New method for comprehensive detection of chemical warfare agents using an electron-cyclotron-resonance ion-source mass spectrometer

We developed a detection technology for vapor forms of chemical warfare agents (CWAs) with an element analysis system using an electron cyclotron resonance ion source. After the vapor sample was introduced directly into the ion source, the molecular material was decomposed into elements using electron cyclotron resonance plasma and ionized. The following CWAs and stimulants were examined: diisopropyl fluorophosphonate (DFP), 2-chloroethylethylsulfide (2CEES), cyanogen chloride (CNCl), and hydrogen cyanide (HCN). The type of chemical warfare agents, specifically, whether it was a nerve agent, blister agent, blood agent, or choking agent, could be determined by measuring the quantities of the monatomic ions or CN(+) using mass spectrometry. It was possible to detect gaseous CWAs that could not be detected by a conventional mass spectrometer. The distribution of electron temperature in the plasma could be closely controlled by adjusting the input power of the microwaves used to generate the electron cyclotron resonance plasma, and the target compounds could be detected as molecular ions or fragment ions, enabling identification of the target agents.     

Macroscopic single‐domain graphene sheet on Ni(111)

We observed in situ growth of a single graphene sheet on Ni(111) by low‐energy electron microscopy. The sheet was grown epitaxially beyond the steps on the substrate. The crystalline shapes of graphene islands were clearly seen; the straight edges of the island are crossed at either 60 or 120°, and the linear edges shifted perpendicular to the edge keeping the equilibrium shape. Graphene islands were united to form a single sheet without any grain boundaries and any wrinkles. The Ni substrate of several centimeters in size was covered with a single‐domain graphene sheet. Copyright © 2011 John Wiley & Sons, Ltd.     

An efficient unnatural base pair for PCR amplification

Expansion of the genetic alphabet by an unnatural base pair system provides a powerful tool for modern biotechnology. As an alternative to previous unnatural base pairs, we have developed a new pair between 7-(2-thienyl)imidazo[4,5-b]pyridine (Ds) and 2-nitropyrrole (Pn), which functions in DNA amplification. Pn more selectively pairs with Ds in replication than another previously reported pairing partner, pyrrole-2-carbaldehyde (Pa). The nitro group of Pn efficiently prevented the mispairing with A. High efficiency and selectivity of the Ds-Pn pair in PCR amplification were achieved by using a substrate mixture of the gamma-amidotriphosphate of Ds and the usual triphosphates of Pn and the natural bases, with Vent DNA polymerase as a 3' to 5' exonuclease-proficient polymerase. After 20 cycles of PCR, the total mutation rate of the Ds-Pn site in an amplified DNA fragment was approximately 1%. PCR amplification of DNA fragments containing the unnatural Ds-Pn pair would be useful for expanded genetic systems in DNA-based biotechnology.     

Drying dissipative patterns of colloidal crystals of silica spheres in organic solvents

Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter) in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics of colloidal particles in the drying dissipative pattern formation.     

Ab initio molecular orbital study of ground and low-lying electronic states of CoCN

The ground and low-lying excited states of CoCN have been studied by ab initio multireference single and double excitation configuration interaction (MR-SDCI) calculations with Davidson's correction Q and Cowan-Griffin's relativistic corrections. The electronic ground state of CoCN is (3)Phi(i) and the equilibrium geometry is linear with bond lengths of r(e)(Co-C)=1.8540 A and r(e)(C-N)=1.1677 A, substantially different from the experimentally derived values of r(0)(Co-C)=1.8827(7) A and r(0)(C-N)=1.1313(10) A. The first excited state is (3)Delta(i), separated from the ground state by 727 cm(-1). Larger dynamical electron correlation energy for the low-spin (3)Phi state than for the high-spin (5)Phi state makes the (3)Phi state to be the ground state, which is discussed in terms of the differences in natural orbitals. A new spin-orbit interaction scheme between the X (3)Phi(i) and 1 (3)Delta(i) states is proposed.     

