Potential psychotropic agents. 7-Chloro-9-phenyl-3,3-diethyl-3H-pyrazolo-[5, 1-b]quinazolin-10-ium-2-olate and 9-Chloro-2,3,4,5-tetrahydro-1-methyl-3,3-diethyl-7-phenyl-1H-benzo-1,5,6-triazonine-2,4-dione

2-Amino-5-chloro-α-phenylbenzylidene hydrazone ( 1 ) or its methyl derivative 2 or acetyl derivative 10 react with diethylmalonic esters to give the corresponding malonyl derivatives 3, 4 and 8 . These esters were hydrolyzed to the acids 5 and 6 . Treating 5 with dehydrating agents the mesoionic compound 7-chloro-9-phenyl-3,3-diethyl-3H-pyrazolo[5,1-b]quinazolin-10-ium-2-olate (14) was obtained, while the methyl derivative 6 afforded the desired 9-chloro-2,3,4,5-tetrahydro-1-methyl-3,3-diethyl-7-phenyl-1H-benzo-1,5,6-triazonine-2,4-dione ( 17 ). Some derivatives of these compounds were also described. The structures of the new compounds were confirmed by an alternative synthesis and by mass and prnr spectral data.     

Sui fibrati con struttura quaternionale generalizzata

Summary Quaternion generalized fiber bundles are studied, both isomorphic to global tensorial product ordinary quaternion fiber bundles right and left respectively) and quite general ones. A cohomology class is considered which represents the obstruction in order the fiber bundle be a tensorial product. Several properties and a splitting principle are proved for bundles . On this ground and founding on a convenient bundle B_E → X associated to jaz (that we call Bonan's bundle and for which ɛ( =ɛ(B_E)) relations are stated among Stiefel-Whitney classes of , B_E and the class ɛ.

---

---

Entrata in Redazione il 14 agosto 1974.

---

Lavoro eseguito con contributo del C.N.R., nell'ambito del Gruppo Nazionale per le Strutture Algebriche e Geometriche e loro Applicazioni.     

Interactions between organic molecules and water: rotational spectrum of the 1:1 oxetane-water complex

The 1:1 molecular complex between oxetane and water has been investigated by using free-jet millimeter-wave spectroscopy. The rotational spectra of five isotopomers (with H(2)O, D(2)O, DOH, HOD and H(2) (18)O) have been assigned. Partial r(0) and r(s) structures of the complex have been derived. The water moiety lies in the plane of symmetry of oxetane, with the "free" hydrogen E with respect to the ring. The oxetane ring appears to be slightly nonplanar, with the C(beta) carbon tilted on the opposite side of the water unity. The three atoms involved in the hydrogen bond adopt a linear arrangement with an O(ring).H distance of about 1.86 A, and the angle between the COC bisector and the O(ring).H bond being congruent with 106 degrees. Additionally, quantum-chemical calculations for the complex were performed and were found to be in agreement with the experimental results.     

Coordination of Schiff bases derived from pyrrole-2-carboxaldehyde and triamines to copper(II) and nickel(II) ions. Crystal structures of [Cu(C15H20N5)]NO3 and [Ni(C15H20N5)]ClO4

The Schiffbases 1,9-bis(2-pyrrolyl)-2,5,8-triazanona-1,8-diene (H₂L¹), 1,10-bis(2-pyrrolyl)-2,5,9-triazaundeca-l,9-diene (H₂L²), and 1,11-bis(2-pyrrolyl)-6-methyl-2,6,10-triazaundeca-l,10-diene (H₂L⁴) react with copper(II) nitrate or nickel(II) perchlorate in the presence of triethylamine to give new complexes [Cu(HL^1,2,4)]NO₃ and [Ni(HL^1,2,4)]ClO₄. The crystal structures of [Cu(HL²)]NO₃ and [Ni(HL²)]CIO₄ have been determined from single crystal diffractometer data and refined to finalR factors of 5.09 and 5.3%, respectively. Crystallographic data: [Cu(HL²)]NO₃: monoclinic,P2₁/c,a=10.036(2),b=14.500(2),c=13.317(2) Å,=108.14(1)°,Z=4, andd _c =11.427 Mg m^–3; [Ni(HL²)]ClO₄: monoclinic,P2₁/n,a=10.578(3),b=13.953(3),c=12.394(4) Å,=93.78(2)°,Z=4, andd _c =1.549 Mg m^–3. In both the structures the potentially pentadentate ligand (HL²)^– acts as a tetradentate one leaving one pyrrole group uncoordinated. Interesting is the metal dependent sequence of the three chelate rings. While the Ni (II) ion coordinates the (HL²)^– ligand to form a 5-5-6-membered ring system, the ring arrangement in the copper complex is of the 5-6-5 type.     

