Asymmetric Mach-Zehnder Interferometric Biosensing for Quantitative and Sensitive Multiplex Detection of Anti-SARS-CoV-2 Antibodies in Human Plasma.

The Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) pandemic has once more emphasized the urgent need for accurate and fast point-of-care (POC) diagnostics for outbreak control and prevention. The main challenge in the development of POC in vitro diagnostics (IVD) is to combine a short time to result with a high sensitivity, and to keep the testing cost-effective. In this respect, sensors based on photonic integrated circuits (PICs) may offer advantages as they have features such as a high analytical sensitivity, capability for multiplexing, ease of miniaturization, and the potential for high-volume manufacturing. One special type of PIC sensor is the asymmetric Mach-Zehnder Interferometer (aMZI), which is characterized by a high and tunable analytical sensitivity. The current work describes the application of an aMZI-based biosensor platform for sensitive and multiplex detection of anti-SARS-CoV-2 antibodies in human plasma samples using the spike protein (SP), the receptor-binding domain (RBD), and the nucleocapsid protein (NP) as target antigens. The results are in good agreement with several CE-IVD marked reference methods and demonstrate the potential of the aMZI biosensor technology for further development into a photonic IVD platform.

Selective Functionalization with PNA of Silicon Nanowires on Silicon Oxide Substrates.

Silicon nanowire chips can function as sensors for cancer DNA detection, whereby selective functionalization of the Si sensing areas over the surrounding silicon oxide would prevent loss of analyte and thus increase the sensitivity. The thermal hydrosilylation of unsaturated carbon-carbon bonds onto H-terminated Si has been studied here to selectively functionalize the Si nanowires with a monolayer of 1,8-nonadiyne. The silicon oxide areas, however, appeared to be functionalized as well. The selectivity toward the Si-H regions was increased by introducing an extra HF treatment after the 1,8-nonadiyne monolayer formation. This step (partly) removed the monolayer from the silicon oxide regions, whereas the Si-C bonds at the Si areas remained intact. The alkyne headgroups of immobilized 1,8-nonadiyne were functionalized with PNA probes by coupling azido-PNA and thiol-PNA by click chemistry and thiol-yne chemistry, respectively. Although both functionalization routes were successful, hybridization could only be detected on the samples with thiol-PNA. No fluorescence was observed when introducing dye-labeled noncomplementary DNA, which indicates specific DNA hybridization. These results open up the possibilities for creating Si nanowire-based DNA sensors with improved selectivity and sensitivity.

Maskless Spatioselective Functionalization of Silicon Nanowires.

Spatioselective functionalization of silicon nanowires was achieved without using a masking material. The designed process combines metal-assisted chemical etching (MACE) to fabricate silicon nanowires and hydrosilylation to form molecular monolayers. After MACE, a monolayer was formed on the exposed nanowire surfaces. A second MACE step was expected to elongate the nanowires, thus creating two different segments. When monolayers of 1-undecene or 1-tetradecyne were formed on the upper segment, however, the second MACE step did not extend the nanowires. In contrast, nanowires functionalized with 1,8-nonadiyne were elongated, but at an approximately 8 times slower etching rate. The elongation resulted in a contrast difference in high-resolution scanning electron microscopy (HR-SEM) images, which indicated the formation of nanowires that were covered with a monolayer only at the top parts. Click chemistry was successfully used for secondary functionalization of the monolayer with azide-functionalized nanoparticles. The spatioselective presence of 1,8-nonadiyne gave a threefold higher particle density on the upper segment functionalized with 1,8-nonadiyne than on the lower segment without monolayer. These results indicate the successful spatioselective functionalization of silicon nanowires fabricated by MACE.

Electrochemistry of Redox-Active Guest Molecules at ß-Cyclodextrin-Functionalized Silicon Electrodes.

