Coupling Miniaturized Stir Bar Sorptive Dispersive Microextraction to Needle-Based Electrospray Ionization Emitters for Mass Spectrometry: Determination of Tetrahydrocannabinol in Human Saliva as a Proof of Concept.

Direct coupling of sample preparation with mass spectrometry (MS) can speed up analysis, enabling faster decision-making. In such combinations, where the analysis time is mainly defined by the extraction procedure, magnetic dispersive solid-phase extraction emerges as a relevant technique because of its rapid workflow. The dispersion and retrieval of the magnetic sorbent are typically uncoupled stages, thus reducing the potential simplicity. Stir bar sorptive dispersive microextraction (SBSDME) is a novel technique that integrates both stages into a single device. Its miniaturization (mSBSDME) makes it more portable and compatible with low-availability samples. This article reports the direct combination of mSBSDME and MS using a needle-based electrospray ionization (NESI) emitter as the interface. This combination is applied to determine tetrahydrocannabinol in saliva samples, a relevant societal problem if the global consumption rates of cannabis are considered. The coupling requires only the transference of the magnet (containing the sorbent and the isolated analyte) from the mSBSDME to the hub of a hypodermic needle, where the online elution occurs. The application of 5 kV on the needle forms an electrospray on its tip, transferring the ionized analyte to the MS inlet. The excellent performance of mSBSDME-NESI-MS/MS relies on the sensitivity (limits of detection as low as 2.25 ng mL-1), the precision (relative standard deviation lower than 15%), and the accuracy (relative recoveries ranged from 87 to 127%) obtained. According to the results, the mSBSDME-NESI-MS/MS technique promises faster and more efficient chemical analysis in MS-based applications.

The role of sustainable materials in sample preparation.

Sample preparation is a constantly evolving step in the measurement process with a positive effect on its performance. Its evolution has been marked by an underlying environmental commitment, with simplification, miniaturization, and automation being three of its driving forces. This trends article deepens how the sample preparation can go sustainable through the efficient design of new sorptive materials, either liquid or solid. This objective can be achieved by using natural and/or biodegradable materials as precursors of the functional sorptive phases and by designing materials that simplify the procedures (thus reducing the energy or resources required). Although environmental performance is a crucial aspect of a new material, its applicability is what really defines its incorporation into the sample preparation toolbox. For this reason, their characteristics and more relevant applications will be briefly presented to conclude with the tendency of their use in the very near future.

Icosahedral gold nanoparticles decorated with hexon protein: a surrogate for adenovirus serotype 5.

The development of synthetic particles that emulate real viruses in size, shape, and chemical composition is vital to the development of imprinted polymer-based sorbent materials (molecularly imprinted polymers, MIPs). In this study, we address surrogates for adenovirus type 5 (Adv 5) via the synthesis and subsequent modification of icosahedral gold nanoparticles (iAuNPs) decorated with the most abundant protein of the Adv 5 (i.e., hexon protein) at the surface. CTAB-capped iAuNPs with dimensions in the range of 40-90 nm were synthesized, and then CTAB was replaced by a variety of polyethylene glycols (PEGs) in order to introduce suitable functionalities serving as anchoring points for the attachment of the hexon protein. The latter was achieved by non-covalent linking of the protein to the iAuNP surface using a PEG without reactive termination (i.e., methoxy PEG thiol, mPEG-SH, Mn=800). Alternatively, covalent anchoring points were generated by modifying the iAuNPs with a bifunctional PEG (i.e., thiol PEG amine, SH-PEG-NH2) followed by the addition of glutaraldehyde. X-ray photoelectron spectroscopy (XPS) confirmed the formation of the anchoring points at the iAuNP surface. Next, the amino groups present in the amino acids of the hexon protein interacted with the glutaraldehyde. iAuNPs before and after PEGylation were characterized using dynamic light scattering (DLS), XPS, transmission electron microscopy (TEM), scanning electron microscopy (SEM), and UV-Vis spectroscopy, confirming the CTAB-PEG exchange. Finally, the distinct red shift obtained in the UV-Vis spectra of the pegylated iAuNPs in the presence of the hexon protein, the increase in the hydrodynamic diameter, the change in the zeta potential, and the selective binding of the hexon-modified iAuNPs towards a hexon-imprinted polymer (HIP) confirmed success in both the covalent and non-covalent attachment at the iAuNP surface.

