A Colorimetric Method for the Rapid Estimation of the Total Cannabinoid Content in Cannabis Samples.

A colorimetric method for the estimation of the total content of cannabinoids in cannabis samples is proposed. The assay is based on the reaction of these compounds with the reagent Fast Blue B (FBB), which has been immobilized into polydimethylsiloxane (PDMS). The reaction and detection conditions have been established according to the results obtained for the individual cannabinoids Δ9-tetrahydrocannabidiol (THC), cannabidiol (CBD), and cannabinol (CBN), as well as for ethanolic extracts obtained from cannabis samples after ultrasonication. In contact with the extract and under basic conditions, the reagent diffuses from the PDMS device, producing a red-brown solution. The absorbances measured at 500 nm after only 1 min of exposure to the FBB/PDMS composites led to responses proportional to the amounts of the cannabinoids in the reaction media. Those absorbances have been then transformed in total cannabinoid content using CBD as a reference compound. The potential utility of the proposed conditions has been tested by analyzing different cannabis samples. The selectivity towards other plants and drugs has been also evaluated. The present method is proposed as a simple and rapid alternative to chromatographic methods for the estimation of the total content of cannabinoids.

A Colorimetric Membrane-Based Sensor with Improved Selectivity towards Amphetamine.

Due to their simplicity, speed and low cost, chemical spot tests are increasingly demanded for the presumptive identification of illicit drugs in a variety of contexts such as point-of-care assistance or prosecution of drug trafficking. However, most of the colorimetric reactions used in these tests are, at best, drug class selective. Therefore, the development of tests based on chemical reactions with improved discrimination power is of great interest. In this work, we propose a new colorimetric assay for amphetamine (AMP) based on its reaction with solutions of alkaline gold bromide to form an insoluble yellow-orange derivative. The resulting suspensions are then filtered onto nylon membranes and the precipitate collected is used for the visual identification of AMP. The measurement of the absorbance of the membranes by diffuse reflectance spectroscopy also allows the quantification of AMP in a simple and rapid way, as demonstrated for different synthetic and drug street samples. On the basis of the results obtained, it was concluded that the proposed procedure is highly selective towards AMP, as this compound could be easily differentiated from other common drugs such as methamphetamine (MET), ephedrine (EPH), scopolamine (SCP) and cocaine (COC).

Portable solid sensor supported in nylon for silver ion determination: testing its liberation as biocide.

This paper reports the fabrication and utility of a new solid sensor, which allows the quantitation of silver ions acting as catalyst at the low micromolar level. The optical sensor was prepared by incorporating both reagents, pyrogallol red (PGR) and 1,10-phenanthroline (Phen), in a nylon membrane. The effect of parameters in determining silver-catalyzed oxidation of PGR by persulfate in the presence of Phen as an activator was studied and optimized for achieving suitable sensitivity. Semiquantitative analysis can be performed by visual inspection of the color of the sensor by comparing it with standard responses and quantitative analysis can be carried out by its diffuse reflectance (DR) measurement or by a digital image-processing tool (GIMP) using a smartphone. The sensor exhibited a linear relationship toward Ag(I) concentrations ranging from 0.4 to 10 µM or 1-25 µM and limits of detection of 0.1 µM or 0.3 µM for incubation times of 50 and 30 min, respectively. The relative standard deviation achieved for several batches of sensors was around 2%. The analysis of water samples from tap and refrigerating circuits containing solid biocides, which leach silver ions, prove that this portable and sustainable sensor is successfully operational in real situations. Graphical abstract.

New Reusable Solid Biosensor with Covalent Immobilization of the Horseradish Peroxidase Enzyme: In Situ Liberation Studies of Hydrogen Peroxide by Portable Chemiluminescent Determination.

