Electric-Field-Assisted Synthesis of Cu/MoS2 Nanostructures for Efficient Hydrogen Evolution Reaction.

Molybdenum sulfide-oxide (MoS2, MS) emerges as the prime electrocatalyst candidate demonstrating hydrogen evolution reaction (HER) activity comparable to platinum (Pt). This study presents a facile electrochemical approach for fabricating a hybrid copper (Cu)/MoS2 (CMS) nanostructure thin-film electrocatalyst directly onto nickel foam (NF) without a binder or template. The synthesized CMS nanostructures were characterized utilizing energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and electrochemical methods. The XRD result revealed that the Cu metal coating on MS results in the creation of an extremely crystalline CMS nanostructure with a well-defined interface. The hybrid nanostructures demonstrated higher hydrogen production, attributed to the synergistic interplay of morphology and electron distribution at the interface. The nanostructures displayed a significantly low overpotential of -149 mV at 10 mA cm-2 and a Tafel slope of 117 mV dec-1, indicating enhanced catalytic activity compared to pristine MoS2.This research underscores the significant enhancement of the HER performance and conductivity achieved by CMS, showcasing its potential applications in renewable energy.

Magnetoplasmonic photonic arrays for rapid and selective colorimetric detection of chloride ions in water.

The rapid and efficient detection of chloride (Cl-) ions is crucial in a variety of fields, making the development of advanced sensing methods such as colorimetric sensors an imperative advancement in analytical chemistry. Herein, a novel, selective, and straightforward paper-based colorimetric sensing platform has been developed utilizing an amorphous photonic array (APA) of magnetoplasmonic Ag@Fe3O4 nanoparticles (MagPlas NPs) for the detection of Cl- in water. Taking advantage of the highly responsive APA, the key principle of this sensing method is based on the chemical reaction between Ag+ and Cl-, which results in the precipitation of high-refractive index (RI) AgCl. This assay, distinct from typical plasmonic sensors that rely heavily on nanoparticle aggregation/anti-aggregation, is premised on the precipitation reaction of Ag+ and Cl-. In the presence of Cl-, a rapid, distinctive color alteration from royal purple to a dark sky blue is visually observable within a short time of a few minutes, eliminating the necessity for any surface modification procedures. Comprehensive assessments substantiated that these sensors display commendable sensitivity, selectivity, and stability, thereby establishing their effective applicability for Cl- analysis in various technological fields.

Electron Detachments of NbSin-/0 (n = 1-3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations.

The electronic states of NbSin-/0/+ (n = 1-3) clusters have been explored using the state-of-the-art DMRG-CASPT2 method with relatively large active spaces. The leading configurations, bond distances, vibrational frequencies, and relative energies of the low-lying states were identified. Electron detachment energies of the anionic cluster and ionization energies of the neutral clusters were reported at the DMRG-CASPT2 level. The ground states of the NbSin-/0/+ (n = 1-3) clusters were predicted as the 3Δ, 4Π, and 5Π states of the linear NbSi-/0/+, the 3A2, 4B1, and 3B1 states of cyclic NbSi2-/0/+, and the 1A', 2A', and 3A″ states of tetrahedral NbSi3-/0/+ isomers. The first feature in the photoelectron spectrum of NbSi- was attributed to the transitions from the anionic 3Δ ground state to the neutral 4Π, 4Δ, and 4Φ states, whereas the second feature was assigned to the transitions to the neutral 2Δ, 2Σ+, and 2Φ states. The first band in the photoelectron spectrum of NbSi3- was ascribed to the transition from the anionic 1A' ground state to the neutral 12A' and 12A″ states; the second band was attributed to the transitions to 22A', 22A″, and 32A' states; and the third band was assigned to the transition to 32A' states.

Unveiling the effect of crystallinity and particle size of biogenic Ag/ZnO nanocomposites on the electrochemical sensing performance of carbaryl detection in agricultural products.

