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Monomer-solvent phase separation in one-step self-etch adhesives.

One-step adhesives bond less effectively to enamel/dentin than do their multi-step versions. To investigate whether this might be due to phase separation between adhesive ingredients, we characterized the interaction of 5 experimental and 3 commercial self-etch adhesives with dentin using transmission electron microscopy. All adhesives were examined for homogeneity by light microscopy. Bonding effectiveness to dentin was determined with the use of a micro-tensile bond-strength protocol. The lower bond strength of the one-step adhesives was associated with light-microscopic observation of multiple droplets that disappeared slowly. Interfacial analysis confirmed the entrapment of droplets within the adhesive layer. The prompt disappearance of droplets upon application of a small amount of HEMA (2-hydroxyethyl methacrylate) or a HEMA-containing bonding agent, as well as the absence of droplets at the interface of all HEMA-containing adhesives, strongly suggests that the adhesive monomers separate from water upon evaporation of ethanol/acetone. Upon polymerization, the droplets become entrapped within the adhesive, potentially jeopardizing bond durability. This can be avoided by strong air-drying of the adhesive, thereby removing interfacial water and thus improving bonding effectiveness.

Acid Etching, Dental↗

Physicochemical evaluation of bioactive polymeric composites based on hybrid amorphous calcium phosphates.

Amorphous calcium phosphate (ACP)-filled methacrylate composites were recently found to effectively remineralize in vitro caries-like enamel lesions. Their inferior mechanical properties compared to glass-filled composites, however, limit their use as a dental restorative material. In this study, the feasibility of introducing glass-forming elements (tetraethoxysilane or zirconyl chloride) during the low-temperature synthesis of ACP was investigated. Composites based on such hybrid fillers (mass fraction, 40%) were evaluated to establish whether hybridization strengthened the composites via improved interfacial interactions with the polymer phase without compromising the release of the mineral ions. Two types of visible-light cured resins were prepared: BTHZ resin from 2, 2-bis[p-(2'-hydroxy-3'-methacryloxypropoxy)phenyl]propane (BisGMA), triethylene glycol dimethacrylate (TEGDMA), 2-hydroxyethyl methacrylate (HEMA) and zirconyl methacrylate (ZrM), and TP resin from TEGDMA and pyromellitic glycerol dimethacrylate (PMGDM). Hybridized fillers and BTHZ- and TP-based composites were characterized by the IR spectroscopy, X-ray diffraction, dissolution/transformation kinetic studies, and biaxial flexure strength (BFS) testing before and after immersion in buffered saline solutions. The feasibility of improving the BFS via hybridization, while retaining, if not enhancing the remineralizing potential was demonstrated for BTHZ-based composites. Both BFS and remineralizing ability of the TP-composites, however, deteriorated upon their exposure to an aqueous environment. Therefore, hybridized ACP-filled BTHZ composites have a potential for utilization in more demanding restorative, sealant, and adhesive applications.

Calcium Phosphates↗

Characteristics of manganese-coated sand using SEM and EDAX analysis.

"Manganese-coated sand" is a type of silica medium coated with manganese oxides, formed from the sorption of manganese oxides during long-term filtration via the process of rapid sand filtration, followed by aeration in a water treatment plant. Locally available manganese-coated sand, both for packing and as a byproduct of filtration processes for water treatment plants in Taiwan, was found to be a low-cost and promising adsorbent for removal of Mn(2+) from raw water. This study was conducted to build the basic data for coating hydrated manganese oxide on the sand surface to utilize the adsorbent properties of the coating and the filtration properties of the sand. In this study, gas adsorption porosimetry and scanning electron microscopy analyses were used to investigate the surface properties of the coated layer. An energy dispersive X-ray (EDAX) technique of analysis was used to characterize metal adsorption sites on a manganese-coated sand surface. Results indicated that manganese-coated sand had more micropores and higher specific surface area, owing to attachment of manganese sand. Manganese ions penetrated into the micropores and mesopores of manganese oxide on a sandy surface; regeneration of manganese-coated sand could be achieved by soaking with pH < 2.0 acid solution. Results of EDAX analysis showed that the interfacial layer constructed the interface of manganese-coated sand. Acid and alkali resistance tests interpret a wide application range of pH for manganese-coated sand, and general temperature conditions do not affect the performance of this sand. Manganese-coated sand is potentially suitable for application as a packed bed for treatment of heavy metals from water. The results of this study can also benefit plant operational capacity data for engineering design.

