The analysis of polymeric 2,2,4-trimethyl-1,2-dihydroquinoline

Polymeric Dihydroquinolines, which are commonly used as antioxidants for macromolecular systems, were prepared by acid-catalyzed condensation of acetone with aniline. The final products may differ in quality according to the purity of the starting materials and conditions of preparation. In the present work, three commercial antioxidants of the type of polymeric 2,2,4-rimethyl-1,2-dihydroquinoline were mutually compared from the chemical point of view. Some of the components of the antioxidants were identified by mass spectrometry after prior separation using GPC and LLC-RP.     

High speed classification of individual bacterial cells using a model-based light scatter system and multivariate statistics

We describe a model-based instrument design combined with a statistical classification approach for the development and realization of high speed cell classification systems based on light scatter. In our work, angular light scatter from cells of four bacterial species of interest, Bacillus subtilis, Escherichia coli, Listeria innocua, and Enterococcus faecalis, was modeled using the discrete dipole approximation. We then optimized a scattering detector array design subject to some hardware constraints, configured the instrument, and gathered experimental data from the relevant bacterial cells. Using these models and experiments, it is shown that optimization using a nominal bacteria model (i.e., using a representative size and refractive index) is insufficient for classification of most bacteria in realistic applications. Hence the computational predictions were constituted in the form of scattering-data-vector distributions that accounted for expected variability in the physical properties between individual bacteria within the four species. After the detectors were optimized using the numerical results, they were used to measure scatter from both the known control samples and unknown bacterial cells. A multivariate statistical method based on a support vector machine (SVM) was used to classify the bacteria species based on light scatter signatures. In our final instrument, we realized correct classification of B. subtilis in the presence of E. coli,L. innocua, and E. faecalis using SVM at 99.1%, 99.6%, and 98.5%, respectively, in the optimal detector array configuration. For comparison, the corresponding values for another set of angles were only 69.9%, 71.7%, and 70.2% using SVM, and more importantly, this improved performance is consistent with classification predictions.     

Microwave characterization of nanostructured ferroelectric Ba(0.6)Sr(0.4)TiO(3) thin films fabricated by pulsed laser deposition

A series of nanostructured ferroelectric thin films of barium strontium titanate were fabricated using a pulsed laser deposition system with real-time in?situ process control. Pulsed laser deposition parameters were controlled during the growth of nanostructured thin films for use in the development of high frequency tunable microwave devices. The thin films were all grown at the same substrate temperature and laser beam energy density, but the chamber oxygen partial pressure (COPP) was varied systematically from 19?mTorr through 1000?Torr. Structural and electromagnetic characterization was performed using atomic force microscopy and evanescent microwave microscopy, respectively. Atomic force microscopy showed a linear increase in grain size with increases in the ambient oxygen pressure from 38 to 150?mTorr and from 300?mTorr to 1000?Torr. The correlation of the microwave properties with the epitaxial film microstructure can be attributed to stresses and polarizability in the film. Microwave characterization showed that a COPP of 75?mTorr yielded the most desirable film in terms of tunability and loss tangent over a wide frequency range.     

Biochemistry of PUFA double bond isomerases producing conjugated linoleic acid

The biotransformation of linoleic acid (LA) into conjugated linoleic acid (CLA) by microorganisms is a potentially useful industrial process. In most cases, however, the identities of proteins involved and the details of enzymatic activity regulation are far from clear. Here we summarize available data on the reaction mechanisms of CLA-producing enzymes characterized until now, from Butyrivibrio fibrisolvens, Lactobacillus acidophilus, Ptilota filicina, and Propionibacterium acnes. A general feature of enzymatic LA isomerization is the protein-assisted abstraction of an aliphatic hydrogen atom from position C-11, while the role of flavin as cofactor for the double bond activation in CLA-producing enzymes is also discussed with regard to the recently published three-dimensional structure of an isomerase from P. acnes. Combined data from structural studies, isotopic labeling experiments, and sequence comparison suggest that at least two different prototypical active site geometries occur among polyunsaturated fatty acid (PUFA) double bond isomerases.     

Unlocking the relationship of biotic integrity of impaired waters to anthropogenic stresses

The Clean Water Act expressed its goals in terms of restoring and preserving the physical, chemical and biological integrity of the Nation's waters. Integrity has been defined as the ability of the water body's ecological system to support and maintain a balanced integrated, adaptive community of organisms comparable to that of a natural biota of the region. Several indices of biotic integrity (IBIs) have been developed to measure quantitatively the biotic composition and, hence, the integrity. Integrity can be impaired by discharges of pollutants from point and nonpoint sources and by other pollution-related to watershed/landscape and channel stresses, including channel and riparian zone modifications and habitat impairment. Various models that link the stressors to the biotic assessment endpoints, i.e., the IBIs, have been presented and discussed. Simple models that link IBIs directly to single or multiple surrogate stressors such as percent imperviousness are inadequate because they may not represent a true cause-effect proximate relationship. Furthermore, some surrogate landscape parameters are irreversible and the relationships cannot be used for development of plans for restoration of the water body integrity. A concept of a layered hierarchical model that will link the watershed, landscape and stream morphology pollution stressors to the biotic assessment endpoints (IBIs) is described. The key groups of structural components of the model are: IBIs and their metrics in the top layer, chemical water and sediment risks and a habitat quality index in the layer below, in-stream concentrations in water and sediments and channel/habitat impairment parameters in the third layer, and watershed/landscaper pollution generating stressors, land use change rates, and hydrology in the lowest layer of stressors. A modified and expanded Maximum Species Richness concept is developed and used to reveal quantitatively the functional relationships between the top two layers of the structural components and parameters of the model.     

