Self-assembly patterning of silica colloidal crystals

We developed a self-assembly process of silica particles to fabricate desired patterns of colloidal crystals having high feature edge acuity and high regularity. A micropattern of colloidal methanol prepared on a self-assembled monolayer in hexane was used as a mold for particle patterning, and slow dissolution of methanol into hexane caused shrinkage of molds to form micropatterns of close-packed SiO2 particle assemblies. This result is a step toward the realization ofnano/micro periodic structures for next-generation photonic devices by a self-assembly process.     

Molecular structure of glucopyranosylamide lipid and nanotube morphology

A series of glucopyranosylamide lipids, N-(X-octadecenoyl)-beta-D-glucopyranosylamine [X = 13-cis (1), 11-cis (2), 9-cis (3), 6-cis (4), and 9-cis,12-cis (5)] and their saturated homologue N-octadecanoyl-beta-d-glucopyranosylamine (6), which differ in the position of a cis double bond in the C18 hydrocarbon chains, have been synthesized. The effect of the cis double bond position on the chiral self-assembly of each glycolipid has been examined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, UV, and circular dichroism (CD). The 11-cis derivative 2 was observed to self-assemble in water to form a uniform hollow cylinder structure with about 200-nm outer diameters in >98% yields. The obtained nanotubes from 2 showed the narrowest distribution of outer diameters and also gave a negative CD band around 234-236 nm, showing the largest CD intensity among the glycolipids investigated. Thus, we found that the position of a cis double bond significantly influences the homogeneity of the outer diameters as well as growth behavior of the self-assembled nanotube structures. Chiral molecular packing driven by a possible bending structure of the unsaturated glycolipids is playing a critical role in determining tubular morphology through molecular self-assembly.     

Application of microcalorimetry to the formulation study

Isothermal microcalorimetry was used to evaluate excipient compatibility of solid dosage form. Oxybutynin hydrochloride and cefaclor were used as model drugs for compatibility test with excipients. The calorimetric data for compatibility test were compared with those of HPLC data. Evaluation of compatibility between drug and excipient of solid dosage form might be possible to use isothermal microcalorimetry instead of conventional method. By using microcalorimetric method, the evaluation of the compatibility between drug and excipient could be successfully performed with a simple operation in a short time. The application of the isothermal microcalorimetry would be useful for the screening test of the drug compatibility with excipients.     

Reactive oligomers. II. Polymerization of glycol bis(allyl phthalate)s and glycol bis(allyl succinate)s

Seven glycol bis(allyl phthalate)s (GBAP) and four glycol bis(allyl succinate)s (GBASu) as reactive oligomers were prepared and their polymerization behaviors were investigated in detail in terms of cyclopolymerization and gelation as compared with diallyl dicarboxylates. Thus, the rates of polymerization of GBAPs were reduced compared to diallyl phthalate, being attributed to the steric effect on the intermolecular propagation of the uncyclized radical, whereas those of GBASus were enhanced as a consequence of intermolecular association by dipole–dipole interaction in polar GBASu monomers. Cyclization was enhanced in the following order: diallyl aliphatic dicarboxylates series < GBASu series < GBAP series. Gelation was discussed according to Gordon's theory; the actual gel-point conversions increased with an increase in the molecular weight of monomers, although the discrepancy between actual and theoretical gel-point conversion inversely tended to be decreased. The decreased delay in gelation with an increase of the molecular weight of monomers is ascribed to the reduction of excluded volume effects on crosslinking.     

Diastereoselective imino-aldol condensation of chiral 3-(p-Tolylsulfinyl)-2-furaldimine and ester enolates

(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams.     

Assembly of Carbohydrates on a Nickel(II) Center by Utilizing N-Glycosidic Bond Formation with Tris(2-aminoethyl)amine (tren). Syntheses and Characterization of [Ni{N-(aldosyl)-tren}(H(2)O)](2+), [Ni{N,N'-bis(aldosyl)-tren}](2+) and [Ni{N,N',N"-tris(aldosyl)-tren}](2+)