Adsorption↗

Characterization of bacterial isolates from industrial wastewater according to probable modes of hexadecane uptake.

Bacterial isolates from industrial wastewater were characterized according to probable modes of hexadecane uptake based on data for cell surface hydrophobicity, emulsifying activity, glycoside content and surface tension of cell-free culture medium. The results obtained suggested that both modes of biosurfactant-enhanced hexadecane uptake by bacterial strains take place, direct uptake and alkane transfer. The increase in cell surface hydrophobicity and glycoside production by the strains suggested the existence of biosurfactant-enhanced interfacial uptake of the alkane. Such mechanism is probably predominant for three isolates, Staphylococcus sp. HW-2, Streptococcus sp. HW-9 and Bacillus sp. HW-4. Secreted biosurfactants enhanced mainly alkane emulsification for most hydrophobic isolate Arthrobacter sp. HW-8, and micellar transfer for most hydrophilic isolate Streptococcus sp. HW-5. For other strains (67%) both mechanisms of biosurfactant-enhanced hexadecane uptake probably take place in similar degree, interfacial uptake and alkane emulsification. The results obtained could contribute to clarifying the natural relationships between the members of water ecosystem studied as well as will reveal potential producers of surface active compounds.

Alkanes↗

Human pancreatic triglyceride lipase expressed in yeast cells: purification and characterization.

A cDNA clone encoding human pancreatic triglyceride lipase was cloned into a yeast expression vector so that the yeast PHO1 signal peptide replaced the native signal peptide. Pichia pastoris cells were transfected with the vector, and clones expressing human pancreatic triglyceride lipase were isolated. Recombinant human pancreatic lipase was expressed in broth cultures and was purified from the medium by DEAE blue Sepharose and hydroxyapatite chromatography. The highly purified lipase had specific activities for various triglyceride substrates identical to those of tissue-purified human pancreatic triglyceride lipase; it was inhibited by bile salts, required colipase for activity, and demonstrated interfacial activation. This expression system is suitable for the rapid, efficient production of human pancreatic triglyceride lipase in amounts adequate for biophysical studies.

Amino Acid Sequence↗

Biochemical and molecular characterization of a lipase produced by Rhizopus oryzae.

A novel strain of Rhizopus oryzae WPG secretes a noninduced lipase (ROLw) in the culture medium; purified ROLw is a protein of 29 kDa, the 45 N-terminal amino acid residues were sequenced, this sequence is very homologous to Rhizopus delemar lipase (RDL), Rhizopus niveus lipase (RNL) and R. oryzae lipase (ROL29) sequences; the cloning and sequencing of the part of the gene encoding the mature ROLw, shows two nucleotides differences with RDL, RNL and ROL29 sequences corresponding to the change of the residues 134 and 200; ROLw does not present the interfacial activation phenomenon when using tripropionin or vinyl propionate as substrates; the lipase activity is maximal at pH 8 and at 37 degrees C, specific activities of 3500 or 900 U mg(-1) were measured at 37 degrees C and at pH 8, using olive oil emulsion or tributyrin as substrates, respectively; ROLw is unable to hydrolyse triacylglycerols in the presence of high concentration of bile salts; it is a serine enzyme as it is inhibited by tetrahydrolipstatin and was stable between pH 5 and pH 8.

Amino Acid Sequence↗

Dielectric characterization of a nanofiltration membrane in electrolyte solutions: its double-layer structure and ion permeation.

Dielectric spectroscopy (DS) was applied to a nanofiltration (NF) membrane to detect its double-layer structure and ion permeation. Dielectric measurements were carried out on the systems composed of the NF membrane NTR7450 and dilute solutions of eight electrolytes, LiCl, NaCl, KCl, NH(4)Cl, MgCl(2), CaCl(2), BaCl(2), and CuCl(2). Two relaxations were observed in the frequency range from 40 Hz to 4 MHz for each system. On the basis of characteristics of the dielectric spectra and the Maxwell-Wagner interfacial polarization theory, the low-frequency relaxation was attributed to inhomogeneity of the membrane structure itself, whereas the high-frequency relaxation was attributed to interfacial polarization between the membrane and the solution. A multiphase dielectric model previously developed by one of the authors and co-workers was adopted to present systems to analyze the dielectric spectra, and electric parameters, i.e., capacitance and conductance, of the two layers composing the membrane were obtained. The electric properties estimated for the two layers were different and changed with the environment in a different manner. Further analyses suggest that the two layers had a different separation mechanism due to their difference in materials, looseness, and fixed charge content. The fixed charge density of one layer was estimated, and the ion permeation difficulties in both layers was compared. This research revealed that DS was by far an effective method to obtain detailed electric parameters about the inner multilayer structure of the NF membrane and to elucidate separation mechanisms of each layer.

