Supramolecular formation by aromatic ring stacking and hydrogen bonding in lanthanide(III) complexes with amino acids and 1,10-phenanthroline

[Eu(ABA)(phen)₂(H₂O)₃](ClO₄)₃·3phen·4.5H₂O (1) and [Eu(Val)(phen)₂(H₂O)₃](ClO₄)₃·3phen·2H₂O (2) are two new europium complexes with amino acids and 1,10-phenanthroline (phen=1,10-phenanthroline, ABA=-amino butyl acid, Val= -valine). Their crystal structures were measured by X-ray crystallography. Europium atoms in both complexes are nine-coordinated with bidentate 1,10-phenanthroline and carboxylate anion of amino acids, and water molecules. In the solid state, 1 and 2 have a structure involving aromatic stacking of the coordinated and non-coordinated 1,10-phenanthroline and the oxygen atoms of non-coordinated perchlorate anions being H-bond acceptors connect [Eu(ABA)(phen)₂(H₂O)₃]³⁺·3phen·4.5H₂O or [Eu(Val)(phen)₂(H₂O)₃]³⁺·3phen·2H₂O in their structures. In their interactions, several C–HO bonds play an important role. Owing to their different amino acid ligands and the number of lattice water molecules, there is some difference in their hydrogen bond patterns in 1 and 2. The side chain of -valine is involved in the formation of C–HO bonds. Hydrogen bond and π–π interactions determine the supramolecular formation of three-dimensional net works of both complexes.     

Photoexcitation and photodissociation lasers. III. mechanisms of CO laser emission from the vacuum UV photodissociation of CH2COO2 and CH2COSO2 mixtures

CO laser emission was detected in the vacuum UV flash photolysis of CH₂CO. The emission is attributed to the initial photodissociation reaction

Addition of O₂ to the CH₂CO system caused a pronounced enhancement in the laser intensity. This effect is believed to be due to the removal of the CH₂ + CH₂CO reaction, which produces uninverted CO molecules. A greater laser output was obtained when SO₂ was used instead of O₂. In the O₂-added system, a total of 16 transitions ranging from Δv(8→7) to (4→3) were identified. Addition of SO₂ increased the total number of lines to 34, lasing in the range between (11→10) and (4→3). This enhancement is ascribed to the occurrence of the reaction

In addition to these chemical effects, the effects of flash energy, inert gases and total pressures have been investigated.     

DiastereoselectiveandEnantioselectiveSynthesisof(1S,2S)-2-Ethyl-1-aminocyclopropaneCarboxylicAcid

During the last decade, 1-aminocyclopropanecarboxylic acid and its derivatives (ACCS) have attracted increasing attention of organic and bioorganic chemists due to their outstanding biological properties, ranging from antimicrobial, insecticidal, plant growth and fruit ripening controls, etc.1. Moreover, the three-membered carbocycle provides building blocks of unprecedented synthetic potential because it undergoes selective ring opening, ring enlargement or cycloaddition reactions2. The mo…     

Redetermination of (6R,7S,9S,11S)‐(–)‐sparteinium monoperchlorate

The structure of the title compound, C₁₅H₂₇N₂⁺·ClO₄^?, consists of a monoprotonated sparteinium cation and a perchlorate anion. The two tertiary N atoms of the cation, one perchlorate O atom and a H atom form a bifurcated hydrogen bond, the four hydrogen‐bonding atoms being nearly in the same plane.     

In situ prepared polypyrrole for low humidity QCM sensor and related theoretical calculation

In situ preparation of polypyrrole (Ppy) by photo-polymerization coated on a quartz crystal microbalance (QCM) as a low humidity sensor was reported. Different concentrations of Ppy films say 0 wt.% (as blank), 0.1, 1, and 10 wt.% were investigated to measure humidity concentrations between 14.7 and 5412.5 ppm_v. The adsorption/desorption behavior was also examined at humidity concentration 510.2 ppm_v. The sensitivities of 0, 0.1 and 1 wt.% Ppy films at 51.5 ppm_v were 0.143, 0.219 and 0.427, respectively. For 1 wt.% Ppy, the highest sensitivity was obtained. The slope and correlation coefficients (R²) for 1 wt.% Ppy at the ranges of 14.7–898.6 ppm_v were 0.0646 and 0.9909, respectively. A series of molecular simulations have been carried out to calculate bond energy for the water molecule interaction with Ppy, which was found to be 3 kcal/mol indicating the existence of hydrogen bonding during the sorption process. Based on Langmuir isotherm adsorption assumption, for 0.1 and 1 wt.% Ppy films, the association constants were 2606.30 and 5792.98, respectively. This larger association constant for 1 wt.% Ppy film explains higher sensitivity.     