In this study, bio-Ag/ZnO NCs were synthesized via a microwave-assisted biogenic electrochemical method using mangosteen (Garcinia mangostana) peel extract as a biogenic reducing agent for the reduction of Zn2+ and Ag+ ions to form hybrid nanoparticles. The as-synthesized NC samples at three different microwave irradiation temperatures (Z 70, Z 80, Z 90) exhibited a remarkable difference in size and crystallinity that directly impacted their electrocatalytic behaviors as well as electrochemical sensing performance. The obtained results indicate that the Z 90 sample showed the highest electrochemical performance among the investigated samples, which is attributed to the improved particle size distribution and crystal microstructure that enhanced charge transfer and the electroactive surface area. Under the optimal conditions for carbaryl pesticide detection, the proposed nanosensor exhibited a high electrochemical sensitivity of up to 0.303 µA µM-1 cm-2 with a detection limit of LOD ∼0.27 µM for carbaryl pesticide detection in a linear range of 0.25-100 µM. Overall, the present work suggests that bio-Ag/ZnO NCs are a potential candidate for the development of a high-performance electrochemical-based non-enzymatic nanosensor with rapid monitoring, cost-effectiveness, and eco-friendly to detect carbaryl pesticide residues in agricultural products.

Electrochemical Investigation of Porosity in Core-Shell Magnetoplasmonic Nanoparticles.

Porous core-shell nanoparticles (NPs) have emerged as a promising material for broad ranges of applications in catalysts, material chemistry, biology, and optical sensors. Using a typical Ag core-Fe3O4 shell NP, a.k.a., magnetoplasmonic (MagPlas) NP, two porous shell models were prepared: i.e., Ag@Fe3O4 NPs and its SiO2-covered NPs (Ag@Fe3O4@SiO2). We suggested using cyclic voltammetry (CV) to provide unprecedented insight into the porosity of the core-shell NPs caused by the applied potential, resulting in the selective redox activities of the core and porous shell components of Ag@Fe3O4 NPs and Ag@Fe3O4@SiO2 NPs at different cycles of CV. The porous and nonporous core-shell nanostructures were qualitatively and quantitatively determined by the electrochemical method. The ratio of the oxidation current peak (µA) of Ag to Ag+ in the porous shell to that in the SiO2 coated (nonporous) shell was 400:3.2. The suggested approach and theoretical background could be extended to other types of multicomponent NP complexes.

Chirality of Fingerprints: Pattern- and Curvature-Induced Emerging Chiroptical Properties of Elastomeric Grating Meta-Skin.

Fingerprint-inspired elastomeric grating meta-skin (EGMS) is herein fabricated to investigate the chirality of fingerprints. The EGMS is made by a facile nanoimprinting method with a diffraction grating as a template using polydimethylsiloxane, followed by gold deposition. The chirality of the surface is caused by symmetry breaking, induced by the pattern (P) and curvature (T). Furthermore, the chiroptical properties of EGMS are reconfigurable through the control of the skew angle (θ), which is the angle between P and T. The chiroptical properties of a fingerprint are also shown and interpreted in this perspective. On the basis of the results, we suggest the strategy to impart chirality on the surface, which is reconfigurable by controlling P and T. It will be a useful method to produce chirality in membranes, thin films, metasurfaces, and 2D nanomaterials, as well as advance biometric recognition.

Rapid Assembly of Magnetoplasmonic Photonic Arrays for Brilliant, Noniridescent, and Stimuli-Responsive Structural Colors.

There are usually trade-offs between maximizing the color saturation and brightness and minimizing the angle-dependent effect in structural colors. Here, a magnetic field-induced assembly for the rapid formation of scalable, uniform amorphous photonic arrays (APAs) featuring unique structural colors is demonstrated. The magnetic field plays a fundamental role in photonic film formation, making this assembly technology versatile for developing structural color patterns on arbitrary substrates. The synergistic combination of surface plasmonic resonance of the Ag core and broadband light absorption of high refractive index (RI) Fe3 O4 shell in hybrid magnetoplasmonic nanoparticles (MagPlas NPs) enables breaking the trade-offs to produce brilliant, noniridescent structural colors with high tunability and responsiveness. These features enable the fabrication of various types of highly sensitive and reliable colorimetric sensors for naked-eye detection without sophisticated instruments. Furthermore, large-scale structural color patterns are effortlessly achieved, demonstrating the high potential of the present approach for full-spectrum displays, active coatings, and rewritable papers.

