Ultrasensitive and Rapid Circulating Tumor DNA Liquid Biopsy Using Surface-Confined Gene Amplification on Dispersible Magnetic Nano-Electrodes.

Circulating tumor DNA (ctDNA) detection has been acknowledged as a promising liquid biopsy approach for cancer diagnosis, with various ctDNA assays used for early detection and treatment monitoring. Dispersible magnetic nanoparticle-based electrochemical detection methods have been proposed as promising candidates for ctDNA detection based on the detection performance and features of the platform material. This study proposes a nanoparticle surface-localized genetic amplification approach by integrating Fe3O4-Au core-shell nanoparticles into polymerase chain reactions (PCR). These highly dispersible and magnetically responsive superparamagnetic nanoparticles act as nano-electrodes that amplify and accumulate target ctDNA in situ on the nanoparticle surface upon PCR amplification. These nanoparticles are subsequently captured and subjected to repetitive electrochemical measurements to induce reconfiguration-mediated signal amplification for ultrasensitive (∼3 aM) and rapid (∼7 min) metastatic breast cancer ctDNA detection in vitro. The detection platform can also detect metastatic biomarkers from in vivo samples, highlighting the potential for clinical applications and further expansion to rapid and ultrasensitive multiplex detection of various cancers.

One-Step Electrochemical Synthesis of Multiyolk-Shell Nanocoils for Exceptional Photocatalytic Performance.

Multiyolk-shell (mYS) nanostructures have garnered significant interest in various photocatalysis applications such as water splitting and waste treatment. Nonetheless, the complexity and rigorous conditions for the synthesis have hindered their widespread implementation. This study presents a one-step electrochemical strategy for synthesizing multiyolk-shell nanocoils (mYSNC), wherein multiple cores of noble metal nanoparticles, such as Au, are embedded within the hollow coil-shaped FePO4 shell structures, mitigating the challenges posed by conventional methods. By capitalizing on the dissimilar dissolution rates of bimetallic alloy nanocoils in an electrochemically programmed solution, nanocoils of different shapes and materials, including two variations of mYSNCs are successfully fabricated. The resulting Au-FePO4 mYSNCs exhibit exceptional photocatalytic performance for environmental remediation, demonstrating up to 99% degradation of methylene blue molecules within 50 min and 95% degradation of tetracycline within 100 min under ultraviolet-visible (UV-vis) light source. This remarkable performance can be attributed to the abundant electrochemical active sites, internal voids facilitating efficient light harvesting with coil morphology, amplified localized surface plasmon resonance (LSPR) at the plasmonic nanoparticle-semiconductor interface, and effective band engineering. The innovative approach utilizing bimetallic alloys demonstrates precise geometric control and design of intricate multicomponent hybrid composites, showcasing the potential for developing versatile hollow nanomaterials for catalytic applications.

Submolecular Ligand Size and Spacing for Cell Adhesion.

Cell adhesion occurs when integrin recognizes and binds to Arg-Gly-Asp (RGD) ligands present in fibronectin. In this work, submolecular ligand size and spacing are tuned via template-mediated in situ growth of nanoparticles for dynamic macrophage modulation. To tune liganded gold nanoparticle (GNP) size and spacing from 3 to 20 nm, in situ localized assemblies of GNP arrays on nanomagnetite templates are engineered. 3 nm-spaced ligands stimulate the binding of integrin, which mediates macrophage-adhesion-assisted pro-regenerative polarization as compared to 20 nm-spaced ligands, which can be dynamically anchored to the substrate for stabilizing integrin binding and facilitating dynamic macrophage adhesion. Increasing the ligand size from 7 to 20 nm only slightly promotes macrophage adhesion, not observed with 13 nm-sized ligands. Increasing the ligand spacing from 3 to 17 nm significantly hinders macrophage adhesion that induces inflammatory polarization. Submolecular tuning of ligand spacing can dominantly modulate host macrophages.

Surface-ligand-induced crystallographic disorder-order transition in oriented attachment for the tuneable assembly of mesocrystals.

In the crystallisation of nanomaterials, an assembly-based mechanism termed 'oriented attachment' (OA) has recently been recognised as an alternative mechanism of crystal growth that cannot be explained by the classical theory. However, attachment alignment during OA is not currently tuneable because its mechanism is poorly understood. Here, we identify the crystallographic disorder-order transitions in the OA of magnetite (Fe3O4) mesocrystals depending on the types of organic surface ligands on the building blocks, which produce different grain structures. We find that alignment variations induced by different surface ligands are guided by surface energy anisotropy reduction and surface deformation. Further, we determine the effects of alignment-dependent magnetic interactions between building blocks on the global magnetic properties of mesocrystals and their chains. These results revisit the driving force of OA and provide an approach for chemically controlling the crystallographic order in colloidal nanocrystalline materials directly related to grain engineering.

Magnetic Control and Real-Time Monitoring of Stem Cell Differentiation by the Ligand Nanoassembly.

