Destabilization of model silica dispersions by polyelectrolyte complex particles with different charge excess,hydrophobicity, and particle size

Nonstoichiometric polyelectrolyte complex dispersions (PECs) with different charge excess and hydrophobicity as well as different average hydrodynamic particle size were used to induce flocculation of oppositely charged silica dispersions. PECs were formed with poly(diallyldimethylammonium chloride) (PD) as polycation and poly(styrene‐p‐sodium sulfonate) (NaPSS) and poly(acrylamide‐co‐sodium acrylate) (PR2540) as polyanions. PD was used as single polymer flocculant too. Flocculation process was characterized by optical densities of supernatants OD₅₀₀, by UV/VIS spectrometry, and determination of average floc sizes D(v; 0.5) as well as volume distribution of floc sizes by laser diffraction and determination of sedimentation velocity s by means of LUMiFuge? 114. It was found that the reaction process between silica and the used flocculants could be divided into three intervals (destabilization, flocculation optimum, and restabilization) as it is known for all other polymer flocculants. For an effective flocculation of a charged substrate, both electrostatic as well as hydrophobic interactions play an important role. The interval up to the beginning of the flocculation optimum is mainly ascertained by electrostatic interactions (the charge density of the flocculant) but the broadness of flocculation optimum depends largely on hydrophobic interactions. Hydrophobic interactions also play an important role for shear stability of the formed flocs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3776–3784, 2007     

Sorbents for removal surfactants from aqueous solutions: Surface modification of natural solids to enhance sorption ability

Particulate materials of natural origin, sulfite cellulose and two kaolinite clays, were modified by the formation of nonstoichiometric polyelectrolyte complex on the surface of particles. This resulted in positive surface charge on cellulose and clays. Modified materials as well as selected commercial polymers were used as sorbents for removal of anionic, nonionic, and cationic surfactants from aqueous solutions. It was stated that cationic surface modification of cellulose and kaolinite clays resulted in a significant increase of sorption rate and degree of removal of oppositely charged anionic surfactants. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1510–1515, 2004     

Structural investigations of aquatic humic substances by pyrolysis-field ionization mass spectrometry and pyrolysis-gas chromatography/mass spectrometry

The present state-of-the-art in structural investigations of aquatic humic substances and their fractions such as fulvic and humic acids by pyrolysis-field ionization mass spectrometry is outlined. An integrated approach to interpretation uses complementary data of elemental analysis, functional group determinations, Cu²⁺-complexation, H⁺-capacity and results from u.v.-vis- and FT-i.r.-spectroscopy. Proposed building blocks of the molecular structure are supported by chromatographic investigations using Curie-point Py-GC/MS and the available literature reports. The potential and limitation of the applied methodology are discussed.     

Characterization of the triterpenoid 4,4′-diaponeurosporene and its isomers in food-associated bacteria

4,4'-Diaponeurosporene isomers were identified by LC/MS in extracts obtained from bacteria isolated from food (three strains of Staphylococcus carnosus, Lactobacillus plantarum LTH 4936, and Enterococcus sulfureus DSM 6905^T) as well as from Enterococcus mundtii DSM 4838^T. In addition to the predominant all-trans-isomer, seven cis-isomers of the C30-carotenoid were detected. Triterpenoid carotenoids have not been found before neither in Staphylococci other than Staphylococcus aureus nor in any species of the genus Lactobacillus.     

Synthesis and thermoelectric properties of Rashba semiconductor BiTeBr with intensive texture

Bismuth tellurohalides with Rashba-type spin splitting exhibit unique Fermi surface topology and are developed as promising thermoelectric materials. However,BiTeBr, which belongs to this class of materials, is rarely investigated in terms of the thermoelectric transport properties. In the study, polycrystalline bulk BiTeBr with intensive texture was synthesized via spark plasma sintering(SPS). Additionally, its thermoelectric properties above room temperature were investigated along both the inplane and out-plane directions, and they exhibit strong anisotropy. Low sound velocity along two directions is found and contributes to its low lattice thermal conductivity. Polycrystalline BiTeBr exhibits relatively good thermoelectric performance along the in-plane direction,with a maximum dimensionless figure of merit(ZT) of 0.35 at 560 K. Further enhancements of ZT are expected by utilizing systematic optimization strategies.     

Monitoring the stability of nanosized silica dispersions in presence of polycations by a novel centrifugal sedimentation method

The stability of Aerosil‐silica dispersions is analyzed in dependence on the addition of polycations with different charge density and hydrophobic modification using the analytical centrifuge LUMiSizer. This novel centrifugal sedimentation method allows the direct calculation of the stability parameters like sedimentation velocity and prediction of the shelf life. The highly charged polycation poly (diallyl‐dimethylammonium chloride) (PDADMAC) is compared with tailored cationic polyelectrolytes of equal degree of polymerization but lower and different charge density as well as various hydrophobic substitutions. The used technique allows to accelerate demixing and to quantify the stability of dispersions in a direct way. All polymers under study are able to stabilize aerosil dispersions, but the shelf life strongly depends on the polymer concentration. Typically for polycations, the stability increases with the polymer concentration whereas at low‐polymer content flocculation can be detected. In this context, the behavior of PDADMAC and three cationic PVB derivatives is similar, but, whereas the stability of PDADMAC containing dispersions decreases at higher polymer concentrations, PVB derivatives are effective stabilizers at higher concentrations too. The highest increase of the stability with increasing polymer concentration is obtained with the ampholytic terpolymer TP that has the lowest cationic charge. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Applicability of ToF-SIMS for monitoring compositional changes in bone in a long-term animal model

