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1.
Molecules ; 29(4)2024 Feb 06.
Artigo em Inglês | MEDLINE | ID: mdl-38398499

RESUMO

In this study, the expression and abundance of two candidate chicken (Gallus gallus; gga) microRNAs (miRNAs, miR), gga-miR-21-5p (miR-21) and gga-miR-126-5p (miR-126), have been analyzed in order to identify biomarkers for the traceability and quality of poultry meat. Two breeds of broiler chickens were tested: the most common Ross308 (fast-growing) and the high-quality Ranger Gold (slow-growing). A preliminary analysis of the two miRNAs expressions was conducted across various tissues (liver, lung, spleen, skeletal muscle, and kidney), and the three tissues (lung, spleen, and muscle) with a higher expression were chosen for further analysis. Using quantitative reverse transcription polymerase chain reaction (RT-qPCR), the expression of miRNAs in the three tissues of a total of thirteen animals was determined. The results indicate that miR-126 could be a promising biomarker for the lung tissue in the Ranger Gold (RG) breed (p < 0.01), thus suggesting a potential applicability for tracing hybrids. RG exhibits a significantly higher miR-126 expression in the lung tissue compared to the Ross308 broilers (R308), an indication of greater respiratory capacity and, consequently, a higher oxidative metabolism of the fast-growing hybrid. During sampling, two R308 broilers presented some anomalies, including airsacculitis, hepatic steatosis, and enlarged spleen. The expression of miR-126 and miR-21 was compared in healthy animals and in those presenting anomalies. Chickens with airsacculitis and hepatic steatosis showed an up-regulation of miR-21 and miR-126 in the most commercially valuable tissue, the skeletal muscle or breast (p < 0.05).


Assuntos
MicroRNAs , Animais , MicroRNAs/genética , MicroRNAs/metabolismo , Galinhas/genética , Galinhas/metabolismo , Aves Domésticas , Músculo Esquelético/metabolismo , Inocuidade dos Alimentos
2.
Sensors (Basel) ; 23(5)2023 Mar 01.
Artigo em Inglês | MEDLINE | ID: mdl-36904910

RESUMO

A central concern for large-scale sensor networks and the Internet of Things (IoT) has been battery capacity and how to recharge it. Recent advances have pointed to a technique capable of collecting energy from radio frequency (RF) waves called radio frequency-based energy harvesting (RF-EH) as a solution for low-power networks where cables or even changing the battery is unfeasible. The technical literature addresses energy harvesting techniques as an isolated block by dealing with energy harvesting apart from the other aspects inherent to the transmitter and receiver. Thus, the energy spent on data transmission cannot be used together to charge the battery and decode information. As an extension to them, we propose here a method that enables the information to be recovered from the battery charge by designing a sensor network operating with a semanticfunctional communication framework. Moreover, we propose an event-driven sensor network in which batteries are recharged by applying the technique RF-EH. In order to evaluate system performance, we investigated event signaling, event detection, empty battery, and signaling success rates, as well as the Age of Information (AoI). We discuss how the main parameters are related to the system behavior based on a representative case study, also discussing the battery charge behavior. Numerical results corroborate the effectiveness of the proposed system.

3.
Molecules ; 27(19)2022 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-36234792

RESUMO

The classification of biological neuron types and networks poses challenges to the full understanding of the human brain's organisation and functioning. In this paper, we develop a novel objective classification model of biological neuronal morphology and electrical types and their networks, based on the attributes of neuronal communication using supervised machine learning solutions. This presents advantages compared to the existing approaches in neuroinformatics since the data related to mutual information or delay between neurons obtained from spike trains are more abundant than conventional morphological data. We constructed two open-access computational platforms of various neuronal circuits from the Blue Brain Project realistic models, named Neurpy and Neurgen. Then, we investigated how we could perform network tomography with cortical neuronal circuits for the morphological, topological and electrical classification of neurons. We extracted the simulated data of 10,000 network topology combinations with five layers, 25 morphological type (m-type) cells, and 14 electrical type (e-type) cells. We applied the data to several different classifiers (including Support Vector Machine (SVM), Decision Trees, Random Forest, and Artificial Neural Networks). We achieved accuracies of up to 70%, and the inference of biological network structures using network tomography reached up to 65% of accuracy. Objective classification of biological networks can be achieved with cascaded machine learning methods using neuron communication data. SVM methods seem to perform better amongst used techniques. Our research not only contributes to existing classification efforts but sets the road-map for future usage of brain-machine interfaces towards an in vivo objective classification of neurons as a sensing mechanism of the brain's structure.


