Modeling and optimization of the ratio of fluorophores: a step towards enhancing the sensitivity of ratiometric probes.

In the ratiometric fluorescent (RF) strategy, the selection of fluorophores and their respective ratios helps to create visual quantitative detection of target analytes. This study presents a framework for optimizing ratiometric probes, employing both two-component and three-component RF designs. For this purpose, in a two-component ratiometric nanoprobe designed for detecting methyl parathion (MP), an organophosphate pesticide, yellow-emissive thioglycolic acid-capped CdTe quantum dots (Y-QDs) (analyte-responsive), and blue-emissive carbon dots (CDs) (internal reference) were utilized. Mathematical polynomial equations modeled the emission profiles of CDs and Y-QDs in the absence of MP, as well as the emission colors of Y-QDs in the presence of MP separately. In other two-/three-component examples, the detection of dopamine hydrochloride (DA) was investigated using an RF design based on blue-emissive carbon dots (B-CDs) (internal reference) and N-acetyl L-cysteine functionalized CdTe quantum dots with red/green emission colors (R-QDs/G-QDs) (analyte-responsive). The colors of binary/ternary mixtures in the absence and presence of MP/DA were predicted using fitted equations and additive color theory. Finally, the Euclidean distance method in the normalized CIE XYZ color space calculated the distance between predicted colors, with the maximum distance defining the real-optimal concentration of fluorophores. This strategy offers a more efficient and precise method for determining optimal probe concentrations compared to a trial-and-error approach. The model's effectiveness was confirmed through experimental validation, affirming its efficacy.

Nanoplasmonic Decoration of Sacrificial Bacteria: Directing Interparticle Coupling Toward Multiplex Analysis of Antiseptic Alcohols.

Engineering interparticle plasmon coupling through controlling the assembly of plasmonic NPs onto the surface of sacrificial substrates is quite promising for establishing inherently absent selectivity or sensitivity toward a particular analyte. Herein, we introduce a robust sensor array strategy based upon the assembly of gold nanoparticles (AuNPs) on the cysteamine-modified surface of two Gram-positive probiotic bacteria, i.e., Lactobacillus reuteri (LBR) and Bifidobacterium lactis (BFL), as potential sacrificial substrates, for discrimination and quantification of antiseptic alcohols (AAs) comprising methanol, ethanol, and isopropanol. In fact, the damage of the bacterial membrane upon exposure to the foregoing alcohols inhibits the assembly of AuNPs, thereby precluding color variations from red to blue. Unequal resistance of the bacterial membranes against damage by the alcohols underlies independent response patterns for each analyte. The supervised classification of visible spectra and RGB data by Linear Discriminant Analysis (LDA) revealed the remarkable potential of the designed sensor array in differentiating single-component and multicomponent samples of AAs. Moreover, the Partial Least Square Regression (PLSR) technique exhibited excellent applicability to multivariate calibration of both spectral and RGB data. The intriguing attributes of the implemented approach not only hold great potential in the authentication and quality assessment of alcohol-based products but open up a new prospect for deployment of sacrificial substrates in the design of interparticle coupling-based sensors.

Paper-based optical nanosensors - A review.

Paper-based analytical devices (PADs) have shown great promise for point-of-care testing and on-site detection of analytes with chemical, biochemical, and environmental importance owing to their low cost, convenience, scalability, portability, and biocompatibility. The World Health Organization stated that sensors should meet the ASSURED criteria (affordable, sensitive, specific, user-friendly, rapid and robust, equipment-free, and deliverable). Paper-based optical sensors meet most of these criteria, making them in high demand and applicable in remote areas. Optical PADs outputs are obtained by different means, such as dyes, nanostructures, redox agents, and pH indicators. The outstanding physical and chemical characteristics of nanostructures, their intense signals, and tunable optical properties make them ideal for many sensing platforms, including paper-based ones. This review focuses primarily on paper-based nanosensors using various nanostructures to fabricate and produce optical signals for visualization. We describe the fundamentals and state of the art of PADs and comprehensively explain the following topics: paper types as the substrate of PADs, PAD fabrication approaches, nanostructure stabilization on PADs, signal acquisition, data handling, interpretation of results, sensing mechanisms, and application areas. We also discuss future trends and strategies to enable PADs to reach their full potential and increase their commercialization opportunities.

