Chloryl nitrate: a novel product of the OClO + NO3 + M recombination

The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10(-14) cm3 molecule-1 s-1 in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere.     

MO-LCAO-Calculations on polymethines. V. PPP-type calculations and configuration analyses of simple prototype dyes in terms of molecular subsystems

In order to elucidate certain controversies in interpreting the π-electronic structure of some simple quinone and indigo dyes the Pariser–Parr–Pople SC _β,γ-wave-functions have been subjected to configuration analyses. Whereas 2,5-diamino-quinone (1) can be excellently represented by coupling of two trimethine-merocyanine chains, the analogous consideration is less appropriate with bispyrrolindigo (2). In this case the results of the configuration analyses indicate clearly the limited applicability of the Longuet/Higgins–Murrell–method.     

pH-metric studies on some ternary complexes of lanthanones

Stepwise mixed ligand complex formation has been cited for the formation of 111,Ln(III)—NTA—catechol ternary complexes potentiometrically [whereLn(III)=La(III), Pr(III) or Nd(III)]. The results of titration curves indicate the formation of 11,Ln(III)—NTA complexes in beginning and the addition of catechol, takes place later on in the higher buffer region. The relative stability of these ternary complexes in terms of metal ion has been reported as La(III)< 相似文献   

CHEMISTRY OF SINGLET OXYGEN—XXVI. PHOTOOXYGENATION OF PHENOLSy†

Abstract— The aerobic dye-sensitized photooxygenation of monohydric phenols proceeds by way of singlet oxygen under the conditions studied. Various phenols give different proportions of reaction with and quenching of singlet oxygen. Para-substituted 2,6-di-t-butylphenols show a linear correlation between the log of the total rate of singlet oxygen removal and their halfwave oxidation potentials; the same correlation is given for certain phenol methyl ethers. A Hammett plot using s?⁺ gives ρ - 1.72 ± 0.12, consistent with development of some charge in the quenching step. Reaction of photo-chemically generated singlet oxygen with 2,4,6-triphenylphenol gives 2,4,6-triphenylphenoxy radical as an intermediate in singlet oxygen quenching, although no overall reaction occurs. Kinetic analysis indicates that the radical is derived exclusively from the interaction of 2,4,6-triphenylphenol with singlet oxygen. A charge-transfer mechanism for quenching of singlet oxygen by phenols is proposed.     

Quantitative structure-property relationship: XXVII. Estimation of the free energy of formation of host-guest complexes of α-cyclodextrin with benzene derivatives

A structure-property relationship was used to estimate the free energy of formation of host-guest complexes of α-cyclodextrin with monosubstituted benzene and phenol derivatives and with symmetrical 1,4-disubstituted benzene derivatives, in which various nonvalent interactions (hydrophobic, van der Waals, donor-acceptor) play a significant role. The calculated values are well consistent with the experiment.     

An application of activation analysis of aluminum in biological materials

The behavior of aluminum compounds in animals was made clear by using non-destructive neutron activation analysis instead of radiotracer method. Basic aluminum sucrose sulfate (BASS) and dried aluminum hydroxide gel (DAHG) were orally administered to rats. The residual BASS and DAHG on gastric walls of rats were determined by neutron activation analysis. It was obtained the following results that BASS was found at the longer time in the stomach. For reason, it is seemed that BASS is hydrolyzed in gastric juice. And it could not find the aluminum in liver, kidney and spleen.     

A 13C- and 195Pt-NMR. Study of the Complexes trans-PtCl2 (amine) (CH2CH2)

¹³C- and ¹⁹⁵Pt-NMR. spectra for the complexes trans-PtCl₂(amine)(CH₂?CH₂) have been measured. For amine = (S)-N-methyl-α-methylbenzylamine the two diastereomers present may be distinguished from the values ³J(Pt,C). The ¹⁹⁵Pt-chemical shift is shown to be sensitive to subtle differences stemming from intramolecular non-bonded interactions.     

Chemical studies on nitrogen heterocyclic skeleton of the Daphniphyllum alkaloids

From a biogenetic point of view, a great variety of related alkaloids isolated from the plant Daphniphyllaceae are related to one another by bond formation or fission. Thus, daphnialcohol acetate (6), a derivative of the degradation products of daphniphylline (1), was subjected to von Braun degradation followed by acid-catalyzed recyclization to give an isomer (8) of daphnialcohol, which has a new type of nitrogen heterocyclic skeleton. Furthermore, daphnilactone-B (3) was converted into a daphniphylline-type compound (19) via a plausible intermediate (21).     

Electron screening in low energy scattering of muonic hydrogen on hydrogen atoms

Electron screening corrections to the cross sections for low energy scattering of muonic hydrogen on hydrogen atoms are calculated. It is shown that the presence of the electron influences considerably the elastic cross sections at collision energies below 1 eV. This influence is relatively small for the spin-flip and isotopic exchange processes.     

Separation and determination of arsenic(V) and arsenic(III) in sea-water by solvent extraction and atomic-absorption spectrophotometry by the hydride-generation technique

Arsenic(V) and arsenic(III) in sea-water have been separated by complexing the arsenic(III) with ammonium pyrrolidinedithiocarbamate (APDC) in the range 4.0-4.5 and extracting the complex with chloroform. The organic phase is then wet-ashed with a 1:1 mixture of concentrated nitric acid and perchloric acid to get rid of all organics, and the arsenic(III) is determined by hydride generation and atomic-absorption spectrophotometry. Total arsenic is determined by first reducing arsenic(V) to arsenic(III) with potassium iodide and then applying the method used for arsenic(III). The arsenic(V) content is determined by difference. The low detection limit of 0.031 ng ml and the high sensitivity and precision make the method suitable for analysis of open ocean waters.