Pre-cleaned bare wooden toothpicks for the determination of drugs in oral fluid by mass spectrometry.

This article deepens the potential of pre-cleaned bare wooden toothpicks (pb-WTs) for extracting drugs (antidepressants and acetaminophen) from oral fluid samples. The leaching of the intrinsic compounds from the wood matrix is identified as the main challenge for the final determination of the targets, even when a very selective instrumental technique, such as mass spectrometry, is employed. The pre-cleaning of the WTs is proposed for improving the analytical performance. The number of cleaning cycles depends on the injection mode (direct infusion or chromatography) into the mass spectrometer. The different variables affecting the extraction of selected antidepressant drugs were studied in detail, and the optimum procedure was validated using the two mentioned injection modes. The limits of detection were in the ranges 0.1-0.5 ng/mL and 0.1-0.3 ng/mL for direct infusion and liquid chromatography, respectively. The intra-day precision (expressed as relative standard deviation) was better than 12.1% and 8.6%, for direct infusion and liquid chromatography, respectively. Single-blind samples were used to study the applicability of the method. Finally, as a proof-of-concept, the potential of pb-WTs for in vivo sampling was outlined.

Wooden-based materials: Eco-friendly materials for direct mass spectrometric analysis and microextraction.

Lignocellulosic materials have arisen as a sustainable alternative in microextraction techniques during the last 10 years. As they are natural materials, their use fits into some of the principles of Green Analytical Chemistry. Their inherent porosity, narrow shape, and rigidity permit their use in ambient ionization mass spectrometry techniques. In particular, the combination of wooden-based materials and direct analysis gives birth to the so-called wooden-tip electrospray ionization mass spectrometry technique. This approach has been used for the direct analysis of complex samples, and as a streamlined tool for fingerprint quality analysis. Also, wooden-based materials can be superficially modified to boost the interaction with target compounds, allowing their isolation from complex samples. This review describes the potential and applicability of direct analysis using lignocellulosic materials, as well as other alternatives related to their use in microextraction.

Passivated graphene quantum dots for carbaryl determination in juices.

This paper reports a simple method for the preparation of suitable graphene quantum dots after surface passivation, to be used for the determination of carbaryl in juice samples. A comparison of synthetic conditions for the preparation of graphene quantum dots following the top-down approach is described. In the one-step route selected, evaluation of diverse reaction time for cutting and modulating the oxidizing sites in the broken pieces of the initial graphene layer is conducted with a mixture of concentrated acids. Exploring the passivation effect on the purified graphene quantum dots, we demonstrated the suitability of the selected graphene quantum dots for practical application in the detection of carbaryl using fluorometric detection. Higher sensitivity was achieved after 8 min of contact, in which graphene quantum dots promotes the degradation of carbaryl into naphthol, being the latter responsible for the analytical signal. The detection and quantification limits were 0.36 and 1.21 µg/L, respectively, being the response linear up to 26 µg/L with excellent precision (better than 3.2% at the limit of detection). The recovery of the analyte from commercial juice samples (91.4-96.7%) testifies to the applicability of the proposal for the analytical problem selected.

A paper-based polystyrene/nylon Janus platform for the microextraction of UV filters in water samples as proof-of-concept.

A new mix-mode cellulose-based sorptive phase is described that combines two different polymeric domains (i.e., nylon and polystyrene), thus providing simultaneous hydrophilic and hydrophobic features as a result. By analogy with Janus materials, the new paper-based sorptive phase has been named paper-based polystyrene/nylon Janus-platform (P-Ps/Ny-JP). The main advantages of the proposed P-Ps/Ny-JP are the sustainability, simplicity in synthesis, and low cost of this extraction device. The main parameters affecting the synthesis (i.e., coating procedure and polymers proportion) have been studied, and the resulting material has been characterized via scanning electron microscopy and infrared spectroscopy. As a proof-of-concept, the simultaneous extraction of fourteen UV filters of a wide range of polarity, with log P values ranging from - 0.234 to 16.129, from water samples and their determination by liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been performed. The proposed methodology enables the determination of these chemicals with limits of detection from 12 to 71 ng L-1, and the precision, expressed as a relative standard deviation, was below 15%. The extraction device was applied to the analysis of real water samples likely to contain UV filters (i.e., two private swimming pool water and one seawater) and the recovery values were in the range 73-121%.

Facile preparation of carbon nanotube-based molecularly imprinted monolithic stirred unit.

