Vortex-assisted dispersive low-density liquid-liquid microextraction of xanthydrol derivatized acrylamide in processed chips and water samples for gas chromatographic analysis.

Acrylamide, a probable human carcinogen present in heat-processed foods and environmental contaminants, requires sample extraction and preconcentration before chromatographic analysis. The method developed in this study employed derivatization with xanthydrol and dispersive liquid-liquid microextraction utilizing low-density anisole. Durian or potato chips were combined with deionized water, defatted with hexane, and subjected to precipitation of soluble carbohydrates and proteins using clarification reagents. Water samples were filtered through a membrane filter. Acrylamide was derivatized by introducing an acidic methanolic solution of xanthydrol at 50 °C. The derivatized acrylamide was extracted with 70 µL of anisole and vortexed, with the methanol from the xanthydrol solution serving as the disperser solvent. The anisole layer was analyzed using gas chromatography with both flame ionization and mass spectrometric detection. Linear calibration plots exhibited coefficients of determination >0.9997. The precision was measured at <10% RSD, and recoveries ranged from 84% to 107%. The quantitation limit varied from 2 to 10 µg kg-1 for processed chips and from 0.05 to 0.10 µg L-1 for water samples. Acrylamide was detected in all processed chip samples, with some concentrations exceeding the benchmark value of 750 µg kg-1. However, no acrylamide was identified in any of the water samples.

Solidification of floating organic droplet microextraction for determination of seven insecticides in fruit juice, vegetables and agricultural runoff using gas chromatography with flame ionization and mass spectrometry detection.

Liquid microextraction employing solidification of the floating organic droplet, with vortexing and heating to optimize extraction efficiency, was developed for the determination of seven insecticides in fruit juice, vegetables, and agricultural runoff water. The extracts were analyzed by gas chromatography with both flame ionization and mass spectrometry detection for the determination of chlorpyrifos, prothiofos, profenofos, ethion, λ-cyhalothrin, permethrin, and cypermethrin, respectively. Using 20 µL of 1-undecanol in 10 mL of aqueous solution containing 1% w/v sodium chloride provided preconcentration factor of 500. The enrichment factor of the analytes was in the range of 355 to 509 with extraction recovery >71%. The linearity ranges were 4-200 µg/kg for gas chromatography with flame ionization detection and 1-100 µg/kg for gas chromatography with mass spectrometry, with limits of detection ranging from 0.04 to 1.2 µg/kg, which are lower than the international maximum residue limits for vegetables and fruit juice. Intra-day and inter-day precisions are less than 5.4 and 7.0% relative standard deviation, respectively. The method was successfully applied to the determination of the seven insecticides in samples of vegetables, fruit juice and agricultural runoff, with recoveries ranging from 61.7 to 120.8%. The extraction method is simple, efficient and environmentally friendly.

Intraosseous concentration and inhibitory effect of different intravenous cefazolin doses used in preoperative prophylaxis of total knee arthroplasty.

BACKGROUND: The aim of this study was to compare the intraosseous concentrations and the inhibitory effects on the growth of Staphylococcus aureus of 1 g versus 2 g of intravenous (IV) prophylactic cefazolin in total knee arthroplasty (TKA). MATERIALS AND METHODS: Eighteen patients (21 knees) with primary knee osteoarthritis were divided into two groups receiving 1 g (12 patients: 14 knees) versus 2 g (six patients: seven knees) IV prophylactic cefazolin prior to the incision in TKA. Subchondral bone samples (proximal tibia, distal femur) were taken during the operation. These samples were analyzed for intraosseous concentration of cefazolin and their inhibitory effects on the growth of S. aureus, using high-performance liquid chromatography (HPLC) and agar disc diffusion bioassays. RESULTS: The mean intraosseous concentration in the 2 g dose group was significantly higher than in the 1 g dose group in the proximal tibia (p = 0.007) and distal femur (p = 0.016). There were no significant differences between the two groups in terms of mean inhibitory effects in the proximal tibia or distal femur (p > 0.05). No significant correlations were found between the intraosseous concentrations and inhibitory effects in the proximal tibia (r = 0.18, p = 0.52) and distal femur (r = -0.29, p = 0.30). CONCLUSION: IV cefazolin at a dose of 2 g produced greater intraosseous concentrations overall than a dose of 1 g. However, the higher intraosseous concentrations did not correlate with higher inhibitory effects.

Unveiling the potential of the capillary-driven microfluidic paper-based device integrated with smartphone-based for simultaneously colorimetric salivary ethanol and △9-tetrahydrocannabinol analysis.

Monitoring various biomarkers in saliva samples emerges as a dynamic and non-invasive method. However, the high viscosity of saliva presents a distinct challenge when integrating paper-based platforms for on-site analysis. In addressing this challenge, we introduced the capillary-driven microfluidic paper-based analytical devices (µCD-PAD) designed for user-friendly and simultaneous detection of ethanol and tetrahydrocannabinol (THC) in saliva without a sample preparation step. Employing a colorimetric approach, we quantified both analytes. Synthetic salivas of varying viscosity flowed seamlessly to the detection zone without needing a sample preparation step, and no impact on colorimetric detection due to viscosity was observed (RSD <5 %). Within 10 min after the solution reached the detection zone, the device produced a homogeneous color signal, easily analyzed by a smartphone camera. To extend the application for determination to cover a legal limit concentration of ethanol and concentration of salivary THC even 24 h after marijuana consumption, the detection time of 30 min was optimized. Moreover, a saliva sample containing both analytes was used to demonstrate the capability of the developed device to detect ethanol and THC simultaneously. No cross-talk between ethanol and THC occurred and showed recovery in the 98-102 % for ethanol and 95-105 % for THC with acceptable accuracy. This developed device exhibits excellent potential for forensic applications, providing a user-friendly, cost-effective, and real-time screening tool for detecting ethanol and THC in saliva.

