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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Schur Function Identities Arising From the Basic Representation of {A^{(2)}_{2}}

A Lie theoretic interpretation is given for some formulas of Schur functions and Schur Q-functions. Two realizations of the basic representation of the Lie algebra \({A^{(2)}_2}\) are considered; one is on the fermionic Fock space and the other is on the bosonic polynomial space. Via the boson–fermion correspondence, simple relations of the vacuum expectation values of fermions turn out to be algebraic relations of Schur functions.     

Terpyridine platinum(ii) complexes containing triazine di- or tri-thiolate bridges: structures, luminescence, electrochemistry, and aggregation

Dinuclear complexes [{Pt(trpy)}(2)(L)](PF(6))(2) (trpy = 2,2':6',2'-terpyridine, L = 2-octylthio-1,3,5-triazine-4,6-dithiolate ion (1), L = 2-octadecylthio-1,3,5-triazine-4,6-dithiolate ion (2), L = 2-di-n-butylamino-1,3,5-triazine-4,6-dithiolate ion (3)) and a trinuclear complex [{Pt(trpy)}(3)(L)](PF(6))(3) (L = 1,3,5-triazine-2,4,6-trithiolate ion (4)) have been synthesized and characterized. The single crystal X-ray analysis revealed that the two {Pt(trpy)}(2+) fragments in 1 and 3 adopt a syn-configuration. The PtPt distances are around 4.3 ?, suggesting no intramolecular PtPt interactions. Complexes 1-4 in acetonitrile show broad absorption bands at around 470 nm, assigned to mainly the ligand-to-ligand charge transfer ((1)LLCT) from triazine thiolates to trpy based on the comparison to the related complexes and the density functional theory (DFT) calculations. The red luminescence of 1-4 in acetonitrile is attributable to emission predominantly from (3)LLCT. Cyclic voltammograms of 1-3 exhibit four redox couples from -2.0 V to 0 V vs. Ag/AgCl. The two consecutive processes at around -0.70 V are assigned to the sequential reduction of two trpy ligands. This assignment was further supported by the observation of the anion radical of trpy in spectroelectrochemical experiments. The splitting of the redox potentials of two trpy ligands evidences the moderate electronic coupling interactions mediated by the triazine dithiolate bridges. Complex 2 formed a transparent red gel in CH(3)CN, whereas 4 produced a gel-like solid in the mixtures of CH(3)CN and other solvents. The interactions dominating the aggregative behaviours have been discussed based on the results of electronic absorption and emission spectroscopy.     

Morphology and dispersion control of titania–silica monolith with macro–meso pore system

Macroporous gels with bicontinuous morphology in micrometer range were prepared in a titania?Csilica system containing 5 and 7.6 mass?% titania using tetraethoxysilane and four kinds of Ti precursors, two titanium alkoxides, titanium chloride and titanium sulfate, under coexistence of poly(ethylene glycol) (PEG) with an average molecular weight of 20,000. In all the systems with different Ti precursors, the addition of PEG induced phase separation, and the macroporous morphology was formed when the transitional structure of phase separation was frozen-in by sol?Cgel transition of inorganic components. However, we can see large differences in phase separation tendency and Ti dispersion in silica network depending on the Ti precursors used. When titanium alkoxides were added into pure silica sol?Cgel system, phase separation tendency largely decreased, so that low temperature reaction was necessary for macropore formation. When we used titanium salts, on the other hand, phase separation tendency does not change much from pure silica system. The difference has been tentatively attributed to the difference in the mixing level of Ti in silica network. Although titania tended to aggregate when titanium alkoxides were used as precursors, Ti could be well dispersed in silica gel matrix when acetylacetone was added in the alkoxide system or when titanium salts were used as Ti precursors.     

Charge‐transfer complexes of N‐methyl‐, N‐iso­propyl‐, N‐butyl‐ and N‐iso­butyl­carbazole with 3,5‐di­nitro­benzoic acid

In the title four compounds, C₁₃H₁₁N·C₇H₄N₂O₆, (I), C₁₅H₁₅N·C₇H₄N₂O₆, (II), C₁₆H₁₇N·C₇H₄N₂O₆, (III), and C₁₆H₁₇N·C₇H₄N₂O₆, (IV), the donor and acceptor mol­ecules are stacked alternately to form one‐dimensional columns. In (I), the N‐methyl group of the donor is nearly eclipsed with respect to one of the nitro groups of the neighboring acceptor in a column, whereas the N‐iso­propyl, N‐butyl and N‐iso­butyl groups are in anti positions with respect to one of the nitro groups of the neighboring acceptor in compounds (II)–(IV).     

Redetermination of bis{[(2‐hydroxy­phenyl­methyl)­bis(2‐pyridyl­methyl)­aminato]copper(II)} diperchlorate

The structure of the title compound, [Cu₂(C₁₉H₁₈N₃O)₂](ClO₄)₂, was reported with insufficient accuracy because of a twinning problem by Adams, Bailey, Campbell, Fenton & He [J. Chem. Soc. DaltonTrans. (1996), pp. 2233–2237]. The dinuclear phenolate‐bridged Cu^II complex has an inversion centre.     

Chloro­[N′,N′‐diethyl‐N,N‐bis(2‐pyri­dyl­methyl)­ethyl­enedi­amine‐κ4N]copper(II) perchlorate

The title mononuclear copper(II) complex, [CuCl(C₁₈H₂₆N₄)]ClO₄, shows a square‐pyramidal coordination with the diethyl­amino N atom at the apical position. Large anisotropies in the displacement parameters of the non‐H atoms of the ligand seem to be due to rotational disorder of the ClO₄^? anion.     

1,3‐Propane­di­ammonium bis(3′‐nitro‐trans‐cinnamate) and trans‐1,2‐cyclo­hexane­di­ammonium bis(3′‐nitro‐trans‐cinnamate)

In the title two adducts, C₃H₁₂N₂²⁺·2C₉H₆NO₄^?, (I), and C₆H₁₆N₂²⁺·2C₉H₆NO₄^?, (II), hydrogen bonds between the di­ammonium and carboxyl­ate ions form a two‐dimensional network parallel to the ab plane in (I) and one‐dimensional chains along the c axis in (II). The cyclo­hexane­di­ammonium ion in (II) has a crystallographic twofold axis.     

Tetra‐μ‐acetato‐O:O′‐bis­[(7‐aza­indole‐N)­copper(II)]

The title complex, [Cu₂(C₂H₃O₂)₄(C₇H₆N₂)₂], shows a binuclear cage structure having an inversion centre. There are intramolecular N—H?O hydrogen bonds between the 7‐aza­indole ligands and the bridging acetate O atoms.