Analysis of Macronutrients in Soil Using Impedimetric Multisensor Arrays.

The need to increase food production to address the world population growth can only be fulfilled with precision agriculture strategies to increase crop yield with minimal expansion of the cultivated area. One example is site-specific fertilization based on accurate monitoring of soil nutrient levels, which can be made more cost-effective using sensors. This study developed an impedimetric multisensor array using ion-selective membranes to analyze soil samples enriched with macronutrients (N, P, and K), which is compared with another array based on layer-by-layer films. The results obtained from both devices are analyzed with multidimensional projection techniques and machine learning methods, where a decision tree model algorithm chooses the calibrations (best frequencies and sensors). The multicalibration space method indicates that both devices effectively distinguished all soil samples tested, with the ion-selective membrane setup presenting a higher sensitivity to K content. These findings pave the way for more environmentally friendly and efficient agricultural practices, facilitating the mapping of cropping areas for precise fertilizer application and optimized crop yield.

Broadband Enhancement of Magneto-Optical Effects in Hybrid Waveguide-Plasmonic Surfaces for Sensing.

Conventional magnetophotonic nanostructures typically function within narrow wavelength and incident angle ranges, where resonance is observed and magneto-optical (MO) effects are amplified. Expanding these operational ranges may allow for improved applications, including in (bio)sensing devices. In this study, we describe a hybrid magnetoplasmonic waveguide grating (HMPWG) in which the coupling of plasmonic resonances and waveguide modes leads to enhanced MO effects and sensitivity, according to full-wave electromagnetic simulations. High transverse magneto-optical Kerr effect (TMOKE) signals were observed for the full range of wavelengths and angles investigated, i.e., for θinc ≥ 1° and 500 nm ≤ λ ≤ 850 nm. As a proof-of-concept we verified that using the HMPWG nanostructure with an aqueous solution as superstrate one may obtain a sensitivity in variation of the refractive index unit (RIU) of S = 166°/RIU and S = 230 nm/RIU in angle and wavelength interrogation modes, respectively. Upon comparing with conventional magnetoplasmonic gratings, which only enable excitation of plasmonic resonances, we demonstrate that HMPWG nanostructures can be further optimized to reach not only high sensitivity but also high resolution in sensing and biosensing.

Solid-State NMR Characterization of Mefloquine Resinate Complexes Designed for Taste-Masking Pediatric Formulations.

Mefloquine (MQ) is an antimalarial medication prescribed to treat or malaria prevention.. When taken by children, vomiting usually occurs, and new doses of medication frequently need to be taken. So, developing pediatric medicines using taste-masked antimalarial drug complexes is mandatory for the success of mefloquine administration. The hypothesis that binding mefloquine to an ion-exchange resin (R) could circumvent the drug's bitter taste problem was proposed, and solid-state 13C cross-polarization magic angle spinning (CPMAS) NMR was able to follow MQ-R mixtures through chemical shift and relaxation measurements. The nature of MQ-R complex formation could then be determined. Impedimetric electronic tongue equipment also verified the resinate taste-masking efficiency in vitro. Variations in chemical shifts and structure dynamics measured by proton relaxation properties (e.g., T1ρH) were used as probes to follow the extension of mixing and specific interactions that would be present in MQ-R. A significant decrease in T1ρH values was observed for MQ carbons in MQ-R complexes, compared to the ones in MQ (from 100-200 ms in MQ to 20-50 ms in an MQ-R complex). The results evidenced that the cationic resin interacts strongly with mefloquine molecules in the formulation of a 1:1 ratio complex. Thus, 13C CPMAS NMR allowed the confirmation of the presence of a binding between mefloquine and polacrilin in the MQ-R formulation studied.

Toward Machine-Learning-Accelerated Design of All-Dielectric Magnetophotonic Nanostructures.