Assuntos
Redes Neurais de Computação , Aprendizado de Máquina Supervisionado , Humanos , Aprendizado de Máquina , Neurônios , Máquina de Vetores de Suporte
4.
Molecules ; 27(15)2022 Aug 06.
Artigo em Inglês | MEDLINE | ID: mdl-35956960

RESUMO

The ethnobotany of the Sahrawi people considers various species of plants and crude drugs as food, cooking spices and traditional health remedies. From among these, the fruits of Ammodaucus leucotrichus Coss. & Dur. (Apiaceae), known as Saharan cumin, were chosen for our research. The present paper reports a proximate composition and mineral element analysis of various samples of A. leucotrichus fruits, collected during the balsamic period (full fruiting) from plants grown in Bir Lehlu (Western Sahara) and purchased in a local market (Tindouf). These analyses pointed out interesting nutritional values of the crude drug. Decoction and alcoholic extract, analyzed by HPLC-DAD, evidenced ammolactone-A and R-perillaldehyde as the two main isolated constituents, particularly in the ethanolic extracts (ammolactone-A, market sample: 51.71 ± 0.39 mg/g dry extract; wild sample: 111.60 ± 1.80 mg/g dry extract; R-perillaldehyde, market sample: 145.95 ± 0.35 mg/g dry extract; wild sample: 221.40 ± 0.30 mg/g dry extract). The essential oils, obtained through hydrodistillation, were characterized by GC-MS and evidenced R-perillaldehyde (market sample: 53.21 ± 1.52%; wild sample: 74.01 ± 1.75%) and limonene (market sample: 35.15 ± 1.68%; wild sample: 19.90 ± 1.86%) as the most abundant compounds. The R configuration of perillaldehyde was ascertained and a complete description of the 1H and 13C NMR spectra of ammolactone-A was performed.


Assuntos
Apiaceae , Óleos Voláteis , Apiaceae/química , Frutas/química , Humanos , Nutrientes/análise , Óleos Voláteis/química , Extratos Vegetais/química
5.
Molecules ; 26(21)2021 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-34770777

RESUMO

Cultivation of asparagus (Asparagus officinalis L.; Asp) for food and medicinal use has taken place since the early Roman Empire. Today, Asp represents a worldwide diffuse perennial crop. Lower portions of the spears represent a food industry waste product that can be used to extract bioactive molecules. In this study, aqueous extracts derived from the non-edible portion of the plant (hard stem) were prepared and characterized for chemical content. Furthermore, the biocompatibility and bioactivity of Asp aqueous extracts were assessed in vitro on normal fibroblasts and on breast cancer cell lines. Results showed no interference with fibroblast viability, while a remarkable cytostatic concentration-dependent activity, with significant G1/S cell cycle arrest, was specifically observed in breast cancer cells without apoptosis induction. Asp extracts were also shown to significantly inhibit cell migration. Further analyses showed that Asp extracts were characterized by specific pro-oxidant activity against tumoral cells, and, importantly, that their combination with menadione resulted in a significant enhancement of oxidants production with respect to menadione alone in breast cancer cells but not in normal cells. This selectivity of action on tumoral cells, together with the easiness of their preparation, makes the aqueous Asp extracts very attractive for further investigation in breast cancer research, particularly to investigate their role as possible co-adjuvant agents of clinical drug therapies.


Assuntos
Antineoplásicos Fitogênicos/farmacologia , Asparagus/química , Extratos Vegetais/farmacologia , Animais , Antineoplásicos Fitogênicos/química , Apoptose/efeitos dos fármacos , Biomarcadores , Neoplasias da Mama , Ciclo Celular/efeitos dos fármacos , Linhagem Celular Tumoral , Movimento Celular/efeitos dos fármacos , Cromatografia Líquida , Feminino , Citometria de Fluxo , Humanos , Camundongos , Espectrometria de Massas em Tandem
6.
Photochem Photobiol Sci ; 18(9): 2150-2163, 2019 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-30931455