Water-ketones hydrogen bonding: the rotational spectrum of cyclobutanone-water

The hydrogen-bonded complex cyclobutanone-water has been studied by Fourier-transform molecular-beam microwave spectroscopy in the frequency range of 6-18.5 GHz. The rotational spectra of ten isotopomers have been assigned and measured. Five of them have been obtained from different isotopic species (or configurations) of water (H2O, D2O, DOH, HOD, and H2 18O). The remaining five correspond to the four singly substituted 13C and to the 18O species of cyclobutanone, observed in natural abundance. For all species the inertial defect is in the range from -10.44 to -10.50 uA2, showing that the cyclobutanone frame is effectively planar and that the water molecule is coplanar to this frame. The hydrogen bond, almost linear, is formed between a water proton and one of the lone pairs of the cyclobutanone oxygen.     

Evaluation of indoor BTX in an outskirt zone of Rome (Italy)

Correlation between indoor and outdoor levels of BTX (benzene, toluene and the sum of ethyl benzene, o-xylene, m-xylene and p-xylene) has been investigated at thirteen homes, thirteen classrooms and related outdoor atmospheres. Non smoking people and low polluted sites were chosen for this campaign, in order to highlight if commonly used domestic materials could act as internal sources. Data, obtained by employing long-term diffusive samplers over a three-month period, are compared with a parallel experiment showing the day-night indoor/outdoor trend. The obtained results let us conclude that there is evidence of internal sources at homes whilst in the schools depletion phenomena prevail, probably due to the walls adsorption.     

New approach to the chemistry of technetium(V) and rhenium(V) phenylimido complexes: novel [M(NPh)PNP]3+ metal fragments (M = Tc, Re; PNP = aminodiphosphine) suitable for the synthesis of stable mixed-ligand compounds

Ligand-exchange reactions of the aminodiphosphine ligand bis[(2-diphenylphosphino)ethyl]amine hydrochloride (PNHP x HCl) with labile M(NPh)Cl3(PPh3)2 precursors (M = Re, Tc) in the presence of triethylamine yield monocationic phenylimido mer,cis-[M(NPh)Cl2(PNHP)]Cl (M = Re, 1; Tc, 2) intermediate complexes. X-ray analyses show that in both compounds the aminodiphosphine acts as a tridentate ligand dictating a mer,cis arrangement. Two chloride ligands, respectively in an equatorial and in the axial position trans to the linear M-NPh moiety, fill the remaining positions in a distorted-octahedral geometry. The chloride trans to the metal-imido core is labile, and is replaced by an alcoholate group, without affecting the original geometry, as established in mer,cis-[Re(NPh)(OEt)Cl(PNHP)]Cl 4. Otherwise, ligand-exchange reactions involving the aminodiphosphine bis[(2-diphenylphosphino)ethyl]methylamine (PNMeP), in which the central secondary amine has been replaced by a tertiary amine function, or its hydrochloride salt (PNMeP x HCl) give rise to three different species, depending on the experimental conditions: fac,cis-[Re(NPh)Cl2(PNMeP)]Cl 3a, cis,fac-Re(NPh)Cl3(PNMeP) x HCl 3b, and mer,trans-[Re(NPh)Cl2(PNMeP)]Cl 3c, which are characterized in solution by multinuclear NMR studies. The monodentate groups incorporated in these intermediate compounds, either halides and/or ethoxide, undergo substitution reactions with bidentate donor ligands such as catechol, ethylene glycol, and 1,2-aminophenol to afford stable mixed ligand complexes of the type [M(NPh)(O,O-cat)(PNP)]Cl [PNP = PNHP M = Re 5, Tc 6; PNP = PNMeP M = Re 7], [Re(NPh)(O,O-gly)(PNP)]Cl [PNP = PNHP 8, PNMeP 9] and [Re(NPh)(O,N-ap)(PNMeP)]Cl 10. X-ray diffraction analyses of the representative compounds 5 and 8 reveal that the aminodiphosphine switches from the meridional to the facial coordination mode placing the heteroatom of the diphosphine trans to the phenylimido unit and the bidentate ligand in the equatorial plane. Solution-state NMR studies suggest an analogous geometry for 6, 7, 9, and 10. Comparison with similar mixed ligand complexes including the terminal nitrido group is discussed.     

