All-Optical Electrochemiluminescence.

Electrochemiluminescence (ECL) is widely employed for medical diagnosis and imaging. Despite its remarkable analytical performances, the technique remains intrinsically limited by the essential need for an external power supply and electrical wires for electrode connections. Here, we report an electrically autonomous solution leading to a paradigm change by designing a fully integrated all-optical wireless monolithic photoelectrochemical device based on a nanostructured Si photovoltaic junction modified with catalytic coatings. Under illumination with light ranging from visible to near-infrared, photogenerated holes induce the oxidation of the ECL reagents and thus the emission of visible ECL photons. The blue ECL emission is easily viewed with naked eyes and recorded with a smartphone. A new light emission scheme is thus introduced where the ECL emission energy (2.82 eV) is higher than the excitation energy (1.18 eV) via an intermediate electrochemical process. In addition, the mapping of the photoelectrochemical activity by optical microscopy reveals the minority carrier interfacial transfer mechanism at the nanoscale. This breakthrough provides an all-optical strategy for generalizing ECL without the need for electrochemical setups, electrodes, wiring constraints, and specific electrochemical knowledge. This simplest ECL configuration reported so far opens new opportunities to develop imaging and wireless bioanalytical systems such as portable point-of-care sensing devices.

Water-mediated photo-induced reduction of platinum films.

Platinum thin films activated ex situ by oxygen plasma become reduced by the combined effect of an intense soft X-ray photon beam and condensed water. The evolution of the electronic structure of the surface has been characterized by near-ambient-pressure photoemission and mimics the inverse two-step sequence observed in the electro-oxidation of platinum, i.e. the surface-oxidized platinum species are reduced first and then the adsorbed species desorb in a second step leading to a surface dominated by metallic platinum. The comparison with measurements performed under high-vacuum conditions suggests that the reduction process is mainly induced by the reactive species generated by the radiolysis of water. When the photon flux is decreased, then the reduction process becomes slower.

Unraveling the Operational Mechanisms of Chemically Propelled Motors with Micropumps.

The development of effective autonomous micro- and nanomotors relies on controlling fluid motion at interfaces. One of the main challenges in the engineering of such artificial machines is the quest for efficient mechanisms to power them without using external driving forces. In the past decade, there has been an important increase of man-made micro- and nanomotors fueled by self-generated physicochemical gradients. Impressive proofs of concept of multitasking machines have been reported demonstrating their capabilities for a plethora of applications. While the progress toward applications is promising, there are still open questions on fundamental physicochemical aspects behind the mechanical actuation, which require more experimental and theoretical efforts. These efforts are not merely academic but will open the door for an efficient and practical implementation of such promising devices. In this Account, we focus on chemically driven motors whose motion is the result of a complex interplay of chemical reactions and (electro)hydrodynamic phenomena. A reliable study of these processes is rather difficult with mobile objects like swimming motors. However, pumps, which are the immobilized motor counterparts, emerge as simple manufacturing and well-defined platforms for a better experimental probing of the mechanisms and key parameters controlling the actuation. Here we review some recent studies using a new methodology that has turned out to be very helpful to characterize micropump chemomechanics. The aim was to identify the redox role of the motor components, to map the chemical reaction, and to quantify the relevant electrokinetic parameters (e.g., electric field and fluid flow). This was achieved by monitoring the velocity of differently charged tracers and by fluorescence imaging of the chemical species involved in the chemical reaction, for example, proton gradients. We applied these techniques to different systems of interest. First, we probed bimetallic pumps as counterparts of the pioneering bimetallic swimmers. We corroborated that fluid motion was due to a self-generated electro-osmotic mechanism driven by the redox decomposition of H2O2. In addition, we analyzed by simulations the key parameters that yield an optimized operation. Moreover, we accomplished a better assessment of the importance of surface chemistry on the metal electrochemical response, highlighting its relevance in controlling the redox role of the metals and motion direction. Second, we focused on metallic and semiconductor micropumps to analyze light-controlled motion mechanisms through photoelectrochemical decomposition of fuels. These pumps were driven by visible light and could operate using just water as fuel. In these systems, we found a very interesting competition between two different mechanisms for fluid propulsion, namely, light-activated electro-osmosis and light-insensitive diffusio-osmosis, stemming from different chemical pathways in the fuel decomposition. In this case, surface roughness becomes a pivotal parameter to enhance or depress one mechanism over the other. These examples demonstrate that pumps are practical platforms to explore operating mechanisms and to quantify their performance. Additionally, they are suitable systems to test novel fuels or motor materials. This knowledge is extensible to swimmers providing not only fundamental understanding of their locomotion mechanisms but also useful clues for their design and optimization.

