Dynamic mechanical analysis on modified bismaleimide resins

Polyaminobismaleimides (PAMBI) with diphenyl methane, diphenyl ether and hexamethylene segments were synthesized according to Michael type addition reaction. The modification of PAMBIs with 2-glycidyl-phenyl-ether (GPE) was performed in order to ameliorate the toughness of the products. Dynamic mechanical analysis allowed the study of the processes that concur in the material through curing by tracking the storage modulus (E′) and loss factor (tanδ) changes. The small drop of E′ with increasing temperature in the glass transition region argues for crosslinked structures. The viscoelastic behavior revealed complex processes, i.e., overlapping of glass transition temperature range with intra-and inter-crosslinking.     

Energy balance in dense microemulsions

A water-in-oil microemulsion composed of water, AOT and decane with volume fraction φ=0.50 and molar ratio X=40.8 was analysed by DSC. The percolation and the bicontinuous transitions as well as the melting endotherms and the freezing exotherms were measured. The main attention was focussed on the system energy balance. It was found that, by freezing the samples after the occurrence of the percolative transition, the total heat released is significantly less than the heat absorbed in the melting endotherms. A simple geometrical model was used as an analysis tool of the aforementioned energy difference. Since the system studied exhibits a percolative transition of dynamic type, on approaching the percolation threshold temperature (T≤T _p) and a static percolation for T≥T _p, the structural change from the connecting water-droplet-cluster to a connecting water channel was schematised in the model as a change from a sphere-necklace to a water-cylindrical channel of equal volume and equal length. The surface energy associated with the formation of the two different geometrical surfaces was evaluated and the amount of saved energy compared with the experimentally measured one.     

Aquation of the ruthenium-based anticancer drug NAMI-A: a density functional study

We carried out density functional theory (DFT) calculations to investigate the thermodynamics and the kinetics of the double aquation reaction of the anticancer drug NAMI-A. Three explicit water molecules were included in the calculations to improve the PB solvation energies. Our calculations show that the chloride substitution reactions on the considered Ru(III) octahedral complex follow a dissociative interchange mechanism, I(d), passing through a loose heptacoordinate transition state. We calculated an activation enthalpy and free energy for the first aquation step of 101.5 and 103.7 kJ mol(-1), respectively, values that are in good agreement with the available experimental results. The activation enthalpy and free energy for the second aquation step were found significantly higher, 118.7 and 125.0 kJ mol(-1), again in agreement with the experimental evidence indicating a slower rate for the second aquation.     

Concentration as the switch for chiral recognition in biomembrane models

Chiral recognition was observed in a biomembrane model. Micellar aggregates formed by enantiopure N-alkyl-N,N-dimethyl-N-(1-phenyl)ethylammonium bromide were in fact able to convert the racemic mixture of bilirubin-IXalpha into an enantiomerically enriched mixture. The stereochemical preference and the extent of enantiomeric enrichment depend on the length of the hydrophobic portion of the surfactant and on the concentration conditions, and changes in the stereochemical bias are reversible.     

Suberythemal Sun Exposures at Swedish Schools Depend on Sky Views of the Outdoor Environments – Possible Implications for Pupils’ Health

More scheduled outdoor stay is increasingly advocated for school children. This study measured 2^nd, 5^th and 8^th graders’ erythemal UV‐exposure in September, March and May at four Swedish schools. We related those exposures, as fractions of total available ambient radiation, to the schools outdoor environments differing in amount of shade, vegetation, and peripheral city‐scape quantified as percentage of free sky view calculated from fish‐eye photographs. Exposures correlated with the sky views (with exceptions in May) and were suberythemal. The exposures were also below the threshold limit of the International Commission on Non‐Ionizing Radiation Protection (ICNIRP) for hazard evaluation of UVR but were potentially enough for adequate vitamin D formation according to a cited model calculation – as illustrated in the results and discussed. The school environments, typical in southern and middle Sweden, offer enough shade to protect children from overexposure during seasons with potentially harmful solar UV radiation. Pupils’ outdoor stay may be extended during September and March. In May extended outdoor stay of the youngest pupils requires a more UVR‐protective environment.     

