Solid-state polymerization of 1,2,3,4-diepoxybutane initiated by cobalt-60 γ-radiation

The solid-state polymerization of 1,2,3,4-diepoxybutane appears to proceed “insource” by an ionic mechanism and has an overall activation energy of 0.4 kcal./mole with an intensity dependency of 0.99. There is a rapid increase in the rate of polymerization just prior to the melting point and a very low rate for the liquid-phase reaction. Limiting conversions of 5% polymer are observed at ?196°C. for irradiation in vacuo. No limiting conversion was observed when the monomer was polymerized in the presence of air or in vacuo at ?78°C. Under all polymerization conditions the reactions were characterized by the absence of an induction period.     

Nonrigid molecule effects in molecules with linear or nongeometrically equivalent equilibrium configurations

A theoretical study is made of the states of nonrigid molecules, extending earlier work to apply Longuet–Higgins' symmetry group of feasible permutation/inversions in two previously untreated cases. The first involves nonrigid molecule processes between different stereoisomers, that is between molecular equilibrium configurations of different geometrical shapes. The second takes into account nonrigid molecule processes in linear molecules. The theory is applied to the specific case of nonrigid molecule effects in the butyl ion C₄H (case i), and the form of the nonrigid molecule energy levels and spectra are determined. The theory is also applied to determine the nonrigid molecule energy levels in linear H₂F₂ (case ii).     

Ferrocene studies. IV. Some furan containing derivatives of ferrocene

The condensation of ferrocenecarboxyhydrazide, ferrocenecarboxaldehyde and acetylferrocene with a number of furan derivatives is reported. The reaction of chalcones containing both the furan and the ferrocene nucleus with Phenylhydrazine and hydrazine proceeds to yield pyrazolines.     

Modeling of phase equilibrium and vapor adsorption on carbon black based on a combination of a lattice theory and equation of state

A thermodynamic approach is developed in this paper to describe the behavior of a subcritical fluid in the neighborhood of vapor-liquid interface and close to a graphite surface. The fluid is modeled as a system of parallel molecular layers. The Helmholtz free energy of the fluid is expressed as the sum of the intrinsic Helmholtz free energies of separate layers and the potential energy of their mutual interactions calculated by the 10-4 potential. This Helmholtz free energy is described by an equation of state (such as the Bender or Peng-Robinson equation), which allows us a convenient means to obtain the intrinsic Helmholtz free energy of each molecular layer as a function of its two-dimensional density. All molecular layers of the bulk fluid are in mechanical equilibrium corresponding to the minimum of the total potential energy. In the case of adsorption the external potential exerted by the graphite layers is added to the free energy. The state of the interface zone between the liquid and the vapor phases or the state of the adsorbed phase is determined by the minimum of the grand potential. In the case of phase equilibrium the approach leads to the distribution of density and pressure over the transition zone. The interrelation between the collision diameter and the potential well depth was determined by the surface tension. It was shown that the distance between neighboring molecular layers substantially changes in the vapor-liquid transition zone and in the adsorbed phase with loading. The approach is considered in this paper for the case of adsorption of argon and nitrogen on carbon black. In both cases an excellent agreement with the experimental data was achieved without additional assumptions and fitting parameters, except for the fluid-solid potential well depth. The approach has far-reaching consequences and can be readily extended to the model of adsorption in slit pores of carbonaceous materials and to the analysis of multicomponent adsorption systems.     

The rotational mobility of fulleropyrrolineoxyl in toluene solution

The rotational mobility of a stable fullerene-based nitroxyl radical (fulleropyrrolineoxyl) in toluene was studied. The rotational correlation time of fulleropyrrolineoxyl was found to be about eight times longer than that of 4-oxy-2,2,6,6-tetramethylpiperidine-1-oxyl. The activation energy of the rotational motion of both probes was determined and their hydrodynamic radii estimated.     

An automated procedure for the simultaneous determination of specific conductance and pH in natural water samples

An automated, continuous-flow system is utilized to determine specific conductance and pH simultaneously in natural waters. A direct electrometric procedure is used to determine values in the range pH 4–9. The specific conductance measurements are made with an electronically modified, commercially available conductivity meter interfaced to a separate module containing the readout control devices and printer. The system is designed to switch ranges automatically to accommodate optimum analysis of widely varying conductances ranging from a few μmhos cm^-1 to 15,000 μmho cm^-1. Thirty samples per hour can be analyzed. Comparison of manual and automated procedures for 40 samples showed that the average differences were 1.3% for specific conductance and 0.07 units for pH. The relative standard deviation for 25 replicate values for each of five samples was significantly less than 1% for the specific conductance determination; the standard deviation for the pH determination was ? 0.06 pH units.     

Column-friendly reversed-phase high-performance liquid chromatography of peptides and proteins using formic acid with sodium chloride and dynamic column coating with crown ethers.

Reversed-phase high-performance liquid chromatography of proteins, traditionally carried out with strong acids like trifluoroacetic acid or phosphoric acid, which can damage reversed-phase columns, can be performed with excellent results using the far milder formic acid in the presence of salt. For certain separations, dynamic coating of the column with crown ethers can bring added resolution. Examples given are for peptides from a digest of methionine growth hormone, protein separations from whey proteins containing alpha-lactalbumin and the beta-lactoglobulins A and B, and bovine and porcine insulins. The separation of methionine-growth hormone from growth hormone is also described.     

The stereochemistry of the hydroboration rearrangement.

Hydroboration of 1,2-dimethylcyclopentene with BH₃·THF affords a product in which boron migrates $\text{stereospecifically}$ at low temperature into the cyclopentane ring. At higher temperatures subsequent (non-stereospecific) isomerisation occurs via a competing reaction mechanism.     

Über die Messung geringer Mengen Radium und Radon

Zusammenfassung Zur Messung geringer²²⁶Radium- und²²²Radongehalte werden auch auf dem Gebiet der Strahlenhygiene verschiedene Verfahren verwendet. Eine zylindrische Szintillationskammer günstigster Abmessungen bietet die Möglichkeit, Personen, die²²⁶Ra inkorporiert haben, ohne vorhergehende Anreicherung des Atem-Radons zu kontrollieren sowie Lebensmittel und andere Proben von niedrigem²²⁶Ra- und²²²Rn-Gehalt zu analysieren.

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Measurement of small amounts of radium and radon

Summary Various procedures employed for the measurement of slight²²⁶radium and²²²radon contents have also been used for the radiation hygiene. A cylindrical scintillation chamber of the most favorable dimensions offers the possibility of checking persons who have incorporated²²⁶Ra, without prior concentration of the breath-radon, and also in the analysis of foods and other samples that contain minute amounts of²²⁶Ra and²²²Ra.

     

Investigations in the fie ld of substituted furanurona ldehydes steric directivity of the nitromethane condensation

Summary 1. The condensation of the anomeric methyl 2,3-di-O-benzyl-D-xylofuranosiduronaldehydes with nitromethane has been studied.2. It has been shown that the position of the substituent at the glycosidic center has an influence on the steric directivity of this reaction.3. The structure of the 6-nitro-6-deoxyhexofuranosides synthesized has been confirmed by their conversion into known derivatives of methyl D-glucofuranosides.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 8–12, January–February, 1972.