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Mitsutoshi Masuda

Publications and source records attributed to Mitsutoshi Masuda.

13 recordsLinked to original sources
PubMed2006

Molecular-level helical stack of a nucleotide-appended oligo(p-phenylenevinylene) directed by supramolecular self-assembly with a complementary oligonucleotide as a template.

The nucleotide-appended oligo(p-phenylenevinylene), {bis[2,5-bis(2-methoxyethoxy)-1,4-phenylene]bis(2,1-ethenediyl-1,4-phenylenemethylene)}bis(2'-deoxy-3'-thymidylic acid) (8), has been synthesized, and self-assembly of the single-component 8 and binary self-assembly of 8 with a complementary single-stranded 20-meric oligodeoxyadenylic acid (9) have been examined in aqueous solutions. Atomic force microscopy (AFM), UV-visible (UV-vis), and circular dichroism (CD) measurements revealed that right-handed helical stacks with 6.4- and 5.1-nm diameters self-assemble from the binary components of 8 and 9 as a template depending on the residual stoichiometry of the two components (thymine (T):adenine (A) = 1:1 and T:A = 2:1, respectively). The concentration of 9 was found to strongly influence the CD spectra of 8 in aqueous solutions. Consequently, we concluded that the one side of the thymine moieties in the stacked assemblies of 8 complexes with a single chain of 9. Complementary T-A base pairs thus formed and induced helical stack of the oligo(p-phenylenevinylene)s in the binary self-assembly. In contrast, self-assembly of the single-component 8 and binary self-assembly of 8 with the noncomplementary 20-meric oligothymidylic acid (10) produced no remarkable formation of fibrous structures like helical stacks.

Circular Dichroism↗
PubMed2006

Alignment of glycolipid nanotubes on a planar glass substrate using a two-step microextrusion technique.

We have developed a two-step microextrusion technique to align lipid nanotubes of 200 nm in diameter in parallel on planar glass substrates. This technique is useful to align self-assembled molecular nanofibers or nanotubes with diameters ranging from 100 to 300 nm. In the first step, we applied relatively large air pressure (approximately 40 hPa) onto a microcapillary filled with aqueous dispersion of lipid nanotubes to push them out. An aqueous droplet with 60 microm diameter was then extruded from the tip of the microcapillary. After one end of the lipid nanotube moved out, we changed the air pressure to be smaller, approximately 20 hPa to reduce the flow rate of the dispersion. The decrease in size of the droplet allowed us to fix the exposed end of the lipid nanotube onto the planar substrate. By dragging the microcapillary along the planar surface, we were able to align the whole nanotube onto the substrate. Using this technique, we have achieved the parallel alignment of the lipid nanotubes on the glass substrate.

Crystallization↗
PubMed2005

Polymorphism of monolayer lipid membrane structures made from unsymmetrical bolaamphiphiles.

The crystal structures of synthetic unsymmetrical 1-glucosamide- and 1-galactosamide bolaamphiphiles, 13-[(beta-d-glucopyranosyl)carbamoyl]tridecanoic acid (1) and 15-[(beta-d-galactopyranosyl)carbamoyl]pentadecanoic acid (2), respectively, were elucidated by single-crystal X-ray analysis. The space group for 1 is P2(1), Z=2 with cell dimensions: a=8.6816(9), b=4.8578(5), c=26.250(3)A, beta=91.460(2) degrees ; that for 2P2(1), Z=2 with cell dimensions: a=4.90(1), b=40.139(1), 6.289(1)A, beta=106.48(1) degrees . The glucopyranosyl and galactopyranosyl rings in 1 and 2, respectively, take a (4)C(1) chair conformation. In the crystal lattice, the 1-glucosamide 1 forms a symmetrical monolayer lipid membrane (MLM) structure in which the molecules are packed in an antiparallel fashion, while 1-galactosamide 2 has an unsymmetrical MLM with parallel molecular packing. The stereochemistry of the sugar hydroxy group proved to affect their hydrogen-bonding networks and induce the polymorphism of the MLM.

Amides↗
PubMed2005

FT-IR study of the interlamellar water confined in glycolipid nanotube walls.

The local hydrogen-bonding environment of water confined in glycolipid nanotubes (LNTs) was investigated by Fourier transform infrared (FT-IR) spectroscopy. Using X-ray diffraction (XRD), we estimated the thickness of an interlamellar water layer, which was confined between the bilayer membranes constructing the walls of the LNTs, to be 1.3 +/- 0.3 nm. FT-IR spectroscopic measurement of the confined water showed an obvious reduction in IR absorption in both the low-energy (around 3000 cm(-1)) and high-energy regions (around 3600 cm(-1)) of the OH stretching band as compared to bulk water. The reduction around 3000 cm(-1) indicated a decrease in the relative proportion of the water molecules with a long-range network structure due to a geometrical restriction. This agrees with the results obtained for other multilamellar systems. On the other hand, the remarkable reduction around 3600 cm(-1), which was not observed in the other systems, indicated the absence of weakly hydrogen-bonded water aggregates due to the effect of sugar headgroups.

