Selective formation of stable triplexes including a TA or a CG interrupting site with new bicyclic nucleoside analogues (WNA)

Triplex-forming oligonucleotides (TFOs) are potential DNA-targeting molecules and would become powerful tools for genomic research. As the stabilization of the TFO is partially provided by hydrogen bonds to purine bases, the most stable triplexes form with homopurine/homopyrimidine sequences, and a pyrimidine base in the purine strand of the duplex interrupts triplex formation. If a TFO can recognize sequences including such an interrupting site, the target regions in the genome would be expanded to a greater extent. However, this problem has not been generally solved despite extensive studies. We have previously reported a new base analogue (WNA) constructed of three parts, a benzene ring, a heterocyclic ring, and a bicyclic skeleton to hold these two parts. In this study, we have further investigated modification of WNA systematically and determined two useful WNA analogues, WNA-beta T and WNA-beta C, for selective stabilization of triplexes at a TA and a CG interrupting site, respectively. The triplexes with WNA analogues have exhibited an interesting property in that they are more stable than natural-type triplexes even at low Mg(2+) concentration. From comparison of the results with H-WNA-beta T lacking benzene and those with WNA-H without thymine, it has been suggested that benzene is a major contributor for triplex stability and thymine provides selectivity. Thus, it has been successfully demonstrated that WNA-beta T/TA and WNA-beta C/CG combinations may expand triplex recognition codes in addition to the natural A/AT and G/GC base triplet codes. The results of this study will provide useful information for the design of new WNA analogues to overcome inherent problems for further expansion of triplex recognition codes.     

Swelling behavior of poly(sodium acrylate) gels crosslinked by aluminum ions

The cylindrical poly(sodium acrylate) gel (SA gel) was synthesized in the glass capillary using aluminum ions as the crosslinker. The swelling ratio of the gel was measured after the repeated exchange of solvent (distilled deionized water, about pH 5.8). The gel exhibited two relaxation processes; at first the gel swells rapidly as exchange of water (the swelling process), then shrinks very slowly (the shrinking process). In order to reveal the microscopic structural change (especially, the formation of hydrogen bonding) by water exchange, attenuated total refraction (ATR) Fourier transform infrared (FT-IR) spectroscopy was applied to the gels with different swelling ratio. The IR absorption peaks of the gel were assigned based on those of poly(sodium acrylate) aqueous solutions at different pH. On the swelling process, the carboxyl groups were gradually protonated, and the intermolecular hydrogen bonding started to form in the gel with maximum swelling ratio. On the shrinking process, the formation of hydrogen bonding gradually increased with long-time repeated water exchange which resulted in the shrinkage of the gel. Effects of the repeated water exchange on the swelling behavior were discussed in terms of the exchange of counter ions and the formation of hydrogen bonding.     

The effect of organic matter and colloidal particles on the determination of chromium(VI) in natural waters

The chromium(VI) contents of two water samples, a river water and a sea-water, were determined by means of solvent extraction with APDC (ammonium pyrrolidinedithiocarbamate) into chloroform and by co-precipitation with iron(III) hydroxide. The analytical results depended on the separation method used, possibly because of differences in the behaviour of the chemical species of chromium in natural waters. Various chromium species, including simple inorganic ions, organic complexes, Cr(III) adsorbed on inorganic colloids and Cr(III) combined with organic polymers, were prepared, and their analytical characteristics were investigated.     

Thermal evolution of mesoporous titania prepared by CO2 supercritical extraction

Porous anatase is attractive because of its notable photo-electronic properties. Titania wet gel prepared by hydrolysis of Ti-alkoxide was immersed in the flow of supercritical CO₂ at 60°C and the solvent was extracted (aerogel). Mesoporous TiO₂ consisting of anatase nano-particles, about 5 nm in diameter, have been obtained. Thermal evolution of the microstructure of the aerogel was evaluated by TGA-DTA, N₂ adsorption, TEM and XRD, and discussed in comparison with that of the corresponding xerogel. The diffraction peaks of anatase were found for the as-extracted gel while the xerogel dried at 90°C was amorphous. After calcination at 600°C, the average pore size of the aerogel, about 20 nm in diameter, was 4 times larger than that of the xerogel, and the pore volume, about 0.35 cm³ g⁻¹, and the specific surface area, about 60 m² g⁻¹, were 2 times larger than those of the xerogel. XRD peaks of rutile have been found after calcination at 600°C. The particle sizes of anatase and rutile are about 13 and 25 nm in diameter, respectively. The surface morphology of TiO₂ nano-particles has been discussed in terms of their surface fractal dimensions estimated from the N₂ gas adsorption isotherms.     

