Theodoros Chatzimitakos

Magnetic ionic liquid in stirring-assisted drop-breakup microextraction: Proof-of-concept extraction of phenolic endocrine disrupters and acidic pharmaceuticals

The use of magnetic ionic liquids (MILs) is in constant growth due to their switchable properties in the presence of an external magnetic field along with the outstanding properties of ionic liquids. In this study, a novel stirring-assisted drop-breakup microextraction (SADBME) approach is put forward, based on the synthesis and utilization of methyltrioctylammonium tetrachloroferrate (N8 8,8,1[FeCl4]), as a MIL. The proposed procedure complies with the principles of the green chemistry, since it uses low volumes of easily synthesized ILs-based magnetic extracting phases avoiding the use of toxic solvents. To demonstrate its applicability, the proposed microextraction procedure is studied in conjunction with HPLC for the determination of selected phenols and acidic pharmaceuticals in aqueous matrices, taking into account the main experimental variables involved. The results obtained are accurate and highly reproducible, thus making it a good alternative approach for routine analysis of phenols and acidic pharmaceuticals. The low-cost approach is straightforward, environmentally safe and exhibits high enrichment factors and absolute extraction percentages and satisfactory recoveries. To the best of our knowledge, this is the first time that a MIL is used for analytical purposes in a practical, efficient and environmentally friendly drop-breakup microextraction approach for small molecules.

1-Butyl-3-aminopropyl imidazolium-functionalized graphene oxide as a nanoadsorbent for the simultaneous extraction of steroids and β-blockers via dispersive solid-phase microextraction.

In this study, we describe the synthesis of graphene oxide functionalized with the ionic liquid 1-butyl-3-aminopropyl imidazolium chloride and its use as an adsorbent for the dispersive solid-phase microextraction (micro SPE) of four anabolic steroids and six β-blockers from aqueous samples of environmental importance, prior to their HPLC-diode array detector analysis. As the ionic liquid is covalently attached to graphene oxide sheets, it is made possible for it to participate in the dispersive micro SPE procedure. The limits of detection and limits of quantification of the proposed method were found to be in the range of 7-23ng/L and between 20 and 70ng/L, respectively. The linearity was satisfactory, with the determination coefficients to range from 0.9940 to 0.9998 while the within- and between-day relative standard deviation of the method ranged between 3.1 and 7.6% and from 4.0 to 8.5%, respectively. In order to test the applicability of the proposed method in real-life samples, the effluent from a municipal wastewater treatment plant as well as natural water samples from two rivers and a lake were collected and analyzed. After the analysis of samples, the effluent from municipal wastewater treatment plant was fortified with the analytes, at concentrations equal to 2 and 10 times the LOQs. Recoveries were calculated after subtracting the native (no-spike) concentrations of analytes, when needed. All the recoveries were in the range of 87-98%. A comparison study attests to the superiority of the developed nanomaterial over graphene oxide and graphene for the dispersive micro SPE of steroids and β-blockers.

Ion-pair assisted extraction followed by 1H NMR determination of biogenic amines in food and biological matrices

A selective method for the extraction and determination of six biogenic amines (BAs) by NMR is presented. Briefly, BAs are extracted into an organic solvent via the use of an ion pairing agent, followed by a back extraction in D2O in order to acquire the (1)H NMR spectra. The method is studied with respect to the critical experimental parameters and is successfully applied to selected food substrates (dark chocolate, banana, gouda cheese) and biological samples (urine and blood plasma) signifying its potential as an alternative tool for BAs determination. Accurate and precise results are consistently achieved with all matrixes studied. The calculated limits of detection and limits of quantitation were found to be in the ranges 0.05-0.13μg/mL and 0.14-0.38μg/mL, respectively, for biological samples while for food samples they were in the ranges 2.25-6.25μg/g and 6.75-18.7μg/g, respectively.

