Self‐Assembled Fibers Containing Stable Organic Radical Moieties: Alignment and Magnetic Properties in Liquid Crystals

Macroscopically oriented stable organic radicals have been obtained by using a liquid–crystalline (LC) gel composed of an l ‐isoleucine‐based low molecular weight gelator containing a 2,2,6,6‐tetramethylpiperidine 1‐oxyl moiety. The LC gel has allowed magnetic measurements of the oriented organic radical. The gelator has formed fibrous aggregates in liquid crystals via intermolecular hydrogen bonds. The fibrous aggregates of the radical gelator are formed and oriented on cooling by applying a magnetic field to the mixture of liquid crystals and the gelator. Superconducting quantum interference device (SQUID) measurements have revealed that both oriented and nonoriented fibrous aggregates exhibited antiferromagnetic interactions, in which super‐exchange interaction constant J is estimated as ?0.89 cm^?1.     

Preparation of dibromopyridines having -(CH2)m-SO3Na groups as monomers for new polypyridines

Dibromopyridines or dibromopyridone with -(CH₂)_m-SO₃Na group(s) has been prepared via the reactions of the corresponding dibromopyridines with -OH and -NH₂ groups with sultone. These compounds were converted into polymers with the -(CH₂)_m-SO₃H groups via organometallic polycondensation. The polymer showed proton conducting properties and high stability toward oxidation.     

Gauss’ law of error revisited in the framework of Sharma-Taneja-Mittal information measure

We reformulate the Gauss’ law of error in presence of correlations which are taken into account by means of a deformed product arising in the framework of the Sharma-Taneja-Mittal measure. Having reviewed the main proprieties of the generalized product and its related algebra, we derive, according to the Maximum Likelihood Principle, a family of error distributions with an asymptotic power-law behavior.      

Influences of aging on thermal decomposition mechanism of high performance oxidizer ammonium dinitramide

Ammonium dinitramide (ADN) is one of the several promising new solid propellant oxidizers. ADN is of interest because its oxygen balance and energy content are high, and it also halogen-free. One of the most important characteristics of a propellant oxidizer, however, is stability and ADN is known to degrade to ammonium nitrate (AN) during storage, which will affect its performance. This study focused on the effects of aging on the thermal decomposition mechanism of ADN. The thermal behaviors of ADN and ADN/AN mixtures were studied, as were the gases evolved during their decomposition, using differential scanning calorimetry (DSC), thermogravimetry–differential thermal analysis-infrared spectrometry (TG–DTA-IR), and thermogravimetry–differential thermal analysis-mass spectrometry (TG–DTA-MS). The results of these analyses demonstrated that the decomposition of ADN occurs via a series of distinct stages in the condensed phase. The gases evolved from ADN decomposition were N₂O, NO₂, N₂, and H₂O. In contrast, ADN mixed with AN (to simulate aging) did not exhibit the same initial reaction. We conclude that aging inhibits early stage, low temperature decomposition reactions of ADN. Two possible reasons were proposed, these being either a decrease in the acidity of the material due to the presence of AN, or inhibition of the acidic dissociation of dinitramic acid by NO ₃ ^? .     

Fully automated reagent peak‐free liquid chromatography fluorescence analysis of highly polar carboxylic acids using a column‐switching system and fluorous scavenging derivatization

In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control.     

Photoswitchable organocatalysis in acylation of alcohol using dithienylethene-linked azoles

Three novel dithienylethenes bearing azole derivatives were synthesized and found to undergo reversible photocyclization of the dithienylethene units upon alternate irradiation with UV and visible light. Among them, the dithienylethene-linked imidazole and N-phenylimidazole exhibited a relatively high organocatalytic activity for the acylation of 2-decanol with acetic anhydride, and the catalytic activity of the dithienylethene-linked imidazole could be switched by reversible photoinduced cyclization/cycloreversion of the dithienylethene unit.     

Synthesis and properties of polyfluoro(silyl)acetylene nanoparticles by reaction of fluoro(silyl)acetylenes with triethylamine

Fluoro(silyl)acetylenes, which were prepared by reaction of 1,1-difluoroethylene with silyl chlorides, reacted with triethylamine to give dark-brown colored polyfluoro(silyl)acetylene powders in excellent to moderate isolated yields. In contrast, the corresponding nonfluorinated acetylene was unable to react with triethylamine at all to afford poly(silyl)acetylene under similar conditions. Polyfluoro(silyl)acetylenes thus obtained were nanometer size-controlled cubic fine particles with a good dispersibility and stability in a variety of solvents. These polyfluoro(silyl)acetylene nanoparticles exhibited clear absorption and emission spectra related to the conjugated units in polymer main chain. Furthermore, these polyfluoro(silyl)acetylene nanoparticles were applied to the surface modification of poly(methyl methacrylate) [PMMA] film to exhibit a higher oleophobicity imparted by fluorine on their surface, compared to that on the reverse side.

Synthesis and application of head-to-head-type styrene dimers bearing two fluoroalkyl end-groups

Head-to-head-type styrene and substituted styrene dimers bearing two fluoroalkyl end-groups have been efficiently synthesized by a simple reaction of perfluoroalkyl iodide with styrene under radical conditions as a mixture of meso and racemic forms. The meso form obtained from the mixture by recrystallization gave a crystal suitable for X-ray diffraction study and the crystal structure was found to be based on π-stacking of benzene rings and aggregation of fluoroalkyl chains. Dynamic light scattering measurements showed that meso-styrene dimers bearing two fluoroalkyl end-groups can form the nanometer size-controlled self-assemblies through the intermolecular π-stacking of benzene rings and aggregation of end-capped fluoroalkyl groups in methanol.

Synthetic study of kosinostatin aglycone: synthesis of BCDE rings using alkoxycarbonylmethylation of diazonaphthoquinone

A synthetic study of kosinostatin aglycone is reported. Synthesis of key intermediate lactone 3, which corresponds to the BCDE ring fragment, was accomplished, and the precursor BCD ring fragment 5 was synthesized via two routes. First, 5 was synthesized from 2,5-dimethoxybenzaldehyde 16 by the combination of typical known transformations including efficient application of non-aqueous OsO₄ oxidation in the presence of PhB(OH)₂. However the synthesis required 15 long steps, and its main difficulty was ortho-alkoxycarbonylmethylation of 1-naphthol. Next we attempted to apply our recently developed alkoxycarbonylmethylation of diazonaphthoquinone for the synthesis of 5, and 5 was successfully synthesized in 9 steps from the same starting compound 16. Finally, 5 was stereoselectively converted to lactone 3 via trifluoroacetic acid-mediated cyclization of the 3,4-epoxycylohexanecarboxylic acid derivative.     

Synthesis of 3′-allylindoline spirobenzopyrans derived from 3-allyl-3H-indoles

In this study, 8 new spirobenzopyrans were synthesized. A novel, three-step, facile route for the synthesis of 3′-allylindoline spirobenzopyrans via 3-allyl-3H-indoles was developed. The newly synthesized spirobenzopyrans were evaluated for their photochromic properties. The presence of an allyl moiety at the 3′ position did not disturb the photochromic response. The steric effects of the diallyl groups at the 3′ position affected the interconversion between colored and colorless forms. Therefore, the allyl chain in 3′-allylindoline spirobenzopyrans can be utilized to attach these compounds to a molecular matrix. Consequently, this synthetic methodology could be readily applied to the creation of new photo-switchable materials.