Fatigue studies of high-palladium dental casting alloys: Part II. Transmission electron microscopic observations†

The microstructures of two representative high-palladium dental alloys, a Pd–Cu–Ga alloy and a Pd–Ga alloy, which had been subjected to cyclic fatigue in uniaxial tension were investigated by transmission electron microscopy (TEM). Two different mechanisms were found to dominate microplastic deformation during fatigue: twinning in the Pd–Cu–Ga alloy, and planar slip of dislocations in the Pd–Ga alloy. In addition, stress-induced precipitation occurred in the Pd–Ga alloy during cyclic loading. Heat treatment simulating the firing cycles for dental porcelain resulted in the formation of a previously unreported bcc phase in the Pd–Cu–Ga alloy, and in the elimination of the characteristic tweed structure found in the Pd–Ga alloy for the as-cast condition.     

Remodeling of fibrinogen by endothelial cells in dependence on fibronectin matrix assembly. Effect of substratum wettability

The endothelization of cardiovascular implants is desirable to improve their blood compatibility. The capacity of the endothelial cells to attach, migrate, proliferate and function on the implant surface depends on the presence of matrix proteins such as fibronectin (FN) and fibrinogen (FNG). In this study, we show that the deposition of fibrinogen into extracellular matrix-like structures by human umbilical vein endothelial cells (HUVEC) is dependent on FN matrix formation. We found further that the process of organization of both adsorbed and soluble FN and FNG is dependent on the wettability of materials since it was observed only on a hydrophilic and not on a hydrophobic model surface. ₃ integrin was involved in the process of cell attachment to adsorbed FNG, while the mechanism of FNG fibrillogenesis required the activity of the ₁ integrin. Studies of EC morphology showed the predominant peripheral organization of actin filaments and the formation of distinct leading and trailing cell edges suggesting a motile phenotype of cells when they are seeded on FNG. In summary, we concluded that adsorbed fibrinogen may enhance the motility of HUVEC and that soluble FNG requires FN matrix assembly to be organized in fibrilar structures.     

Electrochemical behavior of titanium-based materials – are there relations to biocompatibility?

For biomedical applications the physico-chemical properties of oxide layers, always present in titanium-based materials, are of special interest because the biological system is in direct contact only with these oxides. Using electrochemical impedance spectroscopy and galvanostatic polarization it is shown that the different compositions of c.p.-titanium, Ti6Al4V, and Ti6Al7Nb result in different physico-chemical properties of air formed passive layers and anodic oxide layers. This may have a direct impact on the biocompatibility of these materials. Results of impedance spectroscopy distinctly differ in the flatband potentials as well as in the donor densities of air-formed passive layers with Ti6Al7Nb showing an approximately 50% smaller donor density than the other materials. Anodic galvanostatic polarization results in voltage–charge density curves with distinct differences in the Faraday efficiency of the oxide formation between Ti6Al7Nb and c.p.-titanium/Ti6Al4V, especially for low current densities. These effects correlate strongly with the donor densities in the air formed passive films of the examined materials. SEM-images of anodic oxide layers show a blister containing surface morphology of the outer part of the oxide layers for all materials. This morphology is probably caused by oxygen evolution, a process which relies on the transfer of electrons through the growing anodic oxide layers and strongly depends on the donor density in the air formed passive layers. Again, the much more pronounced morphology on c.p. titanium/Ti6Al4V agrees with the different donor densities in the air formed passive layers on the materials. These findings correlate with the good biocompatibility of Ti6Al7Nb and suggest that conduction mechanisms, in air formed passive layers and anodic oxide layers, contribute to processes that determine the biocompatibility of these materials.     