Toward visual chiral recognition of amino acids using a wide-range color tonality ratiometric nanoprobe.

Chiral recognition has long been a challenging issue to deal with in biological systems, drug design and food authentication. Implementing nanoparticle-based probes with intrinsic or induced chirality in this field has addressed several issues concerning sensitivity, reliability, rapidness and the cost of chiral sensing platforms. Yet, research into chiral nanoprobes that can be used for visual monitoring of chiral substances is still in its infancy. As part of this study, a visual chiral recognition platform has been developed in which a combination of blue-emitting carbon dots (BCDs) and mercaptopropionic acid-capped CdTe quantum dots (MPA-QDs) with inherent chiroptical activity were employed for enantiomeric detection. The ratiometric probe displayed unique fluorescence response patterns in the presence of arginine (Arg) and histidine (His) enantiomers. Upon addition of l-amino acids, successive enhancement and quenching of emission intensity as well as a red-shift in emission wavelength of MPA-QDs were observed. The emission color of the nanoprobe changed from green to pink-red and green to brick-red red by increasing the concentration of L-Arg and L-His, respectively. In contrast, their d-amino acid equivalents have a negligible influence on the emission color and fluorescence signal of the developed nanoprobe. Due to the enantioselective vibrant color changes of the nanoprobe, RGB analysis was applied for the determination of enantiomeric excess (ee) in racemic mixture with satisfactory results, allowing smartphone-based onsite visual evaluation of ee (%). Circular dichroism, lifetime, size distribution and ζ-potential measurements were employed to study the chiroselective responses. First-principle calculations were also carried out with density functional theory (DFT) to confirm the experimental observation. Furthermore, chiroselective response patterns of the ratiometric nanoprobe were manipulated to construct a logic gate system mimicking AND, OR, and INHIBIT functions. The capability of the proposed chiral platform in visual monitoring of the fraction of enantiomers in racemic mixtures has a great potential for rapid and onsite visual discrimination of chiral compounds in the field of clinical diagnostics and drug analysis.

Development of a colorimetric sensor array based on monometallic and bimetallic nanoparticles for discrimination of triazole fungicides.

Due to the widespread use of pesticides and their harmful effects on humans and wildlife, monitoring their residual amounts in crops is critically essential but still challenging regarding the development of high-throughput approaches. Herein, a colorimetric sensor array has been proposed for discrimination and identification of triazole fungicides using monometallic and bimetallic silver and gold nanoparticles. Aggregation-induced behavior of AgNPs, AuNPs, and Au-AgNPs in the presence of four triazole fungicides produced a fingerprint response pattern for each analyte. Innovative changes to the metal composition of nanoparticles leads to the production of entirely distinct response patterns that can be used for the detection and discrimination of triazoles. Pattern recognition methods, including linear discriminant analysis (LDA) and hierarchical cluster analysis, have been employed for the differentiation of triazoles in the concentration range of 0.1-0.55 µg mL-1. Besides, the sensor array demonstrates promising practicability to satisfactorily distinguished triazole in mixtures and complex media of wheat flour and cucumber samples. The proposed colorimetric sensor array might pave the way towards a cost-effective and rapid, yet sensitive platform for high-throughput monitoring of residual amounts of pesticides for on-site applications.

Optical nanoprobes for chiral discrimination.