Theoretical study of the double Renner effect for A2Pi MgNC/MgCN: higher excited rovibrational states

The authors report here the implementation of a newly developed, highly efficient matrix diagonalization routine in the DR program [T. E. Odaka et al., J. Mol. Struct. 795, 14 (2006)]. The DR program solves the rovibronic Schrodinger equation for a triatomic molecule with a double Renner effect, i.e., with two accessible linear arrangements of the nuclei at which the electronic energy is doubly degenerate. With the new routines, the authors can extend the DR calculations of rovibronic energies for A 2Pi MgNC/MgCN by considering a much larger set of rovibronic states, in particular, states at higher J values, than the authors were able to access previously.     

In-Line Reactions and Ionizations of Vaporized Diphenylchloroarsine and Diphenylcyanoarsine in Atmospheric Pressure Chemical Ionization Mass Spectrometry

We propose detecting a fragment ion (Ph₂As⁺) using counter-flow introduction atmospheric pressure chemical ionization ion trap mass spectrometry for sensitive air monitoring of chemical warfare vomiting agents diphenylchloroarsine (DA) and diphenylcyanoarsine (DC). The liquid sample containing of DA, DC, and bis(diphenylarsine)oxide (BDPAO) was heated in a dry air line, and the generated vapor was mixed into the humidified air flowing through the sampling line of a mass spectrometer. Humidity effect on the air monitoring was investigated by varying the humidity of the analyzed air sample. Evidence of the in-line conversion of DA and DC to diphenylarsine hydroxide (DPAH) and then BDPAO was obtained by comparing the chronograms of various ions from the beginning of heating. Multiple-stage mass spectrometry revealed that the protonated molecule (MH⁺) of DA, DC, DPAH, and BDPAO could produce Ph₂As⁺ through their in-source fragmentation. Among the signals of the ions that were investigated, the Ph₂As⁺ signal was the most intense and increased to reach a plateau with the increased air humidity, whereas the MH⁺ signal of DA decreased. It was suggested that DA and DC were converted in-line into BDPAO, which was a major source of Ph₂As⁺.

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Aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) as a highly efficient and reusable catalyst for alcoholysis,hydrolysis, and acetolysis of epoxides

Alcoholysis, hydrolysis, and acetolysis of epoxides were carried out in the presence of a catalytic amount of aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) to give the corresponding β-substituted alcohols in good yields. Alcoholysis and hydrolysis of epoxides catalyzed by ATRT proceeded faster than those by pyridinium p-toluenesulfonate (PPTS).     

Synthesis of thermally stable aromatic poly(spiroorthocarbonate)s having a Cardo or bent structure

Novel poly(spiroorthocarbonate)s [poly(SOC)]s having a Cardo or bent structure were synthesized by polycondensation of several bis‐catechols having fluorene (BCFL), spirobisindane (BCSPI), or spirobischromane (BCSPC) in the structure with 2,2,6,6‐tetrachlorobenzo[1,2‐d:4,5‐d’]bis[1,3]dioxole (4ClBD). Synthesis of poly(SOC)s was confirmed by NMR and IR spectrometry. The poly(SOC)s obtained from BCFL or BCSPC were soluble in common organic solvents. The glass transition temperature of the poly(SOC)s was not detected by differential scanning calorimetry (DSC) in the range of 50–300 °C. The 10 wt % decomposition temperature of the poly(SOC)s was found to be above 400 °C. These results indicated the high thermal stability of the poly(SOC)s. Soluble poly(SOC)s could be possessed to form a film on a glass plate by the spin coat method. The obtained polymer films were 0.2 μm in thickness with 95% light transmission in the optical wavelength range. These results suggested that the Cardo or bent structure may block the packing of the main‐chain of the structure, which improves the solubility of the polymers, increases transparency, and enhances the thermal stability of SOCs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1409‐1416     

Furan derivatives. Part 12 . Synthesis of 2,5-dioxacyclohepta[jkl]-as-indacenes

A variety of 2,5-dioxacyclohepta[jkl]-as-indacenes 5, 7–14 were synthesized as a new heterocycle by the treatment of diethyl (5,9-dioxobenzocyclohepten-1,4-diyloxy)diacetates 4a-e with potassium hydroxide or sodium hydride in dioxane. The mechanism of furan-ring formation from 4a-e was discussed.