Chirality-antimicrobial relationship of quaternary ammonium cationics

Optically active and racemic quaternary ammonium cationics containing a chiral alkyl group, such as N,N-dimethyl-N-(1-phenylethyl)alkylammonium bromides were prepared and showed excellent antimicrobial properties against Gram positive and negative bacteria, with some exceptions, and against fungi. The influence of optical isomerism on their antimicrobial properties showed that the antimicrobial properties between racemic and optically active cationics were obscure. The order of activity of substituted alkyl groups was tetradecyl > dodecyl ° hexadecyl.     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

Experimental examination of the characteristics of bright-field scanning confocal electron microscopy images

We experimentally examined the characteristics of bright-field (BF) scanning confocal electron microscopy (SCEM) images by changing the observation conditions and comparing the images with those obtained by BF transmission electron microscopy (TEM) and BF scanning TEM (STEM) modes. The observation of 5-nm-diameter Au nanoparticles demonstrated that BF-SCEM produces object elongation of more than 2000?nm along the optical axis, as do BF-TEM and BF-STEM. We demonstrated the relationship between elongation length and geometric effects such as convergence and collection angles of a probe and the lateral size of an object; the relationship is consistent with previous theoretical prediction. Further, we observed interesting features that are seen only in the BF-SCEM images; the film contrast was strongly enhanced, compared with that of BF-STEM. In addition, a bright contrast appeared around the object position in the elongated images. Using this characteristic, we could determine the object position and structure.     

Sintering of Ceria-Doped Tetragonal Zirconia Crystallized in Organic Solvents, Water, and Air

Amorphous CeO₂–ZrO₂ gels were prepared by coprecipitation in ammonia solutions. The onset of crystallization of the gels, from calcining in air, was 420°C, while 200° to 250°C in the presence of water and organic solvents such as methanol and ethanol. The sintering behaviors of CeO₂–ZrO₂ powders were sensitive to the crystallizing conditions, since hard agglomerates formed when the precipitated gels were crystallized by normal calcination in air, whereas soft agglomerates formed when they were crystallized in water or organic solvents. CeO₂–ZrO₂ powders crystallized in methanol and water at 250°C were sintered to full theoretical density at 1150° and 1400°C, respectively, whereas that crystallized by calcination in air at 450°C was sintered to only 95.2% of theoretical density, even at 1500°C.     

Influence of particle size and fluid fraction on rheological and extrusion properties of crosslinked hyaluronic acid hydrogel dispersions

Crosslinked hyaluronic acid (HA) hydrogels are widely used in gel/HA fluid formulations as a viscosupplement to treat joint diseases; thus, it is important to characterize these hydrogels in terms of their particle size and to investigate the effects of the gel/fluid mixtures on their rheological properties and extrusion force. Hydrogels previously crosslinked with divinyl sulfone were sheared in an Ultra‐Turrax unit to produce particles with mean diameters ranging from 20 to 200 μm. Hydrogels with 75–100 μm mean diameters were also evaluated in dispersions containing a 20–40% mass fraction of HA fluid. The mean diameters were measured by laser light scattering and the rheological behavior was determined by oscillatory and steady measurements in parallel plate geometry. The HA hydrogels exhibited the typical behavior of so‐called weak gels, as analyzed by the storage and loss moduli G′ and G″, respectively. The viscoelasticity, the viscosity, and the extrusion force increased with the hydrogel particle size. The fluid phase dispersions decreased both moduli. At 40% fluid fraction, the gel characteristics were lost and the dispersion behaved as a fluid. Based on these results, the particle size and HA fluid fraction in hydrogel dispersions may be optimized to develop more efficient viscosupplement formulations. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis of rodlike polysiloxane containing polyol moieties derived from glucose with regularly controlled higher-ordered structure

A rodlike polysiloxane (3) containing polyol moieties derived from the sugar has been synthesized by reaction of an amine-functionalized rodlike polysiloxane (1) with gluconolactone (2) in the presence of triethylamine in DMF. Formation of 3 was estimated by the IR and ¹H NMR measurements. The functionality of 2 to the amino groups in 1 was ca. 75%, based on the ¹H NMR spectrum of the product. The XRD profile of 3 showed three peaks for a typical hexagonal phase, and the d-value of (100) peak of 3 was larger than that of 1, indicating the regularly controlled higher-ordered structure of 3.     

Double-stimuli responsive O/W emulsion gel based on a novel amidoamine surfactant

A heat-induced O/W emulsion gel that undergoes a phase transition from sol to gel on heating was formed from the addition of aqueous HCl to a toluene solution of a long-chain amidoamine derivative (C18AA). The heat induced O/W emulsions are highly sensitive to temperature, and the sol-gel transition temperature could be simply controlled by adjusting the C18AA concentration. Interestingly, the sol-gel transition of the O/W emulsions was also very sensitive to pH. Thus, we have successfully prepared a novel double-stimuli responsive gel based on O/W emulsions consisting of C18AA and HCl.     

Competitive sorption of water vapor and CO2 in photocrosslinked PVCA film for a capacitive‐type humidity sensor

The sorption behavior of water vapor and CO₂ gas in photocrosslinked poly(vinyl cinnamate) (PVCA) film was examined at 30°C under atmospheric pressure. Both the water sorption isotherm and the CO₂ sorption isotherm obtained with quartz crystal microbalance (QCM) method obeyed the simple Langmuir's equation. Water vapor/CO₂ mixed‐gas sorption isotherms were also obtained. Total amount of sorbed mixed gases was clearly influenced by the partial pressure of water vapor (p_w) and CO₂ gas (p_c) in the atmosphere. A modified Langmuir's equation based on a dual‐site model was employed for predicting the competitive adsorption isotherm, and the isotherm was clearly described by the equation. The theoretically estimated amount of adsorbed water at the constant p_w decreased slightly with increasing p_c. The effect of this phenomenon on the sensitivity of the capacitive‐type relative humidity sensor was examined. As expected, the electrical capacitance of the sensor at the constant relative humidity decreased because of the coexistence of CO₂ gas. However, the influence was quite small in the CO₂ concentration range in the ordinary environment. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 401–407, 2002     

Synthesis and characterization of 1,3,2-diazaboroine derivatives for organic thin-film transistor applications

2,2′-(1,4-Phenylene)bis(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaboroine) [PND] and 2,2′-(4,4′-biphenylene)bis(2,3-dihydro-1H-naphtho[1,8-de]-1,3,2-diazaboroine) [BND] were synthesized and characterized by using differential scanning calorimetry (DSC) measurements, single crystal X-ray structure analysis, UV–vis absorption and electrochemical measurements, thin-film X-ray diffraction (XRD) and AFM studies. Organic field-effect transistors (OFETs) were fabricated by vacuum deposition with a bottom contact geometry using Au electrodes. Annealing treatment optimizes the organic active layer and increases the charge carrier mobility. Field-effect mobilities of 7.2 × 10^?3 for PND and 4.1 × 10^?4 cm² V^?1 s^?1 for BND were found.     

Effect of crosslinking structure on sorption of CO2 in photocrosslinked PVCA film

The sorption behavior of CO₂ gas in photocrosslinked poly(vinyl cinnamate) film was examined under atmospheric pressure. The sorption isotherm was well described by the Langmuir equation, suggesting that sorption of CO₂ is mainly governed by adsorption in the microvoids. The amount of sorbed CO₂ was significantly affected by the degree of crosslinking. The CO₂ sorption was enhanced at a lower degree of crosslinking but was decreased at a higher degree of crosslinking. The unexpected increase in the amount of adsorbed CO₂ correlated with the increase in the number of microvoids that occurred as a result of the crosslinking reaction. However, further crosslinking led to a decrease in the mean size of the microvoids. The smaller microvoids, in comparison to CO₂ molecules, did not act as adsorption sites, so that the amount of sorbed CO₂ decreased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1744–1750, 2000