Chemo-enzymatic synthesis and properties of novel optically active cationics containing carbonate linkages

Novel optically active carbonate-type cationics were designed and synthesized via a green method. A series of n-alkyl N,N-dimethylaminoalkyl carbonates was prepared via a two-step successive carbonate exchange reaction of diphenyl carbonate with 1-alkanol followed by the reaction of the optically active or racemic amino alcohol in the presence of triethylamine. The quaternarization of the N,N-dimethylamino group was carried out using methyl iodide. Furthermore, optically active cationics were prepared by the lipase-catalyzed enantioselective hydrolysis of the racemic cationics. Carbonate-type cationics having an isopropylene linkage showed high hydrolytic stability. They exhibited surfactant properties similar to those of the corresponding racemic cationics. Although no significant differences in the antimicrobial activities were observed owing to the stereochemistry of the cationics, the biodegradability was strongly influenced by the stereochemistry. Some optically active cationics were rapidly biodegraded by activated sludge.     

Organocatalytic Enantioselective Decarboxylative Addition of Malonic Acids Half Thioesters to Isatins

The organocatalytic enantioselective decarboxylative addition of malonic acids half thioesters to isatins using a squaramide catalyst afforded the products with high enantioselectivity. These products are key intermediates in the synthesis of 3‐substituted 3‐hydroxy‐2‐oxindole derivatives. The first enantioselective synthesis of (−)‐flustraminol B has been accomplished.     

Direct Enantioselective Three‐Component Kabachnik–Fields Reaction Catalyzed by Chiral Bis(imidazoline)‐Zinc(II) Catalysts

A direct three‐component reaction of aldehydes, amines and diaryl phosphites was catalyzed by a zinc(II) complex of 1,3‐bis(imidazolin‐2‐ly)pyridine (pybim) giving the corresponding α‐aminophosphonates in good yield with good enantioselectivity. The reaction was applied to a wide variety of aromatic aldehydes to give products with excellent yields (up to 99%) and enantiomeric excesses (up to 93% ee).     

Size dependence of crystallization within spherical microdomain structures

We have investigated the size dependence of crystallization within spherical microdomains formed in various poly(ε-caprolactone)-block-polybutadiene diblock copolymers (PCL-b-PB). The crystallinity (χ) and melting temperature (T_m) of the PCL block are considerably lower than those of PCL homopolymer, and χ decreases steadily and T_m decreases only slightly with decreasing radius of PCL spheres (R) for a series of PCL-b-PB with a same molecular weight (M_n). When PCL-b-PB is compared with the similar R but different M_n, χ is significantly different, suggesting that the sphere size is not the unique factor to control crystallization within spherical microdomains.     

Marked particle size and support effect of Pd catalysts upon the direct decomposition of nitric oxide

The catalytic behavior of beryllia-supported Pd catalyst for the direct decomposition of NO was compared with that of silica supported one. The TOF of NO decomposition was one order of magnitude larger in the case of Pd/BeO. Over Pd/SiO₂, the TOF was increased with the increase of the Pd particle size. On the contrary, over Pd/BeO smaller Pd particles exhibited higher TOF for NO decomposition suggesting some strong electronic or structural interaction between Pd and beryllia. TPD spectra of NO(a) over reduced catalysts indicated that NO was adsorbed on Pd/SiO₂ more strongly than on Pd/BeO, and dissociation of NO(a) was easier on the former catalyst. FT-IR spectra of adsorbed NO at room temperature followed by the evacuation at elevated temperatures confirmed this. TPD spectra of O₂ desorbed from oxidized surface indicated that adsorption strength of O(a) is one of the most important factors to determine the catalytic activity of NO decomposition over supported Pd catalysts.     

