Ionic-liquid-based microextraction method for the determination of silver nanoparticles in consumer products.

A simple method to determine hazardous silver nanoparticles (AgNPs) based on ionic liquid (IL) dispersive liquid-liquid microextraction and back-extraction is described. This approach involves AgNP stabilization using a cationic surfactant followed by extraction from the sample matrix by means of an IL as an extraction phase. Certain ILs have high affinity for metals, and preliminary experiments showed that those ILs consisting of imidazolium cation efficiently extracted AgNPs in the presence of a cationic surfactant and a chelating agent. Afterward, histamine was used as a dispersing agent to promote phase transfer of differently coated AgNPs from the IL in aqueous solution to be subsequently analyzed by UV-visible spectrometry. The analytical procedure allows AgNPs to be recovered from the sample matrix in an aqueous medium, the enrichment factor being up to 4, preserving both AgNP size and AgNP shape as demonstrated by transmission electron microscopy images and the localized surface plasmon resonance band characteristic of each AgNP. The present method exhibited a linear response for AgNPs in the range from 3 to 20 µg/mL, the limit of detection being 0.15 µg/mL. Method efficiency was assessed in spiked orange juice and face cream, yielding recoveries ranging from 75.7% to 96.6%. The method was evaluated in the presence of other nanointerferents (namely, gold nanoparticles). On the basis of diverse electrophoretic mobilities and surface plasmon resonance bands for metal nanoparticles, capillary electrophoresis was used to prove the lack of interaction of the target AgNPs with gold nanoparticles during the whole protocol; thus, interferents do not affect AgNP determination. As a consequence, the analytical approach described has great potential for the analysis of engineered nanosilver in consumer products. Graphical abstract Simple protocol for the determination of silver nanoparticles (AgNPs) based on dispersive liquid-liquid extraction with a specific short alkyl side chain ionic liquid and their quantitative detection with a UV-visible spectrometer. HMIM•PF6 1-hexyl-3-methylimidazolium hexafluorophosphate, NP nanoparticle, SPR surface plasmon resonance.

Bases nanotecnológicas de una "nueva" Nefrología / Nanotechnological foundations of a "new" Nephrology

Después de una contextualización en los marcos genéricos de la nanotecnología y la nanomedicina, se exponen las 2 connotaciones nanotecnológicas de la Nefrología. La potencial faceta negativa de la nanonefrología es el aclaramiento renal de las nanopartículas usadas con fines nanomédicos o ingeridas en los nanoalimentos, cada vez más abundantes. El impacto positivo de la nanotecnología en la Nefrología se centra en el desarrollo de nanodiagnósticos renales para estudios básicos de la función renal, diagnóstico precoz del fallo renal agudo, seguimiento fiable y simple de la enfermedad renal crónica o la mejora de las imágenes de resonancia magnética nuclear. Las nanoterapias renales con fármacos es un tema de importancia que tiene 2 connotaciones: la protección de fármacos y agentes nefrotóxicos (ej. antibióticos, retrovirales, medios de contraste, etc.) y el desarrollo de nuevos medicamentos para enfermedades renales. La nanoteragnosis renal es una línea prometedora poco desarrollada. Se explicita también el impacto de los soportes nanoestructurados en la regeneración tisular renal. El artículo finaliza con un breve análisis de las perspectivas de la nanonefrología

After contextualising the generic frameworks of nanotechnology and nanomedicine, the 2 disciplines are discussed in the field of Nephrology. The potential downside to nanonephrology is the renal clearance of nanoparticles, the use of which is ever-increasing both for nanomedicinal purposes and in nanofoods. The positive impact of nanotechnology in Nephrology is centred on the development of renal nanodiagnostics for basic renal function studies, the early diagnosis of acute kidney injury, reliable and simple follow-up of chronic kidney disease and the improvement of magnetic resonance imaging. Renal drug nanotherapies comprise an important and dual-faceted area: The protection of drugs and nephrotoxic agents (e.g. antibiotics, antiretrovirals, contrast media, etc.) on the one hand, and the development of new kidney disease medications on the other. Renal ‘nanotheranostics’ is a promising but little-studied area. The impact of nanostructured supports on renal tissue regeneration is also discussed. The article concludes with a brief analysis of the various nanonephrology perspectives

Nanotechnological foundations of a «new¼ Nephrology. / Bases nanotecnológicas de una «nueva¼ Nefrología.