Correction for particle-wall interactions in the separation of colloids by flow field-flow fractionation

In the characterization of materials by field-flow fractionation (FFF), the experienced analyst understands the importance of incorporating additives in the carrier liquid that minimize or eliminate interactions between the analyte and accumulation wall, particularly in aqueous systems. However, as FFF is applied to more difficult samples, such as those with high surface energies, it is increasingly difficult to find additives that completely eliminate particle-wall interactions. Furthermore, the analyst may wish to use specific conditions that preserve the high surface energy of particles, to study their interaction with other materials through their behavior in the FFF channel. With this in mind, Williams and co-workers developed a model that quantifies the effect of particle-wall interactions in FFF using an empirically determined interaction parameter. In this work, the model is evaluated for the application of flow FFF in carrier liquids of low ionic strength, where particle-wall interactions are magnified. The retention of particles ranging in size from 64 to 1000 nm is measured using a wide range of field strengths and retention levels. The model is found to be generally valid over the entire range, except for minor discrepancies at lower levels of retention. Although retention levels are dramatically affected by particle-wall interactions, the point of steric inversion (500 nm), where the size-based elution order reverses, is not affected. When particle-wall interactions are not accounted for, they lead to a bias in particle sizes calculated from standard retention theory of up to 70%. The model can also be used to refine the measurement of channel thickness, which is important for the accurate conversion of retention parameters to particle sizes. In this work, for example, errors in channel thickness led to systematic errors on the order of 10% in particle diameter.     

Mass transfer and flow in electrically charged micro- and nanochannels

In this work, the fluid flow and mass transfer due to the presence of an electric field in a rectangular channel is examined. We consider a mixture of water or another neutral solvent and a salt compound, such as sodium chloride, for which the ionic species are entirely dissociated. Results are produced for the case in which the channel height is much greater than the electric double layer (EDL) (microchannel) and for the case in which the channel height is of the order of the width of the EDL (nanochannel). Both symmetric and nonsymmetric velocity, potential, and mole fraction distributions are considered, unlike previous work on this problem. At small electrolyte concentrations, the Debeye-Huckel picture of the electric double layer is recovered; at larger concentrations, the Gouy-Chapman picture of the electric double emerges naturally. The numerical results presented here agree with analytical solutions of a singular perturbation analysis, which is valid as the channel height increases. In the symmetric case for the electroosmotic flow so induced, the velocity field and the potential are similar. In the asymmetric case corresponding to different wall potentials, the velocity and potential can be vastly different. The fluid is assumed to behave as a continuum, and the volume flow rate is observed to vary linearly with channel height for electrically driven flow, in contrast to pressure-driven flow, which varies as height cubed. This means that very large pressure drops are required to drive flows in small channels. However, useful volume flow rates may be obtained at a very low driving voltage.     

Determination of total polyphenolic content in red wines by means of the combined He-Ne laser optothermal window and Folin-Ciocalteu colorimetry assay

The He-Ne laser (632.8 nm) and the concept of optothermal window (OW), a variant of the open photoacoustic cell, were combined with the Folin-Ciocalteu colorimetry assay to quantitate phenolics in four red wines. The total polyphenolic content in selected red wines varied between 786 and 1630 mg/L gallic acid equivalent (GAE) as determined by OW-Folin-Ciocalteu colorimetry, which compares well to 778 and 1614 mg/L GAE obtained for the same wines by means of classical spectrophotometry. The originality and merit of OW colorimetry used here is that, unlike what is encountered in conventional spectrometry, no intermediate dilution step is required when total polyhenolics are determined in red wine. The precision, defined as the closeness to each other of 256 replicate readings of the OW signal, is generally better than 2%.     

Application of isotopically labeled methylmercury for isotope dilution analysis of biological samples using gas chromatography/ICPMS

