Determination of benzomercaptans in environmental complex samples by combining zeolitic imidazolate framework-8-based solid-phase extraction and high-performance liquid chromatography with UV detection.

In this work, the synthesis of zeolitic imidazolate framework-8 (ZIF-8) crystals and their subsequent application as effective sorbents for extraction and preconcentration of several benzomercaptans from environmental complex samples is described. These materials were prepared by solvothermal approach varying the concentration of n-butylamine modulator to modify the surface of the metal-organic framework. The resulting materials were characterized by scanning and transmission electron microscopy, powder X-ray diffraction and Fourier transform infrared spectroscopy. The ZIF-8 material that gave the best features was selected as extractive phase and the influence of various parameters (sample pH and elution solvent composition, among others) on the extraction efficiency of target compounds were investigated. Under the optimal conditions of the method, the tested analytes (2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercapto-6-nitrobenzothiazole) were retained and eluted quantitatively with alkaline 50:50 (v:v) methanol-water mixture. Using the proposed method, low limits of detection, in the range of 16-21 ng L-1 for aqueous samples and 0.4-0.5 µg kg-1 for soil samples, were achieved whereas the precision (expressed as relative standard deviation) was lower than 7%. The resulting solid-phase extraction protocol, using the zeolitic material as sorbent, was combined with liquid chromatography and ultraviolet-vis detector and successfully applied to determine traces of these organic pollutants in environmental samples.

Dream engineering: Simulating worlds through sensory stimulation.

We explore the application of a wide range of sensory stimulation technologies to the area of sleep and dream engineering. We begin by emphasizing the causal role of the body in dream generation, and describe a circuitry between the sleeping body and the dreaming mind. We suggest that nearly any sensory stimuli has potential for modulating experience in sleep. Considering other areas that might afford tools for engineering sensory content in simulated worlds, we turn to Virtual Reality (VR). We outline a collection of relevant VR technologies, including devices engineered to stimulate haptic, temperature, vestibular, olfactory, and auditory sensations. We believe these technologies, which have been developed for high mobility and low cost, can be translated to the field of dream engineering. We close by discussing possible future directions in this field and the ethics of a world in which targeted dream direction and sleep manipulation are feasible.

Extraction of ß-blockers from urine with a polymeric monolith modified with 1-allyl-3-methylimidazolium chloride in spin column format.

A glycidyl methacrylate-based monolith was modified with imidazolium-based ionic liquid (IL) to be used as stationary phase for solid-phase extraction (SPE). The host monolithic support was prepared by in-situ UV polymerization in spin column format. Two approaches were developed to incorporate the IL into the polymeric monolithic matrix: generation of IL onto the surface monolith, and copolymerization by addition of the IL to the polymerization mixture, which gave the best results. The resulting sorbent materials were morphologically characterized and used for the isolation of five ß-blockers from human urine samples. All SPE steps were accomplished by centrifugation, which reduces significantly costs and time in sample treatment. Under optimal conditions, ß-blockers were quantitatively retained in the modified monolith at pH 12, and desorbed with a water-methanol mixture, to be subsequently determined via HPLC with UV detection. The limits of detection ranged between 1.4 and 40 µg L-1, and the reproducibility among extraction units (expressed as relative standard deviation) was below 8.2%. The novel phase was successfully applied to the extraction of propranolol in urine samples with recoveries above 90%.

In syringe hybrid monoliths modified with gold nanoparticles for selective extraction of glutathione in biological fluids prior to its determination by HPLC.

In this work, a simple device for extraction glutathione (GSH) in biological fluids using a hybrid monolithic material within a polypropylene syringe is developed. For this purpose, glycidyl methacrylate-based monolith was firstly prepared within this housing material, and the polymer was modified with different ligands (ammonia, cysteamine and cystamine). The resulting materials (containing amine or thiol groups, respectively) were then functionalized with gold nanoparticles (AuNPs). The hybrid material that gave the largest AuNPs coverage was selected as solid-phase (SPE) sorbent and several variables affecting the extraction recovery of this compound were investigated. Under optimal conditions, GSH was quantitatively retained at pH 6.0, and then it was desorbed with aqueous dithiothreitol solution and determined, after derivatization with o-phthaldialdehyde, via reversed-phase LC with fluorometric detection. The limit of detection was ca. 1.5 ng mL-1, and the reproducibility between extraction units was below 8% (expressed as relative standard deviation), which demonstrates the robustness of the method. The developed material was also applied for the extraction of GSH in saliva and urine samples yielding recoveries ranging from 86 to 105%.

Poly(ethylene glycol) diacrylate based monolithic capillary columns for the analysis of polar small solutes by capillary electrochromatography.

Monolithic stationary phases based on poly(ethylene glycol) diacrylates for capillary electrochromatography were developed. Several poly(ethylene glycol) diacrylates (Mn 250, 575, and 700) were used as single monomers and the resulting columns were carefully compared. Methanol and ethyl ether were selected as porogenic solvents, and in all cases ultraviolet radiation was selected as initiation method to prepare polymeric monoliths. The influence of the monomer chain length and ratio monomer/porogen on the morphological and electrochromatographic properties of the resulting monoliths was investigated. Several families of compounds with different polarity (alkyl benzenes, organophosphorous pesticides, benzoic acid derivatives, and sulfonamides) were selected to evaluate the performance of the fabricated monolithic columns. The best results were obtained for poly(ethylene glycol) diacrylate 700 monoliths affording efficiencies of 144 000 plates/m for retained polar aromatic small molecules and excellent reproducibility in column preparation (RSD values below 2.5%).

Carbon nanotube-modified monolithic polymethacrylate pipette tips for (micro)solid-phase extraction of antidepressants from urine samples.

This work evaluates the potential of methacrylate monoliths with multi-walled carbon nanotubes incorporated into the polymeric network for the extraction of antidepressants from human urine. The method is based on a micropipette solid-phase extraction tip containing a hybrid monolithic material covalently attached to the polypropylene housing. A polymer layer made from poly(ethylene dimethacrylate) was bound to the inner surface of a polypropylene tip via UV grafting. The preparation of the monolith and the microextraction steps were optimized in terms of adsorption capacity. Limits of detection ranged from 9 to 15 µg·L-1. The average precision of the method varied between 3 and 5% (intra-tips), and from 4 to 14% (inter-tips). The accuracy of the method was evaluated through a recovery study by using spiked samples. Graphical abstract Hybrid polymer monoliths containing multi-walled carbon nanotubes (MWCNTs) were prepared in pipette tips by photo-polymerization approach. The extraction devices were used for the extraction of antidepressants in urine samples.