A SHORT-CUT METHOD FOR DETERMINING CONCENTRATION DEPENDENT DIFFUSIVITY IN LIQUID FOODS AND POLYMER SOLUTIONS FROM REGULAR REGIME DRYING CURVES

A simple method for determining concentration (water or solvent content) dependent diffusivity in liquid foods and polymer solutions from the regular regime drying curve was developed on the basis of the power-law diffusion model. The method was first tested to the drying data generated from numerical solutions of the diffusion equation with various types of concentration dependent diffusivities. The present method was found to be very simple yet accurate compared with the previous methods. Then, the drying rates of various sugar solutions experimentally obtained were analyzed on the basis of the present method to determine the moisture content dependent diffusivities.     

Determination of atomistic deformation of tricalcium silicate paste with high-volume fly ash

We examined the effect of incorporating high-volume fly ash on the atomic arrangement and interatomic deformation behavior of calcium silicate hydrates in tricalcium silicate paste upon exposure to external forces. The interatomic structural changes and strains under compressive load were assessed using synchrotron in situ high-energy X-ray scattering-based atomic pair distribution function analysis. Three different types of strains, which were (a) macroscopic strains from gauges on the surfaces of specimen, (b) strains in a reciprocal space (Bragg peak shift), and (c) strains in real space (PDF peak shift), were compared to each other. All monitored and calculated strains for tricalcium silicate-fly ash (50 wt% fly ash) paste were compared with the counterparts of the pure tricalcium silicate paste. Pair distribution function analysis in the range of r < 10 Å indicated that the atomic arrangement of tricalcium silicate-fly ash was similar to that of synthetic calcium silicate hydrates followed by that of pure tricalcium silicate paste. Moreover, the pair distribution function refinement results revealed that the calcium silicate hydrate structure in tricalcium silicate-fly ash paste was similar to tobermorite 11 Å, unlike that in pure tricalcium silicate paste. The interatomic strain of tricalcium silicate-fly ash in the real space (r < 20 Å) was smaller than that of tricalcium silicate under compression, which suggested that the incompressibility of calcium silicate hydrates at atomistic scale was enhanced by the incorporation of fly ash into it. This was likely to be caused by the increased silicate polymerization of calcium silicate hydrates, which was attributed to the increase in the amount of silicate in their structure via the addition of fly ash.     

Power characteristics of unsteadily forward–reverse rotating impellers in an unbaffled aerated agitated vessel

Power characteristics of an unbaffled aerated agitated vessel with unsteadily forward‐reverse rotating impellers, ie a new type of gas–liquid agitator named ‘AJITER’, treating viscous Newtonian liquids were studied experimentally. Measurements were first made on the agitation torque, ie the torque on the drive shaft on which forward–reverse rotating impellers with four delta‐type blades were attached, and the data obtained were analyzed by fitting them to an equation consisting of two terms with respect to the resistance of the fluid, one due to viscous drag and the other due to added moment of inertia. The effects of operating conditions and physical properties of liquids on the drag and added moment of inertia coefficients were then evaluated, and empirical relationships which estimate values of these coefficients, useful to predict the unsteady behavior and magnitude of agitation torque, were presented. Furthermore, equations were developed for estimating the average and maximum power consumptions as a function of the drag and added moment of inertia coefficients. Prediction of respective power levels in AJITER by these equations was also discussed. © 2001 Society of Chemical Industry     

Water vapor solubility of poly(lactic acid) films modified the surface by vacuum ultraviolet irradiation

Surface modification of poly(lactic acid) (PLA) film is performed via 172 nm excimer lamp irradiation. Effects on water vapor solubility and physical properties via vacuum ultraviolet (VUV) irradiation are studied systematically. After VUV irradiation, water vapor solubility increases approximately 11–43% in the low‐pressure region and approximately 20–38% in the high‐pressure region as surface hydrophilicity increased. The increase is attributed to hydrogen bonding with the carboxyl groups because of VUV radiation. The modified layer is significantly swelling after water vapor sorption. The hydrophilic layer forms a thickness of 2–3 μm from the irradiated surface via VUV radiation, but no changes are observed inside the irradiated film. Therefore, PLA film solubility after irradiation is enhanced by hydrophilicity and the swelling effect of the surface. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42200.