High-temperature solvent-free synthesis of low-molecular-weight organogelators consisting of starch-derived 1,5-anhydro-d-glucitol coupled with fatty acids.

We previously developed low-molecular-weight organogelators that can gel various types of oils by introducing various fatty acids into 1,5-anhydro-d-glucitol (1,5-AG), a cyclic polyol derived from starch. These gelators are composed of ester bonds between naturally occurring materials. We have established a method to synthesize these gelators by heating powdered 1,5-AG and powdered fatty acids to 230 °C to liquefy the compounds without using organic solvents or activated fatty acids and then performing the esterification reaction without a catalyst or with a base catalyst. This has created the possibility of synthesizing these gelling agents at very low cost.

Development of Low-Molecular-Mass Organogelators: Synthesis and Physical Properties of N-Linear Saturated Fatty Acyl-GABAs and Their Ester Derivatives.

We determined that compounds in which γ-aminobutyric acid (GABA) and linear saturated fatty acids of various lengths are amide-bonded, as found in the human brain, have the ability to gelate organic solvents. We also synthesized compounds of these GABA derivatives attached to 1,5-anhydro-d-glucitol (1,5-AG) or d-glucopyranose (Glc) via ester linkages, and these compounds were also found to be able to gelate organic solvents. From the comparative experiments of gelation using various lengths of N-linear saturated fatty acyl-GABAs and their ester derivatives, it was determined that the compound of N-tetradecanoic acyl-GABA bonded to 1,5-AG via ester linkage (C14GABA-AG) had a particularly high gel hardness and could gelate various organic solvents. Furthermore, field-emission scanning electron microscopy observations revealed the formation of a fibrous structure, which encapsulates the organic solvent and forms a gel. A variable-temperature Fourier transform infrared spectroscopy analysis revealed that the alkyl chains of N-linear saturated fatty acyl-GABAs are packed with an all-trans conformation, whereas the alkyl chains of the ester compounds attached to 1,5-AG or Glc are slightly skewed from the all-trans conformation due to the intermolecular hydrogen bonding of the amide groups. Here, we report the synthesis and analysis of N-linear saturated fatty acyl-GABA derivatives and the gelation mechanism.

Supramolecular fibrous gels with helical pitch tunable by polarity of alcohol solvents.

A sugar-based, low-molecular-weight gelator 16AG, can gelatinize primary alcohols by forming supramolecular fibers. We obtained non-helical, tape-like fibers in methanol and ethanol but helical fibers in alcohols with at least three carbons. The pitch of the helical fibers became shorter with increasing carbon number.

Supramolecular Organogelation Directed by Weak Noncovalent Interactions in Palmitoylated 1,5-Anhydro-d-Glucitol Derivatives.

We synthesized a series of novel alicyclic compounds by modifying 1,5-anhydro-d-glucitol with two to four palmitoyl chains, and we explored their self-assembly and gelation behaviors in paraffin. The obtained organogels were studied by field emission scanning electron microscopy, atomic force microscopy, variable-temperature Fourier transform IR spectroscopy, X-ray diffraction analysis, polarized optical microscopy, and transmission spectroscopy. While all the palmitoylated derivatives spontaneously formed fibrous networks and gelated the paraffin, an acetylated derivative of 1,5-anhydro-d-glucitol did not gelatinize the solvent, thus indicating the importance of aliphatic chains for gelation. Interestingly, α- and ß- d-glucopyranose with five palmitoyl chains neither gelatinized the solvent nor formed fibrous networks, thus suggesting that the absence of C-1 substitution in 1,5-anhydro-d-glucitol is important for gelation. Fourier transform IR spectroscopy suggested that the formation of weak hydrogen bonds between the carbonyl groups and the C-H groups was the driving force for formation of the supramolecular fibers and for gelation of the solvent.

Construction of a DNA-Based Supramolecular Nanosheet That Emits Bluish-White Light from Charge-Transfer Excited States of the Nucleobases.

