Length-Dependent Cellular Internalization of Nanobody-Functionalized Poly(2-oxazoline) Nanorods.

The ability to target specific tissues and to be internalized by cells is critical for successful nanoparticle-based targeted drug delivery. Here, we combined "stealthy" rod-shaped poly(2-oxazoline) (POx) nanoparticles of different lengths with a cancer marker targeting nanobody and a fluorescent cell internalization sensor via a heat-induced living crystallization-driven self-assembly (CDSA) strategy. A significant increase in association and uptake driven by nanobody-receptor interactions was observed alongside nanorod-length-dependent kinetics. Importantly, the incorporation of the internalization sensor allowed for quantitative differentiation between cell surface association and internalization of the targeted nanorods, revealing unprecedented length-dependent cellular interactions of CDSA nanorods. This study highlights the modularity and versatility of the heat-induced CDSA process and further demonstrates the potential of POx nanorods as a modular nanomedicine platform.

Controllable Pseudoelasticity in Metallic Nanocrystals by Grain Boundary Engineering.

Materials with pseudoelasticity can recover from large strains exceeding their elastic limits during unloading, making them promising damage-tolerant building blocks for advanced nanodevices. Nevertheless, a practical approach to realize controllable pseudoelastic behavior at nanoscale remains challenging. Here, we proposed a grain boundary (GB) engineering approach to endow metallic nanocrystals with a controllable pseudoelasticity. Both in situ nanomechanical testing and atomistic simulations demonstrate that such controllable pseudoelasticity is governed by the extension and contraction of an inherent stacking fault array at the GB. By precisely tuning GB misorientation and inclination, our simulation results reveal that metallic nanocrystals can exhibit tailored pseudoelastic performance across a broad spectrum of GBs in different face-centered cubic metals. These findings enrich our understanding of the intrinsic pseudoelasticity of GBs and provide a GB engineering approach toward metallic materials with reversible deformability.

Blue Shift of Localized Surface Plasmon Resonance of Gold Ultrathin Nanorod by Forming a Single Atomic Silver Shell via Antigalvanic Process.

Gold ultrathin nanorods (Au UNRs) are anisotropic nanostructures constructed by attaching gold nanoclusters in one dimension. Au UNRs exhibit localized surface plasmon resonance (LSPR) only in the longitudinal direction because their diameter is smaller than the Fermi wavelength of an electron (<2 nm). In this study, we found that the LSPR wavelength of oleylamine-stabilized Au UNRs is blue-shifted simply by mixing with Ag(I). High-resolution elemental mapping and X-ray photoelectron spectroscopy of the resulting UNRs indicate that a Ag monatomic layer is formed on the Au UNR surface by the antigalvanic reduction of Ag(I). This process allowed us to synthesize a series of Au@Ag core-shell UNRs with LSPR wavelengths in the range of 1.2-2.0 µm.

4D Printed Protein-AuNR Nanocomposites with Photothermal Shape Recovery.

4D printing is the 3D printing of objects that change chemically or physically in response to an external stimulus over time. Photothermally responsive shape memory materials are attractive for their ability to undergo remote activation. While photothermal methods using gold nanorods (AuNRs) have been used for shape recovery, 3D patterning of these materials into objects with complex geometries using degradable materials has not been addressed. Here, we report on the fabrication of 3D printed shape memory bioplastics with photo-activated shape recovery. Protein-based nanocomposites based on bovine serum albumin (BSA), poly (ethylene glycol) diacrylate and gold nanorods were developed for vat photopolymerization. These 3D printed bioplastics were mechanically deformed under high loads, and the proteins served as mechanoactive elements that unfolded in an energy-dissipating mechanism that prevented fracture of the thermoset. The bioplastic object maintained its metastable shape-programmed state under ambient conditions. Subsequently, up to 99% shape recovery was achieved within 1 min of irradiation with near-infrared light. Mechanical characterization and small angle X-ray scattering (SAXS) analysis suggest that the proteins mechanically unfold during the shape programming step and may refold during shape recovery. These composites are promising materials for the fabrication of biodegradable shape-morphing devices for robotics and medicine.

Electron Donor-Specific Surface Interactions Promote the Photocatalytic Activity of Metal-Semiconductor Nanohybrids.

In the past two decades, the application of colloidal semiconductor-metal nanoparticles (NPs) as photocatalysts for the hydrogen generation from water has been extensively studied. The present body of literature studies agrees that the photocatalytic yield strongly depends on the electron donating agent (EDA) added for scavenging the photogenerated holes. The highest reported hydrogen production rates are obtained in the presence of ionic EDAs and at high pH. The large hydrogen production rates are attributed to fast hole transfer from the NP onto the EDAs. However, the present discussions do not treat the influence of EDA-specific surface interactions. This systematic study focuses on that aspect by combining steady-state hydrogen production measurements with time-resolved and static optical spectroscopy, employing 11-mercaptoundecanoic acid-capped, Pt-tipped CdSe/CdS dot-in-rods in the presence of a large set of EDAs. Based on the experimental results, two distinct EDA groups are identified: surface-active and diffusion-limited EDAs. The largest photocatalytic efficiencies are obtained in the presence of surface-active EDAs that induce an agglomeration of the NPs. This demonstrates that the introduction of surface-active EDAs can significantly enhance the photocatalytic activity of the NPs, despite reducing their colloidal stability and inducing the formation of NP networks.

Hierarchically Superstructured Anisotropic Carbon Particles by Multiscale Assembly Driven by Spinodal Decomposition.

Hierarchical superstructures have novel shape-dependent properties, but well-defined anisotropic carbon superstructures with controllable size, shape, and building block dimensionality have rarely been accomplished thus far. Here, a hierarchical assembly technique is presented that uses spinodal decomposition (SD) to synthesize anisotropic oblate particles of mesoporous carbon superstructure (o-MCS) with nanorod arrays by integrating block-copolymer (BCP) self-assembly and polymer-polymer interface behaviors in binary blends. The interaction of major and minor phases in binary polymer blends leads to the formation of an anisotropic oblate particle, and the BCP-rich phase enables ordered packing and unidirectional alignment of carbon nanorods. Consequently, this approach enables precise control over particles' size, shape, and over the dimensionality of their components. Exploiting this functional superstructure, o-MCS are used as an anode material in potassium-ion batteries, and achieve a notable specific capacity of 156 mA h g-1 at a current density of 2 A g-1, and long-term stability for 3000 cycles. This work presents a significant advancement in the field of hierarchical superstructures, providing a promising strategy for the design and synthesis of anisotropic carbon materials with controlled properties, offering promising applications in energy storage and beyond.

Hybrid Acid/Base Electrolytic Cell for Hydrogen Generation and Methanol Conversion Implemented by Bifunctional Ni/MoN Nanorod Electrocatalyst.

Combining the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) within an integrated electrolytic system may offer the advantages of enhanced kinetics of the anode, reduced energy consumption, and the production of high-purity hydrogen. Herein, it is reported the construction of Ni─MoN nanorod arrays supported on a nickel foam substrate (Ni─MoN/NF) as a bifunctional electrocatalyst for electrocatalytic hydrogen production and selective methanol oxidation to formate. Remarkably, The optimal Ni─MoN/NF catalyst displays exceptional HER performance with an overpotential of only 49 mV to attain 10 mA cm-2 in acid, and exhibits a high activity for MOR to achieve 100 mA cm-2 at 1.48 V in alkali. A hybrid acid/base electrolytic cell with Ni─MoN/NF electrode as anode and cathode is further developed for an integrated HER-MOR cell, which only requires a voltage of 0.56 V at 10 mA cm-2 , significantly lower than that of the HER-OER system (0.70 V). The density functional theory studies reveal that the incorporation of Ni effectively modulates the electronic structure of MoN, thereby resulting in enhanced catalytic activity. The unique combination of high electrocatalytic activity and excellent stability make the Ni─MoN/NF catalyst a promising candidate for practical applications in electrocatalytic hydrogen production and methanol oxidation.

Glutamic Acid Modified Gold Nanorod Sensor for the Detection of Calcium ions in Neuronal Cells.

Calcium (Ca2+) ions play a crucial role in the functioning of neurons, governing various aspects of neuronal activity such as rapid modulation and alterations in gene expression. Ca2+ signaling has a significant impact on the development of diseases and the impairment of neuronal functions. Herein, the study reports a Ca2+ ion sensor in neuronal cells using a gold nanorod. The gold nanorod (GA-GNR) conjugated glutamic acid developed in the study was used as a nano-bio probe for the experimental and in vitro detection of calcium. The nanosensor is colloidally stable, preserves plasmonic properties, and shows good viability in neuronal cells, as well as promoting neuron cell line growth. The cytotoxicity and cell penetration of the nanosensor are studied using Raman spectroscopy, brightfield and darkfield microscopy imaging, and MTT assays. The quantification of Ca2+ ions in neuronal cells is determined by monitoring the surface plasmon resonance (SPR) of the GA-GNR. The change in the intensity profile in the presence of Ca2+ incubated neurons was effectively used to develop a portable prototype of an optical Ca2+ sensor, proposing it as a tool for neurodegenerative disease diagnosis and neuromodulation evaluation.

A Schottky/Z-Scheme Hybrid for Augmented Photocatalytic H2 and H2O2 Production.

The prodigious employment of fossil fuels to conquer the global energy demand is becoming a dreadful threat to the human society. This predicament is appealing for a potent photocatalyst that can generate alternate energy sources via solar to chemical energy conversion. With this interest, we have fabricated a ternary heterostructure of Ti3C2 nanosheet modified g-C3N4/Bi2O3 (MCNRBO) Z-scheme photocatalyst through self-assembly process. The morphological analysis clearly evidenced the close interfacial interaction between g-C3N4 nanorod, Bi2O3 and Ti3C2 nanosheets. The oxygen vacancy created on Bi2O3 surface, as suggested by XPS and EPR analysis, supported the Z-scheme heterojunction formation between g-C3N4 nanorod and Bi2O3 nanosheets. The collaborative effect of Z-scheme and Schottky junction significantly reduced charge transfer resistance promoting separation efficiency of excitons as indicated from PL and EIS analysis. The potential of MCNRBO towards photocatalytic application was investigated by H2O2 and H2 evolution reaction. A superior photocatalytic H2O2 and H2 production rate for MCNRBO is observed, which are respectively around 5 and 18 folds higher as compared to pristine CNR nanorod. The present work encourages for the development of a noble, eco-benign and immensely efficient dual heterojunction based photocatalyst, which can acts as saviour of human society from energy crisis.

Gold Nanorod-Embedded PDMS Micro-Pillar Array for Localized Photothermal Stimulation.

Gold nanorods (GNRs) are one of the most promising biomaterial choices for the photothermal activation of neurons due to their relative biocompatibility, unique photothermal properties, and broad optical tunability through their synthetic shape control. While photothermal stimulation using randomly accumulated GNRs successfully demonstrates the potential treatment of functional neural disorders by modulating the neuronal activities using localized heating, there are limited demonstrations to translate this new concept into large-arrayed neural stimulations. In this paper, we report an arrayed PDMS micropillar platform in which GNRs are embedded as pixel-like, arrayed photothermal stimulators at the tips of the pillars. The proposed platform will be able to localize GNRs at predetermined pillar positions and create thermal stimulations using near-infrared (NIR) light. This will address the limitations of randomly distributed GNR-based approaches. Furthermore, a flexible PDMS pillar structure will create intimate interfaces on target cells. By characterizing the spatiotemporal temperature change in the platform with rhodamine B dye, we have shown that the localized temperature can be optically modulated within 4°C, which is in the range of temperature variation required for neuromodulation using NIR light. We envision that our proposed platform has the potential to be applied as a photothermal, neuronal stimulation interface with high spatiotemporal resolution.

Wetting behavior of stainless-steel surface with zinc oxide nanorod coatings: modulations in nanorod alignment through atomic layer deposition.

This study investigated the hydrophobic-hydrophilic characteristics of zinc oxide (ZnO) nanorod coatings for potential biomedical applications. We examined the effects of different alignments of ZnO nanorods on the wetting and mechanical characteristics of the coatings. ZnO seed layers were prepared on stainless-steel plates using atomic layer deposition (ALD) at five different temperatures ranging from 50 to 250 °C. The ZnO nanorod coatings were then deposited on these seed layers through chemical bath deposition. The polycrystalline structure of the seed layers and the morphology of the nanorods were analyzed using grazing incidence angle x-ray diffraction, transmission electron microscopy, and scanning electron microscopy. Mechanical and wetting properties of the nanorod coatings were examined using nanoindentation and water-droplet tests. The seed layers produced at 50 and 250 °C showed stronger (0 0 2) peaks than the other layers. ZnO nanorods on these seed layers exhibited greater vertical orientation and lower water contact angles indicating a more hydrophilic surface. Additionally, vertically oriented nanorod coatings demonstrated greater elastic modulus and hardness than those of oblique nanorods. Our findings indicate that ALD technology can be used to control the spatial arrangement of ZnO nanorods and optimize the hydrophobic-hydrophilic and mechanical properties of coating surfaces.

TiO2nanorod arrays/Ti3C2TxMXene nanosheet composites with efficient photocatalytic activity.

Semiconductor photocatalysis holds significant promise in addressing both environmental and energy challenges. However, a major hurdle in photocatalytic processes remains the efficient separation of photoinduced charge carriers. In this study, TiO2nanorod arrays were employed by glancing angle deposition technique, onto which Ti3C2TxMXene was deposited through a spin-coating process. This hybrid approach aims to amplify the photocatalytic efficacy of TiO2nanorod arrays. Through photocurrent efficiency characterization testing, an optimal loading of TiO2/Ti3C2Txcomposites is identified. Remarkably, this composite exhibits a 40% increase in photocurrent density in comparison to pristine TiO2. This enhancement is attributed to the exceptional electrical conductivity and expansive specific surface area inherent to Ti3C2TxMXene. These attributes facilitate swift transport of photoinduced electrons, consequently refining the separation and migration of electron-hole pairs. The synergistic TiO2/Ti3C2Txcomposite showcases its potential across various domains including photoelectrochemical water splitting and diverse photocatalytic devices. As such, this composite material stands as a novel and promising entity for advancing photocatalytic applications. This study can offer an innovative approach for designing simple and efficient photocatalytic materials composed of MXene co-catalysts and TiO2for efficient water electrolysis on semiconductors.

Photoelectrochemical properties of self-powered corundum-structured Ga2O3nanorod array/fluorine-doped SnO2photodetectors modulated by precursor concentrations.

Herein, corundum-structured Ga2O3(α-Ga2O3) nanorod array/fluorine-doped SnO2(FTO) structures have been fabricated by hydrothermal and thermal annealing processes with different precursor concentrations from 0.01 to 0.06 M. The diameter and length of the nanorod arrays are much larger with increasing precursor concentrations due to more nucleation sites and precursor ions participating in the reaction procedures. The optical bandgap decreases from 4.75 to 4.47 eV because of the tensile stress relieving with increasing the precursor concentrations. Based on self-powered photoelectrochemical (PEC) photodetectors, the peak responsivity is improved from ∼0.33 mA W-1for 0.06 M to ∼1.51 mA W-1for 0.02 M. Schottky junctions can be formed in PEC cells. More photogenerated carriers can be produced in wider depletion region. From Mott-Schottky plots, the depletion regions become much wider with decreasing the precursor concentrations. Therefore, the enhance responsivity is owing to the wider depletion regions. Due to the reduced possibility of photogenerated holes captured by traps ascribed from fewer green and yellow luminescence defects, smaller charge transfer resistance, and shorter transportation route, the decay time becomes much faster through decreasing the precursor concentrations. Compared with the other self-poweredα-Ga2O3-nanorod-array-based PEC photodetectors, it shows the fastest response time (decay time of 0.005 s/0.026 s) simply modulated by precursor concentrations for the first time without employing complex precursors, seed layers or special device designs. Compared with other high-responsivity monoclinic Ga2O3(ß-Ga2O3) self-powered photodetectors, our devices also show comparable response speed with simple control and design. This work provides the realization of fast-speed self-powered Ga2O3based solar-blind ultraviolet photodetectors by simple modulation processes and design, which is a significant guidance for their applications in warnings, imaging, computing, communication and logic circuit, in the future.

Chitosan-enhanced sensitivity of mercaptoundecanoic acid (MUA)- capped gold nanorod based localized surface plasmon resonance (LSPR) biosensor for detection of alpha-synuclein oligomer biomarker in parkinson's disease.

