Search

Nonstoichiometric nickel oxide (NiO x ) is one of the very few metal oxides successfully used as hole extraction layer in p-i-n type perovskite solar cells (PSCs). Its favorable optoelectronic properties and facile large-scale preparation methods are potentially relevant for future commercialization of PSCs, though currently low operational stability of PSCs is reported when a NiO x hole extraction layer is used in direct contact with the perovskite absorber. Poorly understood degradation reactions at this interface are seen as cause for the inferior stability, and a variety of interface passivation approaches have been shown to be effective in improving the overall solar cell performance. To gain a better understanding of the processes happening at this interface, we systematically passivated specific defects on NiO x with three different categories of organic/inorganic compounds. The effects on NiO x and the perovskite (MAPbI 3 ) deposited on top were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Here, we find that the perovskite's structural stability and film formation can be significantly affected by the passivation treatment of the NiO x surface. In combination with density functional theory (DFT) calculations, a likely origin of NiO x -perovskite degradation interactions is proposed. The surface passivated NiO x layers were incorporated into MAPbI 3 -based PSCs, and the influence on device performance and operational stability was investigated by current-voltage ( J - V ) characterization, impedance spectroscopy (IS), and open circuit voltage decay (OCVD) measurements. Interestingly, we find that a superior structural stability due to interface passivation must not relate to high operational stability. The discrepancy comes from the formation of excess ions at the interface, which negatively impacts all solar cell parameters.

Self-assembling molecules (SAMs), as selective contacts, play an important role in perovskite solar cells (PSCs), determining the performance and stability of these photovoltaic devices. These materials offer many advantages over other traditional materials used as hole-selective contacts, as they can be easily deposited on a large area of metal oxides, can modify the work function of these substrates, and reduce optical and electric losses with low material consumption. However, the most interesting thing about SAMs is that by modifying the chemical structure of the small molecules used, the energy levels, molecular dipoles, and surface properties of this assembled monolayer can be modulated to fine-tune the desired interactions between the substrate and the active layer. Due to the important role of organic chemistry in the field of photovoltaics, in this review, we will cover the current challenges for the design and synthesis of SAMs PSCs. Discussing, the structural features that define a SAM, (ii) disclosing how commercial molecules inspired the synthesis of new SAMs; and (iii) detailing the pros- and cons- of the reported synthetic protocols that have been employed for the synthesis of molecules for SAMs, helping synthetic chemists to develop novel structures and promoting the fast industrialization of PSCs., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Electro- and photochemical CO 2 reduction (CO 2 R) is the quintessence of modern-day sustainable research. We report our studies on the electro- and photoinduced interfacial charge transfer occurring in a nanocrystalline mesoporous TiO 2 film and two TiO 2 /iron porphyrin hybrid films ( meso -aryl- and β-pyrrole-substituted porphyrins, respectively) under CO 2 R conditions. We used transient absorption spectroscopy (TAS) to demonstrate that, under 355 nm laser excitation and an applied voltage bias (0 to -0.8 V vs Ag/AgCl), the TiO 2 film exhibited a diminution in the transient absorption (at -0.5 V by 35%), as well as a reduction of the lifetime of the photogenerated electrons (at -0.5 V by 50%) when the experiments were conducted under a CO 2 atmosphere changing from inert N 2 . The TiO 2 /iron porphyrin films showed faster charge recombination kinetics, featuring 100-fold faster transient signal decays than that of the TiO 2 film. The electro-, photo-, and photoelectrochemical CO 2 R performance of the TiO 2 and TiO 2 /iron porphyrin films are evaluated within the bias range of -0.5 to -1.8 V vs Ag/AgCl. The bare TiO 2 film produced CO and CH 4 as well as H 2 , depending on the applied voltage bias. In contrast, the TiO 2 /iron porphyrin films showed the exclusive formation of CO (100% selectivity) under identical conditions. During the CO 2 R, a gain in the overpotential values is obtained under light irradiation conditions. This finding was indicative of a direct transfer of the photogenerated electrons from the film to absorbed CO 2 molecules and an observed decrease in the decay of the TAS signals. In the TiO 2 /iron porphyrin films, we identified the interfacial charge recombination processes between the oxidized iron porphyrin and the electrons of the TiO 2 conduction band. These competitive processes are considered to be responsible for the diminution of direct charge transfer between the film and the adsorbed CO 2 molecules, explaining the moderate performances of the hybrid films for the CO 2 R.

The tobacco-specific nitrosamine 4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) is a carcinogenic and ubiquitous environmental pollutant for which toxic activity has been thoroughly investigated in murine models and human tissues. However, its potential deleterious effects on vertebrate early development are yet poorly understood. In this work, we characterized the impact of NNK exposure during early developmental stages of zebrafish embryos, a known alternative model for mammalian toxicity studies. Embryos exposed to different NNK concentrations were monitored for lethality and for the appearance of malformations during the first five days after fertilization. LC-MS based untargeted metabolomics was subsequently performed for a wide-scope assay of NNK-related metabolic alterations. Our results revealed the presence of not only the parental compound, but also of two known NNK metabolites, 4-Hydroxy-4-(3-pyridyl)-butyric acid (HPBA) and 4-(Methylnitrosamino)-1-(3-pyridyl-N-oxide)-1-butanol (NNAL-N-oxide) in exposed embryos likely resulting from active CYP450-mediated α-hydroxylation and NNK detoxification pathways, respectively. This was paralleled by a disruption in purine and pyrimidine metabolisms and the activation of the base excision repair pathway. Our results confirm NNK as a harmful embryonic agent and demonstrate zebrafish embryos to be a suitable early development model to monitor NNK toxicity., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