All-dielectric magnetophotonic nanostructures are promising for integrated nanophotonic devices with high resolution and sensitivity, but their design requires computationally demanding electromagnetic simulations evaluated through trial and error. In this paper, we propose a machine-learning approach to accelerate the design of these nanostructures. Using a data set of 12 170 samples containing four geometric parameters of the nanostructure and the incidence wavelength, trained neural network and polynomial regression algorithms were capable of predicting the amplitude of the transverse magneto-optical Kerr effect (TMOKE) within a time frame of 10-3 s and mean square error below 4.2%. With this approach, one can readily identify nanostructures suitable for sensing at ultralow analyte concentrations in aqueous solutions. As a proof of principle, we used the machine-learning models to determine the sensitivity (S = |Δθres/Δna|) of a nanophotonic grating, which is competitive with state-of-the-art systems and exhibits a figure of merit of 672 RIU-1. Furthermore, researchers can use the predictions of TMOKE peaks generated by the algorithms to assess the suitability for experimental setups, adding a layer of utility to the machine-learning methodology.

Understanding the effects of omega-3 fatty acid supplementation on the physical properties of brain lipid membranes.

A deficiency in omega-3 fatty acids (ω3 FAs) in the brain has been correlated with cognitive impairment, learning deficiencies, and behavioral changes. In this study, we provided ω3 FAs as a supplement to spontaneously hypertensive rats (SHR+ ω3). Our focus was on examining the impact of dietary supplementation on the physicochemical properties of the brain-cell membranes. Significant increases in ω3 levels in the cerebral cortex of SHR+ ω3 were observed, leading to alterations in brain lipid membranes molecular packing, elasticity, and lipid miscibility, resulting in an augmented phase disparity. Results from synthetic lipid mixtures confirmed the disordering effect introduced by ω3 lipids, showing its consequences on the hydration levels of the monolayers and the organization of the membrane domains. These findings suggest that dietary ω3 FAs influence the organization of brain membranes, providing insight into a potential mechanism for the broad effects of dietary fat on brain health and disease.

Enhancing Phototoxicity in Human Colorectal Tumor Cells Through Nanoarchitectonics for Synergistic Photothermal and Photodynamic Therapies.

Phototherapies are promising for noninvasive treatment of aggressive tumors, especially when combining heat induction and oxidative processes. Herein, we show enhanced phototoxicity of gold shell-isolated nanorods conjugated with toluidine blue-O (AuSHINRs@TBO) against human colorectal tumor cells (Caco-2) with synergic effects of photothermal (PTT) and photodynamic therapies (PDT). Mitochondrial metabolic activity tests (MTT) performed on Caco-2 cell cultures indicated a photothermal effect from AuSHINRs owing to enhanced light absorption from the localized surface plasmon resonance (LSPR). The phototoxicity against Caco-2 cells was further increased with AuSHINRs@TBO where oxidative processes, such as hydroperoxidation, were also present, leading to a cell viability reduction from 85.5 to 39.0%. The molecular-level mechanisms responsible for these effects were investigated on bioinspired tumor membranes using Langmuir monolayers of Caco-2 lipid extract. Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) revealed that the AuSHINRs@TBO incorporation is due to attractive electrostatic interactions with negatively charged groups of the Caco-2 lipid extract, resulting in the expansion of surface pressure isotherms. Upon irradiation, Caco-2 lipid extract monolayers containing AuSHINRs@TBO (1:1 v/v) exhibited ca. 1.0% increase in surface area. This is attributed to the generation of reactive oxygen species (ROS) and their interaction with Caco-2 lipid extract monolayers, leading to hydroperoxide formation. The oxidative effects are facilitated by AuSHINRs@TBO penetration into the polar groups of the extract, allowing oxidative reactions with carbon chain unsaturations. These mechanisms are consistent with findings from confocal fluorescence microscopy, where the Caco-2 plasma membrane was the primary site of the cell death induction process.

Sticky Multicolor Mechanochromic Labels.

