16 research outputs found
Additional file 1 of Interpersonal predictors of loneliness in Japanese children: variable- and person-centered approaches
Additional file 1: Appendix 1. Syntax for mover-stayer LTA in Mplus
Preparation and Photophysical and Photoelectrochemical Properties of Supramolecular Porphyrin Nanorods Structurally Controlled by Encapsulated Fullerene Derivatives
A new class of porphyrin nanorods structurally controlled by encapsulated fullerene derivatives is prepared via a solvent mixture technique. These nanorods, composed of fullerenes (C60, C60 derivatives and C70) and zinc meso-tetra(4-pyridyl)porphyrin [ZnP(Py)4], are formed with the aid of a surfactant, cetyltrimethylammonium bromide (CTAB), in a DMF/acetonitrile mixture. In scanning electron microscopy (SEM) measurement, ZnP(Py)4 pristine hexagonal nanotubes with a large hollow structure [denoted as ZnP(Py)4 tube] are observed, whereas the hollow hole is completely closed in the case of nanorods composed of fullerenes (C60 and C70) and ZnP(Py)4 [fullerene−ZnP(Py)4 rod]. In C60 derivative−ZnP(Py)4 rods, the distorted polygonal columnar structures with large diameter and length are formed, as compared to the hexagonal structures of C60−ZnP(Py)4 and C70−ZnP(Py)4 rods. X-ray diffraction (XRD) analyses also reveals that ZnP(Py)4 alignment in the nanorod is based on the stacked assemblies of ZnP(Py)4 coordinated hexagonal formations. Elemental analysis and titration experiment by absorption measurement were also performed to quantitatively check the relative molecular ratio between porphyrins and fullerenes. Steady-state and time-resolved fluorescence spectra show efficient fluorescence quenching, suggesting the forward electron-transfer process from the singlet excited state of ZnP(Py)4 to fullerenes. Moreover, the back electron-transfer processes are detected by nanosecond transient absorption measurements. The forward and back electron-transfer rate constants are largely dependent on the structures of the nanorods. To construct photoelectrochemical solar cells, fullerene−ZnP(Py)4 rods are deposited onto nanostructured SnO2 films (OTE/SnO2). Fullerene−ZnP(Py)4 rod-modified electrodes exhibited efficient light energy conversion properties, such as a power conversion efficiency (η) of 0.63% and an incident photon to current conversion efficiency (IPCE) of 35%, which are much larger than those of ZnP(Py)4 tube
Comprehensive Analysis of Drug Loading into Engineered Lipoprotein Nanoparticles toward Their Eye Drop Application
The
drug loading capacity of an engineered lipoprotein (eLP1) and
the colloidal stability of drug-loaded eLP1s were assessed with 12
drugs with different charges/hydrophobicities. The capacity was largely
correlated with their log P values, and the binding to the protein
moiety was suggested for two drugs. The size of drug-loaded eLP1 formulations
after freeze-drying followed by resolubilization hardly changed. The
eLP1 formulation of travoprost, a clinically used drug in eye drop
formulations, maintained its small size (19 nm) for 1 h at 37 °C
in an artificial tear solution, whereas the liposome counterpart of
112 nm in diameter aggregated
Solubilization of Single-Wall Carbon Nanohorns Using a PEG−Doxorubicin Conjugate
A procedure for dispersing oxidized single-wall carbon nanohorns (oxSWNHs) in
aqueous solution using a polyethylene glycol−doxorubicin (PEG−DXR) conjugate is described.
In this procedure, oxSWNHs were first incubated with PEG−DXR in dimethyl sulfoxide (DMSO)
or N,N-dimethylformamide (DMF), two organic solvents with relatively high electric dipole
moments, after which the solvent was gradually changed to an aqueous one via addition of
water until the final concentration of DMSO or DMF reached 10%. The PEG−DXR−oxSWNH
complex that was obtained was able to pass through dextran-based chromatographic media
(Sephadex G25) equilibrated with water. By contrast, untreated oxSWNHs and DXR-treated or
PEG-treated oxSWNHs were unable to penetrate the column, indicating that the PEG−DXR
conjugate endowed oxSWNHs with dispersibility in aqueous solution. In gel filtration experiments,
the presence of free DXR had an inhibitory effect on the penetrability of PEG−DXR−oxSWNH
complexes, which is consistent with the idea that PEG−DXR interacts with the surfaces of
oxSWNHs via its DXR moiety. Quantitative analyses showed that the complex contained more
than 250 mg of PEG−DXR for each gram of oxSWNHs. The average diameter of the dispersed
complex was estimated to be approximately 160 nm using dynamic light scattering analysis.