After contextualising the generic frameworks of nanotechnology and nanomedicine, the 2disciplines are discussed in the field of Nephrology. The potential downside to nanonephrology is the renal clearance of nanoparticles, the use of which is ever-increasing both for nanomedicinal purposes and in nanofoods. The positive impact of nanotechnology in Nephrology is centred on the development of renal nanodiagnostics for basic renal function studies, the early diagnosis of acute kidney injury, reliable and simple follow-up of chronic kidney disease and the improvement of magnetic resonance imaging. Renal drug nanotherapies comprise an important and dual-faceted area: The protection of drugs and nephrotoxic agents (e.g. antibiotics, antiretrovirals, contrast media, etc.) on the one hand, and the development of new kidney disease medications on the other. Renal 'nanotheranostics' is a promising but little-studied area. The impact of nanostructured supports on renal tissue regeneration is also discussed. The article concludes with a brief analysis of the various nanonephrology perspectives.

Cyclodextrin-modified nanodiamond for the sensitive fluorometric determination of doxorubicin in urine based on its differential affinity towards ß/γ-cyclodextrins.

The manuscript reports on the preparation of ß-cyclodextrin-modified nanodiamonds (ßCD-ND) for the extraction and preconcentration of the fluorescent anticancer drug doxorubicin (DOX) from biological samples. The inclusion of DOX into the cavities of ß- and γ-cyclodextrin (CD) confirms their utility for selective extraction and elution of the drug based on its good fit to the cyclodextrin cavity. Although both larger cyclodextrins (ßCD and γCD) accommodate DOX, DOX clearly prefers the bigger γCD cavities. Dispersive micro solid-phase extraction using ßCD-ND as sorbent enables the inclusion complexation of DOX. The elution of DOX from ßCD-ND cavities occurs with a basic solution of γCD containing 10% acetonitrile owing to the preferential affinity (i.e. optimal fit) of DOX into the larger γCD cavity. DOX is quantified by monitoring its intrinsic fluorescence (exc/em = 475/595 nm). The method can determine DOX in urine with a limit of detection of 18 ng·mL-1. Recoveries (93.2% and 94.0%) and precision (RSDs of 5.9% and 4.7%) at 100 and 400 ng·mL-1 DOX levels in urine are satisfactory. The matrix effect is negligible even when working with undiluted urine samples. Graphical abstract Nanodiamonds functionalized with ß-cyclodextrin (ßCD-ND) were used as sorbent for the determination of nanomolar levels of doxorubicin (DOX). It is based on host:guest interactions ruled by different stabilities of DOX within cyclodextrin (CD) cavity-size: ßCD/γCD.

Analytical Nanoscience and Nanotechnology: Where we are and where we are heading.

The main aim of this paper is to offer an objective and critical overview of the situation and trends in Analytical Nanoscience and Nanotechnology (AN&N), which is an important break point in the evolution of Analytical Chemistry in the XXI century as they were computers and instruments in the second half of XX century. The first part of this overview is devoted to provide a general approach to AN&N by describing the state of the art of this recent topic, being the importance of it also emphasized. Secondly, particular but very relevant trends in this topic are outlined: the analysis of the nanoworld, the so "third way" in AN&N, the growing importance of bioanalysis, the evaluation of both nanosensors and nanosorbents, the impact of AN&N in bioimaging and in nanotoxicological studies, as well as the crucial importance of reliability of the nanotechnological processes and results for solving real analytical problems in the frame of Social Responsibility (SR) of science and technology. Several reflections are included at the end of this overview written as a bird's eye view, which is not an easy task for experts in AN&N.

Usefulness of Analytical Research: Rethinking Analytical R&D&T Strategies.

