Adsorption of bacteria and polycations on model surfaces of cellulose, hemicellulose and wood extractives studied by QCM-D

Quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) were used as the tools to study the adsorption of bacteria onto surfaces of silica and polystyrene coated with materials related to papermaking. Cationic polyelectrolytes used as fixatives and retention aids in paper industry were found to promote irreversible adsorption of the ubiquitous white water bacterium, Pseudoxanthomonas taiwanensis, onto model surfaces of cellulose (pH 8). The high charged low molecular weight polyelectrolyte, poly(diallyldimethyl) ammonium chloride (pDADMAC) adsorbed to silica surface as a flat and rigid layer, whereas the low charged cationic polyacryl amide (C-PAM) of high molecular weight adsorbed as a thick and loose layer. AFM images showed that the polyelectrolytes accumulated as layers around each bacterial cell. In the presence of wood hemicellulose (O-acetyl-galactoglucomannan) the bacteria adsorbed massively, as large, tightly packed rafts (up to 0.05mm in size) onto the polystyrene crystal surface coated with wood extractives (pH 4.7). AFM and FESEM micrographs also showed large naked areas (with no bacteria) in between the bacterial rafts on the crystal surface. In this case, QCM-D only incompletely responded to the massiveness of the bacterial adsorption. The results indicate that cationic polymers can be used to increase the retention of bacteria from the process water onto the fibre web and that, depending on the balance between hemicelluloses and wood extractives and pH of the process waters, bacteria can be drawn from process waters onto surfaces.     

Desorption of bottle-brush polyelectrolytes from silica by addition of linear polyelectrolytes studied by QCM-D and reflectometry

The possibility of exchanging adsorbed layers of PEO(45)MEMA:METAC-X brush polyelectrolytes (with two different charge densities, 10 and 75 mol%, denoted by X), with poly(MAPTAC), a highly charged linear polyelectrolyte, was investigated by quartz crystal microbalance with dissipation and reflectometry. The studies were conducted on a silica substrate at pH 10, conditions under which only electrostatic interactions are effective in the adsorption process. Based on the results, it was concluded that PEO(45)MEMA:METAC-10 forms an inhomogeneous layer at the interface through which poly(MAPTAC) chains can easily diffuse to reach the surface. On the other hand, the PEO(45)MEMA:METAC-75 layer was not affected when exposed to a poly(MAPTAC) solution. We argue that the observed effect for PEO(45)MEMA:METAC-75 is due to the formation of a homogeneous protective brush layer, in combination with the small difference in surface affinity between the bottle-brush polyelectrolyte and poly(MAPTAC), together with the difficulty of displacing highly charged polyelectrolyte chains once they are adsorbed on the oppositely charged surface. We also use the combination of QCM-D and reflectometry data to calculate the water content and layer thickness of the adsorbed layers.     

Probing protein adsorption onto mercaptoundecanoic acid stabilized gold nanoparticles and surfaces by quartz crystal microbalance and zeta-potential measurements

The adsorption characteristics of three proteins [bovine serum albumin (BSA), myoglobin (Mb), and cytochrome c (CytC)] onto self-assembled monolayers of mercaptoundecanoic acid (MUA) on both gold nanoparticles (AuNP) and gold surfaces (Au) are described. The combination of quartz crystal microbalance measurements with dissipation (QCM-D) and pH titrations of the zeta-potential provide information on layer structure, surface coverage, and potential. All three proteins formed adsorption layers consisting of an irreversibly adsorbed fraction and a reversibly adsorbed fraction. BSA showed the highest affinity for the MUA/Au, forming an irreversibly adsorbed rigid monolayer with a side-down orientation and packing close to that expected in the jamming limit. In addition, BSA showed a large change in the adsorbed mass due to reversibly bound protein. The data indicate that the irreversibly adsorbed fraction of CytC is a monolayer structure, whereas the irreversibly adsorbed Mb is present in form of a bilayer. The observation of stable BSA complexes on MUA/AuNPs at the isoelectric point by zeta-potential measurements demonstrates that BSA can sterically stabilize MUA/AuNP. On the other hand, MUA/AuNP coated with either Mb or CytC formed a reversible flocculated state at the isoelectric point. The colloidal stability differences may be correlated with weaker binding in the reversibly bound overlayer in the case of Mb and CytC as compared to BSA.     

Nitroxide‐Mediated Controlled/Living Free Radical Copolymerization of Styrene and Divinylbenzene in Aqueous Miniemulsion

Summary: The nitroxide‐mediated controlled/living free radical copolymerization of styrene and divinylbenzene using a polystyrene‐TEMPO macroinitiator in aqueous miniemulsion and in bulk have been investigated. The crosslink densities were estimated based on the content of pendant vinyl groups as determined by ¹H NMR. Considerably lower crosslink densities were revealed in the miniemulsion than in the corresponding bulk system. The rate of polymerization in the miniemulsion increased with decreasing particle size, and was significantly higher than in bulk.

Crosslink density for the TEMPO‐mediated free radical copolymerization of S(1) and DVB(2) (f = 0.99, f = 0.01) at 125 °C in bulk (□) and in miniemulsions with d_n = 585 nm (○) and 53.3 nm (•).     

