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The purpose of this research is to analyze the different effects of the green intellectual capital (GIC) of wine companies on the fulfillment of the Sustainable Development Goals (SDGs), contributing to academic literature in a remarkable way, since, to the authors' knowledge, there is no previous research that has addressed this relationship. In order to achieve the proposed objective, the research follows a qualitative approach, since the single case study was used. The research results demonstrate how the three dimensions of the GIC (green human capital, green structural capital, green relational capital) act as catalysts for the fulfillment of SDGs 3, 5, 6, 7, 8, 9, 11, 12, 13, 15, and 17.

Development of Quaternary fluvial tufa buildings are often associated with warm and humid phases and are commonly used as climate indicators. El Nogal de El Batán Holocene fluvial tufa buildup, located in Las Parras River valley (Iberian Range, NE Spain), is investigated, following radiocarbon dating, stratigraphic description and palynological analysis. The studied deposit, 8.2 m-thick, is formed of gravels, phytoclast rudstones, calcite- coated stem boundstones and fine carbonate deposits (sands, silts and marls) with peaty horizons and carbonaceous debris. It has been dated within the upper early Holocene (ca. 8400 cal BP) and correlated with the environmental changes reconstructed for the region, identifying at least, three main phases. Pollen results highlight the existence of a conifer landscape, mainy dominated by Pinus nigra/sylvestris type and Juniperus, and locally dense riparian woodland with Corylus, Alnus, Salix, Populus, Celtis, Fraxinus, Tamarix and Rosaceae. Deciduous and evergreen oaks were the main spread regional forests accompanied by many warm-loving taxa like Pistacia, Rhamnus, Arbutus and Olea during the middle Holocene (ca. 8000-5000 cal BP). The transition towards the late Holocene (ca. 4300 cal BP) is evidenced by the rise of herbs and ruderal taxa, and especially the presence of coprophilous fungi, which are linked to the spread of agricultural and grazing practices along the river valley., El desarrollo de edificios tobáceos de origen fluvial se asocia a menudo con fases cálidas y húmedas cuaternarias y son comúnmente empleados como indicadores climáticos. En el presente trabajo se estudia el depósito tobáceo fluvial Holoceno del Nogal de El Batán, situado en el valle del río Las Parras (Cordillera Ibérica, NE España), bajo una perspectiva cronológica, estratigráfica y palinológica. La acumulación tobácea de 8,2 m de espesor, intercala gravas, facies de rudstones de fitoclastos, boundstones de tallos, limos y arenas de composición carbonatada, además de margas, lime mud y niveles turbosos. La acumulación tobácea se emplaza en el Holoceno temprano final (ca. 8400 cal BP) y se correlaciona con los cambios ambientales ocurridos en la región, identificando tres fases principales. Los análisis polínicos señalan un paisaje dominado por coníferas en la base de la secuencia, esencialmente con Pinus nigra/sylvestris tipo y Juniperus, mientras que localmente se desarrolla un bosque ripario donde destacan Corylus, Alnus, Salix, Populus, Celtis, Fraxinus, Tamarix y Rosaceae. En el Holoceno medio (ca. 8000-5000 cal BP) se produce la máxima expansión de las quercíneas, junto con taxones termófilos como Pistacia, Rhamnus, Arbutus y Olea. El incremento de taxones herbáceos y ruderales, y en especial la aparición de esporas coprófilas, marca la expansión agro-pastoril a lo largo del valle fluvial durante el Holoceno tardío (ca. 4300 cal BP).

The aim of this study was to assess the toxicological risks arising from the coexistence of polyethylene glycol coated single-walled carbon nanotubes (SWCNTs-PEG) and a known environmental contaminant: 4-nonylphenol (NP). To this end, in vitro toxicity assays involving the exposure of 3T3-L1 cells (mouse embryonic fibroblasts) to SWCNTs-PEG alone or in combination with NP for 24 or 48 h were performed. Experimental treatments were conducted in both presence (10%) and absence of serum in order to evaluate its influence on the toxicity of SWCNTs-PEG. Although the results provided no unambiguous evidences of synergistic toxicity between SWCNTs-PEG and NP, some specific treatments with mixtures (SWCNTs-PEG + NP) resulted in an unexpected combined toxicity in relation to the individual treatments. Only in those cases the interaction between SWCNTs-PEG and NP could have a synergistic effect on the resulting toxicity. The addition of 10% serum increased the stability of SWCNTs-PEG in the culture medium—possibly by steric repulsions—and reduced the toxicity of nanoparticles as a result. Overall, the serum had a “protective effect” on cells against all treatments: SWCNTs-PEG, NP or their mixtures (SWCNTs-PEG + NP). Raman spectroscopy allowed the intracellular distribution of SWCNTs-PEG to be elucidated.

Microextraction by packed sorbents (MEPS) combined with Surface-enhanced Raman spectroscopy (SERS) was investigated, and applied to the determination of musk ketone (MK) in river water samples. The full MEPS-SERS method includes analyte enrichment by MEPS preconcentration with C18 sorbent followed by SERS detection supported by silver nanoparticles. An eluent drop containing the analyte is deposited directly from the MEPS syringe on a CaF2 glass plate. When the drop has dried, a specific volume of silver nanoparticles solution is added on it before each SERS measurement. Several experimental variables were studied in depth; under the optimum experimental conditions MK can be extracted from a 500 μL sample with recoveries in the range 47-63 %. The limit of detection was 0.02 mg L(-1) and the relative standard deviation 15.2 % (n = 4). Although not investigated in this work, the proposed method might be suitable for in-situ monitoring, because of the portability of the Raman spectrometer used.