These results suggest that our method has the potential to open the way for the use of oxSWNHs
as a clinically practical drug carrier.
Keywords: Nanomedicine; carbon nanohorns; drug delivery systems; dispersion; anticancer agent;
biocompatibilit
Urea-Assisted Reconstitution of Discoidal High-Density Lipoprotein
High-density
lipoprotein (HDL) is a naturally occurring composite
of lipids and lipid-binding proteins. The cholate dialysis method,
first reported by Jonas in 1969, is the most widely used approach
for reconstituting discoidal HDL (dHDL) in test tubes with phospholipids
and the most dominant protein, apolipoprotein A-1 (apoA-I). Here,
we show that a dHDL-relevant complex can also be prepared by gently
mixing 1,2-dimyristoyl-sn-glycero-3-phosphocholine
(DMPC) and apoA-I or its mutants in ethanol/H2O solutions
containing urea at a concentration of a few molar and then incubating
the mixture at the gel–liquid crystalline phase transition
temperature in test tubes. Subsequent
purification steps involve quick dialysis following size exclusion
chromatography. The yields (73 ± 3% and 70 ± 1% protein
and DMPC, respectively) of the resulting HDL-like nanoparticles, designated
as uHDL, were comparable to the values of 68 ± 9% and 71 ±
12% obtained in the cholate dialysis method. Using apoA-I and two
mutants, the key factor in this method was found to be urea at the
folded and unfolded transition midpoint concentration. By using this
urea-assisted method in the presence of a hydrophobic drug, all-trans-retinoic acid (ATRA), one-step preparation of ATRA-loaded
uHDL was also possible. The loading efficiency was comparable to that
in the mixing of ATRA and uHDL or dHDL reconstituted by the cholate
dialysis method. Atomic force microscopy analysis revealed that uHDL
and ATRA-loaded uHDL were discoidal. Our urea-assisted method is an
easy and efficient method for reconstituting dHDL and can be utilized
to prepare various drug–dHDL complexes
Selective Protein Separation Using Siliceous Materials with a Trimethoxysilane-Containing Glycopolymer
A copolymer with α-d-mannose (Man) and
trimethoxysilane
(TMS) units was synthesized for immobilization on siliceous matrices
such as a sensor cell and membrane. Immobilization of the trimethoxysilane-containing
copolymer on the matrices was readily performed by incubation at high
heat. The recognition of lectin by poly(Man-r-TMS)
was evaluated by measurement with a quartz crystal microbalance (QCM)
and adsorption on an affinity membrane, QCM results showed that the
mannose-binding protein, concanavalin A, was specifically bound on
a poly(Man-r-TMS)-immobilized cell with a higher
binding constant than bovine serum albumin. The amount of concanavalin
A adsorbed during permeation through a poly(Man-r-TMS)-immobilized membrane was higher than that through an unmodified
membrane. Moreover, the concanavalin A adsorbed onto the poly(Man-r-TMS)-immobilized membrane was recoverable by permeation
of a mannose derivative at high concentration
Inhibition of Bacterial Adhesion on Hydroxyapatite Model Teeth by Surface Modification with PEGMA-Phosmer Copolymers
Modification
of the interface properties on hydroxyapatite and
tooth enamel surfaces was investigated to fabricate bacterial resistance <i>in situ</i>. A series of copolymers containing pendants of poly(ethylene
glycol) methyl ether methacrylate (PEGMA) and ethylene glycol methacrylate
phosphate (Phosmer) were polymerized by conventional free radical
polymerization and changing the feed ratio of monomers. The copolymers
were immobilized on hydroxyapatite and tooth enamel via the affinity
of phosphate groups to hydroxyapatite to form the stable and durable
polymer brushes on the surfaces. The amounts of polymer immobilized
depended on the phosphate group ratio in the copolymers. Surface modification
altered the interfacial properties of hydroxyapatite and inhibited
bacterial adhesion. Copolymers containing 40–60% PEGMA segments
showed a significant inhibitory effect on bacterial adhesion of <i>S. epidermidis</i> both in the presence and absence of plaque
model biomacromolecules
Bacterial Inhibition and Osteoblast Adhesion on Ti Alloy Surfaces Modified by Poly(PEGMA‑<i>r</i>‑Phosmer) Coating
We have synthesized and immobilized PEGMA<sub>500</sub>-Phosmer to Ti6Al4V surfaces by a simple procedure to reduce
bacteria-associated infection without degrading the cell response.