RESUMO

WO3/BiVO4 films obtained by electrochemical deposition of BiVO4 over mesoporous WO3 were applied to the photoelectrochemical degradation of selected emerging contaminants (ketoprofen and levofloxacine) in aqueous solutions. The WO3/BiVO4 films in this work are characterized by a mesoporous morphology with a maximum photoconversion efficiency >40% extending beyond 500 nm in Na2SO4 electrolytes. Oxygen was found to be the dominant water oxidation product (ca. 90% faradaic yield) and no evidence for the photogeneration of OH radicals was obtained. Nevertheless, both 10 ppm levofloxacine and ketoprofen could be degraded at WO3/BiVO4 junctions upon a few hours of illumination under visible light. However, while levofloxacine degradation intermediates were progressively consumed by further oxidation at the WO3/BiVO4 interface, ketoprofen oxidation byproducts, being stable aromatic species, were found to be persistent in aqueous solution even after 15 hours of solar simulated illumination. This indicates that, due to the lower oxidizing power of photogenerated holes in BiVO4 and a different water oxidation mechanism, the employment of WO3/BiVO4 in photoelectrochemical environmental remediation processes is much less universal than that possible with wider band gap semiconductors such as TiO2 and WO3.

7.
Molecules ; 24(19)2019 Oct 08.
Artigo em Inglês | MEDLINE | ID: mdl-31597364

RESUMO

Asparagus waste represents products of great interest since many compounds with high biological value are located in the lower portion of the spears. The extraction of bioactive compounds from asparagus by-products is therefore crucial for the purpose of adding value to these by-products. In this paper, bioactive peptides from asparagus waste were extracted, digested, purified and identified. In particular, Alcalase® was chosen as the enzyme to use to obtain protein hydrolysate due to its low cost and, consequently, the possibility of implementing the method on a large scale. In order to simplify the peptide extract to reach better identification, the hydrolysate was fractionated by reversed-phase chromatography in 10 fractions. Two tests were carried out for antioxidant activity (ABTS-DPPH) and one for antihypertensive activity (ACE). Fractions with a higher bioactivity score were identified by peptidomics technologies and screened for bioactivity with the use of bioinformatics. For ACE-inhibitor activity, two peptides were synthetized, PDWFLLL and ASQSIWLPGWL, which provided an EC50 value of 1.76 µmol L-1 and 4.02 µmol L-1, respectively. For the antioxidant activity, by DPPH assay, MLLFPM exhibited the lowest EC50 value at 4.14 µmol L-1, followed by FIARNFLLGW and FAPVPFDF with EC50 values of 6.76 µmol L-1 and 10.01 µmol L-1, respectively. A validation of the five identified peptides was also carried out. The obtained results showed that peptides obtained from asparagus by-products are of interest for their biological activity and are suitable for being used as functional ingredients.


Assuntos
Anti-Hipertensivos/química , Antioxidantes/química , Asparagus/química , Peptídeos/química , Extratos Vegetais/química , Proteômica , Sequência de Aminoácidos , Anti-Hipertensivos/isolamento & purificação , Anti-Hipertensivos/farmacologia , Antioxidantes/isolamento & purificação , Extratos Vegetais/isolamento & purificação , Extratos Vegetais/farmacologia , Proteínas de Plantas/química , Proteômica/métodos , Espectrometria de Massas em Tandem
8.
Anal Bioanal Chem ; 410(10): 2457-2465, 2018 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-29340722

RESUMO

About ten years after their introduction to the market (happened in 2006), the so-called second generation superficially porous particles (SPPs) have undoubtedly become the benchmark as well as, very often, the preferred choice for many applications in liquid chromatography (LC), when high efficiency and fast separations are required. This trend has interested practically all kinds of separations, with the only exception of chiral chromatography (at least so far). The technology of production of base SPPs is advanced, relatively simple and widely available. The deep investigation of mass transfer mechanisms under reversed-phase (RP) and normal-phase (NP) conditions for achiral separations has shown the advantages in the use of these particles over their fully porous counterparts. In addition, it has been demonstrated that SPPs are extremely suitable for the preparation of efficient packed beds through slurry packing techniques. However, the research in this field is in continual evolution. In this article, some of the most advanced concepts and modern applications based on the use of SPPs, embracing in particular ultrafast chiral chromatography and the design of SPPs with engineered pore structures or very reduced particle diameter, are revised. We describe modern trends in these fields and focus on those aspect where further innovation and research will be required. Graphical Abstract Word cloud of cutting edge applications of superficially porous particles in liquid chromatography.

