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1.
Int Endod J ; 2023 May 20.
Artículo en Inglés | MEDLINE | ID: mdl-37209012

RESUMEN

AIM: To analyse and compare the root canal microbiome present in root-filled teeth of two different geographical populations, and to study their functional potential using a next-generation sequencing approach. METHODOLOGY: Sequencing data obtained from surgical specimens from previously treated teeth with periapical bone loss from Spain and USA were included in the study. Taxa were classified using SILVA v.138 database. Differences in genera abundances among the 10 most abundant genera were evaluated using a Kruskal-Wallis test. Alpha diversity indices were calculated in mothur. The Shannon and Chao1 indices were used. Analyses of similarity (ANOSIM) to determine differences in community composition were done in mothur, with Bonferroni correction for multiple comparisons. p-Values < .05 were considered statistically significant. Identification of enriched bacteria function prediction in the study groups (KEGG pathways) was carried out by linear discriminant analysis effect size (LEfSe) via Python 3.7.6. RESULTS: A greater alpha-diversity (Shannon and Chao1 indices) was observed from samples obtained in Spain (p = .002). Geography showed no significant effects on community composition via an ANOSIM using Bray-Curtis dissimilarities (R = 0.03, p = .21). Bacterial functional analysis prediction obtained by PICRUSt showed that 5.7% KEGG pathways differed between the Spain and US samples. CONCLUSIONS: The taxonomic assessment alone does not fully capture the microbiome's differences from two different geographical locations. Carbohydrate and amino acid metabolism were enriched in samples from Spain, while samples from USA had a higher representation of pathways related to nitrogen, propanoate metabolism, and secretion systems.

2.
Mikrochim Acta ; 190(2): 60, 2023 01 19.
Artículo en Inglés | MEDLINE | ID: mdl-36656431

RESUMEN

An innovative electrochemical approach based on screen-printed carbon electrodes (SPCEs) modified with graphene quantum dots (GQDs) functionalized with γ-cyclodextrin (γ-CD) and assembled to chitosan (CHI) is designed for the assessment of the total content of fluoroquinolones (FQs) in animal source products. For the design of the bionanocomposite, carboxylated graphene quantum dots synthesized from uric acid as precursor were functionalized with γ-CD using succinic acid as a linker. Physic-chemical and nanostructural characterization of the ensuing nanoparticles was performed by high-resolution transmission scanning microscopy, dynamic light scattering, Z potential measurement, Fourier transformed infrared spectroscopy and X-ray diffraction. Electrochemical properties of assembled bionanocomposite like potential difference, kinetic electronic transfer constant and electroactive area among other parameters were assessed by cyclic voltammetry and differential pulse voltammetry using potassium ferricyanide as redox probe. The oxidation behaviour of four representative quinolones with distinctive structures was studied, obtaining in all cases the same number of involved e- (2) and H+ (2) in their oxidation. These results led us to propose a single and consistent oxidation mechanism for all the checked analytes. The γ-CD-GQDs-CHI/SPCE sensor displayed a boosted electroanalytical performance in terms of linear range (4-250 µM), sensibility (LOD = 1.2 µM) and selectivity. This electrochemical strategy allowed the determination of FQs total amount in complex processed food like broths, bouillon cubes and milkshakes at three concentration levels (150, 75 and 37.5 µM) for both equimolar and different ratio FQs mixtures with recovery values ranging from 90 to 106%.


Asunto(s)
Quitosano , Grafito , Puntos Cuánticos , gamma-Ciclodextrinas , Grafito/química , Puntos Cuánticos/química , Fluoroquinolonas , Técnicas Electroquímicas/métodos , Electrodos
3.
Environ Sci Technol ; 56(19): 13761-13773, 2022 10 04.
Artículo en Inglés | MEDLINE | ID: mdl-36129683

