endo/exo isomerism in norcarane and 2-norcaranol hydrotrioxides (ROOOH)

Ozonation of norcarane (1) yielded endo and exo norcarane hydrotrioxides (2a, 2b), as characterized by (1)H and (13)C NMR spectroscopy. Further ozonation of the primary decomposition products of these hydrotrioxides, i.e., 2-norcaranols (3), produced the corresponding isomeric 2-norcaranol hydrotrioxides (4a, 4b), and hydrogen trioxide (HOOOH).     

Copper(II)–lanthanide(III) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platforms with Lewis amphoteric nature

Reaction of copper(II) acetate, lanthanium(III) or gadolinium(III) nitrate (1/5 equiv.) with pyrazinohydroxamic acid (H₂Pyzha) in DMF led to a series of new heterobimetallic 15-metallacrown-5 complexes. In a MeOH/H₂O solution the complexes exist as molecular unassociated metallacrowns. In solid state their structures are more complicated as it has been confirmed by X-ray analysis: discrete molecular metallacrowns [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(NO₃)] · 0.5C₆H₆ · H₂O (1), [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅](NO₃) · 1.5DMF · 0.5H₂O (2), [La(NO₃)₂{Cu(pyzha)}₅(DMF)₅]NO₃ · 1.5DMF · 2C₆H₆ (3) are solvates, whereas compound [{La(NO₃)₂{Cu(pyzha)}₅(DMF)₅}₂(μ²-NO₃)](NO₃) · 3DMF (4) is a dimer, where μ-bridged nitrate links two copper centres of the adjacent metallamacrocycles. Complex [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₂(H₂O)(NO₃)] · CH₂Cl₂ · DMF (5) self-associates into a polymer chain by means of one pyrazine moiety and the copper ring atom. Reaction of the molecular metallacrowns with excess of inorganic salts CdBr₂ or Cu(OAc)₂ proceeds as anion methathesis process affording heteroanionic metallacrowns: molecular [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅] [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(H₂O)][CdBr₄] · 1.5DMF (6), and 3D hydrogen bonded polymer [La(μ²-OAc)(H₂O)₃{Cu(pyzha)}₅ (H₂O)₄(NO₃)](NO₃) · 4H₂O (7).     

Experimental determination of human erythrocyte membrane permeability coefficients for a series of amides

Erythrocyte membrane permeability coefficients have been determined for a series of amides by a method based on the physical and mathematical modelling of hypotonic haemolysis process. The results show that penetration of the substances occurs by two alternative ways through aqueous pores formed by proteins and by the direct dissolving of the molecules in membrane lipids. This conclusion can be confirmed by the correlation analysis between permeability coefficients of native erythrocytes and those pre-incubated with the monosodium salt of p-chloromercuribenzenesulfonic acid (pCMBS), and the partition coefficients of the substances in hydrophilic-hydrophobic phases. Penetration of substances through hydrophilic channels is limited by the sterical factor and diameter in particular. Permeability coefficients for erythrocytes pre-incubated with pCMBS increase in an accordance with the rise of the partition coefficients with correlation coefficient of 0.94, thereby indicating a lipid route of permeation of molecules through erythrocyte membranes.     

Relaxations in chitin: Evidence for a glass transition

Relaxations in chitin have been investigated in the temperature range 298–523 K using impedance spectroscopy in the frequency range 10⁻¹–10⁸ Hz. The objective was to detect a glass‐transition temperature for this naturally occurring, semicrystalline polysaccharide. The impedance study was complemented with X‐ray diffraction, thermogravimetric, and differential scanning calorimetry measurements. Preliminary impedance data treatment includes the subtraction of the dc conductivity contribution, the exclusion of contact and interfacial polarization effects, and obtaining a condition of minimum moisture content for further analysis. When all these aspects are taken into account, two relaxations are clearly revealed in the impedance data. For the first time, evidence is presented for a relaxation process, which exhibits a non‐Arrhenius temperature dependence, in dry α‐chitin (∼0.1% moisture content), and likely represents the primary α‐relaxation. This evidence suggests a glass transition temperature for chitin of 335 ± 10 K estimated on the basis of the temperature dependence of the conductivity and of the relaxation time. A second relaxation in dry α‐chitin, not previously reported in the literature, is observed from 353 K to the onset of thermal degradation (∼483 K) and is identified as the σ‐relaxation often associated with proton mobility. It exhibits a normal Arrhenius‐type temperature dependence with activation energy of 113 ± 3 kJ/mol. The latter has not been previously reported in the literature. A high frequency secondary β‐relaxation is also observed with Arrhenius activation energy of 45 ± 1 kJ/mol. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 932–943, 2009     

Metal-organic frameworks incorporating Cu3(mu3-OH) clusters

Interaction of 4,4-bi(1,2,4-triazole) (btr) with copper(II) chloride (bromide) in aqueous or aqueous alcohol media led to a series of coordination polymers featuring the formation of mu 3-hydroxotricopper(II) clusters and their integration into 3D frameworks. These unprecedented structures originate in the propagation of trigonal hydroxotricopper(II) clusters bridged by tri- or tetradentate organic ligands. Complex [{Cu3(mu3-OH)}{Cu3(mu3-O)}(mu4-btr)3(H2O)4(OH)2Cl6]Cl.0.5H2O adopts a structure of SrSi2 topology, with eight-fold interpenetration of the coordination frameworks. The structure of [{Cu3(mu3-OH)}2(mu3-btr)6(mu4-btr)(mu-X)X4]X5.nH2O (X = Br, n = 6; X = Cl, n = 8) involves 2D coordination layers [{Cu3(mu3-OH)}(mu3-btr)3]n with an exceptional (3,6)-net topology, which are cross-linked by tetradentate btr ligands and bridging chloride (bromide) ions.     