One-Pot Synthesis of Magnetoplasmonic Au@FexOy Nanowires: Bioinspired Bouligand Chiral Stack.

One-dimensional hybrid nanostructures composed of a plasmonic gold nanowire core covered by a shell of magnetic oxide nanoparticles (Au@FexOy NWs) were synthesized by a one-pot solvothermal synthesis process. The effects of reaction temperature, time, reducing agent, and precursor as well as postsynthesis treatment were optimized to produce highly uniform NWs with a diameter of 226 ± 25 nm and a plasmonic core aspect ratio of 25 to 82. By exploiting the interaction of NWs with an external magnetic field, precise arrangements into highly periodic photonic structures were achieved, which can generate distinctive structural colors that are vividly iridescent and polarization-sensitive. Furthermore, a Bouligand-type chiral nematic film consisting of multistacked unidirectional layers of achiral NWs was fabricated using a modified layer-by-layer deposition method, which displays circular dichroism (CD) and chiral sensing capability. The addition of bovine serum albumin (BSA) as a model protein analyte induced a concentration-dependent wavelength shift of CD peaks. These intriguing properties of magnetoplasmonic anisotropic NWs and their self-assemblies could be consequently valuable for developing nature-inspired structural color imprints as well as solid-state chiral sensing devices.

Clinical Trial: Magnetoplasmonic ELISA for Urine-based Active Tuberculosis Detection and Anti-Tuberculosis Therapy Monitoring.

The coronavirus disease 2019 (COVID-19) pandemic has proved the importance of fast and widespread diagnostic testing to prevent serious epidemics timely. The first-line weapon against rapidly transmitted disease is a quick and massive screening test to isolate patients immediately, preventing dissemination. Here, we described magnetoplasmonic nanozymes (MagPlas NZs), i.e., hierarchically coassembled Fe3O4-Au superparticles, that are capable of integrating magnetic enrichment and catalytic amplification, thereby the assay can be streamlined amenable to high-throughput operation and achieve ultrahigh sensitivity. Combining this advantage with conventional enzyme-linked immunosorbent assay (ELISA), we propose a MagPlas ELISA for urine-based tuberculosis (TB) diagnosis and anti-TB therapy monitoring, which enables fast (<3 h), and highly sensitive (up to pM with naked-eyes, < 10 fM with plate reader) urinary TB antigen detection. A clinical study with a total of 297 urine samples showed robust sensitivity for pulmonary tuberculosis (85.0%) and extra-pulmonary tuberculosis (52.8%) patients with high specificity (96.7% and 96.9%). Furthermore, this methodology offers a great promise of noninvasive therapeutic response monitoring, which is impracticable in the gold-standard culture method. The MagPlas ELISA showed high sensitivity comparable to the PCR assay while retaining a simple and cheap ELISA concept, thus it could be a promising point-of-care test for TB epidemic control and possibly applied to other acute infections.

Plasmonic Enhancement of Chiroptical Property in Enantiomers Using a Helical Array of Magnetoplasmonic Nanoparticles for Ultrasensitive Chiral Recognition.

Recognition of enantiomeric molecules is essential in pharmaceutical and biomedical applications. In this Article, a novel approach is introduced to monitor chiral molecules via a helical magnetic field (hB), where chiral-inactive magnetoplasmonic nanoparticles (MagPlas NPs, Ag@Fe3O4 core-shell NPs) are assembled into helical nanochain structures to be chiral-active. An in-house generator of hB-induced chiral NP assembly, that is, a plasmonic chirality enhancer (PCE), is newly fabricated to enhance the circular dichroism (CD) signals from chiral plasmonic interaction of the helical nanochain assembly with circularly polarized light, reaching a limit of detection (LOD) of 10-10 M, a 1000-fold enhancement as compared to that of conventional CD spectrometry. These enhancements were successfully observed from enantiomeric molecules, oligomers, polymers, and drugs. Computational simulation studies also proved that total chiroptical properties of helical plasmonic chains could be readily changed by modifying the chiral structure of the analytes. The proposed PCE has the potential to be used as an advanced tool for qualitative and quantitative recognition of chiral materials, enabling further application in pharmaceutical and biomedical sensing and imaging.