Simple gunshot residue analyses for estimating firing distance: Investigation with four types of fabrics.

This work presents two simple methods for estimating the firing distance from the gunshot residues (GSRs) on fabric targets. Four types of fabric targets, namely twill weave denim cotton-polyester (80/20), jersey knitting 100% cotton, plain weave cotton-polyester (80/20) and plain weave cotton-polyester (60/40), were employed. The firing tests were carried out using these white fabrics as targets at distances of 5-100 cm, respectively. In the first method, digital images of the black GSRs on fabric materials were recorded inside an illuminated box and the inverted gray intensity values were plotted against the firing distances. Since the plots of all fabrics are not significantly different, the estimation of firing distance employs the same exponential curve for all test fabrics. Although simple, the imaging method is not suitable for dark-colored materials. A chemical-based method was therefore developed as an alternative method. In the second method, a small disposable microfluidic paper-based analytical device (µPAD) was employed for detecting Pb(II) extracted from the GSRs. The µPAD method uses the measurement of the length of a narrow band of a pink color resulting from reaction between rhodizonate reagent and the Pb(II) extract. The plots indicated that the data of thick denim material are significantly different to other test fabrics which are much thinner. These three fabrics share the same estimation curve. However, it is recommended that the separate estimation curve for denim materials must be used. Both methods are suitable for short range firing distance, no further than 60 cm, since at greater distances the inverted gray intensity and the 'band-length' methods are unable to detect the GSRs.

Characterization of biodiesel and biodiesel blends using comprehensive two-dimensional gas chromatography.

In this work the development of a comprehensive 2-D GC flame ionization detection (GC x GC FID) method for biodiesel fuels is reported. This method is used for the analysis of fatty acid methyl esters (FAMEs) in both biodiesel (B100) and biodiesel blend (B5) samples. The separation of FAME was based on component boiling point in the first dimension and polarity in the second dimension by using a BPX5/BP20 column set to provide a measure of 'orthogonality' in the 2-D space. Here the columns are coupled with a cryogenic modulator operating in a novel temperature programmed mode (T(M)) whereby the cryotrap is progressively incremented in temperature as the oven temperature is increased. The final method employs eight cryotrap temperature settings. The developed GC x GC method is able to successfully characterize and identify both B100 and B5 FAME components, which are produced from a variety of vegetable oils, animal fats and waste cooking oils, with high precision. The method is capable of analysing FAME with carbon numbers C4-C24, and is particularly suitable to characterize various types of biodiesel, making it possible to differentiate the origin and type of FAME used in the biodiesel samples.

Microfluidic Paper-based Analytical Device for Quantification of Lead Using Reaction Band-length for Identification of Bullet Hole and Its Potential for Estimating Firing Distance.

A low-cost and user-friendly microfluidic paper-based analytical device (µPAD) was developed for identification of bullet hole from gunshot residue (GSR) on cotton fabric target. The device (25 × 82 mm) is made of filter paper with a printed pattern consisting of a circular sample loading reservoir (6 mm i.d.), a circular waste reservoir (4 mm i.d.) and a straight flow channel (3 mm wide and 60 mm long). A sticker with a ruler scale in millimeters was mounted alongside the channel. The straight channel is first impregnated with rhodizonate and dried at ambient temperature. Tartrate extract of the target fabric is loaded on the sample reservoir. If Pb(II) ions are present in the extract, pink streak of Pb(II)-rhodizonate precipitate is formed as the sample solution flows from the reservoir along the channel. The length of the pink strip is employed to estimate the firing distance.

Greener liquid chromatography using a guard column with micellar mobile phase for separation of some pharmaceuticals and determination of parabens.

In this research, a greener chromatography employing a short column, Zorbax SB C18 cartridge (12.5 × 4.6 mm, 5 µm) commonly used as a guard column in a reverse phase high performance liquid chromatography (RP-HPLC), was utilized as the analytical column in conjunction with a more eco-friendly micellar mobile phase of sodium dodecyl sulfate (SDS) for separation tertiary mixtures of local anesthetics and antihistamines; and binary mixture of colds drugs; and quaternary mixture of some parabens with different separation conditions. The chromatographic behavior of these analytes was studied to demonstrate separation efficiency of this guard column in a micellar mobile phase. Moreover, this column and SDS mobile phase was exploited for determination of parabens in 64 samples of cosmetic product, both those that were produced locally in the community and those that were commercially manufactured. Linear calibration graphs of the parabens as detected at 254 nm were obtained in the range of 1-100 µmol L(-1) with R(2)>0.9990. Percentage recoveries were 92.4-109.2 with %RSD<3, and the limit of detection and quantitation were 0.04-0.10 and 0.20-0.80 µmol L(-1), respectively. This analytical system is not only greener but also faster and employing simpler sample preparation than a conventional liquid chromatographic system.