Zinc(II) and cadmium(II) chloride complexes with 4,4′‐bi‐1,2,4‐triazole

New coordination compounds with the 4,4′‐bi‐1,2,4‐triazole ligand (btr), namely tetraaqua‐2κ⁴O‐di‐μ₂‐4,4′‐bi‐1,2,4‐triazole‐1:2κ²N¹:N^1′;2:3κ²N¹:N^1′‐hexachlorido‐1κ³Cl,3κ³Cl‐trizinc(II), [Zn₃Cl₆(C₄H₄N₆)₂(H₂O)₄], (I), and poly[cadmium(II)‐μ₂‐4,4′‐bi‐1,2,4‐triazole‐κ²N¹:N²‐di‐μ₂‐chlorido], [CdCl₂(C₄H₄N₆)]_n, (II), reveal an unprecedented molecular zwitterionic structure for (I) and a polymeric two‐dimensional layer structure for (II). Differences between these products, which involve the formation of either charge‐separated chlorometallate/aquametal fragments or complementary organic and inorganic bridges, are attributable to the hardness–softness characters of the metal cations. In (I), two N¹,N^1′‐bidentate btr molecules connect one [Zn(H₂O)₄]²⁺ cation and two [ZnCl₃]⁻ anions into a linear trizinc motif (the Zn atom of the cation occupies a centre of inversion in an N₂O₄ coordination octahedron, whereas the Zn atom of the anion possesses a distorted tetrahedral Cl₃N environment). In (II), the distorted vertex‐sharing CdCl₄N₂ octahedra are linked into binuclear [Cd₂(μ₂‐Cl)(μ₂‐btr)₂]³⁺ fragments by unprecedented N¹:N²‐bidentate btr double bridges and bridging chloride ligands, while the additional chloride anions are also bridging, providing further propagation of the fragments into a two‐dimensional network [Cd—Cl = 2.5869 (2)–2.6248 (7) Å].     

Giant thermodynamical optical effect near ferroelastic phase transition point in Cs3Bi2I9 layered crystal

For the first time we have found a new giant thermodynamical optical effect near the ferroelastic phase transition point in Cs₃Bi₂I₉ layered crystal. The effect is appeared as periodical oscillations in time of the reflection coefficient. This phenomenon is caused by the small temperature deviations in thermodynamical system the appearance of which in the reflection spectra is strongly amplified in the ferroelastic phase transition point. The optical oscillations are explained on the base of a model that takes into account the temperature dependence of the refractive index through the order parameter (spontaneous strain) of the crystal.     

Evaluation of the Effect of the Furazane Fragment on the NH Acidity of 4- and 5-Picrylaminobenzofurazanes in DMF and DMSO

The products of the reactions of picryl chloride with isomeric aminobenzofurazanes in DMF and DMSO were studied by means of nonaquoeus potentiometric titration. The effect of the position of the furazane fragment in 4- and 5-picrylaminobenzofurazanes on the NH acidity is considered. The electron-acceptor properties of the furazane fragment were evaluated via inclusion of the resulting data into the pK _a-σ correlation for 2,4,6-trinitrodiphenylamines. On this basis, conventional Hammett σ constants were calculated for the furazane fragment located in the immediate vicinity of the N-H center and one position distant from it.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 988–990.(-10V)Original Russian Text Copyright © 2005 by Levinson, Akimova, Ermolaeva, Khairutdinov, Evgen’ev.     

Extraction-chromatographic determination of hydrazine in natural water as a 5,7-Dinitrobenzofurazan derivative using diode-array detection

The conditions for the derivatization of hydrazine withp-dimethylaminobenzaldehyde and 4-chloro-5,7-dinitrobenzofurazan, extraction preconcentration of derivatives from natural water, and HPLC determination of the toxicant with diode-array detection were studied. The 5,7-dinitrobenzofurazan derivative was quantitatively extracted from water with isoamyl alcohol and a mixture of isoamyl alcohol with methylene chloride at pH 3–4. A procedure was developed for the extraction-chromatographic determination of hydrazine in water with c_min = 0.05 Μg/L and the analytical range 0.12-60 Μg/L. The concentration of hydrazine in lake Kaban water was determined.     

Nontraditional temperature shift of the fundamental absorption edge for layered substances and the ferroelastic phase transition in Cs3Bi2I9

We have carried out investigations of the exciton reflection spectra of Cs₃Bi₂I₉ layered crystals as a function of temperature. For the first time for the layered substances we have found nontraditional temperature shift of the energy gap E_g(T) described by the Varshni formula. We have registered a transition region in the temperature broadening of the half-width, H(T), of the exciton band with increasing of temperature in the interval between 150 and 220 K. It is shown that this region may be identified as the heterophase structure region where ferroelastic and paraelastic phases coexist. We have also found a surge in H(T) at the ferroelastic phase transition point