Helix-sense selective polymerization of carbodiimides: building permanently optically active polymers from achiral monomers

The helix-sense selective polymerization of achiral monomers by homochiral catalysts was investigated. Polymerization of chiral carbodiimides (N-(R)-2,6-(dimethylheptyl)-N'-phenylcarbodiimide) by achiral catalysts yields polymers that undergo mutorotation at elevated temperatures, thus illustrating that these chains are formed under kinetic rather than thermodynamic control. Building on this observation, the polymerization of achiral carbodiimides by (S-BINOL)Ti(OiPr)2, I, was studied. Monomers (N-hexyl-N'-(X)carbodiimide, where X = isopropyl (3), hexyl (4) or phenyl (5)), N-methyl-N'-(2-methyl-6-isopropylphenyl)carbodiimide, 6, and N-dodecyl-N'-(1-naphthyl)carbodiimide, 7, were all polymerized with I in good yields (86-95%), and all showed varying degrees of asymmetric induction. Poly-3, -4, and -5 racemized upon heating at elevated temperatures, but poly-6 and poly-7, bearing nonsymmetric phenyl groups, yielded optically active polymers that could not be racemized even at elevated temperatures. Thin films of poly-7 were found to be highly opalescent.     

Ab initio vs molecular mechanics thermochemistry: homocubanes

The standard enthalpies of formation and strain energies for a series of homocubanes have been investigated by high-level ab initio G3(MP2)/B3LYP method. The relative stabilities of isomers are discussed. The comparison is made between the results of ab initio and molecular mechanics methods with the aim of assessing their performances. The usefulness of high-level calculations for generating thermochemical databases of relatively large molecules (e.g. C(11)H(14)) was also demonstrated.     

Organometallic 3-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines as potential anticancer agents

Six organometallic complexes of the general formula [M(II)Cl(η(6)-p-cymene)(L)]Cl, where M = Ru (11a, 12a, 13a) or Os (11b, 12b, 13b) and L = 3-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines (L1-L3) have been synthesized. The latter are known as potential cyclin-dependent kinase (Cdk) inhibitors. All compounds have been comprehensively characterized by elemental analysis, one- and two-dimensional NMR spectroscopy, UV-vis spectroscopy, ESI mass spectrometry, and X-ray crystallography (11b and 12b). The multistep synthesis of 3-(1H-benzimidazol-2-yl)-1H-pyrazolo[3,4-b]pyridines (L1-L3), which was reported by other researchers, has been modified by us essentially (e.g., the synthesis of 5-bromo-1H-pyrazolo[3,4-b]pyridine-3-carboxylic acid (3) via 5-bromo-3-methyl-1H-pyrazolo[3,4-b]pyridine (2); the synthesis of 1-methoxymethyl-2,3-diaminobenzene (5) by avoiding the use of unstable 2,3-diaminobenzyl alcohol; and the activation of 1H-pyrazolo[3,4-b]pyridine-3-carboxylic acids (1, 3) through the use of an inexpensive coupling reagent, N,N'-carbonyldiimidazole (CDI)). Stabilization of the 7b tautomer of methoxymethyl-substituted L3 by coordination to a metal(II) center, as well as the NMR spectroscopic characterization of two tautomers 7b-L3 and 4b'-L3 in a metal-free state are described. Structure-activity relationships with regard to cytotoxicity and cell cycle effects in human cancer cells, as well as Cdk inhibitory activity, are also reported.     

Structure and morphology of spinel MFe2O4 (M=Fe, Co, Ni) nanoparticles chemically synthesized from heterometallic complexes

We synthesized magnetic spinel ferrites from trimetallic single-source precursors. Fe(II), Co(II), and Ni(II) ferrite nanoparticles in the range of 9-25 nm were synthesized by solvothermal decomposition of trimetallic acetate complex precursors in benzyl ether in the presence of oleic acid and oleylamine, using 1,2-dodecanediol as the reducing agent. For comparison, spinel ferrite nanoparticles were synthesized by stoichiometric mixtures of metal acetate or acetylacetonate salts. The nanoparticles (NP) were characterized by TEM, DLS, powder XRD, and Raman spectroscopy; and their magnetic properties were characterized by ZFC-FC and M(H) measurements. The ferrite-NP were more homogeneous and had a narrower size distribution when trimetallic complexes were used as precursors. As a consequence, the magnetic properties of these ferrite-NP are closer to the aimed room temperature superparamagnetic behavior, than are those of other ferrites obtained by a mixture of salts.     

Semi-Solid o/w Emulsions Based on Sucrose Stearates: Influence of Oil and Surfactant Type on Morphology and Rheological Properties

Sucrose stearate blends of intermediate lipophilicity are mild surfactants with thermosensitive gelling behavior. Binary systems and emulsions with sucrose stearate S-970 or S-1170 were developed and investigated by thermoanalytical and rheological measurements. The presence of an oil phase promoted the gelling potential of the esters especially at higher production temperatures. Semi-solid emulsions with viscoelastic properties comparable to weak gels were obtained with different dermatologically acceptable oils. The complex internal structure as visualized by fluorescence microscopy exhibited changes during storage in dependence of oil and surfactant type. A combination of S-970 with cetearyl ethylhexanoate-based oil phases led to superior physical stability.     