The photocatalytic and electrocatalytic conversion of CO 2 has the potential to provide valuable products, such as chemicals or fuels of interest, at low cost while maintaining a circular carbon cycle. In this context, carbon dots possess optical and electrochemical properties that make them suitable candidates to participate in the reaction, either as a single component or forming part of more elaborate catalytic systems. In this review, we describe several strategies where the carbon dots participate, both with amorphous and graphitic structures, in the photocatalysis or electrochemical catalysis of CO 2 to provide different carbon-containing products of interest. The role of the carbon dots is analyzed as a function of their redox and light absorption characteristics and their complementarity with other known catalytic systems. Moreover, detailed information about synthetic procedures is also reviewed.

High-order switched DC-DC converters, such as SEPIC, Ćuk and Zeta, are classic energy processing elements, which can be used in a wide variety of applications due to their capacity to step-up and/or step-down voltage characteristic. In this paper, a novel methodology for analyzing the previous converters operating in discontinuous conduction mode (DCM) is applied to obtain full-order dynamic models. The analysis is based on the fact that inductor currents have three differentiated operating sub-intervals characterized by a third one in which both currents become equal, which implies that the current flowing through the diode is zero (DCM). Under a small voltage ripple hypothesis, the currents of all three converters have similar current piecewise linear shapes that allow us to use a graphical method based on the triangular shape of the diode current to obtain the respective non-linear average models. The models' linearization around their steady-state operating points yields full-order small-signal models that reproduce accurately the dynamic behavior of the corresponding switched model. The proposed methodology is applicable to the proposed converters and has also been extended to more complex topologies with magnetic coupling between inductors and/or an RC damping network in parallel with the intermediate capacitor. Several tests were carried out using simulation, hardware-in-the-loop, and using an experimental prototype. All the results validate the theoretical models.

This work presents a novel dc-dc bidirectional buck-boost converter between a battery pack and the inverter to regulate the dc-bus in an electric vehicle (EV) powertrain. The converter is based on the versatile buck-boost converter, which has shown an excellent performance in different fuel cell systems operating in low-voltage and hard-switching applications. Therefore, extending this converter to higher voltage applications such as the EV is a challenging task reported in this work. A high-efficiency step-up/step-down versatile converter can improve the EV powertrain efficiency for an extended range of electric motor (EM) speeds, comprising urban and highway driving cycles while allowing the operation under motoring and regeneration (regenerative brake) conditions. DC-bus voltage regulation is implemented using a digital two-loop control strategy. The inner feedback loop is based on the discrete-time sliding-mode current control (DSMCC) strategy, and for the outer feedback loop, a proportional-integral (PI) control is employed. Both digital control loops and the necessary transition mode strategy are implemented using a digital signal controller TMS320F28377S. The theoretical analysis has been validated on a 400 V 1.6 kW prototype and tested through simulation and an EV powertrain system testing.

Many electronic power distribution systems have strong needs for highly efficient AC-DC conversion that can be satisfied by using a buck-boost converter at the core of the power factor correction (PFC) stage. These converters can regulate the input voltage in a wide range with reduced efforts compared to other solutions. As a result, buck-boost converters could potentially improve the efficiency in applications requiring DC voltages lower than the peak grid voltage. This paper compares SEPIC, noninverting, and versatile buck-boost converters as PFC single-phase rectifiers. The converters are designed for an output voltage of 200 V and an rms input voltage of 220 V at 3.2 kW. The PFC uses an inner discrete-time predictive current control loop with an output voltage regulator based on a sensorless strategy. A PLECS thermal simulation is performed to obtain the power conversion efficiency results for the buck-boost converters considered. Thermal simulations show that the versatile buck-boost (VBB) converter, currently unexplored for this application, can provide higher power conversion efficiency than SEPIC and non-inverting buck-boost converters. Finally, a hardware-in-the-loop (HIL) real-time simulation for the VBB converter is performed using a PLECS RT Box 1 device. At the same time, the proposed controller is built and then flashed to a low-cost digital signal controller (DSC), which corresponds to the Texas Instruments LAUNCHXL-F28069M evaluation board. The HIL real-time results verify the correctness of the theoretical analysis and the effectiveness of the proposed architecture to operate with high power conversion efficiency and to regulate the DC output voltage without sensing it while the sinusoidal input current is perfectly in-phase with the grid voltage.

In this work, a methodology that exploits the optical properties of the nanoporous anodic alumina gradient index filters (NAA-GIFs) has been developed and applied to evaluate in real time the release dynamics of a cargo molecule, acting as a model drug, filling the pores. NAA-GIFs with two photonic stopbands (PSBs) were prepared with one of its stop bands in the same absorption wavelength range of the cargo molecule, whereas the second stopband away from this absorption range. Numerical simulation and experiments confirm that the relative height of the high reflectance bands in the reflectance spectra of NAA-GIFs filled with the drug can be related to the relative amount of drug filling the pores. This property has been applied in a flow cell setup to measure in real-time the release dynamics of NAA-GIFs with the inner pore surface modified by layer-by-layer deposition of polyelectrolytes and loaded with the cargo molecule. The methodology developed in this work acts as a tool for the study of drug delivery from porous nanostructures.

