Repeatability, reproducibility, and accuracy of a novel pushbroom hyperspectral system

This study analyzes the repeatability, reproducibility and accuracy of a new hyperspectral system based on a pushbroom sensor as a means of measuring spectral features and color of materials and objects. The hyperspectral system consisted of a CCD camera, a spectrograph and an objective lens. An additional linear moving system allowed the mechanical scanning of the complete scene. A uniform overhead luminaire with daylight configuration was used to irradiate the scene using d:45 geometry. We followed the guidelines of the ASTM E2214-08 Standard Practice for Specifying and Verifying the Performance of Color-Measuring Instruments that define the standards and latest multidimensional procedures. The results obtained are analyzed in-depth and compared to those recently reported by other authors for spectrophotometers and multispectral systems. It can be concluded that hyperspectral systems are reliable and can be used in the industry to perform spectral and color readings with a high spatial resolution.

Intrasubject repeatability in keratoconus-eye measurements obtained with a new Scheimpflug photography–based system

Purpose: To evaluate in keratoconus eyes the intrasubject repeatability of anterior and posterior corneal curvature and of other anterior segment anatomic measurements obtained with a new topography system combining Scheimpflug-photography and Placido-disk technology. Setting: Vissum Corporation, Alicante, Spain. Design: Evaluation of technology. Methods: All keratoconus eyes had a comprehensive ophthalmologic examination including analysis with the Sirius system. Three consecutive measurements were obtained to assess the intrasubject repeatability of the following parameters: anterior and posterior corneal curvature and shape factor, white-to-white (WTW) corneal diameter, central and minimum corneal thickness, and anterior chamber depth (ACD). The within-subject standard deviation (Sw) and intraclass correlation coefficient (ICC) were calculated. Results: This study comprised 61 eyes of 61 patients ranging in age from 14 to 64 years. For anterior and posterior corneal curvatures and power vector components, the Sw was 0.29 mm or less in all cases. The ICC was above 0.990 in all cases except the flattest curvature of the posterior corneal surface at 3.0 mm, which was 0.840 (moderate agreement), and the posterior power vector J0, which was 0.665 (poor agreement), 0.752, and 0.758 (moderate agreement) for 3.0 mm, 5.0 mm, and 7.0 mm, respectively. In shape factor measurements, the Sw was 0.12 or less in all cases and the ICC ranged between 0.989 and 0.999. Pachymetry, ACD, and WTW had ICC values very close to 1. Conclusion: The new topography system provided repeatable measurements of corneal shape and other anatomic parameters in eyes with keratoconus.

Repeatability and reproducibility of corneal thickness using SOCT Copernicus HR

Purpose: The aim of this study is to determine the reliability of corneal thickness measurements derived from SOCT Copernicus HR (Fourier domain OCT). Methods: Thirty healthy eyes of 30 subjects were evaluated. One eye of each patient was chosen randomly. Images were obtained of the central (up to 2.0 mm from the corneal apex) and paracentral (2.0 to 4.0 mm) cornea. We assessed corneal thickness (central and paracentral) and epithelium thickness. The intra-observer repeatability data were analysed using the intra-class correlation coefficient (ICC) for a range of 95 per cent within-subject standard deviation (SW) and the within-subject coefficient of variation (CW). The level of agreement by Bland–Altman analysis was also represented for the study of the reproducibility between observers and agreement between methods of measurement (automatic versus manual). Results: The mean value of the central corneal thickness (CCT) was 542.4 ± 30.1 μm (SD). There was a high intra-observer agreement, finding the best result in the central sector with an intra-class correlation coefficient of 0.99, 95 per cent CI (0.989 to 0.997) and the worst, in the minimum corneal thickness, with an intra-class correlation coefficient of 0.672, 95 per cent CI (0.417 to 0.829). Reproducibility between observers was very high. The best result was found in the central sector thickness obtained both manually and automatically with an intra-class correlation coefficient of 0.990 in both cases and the worst result in the maximum corneal thickness with an intra-class correlation coefficient of 0.827. The agreement between measurement methods was also very high with intra-class correlation coefficient greater than 0.91. On the other hand the repeatability and reproducibility for epithelial measurements was poor. Conclusion: Pachymetric mapping with SOCT Copernicus HR was found to be highly repeatable and reproducible. We found that the device lacks an appropriate ergonomic design as proper focusing of the laser beam onto the cornea for anterior segment scanning required that patients were positioned slightly farther away from the machine head-rest than in the setup for retinal imaging.

Determination of cyclic and linear siloxanes in wastewater samples by ultrasound-assisted dispersive liquid-liquid microextraction followed by gas chromatography-mass spectrometry

A fast, simple and environmentally friendly ultrasound-assisted dispersive liquid-liquid microextraction (USA-DLLME) procedure has been developed to preconcentrate eight cyclic and linear siloxanes from wastewater samples prior to quantification by gas chromatography-mass spectrometry (GC-MS). A two-stage multivariate optimization approach has been developed employing a Plackett-Burman design for screening and selecting the significant factors involved in the USA-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were: extractant solvent volume, 13 µL; solvent type, chlorobenzene; sample volume, 13 mL; centrifugation speed, 2300 rpm; centrifugation time, 5 min; and sonication time, 2 min. Under the optimized experimental conditions the method gave levels of repeatability with coefficients of variation between 10 and 24% (n=7). Limits of detection were between 0.002 and 1.4 µg L−1. Calculated calibration curves gave high levels of linearity with correlation coefficient values between 0.991 and 0.9997. Finally, the proposed method was applied for the analysis of wastewater samples. Relative recovery values ranged between 71–116% showing that the matrix had a negligible effect upon extraction. To our knowledge, this is the first time that combines LLME and GC-MS for the analysis of methylsiloxanes in wastewater samples.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid–liquid microextraction for determination of 2,4,6-trinitrotoluene

