Differently coloured polymorphs of 4‐[(2‐nitrophenyl)azo]phenol

The crystal structures of the brown–yellow and orange polymorphs of the title compound, 4‐[(2‐nitro­phenyl)­diazenyl]­phenol, C₁₂H₉N₃O₃, have been determined and their visible reflection spectra recorded. Both structures adopt a stacking arrangement with interstack hydrogen bonds. Ab initio and semi‐empirical (AM1 and INDO‐CISD) calculations were performed in order to rationalize the difference in colour. It can be attributed neither to the subtle distinctions in molecular geometry nor to the effect of intermolecular electrostatic interactions. The most probable origin of this difference is the mixing of intramolecular n π* and intermolecular charge‐transfer excitations.     

Nondegenerate cohomology pairing for transitive Lie algebroids,characterization

The Evens-Lu-Weinstein representation (Q _A , D) for a Lie algebroid A on a manifold M is studied in the transitive case. To consider at the same time non-oriented manifolds as well, this representation is slightly modified to (Q _A ^or , D^or) by tensoring by orientation flat line bundle, Q _A ^or =Q_A⊗or (M) and D ^or=D⊗∂ _A ^or . It is shown that the induced cohomology pairing is nondegenerate and that the representation (Q _A ^or , D^or) is the unique (up to isomorphy) line representation for which the top group of compactly supported cohomology is nontrivial. In the case of trivial Lie algebroid A=TM the theorem reduce to the following: the orientation flat bundle (or (M), ∂ _A ^or ) is the unique (up to isomorphy) flat line bundle (ξ, ∇) for which the twisted de Rham complex of compactly supported differential forms on M with values in ξ possesses the nontrivial cohomology group in the top dimension. Finally it is obtained the characterization of transitive Lie algebroids for which the Lie algebroid cohomology with trivial coefficients (or with coefficients in the orientation flat line bundle) gives Poincaré duality. In proofs of these theorems for Lie algebroids it is used the Hochschild-Serre spectral sequence and it is shown the general fact concerning pairings between graded filtered differential ℝ-vector spaces: assuming that the second terms live in the finite rectangular, nondegeneration of the pairing for the second terms (which can be infinite dimensional) implies the same for cohomology spaces.     

Addition of some aminoheterocycles to N-benzyl-3-cyanopyridinium chloride

5-Aminopyrazoles react with N-benzyl-3-cyanopyridinium chloride giving 1-benzyl-3-cyano-4-(5-aminopyrazol-4-yl)-1,4-dihydropyridines with high regioselectivity. 5-Aminoisoxazole, 2-aminothiazole and 6-aminouracil react analogously.     

A simple method for the preparation of 5-alkylsulfinyl-1-aryltetrazoles

A simple method is suggested for the preparation of 5-alkylsulfinyl-1-aryltetrazoles via oxidation of 5-alkylsulfanyltetrazoles with 34% peracetic acid in high yields under mild conditions.     

Magnetohydrodynamic thermochemotherapy and MRI of mouse tumors

A dextran-ferrite magnetic fluid was successfully tested as magnetic resonance imaging (MRI) contrast agent. The same magnetic fluid was then combined with Melphalan, a chemotherapeutic drug, and used for magnetohydrodynamic thermochemotherapy of different tumors. The placement of the tumors in an AC magnetic field led to hyperthermia at 46 °C for 30 min. In combination with tumor slime aspiration, a 30% regression of ∼130 mm³ non-metastatic P388 tumors in BDF₁ mice was reached, together with a life span increase of 290%. The same procedure associated with cyclophosphamide treatment of ∼500 mm³ metastases tumor increased the animal's life span by 180%.     