This Perspective is intended to help foster true innovation in Research & Development & Transfer (R&D&T) in Analytical Chemistry in the form of advances that are primarily useful for analytical purposes rather than solely for publishing. Devising effective means to strengthen the crucial contribution of Analytical Chemistry to progress in Chemistry, Science & Technology, and Society requires carefully examining the present status of our discipline and also identifying internal and external driving forces with a potential adverse impact on its development. The diagnostic process should be followed by administration of an effective therapy and supported by adoption of a theragnostic strategy if Analytical Chemistry is to enjoy a better future.

Fluorescent nanocellulosic hydrogels based on graphene quantum dots for sensing laccase.

A novel low-cost fluorimetric platform based on sulfur, nitrogen-codoped graphene quantum dots immersed into nanocellulosic hydrogels is designed and applied in detecting the laccase enzyme. Although most of methods for detecting laccase are based on their catalytic activity, which is strongly dependent on environmental parameters, we report a sensitive and selective method based on the fluorescence response of hydrogels containing graphene quantum dots (GQDs) acting as luminophore towards laccase. The easily-prepared gel matrix not only improves the fluorescence signal of GQDs by avoiding their self-quenching but also stabilizes their fluorescence signal and improves their sensitivity towards laccase. Noncovalent interactions between the sensor and the analyte are believed to be causing this significant quenching without peak-shifts of GQD fluorescence via energy transfer. The selective extraction of laccase was proved in different shampoos as complex matrices achieving a detection limit of 0.048 U mL-1 and recoveries of 86.2-94.1%. As the unusual properties of nanocellulose and GQDs, the fluorescent sensor is simple, eco-friendly and cost-efficient. This straightforward strategy is able to detect and stabilize laccase, being an added-value for storage and recycling enzymes.

Integrated sampling and analysis unit for the determination of sexual pheromones in environmental air using fabric phase sorptive extraction and headspace-gas chromatography-mass spectrometry.

This article presents a novel unit that integrates for the first time air sampling and preconcentration based on the use of fabric phase sorptive extraction principles. The determination of Tuta absoluta sexual pheromone traces in environmental air has been selected as analytical problem. For this aim, a novel laboratory-built unit made up of commercial brass elements as holder of the sol-gel coated fabric extracting phase has been designed and optimized. The performance of the integrated unit was evaluated analyzing environmental air sampled in tomato crops. The unit can work under sampling and analysis mode which eliminates any need for sorptive phase manipulation prior to instrumental analysis. In the sampling mode, the unit can be connected to a sampling pump to pass the air through the sorptive phase at a controlled flow-rate. In the analysis mode, it is placed in the gas chromatograph autosampler without any instrumental modification. It also diminishes the risk of cross contamination between sampling and analysis. The performance of the new unit has been evaluated using the main components of the sexual pheromone of Tuta absoluta [(3E,8Z,11Z)-tetradecatrien-1-yl acetate and (3E,8Z)-tetradecadien-1-yl acetate] as model analytes. The limits of detection for both compounds resulted to be 1.6µg and 0.8µg, respectively, while the precision (expressed as relative standard deviation) was better than 3.7%. Finally, the unit has been deployed in the field to analyze a number of real life samples, some of them were found positive.

Preparation and evaluation of micro and meso porous silica monoliths with embedded carbon nanoparticles for the extraction of non-polar compounds from waters.