A lab-made stirring extraction unit based on a selective monolithic solid was developed. The monolith was formed by interconnected carbon nanotubes which were covered by a thin polymeric layer, where specific cavities were generated to provide selective recognition sites in the material. To reach this goal, a water-in-oil (W/O) medium internal phase emulsion (40/60 w/w%), was prepared and photopolymerized. The polymerization reaction took place in the organic or external phase containing the carbon nanotubes, polymeric monomers (cross-linker and functional monomer) and a molecule template. Therefore, it was possible to coat the nanotubes with a layer of molecularly imprinted polymer (MIP) with the target analyte while forming a monolithic and macroscopic structure. The developed selective monolithic stirring extraction units were applied for the determination of secbumeton and structurally related compounds (triazine herbicides) in peppermint mint and tea samples. Their adsorption capacity and selectivity were also compared with a non-imprinted polymer (NIP). Finally, the performance of the method was evaluated for quantitative analysis, achieving limits of detection (LODs) between 0.4 and 2.5 µg·L-1. The intra- and inter-day precision of the method was also evaluated as relative standard deviation, observing values which ranged from 3% to 9% and 9% to 15%, respectively. Graphical Abstract.

Effervescence-Assisted Microextraction-One Decade of Developments.

Dispersive microextraction techniques are key in the analytical sample treatment context as they combine a favored thermodynamics and kinetics isolation of the target analytes from the sample matrix. The dispersion of the extractant in the form of tiny particles or drops, depending on the technique, into the sample enlarges the contact surface area between phases, thus enhancing the mass transference. This dispersion can be achieved by applying external energy sources, the use of chemicals, or the combination of both strategies. Effervescence-assisted microextraction emerged in 2011 as a new alternative in this context. The technique uses in situ-generated carbon dioxide as the disperser, and it has been successfully applied in the solid-phase and liquid-phase microextraction fields. This minireview explains the main fundamentals of the technique, its potential and the main developments reported.

Molecularly Imprinted Polymer Micro- and Nano-Particles. A review.

In recent years, molecularly imprinted polymers (MIPs) have become an excellent solution to the selective and sensitive determination of target molecules in complex matrices where other similar and relative structural compounds could coexist. Although MIPs show the inherent properties of the polymers, including stability, robustness, and easy/cheap synthesis, some of their characteristics can be enhanced, or new functionalities can be obtained when nanoparticles are incorporated in their polymeric structure. The great variety of nanoparticles available significantly increase the possibility of finding the adequate design of nanostructured MIP for each analytical problem. Moreover, different structures (i.e., monolithic solids or MIPs micro/nanoparticles) can be produced depending on the used synthesis approach. This review aims to summarize and describe the most recent and innovative strategies since 2015, based on the combination of MIPs with nanoparticles. The role of the nanoparticles in the polymerization, as well as in the imprinting and adsorption efficiency, is also discussed through the review.

Synthesis, characterization, and application of chemically interconnected carbon nanotube monolithic sorbents by photopolymerization in polypropylene caps.

A facile and convenient approach for the preparation of interconnected multiwalled carbon nanotube (MWCNT) monolithic sorbents in recycled plastic caps has been developed. The method, which was based on the photopolymerization of the individual MWCNTs via the formation of a W/O medium internal phase emulsion (40/60 w/w%), provides control over the size of pores, rigidity, and the mechanical stability of the final solid. Pluronic L121 was used as a surfactant containing the water phase inside it and, consequently, the organic and non-polar phase, in which the MWCNTs and the cross-linker were trapped, remained on the outside of the droplets. Optical microscopy and scanning electron microscopy (SEM) were employed to characterize the morphology of both the emulsions and the final solids, respectively. In addition, nitrogen intrusion porosimetry was performed in order to study how the specific surface area of the final monolithic solid changed (from 19.6 to 372.2 m2 g-1) with the variables involved in the polymerization step. To exemplify the great sorbent potential of the synthesized material, a colorimetric assay based on the retention of methylene blue within the interconnected MWCNT monolithic structure was carried out. Finally, following the positive results, the carbon nanotube-monolithic stirred caps were applied for the determination of chlorophenols in a biological matrix such as human urine, obtaining excellent recovery values (91-98%) and good precision (5.4-9.1%) under optimized extraction conditions. Graphical abstract.

Ultrafast spectroscopic investigation on fluorescent carbon nanodots: the role of passivation.

