Nanopore Blockade Sensors for Quantitative Analysis Using an Optical Nanopore Assay.

Nanopore sensing is a popular biosensing strategy that is being explored for the quantitative analysis of biomarkers. With low concentrations of analytes, nanopore sensors face challenges related to slow response times and selectivity. Here, we demonstrate an approach to rapidly detect species at ultralow concentrations using an optical nanopore blockade sensor for quantitative detection of the protein vascular endothelial growth factor (VEGF). This sensor relies on monitoring fluorescent polystyrene nanoparticles blocking nanopores in a nanopore array of 676 nanopores. The fluorescent signal is read out using a wide-field fluorescence microscope. Nonspecific blockade events are then distinguished from specific blockade events based on the ability to pull the particles out of the pore using an applied electric field. This allows the detection of VEGF at sub-picomolar concentration in less than 15 min.

A Halogen Bonding [2]Rotaxane Shuttle for Chloride-Selective Optical Sensing.

The first example of a [2]rotaxane shuttle capable of selective optical sensing of chloride anions over other halides is reported. The rotaxane was synthesised via a chloride ion template-directed cyclisation of an isophthalamide macrocycle around a multi-station axle containing peripheral naphthalene diimide (NDI) stations and a halogen bonding (XB) bis(iodotriazole) based station. Proton NMR studies indicate the macrocycle resides preferentially at the NDI stations in the free rotaxane, where it is stabilised by aromatic donor-acceptor charge transfer interactions between the axle NDI and macrocycle hydroquinone moieties. Addition of chloride ions in an aqueous-acetone solvent mixture induces macrocycle translocation to the XB anion binding station to facilitate the formation of convergent XB⋅⋅⋅Cl- and hydrogen bonding HB⋅⋅⋅Cl- interactions, which is accompanied by a reduction of the charge-transfer absorption band. Importantly, little to no optical response was induced by addition of bromide or iodide to the rotaxane, indicative of the size discriminative steric inaccessibility of the interlocked cavity to the larger halides, demonstrating the potential of using the mechanical bond effect as a potent strategy and tool in chloride-selective chemo-sensing applications in aqueous containing solvent environments.

A series of triphenylamine-derived fluorophores attached to a Cu-based MOF for gaseous CO optical sensing: synthesis, performance, and mechanism.

A series of triphenylamine-derived fluorescent dyes were attached to a Cu2+-containing MOF (metal-organic framework), denoted as Pm@CuMOF. The molecular structures of these dyes were discussed by the single crystal structures. Their major absorption bands peaked at 410-450 nm, showing emission bands ranging from 556 to 586 nm with emission quantum yields ranging from 8.0 to 15.1%. It was found that the [-N(C2H5)2] group generally improved sensing performance, and the -OH group in the dyes helped the Cu2+ quenching effect. Pm@CuMOF was observed by SEM as nanorods with a width of ~100 nm and a length of 300 nm. Their XRD patterns and N2 adsorption/desorption isotherms were recorded to confirm their porous structure. A low probe loading level of ~4% was determined by TGA result. The CO sensing mechanism was revealed as a Cu2+/Cu+-involved sensing mechanism based on the result of NMR titration, IR, XPS, and EPR. The fluorescence of these triphenylamine-derived dyes was firstly quenched by CuMOF. In contact with CO, Cu2+ was reduced to Cu+, accompanied by the release and fluorescence recovery of the fluorescent dyes, showing emission turn-on effect towards CO gas. Pm@CuMOF showed increased emission intensity at CO level of 0.005% (versus N2), with response times ranging from 123 s to 280 s (depending on various temperatures). Good selectivity was observed over competing alkane gases, with stable emission for at least 5 days, but no linear calibration plots were observed.

Mouthguard-Type Wearable Sensor for Monitoring Salivary Turbidity to Assess Oral Hygiene.