A novel hybrid micro and meso porous silica monolith with embedded carbon nanoparticles (Si-CNPs monolith) was prepared inside a fused silica capillary (3cm in length) and used as a sorbent for solid-phase microextraction. The hybrid monolithic capillary was synthetized by hydrolysis and polycondensation of a mixture of tetraethoxysilane (TEOS), ethanol, and three different carbon nanoparticles such as carboxylated single-walled carbon nanotubes (c-SWCNTs), carboxylated multi-walled carbon nanotubes (c-MWCNTs), and oxidized single-walled carbon nanohorns (o-SWNHs) via a two-step catalytic sol-gel process. Compared with silica monolith without carbon nanoparticles, the developed monolithic capillary column exhibited a higher extraction efficiency towards the analytes which can be ascribed to the presence of the carbon nanoparticles. In this regard, the best performance was achieved for silica monolith with embedded c-MWCNTs. The resulted monolithic capillaries were also characterized by scanning electron microscopy (SEM), elemental analysis and nitrogen intrusion porosimetry. Variables affecting to the preparation of the sorbent phase including three different carbon nanoparticles and extraction parameters were studied in depth using polycyclic aromatic hydrocarbons (PAHs) as target analytes. Gas chromatography-mass spectrometry was selected as instrumental technique. Detection limits range from 0.1 to 0.3µgL-1, and the inter-extraction units precision (expressed as relative standard deviation) is between 5.9 and 14.4%.

Determination of propranolol and carvedilol in urine samples using a magnetic polyamide composite and LC-MS/MS.

AIM: ß-blockers are compounds that bind with adrenoreceptors hindering their interaction with adrenalin and noradrenalin. They are clinically relevant and they are also used in some sport as doping agents. RESULTS: A new method based on the combination of dispersive micro-solid phase extraction and LC-MS/MS has been developed to determine propranolol and carvedilol in urine samples. For this purpose a magnetic-polyamide composite is synthesized and used as sorbent. Working under the optimum conditions, the method provides limits of detection and quantification in the range of 0.1-0.15 µg/l and 0.3-0.5 µg/l, for carvedilol and propranolol, respectively. The precision, expressed as RSD, was better than 9.6% and the relative recoveries varied between 73.7 and 81.3%. CONCLUSION: The methodology is appropriate for the determination of ß-blockers in urine samples at the low microgram per liter range for therapeutic purposes.

Selective extraction of Bactrocera oleae sexual pheromone from olive oil by dispersive magnetic microsolid phase extraction using a molecularly imprinted nanocomposite.

Bactrocera oleae Gmelin, also known as olive fruit fly, is the main olive tree pest. It produces a severe effect not only on the productivity but also on the quality of the olive-related products. In fact, the oil obtained from infected olives has a lower antioxidant power. In addition, an increase of the oil acidity, peroxide index and UV-absorbance can also be observed. 1,7-dioxaspiro-[5,5]-undecane (DSU), is the main component of the sexual pheromone of this pest and may be used as marker of the pest incidence. In this context, the development of new methods able to detect the pheromones in several samples, including agri-food or environmental ones, is interesting. In this work, we synthesized a molecularly imprinted polymer (MIPS) layer over magnetic nanoparticles (Fe3O4@SiO2@MIP) for the selective recognition of DSU. They were prepared using DSU as template and 3-aminopropyltriethoxysilane (APTES) to associate the target analyte on the surface of the magnetic substrate and the later polymerization of ethylene glycol dimethacrylate (EGDMA) in presence of 2,2-azobisisobutyonnitrile (AIBN). The resulting Fe3O4@SiO2@MIP composite was characterized by different techniques. The maximum adsorption capacity of DSU on Fe3O4@SiO2@MIP in hexane was 32mg/g (5.3 times than that obtained for the non-imprinted composite). In addition, Fe3O4@SiO2@MIP showed a short equilibrium time (45min) and potential reusability. The combination of dispersive magnetic microsolid phase extraction and gas chromatography with mass spectrometric detection allows the determination of DSU in real samples at concentrations as low as 10µg/L with precision better than 7.5% (expressed as relative standard deviation). The relative recoveries are in the range between 95 and 99%, which indicates the potential of the methodology. Finally, it has been applied to real olive oil samples being the presence of the pest detected is some of them.

Pharmaceutical crystallization with nanocellulose organogels.

Carboxylated nanocellulose forms organogels at 0.3 wt% in the presence of a cationic surfactant. The resulting gels can be used as novel crystallization media for pharmaceutical solid form control, resulting in isolation a new sulfapyridine solvate, morphology modification and crystallization of an octadecylammonium salt of sulfamethoxazole.

ß-Cyclodextrin functionalized carbon quantum dots as sensors for determination of water-soluble C60 fullerenes in water.

