Printing of In Situ Functionalized Mesoporous Silica with Digital Light Processing for Combinatorial Sensing.

Combinatorial sensing is especially important in the context of modern drug development to enable fast screening of large data sets. Mesoporous silica materials offer high surface area and a wide range of functionalization possibilities. By adding structural control, the combination of structural and functional control along all length scales opens a new pathway that permits larger amounts of analytes being tested simultaneously for complex sensing tasks. This study presents a fast and simple way to produce mesoporous silica in various shapes and sizes between 0.27-6 mm by using light-induced sol-gel chemistry and digital light processing (DLP). Shape-selective functionalization of mesoporous silica is successfully carried out either after printing using organosilanes or in situ while printing through the use of functional mesopore template for the in situ functionalization approach. Shape-selective adsorption of dyes is shown as a demonstrator toward shape selective screening of potential analytes.

Simultaneous Nanolocal Polymer and In Situ Readout Unit Placement in Mesoporous Separation Layers.

Bioinspired solid-state nanopores and nanochannels have attracted interest in the last two decades, as they are envisioned to advance future sensing, energy conversion, and separation concepts. Although much effort has been made regarding functionalization of these materials, multifunctionality and accurate positioning of functionalities with nanoscale precision still remain challenging. However, this precision is necessary to meet transport performance and complexity of natural pores in living systems, which are often based on nonequilibrium states and compartmentalization. In this work, a nanolocal functionalization and simultaneous localized sensing strategy inside a filtering mesoporous film using precisely placed plasmonic metal nanoparticles inside mesoporous films with pore accessibility control is demonstrated. A single layer of gold nanoparticles is incorporated into mesoporous thin films with precise spatial control along the nanoscale layer thickness. The local surface plasmon resonance is applied to induce a photopolymerization leading to a nanoscopic polymer shell around the particles and thus nanolocal polymer placement inside the mesoporous material. As near-field modes are sensitive to the dielectric properties of their surrounding, the in situ sensing capability is demonstrated using UV-vis spectroscopy. It is demonstrated that the sensing sensitivity only slightly decreases upon functionalization. The presented nanolocal placement of responsive functional polymers into nanopores offers a simultaneous filtering and nanoscopic readout function. Such a nanoscale local control is envisioned to have a strong impact onto the development of new transport and sensor concepts, especially as the system can be developed into higher complexity using different metal nanoparticles and additional design of mesoporous film filtering properties.

Functionalized Gold Nanorod Probes: A Sophisticated Design of SERS Immunoassay for Biodetection in Complex Media.

Surface-enhanced Raman scattering (SERS) probes offer considerable opportunities in label-based biosensing and analysis. However, achieving specific and reproducible performance, where low detection limits are needed in complex media, remains a challenge. Herein, we present a general strategy employing gold nanorod SERS probes and rationally designed surface chemistry involving protein resistant layers and antibodies to allow for the selective detection of species in complex media. By utilizing the ability of gold nanorods for selective surface modification, Raman reporters (4-mercaptobenzoic acid) were attached to the tips. Importantly, the sides of the nanorods were modified using a mixed layer of two different length stabilizing ligands (carboxyl-terminated oligo ethylene glycols) to ensure colloidal stability, while antibodies were attached to the stabilizing ligands. The nanoparticle interfacial design improves the colloidal stability, unlocks the capability of the probes for targeting biomolecules in complex matrices, and gives the probes the high SERS efficiency. The utility of this probe is demonstrated herein via the detection of Salmonella bacteria at the single bacterium level in complex food matrices using an anti-Salmonella IgG antibody-conjugated probe. The modular nature of the surface chemistry enables the SERS probes to be employed with a molecularly diverse range of biorecognition species (e.g., antibodies and peptides) for many different analytes, thus opening up new opportunities for efficient biosensing applications.

Patterned Molecular Films of Alkanethiol and PLL-PEG on Gold-Silicate Interfaces: How to Add Functionalities while Retaining Effective Antifouling.

