Kanjiro Torigoe

Synthesis and aqueous solution properties of novel anionic heterogemini surfactants containing a phosphate headgroup.

The physicochemical properties of aqueous solutions of novel anionic heterogemini surfactants (POH-n-ODAm) have been studied on the basis of static/dynamic surface tension, fluorescence, dynamic light scattering (DLS) and cryogenic transmission electron microscope (cryo-TEM) data. The surfactants are synthesized from oleic acid: the hydrocarbon chain (n=6, 8 and 10) is covalently bound to the terminal carbonyl group and a phosphate headgroup is introduced to the cis double bond of an oleic acid derivative. The static surface tension and fluorescence measurements demonstrate that the critical aggregation concentration (cac) is decreased significantly with increasing hydrocarbon chain length, resulting from the increased hydrophobicity and the increased degree of dissymmetry of the surfactants. As is generally seen for gemini surfactants, the measured cac is much lower than that of the monomeric phosphate-type surfactant reported previously. At concentrations well above the cac, the heterogemini surfactants spontaneously form vesicular assemblies in bulk solution, which is confirmed with DLS and cryo-TEM measurements.

Surfactant assisted synthesis and spectroscopic characterization of selenium nanoparticles in ambient conditions

In this work, an attempt has been made to synthesize well-distributed stable selenium (Se) particles of nanosize dimensions via an aqueous micellar solution by the assistance of surfactants of two different polarities (anionic, sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and cationic, hexadecyltrimethylammonium bromide (CTAB)). The morphology of the particles was examined with transmission electron microscopy (TEM). X-ray analysis reveals that the particles have a monoclinic structure. The band gap of the particles was determined from UV-visible optical spectroscopic results. The size variation was estimated by employing a quantum confinement effect equation. The evolution of the selenium nanoparticles in AOT and CTAB micellar media was corroborated with the time-dependent absorption spectra. The influence of hydrazine hydrate concentrations on the formation kinetics of Se nanoparticles was also investigated. The capping ability of the surfactants has been quantitatively evaluated from Fourier transform infrared (FTIR) studies.

Mid-infrared free-electron laser tuned to the amide I band for converting insoluble amyloid-like protein fibrils into the soluble monomeric form

A mid-infrared free-electron laser (FEL) is operated as a pulsed and linearly polarized laser with tunable wavelengths within infrared region. Although the FEL can ablate soft tissues with minimum collateral damage in surgery, the potential of FEL for dissecting protein aggregates is not fully understood. Protein aggregates such as amyloid fibrils are in some cases involved in serious diseases. In our previous study, we showed that amyloid-like lysozyme fibrils could be disaggregated into the native form with FEL irradiation specifically tuned to the amide I band (1,620xa0cm−1). Here, we show further evidence for the FEL-mediated disaggregation of amyloid-like fibrils using insulin fibrils. Insulin fibrils were prepared in acidic solution and irradiated by the FEL, which was tuned to either 1,620 or 2,000xa0cm−1 prior to the experiment. The Fourier transform infrared spectroscopy (FT-IR) spectrum after irradiation with the FEL at 1,620xa0cm−1 indicated that the broad peak (1,630–1,660xa0cm−1) became almost a single peak (1,652xa0cm−1), and the β-sheet content was reduced to 25 from 40xa0% in the fibrils, while that following the irradiation at 2,000xa0cm−1 remained at 38xa0%. The Congo Red assay as well as transmission electron microscopy observation confirmed that the number of fibrils was reduced by FEL irradiation at the amide I band. Size-exclusion chromatography analysis indicated that the disaggregated form of fibrils was the monomeric form. These results confirm that FEL irradiation at the amide I band can dissect amyloid-like protein fibrils into the monomeric form in vitro.

A cinnamic acid-type photo-cleavable surfactant

We have developed a novel cinnamic acid-type photo-cleavable surfactant. This surfactant experiences photo-cleavage through UV-induced cyclization in aqueous solutions. The photo-cleavage not only reduces its capabilities as a surfactant but also yields two functional materials including a coumarin derivative and an aminated polyoxyethylene compound. This means that the photo-cleavable surfactant synthesized in this study is a photo-responsive function-exchangeable material. In our current study, we have characterized the photo-cleavable behavior that occurs in aqueous solutions and a resulting change in interfacial properties. The photo-cleavage induces an increased interfacial tension of a squalane/water interface and a decreased solubilization capability of the surfactant micelles.