Salivary turbidity is a promising indicator for evaluating oral hygiene. This study proposed a wearable mouthguard-type sensor for continuous and unconstrained measurement of salivary turbidity. The sensor evaluated turbidity by measuring the light transmittance of saliva with an LED and a phototransistor sealed inside a double-layered mouthguard. The sensor was also embedded with a Bluetooth wireless module, enabling the wireless measurement of turbidity. The mouthguard materials (polyethylene terephthalate-glycol and ethylene-vinyl acetate) and the wavelength of the LED (405 nm) were experimentally determined to achieve high sensitivity in salivary turbidity measurement. The turbidity quantification characteristic of the proposed sensor was evaluated using a turbidity standard solution, and the sensor was capable of turbidity quantification over a wide dynamic range of 1-4000 FTU (formazine turbidity unit), including reported salivary turbidity (400-800 FTU). In vitro turbidity measurement using a saliva sample showed 553 FTU, which is equivalent to the same sample measured with a spectrophotometer (576 FTU). Moreover, in vivo experiments also showed results equivalent to that measured with a spectrophotometer, and wireless measurement of salivary turbidity was realized using the mouthguard-type sensor. Based on these results, the proposed mouthguard-type sensor has promising potential for the unconstrained continuous evaluation of oral hygiene.

Label- and Reagent-Free Optical Sensor for Absorption-Based Detection of Urea Concentration in Water Solutions.

Contactless and label-free detection of urea content in aqueous solutions is of great interest in chemical, biomedical, industrial, and automotive applications. In this work, we demonstrate a compact and low-cost instrumental configuration for label-free, reagent-free, and contactless detection of urea dissolved in water, which exploits the absorption properties of urea in the near-infrared wavelength region. The intensity of the radiation transmitted through the fluid under test, contained in a rectangle hollow glass tubing with an optical pathlength of 1 mm, is detected in two spectral bands. Two low-cost, low-power LEDs with emission spectra centered at λ = 1450 nm and λ = 2350 nm are used as readout sources. The photodetector is positioned on the other side of the tubing, in front of the LEDs. The detection performances of a photodiode and of a thermal optical power detector have been compared, exploiting different approaches for LED driving current modulation and photodetected signal processing. The implemented detection system has been tested on urea-water solutions with urea concentrations from 0 up to 525 mg/mL as well as on two samples of commercial diesel exhaust fluid ("AdBlue™"). Considering the transmitted intensity in presence of the urea-water solution, at λ = 1450 nm and λ = 2350 nm, normalized to the transmitted intensity in presence of water, we demonstrate that their ratio is linearly related to urea concentration on a wide range and with good sensitivity.

Optical Sensing of Tissue Freezing Depth by Sapphire Cryo-Applicator and Steady-State Diffuse Reflectance Analysis.

This work describes a sapphire cryo-applicator with the ability to sense tissue freezing depth during cryosurgery by illumination of tissue and analyzing diffuse optical signals in a steady-state regime. The applicator was manufactured by the crystal growth technique and has several spatially resolved internal channels for accommodating optical fibers. The method of reconstructing freezing depth proposed in this work requires one illumination and two detection channels. The analysis of the detected intensities yields the estimation of the time evolution of the effective attenuation coefficient, which is compared with the theoretically calculated values obtained for a number of combinations of tissue parameters. The experimental test of the proposed applicator and approach for freezing depth reconstruction was performed using gelatin-based tissue phantom and rat liver tissue in vivo. It revealed the ability to estimate depth up to 8 mm. The in vivo study confirmed the feasibility of the applicator to sense the freezing depth of living tissues despite the possible diversity of their optical parameters. The results justify the potential of the described design of a sapphire instrument for cryosurgery.

Intensity-Product-Based Optical Sensing to Beat the Diffraction Limit in an Interferometer.