The paper proposes a simple and portable approach for the surface enhanced Raman scattering (SERS) spectroscopy in situ determination of carboxylated single walled carbon nanotubes (SWNTs) in river water samples. The method is based on the subsequent microfiltration of a bare gold nanoparticles solution and the water sample containing soluble carbon nanotubes by using a home-made filtration device with a small filtration diameter. An acetate cellulose membrane with a pore size of 0.2 μm first traps gold nanoparticles to form the SERS-active substrate and then concentrates the carbon nanotubes. The measured SERS intensity data were closely fit with a Langmuir isotherm. A portable Raman spectrometer was employed to measure SERS spectra, which enables in situ determination of SWNTs in river waters. The limit of detection was 10 μg L−1. The precision, for a 10 mg L−1 concentration of carbon nanotubes, is 1.19% intra-membrane and 10.5% inter-membrane.

Soft materials resulting from the combination of carbon nanotubes with ionic liquids have aroused analytical interest; thank to their peculiar characteristics. This paper compares the sorption capacity of eight different soft materials obtained from the combination of 1-hexyl 3-methylimidazolium hexafluorophosphate (ionic liquid) with different types of carbon nanotubes. The main characteristics of carbon nanotubes were established by Raman spectroscopy. The results obtained pointed out the critical role of the carbon nanotube types on the stability as well as the sorption capacity of the soft material. By using the adequate carbon nanotube it is possible to improve the LOD 4 times when they are used as sorbent materials for SPE. Working in the recommended conditions the LOD for the analysis of 5 mL of water sample was 5 μg/L of fluoranthene and the precision 5.9%.

Background: The pathophysiology of muscle wasting in the elderly is multifactorial and not fully understood. Objective: To assess the main factors associated with poor muscle mass and strength in an elderly population and to assess differences by sex. Methodology: An observational cross-sectional study of community-dwelling adults aged 75 years and older. Muscle mass was assessed by bio impedance analysis and muscle strength by handheld dynamometer. Main study factors included physical exercise, nutritional status, co-morbidities, anabolic and catabolic hormones (ghrelin, insulinlike growth factor1, testosterone, insulin and cortisol), and inflammatory markers (interleukin-6, C-reactive protein). Other study variables included sociodemographic characteristics, chronic medication, functional capacity, a complete blood count and basic biochemical analyses. Results: A total of 324 persons were recruited: 170 men and 154 women, mean age 80.1 years. Muscle mass was independently associated with age, physical activity, obesity, gastro-duodenal ulcer and interleukin-6 levels in men and with physical activity, obesity, insulin-like growth factor 1 levels and fiber intake in women. In men, muscle strength was independently associated with previous falls, number of medications, dyspepsia and good nutrition and, in women, with age, physical activity, arthritis, diabetes, number of medications and cortisol levels. Conclusions: Physical activity and obesity are the main factors associated with muscle mass in community-dwelling elderly men and women. Sex differences identified in certain biomarkers associated with loss of muscle mass and strength would suggest a more important role for inflammation in men and for anabolic/catabolic imbalances in women.

Durante un año hidrológico se han monitorizado, en Ortigosa de Cameros, la lluvia, la tasa de goteo y sus valores de d13C y Mg/Ca de dos cuevas, junto con los de un río y un manantial próximos. La tasa de goteo concuerda con la lluvia, excepto por un retraso en otoño, debido a que el epikarst se seca en verano. En general, la cueva de La Viña responde más lentamente, debido al mayor espesor de roca que la cubre. Las evoluciones de d13C y Mg/Ca del agua de goteo son paralelas a la de la tasa de goteo, observándose el mismo retraso en otoño, relacionado con la pérdida de agua del epikarst en verano. El mínimo de d13C y Mg/Ca en primavera se corresponde con el máximo de lluvia y la reanudación del goteo tras el invierno, así como al aumento de la actividad biológica en primavera. Los valores de d13C, semejantes en las cuevas, el río y el manantial, reflejan claramente la mayor humedad en primavera, junto con la actividad biológica asociada, mientras que la relación Mg/Ca es más variable y más sensible a la sequía de verano, diferida al otoño. Rainfall on Ortigosa de Cameros (La Rioja), dripping rate and drip water d13C, and Mg/Ca from the caves, as well as d13C and Mg/Ca from a close river and spring, were monitored during a hydrological year. Dripping rate follows local rainfall, excepting for an autumn delay, due to the drying of the epikarst after summer. The general more slowly response of La Viña Cave is likely due to the thicker vadose zone above the cave. d13C and Mg/Ca patterns are consistent with the dripping rate, showing the dripping autumn delay, related to the water decrease in the epikarst during summer and the subsequent decline of the biological activity. The spring d13C and Mg/Ca minimum values correspond to the rainfall maximum and dripping resume after winter, and are linked to the spring biological activity surge. d13C, similar in dripping caves, river and spring, reflects clearly the general spring humidity and the accompanying biological activity, whereas Mg/Ca values are more variable and more sensitive to the summer drought, delayed to autumn.

