Terpenoids of the oleoresin ofPinus kochiana

The chemical composition of the oleoresin of Koch's pine growing in the Caucasus has been studied. It has been shown that, with respect to the composition of the monoterpenes and the resin acids, the oleoresin of this species does not differ from oleoresins of the subgenusDiploxylon studied previously. Predominating among the sesquiterpenes is germacrene D, which has not previously been found in the resins of the conifers of the USSR. The diterpenoids are represented by tricyclic compounds (pimarinol, isopimarinol, and methyl 15-hydroxydehydroabietate and the hydrocarbons corresponding to them).     

The investigation of ancient pottery

Summary Ancient ceramic samples (single fragments and different parts of pots, unbroken and repaired; total about 180 samples) dated from the transitional period of late Bronze to early Iron Age (VIII-VI centuries BC) and early Iron Age (VII-IV centuries BC) were investigated by thermal analysis, X-ray powder diffraction, petrography, and scanning electron microscopy equipped with the energy-dispersive X-ray analyzer. In addition to that, to identify the clay sources for the ceramic manufacturing, about 15 samples of clays and soils found near archeological digs and taken from the mineralogical museum were investigated. We found out that the calcite content of ceramics is a very informative parameter for the identification of the clay source for the pottery manufactured at low technological level (low-temperature firing).     

Crystal Structure Study of the Metastable β-modification of Glycine and its Transformation into the α-modification

Crystal structure refinement was performed of the metastable modification of glycine (space gr. P2₁, a = 5.092(2) , b = 6.273(3) , c = 5.384(3), = 113.17(4)°, Z = 2, R = 0.0274). The crystals were obtained by a new method (not described in the literature): they were precipitated from a water solution with the addition of glacial acetic acid. The crystal structure of the glycine modification [space gr. P2₁/n, a =5.106(1) , b = 11.979(5) , c = 5.463(2) , = 111.75(2)°:, Z =4] was refined for comparison. Transition from the to the modification in a damp atmosphere was revealed, resulting in the formation of a strongly strained crystal of a mosaic structure. The orientation of the crystallographic axes in the newly formed crystal of the modification relative to the axes in the initial crystal of the modification was determined. It is shown that as in glycine, the lengths of the intramolecular C—O bonds in the modification are fairly similar [1.248(2) and 1.253(2) ] and the previously found significant difference between them is most likely due to the errors of the photomethod. A comparative analysis of the crystal structures of the and glycine modifications (glycine zwitterion packings and structure of intermolecular hydrogen bond networks) was performed. Data of the analysis are used to discuss the properties of the glycine modifications, the possible reasons for the stability of the modification in dry air, the difficulties of crystal growth from solutions, and the ease of crystallization of the modification under various conditions.     

Calibration coefficient of a heat-flow DSC; Part II. Optimal calibration procedure

One-point (Mettler) and many-point (Netzsch) heat flow calibration of a DSC is discussed. It is shown that the two types of calibration are the alternative extremes between quick but rough procedure and time-consuming but accurate one. One-point calibration compares a typical function k(T) at the melting point of indium with the measured value for particular DSC and multiplies k(T) by a scaling factor. Many-point calibration is based on general mathematical procedure, namely fitting a set of experimental values of sensitivity to a polynomial. The polynomial coefficients are evaluated by the method of least squares. Based on the relationship between the sensitivity of a thermocouple and calibration coefficient of a DSC sensor made from it, two-point heat flow calibration is suggested. This is an optimal calibration procedure, for the relationship contains only two unknown coefficients. An example of how to perform the two-point calibration with Netzsch-Proteus Software is described in the Appendix.     

Natural specimen of triple solid solution ettringite–thaumasite–chromate-ettringite

Three natural minerals of ettringite group were investigated by TG to refine their chemical composition. Two samples are ettringite Ca_5.97Mg_0.01Sr_0.02Al_1.99Cr_0.01(SO₄)₃(OH)₁₂·23.7H₂O and bentorite Ca_5.99Mg_0.01Cr_1.95Al_0.01Si_0.03(SO₄)_2.82·(CO₃)_0.20(OH)₁₂·19.4H₂O, but the third one Ca_5.99Na_0.01Al_1.38Si_0.62(SO₄)_2.49·(CrO₄)_0.36·(CO₃)_0.46(OH)₁₂·15.8H₂O has found to be a solid solution among ettringite, thaumasite, and chromate-ettringite, not registered yet as a new mineral species. Similar phase is well known in concrete formed with Cr⁶⁺ admixture, but is found for the first time as a natural compound. X-ray single-crystal investigation allowed us to refine the structure and support substitution (SO₄)^2? ? (CrO₄)^2? in natural minerals of ettringite group.     

New interpretation of heat effects in polymorphic transitions

Overlapping endothermic and exothermic effects in DSC measurements of polymorphic transitions is often detected in molecular crystals and drugs. It is explained by the sequence of melting and crystallization. In this paper, we argue that this explanation is incorrect. In revealing the kinetic nature of the endo/exo thermal effect, we suggest another explanation, based on the nucleation. New interpretation does allow us to measure the energetic barrier in the nucleation of bulk sample, thus providing a tool for testing the nucleation models.     

Melting of PbBr2: A DSC investigation

The melting of PbBr₂ in sealed crucibles was investigated by means of DSC. Three factors were considered to affect melting point: i) impurities, ii) the bromine pressure over the PbBr₂, and iii) photolysis. Both crystals and powders were investigated. The peak of the melting changed after sample grinding. The bromine pressure over the PbBr₂ was found to cause a significant error in the determination of the melting point.Lead bromide melts at 370.6±0.2°C. The heat of melting is 42.9±1.8 J g^–1.This revised version was published online in November 2005 with corrections to the Cover Date.