"Soft and rigid" dithiols and Au nanoparticles grafting on plasma-treated polyethyleneterephthalate

ABSTRACT: Surface of polyethyleneterephthalate (PET) was modified by plasma discharge and subsequently grafted with dithiols (1, 2-ethanedithiol (ED) or 4, 4'-biphenyldithiol) to create the thiol (-SH) groups on polymer surface. This "short" dithiols are expected to be fixed via one of -SH groups to radicals created by the plasma treatment on the PET surface. "Free" -SH groups are allowed to interact with Au nanoparticles. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and electrokinetic analysis (EA, zeta potential) were used for the characterization of surface chemistry of the modified PET. Surface morphology and roughness of the modified PET were studied by atomic force microscopy (AFM). The results from XPS, FTIR, EA and AFM show that the Au nanoparticles are grafted on the modified surface only in the case of biphenyldithiol pretreatment. The possible explanation is that the "flexible" molecule of ethanedithiol is bounded to the activated PET surface with both -SH groups. On the contrary, the "rigid" molecule of biphenyldithiol is bounded via only one -SH group to the modified PET surface and the second one remains "free" for the consecutive chemical reaction with Au nanoparticle. The gold nanoparticles are distributed relatively homogenously over the polymer surface.     

Hydrolase-like properties of a cofactor-independent dioxygenase

Mechanistic promiscuity: The (2-alkyl)-3-hydroxy-4(1H)-quinolone-cleaving dioxygenase Hod has an α/β-hydrolase fold and a Ser/His/Asp triad in its active site. Isatoic anhydride, a suicide substrate of serine hydrolases, inactivates Hod by covalent modification of the active-site serine, thus indicating that the α/β-hydrolase fold can accommodate dioxygenase chemistry without completely abandoning hydrolase-like properties.     

Novel Hybrid Compounds Containing Benzofuroxan and Aminothiazole Scaffolds: Synthesis and Evaluation of Their Anticancer Activity

A series of novel hybrid compounds containing benzofuroxan and 2-aminothiazole moieties are synthesized via aromatic nucleophilic substitution reaction. Possible reaction pathways have been considered quantum-chemically, which allowed us to suggest the most probable products. The quantum chemical results have been proved by X-ray data on one compound belonging to the synthesized series. It was shown that the introduction of substituents to both the thiazole and amine moieties of the compounds under study strongly influences their UV/Vis spectra. Initial substances and obtained hybrid compounds have been tested in vitro as anticancer agents. Target compounds showed selectivity towards M-HeLa tumor cell lines and were found to be more active than starting benzofuroxan and aminothiazoles. Furthermore, they are considerably less toxic to normal liver cells compared to Tamoxifen. The mechanism of action of the studied compounds can be associated with the induction of apoptosis, which proceeds along the mitochondrial pathway. Thus, new hybrids of benzofuroxan are promising candidates for further development as anticancer agents.     

Determination of antioxidant activity and antioxidant content in tomato varieties and evaluation of mutual interactions between antioxidants

Major antioxidants and antioxidant activity in eight varieties of tomatoes were determined. Hydrophilic and lipophilic antioxidant activity (HAA and LAA) was determined by the ABTS assay and ascorbic acid and carotenoid contents were determined by HPLC-DAD. The HAA has far more significant impact on total antioxidant activity (83%) as compared with LAA. HAA was increasing during all ripening stages and was strongly correlated with ascorbic acid content (r = 0.83). During the ripening the LAA was increasing till the III. stage of maturity and then decreased. The main carotenoids determined in the red-fruit tomatoes were lycopene, β-carotene and lutein. The content of lycopene has been increasing equally during the ripening. β-Carotene and lutein were intensively synthesized between the I. and II. stage of maturity. Among ascorbic acid, α-tocopherol, lycopene, β-carotene and lutein standards ascorbic acid was determined as the most efficient antioxidant followed by α-tocopherol and β-carotene. Antioxidant activity of ascorbic acid, α-tocopherol, β-carotene and lutein grew equally with increasing concentration, however lycopene was the most effective in its lowest concentration. The analysis of two-component mixtures showed significant synergism between lycopene-lutein, lycopene-β-carotene and α-tocopherol-β-carotene.