The classically defined minimum uncertainty of the optical phase is known as the standard quantum limit or shot-noise limit (SNL), originating in the uncertainty principle of quantum mechanics. Based on the SNL, the phase sensitivity is inversely proportional to K, where K is the number of interfering photons or statistically measured events. Thus, using a high-power laser is advantageous to enhance sensitivity due to the K gain in the signal-to-noise ratio. In a typical interferometer, however, the resolution remains in the diffraction limit of the K = 1 case unless the interfering photons are resolved as in quantum sensing. Here, a projection measurement method in quantum sensing is adapted for classical sensing to achieve an additional K gain in the resolution. To understand the projection measurements, several types of conventional interferometers based on N-wave interference are coherently analyzed as a classical reference and numerically compared with the proposed method. As a result, the Kth-order intensity product applied to the N-wave spectrometer exceeds the diffraction limit in classical sensing and the Heisenberg limit in quantum sensing, where the classical N-slit system inherently satisfies the Heisenberg limit of π/N in resolution.

Integrated Flexible Microscale Mechanical Sensors Based on Cascaded Free Spectral Range-Free Cavities.

Photonic mechanical sensors offer several advantages over their electronic counterparts, including immunity to electromagnetic interference, increased sensitivity, and measurement accuracy. Exploring flexible mechanical sensors on deformable substrates provides new opportunities for strain-optical coupling operations. Nevertheless, existing flexible photonics strategies often require cumbersome signal collection and analysis with bulky setups, limiting their portability and affordability. To address these challenges, we propose a waveguide-integrated flexible mechanical sensor based on cascaded photonic crystal microcavities with inherent deformation and biaxial tensile state analysis. Leveraging the advanced multiplexing capability of the sensor, for the first time, we successfully demonstrate 2D shape reconstruction and quasi-distributed strain sensing with 110 µm spatial resolution. Our microscale mechanical sensor also exhibits exceptional sensitivity with a detected force level as low as 13.6 µN in real-time measurements. This sensing platform has potential applications in various fields, including biomedical sensing, surgical catheters, aircraft and spacecraft engineering, and robotic photonic skin development.

Optical Relay Sensing of Cryptochiral Alcohols Displaying α-, ß-, γ- and δ-Stereocenters or Chirality by Virtue of Isotopic Substitution.

A reaction-based optical relay sensing strategy that enables accurate determination of the concentration and enantiomeric ratio (er) of challenging chiral alcohols exhibiting stereocenters at the α-, ß-, γ- or even δ-position or hard-to-detect cryptochirality arising from H/D substitution is described. This unmatched application scope is achieved with a conceptually new sensing approach by which the alcohol moiety is replaced with an optimized achiral sulfonamide chromophore to minimize the distance between the covalently attached chiroptical reporter unit and the stereogenic center in the substrate. The result is a remarkably strong, red-shifted CD induction that increases linearly with the sample er. The CD sensing part of the tandem assay is seamlessly coupled to a redox reaction with a quinone molecule to generate a characteristic UV response that is independent of the enantiopurity of the alcohol and thus allows determination of the total analyte concentration. The robustness and utility of the CD/UV relay are further verified by chromatography-free asymmetric reaction analysis with small aliquots of crude product mixtures, paving the way toward high-throughput chiral compound screening workflows which is a highly sought-after goal in the pharmaceutical industry.

Organometallic Chirality Sensing via "Click"-Like η6-Arene Coordination with an Achiral Cp*Ru(II) Piano Stool Complex.

Piano stool complexes have been studied over many years and found widespread applications in organic synthesis, catalysis, materials and drug development. We now report the first examples of quantitative chiroptical molecular recognition of chiral compounds through click-like η6-arene coordination with readily available half sandwich complexes. This conceptually new approach to chirality sensing is based on irreversible acetonitrile displacement of [Cp*Ru(CH3CN)3]PF6 by an aromatic target molecule, a process that is fast and complete within a few minutes at room temperature. The metal coordination coincides with characteristic circular dichroism inductions that can be easily correlated to the absolute configuration and enantiomeric ratio of the bound molecule. A relay assay that decouples the determination of the enantiomeric composition and of the total sample amount by a practical CD/UV measurement protocol was developed and successfully tested. The introduction of piano stool complexes to the chiroptical sensing realm is mechanistically unique and extends the scope of currently known methods with small-molecule probes that require the presence of amino, alcohol, carboxylate or other privileged functional groups for binding of the target compound. A broad application range including pharmaceutically relevant multifunctional molecules and the use in chromatography-free asymmetric reaction analysis are also demonstrated.

