Reproduction of distance matrices and original time series from recurrence plots and their applications

We propose a method to reproduce distance matrices and original time series from recurrence plots. The procedure is to (i)convert a recurrence plot to a weighted graph and (ii)calculate a distance between each pair of nodes on this weighted graph. We demonstrate this method by reproducing the topological shape of original time series. We also propose two applications. The first application is to obtain the maximal Lyapunov exponent from a recurrence plot without reproducing the shapes of original time series. The second application is to reconstruct a common deterministic driving force from observations of forced systems. Thus, the method opens new fields in data analysis.     

Nucleophilic substitution reaction at an sp carbon of vinyl halides with an intramolecular thiol moiety: synthesis of thio-heterocycles

This article presents a full account of intramolecular vinylic substitution reactions of bromoalkenes having an acetylthio moiety, which give sulfur-containing heterocycles such as dihydrothiophene, tetrahydrothiopyran, and 2-alkylidenethietane derivatives. The reaction pathways of the substitution reactions were investigated by theoretical and experimental studies.     

Irreversible temperature‐responsive formation of high‐strength hydrogel from an enantiomeric mixture of starburst triblock copolymers consisting of 8‐arm PEG and PLLA or PDLA

Starburst triblock copolymers consisting of 8‐arm poly(ethylene glycol) (8‐arm PEG) and biodegradable poly(L ‐lactide) (PLLA) or its enantiomer poly(D ‐lactide) (PDLA), 8‐arm PEG‐b‐PLLA‐b‐PEG ( Stri‐L ), and 8‐arm PEG‐b‐PDLA‐b‐PEG ( Stri‐D ) were synthesized. An aqueous solution of a 1:1 mixture ( Stri‐Mix ) of Stri‐L and Stri‐D assumed a sol state at room temperature, but instantaneously formed a physically crosslinked hydrogel in response to increasing temperature. The resulting hydrogel exhibited a high‐storage modulus (9.8 kPa) at 37 °C. Interestingly, once formed at the transition temperature, the hydrogel was stable even after cooling below the transition temperature. The hydrogel formation process was irreversible because of the formation of stable stereocomplexes. In aqueous solution, gradual hydrolytic erosion was observed because of degradation of the hydrogel. The combination of rapid temperature‐triggered irreversible hydrogel formation, high‐mechanical strength, and degradation behavior render this polymer mixture system suitable for use in injectable biomedical materials, for example, as a drug delivery system for bioactive reagents or a biodegradable scaffold for tissue engineering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6317–6332, 2008     

Oxidative Degradation of Aqueous Cresols Induced by Gaseous Plasma with Contact Glow Discharge Electrolysis

The oxidative degradation of cresols smoothly proceeded toward inorganic end products when a gaseous plasma generated by means of dc glow discharge was sustained in contact with the surface of aqueous solution containing organic compounds. In order to get mechanistic insight, the monohydroxylation products from each isomeric cresol were closely examined as primary intermediates to reveal that the aromatic hydroxylation preferentially occurred at the position para to the hydroxyl group of each starting material. It was also established that the degradation of cresols strictly followed the first-order rate law. On the basis of the orientational analysis and the kinetical consideration including the effects of Fe ions added on the reaction rate, it was concluded that hydroxyl radical, which might result from the homolytic cleavage of water molecules by the action of plasma, was the most likely reagent responsible for the mineralization of cresols.     

Addition of ArSSAr to carbon-carbon multiple bonds using electrochemistry

ArS(ArSSAr)⁺ (arylbis(arylthio)sulfonium ions), which were generated and accumulated by the electrochemical oxidation of diaryl disulfides (ArSSAr) in CH₂Cl₂ at −78 °C, reacted with alkenes to give the corresponding diarylthio-substituted compounds in a stereospecific manner in good yields, when the reaction was quenched with a soft nucleophile, such as allylsilanes, ketene silyl acetals, and triethylamine. A mechanism involving the initial formation of an episulfonium ion followed by ring-opening by the attack of ArSSAr has been suggested. The reactions of ArS(ArSSAr)⁺ with alkynes also took place to give 1,2-diorganothio-substitued alkenes stereoselectively under similar conditions.     

