Easy determination of benzophenone and its derivatives in sunscreen samples by direct-immersion solid-phase microextraction and gas chromatography-mass spectrometry.

Benzophenones (BPs) absorb different sun radiation wavelengths, making them effective UVA and UVB filters, widely used in industry. In Europe, sunscreen products contain regulated amounts (6 % w/w) of benzophenone-3 (BP-3), usually combined with other filters like octocrylene. BPs are mutagens in UV radiation, and octocrylene may degrade into BPs, making their monitoring crucial. The present manuscript proposed a novel procedure based on liquid-liquid extraction followed by direct-immersion solid-phase microextraction (LLE-DI-SPME) to isolate and determine 10 BPs in sunscreen lotions with potential results. Parameters like extraction solvent, pH, adsorption, desorption time, stirring, sating effect, and presence of organic solvents were optimized and compared with different SPME fibers, being polyacrylate (PA) fiber the most effective. Detection and quantification were performed by gas chromatography-mass-spectrometry. Analytical parameters as limits of detection were 0.05-0.10 µg kg-1, while the linear range was 0.16 up to 2000 µg kg-1. In terms of recovery, the method ranged from 83 % to 103 %; the precision of the method was good in terms of relative standard deviation (RSD) from 3.2 % to 18.7 % and without a remarkable matrix effect (-15.06-8.45 %). Despite the complexity of the samples and the difficulty posed by the DI-SPME technique, the method proved robust. The proposed method successfully detected 10 BPs in 6 different sunscreen lotions. The total presence of BPs in sunscreens ranged from 165 to 931 mg kg-1, with BP-3 detected in all samples from 4.2 to 740 mg kg-1.

Ion Heating in Advanced Dielectric Barrier Discharge Ion Sources for Ambient Mass Spectrometry.

Dielectric barrier discharges (DBD) are highly versatile plasma sources for forming ions at atmospheric pressure and near ambient temperatures for the rapid, direct, and sensitive analysis of molecules by mass spectrometry (MS). Ambient ion sources should ideally form intact ions, as in-source fragmentation can limit sensitivity, increase spectral complexity, and hinder interpretation. Here, we report the measurement of ion internal energy distributions for the four primary classes of DBD-based ion sources, specifically DBD ionization (DBDI), low-temperature plasma (LTP), flexible microtube plasma (FµTP), and active capillary plasma ionization (ACaPI), in addition to atmospheric pressure chemical ionization (APCI) using para-substituted benzylammonium thermometer ions. Surprisingly, the average extent of energy deposited by the use of ACaPI (90.6 kJ mol-1) was ∼40 kJ mol-1 lower than the other ion sources (DBDI, LTP, FµTP, and APCI; 130.2 to 134.1 kJ mol-1) in their conventional configurations, and slightly higher than electrospray ionization (80.8 kJ mol-1). The internal energy distributions did not depend strongly on the sample introduction conditions (i.e., the use of different solvents and sample vaporization temperatures) or the DBD plasma conditions (i.e., maximum applied voltage). By positioning the DBDI, LTP, and FµTP plasma jets on axis with the capillary entrance to the mass spectrometer, the extent of internal energy deposition could be reduced by up to 20 kJ mol-1, although at the expense of sensitivity. Overall, the use of an active capillary-based DBD can result in substantially less fragmentation of ions with labile bonds than alternate DBD sources and APCI with comparably high sensitivity.

Aroma determination in alcoholic beverages: Green MS-based sample preparation approaches.

Aroma determination in alcoholic beverages has become a hot research topic due to the ongoing effort to obtain quality products, especially in a globalized market. Consumer satisfaction is mainly achieved by balancing several aroma compounds, which are mixtures of numerous volatile molecules enclosed in challenging matrices. Thus, sample preparation strategies for quality control and product development are required. They involve several steps including copious amounts of hazardous solvents or time-consuming procedures. This is bucking the trend of the ever-increasing pressure to reduce the environmental impact of analytical chemistry processes. Hence, the evolution of sample preparation procedures has directed towards miniaturized techniques to decrease or avoid the use of hazardous solvents and integrating sampling, extraction, and enrichment of the targeted analytes in fewer steps. Mass spectrometry coupled to gas or liquid chromatography is particularly well suited to address the complexity of these matrices. This review surveys advancements of green miniaturized techniques coupled to mass spectrometry applied on all categories of odor-active molecules in the most consumed alcoholic beverages: beer, wine, and spirits. The targeted literature consider progresses over the past 20 years.