Simultaneous Local Heating/Thermometry Based on Plasmonic Magnetochromic Nanoheaters.

A crucial challenge in nanotherapies is achieving accurate and real-time control of the therapeutic action, which is particularly relevant in local thermal therapies to minimize healthy tissue damage and necrotic cell deaths. Here, a nanoheater/thermometry concept is presented based on magnetoplasmonic (Co/Au or Fe/Au) nanodomes that merge exceptionally efficient plasmonic heating and simultaneous highly sensitive detection of the temperature variations. The temperature detection is based on precise optical monitoring of the magnetic-induced rotation of the nanodomes in solution. It is shown that the phase lag between the optical signal and the driving magnetic field can be used to detect viscosity variations around the nanodomes with unprecedented accuracy (detection limit 0.0016 mPa s, i.e., 60-fold smaller than state-of-the-art plasmonic nanorheometers). This feature is exploited to monitor the viscosity reduction induced by optical heating in real-time, even in highly inhomogeneous cell dispersions. The magnetochromic nanoheater/thermometers show higher optical stability, much higher heating efficiency and similar temperature detection limits (0.05 °C) compared to state-of-the art luminescent nanothermometers. The technological interest is also boosted by the simpler and lower cost temperature detection system, and the cost effectiveness and scalability of the nanofabrication process, thereby highlighting the biomedical potential of this nanotechnology.

Direct detection of protein biomarkers in human fluids using site-specific antibody immobilization strategies.

Design of an optimal surface biofunctionalization still remains an important challenge for the application of biosensors in clinical practice and therapeutic follow-up. Optical biosensors offer real-time monitoring and highly sensitive label-free analysis, along with great potential to be transferred to portable devices. When applied in direct immunoassays, their analytical features depend strongly on the antibody immobilization strategy. A strategy for correct immobilization of antibodies based on the use of ProLinker™ has been evaluated and optimized in terms of sensitivity, selectivity, stability and reproducibility. Special effort has been focused on avoiding antibody manipulation, preventing nonspecific adsorption and obtaining a robust biosurface with regeneration capabilities. ProLinker™-based approach has demonstrated to fulfill those crucial requirements and, in combination with PEG-derivative compounds, has shown encouraging results for direct detection in biological fluids, such as pure urine or diluted serum. Furthermore, we have implemented the ProLinker™ strategy to a novel nanoplasmonic-based biosensor resulting in promising advantages for its application in clinical and biomedical diagnosis.

The efficient magneto-mechanical actuation of cancer cells using a very low concentration of non-interacting ferrimagnetic hexaferrite nanoplatelets.

Magneto-mechanical actuation (MMA) using the low-frequency alternating magnetic fields (AMFs) of magnetic nanoparticles internalized into cancer cells can be used to irreparably damage these cells. However, nanoparticles in cells usually agglomerate, thus greatly augmenting the delivered force compared to single nanoparticles. Here, we demonstrate that MMA also decreases the cell viability, with the MMA mediated by individual, non-interacting nanoparticles. The effect was demonstrated with ferrimagnetic (i.e., permanently magnetic) barium-hexaferrite nanoplatelets (NPLs, ∼50 nm wide and 3 nm thick) with a unique, perpendicular orientation of the magnetization. Two cancer-cell lines (MDA-MB-231 and HeLa) are exposed to the NPLs in-vitro under different cell-culture conditions and actuated with a uniaxial AMF. TEM analyses show that only a small number of NPLs internalize in the cells, always situated in membrane-enclosed compartments of the endosomal-lysosomal system. Most compartments contain 1-2 NPLs and only seldom are the NPLs found in small groups, but never in close contact or mutually oriented. Even at low concentrations, the single NPLs reduce the cell viability when actuated with AMFs, which is further increased when the cells are in starvation conditions. These results pave the way for more efficient in-vivo MMA at very low particle concentrations.