RESUMEN

Domestic wells serve as the primary drinking-water source for rural residents in the northern Appalachian Basin (NAB), despite a limited understanding of contaminant distributions in groundwater sources. We employ a newly collected dataset of 216 water samples from domestic wells in Ohio and West Virginia and an integrated contaminant-source attribution method to describe water quality in the western NAB and characterize key agents influencing contaminant distributions. Our results reveal arsenic and nitrate concentrations above federal maximum contaminant levels (MCLs) in 6.8 and 1.3% of samples and manganese concentrations above health advisory in 7.3% of samples. Recently recharged groundwaters beneath upland regions appear vulnerable to surface-related impacts, including nitrate pollution from agricultural activities and salinization from road salting and domestic sewage sources. Valley regions serve as terminal discharge points for long-residence-time groundwaters, where mixing with basin brines is possible. Arsenic impairments occurred in alkaline groundwaters with major-ion compositions altered by ion exchange and in low-oxygen metal-rich groundwaters. Mixing with as much as 4-10% of mine discharge-like waters was observed near coal mining operations. Our study provides new insights into key agents of groundwater impairment in an understudied region of the NAB and presents an integrated approach for contaminant-source attribution applicable to other regions of intensive resource extraction.


Asunto(s)
Arsénico , Agua Subterránea , Contaminantes Químicos del Agua , Arsénico/análisis , Monitoreo del Ambiente , Manganeso , Nitratos , Compuestos Orgánicos , Oxígeno , Aguas del Alcantarillado , Contaminantes Químicos del Agua/análisis
4.
Hum Reprod ; 36(9): 2514-2528, 2021 08 18.
Artículo en Inglés | MEDLINE | ID: mdl-34333622

RESUMEN

STUDY QUESTION: Does LH protect mouse oocytes and female fertility from alkylating chemotherapy? SUMMARY ANSWER: LH treatment before and during chemotherapy prevents detrimental effects on follicles and reproductive lifespan. WHAT IS KNOWN ALREADY: Chemotherapies can damage the ovary, resulting in premature ovarian failure and reduced fertility in cancer survivors. LH was recently suggested to protect prepubertal mouse follicles from chemotoxic effects of cisplatin treatment. STUDY DESIGN, SIZE, DURATION: This experimental study investigated LH effects on primordial follicles exposed to chemotherapy. Seven-week-old CD-1 female mice were randomly allocated to four experimental groups: Control (n = 13), chemotherapy (ChT, n = 15), ChT+LH-1x (n = 15), and ChT+LH-5x (n = 8). To induce primary ovarian insufficiency (POI), animals in the ChT and ChT+LH groups were intraperitoneally injected with 120 mg/kg of cyclophosphamide and 12 mg/kg of busulfan, while control mice received vehicle. For LH treatment, the ChT+LH-1x and ChT+LH-5x animals received a 1 or 5 IU LH dose, respectively, before chemotherapy, then a second LH injection administered with chemotherapy 24 h later. Then, two animals/group were euthanized at 12 and 24 h to investigate the early ovarian response to LH, while remaining mice were housed for 30 days to evaluate short- and long-term reproductive outcomes. The effects of LH and chemotherapy on growing-stage follicles were analyzed in a parallel experiment. Seven-week-old NOD-SCID female mice were allocated to control (n = 5), ChT (n = 5), and ChT+LH-1x (n = 6) groups. Animals were treated as described above, but maintained for 7 days before reproductive assessment. PARTICIPANTS/MATERIALS, SETTING, METHODS: In the first experiment, follicular damage (phosphorylated H2AX histone (γH2AX) staining and terminal deoxynucleotidyl transferase-mediated dUTP nick-end labeling (TUNEL) assay), apoptotic biomarkers (western blot), and DNA repair pathways (western blot and RT-qPCR) were assessed in ovaries collected at 12 and 24 h to determine early ovarian responses to LH. Thirty days after treatments, remaining mice were stimulated (10 IU of pregnant mare serum gonadotropin (PMSG) and 10 IU of hCG) and mated to collect ovaries, oocytes, and embryos. Histological analysis was performed on ovarian samples to investigate follicular populations and stromal status, and meiotic spindle and chromosome alignment was measured in oocytes by confocal microscopy. Long-term effects were monitored by assessing pregnancy rate and litter size during six consecutive breeding attempts. In the second experiment, mice were stimulated and mated 7 days after treatments and ovaries, oocytes, and embryos were collected. Follicular numbers, follicular protection (DNA damage and apoptosis by H2AX staining and TUNEL assay, respectively), and ovarian stroma were assessed. Oocyte quality was determined by confocal analysis. MAIN RESULTS AND THE ROLE OF CHANCE: LH treatment was sufficient to preserve ovarian reserve and follicular development, avoid atresia, and restore ovulation and meiotic spindle configuration in mature oocytes exposed at the primordial stage. LH improved the cumulative pregnancy rate and litter size in six consecutive breeding rounds, confirming the potential of LH treatment to preserve fertility. This protective effect appeared to be mediated by an enhanced early DNA repair response, via homologous recombination, and generation of anti-apoptotic signals in the ovary a few hours after injury with chemotherapy. This response ameliorated the chemotherapy-induced increase in DNA-damaged oocytes and apoptotic granulosa cells. LH treatment also protected growing follicles from chemotherapy. LH reversed the chemotherapy-induced depletion of primordial and primary follicular subpopulations, reduced oocyte DNA damage and granulosa cell apoptosis, restored mature oocyte cohort size, and improved meiotic spindle properties. LARGE SCALE DATA: N/A. LIMITATIONS, REASONS FOR CAUTION: This was a preliminary study performed with mouse ovarian samples. Therefore, preclinical research with human samples is required for validation. WIDER IMPLICATIONS OF THE FINDINGS: The current study tested if LH could protect the adult mouse ovarian reserve and reproductive lifespan from alkylating chemotherapy. These findings highlight the therapeutic potential of LH as a complementary non-surgical strategy for preserving fertility in female cancer patients. STUDY FUNDING/COMPETING INTEREST(S): This study was supported by grants from the Regional Valencian Ministry of Education (PROMETEO/2018/137), the Spanish Ministry of Science and Innovation (CP19/00141), and the Spanish Ministry of Education, Culture and Sports (FPU16/05264). The authors declare no conflict of interest.


