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Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom %. By employing the (photo)electrocatalytic nitrite reduction reaction (NO 2 RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.

The hydrogen evolution and nitrite reduction reactions are key to producing green hydrogen and ammonia. Antenna-reactor nanoparticles hold promise to improve the performances of these transformations under visible-light excitation, by combining plasmonic and catalytic materials. However, current materials involve compromising either on the catalytic activity or the plasmonic enhancement and also lack control of reaction selectivity. Here, we demonstrate that ultralow loadings and non-uniform surface segregation of the catalytic component optimize catalytic activity and selectivity under visible-light irradiation. Taking Pt-Au as an example we find that fine-tuning the Pt content produces a 6-fold increase in the hydrogen evolution compared to commercial Pt/C as well as a 6.5-fold increase in the nitrite reduction and a 2.5-fold increase in the selectivity for producing ammonia under visible light excitation relative to dark conditions. Density functional theory suggests that the catalytic reactions are accelerated by the intimate contact between nanoscale Pt-rich and Au-rich regions at the surface, which facilitates the formation of electron-rich hot-carrier puddles associated with the Pt-based active sites. The results provide exciting opportunities to design new materials with improved photocatalytic performance for sustainable energy applications., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Plasmonic photocatalysis has been limited by the high cost and scalability of plasmonic materials, such as Ag and Au. By focusing on earth-abundant photocatalyst/plasmonic materials (H x MoO 3 ) and Pd as a catalyst, we addressed these challenges by developing a solventless mechanochemical synthesis of Pd/H x MoO 3 and optimizing photocatalytic activities in the visible range. We investigated the effect of H x MoO 3 band gap excitation (at 427 nm), Pd interband transitions (at 427 nm), and H x MoO 3 localized surface plasmon resonance (LSPR) excitation (at 640 nm) over photocatalytic activities toward the hydrogen evolution and phenylacetylene hydrogenation as model reactions. Although both excitation wavelengths led to comparable photoenhancements, a 110% increase was achieved under dual excitation conditions (427 + 640 nm). This was assigned to a synergistic effect of optical excitations that optimized the generation of energetic electrons at the catalytic sites. These results are important for the development of visible-light photocatalysts based on earth-abundant components.

Prussian blue analogs (PBAs) are promising catalysts for green hydrogen production. However, the rational design of high-performing PBAs is challenging, which requires an in-depth understanding of the catalytic mechanism. Here FeMn@CoNi core-shell PBAs are employed as precursors, together with Se powders, in low-temperature pyrolysis in an argon atmosphere. This synthesis method enables the partial dissociation of inner FeMn PBAs that results in hollow interiors, Ni nanoparticles (NPs) exsolution to the surface, and Se incorporation onto the PBA shell. The resulting material presents ultralow oxygen evolution reaction (OER) overpotential (184 mV at 10 mA cm -2 ) and low Tafel slope (43.4 mV dec -1 ), outperforming leading-edge PBA-based electrocatalysts. The mechanism responsible for such a high OER activity is revealed, assisted by density functional theory (DFT) calculations and the surface examination before and after the OER process. The exsolved Ni NPs are found to help turn the PBAs into Se-doped core-shell metal oxyhydroxides during the OER, in which the heterojunction with Ni and the Se incorporation are combined to improve the OER kinetics. This work shows that efficient OER catalysts could be developed by using a novel synthesis method backed up by a sound understanding and control of the catalytic pathway., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

β-glucosidases play a pivotal role in second-generation biofuel (2G-biofuel) production. For this application, thermostable enzymes are essential due to the denaturing conditions on the bioreactors. Random amino acid substitutions have originated new thermostable β-glucosidases, but without a clear understanding of their molecular mechanisms. Here, we probe by different molecular dynamics simulation approaches with distinct force fields and submitting the results to various computational analyses, the molecular bases of the thermostabilization of the Paenibacillus polymyxa GH1 β-glucosidase by two-point mutations E96K (TR1) and M416I (TR2). Equilibrium molecular dynamic simulations (eMD) at different temperatures, principal component analysis (PCA), virtual docking, metadynamics (MetaDy), accelerated molecular dynamics (aMD), Poisson-Boltzmann surface analysis, grid inhomogeneous solvation theory and colony method estimation of conformational entropy allow to converge to the idea that the stabilization carried by both substitutions depend on different contributions of three classic mechanisms: (i) electrostatic surface stabilization; (ii) efficient isolation of the hydrophobic core from the solvent, with energetic advantages at the solvation cap; (iii) higher distribution of the protein dynamics at the mobile active site loops than at the protein core, with functional and entropic advantages. Mechanisms i and ii predominate for TR1, while in TR2, mechanism iii is dominant. Loop A integrity and loops A, C, D, and E dynamics play critical roles in such mechanisms. Comparison of the dynamic and topological changes observed between the thermostable mutants and the wildtype protein with amino acid co-evolutive networks and thermostabilizing hotspots from the literature allow inferring that the mechanisms here recovered can be related to the thermostability obtained by different substitutions along the whole family GH1. We hope the results and insights discussed here can be helpful for future rational approaches to the engineering of optimized β-glucosidases for 2G-biofuel production for industry, biotechnology, and science., (© 2022 Wiley Periodicals LLC.)

Plasmonic catalysis enables the use of light to accelerate molecular transformations. Its application to the control reaction selectivity is highly attractive but remains challenging. Here, we have found that the plasmonic properties in AgPd nanoparticles allowed different reaction pathways for tunable product formation under visible-light irradiation. By employing the hydrogenation of phenylacetylene as a model transformation, we demonstrate that visible-light irradiation can be employed to steer the reaction pathway from hydrogenation to homocoupling. Our data showed that the decrease in the concentration of H species at the surface due to plasmon-enhanced H 2 desorption led to the control in selectivity. These results provide important insights into the understanding of reaction selectivity with light, paving the way for the application of plasmonic catalysis to the synthesis of 1,3-diynes, and bringing the vision of light-driven transformations with target selectivity one step closer to reality., (© 2022 Wiley-VCH GmbH.)