Fe/Au galvanic nanocells to generate self-sustained Fenton reactions without additives at neutral pH.

The generation of reactive oxygen species (ROS) via the Fenton reaction has received significant attention for widespread applications. This reaction can be triggered by zero-valent metal nanoparticles by converting externally added H2O2 into hydroxyl radicals (˙OH) in acidic media. To avoid the addition of external additives or energy supply, developing self-sustained catalytic systems enabling onsite production of H2O2 at a neutral pH is crucial. Here, we present novel galvanic nanocells (GNCs) based on metallic Fe/Au bilayers on arrays of nanoporous silica nanostructures for the generation of self-sustained Fenton reactions. These GNCs exploit the large electrochemical potential difference between the Fe and Au layers to enable direct H2O2 production and efficient release of Fe2+ in water at neutral pH, thereby triggering the Fenton reaction. Additionally, the GNCs promote Fe2+/Fe3+ circulation and minimize side reactions that passivate the iron surface to enhance their reactivity. The capability to directly trigger the Fenton reaction in water at pH 7 is demonstrated by the fast degradation and mineralization of organic pollutants, by using tiny amounts of catalyst. The self-generated H2O2 and its transformation into ˙OH in a neutral environment provide a promising route not only in environmental remediation but also to produce therapeutic ROS and address the limitations of Fenton catalytic nanostructures.

Near-IR Photoinduced Electrochemiluminescence Imaging with Structured Silicon Photoanodes.

Infrared (IR) imaging devices that convert IR irradiation (invisible to the human eye) to a visible signal are based on solid-state components. Here, we introduce an alternative concept based on light-addressable electrochemistry (i.e., electrochemistry spatially confined under the action of a light stimulus) that involves the use of a liquid electrolyte. In this method, the projection of a near-IR image (λexc = 850 or 840 nm) onto a photoactive Si-based photoanode, immersed into a liquid phase, triggers locally the photoinduced electrochemiluminescence (PECL) of the efficient [Ru(bpy)3]2+-TPrA system. This leads to the local conversion of near-IR light to visible (λPECL = 632 nm) light. We demonstrate that compared to planar Si photoanodes, the use of a micropillar Si array leads to a large enhancement of local light generation and considerably improves the resolution of the PECL image by preventing photogenerated minority carriers from diffusing laterally. These results are important for the design of original light conversion devices and can lead to important applications in photothermal imaging and analytical chemistry.

Sensing with magnetic dipolar resonances in semiconductor nanospheres.

In this work we propose two novel sensing principles of detection that exploit the magnetic dipolar Mie resonance in high-refractive-index dielectric nanospheres. In particular, we theoretically investigate the spectral evolution of the extinction and scattering cross sections of these nanospheres as a function of the refractive index of the external medium (next). Unlike resonances in plasmonic nanospheres, the spectral position of magnetic resonances in high-refractive-index nanospheres barely shifts as next changes. Nevertheless, there is a drastic reduction in the extinction cross section of the nanospheres when next increases, especially in the magnetic dipolar spectral region, which is accompanied with remarkable variations in the radiation patterns. Thanks to these changes, we propose two new sensing parameters, which are based on the detection of: i) the intensity variations in the transmitted or backscattered radiation by the dielectric nanospheres at the magnetic dipole resonant frequency, and ii) the changes in the radiation pattern at the frequency that satisfies Kerker's condition of near-zero forward radiation. To optimize the sensitivity, we consider several semiconductor materials and particles sizes.

