Ion-track technology based synthesis and characterization of gold and gold alloys nanowires and nanocones

Metallic nanostructures are attracting growing interest because of their potential application in various devices such as batteries, solar cells, or drug delivery systems. This thesis focuses on the synthesis and characterization of three different nanostructures: (1) solid cylindrical AuAg nanowires with controlled composition and size, fabricated by electrodeposition in etched ion-track membranes with cylindrical channels, (2) porous cylindrical Au nanowires attained by selective dealloy-ing of AuAg nanowires, and (3) Au nanocones synthesized by electrodeposition in conical channels. AuAg nanowires with controlled diameter and composition, namely Au, Au40Ag60, Au60Ag40, and Ag were synthesized and characterized. By dealloying these nanowires were converted into porous Au-based nanowires with diameters above and below 100 nm possessing an enhanced surface area. Surface morphology and com-position of the nanostructures before and after dealloying were studied by means of high spatial resolution energy-dispersive X-ray spectroscopy (EDX) in a high-resolution transmission electron microscope (TEM). The results demonstrate surface segregation effects in solid AuAg nanowires that strongly vary with the initial composition. Surface segregation occurs on a time scale of days (< 3 days) inde-pendently of the wire dimensions. After dealloying of Au40Ag60 nanowires, the porous nanowires have a silver content below 10% and ligament size from 5 to 30 nm. Solid and porous wires are particularly attractive for future applications, e.g., in sensorics. The characterization of such small nanostructures regarding, e.g. electrical transport properties, requires suitable contacts. Special designs to contact nanowires by laser lithography as well as by using pre-patterned templates were developed. Gold nanocones with sharp tips down to 50 nm diameter and several microns large bases were fabricated. Given by this special geometry, the nanostructures exhibit a high mechanical stability and are freestanding with an aspect ratio of 500 and above. Stable gold nanocone arrays are attractive for a large range of applications including field emission and as coating for hydrophobic surfaces. In this work, the standard wire deposition process from base to tip was inverted in order to improve the electrical and thermal contact of the nanocones to the substrate. After selective removal of the template, 30 µm long gold nanocones with ~ 50 nm sharp tips were freestanding and vertically aligned. Such structures are highly tunable in terms of cone dimensions and number density. The field emission properties of patterned nanocone arrays, investigated in collaboration with the Bergische Universität Wuppertal, exhibit field enhancement factors between 200 and 1000 as well as a maximum emission current ranging from ~ 1 to 100 μA. The results presented in this thesis emphasize the variety of possibilities that ion-track technology offers in order to tailor dimensions and characteristics of nanostructures

Conical Nanotubes Synthesized by Atomic Layer Deposition of Al₂O₃, TiO₂, and SiO₂ in Etched Ion-Track Nanochannels

Etched ion-track polycarbonate membranes with conical nanochannels of aspect ratios of ~3000 are coated with Al₂O₃, TiO₂, and SiO₂ thin films of thicknesses between 10 and 20 nm by atomic layer deposition (ALD). By combining ion-track technology and ALD, the fabrication of two kinds of functional structures with customized surfaces is presented: (i) arrays of free-standing conical nanotubes with controlled geometry and wall thickness, interesting for, e.g., drug delivery and surface wettability regulation, and (ii) single nanochannel membranes with inorganic surfaces and adjustable isoelectric points for nanofluidic applications

Versailles project on advanced materials and standards (VAMAS) interlaboratory study on measuring the number concentration of colloidal gold nanoparticles

We describe the outcome of a large international interlaboratory study of the measurement of particle number concentration of colloidal nanoparticles, project 10 of the technical working area 34, "Nanoparticle Populations" of the Versailles Project on Advanced Materials and Standards (VAMAS). A total of 50 laboratories delivered results for the number concentration of 30 nm gold colloidal nanoparticles measured using particle tracking analysis (PTA), single particle inductively coupled plasma mass spectrometry (spICP-MS), ultraviolet-visible (UV-Vis) light spectroscopy, centrifugal liquid sedimentation (CLS) and small angle X-ray scattering (SAXS). The study provides quantitative data to evaluate the repeatability of these methods and their reproducibility in the measurement of number concentration of model nanoparticle systems following a common measurement protocol. We find that the population-averaging methods of SAXS, CLS and UV-Vis have high measurement repeatability and reproducibility, with between-labs variability of 2.6%, 11% and 1.4% respectively. However, results may be significantly biased for reasons including inaccurate material properties whose values are used to compute the number concentration. Particle-counting method results are less reproducibile than population-averaging methods, with measured between-labs variability of 68% and 46% for PTA and spICP-MS respectively. This study provides the stakeholder community with important comparative data to underpin measurement reproducibility and method validation for number concentration of nanoparticles

Nanocellulose aerogel inserts for quantitative lateral flow immunoassays

The Lateral Flow Immuno Assay (LFIA) is a well-established technique that provides immediate results without high-cost laboratory equipment and technical skills from the users. However, conventional colorimetric LFIA strips suffer from high limits of detection, mainly due to the analysis of a limited sample volume, short reaction time between the target analyte and the conjugation molecules, and a weak optical signal. Thus, LFIAs are mainly employed as a medical diagnostic tool for qualitative and semi/quantitative detection, respectively. We applied a novel cellulose nanofiber (CNF) aerogel material incorporated into LFIA strips to increase the sample flow time, which in turn extends the binding interactions between the analyte of interest and the detection antibody, thus improving the limit of detection (LOD). Compared to a conventional LFIA strip, the longer sample flow time in the aerogel modified LFIA strips improved the LOD for the detection of mouse IgG in a buffer solution by a 1000-fold. The accomplished LOD (0.01 ng/mL) even outperformed specifications of a commercial ELISA kit by a factor of 10, and the CNF aerogel assisted LFIA was successfully applied to detect IgG in human serum with a LOD of 0.72 ng/mL. Next to the improved LOD, the aerogel assisted LFIA could quantify IgG samples in buffer and human serum in the concentration ranges of 0.17 ng/mL - 100 ng/mL (in buffer) and 4.6 ng/mL - 100 ng/mL (in human serum). The presented solution thus poses a unique potential to transform lateral flow assays into highly sensitive, fully quantitative point-of-care diagnostics