Photocatalytic nonoxidative coupling of CH 4 to multicarbon (C 2+ ) hydrocarbons (e.g., C 2 H 4 ) and H 2 under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource. However, as the methyl intermediates prefer to undergo self-coupling to produce ethane, it is a challenging task to control the selective conversion of CH 4 to higher value-added C 2 H 4 . Herein, we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO 3 nanosheets for synergizing the adsorption, activation, and dehydrogenation processes in CH 4 to C 2 H 4 conversion. Benefiting from the synergy, our model catalyst achieves a remarkable C 2+ compounds yield of 31.85  μ mol·g -1 ·h -1 with an exceptionally high C 2 H 4 selectivity of 75.3% and a stoichiometric H 2 evolution. In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH 4 molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen, while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C 2 H 4 and suppress overoxidation. This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH 4 to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions., Competing Interests: The authors declare that there is no conflict of interest regarding the publication of this article., (Copyright © 2022 Yanduo Liu et al.)

Gold nanoparticles (Au NPs) have been extensively used as artificial enzymes, but their performance is still limited. We address this challenge by focusing on multimetallic nanorattles comprising an Au core inside a bimetallic AgAu shell, separated by a void (Au@AgAu NRs). They were prepared by a galvanic replacement approach and contained an ultrathin and porous shell comprising an AgAu alloy. By investigating the peroxide-like activity using TMB oxidation as a model transformation, we have found an increase of 152 fold in activities for the NRs relative to conventional Au NPs. Based on the kinetics results, the NRs also showed the lowest K m , indicating better interaction with the substrate and faster product formation. We also observed a linear relationship between the concentration of the product and oxTMB as a function of H 2 O 2 concentration, which could be further applied for H 2 O 2 sensing applications (colorimetric detection). These data suggest that the NRs enable the combined effect of an increased surface area relative to solid counterparts, the possibility of exposing highly active surface sites, and the exploitation of nanoconfinement effects due to the void regions between the core and shell components. These results provide important insights into the optimization of peroxidase-like performances beyond what can be achieved in conventional NPs and may inspire the development of better-performing artificial enzymes.

Catalysis is central to a more sustainable future and a circular economy. If the energy required to drive catalytic processes could be harvested directly from sunlight, the possibility of replacing contemporary processes based on terrestrial fuels by the conversion of light into chemical energy could become a step closer to reality. Plasmonic catalysis is currently at the forefront of photocatalysis, enabling one to overcome the limitations of "classical" wide bandgap semiconductors for solar-driven chemistry. Plasmonic catalysis enables the acceleration and control of a variety of molecular transformations due to the localized surface plasmon resonance (LSPR) excitation. Studies in this area have often focused on the fundamental understanding of plasmonic catalysis and the demonstration of plasmonic catalytic activities towards different reactions. In this feature article, we discuss recent contributions from our group in this field by employing plasmonic nanoparticles (NPs) with controllable features as model systems to gain insights into structure-performance relationships in plasmonic catalysis. We start by discussing the effect of size, shape, and composition in plasmonic NPs over their activities towards LSPR-mediated molecular transformations. Then, we focus on the effect of metal support interactions over activities, reaction selectivity, and reaction pathways. Next, we shift to the control over the structure in hollow NPs and nanorattles. Inspired by the findings from these model systems, we demonstrate a design-driven strategy for the development of plasmonic catalysts based on plasmonic-catalytic multicomponent NPs for two types of molecular transformations: the selective hydrogenation of phenylacetylene and the oxygen evolution reaction. Finally, future directions, challenges, and perspectives in the field of plasmonic catalysis with designer NPs are discussed. We believe that the examples and concepts presented herein may inspire work and progress in plasmonic catalysis encompassing the design of plasmonic multicomponent materials, new strategies to control reaction selectivity, and the unraveling of stability and reaction mechanisms.

Recently, the widespread use of antibiotics is becoming a serious worldwide public health challenge, which causes antimicrobial resistance and the occurrence of superbugs. In this context, MnO 2 has been proposed as an alternative approach to achieve target antibacterial properties on Streptococcus mutans (S. mutans). This requires a further understanding on how to control and optimize antibacterial properties in these systems. We address this challenge by synthesizing δ-MnO 2 nanoflowers doped by magnesium (Mg), sodium (Na), and potassium (K) ions, thus displaying different bandgaps, to evaluate the effect of doping on the bacterial viability of S. mutans. All these samples demonstrated antibacterial activity from the spontaneous generation of reactive oxygen species (ROS) without external illumination, where doped MnO 2 can provide free electrons to induce the production of ROS, resulting in the antibacterial activity. Furthermore, it was observed that δ-MnO 2 with narrower bandgap displayed a superior ability to inhibit bacteria. The enhancement is mainly attributed to the higher doping levels, which provided more free electrons to generate ROS for antibacterial effects. Moreover, we found that δ-MnO 2 was attractive for in vivo applications, because it could nearly be degraded into Mn ions completely following the gradual addition of vitamin C. We believe that our results may provide meaningful insights for the design of inorganic antibacterial nanomaterials., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Yan, Jiang, Liu, Pan, Li, Wang, Camargo and Wang.)

