Dynamics and thermodynamics of dimerization of parallel G-quadruplexed DNA formed from d(TTAGn) (n=3-5)

Parallel G-quadruplexes formed from oligonucleotide sequences, d(TTAGn), where n = 3-5, have been shown to form a dimer through end-to-end stacking of 3'-terminal G-tetrads. The monomers and dimers of the G-quadruplexes are in dynamic equilibrium with an exchange rate of approximately 1 s-1. A thermodynamic study demonstrated that the dimerization of the G-quadruplexes is largely enthalpic in origin.     

Small-angle x-ray scattering from solution of rodlike particles with length distribution

The scattering function of rods with a constant radius, 8 Å, and a length distribution of the Schulz–Zimm type was calculated on a computer as a model of helical synthetic polypeptide. The influence of length and length distribution on the scattered intensity of small-angle x-ray scattering was clarified. As length grows and length distribution broadens it is difficult to obtain reliable values of molecular weight and radius of gyration from a Zimm plot. The influence of length distribution on the mass per unit length, M_q, and the radius of gyration of the cross section, 〈S〉^1/2, from the Guinier plot of the cross-sectional factor decreases as the length increases, and reliable values of M_q and 〈S〉^1/2 can be obtained even for rods with wide distribution for rods more than 600 Å long. In particular, it is pointed out that the value of 〈S〉^1/2 is little influenced by length and length distribution.     

The effect of a cystamine derivative, bis[2-(E-2-hexenoylamino)ethyl] disulfide, on rat platelet aggregation

Bis[2-(E-2-alkenoylamino)ethyl] disulfides (compds. I), synthesized from cystamine and 2-trans fatty acids, inhibited collagen-induced rat and rabbit platelet aggregation. The most potent compound was bis[2-(E-2-hexenoylamino)ethyl] disulfide (compd. I-1), and this compound suppressed thromboxane B2 formation from arachidonic acid in rat platelets. The results suggested that compd. I-1 has an inhibitory effect on cyclooxygenase.     

Simultaneous operation of plural separation modes in capillary electrophoresis with a chemiluminescence detector possessing a micro-space area for reaction/detection

Analysis of alpha-amino acids, proteins, and phenolic compounds was simultaneously performed using three capillaries in capillary electrophoresis with chemiluminescence detection, taking advantage of the micro-space area for reaction/detection at the tip of the capillary. The three capillaries included usual, polymer-containing, and sodium docley sulfate (SDS)-containing migration buffers for separation. The eluted samples from the capillaries, which were inserted into the chemiluminescence detection cell, were mixed with chemiluminescence reagent at the tips of the capillaries to generate visible light. The specific micro-space area for reaction/detection at the tips of the capillaries enabled the simultaneous operation of the three separation modes in the present system.     

Effects of type and physical properties of oil phase on oil-in-water emulsion droplet formation in straight-through microchannel emulsification, experimental and CFD studies

Straight-through microchannel (MC) emulsification is a novel technique for formulating monodisperse emulsions using an array of micrometer-sized channels vertical to the surface of a silicon plate (a straight-through MC). We studied the effects of the type and physical properties of the dispersed oil phase and of the surfactant concentration on droplet formation from a straight-through MC by experiments and computational fluid dynamics (CFD) simulations. Monodisperse oil-in-water emulsions with coefficients of variation below 4% were formulated from an oblong straight-through MC using silicone oils, tetradecane, medium-chain triglyceride, soybean oil, and liquid paraffin as the oil phase. At oil viscosities (eta(d)) lower than a threshold value of 100 mPa s, the values of the resultant droplet diameter (d(ex)) gradually decreased with increasing eta(d), whereas they were not affected by the surfactant concentration. Conversely, at eta(d) higher than the threshold value, the d(ex) values significantly increased with increasing eta(d), and they were affected by the surfactant concentration. An analysis on the basis of droplet formation time and interfacial tension clarified that the trends in d(ex) at eta(d) above the threshold value would be caused by the significant decrease in the dynamic interfacial tension during droplet formation. We thus discovered that the dynamic interfacial tension is also a parameter affecting the d(ex) along with eta(d) in straight-through MC emulsification. CFD simulations using a three-dimensional (3D) model including a straight-through MC confirmed successful formation of micrometer-sized droplets for the above-mentioned oils. The experimental and CFD results for the resultant droplet size were compared using the dimensionless droplet diameter (d, droplet diameter/channel equivalent diameter). The d(CFD) values agreed well with the d(ex) values at eta(d) below the threshold value of 100 mPa s for all the experiment systems and at eta(d) above the threshold value for the experiment systems that did not contain a surfactant.     

