New dehydration in the pyrrolo[1,2–6-b]isoquinoline series. Preparation and structural identification of 3,5-dihydrobenz[f]indolizin-3-one

3,5-Dihydrobenz[f]indolizin-3-one was prepared by a novel dehydration reaction involving the heating of 1,2,3,5,10,10a-hexahydro[f]indolizine-3,10-dione with polyphosphoric acid. The structure of this new compound was established by X-ray crystallography, by nmr spectroscopy and by reduction to the known products 1,2,3,5-tetrahydrobenz[f]indolizin-3-one and 1,2,3,5,10,10a-hexahydrobenz[f]indolizin-3-one.     

X-ray diffraction and ab initio determinations of the structure of Rb4CdCl6

The structure of Rb₄CdCl₆ has been examined both at the experimental and at the ab initio levels. Experimentally, new X-ray diffraction measurements have been performed on a single crystal grown at room temperature from aqueous solution. The compound is confirmed to crystallize with a rhombohedral unit cell (space group ) but with a distorsion from cubic symmetry noticeably smaller than in a previous study [Kristallografiya, 37 (1992) 815]. From the ab initio point of view, three distinct sets of first-principles density functional theory calculations (Perdew-Wang generalized-gradient-approximation (PWGGA), Perdew, Burke and Ernzerhof parametrization and Becke-Lyp exchange-correlation functions) have been carried out. These ab initio results corresponding to the ideal crystal (i.e. infinite, periodic in a definite phase and defect-free) are in correct agreement with our own experimental findings, especially for the distorsion. Nevertheless, due to the relative flatness of the ideal crystal potential energy surface with respect to distorsion around the minimum, it is quite plausible the two presently available X-ray diffraction analyses, made on two different real (imperfect) samples, are both correct even though they come out onto significantly different mean distorsion parameters. The shape, orientation and relative sizes of the thermal vibration ellipsoids are discussed in relation with relevant aspects of the calculated potential energy surface. The PWGGA wavefunction is used to plot valence electronic charge density maps. The comparison of the charge distribution in Rb₄CdCl₆ with that in Rb₂CdCl₄ is discussed in terms of compound structures.     

Use of membrane processing to concentrate TGF-β2 and IGF-I from bovine milk and whey

The aim of this study was to evaluate the potential of using membrane processing such as microfiltration and ultrafiltration to concentrate TGF-β2 and IGF-I from milk and whey. Cheese wheys were obtained from Cheddar and Mozzarella cheeses made from pasteurized or thermized milk. Microfiltered or unheated whey (MF-whey) obtained by microfiltration of raw skim milk was used as control. Important losses of TGF-β2 were observed during clarification of pasteurized cheese wheys by microfiltration using a 1.4 μm pore size membrane. The ratio of IGF-I/TGF-β2 decreased from >3500 to 17 upon concentration of cheese whey by ultrafiltration (UF) and diafiltration (DF). UF concentration of MF-whey showed an increased concentration of TGF-β2 by a 13× factor. Lymphocyte proliferations increased upon MF/UF concentration and reached 25.5% inhibition at a 100 μg/mL concentration for MF-WPI, whereas a maximum of 8.5% of lymphocyte proliferation's inhibition was observed for cheese-WPI. Our results suggest that that UF/DF concentration of MF-whey may be a suitable method to prepare whey protein isolates enriched in TGF-β2 and IGF-I.     

Influence of the growth method upon the phase transition of RbCdCl $\mathsf{_{3}}$

Structural properties of two RbCdCl₃ samples grown either from the melt or from aqueous solution are studied via X-ray diffraction over a closed temperature cycle between 20 C and 300 C. During cooling step (300 C), the crystal grown from the melt undergoes a phase transition at 110 C that drives it from the cubic structure into a tetragonal structure that still persists at 20 C. It undergoes exactly the reverse phase transition at the same temperature during the heating ( C) step that immediately follows. The other crystal grows from aqueous solution at 20 C in an orthorhombic structure (i.e. not tetragonal as that of the crystal grown from the melt and cooled down to this temperature). During the heating ( C) step, it undergoes a direct orthorhombic-cubic phase transition at 240 C (without passing through the tetragonal phase) whereas, during subsequent cooling (300 C), it does not exhibit the corresponding reverse phase transition but rather exhibits exactly the same cubic-tetragonal phase transition at 110 C as the crystal grown from the melt. However, for both crystals, this tetragonal phase observed at room temperature is unstable and slowly converts into an orthorhombic phase over the course of time. Complementary Differential Scanning Calorimetry (D.S.C.) and Thermo Gravimetric Analysis (T.G.A.) measurements have been carried out over the range ( ) C in order to interpret diffraction experiments.Received: 19 May 2004, Published online: 30 September 2004PACS: 61.10.Nz X-ray diffraction - 64.70.Kb Solid-solid transitions - 65.40.Ba Heat capacity     

A new crystalline phase of nitric acid dihydrate

The crystal structure of a new high-temperature phase of nitric acid dihydrate, HNO₃·2H₂O, has been determined at 225 K by single-crystal X-ray diffraction. The H atom of the nitric acid is delocalized to one water mol­ecule, leading to an association of equimolar NO₃⁻ and H₅O₂⁺ ionic groups. The asymmetric unit contains two mol­ecules of HNO₃·2H₂O. The two independent mol­ecules are related by a pseudo-twofold c axis, by a translation of 0.54 (approximately ½) along b , with a mean atomic distance difference of 0.3 Å, except for one H atom of the water mol­ecules (1.5 Å), because of their different orientations in the two mol­ecules. The two independent mol­ecules, linked by strong hydrogen bonds, are arranged in layers. These layers are linked by weaker hydrogen bonds oriented approximately along the c axis. A three-dimensional hydrogen-bond network is observed.