Photonic control of image-guided ferroptosis cancer nanomedicine.

Photonic nanomaterials, characterized by their remarkable photonic tunability, empower a diverse range of applications, including cutting-edge advances in cancer nanomedicine. Recently, ferroptosis has emerged as a promising alternative strategy for effectively killing cancer cells with minimizing therapeutic resistance. Novel design of photonic nanomaterials that can integrate photoresponsive-ferroptosis inducers, -diagnostic imaging, and -synergistic components provide significant benefits to effectively trigger local ferroptosis. This review provides a comprehensive overview of recent advancements in photonic nanomaterials for image-guided ferroptosis cancer nanomedicine, offering insights into their strengths, constraints, and their potential as a future paradigm in cancer treatment.

Interwire and Intrawire Magnetostatic Interactions in Fe-Au Barcode Nanowires with Alternating Ferromagnetically Strong and Weak Segments.

Metallic barcode nanowires (BNWs) composed of repeating heterogeneous segments fabricated by template-assisted electrodeposition can offer extended functionality in magnetic, electrical, mechanical, and biomedical applications. The authors consider such nanostructures as a 3D system of magnetically interacting elements with magnetic behavior strongly affected by complex magnetostatic interactions. This study discusses the influence of geometrical parameters of segments on the character of their interactions and the overall magnetic behavior of the array of BNWs having alternating magnetization, because the Fe and Au segments are made of Fe-Au alloys with high and low magnetizations. By controlling the applied current densities and the elapsed time in the electrodeposition, the dimension of the Fe-Au BNWs can be regulated. This study reveals that the influence of the length of magnetically weak Au segments on the interaction field between nanowires is different for samples with magnetically strong 100 and 200 nm long Fe segments using the first-order reversal curve (FORC) diagram method. With the help of micromagnetic simulations, three types of magnetostatic interactions in the BNW arrays are discovered and analy. This study demonstrates that the dominating type of interaction depends on the geometric parameters of the Fe and Au segments and the interwire and intrawire distances.

Enhanced natural killer cell anti-tumor activity with nanoparticles mediated ferroptosis and potential therapeutic application in prostate cancer.

Ferroptosis provides an opportunity to overcome the cancer cell therapeutic resistance and modulate the immune system. Here an interaction between ferroptosis of cancer cells and natural killer (NK) cells was investigated with a clinical grade iron oxide nanoparticle (ferumoxytol) for potential synergistic anti-cancer effect of ferroptosis and NK cell therapy in prostate cancer. When ferumoxytol mediated ferroptosis of cancer cells was combined with NK cells, the NK cells' cytotoxic function was increased. Observed ferroptosis mediated NK cell activation was also confirmed with IFN-γ secretion and lytic degranulation. Upregulation of ULBPs, which is one of the ligands for NK cell activating receptor NKG2D, was observed in the co-treatment of ferumoxytol mediated ferroptosis and NK cells. Additionally, HMGB1 and PD-L1 expression of cancer cells were observed in the treatment of ferroptosis + NK cells. Finally, in vivo therapeutic efficacy of ferumoxytol mediated ferroptosis and NK cell therapy was observed with significant tumor volume regression in a prostate cancer mice model. These results suggest that the NK cells' function can be enhanced with ferumoxytol mediated ferroptosis.

Inorganic Hollow Nanocoils Fabricated by Controlled Interfacial Reaction and Their Electrocatalytic Properties.

The fabrication of 3D hollow nanostructures not only allows the tactical provision of specific physicochemical properties but also broadens the application scope of such materials in various fields. The synthesis of 3D hollow nanocoils (HNCs), however, is limited by the lack of an appropriate template or synthesis method, thereby restricting the wide-scale application of HNCs. Herein, a strategy for preparing HNCs by harnessing a single sacrificial template to modulate the interfacial reaction at a solid-liquid interface that allows the shape-regulated transition is studied. Furthermore, the triggering of the Kirkendall effect in 3D HNCs is demonstrated. Depending on the final state of the transition metal ions reduced during the electrochemical preparation of HNCs, the surface states of the binding anions and the composition of the HNCs can be tuned. In a single-component CrPO4 HNC with a clean surface, the Kirkendall effect of the coil shape is analyzed at various points throughout the reaction. The rough-surface multicomponent MnOx P0.21 HNCs are complexed with ligand-modified BF4 -Mn3 O4 nanoparticles. The fabricated nanocomposite exhibits an overpotential decrease of 25 mV at neutral pH compared to pure BF4 -Mn3 O4 nanoparticles because of the increased active surface area.