Redox characteristics of a de novo quinone protein

The electrochemistry of 2,6-dimethylbenzoquinone (DMBQ) has been characterized for three different systems: DMBQ freely solvated in aqueous buffer; DMBQ bound to a neutral, blocked cysteine (N-acetyl-L-cysteine methyl ester) and the resulting DMBQ-bCys compound solvated in aqueous buffer; and DMBQ bound to a small model protein denoted alpha(3)C. The goal of this study is to detect and characterize differences in the redox properties of the protein-ligated DMBQ relative to the solvated quinones. The alpha(3)C protein used here is a tryptophan-32 to cysteine-32 variant of the structurally defined alpha(3)W de novo protein (Dai et al. J. Am. Chem. Soc. 2002, 124, 10952-10953). The properties of alpha(3)C were recently described (Hay et al. Biochemistry 2005, 44, 11891-11902). DMBQ was covalently bound to bCys and alpha(3)C through a sulfur substitution reaction with the cysteine thiol. In contrast to the solvated DMBQ and DMBQ-bCys compounds, diffusion controlled electrochemistry of DMBQ-alpha(3)C showed well-behaved and fully reversible n = 2 oxidation/reduction with a peak separation of approximately 30 mV between pH 5 and 9. DMBQ-alpha(3)C could also be immobilized on a gold electrode modified with a self-assembled monolayer of 3-mercaptopropionoic acid, allowing the measurement, by cyclic voltammetry, of an apparent rate of electron transfer of 22 s(-1). The (cysteine) sulfur substitution significantly lowers one of the hydroquinone pKA's from 10.4 in DMBQ to 6.8 in DMBQ-bCys. This pKA is slightly elevated in DMBQ-alpha(3)C to 7.0 and the E1/2 at pH 7.0 is raised by 110 mV from +190 mV in DMBQ-bCys to +297 mV in DMBQ-alpha(3)C.     

Interactions between benzyl benzoate and single- and double-chain quaternary ammonium surfactants

Interactions between benzyl benzoate and two different twin-tailed cationic surfactants have been studied. NMR diffusometry measurements have shown that cationic micelles grow in one dimension when benzyl benzoate is added. The location of benzyl benzoate in the micelles was evaluated by NOESY, showing that benzyl benzoate gave cross-peaks both to the hydrophobic groups in the surfactant and to the surfactant head group. Additions of benzyl benzoate to a lamellar phase of double-tailed quaternary surfactants revealed differences in responses. With an increasing concentration of benzyl benzoate, the structure of the dialkyl quat aggregate goes from lamellar to cubic, while the dialkyl ester quat forms a lamellar structure for all benzyl benzoate concentrations.     

Chemical composition and volatile constituents of Anthyllis barba-jovis

Six flavonol glycosides were isolated and identified from the aerial parts of Anthyllis barba-jovis L. (Leguminosae), together with two coumarins and D-pinitol, a taxonomic marker of Leguminosae family. The structural elucidation of all compounds was based on their (1)H- and (13)C-NMR spectral data and bidimensional experiments. The total flavonoid content was also determined, according to the method described in the Italian pharmacopoeia. In order to complete the phytochemical investigation on A. barba-jovis, the essential oils from flowers and seeds were obtained by hydrodistillation and analysed by GC-MS; fresh flowers were analysed also directly by solid phase micro extraction (SPME).     

Rate constants for the gas-phase reaction of the hydroxyl radical with a series of dimethylbenzaldehydes and trimethylphenols at atmospheric pressure

Rate constants for three dimethylbenzaldehydes and two trimethylphenols have been determined for the OH reactions at 298±2 K and atmospheric pressure using a relative rate method. The OH reaction rate constants were placed on an absolute basis using the literature rate constant for 1,2,4-trimethylbenzene of (3.25±0.5)×10⁻¹¹ cm³ molecule⁻¹s⁻¹). The measured rate constants were (in units of cm³ molecule⁻¹ s⁻¹) 2,4-dimethyl-benzaldehyde, (4.32±0.67)×10⁻¹¹; 2,5-dimethylbenzaldehyde, (4.37±0.68)×10⁻¹¹; 3,4-dimethylbenzaldehyde, (2.14±0.34)×10⁻¹¹; and 2,3,5- trimethylphenol, (12.5±1.9)×10⁻¹¹, 2,3,6-trimethylphenol, (11.8±1.8)×10⁻¹¹. Using an average OH concentration of 8.7×10⁵ molecule cm⁻³, the estimated atmospheric lifetimes are ca. 7.5 h for 2,4- and 2,5-dimethylbenzaldehydes, ca. 15 h for 3,4-dimethylbenzaldehyde, ca. 2.5 h for 2,3,5- and 2,3,6-trimethylphenols. The reactivities of the trimethylphenols exceed those of the dimethyl-benzaldehydes by more than a factor of 3. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 523–525, 1997.