The effect of the morphology and chemical composition of a surface on the wettability of porous silicon structures is analyzed in the present work. Hydrophobic and superhydrophobic macroporous substrates are attractive for different potential applications. Herein, different hydrophobic macroporous silicon structures were fabricated by the chemical etching of p-type silicon wafers in a solution based on hydrofluoric acid and coated with a fluoro silane self-assembled monolayer. The surface morphology of the final substrate was characterized using a scanning electron microscope. The wettability was assessed from contact angle measurements using water and organic solvents that present low surface energy. The experimental data were compared with the classical wetting states theoretical models described in the literature. Perfluoro-silane functionalized macroporous silicon surfaces presented systematically higher contact angles than untreated silicon substrates. The influence of porosity on the surface wettability of macoporous silicon structures has been established. These results suggest that the combination of etching conditions with a surface chemistry modification could lead to hydrophobic/oleophilic or superhydrophobic/oleophobic structures.

In this work, we present the process to provide anodic alumina nanotubes with magnetic responsivity based on magnetic nanoparticles. We demonstrate the possibility to cause the motion of these composite nanotubes under magnetic field, providing them with guided mobility. The obtained magnetic anodic alumina nanotubes are completely characterized and their potential to undergo selective and effective functionalization, and stimuli-responsive load release is demonstrated. For this purpose, protease-triggered release of fluorescent molecules loaded inside the magnetic anodic alumina nanotubes (MAANTs) by selective functionalization is performed. The inner walls of the MAANTs were selectively covered with protein padding of albumin-fluorescein isothiocyanate conjugate (FITC-BSA) through means of silanization. Protein functionalization was designed to undergo proteolytic hydrolysis in presence of cathepsin B- protease highly expressed during growth and initial stages of tumor metastasis - in order to cleave peptide bond of albumin and release fluorescent fragments of the protein. Proteolytic reaction with the enzyme is performed under acidic conditions. Presented arrangement is an exemplary combination of functionalities - which are vast - and of value for applications like drug delivery and biosensing applications., 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 Inc. All rights reserved.)

The development of aluminum anodization technology features many stages. With the story stretching for almost a century, rather straightforward-from current perspective-technology, raised into an iconic nanofabrication technique. The intrinsic properties of alumina porous structures constitute the vast utility in distinct fields. Nanoporous anodic alumina can be a starting point for: Templates, photonic structures, membranes, drug delivery platforms or nanoparticles, and more. Current state of the art would not be possible without decades of consecutive findings, during which, step by step, the technique was more understood. This review aims at providing an update regarding recent discoveries-improvements in the fabrication technology, a deeper understanding of the process, and a practical application of the material-providing a narrative supported with a proper background.

Four hole transport materials (HTMs) based on a benzothiadiazole (BT) central core have been synthesized and successfully employed in triple-cation mixed-halide perovskite solar cells (PSCs), reaching 18.05% solar to energy conversion efficiency. The synthesis of these HTMs follows the push-and-pull approach to modulate the HOMO energy level by combining the BT group as an electron acceptor and diphenyl- and triphenyl-amines as electron donors. Here we show that despite adjusting the HOMO energy level to that of the perovskite is a believed requisite to achieve efficient interfacial hole transfer, additional factors must be taken into account to design novel and efficient HTMs, such as a high hole mobility, solubility in organic solvents, and thermal stability.

Scope: Postprandial dysmetabolism plays a major role in the pathogenesis of metabolic disorders such as obesity and the polycystic ovary syndrome (PCOS). The aim is to characterize the circulating lipoprotein particle profiles in response to oral glucose, lipid, and protein challenges., Methods and Results: 17 women with PCOS, 17 control women, and 19 healthy men selected to have similar age and body mass index are studied. Blood samples are collected following the ingestion of 300 kcal in the form of glucose, lipids, or proteins, and they are submitted to two-dimensional (2D) diffusion-ordered 1 H-NMR spectroscopy. Regardless of macronutrient administered, the number of very low-density (VLDL) particles increases whereas low density-lipoprotein (LDL) decreases. High density-lipoprotein (HDL) particles increase only after lipid ingestion. Obese subjects show an increase in the number of large VLDL particles and a decrease in large LDL particles, with a significant reduction in the average particle size of LDL. Patients with PCOS show a particularly unfavorably smaller LDL particle size response to oral lipid intake, regardless of obesity., Conclusions: Oral macronutrient challenges induce immediate class-specific postprandial changes in particle number and size of lipoproteins, with lipids inducing a more pro-atherogenic lipoprotein profile compared to glucose and proteins, particularly in obese subjects and women with PCOS., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study presents a Gaussian pulse anodization approach to generate nanoporous photonic crystals with highly tunable and controllable optical properties across the visible-NIR spectrum. Nanoporous anodic alumina Gaussian photonic crystals (NAA-GPCs) are fabricated in oxalic acid electrolyte by Gaussian pulse anodization, a novel form of pulse-like anodization. The effect of the Gaussian pulse width in the anodization profile on the optical properties of these photonic crystals is assessed by systematically varying this fabrication parameter from 5 to 60 s. The optical features of the characteristic photonic stopband (PSB) of NAA-GPCs-the position of the central wavelength, full width at half-maximum, and intensity-are found to be highly dependent on the Gaussian pulse width, the angle of incidence of incoming photons, and the nanopore diameter of NAA-GPCs. The effective medium of NAA-GPCs is assessed by monitoring spectral shifts in their characteristic PSB upon infiltration of their nanoporous structure with analytical solutions of d-glucose of varying concentration (0.0125-1 M). Experimental results are validated and mechanistically described by theoretical simulations, using the Looyenga-Landau-Lifshitz effective medium approximation model. Our findings demonstrate that Gaussian pulse anodization is an effective nanofabrication approach to producing highly sensitive NAA-based PC structures with versatile and tunable PSBs across the spectral regions. The findings provide new exiting opportunities to integrate these unique PC structures into photonic sensors and other platform materials for light-based technologies.