Plasmonic photocatalysis has emerged as a prominent and growing field. It enables the efficient use of sunlight as an abundant and renewable energy source to drive a myriad of chemical reactions. For instance, plasmonic photocatalysis in materials comprising TiO 2 and plasmonic nanoparticles (NPs) enables effective charge carrier separation and the tuning of optical response to longer wavelength regions (visible and near infrared). In fact, TiO 2 -based materials and plasmonic effects are at the forefront of heterogeneous photocatalysis, having applications in energy conversion, production of liquid fuels, wastewater treatment, nitrogen fixation, and organic synthesis. This review aims to comprehensively summarize the fundamentals and to provide the guidelines for future work in the field of TiO 2 -based plasmonic photocatalysis comprising the above-mentioned applications. The concepts and state-of-the-art description of important parameters including the formation of Schottky junctions, hot electron generation and transfer, near field electromagnetic enhancement, plasmon resonance energy transfer, scattering, and photothermal heating effects have been covered in this review. Synthetic approaches and the effect of various physicochemical parameters in plasmon-mediated TiO 2 -based materials on performances are discussed. It is envisioned that this review may inspire and provide insights into the rational development of the next generation of TiO 2 -based plasmonic photocatalysts with target performances and enhanced selectivities., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

Localized surface plasmons generated on metallic nanostructures can be used to accelerate molecular transformations; however, the efficiency is limited by the challenge to control the energy/charge transfer at the interfaces. Here, we combine density functional theory (DFT) calculations and experiments to reveal the mechanism of nitrophenol reduction on Au nanoparticles under visible-light irradiation and propose a strategy to further enhance the reaction rates. DFT calculations show a reduced activation barrier under electronic excitation on Au(111), thus explaining the measured higher rates under visible-light irradiation. Furthermore, we propose a heterostructure with Au nanoparticles covered by a thin film of hexagonal boron nitride; the latter is used to decouple the molecular orbitals from the metal to enable charge localization in the molecule. DFT calculations show that by this electronic decoupling, the activation barrier can be lowered by a factor of five. This work thus provides a valuable strategy for optimizing catalytic efficiency in plasmonic photocatalysis.

A photoelectrochemical biosensing strategy for the highly sensitive detection of the flavonoid rutin was developed by synergizing the photoelectrocatalytic properties of hematite (α-Fe 2 O 3 ) decorated with palladium nanoparticles (PdNPs) and the biocatalysis towards laccase-based reactions. The integration of α-Fe 2 O 3 .PdNPs with a polyphenol oxidase as a biorecognition element yields a novel biosensing platform. Under visible light irradiation, the photoactive biocomposite can generate a stable photocurrent, which was found to be directly dependent upon the concentration of rutin. Under the optimal experimental conditions, the cathodic photocurrent, measured at 0.33 V vs. Ag/AgCl, from the square-wave voltammograms presented a linear dependence on the rutin concentration within the range of 0.008-30.0 × 10 -8  mol L -1 (sensitivity: 1.7 μA·(× 10 -8  M -1 )·cm -2 ), with an experimental detection limit (S/N = 3) of 8.4 × 10 -11  mol L -1 . The proposed biosensor device presented good selectivity towards rutin in the presence of various organic compounds and inorganic ions, demonstrating the potential application of this biosensing platform in complex matrices. This bioanalytical device also exhibited excellent operational and analytical properties, such as intra-day (standard deviation, SD = 0.21%) and inter-day (SD = 1.30%) repeatability, and long storage stability (SD = 2.80% over 30 days).Graphical abstract.

Single-particle reconstruction can be used to perform three-dimensional (3D) imaging of homogeneous populations of nano-sized objects, in particular viruses and proteins. Here, it is demonstrated that it can also be used to obtain 3D reconstructions of heterogeneous populations of inorganic nanoparticles. An automated acquisition scheme in a scanning transmission electron microscope is used to collect images of thousands of nanoparticles. Particle images are subsequently semi-automatically clustered in terms of their properties and separate 3D reconstructions are performed from selected particle image clusters. The result is a 3D dataset that is representative of the full population. The study demonstrates a methodology that allows 3D imaging and analysis of inorganic nanoparticles in a fully automated manner that is truly representative of large particle populations.

Current time-resolved in situ approaches limit the scope of mechanochemical investigations possible. Here we develop a new, general approach to simultaneously follow the evolution of bulk atomic and electronic structure during a mechanochemical synthesis. This is achieved by coupling two complementary synchrotron-based X-ray methods: X-ray absorption spectroscopy (XAS) and X-ray diffraction. We apply this method to investigate the bottom-up mechanosynthesis of technologically important Au micro and nanoparticles in the presence of three different reducing agents, hydroquinone, sodium citrate, and NaBH 4 . Moreover, we show how XAS offers new insight into the early stage generation of growth species (e.g. monomers and clusters), which lead to the subsequent formation of nanoparticles. These processes are beyond the detection capabilities of diffraction methods. This combined X-ray approach paves the way to new directions in mechanochemical research of advanced electronic materials.