Journal Article↗

A morphometric analysis of the muscle-tendon junction.

Transmission of the contractile force produced by skeletal muscle fibers from myofilaments to tendon fibers occurs at the muscle-tendon junction. This interface between muscle and tendon is characterized by an amplification of the membrane area across which force is transmitted, with the result that stress at the muscle-tendon interface is less than it would be if the muscle fiber ended without surface folding. The amount of stress reduction is proportional to the degree of surface amplification. Because an understanding of the mechanical properties of the muscle-tendon junction requires a quantitative appreciation of the amplification of interfacial area, and hence the reduction of stress, produced by membrane elaboration at the muscle-tendon junction, we have developed a reliable morphometric approach for quantifying this surface amplification. The approach reported here makes use of point-counting techniques applied to thin sections of murine muscle-tendon junctions, together with a statistical analysis of the data. The results indicate that the load on the cell membrane at the muscle-tendon junction is reduced approximately 1 order of magnitude by membrane amplification, compared to the load calculated to occur if the muscle fiber ended as a right cylinder. In addition, significant differences in the degree of membrane amplification have been detected among the four muscle-tendon junctions analyzed in this study. These results and methods should prove useful in future analyses of normal and abnormal muscle-tendon junctions.

Analysis of Variance↗

Hydrodynamic focusing investigation in a micro-flow cytometer.

Hydrodynamic focusing behavior is characterized by two fluids coflowing at different velocities inside a micro-flow cytometer. In this study, a two-fluid model has been established to describe the flow transport behavior and interaction of sample and sheath fluids. The analysis treats the sample and sheath fluids as two-dimensional, laminar, incompressible, and isothermal. The theoretical model comprises two groups of transient conservation equations of mass and momentum with consideration of the interfacial momentum exchange. The governing equations are solved numerically through an iterative SIMPLEC algorithm to determine the flow properties. Since the ratio of the sheath velocity to the sample velocity varies from 5 to 70, the predicted focusing width and length are in good agreement with the experimental data in the literature. In addition, the present study explored the hydrodynamic focusing flowfield as well as the pressure drop across a micro-flow cytometer and the time needed for the completion of one focusing event in detail. To enhance the understanding of hydrodynamic focusing in the design of cytometers, ten numerical experiments were conducted to examine the effects of the inner nozzle length, inner nozzle exit width, inner nozzle shape, and fluid properties on the width of the focused sample stream.

Computer Simulation↗

Quantitative measurements of contact interactions between solid surfaces--a novel method for characterizing surface properties of biomaterials.

A method developed in colloid chemistry for quantitative measurements of adhesion forces in dispersive systems was adapted for the characterization of surface properties of biomaterials in electrolyte solutions and in the presence of macromolecular adsorption layers. The adhesion force between a reference surface (glass) and different polymers (polyurethanes and cellulose derivatives) was found to be dependent on the immersion time of polymers in electrolyte and on the formation of adsorption layers of serum albumin and fibrinogen. It was concluded that the adhesion forces measured can be considered as a further complex interfacial parameter reflecting such microscopic surface properties of biomaterials, which are responsible for biocompatibility.

Adhesiveness↗

Blood compatibility of thermoplastic polyurethane membrane immobilized with water-soluble chitosan/dextran sulfate.

Water-soluble chitosan (WSC)/dextran sulfate (DS) was immobilized onto the surface of thermoplastic polyurethane (TPU) membrane after ozone-induced graft polymerization of poly(acrylic acid) (PAA). The surface was characterized with contact angle measurement and X-ray photoelectron spectroscopy (XPS). The adsorption of human plasma fibrinogen (HPF) followed the Langmuir adsorption isotherm. The results showed that the surface density of peroxides generated and poly(acrylic acid) (PAA) grafted reached the maximum value at 20 min of ozone treatment. It was found that the WSC- and DS-immobilized amount increased with pH and the molecular weight of WSC. The membrane/water interfacial free energy increased with PAA-grafting and WSC/DS-immobilization, indicating the increasing wettability of TPU membrane. The adsorption of HPF on TPU-WSC/DS membranes could be effectively curtailed and exhibited unfavorable adsorption. Moreover, WSC/DS immobilization could effectively reduce platelet adhesion and prolong the blood coagulation time, thereby membrane improving blood compatibility of TPU membrane. In addition, the in vitro cytotoxicity test of PEC modification was non-cytotoxic according to much low growth inhibition of L929 fibroblasts. Furthermore, TPU-WSC/DS membranes exhibited higher cell viability than native TPU membrane.