Complexation and Self-Assembling of Sulfonatomethylated Calix[4]resorcinarene with Both Organic and Lanthanide Ions in Aqueous Media

The stoichiometry and binding constant of the paramagnetic lanthanide ion(Gd³⁺) with sulfonatomethylated calix[4]resorcinarene (H₈Xna₄) were evaluated from the NMR relaxation data. Both ¹H NMR spectroscopy and NMR relaxation data indicate that interaction of tetramethylammonium (TEMA) and N-methylpyridinium (MePy) cations with H₈Xna₄ in the presence of Ln³⁺ (Lu³⁺ or Gd³⁺) results in theformation of ternary complexes [Ln(G)H₈X] with lanthanide ions,coordinated via sulfonate groups and organic cation included intothe cavity of H₈Xna₄. The inclusion of long-chainedN-decyl-(DePy) and N-cetylpyridinium (CPy) ions into H₈Xna₄ cavity leads to self-assembling which can be revealed by NMR relaxation method with Gd³⁺ probe ions. The excess of alkylpyridinium or TEMA cations leads to disassembling of (Gd)_n(H₈X)_m(RPy)_maggregates.     

Features of the fluorine‐substituted acetaldehydes dynamics in the low‐lying electronic states: Quantum mechanical study of the CHF2CHO molecule lowest excited singlet state

The potential energy surface (PES) for the CHF₂CHO molecule in the excited S₁ state is calculated by the CASSCF method. The features of the 1‐ and 2‐D cross‐sections of PES are considered in comparison with those of the relative molecules. The vibrational frequencies are calculated in harmonic approximation and the vibrational energy levels for the inversion motion of the carbonyl fragment CCH_aO and for the torsion motion of the CHF₂‐top are calculated in anharmonic approximation by the 1‐ and 2‐D variational methods. The calculated data are compared with the experimental ones. The problems of the experimental data interpretation are considered. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Termination and transfer of the polymer chain to a maleimide derivative containing the azo group

The copolymerizations of N-(3-dimethylaminophenyl) maleimide (I) and 4-(2-chlorophenyl)azo-3-maleimido-N,N-dimethylaniline (II) with styrene were investigated; the copolymerization parameters of the pairs ($\text{I}\text{+}\text{styrene}$) and ($\text{II}\text{+}\text{styrene}$) and $\text{k}{}_{\mathrm{p}}\text{/k}{}_{\mathrm{t}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ hr I at 50° were determined; chain transfer to the maleimide ring of I was proved. The homopolymerization of styrene in the presence of 4-(2-chlorophenyl)azo-succinimide-N,N-dimethylaniline (III) was used to determine the ratio of the rate constant for addition of the polystyrene radical to the azo group in III to k_p for styrene.     

High resolution capillary gas chromatography and gas chromatography–mass spectrometry of protein and non-protein amino acids,amino alcohols,and hydroxycarboxylic acids as their tert-butyldimethylsilyl derivatives

A simple, single-step derivatization technique is presented for capillary GC-FID and GC-MS separation and identification of common protein and non-protein constituents of natural peptides as their tert-butyldimethylsilyl (TBDMS) derivatives. The tert-butyldimethyl-silylation of more than sixty compounds was accomplished with high yields and a single peak observed for each component. The TBDMS derivatives of both the protein and non-protein substances, moreover, exhibit excellent separation on apolar capillary columns and can be resolved completely using a polydimethylsiloxane or 5 % phenyl polydimethylsiloxane column and, complementarily, a 50 % phenyl polydimethylsiloxane column. Retention data and molar responses of the TBDMS derivatives on the polydimethylsiloxane column are compiled. Direct coupling of the 5 % phenyl polydimethylsiloxane column to an ion trap mass spectrometer enabled fast separation and identification of the investigated components, at nanomole to picomole levels, on the basis of retention and mass spectral data. The general usefulness of the method is demonstrated by research into new biologically active peptides isolated from entomopathogenic fungi.     

Synthesis of C59Hx and C58Hx fullerenes stabilized by hydrogen

Prolonged hydrogenation of C(60) molecules by reaction with H(2) at elevated temperature and pressure results in fragmentation and collapse of the fullerene cage structure. However, fragments can be preserved by immediate termination of dangling bonds by hydrogen. Here we demonstrate that not only fullerene fragments but also hydrogenated fragmented fullerenes (e.g., C(58)H(40) and C(59)H(40)) can be synthesized in bulk amount by high-temperature hydrogenation of C(60). We confirm successful synthesis of these species by matrix-assisted laser desorption ionization time-of-flight mass spectrometry and complete speciation of the resultant complex fullerene mixtures by high-resolution field desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry.