Calorimetric approach to tetronic/water interactions

Tetronic^®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers.     

CHEMILUMINESCENCE FROM THE OXIDATION OF AUXIN DERIVATIVES

Abstract— The thiophenyl ester of indole-3-acetic acid and indole-3-acetonitrile produce chemiluminescence in aerated dimethylsulfoxide in the presence of potassium t -butoxide. The emitter is the aromatic aldehyde. In the case of acetonitrile, the other product expected from the cleavage of an intermediate dioxetane, cyanate/isocyanate, has also been identified. Other auxins also chemiluminesce under similar conditions, but the emitters have not been properly identified.
These systems are models for the peroxidase catalyzed oxidation of indole-3-acetic acid to indole-3-carboxaldehyde and as such support the earlier inference (Vidigal et al , 1975) that the excited aldehyde is generated in the enzymic process.
An additional result is the observation of an exciplex between excited indole-3-carboxaldehyde and the thiophenylester of indole-3-acetic acid. This appears to be the first case of chemical generation of an exciplex by a route other than radical ion reaction, presumably by the dioxetane route.     

Z/E-photoisomerizations of olefins with 4npi- or (4n + 2)pi-electron substituents: zigzag variations in olefin properties along the T(1) state energy surfaces

[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields.     

Organonickel(II) Complexes with Anionic N-Donor Ligands. Hydration of coordinated nitriles at a nickel(II) site

The hydroxo complex (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-OH)₂]reacts with 2,3,4,5,6-pentafluoro benzenamine (C₆F₅-NH₂), 1,3-diaryltriaz-1-enes (ArNH? N=N? Ar, Ar = Ph, 4-MeC₆H₄, 4-MeOC₆H₄), 7-aza-1H-indole (= 1H-pyrrolo[2.3-b]pyridine; Hazind), N-phenylpyridin-2-amine(pyNHPh), and N-phenylpyridine-2-carboxamide (py-CONHPh) at room temperature in acetone to give the binuclear complexes (Bu₄N)₂[Ni₂(C₆F₅)₄(μ-C₆F₅NH)₂] ( 1 ) and (Bu₄N)₂[{Ni(C₆F₅)₂} 2(μ-OH)(μ-azind)] ( 2 ) and the mononuclear complexes Bu₄N[Ni(C₆F₅)2(ArN₃Ar)] ( 3 – 5 ), Bu₄N[Ni(C₆F₅)₂(pyNPh)] ( 6 ), and Bu₄N[Ni(C₆F₅)₂(pyCONPh)] ( 7 ). The hydroxo.complex (Bu₄N)₂[{Ni(C₆F₅)2-(μ-OH)}₂] promotes the nucleophilic addition of water to pyridine-2-carbonitrile, 2-aminoacetonitrile, and 2-(dimethylamino)acetonitrile, and complexes 8 – 10 containing pyridine-2-carboxamidato, 2-aminoacetamidato and 2-(dimethylamino)acetamidato ligands are formed. Analytical (C, H, N) and spectroscopic (IR, ¹H and ¹⁹F-NMR, and FAB-MS) data were used for structural assignments. A single-crystal X-ray diffraction study of (Bu₄N)₂[{Ni(C₆F₅)₂}₂(μ-OH)(μ-azind)] ( 2 ) established the binuclear nature of the anion; the two Ni-atoms are bridged by an OH group and a 7-aza-7H-indol-7-yl group, but the central Ni? O? Ni? N? C? N ring is not planar, the dihedral angle between the Ni? O? Ni and Ni? N? C? N? Ni planes being 84.4°.     

Energetic and topological analysis of the reaction of Mo and Mo2 with NH3, C2H2, and C2H4 molecules

The Density functional theory has been applied to characterize the structural features of Mo(1,2)-NH(3),-C(2)H(4), and -C(2)H(2) compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo(1,2)-NH(3)), the interaction between Mo (or Mo(2)) and C(2)H(4) (or C(2)H(2)) are the low-spin (Mo-C(2)H(4) and -C(2)H(2)) and high-spin (Mo(2)-C(2)H(4) and -C(2)H(2)) complexes. In the ground state of Mo(1,2)-C(2)H(4) and -C(2)H(2), the metal-center always reacts with the C-C center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a pi-acceptor ligand correlates with a maximum charge transfer from the metal center to the C-C bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the C-C basin. The interaction between Mo(1,2) and C(2)H(4) (or C(2)H(2)) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo(1,2) and NH(3), and the partners are bound by an electrostatic interaction.     

Multiresidue determination of fluoroquinolones in shrimp by liquid chromatography-fluorescence-mass spectrometry

An efficient multiresidue method for analysis of fluoroquinolones in shrimp has been developed in which quantitation by fluorescence and confirmation by Multiple Stage Mass Spectrometry (MS) is achieved simultaneously. In this method, shrimp tissue is extracted with ammoniacal acetonitrile and the extract is defatted and then evaporated. After dissolution in basic phosphate buffer, fluoroquinolones in the extract are separated by liquid chromatography and quantitated, taking advantage of their intense fluorescence. Eluate from the fluorescence detector enters the MS, which allows for confirmation by monitoring ratios of 2 prominent product ions in the MS3 or MS2 spectrum. Using this method, 8 fluoroquinolones have been analyzed in shrimp samples fortified at 10, 25, 50, or 100 ppb levels. Recoveries for desethyleneciprofloxacin, norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin, orbifloxacin, sarafloxacin, and difloxacin ranged from 75 to 92%, with relative standard deviation values of <6%. The limits of quantitation ranged from 0.1 to 1 ng/g. Enrofloxacin and ciprofloxacin were also successfully determined in enrofloxacin-incurred shrimp using this method.