The interaction of metallic nanoparticles with light excites a local surface plasmon resonance (LSPR). This phenomenon enables the transfer of hot electrons to substrates that release Reactive Oxygen Species (ROS). In this context, the present study aimed at enhancing the antibacterial effect of citrate-covered silver nanoparticles (AgNPs) by LSPR excitation with visible LED. AgNPs possess excellent antimicrobial properties against Pseudomonas aeruginosa, one of the most refractory organisms to antibiotic treatment. The Minimum Inhibitory Concentration (MIC) of the AgNPs was 10 μg/ml under dark conditions and 5 μg/ml under light conditions. The combination of light and AgNPs led to 100% cell death after 60 min. Flow cytometry quantification showed that bacteria treated with LSPR-stimulated AgNPs displayed 4.8 times more ROS. This significant increase in ROS possibly accounts for most of the antimicrobial effect of the AgNPs. In addition, light exposition caused a small release of silver ions (0.4%) suggesting that silver ions may play a secondary role in P. aeruginosa death. Overall, the results presented here show that LSPR stimulation of AgNPs by visible light enhances the antimicrobial activity of silver nanoparticles and can be an alternative for the treatment of topic infections caused by antibiotic-resistant bacteria such as P. aeruginosa., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Localized surface plasmon resonance (LSPR) in plasmonic nanoparticles (NPs) can accelerate and control the selectivity of a variety of molecular transformations. This opens possibilities for the use of visible or near-IR light as a sustainable input to drive and control reactions when plasmonic nanoparticles supporting LSPR excitation in these ranges are employed as catalysts. Unfortunately, this is not the case for several catalytic metals such as palladium (Pd). One strategy to overcome this limitation is to employ bimetallic NPs containing plasmonic and catalytic metals. In this case, the LSPR excitation in the plasmonic metal can contribute to accelerate and control transformations driven by the catalytic component. The method reported herein focuses on the synthesis of bimetallic silver-palladium (Ag-Pd) NPs supported on ZrO2 (Ag-Pd/ZrO2) that acts as a plasmonic-catalytic system. The NPs were prepared by co-impregnation of corresponding metal precursors on the ZrO2 support followed by simultaneous reduction leading to the formation of bimetallic NPs directly on the ZrO2 support. The Ag-Pd/ZrO2 NPs were then used as plasmonic catalysts for the reduction of nitrobenzene under 425 nm illumination by LED lamps. Using gas chromatography (GC), the conversion and selectivity of the reduction reaction under the dark and light irradiation conditions can be monitored, demonstrating the enhanced catalytic performance and control over selectivity under LSPR excitation after alloying non-plasmonic Pd with plasmonic metal Ag. This technique can be adapted to a wide range of molecular transformations and NPs compositions, making it useful for the characterization of the plasmonic catalytic activity of different types of catalysis in terms of conversion and selectivity.

Solar-to-chemical conversion via photocatalysis is of paramount importance for a sustainable future. Thus, investigating the synergistic effects promoted by light in photocatalytic reactions is crucial. The tandem oxidative coupling of alcohols and amines is an attractive route to synthesize imines. Here, we unravel the performance and underlying reaction pathway in the visible-light-driven tandem oxidative coupling of benzyl alcohol and aniline employing Au/CeO 2 nanorods as catalysts. We propose an alternative reaction pathway for this transformation that leads to improved efficiencies relative to individual CeO 2 nanorods, in which the localized surface plasmon resonance (LSPR) excitation in Au nanoparticles (NPs) plays an important role. Our data suggests a synergism between the hot electrons and holes generated from the LSPR excitation in Au NPs. While the oxygen vacancies in CeO 2 nanorods trap the hot electrons and facilitate their transfer to adsorbed O 2 at surface vacancy sites, the hot holes in the Au NPs facilitate the α-H abstraction from the adsorbed benzyl alcohol, evolving into benzaldehyde, which then couples with aniline in the next step to yield the corresponding imine. Finally, cerium-coordinated superoxide species abstract hydrogen from the Au surface, regenerating the catalyst surface.

We develop herein plasmonic-catalytic Au-IrO 2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO 2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO 2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO 2 , by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au-IrO 2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO 2 and to the activation of Ir-O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

In this work we propose the use of statistical mixture design in the construction of a biosensor device based on graphite oxide, platinum nanoparticles and biomaterials obtained from Botryosphaeria rhodina MAMB-05. The biosensor was characterized by electrochemical impedance spectroscopy. Under optimized experimental parameters by factorial design, the biosensor was applied to the voltammetric determination of chlorogenic acid (CGA) measured as 5-O-caffeoylquinic acid (5-CQA). The biosensor response was linear (R 2  = 0.998) for 5-CQA in the concentration range 0.56-7.3 µmol L -1 , with limit of detection and quantification of 0.18 and 0.59 µmol L -1 , respectively. The new biosensing device was applied to quality control analysis based upon the determination of CGA content in specialty and traditional coffee beverages. The results indicated that specialty coffee had a significantly higher content of CGA. Principal component analysis of the voltammetric fingerprint of brewed coffees revealed that the laccase-based biosensor can be used for their discrimination., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Colloidal particles with a spherical shape and diameters in the range of 0.01-1 μm have been a subject of extensive research, with applications in areas such as photonics, electronics, catalysis, drug delivery, and medicine. For most of these applications, it is of critical importance to achieve monodispersity for the size while expanding the diversity in terms of structure and composition. The uniformity in size allows one to establish rigorous correlations between this parameter and the physicochemical properties of the colloidal particles while ensuring experimental repeatability and measurement accuracy. On the other hand, the diversity in structure and composition offers additional handles for tailoring the properties. By switching from the conventional plain, solid structure to a core-shell, hollow, porous, or Janus structure, it offers immediate advantages and creates new opportunities, especially in the context of self-assembly, encapsulation, and controlled release. As for composition, monodispersed colloidal spheres were traditionally limited to amorphous materials such as polystyrene and silica. For metals and semiconducting materials, which are more valuable to applications in photonics, electronics, and catalysis, they tend to crystallize and thus grow anisotropically into nonspherical shapes, especially when their sizes pass 0.1 μm. Taken together, it is no wonder why chemical synthesis of monodispersed colloidal spheres has been a constant theme of research in areas such as colloidal science, materials chemistry, materials science, and soft matter. In this Account, we summarize our efforts over the past two decades in developing solution-phase methods for the facile synthesis of colloidal spheres that are uniform in size, together with a broad range of compositions (including metals and semiconductors) and structures (e.g., solid, core-shell, hollow, porous, and Janus, among others). We start with the synthesis of monodispersed colloidal spheres made of semiconductors, metals with low melting points, and precious metals. Through chemical reactions, these colloidal spheres can be transformed into core-shell or hollow structures with new compositions and properties. Next, we discuss the synthesis of colloidal spheres with a Janus structure while taking a pseudospherical shape. Specifically, metal-polymer hybrid particles composed of one metal nanoparticle partially embedded in the surface of a polymer sphere can be produced through precipitation polymerization in the presence of metal seed. With these Janus particles serving as templates, other types of Janus structures such as hollow spheres with a single hole in the surface can be obtained via site-selected deposition. Alternatively, such hollow spheres can be fabricated through a physical transformation process that involves swelling of polymer spheres, followed by freeze-drying. All these synthesis and transformation processes are solution-based, offering flexibility and potential for large-scale production. At the end, we highlight some of the applications enabled by these colloidal spheres, including fabrication of photonic devices, encapsulation, and controlled release for nanomedicine.

