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1.
Int J Biol Macromol ; 266(Pt 1): 131233, 2024 May.
Artículo en Inglés | MEDLINE | ID: mdl-38554907

RESUMEN

Full-thickness wounds are severe cutaneous damages with destroyed self-healing function, which need efficient clinical interventions. Inspired by the hierarchical structure of natural skin, we have for the first time developed a biomimetic tri-layered artificial skin (TLAS) comprising silica gel-collagen membrane-collagen porous scaffold for enhanced full-thickness wound healing. The TLAS with the thickness of 3-7 mm displays a hierarchical nanostructure consisting of the top homogeneous silica gel film, the middle compact collagen membrane, and the bottom porous collagen scaffold, exquisitely mimicking the epidermis, basement membrane and dermis of natural skin, respectively. The 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide/N-Hydroxysuccinimide-dehydrothermal (EDC/NHS-DHT) dual-crosslinked collagen composite bilayer, with a crosslinking degree of 79.5 %, displays remarkable biocompatibility, bioactivity, and biosafety with no risk of hemolysis and pyrogen reactions. Notably, the extra collagen membrane layer provides a robust barrier to block the penetration of silica gel into the collagen porous scaffold, leading to the TLAS with enhanced biocompatibility and bioactivity. The full-thickness wound rat model studies have indicated the TLAS significantly facilitates the regeneration of full-thickness defects by accelerating re-epithelization, collagen deposition and migration of skin appendages. The highly biocompatible and bioactive tri-layered artificial skin provides an improved treatment for full-thickness wounds, which has great potential in tissue engineering.


Asunto(s)
Materiales Biomiméticos , Colágeno , Gel de Sílice , Piel Artificial , Andamios del Tejido , Cicatrización de Heridas , Cicatrización de Heridas/efectos de los fármacos , Animales , Colágeno/química , Colágeno/farmacología , Porosidad , Ratas , Andamios del Tejido/química , Materiales Biomiméticos/química , Materiales Biomiméticos/farmacología , Gel de Sílice/química , Materiales Biocompatibles/química , Materiales Biocompatibles/farmacología , Biomimética/métodos , Humanos , Piel/efectos de los fármacos , Piel/lesiones , Masculino
2.
Anal Methods ; 15(9): 1206-1214, 2023 03 02.
Artículo en Inglés | MEDLINE | ID: mdl-36807579

RESUMEN

Steroid hormones have been listed as priority pollutants in the environment, and their detection and pollution control deserve our extensive attention. In this study, a modified silica gel adsorbent material was synthesized by benzoyl isothiocyanate reaction with hydroxyl groups on the silica gel surface. The modified silica gel was used as a solid phase extraction filler for the extraction of steroid hormones from water, which was further analyzed by the HPLC-MS/MS method. The FT-IR, TGA, XPS, and SEM analysis indicated that benzoyl isothiocyanate was successfully grafted on the surface of silica gel to form a bond with an isothioamide group and benzene ring as the tail chain. The modified silica gel synthesized at 40 °C showed excellent adsorption and recovery rates for three steroid hormones in water. Methanol at pH 9.0 was selected as the optimal eluent. The adsorption capacity of the modified silica gel for epiandrosterone, progesterone, and megestrol acetate was 6822 ng mg-1, 13 899 ng mg-1, and 14 301 ng mg-1, respectively. Under optimal conditions, the limit of detection (LOD) and limit of quantification (LOQ) for 3 steroid hormones by modified silica gel extraction with HPLC-MS/MS detection were 0.02-0.88 µg L-1 and 0.06-2.22 µg L-1, respectively. The recovery rate of epiandrosterone, progesterone, and megestrol was between 53.7% and 82.9%, respectively. The modified silica gel has been successfully used to analyze steroid hormones in wastewater and surface water.