Herein, we reported a chemiluminescent biosensor based on the covalent immobilization of the horseradish peroxidase (HRP) enzyme on a polydimethylsiloxane (PDMS) support to quantify in situ hydrogen peroxide (H2O2). The chemiluminescent reaction based on the use of luminol as an oxidizable substrate, with HRP as the catalyst, has been used in order to quantify H2O2 as the oxidizing agent. The performance of the proposed biosensor has been demonstrated to determine H2O2 liberated by cells in a culture medium and for evaluating the delivery of H2O2 from denture cleaner tablets, as examples of application. For both analyses, the results indicated that the biosensor is cost-effective, sensitive, and selective with a detection limit of 0.02 µM and good linearity over the range 0.06-10 µM. Precision was also satisfactory (relative standard deviation, % RSD < 6). The strength of this biosensing system is the simplicity, portability, and reusability of the devices; it can be applied up to 60 times with 90% of its activity maintained.

Nylon-Supported Plasmonic Assay Based on the Aggregation of Silver Nanoparticles: In Situ Determination of Hydrogen Sulfide-like Compounds in Breath Samples as a Proof of Concept.

A procedure for supporting silver nanoparticles (AgNPs) on nylon is proposed. Besides, the membrane has been developed as a solid-phase colorimetric plasmonic sensor for volatile sulfide compounds (VSCs) like H2S, CH3SH, and (CH3)2S. AgNP behavior in the membrane has been studied by UV-vis diffuse reflectance spectrometry, Raman spectrometry, High-resolution transmission electron microscopy (HR-TEM), and Scanning electron microscopy (SEM). The sensor responded by changing its color from yellow in absence of VSCs to several orange/brown colors in the function of VSC concentration as occurs in solution; an increase in the hydrodynamic diameter, estimated by both asymmetrical flow field-flow fractionation (AF4) coupled on line to Dynamic light scattering (DLS) detector and batch DLS, is achieved when sulfide is added to the citrate-capped AgNPs. Diffuse reflectance spectrometry and processed digital images obtained with a smartphone have been used as measurements and several transformations for quantitation are proposed; a linear concentration range of hydrogen sulfide from 150 to 1000 ppbv and a detection limit (LOD) of 45 ppbv were achieved, measuring after 10 min of the sensor exposition to the hydrogen sulfide atmosphere (2 L) for humidity percentages between 50 and 96% and room temperature. Satisfactory results in terms of precision (<10%) and selectivity were obtained. The new sensor reported was stable, sensitive, inexpensive, disposable, safe, and user-friendly. Furthermore, it has successfully been applied to determine VSCs expressed as hydrogen sulfide in breath samples (2 L and 250 mL) as a proof of concept. The limit of detection can be improved by increasing the exposition time, if necessary.

Quantifying both ammonium and proline in wines and beer by using a PDMS composite for sensoring.

Two of the reagents involved in the Berthelot's reaction, thymol and nitroprusside, were embedded in a PDMS composite in order to apply this assay to determine ammonium and proline, in wine and beers. Safety, portability, rapidity, cost-effectiveness and simplicity of the assay were improved. For the proline determination, a modified Berthelot's reaction, which included a ring cleavage of proline, was optimized. The accuracy of the assay was tested. The limits of detection for ammonium was 0.12 µg mL-1 and for proline was in the range from 0.7 to 4.1 µg mL-1, depending on the kind of wine (white, red, or sweet), for beer the LOD was 6 µg mL-1. The precision achieved was slower than 10%. The accuracy of the assay was tested by means of a confirmatory validation study. Good results were obtained for real samples.

Stabilization of formaldehyde into polydimethylsiloxane composite: application to the in situ determination of illicit drugs.

The Marquis test is the most frequently used spot color assay for the screening of unknown drugs such as amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-metilenedioxymethamphetamine, and morphine. However, this test involves the use of the toxic reagent formaldehyde, as well as the manipulation of concentrated sulfuric acid. Here, we report a new format of this test that improves the sustainability and safety for the operator by immobilizing formaldehyde into a polydimetylsiloxane composite. In contact with a solution (or suspension) of the suspected sample in sulfuric acid, the dispositive delivers formaldehyde and the reaction takes place in a few seconds. Under the proposed conditions, only small amounts of the drug (µg) are necessary to produce intense changes of color. In addition, the percentage of the drug in the sample can be established by obtaining pictures of the test vials and subsequent analysis of the digitalized images. The responses were linear for amphetamine-like drugs up to a concentration of 100 mg L-1, and the precision achieved was adequate (relative standard deviations, RSDs < 10%). The developed composites were tested for the determination of MDMA in several drug street samples, and a good correlation with the results obtained by a reference method based on liquid chromatography was found. The main advantages of the proposed approach over the traditional Marquis test format are better portability and safety for the operator at a lower cost and the possibility of using it for quantitative analysis.