Octyl‐modified magnetic graphene as a sorbent for the extraction and simultaneous determination of fragrance allergens, musks, and phthalates in aqueous samples by gas chromatography with mass spectrometry

An effective, simple, and low-cost sample preparation method based on dispersive SPE followed by GC with MS is developed for the multianalyte determination of fragrance allergens, musks, and phthalates, at sub-ppb levels. The extraction procedure is based on a novel magnetic graphene sorbent, which is functionalized with octylamine, taking advantage of the functionalizations hydrophobic properties and π-π interactions with the analytes. Two alkyl amines, the octylamine and octadecylamine are studied to introduce alkyl chains in the basal plane of graphene. Magnetic graphene- octadecylamine is proved to be highly hydrophobic to such a degree that is hard to disperse in the bulk aqueous matrixes. Because of this behavior, its extraction efficiency for the target analytes is low. The synthesis and applicability of the magnetic graphene-octylamine as more favored sorbent are optimized in terms of the most determining experimental conditions. The detection and quantification limits, which are calculated based on S/N ratio of 3 and 10, respectively, ranged from 0.29 to 3.2 ng L(-1) and from 0.89 to 9.6, respectively. The dispersive SPE is successfully applied to routine analysis for the determination of the target analytes in samples from municipal treatment plant of Ioannina (Greece), from Pamvotis Lake and baby bathwater. The reproducibility of the spiked biological treatment plant water sample is evaluated and the relative standard deviation values range between 2.1 and 9.4%.

Two of a kind but different: Luminescent carbon quantum dots from Citrus peels for iron and tartrazine sensing and cell imaging

Citrus sinensis and Citrus limon peels were used to synthesize two different kinds of carbon quantum dots (CQDs) via an unsophisticated and inexpensive carbonization procedure. The proposed synthesis is straightforward and adheres to the principles of green chemistry since no organic solvents are used and no toxic by-products are formed, while the residual resources employed facilitate the large scale synthesis of dots. The Citrus sinensis and Citrus limon peels are proved to be excellent precursors for the synthesis of CQDs with highly practical applications. The CQDs display strong excitation-independent, blue fluorescence, which is stable over time. Splendid water dispersibility, photostability and stability over a wide range of pH are some of the main advantages of the CQDs, which enable them to be used as a fluorescent probes. Although many of their features are alike, our findings demonstrate that each kind of the CQDs lend itself to quite distinct analytical applications. The developed fluorescent probes possess high potential for sensitive and selective detection of Fe3+ (Citrus sinensis CQDs) and tartrazine (Citrus limon CQDs) via a quenching mechanism. The decrease in fluorescence intensity is in linear relationship with the concentrations of Fe3+ and tartrazine in the ranges of 0.01-1.0μM and 0.6-23.5μΜ, respectively. Moreover, their low cytotoxicity reinforces their applicability towards cell bioimaging and intracellular detection of Fe3+, which were further studied.

Graphene-functionalized melamine sponges for microextraction of sulfonamides from food and environmental samples

The study describes the functionalization of melamine sponges with graphene and its use as an adsorbent for the microextraction of sulfonamides from food and environmental samples. The graphene-functionalized melamine sponge (GMeS) was prepared by an easy, one-step procedure, which complies with the principles of green chemistry and is proved advantageous over previously described methods. The applicability of the GMeS in extraction procedures was studied and an analytical method for the determination of sulfonamides in milk, eggs and lake water was developed and validated according to SANCO/12571/2013 guideline. The developed method was highly accurate and reproducible, while the limits of quantification were found to be relatively low (0.31-0.91μgkg-1, 0.96-1.32μgkg-1 and 0.10-0.29μgL-1 in the case of milk, eggs and lake water respectively). Furthermore, matrix effects were absent in all cases, since the microextraction procedure serves also as a clean-up step. The low cost of synthesis, the environmentally friendly conditions, the efficiency and high extraction recoveries are some additional advantages of the proposed procedure. To the best of our knowledge, this is the first time that a GMeS is prepared in a straightforward way and used for analytical purposes.

Qualitative Alterations of Bacterial Metabolome after Exposure to Metal Nanoparticles with Bactericidal Properties: A Comprehensive Workflow Based on 1H NMR, UHPLC-HRMS, and Metabolic Databases

Metal nanoparticles (NPs) have proven to be more toxic than bulk analogues of the same chemical composition due to their unique physical properties. The NPs, lately, have drawn the attention of researchers because of their antibacterial and biocidal properties. In an effort to shed light on the mechanism through which the bacteria elimination is achieved and the metabolic changes they undergo, an untargeted metabolomic fingerprint study was carried out on Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) bacteria species. The (1)H NMR spectroscopy, in conjunction with high resolution mass-spectrometry (HRMS) and an unsophisticated data processing workflow were implemented. The combined NMR/HRMS data, supported by an open-access metabolomic database, proved to be efficacious in the process of assigning a putative annotation to a wide range of metabolite signals and is a useful tool to appraise the metabolome alterations, as a consequence of bacterial response to NPs. Interestingly, not all the NPs diminished the intracellular metabolites; bacteria treated with iron NPs produced metabolites not present in the nonexposed bacteria sample, implying the activation of previously inactive metabolic pathways. In contrast, copper and iron-copper NPs reduced the annotated metabolites, alluding to the conclusion that the metabolic pathways (mainly alanine, aspartate, and glutamate metabolism, beta-alanine metabolism, glutathione metabolism, and arginine and proline metabolism) were hindered by the interactions of NPs with the intracellular metabolites.

