Fiber-optics based fluorescence detection. Part I: Basic concepts.

Continuous in-line detection and process monitoring are essential for industrial, analytical, and biomedical applications. Lightweight, highly flexible, and low-cost fiber optics enable the construction of compact and robust hand-held devices for in situ chemical and biological species analysis in both industrial and biomedical in vitro/in vivo detection. Despite the broad range of fiber-optic based applications, we lack a good understanding of the parameters that govern the efficiency of light collection or the sensitivity of detection. Consequently, comparing samples of different optical density and/or geometry becomes challenging and can lead to misinterpretation of results; especially when we lack the approaches necessary to correct the detected signal (spectra) for artifacts such as inner-filter effect or scattering. Hence, in this work, we discuss factors affecting the signal detected by the fiber optic in the bare and lens-coupled flat-tipped configurations that lead to signal/spectral distortions. We also present a simple generic model describing the excitation profile and emission collection efficiency that we verify with experimental data. Understanding the principles governing the signal collected by the fiber will provide rationales for correcting the measured emission spectra and recovering the true emission profile of optically dense samples.

Investigating structural and optoelectronic properties of Cr-substituted ZnSe semiconductors.

The optoelectronic and structural characteristics of the Zn1-xCrxSe (0 ≤ x ≤ 1) semiconductor are reported by employing density functional theory (DFT) within the mBJ potential. The findings revealed that the lattice constant decreases with increasing Cr concentration, although the bulk modulus exhibits the opposite trend. ZnSe is a direct bandgap material; however, a change from direct to indirect electronic bandgap has been seen with Cr presence. This transition is caused by structural alterations by Cr and defects forming, which results in novel optical features, including electronic transitions. The electronic bandgap decreases from 2.769 to 0.216 eV, allowing phonons to participate and improving optical absorption. A higher concentration of Cr boosts infrared absorption and these Cr-based ZnSe (ZnCrSe) semiconductors also cover a wider spectrum in the visible range from red to blue light. Important optical parameters such as reflectance, optical conductivity, optical bandgap, extinction coefficient, refractive index, magnetization factor, and energy loss function are discussed, providing a theoretical understanding of the diverse applications of ZnCrSe semiconductors in photonic and optoelectronic devices.

Mueller matrix polarimetry approach for noninvasive glucose sensing with absorbance and anisotropic parameters on fingertips.

A Mueller matrix polarimetry system at 532 nm wavelength is developed for noninvasive glucose sensing in turbid media such as human's fingertip. The system extracts mean absorbance and anisotropic properties, demonstrated numerically and experimentally with phantom glucose samples. It is found that mean absorbance ( A e $$ {A}_e $$ ), depolarization index (Δ), and linear dichroism (LD) show linear variation with glucose concentration 100-500 mg/dL. In addition, LightTools simulations indicate proportional scaling of scattering effects with A e $$ {A}_e $$ , Δ, and LD. Real-world tests on fingertip show a strong correlation between these properties and blood glucose levels with a mean absolute relative deviation (MARD) of 12.56% and a correlation coefficient (R2) of 0.875 in prediction by a neural network (NN) model, highlighting the advantages of Mueller matrix in extracting more parameters related to blood glucose.

Secondary metabolites, spectra characterization, and antioxidant correlation analysis of the polar and nonpolar extracts of Bryophyllum pinnatum (Lam) Oken.