Disentangling the respective roles of the surface and core structures in the photocycle of carbon nanodots is a critical open problem in carbon nanoscience. While the need of passivating carbon dot surfaces to obtain efficiently emitting nanoparticles is very well-known in the literature, it is unclear if passivation introduces entirely new surface emitting states, or if it stabilizes existing states making them fluorescent. In this multi-technique femtosecond spectroscopy study, the relaxation dynamics of non-luminescent (non-passivated) carbon dots are directly compared with their luminescent (passivated) counterparts. Non-passivated dots are found to host emissive states, albeit very short-lived and practically incapable of steady-state fluorescence. In contrast, the passivation procedure gives birth to a distinctive new manifold of emitting states, localized on the surface of the dots, and capable of intense, tunable, long-lived fluorescence. It turns out that these surface states are instantaneously populated by photo-excitation, and their subsequent dynamics are entirely independent of core electronic transitions. The experiments reveal the lack of any crosstalk between core- and surface states, at least for certain common types of carbon dots, and open a new perspective on the mechanisms by which surface passivation governs the fluorescence properties of these nanoparticles.

Magnetic Polyamide Nanocomposites for the Microextraction of Benzophenones from Water Samples.

In this article, the influence of the monomers on the extraction efficiency and the effect of the addition of surfactants during the synthesis have also been considered. The sorption capacity of the resulting nanocomposites has been evaluated, in the dispersive micro-solid phase extraction format, by determining that of six benzophenones in water using ultra performance liquid chromatography (UPLC) combined with photodiode array detection. Under the optimum conditions, the limits of detection were in the range of 0.5⁻4.3 ng/mL and the repeatability, expressed as the relative standard deviation (RSD), varied between 1.5% and 5.6%. The proposed method has been applied for the analysis of real water samples, providing relative recoveries in the interval of 84⁻105.

Lab-on-a-Valve Mesofluidic Platform for On-Chip Handling of Carbon-Coated Titanium Dioxide Nanotubes in a Disposable Microsolid Phase-Extraction Mode.

Mesofluidic lab-on-a-valve (LOV) platforms have been proven suitable to accommodate automatic micro-solid-phase extraction (µSPE) approaches with on-chip handling of micrometer-bead materials in a fully disposable mode to prevent sample cross-contamination and pressure-drop effects. The efficiency of the extraction process notably depends upon the sorptive capacity of the material because the sorbent mass is usually down to 10 mg in LOV devices. Nanomaterials, capitalizing upon their enhanced surface-to-volume ratio and diversity of potential chemical moieties, are appealing alternatives to microbead sorbents. However, the handling and confinement of nanomaterials in fluidic chip structures have been challenging to date. This is most likely a consequence of the aggregation tendency of a number of nanomaterials, including carbon-based sorbents, that leads to excessive back-pressure in flowing systems along with irreproducible bead loading. This paper addresses these challenges by ad hoc synthesis of hybrid nanomaterials, such as porous carbon-coated titanium dioxide nanotubes (TiO2-NT@pC). Tailoring of the surface polarity of the carbon coating is proven to foster the dispersion of TiO2-NT@pC in LOV settings while affording superior extraction capability of moderately nonpolar species from aqueous matrices. The determination of trace-level concentrations of butylparaben (BPB) and triclosan (TCS) in seawater samples is herein selected as a proof-of-concept of the exploitation of disposable nanomaterials in LOV. The mesofluidic platform accommodating µSPE features online hyphenation to liquid chromatography/tandem mass spectrometry (LC/MS/MS) for reliable determination of the target analytes with excellent limits of detection (0.5 and 0.6 ng/L for BPB and TCS, respectively) and intermediate precision (relative standard deviation <5.8%). For 5.0 mL of sample and 200 µL of eluent, enrichment factors of 23 and 14 with absolute extraction efficiencies of 90% ± 14% and 58 ± 8% for BPB and TCS, respectively, were obtained. The relative recovery values of 107% (BPB) and 97% (TCS) in seawater demonstrate the applicability of online LOV-LC/MS/MS using TiO2-NT@pC for handling troublesome environmental samples.

Gold-nanostar-based SERS substrates for studying protein aggregation processes.