Efficient Tumor Eradication at Ultralow Drug Concentration via Externally Controlled and Boosted Metallic Iron Magnetoplasmonic Nanocapsules.

With the aim to locally enhance the efficacy of cancer nanotherapies, here we present metal iron based magnetoplasmonic drug-loaded nanocapsules (MAPSULES), merging powerful external magnetic concentration in the tumor and efficient photothermal actuation to locally boost the drug therapeutic action at ultralow drug concentrations. The MAPSULES are composed of paclitaxel-loaded polylactic-co-glycolic acid (PLGA) nanoparticles partially coated by a nanodome shape iron/silica semishell. The iron semishell has been designed to present a ferromagnetic vortex for incorporating a large quantity of ferromagnetic material while maintaining high colloidal stability. The large iron semishell provides very strong magnetic manipulation via magnetophoretic forces, enabling over 10-fold higher trapping efficiency in microfluidic channels than typical superparamagnetic iron oxide nanoparticles. Moreover, the iron semishell exhibits highly damped plasmonic behavior, yielding intense broadband absorbance in the near-infrared biological windows and photothermal efficiency similar to the best plasmonic nanoheaters. The in vivo therapeutic assays in a mouse xenograft tumor model show a high amplification of the therapeutic effects by combining magnetic concentration and photothermal actuation in the tumor, leading to a complete eradication of the tumors at ultralow nanoparticle and drug concentration (equivalent to only 1 mg/kg PLGA nanoparticles containing 8 µg/kg of paclitaxel, i.e., 100-500-fold lower than the therapeutic window of the free and PLGA encapsulated drug and 13-3000-fold lower than current nanotherapies combining paclitaxel and light actuation). These results highlight the strength of this externally controlled and amplified therapeutic approach, which could be applied to locally boost a wide variety of drugs for different diseases.

Enhanced Proliferation and Differentiation of Human Osteoblasts by Remotely Controlled Magnetic-Field-Induced Electric Stimulation Using Flexible Substrates.

With the progressive aging of the population, bone fractures are an increasing major health concern. Diverse strategies are being studied to reduce the recovery times using nonaggressive treatments. Electrical stimulation (either endogenous or externally applied electric pulses) has been found to be effective in accelerating bone cell proliferation and differentiation. However, the direct insertion of electrodes into tissues can cause undesirable inflammation or infection reactions. As an alternative, magnetoelectric heterostructures (wherein magnetic fields are applied to induce electric polarization) could be used to achieve electric stimulation without the need for implanted electrodes. Here, we develop a magnetoelectric platform based on flexible kapton/FeGa/P(VDF-TrFE) (flexible substrate/magnetostrictive layer/ferroelectric layer) heterostructures for remote magnetic-field-induced electric field stimulation of human osteoblast cells. We show that the use of flexible supports overcomes the clamping effects that typically occur when analogous magnetoelectric structures are grown onto rigid substrates (which preclude strain transfer from the magnetostrictive to the ferroelectric layers). The study of the diverse proliferation and differentiation markers evidence that in all the stages of bone formation (cell proliferation, extracellular matrix maturation, and mineralization), the electrical stimulation of the cells results in a remarkably better performance. The results pave the way for novel strategies for remote cell stimulation based on flexible platforms not only in bone regeneration but also in many other applications where electrical cell stimulation may be beneficial (e.g., neurological diseases or skin regeneration).

Modular Drug-Loaded Nanocapsules with Metal Dome Layers as a Platform for Obtaining Synergistic Therapeutic Biological Activities.

