Porous Au–Ag Nanoparticles from Galvanic Replacement Applied as Single-Particle SERS Probe for Quantitative Monitoring

Plasmonic nanostructures have raised the interest of biomedical applications of surface-enhanced Raman scattering (SERS). To improve the enhancement and produce sensitive SERS probes, porous Au–Ag alloy nanoparticles (NPs) are synthesized by dealloying Au–Ag alloy NP-precursors with Au or Ag core in aqueous colloidal environment through galvanic replacement reaction. The novel designed core–shell Au–Ag alloy NP-precursors facilitate controllable synthesis of porous nanostructure, and dealloying degree during the reaction has significant effect on structural and spectral properties of dealloyed porous NPs. Narrow-dispersed dealloyed NPs are obtained using NPs of Au/Ag ratio from 10/90 to 40/60 with Au and Ag core to produce solid core@porous shell and porous nanoshells, having rough surface, hollowness, and porosity around 30–60%. The clean nanostructure from colloidal synthesis exhibits a redshifted plasmon peak up to near-infrared region, and the large accessible surface induces highly localized surface plasmon resonance and generates robust SERS activity. Thus, the porous NPs produce intensely enhanced Raman signal up to 68-fold higher than 100 nm AuNP enhancement at single-particle level, and the estimated Raman enhancement around 7800, showing the potential for highly sensitive SERS probes. The single-particle SERS probes are effectively demonstrated in quantitative monitoring of anticancer drug Doxorubicin release.     

Bioactive TiOB‐Coating on Titanium Alloy Implants Enhances Osseointegration in a Rat Model

The surface properties of titanium alloy implants for improved osseointegration in orthopaedic and dental surgery have been modified by many technologies. Hydroxyapatite coatings with a facultative integration of growth factors deposited by plasma spraying showed improved osseointegration. Our approach in order to enhance osseointegration was carried out by a surface modification method of titanium alloy implants called plasma chemical oxidation (PCO). PCO is an electrochemical procedure that converts the nm‐thin natural occurring titanium‐oxide layer on an implant to a 5 µm thick ceramic coating (TiOB‐surface). Bioactive TiOB‐surfaces have a porous microstructure and were loaded with calcium and phosphorous, while bioinert TiOB‐surfaces with less calcium and phosphorous loadings are smooth. A rat tibial model with bilateral placement of titanium alloy implants was employed to analyze the bone response to TiOB‐surfaces in vivo. 64 rats were randomly assigned to four groups of implants: (i) pure titanium alloy (control), ii) titanium alloy, type III anodization, (iii) bioinert TiOB‐surface, and (iv) bioactive TiOB‐surface. Mechanical fixation was evaluated by pull out tests at 3 and 8 weeks. The bioactive TiOB‐surface showed significantly increased shear strength at 8 weeks compared to all other groups.     

Foreword: International Symposium on the Stress Corrosion Cracking in Structural Materials at Ambient Temperatures

Stress corrosion cracking of the high-strength martensitic steel AISI 4340 (yield stress = 1503 MPa) in NaCl aqueous solutions of different concentrations was studied experimentally using compact tension specimens in free corroding conditions. The experiments were conducted under the controls of constant load, constant crack opening displacement (COD), constant loading rate, and constant COD rate. Despite the differences in controlling conditions, the experiments yielded similar results for the threshold stress intensity factor and the plateau velocity in the 3.5 wt pct NaCl solution. Dependence of the plateau velocity on the NaCl concentration was observed, whereas the values of the threshold stress intensity factors seem to be independent of the NaCl concentration in distilled water.     

Enhancement of the em field inside a local probe microscope

Abstract

We deal with the two-dimensional scattering problem of an incoming monochromatic p-polarized wave inside a tip—surface junction of a local probe microscope. We find enhancement of the field with lateral size less than 40nm and a maximum of the order of 10⁴. This result is very encouraging for experimental work on the aperture less-SNOM (perturbation mode). The solution is obtained by means of the method of discrete sources.     

