Open porous dealloying-based biomaterials as a novel biomaterial platform.

The close match of stiffness between implant material and bone is critically important to avoid stress-shielding effect and ensure a fast healing of injured tissues. Here, we introduce liquid metal dealloying method for synthesis of robust open porous biomaterials possessing low Young's modulus. The remarkable advantage of the liquid metal dealloying method is a large flexibility in selecting chemical composition of a desired porous biomaterial together with unique tunable microstructure. To demonstrate the versatility of the method, a number of open porous TixZr100-x alloys with different chemical compositions and microstructural characteristics was developed by dealloying precursor (TixZr100-x)yCu100-y alloys in liquid magnesium. The effects of the processing conditions and the precursors' chemical composition on the microstructure of the porous TixZr100-x as well as their mechanical behavior were discussed in detail. In particular, the porous TixZr100-x distinguish themselves due to a low and tunable stiffness ranging from 3.2 to 15.1 GPa and a rather high strength reaching up to 480 MPa. This unique combination of mechanical properties of the new open porous TixZr100-x alloys becomes even more interesting in view of preliminary biological tests highlighting their excellent cytocompatibility. Overall, the liquid metal dealloying provides an opportunity for designing a new biomaterials platform with flexible tunable functionality.

Electrochemical tuning of the optical properties of nanoporous gold.

Using optical in-situ measurements in an electrochemical environment, we study the electrochemical tuning of the transmission spectrum of films from the nanoporous gold (NPG) based optical metamaterial, including the effect of the ligament size. The long wavelength part of the transmission spectrum around 800 nm can be reversibly tuned via the applied electrode potential. The NPG behaves as diluted metal with its transition from dielectric to metallic response shifted to longer wavelengths. We find that the applied potential alters the charge carrier density to a comparable extent as in experiments on gold nanoparticles. However, compared to nanoparticles, a NPG optical metamaterial, due to its connected structure, shows a much stronger and more broadband change in optical transmission for the same change in charge carrier density. We were able to tune the transmission through an only 200 nm thin sample by 30%. In combination with an electrolyte the tunable NPG based optical metamaterial, which employs a very large surface-to-volume ratio is expected to play an important role in sensor applications, for photoelectrochemical water splitting into hydrogen and oxygen and for solar water purification.

Dealloying-based interpenetrating-phase nanocomposites matching the elastic behavior of human bone.

The long-term performance of orthopedic implants depends crucially on a close match between the mechanical behavior of bone and of the implant material. Yet, the present man-made materials with the required biocompatibility and strength are substantially stiffer than bone. This mismatch results in stress shielding, which can lead to the loss of bone mass and may even lead to a revision surgery. Here we report a new materials design strategy towards metal-polymer composites that are based on constituents with established biocompatibility and that can be matched to bone. Ti-based nanoporous alloys, prepared by liquid-metal dealloying, are infiltrated with epoxy to form interpenetrating-phase nanocomposites. At up to 260 MPa, their yield strength is technologically interesting for a deformable light-weight material. More importantly, Young's modulus can be adjusted between 4.4 and 24 GPa, which affords matching to bone. As another parallel to bone, the strength of the composite materials is strain-rate dependent. These findings suggest that the novel composite materials may provide the basis for promising future implant materials.

Wrinkling of atomic planes in ultrathin Au nanowires.

A detailed understanding of structure and stability of nanowires is critical for applications. Atomic resolution imaging of ultrathin single crystalline Au nanowires using aberration-corrected microscopy reveals an intriguing relaxation whereby the atoms in the close-packed atomic planes normal to the growth direction are displaced in the axial direction leading to wrinkling of the (111) atomic plane normal to the wire axis. First-principles calculations of the structure of such nanowires confirm this wrinkling phenomenon, whereby the close-packed planes relax to form saddle-like surfaces. Molecular dynamics studies of wires with varying diameters and different bounding surfaces point to the key role of surface stress on the relaxation process. Using continuum mechanics arguments, we show that the wrinkling arises due to anisotropy in the surface stresses and in the elastic response, along with the divergence of surface-induced bulk stress near the edges of a faceted structure. The observations provide new understanding on the equilibrium structure of nanoscale systems and could have important implications for applications in sensing and actuation.

Sign-inverted response of aluminum work function to tangential strain.

We have investigated the response of the work function, W, of low-index aluminum surfaces to tangential strain by using first-principles calculations based on density functional theory. This response parameter is a central quantity in electrocapillary coupling of metal electrodes relating to the performance of porous metal actuators and surface stress based sensing devices. We find that Al surfaces exhibit a positive response for all orientations considered. By contrast, previous studies reported negative-valued response parameters for clean surfaces of several transition metals. We discuss separately the response of W to different types of strain and the impact of the strain on the Fermi energy and the surface dipole. We argue that the reason for the abnormal positive sign of the Al response parameter lies in its high valence electron density.

