Fabrication of heterogeneous bimetallic nanochains through photochemical welding for promoting the electrocatalytic hydrogen evolution reaction.

Heterogeneous bimetallic nanochains (NCs) have gained significant attention in the field of catalysis due to their abundant active sites, multi-component synergistic catalytic, and exotic electronic structures. Here, we present a novel approach to synthesize one-dimensional heterogeneous bimetallic nanochains using a local surface plasmon resonance (LSPR) based strategy of liquid-phase photochemical welding method containing self-assembly and subsequent welding processes. Initially, we introduce additives that facilitate the self-assembly and alignment of Au nanoparticles (NPs) into orderly lines. Subsequently, the LSPR effect of the Au NPs is stimulated by light, enabling the second metal precursor to overcome the energy barrier and undergo photodeposition in the gap between the arranged Au NPs, thereby connecting the nano-metal particles. This strategy can be extended to the photochemical welding of Au NPs-Ag and Au NRs. Using electrocatalytic hydrogen evolution reaction (HER) as a proof-of-concept application, the obtained one-dimensional structure of Au5Pt1 NCs exhibit promoted HER performances, where the mass activity of the Au5Pt1 nanochains is found to be 4.8 times higher than that of Au5Pt1 NPs and 10.4 times higher than that of commercial 20 wt% Pt/C catalysts. The promoted HER performance is benefited from the electron conduction ability and abundant active sites.

Arsenic Monolayers Formed by Zero-Dimensional Tetrahedral Clusters and One-Dimensional Armchair Nanochains.

One-dimensional (1D) arsenene nanostructures are predicted to host a variety of interesting physical properties including antiferromagnetic, semiconductor-semimetal transition and quantum spin Hall effect, which thus holds great promise for next-generation electronic and spintronic devices. Herein, we devised a surface template strategy in a combination with surface-catalyzed decomposition of molecular As4 cluster toward the synthesis of the superlattice of ultranarrow armchair arsenic nanochains in a large domain on Au(111). In the low annealing temperature window, zero-dimensional As4 nanoclusters are assembled into continuous films through intermolecular van der Waals and molecule-substrate interactions. At the elevated temperature, the subsequent surface-assisted decomposition of molecular As4 nanoclusters leads to the formation of a periodic array of 1D armchair arsenic nanochains that form a (2 × 3) superstructure on the Au(111) surface. These ultranarrow armchair arsenic nanochains are predicted to have a small bandgap of ∼0.50 eV, in contrast to metallic zigzag chains. In addition, the Au-supported arsenic nanochains can be flipped to form a bilayer structure through tip indentation and manipulation, suggesting the possible transfer of these nanochains from the substrate. The successful realization of arsenic nanostructures is expected to advance low-dimensional physics and infrared optoelectronic nanodevices.

PtCuFe alloy nanochains: Synthesis and composition-performance relationship in methanol oxidation and hydrogen evolution reactions.

The controllable synthesis of 1-dimensional (1D) multi-metal Pt-based alloys, with enhanced electro-chemical properties remains a challenge, despite the wide application of Pt-based catalysts in fuel cells and in the hydrogen evolution reaction (HER). Herein, we fabricate PtCuFe alloy nanochains (NCs) that have a tunable composition by flexibly adjusting the molar ratios of the metal precursors. It was found that Cu2+ is key in the formation of 1D NCs, as confirmed by transmission electron microscopy characterizations. In addition, the alloyed Fe can further increase the content of the metallic state of Cu in the PtCuFe NCs. The as-prepared PtCuFe NCs exhibited higher catalytic activity and stability than those of the Pt nanoparticles (NPs), PtFe NPs, and PtCu NCs, for the methanol oxidation reaction (MOR) and HER. Additionally, the composition-performance relationship of PtCuxFey NCs toward the MOR and HER were investigated. The hybrid density functional theory calculation and analysis showed that the 1D PtCuFe NCs have a lower lowest unoccupied molecular orbital (LUMO) than those of the 2- and 3-dimensional PtCuFe, verifying that the 1D PtCuFe NCs exhibit the highest activity for the MOR. This work has established a new method for the controllable synthesis of multi-metal Pt-based NCs/alloy catalysts and their subsequent applications in other electro-catalytic reactions.

SHMT1 siRNA-Loaded hyperosmotic nanochains for blood-brain/tumor barrier post-transmigration therapy.

The near-perivascular accumulation in solid tumors and short-lived span in circulation, derails even the most competent nanoparticles (NPs) from achieving their maximum therapeutic potential. Moreover, delivering them across the blood brain/tumor barrier (BBB/BTB) is further challenging to sought anticancer effect. To address these key challenges, we designed a linearly aligned nucleic acid-complexed polydixylitol-based polymeric nanochains (X-NCs), with inherent hyperosmotic properties enabling transmigration of the BBB/BTB and navigation through deeper regions of the brain tumor. The high aspect ratio adds shape-dependent functional aspects to parent particles by providing effective payload increment and nuclear factor of activated T cells-5 (NFAT5)-mediated cellular uptake. Therefore, serine hydroxymethyltransferase 1 (SHMT1) siRNA-loaded nanochains not only demonstrated to transmigrate the BTB, but also resulted in remarkably reducing the tumor size to 97% in the glioblastoma xenograft brain tumor mouse models. Our study illustrates how the hyperosmotic nanochains with high aspect ratio and aligned structure can accelerate a therapeutic effect in aggressive brain tumors post-transmigration of the BBB/BTB by utilizing an NFAT5 mode of uptake mechanism.

Magnetic-Field-Induced Improvement of Photothermal Sterilization Performance by Fe3O4@SiO2@Au/PDA Nanochains.

Due to the abuse of antibiotics, the sensitivity of patients to antibiotics is gradually reduced. This work develops a Fe3O4@SiO2@Au/PDA nanochain which shows an interesting magnetic-field-induced improvement of its photothermal antibacterial property. First, SiO2 was wrapped on Fe3O4 nanospheres assembled in a chain to form a Fe3O4@SiO2 nanocomposite with a chain-like nanostructure. Then, the magnetic Fe3O4@SiO2@Au/PDA nanochains were prepared using in situ redox-oxidization polymerization. Under the irradiation of an 808 nm NIR laser, the temperature rise of the Fe3O4@SiO2@Au/PDA nanochain dispersion was obvious, indicating that they possessed a good photothermal effect. Originating from the Fe3O4, the Fe3O4@SiO2@Au/PDA nanochain showed a typical soft magnetic behavior. Both the NIR and magnetic field affected the antimicrobial performance of the Fe3O4@SiO2@Au/PDA nanochains. Escherichia coli and Staphylococcus aureus were used as models to verify the antibacterial properties. The experimental results showed that the Fe3O4@SiO2@Au/PDA nanochains exhibited good antibacterial properties under photothermal conditions. After applying a magnetic field, the bactericidal effect was further significantly enhanced. The above results show that the material has a broad application prospect in inhibiting the growth of bacteria.

Near-Field Imaging and Time-Domain Dynamics of Photonic Topological Edge States in Plasmonic Nanochains.

Time-domain dynamic evolution properties of topological states play an important role in both fundamental physics study and practical applications of topological photonics. However, owing to the absence of available ultrafast time-domain dynamic characterization methods, studies have mostly focused on the frequency-domain-based properties, and there are few reports demonstrating the time-domain-based properties. Here, we measured the dynamic near-field responses of plasmonic topological structures of gold nanochains with the configuration of the Su-Schrieffer-Heeger model by using ultrahigh spatial-temporal resolution photoemission electron microscopy. The dephasing time of plasmonic topological edge states increases with increasing the bulk lattice number that has a threshold requirement and finally reaches saturation. We directly revealed through simulation that there is a transient bulk state in the evolution of topological edge states, that is, the energy undergoes relaxation from oscillation between the bulk lattice and the edge. This work shows a new perspective of time-domain dynamic topological photonics.

3D Magnetic Field-Controlled Synthesis, Collective Motion, and Bioreaction Enhancement of Multifunctional Peasecod-like Nanochains.

Magnetic field-induced synthesis and biocatalysis of magnetic materials have inspired great interest due to the flexible controllability of morphologies and unique magnetoelectrical properties. However, the interaction of the magnetic field and the reaction kinetics during the synthesis of magnetic nanochains has not been revealed. The collective motions in fluids and the multifunctional enhancements for bioreaction of 3D magnetic-controlled nanochains have not been systematically researched. Here, an integrated 3D magnetic control method was reported for the synthesis, collective motion, and multifunctional bioreaction enhancement of peasecod-like nanochains. The interactions of magnetic field and reaction kinetics were rationally controlled to synthesize magnetic nanochains of different morphologies. Collective motions of nanochains under alternating magnetic fields were studied to provide insights into the disturbance on confined fluids. Three mechanisms of reaction enhancement of nanostir, magnetic agent, and nanocatalyst were achieved simultaneously via 3D magnetic-controlled nanochains using a glucose oxidase-horseradish peroxidase multi-enzyme system. The peasecod-like nanochain also exhibited excellent reaction enhancement in cell-free protein synthesis reaction, which is desired for effective high-throughput screening. The integrated 3D magnetic control method through the whole process from fabrication to applications of magnetic nanomaterials could be extended to multifunctional biocatalysis and multi-task biomedicine.

Magnetic nanochains-based dynamic ELISA for rapid and ultrasensitive detection of acute myocardial infarction biomarkers.

Acute myocardial infarction (AMI) is the leading cause of morbidity and mortality globally. The serum levels of a group of cardiac biomarkers have been regarded as important indicators in the routine diagnosis of AMI. The development of rapid, sensitive, and accurate detection methods of AMI biomarkers is urgently needed for the early diagnosis of AMI. Here, a dynamic and pseudo-homogeneous enzyme-linked immunosorbent assay (ELISA) was reported based on the combined use of bioconjugated magnetic nanochains (MNCs) and gold nanoparticles (AuNPs) probes. The capture antibodies-conjugated MNCs served as dynamic nano-mixers to facilitate liquid mixing and as homogeneously dispersed capturing agents to capture and separate specific targets. The AuNPs probes were prepared by co-immobilization of detection antibodies and horseradish peroxidase (HRP) for signals amplification. The design of bioconjugated MNCs and AuNPs probes significantly increased the assay kinetics and improves the assay sensitivity. This novel ELISA strategy realized accurate detection of a panel of AMI biomarkers within 35 min, leading to considerably improved sensitivities compared to that of conventional ELISA method.

Tailoring Broad-Band-Absorbed Thermoplasmonic 1D Nanochains for Smart Windows with Adaptive Solar Modulation.

Controlling solar transmission through windows promises to reduce building energy consumption. A new smart window for adaptive solar modulation is presented in this work proposing the combination of the photothermal one-dimensional (1D) Au nanochains and thermochromic hydrogel. In this adaptive solar modulation system, the Au nanochains act as photoresponsive nanoheaters to stimulate the optical switching of the thermochromic hydrogel. By carefully adjusting the electrostatic interactions between nanoparticles, different chain morphologies and plateau-like broad-band absorption in the NIR region are achieved. Such broad-band-absorbed 1D nanochains possess excellent thermoplasmonic effect and enable the solar modulation with compelling features of improved NIR light shielding, high initial visible transmittance, and fast response speed. The designed smart window based on 1D Au nanochains is capable of shielding 94.1% of the solar irradiation from 300 to 2500 nm and permitting 71.2% of visible light before the optical switching for indoor visual comfort. In addition, outdoor cooling tests in model house under continuous natural solar irradiation reveal the remarkable passive cooling performance up to ∼7.8 °C for the smart window based on 1D Au nanochains, showing its potential in the practical application of building energy saving.

Transmittance Tunable Smart Window Based on Magnetically Responsive 1D Nanochains.