Native extracellular matrix (ECM) exhibits dynamic change in the ligand position. Herein, the ECM-emulating control and real-time monitoring of stem cell differentiation are demonstrated by ligand nanoassembly. The density of gold nanoassembly presenting cell-adhesive Arg-Gly-Asp (RGD) ligand on Fe3 O4 (magnetite) nanoparticle in nanostructures flexibly grafted to material is changed while keeping macroscale ligand density invariant. The ligand nanoassembly on the Fe3 O4 can be magnetically attracted to mediate rising and falling ligand movements via linker stretching and compression, respectively. High ligand nanoassembly density stimulates integrin ligation to activate the mechanosensing-assisted stem cell differentiation, which is monitored via in situ real-time electrochemical sensing. Magnetic control of rising and falling ligand movements hinders and promotes the adhesion-mediated mechanotransduction and differentiation of stem cells, respectively. These rising and falling ligand states yield the difference in the farthest distance (≈34.6 nm) of the RGD from material surface, thereby dynamically mimicking static long and short flexible linkers, which hinder and promote cell adhesion, respectively. Design of cytocompatible ligand nanoassemblies can be made with combinations of dimensions, shapes, and biomimetic ligands for remotely regulating stem cells for offering novel methodologies to advance regenerative therapies.

Fluorescent detection of dipicolinic acid as a biomarker in bacterial spores employing terbium ion-coordinated magnetite nanoparticles.

Anthrax is a bioterror agent because of its toxicity and the tolerance of its bacterial spores. Thus, researchers have attempted to develop various nanomaterials to detect dipicolinic acid (DPA), a biomarker of bacterial spores. Nanomaterials containing lanthanide ions have received considerable attention, owing to their potential to exhibit high sensitivity and selectivity in the detection of DPA via chelation with molecules. However, the fluorescent signals of the lanthanide complex are quenchable because the nanomaterials simultaneously absorb the excitation and emission light. For the precise detection of DPA, pure signals have to be obtained from the complex by alleviating the quenching effect of the nanomaterials. In this study, we develop a structure with terbium ion (Tb3+)-coordinated magnetite (Fe3O4) nanoparticle to detect DPA. Tb3+ can be detached from the magnetite during chelation with the DPA, and the complex can emit the unencumbered signals with improved detection limit through the application of a magnetic field. The detection system exhibits a significantly lower detection limit (5.4 nM) than the infectious dosage of anthrax (60 µM) with high selectivity and chemical stability. This study informs the improvement of detection limits via the separation of nanomaterials and lanthanide complex.

Multi-Component Mesocrystalline Nanoparticles with Enhanced Photocatalytic Activity.

Mesocrystals, consisting of small subunits, have gained research interests owing to their ability to simultaneously modify material-specific properties and interactions among subunits. However, despite these unique characteristics, most mesocrystals are composed of a single material, and there is a disjunction between academic discovery and practical application. In this study, the synthesis of multi-component mesocrystalline nanoparticles composed of Fe3 O4 , ZnFe2 O4 , and ZnO subunits using a polymerization induced heterogeneous nucleation method is reported. The structure has small ZnFe2 O4 and ZnO nanocrystals covering the Fe3 O4 crystallites. It exhibits not only magnetic and catalytic properties determined by the size of each subunit nanocrystal, but also enhances photocatalytic and colloidal properties that originates because of its crowded arrangement. The magnetically recoverable catalysts exhibit remarkable photodegradation of organic molecules under the irradiation of visible light for 1 h; thus, improving its applicability in purifying a large amount of wastewater during the daytime.

Design of Magnetic-Plasmonic Nanoparticle Assemblies via Interface Engineering of Plasmonic Shells for Targeted Cancer Cell Imaging and Separation.

Magnetic-plasmonic nanoparticles have received considerable attention for widespread applications. These nanoparticles (NPs) exhibiting surface-enhanced Raman scattering (SERS) activities are developed due to their potential in bio-sensing applicable in non-destructive and sensitive analysis with target-specific separation. However, it is challenging to synthesize these NPs that simultaneously exhibit low remanence, maximized magnetic content, plasmonic coverage with abundant hotspots, and structural uniformity. Here, a method that involves the conjugation of a magnetic template with gold seeds via chemical binding and seed-mediated growth is proposed, with the objective of obtaining plasmonic nanostructures with abundant hotspots on a magnetic template. To obtain a clean surface for directly functionalizing ligands and enhancing the Raman intensity, an additional growth step of gold (Au) and/or silver (Ag) atoms is proposed after modifying the Raman molecules on the as-prepared magnetic-plasmonic nanoparticles. Importantly, one-sided silver growth occurred in an environment where gold facets are blocked by Raman molecules; otherwise, the gold growth is layer-by-layer. Moreover, simultaneous reduction by gold and silver ions allowed for the formation of a uniform bimetallic layer. The enhancement factor of the nanoparticles with a bimetallic layer is approximately 107 . The SERS probes functionalized cyclic peptides are employed for targeted cancer-cell imaging and separation.