The use of C 60 as an interfacial layer between TiO 2 and methylammonium lead iodide perovskite is probed to reduce the current-voltage hysteresis in perovskite solar cells (PSCs) and, in turn, to impact the interfacial carrier injection and recombination processes that limit solar cell efficiencies. Detailed kinetic analyses across different time scales, that is, from the femtoseconds to the seconds, reveal that the charge carrier lifetimes as well as the charge injection and charge recombination dynamics depend largely on the presence or absence of C 60 . In addition, we corroborate that C 60 is applicable in hot carrier PSCs as it is capable of extracting hot carriers generated throughout the early time scales following photoexcitation.

Many sensors are developed over flexible substrates to be used as wearables, which does not guarantee that they will actually withstand being bent. This work evaluates the gas sensing performance of metal oxide devices of three different types, before and after having undergone automated, repetitive bending tests. These tests were aimed at demonstrating that the fabricated sensors were actually flexible, which cannot be taken for granted beforehand. The active layer in these sensors consisted of WO 3 nanowires (NWs) grown directly over a Kapton foil by means of the aerosol-assisted chemical vapor deposition. Their response to different H 2 concentrations was measured at first. Then, they were cyclically bent, and finally, their response to H 2 was measured again. Sensors based on pristine WO 3 -NWs over Ag electrodes and on Pd-decorated NWs over Au electrodes maintained their performance after having been bent. Ag electrodes covered with Pd-decorated NWs became fragile and lost their usefulness. To summarize, two different types of truly flexible metal oxide gas sensor were fabricated, whereas a third one was not flexible, despite being grown over a flexible substrate following the same method. Finally, we recommend that one standard bending test procedure should be established to clearly determine the flexibility of a sensor considering its intended application.

Aptamer biosensors are one of the most powerful techniques in biosensing. Achieving the best platform to use in aptamer biosensors typically includes crucial chemical modifications that enable aptamer immobilization on the surface in the most efficient manner. These chemical modifications must be well defined. In this work we propose nanoporous anodic alumina (NAA) chemically modified with streptavidin as a platform for aptamer immobilization. The immobilization of biotinylated thrombin binding aptamer (TBA) was monitored in real time by means of reflective interferometric spectroscopy (RIfS). The study has permitted to characterize in real time the path to immobilize TBA on the inner pore walls of NAA. Furthermore, this study provides an accurate label-free method to detect thrombin in real-time with high affinity and specificity.

Truxene derivatives, due to their molecular structure and properties, are good candidates for the passivation of defects when deposited onto hybrid lead halide perovskite thin films. Moreover, their semiconductor characteristics can be tailored through the modification of their chemical structure, which allows-upon light irradiation- the interfacial charge transfer between the perovskite film and the truxene molecules. In this work, we analysed the use of the molecules as surface passivation agents and their use in complete functional solar cells. We observed that these molecules reduce the non-radiative carrier recombination dynamics in the perovskite thin film through the supramolecular complex formation between the Truxene molecule and the Pb 2+ defects at the perovskite surface. Interestingly, this supramolecular complexation neither affect the carrier recombination kinetics nor the carriers collection but induced noticeable hysteresis on the photocurrent vs voltage curves of the solar cells under 1 sun illumination., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We describe the preparation of inverted white light emitting diodes by solution processing. The active layer is formed uniquely by Carbon Nanodots (C-dots) that display white-light emission at voltage close to 5 V when combined with metal oxides as charge transport layers. Moreover, we have demonstrated that the white light is not the product of charge transfer between the polymer selective contact and the C-dots but the result of the different recombination processes within the C-dots.

The chemical modification, or functionalization, of the surfaces of nanomaterials is a key step to achieve biosensors with the best sensitivity and selectivity. The surface modification of biosensors usually comprises several modification steps that have to be optimized. Real-time monitoring of all the reactions taking place during such modification steps can be a highly helpful tool for optimization. In this work, we propose nanoporous anodic alumina (NAA) functionalized with the streptavidin-biotin complex as a platform towards label-free biosensors. Using reflective interferometric spectroscopy (RIfS), the streptavidin-biotin complex formation, using biotinylated thrombin as a molecule model, was monitored in real-time. The study compared the performance of different NAA pore sizes in order to achieve the highest response. Furthermore, the optimal streptavidin concentration that enabled the efficient detection of the biotinylated thrombin attachment was estimated. Finally, the ability of the NAA-RIfS system to quantify the concentration of biotinylated thrombin was evaluated. This study provides an optimized characterization method to monitor the chemical reactions that take place during the biotinylated molecules attachment within the NAA pores.