Liquid chromatography-dielectric barrier discharge ionization mass spectrometry for the analysis of neutral lipids of archaeological interest.

Dielectric barrier discharge ionization has gained attention in the last few years due to its versatility and the vast array of molecules that can be ionized. In this study, we report on the assessment of liquid chromatography coupled to dielectric barrier discharge ionization with mass spectrometry for neutral lipid analysis. A set of different neutral lipid subclasses (triacylglycerides, diacylglycerides, and sterols) were selected for the study. The main species detected from our ionization source were [M-H2 O+H]+ , [M+H]+ or [M-R-H2 O+H]+ , attributed to sterol dehydration, protonation or the fragmentation of an acyl chain accompanied by a water loss of the glycerolipids, respectively. In terms of sensitivity, the dielectric barrier discharge displayed overall improved abundances and comparable or better limits of quantitation than atmospheric pressure chemical ionization for both acylglycerols and sterols. As a case study, different archaeological samples with variable content in neutral lipids, particularly triacylglycerides, were studied. The identification was carried out by combining accurate mass and the tentative formula associated with the exact mass, retention time matching with standards, and additional structural information from in-source fragmentation. The high degree of unsaturation and the presence of sterols revealed the potential vegetal origin of the material stored in the analyzed samples.

Direct Coupling of Bio-SPME to Liquid Electron Ionization-MS/MS via a Modified Microfluidic Open Interface.

We present a modified microfluidic open interface (MOI) for the direct coupling of Bio-SPME to a liquid electron ionization-tandem mass spectrometry (LEI-MS/MS) system as a sensitive technique that can directly analyze biological samples without the need for sample cleanup or chromatographic separations as well as without measurable matrix effects (ME). We selected fentanyl as test compound. The method uses a C18 Bio-SPME fiber by direct immersion (DI) in urine and plasma and the subsequent quick desorption (1 min) in a flow-isolated volume (2.5 µL) filled with an internal standard-acetonitrile solution. The sample is then transferred to an EI source of a triple-quadrupole mass spectrometer via a LEI interface at a nanoscale flow rate. The desorption and analysis procedure requires less than 10 min. Up to 150 samples can be analyzed without observing a performance decline, with fentanyl quantitation at microgram-per-liter levels. The method workflow is extremely dependable, relatively fast, sustainable, and leads to reproducible results that enable the high-throughput screening of various biological samples.

Microfluidic water-assisted trap focusing method for ultra-large volume injection in reversed-phase nano-liquid chromatography coupled to electron ionization tandem-mass spectrometry.

Herein we present an efficient, column-switching method that relies on a custom-made T-union passive diffusion micromixer to assist water dilution and promote trap solute focusing of a high sample volume dissolved in pure organic solvent using a 0.075 mm i.d. nano-LC column. This method allows injecting 20 µL (or higher) of sample volume, speeding up the analysis time, with a 400-fold increase of the limits of quantitation for selected compounds. Five pesticides in different media were used as model compounds, and the analyses were carried out with a triple quadrupole mass spectrometer equipped with a Liquid Electron Ionization (LEI) LC-MS interface working in multiple reaction monitoring (MRM) mode. The system microfluidics were investigated using COMSOL modeling software. Robustness of the entire system was evaluated using a post-extraction addition soil extracts with limits of detection values spanning from 0.10 to 0.45 µg/L. Reproducible results in terms of peak area, peak shape, and retention times were achieved in soil matrix. Repeatability test on peak area variations were lower than 10%.

Solid-phase microextraction coatings based on the metal-organic framework ZIF-8: Ensuring stable and reusable fibers.