Alpha-synuclein oligomers play a crucial role in the early diagnosis of Parkinson's disease (PD). In this study, a mercaptoundecanoic acid (MUA)-capped gold nanorod (GNR)-coated and chitosan (CH)-immobilized fiber optic probe has shown considerable sensitivity of its detection. The proposed U-shaped fiber optic biosensor based on localized surface plasmon resonance (LSPR) was applied to detect α-syn oligomer (OA) biomarker. By analyzing OA concentrations, the biosensor achieved a limit of detection of (LOD) 11 pM within the concentration range of 10-100 pM and the sensitivity value was found as 502.69 Δλ/RIU. Upon analysis of the CV% (coefficient of variation) and accuracy/recovery values, it is revealed that the sensor successfully fulfilled the criteria for success, displaying accuracy/recovery values within the range of 80%-120% and CV% values below 20%. This sensor presents significant advantages, including high sensitivity, specificity, and ability to detect very low concentrations of OA. In conclusion, the suggested U-shaped fiber optic biosensor has the potential to be valuable in the early detection of PD from a clinical perspective.

Electrostatically self-assembled gold nanorods with sulfated hyaluronic acid for targeted photothermal therapy for CD44-positive tumors.

Gold nanorods (GNR) produce heat upon irradiation with near-infrared light, enabling a tumor-targeted photothermal therapy. In this study, we prepared GNR coated with sulfated hyaluronic acid (sHA) with a binding affinity for CD44 via electrostatic interactions to deliver GNR to tumors efficiently and stably, and evaluated their usefulness for photothermal therapy. Cationic GNR modified with trimethylammonium groups electrostatically interacted with native HA or sHA with varying degrees of sulfation to form complexes. While GNR/HA was unstable in saline, GNR/sHA maintained the absorbance peak in the near-infrared region, particularly for GNR/sHA with higher degrees of sulfation. GNR/sHA exhibited an intense photothermal effect upon irradiation with near-infrared light. Furthermore, in vitro and in vivo studies revealed that GNR coated with sHA containing approximately 1.2 sulfated groups per HA unit could accumulate in CD44-positive tumors via an HA-specific pathway. These findings indicate the effectiveness of GNR/sHA as a tumor-targeted photothermal therapeutic agent.

Enhanced Acetone Sensing Properties Based on Au-Pd Decorated ZnO Nanorod Gas Sensor.

The mature processes of metal oxide semiconductors (MOS) have attracted considerable interest. However, the low sensitivity of metal oxide semiconductor gas sensors is still challenging, and constrains its practical applications. Bimetallic nanoparticles are of interest owing to their excellent catalytic properties. This excellent feature of bimetallic nanoparticles can solve the problems existing in MOS gas sensors, such as the low response, high operating temperature and slow response time. To enhance acetone sensing performance, we successfully synthesized Au-Pd/ZnO nanorods. In this work, we discovered that Au-Pd nanoparticles modified on ZnO nanorods can remarkably enhance sensor response. The Au-Pd/ZnO gas sensor has long-term stability and an excellent response/recovery process. This excellent sensing performance is attributed to the synergistic catalytic effect of bimetallic AuPd nanoparticles. Moreover, the electronic and chemical sensitization of noble metals also makes a great contribution. This work presents a simple method for preparing Au-Pd/ZnO nanorods and provides a new solution for the detection of acetone based on metal oxide semiconductor.

One-Dimensional ZnO Nanorod Array Grown on Ag Nanowire Mesh/ZnO Composite Seed Layer for H2 Gas Sensing and UV Detection Applications.

Photodetectors and gas sensors are vital in modern technology, spanning from environmental monitoring to biomedical diagnostics. This paper explores the UV detection and gas sensing properties of a zinc oxide (ZnO) nanorod array (ZNA) grown on silver nanowire mesh (AgNM) using a hydrothermal method. We examined the impact of different zinc acetate precursor concentrations on their properties. Results show the AgNM forms a network with high transparency (79%) and low sheet resistance (7.23 Ω/□). A sol-gel ZnO thin film was coated on this mesh, providing a seed layer with a hexagonal wurtzite structure. Increasing the precursor concentration alters the diameter, length, and area density of ZNAs, affecting their performance. The ZNA-AgNM-based photodetector shows enhanced dark current and photocurrent with increasing precursor concentration, achieving a maximum photoresponsivity of 114 A/W at 374 nm and a detectivity of 6.37 × 1014 Jones at 0.05 M zinc acetate. For gas sensing, the resistance of ZNA-AgNM-based sensors decreases with temperature, with the best hydrogen response (2.71) at 300 °C and 0.04 M precursor concentration. These findings highlight the potential of ZNA-AgNM for high-performance UV photodetectors and hydrogen gas sensors, offering an alternative way for the development of future sensing devices with enhanced performance and functionality.