Effect of polymer charge on the formation and stability of anti-inflammatory drug loaded nanostructured lipid carriers: physicochemical approach

Nanostructured lipid carriers (NLCs), with potential drug delivery capabilities, were formulated using soy lecithin (SLC), tristearin (TS) and palmitic acid (PA) in the absence and presence of two anti-inflammatory drugs, diclofenac sodium (DNa) and indomethacin (IMC). Tween 60 was used as a stabilizer separately and in combination with sodium carboxymethyl cellulose (NaCMC, anionic), polyethylene glycol (PEG, nonionic) and an N,N-dimethyl-N-dodecyl derivative of hydroxyethyl cellulose (LM200, cationic). Both DNa and IMC substantially decreased the size and increased the polydispersity index (PDI) of the NLCs. The hydrodynamic parameters, viz., size, zeta potential, and polydispersity index, as well as the thermal behaviour of the NLCs, depended on the type and charge of the added polymers. Weak interactions between the drug and lipid matrices in the bulk mixtures were confirmed through FT-IR studies. The NLC formulations exhibited lower entrapment efficiency and loading content in the case of DNa compared to IMC due to the higher ionic nature of the former drug. The polymers influenced the entrapment efficiency and loading ability of the NLCs in case of both DNa and IMC. 85% of the entrapped DNa was released from the NLC, compared to 54% release in the case of IMC; the drug release rates were higher for the PEG and NaCMC coated systems. LM200 delayed the drug release process with respect to NaCMC and PEG. Both DNa- and IMC-loaded NLCs inhibited the growth of Gram-positive bacteria, Bacillus amyloliquefaciens. It was concluded that the physicochemical properties of NLCs could effectively be modified using polymers; thus, the biomimetic characteristics of lipids and architectural advantage of polymers can be combined to yield a superior drug delivery system.

Synthesis of Silica Nanotube Using Myelin Figure as Template and their Formation Mechanism

Silica nanotubes are synthesized through a sol-gel reaction of tetraethyl orthosilicate (TEOS) using myelin figures of Pluronic P123 as the structure-directing agent. The simultaneous progression of the formation of molecular assemblies that act as templates and the formation of silica frameworks though a sol-gel reaction of the silica precursor is a characteristic of this reaction system. The synthesized silica nanotubes were characterized using transmission electron microscopy (TEM), nitrogen adsorption/desorption measurements, and Fourier-transform infrared spectroscopy (FT-IR). The silica nanotubes were unilamellar with diameters of approximately 30 nm, membrane thicknesses of approximately 10 nm, and lengths exceeding a few hundred nanometers. The Brunauer-Emmett-Teller (BET) specific surface area was 589.46 m(2)/g. Silica nanotubes can also be obtained using other Pluronic surfactants that can form myelin figures. In this work, we also investigated the formation mechanism of the silica nanotubes. The typical diameter of a myelin figure is a few tens of micrometers. However, myelin figures with diameters of approximately 10 µm can form in systems with TEOS because bifurcation is induced by minute silica nuclei that form during the initial reaction between TEOS and water. Freeze fracture TEM (FF-TEM) observations revealed the existence of myelin figures with diameters of 20 to 30 nm, which are the same size and shape as the synthesized silica nanotubes. These results indicate that bifurcation of the myelin figures is induced by the silica nuclei that form via the initial reaction of TEOS, which result in the formation of bifurcated myelin figures with diameters of ~10 µm. Myelin figures with diameters of 20 to 30 nm form on the surface, and they become templates where the reaction of TEOS progresses to form silica nanotubes with diameters of approximately 30 nm.