Smart optical materials are drawing more and more attention because of their wide application in energy conservation, wearable sensors, optical tuning, and medical devices. However, current smart optical materials, including electroresponsive, thermoresponsive, and mechanoresponsive materials, are greatly restricted in practical applications because of their long response time, complicated preparation, and high cost. This study develops a novel, magnetically tunable, smart optical material with swift and high-contrast optical switching based on one-dimensional (1D) Fe3O4@SiO2 nanochains (NCs), which have the large shape anisotropy of the 1D structure and the superparamagnetic properties of Fe3O4 particles. The material exhibited a clear transparent state when NCs were arranged parallel to the viewing direction under an applied magnetic field, whereas it showed good shielding effect when the NCs were randomly oriented upon removal of the field. The light transmittance could be dynamically adjusted over the wide range of 20-80% through a small applied magnetic field of 50-100 Oe, which is superior to most of the currently reported systems. This swift, sensitive, and reversible response is attributed to the good responsivity of magnetic NCs. Also, an effective model was proposed to explain the transmittance modulation scheme and forecast its optical potential. The large tunable range and the low triggered field make Fe3O4@SiO2 NCs an advantageous candidate for application in smart windows, optical switchers, and other fields.

Synthesis of Podlike Magnetic Mesoporous Silica Nanochains for Use as Enzyme Support and Nanostirrer in Biocatalysis.

Magnetic mesoporous materials have attracted great interest due to their combined property of magnetic nanomaterials and mesoporous materials as well as their potential applications in catalysis, bioenrichment, drug delivery, nanoreactors, etc. In this study, one-dimensional (1D) podlike magnetic mesoporous silica nanochains with tunable hollow space (Fe3O4@nSiO2@void@mSiO2 nanochain named as podlike 1D magnetic mesoporous silica (PL-MMS) nanochain) are rationally synthesized for the first time through a controlled magnetic-induced interface coassembly approach. The obtained PL-MMS possesses a tunable diameter (300-500 nm), large and perpendicular mesopores (8.2 nm) in the outer shell, a silica-protected magnetic-responsive core, and a high surface area (325 m2/g). Benefiting from the large voids and unique mesopores, these mesoporous nanochains exhibit superior performance in enzyme (lipase with a size of 4.0 nm) immobilization with a high loading capacity of 223 µg/mg, and the immobilized lipase demonstrates enhanced catalytic activity in different pH values and temperatures as well as excellent tolerance of organic solvent.

Magnetic Layer-by-Layer Assembly: From Linear Plasmonic Polymers to Oligomers.

One-dimensional nanostructures with controllable aspect ratios are essential for a wide range of applications. An approach for magnetic superparticle (SP) assembly over large areas (55 mm × 25 mm) is introduced via co-assistance of electrostatic and magnetic fields, so-called magnetic layer-by-layer assembly, on an arbitrary hydrophilic substrate within minutes. The SP structures [diameter (d) = 120-350 nm] of Fe3O4 or Ag@Fe3O4 composites composed of hundreds of magnetite nanocrystals (d = 10-20 nm) are used as colloidal monomers to fabricate arrays of high aspect ratio (up to 102) linear nanochains, viz. colloidal polymers, where thermal disturbances were minimized. The arrays of colloidal polymers exhibit strong optical polarization effects owing to their geometrical anisotropy, which can be used as a simple optical filter. Furthermore, by using the binary colloidal mixture of different magnetic colloids, including different sized Fe3O4 and magnetoplasmonic Ag@Fe3O4, low aspect ratio (2-15) colloidal chains, viz. magnetic/plasmonic oligomers, with tunable lengths were fabricated, affording a facile but an effective approach to modulate the optical properties of the chains. The scalable fabrication of well-aligned, linear colloidal polymers and oligomers opens up appealing opportunities for the development of sensors, subwavelength waveguides, optical tweezers, and enhanced solar harvesting devices.

Polyhedron-Assembled Ternary PtCuCo Nanochains: Integrated Functions Enhance the Electrocatalytic Performance of Methanol Oxidation at Elevated Temperature.