A selective photoluminescence method based on Carbon Quantum Dots (CQDs) functionalized with carboxymethyl-ß-cyclodextrin for the direct determination of water-soluble C60 fullerene has been developed. CQDs were synthesized using a top-down methodology from multiwall carbon nanotubes (MWCNTs) and further functionalized with N-Boc-ethylenediamine to confer monoprotected amine groups onto their surface. Once amine-functionalized CQDs were obtained after deprotection, an amidation reaction with carboxymethyl-ß-cyclodextrin cavitands was achieved and the obtained fluorescent ß-cyclodextrin functionalized Carbon Quantum Dots (cd-CQDs) were investigated for the inclusion complexation of water-soluble C60. Quenching of their fluorescence was observed owing to the non-covalent self-assembly of cd-CQDs and C60, making possible the quantification of C60. A method to determine water-soluble C60 is then proposed with detection and quantification limits of 0.525 and 1.751 µg mL(-1), respectively. The method was validated by determining soluble C60 fullerene in spiked river water. One added value of the paper is the fact that it can be ascribed to the "Third Way in Analytical Nanoscience and Nanotechnology".

One-Step Synthesis and Characterization of N-Doped Carbon Nanodots for Sensing in Organic Media.

Photoluminescent nitrogen-doped carbon nanodots (N-doped CNDs) soluble in organic media are synthesized in a one-step synthesis from a single-source precursor (an amphiphilic polymer), which exhibits a very high quantum yield (QY = 78%), excitation wavelength-dependent emission, and upconversion emission properties. The evolution of N-doped CND formation is studied via ultraviolet-visible and photoluminescence spectroscopy. Their analytical application as an effective sensor for the direct determination of nitroaromatic explosives and byproducts is shown based on their selective response via a fluorescence quenching mechanism. The proposed method is validated in soil samples by directly using the sensor in organic media without any further treatment or additional functionalization, which is an interesting aspect for practical applications.

Quo vadis, analytical chemistry?

This paper presents an open, personal, fresh approach to the future of Analytical Chemistry in the context of the deep changes Science and Technology are anticipated to experience. Its main aim is to challenge young analytical chemists because the future of our scientific discipline is in their hands. A description of not completely accurate overall conceptions of our discipline, both past and present, to be avoided is followed by a flexible, integral definition of Analytical Chemistry and its cornerstones (viz., aims and objectives, quality trade-offs, the third basic analytical reference, the information hierarchy, social responsibility, independent research, transfer of knowledge and technology, interfaces to other scientific-technical disciplines, and well-oriented education). Obsolete paradigms, and more accurate general and specific that can be expected to provide the framework for our discipline in the coming years are described. Finally, the three possible responses of analytical chemists to the proposed changes in our discipline are discussed.

Sulfonated nanocellulose for the efficient dispersive micro solid-phase extraction and determination of silver nanoparticles in food products.

This paper reports a simple approach to Analytical Nanoscience and Nanotechnology (AN&N) that integrates the nanotool, sulfonated nanocellulose (s-NC), and nanoanalyte, silver nanoparticles (AgNPs), in the same analytical process by using an efficient, environmentally friendly dispersive micro solid-phase extraction (D-µSPE) capillary electrophoresis (CE) method with s-NC as sorbent material. Introducing negatively charged sulfate groups onto the surface of cellulose enhances its surface chemistry and enables the extraction and preconcentration of AgNPs of variable diameter (10, 20 and 60nm) and shell composition (citrate and polyvinylpyrrolidone coatings) from complex matrices into a cationic surfactant. In this way, AgNPs of diverse nature were successfully extracted onto the s-NC sorbent and then desorbed into an aqueous solution containing thiotic acid (TA) prior to CE without the need for any labor-intensive cleanup. The ensuing eco-friendly D-µSPE method exhibited a linear response to AgNPs with a limit of detection (LOD) of 20µg/L. Its ability to specifically recognize AgNPs of different sizes was checked in orange juice and mussels, which afforded recoveries of 70.9-108.4%. The repeatability of the method at the limit of quantitation (LOQ) level was 5.6%. Based on the results, sulfonated nanocellulose provides an efficient, cost-effective analytical nanotool for the extraction of AgNPs from food products.