Adhered bacteria coverage was lessened to 1% on polymer-coated surfaces
when exposed to Escherichia coli, Staphylococcus epidermidis, and Streptococcus
mutans. Moreover, PEGMA<sub>500</sub>-Phosmer and
homoPhosmer coatings presented better responses to MC3T3-E1 preosteoblast
cells when compared with the results for PEGMA<sub>2000</sub>-Phosmer-coated
and raw Ti alloy surfaces. The behavior of balancing bacterial inhibition
and cell attraction of the PEGMA<sub>500</sub>-Phosmer coating was
explained by the grafted phosphate groups, with an appropriate PEG
brush length facilitating greater levels of calcium deposition and
further fibronectin adsorption when compared with that of the raw
Ti alloy surface
Surface Modification of Siliceous Materials Using Maleimidation and Various Functional Polymers Synthesized by Reversible Addition–Fragmentation Chain Transfer Polymerization
A novel surface modification method was investigated.
The surface
of siliceous materials was modified using polystyrene, poly(acrylic
acid), poly(<i>N</i>-isopropylacrylamide), and poly(<i>p</i>-acrylamidophenyl-α-mannoside) synthesized by reversible
addition–fragmentation chain transfer polymerization. Thiol-terminated
polymers were obtained by reduction of the thiocarbonate group using
sodium borohydride. The polymers were immobilized on the surface via
the thiol–ene click reaction, known as the Michael addition
reaction. Immobilization of the polymers on the maleimidated surface
was confirmed by X-ray photoelectron spectroscopy, infrared spectroscopy,
and contact angle measurements. The polymer-immobilized surfaces were
observed by atomic force microscopy, and the thickness of the polymer
layers was determined by ellipsometry. The thickness of the polymer
immobilized by the maleimide–thiol reaction was less than that
formed by spin coating, except for polystyrene. Moreover, the polymer-immobilized
surfaces were relatively smooth with a roughness of less than 1 nm.
The amounts of amine, maleimide, and polymer immobilized on the surface
were determined by quartz crystal microbalance measurements. The area
occupied by the amine-containing silane coupling reagent was significantly
less than the theoretical value, suggesting that a multilayer of the
silane coupling reagent was formed on the surface. The polymer with
low molecular weight had the tendency to efficiently immobilize on
the maleimidated surface. When poly(<i>p</i>-acrylamidophenyl-α-mannoside)-immobilized
surfaces were used as a platform for protein microarrays, strong interactions
were detected with the mannose-binding lectin concanavalin A. The
specificity of poly(<i>p</i>-acrylamidophenyl-α-mannoside)-immobilized
surfaces for concanavalin A was compared with poly-l-lysine-coated
surfaces. The poly-l-lysine-coated surfaces nonspecifically
adsorbed both concanavalin A and bovine serum albumin, while the poly(<i>p</i>-acrylamidophenyl-α-mannoside)-immobilized surface
preferentially adsorbed concanavalin A. Moreover, the poly(<i>p</i>-acrylamidophenyl-α-mannoside)-immobilized surface
was applied to micropatterning with photolithography. When the micropattern
was formed on the poly(<i>p</i>-acrylamidophenyl-α-mannoside)-spin-coated
surface by irradiation with ultraviolet light, the pattern of the
masking design was not observed on the surface adsorbed with fluorophore-labeled
concanavalin A using a fluorescent microscope because of elution of
poly(<i>p</i>-acrylamidophenyl-α-mannoside) from the
surface. In contrast, fluorophore-labeled concanavalin A was only
adsorbed on the shaded region of the poly(<i>p</i>-acrylamidophenyl-α-mannoside)-immobilized
surface, resulting in a distinctive fluorescent pattern. The surface
modification method using maleimidation and reversible addition–fragmentation
chain transfer polymerization can be used for preparing platforms
for microarrays and micropatterning of proteins
Effects of the Arrangement of a Distal Catalytic Residue on Regioselectivity and Reactivity in the Coupled Oxidation of Sperm Whale Myoglobin Mutants
The coupled oxidations of sperm whale myoglobin (Mb) mutants are performed to examine active
site residues controlling the regiospecific heme degradation. HPLC analysis of biliverdin isomers shows that
L29H/H64L Mb almost exclusively gives biliverdin IXγ, although H64L and wild-type Mb mainly afford the
α-isomer. Relocation of the distal histidine at the 43 and 107 positions increases the amount of γ-isomer to 44
and 22%, respectively. Interestingly, the increase in the ratio of γ-isomer is also observed by a single replacement
of either His-64 with Asp or Phe-43 with Trp. It appears that the polarity of the active site as well as hydrogen
bonding between oxygen molecule bound to the heme iron and His or Trp is important in controlling the
regioselectivity. The results of coupled oxidation kinetics, autoxidation kinetics, and redox potential of the
Fe3+/Fe2+ couple are discussed with regard to their implications for the active site and mechanism of heme
oxygenase
