Peripherally fused porphyrins via the Scholl reaction: synthesis, self-assembly, and mesomorphism

Oxidative coupling of activated aryl groups attached to β-positions of the porphyrin ring provides convenient access to derivatives containing peripherally fused phenanthrene and benzo[g]chrysene units. Tetra(benzochryseno)porphyrin, reported here for the first time, contains a nonplanar, sterically locked π system and shows very intense electronic absorptions in the Q range of the electronic spectrum. Tetraphenanthroporphyrins show a tendency to aggregate in solution. In one case, a discrete dimer is formed, whose structure was investigated spectroscopically and theoretically. Derivatives bearing long alkyl chains are mesomorphic and exhibit columnar phases (tetraphenanthroporphyrins) and a monoclinic 3D phase (tetrabenzochrysenoporphyrin). The symmetry of column packing in the columnar phases is dependent on the number of alkyl chains per molecule. X-ray diffraction measurements show that, in spite of their nonplanarity, the aromatic cores in the mesophases are tightly stacked within the column. The corresponding stacking patterns were derived from the structure of the dimer, on the basis of geometrical analysis and molecular modeling.     

Antioxidant potential and authenticity of some commercial fruit juices studied by EPR and IRMS

Antioxidant status of foods, plant, or fruit products is generally characterized by means of spectroscopic methods. Methods like HPLC, UV-VIS, or MS spectroscopy are used to understand the chemical and physical properties of different samples, and also EPR spectroscopy seems to be a valuable tool to characterize antioxidant activity of juice beverages. In this technique, certain antioxidants present in fruit juices interact with free radicals interrupting the chain reaction that can possibly damage essential molecules. Recording the EPR signal decay caused by the reaction with a natural or artificial reducing agent, it is possible to draw conclusions about the antioxidant capability of materials. IRMS is a powerful tool to distinguish between an authentic fruit juice and a juice obtained by concentrate dilution. This technique allows also the detection of commercial C₄ cane or corn derived sugar syrups in C₃ fruit juices. In the present study, four commercial fruit juices were investigated using stable isotope measurements (oxygen, hydrogen, and carbon) and EPR measurements in order to check the correct labeling in the Romanian markets and to compare antioxidant activity of the studied juices and the reference. It was proven that the number of paramagnetic species decreases in time with different reaction rates and this was correlated with the antioxidant activity of the studied juices. Stable isotope ratio measurements have demonstrated that the fruit juices studied were reconstructed from concentrates with tap water, according to their label.     

Floer–Novikov homology and applications to Lagrangian submanifolds

We use a non-Hamiltonian version of Lagrangian Floer homology to prove that an exact Lagrangian submanifold in the cotangent bundle of the 3-torus T ³ must be diffeomorphic to T ³. This improves a previous result of Fukaya, Seidel and Smith.     

Effects of external electromagnetic fields on the conformational sampling of a short alanine peptide

Non‐equilibrium molecular dynamics simulations of a solvated 21‐residue polyalanine (A21) peptide, featuring a high propensity for helix formation, have been performed at 300 K and 1 bar in the presence of external electromagnetic (e/m) fields in the microwave region (2.45 GHz) and an r.m.s. electric field intensity range of 0.01–0.05 V/Å. To investigate how the field presence affects transitions between the conformational states of a protein, we report 16 independent 40 ns‐trajectories of A21 starting from both extended and fully folded states. We observe folding‐behavior of the peptide consistent with prior simulation and experimental studies. The peptide displays a natural tendency to form stable elements of secondary structure which are stabilized by tertiary interactions with proximate regions of the peptide. Consistent with our earlier work, the presence of external e/m fields disrupts this behavior, involving a mechanism of localized dipolar alignment which serves to enhance intra‐protein perturbations in hydrogen bonds (English, et al., J. Chem. Phys. 2010 , 133, 091105), leading to more frequent transitions between shorter‐lifetime states. © 2012 Wiley Periodicals, Inc.     

ESR study of some solvent effects of the Cu(II)-aspirinate complex

Powder ESR spectra of the [Cu₂(Asp)₄](H₂O)₂ complex show the existence of Cu(II) acetate like dimers characterized by a strong antiferromagnetic exchange interaction (J=?288 cm^?1). In pyridine-dimethylformamide solutions the monomeric species prevail. Two different monomeric species, the Cu(DMF)₄ of planar-distorted tetrahedral (T_d) symmetry and the Cu(Asp)₂(DMF)₂ with elongated tetrahedral-octahedral symmetry were evidenced in DMF solution adsorbed on NaY zeolite. In 40 % Py+60 % DMF solution two monomeric species were also identified. These are Cu(Asp)₂(DMF)₂ and Cu(Asp)₂(Py)₂, the last species having a CuN₂O₂ chromophore in atrans squareplanar arrangement. In pyridine Cu(II)-aspirinate solution only the Cu(Py)₄ monomeric species of CuN₄ chromophore was evidenced.     

ESR investigation of gamma-irradiated Aspirin

Electron spin resonance spectroscopy was used to investigate the radiation damage in a powder of 2-acetoxybenzoic acid (Aspirin). Three types of radicals occur by -irradiation of Aspirin at room temperature. Two of them are the result of hydrogen abstraction while the third is produced by hydrogen addition at one of the carbon atoms of the ring. The relative yielding of the free radicals as a function of absorbed dose in the range of 2.4 kGy to 160 kGy is also discussed.     

Non-symmetrical bent-shaped liquid crystals based on a laterally substituted naphthalene central core with four ester groups

In the continuation of our study of the role of direction of the linking ester group and lateral substitution, we present three series of bent-core liquid crystals based on 7-hydroxynaphthalene-2-carboxylic acid. The mesomorphic properties were investigated by polarised optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical methods. For non-substituted and laterally methyl-substituted compounds, columnar phases of broken-layer type and a smectic A phase were found. With the increasing length of the terminal alkyl chain, an increasing stability of the lamellar smectic A phase was observed. Substitution with a methyl group led to substantial narrowing of the mesophase range and the chloro-substituted materials exhibited no mesophases. The results are also discussed in context with the earlier studied naphthalene based mesogens.     

Deposition of calcium carbonate films by a polymer-induced liquid-precursor (PILP) process

A polypeptide additive has been used to transform the solution crystallization of calcium carbonate to a solidification process of a liquid-phase mineral precursor. In situ observations reveal that polyaspartate induces liquid–liquid phase separation of droplets of a mineral precursor. The droplets deposit on the substrate and coalesce to form a coating, which then solidifies into calcitic tablets and films. Transition bars form during the amorphous to crystalline transition, leading to sectorization of calcite tablets, and the defect textures and crystal morphologies are atypical of solution grown crystals. The formation of nonequilibrium crystal morphologies using an acidic polypeptide may have implications in the field of biomineralization, and the environmentally friendly aspects of this polymer-induced liquid-precursor (PILP) process may offer new techniques for aqueous-based processing of ceramic films, coatings, and particulates.