Although various efforts have been made to develop effective treatments for alveolar bone defect, alveolar regeneration has been emerging as the one with the most potential Herein, we investigated the potential of gelatin methacrylate (GelMA) hydrogels-encapsulated human periodontal ligament stem cells (hPDLSCs) to regenerate alveolar bone. The easy, rapid, and cost-effective nature of GelMA hydrogels makes them a promising mode of stem cell-delivery for clinically relevant alveolar bone regeneration. More importantly, GelMA hydrogels provide an optimal niche for hPDLSCs proliferation, migration and osteogenic differentiation, which are critical for alveolar bone regeneration. In this study, we examined the microstructure of GelMA hydrogels, and identified a highly porous and interconnected network. Compressive test of GelMA hydrogels showed that the stress reached a maximum value of 13.67 ± 0.03 kPa when the strain reached 55%. The maximum values of swelling ratio were 700 ± 47% at the fifth hour. The proliferation rate of hPDLSCs in the GelMA hydrogels resembled that in 2D culture and gradually increased. We established a critical-sized rat model of alveolar bone defects, and applied Micro-CT to assess new bone formation. Compared to the control group, there was substantial bone regeneration in the GelMA + hPDLSCs group at both 4 and 8 weeks after the operation. Histological analysis results were consistent with Micro-CT results. Our study demonstrates that the GelMA hydrogels-encapsulated hPDLSCs have a significant alveolar regenerative potential, and may represent a new strategy for the therapy of alveolar bone defects.

A mechano-colloidal approach was developed to produce Au nanotadpoles. It comprises the generation of seeds by ball-milling from a solid mixture containing a precursor, reductant, and capping agent, followed by the dispersion of this mixture in water leading to seeded-growth to generate the target nanoparticle morphology.

In this study, (1→3)(1→6)-β-D-glucan (botryosphaeran) from Botryosphaeria rhodina MAMB-05 was used, for the first time, to immobilize laccase on a carbon black paste electrode modified with gold nanoparticles. The physicochemical characterization of the proposed laccase-biosensor was performed using transmission electron microscopy and electrochemical impedance spectroscopy. The performance of this novel bio-device was evaluated by choosing hydroquinone as a typical model of a phenolic compound. For hydroquinone determination, experimental variables such as enzyme concentration, pH and operational parameters of the electroanalytical technique were optimized. From square-wave voltammograms, a linear dependence between the cathodic current peak and the hydroquinone concentration was observed within the range 2.00-56.5μmolL -1 , with a theoretical detection limit of 0.474μmolL -1 . The proposed method was successfully applied to determine hydroquinone in dermatological cream, and samples from biological and environmental niches. The proposed biosensor device presented good selectivity in the presence of uric acid, various inorganic ions, as well as other phenolic compounds, demonstrating the potential application of this biosensing platform in complex matrices. Operational and analytical stability of the laccase biosensor were evaluated, and demonstrated good intra-day (SD=0.3%) and inter-day (SD=3.4%) repeatability and long storage stability (SD=4.9%)., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Gold nanoparticles (Au NPs) have been widely employed in catalysis. Here, we report on the synthesis and catalytic evaluation of a hybrid material composed of Au NPs deposited at the surface of magnetic cobalt ferrite (CoFe 2 O 4 ). Our reported approach enabled the synthesis of well-defined Au/CoFe 2 O 4 NPs. The Au NPs were uniformly deposited at the surface of the support, displayed spherical shape, and were monodisperse in size. Their catalytic performance was investigated towards the reduction of 4-nitrophenol and the selective oxidation of dimethylphenylsilane to dimethylphenylsilanol. The material was active towards both transformations. In addition, the LSPR excitation in Au NPs could be employed to enhance the catalytic performance, which was demonstrated in the 4-nitrophenol reduction. Finally, the magnetic support allowed for the easy recovery and reuse of the Au/CoFe 2 O 4 NPs. In this case, our data showed that no significant loss of performance took place even after 10 reaction cycles in the oxidation of dimethylphenylsilane to dimethylphenylsilanol. Overall, our results indicate that Au/CoFe 2 O 4 are interesting systems for catalytic applications merging high performances, recovery and re-use, and enhancement of activities under solar light illumination., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Sodium (Na)- and potassium (K)-doped δ-MnO 2 , which presented different band gaps, were synthesized by a hydrothermal method. Then, uniform Au nanoparticles (NPs) were deposited on MnO 2 to form metal-semiconductor nano-heterojunctions (MnO 2 -Au). By comparing their temperature-dependent thermal catalytic performances, p-aminothiophenol to p, p'-dimercaptoazobenzene conversion was used as proof-of-concept transformations. MnO 2 -Au hybrid materials demonstrated better thermal catalytic performances relative to individual Au NPs. Meanwhile, K-doped MnO 2 -Au, with a MnO 2 support displaying a narrower bandgap, displayed superior catalytic activities relative to Na-doped MnO 2 -Au. To get the same catalytic performance by individual Au NPs, it can be ∼50 K less by Na-doped MnO 2 -Au and ∼100 K less by K-doped MnO 2 -Au. The enhancement is mainly attributed to the thermally excited electrons in MnO 2 , which were transferred to Au NPs. The additional electrons in Au NPs increase the electron density and thus contribute to the improvement of thermal catalysis. Our findings show that the establishment of a nano-heterojunction formed by metal NPs on a semiconductor support has a significant impact on thermal catalysis, where a narrower band gap can facilitate thermally excited carriers and thus bring about better catalytic performances. Thus, the results presented here shed light on the design of a nano-heterojunction catalyst to approach reactions with superior performance under moderate conditions.