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid–liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett–Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L−1 and 9 μg L−1, respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L−1), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

Choroidal Thickness And Volume In Healthy Young Whites And Their Relationship With Axial Length, Ammetropy And Sex

Purpose: To evaluate choroidal thickness in young subjects using Enhanced Depth Imaging Spectral Domain Optical Coherence Tomography (EDI SD-OCT) describing volume differences between all the defined areas of the Early Treatment Diabetic Retinopathy Study (ETDRS). Design: Prospective, clinical study. Methods: Seventy-nine eyes of 95 healthy, young (23.8±3.2years), adult volunteers were prospectively enrolled. Manual choroidal segmentation on a 25-raster horizontal scan protocol was performed. The measurements of the nine subfields defined by the ETDRS were evaluated. Results: Mean subfoveal choroidal thickness was 345.67±81.80μm and mean total choroidal volume was 8.99±1.88mm3. Choroidal thickness and volume were higher at the superior and temporal areas compared to inferior and nasal sectors of the same diameter respectively. Strong correlations between subfoveal choroidal thickness and axial length (AL) and myopic refractive error were obtained, r = -0.649, p<0.001 and r = 0.473, p<0.001 respectively. Emmetropic eyes tended to have thicker subfoveal choroidal thickness (381.94±79.88μm versus 307.04±64.91μm) and higher total choroidal volume than myopic eyes (9.80± 1.87mm3 versus 8.14±1.48mm3). The estimation of the variation of the subfoveal choroidal thickness with the AL was-43.84μm/mm. In the myopic group, the variation of the subfoveal choroidal thickness with the myopic refractive error was -10.45μm/D. Conclusions: This study establishes for the first time a normal database for choroidal thickness and volume in young adults. Axial length, and myopic ammetropy are highly associated with choroidal parameters in healthy subjects. EDI SD-OCT exhibited a high degree of intraobserver and interobserver repeatability.

Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction for determination of mercury in water samples

A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid–liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L−1 was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L−1, which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L−1 and 1 µg L−1, respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L−1) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained.

A reliable and valid questionnaire was developed to measure computer vision syndrome at the workplace

Objectives: To design and validate a questionnaire to measure visual symptoms related to exposure to computers in the workplace. Study Design and Setting: Our computer vision syndrome questionnaire (CVS-Q) was based on a literature review and validated through discussion with experts and performance of a pretest, pilot test, and retest. Content validity was evaluated by occupational health, optometry, and ophthalmology experts. Rasch analysis was used in the psychometric evaluation of the questionnaire. Criterion validity was determined by calculating the sensitivity and specificity, receiver operator characteristic curve, and cutoff point. Testeretest repeatability was tested using the intraclass correlation coefficient (ICC) and concordance by Cohen’s kappa (k). Results: The CVS-Q was developed with wide consensus among experts and was well accepted by the target group. It assesses the frequency and intensity of 16 symptoms using a single rating scale (symptom severity) that fits the Rasch rating scale model well. The questionnaire has sensitivity and specificity over 70% and achieved good testeretest repeatability both for the scores obtained [ICC 5 0.802; 95% confidence interval (CI): 0.673, 0.884] and CVS classification (k 5 0.612; 95% CI: 0.384, 0.839). Conclusion: The CVS-Q has acceptable psychometric properties, making it a valid and reliable tool to control the visual health of computer workers, and can potentially be used in clinical trials and outcome research.

Tungsten coil atomic emission spectrometry combined with dispersive liquid–liquid microextraction: A synergistic association for chromium determination in water samples

A novel and environment friendly analytical method is reported for total chromium determination and chromium speciation in water samples, whereby tungsten coil atomic emission spectrometry (WCAES) is combined with in situ ionic liquid formation dispersive liquid–liquid microextraction (in situ IL-DLLME). A two stage multivariate optimization approach has been developed employing a Plackett–Burman design for screening and selection of the significant factor involved in the in situ IL-DLLME procedure, which was later optimized by means of a circumscribed central composite design. The optimum conditions were complexant concentration: 0.5% (or 0.1%); complexant type: DDTC; IL anion: View the MathML sourcePF6−; [Hmim][Cl] IL amount: 60 mg; ionic strength: 0% NaCl; pH: 5 (or 2); centrifugation time: 10 min; and centrifugation speed: 1000 rpm. Under the optimized experimental conditions the method was evaluated and proper linearity was obtained with a correlation coefficient of 0.991 (5 calibration standards). Limits of detection and quantification for both chromium species were 3 and 10 µg L−1, respectively. This is a 233-fold improvement when compared with chromium determination by WCAES without using preconcentration. The repeatability of the proposed method was evaluated at two different spiking levels (10 and 50 µg L−1) obtaining coefficients of variation of 11.4% and 3.6% (n=3), respectively. A certified reference material (SRM-1643e NIST) was analyzed in order to determine the accuracy of the method for total chromium determination and 112.3% and 2.5 µg L−1 were the recovery (trueness) and standard deviation values, respectively. Tap, bottled mineral and natural mineral water samples were analyzed at 60 µg L−1 spiking level of total Cr content at two Cr(VI)/Cr(III) ratios, and relative recovery values ranged between 88% and 112% showing that the matrix has a negligible effect. To our knowledge, this is the first time that combines in situ IL-DLLME and WCAES.