This study presents the development and optical engineering of stacked nanoporous anodic alumina gradient-index (NAA-GIFs) filters with tunable multispectral photonic stopbands for sensing applications. The structure of these photonic crystals (PC) is formed by stacked layers of NAA produced with sinusoidally modified effective medium. The progressive modification of the sinusoidal period during the anodization process enables the generation and precise tuning of the characteristic photonic stopbands (PSB) (i.e., one per sinusoidal period in the anodization profile) of these PC structures. Four types of NAA-GIFs featuring three distinctive PSBs positioned within the visible spectral region are developed. The sensitivity of the effective medium of these NAA-GIFs is systematically assessed by measuring spectral shifts in the characteristic PSBs upon infiltration of their nanoporous structure with analytical solutions of d-glucose with several concentrations (0.025-1 M). This study provides new insights into the intrinsic relationship between the nanoporous architecture of these PCs and their optical properties, generating opportunities to fabricate advanced optical sensing systems for high-throughput and multiplexed detection of analytes in a single sensing platform.

In this paper, we demonstrate that zinc oxide (ZnO) layers deposited by inkjet printing (IJP) can be successfully applied to the low-temperature fabrication of efficient inverted polymer solar cells (i-PSCs). The effects of ZnO layers deposited by IJP as electron transport layer (ETL) on the performance of i-PSCs based on PTB7-Th:PC 70 BM active layers are investigated. The morphology of the ZnO-IJP layers was analysed by AFM, and compared to that of ZnO layers deposited by different techniques. The study shows that the morphology of the ZnO underlayer has a dramatic effect on the band structure and non-geminate recombination kinetics of the active layer deposited on top of it. Charge carrier and transient photovoltage measurements show that non-geminate recombination is governed by deep trap states in devices made from ZnO-IJP while trapping is less significant for other types of ZnO. The power conversion efficiency of the devices made from ZnO-IJP is mostly limited by their slightly lower J SC , resulting from non-optimum photon conversion efficiency in the visible part of the solar spectrum. Despite these minor limitations their J - V characteristics compare very favourably with that of devices made from ZnO layer deposited using different techniques., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Two new perylenediimides (PDIs) have been developed for use as electron acceptors in solution-processed bulk heterojunction solar cells. The compounds were designed to exhibit maximal solubility in organic solvents, and reduced aggregation in the solid state. In order to achieve this, diphenylphenoxy groups were used to functionalize a monomeric PDI core, and two PDI dimers were bridged with either one or two thiophene units. In photovoltaic devices prepared using PDI dimers and a monomer in conjunction with PTB7, it was found that the formation of crystalline domains in either the acceptor or donor was completely suppressed. Atomic force microscopy, X-ray diffraction, charge carrier mobility measurements and recombination kinetics studies all suggest that the lack of crystallinity in the active layer induces a significant drop in electron mobility. Significant surface recombination losses associated with a lack of segregation in the material were also identified as a significant loss mechanism. Finally, the monomeric PDI was found to have sub-optimum LUMO energy matching the cathode contact, thus limiting charge carrier extraction. Despite these setbacks, all PDIs produced high open circuit voltages, reaching almost 1 V in one particular case., Competing Interests: The authors declare no conflict of interest.

The fluid imbibition-coupled laser interferometry (FICLI) technique has been applied to detect and quantify surface changes and pore dimension variations in nanoporous anodic alumina (NAA) structures. FICLI is a noninvasive optical technique that permits the determination of the NAA average pore radius with high accuracy. In this work, the technique is applied after each step of different surface modification paths of the NAA pores: (i) electrostatic immobilization of bovine serum albumin (BSA), (ii) covalent attachment of streptavidin via (3-aminipropyl)-triethoxysilane and glutaraldehyde grafting, and (iii) immune complexation. Results show that BSA attachment can be detected as a reduction in estimated radius from FICLI with high accuracy and reproducibility. In the case of the covalent attachment of streptavidin, FICLI is able to recognize a multilayer formation of the silane and the protein. For immune complexation, the technique is able to detect different antibody-antigen bindings and distinguish different dynamics among different immune species.

The use of nanoporous anodic alumina (NAA) for the development of drug delivery systems has gained much attention in recent years. The release of drugs loaded inside NAA pores is complex and depends on the morphology of the pores. In this study, NAA, with different three-dimensional (3D) pore structures (cylindrical pores with several pore diameters, multilayered nanofunnels, and multilayered inverted funnels) were fabricated, and their respective drug delivery rates were studied and modeled using doxorubicin as a model drug. The obtained results reveal optimal modeling of all 3D pore structures, differentiating two drug release stages. Thus, an initial short-term and a sustained long-term release were successfully modeled by the Higuchi and the Korsmeyer-Peppas equations, respectively. This study demonstrates the influence of pore geometries on drug release rates, and further presents a sustained long-term drug release that exceeds 60 days without an undesired initial burst., Competing Interests: The authors declare no conflict of interest.