Oxidative stress-related pathologies have guided the scientific community into delving into natural product-based research on plant-based metabolites. Plant secondary metabolites serve as a valid alternative in managing oxidative stress-related pathologies. In this study, we present the secondary metabolite constituents of the polar extract (PE) and nonpolar extract (NPE) from the leaves of Bryophyllum pinnatum. These constituents were determined through qualitative and quantitative phytochemical screening. The functional groups and structures of these metabolites were determined based on FTIR and GC-MS experiments, respectively. Antioxidant and free radical scavenging (FRS) activities were determined using standard methods, including phosphomolybdenum, FRAP, DPPH, HRSA, and reducing power assays, with comparisons made to the ascorbic acid (AA) standard. Through Pearson correlation analysis, we estimated the relationship between antioxidant and FRS activities. The DPPH results revealed IC50s of 380.104 ± 0.001, 16.763 ± 0.001, and 7.684 ± 0.003 µg/ml for NPE, AA, and PE, respectively, indicating a trend of PE > AA > NPE. However, all other experiments showed a trend of AA > PE > NPE in antioxidant and FRS activities. These results showed the potential antioxidant and FRS properties of both PE and NPE. Additionally, the correlation analysis indicated a strong positive correlation between the antioxidant and FRS activities of PE and NPE. The research results suggest high antioxidant and FRS activities of PE and validate the use of B. pinnatum in managing free radical-related pathologies.

Dichroic switching of core-shell plasmonic nanoparticles on reflective surfaces.

Plasmonic metal nanostructures can simultaneously scatter and absorb light, with resonance wavelength and strength depending on their morphology and composition. This work demonstrates that unique dichroic effects and high-contrast colour-switching can be achieved by leveraging the resonant scattering and absorption of light by plasmonic nanostructures and the specular reflection of the resulting transmitted light. Using core/shell nanostructures comprising a metal core and a dielectric shell, we show that their spray coating on reflective substrates produces dichroic films that can display colour switching at different viewing angles. The high-contrast colour switching, high flexibility in designing multicolour patterns, and convenience for large-scale production promise their wide range of applications, including anticounterfeiting, mechanochromic sensing, colour display, and printing.

A microchip based Z-cell absorbance detector integrating micro-lenses and slits for portable liquid chromatography.

A miniaturized microchip-based absorbance detector was developed for portable high-performance liquid chromatography (HPLC) to test glycated hemoglobin (HbA1c). The microchip integrating a Z-shaped cell, two collimating micro-lenses and two ink-filled optical slits is small in size (30 mm × 15 mm × 7 mm). The Z-shaped cell has a cross-sectional size of 500 µm × 500 µm and a physical optical path length of 2 mm. Two collimating micro-lenses were inserted in empty grooves on both sides of the cell, one micro-lens for collimating the initial light and the other for focusing the transmitted light. Optical slits on each end of the cell were used to block the stray light. Therefore, this detector indicated a low stray light level (0.011 %) and noise level (2.5 × 10-4 AU). This detector was applied for the commercial HPLC system to detect HbA1c level, and showed a low limit of detection (0.5 µg/mL) and excellent repeatability (≤ 2.03 %). The sensitivity was enhanced by 3.4 times when the optical path length was increased from 0.5 mm to 2 mm and the stray light was blocked by optical slits. The miniaturized microchip-based absorbance detector developed shows a great potential for application in portable and compact HPLC.

Ampicillin detection using absorbance biosensors utilizing Mn-doped ZnS capped with chitosan micromaterials.

The detection of ampicillin plays a crucial role in managing and monitoring its usage and resistance. This study introduces a simple and effective biosensor for ampicillin detection, utilizing the unique absorbance features of Mn-doped ZnS capped by chitosan micromaterials in conjunction with ß-lactamase activity. The biosensors can detect ampicillin concentrations from 13.1 to 72.2 µM, with a minimum detection limit of 2.93 µM for sensors based on 300 mg/L of the sensing material. In addition, these sensors show high specificity for ampicillin over other antibiotics such as penicillin, tetracycline, amoxicillin, cephalexin, and a non-antibiotic-glucose. This specificity is demonstrated by an enhancing effect when beta-lactamase is used, as opposed to a quenching effect observed at 340 nm in the absorbance spectrum when no beta-lactamase is present. This research highlights the potential of affordable chitosan-capped Mn-doped ZnS micromaterials for detecting ampicillin through simple absorbance measurements, which could improve the monitoring of antibiotics in both clinical and environmental settings.

Formation of Black Silicon in a Process of Plasma Etching with Passivation in a SF6/O2 Gas Mixture.