Recently, the preparation of a high-performance one-dimensional alloy nanostructure for fuel cells has been given increasing attention due to its smart-structure merits and electronic effect triggered by alloying different kinds of metals at the nanoscale. In this study, unique ternary PtCuCo nanochains assembled with small polyhedra are first achieved and used as high-performance anode electrocatalysts toward methanol oxidation at elevated temperature (60 °C) that is closer to the operating temperature of direct methanol fuel cells than room temperature. The specific activity/mass activity of Pt45Cu35Co20 one-dimensional nanochains can reach up to 18.24 mA cm-2/4.19 A mg-1Pt that is 9.25/10.47 times that of commercial Pt black in sulfuric acid medium. After a 3600 s durability test, the remaining current density of Pt45Cu35Co20 one-dimensional nanochains is 73.3 times that of commercial Pt black. The structure characterizations show that the high density of surface active sites, d-band center of the Pt downshift, moderate strain effect, and synergetic effect are jointly responsible for the enhanced electrocatalytic performance of one-dimensional ternary PtCuCo nanochains.

Promising Ti3C2Tx MXene/Ni Chain Hybrid with Excellent Electromagnetic Wave Absorption and Shielding Capacity.

Electromagnetic (EM) pollution affecting people's normal lives and health has attracted considerable attention in the current society. In this work, a promising EM wave absorption and shielding material, MXene/Ni hybrid, composed of one-dimensional Ni nanochains and two-dimensional Ti3C2Tx nanosheets (MXene), is successfully designed and developed. As expected, excellent EM wave absorption and shielding properties are obtained and controlled by only adjusting the MXene content in the hybrid. A minimum reflection loss of -49.9 dB is obtained only with a thickness of 1.75 mm at 11.9 GHz when the MXene content is 10 wt %. Upon further increasing the MXene content to 50 wt %, the optimal EM shielding effectiveness (SE) reaches 66.4 dB with an absorption effectiveness (SEA) of 59.9 dB. Mechanism analysis reveals that the excellent EM wave absorption and shielding performances of the hybrid are contributed to the synergistic effect of conductive MXene and magnetic Ni chains, by which, the dielectric properties and electromagnetic loss can be easily controlled to obtain appropriate impedance matching conditions and good EM wave dissipation ability. This work provides a simple but effective route to develop MXene-based EM wave absorption and shielding materials. A universal guideline for designing the absorbing and shielding materials for the future is also proposed.

Synthesis of defect-rich palladium-tin alloy nanochain networks for formic acid oxidation.

Unique and novel Pd4Sn nanochain networks were successfully synthesized with an average diameter of 5 nm, rendering a modified Pd electronic structure with rich defects such as atomic corners, steps or ledges as catalytic active sites for great enhancement of charge transfer and electrode kinetics. The prepared Pd4Sn nanochain networks held an electrochemically active surface area as high as 119.40 m2 g-1, and exhibited higher catalytic activity and stability toward formic acid oxidation compared with Pd3Sn nanochain networks, Pd5Sn nanochain networks, Pd4Sn dendrites and Pd/C. The fundamental insight of the enhancement mechanism is discussed, and this work offers a novel, less expensive but highly active catalyst for direct formic acid fuel cells.

A Magnetic-Field Guided Interface Coassembly Approach to Magnetic Mesoporous Silica Nanochains for Osteoclast-Targeted Inhibition and Heterogeneous Nanocatalysis.

1D core-shell magnetic materials with mesopores in shell are highly desired for biocatalysis, magnetic bioseparation, and bioenrichment and biosensing because of their unique microstructure and morphology. In this study, 1D magnetic mesoporous silica nanochains (Fe3 O4 @nSiO2 @mSiO2 nanochain, Magn-MSNCs named as FDUcs-17C) are facilely synthesized via a novel magnetic-field-guided interface coassembly approach in two steps. Fe3 O4 particles are coated with nonporous silica in a magnetic field to form 1D Fe3 O4 @nSiO2 nanochains. A further interface coassembly of cetyltrimethylammonium bromide and silica source in water/n-hexane biliquid system leads to 1D Magn-MSNCs with core-shell-shell structure, uniform diameter (≈310 nm), large and perpendicular mesopores (7.3 nm), high surface area (317 m2 g-1 ), and high magnetization (34.9 emu g-1 ). Under a rotating magnetic field, the nanochains with loaded zoledronate (a medication for treating bone diseases) in the mesopores, show an interesting suppression effect of osteoclasts differentiation, due to their 1D nanostructure that provides a shearing force in dynamic magnetic field to induce sufficient and effective reactions in cells. Moreover, by loading Au nanoparticles in the mesopores, the 1D Fe3 O4 @nSiO2 @mSiO2 -Au nanochains can service as a catalytically active magnetic nanostirrer for hydrogenation of 4-nitrophenol with high catalytic performance and good magnetic recyclability.