Aggregation of proteins has been related to some neurodegenerative diseases such as Alzheimer's and Parkinson's among others. Raman spectroscopy is a useful technique for the investigation of protein conformation and of changes in their secondary structure. In this study, a surface enhanced Raman spectroscopy (SERS) substrate based on the immobilization of plasmonic gold nanostars on a glass slide via silanization of the surface has been prepared and characterized. Gold nanostars were synthesized via a seed-growth method using gold nanoparticles as seeds obtained via stainless steel as the reducing agent. The plasmonic substrate provided an enhancement of 5.7 × 102 fold, as shown for the Raman signal of crystal violet. Using this SERS-active substrate, the investigation of aggregation processes of bovine serum albumin (BSA) and myoglobin proteins upon temperature and solvent modification has been enabled with enhanced sensitivity. Both curve fitting and deconvolution of the amide I band, as well as 2D correlation analysis, were employed for the evaluation of the changes in the SERS spectra of the protein samples. The amide I band within the SERS spectra of the BSA protein revealed a decrease in the α-helix structures within the secondary structure of the protein while the presence of ß-sheet structures increased with temperature and solvent concentration.

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.

Ion beam sputtering deposition of silver nanoparticles and TiOx/ZnO nanocomposites for use in surface enhanced vibrational spectroscopy (SERS and SEIRAS).

Hybrids consisting of silver nanoparticles (in varying fractions) and of TiOx/ZnO were prepared via top-down ion beam sputtering (IBS) deposition on silicon substrates. The deposited nanomaterials were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. It is shown that such composites represent a viable substrate for use in both surface enhanced Raman spectroscopy (SERS) and surface enhanced infrared absorption spectroscopy (SEIRAS), as exemplarily shown for crystal violet as the model analyte. The C-H bending mode at about 1181 cm-1 and the C-N vibration at 1361 cm-1 observed in the SERS and SEIRAS spectra, respectively, have been used as analytical signal. The substrate consisting of TiOx NPs with 33% fraction of silver provides the strongest enhancement in SERS (up to 10,000-fold), while TiOx/AgNPs with thickness of 2 and 1 nm in ion beam sputtering, respectively, provides the best sensitivity in SEIRAS. The substrates also display photocatalytic activity as shown by the degradation of adsorbed crystal violet under ultraviolet irradiation. Graphical abstract Schematic of the preparation of hybrid substrates consisting of Ag and TiOx/ZnO nanoparticles via ion beam sputtering deposition. They were applied in both surface enhanced Raman and surface enhanced infrared absorption spectroscopies using crystal violet as model analyte, showing enhancements up to >10,000-fold in Raman.

Melamine Sponge Functionalized with Urea-Formaldehyde Co-Oligomers as a Sorbent for the Solid-Phase Extraction of Hydrophobic Analytes.

A new procedure for the functionalization of melamine sponge (MeS) with urea-formaldehyde (UF) co-oligomers is put forward. The procedure differs from the typical synthesis of the UF co-polymer, as it employs a base-catalyzed condensation step at certain concentrations of urea and formaldehyde. The produced melamine-urea-formaldehyde (MUF) sponge cubes are hydrophobic, despite the presence of hydrophilic groups in the oligomers. The MUF sponge developed herein is used as a sorbent for the solid-phase extraction of 10 analytes, from 6 different classes (i.e., non-steroidal anti-inflammatory drugs, benzophenones, parabens, phenols, pesticides and musks) and an analytical method is developed for their liquid chromatographic separation and detection. Low limits of quantification (0.03 and 1.0 µg L-1), wide linear ranges and excellent recoveries (92⁻100%) are some of the benefits of the proposed procedure. The study of the synthesis conditions of MUF cubes reveals that by altering them the hydrophilic/lipophilic balance of the MUF cubes can be tuned, hinting towards a strong potential for many other applications.

Carbon Nanohorn Suprastructures on a Paper Support as a Sorptive Phase.

This article describes a method for the modification of paper with single-wall carbon nanohorns (SWCNHs) to form stable suprastructures. The SWCNHs form stable dahlia-like aggregates in solution that are then self-assembled into superior structures if the solvent is evaporated. Dipping paper sections into a dispersion of SWCNHs leads to the formation of a thin film that can be used for microextraction purposes. The coated paper can be easily handled with a simple pipette tip, paving the way for disposable extraction units. As a proof of concept, the extraction of antidepressants from urine and their determination by direct infusion mass spectrometry is studied. Limits of detection (LODs) were 10 ng/L for desipramine, amitriptyline, and mianserin, while the precision, expressed as a relative standard deviation, was 7.2%, 7.3%, and 9.8%, respectively.