Impact of surface mechanics on the reactivity of electrodes.

Theory links the reactivity of metal surfaces to the interatomic spacing and, hence, to the tangential strain. We point out that this proposition can be experimentally verified by exploiting a seemingly unrelated phenomenon, the mechanical deformation of solid bodies when charged in an electrolyte. Such experiments allow the strength of coupling between adsorption enthalpy and strain to be quantified. For hydrogen adsorption on Pd, the result agrees with ab initio computation and with trends that can be inferred from experiment on pseudomorphic layers strained by epitaxy with misfitting substrates. The data suggest that experimentally accessible strain values afford a variation of the adatom concentration by several orders of magnitude and a significant shift of the reaction along the 'volcano curve' of reactivity versus adsorption strength.

Response of the potential of a gold electrode to elastic strain.

We describe the measurement of the response, sigma, of the potential of a metal electrode to elastic strain under open circuit conditions. The experimental response exhibits a frequency dependence due to Faraday loss currents, which become negligible beyond 30 Hz. For a (111)-textured gold film the experimental value at higher frequency, sigma = -1.83 V, compares well with the intrinsic value of Au(111) predicted by recent ab initio computation.

Surface-chemistry-driven actuation in nanoporous gold.

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry-driven actuation can be realized in high-surface-area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes of the order of a few tenths of a per cent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into a mechanical response, thus opening the door to surface-chemistry-driven actuator and sensor technologies.

[Urethral duplication: long-term results for a rare urethral anomaly]. / Urethralduplikatur : Langzeitergebnisse einer seltenen Urethralfehlbildung.

INTRODUCTION: Urethral duplication is a rare anomaly that can occur in various forms. Urethral duplication must be diagnosed and adequately treated. Only if clinical complaints develop should surgical management be considered. PATIENTS AND METHODS: The aim of this study was to retrospectively analyze patients with congenital urethral duplication: age at the time of diagnosis, type of urethral duplication, diagnostic and therapeutic measures as well as clinical aftercare were evaluated. RESULTS: This homogeneous and selected cohort included nine male children. The average follow-up was 6.2 years. Seven children were symptomatic (77.7%). We found a double urethra with epispadias in four boys and with hypospadias in three boys and urethral duplication with perineal/anal meatus in one patient and normotopia in another patient. In two children without symptoms, the urethral duplication was an incidental finding during diagnostic work-up for other anomalies. Seven children had additional urological anomalies: one fusiform megalourethra, three urethral valves with hypospadias, and two epispadias. Two children without symptoms were managed conservatively. An open operation joining the urethras was performed in three children, and four boys underwent endoscopic treatment of the urethral duplication. Long-term results revealed normal continence in all of the children. One child exhibited recurrent urinary tract infections and late stricture, which was opened endoscopically in a second session. CONCLUSION: A surgical approach is only indicated in the presence of clinical complaints. There is no surgical gold standard. The decision is ultimately reached on an individual basis depending on the findings and anatomy in view of the rarity and variability of the clinical picture. The functional result is of foremost importance for the urethra that requires reconstruction, but the cosmetic aspect should be respected to the same extent. We present the results of our experience in treating children with this urological condition. At the same time larger (multicenter) studies are needed, which will make it possible to formulate guidelines for this rare anomaly.

Surface stress-charge response of a (111)-textured gold electrode under conditions of weak ion adsorption.

We report a cantilever bending investigation into the variation of surface stress, f, with surface charge density, q, for (111)-textured thin films of gold in aqueous NaF and HClO 4. The graphs of f(q) are highly linear, and the surface stress-charge coefficients, d f/d q, are -1.95 V for 7 mM NaF and -2.0 V for 10 mM HClO 4 near the potential of zero charge. These values exceed some previously published experimental data by a factor of 2, but they agree with recent ab initio calculations of the surface stress-charge response of gold in vacuum.

Small-angle neutron scattering of nanocrystalline terbium with random paramagnetic susceptibility.

We report magnetic small-angle neutron scattering (SANS) data for the nanocrystalline rare earth metal Terbium in its paramagnetic state. Whereas critical scattering dominates at large momentum transfer, q, the (magnetic-) field response of the scattering at small q arises from the spatial nonuniformity of the paramagnetic susceptibility tensor. The finding of an interrelation between SANS and the susceptibility suggests a way for characterizing the nonuniform magnetic interactions in hard magnets by neutron scattering.

Synthesis, characterization and magnetic interactions study of epsilon-Fe3N-CrN nanorods.