Electronic States of CoSin-/0/+ (n = 1-3) Clusters from Density Matrix Renormalization Group-CASPT2 Calculations.

Density matrix renormalization group-CASPT2 (DMRG-CASPT2), CASPT2, and density functional theory are employed to describe the complicated geometrical and electronic structures of CoSin-/0/+ (n = 1-3) clusters. The active spaces of DMRG-CASPT2 are extended to 23 orbitals. The DMRG-CASPT2 method with such large active spaces is reasonable to provide highly accurate relative energies of the electronic states. The pure BP86, PBE, and TPSS functionals appear to be suitable to compute the relative energies of the electronic states of cobalt-doped silicon clusters. The leading configurations, bond distances, vibrational frequencies, normal modes, and relative energies of the electronic states are reported. The electron detachment energies of the removals of one electron from the anionic and neutral clusters are estimated. All six bands in the photoelectron spectrum of CoSi3- are interpreted based on the computed electron detachment energies and Franck-Condon factor simulations.

Interpretation of photoelectron spectra of CoGen- (n = 4, 5) clusters by multiconfigurational RASPT2 calculations.

The low-lying electronic states CoGen-/0 (n = 4, 5) have been investigated with density functional theory and the state-of-the-art RASSCF/RASPT2 method to give assignments for the anion photoelectron spectra. The BP86 functional was employed to optimize the geometrical structures of the electronic states, while the RASSCF/RASPT2 was applied to calculate the single-point energies. With the RASSCF/RASPT2 approach, the active spaces are extended to a size of 21 orbitals for CoGe4-/0 and 24 orbitals for CoGe5-/0. The ground states of CoGe4-/0 are determined to be 3A″ and 2A″ of a trigonal bipyramidal structure in which the Co atom is situated at the equatorial corner of the bipyramid. The vertical detachment energies of the transitions from the anionic ground state to the neutral 2A″, 14A″, 2A', 24A″, 34A″, 14A', 24A', and 64A″ states are evaluated to be 2.29, 2.39, 2.60, 2.83, 3.17, 3.24, 3.47, and 4.00 eV. For the CoGe5-/0 clusters, the ground states are computed to be 1A1 and 12A2 of an octahedral structure. The vertical detachment energies of the removal of one electron from the anionic ground state to result in the 12A2, 12A1, 22A1, 12B1, 12B2, 42B1, 42B2, and 62A2 states are estimated to be 2.16, 2.79, 2.84, 3.06, 3.06, 3.59, 3.59, and 4.22 eV. All features in the photoelectron spectra of CoGe4- and CoGe5- are interpreted based on the computed electron detachment energies of the anionic ground states.

Photonic-Plasmonic Nanostructures for Solar Energy Utilization and Emerging Biosensors.

Issues related to global energy and environment as well as health crisis are currently some of the greatest challenges faced by humanity, which compel us to develop new pollution-free and sustainable energy sources, as well as next-generation biodiagnostic solutions. Optical functional nanostructures that manipulate and confine light on a nanometer scale have recently emerged as leading candidates for a wide range of applications in solar energy conversion and biosensing. In this review, recent research progress in the development of photonic and plasmonic nanostructures for various applications in solar energy conversion, such as photovoltaics, photothermal conversion, and photocatalysis, is highlighted. Furthermore, the combination of photonic and plasmonic nanostructures for developing high-efficiency solar energy conversion systems is explored and discussed. We also discuss recent applications of photonic-plasmonic-based biosensors in the rapid management of infectious diseases at point-of-care as well as terahertz biosensing and imaging for improving global health. Finally, we discuss the current challenges and future prospects associated with the existing solar energy conversion and biosensing systems.