The combination of ionic liquids with carbon nanotubes has opened a new possibility of ionic liquids as modifiers for carbon nanotubes. Upon being ground into ionic liquids, carbon nanotube bundles are untangled, and the resultant fine bundles form a network structure. This is due to the possible specific interaction between the imidazolium ion component and the p-electronic nanotube surface. The resultant soft material has a high capacity to adsorb/absorb analytes from samples. In this work, the soft material was prepared by mixing 15 mg of carbon nanotubes with 300 μL of IL. The soft material was immobilized on cotton fibers to perform the preconcentration of aromatic compounds such as PAHs from river water samples. The most important fact is the synergic effect between the ionic liquid and the carbon nanotubes which results in a high capacity to preconcentrate analytes. In fact, the sorption capacity of 15 mg of the soft material containing 0.55 mg of MWNT and 11 μl of IL is two times higher than the capacity of 15 mg of MWNT and 3.7 times higher than that of 100 μl IL.

This paper describes the combined use of carbon nanotubes and an ionic liquid directly coupled in-line to commercial CE equipment for sample treatment. The extraction unit operates as a spin column to preconcentrate the analytes. The extraction unit is inserted into the sample vial. The elution is performed in-line, placing the vial on the carrousel of the CE equipment. The joint use of carbon nanotubes and ionic liquids as sorbent is based on the high adsorption capacity of these materials, which makes them highly suitable for microextraction purposes. The LOQ of analytes were within the range of 0.65-0.83 μg/L with a RSD of less than 7%. The values of recovery range between 90 and 112%. The absolute recovery obtained from samples containing 1 μg/L of analytes was 38%.

With the global surge of terrorism and the increased use of bombs in terrorist attacks, national defence and security departments now demand techniques for quick and reliable analysis, in particular, for detection of toxic and explosive substances. One approach is to separate different analytes and matrix material before detection. In this work microliquid chromatography was used to separate two dinitrotoluene (DNT) isomers prior to detection via online UV–Vis spectroscopy. For identification, retention times were compared with reference samples and quantification was done by integration of UV–Vis absorption. Because UV detection is not particularly selective, Raman microscopic analysis was coupled to the liquid chromatography using a flow-through microdispenser. Because DNT is difficult to detect with conventional Raman spectroscopy, the sensitivity was increased via surface-enhanced Raman scattering (SERS) using silver-quantum dots. Different analytical approaches to identify and quantify mixtures of two DNT isomers were evaluated. Good quantitative results were obtained using UV detection after microchromatographic separation (Limit of Detection: 0.11 and 0.06 for 2,4-DNT and 2,6-DNT). Coupling with SERS allowed for more confident differentiation between the highly structurally similar DNT isomers because of the additional spectral information provided by SERS. The application of a partial least squares algorithm also allowed direct SERS detection of DNT mixtures (root mean square error of prediction: 0.82 and 0.79 mg·L–1 for 2,4-DNT and 2,6-DNT), circumventing the time-consuming separation step completely. Copyright © 2012 John Wiley & Sons, Ltd.

In this work the at-line capillary-liquid chromatography-(microdispenser)-surface-enhanced Raman spectroscopy coupling was investigated and applied to the determination of pesticides. The use of a microdispenser combined with the use of a precise and reproducible surface enhanced Raman spectroscopy (SERS) substrate yielded a chromatographic detection system with excellent analytical properties. The microdispenser was coupled to a moving CaF 2 hot (80 °C) plate using a flow-through microdispenser interface to collect the microdrops. Ag-QD nanocomposites, which are highly reproducible thanks to their sponge-shaped structure, were used as substrate with which to measure the SERS spectra in each spot of the plate. The limits of detection ranged from 0.2 to 0.5 ng of pesticide injected (chlortoluron, atrazine, diuron and terbuthylazine) and the precision ranged between 10.2 and 12.5%.

With the development of nanotechnology, there is a need for methodologies to determine and characterize nanomaterials. Electrophoresis has emerged as a useful tool, which has been employed in various formats (e.g., capillary-zone electrophoresis, gel electrophoresis or isotachophoresis) for the size- or shape-based separation of different types of nanoparticle (NP) (e.g., metallic, semi-metallic or carbon). This article reviews the main progress in electrophoresis techniques in order to achieve separation of NPs.

The growing use of nanoparticles in the analytical process in recent years has set a new trend towards the simplification of analytical methods and improvement of their performance. Miniaturization and nanotechnology have allowed new analytical challenges to be met. Hybrid nanoparticles in particular possess exceptional properties enabling further improvement of analytical methods. Despite the continuous developments in their synthesis and characterization, hybrid nanomaterials have scarcely been used in analytical chemistry, however. This paper discusses the analytical potential of hybrid nanoparticles in terms of their special characteristics and properties, and describes their analytical applications.