Drug-Free Antimicrobial Nanomotor for Precise Treatment of Multidrug-Resistant Bacterial Infections.

Manufacturing heteronanostructures with specific physicochemical characteristics and tightly controllable designs is very appealing. Herein, we reported NIR-II light-driven dual plasmonic (AuNR-SiO2-Cu7S4) antimicrobial nanomotors with an intended Janus configuration through the overgrowth of copper-rich Cu7S4 nanocrystals at only one high-curvature site of Au nanorods (Au NRs). These nanomotors were applied for photoacoustic imaging (PAI)-guided synergistic photothermal and photocatalytic treatment of bacterial infections. Both the photothermal performance and photocatalytic activity of the nanomotors are dramatically improved owing to the strong plasmon coupling between Au NRs and the Cu7S4 component and enhanced energy transfer. The motion behavior of nanomotors promotes transdermal penetration and enhances the matter-bacteria interaction. More importantly, the directional navigation and synergistic antimicrobial activity of the nanomotors could be synchronously driven by NIR-II light. The marriage of active motion and enhanced antibacterial activity resulted in the expected good antibacterial effects in an abscess infection mouse model.

Size Dependence of Gold Nanorods for Efficient and Rapid Photothermal Therapy.

In recent years, gold nanomaterials have become a hot topic in photothermal tumor therapy due to their unique surface plasmon resonance characteristics. The effectiveness of photothermal therapy is highly dependent on the shape and size of gold nanoparticles. In this work, we investigate the photothermal therapeutic effects of four different sizes of gold nanorods (GNRs). The results show that the uptake of short GNRs with aspect ratios 3.3-3.5 by cells is higher than that of GNRs with aspect ratios 4-5.5. Using a laser with single pulse energy as low as 28 pJ laser for 20 s can induce the death of liver cancer cells co-cultured with short GNRs. Long GNRs required twice the energy to achieve the same therapeutic effect. The dual-temperature model is used to simulate the photothermal response of intracellular clusters irradiated by a laser. It is found that small GNRs are easier to compact because of their morphological characteristics, and the electromagnetic coupling between GNRs is better, which increases the internal field enhancement, resulting in higher local temperature. Compared with a single GNR, GNR clusters are less dependent on polarization and wavelength, which is more conducive to the flexible selection of excitation laser sources.

Tungsten-based nanocatalysts with different structures for visible light responsive photocatalytic degradation of bisphenol A.

Environmental pollution, such as water contamination, is a critical issue that must be absolutely addressed. Here, three different morphologies of tungsten-based photocatalysts (WO3 nanorods, WO3/WS2 nanobricks, WO3/WS2 nanorods) are made using a simple hydrothermal method by changing the solvents (H2O, DMF, aqueous HCl solution). The as-prepared nanocatalysts have excellent thermal stability, large porosity, and high hydrophilicity. The results show all materials have good photocatalytic activity in aqueous media, with WO3/WS2 nanorods (NRs) having the best activity in the photodegradation of bisphenol A (BPA) under visible-light irradiation. This may originate from increased migration of charge carriers and effective prevention of electron‒hole recombination in WO3/WS2 NRs, whereby this photocatalyst is able to generate more reactive •OH and •O2- species, leading to greater photocatalytic activity. About 99.6% of BPA is photodegraded within 60 min when using 1.5 g/L WO3/WS2 NRs and 5.0 mg/L BPA at pH 7.0. Additionally, the optimal conditions (pH, catalyst dosage, initial BPA concentration) for WO3/WS2 NRs are also elaborately investigated. These rod-like heterostructures are expressed as potential catalysts with excellent photostability, efficient reusability, and highly active effectivity in different types of water. In particular, the removal efficiency of BPA by WO3/WS2 NRs reduces by only 1.5% after five recycling runs and even reaches 89.1% in contaminated lake water. This study provides promising insights for the nearly complete removal of BPA from wastewater or different water resources, which is advantageous to various applications in environmental remediation.