Sticky-colored labels are an efficient way to communicate visual information. However, most labels are static. Here, we propose a new category of dynamic sticky labels that change structural colors when stretched. The sticky mechanochromic labels can be pasted on flexible surfaces such as fabric and rubber or even on brittle materials. To enhance their applicability, we demonstrate a simple method for imprinting structural color patterns that are either always visible or reversibly revealed or concealed upon mechanical deformation. The mechanochromic patterns are imprinted with a photomask during the ultraviolet (UV) cross-linking of acrylate-terminated cholesteric liquid crystal oligomers in a single step at room temperature. The photomask locally controls the cross-linking degree and volumetric response of the cholesteric liquid crystal elastomers (CLCEs). A nonuniform thickness change induced by the Poisson's ratio contrast between the pattern and the surrounding background might lead to a color-separation effect. Our sticky multicolor mechanochromic labels may be utilized in stress-strain sensing, building environments, smart clothing, security labels, and decoration.

Magnetochiroptical nanocavities in hyperbolic metamaterials enable sensing down to the few-molecule level.

In this work, we combine the concepts of magnetic circular dichroism, nanocavities, and magneto-optical hyperbolic metamaterials (MO-HMMs) to demonstrate an approach for sensing down to a few molecules. Our proposal comprises a multilayer MO-HMM with a square, two-dimensional arrangement of nanocavities. The magnetization of the system is considered in polar configuration, i.e., in the plane of polarization and perpendicular to the plane of the multilayer structure. This allows for magneto-optical chirality to be induced through the polar magneto-optical Kerr effect, which is exhibited by reflected light from the nanostructure. Numerical analyses under the magnetization saturation condition indicate that magnetic circular dichroism peaks can be used instead of reflectance dips to monitor refractive index changes in the analyte region. Significantly, we obtained a relatively high sensitivity value of S = 40 nm/RIU for the case where refractive index changes are limited to the volume inside nanocavities, i.e., in the limit of a few molecules (or ultralow concentrations), while a very large sensitivity of S = 532 nm/RIU is calculated for the analyte region distributed along the entire superstrate layer.

Core-Shell Nanocables Decorated with Carbon Spherical Shells and Silver Nanoparticles for Sensing Ethinylestradiol Hormone in Water Sources and Pills.

The selective, rapid detection of low levels of hormones in drinking water and foodstuffs requires materials suitable for inexpensive sensing platforms. We report on core-shell Ag@C nanocables (NCs) decorated with carbon spherical shells (CSSs) and silver nanoparticles (AgNPs) by using a hydrothermal green approach. Sensors were fabricated with homogeneous, porous films on screen-printed electrodes, which comprised a 115 nm silver core covered by a 122 nm thick carbon layer and CSSs with 168 nm in diameter. NCs and CSSs were also decorated with 10-25 nm AgNPs. The NC/CSS/AgNP sensor was used to detect ethinylestradiol using square wave voltammetry in 0.1 M phosphate buffer (pH 7.0) over the 1.0-10.0 µM linear range with a detection limit of 0.76 µM. The sensor was then applied to detect ethinylestradiol in tap water samples and a contraceptive pill with recovery percentages between 93 and 101%. The high performance in terms of sensitivity and selectivity for hormones is attributed to the synergy between the carbon nanomaterials and AgNPs, which not only increased the sensor surface area and provided sites for electron exchange but also imparted an increased surface area.

Revisiting the conformational transition model for the pH dependence of BSA structure using photoluminescence, circular dichroism, and ellipsometric Raman spectroscopy.