Large and Externally Positioned Ligand-Coated Nanopatches Facilitate the Adhesion-Dependent Regenerative Polarization of Host Macrophages.

Macrophages can associate with extracellular matrix (ECM) demonstrating nanosequenced cell-adhesive RGD ligand. In this study, we devised barcoded materials composed of RGD-coated gold and RGD-absent iron nanopatches to show various frequencies and position of RGD-coated nanopatches with similar areas of iron and RGD-gold nanopatches that maintain macroscale and nanoscale RGD density invariant. Iron patches were used for substrate coupling. Both large (low frequency) and externally positioned RGD-coated nanopatches stimulated robust attachment in macrophages, compared with small (high frequency) and internally positioned RGD-coated nanopatches, respectively, which mediate their regenerative/anti-inflammatory M2 polarization. The nanobarcodes exhibited stability in vivo. We shed light into designing ligand-engineered nanostructures in an external position to facilitate host cell attachment, thereby eliciting regenerative host responses.

In Situ Magnetic Control of Macroscale Nanoligand Density Regulates the Adhesion and Differentiation of Stem Cells.

Developing materials with remote controllability of macroscale ligand presentation can mimic extracellular matrix (ECM) remodeling to regulate cellular adhesion in vivo. Herein, we designed charged mobile nanoligands with superparamagnetic nanomaterials amine-functionalized and conjugated with polyethylene glycol linker and negatively charged RGD ligand. We coupled negatively a charged nanoligand to a positively charged substrate by optimizing electrostatic interactions to allow reversible planar movement. We demonstrate the imaging of both macroscale and in situ nanoscale nanoligand movement by magnetically attracting charged nanoligand to manipulate macroscale ligand density. We show that in situ magnetic control of attracting charged nanoligand facilitates stem cell adhesion, both in vitro and in vivo, with reversible control. Furthermore, we unravel that in situ magnetic attraction of charged nanoligand stimulates mechanosensing-mediated differentiation of stem cells. This remote controllability of ECM-mimicking reversible ligand variations is promising for regulating diverse reparative cellular processes in vivo.

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.

Magnetic nanoparticles for ferroptosis cancer therapy with diagnostic imaging.

Ferroptosis offers a novel method for overcoming therapeutic resistance of cancers to conventional cancer treatment regimens. Its effective use as a cancer therapy requires a precisely targeted approach, which can be facilitated by using nanoparticles and nanomedicine, and their use to enhance ferroptosis is indeed a growing area of research. While a few review papers have been published on iron-dependent mechanism and inducers of ferroptosis cancer therapy that partly covers ferroptosis nanoparticles, there is a need for a comprehensive review focusing on the design of magnetic nanoparticles that can typically supply iron ions to promote ferroptosis and simultaneously enable targeted ferroptosis cancer nanomedicine. Furthermore, magnetic nanoparticles can locally induce ferroptosis and combinational ferroptosis with diagnostic magnetic resonance imaging (MRI). The use of remotely controllable magnetic nanocarriers can offer highly effective localized image-guided ferroptosis cancer nanomedicine. Here, recent developments in magnetically manipulable nanocarriers for ferroptosis cancer nanomedicine with medical imaging are summarized. This review also highlights the advantages of current state-of-the-art image-guided ferroptosis cancer nanomedicine. Finally, image guided combinational ferroptosis cancer therapy with conventional apoptosis-based therapy that enables synergistic tumor therapy is discussed for clinical translations.

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.

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.

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.

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.

Remote Control of Time-Regulated Stretching of Ligand-Presenting Nanocoils In Situ Regulates the Cyclic Adhesion and Differentiation of Stem Cells.