There is a growing interest in controlling the synthesis of colloidal metal nanocrystals and thus tailoring their properties toward various applications. In this context, choosing an appropriate combination of reagents (e.g., salt precursor, reductant, capping agent, and stabilizer) plays a pivotal role in enabling the synthesis of metal nanocrystals with diversified sizes, shapes, and structures. Here we present a comprehensive review that highlights one of the key reagents for the synthesis of metal nanocrystals via chemical reduction: the reductants. We start with a brief introduction to the compounds commonly employed as reductants in the colloidal synthesis of metal nanocrystals by showing their oxidation half-reactions and the corresponding oxidation potentials. Then we offer specific examples pertaining to the controlled synthesis of metal nanocrystals, followed by some fundamental aspects covering the general mechanisms of metal ion reduction based on the Marcus Theory. Afterwards, we present a case-by-case discussion on a wide variety of reductants, including their major properties, reduction mechanisms, and additional effects on the final products. We illustrate these aspects by selecting key examples from the literature and paying close attention to the underlying mechanism in each case. At the end, we conclude by summarizing the highlights of the review and providing some perspectives on future directions., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Among the several classes of chemical reactions, the green oxidation of organic compounds has emerged as an important topic in nanocatalysis. Nonetheless, examples of truly green oxidations remain scarce due to the low activity and selectivity of reported catalysts. In this paper, we present an approach based on the optimization of both the support material and the active phase to achieve superior catalytic performances towards green oxidations. Specifically, our catalysts consisted of ultrasmall Au NPs deposited onto MnO 2 nanoflowers. They displayed hierarchical morphology, large specific surface areas, ultrasmall and uniform Au NPs sizes, no agglomeration, strong metal-support interactions, oxygen vacancies, and Au δ+ species at their surface. These features led to improved performances towards the green oxidations of CO, benzene, toluene, o-xylene, glucose, and fructose relative to the pristine MnO 2 nanoflowers, commercial MnO 2 decorated with Au NPs, and other reported catalysts. We believe that the catalytic activities, stabilities, and mild/green reaction conditions described herein for both gas and liquid phase oxidations due to the optimization of both the support and active phase may inspire the development of novel catalytic systems for a wealth of sustainable transformations., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles has been used to accelerate several catalytic transformations under visible-light irradiation. In order to fully harness the potential of plasmonic catalysis, multimetallic nanoparticles containing a plasmonic and a catalytic component, where LSPR-excited energetic charge carriers and the intrinsic catalytic active sites work synergistically, have raised increased attention. Despite several exciting studies observing rate enhancements, controlling reaction selectivity remains very challenging. Here, by employing multimetallic nanoparticles combining Au, Ag, and Pt in an Au@Ag@Pt core-shell and an Au@AgPt nanorattle architectures, we demonstrate that reaction selectivity of a sequential reaction can be controlled under visible light illumination. The control of the reaction selectivity in plasmonic catalysis was demonstrated for the hydrogenation of phenylacetylene as a model transformation. We have found that the localized interaction between the triple bond in phenylacetylene and the Pt nanoparticle surface enables selective hydrogenation of the triple bond (relative to the double bond in styrene) under visible light illumination. Atomistic calculations show that the enhanced selectivity toward the partial hydrogenation product is driven by distinct adsorption configurations and charge delocalization of the reactant and the reaction intermediate at the catalyst surface. We believe these results will contribute to the use of plasmonic catalysis to drive and control a wealth of selective molecular transformations under ecofriendly conditions and visible light illumination.

The use of sunlight to drive chemical reactions via photocatalysis is of paramount importance towards a sustainable future. Among several photocatalysts, earth-abundant polymeric carbon nitride (PCN, often wrongly named g-C3N4) has emerged as an attractive candidate due to its ability to absorb light efficiently in the visible and near-infrared ranges, chemical stability, non-toxicity, straightforward synthesis, and versatility as a platform for constructing hybrid materials. Especially, hybrids with metal nanoparticles offer the unique possibility of combining the catalytic, electronic, and optical properties of metal nanoparticles with PCN. Here, we provide a comprehensive overview of PCN materials and their hybrids, emphasizing heterostructures with metal nanoparticles. We focus on recent advances encompassing synthetic strategies, design principles, photocatalytic applications, and charge-transfer mechanisms. We also discuss how the localized surface plasmon resonance (LSPR) effect of some noble metals NPs (e.g. Au, Ag, and Cu), bimetallic compositions, and even non-noble metals NPs (e.g., Bi) synergistically contribute with PCN in light-driven transformations. Finally, we provide a perspective on the field, in which the understanding of the enhancement mechanisms combined with truly controlled synthesis can act as a powerful tool to the establishment of the design principles needed to take the field of photocatalysis with PCN to a new level, where the desired properties and performances can be planned in advance, and the target material synthesized accordingly.