Multifunctional drug-loaded polymer-metal nanocapsules have attracted increasing attention in drug delivery due to their multifunctional potential endowed by drug activity and response to physicochemical stimuli. Current chemical synthesis methods of polymer/metal capsules require specific optimization of the different components to produce particles with precise properties, being particularly complex for Janus structures combining polymers and ferromagnetic and highly reactive metals. With the aim to generate tunable synergistic nanotherapeutic actuation with enhanced drug effects, here we demonstrate a versatile hybrid chemical/physical fabrication strategy to incorporate different functional metals with tailored magnetic, optical, or chemical properties on solid drug-loaded polymer nanoparticles. As archetypical examples, we present poly(lactic-co-glycolic acid) (PLGA) nanoparticles (diameters 100-150 nm) loaded with paclitaxel, indocyanine green, or erythromycin that are half-capped by either Fe, Au, or Cu layers, respectively, with application in three biomedical models. The Fe coating on paclitaxel-loaded nanocapsules permitted efficient magnetic enhancement of the cancer spheroid assembly, with 40% reduction of the cross-section area after 24 h, as well as a higher paclitaxel effect. In addition, the Fe-PLGA nanocapsules enabled external contactless manipulation of multicellular cancer spheroids with a speed of 150 µm/s. The Au-coated and indocyanine green-loaded nanocapsules demonstrated theranostic potential and enhanced anticancer activity in vitro and in vivo due to noninvasive fluorescence imaging with long penetration near-infrared (NIR) light and simultaneous photothermal-photodynamic actuation, showing a 3.5-fold reduction in the tumor volume growth with only 5 min of NIR illumination. Finally, the Cu-coated erythromycin-loaded nanocapsules exhibited enhanced antibacterial activity with a 2.5-fold reduction in the MIC50 concentration with respect to the free or encapsulated drug. Altogether, this technology can extend a nearly unlimited combination of metals, polymers, and drugs, thus enabling the integration of magnetic, optical, and electrochemical properties in drug-loaded nanoparticles to externally control and improve a wide range of biomedical applications.

All-optical phase modulation for integrated interferometric biosensors.

We present the theoretical and the experimental implementation of an all-optical phase modulation system in integrated Mach-Zehnder Interferometers to solve the drawbacks related to the periodic nature of the interferometric signal. Sensor phase is tuned by modulating the emission wavelength of low-cost commercial laser diodes by changing their output power. FFT deconvolution of the signal allows for direct phase readout, immune to sensitivity variations and to light intensity fluctuations. This simple phase modulation scheme increases the signal-to-noise ratio of the measurements in one order of magnitude, rendering in a sensor with a detection limit of 1.9·10⁻7 RIU. The viability of the all-optical modulation approach is demonstrated with an immunoassay detection as a biosensing proof of concept.

Polypeptide folding-mediated tuning of the optical and structural properties of gold nanoparticle assemblies.

Responsive hybrid nanomaterials with well-defined properties are of significant interest for the development of biosensors with additional applications in tissue engineering and drug delivery. Here, we present a detailed characterization using UV-vis spectroscopy and small angle X-ray scattering of a hybrid material comprised of polypeptide-decorated gold nanoparticles with highly controllable assembly properties. The assembly is triggered by a folding-dependent bridging of the particles mediated by the heteroassociation of immobilized helix-loop-helix polypeptides and a complementary nonlinear polypeptide present in solution. The polypeptides are de novo designed to associate and fold into a heterotrimeric complex comprised of two disulfide-linked four-helix bundles. The particles form structured assemblies with a highly defined interparticle gap (4.8±0.4 nm) that correlates to the size of the folded polypeptides. Transitions in particle aggregation dynamics, mass-fractal dimensions and ordering, as a function of particle size and the concentration of the bridging polypeptide, are observed; these have significant effects on the optical properties of the assemblies. The assembly and ordering of the particles are highly complex processes that are affected by a large number of variables including the number of polypeptides bridging the particles and the particle mobility within the aggregates. A fundamental understanding of these processes is of paramount interest for the development of novel hybrid nanomaterials with tunable structural and optical properties and for the optimization of nanoparticle-based colorimetric biodetection strategies.

Elastic Plasmonic-Enhanced Fabry-Pérot Cavities with Ultrasensitive Stretching Tunability.