1,ω-Inosinic acid-bearing bolaamphiphiles dI(18), dI(19), and dI(20) with a 3'-phosphorylated inosine as a universal base connected to each end of an oligomethylene chain were synthesized for the first time. Single-component self-assemblies of these bolaamphiphiles and their binary self-assemblies with salmon sperm DNA were studied by AFM; temperature-dependent UV absorption, fluorescence, and circular dichroism spectroscopy; and gel electrophoresis. The binary self-assembly of dI(20) and salmon sperm DNA (dI(20)-DNA) had a nanosheet structure with a homogeneous thickness of about 6 nm and widths of several micrometers. Interestingly, an aqueous solution of the nanosheets showed a broad absorption band originating from the charge-transfer (CT) states of the nucleobase in the long-wavelength region (>300 nm), and the molar absorptivity per nucleobase was calculated to be approximately 150 times that of single-stranded (dT20 and dA20) and double-stranded (dT20-dA20) oligonucleotides. In addition, a continuous and broad emission band originating from CT excited states of the nucleobases was observed in the visible region. These observations indicate that CT states of the nucleobases were formed and stabilized in the supramolecular nanosheet and that bluish white light was emitted from CT excited states of the nucleobases.

Visualization of periodic electric polarizability of helical nanofibers formed by self-assembly of nucleotide-bearing bolaamphiphiles and natural-source DNA as a template.

The possibility of fabricating DNA-based electronics has attracted considerable attention, but constructing robust, functional DNA nanowires on hard substrates has proven to be difficult. This paper describes the production of robust one-dimensional nanofibers by self-assembly of 1,18-nucleotide-bearing bolaamphiphiles templated by salmon sperm DNA. Electrostatic force microscopy measurements of the nanofibers on a highly oriented pyrolytic graphite substrate revealed that they showed electric polarizability that varied periodically with a pitch of 20-30 nm. Atomic force microscopy, gel electrophoresis, and circular dichroism spectroscopy suggested that the periodic polarizability was derived from right-handed helicity induced by the template DNA. Salmon sperm DNA itself did not show electric polarizability.

Investigation of Supramolecular Nanofibers Formed from Multicomponent Nucleotide-Appended Bolaamphiphiles and Heteropolymeric DNA as a Template.

A novel DNA-templated multicomponent self-assembly of well-defined, molecular-level-controlled nanostructures in aqueous solution is demonstrated by using a thermal cycling procedure. The strategy uses four building blocks comprising 1,18-nucleotide-appended bolaamphiphiles (3'-phosphorylated adenosine, thymidine, guanosine, or cytidine connected to each end of an oligomethylene chain) and a heteropolymeric 58-mer containing a palindromic sequence as the template DNA. Atomic force microscopic observations, circular dichroism, and temperature-dependent absorption spectra revealed that the multicomponent self-assembly of the four nucleotide bolaamphiphiles and template DNA formed right-handed helical nanofibers with complementary base pairs during thermal cycling. Nanofibers were not formed if one of the four nucleotide bolaamphiphiles was missing, suggesting that construction of the helical nanofiber resulted from self-assembly of all four bolaamphiphiles to form matched base pairs sorted according to the sequence of the template DNA.

Accumulation of supramolecular nanoparticles self-assembled from a bola-shaped cytidylic acid-appended fluorescein dye in cell nuclei.

We examined the cellular uptake of the nanoparticles self-assembled from a bola-shaped cytidylic acid-appended fluorescein derivative (C-FLU-C). The accumulation of fluorescence in the Caco-2 cell nucleus was observed mainly after the plateau phase of cell growth, indicating that C-FLU-C permeated the nuclear envelope without nuclear-localizing tags.

Construction of energy transfer pathways self-assembled from DNA-templated stacks of anthracene.

We describe optical properties of anthracene stacks formed from single-component self-assembly of thymidylic acid-appended anthracene 2,6-bis[5-(3'-thymidylic acid)pentyloxy] anthracene (TACT) and the binary self-assembly of TACT and complementary 20-meric oligoadenylic acid (TACT/dA20) in an aqueous buffer. UV-Vis and emission spectra for the single-component self-assembly of TACT and the binary self-assembly of TACT/dA20 were very consistent with stacked acene moieties in both self-assemblies. Interestingly, time-resolved fluorescence spectra from anthracene stacks exhibited very different features of the single-component and binary self-assemblies. In the single-component self-assembly of TACT, a dynamic Stokes shift (DSS) and relatively short fluorescence lifetime (τ=0.35ns) observed at around 450nm suggested that the anthracene moieties were flexible. Moreover, a broad emission at 530nm suggested the formation of an excited dimer (excimer). In the binary self-assembly of TACT/dA20, we detected a broad, red-shifted emission component at 534nm with a lifetime (τ=0.4ns) shorter than that observed in the TACT single-component self-assembly. Combining these results with the emission spectrum of the binary self-assembly of TACT/5'-HEX dA20, we concluded that the energy transfer pathway was constructed by columnar anthracene stacks formed from the DNA-templated self-assembly of TACT.