This work describes the electrochemical degradation of Reactive Black 5 (RB5) by two methods: electrochemical and photo-assisted electrochemical degradation with and without a Fenton reagent. Two anodes were used, Pt and boron-doped diamond (BDD, 2500 ppm), and the cathode was 3% MnO 2 nanoflowers (NFMnO 2 ) on a carbon gas diffusion electrode (GDE). An electrochemical cell without a divider with a GDE with 3% w/w NFMnO 2 /C supported on carbon Vulcan XC72 was used. The decolorization efficiency was monitored by UV-vis spectroscopy, and the degradation was monitored by Total Organic Carbon (TOC) analysis. For dissolution monitoring, aliquots (1 mL) were collected during the degradation. After 6 h of H 2 O 2 electrogeneration, the manganese concentration in the RB5 solution was only 23.1 ± 1.2 μg L -1 . It was estimated that approximately 60 μg L -1 (<0.2%) of manganese migrated from the GDE to the solution after 12 h of electrolysis, which indicated the good stability of the GDE. The photoelectro-Fenton-BDD (PEF-BDD) processes showed both the best color removal percentage (∼93%) and 91% of mineralization. The 3% NFMnO 2 /C GDE is promising for RB5 degradation., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

In this study, we investigated hollow AgAu nanoparticles with the goal of improving our understanding of the composition-dependent catalytic activity of these nanoparticles. AgAu nanoparticles were synthesized via the galvanic replacement method with controlled size and nanoparticle compositions. We studied extinction spectra with UV-Vis spectroscopy and simulations based on Mie theory and the boundary element method, and ultrafast spectroscopy measurements to characterize decay constants and the overall energy transfer dynamics as a function of AgAu composition. Electron-phonon coupling times for each composition were obtained from pump-power dependent pump-probe transients. These spectroscopic studies showed how nanoscale surface segregation, hollow interiors and porosity affect the surface plasmon resonance wavelength and fundamental electron-phonon coupling times. Analysis of the spectroscopic data was used to correlate electron-phonon coupling times to AgAu composition, and thus to surface segregation and catalytic activity. We have performed all-atom molecular dynamics simulations of model hollow AgAu core-shell nanoparticles to characterize nanoparticle stability and equilibrium structures, besides providing atomic level views of nanoparticle surface segregation. Overall, the basic atomistic and electron-lattice dynamics of core-shell AgAu nanoparticles characterized here thus aid the mechanistic understanding and performance optimization of AgAu nanoparticle catalysts.

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles can enhance or mediate chemical transformations. Increased reaction rates for several reactions have been reported due to this phenomenon; however, the fundamental understanding of mechanisms and factors that affect activities remains limited. Here, by investigating hydrogenation reactions as a model transformation and employing different reducing agents, H 2 and NaBH 4 , which led to different hydrogenation reaction pathways, we observed that plasmonic excitation of Au nanoparticle catalysts can lead to negative effects over the activities. The underlying physical reason was explored using density functional theory calculations. We observed that positive versus negative effects on the plasmonic catalytic activity is reaction-pathway dependent. These results shed important insights on our current understanding of plasmonic catalysis, demonstrating reaction pathways must be taken into account for the design of plasmonic nanocatalysts., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Plasmonic catalysis takes advantage of the surface plasmon resonance (SPR) excitation to drive or accelerate chemical transformations. In addition to the plasmonic component, the control over metal-support interactions in these catalysts is expected to strongly influence the performances. For example, CeO2 has been widely employed towards oxidation reactions due to its oxygen mobility and storage properties, which allow for the formation of Ce3+ sites and adsorbed oxygen species from metal-support interactions. It is anticipated that these species may be activated by the SPR excitation and contribute to the catalytic activity of the material. Thus, a clear understanding of the role played by the SPR-mediated activation of surface oxide species at the metal-support interface is needed in order to take advantage of this phenomenon. Herein, we describe and quantify the contribution from active surface oxide species at the metal-support interface (relative to O2 from air) to the activities in green SPR-mediated oxidation reactions. We employed CeO2 decorated with Au NPs (Au/CeO2) as a model plasmonic catalyst and the oxidation of p-aminothiophenol (PATP) and aniline as proof-of-concept transformations. We compared the results with SiO2 decorated with Au NPs (Au/SiO2), in which the formation of surface oxide species at the metal-support interface is not expected. We found that the SPR-mediated activation of surface oxide species at the metal-support interface in Au/CeO2 played a pivotal role in the detected activities, being even higher than the contribution coming from the activation of O2 from air.

This review describes some principles of the controlled synthesis of metal nanoparticles, focusing on how the fundamental understanding of their synthesis in the solution-phase can be put to tailor size, shape, composition, and architecture. The maneuvering over these parameters not only enable the tuning of properties, but also the maximization and optimization of performances for various applications. Herein, we start with a brief description of metallic nanoparticles, highlighting the motivation for achieving physicochemical control in their synthesis. After that, we turn our attention to some important definitions and classifications as well as their unique properties such as surface and quantum effects. Moreover, we discuss the strategies for the controlled synthesis of metal nanomaterials based on the top-down and bottom-up approaches, focusing our discussion on their formation mechanisms in liquid-phase in terms of both thermodynamic and kinetic control. Finally, we point out the promising applications of controlled nanomaterials in the field of nanocatalysis and plasmon-enhanced catalysis, describing some of the current challenges in these fields.

A glassy carbon electrode was modified with a TiO 2 -gold nanoparticle hybrid integrated with multi-walled carbon nanotubes in a dihexadecylphosphate film (TiO 2 -Au NP-MWCNT-DHP/GCE) and applied to amperometric determination of ascorbic acid (AA). The modified sensor displays fast charge transfer and shows an irreversible anodic behavior for AA by cyclic voltammetry. Under optimal experimental conditions and using amperometry at 0.4 V, the analytical curve presented a statistical linear concentration range for AA from 5.0 to 51 μmol L -1 , with a limit of detection of 1.2 μmol L -1 . The electrode was successfully applied to the determination of AA in pharmaceutical and fruit juice without the need for major pretreatment of samples. Graphical abstract Schematic of a new sensing platform for ascorbic acid (AA). It is based on a glassy carbon electrode (GCE) modified with TiO 2 -Au nanoparticles integrated into carbon nanotubes in a dihexadecylphosphate film. The sensor was applied to amperometric determination of AA in juice and pharmaceutical samples.