Functionalization of silicon-based sensing devices with self-assembled receptor monolayers offers flexibility and specificity towards the requested analyte as well as the possibility of sensor reuse. As electrical sensor performance is determined by electron transfer, we functionalized H-terminated silicon substrates with ß-cyclodextrin (ß-CD) molecules to investigate the electronic coupling between these host monolayers and the substrate. A trivalent (one ferrocene and two adamantyl moieties), redox-active guest was bound to the ß-CD surface with a coverage of about 10-11 mol/cm2 and an overall binding constant of 1.5⋅109 M-1. This packing density of the host monolayers on silicon is lower than that for similar ß-CD monolayers on gold. The monolayers were comparable on low-doped p-type and highly doped p++ substrates regarding their packing density and the extent of oxide formation. Nonetheless, the electron transfer was more favorable on p++ substrates, as shown by the lower values of the peak splitting and peak widths in the cyclic voltammograms. These results show that the electron-transfer rate on the host monolayers is not only determined by the composition of the monolayer, but also by the doping level of the substrate.

Highly doped silicon nanowires by monolayer doping.

Controlling the doping concentration of silicon nanostructures is challenging. Here, we investigated three different monolayer doping techniques to obtain silicon nanowires with a high doping dose. These routes were based on conventional monolayer doping, starting from covalently bound dopant-containing molecules, or on monolayer contact doping, in which a source substrate coated with a monolayer of a carborane silane was the dopant source. As a third route, both techniques were combined to retain the benefits of conformal monolayer formation and the use of an external capping layer. These routes were used for doping fragile porous nanowires fabricated by metal-assisted chemical etching. Differences in porosity were used to tune the total doping dose inside the nanowires, as measured by X-ray photoelectron spectroscopy and secondary ion mass spectrometry measurements. The higher the porosity, the higher was the surface available for dopant-containing molecules, which in turn led to a higher doping dose. Slightly porous nanowires could be doped via all three routes, which resulted in highly doped nanowires with (projected areal) doping doses of 1014-1015 boron atoms per cm2 compared to 1012 atoms per cm2 for a non-porous planar sample. Highly porous nanowires were not compatible with the conventional monolayer doping technique, but monolayer contact doping and the combined route resulted for these highly porous nanowires in tremendously high doping doses up to 1017 boron atoms per cm2.

Molecular Monolayers for Electrical Passivation and Functionalization of Silicon-Based Solar Energy Devices.

Silicon-based solar fuel devices require passivation for optimal performance yet at the same time need functionalization with (photo)catalysts for efficient solar fuel production. Here, we use molecular monolayers to enable electrical passivation and simultaneous functionalization of silicon-based solar cells. Organic monolayers were coupled to silicon surfaces by hydrosilylation in order to avoid an insulating silicon oxide layer at the surface. Monolayers of 1-tetradecyne were shown to passivate silicon micropillar-based solar cells with radial junctions, by which the efficiency increased from 8.7% to 9.9% for n+/p junctions and from 7.8% to 8.8% for p+/n junctions. This electrical passivation of the surface, most likely by removal of dangling bonds, is reflected in a higher shunt resistance in the J-V measurements. Monolayers of 1,8-nonadiyne were still reactive for click chemistry with a model catalyst, thus enabling simultaneous passivation and future catalyst coupling.

Spatially Controlled Out-of-Equilibrium Host-Guest System under Electrochemical Control.

Self-assembly to create molecular and nanostructures is typically performed at the thermodynamic minimum. To achieve dynamic functionalities, such as adaptability, internal feedback, and self-replication, there is a growing focus on out-of-equilibrium systems. This report presents the dynamic self-assembly of an artificial host-guest system at an interface, under control by a dissipative electrochemical process using (electrical) energy, resulting in an out-of-equilibrium system exhibiting a supramolecular surface gradient. The gradient, its steepness, rate of formation, and complex surface composition after backfilling, as well as the surface compositions after switching between the different states of the system, are assessed and supported by modelling. Our method shows for the first time an artificial surface-confined out-of-equilibrium system. The electrochemical process parameters provide not only control over the system in time, but also in space.