Chemical vapor deposition of MOFs (MOF-CVD) has been used to coat solid-phase microextraction (SPME) fibers with ZIF-8, by exposing ZnO layers to the linker vapor (2-methylimidazole). This ZIF-8 coating has been used as a seed layer in a following solvothermal MOF growth step in order to increase the ZIF-8 thickness. The combined MOF-CVD and solvothermal growth of ZIF-8 on the fibers result in a thickness of ~3 µm, with adequate thermal stability, and mechanical integrity when tested with methanol and acetonitrile ultrasonic treatments. The fibers have been evaluated in direct immersion mode using gas chromatography and flame ionization detection (GC-FID), for a group of target analytes including three polycyclic aromatic hydrocarbons (PAHs) and five personal care products (PCPs). The optimized conditions of the SPME-GC-FID methods include low amount of aqueous sample (5 mL), stirring for 45 min at 35 °C, and desorption at 280 °C for 5 min. The method presents limits of detection down to 0.6 µg L-1; intra-day, inter-day and inter-batch relative standard deviation values lower than 16%, 19%, and 23%, respectively; and a lifetime higher than 70 cycles.

Evaluation of a liquid electron ionization liquid chromatography-mass spectrometry interface.

Liquid Electron Ionization (LEI), is an innovative liquid chromatography-mass spectrometry (LC-MS) interface that converts liquid HPLC eluent to the gas-phase in a mass spectrometer equipped with an electron ionization (EI) source. LEI extends the electronic spectra libraries access to liquid chromatography, providing a powerful tool in the untargeted approacssh. Negligible matrix effects allow accurate quantitative information. The purpose of this research was to evaluate the main aspects concerning the interfacing process. These fundamental studies were necessary to understand the mechanism of LEI in details, and improve the interfacing process, especially regarding robustness and sensitivity. Hardware components were installed to prevent analytes precipitation, reduce thermal decomposition of sensitive compounds, and to stabilize the nano-flow delivery with different mobile-phase compositions. Particular attention was devoted to insulating the heated vaporization area from the LC part of the system. Experiments were performed to optimize the interface inner capillary dimensions, and other operative parameters, including temperature, gas and liquid flow rates. Test compounds of environmental interest were selected based on molecular weight, thermal stability, volatility, and polarity. Robustness was evaluated with a set of replicated injections and calibration experiments using a soil matrix as a test sample. MRM detection limits in the low-picogram range were obtained for five pesticides belonging to different classes in a soil sample. High-quality electron ionization mass spectra of a mixture of pesticides were also obtained.

Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants.

Four metal-organic frameworks (MOFs), specifically UiO-66, UiO-66-NH2, UiO-66-NO2, and MIL-53(Al), were synthesized, characterized, and used as sorbents in a dispersive micro-solid phase extraction (D-µSPE) method for the determination of nine pollutants of different nature, including drugs, phenols, polycyclic aromatic hydrocarbons, and personal care products in environmental waters. The D-µSPE method, using these MOFs as sorbents and in combination with high-performance liquid chromatography (HPLC) and diode-array detection (DAD), was optimized. The optimization study pointed out to UiO-66-NO2 as the best MOF to use in the multi-component determination. Furthermore, the utilization of isoreticular MOFs based on UiO-66 with the same topology but different functional groups, and MIL-53(Al) to compare with, allowed us for the first time to evaluate the influence of such functionalization of the ligand with regards to the efficiency of the D-µSPE-HPLC-DAD method. Optimum conditions included: 20 mg of UiO-66-NO2 MOF in 20 mL of the aqueous sample, 3 min of agitation by vortex and 5 min of centrifugation, followed by the use of only 500 µL of acetonitrile as desorption solvent (once the MOF containing analytes was separated), 5 min of vortex and 5 min of centrifugation. The validation of the D-µSPE-HPLC-DAD method showed limits of detection down to 1.5 ng·L-1, average relative recoveries of 107% for a spiked level of 1.50 µg·L-1, and inter-day precision values with relative standard deviations lower than 14%, for the group of pollutants considered.

Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography.