Electronic structures of NbGen -/0/+ (n = 1-3) clusters from multiconfigurational CASPT2 and density matrix renormalization group-CASPT2 calculations.

Density functional theory and multiconfigurational CASPT2 and density matrix renormalization group DMRG-CASPT2 have been employed to study the low-lying states of NbGen -/0/+ (n = 1-3) clusters. With the DMRG-CASPT2 method, the active spaces are extended to a size of 20 orbitals. For most of the states, the CASPT2 relative energies are comparable with the DMRG-CASPT2 results. The leading configuration, bond distances, vibrational frequencies, and relative energies of the low-lying states of these clusters were calculated. The ground states of these clusters were computed to be 3 Δ, 4 Φ, and 5 Φ of NbGe-/0/+ ; 3 A2 , 4 B1 , and 3 B1 of cyclic-NbGe2 -/0/+ ; and 1 A', 12 A″ and 12 A'' (2 E), and 3 A″ of tetrahedral-NbGe3 -/0/+ isomers. For NbGe cluster, our calculations proposed that the 6 ∑ is almost degenerate with the 4 Φ with the CASPT2 and DMRG-CASPT2 relative energies of 0.05 and 0.06 eV. The adiabatic detachment energies of NbGen - (n = 1-3) clusters were estimated to be 1.46, 1.55, and 2.18 eV by the CASPT2 method. The relevant detachment energies of the anionic ground state and the ionization energies of the neutral ground states are evaluated at the CASPT2 level.

Helical Magnetic Field-Induced Real-Time Plasmonic Chirality Modulation.

The astrophysical phenomenon of mimetic helical magnetic field (hB)-assisted self-assembly is herein introduced to build helical superstructures that display chiroptical properties. As a building block, magnetoplasmonic (MagPlas) Ag@Fe3O4 core-shell nanoparticles are used to guide plasmonic Ag nanoparticles onto a helical magnetic flux. The chirality of the assembled helical structures and tailored circular dichroism are successfully tuned in real time, and the handedness of the assembled structures is dynamically switched by the hB at the millisecond level, which is at least 6000-fold faster than other template-assisted methods. The peak position of circular dichroism can be reconfigured by altering the plasmonic resonance or coupling by controlling the size of the Ag core and magnetic flux density. The hB-induced chirality modulation represents a method to control the polarization state of light at the nexus of plasmonics, magnetic self-assembly, colloidal science, liquid crystals, and chirality. It presents active and dynamic chiral assemblies of magnetoplasmonic nanomaterials, enabling further practical applications in optical devices.

Low-Lying Electronic States of FeGen-/0 (n = 1-3) Clusters Calculated with Multireference Second-Order Perturbation Theory.

The geometrical and electronic structures of the low-lying states of FeGen-/0 (n = 1-3) clusters are studied with density functional theory and state-of-the-art multiconfigurational CASSCF/CASPT2 and RASSCF/RASPT2 methods. For FeGe-/0 clusters, the CASSCF/CASPT2 results reveal that the relevant 3d, 4s, and 4d orbitals of Fe and 4p orbitals of Ge should be included into the active spaces to obtain the reliable relative energy order of the low-lying states. For FeGe2-/0 and FeGe3-/0 clusters, because the active spaces increase to a size of 17 and 20 orbitals, the CASSCF/CASPT2 calculations become very time-consuming. Therefore, the RASSCF/RASPT2 method is utilized to overcome the limitations of the active space. The accuracy of RASSCF/RASPT2 with several active spaces is calibrated based on the CASSCF/CASPT2 results. The structural parameters, vibrational frequencies, and relative energies of the ground and low-lying excited states of FeGen-/0 (n = 1-3) are reported. The electron detachment energies of the anionic clusters are provided. The computed results are employed to interpret the photoelectron spectrum of the FeGe3- cluster.