Asunto(s)
Reserva Ovárica , Alquilantes/toxicidad , Animales , Femenino , Humanos , Ratones , Ratones Endogámicos NOD , Ratones SCID , Folículo Ovárico , Embarazo
5.
J Sep Sci ; 44(8): 1652-1661, 2021 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-33527734

RESUMEN

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


Asunto(s)
Carbaril/análisis , Jugos de Frutas y Vegetales/análisis , Grafito/química , Puntos Cuánticos/química , Tamaño de la Partícula , Propiedades de Superficie
6.
Mikrochim Acta ; 188(12): 440, 2021 11 30.
Artículo en Inglés | MEDLINE | ID: mdl-34845524

RESUMEN

Highly reliable separation and determination of various biologically active compounds were achieved using capillary electrophoresis (CE) based on ß-cyclodextrin-functionalized graphene quantum dots (ßcd-GQDs) as the background electrolyte additive. ßcd-GQDs improve the separation efficiency between peaks of all analytes. No addition of surfactants or organic solvents was needed in the running buffer containing ßcd-GQDs. Up to eight consecutive runs were acquired with high precision for the separation of resveratrol, pyridoxine, riboflavin, catechin, ascorbic acid, quercetin, curcumin, and even of several of their structural analogs. Baseline separation was achieved within just 13 min as a result of the effective mobility of the analytes along the capillary owing to the differential interaction with the additive. The proposed analytical method displayed a good resolution of peaks for all species selecting two absorption wavelengths in the diode array detector. Detection limits lower than 0.28 µg mL-1 were found for all compounds and precision values were in the range of 2.1-4.0% in terms of the peak area of the analytes. The usefulness of the GQD-assisted selectivity-enhanced CE method was verified by the analysis of food and dietary supplements. The applicability to such complex matrices and the easy and low-cost GQD preparation open the door for routine analyses of food and natural products. The concept of using such a dual approach (macromolecules and nanotechnology) has been explored to tackle the separation of various bioactive compounds in nutritional supplements and food. Schematic illustration of the electrophoretic separation of the bioactive molecules in the capillary which is filled with the running solution without (top) and with ßcd-GQDs (bottom). The fused silica capillary with negatively ionizable silanol groups at the wall. The voltage is applied at positive polarity at the outlet. R, riboflavin; r, resveratrol; P, pyridoxine; C, catechin; c, curcumin; A, ascorbic acid; Q, quercetin.