Poly-l-lysine mediated synthesis of palladium nanochain networks and nanodendrites as highly efficient electrocatalysts for formic acid oxidation and hydrogen evolution.

The morphology- and size-tunable synthesis of nanocatalysts has attracted substantial research interest especially in catalysis. In this work, we synthesized free-standing Pd nanochain networks (Pd NCNs) and Pd nanodendrites (Pd NDs) through a direct poly-l-lysine (PLL)-mediated one-pot aqueous method. The presence of PLL and its concentrations were critical in this regard, showing PLL as the structure-directing and capping agents during the nucleation and crystal growth procedures. The synthesized architectures exhibited improved catalytic activity and enhanced durability towards formic acid oxidation and hydrogen evolution reactions relative to commercial Pd black catalyst. Moreover, the electrochemical active surface area and the electrocatalytic performance of Pd NCNs were dramatically enhanced in comparison to Pd NDs mainly owing to the unique network-like structure of Pd NCNs.

Tuning Plasmon Resonance in Magnetoplasmonic Nanochains by Controlling Polarization and Interparticle Distance for Simple Preparation of Optical Filters.

Magnetoplasmonic Fe3O4-coated Ag nanoparticles (NPs) are assembled in large scale (18 × 18 mm2) in order to observe unique modulation of plasmonic coupling and optical tunable application via both external magnetic field and the combination of magnetic dipole and electrostatic interactions of particle-particle and particle-substrate. These large nanochains film exhibits outstanding tunability of plasmonic resonance from visible to near-infrared range by controlling the polarization angle and interparticle distance (IPD). The enormous spectral shift mainly originated from far-field rather than near-field coupling of Ag cores because of the sufficiently large separation between them in which Fe3O4 shell acts as spacer. This tunable magnetoplasmonic film can be applicable in the field of anisotropic optical waveguides, tunable optical filter, and nanoscale sensing platform.

A theoretical study on monoatomic BN nanochains and nanorings.

Boron nitride (BN) nanochains were successfully synthesized recently. In this work, we investigate the electronic, energetic, and structural properties of BN nanochains and nanorings by means of density functional theory calculations. Our calculations support the experimental findings and offer additional physical insights into these new nanostructured materials. We show that BN nanochains are biracial compounds that tend to be closed and form a ring. They have single and double bonds alternately throughout the chain. The boron atoms are not saturated and are strong Lewis acids. Increase in the length of the chain tends to result in the conversion from a semiconductor to a semimetal material. The ring structures are stabler than the corresponding chains, and unlike the chains these structures are predicted to be insulators. The binding energy of the chains and rings increases with an increase in their size. Rings with odd or even numbers of BN units show different electronic properties.

A new silver nanochain SERS analytical platform to detect trace hexametaphosphate with a rhodamine S molecular probe.

Using AgNO3 as the precursor, stable silver nanochain (AgNC) sols, orange-red in color, were prepared using hydrazine hydrate. A strong surface plasmon resonance Rayleigh scattering (RRS) peak occurred at 420 nm plus two surface plasmon resonance (SPR) absorption peaks at 410 nm and 510 nm. Rhodamine S (RhS) cationic dye was absorbed on the as-prepared AgNC substrate to obtain a RhS-AgNC surface-enhanced Raman scattering (SERS) nanoprobe that exhibited a strong SERS peak at 1506 cm(-1) and a strong RRS peak at 375 nm. Upon addition of the analyte sodium hexametaphosphate (HP), it reacted with RhS, which resulted in a decrease in the SERS and RRS peaks that was studied in detail. The decreased SERS and RRS intensities correlated linearly with HP concentration in the range of 0.0125-0.3 µmol/L and 0.05-1.0 µmol/L, with a detection limit of 6 nmol/L and 20 nmol/L HP respectively. Due to advantages of high sensitivity, good selectivity and simple operation, the RhS molecular probes were used to determine HP concentration in real samples.