9.
Chem Biodivers ; 15(2)2018 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-29282856

RESUMO

New drugs would be beneficial to fight resistant HIV strains, in particular those capable of interfering with essential viral functions other than those targeted by highly active antiretroviral therapy drugs. Despite the central role played by Tat protein in HIV transcription, a search for vegetable extracts able to hamper this important viral function was never carried out. In this work, we evaluated the chemical composition and possible interference of essential oil from Thymus vulgaris, Cananga odorata, Cymbopogon citratus, and Rosmarinus officinalis with the Tat/TAR-RNA interaction and with Tat-induced HIV-1 LTR transcription. GC/MS Analysis demonstrated the biodiversity of herbal species translated into essential oils composed of different blends of terpenes. In all of them, 4 - 6 constituents represent from 81.63% to 95.19% of the total terpenes. Essential oils of Thymus vulgaris, Cymbopogon citratus, and Rosmarinus officinalis were active in interfering with Tat functions, encouraging further studies to identify single terpenes responsible for the antiviral activity. In view of the quite different composition of these essential oils, we concluded that their interference on Tat function depends on specific terpene or a characteristic blend.


Assuntos
Cymbopogon/química , HIV-1/efeitos dos fármacos , Óleos Voláteis/farmacologia , Rosmarinus/química , Thymus (Planta)/química , Produtos do Gene tat do Vírus da Imunodeficiência Humana/antagonistas & inibidores , Proliferação de Células/efeitos dos fármacos , Relação Dose-Resposta a Droga , Ensaios de Seleção de Medicamentos Antitumorais , Células HeLa , Humanos , Conformação Molecular , Óleos Voláteis/química , Óleos Voláteis/isolamento & purificação , Relação Estrutura-Atividade , Células Tumorais Cultivadas , Produtos do Gene tat do Vírus da Imunodeficiência Humana/metabolismo
10.
Molecules ; 23(11)2018 Oct 27.
Artigo em Inglês | MEDLINE | ID: mdl-30373266

RESUMO

Carotenoids are a widespread group of fat-soluble pigments, and their major nutritional importance comes from their pro-vitamin A activity and their antioxidant capacity. In this study, two different pumpkin cultivars (Cucurbita maxima, also named `Delica' and Cucurbita moschata, also known as `Violina') from the southern Po Delta area were investigated in terms of carotenoid content and the influence of food processing on compositional changes and carotenoid bioaccessibility. Quali- and quantitative determination of carotenoids in sample extracts were performed on a C30 column by means of an online coupled HPLC-UV/Vis-APCI-MS/MS technique. The identification of separated compounds was tentatively achieved by merging (i) chromatographic data, (ii) UV-Vis spectra, and (iii) MS/MS fragmentation spectra. The chromatographic profiles for the two cultivars showed qualitative differences. Two major carotenoids were considered for quantification purposes and further investigations: lutein and ß -carotene. Quantification of target carotenoids was performed with external calibration through analytical standards. The concentration of lutein and ß -carotene was higher in C. maxima than in the other variety, C. moschata. Carotenoids are susceptible to degradation (isomerization and oxidation) during food processing (i.e., cooking), and the concentration of lutein and ß -carotene were monitored in oven-cooked and steam-cooked pumpkins. The steam-cooking process was superior in terms of limiting carotenoid loss. A complete functional profile of pumpkins as a source of carotenoids was gained with the evaluation of their in vitro bioaccessibility and their bioavailability after intake during human digestion. Bioaccessibility of lutein and ß -carotene were estimated by an in vitro static digestion model that involved salivary, gastric, and duodenal phases. Bioaccessibility values progressively increased from the salivary to the duodenal phase for both pumpkin varieties and cooking methods. Bioaccessibility of lutein was always lower than ß -carotene for both cultivars and for both cooking methods. Bioaccessibility values for lutein and ß -carotene changed from 1.93% to 2.34% vs. 4.94% and 8.83% in the salivary phase, from 2.7% to 4.63% vs. 7.83% and 15.60% in the gastric phase, and from 10.04% to 13.42% vs. 25.81% and 35.32% in the duodenal phase. For both target compounds, bioaccessibility in the duodenal phase was more than twice the gastric values, and it underlined that the type of cooking did not influence release from the initial matrix.