Five metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5(Zn), MIL-53(Al), UiO-64 and MOF-74(Zn) are synthesized, characterized, and utilized in a miniaturized solid-phase extraction method under dispersive mode (D-µSPE) for the determination of six pollutants of different nature, including one polycyclic aromatic hydrocarbon, two hormones, two drugs, and one disinfectant, from environmental waters (tap water and wastewater). A discussion of possible interactions justifying the partitioning of target analytes to the MOFs is included, considering not only the analytes' physicochemical characteristics but also those of MOFs: metal nature, structural environment of MOF pores, pore size and pore aperture widths, among others. MIL-53(Al) is selected for its versatility and high extraction efficiency for the target compounds. The D-µSPE method using MIL-53(Al) is optimized and used in combination with high-performance liquid chromatography (HPLC) with diode array detector (DAD) or liquid-chromatography with time-of-flight mass spectrometric detector (LC-TOF). Under optimum conditions, only 5mg of MIL-53(Al) are required for 10mL of water, with the aid of 5min of vortex and 5min of centrifugation. Elution is accomplished with 200µL of acetonitrile (3 times), and evaporation down to 100µL before LC injection. Detection limits down to 0.040µgL-1 for triclosan and 0.013µgL-1 for atrazine are obtained for the entire method using HPLC-DAD and LC-TOF, respectively. The method, operating at low spiked levels (2µgL-1 for HPLC-DAD and 0.7µgL-1 for LC-TOF), is also characterized for average relative recoveries of 109% and 105%; relative standard deviation values lower than 8.7% and 7.5%; and average extraction efficiencies of 41.2% and 49.1%; using HPLC-DAD and LC-TOF, respectively; while demonstrating adequate analytical performance with complex samples such as wastewaters.

A green metal-organic framework to monitor water contaminants.

The CIM-80 material (aluminum(iii)-mesaconate) has been synthetized in high yield through a novel green procedure involving water and urea as co-reactants. The CIM-80 material exhibits good thermal stability with a working range from RT to 350 °C with a small contraction upon desolvation. Moreover, this material is stable in water at different pH values (1-10) for at least one week, and shows a LC50 value higher than 2 mg mL-1. The new material has been tested in a microextraction methodology for the monitoring of up to 22 water pollutants while presenting little environmental impact: only 20 mg of CIM-80 and 500 µL of acetonitrile are needed per analysis. The analytical performance of the CIM-80 in the microextraction strategy is similar to or even better for several pollutants than that of MIL-53(Al). The average extraction efficiencies range from ∼20% for heavy polycyclic aromatic hydrocarbons to ∼70-100% for the lighter ones. In the case of the emerging contaminants, the average extraction efficiency can reach values up to 70% for triclosan and carbamazepine.

Gold nanoparticles based solid-phase microextraction coatings for determining organochlorine pesticides in aqueous environmental samples.

The use of solid-phase microextraction coatings based on gold nanoparticles was investigated, focusing the attention on the preparation of nanoparticles with nonclassical reduction agents of HAuCl4 such as gallic acid and H2 O2 , rather than the conventional sodium citrate. All nanoparticles were characterized by diode array spectroscopy, whereas novel nanoparticles prepared with gallic acid and H2 O2 were also characterized by microscopic techniques. Solid-phase microextraction coatings were prepared with a layer-by-layer approach. Gallic acid permitted the preparation of stable nanoparticles with milder experimental conditions (1 min, room temperature) and provided the most uniform coatings (thickness ∼3 µm). Seven organochlorine pesticides were determined in different environmental waters using gas chromatography with electron capture detection. Despite the low thickness of the coatings, limits of detection of the entire method down to 0.13 µg/L were obtained. A comparison with the commercial polyacrylate in terms of the partition coefficients of the analytes to the coatings gave logarithm of the partition coefficient values two times higher with gallic acid than polyacrylate (although the commercial fiber is 28 times thicker). Interfiber relative standard deviation values ranged from 8.67 to 21.3%. Optimum fibers also presented an adequate lifetime (>100 extractions).

Are metal-organic frameworks able to provide a new generation of solid-phase microextraction coatings? - A review.

Solid-phase microextraction (SPME) is a powerful technique commonly used in sample preparation for extraction/preconcentration of analytes from a wide variety of samples. Among the trends in improving SPME applications, current investigations are focused on the development of novel coatings able to improve the extraction efficiency, sensitivity, and thermal and mechanical stability, within other properties, of current commercial SPME fibers. Metal-organic frameworks (MOFs) merit to be highlighted as promising sorbent materials in SPME schemes. MOFs are porous hybrid materials composed by metal ions and organic linkers, presenting the highest surface areas known, with ease synthesis and high tuneability, together with adequate chemical and thermal stability. For MOF based-SPME fibers, it results important to pretreat adequately the SPME supports to ensure the correct formation of the MOF onto the fiber or the attachment MOF-support. This, in turn, will increase the final stability of the fiber while generating uniform coatings. This review provides a critical overview of the current state of the use of MOFs as SPME coatings, not only highlighting the advantages of these materials versus commercial SPME coatings in terms of stability, selectivity, and sensitivity; but also insightfully describing the current methods to obtain reproducible MOF-based SPME coatings.