Asunto(s)
Ciclodextrinas/metabolismo , Electroforesis Capilar/métodos , Grafito/química , Puntos Cuánticos/química
7.
Nonlinear Dynamics Psychol Life Sci ; 25(1): 1-18, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33308387

RESUMEN

The analysis of handwriting has been used in several contexts. For example, handwriting has shown to be of value in the study of motor symptoms in neurological and mental disorders. In the present work, the geometric analysis of handwriting patterns is proposed as a tool to evaluate motor symptoms in psychotic disorders. Specifically, we have employed the lacunarity, a measure of the heterogeneity of a spatial structure. Forty-two patients with a psychotic disorder and 35 matched healthy controls participated in the study. Participants were asked to copy some patterns with a pen on a white paper. The results showed that lacunarity was significantly higher in handwritten patterns from patients than from controls. In addition, we found higher values of lacunarity in handwritten patterns from patients with severe motor symptoms in comparison with patients with mild or absent motor symptoms. Lacunarity of handwritten patterns was significantly correlated with clinical scores of rigidity. In conclusion we argue that the heterogeneity of handwritten patterns could be used as a simple and objective measure of motor symptoms.


Asunto(s)
Escritura Manual , Trastornos Motores , Trastornos Psicóticos , Humanos , Trastornos Motores/diagnóstico , Trastornos Motores/fisiopatología , Trastornos Motores/psicología , Trastornos Psicóticos/diagnóstico , Trastornos Psicóticos/fisiopatología
8.
Mikrochim Acta ; 187(8): 446, 2020 07 16.
Artículo en Inglés | MEDLINE | ID: mdl-32676763

RESUMEN

Accurate-controlled sized graphene quantum dots (GQDs) have been used as an analytical nanoprobe for detecting curcumin as a function of the photoluminescent quenching upon increasing concentrations of the analyte. Regarding the importance of curcumin nanoparticles in nutraceutical food, the analytical method described herein was also proven for the discrimination of curcumin remaining in free solution from that encapsulated into water-soluble nanomicelles of ca. 11 nm. This recognition is based on the displacement of GQD emission when interacting with both curcumin species. Maximum emission wavelength of GQDs suffers a gradual quenching as well as a red-shifting upon increasing concentrations of free curcumin (from 458 to 490 nm, exciting at 356 nm). On the other hand, in the presence of nanocurcumin, GQD photoluminescent response only displays a quenching effect (458/356 nm). The sensitivity of the described method in terms of detection limits was 0.3 and 0.1 µg mL-1 for curcumin and nanocurcumin, respectively. The applicability of the photoluminescent probe for the quantification and discrimination between both curcumin environments was demonstrated in nutraceutical formulations namely functional food capsules and fortified beverages such as ginger tea. Graphical abstract.


Asunto(s)
Curcumina/análisis , Colorantes Fluorescentes/química , Grafito/química , Nanopartículas/química , Puntos Cuánticos/química , Espectrometría de Fluorescencia/métodos , Curcumina/química , Suplementos Dietéticos/análisis , Zingiber officinale/química , Límite de Detección , Tés de Hierbas/análisis
9.
Electrophoresis ; 40(18-19): 2336-2341, 2019 09.
Artículo en Inglés | MEDLINE | ID: mdl-31116440

RESUMEN

A new CE method with fluorescence detection is reported on the determination of ofloxacin in milk samples using graphene quantum dots (GQDs) for sensitivity enhancement. Injection of GQDs prior the standards/sample is crucial to increase the antibiotic fluorescence response. Clean-up and preconcentration steps allowed for a good linear correlation in a concentration range between 50 and 1000 ng/mL for the ofloxacin, detection and quantification limits being 10.7 and 35.5 ng/mL, respectively. Optimal CE conditions for the seven-fluoroquinolone separation method were assessed in terms of buffer type, pH, and voltage. The selective interaction of GQDs with ofloxacin as model analyte was subsequently studied finding a significant sensitivity improvement; therefore, the analytes would be detected at low concentrations by means of a commercial CE device equipped with a multi-wavelength photoluminescence detector. Due to the different maximum emission wavelengths of the target compounds and the limitations shown by the single-wavelength photoluminescence detector coupled to the CE system, we demonstrated the usefulness of the GQD-assisted sensitivity-enhanced CE method to determine ofloxacin in milk samples. This work opens an interesting possibility of using GQDs in separation techniques combined with photoluminescence detectors for lowering sensitivity levels typically provided by the mere device.