An effective synthesis of N,N-dimethylamides from carboxylic acids and a new route from N,N-dimethylamides to 1,2-diaryl-1,2-diketones

Carboxylic acids were heated at 150 °C in DMF in the presence of 1.25 equiv of thionyl chloride to give corresponding N,N-dimethylamides in good yields. Tandem chlorination and amidation reactions occurred in the one-pot procedure. Dicarboxylic acids needed prolonged reaction time to produce bisamides in good yields. Some benzamides were efficiently converted into corresponding 1,2-diaryl-1,2-diketones (benzils) under acyloin condensation conditions in the presence of 4,4′-di-tert-butylbiphenyl (DBB) in THF. Ultrasonic irradiation effectively accelerates the reaction, but it is not critical. However, the presence of DBB is fatal to the reaction. Although a few synthetic methods for benzils from benzoic acids have been reported so far, this method is one of the most convenient and highly reproducible procedures.     

Effect of industrial water components on thermal stability of nitrocellulose

In order to prevent the spontaneous ignition of nitrocellulose (NC), NC is stabilized by washing with industrial water in its synthesis process. However, there is a possibility that the components in industrial water contribute to the thermal stability of NC. In this way, the purpose of this study is to clarify the effect of industrial water components on the thermal stability of NC. In experiments, a heat flux calorimeter was used to observe the thermal behavior of NC with the residue of vaporized industrial water. The induction period of heat release of NC with 2-mass% residues was approximately 2–5 h shorter than that of NC alone whose induction period was observed at 7 h. Those results indicate that the residue destabilized NC. On the other hand, when the additive amount of the residue was increased, the induction period gradually increased as well. Based upon these results, we assume that inorganic salts contributing to stabilization and destabilization competitively coexist in the industrial water components. The same thermal analysis was performed on NC with CaCO₃, CaSO₄, CaCl, ZnSO₄, NaCl, and CuCl. Those salts are predicted to exist in the industrial water. In the results, the induction period of NC with 2-mass% CaCO₃ was approximately 15-h longer than that of NC alone, while the induction period with the inorganic salts CaSO₄, CaCl, ZnSO₄, NaCl, and CuCl was 4–5-h shorter. Therefore, when the industrial water components accumulate in NC, the destabilization by inorganic salts such as CaSO₄, CaCl, ZnSO₄, NaCl, and CuCl and the stabilization by compounds such as CaCO₃ are thought to countervail against each other.     

Synthesis of a highly luminescent three-dimensional pyrene dye based on the spirobifluorene skeleton

We have synthesized a highly luminescent (log e > 5.0, F > 0.9) pyrene dye based on a spirobifluorene skeleton [2,2',7,7'-tetrakis(7-tert-butyl-1-pyrenyl)-9,9'-spirobi[9H-fluorene; 4-PySBF]. The use of spirobifluorene prevents fluorescence quenching by intramolecular energy transfer and/or electron transfer among the chromophores in the excited state. The emission spectra of 4-PySBF exhibited a red shift of 20 nm in comparison to a model compound [9,9'-dioctyl-2,7-bis(7-tert-butyl-1-pyrenyl)-9H-fluorene; 2-PyF], but its UV-Vis spectrum remained unchanged.     

Rhodium(III)-catalyzed synthesis of isoquinolines from aryl ketone O-acyloxime derivatives and internal alkynes

A synthetic method of isoquinolines from aryl ketone O-acyloxime derivatives and internal alkynes has been developed using [Cp*RhCl(2)](2)-NaOAc as the potential catalyst system. The present transformation is carried out by a redox-neutral sequence of C-H vinylation via ortho-rhodation and C-N bond formation of the putative vinyl rhodium intermediate on the oxime nitrogen, where the N-O bond of oxime derivatives could work as an internal oxidant to maintain the catalytic cycle.