Spatial control of surface functionalization and interactions is essential for microarray-based analysis. This study reports the fabrication of two-dimensional molecular films with site-specific functionalities, forming microarrays at discrete locations. Arrays of microsized gold disks were produced on a silicate membrane using microfabrication. On these arrays, orthogonal self-assembly of molecules was performed that can specifically bind to gold or silicate. The gold array elements were functionalized with a range of alkanethiols and the silicate with polymeric poly-l-lysine-grafted-poly(ethylene glycol) (PLL-PEG). The surface functionalization on the gold disk array and the surrounding substrate was characterized at each step using X-ray photoelectron spectroscopy (XPS) to show that alkanethiols are specifically attached to the gold. PLL-PEG was used to provide resistance against nonspecific protein and cell adsorption and attached exclusively to the silicate. The effectiveness of the surface chemistry was validated by the selective self-assembly of a gold nanoparticle monolayer array on the gold regions. In a more sophisticated example, selective adhesion of MCF-7 cells to anti-EpCAM antibody modified gold areas of the gold-silicate surface was demonstrated to give a cell microarray. This study provides a general approach to fabricate chemical patterns on silicon-based devices with the convergence of microfabrication and material-specific surface modification, which may be useful to expand the functionalities and potential applications for patterned biomolecular films. Importantly, the ability to pattern surfaces with different surface chemistries is not limited to planar surfaces using this orthogonal surface-coupling approach.

Single-fibre coating and additive manufacturing of multifunctional papers.

Paper-based materials with precisely designed wettabilities show great potential for fluid transport control, separation, and sensing. To tune the wettability of paper, paper sheets are usually modified after the paper manufacturing process. This limits the complexity of the local wettability design. We combined the wettability design of the individual fibres with subsequent paper sheet fabrication through either fibre deposition or fibre printing. Using silica-based cellulose fibre functionalization, the wettability of the paper sheets, containing only one specific fibre type, could be gradually tuned from highly hydrophilic to highly hydrophobic, resulting in water exclusion. The development of a silica-functionalized fibre library containing mesoporous or dense silica coatings, as well as silica with varying precursor compositions, further enabled the variation of the paper wettability and fluid flow. By combining this fibre library with the paper fabrication process by (i) fibre deposition or (ii) fibre printing, the paper wettability architecture and thus the local fibre composition were adjusted without any further processing steps. This enabled the fabrication of papers with wettability integration, such as a wettability pattern or a Janus paper design, containing wettability gradients along the paper sheet cross section. This asymmetric wettability along all three spatial dimensions enabled side-selective oil-water separation.

Self-decorating cells via surface-initiated enzymatic controlled radical polymerization.

Through the innovative use of surface-displayed horseradish peroxidase, this work explores the enzymatic catalysis of both bioRAFT polymerization and bioATRP to prompt polymer synthesis on the surface of Saccharomyces cerevisiae cells, with bioATRP outperforming bioRAFT polymerization. The resulting surface modification of living yeast cells with synthetic polymers allows for a significant change in yeast phenotype, including growth profile, aggregation characteristics, and conjugation of non-native enzymes to the clickable polymers on the cell surface, opening new avenues in bioorthogonal cell-surface engineering.

Pushing the limits of nanopore transport performance by polymer functionalization.

Inspired by the design and performance of biological pores, polymer functionalization of nanopores has emerged as an evolving field to advance transport performance within the last few years. This feature article outlines developments in nanopore functionalization and the resulting transport performance including gating based on electrostatic interaction, wettability and ligand binding, gradual transport controlled by polymerization as well as functionalization-based asymmetric nanopore and nanoporous material design going towards the transport direction. Pushing the limits of nanopore transport performance and thus reducing the performance gap between biological and technological pores is strongly related to advances in polymerization chemistry and their translation into nanopore functionalization. Thereby, the effect of the spatial confinement has to be considered for polymer functionalization as well as for transport regulation, and mechanistic understanding is strongly increased by combining experiment and theory. A full mechanistic understanding together with highly precise nanopore structure design and polymer functionalization is not only expected to improve existing application of nanoporous materials but also opens the door to new technologies. The latter might include out of equilibrium devices, ionic circuits, or machine learning based sensors.

Intrinsic and well-defined second generation hot spots in gold nanobipyramids versus gold nanorods.

An effective strategy for regioselective modification and directional assembly of anisotropic nanoparticles is demonstrated to explore the electric field enhancement in assembled gold nanobipyramids compared with gold nanorods. The well-defined secondary plasmonic hot spots between the coupled gold nanobipyramids exhibit the capability for single molecule detection.

Coordination Polymer to Atomically Thin, Holey, Metal-Oxide Nanosheets for Tuning Band Alignment.

Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal-based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two-unit cells. The process involves rapid exfoliation of bulk-layered, MCPs (Ce-, Ti-, Zr-based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high-yield, room-temperature, and template-free approach to synthesize ultrathin holey nanosheets with high-level functionalities.