Asunto(s)
Electroforesis Capilar/métodos , Grafito/química , Ofloxacino/análisis , Puntos Cuánticos/química , Espectrometría de Fluorescencia/métodos , Animales , Residuos de Medicamentos/análisis , Residuos de Medicamentos/aislamiento & purificación , Límite de Detección , Modelos Lineales , Leche/química , Ofloxacino/aislamiento & purificación , Reproducibilidad de los Resultados
10.
Anal Bioanal Chem ; 411(20): 5023-5031, 2019 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-31177332

RESUMEN

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.


Asunto(s)
Cosméticos/química , Jugos de Frutas y Vegetales/análisis , Líquidos Iónicos/química , Microextracción en Fase Líquida/métodos , Nanopartículas del Metal/análisis , Plata/química , Artefactos , Estudios de Factibilidad , Límite de Detección , Nanopartículas del Metal/química , Espectrofotometría Ultravioleta/métodos , Resonancia por Plasmón de Superficie
11.
Chaos ; 29(11): 113113, 2019 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-31779359

RESUMEN

In real-world dynamical systems, technical limitations may prevent complete access to their dynamical variables. Such a lack of information may cause significant problems, especially when monitoring or controlling the dynamics of the system is required or when decisions need to be taken based on the dynamical state of the system. Cross-predicting the missing data is, therefore, of considerable interest. Here, we use a machine learning algorithm based on reservoir computing to perform cross-prediction of unknown variables of a chaotic dynamical laser system. In particular, we chose a realistic model of an optically injected single-mode semiconductor laser. While the intensity of the laser can often be acquired easily, measuring the phase of the electric field and the carriers in real time, although possible, requires a more demanding experimental scheme. We demonstrate that the dynamics of two of the three dynamical variables describing the state of the laser can be reconstructed accurately from the knowledge of only one variable, if our algorithm has been trained beforehand with all three variables for a limited period of time. We analyze the accuracy of the method depending on the parameters of the laser system and the reservoir. Finally, we test the robustness of the cross-prediction method when adding noise to the time series. The suggested reservoir computing state observer might be used in many applications, including reconstructing time series, recovering lost time series data and testing data encryption security in cryptography based on chaotic synchronization of lasers.

12.
Biochem Biophys Res Commun ; 500(1): 94-101, 2018 05 27.
Artículo en Inglés | MEDLINE | ID: mdl-28438601

RESUMEN

Mitochondrial adaptation to different physiological conditions highly relies on the regulation of mitochondrial ultrastructure, particularly at the level of cristae compartment. Cristae represent the membrane hub where most of the respiratory complexes embed to account for OXPHOS and energy production in the form of adenosine triphosphate (ATP). Changes in cristae number and shape define the respiratory capacity as well as cell viability. The identification of key regulators of cristae morphology and the understanding of their contribution to the mitochondrial ultrastructure and function have become an strategic goal to understand mitochondrial disorders and to exploit as therapeutic targets. This review summarizes the known regulators of cristae ultrastructure and discusses their contribution and implications for mitochondrial dysfunction.


Asunto(s)
Proteínas del Complejo de Cadena de Transporte de Electrón/metabolismo , Células Eucariotas/metabolismo , Mitocondrias/metabolismo , Proteínas de Transporte de Membrana Mitocondrial/metabolismo , Membranas Mitocondriales/metabolismo , ATPasas de Translocación de Protón Mitocondriales/metabolismo , Adenosina Trifosfato/biosíntesis , Supervivencia Celular , Proteínas del Complejo de Cadena de Transporte de Electrón/genética , Células Eucariotas/ultraestructura , GTP Fosfohidrolasas/genética , GTP Fosfohidrolasas/metabolismo , Regulación de la Expresión Génica , Humanos , Mitocondrias/ultraestructura , Proteínas de Transporte de Membrana Mitocondrial/genética , Membranas Mitocondriales/ultraestructura , ATPasas de Translocación de Protón Mitocondriales/genética , Forma de los Orgánulos/fisiología , Fosforilación Oxidativa , Multimerización de Proteína , Transducción de Señal
13.
Mikrochim Acta ; 185(2): 115, 2018 01 15.
Artículo en Inglés | MEDLINE | ID: mdl-29594454

RESUMEN

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.