Analysis of Contact Traces of Cannabis by In-Tube Solid-Phase Microextraction Coupled to Nanoliquid Chromatography.

Because of its inherent qualities, in-tube solid-phase microextraction (IT-SPME) coupled on-line to nanoliquid chromatography (nanoLC) can be a very powerful tool to address the new challenges of analytical laboratories such as the analysis of traces of complex samples. This is the case of the detection of contact traces of drugs, especially cannabis. The main difficulties encountered in the analysis of traces of cannabis plants on surfaces are the low amount of sample available (typically < 1 mg), the complexity of the matrix, and the low percentages of cannabinoic compounds in the samples. In this work, a procedure is described for the detection of residues of cannabis on different surfaces based on the responses obtained by IT-SPME coupled to nanoLC with UV diode array detection (DAD) for the cannabinoids Δ8-tetrahydrocannabinol (THC), cannabidiol (CBD), and cannabinol (CBN); the proposed conditions can also be applied for quantitative purposes through the measurement of the percentage of THC, the most abundant cannabinoid in plants. The method is based on collecting the suspected drug samples with cotton swabs, followed by the extraction of the target compounds by ultrasound assisted extraction. The extracts are then separated and processed by IT-SPME-nanoLC. The proposed approach has been applied to the detection of traces of cannabis in different kind of items (plastic bags, office paper, aluminum foil, cotton cloths, and hand skin). Sample amounts as low as 0.08 mg have been collected and analysed for THC. The selectivity and effect of the storage conditions on the levels of THC have also been evaluated. The percentages of THC in the samples typically ranged from 0.6% to 2.8%, which means that amounts of this compound as low as 1⁻2 µg were adequately detected and quantified. For the first time, the reliability of IT-SPME-nanoLC for the analysis of complex matrices such as cannabis plant extracts has been demonstrated.

Delivering Inorganic and Organic Reagents and Enzymes from Zein and Developing Optical Sensors.

Nowadays, interest in using environmentally friendly materials is increasing in many fields. However, the rational design of sensors with biodegradable materials is a challenge. The main aim of this work is to show the possibility of using zein, a protein from corn, as a biodegradable and low-cost material for immobilizing, stabilizing, and delivering different kind of reagents for developing optical sensors. Enzymes, metallic salts, and aromatic and small organic compounds were tested. In addition, different techniques of immobilization, entrapment and adsorption, were used, and different formats, such as solid devices and also multiwell platforms, were proposed. The capacity of zein for immobilizing two reagents together, enzyme and substrate, into a multianalysis format was also shown. Two applications were developed as examples: a colorimetric assay based on a ferric hydroxamate reaction for ester drugs, which was applied in atropine determination in pills, and a fluorimetric enzymatic multiwell-plate biodevice applied in phosphate determination in human serum and urine. Zein demonstrated being not only a green alternative but also a versatile polymer for developing sensors from reagents with different natures in different formats and matrices, thereby resulting in different applications.

Microextraction with phases containing nanoparticles.

In this article, the state of the art of microextraction techniques that involve nanoparticles or nanomaterials (NPs) is reviewed, with special emphasis on the applications described in the biomedical field. The uses and advantages of the different types of NPs such as carbon nanotubes (either single- and multi-walled) and other carbon-based materials, metallic NPs, including gold, silver and magnetic NPs, and silica NPs are summarized. The main strategies used to modify the selectivity, extractive capacity and/or the stability of NPs through a chemical reaction are also reviewed. The potential advantages of NPs in different forms of off-line and on-line microextraction are discussed, and illustrative examples of application in the biomedical field are shown.