Construction of supramolecular helical nanofibers using renewable biomaterials: self-assembly of a cytidylic acid-appended bolaamphiphile in lemon juice.

We performed the self-assembly of a 1,18-cytidylic acid-appended bolaamphiphile (C18C) in lemon juice, which contained citric acid, and succeeded in forming left-handed helical nanofibers with diameters, lengths, and pitches of ca. 6-7 nm, several hundred nm to 5 µm, and ca. 30-40 nm, respectively.

Isolation and identification of flavonoids accumulated in proanthocyanidin-free barley.

Flavonoids accumulated in proanthocyanidin-free near-isogenic lines iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi, developed by backcross breeding using a leading cultivar, Nishinohoshi, as a recurrent parent and a proanthocyanidin-free mutant as a nonrecurrent parent in Japan, were examined. A new flavanone, (2RS)-dihydrotricin 7-O-ß-D-glucopyranoside (1), known flavanones (2RS)-dihydrotricin (2) and (2RS)-homoeriodictyol (3), and known flavones chrysoeriol 7-O-[α-L-rhamnopyranosyl-(1→6)-ß-D-glucopyranoside] (4), chrysoeriol 7-O-ß-D-glucopyranoside (5), tricin (6), and chrysoeriol (7) were isolated from iso ant 17 of Nishinohoshi. The structures and stereochemistries of the isolated flavonoids (1-7) were elucidated on the basis of spectroscopic analyses. The concentrations of the isolated flavonoids (1-7) in iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi were similar to each other, whereas the flavonoids 1-5 and 7 were not detected in Nishinohoshi, an old Japanese cultivar, Amaginijo, and North American cultivar Harrington. The concentration of tricin (6) in Nishinohoshi was a half those in iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi. Except for iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi, the concentration of tricin (6) was highest in Nishinohoshi, followed by Amaginijo and Harrington. Thus, tricin (6), its precursor dihydrotricin (2), and its glucopyranoside, dihydrotricin 7-O-ß-D-glucopyranoside (1), as well as chrysoeriol (7) and homoeriodictyol (3) were accumulated in iso ant 13, iso ant 17, and iso ant 22 of Nishinohoshi probably by blocking at the step of flavanone 3-hydroxylase in the procyanidin biogenetic pathway, resulting in enhancement of the alternative biogenetic pathway.

Diverse morphologies of self-assemblies from homoditopic 1,18-nucleotide-appended bolaamphiphiles: effects of nucleobases and complementary oligonucleotides.

The synthesis of 1,18-nucleotide-appended bolaamphiphiles (1, 2, 4, and 6) is reported, in which a 3'-phosphorylated guanidine, adenosine, thymidine, or cytidine is connected to each end of an octadecamethylene chain. Single-component self-assemblies and binary self-assemblies with the complementary oligonucleotides dC(20), dT(20), dA(20), and dG(20) are studied by atomic force microscopy, powder X-ray diffraction analysis, temperature-dependent UV absorption, circular dichroism, and attenuated total-reflection Fourier-transform infrared spectroscopy. The single-component self-assembly of 1 forms a two-dimensional sheet, whereas the binary self-assembly 1/dC(20) gives helical nanofibers. Non-helical nanofibers are observed for the single-component self-assemblies of 2 and 4, and helical nanofibers form from the binary self-assembly 2/dT(20). Interestingly, helical nanorod structures are obtained from the binary self-assembly 4/dA(20), and the aligned nanorods form a nematic phase. The single-component and binary self-assemblies from 6 give unilamellar vesicles owing to a lack of stacking interaction between the cytosine moieties.

Construction of helical J-aggregates self-assembled from a thymidylic acid appended anthracene dye and DNA as a template.