This article discusses a method for forming black silicon using plasma etching at a sample temperature range from -20 °C to +20 °C in a mixture of oxygen and sulfur hexafluoride. The surface morphology of the resulting structures, the autocorrelation function of surface features, and reflectivity were studied depending on the process parameters-the composition of the plasma mixture, temperature and other discharge parameters (radical concentrations). The relationship between these parameters and the concentrations of oxygen and fluorine radicals in plasma is shown. A novel approach has been studied to reduce the reflectance using conformal bilayer dielectric coatings deposited by atomic layer deposition. The reflectivity of the resulting black silicon was studied in a wide spectral range from 400 to 900 nm. As a result of the research, technologies for creating black silicon on silicon wafers with a diameter of 200 mm have been proposed, and the structure formation process takes no more than 5 min. The resulting structures are an example of the self-formation of nanostructures due to anisotropic etching in a gas discharge plasma. This material has high mechanical, chemical and thermal stability and can be used as an antireflective coating, in structures requiring a developed surface-photovoltaics, supercapacitors, catalysts, and antibacterial surfaces.

Developing new Hydrazine Carbothioamide Molecules for Selective Colorimetric/Fluorometric Detection of Environmentally Essential Hg2+ and Ag+ Metal Ions in Mixed Aqueous Media.

A novel colorimetric and fluorogenic probe L based on hydrazine carbothioamide and 1,8-naphthalimide moieties has been designed and synthesized for the hypersensitive detection of Hg2+ or Ag+ ions. The observed probe L showed colorimetric and fluorometric responses for these studies when Hg2+ or Ag+ was added to the DMSO - HEPES buffer solution (pH = 7). An interference test with other metal ions was determined, and the high selectivity of Hg2+ and Ag+ did not interfere with other metal ions in colorimetric and fluorogenic methods. The possible mechanism of binding of these metal ions and the probe L 1:1 complex was determined by H1 NMR. Additionally, the reversibility of the affinity of probe L with mercury (Hg2+) and silver (Ag+) ions was investigated by adding Na2EDTA. The naked eye detected the "Off-On" type fluorescence sensor in the presence of Hg2+ and EDTA. The tested test strip kits provided a strong probability of probe L with high response and rapid, sensitive detection with Hg2+ ion, which may be suitable for practical use.

Various techniques for resolving overlapping ultraviolet spectra of combination pharmaceutical dosage forms containing hydroxychloroquine and paracetamol.

Ten novel spectrophotometric approaches were developed for the initial examination of the Hydroxychloroquine and Paracetamol medications. These procedures are straightforward, specific, easy to use, and provide exact and accurate results. The determination was conducted through the utilization of several approaches, including zero order (dual wavelength, zero crossing, advanced absorption subtraction and spectrum subtraction), derivative (first derivative of zero crossing), ratio (ratio difference, ratio derivative) and mathematical (bivariate, simultaneous equation, and Q-absorbance) techniques. After undergoing validation in accordance with ICH criteria, it was established that each of these methods achieved acceptable levels of precision, repeatability, robustness, and accuracy. The advantages and disadvantages of each method are demonstrated, and the proposed and reported methodologies were statistically compared.

Standardization and quantification of backscattered electron imaging in scanning electron microscopy.

Backscattered electron (BSE) imaging based on scanning electron microscopy (SEM) has been widely used in scientific and industrial disciplines. However, achieving consistent standards and precise quantification in BSE images has proven to be a long-standing challenge. Previous methods incorporating dedicated calibration processes and Monte Carlo simulations have still posed practical limitations for widespread adoption. Here we introduce a bolometer platform that directly measures the absorbed thermal energy of the sample and demonstrates that it can help to analyze the atomic number (Z) of the investigated samples. The technique, named Atomic Number Electron Microscopy (ZEM), employs the conservation of energy as the foundation of standardization and can serve as a nearly ideal BSE detector. Our approach combines the strengths of both BSE and ZEM detectors, simplifying quantitative analysis for samples of various shapes and sizes. The complementary relation between the ZEM and BSE signals also makes the detection of light elements or compounds more accessible than existing microanalysis techniques.