Development of a chemical vapor sensor using piezoelectric quartz crystals with coated unusual lipids

Piezoelectric quartz crystal sensors were developed using lipids with various properties for highly sensitive detection of chemical vapors. Lipids with varying lengths of alkyl chains were coated onto 10 MHz AT-cut quartz crystal resonators and the response of these modified crystals to chemical vapors were measured. It was shown that hydrophilic compounds, such as ethanol and methanol, could be recognized efficiently by lipids having shorter alkyl chains, whereas lipids with longer alkyl chains showed affinity to more hydrophobic vapors, such as toluene, hexane and cyclohexane. Frequency changes caused by adsorption of alcohols could be enhanced when cholesterol was co-immobilized in the lipid layer. To confirm the assumption that the sensor-response might be affected by the properties of lipids derived from acyl chains, we have examined the effects of two types of newly synthesized unusual lipids on sensor response. When lipids having one triple bond each at different positions on their alkyl chains were coated onto quartz crystals separately, lower responses were observed compared to responses obtained for a sensor with immobilized, saturated phosphatidylcholine. Lipids containing -branched acyl chains, however, showed good affinity for organic vapors, and sensor responses improved 4–5-fold. Moreover, these sensors were shown to have sensitivity of the same order as the humans' sense of smell (10⁻⁵–10⁻⁶ w/w in liquid paraffin) when measured using standard odorants (isovaleric acid, skatole, etc.) for an olfactometry established in Japan.     

Carbon-Fluorine Bondings of Fluorinated Fullerene and Graphite

Carbon-fluorine bondings of fluorinated fullerenes and fluorine-graphite intercalation compound C_xF were investigated in detail on the basis of XPS data and the potential model using the charge distribution calculated by semiempirical method. It has been confirmed by the present study that two peaks in the C_1s spectra observed for fluorinated fullerenes are assigned to carbon atoms bonded to fluorine atoms and those unbound to fluorine atoms, and the small difference in charges and Madelung potentials of fluorine atoms in different circumstances well explains the single peak in F_1s spectra of fluorinated fullerenes. In the calculated structures of 1,3-C₆₀F₂ and 1,2-C₆₀F_x (x = 2?6) used as the models of C_xF, three kinds of carbon-fluorine bondings were observed corresponding to nearly ionic, semicovalent and covalent C? F bondings. The calculated result supports that the bi-intercalation structure of stage 1 C_xF consists of nearly ionic and semi-covalent fluorines.     

The effect of the counteranion on the formation of mesoporous materials under the acidic synthesis process

The presence of various counteranions at the interfacial region of the silicate-surfactant mesophase introduces opportunities for manipulation of the phase structure. Well-ordered 3D-hexagonal P63/mmc, cubic Pmn, 2D-hexagonal p6mm, and cubic Iad mesoporous materials have been synthesized with the same surfactant, cetyltriethylammonium bromide, in the presence of various acids. The counteranions of acidic media have resulted in increasing the surfactant packing parameter g in the order SO42- < Cl- < Br- < NO3-, which leads to the different time course of formation of mesostructures. The effect of counteranions on the formation of mesostructures is explained in terms of not only the adsorption strength on the headgroups of the surfactant micelle but also the rate of silica condensation affecting the charge density matching between the surfactant and silica. It has been found that the mesophase is always transformed from the larger g parameter into the smaller one. The distinct morphologies of the 3D-hexagonal P63/mmc mesophases have been rationally explained by supposing this particular mesostructure. The cubic Iad phase has been first synthesized under acidic conditions.     

Novel asymmetric through-hole array microfabricated on a silicon plate for formulating monodisperse emulsions

We have proposed a novel microchannel (MC) structure for formulating monodisperse emulsions. The emulsification device is a silicon array of microfabricated, asymmetric through-holes with a slit and a circular channel (an asymmetric straight-through MC). The asymmetric through-holes of a uniform size stably yielded monodisperse emulsions with average droplet diameters of 35-41 mum and coefficients of variation of less than 2% by forcing the to-be-dispersed phase into the continuous phase via the through-holes. Their asymmetry enabled the stable formation of monodisperse emulsion droplets by spontaneous transformation, even using a to-be-dispersed phase with a very low viscosity below 1 mPa s. Additionally, the asymmetric straight-through MC with a high-density through-hole layout has the potential for high-throughput formulation of monodisperse emulsions.