Post-Synthetic Modification of Zr-based Metal-Organic Frameworks with Imidazole: Variable Optical Behavior and Sensing.

UiO-66-NH2 -IM, a fluorescent metal-organic framework (MOF), was synthesized by post-synthetic modification of UiO-66-NH2 with 2-imidazole carboxaldehyde via a Schiff base reaction. It was examined using various characterization techniques (PXRD, FTIR, NMR, SEM, TGA, UV-Vis DRS, and photoluminescence spectroscopy). The emissive feature of UiO-66-NH2 -IM was utilized to detect volatile organic compounds (VOCs), metal ions, and anions, such as acetone, Fe3+ , and carbonate (CO3 2- ). Acetone turns off the high luminescence of UiO-66-NH2 -IM in DMSO, with the limit of detection (LOD) being 3.6 ppm. Similarly, Fe3+ in an aqueous medium is detected at LOD=0.67 µM (0.04 ppm) via quenching. On the contrary, CO3 2- in an aqueous medium significantly enhances the luminescence of UiO-66-NH2 -IM, which is detected with extremely high sensitivity (LOD=1.16 µM, i. e., 0.07 ppm). Large Stern-Volmer constant, Ksv , and low LOD values indicate excellent sensitivity of the post-synthetic MOF. Experimental data supported by density functional theory (DFT) calculations discern photo-induced electron transfer (PET), resonance energy transfer (RET), inner filter effect (IFE), or proton abstraction as putative sensing mechanisms. NMR and computational studies propose a proton abstraction mechanism for luminescence enhancement with CO3 2- . Moreover, the optical behavior of the post-synthetic material toward analytes is recyclable.

Optode-based chemical imaging of laboratory burned soil reveals millimeter-scale heterogeneous biogeochemical responses.

Soil spatial responses to fire are unclear. Using optical chemical sensing with planar 'optodes', pH and dissolved O2 concentration were tracked spatially with a resolution of 360 µm per pixel for 72 h after burning soil in the laboratory with a butane torch (∼1300 °C) and then sprinkling water to simulate a postfire moisture event. Imaging data from planar optodes correlated with microbial activity (quantified via RNA transcripts). Post-fire and post-wetting, soil pH increased throughout the entire ∼13 cm × 17 cm × 20 cm rectangular cuboid of sandy loam soil. Dissolved O2 concentrations were not impacted until the application of water postfire. pH and dissolved O2 both negatively correlated (p < 0.05) with relative transcript expression for galactose metabolism, the degradation of aromatic compounds, sulfur metabolism, and narH. Additionally, dissolved O2 negatively correlated (p < 0.05) with the relative activity of carbon fixation pathways in Bacteria and Archaea, amoA/amoB, narG, nirK, and nosZ. nifH was not detected in any samples. Only amoB and amoC correlated with depth in soil (p < 0.05). Results demonstrate that postfire soils are spatially complex on a mm scale and that using optode-based chemical imaging as a chemical navigator for RNA transcript sampling is effective.

Design and Fabrication of a Thin and Micro-Optical Sensor for Rapid Prototyping.

Optical sensing offers several advantages owing to its non-invasiveness and high sensitivity. The miniaturization of optical sensors will mitigate spatial and weight constraints, expanding their applications and extending the principal advantages of optical sensing to different fields, such as healthcare, Internet of Things, artificial intelligence, and other aspects of society. In this study, we present the development of a miniature optical sensor for monitoring thrombi in extracorporeal membrane oxygenation (ECMO). The sensor, based on a complementary metal-oxide semiconductor integrated circuit (CMOS-IC), also serves as a photodiode, amplifier, and light-emitting diode (LED)-mounting substrate. It is sized 3.8 × 4.8 × 0.75 mm3 and provides reflectance spectroscopy at three wavelengths. Based on semiconductor and microelectromechanical system (MEMS) processes, the design of the sensor achieves ultra-compact millimeter size, customizability, prototyping, and scalability for mass production, facilitating the development of miniature optical sensors for a variety of applications.