Journal Article↗
PubMed2005

Local environment and property of water inside the hollow cylinder of a lipid nanotube.

We investigated the local environment of water confined inside the hollow cylinder of lipid nanotubes (LNTs) by time-resolved fluorescent measurements and attenuated-total-reflectance infrared (ATR-IR) spectroscopy. The LNT was obtained by self-assembly of cardanyl glucosides in water at room temperature and had an open-ended cylindrical nanospace with a diameter of 10-15 nm, a length of 10-100 microm, and hydrophilic inner and outer surfaces. We introduced a fluorescent probe of 8-anilinonaphthalene-1-sulfonate into the confined water and observed an extremely slow dynamic Stokes shift with a correlation time of 1.26 ns, which was 2-3 orders of magnitude longer than that of bulk-phase water. From the peak shift of the fluorescent spectrum, the local solvent polarity (ET(30)) of the confined water was estimated as 50 kcal/mol, which is 20% lower than that in bulk water. ATR-IR measurements showed that the hydrogen-bond network of water inside the LNT was more developed than that in bulk water at room temperature, which is in contrast to the water in other self-assembled confined geometries, such as Aerosol-OT (AOT) reversed micelles.

Anilino Naphthalenesulfonates↗
PubMed2005

Molecular structure of glucopyranosylamide lipid and nanotube morphology.

A series of glucopyranosylamide lipids, N-(X-octadecenoyl)-beta-D-glucopyranosylamine [X = 13-cis (1), 11-cis (2), 9-cis (3), 6-cis (4), and 9-cis,12-cis (5)] and their saturated homologue N-octadecanoyl-beta-d-glucopyranosylamine (6), which differ in the position of a cis double bond in the C18 hydrocarbon chains, have been synthesized. The effect of the cis double bond position on the chiral self-assembly of each glycolipid has been examined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV, and circular dichroism (CD). The 11-cis derivative 2 was observed to self-assemble in water to form a uniform hollow cylinder structure with about 200-nm outer diameters in >98% yields. The obtained nanotubes from 2 showed the narrowest distribution of outer diameters and also gave a negative CD band around 234-236 nm, showing the largest CD intensity among the glycolipids investigated. Thus, we found that the position of a cis double bond significantly influences the homogeneity of the outer diameters as well as growth behavior of the self-assembled nanotube structures. Chiral molecular packing driven by a possible bending structure of the unsaturated glycolipids is playing a critical role in determining tubular morphology through molecular self-assembly.

Amides↗
PubMed2004

Lipid nanotubes and microtubes: experimental evidence for unsymmetrical monolayer membrane formation from unsymmetrical bolaamphiphiles.

Unsymmetrical bolaamphiphiles, omega- [N-beta-D-glucopyranosylcarbamoyl] alkanoic acids, with even-numbered oligomethylene chains (12, 14, 16, 18, and 20 carbons) self-assembled in water to form lipid nano- and microtubes. The tubular assemblies were separated by centrifugation and examined by transmission electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy to study the molecular packing within the tubular membranes. The nanotubes encapsulated the staining reagent phosphotungstate, which revealed them to be hollow cylinders up to several hundred micrometers long with 30-43-nm outer diameters and 14-29-nm inner diameters. By comparing the membrane stacking periodicity obtained from powder X-ray diffraction analysis of the dehydrated tubes with the molecular packing within single crystals, we found that the nanotubes consist of an unsymmetrical monolayer lipid membrane (MLM) in which the molecules are packed in a parallel fashion. This suggests that the inner surface of the nanotubes is covered with carboxy headgroups and the outer surface with 1-glucosamide headgroups. The inner diameters of the lipid nanotubes could be controlled in the range 17.7-22.2 nm in steps of approximately 1.5 nm/two carbons by varying the oligomethylene spacer length. The microtubes had three types of molecular arrangements. The first type was a symmetrical MLM in which the molecules were packed in an antiparallel fashion. The other two types had unsymmetrical MLM stacking with head-to-head and head-to-tail motifs. Increasing the number of oligomethylene spacers stabilized the unsymmetrical MLM structure in both nano- and microtubes.

Carboxylic Acids↗
PubMed2004

Unsaturation effect on gelation behavior of aryl glycolipids.

Structurally simple, renewable-resource-based cardanyl (glucoside)s [1, 1-O-3'-n-(pentadecyl) phenyl-beta-D-glucopyranoside; 2, 1-O-3'-n-(8'(Z)-pentadeceenyl)-beta-glucopyranoside; 3, 1-O-3'-n-(8'(Z),11'(Z)pentadecadienyl)phenyl-beta-D-glucopyranoside, 4; 1-O-3'-n-(8'(Z),11'(Z),14'-pentadecatrienyl)phenyl-beta-D-glucopyranoside; and the mixture 5] form thermally reversible transparent gels in a water/alcohol mixture and a number of organic solvents, strongly influenced by the unsaturation of the aliphatic alkyl chain. DSC studies revealed that the Tgel of 1 in water/ethanol (1:1, vol/vol) gel is 69.0 degrees C, while of the introduction of a single double bond reduces the value to 30.0 degrees C in the case of monoene 2, indicating that the stability of the gel is related to the number of double bonds on the lipophilic part of the gelator. Furthermore, XRD measurements showed that the aqueous gel 1 maintains an interdigitated bilayered structure with 3.14 nm long-range ordering, and the corresponding organogel maintains an extended bilayer structure for 4.34 nm, indicating a clear difference in the aggregation behavior in different solvents.