Assuntos
Carotenoides/análise , Carotenoides/química , Cromatografia Líquida de Alta Pressão , Cucurbita/química , Espectrometria de Fluorescência , Espectrometria de Massas em Tandem , Culinária/métodos , Pigmentos Biológicos/análise , Pigmentos Biológicos/química
11.
Molecules ; 23(11)2018 Nov 03.
Artigo em Inglês | MEDLINE | ID: mdl-30400320

RESUMO

The Vesuvian Piennolo cherry tomato (Lycopersicon esculentum Miller) (PdP) is an old and typical variety grown in the Campania region (Italy). PdP is referred to as a long-storage tomato due to its thick and coriaceous skin that allows long post-harvest storage and it has been granted Protected Designation of Origin (PDO) status since 2009. In this study, the chemical composition, focusing in particular on organic acids, antioxidant molecules and volatile compounds, were investigated in PdP and compared to another typical variety in Campania, the Ciliegino tomato (CIL). Chemical characterization was evaluated for both the CIL and PdP varieties during storage in the same environmental conditions until deterioration of 50% of the fruits; deterioration occurred in PdP after 6 months and in CIL tomatoes after 1 month. The results demonstrated variation in the chemical profiles of both varieties with storage length. Particularly, the PdP variety appears richer in antioxidants compounds (i.e., chlorogenic acids and lycopene) and organic acids (i.e., glutamic and malic acids) than does CIL. Additionally, both varieties display different profiles of volatile bioactive compounds and they are differently influenced by the storage time. The results indicate a typical chemical composition of this long-storage tomato closely linked to the geographic origin area.


Assuntos
Antioxidantes/química , Solanum lycopersicum/química , Frutas/química , Compostos Orgânicos Voláteis/química
12.
Molecules ; 23(10)2018 Oct 20.
Artigo em Inglês | MEDLINE | ID: mdl-30347852

RESUMO

Until less than 10 years ago, chiral separations were carried out with columns packed with 5 or 3 µ m fully porous particles (FPPs). Times to resolve enantiomeric mixtures were easily larger than 30 min, or so. Pushed especially by stringent requirements from medicinal and pharmaceutical industries, during the last years the field of chiral separations by liquid chromatography has undergone what can be defined a "true revolution". With the purpose of developing ever faster and efficient method of separations, indeed, very efficient particle formats, such as superficially porous particles (SPPs) or.


Assuntos
Cromatografia Líquida , Cromatografia com Fluido Supercrítico , Compostos Fitoquímicos/isolamento & purificação , Extratos Vegetais/química , Humanos , Cinética , Compostos Fitoquímicos/química , Compostos Fitoquímicos/uso terapêutico , Extratos Vegetais/uso terapêutico , Porosidade , Estereoisomerismo
13.
Analyst ; 142(4): 555-566, 2017 Feb 14.
Artigo em Inglês | MEDLINE | ID: mdl-28091634

RESUMO

This review focuses on the use of superficially porous particles (SPPs) as chiral stationary phases for ultra-high performance liquid enantioseparations. In contrast to what happened in achiral separations where core-shell particles invaded the market, the introduction of SPPs in chiral liquid chromatography (LC) has been relatively recent. This is due in part to the technical difficulties in the preparation of these phases, and in part to scarce understanding of mass transfer phenomena in chiral chromatography. As a matter of fact, nowadays, the development of superficially porous CSPs is still in its infancy. This paper covers the most recent advancements in the field of core-shell technology applied to chiral separations. We review the kinds of chiral selectors that have been used for the preparation of these phases, by discussing the advantages of chiral SPPs over their fully-porous counterparts for high efficient high throughput enantioseparations. Notwithstanding the apparently obvious advantages in terms of the mass transfer of chiral SPPs, some critical aspects that could impact their development are presented.