CoFe 2 O 4 and NiFe 2 O 4 nanoparticles (NPs) represent promising candidates for biomedical applications. However, in these systems, the knowledge over how various physical and chemical parameters influence their cytotoxicity remains limited. In this article, we investigated the effect of different calcination temperatures over cytotoxicity of CoFe 2 O 4 and NiFe 2 O 4 NPs, which were synthesized by a sol-gel proteic approach, toward L929 mouse fibroblastic cells. More specifically, we evaluated and compared CoFe 2 O 4 and NiFe 2 O 4 NPs presenting low crystallinity (that were calcined at 400 and 250 °C, respectively) with their highly crystalline counterparts (that were calcined at 800 °C). We found that the increase in the calcination temperature led to the reduction in the concentration of surface defect sites and/or more Co or Ni atoms located at preferential crystalline sites in both cases. A reduction in the cytotoxicity toward mouse fibroblast L929 cells was observed after calcination at 800 °C. Combining with inductively coupled plasma mass spectrometry data, our results indicate that the calcination temperature can be employed as a facile strategy to reduce the cytotoxicity of CoFe 2 O 4 and NiFe 2 O 4 , in which higher temperatures contributed to the decrease in the dissolution of Co 2+ or Ni 2+ from the NPs. We believe these results may shed new insights into the various parameters that influence cytotoxicity in ferrite NPs, which may pave the way for their widespread applications in biomedicine.

Metallic nanoparticles have been extensively studied towards applications in catalysis. Among the several methods for their controlled synthesis, galvanic replacement is particularly attractive as it enables the production of bimetallic and hollow nanomaterials displaying ultrathin walls in a single reaction step. This procedure is versatile, but final morphologies are often limited to shapes that represent the hollow analogues of the starting template nanocrystals. For catalytic applications, it is highly desirable to broaden the scope of physicochemical control that can be achieved by this method. This feature article discusses recent strategies developed in our group for the synthesis of hollow bimetallic nanomaterials by galvanic replacement that enable a further level of control over surface morphologies and composition. We begin by briefly explaining the fundamentals of the conventional galvanic replacement reaction between Ag and AuCl 4 - . This is one of the most characteristic galvanic replacement reactions, and it can be tuned to create a huge variety of nanoparticle morphologies. We will discuss how advanced electron microscopy characterization enables us to uncover surface-segregation behavior as a function of compositions, and relate this to the detected catalytic performance. We will also discuss how galvanic replacement can be extended to trimetallic compositions, leading to improvements in catalytic activities compared to mono or bimetallic counterparts. Furthermore, we will show how surface morphology, size, and anisotropic growth can be controlled by tuning the temperature during the synthesis and by combining galvanic replacement reaction with co-reduction. Finally, we will demonstrate how these approaches are promising for large-scale synthesis of controlled hollow nanostructures and their incorporation into supports to produce catalysts at the gram-scale. We believe the developments described herein shed important insights and may inspire the development of sophisticated and controlled nanomaterials at relatively larger scales for catalytic applications.

In hybrid materials containing plasmonic nanoparticles such as Au and Ag, charge-transfer processes from and to Au or Ag can affect both activities and selectivity in plasmonic catalysis. Inspired by the widespread utilization of commercial Si wafers in surface-enhanced Raman spectroscopy (SERS) studies, we investigated herein the effect of the native SiO 2 layer on Si wafers over the surface plasmon resonance (SPR)-mediated activities of the Au and Ag nanoparticles (NPs). We prepared SERS-active plasmonic comprised of Au and Ag NPs deposited onto a Si wafer. Here, two kinds of Si wafers were employed: Si with a native oxide surface layer (Si/SiO 2 ) and Si without a native oxide surface layer (Si). This led to Si/SiO 2 /Au, Si/SiO 2 /Ag, Si/Au, and Si/Ag NPs. The SPR-mediated oxidation of p-aminothiophenol (PATP) to p,p'-dimercaptoazobenzene (DMAB) was employed as a model transformation. By comparing the performances and band structures for the Si/Au and Si/Ag relative to Si/SiO 2 /Au and Si/SiO 2 /Ag NPs, it was found that the presence of a SiO 2 layer was crucial to enable higher SPR-mediated PATP to DMAB conversions. The SiO 2 layer acts to prevent the charge transfer of SPR-excited hot electrons from Au or Ag nanoparticles to the Si substrate. This enabled SPR-excited hot electrons to be transferred to adsorbed O 2 molecules, which then participate in the selective oxidation of PATP to DMAB. In the absence of a SiO 2 layer, SPR-excited hot electrons are preferentially transferred to Si instead of adsorbed O 2 molecules, leading to much lower PATP oxidation., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This paper presents an investigation of the limitations and optimisation of energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope, focussing on application of the technique to characterising the 3D elemental distribution of bimetallic AgAu nanoparticles. The detector collection efficiency when using a standard tomography holder is characterised using a tomographic data set from a single nanoparticle and compared to a standard low background double tilt holder. Optical depth profiling is used to investigate the angles and origin of detector shadowing as a function of specimen field of view. A novel time-varied acquisition scheme is described to compensate for variations in the intensity of spectrum images at each sample tilt. Finally, the ability of EDX spectrum images to satisfy the projection requirement for nanoparticle samples is discussed, with consideration of the effect of absorption and shadowing variations., (Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.)

This contribution highlights some recent advances in the synthesis of monodispersed colloidal spheres loaded with superparamagnetic components for external manipulation. We firstly discuss how FeO nanoparticles can be directly coated with silica to form core-shell particles using a sol-gel approach. We then focus on the demonstration of new materials for such an application, with Pb and amorphous Se as the typical examples of metals and semiconductors, respectively. We also illustrate how colloidal spheres of amorphous Se can be converted into AgSe and then MSe (M = Zn, Cd, and Pb) without changing the spherical shape. Combined together, these synthetic methods could enable the synthesis of monodispersed colloidal spheres with controlled size, smooth surface, and superparamagnetic features for fabricating photonic crystals whose band structures can be configured using an external magnetic field.