Asunto(s)
Espectrometría de Masas en Tándem , Agua , Gel de Sílice/química , Progesterona , Espectroscopía Infrarroja por Transformada de Fourier , Androsterona , Esteroides , Isotiocianatos
3.
Molecules ; 28(2)2023 Jan 13.
Artículo en Inglés | MEDLINE | ID: mdl-36677888

RESUMEN

The main objectives of this study are to synthesize a new solid-supported ionic liquid (SSIL) that has a covalent bond between the solid support, i.e., activated silica gel, with thiosalicylate-based ionic liquid and to evaluate the performance of this new SSIL as an extractant, labelled as Si-TS-SSIL, and to remove Pb(II) ions from an aqueous solution. In this study, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium thiosalicylate ([MTMSPI][TS]) ionic liquid was synthesized and the formation of [MTMSPI][TS] was confirmed through structural analysis using NMR, FTIR, IC, TGA, and Karl Fischer Titration. The [MTMSPI][TS] ionic liquid was then chemically immobilized on activated silica gel to produce a new thiosalicylate-based solid-supported ionic liquid (Si-TS-SSIL). The formation of these covalent bonds on Si-TS-SSIL was confirmed by solid-state NMR analysis. Meanwhile, BET analysis was performed to study the surface area of the activated silica gel and the prepared Si-TS-SSIL (before and after washing with solvent) with the purpose to show that all physically immobilized [MTMSPI][TS] has been washed off from Si-TS-SSIL, leaving only chemically immobilized [MTMSPI][TS] on Si-TS-SSIL before proceeding with removal study. The removal study of Pb(II) ions from an aqueous solution was carried out using Si-TS-SSIL as an extractant, whereby the amount of Pb(II) ions removed was determined by AAS. In this removal study, the experiments were carried out at a fixed agitation speed (400 rpm) and fixed amount of Si-TS-SSIL (0.25 g), with different contact times ranging from 2 to 250 min at room temperature. The maximum removal capacity was found to be 8.37 mg/g. The kinetics study was well fitted with the pseudo-second order model. Meanwhile, for the isotherm study, the removal process of Pb(II) ions was well described by the Freundlich isotherm model, as this model exhibited a higher correlation coefficient (R2), i.e., 0.99, as compared to the Langmuir isotherm model.


Asunto(s)
Líquidos Iónicos , Contaminantes Químicos del Agua , Líquidos Iónicos/química , Plomo , Gel de Sílice/química , Adsorción , Agua , Iones/química , Cinética , Contaminantes Químicos del Agua/química
4.
Anal Biochem ; 655: 114837, 2022 10 15.
Artículo en Inglés | MEDLINE | ID: mdl-35952850

RESUMEN

Nicotinamide adenine dinucleotide, a coenzyme involved in the activation of sirtuins, contributes to various regulations in vivo. However, highly hydrophilic nicotinamide metabolites are difficult to separate by high-performance liquid chromatography (HPLC) using octadecyl (C18) columns, which operate via hydrophobic interaction. PBr columns packed with silica gel modified with the pentabromobenzyl group having strong dispersion forces show good retention ability for various highly hydrophilic compounds. Additionally, the peak shape obtained with the PBr column did not collapse like that of the HILIC column, even when a large amount of water was injected. Separation of 11 highly hydrophilic nicotinamide metabolites using a PBr column under simple conditions resulted in baseline separation, but separation on a C18 column was not complete. The peak shape for each compound was better than that in previous studies. Furthermore, the separation of nicotinamide metabolites in tomato using a PBr column enable a more sensitive detection than that using a C18 column. SUBJECT CATEGORY: Chromatographic Technique.


Asunto(s)
Niacinamida , Agua , Cromatografía Líquida de Alta Presión/métodos , Interacciones Hidrofóbicas e Hidrofílicas , Gel de Sílice/química , Dióxido de Silicio/química
5.
J Chromatogr A ; 1677: 463294, 2022 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-35809518