14.
Anal Chem ; 87(13): 6854-60, 2015 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-26047527

RESUMO

Terms such as "fluorous affinity" and "fluorophilicity" have been used to describe the unique partition and sorption properties often exhibited by highly fluorinated organic compounds, that is molecules rich in sp(3) carbon-fluorine bonds. In this work, we made use of a highly fluorinated stationary phase and a series of benzene derivatives to study the effect of one single perfluorinated carbon on the chromatographic behavior and adsorption properties of molecules. For this purpose, the adsorption equilibria of α,α,α-trifluorotoluene, toluene, and other alkylbenzenes have been studied by means of nonlinear chromatography in a variety of acetonitrile/water eluents. Our results reveal that one single perfluorinated carbon is already enough to induce a drastic change in the adsorption properties of molecules on the perfluorinated stationary phase. In particular, it has been found that adsorption is monolayer if the perfluoroalkyl carbon is present but that, when this unit is missing, molecules arrange as multilayer stack structures. These findings can contribute to the understanding of molecular mechanisms of fluorous affinity.


Assuntos
Cromatografia de Afinidade/métodos , Flúor/química , Adsorção
15.
Anal Bioanal Chem ; 407(1): 17-21, 2015 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-25358910

RESUMO

Perfluorinated (F-) adsorbents are generally prepared by bonding perfluoro-functionalized silanes to silica gels. They have been employed for a long time essentially as media for solid-phase extraction of F-molecules or F-tagged molecules in organic chemistry and heterogeneous catalysis. More recently, this approach has been extended to proteomics and metabolomics. Owing to their unique physicochemical properties, namely fluorophilicity and proteinophilicity, and a better understanding of some fundamental aspects of their behavior, new applications of F-adsorbents in the field of environmental science and bio-affinity studies can be envisaged. In this article, we revisit the most important features of F-adsorbents by focusing, in particular, on some basic information that has been recently obtained through (nonlinear) chromatographic studies. Finally, we try to envisage new applications and possibilities that F-adsorbents will allow in the near future.


Assuntos
Cromatografia Líquida de Alta Pressão/instrumentação , Compostos de Flúor/química , Extração em Fase Sólida/instrumentação , Adsorção , Animais , Humanos , Proteômica/instrumentação
16.
Anal Chem ; 86(10): 4919-26, 2014 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-24725093

RESUMO

The chromatographic retention mechanisms of two hydrophobic bonded phases, octadecyl ethyl-bridged organic/inorganic (BEH-C18) and straight-chain perfluorohexylpropyl silica (C6F13), have been investigated by using a homologous series of alkyl-benzenes and perfluoroalkyl acids as test compounds in a variety of acetonitrile/water mobile phases and at different temperatures. On both columns, polar compounds exhibited a characteristic U-shape retention behavior in function of acetonitrile amount in the eluent, whereas retention of neutral molecules decreased continuously, following an increase of organic modifier, over the entire mobile phase range. The dependence of perfluoromethylene selectivity upon eluent composition explains the typical reversed-phase behavior (decreasing in retention following an increase of acetonitrile in mobile phase) initially exhibited by perfluoroalkyl acids, but alone it cannot justify their increasing of retention at organic-rich mobile phases (approximately >90% v/v for acetonitrile with the C6F13 column and acetonitrile >80% v/v for the BEH-C18 one). It actually predicts an opposite trend, indicating thus the presence of mixed-mode retention mechanisms. Indeed it was found that, at organic-rich mobile phases, the transfer from the mobile to the stationary phase of the polar moiety of molecules drives retention. This finding has been correlated to the excess adsorption isotherm of acetonitrile/water binary mixtures and thus to the composition of the stationary phase. At organic-rich mobile phases, in fact, stationary phases are characterized by a positive excess of adsorbed water that creates an "environment" suitable to the transfer herein of polar groups.

17.
Chemistry ; 20(26): 8138-48, 2014 Jun 23.
Artigo em Inglês | MEDLINE | ID: mdl-24890919

RESUMO

The structural and chromatographic characterization of two novel fluorinated mesoporous materials prepared by covalent reaction of 3-(pentafluorophenyl)propyldimethylchlorosilane and perfluorohexylethyltrichlorosilane with 2.5 µm fully porous silica particles is reported. The adsorbents were characterized by solid state (29)Si, (13)C, and (19)F NMR spectroscopy, low-temperature nitrogen adsorption, elemental analysis (C and F), and various chromatographic measurements, including the determination of adsorption isotherms. The structure and abundance of the different organic surface species, as well as the different silanol types, were determined. In particular, the degree of so-called horizontal polymerization, that is, Si-O-Si bridging parallel to the silica surface due to the reaction, under "quasi-dry" conditions, of trifunctional silanizing agents with the silica surface was quantified. Significant agreement was found between the information provided by solid-state NMR, elemental analysis, and excess isotherms regarding the amount of surface residual silanol groups, on the one hand, and the degree of surface functionalization, on the other. Finally, the kinetic performance of the fluorinated materials as separation media for applications in near-ultrahigh-performance liquid chromatography was evaluated. At reduced velocities of about 5.5 (ca. 600 bar backpressure at room temperature) with 3 mm diameter columns and toluene as test compound, reduced plate heights on the order of 2 were obtained on columns of both adsorbents.