Interaction of Photons with Electrons in Dielectric Media

The question of the field energy-momentum tensor in a medium is not new and many workers, in the past, attempted to find the answer to it. Nevertheless, there was no general agreement about the form of such a tensor, thus resulting in a confusion involving the very fundaments of physics. Although the present work uses well established theories, the underlying philosophy is completely novel. Investigations are mainly centered around the collisionless plasma as, in that state, development of the argument is most transparent. On the basis of a simple theoretical reasoning, it is, first of all, postulated that the momentum of the photon in a plasma is given by the Minkowski expression. This hypothesis becomes more viable as it directly leads to the accepted form for the field energy density. Furthermore, utilizing the concepts of stimulated and spontaneous emission and absorption, it is confirmed that, in the equilibrium (between radiation and plasma), the transferred momentum has the value given by the Minkowski theory. However, as will be seen, this result is valid only in the region of high frequencies. Put otherwise, when conditions are such that the laws of geometrical optics apply, the momentum of the photon is, to a good approximation, given by the Minkowski theory. In order to arrive at a more general result, valid in the domain of wave optics, a similarity between the dispersion relation (describing the wave propagation through a medium) and the relativistic energy-momentum of a particle moving through vacuum, is explored. Accepting the equivalence of these two relations implies that some of the properties of radiation in a medium, can also be described by a massive particle travelling through empty space. In other words, the task of analysing the behaviour of electromagnetic waves in a medium, can be replaced by the analysis of the free neutral vector meson field. Adoption of this equivalence results in the field energy-momentum tensor being symmetrical. A thorough study of the field theory then provides the basis for interpreting the Abraham tensor as the sum of the “orbital” and “spin” tensors. The former is directly connected with the energy transport, whereas the latter one is not. Realising that the magnitude of the spin term increases towards the lower end of the frequency spectrum provides the resolution of the Abraham-Minkowski dilemma: the energy-momentum tensor, corresponding to the electromagnetic wave in a medium, is that given by Abraham, while the one of Minkowski is only an approximation valid at high frequencies. Although this conclusion stems from studies involving collisionless isotropic plasma, it is in excellent agreement with the experimental data.     

Theoretical study of I2O

We present high-level density functional calculations (DFT) on the unknown I₂O molecule. The results suggest that the compound may be sufficiently stable for detection and synthesis. Our results also suggest that the DFT method is a reliable and computationally cheap alternative to G2, for estimating thermodynamic properties. The trends in relative stabilities within the HOX and X₂O series are discussed (X=halogen). © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:383–385, 1998     

Structural temperature-induced transitions in polar Langmuir-Blodgett films of p-(p-octadecyloxyphenylazo)benzenesulfonamide

We have studied the temperature dependence of the pyroelectric coefficient, dielectric constant and spacings of polar LB-films building from molecules of p-(p-octadecyloxyphenylazo)benzenesulfonamide (18-OABS) with a large dipole moment. The films were deposited by the Langmuir-Schaefer method. A significant pyroelectric effect in the films proved them to be polar. The periodicity of structure in films was approximately equal to the length of the molecules used. An irreversible transition at 90°C from polar to nonpolar phase has been observed in these films. At this transition the structural period of the films changes (39Å ⟹ 69Å). Also these LB-films exhibited several structure transitions. The films did not show a single solid-to-liquid transition but were liquid-crystalline. In the liquidcrystal state the films have several smectic mesophases. Transitions to the mesophases take place at 124°C (69Å ⇔︁ 63Å) and at 136°C (63Å ⇔︁ 41Å). During the transitions the structural periods of the films and the value of dielectric constant change.     

A Lactic Acid Bacteria Consortium Impacted the Content of Casein-Derived Biopeptides in Dried Fresh Cheese

This study aimed to define a consortium of lactic acid bacteria (LAB) that will bring added value to dried fresh cheese through specific probiotic properties and the synthesis of bioactive peptides (biopeptides). The designed LAB consortium consisted of three Lactobacillus strains: S-layer carrying Levilactobacillus brevis D6, exopolysaccharides producing Limosilactobacillus fermentum D12 and plantaricin expressing Lactiplantibacillus plantarum D13, and one Enterococcus strain, Enterococcus faecium ZGZA7-10. Chosen autochthonous LAB strains exhibited efficient adherence to the Caco-2 cell line and impacted faecal microbiota biodiversity. The cheese produced by the LAB consortium showed better physicochemical, textural and sensory properties than the cheese produced by a commercial starter culture. Liquid chromatography coupled with matrix-assisted laser desorption/ionization-time of flight tandem mass spectrometry (LC-MALDI-TOF/TOF) showed the presence of 18 specific biopeptides in dried fresh cheeses. Their identification and relative quantification was confirmed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) using multiple reaction monitoring (MRM). The results also showed that their synthesis resulted mainly from β-casein and also α-S1 casein degradation by proteolytic activities of the LAB consortium. The designed LAB consortium enhanced the functional value of the final product through impact on biopeptide concentrations and specific probiotic properties.     

Living bimetallic initiators for the preparation of triblock copolymers

The compound [(η-C₃H₅)Ni(OC(O)CF₃)]₂ ( I ), which has been used extensively as a butadiene polymerization catalyst and more recently as an isocyanide polymerization catalyst, has been successfully used in the preparation of polyisocyanide - polybutadiene block copolymers. Since both monomer polymerizations are living, this block copolymer synthesis is highly versatile with respect to polymer segment chain lengths and the types of monomers used. Because non-reciprocal end-group activities prevent the preparation of triblock copolymers of the type polyisocyanide-butadiene-polyisocyanide, bimetallic initiators possessing two allylnickel moieties linked through a central core have been prepared and used to synthesize these desirable triblock copolymers. These materials have been characterized by using gel-permeation chromatography, differential scanning calorimetry, ¹³C NMR and scanning electron microscopy.