A magnetic-based dispersive micro-solid-phase extraction method using the metal-organic framework HKUST-1 and ultra-high-performance liquid chromatography with fluorescence detection for determining polycyclic aromatic hydrocarbons in waters and fruit tea infusions.

A hybrid material composed by the metal-organic framework (MOF) HKUST-1 and Fe3O4 magnetic nanoparticles (MNPs) has been synthetized in a quite simple manner, characterized, and used in a magnetic-assisted dispersive micro-solid-phase extraction (M-d-µSPE) method in combination with ultra-high-performance liquid chromatography (UHPLC) and fluorescence detection (FD). The application was devoted to the determination of 8 heavy polycyclic aromatic hydrocarbons (PAHs) in different aqueous samples, specifically tap water, wastewaters, and fruit tea infusion samples. The overall M-d-µSPE-UHPLC-FD method was optimized and validated. The method is characterized by: its simplicity in both the preparation of the hybrid material (simple mixing) and the magnetic-assisted approach (∼10min extraction time), the use of low sorbent amounts (20mg of HKUST-1 and 5mg of Fe3O4 MNPs), and the low organic solvent consumption in the overall M-d-µSPE-UHPLC-FD method (1.5mL of acetonitrile in the M-d-µSPE method and 2.8mL of acetonitrile in the UHPLC-FD run). The resulting method has high sensitivity, with LODs down to 0.8ngL(-1); adequate intermediate precision, with relative standard deviation values (RSD) always lower than 6.3% (being the range 5.9-9.0% in tap water for a spiked level of 45ngL(-1), 6.1-14% in wastewaters for a spiked level of 45ngL(-1), and 7.2-17% in fruit tea infusion samples for a spiked level of 45ngL(-1)); and adequate relative recoveries, with average values of 82% in tap water, and 94% and 75% in wastewater and fruit tea infusion samples, respectively, if using the proper matrix-matched calibration.

The metal-organic framework HKUST-1 as efficient sorbent in a vortex-assisted dispersive micro solid-phase extraction of parabens from environmental waters, cosmetic creams, and human urine.

Three metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5, and MIL-53(Al), have been synthetized, characterized, studied and compared in a vortex-assisted dispersive micro-solid-phase extraction (VA-D-µ-SPE) procedure in combination with high-performance liquid chromatography (HPLC) with diode-array detection (DAD) for determining seven parabens in environmental waters (tap water, swimming pool water, and water coming from a spa pool), human urine (from two volunteers), and cosmetic creams (two commercial brands). Experimental parameters, such as nature and amount of MOF, sample volume, nature of elution solvent and its amount, vortex and centrifugation time, among others, were properly optimized. HKUST-1 was the most adequate MOF to work with. Detection limits for the overall method down to 0.1 µgL(-1) for butylparaben (BPB) and benzylparaben (BzPB) were obtained, with determination coefficients (R(2)) higher than 0.9966 for a range of 0.5-147 µgL(-1) (depending on the paraben), average relative recoveries (RR, in %) of 80.3% at the low spiked level (7 µgL(-1)), and relative standard deviation (RSD) values below 10% also at the low spiked level. The strength of the affinity between HKUST-1 and parabens was evaluated, and it ranged from 33.5% for isopropylparaben (iPPB) to 77.0% for isobutylparaben (iBPB). When analyzing complex environmental waters, RR values of 78%, inter-day precision values (as RSD) lower than 15%, and intra-day precision values lower than 7.8% were obtained, despite the observed matrix effect. When analyzing cosmetic creams, parabens were detected, with contents ranging from 0.14 ± 0.01 µgg(-1) for EPB in the healing cream analyzed to 1.12 ± 0.07 mgg(-1) for MPB in the mask cream analyzed, with precision values (RSD) lower than 12% and RR values from 63.7% for propylparaben (PPB) to 121% for iPPB. When analyzing human urine, no parabens were detected but the method could be performed with RSD values lower than 19%. These results show the adequateness of MOFs as sorbents in VA-D-µ-SPE procedures despite sample complexity.