Highly sensitive absorbance measurement using droplet microfluidics integrated with an oil extraction and long pathlength detection flow cell.

In droplet microfluidics, UV-Vis absorption spectroscopy along with colorimetric assays have been widely used for chemical and biochemical analysis. However, the sensitivity of the measurement can be limited by the short optical pathlength. Here we report a novel design to enhance the sensitivity by removing oil and converting the droplets into a single-phase aqueous flow, which can be measured within a U-shape channel with long optical pathlength. The flow cells were fabricated via 3D printing. The calibration results have demonstrated complete oil removal and effective optical pathlengths similar to the designed channel lengths (from 5 to 20 mm). The flow cell was further employed in a droplet microfluidic-based phosphate sensing system. The measured phosphate levels displayed excellent consistency with data obtained from traditional UV spectroscopy analysis. This flow cell design overcomes the limitations of short optical pathlengths in droplet microfluidics and has the potential to be used for in situ and continuous monitoring.

Inferring the Molecular Basis for Dissolved Organic Matter Photochemical and Optical Properties.

Despite the widespread use of photochemical and optical properties to characterize dissolved organic matter (DOM), a significant gap persists in our understanding of the relationship among these properties. This study infers the molecular basis for the optical and photochemical properties of DOM using a comprehensive framework and known structural moieties within DOM. Utilizing Suwannee River Fulvic Acid (SRFA) as a model DOM, carboxylated aromatics, phenols, and quinones were identified as dominant contributors to the absorbance spectra, and phenols, quinones, aldehydes, and ketones were identified as major contributors to radiative energy pathways. It was estimated that chromophores constitute ∼63% w/w of dissolved organic carbon in SRFA and ∼47% w/w of overall SRFA. Notably, estimations indicate the pool of fluorescent compounds and photosensitizing compounds in SRFA are likely distinct from each other at wavelengths below 400 nm. This perspective offers a practical tool to aid in the identification of probable chemical groups when interpreting optical and photochemical data and challenges the current "black box" thinking. Instead, DOM photochemical and optical properties can be closely estimated by assuming the DOM is composed of a mixture of individual compounds.

Utilization of absorbance subtraction and ratio difference green spectrophotometric methods for the quantification of alfuzosin hydrochloride and tadalafil in their binary mixture.

Alfuzosin hydrochloride and tadalafil fixed-dose combination tablets were recently formulated for the treatment of individuals with lower urinary tract symptoms caused by benign prostatic hyperplasia. Herein, the first spectrophotometric methods for quantitative analysis of alfuzosin hydrochloride and tadalafil in their binary mixture were established. The spectral overlapping of alfuzosin hydrochloride and tadalafil made direct simultaneous analysis unfeasible. Therefore, two mathematical methods were used to solve these overlapping spectra: absorbance subtraction and ratio difference. The absorbance subtraction method manipulates the zero absorption spectra of the studied drugs at the isoabsorptive point (272 nm) and uses the absorbance factor of pure ALF to calculate the absorbance of the studied drugs in the mixture at the isoabsorptive point. The ratio spectra method, on the other hand, manipulates the ratio spectra of the studied drugs, which are obtained by dividing each drug's zero absorption spectra by a divisor spectrum from the second drug. The ratio amplitude difference between 251 nm and 211 nm was directly proportional to alfuzosin hydrochloride, whereas between 292 nm and 222 nm it was directly proportional to tadalafil. The methods used were verified in accordance with the recommendations of the ICH and demonstrated adequate linear regression in working ranges of 1-15 µg/mL for alfuzosin hydrochloride and 3-40 µg/mL for tadalafil. The methods were accurate, precise, and selectively employed to quantify alfuzosin hydrochloride and tadalafil in their combined tablets.

Meta-Analysis of Optical Surrogates for the Characterization of Dissolved Organic Matter.