Nanostructured Vanadium Dioxide Materials for Optical Sensing Applications.

Vanadium dioxide (VO2) is one of the strongly correlated materials exhibiting a reversible insulator-metal phase transition accompanied by a structural transition from a low-temperature monoclinic phase to high-temperature rutile phase near room temperature. Due to the dramatic change in electrical resistance and optical transmittance of VO2, it has attracted considerable attention towards the electronic and optical device applications, such as switching devices, memory devices, memristors, smart windows, sensors, actuators, etc. The present review provides an overview of several methods for the synthesis of nanostructured VO2, such as solution-based chemical approaches (sol-gel process and hydrothermal synthesis) and gas or vapor phase synthesis techniques (pulsed laser deposition, sputtering method, and chemical vapor deposition). This review also presents stoichiometry, strain, and doping engineering as modulation strategies of physical properties for nanostructured VO2. In particular, this review describes ultraviolet-visible-near infrared photodetectors, optical switches, and color modulators as optical sensing applications associated with nanostructured VO2 materials. Finally, current research trends and perspectives are also discussed.

Electrochemical and Optical Sensors for Real-Time Detection of Nitrate in Water.

The health and integrity of our water sources are vital for the existence of all forms of life. However, with the growth in population and anthropogenic activities, the quality of water is being impacted globally, particularly due to a widespread problem of nitrate contamination that poses numerous health risks. To address this issue, investigations into various detection methods for the development of in situ real-time monitoring devices have attracted the attention of many researchers. Among the most prominent detection methods are chromatography, colorimetry, electrochemistry, and spectroscopy. While all these methods have their pros and cons, electrochemical and optical methods have emerged as robust and efficient techniques that offer cost-effective, accurate, sensitive, and reliable measurements. This review provides an overview of techniques that are ideal for field-deployable nitrate sensing applications, with an emphasis on electrochemical and optical detection methods. It discusses the underlying principles, recent advances, and various measurement techniques. Additionally, the review explores the current developments in real-time nitrate sensors and discusses the challenges of real-time implementation.

Colorimetric and Fluorescent Sensing of Copper Ions in Water through o-Phenylenediamine-Derived Carbon Dots.

Fluorescent nitrogen and sulfur co-doped carbon dots (NSCDs) were synthesized using a simple one-step hydrothermal method starting from o-phenylenediamine (OPD) and ammonium sulfide. The prepared NSCDs presented a selective dual optical response to Cu(II) in water through the arising of an absorption band at 660 nm and simultaneous fluorescence enhancement at 564 nm. The first effect was attributed to formation of cuprammonium complexes through coordination with amino functional groups of NSCDs. Alternatively, fluorescence enhancement can be explained by the oxidation of residual OPD bound to NSCDs. Both absorbance and fluorescence showed a linear increase with an increase of Cu(II) concentration in the range 1-100 µM, with the lowest detection limit of 100 nM and 1 µM, respectively. NSCDs were successfully incorporated in a hydrogel agarose matrix for easier handling and application to sensing. The formation of cuprammonium complexes was strongly hampered in an agarose matrix while oxidation of OPD was still effective. As a result, color variations could be perceived both under white light and UV light for concentrations as low as 10 µM. Since these color changes were similarly perceived in tap and lake water samples, the present method could be a promising candidate for simple, cost-effective visual monitoring of copper onsite.

Development of a Stable Oxygen Sensor Using a 761 nm DFB Laser and Multi-Pass Absorption Spectroscopy for Field Measurements.