Acrylic Resins↗

Structured water in partially dehydrated yeast cells and at partially hydrophobized fumed silica surface.

Nonfreezable water structured due to interaction with endocellular objects in yeast cells (endocellular water) or with partially hydrophobic fumed silica (interfacial water) was studied by means of (1)H NMR spectroscopy with layer-by-layer freezing-out of bulk water and quantum chemical methods applied to water clusters in the gas and liquid (chloroform and cyclohexene) phases and adsorbed on silylated silica. Variation in cell hydration as well as in amount of water adsorbed on modified fumed silica leads to changes in the ratio between contributions of two water states characterized by NMR chemical shifts at delta(H)=1.1-1.7 and 4-5 ppm. Lowering of hydration and temperature results in an enhancement of the first signal, and the opposite result is observed for the second signal. These effects may be explained by structured water distribution in the form of relatively large nanodroplets (delta(H)=4-5 ppm is close to that for bulk water) and small clusters of the 2D structure, in which the fraction of hydrogen atoms out of the hydrogen bonds (delta(H)=1.1-1.7 ppm) is larger than that in nanodroplets.

Desiccation↗

Colloidal crystallization and banding in a cylindrical geometry.

Colloidal crystallization takes advantage of the strong interfacial forces and tunable interactions that organize particles into regular structures at small scales. Thus, colloidal crystallization and patterning provide a powerful and simple method to functionalize planar surfaces with applications to optical, catalytic, sensing, and cleansing materials. Nevertheless, the ability to pattern topologically more complex surfaces such as curved, confined, or soft substrates can open new avenues for novel, "intelligent", and responsive materials. We present one step in this direction by characterizing colloidal crystallization inside circular capillaries: a nearly periodic banding is observed, and the colloidal packing is dictated by confinement produced by the wedge-like region formed by a capillary confined meniscus. The packing consists of a succession of hexagonally close-packed regions, which are separated by narrow regions of "buckled phase crystals".

Journal Article↗

Lactobionamide surfactants with hydrogenated, perfluorinated or hemifluorinated tails: physical-chemical and biochemical characterization.

Detergents are customarily used to solubilize cell membranes and keep membrane proteins soluble in aqueous buffers, but they often lead to irreversible protein inactivation. Hemifluorinated amphiphiles with hybrid hydrophobic chains have been specifically designed to minimize the denaturating propensity of surfactants toward membrane proteins. We have studied the physical-chemical and biochemical properties of lactobionamide surfactants bearing either a hydrogenated, a fluorinated or a hemifluorinated chain (respectively H-, F-, and HF-Lac). We show that the dual composition of the hydrophobic chain of HF-Lac endows it with unusual physical-chemical properties as regards its critical micellar concentration, interfacial area per molecule, and behavior upon reverse phase chromatography. Analytical ultracentrifugation shows that, whereas H-Lac assembles into well-defined micelles, F-Lac and HF-Lac form large and heterogeneous assemblies, whose size increases with surfactant concentration. Molecular dynamics calculations suggest that F-Lac forms cylindrical micelles. The ability of HF-Lac to keep membrane proteins soluble was examined using the cytochrome b(6) f complex from Chlamydomonas reinhardtii's chloroplast as a model protein. HF-Lac/b(6) f complexes form particles relatively homogeneous in size, in which the b(6) f complex is as stable or markedly more stable, depending on the surfactant concentration, than it is in equivalent concentrations of hydrogenated surfactants, including H-Lac.

Biochemical Phenomena↗

Nanoscale lead and noble gas inclusions in aluminum: structures and properties.