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a well-established technique in material sciences but has not yet been widely explored for implementation in life sciences. Here, we demonstrate the applicability and advantages of ToF-SIMS analysis for the study of minerals and biomolecules in osseous tissue. The locally resolved analysis of fragment ions deriving from the sample surface enables imaging and differentiation of bone tissue and facilitates histology on non-stained cross sections. In a rat model, bilateral ovariectomy combined with either a multi-deficiency diet or steroid treatment was carried out to create osteoporotic conditions. We focused our study on the Ca content of the mineralized tissue and monitored its decline. Calcium mass images of cross sections show the progressive degenerative changes in the bone. We observed a decreased Ca concentration in the edge region of the trabeculae and a decline in the Ca/P ratio. Additionally, we focused on the non-mineralized matrix and identified fragment ions that are characteristic for the collagen matrix. We observed trabeculae with wide ranges of non-mineralized collagen for the diet group owing to an impaired mineralization process. Here, the advantage of coeval monitoring of collagen and minerals indicated an osteomalacic model rather than an osteoporotic one.     

Biological activities of malvidin, a red wine anthocyanidin

Malvidin (mv) has been identified as a potential inhibitor of 3',5'-cyclic adenosine monophosphate (cAMP) phosphodiesterases (PDE). This study was to investigate if, as a possible consequence of intracellular PDE inhibition, the activity of the mitogen-activated protein kinase (MAPK) cascade is affected by mv treatment. At a concentration of 5 microM of mv a significant decrease of phosphorylated ERK1 and ERK2 (ERK, extracellular regulated kinase) in HT29 cells was observed. However, an increase in substance concentration led to a substantial recurrence of the phosphorylated enzymes. Cell cycle analysis underlined that indeed G(1)-relevant targets are only marginally affected by mv. The recurrence of phosphorylated ERK1/2 and the lack of effectiveness on the G(1)-passage up to 100 microM indicated that the inhibition of cAMP-specific PDEs is of minor relevance for the growth-inhibitory properties of mv in HT29 cells. In contrast, the release of cells, synchronised in the G(2)/M-phase of the cell cycle by nocodazole treatment, was effectively blocked in the presence of 1 microM mv. These results suggest that mv interferes with cellular targets relevant for G(2)/M-progression which have not been identified so far.     

Identification of Queen Sex Pheromone Components of the Bumblebee Bombus terrestris

We investigated the origin and chemical composition of the queen sex pheromone of the primitively eusocial bumblebee, Bombus terrestris (Apidae). Physiologically and behaviorally active compounds were identified by coupled gas chromatography electroantennography (GC-EAD), gas chromatography-mass spectrometry (GC-MS), and laboratory behavioral tests. In the behavioral assays, virgin queens frozen previously at −20°C were highly attractive to males. Dummies impregnated with surface and cephalic extracts obtained from virgin queens that had been frozen at −50°C were more attractive to males than odorless dummies. Male mating behavior was stimulated by components of cephalic secretions that are smeared onto the cuticle surface by the queen. Overall, 21 compounds present in surface and cephalic extracts evoked electroantennographic responses in male antennae. These included saturated and unsaturated fatty acids, ethyl- and methyl esters of the fatty acids, heptacosene, 2-nonanone, and geranyl geraniol. A blend of synthetic versions of these compounds elicited typical male mating behavior. Since solvent-impregnated dummies were approached by the males, but did not release copulatory behavior, visual cues may be important in the initial step of stimulating male mating behavior. Close-range olfactory signals are more important for releasing male mating behavior as well as for species recognition. In further behavioral assays, the attractiveness of a frozen virgin queen decreased as the storage time at −20°C increased from 2 hr to 1 d. Therefore, the chemical composition of the sex pheromone may change during freezing as behaviorally active compounds may decompose.     

Effects of storage time and added antioxidant on fatty acid composition of red blood cells at −20°C

The stability of PUFA in venous red blood cells (RBC) of women aged 25 to 55 years (n=12) was investigated during storage at −20°C. The RBC sample from each participant was divided into seven portions: one baseline with the antioxidant BHT, another without BHT, samples without BHT stored for 2, 4, 9, or 17 wk, and samples with BHT stored for 17 wk. No difference was found in proportions of PUFA at baseline and after storage for 2 and 4 wk without BHT, and 17 wk with BHT. After 9 wk without BHT the proportion of 22∶6n−3 in RBC was lower, and after 17 wk without BHT proportions of all PUFA were lower than at baseline. High proportion of 22∶6n−3 in RBC at baseline was associated with more stable concentration of total FA in RBC without BHT during 17 wk. The findings indicate that PUFA in RBC from healthy women are stable at −20°C for 4 wk, without BHT and for at least 17 wk with BHT.