Gels↗
PubMed2004

Below Knee Impact Responses using Cadaveric Specimens.

Knee injuries represent about 10% of all injuries suffered during car crashes. Efforts to assess the injury risk to the posterior cruciate ligament (PCL) have been based on a study available in the literature (Viano et al., 1978), in which only two of the five knees tested had PCL ruptures. The aims of the current study were to repeat the study with a higher number of samples, study the effects of other soft tissues on knee response, and assess the adequacy of the experimental setup for the identification of a PCL tolerance. A total of 14 knees were tested using a high-speed materials testing machine. Eight were intact knees (with the patella and all the muscular and ligamentous structures), three were PCL-only knees (patella and all the muscular and ligamentous structures other than the PCL removed), and the last three were PCL-only knees with the tibia protected from bending fracture. Of the eight intact knees tested, only one had PCL mid substance rupture, one had a partial articular fracture of the tibia below the plateau, and six had simple transverse fracture of the tibial metaphysis. Of the three PCL-only knees without tibial protection, one had PCL mid substance rupture, one had avulsion at the posterior intercondylar attachment point, and the last one had a simple oblique fracture of the tibial metaphysis. Of the three PCL only knees with tibia protection, two had PCL mid-substance ruptures and the third one had an avulsion at the tibial insertion site with partial articular fracture of the lateral plateau. Overall, the results of the current study were similar to those observed by Viano et al. (1978). The average displacement at failure for all PCL related injuries was 17.2+/-2.8 mm for the current study (n=6) and 16.2+/-3.9 mm for Viano et al. (1978) (n=4). This value is higher than the Injury Assessment Reference Value of 15 mm proposed by Mertz (1984) and used in various regulations. Both studies suggest that the existence of the soft tissues other than the PCL affect the injury outcome and that the intact knee would suffer predominantly tibial metaphyseal fractures possibly due to bending. Consequently, it is concluded that the current experimental setup can produce isolated PCL injuries but the data available are inadequate to characterize PCL tolerance. A Hybrid III knee equipped with a ball bearing knee slider was also tested using a pendulum setup. Apart from the initial higher stiffness, the overall response of this knee lies within the force-deflection corridors defined using the response of the cadaver knees with PCL mid-substance failure.

Journal Article↗
PubMed2003

Photoinitiated polymerization of columnar stacks of self-assembled trialkyl-1,3,5-benzenetricarboxamide derivatives.

A disk-shaped molecule, N-(5-sorbyl-pentyl)-N',N"-di(n-octyl)benzene-1,3,5-tricarboxamide (1), has been synthesized and assembled into a columnar stack in cyclohexane. Using a photoinitiated process, we polymerized monomer 1 in its self-assembled state and analyzed the resulting poly-1. On cooling a boiling cyclohexane solution of 1, the molecules aggregate via amide hydrogen bonds, as supported by the position of the N-H stretching band in FT-IR spectroscopy. Evidence of helical columnar stacking of 1 in the aggregate is provided by an induced CD effect upon blending 1 with a chiral side-chain homologue 3 in a so-called "sergeants and soldiers" experiment. The columnar assembly in cyclohexane was polymerized by UV light (365 nm) irradiation in the presence of 2,2-dimethoxy-2-phenylacetophenone as radical photoinitiator. The polymerization occurs selectively to give 1,4-polymer with isolated trans C=C bonds, as shown by FT-IR, and (1)H and (13)C NMR spectroscopy. Lack of polymerization of methyl sorbate (4) under identical conditions, and low incorporation of 4 in copolymerizations with 1 in cyclohexane, suggests that the polymerization preferentially occurs within the columnar assembly. Size exclusion chromatography shows that the degree of polymerization (X(n)()) based on number average molecular weight is approximately 65. Incorporation of small amounts of nonpolymerizable derivatives 2 and 3 into the columns has no effect on X(n)() and conversion. Molecular models show that the polymerizable sidearm of 1 is long enough to span the distance between the monomers in the chiral stack. Under the atomic force microscope (AFM), purified samples of polymerized 1 displayed nanometer-sized fibrous morphologies with a high-axial-ratio (>150), uniform width (60 nm), and a thickness (1.0 nm) which corresponds to the width of the benzene tricarboxamide core of 1, whereas aggregates of nonpolymerized 1 yield a featureless image due to their instability.

Journal Article↗