Noncovalent functionalization of solid-state nanopores via self-assembly of amphipols

In recent years there has been increasing interest in the development of new methods for conferring functional features to nanopore-based fluidic devices. In this work, we describe for the first time the noncovalent integration of amphoteric-amphipathic polymers, also known as "amphipols", into single conical nanopores in order to obtain signal-responsive chemical nanodevices. Highly-tapered conical nanopores were fabricated by single-sided chemical etching of polycarbonate foils. After etching, the surface of the conical nanopores was chemically modified, by first metallizing the surface via gold sputtering and then by amphiphilic self-assembly of the amphipol. The net charge of adsorbed amphipols was regulated via pH changes under the environmental conditions. The pH-dependent chemical equilibrium of the weak acidic and basic monomers facilitates the regulation of the ionic transport through the nanopore by adjusting the pH of the electrolyte solution. Our results demonstrate that functional amphipathic polymers are powerful building blocks for the surface modification of nanopores and might ultimately pave the way to a new means of integrating functional and/or responsive units within nanofluidic structures.Fil: Perez Mitta, Gonzalo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Burr, Loïc. GSI Helmholtzzentrum für Schwerionenforschung; Alemania. Technische Universität Darmstadt. Materialwissenschaft; AlemaniaFil: Tunineti, Jimena S.. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Trautmann, Christina. GSI Helmholtzzentrum für Schwerionenforschung; Alemania. Technische Universität Darmstadt. Materialwissenschaft; AlemaniaFil: Toimil- Molares, María Eugenia. GSI Helmholtzzentrum für Schwerionenforschung; AlemaniaFil: Azzaroni, Omar. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentin

Surface Enrichment in Au–Ag Alloy Nanowires and Investigation of the Dealloying Process

The fabrication of nanowires by electrodeposition of Au−Ag alloy into the pores of etched ion track polymer membrane is presented. The crystallinity, morphology, and composition of wires with diameters of 85, 45, and 30 nm are investigated by means of X-ray diffraction, high-resolution scanning transmission electron microscopy, and energy-dispersive X-ray analysis. Energy-dispersive X-ray analysis with very high spatial resolution (below 1 nm) reveals the presence of surface enrichment. A Ag-rich layer in Au40Ag60 wires and a Au-rich layer in Au60Ag40 wires with thicknesses between 1 and 4 nm are observed. After dealloying in nitric acid, Ag-rich wires exhibit porous morphologies whereas Au-rich wires remain solid cylinders. The results clearly indicate that the analyzed AuAg alloy nanowires do not consist of homogeneous solid solution, but surface effects before and during the dealloying play an important role for the final morphology of dealloyed nanowires

Conical Nanotubes Synthesized by Atomic Layer Deposition of Al2O3, TiO2, and SiO2 in Etched Ion-Track Nanochannels

Etched ion-track polycarbonate membranes with conical nanochannels of aspect ratios of ~3000 are coated with Al2O3, TiO2, and SiO2 thin films of thicknesses between 10 and 20 nm by atomic layer deposition (ALD). By combining ion-track technology and ALD, the fabrication of two kinds of functional structures with customized surfaces is presented: (i) arrays of free-standing conical nanotubes with controlled geometry and wall thickness, interesting for, e.g., drug delivery and surface wettability regulation, and (ii) single nanochannel membranes with inorganic surfaces and adjustable isoelectric points for nanofluidic applications

Smartphone-based magneto-immunosensor on carbon black modified screen-printed electrodes for point-of-need detection of aflatoxin B1 in cereals

Considering the complexities and speed of modern food chains, there is an increasing demand for point-of-need detection of food contaminants, particularly highly regulated chemicals and carcinogens such as aflatoxin B1. We report a user-friendly smartphone-based magneto-immunosensor on carbon black modified electrodes for point-of-need detection of aflatoxin B1 in cereals. For buffered analyte solutions and a corn extract sample, the assay demonstrated a low limit of detection of 13 and 24 pg/mL, respectively. The assay was also highly reproducible, exhibiting mean relative standard deviations of 3.7% and 4.0% for the buffered analyte and corn extract samples. The applicability of the assay was validated on the basis of EU guidelines and the detection capability was lower than or equal to 2 μg/kg, which is the EU maximum residue limit for aflatoxin B1 in cereals. False-positive and false-negative rates were less than 5%. Additionally, an open-source android application, AflaESense, was designed to provide a simple interface that displays the result in a traffic-light-type format, thus minimizing user training and time for data analysis. AflaESense was used for smartphone-based screening of spiked corn samples containing aflatoxin B1 (0.1, 2, and 10 ng/mL), and naturally contaminated corn containing 0.15 ng aflatoxin B1/mL. The measured values were in close agreement with spiked concentrations (r2 = 0.99), with recovery values ranging between 80 and 120%. Finally, contaminated samples correctly triggered a red alert while the non-contaminated samples led to the display of a green color of AflaESense. To the best of our knowledge, this is the first smartphone-based electrochemical system effective for screening samples for contamination with aflatoxin B1.We thank Prof. Michel Nielen ((Wageningen Food Safety Research (WFSR), part of Wageningen University & Research, Wageningen, The Netherlands) for kindly providing the certified non-contaminated (blank) and naturally contaminated samples.Peer reviewe