RESUMEN

Considering the vulnerability of silica gel to alkaline mobile phases, a highly alkaline stable stationary phase for HPLC is required to separate basic compounds with high separation efficiency. To address this issue, we have developed a high alkaline stable packing material (CaCO3-PMAcO) based on mesoporous calcium carbonate microspheres modified with poly(maleic acid-alt-1-octadecene). In this study, we report further investigation of the separation performance of CaCO3-PMAcO column by systematically evaluating the effects of particle size and chromatographic conditions. Based on the theory of the van Deemter equation, the separation efficiency was related to the size of CaCO3-PMAcO particles (2.9 - 5.7 µm). The evaluation of thermodynamics of retention by changing the column temperature from 20 °C to 45 °C implied that the retention mode was dominated by hydrophobic interaction associated with the exothermic enthalpy changes (-11.1 to -12.5 kJ/mol). The results of column selectivity tests revealed that the CaCO3-PMAcO column had hydrophobic selectivity comparable to C18 silica gel columns (αP/B; CaCO3-PMAcO column: 1.53, C18 column: 1.69), and higher shape/steric selectivity (αTri/Ter; CaCO3-PMAcO column: 1.56, C18 column: 0.955). In practice, the CaCO3-PMAcO column could be applied to the separation of not only alkylbenzenes and polycyclic aromatic hydrocarbons, but also to basic tricyclic antidepressants by using an alkaline mobile phase (pH 12).


Asunto(s)
Carbonato de Calcio , Cromatografía de Fase Inversa , Cromatografía Líquida de Alta Presión/métodos , Cromatografía de Fase Inversa/métodos , Interacciones Hidrofóbicas e Hidrofílicas , Microesferas , Polímeros/química , Gel de Sílice/química , Dióxido de Silicio/química
6.
Molecules ; 27(10)2022 May 12.
Artículo en Inglés | MEDLINE | ID: mdl-35630589

RESUMEN

In this research, we explored the synthesis optimization of the silica-based quaternized adsorption material (SG-VTS-VPQ) and its adsorption behavior for Pu(IV). By optimizing the synthesis process, the grafting amount of 4-vinylpyridine reached 1.25 mmol·g-1. According to the analysis of NMR and XPS, the quaternization rate of pyridine groups reached 91.13%. In the adsorption experiments, the thermodynamic experiment results show that the adsorption of Pu(IV) by SG-VTS-VPQ is more in line with the Langmuir adsorption model and the adsorption type is a typical chemical adsorption; the kinetic results show that adsorption process is more in line with the pseudo first-order kinetic model, and the larger specific surface area of SG-VTS-VPQ plays an important role in the adsorption. The results of the adsorption mechanism show that the adsorption of Pu(IV) by SG-VTS-VPQ is mainly complex anion Pu(NO3)62- and Pu(NO3)5-. This research provides in-depth and detailed ideas for the surface modification and application of porous silica gel, and at the same time provides a new way to develop the direction of the analysis of pretreatment materials in the spent fuel reprocessing field.


Asunto(s)
Dióxido de Silicio , Adsorción , Cinética , Gel de Sílice/química , Dióxido de Silicio/química , Termodinámica
7.
J Sci Food Agric ; 102(3): 995-1001, 2022 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-34302362

RESUMEN

BACKGROUND: Recently, methods have been developed for the better quality control, fraud detection and analytical investigation of olive oil. Magnetic graphene oxide (GO) material is known for its reusability, high adsorption capability and stability in food sample preparation. Monopalmitine or 2-glycerol monopalmitate (2-GMP) is one of the main parameters in the quality assay and classification of olive oil, which can be classified as extra virgin ≤ 0.9% and olive pomace ≤ 1.2. Hence, newly synthesized magnetic GO (MGO) and commercial silica-gel were used as a dispersive solid-phase clean-up (d-SPE) sorbent to determine 2-GMP value in olive oil samples prior to gas chromatography (GC) analysis. The d-SPE method is validated with olive oil certified reference material (CRM) with respect to silica-gel and a MGO nanocomposite. RESULTS: The developed d-SPE method was applied for various virgin, refined and pomace olive oil samples to determine the value of 2-GMP%. The presence of 2-GMP in the samples was confirmed by GC-mass spectrometry analysis based on silylation derivatives of the analyte. Finally, the d-SPE-MGO method was determined 2-GMP% as 1.9% for pomace olive oil, 0.6% for refined olive oil, 0.4% for virgin olive oil and 3.1% for CRM. The MGO provided satisfactory clean-up recovery (124%) in the acceptable data range for CRM2018, and silica-gel also provided satisfactory recovery (83%) for CRM2018. The proposed method performed with higher sensitivity and efficiency for screening 2-GMP% in olive oil. CONCLUSION: The MGO based d-SPE method was applied for clean-up purposes to determine 2-GMP%. It proved superior via its advantageous features of super quickness, easy isolation with an external magnet and the highly efficient exclusion of all the coexisting interfering peaks conventionally generated with a standard silica-gel material. These methods based on MGO and silica-gel are reflected in the dispersive mode of extraction and can be used as alternatives to conventional methods. Considering the benefits of the consumption of significantly fewer sorbents and less time required regarding the dispersive methods, the methods can be utilized as alternatives in contrast to conventional techniques. © 2021 Society of Chemical Industry.