Effects of Fatty Acids on the Interfacial and Solution Behavior of Mixed Lipidic Aggregates Called Solid Lipid Nanoparticles

Mutual miscibility of soylecithin, tristearin, fatty acids (FAs), and curcumin was assessed by means of surface pressure-area isotherms at the air-solution interface in order to formulate modified solid lipid nanoparticles (SLN). Appearance of minima in the excess area (Aex) and changes in free energy of mixing (∆G(0)ex) were recorded for systems with 20 mole% FAs. Modified SLNs, promising as topical drug delivery systems, were formulated using the lipids in combination with curcumin, stabilized by an aqueous Tween 60 solution. Optimal formulations were assessed by judiciously varying the FA chain length and composition. Physicochemical properties of SLNs were studied such as the size, zeta potential (by dynamic light scattering), morphology (by freeze fracture transmission electron microscopy), and thermal behavior (by differential scanning calorimetry). The size and zeta potential of the formulations were in the range 300-500 nm and -10 to -20 mV, respectively. Absorption and emission spectroscopic analyses supported the dynamic light scattering and differential scanning calorimetry data and confirmed localization of curcumin to the palisade layer of SLNs. These nanoparticles showed a sustained release of incorporated curcumin. Curcumin-loaded SLNs were effective against a gram-positive bacterial species, Bacillus amyloliquefaciens. Our results on the physicochemical properties of curcumin-loaded SLNs, the sustained release, and on antibacterial activity suggest that SLNs are promising delivery agents for topical drugs.

Interaction of Tyrosine Analogues with Quaternary Ammonium Head Groups at the Micelle/Water Interface and Contrasting Effect of Molecular Folding on the Hydrophobic Outcome and End-Cap Geometry

The surface property of the cationic micelles of cetyltrimethylammonium bromide (CTAB) in an aqueous medium is highly modified in the presence of tyrosineoctyl ester (TYOE) and tyrosinedodecyl ester (TYDE), the models for aromatic amino acid side chains of transmembrane proteins. While the synergistic interaction between the quaternary ammonium head group of CTAB and the π-electron cloud of aromatic amino acid ester is influenced by the relative orientation and the unusual molecular geometry of the latter, this eventually triggers a morphology transition of the spherical micelle to cylindrical/wormlike micelles and imparts a strong viscoelasticity in the medium. Physical characteristics of the elongated micelles have been investigated by high resolution transmission electron microscopy (HRTEM) and the small angle neutron scattering (SANS) technique; the complex fluidic nature of the system is investigated by a dynamic rheological measurement. The intermolecular interactions have been recognized via 1H NMR and 2D nuclear Overhauser effect spectroscopy (NOESY), and the unambiguous geometry of the end-caps of the rods has been ascertained for the first time. While the interplay between lipids and transmembrane proteins is thought to be crucial in controlling the membrane shape of the cells during many vital events such as cellular fission, fusion, and virus entry, the observed tuning of the micellar surface curvature via the cation-π interaction involving tyrosine analogues is thought provoking and opens up an avenue for new physical chemistry research on a vital biological phenomena.

Biophysical Correlates on the Composition, Functionality, and Structure of Dendrimer–Liposome Aggregates

Interaction between negatively charged liposomes and cationic polyamidoamine dendrimers of different generations was investigated through size, zeta potential, turbidity, electron microscopy, atomic force microscopy, fluorescence spectroscopy, and calorimetric studies. Liposomes with the binary combination of 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) + dihexadecyl phosphate, DPPC + 1,2-dimyristoyl-sn-glycero-3-phosphoglycerol, DPPC + 1,2-dipalmitoyl-sn-glycero-3-phosphate, and DPPC + 1,2-dipalmitoyl-sn-glycero-3-phosphoethanol were stable up to 60 days. The electrostatic nature of dendrimer–lipid bilayer interaction was evidenced through charge neutralization and subsequent reversal upon added dendrimer to liposome. Dendrimer–liposome interaction depended on its generation (5 > 4 > 3) in addition to the charge, head groups, and hydrocarbon chain length of lipids. Fluorescence anisotropy and differential scanning calorimetry studies suggest the fluidization of the bilayer, although the surface rigidity was enhanced by the added dendrimers. Thermodynamic parameters of the interaction processes were evaluated by isothermal titration and differential scanning calorimetric studies. The binding processes were exothermic in nature. The enthalpy of transition of the chain melting of lipids decreased systematically with increasing dendrimer concentration and generation. Dendrimer–liposome aggregates were nontoxic to healthy human blood cell, suggesting the potential of such aggregates as drug delivery systems.