Small angle X-ray scattering from lamellar phase for β-3,7-dimethyloctylglucoside/water system: comparison with β-n-alkylglucosides

Small angle X-ray scattering (SAXS) is measured for the lamellar phase in aqueous systems of 1-o-β-3,7-dimethyoctyl-D-glucopyranoside (β-Glc(Ger)), which has recently been prepared by us, 1-o-β-decyl-D-glucopyranoside (β-GlcC₁₀), and 1-o-β-octyl-D-glucopyranoside (β-GlcC₈). The repeat distance d obtained from the position of the diffraction peak does not follow the swelling law d = 2δ_hc/_hc, where δ_hc and _hc are the thickness and the volume fraction of the hydrophobic layer, respectively. This may result from the fact that δ_hc increases and, equivalently, the surface area per surfactant molecule (a_s) decreases with increasing concentration. So we calculate δ_hc and a_s from the observed d value at each concentration using the above swelling law. The half-thickness δ_hc increases in the order β-GlcC₈ < β-Glc(Ger) < β-GlcC₁₀ at a fixed concentration. On the other hand, the data on a_s for β-GlcC₁₀ and β-GlcC₈ lie on the same line and the data for β-Glc(Ger) lies above this line. These results suggest that the cross-sectional area of the geranyl chain is larger than that of the glucose headgroup. Existence of water filled defects in bilayer sheets is also discussed based on the SAXS pattern and the concentration dependence of d.     

Aqueous phase behavior of a 1-O-phytanyl-beta-D-xyloside/water system. Glycolipid-based bicontinuous cubic phases of crystallographic space groups Pn3m and Ia3d

Temperature- and concentration-dependent aqueous phase diagram of a novel alkylglycoside, 1-O-phytanyl-beta-D-xyloside (beta-Xyl(Phyt)), was studied using small-angle X-ray scattering, polarizing optical microscopy, and differential scanning calorimetry. The phases found in this system include an Lc phase, an Lalpha phase, an HII phase, two inverted cubic phases of crystallographic space groups Pn3m and Ia3d, and a fluid isotropic phase, FI. The phase diagram of the beta-Xyl(Phyt)/water system is similar to that for the 1-monooleylglycerol (MO)/water system, suggesting that the phase behavior is largely determined by the overall molecular shape rather than the details of surfactant molecular structure. Moreover, the structural parameters of the beta-Xyl(Phyt) liquid crystals are also similar to those of the MO/water, due primarily to the similar molecular dimensions of two molecules. As compared to the MO/water system, however, the beta-Xyl(Phyt)/water system displays a lower value of TK ( approximately 8.(5) degrees C) and a wider temperature window for the mesophases (8.(5)-120 degrees C). Moreover, beta-Xyl(Phyt) is chemically more robust than MO, as the ether linkage is more stable against hydrolysis than the ester linkage and the phytanyl chain is fully saturated.     

Micelle structures in aqueous solutions of glucose-based surfactants having an isoprenoid-type hydrophobic chain

Surfactant self-diffusion coefficients have been measured on a binary system of 1-O-beta-3,7-dimethyloctyl-D-maltopyranoside (beta-Mal(2)(Ger))/water and a mixed surfactant system of beta-Mal(2)(Ger)/1-O-beta-3,7-dimethyloctyl-D-glucopyranoside (beta-Glc(Ger))/water at 25 degrees C. For comparison, measurements have also been made on 1-O-beta-decyl-D-maltopyranoside (beta-Mal(2)C(10))/water and beta-Mal(2)C(10)/1-O-beta-decyl-D-glucopyranoside (beta-GlcC(10))/water. The hydrodynamic radius of beta-Mal(2)(Ger) micelles obtained from the micellar diffusion coefficient is around 3 nm and nearly equal to that of beta-GlcC(10) micelles within experimental error. In the mixed surfactant systems, the hydrodynamic radii for both systems increase with increasing X(G) (the mole fraction of beta-Glc(Ger) or beta-GlcC(10) in the total mixed solute) above X(G) congruent with 0.4 when the total surfactant concentration is kept constant at 2 wt%. The R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles, and then phase separation occurs at X(G) congruent with 0.65. On the other hand, the R(H) of beta-GlcC(10)/beta-Mal(2)C(10) micelles continues to increase until the phase separation occurs at X(G) congruent with 0.92. Measurements have also been performed as a function of total surfactant concentration at constant X(G) (=0.6). The CMC of the beta-Glc(Ger)/Mal(2)(Ger) system is larger than that of the beta-GlcC(10)/beta-Mal(2)C(10) system as expected from the results of the pure surfactant systems published previously. The R(H) increases with increasing total surfactant concentration for both systems. At higher concentrations, the R(H) of beta-Glc(Ger)/Mal(2)(Ger) micelles increases more rapidly than beta-GlcC(10)/beta-Mal(2)C(10) micelles. These results can be explained by the fact that the geranyl and decyl chains have the same volume but different chain lengths.     