Asunto(s)
Grafito/química , Nanocompuestos/química , Aceite de Oliva/química , Palmitatos/química , Extracción en Fase Sólida/métodos , Adsorción , Cromatografía de Gases y Espectrometría de Masas , Gel de Sílice/química , Extracción en Fase Sólida/instrumentación
8.
Molecules ; 26(19)2021 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-34641489

RESUMEN

Nitisinone (NTBC) is used in the treatment of disorders affecting the tyrosine pathway, including hereditary tyrosinemia type I, alkaptonuria, and neuroblastoma. An inappropriate dosage of this therapeutic drug causes side effects; therefore, it is necessary to develop a rapid and sensitive method to monitor the content of NTBC in patients' blood. This study aimed to develop anew polymeric sorbent containing ß-cyclodextrin (ß-CD) derivatives grafted on silica gel to effectively extract NTBC from model physiological fluids. The inclusion complex formed between ß-CD and NTBC was examined by proton nuclear magnetic resonance spectroscopy. The novel sorbents with derivatives of ß-CD were prepared on modified silica gel using styrene as a comonomer, ethylene glycol dimethacrylate as a crosslinking agent, and 2,2'-azo-bis-isobutyronitrile as a polymerization initiator. The obtained products were characterized via Fourier transform infrared spectroscopy and then used as sorbents as part of a solid phase extraction technique. High NTBC recovery (70%indicated that the developed polymeric sorbent may be suitable for extracting this compound from patients' blood samples.


Asunto(s)
Ciclohexanonas/aislamiento & purificación , Inhibidores Enzimáticos/aislamiento & purificación , Nitrobenzoatos/aislamiento & purificación , Polímeros/química , Gel de Sílice/química , Dióxido de Silicio/química , Extracción en Fase Sólida/métodos , beta-Ciclodextrinas/química , Adsorción , Ciclohexanonas/sangre , Inhibidores Enzimáticos/sangre , Humanos , Nitrobenzoatos/sangre , Polimerizacion
9.
Food Chem ; 354: 129497, 2021 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-33752112

RESUMEN

Aflatoxin B1 is the potential chemical contaminant of most concern during the production and storage of fermented tea. In this work, a simple, fast, sensitive, accurate, and inexpensive method has been developed and validated for the simultaneous detection of four aflatoxins in fermented tea based on a modified sample pretreatment method and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Aflatoxins were extracted using acetonitrile and purified using mixed fillers (carboxyl multiwalled carbon nanotubes, hydrophilic-lipophilic balance, silica gel). Under optimum LC-MS conditions, the limits of quantification (LOQs) were 0.02-0.5 µg·kg-1. Recoveries from aflatoxins-fortified tea samples (1-12 µg·kg-1) were in the range of 78.94-105.23% with relative standard deviations (RSDs) less than 18.20%. The proposed method was applied successfully to determine aflatoxin levels in fermented tea samples.


Asunto(s)
Aflatoxinas/análisis , Cromatografía Líquida de Alta Presión/métodos , Tés de Hierbas/análisis , Aflatoxinas/aislamiento & purificación , Interacciones Hidrofóbicas e Hidrofílicas , Límite de Detección , Nanotubos de Carbono/química , Reproducibilidad de los Resultados , Gel de Sílice/química , Espectrometría de Masas en Tándem
10.
J Chromatogr A ; 1639: 461932, 2021 Feb 22.
Artículo en Inglés | MEDLINE | ID: mdl-33535117