An isotope dilution (ID) procedure for the determination of methylmercury (MMHg) in biological samples using an inductively coupled plasma mass spectrometer as detector after the capillary gas chromatographic separation (CGC/ICPMS) has been developed. For the first time, open-focused-microwave pretreatment has been used in conjunction with ID. Optimum conditions for the measurement of isotope ratios on the fast transient chromatographic peaks have been established. Mass bias was found to be about 1.5%/mass unit and was corrected by using the simultaneously measured thallium signals at 203Tl and 205Tl. After mass-bias correction, deviation of the theoretical mercury ratio values was found to be as low as 0.2%. Isotope ratio precisions based on the peak areas measurements were 0.3% RSD for 20 pg injected (as Hg absolute). The absolute detection limits were in the range of 20-30 fg for 202Hg and 201Hg. Methylmercury enriched in 201Hg has been synthesized by direct reaction with methylcobalamine. The concentration of the MMHg spike has been measured by reverse isotope dilution with a natural MMHg standard. The capabilities of CGC/ICPMS to measure isotope ratios were used to optimize sample derivatization by aqueous ethylation with NaBEt4 with respect to MMHg degradation pathways and quantitative recovery. The accuracy of the method developed has been validated with biological certified reference materials (CRM-463, DORM-1).     

An electrospray ionization source for integration with microfluidics

We have demonstrated a new electrospray ionization (ESI) device incorporating a tip made from a shaped thin film, bonded to a microfluidic channel, and interfaced to a time-of-flight mass spectrometer (TOFMS). A triangular-shaped thin polymer tip was formed by lithography and etching. A microfluidic channel, 20 microm wide and 10 microm deep, was embossed in a cyclo olefin substrate using a silicon master. The triangular tip was aligned with the channel and bonded between the channel plate and a flat plate to create a microfluidic channel with a wicking tip protruding from the end. This structure aided the formation of a stable Taylor cone at the apex of the tip, forming an electrospray ionization source. This source was tested by spraying several solutions for mass spectrometric analysis. Because the components are all made by lithographic approaches with high geometrical fidelity, an integrated array system with multiple channels can be formed with the same method and ease as a single channel. We tested a multichannel system in a multiplexed manner and showed reliable operation with no significant cross contamination between closely spaced channels.     

Negligible depletion solid-phase microextraction with radiolabeled analytes to study free concentrations and protein binding: an example with [3H]estradiol

A new method is presented that enables sensitive measurement of free concentrations of radiolabeled ligands. Additionally, protein binding of radiochemicals in complex matrixes can be determined with this new technique that combines negligible depletion solid-phase microextraction (nd-SPME) with liquid scintillation counting (LSC) as detection. [3H]Estradiol was taken as an example compound. Possible matrix effects of protein on fiber uptake kinetics were studied. No matrix effect was found, either by fouling of the fiber, or by changed uptake kinetics. The validity of the method was shown in the determination of the affinity constant (Ka) of estradiol for human serum albumin (HSA). The Ka was estimated at 8.9 x 10(4) M(-1), which corresponds well with literature values. This study shows that nd-SPME is suitable to study the free concentration and protein binding of [3H]estradiol. The method described in this paper combines the advantages of nd-SPME with the advantages of radiolabeled analytes, creating a timesaving, simple, and sensitive analytical tool that will be particularly useful in complex matrixes containing many potential interferences for chromatographic methods.     

Building blocks for a two-frequency laser lidar-radar: a preliminary study

A new principle of lidar-radar is theoretically and experimentally investigated. The proposed architecture is based on the use of an rf modulation of the emitted light beam and a direct detection of the backscattered intensity. Use of a radar-processing chain allows one to obtain range and Doppler measurements with the advantages of lidar spatial resolution. We calculate the maximum range of this device, taking into account different possible improvements. In particular, we show that use of a pulsed two-frequency laser and a spatially multimode optical preamplification of the backscattered light leads to calculated ranges larger than 20 km, including the possibility of both range and Doppler measurements. The building blocks of this lidar-radar are tested experimentally: The radar processing of an rf-modulated backscattered cw laser beam is demonstrated at 532 nm, illustrating the Doppler and identification capabilities of the system. In addition, signal-to-noise ratio improvement by optical pre-amplification is demonstrated at 1.06 microm. Finally, a two-frequency passively Q-switched Nd:YAG laser is developed. This laser then permits two-frequency pulses with tunable pulse duration (from 18 to 240 ns) and beat frequency (from 0 to 2.65 GHz) to be obtained.