A Bulky Thiyl‐Radical Catalyst for the [3+2] Cyclization of N‐Tosyl Vinylaziridines and Alkenes

Thiyl‐radical‐catalyzed cyclization reactions of N‐tosyl vinylaziridines and alkenes were developed as a new synthetic method for the generation of substituted pyrrolidines. The key to making this process accessible to a broad range of substrates is the use of a sterically demanding thiyl radical, which prevents the undesired degradation of the catalyst.     

Sequential multiple analyses of atmospheric nitrous acid and nitrogen oxides

Sequential injection analysis (SIA) was applied to multi-gas monitoring for atmospheric analysis. HONO, NO₂ or NO was collected in an individual diffusion scrubber in which the channel array was filled with either HCl or triethanolamine solution. All analytes were collected in the form of nitrite ions in the scrubber, and were transferred via a 12-port selection valve into a 2.5-ml syringe. The reagent, 3-amino-1,5-naphthalenedisulfonic acid (C-acid) solution was subsequently introduced into the syringe, and inter-mixed with the nitrite sample, whereafter the mixed solution was transferred to a heated reactor and held for 3 min at 100 °C. After that, the sample/reagent solution was returned to the syringe and alkalinized. Then, the final solution was analyzed using a homemade fluorescence detector. Atmospheric HONO, NO₂ and NO were successfully monitored 3 or 4 times/h. The limits of detection were 0.22, 0.28 and 0.35 ppbv for HONO, NO₂ and NO, respectively. It was demonstrated for the first time that SIA is a good tool for multi-gas atmospheric analysis. These nitrogen-oxygen compounds are interconvertible, and the simultaneous measurement of these gases is important. Especially, HONO is a source of OH radicals which contribute greatly to atmospheric pollution, and indeed atmospheric chemistry. This method allows the three gases to be measured using one system. The NO₂ and NO data obtained by SIA was compared with those obtained using chemiluminescence instrument. SIA has been successfully applied to atmospheric measurements. Interestingly, it was observed that HONO levels rose toward the end of periods of rain.     

Factors contributing to bone conduction: the outer ear

The ear canal sound pressure and the malleus umbo velocity with bone conduction (BC) stimulation were measured in nine ears from five cadaver heads in the frequency range 0.1 to 10 kHz. The measurements were conducted with both open and occluded ear canals, before and after resection of the lower jaw, in a canal with the cartilage and soft tissues removed, and with the tympanic membrane (TM) removed. The sound pressure was about 10 dB greater in an intact ear canal than when the cartilage part of the canal had been removed. The occlusion effect was close to 20 dB for the low frequencies in an intact ear canal; this effect diminished with sectioning of the canal. At higher frequencies, the resonance properties of the ear canal determined the effect of occluding the ear canal. Sectioning of the lower jaw did not significantly alter the sound pressure in the ear canal. The sound radiated from the TM into the ear canal was investigated in four temporal bone specimens; this sound is significantly lower than the sound pressure in an intact ear canal with BC stimulation. The malleus umbo velocity with air conduction stimulation was investigated in nine temporal bone specimens and compared with the umbo velocity obtained with BC stimulation in the cadaver heads. The results show that for a normal open ear canal, the sound pressure in the ear canal with BC stimulation is not significant for BC hearing. At threshold levels and for frequencies below 2 kHz, the sound in the ear canal caused by BC stimulation is about 10 dB lower than air conduction hearing thresholds; this difference increases at higher frequencies. However, with the ear canal occluded, BC hearing is dominated by the sound pressure in the outer ear canal for frequencies between 0.4 and 1.2 kHz.     

Factors contributing to bone conduction: the middle ear

Measurement of the motion of the malleus umbo and stapes footplate during bone conduction (BC) stimulation was conducted in vitro in 26 temporal bones using a laser Doppler vibrometer over the frequency range 0.1 to 10 kHz. For lower frequencies, both ossicular sites followed the motion of the temporal bone. The differential motion between the malleus and the surrounding bone was greater than the differential motion of the stapes footplate; both resonated near 1.5 kHz. Different lesions were shown to affect the response: (1) a mass attached to the umbo lowered the resonance frequency of the ossicular vibration; (2) fixation of either the malleus or stapes increased the stiffness and shifted the resonance frequency upward; and (3) dislocation of the incudo-stapedial joint did not significantly affect the ossicular vibration. The sound radiated from the tympanic membrane was approximately 85 dB SPL at an umbo differential velocity of 1 mm/s for low frequencies in an open ear canal and about 10 dB higher for an occluded one; at higher frequencies (above 2 kHz) resonances of the canal determine the response. It was also found that the motion between the footplate and promontory was within 5 dB when the specimen was stimulated orthogonal to the vibration direction of the ossicles than in line with the same. Measurement of the differential motion of the umbo in one live human skull gave similar response as the average result from the temporal bone specimens.