RESUMEN

Position-specific isotope analysis by Nuclear Magnetic Resonance spectrometry was employed to study the 13C intramolecular isotopic fractionation associated with the migration of organic substrates through different stationary phases chromatography columns. Liquid chromatography is often used to isolate compounds prior to their isotope analysis and this purification step potentially alters the isotopic composition of target compounds introducing a bias in the later measured data. Moreover, results from liquid chromatography can yield the sorption parameters needed in reactive transport models that predict the transport and fate of organic contaminants to in the environment. The aim of this study was to use intramolecular isotope analysis to study both 13C and 15N isotope effects associated with the elution of paracetamol (acetaminophen) through different stationary phases and to compare them to effects observed previously for vanillin. Results showed very different intramolecular isotope fractionation profiles depending on the chemical structure of the stationary phase. The data also demonstrate that both the amplitude and the distribution of measured isotope effects depend on the nature of the non-covalent interactions involved in the migration process. Results provided by theoretical calculation performed during this study also confirmed the direct link between observed intramolecular isotope fractionation and the nature of involved intermolecular interactions. It is concluded that the nature of the stationary phase through which the substrate passes has a major impact on the intramolecular isotopic composition of organic compounds isolated by chromatography methods..


Asunto(s)
Acetaminofén/análisis , Isótopos de Carbono/química , Cromatografía Liquida/métodos , Isótopos de Nitrógeno/química , Espectroscopía de Resonancia Magnética con Carbono-13 , Celulosa/química , Carbón Orgánico/química , Fraccionamiento Químico , Reproducibilidad de los Resultados , Gel de Sílice/química , Solventes/química
11.
Biotechnol Lett ; 43(1): 43-59, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33025334

RESUMEN

OBJECTIVE: Extracellular fructosyltransferase (FTase, E.C.2.4.1.9) from Aspergillus oryzae IPT-301 was immobilized on silica gel by adsorption and biochemically characterized aiming at its application in the transfructosylation reaction of sucrose for the production of fructooligossaccarides (FOS). RESULTS: The transfructosylation activity (AT) was maximized by the experimental design in function of the reaction pHs and temperatures. The AT of the immobilized enzyme showed the kinetics behavior described by the Hill model. The immobilized FTase showed reuse capacity for six consecutive reaction cycles and higher pH and thermal stability than the soluble enzyme. CONCLUSION: These results suggest a high potential of application of silica gel as support for FTase immobilization aiming at FOS production.


Asunto(s)
Aspergillus oryzae/enzimología , Proteínas Bacterianas , Enzimas Inmovilizadas , Hexosiltransferasas , Oligosacáridos/metabolismo , Proteínas Bacterianas/química , Proteínas Bacterianas/metabolismo , Estabilidad de Enzimas , Enzimas Inmovilizadas/química , Enzimas Inmovilizadas/metabolismo , Hexosiltransferasas/química , Hexosiltransferasas/metabolismo , Concentración de Iones de Hidrógeno , Oligosacáridos/análisis , Gel de Sílice/química , Sacarosa/metabolismo , Temperatura
12.
Artículo en Inglés | MEDLINE | ID: mdl-33284726

RESUMEN

Octolig, a commercially available (a polyethylene diamine covalently attached to silica gel), was subjected to modifications to incorporate sulfur for enhanced removal of lead ion from aqueous solutions. The basic approach was attempted formation of "ThioOctolig" by the reaction of Octolig with thioacetamide in toluene using a shaker bath for 24 or 48 h or in the presence of 10% HCl (1 h). Our experience was that conversion was limited to about 20% based on sulfur analysis for 24 or 48 h reaction time, or in the presence of 10% HCl. In fact, with acidification, the results were poorer. Duplicate runs indicated consistent results. Literature reported that SbCl3 was an effective catalyst with a reaction time of 1 h. Use of this reagent (1-h reaction time) produced a bright orange red product, in contrast with previous yellow-colored products. A control run indicated that this reagent reacted with Octolig in toluene (in the dark) to produce a red-colored sample; thioacetamide reacted to produce a yellow sample. Use of SbCl3 (∼5 mole %) did not enhance the sulfur content of Octolig. A sample of Octolig removed 68% lead ion from a 120 ppm aqueous lead while a sample of ThioOctolig (10% S) removed 99.4% lead ions. We also investigated enhancing the sulfur incorporation upon raising the reaction temperature with thioacetamide.