The emerging stretchable photonics field faces challenges, like the robust integration of optical elements into elastic matrices or the generation of large optomechanical effects. Here, the first stretchable plasmonic-enhanced and wrinkled Fabry-Pérot (FP) cavities are demonstrated, which are composed of self-embedded arrays of Au nanostructures at controlled depths into elastomer films. The novel self-embedding process is triggered by the Au nanostructures' catalytic activity, which locally increases the polymer curing rate, thereby inducing a mechanical stress that simultaneously pulls the Au nanostructures into the polymer and forms a wrinkled skin layer. This geometry yields unprecedented optomechanical effects produced by the coupling of the broad plasmonic modes of the Au nanostructures and the FP modes, which are modulated by the wrinkled optical cavity. As a result, film stretching induces drastic changes in both the spectral position and intensity of the plasmonic-enhanced FP resonances due to the simultaneous cavity thickness reduction and cavity wrinkle flattening, thus increasing the cavity finesse. These optomechanical effects are exploited to demonstrate new strain-sensing approaches, achieving a strain detection limit of 0.006%, i.e., 16-fold lower than current optical strain-detection schemes.

Suitable combination of noble/ferromagnetic metal multilayers for enhanced magneto-plasmonic biosensing.

We present a theoretical and experimental study on the biosensing sensitivity of Au/Co/Au multilayers as transducers of the magneto-optic surface-plasmon-resonance (MOSPR) sensor. We demonstrate that the sensing response of these magneto-plasmonic (MP) transducers is a trade-off between the optical absorption and the magneto-optical activity, observing that the MP multilayer with larger MO effect does not provide the best sensing response. We show that it is possible to design highly-sensitive MP transducers able to largely surpass the limit of detection of the conventional surface-plasmon-resonance (SPR) sensor. This was proved comparing the biosensing performance of both sensors for the label-free detection of short DNA chains hybridization. For this purpose, we used and tested a novel label-free biofunctionalization protocol based on polyelectrolytes, which increases the resistance of MP transducers in aqueous environments.

Mechanochromic Detection for Soft Opto-Magnetic Actuators.

New multi-stimuli responsive materials are required in smart systems applications to overcome current limitations in remote actuation and to achieve versatile operation in inaccessible environments. The incorporation of detection mechanisms to quantify in real time the response to external stimuli is crucial for the development of automated systems. Here, we present the first wireless opto-magnetic actuator with mechanochromic response. The device, based on a nanostructured-iron (Fe) layer transferred onto suspended elastomer structures with a periodically corrugated backside, can be actuated both optically (in a broadband spectral range) and magnetically. The combined opto-magnetic stimulus can accurately modulate the mechanical response (strength and direction) of the device. The structural coloration generated at the corrugated back surface enables to easily map and quantify, in 2D, the mechanical deflections by analyzing in real time the hue changes of images taken using a conventional RGB smartphone camera, with a precision of 0.05°. We demonstrate the independent and synergetic optical and magnetic actuation and detection with a detection limit of 1.8 mW·cm-2 and 0.34 mT, respectively. The simple operation, versatility, and cost-effectiveness of the wireless multiactuated device with highly sensitive mechanochromic mapping paves the way to a new generation of wirelessly controlled smart systems.

Highly reduced ecotoxicity of ZnO-based micro/nanostructures on aquatic biota: Influence of architecture, chemical composition, fixation, and photocatalytic efficiency.