Changes in pH affect metabolic pathways, primarily by modulating enzyme conformations, which is why a detailed analysis of pH-driven conformational transitions is required to understand the underlying biochemistry of diseases and biological organisms. In this work, we examined the pH-driven conformational dynamics of Bovine Serum Albumin (BSA), within the framework of the Foster Model. Circular Dichroism and Raman Optical Activity showed the conversion of helical into ß-rich structures in the acid and basic regions, while an opening of BSA tertiary structure was shown by the upsurging of accessibility of ANS-BSA binding sites and the increasing of random contributions at regions F and B. We could then revisit the Foster Model by introducing two additional intermediate conformational states and structural reorganization at extreme pH values. This expanded model opens up new possibilities concerning protein-molecule interactions, promising far-reaching implications for fields such as drug design and biomaterials.

Network Analysis and Natural Language Processing to Obtain a Landscape of the Scientific Literature on Materials Applications.

Recent progress in natural language processing (NLP) enables mining the literature in various tasks akin to knowledge discovery. Obtaining an updated birds-eye view of key research topics and their evolution in a vast, dynamic field such as materials science is challenging even for experienced researchers. In this Perspective paper, we present a landscape of the area of applied materials in selected representative journals based on a combination of methods from network science and simple NLP strategies. We found a predominance of energy-related materials, e.g., for batteries and catalysis, organic electronics, which include flexible sensors and flexible electronics, and nanomedicine with various topics of materials used in diagnosis and therapy. As for the impact calculated through standard metrics of impact factor, energy-related materials and organic electronics are again top of the list across different journals, while work in nanomedicine has been found to have a lower impact in the journals analyzed. The adequacy of the approach to identify key research topics in materials applications was verified indirectly by comparing the topics identified in journals with diverse scopes, including journals that are not specific to materials. The approach can be employed to obtain a fast overview of a given field from the papers published in related scientific journals, which can be adapted or extended to any research area.

Nanoarchitectonic E-Tongue of Electrospun Zein/Curcumin Carbon Dots for Detecting Staphylococcus aureusin Milk.

We report a nanoarchitectonic electronic tongue made with flexible electrodes coated with curcumin carbon dots and zein electrospun nanofibers, which could detect Staphylococcus aureus(S. aureus) in milk using electrical impedance spectroscopy. Electronic tongues are based on the global selectivity concept in which the electrical responses of distinct sensing units are combined to provide a unique pattern, which in this case allowed the detection of S. aureus through non-specific interactions. The electronic tongue used here comprised 3 sensors with electrodes coated with zein nanofibers, carbon dots, and carbon dots with zein nanofibers. The capacitance data obtained with the three sensors were processed with a multidimensional projection technique referred to as interactive document mapping (IDMAP) and analyzed using the machine learning-based concept of multidimensional calibration space (MCS). The concentration of S. aureus could be determined with the sensing units, especially with the one containing zein as the limit of detection was 0.83 CFU/mL (CFU stands for colony-forming unit). This high sensitivity is attributed to molecular-level interactions between the protein zein and C-H groups in S. aureus according to polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) data. Using machine learning and IDMAP, we demonstrated the selectivity of the electronic tongue in distinguishing milk samples from mastitis-infected cows from milk collected from healthy cows, and from milk spiked with possible interferents. Calibration of the electronic tongue can also be reached with the MCS concept employing decision tree algorithms, with an 80.1% accuracy in the diagnosis of mastitis. The low-cost electronic tongue presented here may be exploited in diagnosing mastitis at early stages, with tests performed in the farms without requiring specialized laboratories or personnel.

Geometry Optimization for Miniaturized Thermoelectric Generators.

Thermoelectric materials capable of converting heat into electrical energy are used in sustainable electric generators, whose efficiency has been normally increased with incorporation of new materials with high figure of merit (ZT) values. Because the performance of these thermoelectric generators (TEGs) also depends on device geometry, in this study we employ the finite element method to determine optimized geometries for highly efficient miniaturized TEGs. We investigated devices with similar fill factors but with different thermoelectric leg geometries (filled and hollow). Our results show that devices with legs of hollow geometry are more efficient than those with filled geometry for the same length and cross-sectional area of thermoelectric legs. This behavior was observed for thermoelectric leg lengths smaller than 0.1 mm, where the leg shape causes a significant difference in temperature distribution along the device. It was found that for reaching highly efficient miniaturized TEGs, one has to consider the leg geometry in addition to the thermal conductivity.