Magnetic nanoparticles (MNPs) were deposited onto multiwalled carbon nanotubes (MWCNTs) by in situ high-temperature decomposition of the magnetic precursor [iron(III)] and MWCNTs, in ethylene glycol. This one-step synthetic method was applied to commercially available carbon nanotubes (CNTs). Scanning electron micrographs of the resulting products revealed that MNPs decorated the surface of the MWCNTs. The hybrid nanoparticles thus obtained were used for sampling and cleanup in the determination of eight fluoroquinolones (FQs) and two quinolones (Qs) at trace levels by ultra performance liquid chromatography (UPLC). A systematic study of analyte adsorption and desorption was conducted with MNPs and MWCNTs separately. Although both solid phases adsorbed the analytes to some extent, the much higher recoveries were obtained by using the MNP-MWCNT composite which was thus selected to treat plasma samples containing FQs and Qs. Lower accuracies were determined at spiked plasma compared to the standard solution caused by the complexation affinity of the analytes with proteins because high recoveries were observed when deproteinization was performed before treating the sample with the magnetic MWCNTs. The performance characteristics of the optimized method were determined, and the method was applied to the analysis of plasma samples from antibiotic-treated patients. On the basis of the results, the use of an in situ synthesized MWCNT-MNP composite allows the simple, expeditious sampling and treatment of such complex biological samples for the subsequent determination of FQs and Qs present at free form.

Sample treatment is one of the most important stages in the analytical process. In the past few years, there have been many advances in preconcentration techniques and extraction of analytes from complex samples. Well-known sample treatments based on extractions (e.g., solid-phase extraction, liquid-liquid extraction, solid-phase microextraction and pressurized liquid extraction) or membranes (e.g., electromicrodialysis) can be improved by using electric fields. This has led to a new trend in analytical chemistry. We present a comprehensive, illustrated review of sample treatments using electric fields.

We review the state of the art in developing liquid-phase microextraction (LPME) systems, including supported liquid membranes, dialysis membranes and hollow fibers for capillary electrophoresis (CE) determination of analytes in complex matrices. Rather than simply cover an exhaustive compilation of available references, we discuss the analytical potential of LPME-CE combinations based on commercially-available and laboratory-made CE equipment. Although we discuss on-batch, on-capillary and coupled combinations, we especially emphasize the interfaces and the approaches used to couple LPME to CE on-line or in-line.

We report the first observation of selective and specific recognition of chiral l-cysteine (l-Cys)- or d-cysteine (d-Cys)-capped CdSe(ZnS) quantum dots (QDs) with carnitine enantiomers in aqueous solution. The intensity fluorescence of l-Cys-capped QDs decay in the presence of d-carnitine but are not affected by l-carnitine. On the other hand, the fluorescence of d-Cys-capped QDs was only affected by l-carnitine. The applicability of chiral Cys-capped QDs for the analysis of chiral mixtures on enantiomers has been demonstrated for 1:100 mixtures, and the results that were obtained had high precision (

This paper reports for the first time the use of microextraction by packed sorbent in combination with CE. The combined system was used to determine anesthetic drugs in human plasma. A microdialysis fiber was coupled on-line to the microextraction unit in order to distinguish between free and total concentrations of drugs. The system was automated by connecting the microextraction unit to a syringe pump and interfacing it to a computer. The ensuing method allows the determination of 10 microg/L concentrations of free drugs and 1 microg/L concentrations of total drugs from only 200 microL of sample with an RSD of less than 9%.

This paper describes a new and innovative way to integrate microextraction by packed sorbents (MEPS) into commercial CE equipment. The suggested integration allows the automatic sample cleanup and preconcentration requiring only a few microliters of sample and no additional hardware and software. The MEPS was integrated in the outlet region of a commercial CE equipment cartridge in order to provide easy manipulation and exchange. The robustness of the proposed integration was demonstrated by the design and use of a (MEPS)-nonaqueous capillary electrophoresis (NACE)-MS method used to determine fluoroquinolones "FQs" (namely, ofloxacin, marbofloxacin, enrofloxacin, danofloxacin, and difloxacin) in urine. The method allows the analysis of micrograms per liter of FQs to be carried out with only 48 microL of urine sample. The obtained LODs were in the range 6.3-10.6 microg/L. An analysis of spiked urine samples was used to validate the method. Absolute recoveries were in the range of 71-109% while the precision expressed as repetitivity of peak area was lower than 5.9%.

Two electrokinetic methods for the separation of phthalates are proposed. One uses 25 mM sodium borate and 50 mM sodium taurodeoxycholate adjusted to pH 2.8, and the other uses 15 mM ammonium tetraborate, 100 mM SDS, 0.25% w:v hydroxypropylmethyl cellulose (HPMC) and 5% v:v methanol (MeoH) adjusted to pH 9. The BGE containing SDS micelles as the pseudo-stationary phase provided better analytical figures of merit, particularly as regards LOD (0.4-1.4 mg/L) and precision (1.1-6.5%). Adding MeoH and HPMC to the BGE proved essential in order to obtain narrow and symmetric peaks. The proposed method was successfully used to determine phthalates in virgin olive oil. Recoveries from spiked samples ranged from 96 to 106%. The precision obtained in the analysis of real samples, as RSD, was better than 6.8%.

This paper provides an overview of the use of carbon nanoparticles (CNPs) as pseudo-stationary phases (PSPs) in EKC. Specifically, it describes the characteristics and properties of the major types of CNPs used as PSPs in EKC separations, namely C(60) fullerenes, carbon nanotubes and covalently modified carbon nanotubes. Based on such properties, a plausible mechanism for the interactions governing EKC separation with these materials is proposed. Also, the most salient uses of CNPs as PSPs are outlined. Finally, CNPs are compared in terms of performance with other well-established types of nanostructures used to enhance selectivity in EKC over the past decade.