Assuntos
Cromatografia Líquida/métodos , Espectroscopia de Ressonância Magnética/métodos , Dióxido de Silício/química , Adsorção , Halogenação
18.
Anal Chem ; 85(1): 19-22, 2013 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-23214970

RESUMO

The intrusion of water into the pores of hydrophobic materials is investigated by means of a dynamic flow system. The porous hydrophobic material is packed into a stainless steel chromatographic column, and water is flushed through by means of a high-pressure pump. Back-pressure control is provided by flow restrictors after the column. The applied pressure forces the water to penetrate the pores of the hydrophobic material. The water volume contained in the column, as a function of the applied pressure, reflects the degree of wetting of the solid by water. This volume is determined by measuring, through a mass spectrometer, the retention time of deuterium oxide injected in the column. The method is applied with alkyl-modified (n-octyl and n-octadecyl) and perfluorinated (alkyl and phenyl) silica surfaces. The information gathered by this study may contribute to explain the retention behavior of reversed-phase chromatographic columns when used under highly aqueous mobile-phase conditions.


Assuntos
Cromatografia Líquida de Alta Pressão/métodos , Água/química , Cromatografia Líquida de Alta Pressão/instrumentação , Halogenação , Interações Hidrofóbicas e Hidrofílicas , Espectrometria de Massas , Porosidade , Pressão , Dióxido de Silício/química , Propriedades de Superfície
19.
Chemistry ; 19(24): 7802-8, 2013 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-23589216

RESUMO

The heterogeneous proline-catalyzed aldol reaction was investigated under continuous-flow conditions by means of a packed-bed microreactor. Reaction-progress kinetic analysis (RPKA) was used in combination with nonlinear chromatography for the interpretation, under synthetically relevant conditions, of important mechanistic aspects of the heterogeneous catalytic process at a molecular level. The information gathered by RPKA and nonlinear chromatography proved to be highly complementary and allowed for the assessment of optimal operating variables. In particular, the determination of the rate-determining step was pivotal for optimizing the feed composition. On the other hand, the competitive product inhibition was responsible for the unexpected decrease in the reaction yield following an apparently obvious variation in the feed composition. The study was facilitated by a suitable 2D instrumental arrangement for simultaneous flow reaction and online flow-injection analysis.


Assuntos
Aldeídos/química , Modelos Químicos , Prolina/química , Catálise , Cromatografia , Cicloexanonas/análise , Análise de Injeção de Fluxo , Cinética , Estrutura Molecular , Termodinâmica
20.
J Sep Sci ; 36(9-10): 1604-11, 2013 May.
Artigo em Inglês | MEDLINE | ID: mdl-23436460

RESUMO

The adsorption behaviour of three commonly used drugs, namely ketoprofen, hydrochlorothiazide and atenolol, from diluted aqueous solutions on beta zeolites with different SiO2/Al2O3 ratio (i.e. 25, 38 and 360) was investigated by changing the ionic strength and the pH, before and after thermal treatment of the adsorbents. The selective adsorption of drugs was confirmed by thermogravimetry and X-ray diffraction. The adsorption capacity of beta zeolites was strongly dependent on both the solution pH and the alumina content of the adsorbent. Such a remarkable difference was interpreted as a function of the interactions between drug molecules and zeolite surface functional groups. Atenolol was readily adsorbed on the less hydrophobic zeolite, under pH conditions in which electrostatic interactions were predominant. On the other hand, ketoprofen adsorption was mainly driven by hydrophobic interactions. For undissociated molecules the adsorption capability increased with the increase of hydrophobicity.


Assuntos
Atenolol/química , Hidroclorotiazida/química , Cetoprofeno/química , Zeolitas/química , Adsorção , Interações Hidrofóbicas e Hidrofílicas , Concentração Osmolar , Termogravimetria , Difração de Raios X
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