The epsilon-Fe3N-CrN composite nanorods are synthesized by wet chemical technique. XRD-Rietveld analysis shows that epsilon-Fe3N and CrN crystallize in the space group P6(3)/mmc and Fm3m with relative mass compositions 53% and 47%, respectively. The nanorods have an average diameter approximately 30 nm and length approximately 400 nm X-ray photoelectron spectroscopy (XPS) studies show the presence of nitrides and oxynitrides (Fe-O-N/Cr-O-N) at the surface and the presence of elemental Cr in CrN matrix along with the nitrides inside the nanorods, probed by the in-depth profile analysis. The magnetic interactions between the spins of ferromagnetic (FM) epsilon-Fe3N and antiferromagnetic (AF) CrN throughout the volume of the nanorods give rise to exchange bias coupling. The exchange bias phenomenon is influenced by the rough and non-uniform AF-FM interface and spin-glass-like ordering at lower temperatures. The ac susceptibility studies confirm the spin-glass-like ordering.

Volume change during the formation of nanoporous gold by dealloying.

We report a macroscopic shrinkage by up to 30 vol % during electrochemical dealloying of Ag-Au. Since the original crystal lattice is maintained during the process, we suggest that the formation of nanoporous gold in our experiments is accompanied by the creation of a large number of lattice defects and by local plastic deformation.

Balance of force at curved solid metal-liquid electrolyte interfaces.

We analyze the simultaneous mechanical and chemical equilibrium at the interface between a fluid electrolyte and a solid conductor in terms of a continuum theory, with attention to surfaces of varying orientation and of arbitrary curvature. On top of the variable which is conjugate to the surface stress, the tangential strain, we introduce an additional degree of freedom for the surface deformation, the surface stretch, to account for the observation of a reversible normal relaxation of the top atomic layer as a function of the electrochemical potential. We derive relations between the materials constants of the surface, for instance, the pressure dependence of the electric potential at constant superficial charge density, and discuss experiments-using cantilevers or porous solids-by which they can be measured.

Variation of the surface stress-charge coefficient of platinum with electrolyte concentration.

We report an experimental study of the variation of surface stress with surface charge density for nanoporous Pt immersed in aqueous solutions of NaF of various concentration. As the concentration is reduced, we find initially an increase in the magnitude of the surface stress-charge coefficient, followed by saturation at a value of -1.9 V. Since specific adsorption is expected to be reduced as the solution becomes more dilute, the results support the notion that changes in the bonding at the metal surface play a decisive role in determining the change in the surface stress during double-layer charging.

Charge-induced reversible strain in a metal.

Dimension changes on the order of 0.1% or above in response to an applied voltage have been reported for many types of materials, including ceramics, polymers, and carbon nanostructures, but not, so far, for metals. We show that reversible strain amplitudes comparable to those of commercial piezoceramics can be induced in metals by introducing a continuous network of nanometer-sized pores with a high surface area and by controlling the surface electronic charge density through an applied potential relative to an electrolyte impregnating the pores.

Range of magnetic correlations in nanocrystalline soft magnets.

We have obtained the magnetic field dependence of static ferromagnetic correlations in nanocrystalline electrodeposited Co and Ni by means of the correlation function of the spin misalignment, determined from small-angle neutron scattering data. The approach yields a correlation length l(C), which is a measure for the spatial extent of inhomogeneities in the magnetization distribution. The correlation length depends strongly on the applied magnetic field with values ranging from 94 nm in nanocrystalline Co at low fields to about 15 nm at saturation. The results for l(C) indicate that in Co the main source of nonuniformity in the spin system is the anisotropy field of each individual crystallite, whereas in nanocrystalline Ni the main sources of spin disorder originate from twin faults or from the defect cores of grain boundaries.

[Laser lithotripsy of ureteral stones. Personal experiences]. / Laserlithotripsie von Harnleitersteinen. Eigene Erfahrungen.

The in vitro evaluation of a pulsed Nd:YAG laser, showed an effective and fine fragmentation of urinary calculi and showed only minimal subepithelial bleeding in the directly irradiated canine ureter. Since 1989 we have treated ureteral calculi in 30 patients. The laser pulses of 15-20 mJ (at fiber tip), 20 ns, 20-25 cps are transmitted by a 300-microns quartz fiber with a specially formed tip focusing the light. The fiber is passed through an 11.5-F ureteroscope within a guide tube, or, without a guide tube, through one of the new minimized ureteroscopies and is placed in front of the calculus. In 27 patients the procedure was successful, without any residual concretions after 1 day. In our opinion the advantages of this method are the very fine-grained, complete fragmentation of all sorts of calculi, the highly atraumatic procedure, and the absence of either optical or acoustic irritation to the operator.