The presence of nanoparticles in the environment can have important implications for both environmental and human health. Nanoscience and nanotechnology are expected to change industrial production and the economy as we know them today. However, nanotechnologies can also be a source of risks. The increasing use of nanoparticles in industrial applications will inevitably lead to the release of such materials into the environment. Accurately assessing the environmental risks posed by nanoparticles requires using effective quantitative analytical methods to determine their mobility, reactivity, ecotoxicity and persistency, many of which have still to be developed. This overview describes some methodological aspects relating to the fields of nanoparticle analysis, nanometrology and analytical chemistry.

A substantial demand currently exists for analytical methods affording the determination of very low concentrations of analytes in complex matrices, such as those of environmental and biological samples, as simply as possible. However, the pretreatment of complex samples, which is unavoidable prior to CE-MS analysis, is usually complicated and time-consuming. In this work, we used voltage-assisted SPE for the first time as an alternative to conventional treatments for preconcentrating and purifying analytes. To this end, we used a simple flow system coupled on-line to CE-MS equipment. The system is quite robust and provides reproducible peak areas (the precision ranges from 2.5 to 3.8%). Also, it provides increased sensitivity affording the determination of trace amounts (nanogram per liter levels) of analytes in only a few milliliters of sample. The proposed system was applied to the determination of members of two compound families (viz. tetracyclines and amines).

We propose a global approach to the different types of output that (bio)chemical measurement processes can provide. We define and classify various types of required and delivered analytical information, including quantitative results, yes/no binary responses, method-defined parameters, arbitrary numbers, total indices and discrete-analyte results, according to three different criteria, namely: • the value of the result; • the method that provides it; and, • its assignation to chemical species. These criteria are mutually related, and a sound knowledge of their specific relationships is crucial with a view to understanding and properly managing chemical information, which is the ultimate outcome of analytical science that is having a growing impact in a variety of scientific, technical and economic fields. We also discuss traceability that is invariably elusive in all types of analytical information and the specific analytical references on which it relies.

Over time, new materials have been used and incorporated in a wide variety of analytical processes. This century, technology has produced novel nanomaterials with unique properties whose use has increased in analytical sciences. Carbon nanostructures are among these new nanomaterials. This overview reports on the use of carbon nanomaterials, mainly fullerenes and carbon nanotubes, as sorbents in the analytical process. After a brief description of their main characteristics, we present their use in the development of selective membranes. Next, we describe their role as sorbent materials and stationary phases in chromatography and provide relevant examples. We also comment on the presence of carbon nanoparticles as components of electrophoretic buffers to improve both resolution and sensitivity of separations. Finally, we briefly describe other applications in which the sorption capabilities of carbon nanostructures play a role.

This paper reviews and discusses the analytical combination of ionic liquids (IL) with CE. On the one hand, it shows CE as a powerful technique to separate impurities from IL as well as being capable to determine physical and chemical properties of IL. On the other hand, it also shows how IL are employed in CE separations to enhance resolution, peak efficiency and peak symmetry. Specifically, IL are used as additives in CZE, NACE, and MEKC and as support coatings of the capillary wall in electrochromatography. The integrity of the IL in the electrophoretic system as well as the roles of the cations and anions of the IL in the electrophoretic separation are also discussed.

La adaptación de la oferta académica de postgrado al Espacio Europeo de Educación Superior en España no ha seguido el desarrollo que la lógica de la nueva ordenación de enseñanzas exigía, dando como resultado una adaptación con evidentes carencias que, aún pasando el umbral de 2010, serán temas de agenda pendiente por resolver en la reforma universitaria. El proceso para la definición del marco normativo ha seguido causes más políticos que estratégicos en el diseño de los nuevos estudios oficiales, dotando al proceso de convergencia elementos de confusión de cara a la comunidad universitaria. El marco para el desarrollo de las competencias de los estudios de postgrado y el sistema de garantía de la calidad en el mismo son dos de los temas que destacan por su deficiente desarrollo, y a los cuáles habrá que hacer frente inexcusablemente. AbstractThe adaptation of the post grade curricula to the European Higher Education Area has not followed a logic way based on the new studies structure approved. The results obtained shows several lacks that, once passed the 2010 goal, will be schedule issues to resolve for the higher education reform. The legislative process has followed a political way instead of a strategic in the new official studies, giving to the university community more confusion elements about the convergence. The frame for the development of the competences in the post grade studies and also the quality assessment system for these studies are two of the themes that arise for its deficient design, that universities and government must face on.

This work describes an efficient in-line extraction-preconcentration unit coupled to the electrophoretic capillary based on a liquid-phase microextraction (LPME) process, which can be directly assembled to the cartridge of the commercial CE equipment. The unit permits analyte extraction, preconcentration and electrophoretic separation to be automatically performed in the commercial CE equipment without the need for additional hardware or software. This new approach was usefully used for the separation and determination of nonsteroidal anti-inflammatory drugs in human urine permitting at least to analyze 30 consecutive real samples. The LODs were lower than 2 microg/L and the reproducibility, expressed as RSD, was 3.1% for the same unit and only 4.8% between different units.

To support the transfer of advances from R + D to routine analytical laboratories, we discuss recent developments in sample preparation for commercial capillary-electrophoresis (CE) equipment. We focus on practical considerations that permit the coupling or the integration of sample-treatment devices into commercial CE equipment. We describe and critically compare at-line and on-line coupling strategies. We also describe integrated in-capillary, in-vial or in-replenishment-system methodologies to perform solid-phase extraction or liquid-phase extraction.

