker and varying chain lengths were tested for their transfection efficiency in three cell lines. The DNA-lipid complexes were characterized for their ability to bind to DNA, protection from nuclease digestion, size, zeta-potential, and toxicity. All four lipids demonstrated efficient transfection in MCF-7, COS, and HeLa cells, and the reporter gene expression was much higher with DOPE as the helper lipid in the formulation when compared to cholesterol. Among these 14-carbon lipids, lipid 2 has shown the highest transfection efficiency, complete protection of DNA from nuclease digestion, and low toxicity. Interestingly, lipid 2 has also shown remarkable enhancement in transfection in the presence of serum.

Animals↗