Developing efficient sunlight photocatalysts with enhanced photocorrosion resistance and minimal ecotoxicological effects on aquatic biota is critical to combat water contamination. Here, the role of chemical composition, architecture, and fixation on the ecotoxicological effects on microalgae of different ZnO and ZnO@ZnS based water decontamination photocatalysts was analyzed in depth. In particular, the ecotoxicological effects of films, nanoparticles and biomimetic micro/nano-ferns were carefully assessed by correlating the algae's viability to the Zn(II) release, the photocatalyst-microalgae interaction, and the production of reactive oxygen species (ROS). The results showed a drastic improvement in algal viability for supported ZnO@ZnS core@shell micro/nanoferns, as their ecotoxicity after 96 h light exposure was significantly lower (3.7-10.0% viability loss) compared to the ZnO films (18.4-35.5% loss), ZnO micro/nanoferns (28.5-53.5% loss), ZnO nanoparticles (48.3-91.7% loss) or ZnO@ZnS nanoparticles (8.6-19.2% loss) for catalysts concentrations ranging from 25 mg L-1 to 400 mg L-1. In particular, the ZnO@ZnS micro/nanoferns with a concentration of 400 mg L-1 exhibited excellent photocatalytic efficiency to mineralize a multi-pollutant solution (81.4 ±â€¯0.3% mineralization efficiency after 210 min under UV-filtered visible light irradiation) and minimal photocorrosion (<5% of photocatalyst dissolution after 96 h of UV-filtered visible light irradiation). Remarkably, the ZnO@ZnS micro/nanoferns showed lower loss of algal viability (9.8 ±â€¯1.1%) after 96 h of light exposure, with minimal reduction in microalgal biomass (9.1 ±â€¯1.0%), as well as in the quantity of chlorophyll-a (9.5 ±â€¯1.0%), carotenoids (8.6 ±â€¯0.9%) and phycocyanin (5.6 ±â€¯0.6%). Altogether, the optimized ZnO@ZnS core@shell micro/nanoferns represent excellent ecofriendly photocatalysts for water remediation in complex media, as they combine enhanced sunlight remediation efficiency, minimal adverse effects on biological microorganisms, high reusability and easy recyclability.

Hybrid Ni@ZnO@ZnS-Microalgae for Circular Economy: A Smart Route to the Efficient Integration of Solar Photocatalytic Water Decontamination and Bioethanol Production.

Water remediation and development of carbon-neutral fuels are a priority for the evermore industrialized society. The answer to these challenges should be simple, sustainable, and inexpensive. Thus, biomimetic-inspired circular and holistic processes combing water remediation and biofuel production can be an appealing concept to deal with these global issues. A simple circular approach using helical Spirulina platensis microalgae as biotemplates to synthesize Ni@ZnO@ZnS photocatalysts for efficient solar water decontamination and bioethanol production during the recycling process is presented. Under solar irradiation, the Ni@ZnO@ZnS-Spirulina photocatalyst exhibits enhanced activity (mineralization efficiency >99%) with minimal photocorrosion and excellent reusability. At the end of its effective lifetime for water remediation, the microalgae skeleton (mainly glycogen and glucose) of the photocatalyst is recycled to directly produce bioethanol by simultaneous saccharification and fermentation process. An outstanding ethanol yield of 0.4 L kg-1, which is similar to the highest yield obtained from oxygenic photosynthetic microorganisms, is obtained. Thus, the entire process allows effective solar photocatalytic water remediation and bioethanol production at room temperature using simple and easily scalable procedures that simultaneously fixes carbon dioxide, thereby constituting a zero-carbon-emission circular process.

Sensitivity enhancement of nanoplasmonic sensors in low refractive index substrates.

Metal films perforated by nanoholes constitute a powerful platform for surface plasmon resonance biosensing. We find that the refractive index sensitivity of nanohole arrays increases if their resonance is red-shifted by increasing the separation distance between holes. However, an additional sensitivity enhancement occurs if the nanohole sensors are manufactured on low index substrates, despite the fact such substrates significantly blue-shift the resonance. We find a approximately 40% higher bulk refractive index sensitivity for a system of approximately 100 nm holes in 20 nm gold films fabricated on Teflon substrates (n=1.32) compared to the case when conventional glass substrates (n=1.52) are used. A similar improvement is observed for the case when a thin layer of dielectric material is deposited on the samples. These results can be understood by considering the electric field distribution induced by the so-called antisymmetric surface plasmon polariton in the thin gold films.