On-line coupling of an automated flow system with a commercially available capillary electrophoresis (CE) system with an electrospray interface (ESI) for mass spectroscopic (MS) detection is described. The peculiarities of CE-ESI-MS interfaces, in which a high electrical field must be applied to the capillary end where the sample is provided by the flow system, introduce significant difficulties for the appropriate work of the entire arrangement. Experimental strategies are proposed for achieving stable conditions for on-line sample pre-treatment, conditioning of the separation capillary, sample injection, as the proper separation. The versatility and robustness of the proposed arrangement is discussed, taken as example the separation of a variety of amines. Connection of the CE system's pressure to the automated flow system enables hydrodynamic introduction of sample with high precision. The developed hyphenated system is of practical relevance as it opens an avenue for the simplification and automation of the whole analytical process required when using powerful CE-ESI-MS equipments.

A new approach to non-aqueous capillary electrophoresis based on the addition of anionic carboxylic surfactants to the basic amphiprotic organic solvent in which form neutral-surfactant aggregates was developed with a view to improving the electrophoretic resolution of charged substances. These aggregates acts as a new pseudostationary phase. The presence of these aggregates allows the effective separation of four tetracyclines with increased selectivity. The efficiency of sodium caprylate, sodium laurate and sodium palmitate as surfactants was examined. The latter two proved more effective than the former as they provided migration times reproducible to within 7% or better in all cases. The additional use of an alcohol allows peak shape to be controlled, which expands the potential of this electrophoretic technique even further. The proposed method was used to determine tetracyclines in water samples. The sensitivity of the determination was improved by using a flow manifold coupled at-line to the capillary electrophoresis system in order to preconcentrate the analytes. The limits of detection thus achieved ranged from 50 to 90 μg/l. Under optimal operating conditions, recoveries ranged from 97 to 104%, and precision from 5.4 to 7.0%.

A capillary electrophoresis-electrospray mass spectrometry (CE-ESI-MS) method for the separation and determination of nine biogenic amines is proposed. Operational variables, such as the voltage, temperature, sheath liquid composition, flow-rate, and MS parameters, were optimized. Samples are injected in the hydrodynamic mode into a 75 cm x 50 microm ID coated capillary and separated by using 25 mM citric acid at pH 2.0. Heptylamine is used as internal standard. The experimental setup includes a flow manifold coupled to the CE system for automatic insertion of samples into the CE vials. The proposed method allows amines to be determined with limits of detection from 0.018 to 0.09 microg x mL(-1) and relative standard deviation (RSD) values from 2.4% to 5.0% (except 6.8% for histamine). The method was successfully used to determine biogenic amines in red and white wines.

A new photometric method for chlorine determination based on the oxidative transformation of iodide to iodine and subsequent extraction in ethyl acetate has been developed. The effects of several chemical variables (pH, ionic strength, and iodide concentration) have been studied. Characteristics of the method were linear range 0–0.6 mg Cl2/L, limit of detection 5 μg Cl2/L, and coefficient of variation 0.6%. The method has been applied to greywater without previous sample treatment.

A method for the determination of three tetracyclines (viz. tetracycline, oxytetracycline and doxycycline) is proposed. The method uses a flow manifold coupled on-line to a capillary electrophoresis (CE) system. The tetracyclines are preconcentrated on a STRATA-X solid-phase minicolumn inserted in the manifold. This provides an average recovery of tetracyclines of 92% from spiked water samples. The proposed method allows the resolution of mixtures of tetracyclines at concentrations ranging from 7 to 45 g l −1 and has a limit of detection of 2 g l −1 . Under optimal conditions, recoveries range from 99 to 106% and the precision is better than 7.5%. Based on the results, the method is a highly efficient choice for the separation and determination of tetracyclines in surface water samples.

A capillary electrophoresis method with UV detection is proposed for the identification and quantitation of bacterial contamination in food samples. The electrophoretic separation relies on the differential mobility of bacteria in the capillary. Electrophoretic resolution is improved by using calcium and myoinositol hexakisphosphate as specific ions that interact with the bacterial surface changing its electrical properties and electrophoretic mobility. The proposed method allows the effective separation of eight different types of bacteria in only 25 min. It was successfully used to detect the presence of bacteria in contaminated food. The precision of the analysis of real spiked samples ranges from 3.3 to 7.0%, and the overall analysis time is 7 h, which is much shorter than the 24-48 h typically required for plate counts. The validity of the method was established by comparison with the standard plate counting method.

Background: Sialolithiasis is a common disease of salivary glands. The etiology of these calculi is little known and their exact mechanism of formation is unknown. Methods: The composition and structure of 21 sialoliths were studied and the composition of the saliva of each corresponding patient was determined (pH, calcium, magnesium, phosphorus, citrate and phytate). Results: Eighteen sialoliths exhibited similar macro and microstructure, being constituted by hydroxyapatite (HAP) and organic matter, normally arranged in a multilayer structure. The three remaining sialoliths were exclusively constituted by organic matter. The salivary Ca of patients with HAP calculi was significantly higher than that found in the saliva of the healthy group. The salivary phytate concentration of patients with HAP calculi was significantly inferior to that found in patients with calculi exclusively formed by organic matter, as well as to that found in saliva of healthy group. Significant differences between the salivary magnesium concentrations of patients with HAP calculi and the control group were also observed. No significant differences between pH and citrate concentrations of the three groups were found. Conclusions: It was concluded that the deficit of crystallization inhibitors such as myo-inositol hexaphosphate (phytate) was also an important etiologic factor implied in the sialolith development.