Chiral discrimination has always been a hot topic in chemical, food and pharmaceutical industries, especially when dealing with chiral drugs. Enantiomeric recognition not only leads to better understanding of the mechanism of molecular recognition in biological systems, but may further assist in developing useful molecular devices in biochemical and pharmaceutical studies. By emerging nanotechnology and exploiting nanomaterials in sensing applications, a great deal of attention has been given to the design of optical nanoprobes that are able to discriminate enantiomers of chiral analytes. This review explains how engineering nanoparticles (NPs) with desired physicochemical properties allows developing novel optical nanoprobes for chiral recognition. Fundamental concepts related to the origin of chirality in NPs have been briefly presented. Colorimetric and fluorimetric assays in which different types of chiral NPs are used for enantioselective recognition, have been comprehensively described. The main types of nanomaterials described in this review consist of luminescent quantum dots (QDs), carbon dots (CDs), silicon NPs and metal nanoclusters (NCs), as well as plasmonic nanostructures. The mechanisms of sensing in these NP-based optical chiral assays along with relevant examples have been also discussed. Finally, the remaining challenges and future directions have been provided for researchers interested in this topic.

Ratiometric fluorescent nanoprobes for visual detection: Design principles and recent advances - A review.

Signal generation techniques for visual detection of analytes have received a great deal of attention in various sensing fields. These approaches are considered to be advantageous when instrumentation cannot be employed, such as for on-site assays, point-of-care tests, and he althcare diagnostics in resource-constrained areas. Amongst various visual detection approaches explored for non-invasive quantitative measurements, ratiometric fluorescence sensing has received particular attention as a potential method to overcome the limitations of intensity-based probes. This technique relies on changes in the intensity of two or more emission bands (induced by an analyte), resulting in an effective internal referencing which improves the sensitivity of the detection. The self-calibration, together with the unique optophysical properties of nanoparticles (NPs) have made the ratiometric fluorescent nanoprobes more sensitive and reliable, which in turn, can result in more precise visual detection of the analytes. Over the past few years, a vast number of ratiometric sensing probes using nanostructured fluorophores have been designed and reported for a wide variety of sensing, imaging, and biomedical applications. In this work, a review on the NP-based ratiometric fluorescent sensors has been presented to meticulously elucidate their development, advances and challenges. With a special emphasis on visual detection, the most important steps in the design of fluorescent ratiometric nanoprobes have been given and based on different classes of analytes, recent applications of fluorescent ratiometric nanoprobes have been summarized. The challenges for the future use of the technique investigated in this review have been also discussed.

Mining the Potential of Label-Free Biosensors for In Vitro Antipsychotic Drug Screening.

The pharmaceutical industry is facing enormous challenges due to high drug attribution rates. For the past decades, novel methods have been developed for safety and efficacy testing, as well as for improving early development stages. In vitro screening methods for drug-receptor binding are considered to be good alternatives for decreasing costs in the identification of drug candidates. However, these methods require lengthy and troublesome labeling steps. Biosensors hold great promise due to the fact that label-free detection schemes can be designed in an easy and low-cost manner. In this paper, for the first time in the literature, we aimed to compare the potential of label-free optical and impedimetric electrochemical biosensors for the screening of antipsychotic drugs (APDs) based on their binding properties to dopamine receptors. Particularly, we have chosen a currently-used atypical antipsychotic drug (Buspirone) for investigating its dopamine D3 receptor (D3R) binding properties using an impedimetric biosensor and a nanoplasmonic biosensor. Both biosensors have been specifically functionalized and characterized for achieving a highly-sensitive and reliable analysis of drug-D3R binding. Our biosensor strategies allow for comparing different affinities against the D3R, which facilitates the identification of strong or weak dopamine antagonists via in vitro assays. This work demonstrates the unique potential of label-free biosensors for the implementation of cost-efficient and simpler analytical tools for the screening of antipsychotic drugs.

Gold Nanorod-Based Chrono-Colorimetric Sensor Arrays: A Promising Platform for Chemical Discrimination Applications.