Brown-Booth-Tillotson theory for classes of exponentiable spaces

Brown, Booth and Tillotson introduced the C-product, or the BBT C-product, for any class C of topological spaces. It is proved that any topological space is exponentiable with respect to the BBT C-product if and only if C is a subclass of the class of exponentiable spaces. The topology of the function space is induced by a canonical manner making use of the exponential topology for the spaces in C. It is not the C-open topology in general. The function space defined by this method enjoys good properties for algebraic topology. A necessary and sufficient condition on the class C is obtained for the exponential function to be a homeomorphism with the BBT C-product.     

Giant intrinsic spin and orbital hall effects in Sr2MO4 (M=Ru, Rh, Mo)

We investigate the intrinsic spin Hall conductivity (SHC) and the d-orbital Hall conductivity (OHC) in metallic d-electron systems, by focusing on the t2g-orbital tight-binding model for Sr2MO4 (M=Ru, Rh, Mo). The conductivities obtained are one or 2 orders of magnitude larger than predicted values for p-type semiconductors with approximately 5% hole doping. The origin of these giant Hall effects is the "effective Aharonov-Bohm phase" that is induced by the d-atomic angular momentum in connection with the spin-orbit interaction and the interorbital hopping integrals. The huge SHC and OHC generated by this mechanism are expected to be ubiquitous in multiorbital transition metal compounds, which opens the possibility of realizing spintronics as well as "orbitronics" devices.     

Sequence- and base-specific delivery of nitric oxide to cytidine and 5-methylcytidine leading to efficient deamination

Nitric oxide (NO) is an important endogenous regulatory molecule, and S-nitrosothiols are believed to play a significant role in NO storage, transport, and delivery. On the basis of their ability to generate NO in vivo, S-nitrosothiols can be used as therapeutic drugs. In this study, we have developed an innovative method for sequence- and base-specific delivery of NO to a specific site of DNA followed by specific deamination. We designed a NO transfer reaction from S-nitroso thioguanine to an imino tautomer of cytosine. Nitrosation of the thioguanosine-containing ODN 1 was carried out with S-nitroso-N-acetylpenicillamine (SNAP) to produce ODN 2. An interstrand NO transfer reaction was performed using ODN 2 and its complementary ODN 3 having dC or dmC at the target site, and a rapid NO transfer reaction was observed. In contrast, a transfer reaction was not observed either with ODN 3 having dT, dA, or dG at the target site or with ODN 5-7 having dC at a nontarget site. In the analysis of deaminated products of the NO-transferred ODN 4, it was found that the transformation ratio from dmC to dT was as high as 42% together with the dmC-diazoate (13%). In conclusion, we have demonstrated the innovative method of sequence- and base-specific delivery of nitric oxide to cytidine and 5-methylcytidine. The selectivity and efficiency of NO transfer followed by deamination exhibited in this study are extremely high compared to those of the conventional methods.     

Synthesis of α‐diaminomethylenebutyrolactams by the reaction of α‐cyanobutyrolactams with n‐trimethylsilylamines

Successive treatment of α‐cyanobutyrolactams 1 with N‐trimethylsilylamines and water gave the corresponding α‐diaminomethylenebutyrolacatms 2 in good yields. In the NOESY spectra of 2 , the E isomer, the NOE observed between β‐CH₂ (butyrolactam) and N‐CH₂ (morpholine, pyrrolidine) or N‐CH₃ (dimethylamine) indicated a cis configuration of these groups.     

Absorption and desorption of organic liquids in elastic superhydrophobic silica aerogels

The experimental results of the studies on the absorption and desorption of organic liquids in elastic superhydrophobic silica aerogels, are reported. The elastic superhydrophobic aerogels were prepared using methyltrimethoxysilane (MTMS) precursor by a two-step sol-gel process followed by supercritical drying. Monolithic superhydrophobic silica aerogels were used as the absorbents. In all, four alkanes, three aromatic compounds, four alcohols and three oils were used. The absorption property of the aerogel was quantified by the mass and moles of the organic liquid absorbed by unit mass of the aerogel. The superhydrophobic aerogels showed a very high uptake capacity and high rate of uptake. The desorption of solvents and oils was studied by maintaining the as-absorbed aerogel samples at various temperatures and weighing them at regular time intervals until all the absorbed liquid got totally desorbed. This was verified by measuring the weights of the aerogel samples before and after desorption. The transmission electron micrograph observations showed that the aerogel structure was not much affected by the solvent absorption, while the oil absorption led to the shrinkage resulting in a dense structure after the desorption. In all the cases, the aerogels retained hydrophobicity and could be re-used as absorbents.