A test case for time-dependent density functional theory calculations of electronic circular dichroism: 2-chloro-4-methoxy-6- [(R)-1-phenylethylamino]-1,3,5- triazine

The three-dimensional structure of an optically active substituted s-triazine derivative, 2-chloro-4-methoxy-6-[(R)-1-phenylethylamino]-1,3,5-triazine, has been studied by conformational analysis using density functional theory (DFT) both in vacuo and in acetonitrile solution in the polarizable continuum model integral equation formalism framework. Time-dependent DFT methods have been used to investigate the molecular electronic CD and absorption UV spectra. Comparison with experimental results allowed the reliability of the theoretical predictions to be enhanced and suggested a possible interpretation of the measured data. Electronic Supplementary Material The online version of this article doi:contains supplementary material, which is available to authorized users.     

Mixed‐Organic‐Cation Perovskite Photovoltaics for Enhanced Solar‐Light Harvesting

Hybrid organic–inorganic lead halide perovskite APbX₃ pigments, such as methylammonium lead iodide, have recently emerged as excellent light harvesters in solid‐state mesoscopic solar cells. An important target for the further improvement of the performance of perovskite‐based photovoltaics is to extend their optical‐absorption onset further into the red to enhance solar‐light harvesting. Herein, we show that this goal can be reached by using a mixture of formamidinium (HN=CHNH₃⁺, FA) and methylammonium (CH₃NH₃⁺, MA) cations in the A position of the APbI₃ perovskite structure. This combination leads to an enhanced short‐circuit current and thus superior devices to those based on only CH₃NH₃⁺. This concept has not been applied previously in perovskite‐based solar cells. It shows great potential as a versatile tool to tune the structural, electrical, and optoelectronic properties of the light‐harvesting materials.     

Recombinant clotting factor VIII concentrates: Heterogeneity and high‐purity evaluation

Factor VIII is an important glycoprotein involved in hemostasis. Insertion of expression vectors containing either the full‐length cDNA sequence of human factor VIII (FLrFVIII) or B‐domain deleted (BDDrFVIII) into mammalian cell lines results in the production of recombinant factor VIII (rFVIII) for therapeutic usage. Three commercially available rFVIII concentrates (Advate^®, Helixate NexGen^® and Refacto^®), either FLrFVIII or BDDrFVIII, were investigated by 1‐ and 2‐DE and MS. The objective of this study was to compare the heterogeneity and the high purity of both rFVIII preparations before and after thrombin digestion. In particular, the 2‐D gel was optimized to better highlight the presence of contaminants and many unexpected proteins. Recombinant strategies consisting of insertion of expression vectors containing BDDrFVIII and FLrFVIII resulted in homogeneous and heterogeneous protein products, respectively, the latter consisting in a heterogeneous mixture of various B‐domain‐truncated forms of the molecule. Thrombin digestion of all the three rFVIII gave similar final products, plus one unexpected fragment of A2 domain missing 11 amino acids. Regarding the contaminants, Helixate NexGen^® showed the presence of impurities, such as Hsp70 kDa, haptoglobin and proapolipoprotein; Refacto^® showed glutathione S‐transferase and β‐lactamase, whereas Advate^® apparently did not contain any contaminants. The proteomic approach will contribute to improving the quality assurance and manufacturing processes of rFVIII concentrates. In this view, the 2‐DE is mandatory for revealing the presence of contaminants.