The thymidylic acid appended anthracene dye 2,6-bis[5-(3'-thymidylic acid)pentyloxy]anthracene (1) was synthesized, and the self-assembly of 1 and the binary self-assembly of 1 with a complementary single-stranded 20-meric oligodeoxyadenylic acid (dA(20)) were performed in 0.1 x TE buffer solution (i.e., 1.0 x 10(-3) M Tris-HCl, 1.0 x 10(-4) M ethylenediaminetriacetic acid (EDTA)). The characteristic J-band, small Stokes shift (6 nm), Cotton effect, and helical nanofibers 5.1 nm in diameter are observed in UV/Vis, fluorescence, and circular dichroism (CD) spectroscopies and atomic force microscopy (AFM) measurements for the binary self-assembly of 1 and dA(20) in aqueous solution. These observations revealed that the helical J-aggregates, in which the short-axis transition dipoles of the anthracene moieties are aligned in a head-to-tail fashion, are formed from the binary self-assembly of 1 and dA(20). The UV/Vis absorption and CD band of the anthracene L(a) region were found to be strongly dependent on temperature and showed cooperative changes for the binary self-assembly of 1 and dA(20). The self-assembly of the single-component 1 produced right- and left-handed helical nanofibers with diameters ranging from 4.0 to 10 nm. In contrast, for the binary self-assembly, the UV/Vis and fluorescence spectra showed no J-band and the Stokes shift was at approximately 107 nm for the single-component 1 in aqueous solution. In addition, the binary self-assembly of 1 and noncomplementary single-stranded 20-meric oligothymidylic acid (dT(20)) showed a small J-band and the J-band disappeared at 50 degrees C upon heating. On the basis of these observations, we concluded that thymine-adenine base-pair formation induced supramolecular helical J-aggregates in the binary self-assembly of 1 and dA(20) in aqueous solutions.

Nanofiber formation from sequence-selective DNA-templated self-assembly of a thymidylic acid-appended bolaamphiphile.

Quaternary self-assembly of a thymidylic acid-appended bolaamphiphile, with heteropolymeric DNA as a template, produced supramolecular helical nanofibers in the presence of specific target DNA.

Effects of oligoDNA template length and sequence on binary self-assembly of a nucleotide bolaamphiphile.

Templated self-assembly of nucleotide bolaamphiphile 1 (in which a 3'-phosphorylated thymidine moiety is connected to each end of a long oligomethylene chain) with a 10-, 20-, 30-, or 40-meric single-stranded oligoadenylic acid (2, 3, 4, or 5) led to the formation of right-handed helical nanofibers in 0.1x Tris/EDTA (TE) buffer solutions. The helical pitch increased as the length of the oligoadenylic acid template increased. DNA composed of oligoadenylic and oligocytidylic acid sequences (6, 7, and 8) also acted as templates to induce the formation of helical nanofiber structures. The diameter of the nanofibers remained constant (6-6.6 nm) irrespective of the template used. The binary self-assembly of 1 with 4 also produced higher-order, double-stranded nanofibers.

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.

Sodium chloride-induced self-assembly of microfibers from nanofiber components.

Self-assembly of a nucleotide bolaamphiphile, terminated with two nucleotide moieties including thymine, deoxyribose, and phosphodiester at both ends of the C20 oligomethylene chain, in sodium chloride aqueous solutions has been studied by SEM, LSM, FE-SEM, micro-FTIR, and zeta-potential measurement. The self-assembly behavior of the nucleotide bolaamphiphile was strongly dependent on the concentration of sodium chloride added. The nucleotide bolaamphiphile was found to hierarchically self-assemble to form micrometer-sized fibers (microfibers) consisting of bundles of entangled nanometer-sized fibers (nanofibers) under certain conditions of sodium chloride concentration (approximately 44 mM). The zeta-potential measurement suggested that the surface-charge tuning of the nanofibers induce the hierarchical self-assembly of the microfibers.

Detection of complementary hydrogen bond complexes in water by electrospray ionization-Fourier-transform ion cyclotron resonance mass spectrometry.

Complementary base paired complex formation of a thymidine-appended bolaamphiphile with adenosine derivatives was able to be detected with high resolution and high sensitivity in aqueous solutions by electrospray ionization-Fourier-transform ion cyclotron resonance mass (ESI-FTICR MS) spectrometry.