A pre-irradiation separation procedure based on ion-exchange chromatography for gallium determination in biological and environmental materials by neutron activation analysis

A pre-irradiation separation procedure, for gallium determination in biological and environmental materials by neutron activation analysis (NAA) is reported. The proposed method, based on ion-exchange chromatography, allows to eliminate the radiation risk, while taking the advantages of high sensitivity of NAA. The single comparator method is employed for gallium quantitative evaluation. Since no standard reference materials with certified gallium contents were available, the reliability of the proposed method was extensively investigated by various approaches. Four biological and one environmental standard reference materials, with gallium contents ranging from 54 g/g-3 ng/g, have been analyzed.     

An improved scheme for the identification of antigens recognized by specific antibodies in two-dimensional gel electrophoresis and immunoblotting

This paper describes an improved scheme for the identification of antigens in crude extracts recognized by specific antibodies when analyzed by a combination of two-dimensional gel electrophoresis and immunoblotting. First, protein components in gels are electrophoretically transferred to a polyvinylidene difluoride membrane which does not shrink or change dimensions in organic solvents. The efficiency of transfer and the localization of sample proteins on the membrane are checked and recorded by staining the blotting membrane with Fast Green FCF and recording the profile on a transparency. After blocking and the immunoassay, the results are recorded by photography. The sites of immune reaction are marked and the same membrane is restained briefly with Coomassie Brilliant Blue R-250 for the protein profile. Thus antigens in complex mixtures, recognized by antibodies of interest, can easily be identified from the restained membrane. If the whole protein profile is not well demonstrated, when used in combination with the profile recorded on the transparency, spots appearing on the restained membrane can still be used as useful landmarks in the final unequivocal antigenic identification. This improved scheme circumvents problems arising from membrane shrinkage and difficulties in accurately matching immunoreactive spots by conventional procedures and thus provides an accurate, simple and fast approach in the identification of antigens after immunoblotting.     

Highly regioselective rearrangement of 2-substituted vinylepoxides catalyzed by gallium(III) triflate

Gallium(III) triflate catalyzed the rearrangement of 2-substituted vinylepoxides into beta,gamma-unsaturated carbonyl compounds with high regio- and chemoselectivity (>97/3) in low catalyst loading (1-5 mol %). The alkyl-substituted trimethylsilylvinyl epoxides gave beta,gamma-unsaturated ketone, but aryl-substituted vinylepoxides gave the aldehydes instead.     

Chemistry of O-Benzoquinones and Masked O-Benzoquinones IV. Synthesis of O-Spirodienonelactones from Unsymmetric Catechols

We describe the syntheses of 6, 8-di-tert-butyl-, 7, 9-di-tert-butyl., 6,7-di-n-propyl and 8, 9-di-n-propyl-O-spirodienonelactone from 3, 5-di-tert-butylcatechol and 3, 4-di-n-propylcatechol.     

气相二茂铁双电荷离子的动能谱研究

The unimolecular charge separation reactions of the doubly charged ions FeC_(10)H_(10)~(2+)、FeC_(10)H_9~(2+)、FeC_(10)H_8~(2+) produced in the ion source by electron impact from ferrocene have been studied using Mass analyzed Ion Kinetic Energy Spectrometry (MIKES) technique. From the values of the kinetic energy releases (T), the intercharge distances (R) of the exploding doubly charged ions in their transition structures have been estimated and some structural informations about the transition states can be obtained. The collision induced reactions of the FeC_(10)H_(10)~(2+) ion with Ar have been studied using MIKES, we postulate a new type of continuing reaction which may be "collisional charge separation induced dissociation".