Transmission electron microscopy has been used for structural and physical characterization of nanoscale inclusions of lead and noble gases in aluminum. When the inclusion sizes approach nanoscale dimensions, many of their properties are seen to deviate from similar properties in bulk and in most cases the deviations will increase as the inclusion sizes decrease. Binary alloys of lead and noble gases with aluminum are characterized by extremely low mutual solubilities and inclusions will, therefore, exist as practically pure components embedded in the aluminum matrix. Furthermore, the thermal vacancy mobility in aluminum at and above room temperature is sufficiently high to accommodate volume strains associated with the inclusions thus leading to virtually strain free crystals. The inclusions grow in parallel cube alignment with the aluminum matrix and have a cuboctahedral shape, which reflects directly the anisotropy of the interfacial energies. Inclusions in grain boundaries can have single crystalline or bicrystalline morphology that can be explained from a generalized Wulff analysis such as the xi-vector construction. The inclusions have been found to display a variety of nanoscale features such as high Laplace pressure, size-dependent superheating during melting, deviations from the Wulff shape displaying magic size effects, a shape dependence of edge energy, and so on. All these effects have been observed and monitored by TEM using conventional imaging conditions and high-resolution conditions in combination with in-situ analysis at elevated temperatures.

Algorithms↗

Investigation of surface properties of amino acids: polarity scale for amino acids as a means to predict surface exposed residues in films of proteins.

It is of great interest and importance to study how different amino acid residues contribute to and affect the properties of proteins coated as films on solid surface. This work shows that the solid/liquid interfacial energy of surface localized amino acid films and their Gibbs energies of transfer at the air/solution interface have the potential to be used as a rapid and simple method for studying the surface properties of proteins. Based on these results, a new polarity scale for amino acids has been proposed. This scale is compared with existing hydropathy scales in a benchmark test using some proteins with solved 3D structure. The proteins were characterized in terms of surface-exposed residues with a computer program, Graphical Representation and Analysis of Surface Properties (GRASP). It was also shown that each amino acid contribution is relative to the total protein surface and the other residues on the surface.

Amino Acids↗

Structure, composition, and peptide binding properties of detergent soluble bilayers and detergent resistant rafts.

Lipid bilayers composed of unsaturated phosphatidylcholine (PC), sphingomyelin (SM), and cholesterol are thought to contain microdomains that have similar detergent insolubility characteristics as rafts isolated from cell plasma membranes. We chemically characterized the fractions corresponding to detergent soluble membranes (DSMs) and detergent resistant membranes (DRMs) from 1:1:1 PC:SM:cholesterol, compared the binding properties of selected peptides to bilayers with the compositions of DSMs and DRMs, used differential scanning calorimetry to identify phase transitions, and determined the structure of DRMs with x-ray diffraction. Compared with the equimolar starting material, DRMs were enriched in both SM and cholesterol. Both transmembrane and interfacial peptides bound to a greater extent to DSM bilayers than to DRM bilayers, likely because of differences in the mechanical properties of the two bilayers. Thermograms from 1:1:1 PC:SM:cholesterol from 3 to 70 degrees C showed no evidence for a liquid-ordered to liquid-disordered phase transition. Over a wide range of osmotic stresses, each x-ray pattern from equimolar PC:SM:cholesterol or DRMs contained a broad wide-angle band at 4.5 A, indicating that the bilayers were in a liquid-crystalline phase, and several sharp low-angle reflections that indexed as orders of a single lamellar repeat period. Electron density profiles showed that the total bilayer thickness was 57 A for DRMs, which was approximately 5 A greater than that of 1:1:1 PC:SM:cholesterol and 10 A greater than the thickness of bilayers with the composition of DSMs. These x-ray data provide accurate values for the widths of raft and nonraft bilayers that should be important in understanding mechanisms of protein sorting by rafts.

1,2-Dipalmitoylphosphatidylcholine↗

The mechanism of the solute-induced chain interdigitation in phosphatidylcholine vesicles and characterization of the isothermal phase transitions by means of dynamic light scattering.

A new method is introduced for the detection of chain interdigitation in phospholipid bilayers. The same method is used to measure the hydrocarbon tilt in the dipalmitoylphosphatidylcholine membranes as a function of the bulk concentration of the interdigitation-inducing solutes, such as ethanol. The hydrocarbon tilt in the phosphatidylcholine bilayers is demonstrated to be limited to angles below approx. 51 degrees. The need for higher tilt values leads to bilayer interdigitation. Solute-induced chain interdigitation is shown to be a cooperative process provoked by the excessively large lateral repulsion in the interfacial region and the concomitant excessive chain tilt. Ethanol-induced phosphatidylcholine interdigitation, for example, proceeds via interdigitated domains formation and finally gives rise to the bilayers with fully intercalated chains tilted by at least 30 degrees (and sometimes as much as 50 degrees) with respect to the membrane normal.

Ethanol↗