Two flow methods for the enzymatic determination of pyrophosphate are described that are used to diminish the consumption of reagents. One method is based on the use of an open-close circuit with manual injection using a syringe. The other is a sequential injection method. The analytical features of both methods are: a linear range of 0.4 - 20 mg L(-1), an LOD of 0.38 mg L(-1), and a CV of 2.0% for the sequential injection method, and a linear range of 0.3 - 15 mg L(-1), an LOD of 0.29 mg L(-1), and CV of 2.2% for the open-close circuit method. The methods were applied to the determination of pyrophosphate in urine. The pyrophosphate concentration determined in urine samples varied from 1.26 to 6.67 mg L(-1).

The determination of chlorine with o-tolidine in greywater has been studied, and a batch method and a sequential injection method have been proposed. It was found that the reaction of o-tolidine with chlorine was slower in a greywater matrix. Grey water samples must be filtered before analysis, or alternatively, a blank of sample must be measured. The samples are very unstable, and after 2 h of storage in dark conditions at 4 degrees C the chlorine concentration can diminish. The standard addition method, in some samples gave unsatisfactory results as a consequence of matrix effects. It was concluded that samples with a total organic carbon (TOC) higher than 60 mgCl(-1) can not be accurately analysed using these methods. However, samples with a TOC lower than 60 mgCl(-1) gave 100+/-3% recoveries. The linear range of the methods was 0-3.0 and 0-5.0 mgCl(2)l(-1), and the limit of quantification 0.2 and 0.5 mgCl(2)l(-1), for the batch method and the sequential injection method, respectively. This is the first paper devoted to grey water from the analytical chemistry point of view.

An enzymatic method for the determination of pyrophosphate which has been applied to renal calculi is described. The method involves the preconcentration of pyrophosphate using anionic exchange resin and development of the enzymatic reactions with the pyrophosphate retained on the resin. The study of calculi treatment according to calculi composition is also reported. The pyrophosphate content was dependent on the calculi composition. The highest amount of pyrophosphate was found in hydroxyapatite calculi (of the order of 10 μg/g), struvite and oxalate calculi showed a lower amount (the order was 2.5 and 4.5 μg/g, respectively) and was not detected in uric acid and cystine stones. The method was also successfully applied to the determination of pyrophosphate in human urine. For urinary pyrophosphate determination, a modification based on a clean-up of urine using activated carbon has been proposed. Pyrophosphate in human urine was of the order of 4 mg l−1.

Raman spectroscopy has been employed in analytical sciences for purity determination of carbon nanotube samples based on the consideration of G-/D-band intensity ratios. This work demonstrates the role of aggregation in these feature bands, which, in the case of single walled carbon nanotubes (SWNTs), has proved to be crucial for G-/D-band intensity ratio measurements. We have found variation in the relative intensities of G- and D-bands across a sample of SWNTs without any other treatment, discarding the possible influence of the laser beam or sample focusing. In the case of multiwalled carbon nanotubes (MWNTs), this effect is less notorious. Thus, to achieve a good representativeness of Raman measurements, it is important to consider the sample preparation procedure in order to avoid aggregation, which has an effect over the signals, making difficult the subsequent interpretation of results.

A simple, environmentally friendly, one-pot method to synthesize highly stable bare gold nanoparticles (AuNPs) has been developed. AuNPs have been synthesized from tetrachloroauric acid solution using steel or stainless steel as solid reducing agent, which can be reused. The proposed method yields bare gold nanoparticles at atmospheric pressure and room temperature for potentially producing large quantities. The obtained AuNPs have been characterized by SEM, TEM and AFM finding an average diameter of around 20 nm, polygonal yet nearly spherical shape and a narrow size distribution. The mechanism of reaction has been investigated by UV–vis spectroscopy, ICP-OES and EDX analysis. The obtained dispersed gold nanoparticles proved to be stable if stored a 4 °C for over four months without the addition of a stabilizing agent. Their analytical potential as SERS substrate has been demonstrated and their performance compared with that showed by citrate-coated gold nanoparticles. Thanks to their unique properties, their use as analytical tools provides analytical processes with enhanced selectivity and precision.

Here, a creatinine-modified CdSe/ZnS quantum dots fluorescent probe has been prepared and used for sensing 2,4,6,-trinitrotoluene explosive (TNT). The proposed method is based on the selective interaction between creatinine and nitroaromatic compounds according to the well-known Jaffe reaction. The procedure for the synthesis of creatinine-CdSe/ZnS reagent is very simple and reproducible and its fluorescent characteristics are reported. We found that the presence of TNT quenches the original fluorescence of creatinine-QD according to the Stern-Volmer model. Under the working conditions, the calibration plot of Io/I versus concentration of TNT was linear in the range 10-300μg L(-1) (R(2)=0.996). The mechanism interaction is discussed. The selectivity of fluorescence quenching of creatinine-QD for TNT has been evaluated. Finally, the potential application of the proposed methodology for the determination of TNT in spiked soils is demonstrated. For the analysis of soil samples a solid-liquid extraction is carried out and a four-point standard addition protocol is used to correct the matrix effect. The method, which is simple and rapid, allows the detection of 0.057μg g(-1) of TNT in soil samples. This sensor could be a useful tool for environmental studies, a crucial topic for nanotechnology nowadays.