A detailed account of the limiting factors of solvent-annealed bulk-heterojunction small-molecule organic solar cells is given. This account is based on the extensive characterisation of solar cell devices made from a library of five diketopyrolopyrole (DPP) donor dyes. Their chemical structure is designed in such a way as to provide insights into the energetics of solar cell active layer micro-structure formation. Numerous chemical and physical properties of the active layers are assessed and inter-related such as light absorption, molecular packing in the solid state, crystal-forming properties in thin films, charge carrier mobility and charge carrier recombination kinetics. A myriad of characterisation techniques are used such as UV/Vis absorption spectroscopy, photoluminescence spectroscopy, XRD, AFM and photo-induced transient measurements, which provide information on the optical properties of the active layers, morphology and recombination kinetics. Consequently, a mechanism for the solvent-vapour-annealing-assisted formation of crystalline domains of donor molecules in the active layer is proposed, and the micro-structural features are related to the J-V characteristics of the devices. According to this model, the crystalline phase in which the donor crystallise in the active layer is the key determinant to direct the formation of the micro-structure., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Inverted organic cells are promising devices for sustainable and low-cost future electric generation. In this work, we present the degradation mechanisms studied in ITO/TiO 2 /PTB7:PC 70 BM/V 2 O 5 /Ag inverted organic solar cells (iOSCs) by impedance spectroscopy (IS). Measurements were performed on encapsulated (controlled environment) and nonencapsulated (ambient condition) cells following their temporal evolution under AM1.5 illumination for several voltage biases. From the impedance spectra, analyzed in terms of resistive/capacitive equivalent circuits, we were able to identify that the most sensitive layers inside of the device are contact layers. According with presented, IS technique is useful for determining the materials that have more influence on the degradation of organic solar cells. We demonstrate that IS is a powerful technique to identify the limiting mechanisms and to establish the limiting materials inside of the iOSCs., Competing Interests: The authors declare no competing financial interest.

Background: Micro- and nanoscale substrates have been fabricated in order to study the influence of the topography on the cellular response. The aim of this work was to prepare different collagen-coated silicon substrates displaying grooves and ridges to mimic the aligned and elongated endothelium found in linear vessels, and to use them as substrates to study cell growth and behaviour. Results: The influence of groove-shaped substrates on cell adhesion, morphology and proliferation were assessed, by comparing them to flat silicon substrates, used as control condition. Using human aortic endothelial cells, microscopy images demonstrate that the cellular response is different depending on the silicon surface, when it comes to cell adhesion, morphology (alignment, circularity and filopodia presence) and proliferation. Moreover, these structures exerted no cytotoxic effect. Conclusion: The results suggest that topographical patterning influences cell response. Silicon groove substrates can be used in developing medical devices with microscale features to mimic the endothelium in lineal vessels.

Native tissues are highly organised at the microscale, so that modulating scaffold microarchitecture is a potent tool to mimic natural tissue structures. Moreover, three-dimensional microtopographical features are now being used to elucidate how extracellular physical cues can directly modulate cell behaviour and organise complex cellular processes such as cell differentiation and tissue organisation. Recent advances in microtechnology have allowed the development of platforms that can be used to further understand and control the complex interactions occurring between biointerfaces and living cells. In this paper, we discuss the use of three-dimensional microstructured substrates such as silicon dioxide micropillars, to interface with living cells. Human aortic endothelial cells were used to assess the biocompatibility of these substrates. Methodological investigations were performed to determine the influence of substrate topography on cell adhesion and growth. The changes on cell spreading and cell morphology induced by the substrates were qualified and quantified using scanning electron and fluorescence confocal microscopy., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Fluid imbibition-coupled laser interferometry (FICLI) is a technique in which the kinetics of a fluid infiltrating a nanoporous anodic alumina (NAA) membrane is monitored by the interference of a laser beam at the membrane top and bottom surfaces. Further processing of the measured data results in an estimate of the pore radius. In this work, we study the accuracy of FICLI in the detection of small changes in pore radius, and we evaluate the possibility of using such detection as a sensing paradigm. The accuracy is estimated by measuring samples with increasing pore radius, obtained by successive wet etching steps, and repeatability is evaluated by using different liquids. For decreasing pore radius, samples obtained by the successive deposition of polyelectrolyte double layers are used. With the aim of evaluating the possibility of the FICLI method to sense biological binding events, BSA attachment detection is demonstrated by applying FICLI to samples before and after immobilization of the protein. Results show that the technique permits an accurate estimation of the pore radius, the pore-etching rate (with a radius variation of r etch,DI = 1.05 nm/min ± 0.11 nm/min), and the polyelectrolyte double layer thickness (with a radius variation of r PAH/PSS = 3.2 nm ± 0.2 nm per polyelectrolyte double layer). Furthermore, the pore radius reduction measured after BSA immobilization (d BSA = 4.9 nm ± 1.1 nm) is in good agreement with the protein size, as reported in the literature. With these results, we provide a sound basis for the applicability of FICLI as a sensitive technique for the characterization of NAA pore radius modifications.