Optimized paper-based electrochemical sensors treated in acidic media to detect carbendazim on the skin of apple and cabbage.

Wearable sensors such as those made with paper are needed for non-destructive routine analysis of pesticides on plants, fruits, and vegetables. Herein we report on electrochemical sensors made with screen-printed carbon electrodes on kraft and parchment papers to detect the fungicide carbendazim. A systematic optimization was performed to find that electrochemical sensors on kraft paper treated in an acidic medium led to the highest performance, with a detection limit of 0.06 µM for carbendazim. The enhanced sensitivity for this sensor was attributed to the porous nature of kraft paper, which allowed for a large electrode surface area, and to the carboxylic groups formed during electrochemical activation. As a proof-of-concept, the electrochemical sensor attached to the skin of apple and cabbage was used to detect carbendazim with the same performance as the gold standard method, thus demonstrating that the sensor can be used in the farm and on supermarket shelves.

Magnetoplasmonic Nanoantennas for On-Chip Reconfigurable Optical Wireless Communications.

On-chip wireless communications require optical nanoantennas with dynamically tunable radiation patterns, which may allow for higher integration with multiple nanoantennas instead of two fixed nanoantennas in existing approaches. In this paper, we introduce a concept to enable active manipulation of radiated beam steering using applied magnetic fields. The proposed system consists of a highly directive Yagi-Uda-like arrangement of magnetoplasmonic nanoribs made of Co6Ag94 and immersed in SiO2. Numerical demonstration of the tilting of the radiated beam from the nanoantenna on its plane is provided with full-wave electromagnetic simulations using the finite element method. The tilt direction of the radiated beam can be changed by reversing the magnetization direction, while the conventional plasmonic nanoantenna pattern is recovered by demagnetizing the system. The geometry of the nanoantenna can be tailored to work at optical or infrared wavelengths, but a proof of concept for λ = 700 nm is conducted for taking advantage of the high magneto-optical activity of Co6Ag94. The design was based on experimental data for materials that can be fabricated via nanolithography, thus permitting magnetically on-chip reconfigurable optical wireless communications.

Colorimetric Detection of SARS-CoV-2 Using Plasmonic Biosensors and Smartphones.

Low-cost, instrument-free colorimetric tests were developed to detect SARS-CoV-2 using plasmonic biosensors with Au nanoparticles functionalized with polyclonal antibodies (f-AuNPs). Intense color changes were noted with the naked eye owing to plasmon coupling when f-AuNPs form clusters on the virus, with high sensitivity and a detection limit of 0.28 PFU mL-1 (PFU stands for plaque-forming units) in human saliva. Plasmon coupling was corroborated with computer simulations using the finite-difference time-domain (FDTD) method. The strategies based on preparing plasmonic biosensors with f-AuNPs are robust to permit SARS-CoV-2 detection via dynamic light scattering and UV-vis spectroscopy without interference from other viruses, such as influenza and dengue viruses. The diagnosis was made with a smartphone app after processing the images collected from the smartphone camera, measuring the concentration of SARS-CoV-2. Both image processing and machine learning algorithms were found to provide COVID-19 diagnosis with 100% accuracy for saliva samples. In subsidiary experiments, we observed that the biosensor could be used to detect the virus in river waters without pretreatment. With fast responses and requiring small sample amounts (only 20 µL), these colorimetric tests can be deployed in any location within the point-of-care diagnosis paradigm for epidemiological control.

Influence of cytochrome P450 3A4 and membrane lipid composition on doxorubicin activity.