Determination of urinary 5-hydroxyindoleacetic acid by combining Dµ-SPE using carbon coated TiO2 nanotubes and LC-MS/MS.

BACKGROUND: In this article, carbon coated titanium dioxide nanotubes (TiO2-NT@C) are employed for the determination of 5-hydroxyindole-3-acetic acid in urine by LC-MS/MS. RESULTS: All the variables involved in the extraction have been studied and optimized in depth. The method has been analytically characterized on the basis of its linearity, accuracy, sensitivity and precision. The LOD is 155.8 µg/l while the repeatability and the reproducibility, expressed as RSD, are better than 5.42 and 5.25%, respectively. The obtained relative recovery is 115%. CONCLUSION: TiO2-NT@C permit the efficient extraction of 5-hydroxyindole-3-acetic acid from complex biological samples such as urine allowing its sensitive determination by LC-MS/MS.

Fluorescent determination of graphene quantum dots in water samples.

This work presents a simple, fast and sensitive method for the preconcentration and quantification of graphene quantum dots (GQDs) in aqueous samples. GQDs are considered an object of analysis (analyte) not an analytical tool which is the most frequent situation in Analytical Nanoscience and Nanotechnology. This approach is based on the preconcentration of graphene quantum dots on an anion exchange sorbent by solid phase extraction and their subsequent elution prior fluorimetric analysis of the solution containing graphene quantum dots. Parameters of the extraction procedure such as sample volume, type of solvent, sample pH, sample flow rate and elution conditions were investigated in order to achieve extraction efficiency. The limits of detection and quantification were 7.5 µg L(-1) and 25 µg L(-1), respectively. The precision for 200 µg L(-1), expressed as %RSD, was 2.8%. Recoveries percentages between 86.9 and 103.9% were obtained for two different concentration levels. Interferences from other nanoparticles were studied and no significant changes were observed at the concentration levels tested. Consequently, the optimized procedure has great potential to be applied to the determination of graphene quantum dots at trace levels in drinking and environmental waters.

Polymer-nanoparticles composites in bioanalytical sample preparation.

The term composite refers to a class of synthetic materials made from different constituents which exhibit final properties which are different from those of the individual components. Composites have been extensively used in the sample treatment context as sorbents since the resulting solid presents better extraction efficiency. In this realm, polymeric nanocomposites are raised as a powerful alternative. They can be tailored-synthesized for selectivity enhancement or include a magnetic core to simplify the extraction/elution process. This review article points out the relevance of such nanomaterials in bioanalysis. Several synergic combinations of nanoparticles (magnetic, carbon-based) as well as polymeric coatings (conventional, conductive or molecularly imprinted) are commented on. Finally, the potential of biopolymers in the microextraction field is briefly highlighted.

Determination of volatile compounds by GC-IMS to assign the quality of virgin olive oil.

The characterisation of different olive oil categories (extra virgin, virgin and lampante) using Ion Mobility Spectrometry (IMS) was improved by replacing the multicapillary column (MCC) with a capillary column (CC). The data obtained with MCC-IMS and CC-IMS were evaluated, studying both the global and the specific information obtained after the analysis of the volatile fraction of olive oils. A better differentiation of the oil categories was obtained employing CC vs MCC, since the classification percentage obtained with the CC-IMS was 92% as opposed to 87% obtained with MCC-IMS; although in productivity analytical terms, MCC offer a faster analysis than GC. The specific information obtained was also used to build a database, with a view to facilitating the characterization of specific attributes of olive oils. A total of 26 volatile metabolites (aldehydes, ketones, alcohols and esters) were identified. Finally, as revealed by an ANOVA test, some volatiles differed markedly in content among the different categories of oil. The data obtained confirms the potential of IMS as a reliable analytical screening technique, which can be used to assign the correct category to an olive oil sample.