Melamine sponge decorated with copper sheets as a material with outstanding properties for microextraction of sulfonamides prior to their determination by high-performance liquid chromatography

In this study, the modification/loading of melamine sponge with metallic copper sheets (CuMeS) is discussed. The CuMeS is prepared in a fast, singe-step procedure, where concurrent production of copper oxides is avoided. The as-prepared CuMeS is utilized to develop a sensitive and selective sample preparation procedure to extract sulfonamides (SAs) from milk and water samples. The surface of the resulting CuMeS, after drying is rendered hydrophobic enabling hydrophobic interactions. To the best of our knowledge, this is the first time that the benefits of the high affinity of copper for SAs are reaped for analytical purposes. Due to the high selectivity, the proposed CuMeS-based procedure acts both as extraction and clean-up for the quantitative determination of SAs. The analytical method developed herein, which is based on the extractive potential of CuMeS, has the merits of wide linearity (including concentrations above and below the maximum residue limit of SAs), low limits of quantification (0.025-0.057μgL-1 for lake water and 0.23-1.05μgL-1 for milk samples), high enrichment factors and highly satisfactory recoveries and repeatability. The analytical method is validated according to the Commission Decision 657/2002/EC. Owing to the low cost of CuMeS and the straightforward procedure followed the proposed method can be applied to routine analysis of SAs.

Enhanced magnetic ionic liquid-based dispersive liquid-liquid microextraction of triazines and sulfonamides through a one-pot, pH-modulated approach

In this study, an enhanced variant of magnetic ionic liquid (MIL)-based dispersive liquid-liquid microextraction is put forward. The procedure combines a water insoluble solid support and the [P66614+][Dy(III)(hfacac)4-] MIL, in a one-pot, pH-modulated procedure for microextraction of triazines (TZs) and sulfonamides (SAs). The solid supporting material was mixed with the MIL to overcome difficulties concerning the weighing of MIL and to control the uniform dispersion of the MIL, rendering the whole extraction procedure more reproducible. The pH-modulation during extraction step makes possible the one-pot extraction of SAs and TZs, from a single sample, in 15 min. Overall, the new analytical method developed enjoys the benefits of sensitivity (limits of quantification: 0.034-0.091 μg L-1) and precision (relative standard deviation: 5.2-8.1%), while good recoveries (i.e., 89-101%) were achieved from lake water and effluent from a municipal wastewater treatment plant. Owing to all of the above, the new procedure can be used to determine the concentrations of SAs and TZs at levels below the maximum residue limits.

Carbonization of Human Fingernails: Toward the Sustainable Production of Multifunctional Nitrogen and Sulfur Codoped Carbon Nanodots with Highly Luminescent Probing and Cell Proliferative/Migration Properties

A simple yet effective method is employed to prepare multifunctional fluorescent carbon nanodots (CNDs) from human fingernails. The results demonstrate that the CNDs have excellent optical properties and a quantum yield of 81%, which is attributed to the intrinsic composition of the precursor material itself. The CNDs are used to develop an ultrasensitive fluorescent probe for the detection of hexavalent chromium (limit of detection: 0.3 nM) via a combined inner-filter and static mechanism. Moreover, the toxicity of the CNDs over four epithelial cell lines is assessed. A negligible toxicity is induced on the three of the cell lines, whereas an increase in HEK-293 cell viability is demonstrated, granting cell proliferation properties to the as-synthesized CNDs. According to cell cycle analysis, cell proliferation is achieved by enhancing the transition of cells from the S phase to the G2/M one. Interestingly, CNDs are found to significantly promote cell migration, maybe because of their free-radical scavenging ability, making the CNDs suitable for wound healing applications. In addition, relevant experiments have revealed the blood compatibility of the CNDs. Finally, the CNDs were found suitable for cell imaging applications, and all of the aforementioned merits make it possible for them to be used for extraordinary, more advanced biological applications.