Native extracellular matrix (ECM) can exhibit cyclic nanoscale stretching and shrinking of ligands to regulate complex cell-material interactions. Designing materials that allow cyclic control of changes in intrinsic ligand-presenting nanostructures in situ can emulate ECM dynamicity to regulate cellular adhesion. Unprecedented remote control of rapid, cyclic, and mechanical stretching ("ON") and shrinking ("OFF") of cell-adhesive RGD ligand-presenting magnetic nanocoils on a material surface in five repeated cycles are reported, thereby independently increasing and decreasing ligand pitch in nanocoils, respectively, without modulating ligand-presenting surface area per nanocoil. It is demonstrated that cyclic switching "ON" (ligand nanostretching) facilitates time-regulated integrin ligation, focal adhesion, spreading, YAP/TAZ mechanosensing, and differentiation of viable stem cells, both in vitro and in vivo. Fluorescence resonance energy transfer (FRET) imaging reveals magnetic switching "ON" (stretching) and "OFF" (shrinking) of the nanocoils inside animals. Versatile tuning of physical dimensions and elements of nanocoils by regulating electrodeposition conditions is also demonstrated. The study sheds novel insight into designing materials with connected ligand nanostructures that exhibit nanocoil-specific nano-spaced declustering, which is ineffective in nanowires, to facilitate cell adhesion. This unprecedented, independent, remote, and cytocompatible control of ligand nanopitch is promising for regulating the mechanosensing-mediated differentiation of stem cells in vivo.

Strategy to control magnetic coercivity by elucidating crystallization pathway-dependent microstructural evolution of magnetite mesocrystals.

Mesocrystals are assemblies of smaller crystallites and have attracted attention because of their nonclassical crystallization pathway and emerging collective functionalities. Understanding the mesocrystal crystallization mechanism in chemical routes is essential for precise control of size and microstructure, which influence the function of mesocrystals. However, microstructure evolution from the nucleus stage through various crystallization pathways remains unclear. We propose a unified model on the basis of the observation of two crystallization pathways, with different ferric (oxyhydr)oxide polymorphs appearing as intermediates, producing microstructures of magnetite mesocrystal via different mechanisms. An understanding of the crystallization mechanism enables independent chemical control of the mesocrystal diameter and crystallite size, as manifested by a series of magnetic coercivity measurements. We successfully implement an experimental model system that exhibits a universal crystallite size effect on the magnetic coercivity of mesocrystals. These findings provide a general approach to controlling the microstructure through crystallization pathway selection, thus providing a strategy for controlling magnetic coercivity in magnetite systems.

Independent Tuning of Nano-Ligand Frequency and Sequences Regulates the Adhesion and Differentiation of Stem Cells.

The native extracellular matrix (ECM) can exhibit heterogeneous nano-sequences periodically displaying ligands to regulate complex cell-material interactions in vivo. Herein, an ECM-emulating heterogeneous barcoding system, including ligand-bearing Au and ligand-free Fe nano-segments, is developed to independently present tunable frequency and sequences in nano-segments of cell-adhesive RGD ligand. Specifically, similar exposed surface areas of total Fe and Au nano-segments are designed. Fe segments are used for substrate coupling of nanobarcodes and as ligand-free nano-segments and Au segments for ligand coating while maintaining both nanoscale (local) and macroscale (total) ligand density constant in all groups. Low nano-ligand frequency in the same sequences and terminally sequenced nano-ligands at the same frequency independently facilitate focal adhesion and mechanosensing of stem cells, which are collectively effective both in vitro and in vivo, thereby inducing stem cell differentiation. The Fe/RGD-Au nanobarcode implants exhibit high stability and no local and systemic toxicity in various tissues and organs in vivo. This work sheds novel insight into designing biomaterials with heterogeneous nano-ligand sequences at terminal sides and/or low frequency to facilitate cellular adhesion. Tuning the electrodeposition conditions can allow synthesis of unlimited combinations of ligand nano-sequences and frequencies, magnetic elements, and bioactive ligands to remotely regulate numerous host cells in vivo.