14.
Phys Chem Chem Phys ; 19(34): 22670-22677, 2017 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-28812086

RESUMEN

The photoluminescence behaviour of carbon-based nanodots is still debated. Both core and surface structures are involved in the emission mechanism, and the electronic transitions can be modified by external agents such as metal ions or pH, but the general relation between the structure and the optical function is poorly understood. Here, we report a comparative study on the effects of these variables, changing the core structure from crystalline to amorphous, and modifying the surface structure by different passivation procedures. Our results highlight that the emission mechanism of the tunable visible fluorescence is identical for crystalline and amorphous samples, indicating the independence of the emission from the core structure. Furthermore, surface functionalization weakly influences the emission peak position, but has large consequences on their interaction with different metal ions. This suggests the involvement of quasi-degenerate electronic states originating from the high density of different interacting groups on the surface. Finally, we report the presence of an unusual ultraviolet emission band for the amorphous sample, likely involving localized molecular-type chromophores with carboxyl ends. Our findings provide new information on the emission mechanisms of CDs and can be used to engineer sub-types of CDs displaying very similar emission features, but specifically tailored for different sensing applications.

15.
Chaos ; 27(11): 114307, 2017 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-29195304

RESUMEN

We investigate the dynamics of semiconductor lasers subject to time-delayed optical feedback from the perspective of dynamical self-injection locking. Based on the Lang-Kobayashi model, we perform an analysis of the well-known Low Frequency Fluctuations (LFFs) in the frequency-intensity plane. Moreover, we investigate a recently found dynamical regime of fragmented LFFs by means of a locking-range analysis, spectral comparison and precursor pulse identification. We show that LFF dynamics can be explained by dynamical optical injection locking due to the delayed optical feedback. Moreover, the fragmented LFFs occur due to a re-injection locking induced by a particular optical pulse structure in the chaotic feedback dynamics. This is corroborated by experiments with a semiconductor laser experiencing delayed feedback from an optical fiber loop. The dynamical nature of the feedback injection results in an eventual loss, but also possible regaining, of the locking, explaining the recently observed phenomenon of fragmented LFFs.

17.
Anal Chem ; 88(6): 3178-85, 2016 Mar 15.
Artículo en Inglés | MEDLINE | ID: mdl-26870878

RESUMEN

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.

18.
Analyst ; 141(9): 2682-7, 2016 04 25.
Artículo en Inglés | MEDLINE | ID: mdl-26870854

RESUMEN

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".

19.
Phys Rev Lett ; 115(5): 053901, 2015 Jul 31.
Artículo en Inglés | MEDLINE | ID: mdl-26274419

RESUMEN

We perform phase-space tomography of semiconductor laser dynamics by simultaneous experimental determination of optical intensity, frequency, and population inversion with high temporal resolution. We apply this technique to a laser with delayed feedback, serving as prominent example for high-dimensional chaotic dynamics and as model system for fundamental investigations of complex systems. Our approach allows us to explore so far unidentified trajectories in phase space and identify the underlying physical mechanism.

20.
Analyst ; 140(10): 3431-8, 2015 May 21.
Artículo en Inglés | MEDLINE | ID: mdl-25781312

RESUMEN

An innovative and versatile strategy of Solid Phase Microextraction (SPME) is shown by using a new type of ß-cyclodextrin-modified nanocellulose (CD-NC) as a sorbent material. ß-cyclodextrin (used as an inclusion-type selector) was covalently bonded to amine-modified nanocellulose by an amidation reaction. Such novel nanocavities were successfully applied to the selective recognition of danofloxacin (DAN), an antibiotic used to treat animal diseases, via supramolecular host-guest interactions. The SPME methodology, using a platform based on ß-cyclodextrin-"decorated" nanocellulose as a sorbent material, showed a wide linear fluorimetric response against DAN from 8 to 800 µg L(-1) and a detection limit of 2.5 µg L(-1). The specific recognition of DAN has been proven to be highly selective and efficient against this metabolite and other fluoroquinolones. The reusability and the high efficiency in the extraction and preconcentration of DAN in milk samples allow recoveries of 94%.


Asunto(s)
Celulosa/química , Fluorometría/métodos , Fluoroquinolonas/análisis , Leche/química , Nanoestructuras/química , beta-Ciclodextrinas/química , Animales , Tampones (Química) , Bovinos , Fluoroquinolonas/química , Fluoroquinolonas/aislamiento & purificación , Contaminación de Alimentos/análisis , Concentración de Iones de Hidrógeno , Microextracción en Fase Sólida
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