Most array-based sensing platforms, to date, utilize static response patterns for discrimination of a wide variety of analytes, but only a few studies have focused on the important task of quantitatively resolving structural isomers, which are nowadays important because of their broad usage in medicines and industries. A possible way of accomplishing this feat is to combine kinetic (rather than static) sensor response profiles with the chemical tongue strategy to allow the development of array-based sensors for isomeric discrimination. Here, by adding the time dimension, a simple and novel gold nanorod (AuNR)-based chrono-colorimetric sensor array is proposed for chemical discrimination applications. Because of their similar structure but different redox potentials, dihydroxybenzene (DHB) structural isomers have been chosen, as models, to evaluate the applicability of the proposed array. The principle of the array relies on various growth rates of silver shells on AuNRs at different silver ion/AuNR concentration ratios owing to the different kinetic behaviors of DHBs, which can be used as fingerprints to identify DHBs with the help of multivariate analysis methods. The combinatorial colorimetric response of AuNRs upon DHB addition has been analyzed by linear discriminant analysis and hierarchical cluster analysis. Finally, identification of individual DHBs or their mixtures in real samples confirms the potential application of the proposed array.

Nanoparticle-based optical sensor arrays.

As in many other methods that have integrated nanoparticles (NPs), the chemical nose/tongue strategy has also progressed greatly since the entrance of NPs into this field. The fascinating tunable physicochemical properties of NPs have made them powerful candidates for array-based sensing platforms and have enabled the development of real-time, sensitive and portable systems that are able to target complex mixtures of analytes. In particular, the unique optical properties of NPs have a key role in providing promising array-based sensing approaches. This review will describe the main aspects and processes of most common NP-based optical sensor arrays. The fundamental steps in the design of a sensor array together with details of each step would be provided. The review begins with the principles of optical sensor arrays and presents the concept of cross-reactivity as the main criterion in the selection of sensing elements. Changes in the absorption and emission properties of the assembled sensing elements are categorized into two main classes of optical signals (colorimetric and fluorometric). Popular chemometric methods used for analyzing the data acquired by a sensor array have also been briefly introduced. On the basis of the objective and the desired application, different types of plasmonic and fluorescent NP that possess unique opto-physical properties have been presented as available choices in the design of sensing elements. The vast number of applications of NP-based optical sensor arrays published throughout the literature have then been reviewed according to their mechanism of interaction and the type of optical signal. Finally, the remaining challenges and future directions in this topic have been highlighted.

Aggregation-based colorimetric sensor for determination of prothioconazole fungicide using colloidal silver nanoparticles (AgNPs).

There is a growing interest in developing high-performance sensors monitoring fungicides, due to their broadly usage and their adverse effects on humans and wildlife. In the present study, a colorimetric probe has been proposed for detection of prothioconazole based on aggregation of unmodified silver nanoparticles (AgNPs). Under optimized condition, linear relationships between the concentration of prothioconazole and the absorbance ratio of A500/A395 were found over the range of 0.01µg·mL-1 to 0.4µg·mL-1 with quantification limit as low as 1.7ng·mL-1. Furthermore, AgNPs color change from yellow to pink-orange in presence of prothioconazole, indicates highly sensitive naked-eye colorimetric assay for quantifying prothioconazole in real applications. The proposed approach was successfully used for the determination of prothioconazole in wheat flour and paddy water sample.

Gold-Nanoparticle-Based Colorimetric Sensor Array for Discrimination of Organophosphate Pesticides.

There is a growing interest in developing high-performance sensors monitoring organophosphate pesticides, primarily due to their broad usage and harmful effects on mammals. In the present study, a colorimetric sensor array consisting of citrate-capped 13 nm gold nanoparticles (AuNPs) has been proposed for the detection and discrimination of several organophosphate pesticides (OPs). The aggregation-induced spectral changes of AuNPs upon OP addition has been analyzed with pattern recognition techniques, including hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA). In addition, the proposed sensor array has the capability to identify individual OPs or mixtures of them in real samples.