Optical surrogates, derived from absorbance and fluorescence spectra, are widely used to infer dissolved organic matter (DOM) composition (molecular weight, aromaticity) and genesis (autochthonous vs allochthonous). Despite the broad adoption of optical surrogates, several limitations exist, such as context- and sample-specific factors. These limitations create uncertainty about how compositional interpretations based on optical surrogates are generalized across contexts, specifically if there is duplicative or contradictory information in those interpretations. To explore these limitations, we performed a meta-analysis of optical surrogates for DOM from diverse sources, both from natural systems and after water treatment processes (n = 762). Prior to analysis, data were screened using a newly developed, standardized methodology that applies systematic quality control criteria before reporting surrogates. There was substantial overlap in surrogate values from natural and treated samples, suggesting that the gradients governing the surrogate variability can be generated in both contexts. This overlap provides justification for using optical surrogates originally developed in the context of natural systems to describe DOM changes in engineered systems, although the interpretations may change. Absorbance-based surrogates that describe the amount of spectral tailing (e.g., E2:E3 and S275-295) had a high frequency of strong correlations with one another but not to specific absorbance (SUVA254) or absorbance slope ratio (SR). The fluorescence index (FI) and biological index (ß/α) were strongly correlated with one another and to the peak emission wavelength but not to the humification index (HIX). Although SUVA254 and FI have both been correlated to DOM aromaticity in prior research, there was a lack of reciprocity between these optical surrogates across this data set. Additionally, there were patterns of deviations in the wastewater subset, suggesting that effluent organic matter may not follow conventional interpretations, urging caution in the use of optical surrogates to track DOM in water reuse applications. Finally, the meta-analysis highlights that three aspects should be captured when optical spectra are used for DOM interpretation: specific absorbance, absorbance tailing, and the extent of red-shifted fluorescence. We recommend that SUVA254, E2:E3, and FI or ß/α be prioritized in future DOM studies to capture these aspects, respectively.

Accounting for photosystem I photoinhibition sheds new light on seasonal acclimation strategies of boreal conifers.

The photosynthetic acclimation of boreal evergreen conifers is controlled by regulatory and photoprotective mechanisms that allow conifers to cope with extreme environmental changes. However, the underlying dynamics of photosystem II (PSII) and photosystem I (PSI) remain unresolved. Here, we investigated the dynamics of PSII and PSI during the spring recovery of photosynthesis in Pinus sylvestris and Picea abies using a combination of chlorophyll a fluorescence, P700 difference absorbance measurements, and quantification of key thylakoid protein abundances. In particular, we derived a new set of PSI quantum yield equations, correcting for the effects of PSI photoinhibition. Using the corrected equations, we found that the seasonal dynamics of PSII and PSI photochemical yields remained largely in balance, despite substantial seasonal changes in the stoichiometry of PSII and PSI core complexes driven by PSI photoinhibition. Similarly, the previously reported seasonal up-regulation of cyclic electron flow was no longer evident, after accounting for PSI photoinhibition. Overall, our results emphasize the importance of considering the dynamics of PSII and PSI to elucidate the seasonal acclimation of photosynthesis in overwintering evergreens. Beyond the scope of conifers, our corrected PSI quantum yields expand the toolkit for future studies aimed at elucidating the dynamic regulation of PSI.

Patent blue interferes with the measurement of lipemia index in a patient with sentinel lymph node.

Lipids interfere with absorbance measurements conducted using colorimetric methods. To monitor lipemia, some systems measure absorbance using an analyzer. This report describes a novel case of interference with the lipemia index without lipemia. A 64-year-old woman with giant basal cell carcinoma underwent resection and sentinel lymph node biopsy. The patient had been subcutaneously injected with patent blue during sentinel lymph node resection. After surgery, her serum and urine were yellow-green, and the lipemia index, calculated by measuring absorbance at 658 nm (main wavelength) and 694 nm (secondary wavelength) using a JCA-BM8040 chemistry analyzer, was high. The absorbance spectrum of the patient's serum and patent blue solution were compared to determine the cause of the high lipemia index. The patient's serum and the patent blue solution showed absorption at wavelengths between 540 and 698 nm. Moreover, the absorbance was concentration-dependent for patent blue. These results thus indicated that the patient's serum contained patent blue. Here, we report a case wherein patent blue affected the lipemia index. Thus, it must be noted that patent blue injection may yield inaccurate results when evaluating lipemia index.

