Nonexponential proton relaxation in (NH4)2 HPO4

Nonexponential relaxation of protons in (NH₄)₂HPO₄ was found from 420 K to 110 K and was interpreted by the three-bath model below 167 K; inter-NH₄ group dipolar coupling above 167 K, and was attributed to non-equivalent NH₄ groups in a molecule.     

Ketonization of Secondary Hydroxy Groups of Alcohols and Diols with Hydrogen Peroxide Under the Influence of Tricetylpyridinium-12-Tungstophosphate

Molydbenum and tungsten-catalyzed oxidations of alcohols with dilute hydrogen peroxide under phase-transfer conditions have been focused in recent years 1–3. In a previous paper, we have reported that tricetylpyridinium-12-molybdophosphate(CMP), [π - C₅H₅N+(CH_{2 15}CH₃]₃ (PMO₁₂O₄₀)³-, prepared from 12-molybdophosphoric acid (MPA) and cetylpyridinium chloride (CPC), catalyzed the oxidation of secondary alcohols to carbonyl compounds with tert-butylhydroperoxide(t-BuOOH)⁴. When hydrogen peroxide in place of t-BuOOH was employed as the oxidant for the above oxidation, however, alcohols were oxidized with difficulty to give carbonyl compounds in poor yields. In continuation of this study, we wish to report here the selective oxidation of secondary hydroxy group of alcohols and diols and diols with H₂O₂ under the influence to tricetylpyridinium-12 tungstophosphate (CWP), [π-C₅H₅N+ (CH₂) 15 CH₃]₃(PW₁₂O₄₀)³-, derived from 12-tungstophosporic acid (WPA) and CPC.     

Measuring the electron affinity of organic solids: an indispensable new tool for organic electronics

Electron affinity is a fundamental energy parameter of materials. In organic semiconductors, the electron affinity is closely related to electron conduction. It is not only important to understand fundamental electronic processes in organic solids, but it is also indispensable for research and development of organic semiconductor devices such as organic light-emitting diodes and organic photovoltaic cells. However, there has been no experimental technique for examining the electron affinity of organic materials that meets the requirements of such research. Recently, a new method, called low-energy inverse-photoemission spectroscopy, has been developed. A beam of low-energy electrons is focused onto the sample surface, and photons emitted owing to the radiative transition to unoccupied states are then detected. From the onset of the spectral intensity, the electron affinity is determined within an uncertainty of 0.1 eV. Unlike in conventional inverse-photoemission spectroscopy, sample damage is negligible and the resolution is improved by a factor of 2. The principle of the method and several applications are reported.

A new application of statistical moment theory to evaluate the swelling behavior of thermo-responsive gels

The loosely cross-linked poly(acryloyl-L -proline methyl ester) gel, which is known as one of the typical thermo-responsive gels, shows a volume transition around approximately 14°C in pure water. This volume transition is shifted to higher temperature by treatment in aqueous sodium dodecyl sulfate (SDS). The analysis of the swelling-temperature curve (frequency distribution) was performed according to a moment analysis, in which the area under the swelling-temperature curve (AUC), mean swelling transition temperature (MSTT) and variance of swelling transition temperature (VSTT) were calculated. It is shown that the apparent volume transition temperature can be estimated from MSTT and that VSTT can be used to characterize the shape of the corresponding curves.     

Facile synthesis of an ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion: from serendipity to design

The stability of singly or multiply negatively charged π-conjugated organic compounds is greatly influenced by their electronic delocalization. Herein, we report a strategic methodology for isolation of a mysterious compound. The isolated compounds, a pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion, were highly stable under ambient conditions due to high delocalization of the negative charge over multiple electron deficient C N groups and pyrene π-scaffolds and allowed purification by column chromatography. To our knowledge, this is the first report on TCNE type reductive condensation of malononitrile involving pyrene di- and tetraone and formation of pyrenopyrrole. All compounds were characterized by spectroscopic methods and X-ray crystallography. A UV-vis spectroscopic study shows an intense low energy absorption band with a large absorption coefficient (ε).

An ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion have been isolated and characterized, showing a low energy intense absorption band with the absorption coefficient reaching 7.1 × 10⁴ dm³ mol⁻¹ cm⁻¹.     

Mixing method influence on compatibility and polymorphism studies by DSC and statistical analysis

Most of the pharmaceutical products are formulated as solid dosage form, which may present drug–excipient interactions that lead to changes in the chemical nature of the drug, such as solubility and bioavailability and may compromise its safety and effectiveness. Differential scanning calorimetry (DSC) is a widely used method for the rapid evaluation of the drug-excipient compatibility and the stability of the mixture formed; however, there is no consensus on the preparation methods of the drug–excipient mixtures. The aim of this study was to investigate the influence of the mixing method on the drug–excipient compatibility studies by means of DSC analysis, using tenofovir disoproxil fumarate as a drug model. Statistical analysis revealed significant differences in the heat of fusion of the drug in the mixtures prepared by several mixing methods. Vortex Mixer with a Pop-Off Cup used for 3 min proved to be very satisfactory for these studies. A polymorphic transition was observed in the mixture prepared with the mortar and pestle. Therefore, this method should be avoided since it may induce errors in the interpretation of DSC results. In this way, the mixing method used to prepare a mixture for studies of interactions between the API and the excipients in a pharmaceutical formulation has a great influence on the results and it must be chosen carefully.