Electrolyte stability determines scaling limits for solid-state 3D Li ion batteries

Rechargeable, all-solid-state Li ion batteries (LIBs) with high specific capacity and small footprint are highly desirable to power an emerging class of miniature, autonomous microsystems that operate without a hardwire for power or communications. A variety of three-dimensional (3D) LIB architectures that maximize areal energy density has been proposed to address this need. The success of all of these designs depends on an ultrathin, conformal electrolyte layer to electrically isolate the anode and cathode while allowing Li ions to pass through. However, we find that a substantial reduction in the electrolyte thickness, into the nanometer regime, can lead to rapid self-discharge of the battery even when the electrolyte layer is conformal and pinhole free. We demonstrate this by fabricating individual, solid-state nanowire core-multishell LIBs (NWLIBs) and cycling these inside a transmission electron microscope. For nanobatteries with the thinnest electrolyte, ≈110 nm, we observe rapid self-discharge, along with void formation at the electrode/electrolyte interface, indicating electrical and chemical breakdown. With electrolyte thickness increased to 180 nm, the self-discharge rate is reduced substantially, and the NWLIBs maintain a potential above 2 V for over 2 h. Analysis of the nanobatteries' electrical characteristics reveals space-charge limited electronic conduction, which effectively shorts the anode and cathode electrodes directly through the electrolyte. Our study illustrates that, at these nanoscale dimensions, the increased electric field can lead to large electronic current in the electrolyte, effectively shorting the battery. The scaling of this phenomenon provides useful guidelines for the future design of 3D LIBs.     

Antimicrobial properties and thermal stability of polycarbonate modified with 1‐alkyl‐3‐methylimidazolium tetrafluoroborate ionic liquids

Four water immiscible ionic liquids (ILs): 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, 1‐heptyl‐3‐methylimidazolium tetrafluoroborate, 1‐octyl‐3‐methylimidazolium tetrafluoroborate and 1‐dodecyl‐3‐methylimidazolium tetrafluoroborate have been synthesized. Polycarbonate (PC) films containing ILs were prepared by solvent casting from methylene chloride solutions. Scanning electron microscopy measurements showed the high homogeneity of PC/IL films with the IL content up to 4 wt %. The tendency to IL aggregation was observed for polymeric films with higher IL content (5%). PC/IL composites were found to have the reduced thermal decomposition temperature under both an air and a nitrogen atmosphere in comparison with the neat PC. The effect of IL content on the antimicrobial activity of PC films against Escherichia coli bacteria was studied. Pronounced antimicrobial efficacy was revealed for PC/IL films for all studied ILs starting from 3 wt % of IL. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40050.     

A novel approach to determine wet restitution coefficients through a unified correlation and energy analysis

Wet particle interactions are observed in many applications, for example, pharmaceutical, food, agricultural, polymerization, agglomeration, and coating, in which an accurate evaluation of the wet restitution coefficient (e_wet) is crucial to understand the particle flowability, operating conditions and product size distribution. Experiments were performed to measure the wet restitution coefficient by impacting a spherical particle on a stationary plate covered with a thin liquid layer of water or glycerol solution in this work. Furthermore, novel approaches for estimation of e_wet were developed using dimensional analysis (using the Buckingham π theorem and regression analysis) in combination with energy budget analysis. In the correlation development, the dominant physical properties of solid and liquid, particle impact velocity and liquid layer thickness are grouped into well‐known dimensionless numbers viz. Reynolds, Weber and Stokes. Whereas in the energy analysis, the energy dissipation rates were determined for five distinct collision phases, that is, dipping, dry collision, undipping, formation and breakage of the liquid bridge, and added mass. The efficacy of the developed approaches was analyzed by comparing obtained results with experiments and an elastohydrodynamic model, and a modified elastohydrodynamic model. © 2014 American Institute of Chemical Engineers AIChE J, 61: 769–779, 2015     

Optical nanosensor platform operating in near-physiological pH range via polymer-brush-mediated plasmon coupling

The nanosensors' platform made of a stimuli-responsive polymer/noble metal nanoparticle composite thin film exploits the combination of the swelling-shrinking transition in a poly(N,N'-dimethylaminoethyl methacrylate) brush and the localized surface plasmon resonance in metal nanoparticles to enable the transduction of changes in the solution pH in the near-physiological range into a pronounced optical signal.