Causal relationship between air pollution and chronic obstructive pulmonary disease in European and East Asian populations: a Mendelian randomization study.

Epidemiologic studies have suggested a possible association between air pollution and chronic obstructive pulmonary disease (COPD), but it is controversial and difficult to draw causal inferences. Five methods were adopted to evaluate the causal relationship between air pollution and COPD in European and East Asian populations by using MR Analysis. A statistically significant causal relationship between PM2.5 and COPD was observed in the European population (OR: 2.34; 95% CI: 1.06-5.05; p = 0.033). Statistical significance remained after adjustment for confounding factors (adjusted OR: 2.28; 95% CI: 1.01-5.20; p = 0.048). In East Asian populations, PM2.5 absorbance, a proxy for black carbon, was statistically associated with COPD (OR: 1.41; 95% CI: 1.09-1.81; p = 0.007). We did not adjust for confounders in East Asian populations, as the association was independent of known confounders (e.g. smoking, respiratory tract infections, etc.). In conclusion, increased concentrations of PM2.5 and PM2.5 absorbance were associated with an increased risk of COPD.

Non-invasive glucose prediction and classification using NIR technology with machine learning.

In this paper, a dual wavelength short near-infrared system is described for the detection of glucose levels. The system aims to improve the accuracy of blood glucose detection in a cost-effective and non-invasive way. The accuracy of the method is evaluated using real-time samples collected with the reference finger prick glucose device. A feed forward neural network (FFNN) regression method is employed to predict glucose levels based on the input data obtained from NIR technology. The system calculates glucose evaluation metrics and performs Surveillance error grid (SEG) analysis. The coefficient of determination R2 and mean absolute error are observed 0.99 and 2.49 mg/dl, respectively. Additionally, the system determines the root mean square error (RMSE) as 3.02 mg/dl. It also shows that the mean absolute percentage error (MAPE) is 1.94% and mean squared error (MSE) is 9.16 (mg/dl)2 for FFNN. The SEG analysis shows that the glucose values measured by the system fall within the clinically acceptable range when compared to the reference method. Finally, the system uses the multi-class classification method of the multilayer perceptron (MLP) and K-nearest neighbors (KNN) classifier to classify glucose levels with an accuracy of 99%.

Spectroscopic evaluation of sesame and mustard oils treated with Murchana method.

In recent years, there has been a growing interest in traditional medicinal practices such as Ayurveda, which emphasizes the use of natural ingredients for various therapeutic purposes. Vegetable oils are an integral part of our diet and have several applications in the cosmetics and healthcare industries. These oils have also been prescribed in ancient Ayurveda texts to treat various health problems. Ayurveda prescribes a processing technique called 'Murchana' to improve the therapeutic nature of the oils. Spectroscopic techniques have been used for quality assessment in many fields. High sensitivity and a low detection rate make spectroscopy a formidable analytical technique. This study focusses on the spectroscopic analysis of sesame and mustard oils prepared using the ayurvedic processing method 'Murchana'. Spectroscopic analysis techniques including UV-Vis absorbance spectroscopy, fluorescence spectroscopy, and FTIR spectroscopy were employed to study the oils. Origin software was used to plot graphs of the spectra. The results indicated that the murchana process may reduce the components of the oil responsible for its oxidation, thereby increasing the shelf life of the oils. However, further investigations, including other spectroscopy and chromatography techniques, will prove beneficial in ascertaining the effects of the murchana process on vegetable oils. The study's findings also suggest that spectroscopic techniques can be used to supplement chemical techniques to investigate the characteristics of vegetable oils.