On the evaluation of dynamic X-ray diffractometric data for kinetic and structural purposes

Possible errors made due to incorrect evaluation of time- or temperature-resolved X-ray data (TXRD) are described. The extraction of compositional information, e.g., for kinetic purposes, can be highly erroneous when neglecting the influence of the changing mass absorption coefficient and a proper conversion of mass fractions to molar fractions. When structural data are computed, care should be given to a possible volume change of the sample. The correct way of evaluation and the extent of these errors is demonstrated for the thermal decarboxylation of calcium carbonate.     

Calcium carbonate modifications in the mineralized shell of the freshwater snail Biomphalaria glabrata

The mineralized shell (consisting of calcium carbonate) of the tropical freshwater snail Biomphalaria glabrata was investigated with high resolution synchrotron X-ray powder diffractometry and X-ray absorption spectroscopy (EXAFS). Parts from different locations of the snail shell were taken from animals of different age grown under various keeping conditions. Additionally, eggs with ages of 60, 72, 120, and 140 hours were examined. Traces of aragonite were found as first crystalline phase in 120 h old eggs, however, Ca K-edge EXAFS indicated the presence of aragonitic structures already in the X-ray amorphous sample of 72 h age. The main component of the shell of adult animals was aragonite in all cases, but in some cases minor amounts of vaterite (below 1.5%) are formed. The content of vaterite is generally low in the oldest part of the shell (the center) and increases towards the mineralizing zone (the shell margin). In juvenile snails, almost no vaterite was detectable in any part of the shell.     

Temperature-resolved X-ray diffractometry as a thermoanalytical method

Development and experimental setup of the time-, and temperature -resolved X-ray powder diffractometry are described. This method allows far deeper insight into solid state reactions than conventional thermoanalytical methods like differential scanning calorimetry (DSC) or thermogravimetry. As an example, the dehydration of caffeine hydrate was investigated. We found that in earlier stages the reaction is nucleation controlled, whereas for higher extent of reaction diffusion limitation becomes rate-controlling.     

Solid-phase synthesis of nucleoside analogues

The synthesis of a 25 000 member library of nucleoside analogues as discrete compounds in milligram quantities is described. The use of the Nanokan technology developed by IRORI (Discovery Partners International) together with macroporous solid support allowed us to develop a highly reliable and practical synthetic route for the high-throughput derivatization of both the pyrimidine and purine nucleoside scaffold. A 2',3'-acetal linkage of the scaffolds to the solid support proved to be stable enough for the chemical transformations employed, yet labile enough for mild cleavage conditions to yield final products in high purity. The publication represents an example for combining synthetic organic chemistry on advanced scaffolds with the latest technologies of combinatorial chemistry in order to provide both industrial and academic institutions with compounds in high number and quality, thereby accelerating the search for novel biological targets and drug development.     

In situ monitoring of solid-state polymerization reactions in sodium chloroacetate and sodium bromoacetate by 23Na and 13C solid-state NMR spectroscopy

The thermally induced solidstate polymerization reactions in sodium chloroacetate and sodium bromoacetate, leading to poly(hydroxyacetic acid) (polyglycolide) and NaCl and NaBr, respectively, were studied by isothermal in situ solid-state NMR spectroscopy at 120, 130 and 140 degrees C with a time resolution of the order of 5 to 25 min. The nuclei probed were 23Na and 13C, allowing the parent compounds (sodium halogenoacetates) and both reaction products (polymer and alkali halide) to be monitored. For sodium chloroacetate, there is no evidence for the involvement of intermediate phases during the reaction whereas this cannot be excluded for sodium bromoacetate. The crystal structure of sodium bromoacetate was determined directly from powder diffraction data by the Monte Carlo method, and was found to be isostructural with sodium chloroacetate. The topochemical reaction mechanism proposed previously for sodium chloroacetate is thus also applicable for the polymerization reaction in sodium bromoacetate. The mechanistic and kinetic information obtained from our in situ solid-state NMR investigations is compared and contrasted with information obtained from other in situ probes of the polymerization reactions in these materials.     

Energetics of C-Cl, C-Br, and C-I bonds in haloacetic acids: enthalpies of formation of XCH2COOH (X=CI, Br, I) compounds and the carboxymethyl radical

The standard molar enthalpies of formation of chloro-, bromo-, and iodoacetic acids in the crystalline state, at 298.15 K, were determined as deltafH(o)m(C2H3O2Cl, cr alpha)=-(509.74+/- 0.49) kJ x mol(-1), deltafH(o)m(C2H3O2Br, cr I)-(466.98 +/- 1.08) kJ x mol(-1), and deltafH(o)m (C2H3O2I, cr)=-(415.44 +/- 1.53) kJ x mol(-1), respectively, by rotating-bomb combustion calorimetry. Vapor pressure versus temperature measurements by the Knudsen effusion method led to deltasubH(o)m(C2H3O2Cl)=(82.19 +/- 0.92) kJ x mol(-1), deltasubH(o)m(C2H3O2Br)=(83.50 +/- 2.95) kJ x mol(-1), and deltasubH(o)m-(C2H3O2I) = (86.47 +/- 1.02) kJ x mol(-1), at 298.15 K. From the obtained deltafH(o)m(cr) and deltasubH(o)m values it was possible to derive deltafH(o)m(C2H3O2Cl, g)=-(427.55 +/- 1.04) kJ x mol(-1), deltafH(o)m (C2H3O2Br, g)=-(383.48 +/- 3.14) kJ x mol(-1), and deltafH(o)m(C2H3O2I, g)=-(328.97 +/- 1.84) kJ x mol(-1). These data, taken with a published value of the enthalpy of formation of acetic acid, and the enthalpy of formation of the carboxymethyl radical, deltafH(o)m(CH2COOH, g)=-(238 +/- 2) kJ x mol(-1), obtained from density functional theory calculations, led to DHo(H-CH2COOH)=(412.8 +/- 3.2) kJ x mol(-1), DHo(Cl-CH2COOH)=(310.9 +/- 2.2) kJ x mol(-1), DHo(Br-CH2COOH)=(257.4 +/- 3.7) kJ x mol(-1), and DHo(I-CH2COOH)=(197.8 +/- 2.7) kJ x mol(-1). A discussion of the C-X bonding energetics in XCH2COOH, CH3X, C2H5X, C2H3X, and C6H5X (X=H, Cl, Br, I) compounds is presented.