Porous silicon has received much attention because of its optical properties and for its usefulness in cell-based biosensing, drug delivery, and tissue engineering applications. Surface properties of the biomaterial are associated with cell adhesion and with proliferation, migration, and differentiation. The present article analyzes the behavior of human aortic endothelial cells in macro- and nanoporous collagen-modified porous silicon samples. On both substrates, cells are well adhered and numerous. Confocal microscopy and scanning electron microscopy were employed to study the effects of porosity on the morphology of the cells. On macroporous silicon, filopodia is not observed but the cell spreads on the surface, increasing the lamellipodia surface which penetrates the macropore. On nanoporous silicon, multiple filopodia were found to branch out from the cell body. These results demonstrate that the pore size plays a key role in controlling the morphology and growth rate of human aortic endothelial cells, and that these forms of silicon can be used to control cell development in tissue engineering as well as in basic cell biology research., (© The Author(s) 2015.)

Porous alumina photoluminescence-inherent particles are produced and proposed for the development of biomarkers detectors and localized treatment of HepG2 cells. Nanoporous alumina particles (NPAPs) are amorphous, consist of hexagonally ordered nanometric pores in an alumina matrix, have high chemical stability in physiological pH, and exhibit a high inherent photoluminescence in the visible spectrum independently of their size, selectable from nanometers to tens of micrometers. The surface of NPAPs is chemically modified using two different functionalization methods, a multistep method with (3-aminopropyl)triethoxysilane (APTES) and glutaraldehyde (GLTA) and a novel simplified-step method with silane-PEG-NHS. Fourier Transform infrared spectroscopy analysis confirmed the proper surface modification of the particles for both functionalization methods. HepG2 cells were cultured during different times with growing concentrations of particles. The analysis of cytotoxicity and cell viability of HepG2 cells confirmed the good biocompatibility of NPAPs in all culture conditions. The results prove the suitability of NPAPs for developing new label-free biomarker detectors and advantageous carriers for localized drug delivery.

Porous silicon (pSi) is a prosperous biomaterial, biocompatible, and biodegradable. Obtaining regularly functionalized pSi surfaces is required in many biotechnology applications. Silane-PEG-NHS (triethoxysilane-polyethylene-glycol-N-hydroxysuccinimide) is useful for single-molecule studies due to its ability to attach to only one biomolecule. We investigate the functionalization of pSi with silane-PEG-NHS and compare it with two common grafting agents: APTMS (3-aminopropylotrimethoxysilane) as electrostatic linker, and APTMS modified with glutaraldehyde as covalent spacer. We show the arrangement of two proteins (collagen and bovine serum albumin) as a function of the functionalization and of the pore size. FTIR is used to demonstrate correct functionalization while fluorescence confocal microscopy reveals that silane-PEG-NHS results in a more uniform protein distribution. Reflection interference spectroscopy (RIfS) is used to estimate the attachment of linker and proteins. The results open a way to obtain homogenous chemical modified silicon supports with a great value in biosensing, drug delivery and cell biology., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Nanoporous anodic alumina (NAA) is a material with great interest in nanotechnology and with promising applications to biotechnology. Obtaining specific and regularly functionalized NAA surfaces is essential to obtain meaningful results and applications. Silane-PEG-NHS (triethoxysilane-polyethylene-glycol-N-hydroxysuccinimide) is a covalent linker commonly used for single-molecule studies. We investigate the functionalization of NAA with silane-PEG-NHS and compared with two common, but not single-molecule, grafting agents, APTMS (3-aminopropylotrimethoxysilane) as an electrostatic linker, and APTMS-GTA (3-aminopropylotrimethoxysilane-glutaraldehyde) as covalent. Another outcome of this study is to show how two proteins (collagen and bovine serum albumin, BSA) with different properties differentially arrange for different functionalizations and NAA pore sizes. FTIR is used to demonstrate the surface modification steps and fluorescence confocal microscopy reveals that silane-PEG-NHS results in a more homogeneous protein distribution in comparison to the other linkers. Reflection interference Fourier transform spectroscopy confirms the confocal fluorescence microscopy results and permits to estimate the amounts of linker and linked proteins within the pores. These results permit to obtain uniformly chemical modified NAA supports with a great value in biosensing, drug delivery and cell biology., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We report on the fabrication of polyelectrolyte multilayer-coated hollow silicon dioxide micropillars as pH-responsive drug delivery systems. Silicon dioxide micropillars are based on macroporous silicon formed by electrochemical etching. Due to their hollow core capable of being loaded with chemically active agents, silicon dioxide micropillars provide additional function such as drug delivery system. The polyelectrolyte multilayer was assembled by the layer-by-layer technique based on the alternative deposition of cationic and anionic polyelectrolytes. The polyelectrolyte pair poly(allylamine hydrochloride) and sodium poly(styrene sulfonate) exhibited pH-responsive properties for the loading and release of a positively charged drug doxorubicin. The drug release rate was observed to be higher at pH 5.2 compared to that at pH 7.4. Furthermore, we assessed the effect of the number of polyelectrolyte bilayers on the drug release loading and release rate. Thus, this hybrid composite could be potentially applicable as a pH-controlled system for localized drug release.

A distributed Bragg reflector based on nanoporous anodic alumina was fabricated using an innovative cyclic anodization voltage approach, which resulted in an in-depth modulation of the pore geometry and the refractive index. The effect of a pore-widening wet-etching step on the structure's photonic stop-band properties was studied. From transmittance measurements, it was shown that by changing the pore-widening time it is possible to modulate the photonic stop band in the range of visible to near infrared. With the help of a theoretical model, we were able to obtain information about the evolution with the pore widening of the material effective refractive indexes. This opens the possibility of obtaining several optoelectronic devices based on nanoporous anodic alumina.