Reactions of [Ni(tren)(H(2)O)(2)]X(2) (tren = tris(2-aminoethyl)amine; X = Cl (1a), Br (1b); X(2) = SO(4) (1c)) with mannose-type aldoses, having a 2,3-cis configuration (D-mannose and L-rhamnose), afforded {bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine}nickel(II) complexes, [Ni(N,N'-(aldosyl)(2)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (2a), Br (2b), X(2) = SO(4) (2c); aldosyl = L-rhamnosyl, X(2) = SO(4) (3c)). The structure of 1c was confirmed by X-ray crystallography to be a mononuclear [Ni(II)N(4)O(2)] complex with the tren acting as a tetradentate ligand (1c.2H(2)O: orthorhombic, Pbca, a = 15.988(2) ?, b = 18.826(4) ?, c = 10.359(4) ?, V = 3118 ?(3), Z = 8, R = 0.047, and R(w) = 0.042). Complexes 2a,c and 3c were characterized by X-ray analyses to have a mononuclear octahedral Ni(II) structure ligated by a hexadentate N-glycoside ligand, bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine (2a.CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 16.005(3) ?, b = 20.095(4) ?, c = 8.361(1) ?, V = 2689 ?(3), Z = 4, R = 0.040, and R(w) = 0.027. 2c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.93(2) ?, b = 21.823(8) ?, c = 9.746(2) ?, V = 3176 ?(3), Z = 4, R = 0.075, and R(w) = 0.080. 3c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.560(4) ?, b = 21.694(5) ?, c = 9.786(2) ?, V = 3091 ?(3), Z = 4, R = 0.072, and R(w) = 0.079). The sugar part of the complex involves novel intramolecular sugar-sugar hydrogen bondings around the metal center. The similar reaction with D-glucose, D-glucosamine, and D-galactosamine, having a 2,3-trans configuration, resulted in the formation of a mono(sugar) complex, [Ni(N-(aldosyl)-tren)(H(2)O)(2)]Cl(2) (aldosyl = D-glucosyl (4b), 2-amino-2-deoxy-D-glucosyl (5a), and 2-amino-2-deoxy-D-galactosyl (5b)), instead of a bis(sugar) complex. The hydrogen bondings between the sugar moieties as observed in 2 and 3 should be responsible for the assembly of two sugar molecules on the metal center. Reactions of tris(N-aldosyl-2-aminoethyl)amine with nickel(II) salts gave the tris(sugar) complexes, [Ni(N,N',N"-(aldosyl)(3)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (6a), Br (6b); L-rhamnosyl, X = Cl (7a), Br (7b); D-glucosyl, X = Cl (9); maltosyl, X = Br (10); and melibiosyl, X = Br (11)), which were assumed to have a shuttle-type C(3) symmetrical structure with Delta helical configuration for D-type aldoses on the basis of circular dichroism and (13)C NMR spectra. When tris(N-rhamnosyl)-tren was reacted with NiSO(4).6H(2)O at low temperature, a labile neutral complex, [Ni(N,N',N"-(L-rhamnosyl)(3)-tren)(SO(4))] (8), was successfully isolated and characterized by X-ray crystallography, in which three sugar moieties are anchored only at the N atom of the C-1 position (8.3CH(3)OH.H(2)O: orthorhombic, P2(1)2(1)2(1), a = 16.035(4) ?, b = 16.670(7) ?, c = 15.38(1) ?, V = 4111 ?(3), Z = 4, R = 0.084, and R(w) = 0.068). Complex 8 could be regarded as an intermediate species toward the C(3) symmetrical tris(sugar) complexes 7, and in fact, it was readily transformed to 7b by an action of BaBr(2).     

Thermal decompositions of formates. Part VI. Thermal dehydration reaction of copper(II) formate dihydrate

The thermal dehydration reactions of two kinds of copper(II) formate dihydrate, which differ in origin and preparation history, have been investigated by means of TG, DTA and DSC. The kinetics of isothermal dehydration were studied by weight loss, and the difference in kinetic behavior between these two samples was related to the difference in origin and preparation history. On the whole, the dehydration mechanisms of these two samples were found to be phase boundary controlled contracting interface reactions.     

Thermal decomposition of formates. Part VIII. Thermal dehydration of Dy(III), Ho(III), Er(III), Tm(III), Yb(III) and Lu(III) formate dihydrates

The thermal dehydration of some rare earth metal formate dihydrates were studied by means of thermogravimetry, differential thermal analysis and differential scanning calorimetry.The dehydration took place successively as a one step reaction for all of the formate dihydrates examined. The reaction order of dehydration was found to be $\text{2}\text{3}$ for all of the salts examined, which indicated that the rate of dehydration was controlled by a chemical process at a phase boundary.The values of the activation energy, frequency factor and the enthalpy change of dehydration for all of the dihydrates were 108–142 kJ mole^?1, 10¹⁶–10¹⁷ min^?1 and 109–147 kJ mole^?1, respectively.Both the temperature at which the dehydration occurred and the enthalpy change increased as the reciprocal of the radius of the metallic ion increased.     

Catalytic oxygenative degradation of 4-chlorocatechol by a nonheme iron(III) complex—Mechanism and prevention of catechol ester formation

We examined the oxygenative degradation of 4-chlorocatechol and 4-tert-butylcatechol catalyzed by iron(III)-tris(pyridin-2-yl)amine complex from the standpoint of repressing the formation of 4-chlorocatechol esters of the oxygenated products that causes the incomplete degradation of 4-chlorocatechol. Analysis of the products revealed that 4-chlorocatechol esters are formed by the reaction of muconic anhydride, which is the monooxygenated product, with catechols. It was found that the use of MeOH as the solvent instead of MeCN completely suppressed the catechol ester formation through the methanolysis of muconic anhydride, which greatly improves the degradation efficiency of 4-chlorocatechol.