Interactions between bottle-brush polyelectrolyte layers: effects of ionic strength and oppositely charged surfactant

Interactions between cationic bottle-brush polyelectrolyte layers adsorbed on mica across salt and oppositely charged surfactant solutions were investigated with the interferometric surface force apparatus, and the results were compared with what is known for similarly charged linear polyelectrolytes. Ellipsometric measurements demonstrated that the bottle-brush polyelectrolytes, which contain 45 units long poly(ethylene oxide) side chains, are more readily desorbed than linear equivalents when the ionic strength of the solution is increased. It is argued that this is due to the steric repulsion between the poly(ethylene oxide) side chains that reduces the surface affinity. The preadsorbed bottle-brush polyelectrolyte layers were also exposed to sodium dodecyl sulfate (SDS) solutions. It was found that the presence of SDS affected the force profiles less than observed for similarly charged linear polyelectrolytes. This observation was attributed to excluded volume constraints imposed by the poly(ethylene oxide) side chains that reduces the accessibility of the charged polyelectrolyte segments and counteracts formation of large aggregates within the layer.     

Urine profiling using capillary electrophoresis-mass spectrometry and multivariate data analysis

This work presents the development of a general and fast method for metabolic profiling of urine, using capillary electrophoresis-electrospray ionisation mass spectrometry (CE-ESIMS) and multivariate data analysis (DA). Human urine samples collected before and after ingestion of paracetamol were analysed at acidic and basic CE conditions, using both positive and negative ESI-MS detection. Analysis of the entire resulting data set, with no prior knowledge of the target compounds, using pair-wise 'fuzzy' correlation and eigenvalue analysis enabled the samples to be discriminated between on the basis of blank urine and urine collected after drug intake. By generating two-dimensional loadings plots, it was also possible to identify the m/z values of the substances responsible for the differentiation between control and dosed samples.     

The homogeneity of heavy metal deposition on glass fibre filters collected using a high-volume sampler in the vicinity of an opencast chrome mine complex at Kemi,Northern Finland

The homogeneity of heavy metal (Cr, Ni, Cu, Fe and Cd) distribution on glass fibre filters (Munktell MG 160, 203 x 254 mm, 75 g m(-2)) collected using a high-volume sampler (Wedding & Associates) at an opencast chrome mine complex at Kemi, Northern Finland was studied. The heavy metals in the total suspended particulate (TSP) material were analysed by inductively coupled plasma atomic emission spectrometry (ICP-AES) or graphite furnace atomic absorption spectrometry (GFAAS). The glass fibre filters were digested in a microwave oven using a mixture of aqua regia+HF acids. There was significant non-uniform distribution of heavy metals on glass fibre filters. The TSP material containing chromite was very difficult to dissolve by acid digestion. The results from X-ray fluorescence spectrometry (XRF), and from energy filtering transmission electron microscope (EFTEM) equipped with energy dispersive X-ray spectrometer (EDS), showed that insoluble residue left after microwave oven digestion with aqua regia+HF acids was probably partly due to chemical reactions occurring during microwave heating.     

Flame-atomic absorption analysis for trace metals after electrochemical preconcentration on a wire filament

To avoid unspecific light losses in the atomic absorption analysis of trace metals in the presence of a high concentration of salts, electrochemical preconcentration on a wire filament is employed, prior to flame atomization. The elements in question are electrolyzed on to a platinum spiral filament which is then heated in an air-acetylene flame. A quartz tube is placed above the filament, to increase the sensitivity of the method. The separation technique is simple and non-destructive; a sample volume of 5–20 ml and an electrolysis time of 2–5 min are recommended. Because of the relatively low filament temperature, the method is limited to elements which are readily volatilized such as silver, bismuth, cadmium, mercury, lead, selenium, tellurium, thallium and zinc. For most elements, the detection limits are of the same order of magnitude as those of the “Delves cup” technique.     

Chromatographic analysis of alkylresorcinols and their metabolites

Alkylresorcinols (AR) are phenolic lipids present in high amounts in the bran fraction of wheat and rye. AR are of scientific interest as bioactive compounds, as markers for the presence of wholegrain or bran fractions of wheat and rye in food products, and as possible biomarkers of intake for wholegrain wheat and rye. This review discusses their extraction from cereal grains, food and biological fluids, and the various chromatographic methods used in their analysis.     

Orientation and conformation of cell-penetrating peptide penetratin in phospholipid vesicle membranes determined by polarized-light spectroscopy

The orientation and conformation of the cell-penetrating peptide "penetratin" associated with phospholipid vesicle membranes has been determined using polarized-light spectroscopy. The magnitude of orientation of penetratin is unprecedented for a solute in our membrane system, which we believe indicates a strong, specific interaction with the membrane. To validate the spectroscopic technique for studying the orientation of the two tryptophan residues of penetratin, we applied tryptophan octyl ester as a model compound. It is found to be incorporated in the membrane and preferentially oriented with its hydrophobic benzene edge of the indole chromophore pointing into the membrane and its hydrophilic groups oriented toward the water. For penetratin, the results indicate that a central alpha-helical part of the peptide is aligned parallel with the membrane surface, while the ends of the peptide adopt a planar structure. The planes of the two tryptophan side chains show a preferred orientation parallel with the membrane surface, indicating that they are not inserted into the membrane.