A cost-effective label-free optical biosensor based on gold-coated self-ordered nanoporous anodic alumina bilayers is presented. The structure is formed by two uniform nanoporous layers of different porosity (i.e., a top layer with large pores and a bottom layer with smaller pores). Each layer presents uniform pore size, regular pore distribution, and regular diameter along its pore length. To increase and improve the output sensing signals, a thin gold layer on the top surface was deposited. The gold layer increases the refractive index contrast between the nanoporous alumina layer and the analytical aqueous solution, and it results in a greater contrast in the interferometric spectrum and a higher sensitivity of the structure. From this structurally engineered architecture, the resulting reflectivity spectrum shows a complex series of Fabry-Pérot interference fringes, which was analyzed by the reflective interferometric Fourier transform spectroscopy (RIFTS) method. To determine the performance of this structure for biosensing applications, we tested bovine serum albumin (BSA) as the target protein. The results show a significant enhancement of the RIFTS peak intensity and position when a gold layer is on the top surface.

Herein, we present a smart enzymatic sensor based on nanoporous anodic alumina (NAA) and its photoluminescence (PL) in the UV-visible range. The as-produced structure of NAA is functionalized and activated in order to perform the enzyme immobilization in a controlled manner. The whole process is monitored through the PL spectrum and each stage is characterized by an exclusive barcode, which is associated with the PL oscillations. This characteristic property allows us to calculate the change in the effective optical thickness that takes place after each stage. This makes it possible to accurately detect and quantify the immobilized enzyme within the NAA structure. Finally, the NAA geometry (i.e., the pore length and its diameter) is optimized to improve the enzyme immobilization and its detection inside the pores. This enzymatic sensor can give quick and accurate measurements of enzyme levels, what is crucial in clinical enzymology to prevent and detect diseases at their primary stage.

Here, we present a systematic study about the effect of the pore length and its diameter on the specular reflection in nanoporous anodic alumina. As we demonstrate, the specular reflection can be controlled at will by structural tuning (i.e., by designing the pore geometry). This makes it possible to produce a wide range of Fabry-Pérot interferometers based on nanoporous anodic alumina, which are envisaged for developing smart and accurate optical sensors in such research fields as biotechnology and medicine. Additionally, to systematize the responsiveness to external changes in optical sensors based on nanoporous anodic alumina, we put forward a barcode system based on the oscillations in the specular reflection.

We report on an exhaustive and systematic study about the photoluminescent properties of nanoporous anodic alumina membranes fabricated by the one-step anodization process under hard conditions in oxalic and malonic acids. This optical property is analysed as a function of several parameters (i.e. hard anodization voltage, pore diameter, membrane thickness, annealing temperature and acid electrolyte). This analysis makes it possible to tune the photoluminescent behaviour at will simply by modifying the structural characteristics of these membranes. This structural tuning ability is of special interest in such fields as optoelectronics, in which an accurate design of the basic nanostructures (e.g. microcavities, resonators, filters, supports, etc.) yields the control over their optical properties and, thus, upon the performance of the nanodevices derived from them (biosensors, interferometers, selective filters, etc.).

Toward a smart optical biosensor based on nanoporous anodic alumina (NAA): by modifying the pore geometry in nanoporous anodic alumina we are able to change the effective medium at will and tune the photoluminescence of NAA. The oscillations in the PL spectrum are converted into exclusive barcodes, which are useful for developing optical biomedical sensors in the UV-Visible region., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We present a systematic study about the influence of the main anodization parameters (i.e., anodization voltage ramp and hard anodization voltage) on the pore rearrangement in nanoporous anodic alumina during mild to hard anodization regime transition. To cover the ranges between mild and hard regimes, the anodization parameters were each set to three levels (i.e., 0.5, 1.0, and 2.0 V s(-1) for the anodization voltage ramp and 80, 110, and 140 V for the hard anodization voltage). To the best of our knowledge, this is the first rigorous study about this phenomenon, which is quantified indirectly by means of a nickel electrodeposition. It is found that pore rearrangement takes place in a relatively random manner. Large areas of pores remain blocked when the anodization regime changes from mild to hard and, under certain anodization conditions, a pore branching takes place based on the self-ordering mechanism at work during anodization. Furthermore, it is statistically demonstrated by means of a design of experiments strategy that the effect of the anodization voltage ramp on the pore rearrangement is practically negligible in contrast to the hard anodization voltage effect. It is expected that this study gives a better understanding of structural changes in nanoporous anodic alumina when anodization is switched from mild to hard regime. Furthermore, the resulting nanostructures could be used to develop a wide range of nanodevices (e.g., waveguides, 1D photonic crystals, Fabry-Pérot interferometers, hybrid mosaic arrays of nanowires)., (© 2011 American Chemical Society)

A fast and cost-effective technique is applied for fabricating cobalt and nickel nanopillars on aluminium substrates. By applying an electrochemical process, the aluminium oxide barrier layer is removed from the pore bottom tips of nanoporous anodic alumina templates. So, cobalt and nickel nanopillars are fabricated into these templates by DC electrodeposition. The resulting nanostructure remains on the aluminium substrate. In this way, this method could be used to fabricate a wide range of nanostructures which could be integrated in new nanodevices.