Porosity-controllable magnetoplasmonic nanoparticles and their assembled arrays.

Control of the chemical and physical properties of nanoscale colloids and their nanoassemblies remains a challenging issue for enhancing the performance and functionalities of nanodevices. In this study, we report a post-synthesis etching method to tailor the porosity of the Fe3O4 shells coating on Ag NPs, establishing a facile but effective approach to regulate the chemical and optical properties of the colloids and their assembled structures. As the shell porosity increases, the NPs are transformed, producing enhanced catalytic activity and the surface-enhanced Raman spectroscopy (SERS) effect, which results from enhanced chemical diffusion into the Ag core. Magnetoplasmonic (MagPlas) one- (1D) and two- (2D) dimensional arrays fabricated using these porosity-controllable NPs exhibit intriguing plasmon properties that are strongly affected by the porosity of the particle shell. Furthermore, the bright coloration of the 2D arrays is tuned by changing the shell porosity or introducing an additional metallic layer. Such 1D and 2D porous MagPlas metastructures possessing Fe3O4 shells with tunable porosities are a fulcrum for developing recyclable catalysts and tunable optical filters with optimized activity, selectivity, and sensitivity, as well as color displays and sensing platforms.

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.

Magnetic-Field-Induced Electrochemical Performance of a Porous Magnetoplasmonic Ag@Fe3O4 Nanoassembly.

The Lorentz or Kelvin force generated by an externally applied magnetic field may introduce additional convection of the electrolyte near the working electrode and consequently produces magnetocurrent (MC), which can be attributed to the magnetohydrodynamic (MHD) flow and an extra electrochemical reaction. A magnetoplasmonic (MagPlas) composite of metallic and superparamagnetic nanoparticles (NPs) with a permanent dipole or magnetic moment have additional degree or order, which corresponds to directional correlation to electric and magnetic dipoles. In particular, an ordered self-assembly may boost up the MHD flow on a collectively reactive surface, leading to remarkable electrochemical performance. In this article, a proof-of-concept work explores the effect of the magnetic field on the electrocatalytic activity of the oxygen reduction reaction (ORR) as well as [Fe(CN)6]3-/4- redox probes using a precisely controlled three-dimensional (3D) nanostructure of a silver core and a porous magnetic shell (Ag@Fe3O4) assembly. Then, the reduction current was carefully monitored in the presence of a magnetic field (B, up to 380 mT), resulting in an extraordinary increment of reduction current (IR) of [Fe(CN)6]3- by 23% and a 1.13-fold high ORR efficiency owing to the additional magnetic field (Bin) from the 3D magnetoplasmonic nanoassembly. The computational simulation explained the plausible mechanism of current enhancement from the MagPlas nanoassembly. From our experimental and computational studies, it is probable that the 3D MagPlas nanoassembly is a unique and efficient catalyst under a low external magnetic field, which would be useful for further biomedical and energy-related applications.

Geometric and Electronic Structures of VB40/+ Clusters and Reactivity of the Cationic Cluster with Methane from Quantum Chemical Calculations.

Quantum chemical methods have been employed to study the geometric and electronic structures of VB40/+ clusters and the mechanism of the reaction of the cationic clusters with methane. It was found that the ground states of the neutral and cationic clusters were 4A' and 3A' of a planar isomer in Cs symmetry in which vanadium atom side-on binds to the rhombic B4 moiety. The ionization energy of the neutral cluster was calculated to be 7.13 eV at the CCSD(T) level. The reaction pathways on the triplet and quintet potential energy profiles of the dehydrogenation and elimination of V+ in the reaction of VB4+ cluster with methane were established based on the BPW91 functional calculations. Both of the dehydrogenation and elimination of V+ in the reaction of VB4+ cluster with methane were initiated by the B4 moiety of the VB4+ cluster, and these two reaction channels were thermodynamically and kinetically favorable. The dehydrogenation and elimination of V+ in the reaction of VB4+ cluster with methane were exothermic processes.