An optical sensor system based on wavelength modulation spectroscopy (WMS) was developed for atmospheric oxygen (O2) detection. A distributed feedback (DFB) laser with butterfly packaging was used to target the O2 absorption line at 760.89 nm. A compact multi-pass gas cell was employed to increase the effective absorption length to 3.3 m. To ensure the stability and anti-interference capability of the sensor in field measurements, the optical module was fabricated with isolation of ambient light and vibration design. A 1f normalized 2f WMS (WMS-2f/1f) technique was adopted to reduce the effect of laser power drift. In addition, a LabVIEW-based dual-channel lock-in amplifier was developed for harmonic detection, which significantly reduced the sensor volume and cost. The detailed detection principle was described, and a theoretical model was established to verify the effectiveness of the technique. Experiments were carried out to obtain the device's sensing performances. An Allan deviation analysis yielded a minimum detection limit of 0.054% for 1 s integration time that can be further improved to 0.009% at ~60 s. Finally, the reliability and anti-interference capability of the sensor system were verified by the atmospheric O2 monitoring.

SPECTRA: A Novel Compact System for Surface Plasmon Resonance Measurements.

Surface plasmon resonance (SPR) is a common and useful measurement technique to perform fast and sensitive optical detection. SPR instrumentations usually comprise optical systems of mirrors and lenses which are quite expensive and impractical for point-of-care applications. In this work, we presented a novel and compact SPR device called SPECTRA, designed as a spectrophotometer add-on with a grating coupling configuration. The device is conceived as a marketable solution to perform quick SPR measurements in grating configuration without the requirement of complex instrumentation. The device can be customized either in a vertical structure to reach lower incident light angles, or in a horizontal configuration, which is suitable for SPR analysis using liquid solutions. The SPECTRA performance was evaluated through SPR measurements in typical applications. The vertical SPECTRA system was employed to detect different functionalization molecules on gold 720 nm-period grating devices. Meanwhile, the horizontal SPECTRA configuration was exploited to carry out fluid-dynamic measurements using a microfluidic cell with glycerol solutions at increasing concentrations to account for different refractive indexes. The experimental tests confirmed that the SPECTRA design is suitable for SPR measurements, demonstrating its capability to detect the presence of analytes and changes in surface properties both in static and dynamic set-ups.

Strain FBG-Based Sensor for Detecting Fence Intruders Using Machine Learning and Adaptive Thresholding.

This paper demonstrates an intruder detection system using a strain-based optical fiber Bragg grating (FBG), machine learning (ML), and adaptive thresholding to classify the intruder as no intruder, intruder, or wind at low levels of signal-to-noise ratio. We demonstrate the intruder detection system using a portion of a real fence manufactured and installed around one of the engineering college's gardens at King Saud University. The experimental results show that adaptive thresholding can help improve the performance of machine learning classifiers, such as linear discriminant analysis (LDA) or logistic regression algorithms in identifying an intruder's existence at low optical signal-to-noise ratio (OSNR) scenarios. The proposed method can achieve an average accuracy of 99.17% when the OSNR level is <0.5 dB.

Bacterial Colony Phenotyping with Hyperspectral Elastic Light Scattering Patterns.

The elastic light-scatter (ELS) technique, which detects and discriminates microbial organisms based on the light-scatter pattern of their colonies, has demonstrated excellent classification accuracy in pathogen screening tasks. The implementation of the multispectral approach has brought further advantages and motivated the design and validation of a hyperspectral elastic light-scatter phenotyping instrument (HESPI). The newly developed instrument consists of a supercontinuum (SC) laser and an acousto-optic tunable filter (AOTF). The use of these two components provided a broad spectrum of excitation light and a rapid selection of the wavelength of interest, which enables the collection of multiple spectral patterns for each colony instead of relying on single band analysis. The performance was validated by classifying microflora of green-leafed vegetables using the hyperspectral ELS patterns of the bacterial colonies. The accuracy ranged from 88.7% to 93.2% when the classification was performed with the scattering pattern created at a wavelength within the 473-709 nm region. When all of the hyperspectral ELS patterns were used, owing to the vastly increased size of the data, feature reduction and selection algorithms were utilized to enhance the robustness and ultimately lessen the complexity of the data collection. A new classification model with the feature reduction process improved the overall classification rate to 95.9%.