Drug resistance is known to depend on the interactions with cell membranes and other molecules such as human cytochromes P450 (CYPs) which are anchored on the endoplasmic reticulum (ER) membrane and involved in the metabolism of anticancer drugs. In this study, we determined the influence from cytochrome P450 3A4 (CYP3A4) on the interaction between the drug doxorubicin (DOX) and Langmuir monolayers mimicking cell membranes. The lipid composition was varied by changing the relative concentrations of cholesterol (Chol), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE), and L-α-phosphatidylinositol (PI). Three compositions were studied in detail which represented a healthy cell membrane and cancerous cell membranes. DOX induced an expansion in the surface pressure isotherms for all monolayers, with stronger effect for the composition of cancerous cell with a high Chol content, thus confirming the relevance of lipid composition. This effect decreased considerably when CYP3A4 was incorporated with the formation of CYP3A4-DOX complexes, according to results from polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS) measurements. Taken together, these results support the hypothesis of CYP3A4 being involved in drug resistance, which may be exploited to design strategies to enhance chemotherapy efficacy.

Three-Dimensional Printing and Its Potential to Develop Sensors for Cancer with Improved Performance.

Cancer is the second leading cause of death globally and early diagnosis is the best strategy to reduce mortality risk. Biosensors to detect cancer biomarkers are based on various principles of detection, including electrochemical, optical, electrical, and mechanical measurements. Despite the advances in the identification of biomarkers and the conventional 2D manufacturing processes, detection methods for cancers still require improvements in terms of selectivity and sensitivity, especially for point-of-care diagnosis. Three-dimensional printing may offer the features to produce complex geometries in the design of high-precision, low-cost sensors. Three-dimensional printing, also known as additive manufacturing, allows for the production of sensitive, user-friendly, and semi-automated sensors, whose composition, geometry, and functionality can be controlled. This paper reviews the recent use of 3D printing in biosensors for cancer diagnosis, highlighting the main advantages and advances achieved with this technology. Additionally, the challenges in 3D printing technology for the mass production of high-performance biosensors for cancer diagnosis are addressed.

Materials Discovery With Machine Learning and Knowledge Discovery.

Machine learning and other artificial intelligence methods are gaining increasing prominence in chemistry and materials sciences, especially for materials design and discovery, and in data analysis of results generated by sensors and biosensors. In this paper, we present a perspective on this current use of machine learning, and discuss the prospects of the future impact of extending the use of machine learning to encompass knowledge discovery as an essential step towards a new paradigm of machine-generated knowledge. The reasons why results so far have been limited are given with a discussion of the limitations of machine learning in tasks requiring interpretation. Also discussed is the need to adapt the training of students and scientists in chemistry and materials sciences, to better explore the potential of artificial intelligence capabilities.

Label-Free Electrochemical Immunosensor Made with Tree-like Gold Dendrites for Monitoring 25-Hydroxyvitamin D3 Metabolite.

Flexible, fully printed immunosensors can meet the requirements of precision nutrition, but this demands optimized molecular architectures to reach the necessary sensitivity. Herein, we report on flexible and label-free immunosensor chips made with tree-like gold dendrites (AuDdrites) electrochemically formed by selective desorption of l-cysteine (L-cys) on (111) gold planes. Electrodeposition was used because it is scalable and cost-effective for a rapid, direct growth of Au hyperbranched dendritic structures. The 25-hydroxyvitamin D3 (25(OH)D3) metabolite was detected within 15 min with a limit of detection (LOD) of 0.03 ng mL-1. This high performance was possible due to the careful optimization of the electroactive layer and working conditions for square wave voltammetry (SWV). Electrocrystallization was manipulated by controlling the deposition potential and the molar ratio between HAuCl4 and L-cys. Metabolite detection was performed on human serum and saliva samples with adequate recovery between 97% and 100%. The immunosensors were stable and reproducible, unresponsive to interference from other molecules in human serum and saliva. They can be extended for use as wearable sensors with their mechanical flexibility and possible customization.