The exceptional properties of graphene (G) were exploited here to facilitate capillary electrokinetic separations. Two types of commercially available G consisting of nanoparticles containing-one to three and-four to six G sheets, respectively, were compared for this purpose. Both proved effective in separating the arylpropyl derivatives of nonsteroidal anti-inflammatory drugs. The highest resolution and shortest migration times were obtained with G containing high amount of single and double G nanosheets. G affords higher resolution than other types of nanoparticles; stable suspensions can be easily prepared and used as BGE without the need of adding an additional surfactant. This results in a high reproducibility in migration times and stability in background noise. The LOD and LOQ obtained by using G nanoparticles as pseudostationary phases spanned the range 0.29-1.18 mg/L and 0.95-3.95 mg/L, respectively, and the RSD was less than 4.7% in all instances.

The concept of social responsibility provides the ideal framework for raising awareness and arousing reflection on the social and environmental impact of nanoparticles in the range of 1–100 nm generated from research activities in nanoscience and production-related activities in nanotechnology. The model proposed here relates the essential aspects of these concepts by connecting the classical sequence Research–Development–Innovation (R&D&I) to nanoscience and nanotechnology (N&N) and social responsibility (SR). This paper identifies the stakeholders of the process and provides an extensive definition of Social Responsibility and related concepts. In addition, it describes the internal and external connotations of the implementation of SR at research centers and nanotechnological industries, and discusses the social implications of nanoscience and nanotechnology with provision for subjects such as nanoethics, nanotoxicity, and nanomedicine, which have emerged from the widespread use of nanomaterials by today’s society.

The main aim of this work is to develop a one-step method for the characterization of mixtures of single- and multi-walled carbon nanotubes using a simple and inexpensive tool, a portable Raman spectrometer. In order to overcome the problem of heat dissipation in solid samples, the suitability of three surfactants-SDS, Triton X-100 and CTAB-to disperse nanotubes has been evaluated. A systematic study of the wavelength and relative intensity of the D and G bands has been carried out with six samples of multiwalled carbon nanotubes (MWNTs) and one of single-walled carbon nanotubes (SWNTs) dispersed in these surfactants, and this has been compared with solid samples. Finally, the possibility has been demonstrated to identify and (semi)quantify the presence of SWNTs in a mixture containing MWNTs.

Sensing and imaging with fluorescent, plasmonic, and magnetic colloidal nano- and microparticles have improved during the past decade. In this review, we describe the concepts and applications of how these techniques can be used in the multiplexed mode, that is, sensing of several analytes in parallel or imaging of several labels in parallel.

The paper proposes a simple approach for the preconcentration of carboxylated single-walled carbon nanotubes and their determination in river water samples. The method is based on a microliquid–liquid extraction into an ionic liquid (bmim PF6) in the presence of a cationic surfactant (CTAC). 10 μL of the ionic liquid phase are microfiltrated by using a home-made filtration device having a small diameter. The membrane was of cellulose with a pore size of 5 μm. Finally, the carbon nanotubes retained in the membrane are directly analyzed by Raman spectroscopy, which allows their direct characterization and quantification. The limit of detection was 0.050 mg L−1. The precision, for a 1.4 mg L−1 concentration of carbon nanotubes, is 3.2%.

For the first time a soft material formed from coiled carbon nanotubes and 1-hexyl-3-methylimidazolium hexafluorophosphate has been used as sorbent material. The soft material has high stability as well as a high capacity to adsorb analytes. In this work we propose using a natural cotton fiber impregnated with the soft material to miniaturize the system. The system was tested for the analysis of polycyclic aromatic hydrocarbons in spiked river water samples. The absolute recovery ranged between 97.5 and 105.5 %, demonstrating the usefulness of the soft material. The limit of detection ranged from 2.5 to 6.1 μg/L and the precision expressed as the relative standard deviation for the analysis of five consecutive analyses ranged between 2.5 and 5.8 %.

Here, we propose the use of ionic liquid-modified QDs for the combination of ionic liquid-based headspace single drop microextraction technique (IL-HS-SDME) and QD-based fluorimetric detection. In that way, we exploit the advantages of ILs as extractant solvent and the use of QDs as fluorescence detection probe. After in situ generation of volatile trimethylamine (TMA) from fish samples, the analyte was extracted and preconcentrated directly onto a (QD)IL microdrop by HS-SDME. Then, TMA was quantified through the enhancing effect produced on the initial fluorescence of the (QD)IL dispersion. The working conditions for the (QD)IL-HS-SDME procedure were: 20 μL microdrop of (QD)IL exposed for 2 min to the headspace of a 5 mL aqueous sample (0.2 g of fish in 10 M NaOH) placed in a 10 mL vial with stirring and thermostatted at 50-60 °C. For the detection, the microdrop was transferred to a microcuvette with 300 μL of acetonitrile and the fluorescence was recorded (λ(em) = 570 nm, λ(exc) = 400 nm). Under the selected conditions, the analytical response was linear over the range from 0.05 to 0.25 mg L(-1) (R(2) = 0.997) with a detection limit of 0.014 mg L(-1) (0.35 μg TMA per gram of fish) and the relative standard deviation was 3.5% (n = 5). The proposed method was applied to the determination of TMA in hake fish samples with satisfactory results.