Asunto(s)
Quelantes/química , Plomo/análisis , Polietilenos/química , Gel de Sílice/química , Tioacetamida/química , Contaminantes Químicos del Agua/análisis , Adsorción , Quelantes/síntesis química , Agua Potable/análisis , Agua Potable/normas , Modelos Teóricos , Propiedades de Superficie , Purificación del Agua/métodos
13.
Anal Chem ; 92(20): 13750-13758, 2020 10 20.
Artículo en Inglés | MEDLINE | ID: mdl-32894935

RESUMEN

Protein immobilization is particularly significant in proteomics, interactomics, and in vitro drug screening. It is an essential primary step for numerous biological techniques that rely on immobilized proteins with controlled orientation, high conformational stability, and high activity (CHH). These have challenged the current immobilization strategy and demanded increasing efforts for an efficient method to meet the CHH immobilization in a single step. Herein, we proposed a covalent inhibitor-based, one-step method for G protein-coupled receptor (GPCR) immobilization inspired by the covalent reaction between an epidermal growth factor receptor (EGFR)-tag and its inhibitor ibrutinib. We immobilized endothelin receptor A (ETA) containing a fusion EGFR tag onto an ibrutinib-coated macroporous silica gel. The immobilized ETA proved to have demonstrable ligand-binding activity and specificity, thus resulting in a chromatographic technology allowing receptor-ligand interaction analysis and lead identification. Such immobilization method is attractable, owing to the properties of mild reacting conditions, fast rate, high yield, and good stability of the conjugated protein. It will be applicable to biochips, biosensors, and biocatalysts.


Asunto(s)
Adenina/análogos & derivados , Piperidinas/química , Receptores de Endotelina/química , Adenina/química , Técnicas Biosensibles/métodos , Cromatografía Liquida , Receptores ErbB/antagonistas & inhibidores , Receptores ErbB/genética , Receptores ErbB/metabolismo , Proteínas Inmovilizadas/química , Proteínas Inmovilizadas/metabolismo , Ligandos , Porosidad , Receptores de Endotelina/genética , Receptores de Endotelina/metabolismo , Proteínas Recombinantes de Fusión/biosíntesis , Proteínas Recombinantes de Fusión/química , Proteínas Recombinantes de Fusión/aislamiento & purificación , Gel de Sílice/química
14.
J Chromatogr A ; 1628: 461472, 2020 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-32822994

RESUMEN

Organic gel (OG) has excellent characteristics, including a large surface area, adjustable pore/channel size, and good chemical stability, and has attracted great attention in the field of materials. However, the OG packed column is difficult to pack due to the weak mechanical strength and poor monodispersity. Herein, 1-allyl-3-methyl imidazolium hexafluorophosphate-co-1-dodecanethiol ([AMIm]PF6-co-TDDM) was prepared on the silica microsphere for chromatographic packing available in multimode liquid chromatography (LC) mode with the good mechanical properties of silica microspheres through a simple OG synthesis method. [AMIm]PF6-co-TDDM@SiO2 hybrid microspheres with uniform particles and narrow particle size distribution are used as stationary phases of LC. These microspheres are used in anion-exchange (IEC), reversed-phase (RP), and hydrophilic interaction (HILIC) mode for the separation of different analytes. Such microspheres can also be used for the preliminary qualitative analysis of active ingredients in actual samples in addition to organic acids, alkylbenzenes, and nucleoside bases. The [AMIm]PF6-co-TDDM@SiO2 chromatography packing also has good reproducibility and stability. The adhesive properties of organogels and the adsorption properties of silica gel simplify the synthesis of stationary phase materials. This simple and effective strategy for preparing [AMIm]PF6-co-TDDM@SiO2 composite microspheres by one-pot method can expand the application of OG as a functional additive on silica microspheres in LC.


Asunto(s)
Cromatografía Liquida/métodos , Microesferas , Compuestos Orgánicos/química , Gel de Sílice/química , Adsorción , Interacciones Hidrofóbicas e Hidrofílicas , Nucleósidos/aislamiento & purificación , Presión , Reproducibilidad de los Resultados , Espectroscopía Infrarroja por Transformada de Fourier
15.
J Chromatogr A ; 1627: 461393, 2020 Sep 13.
Artículo en Inglés | MEDLINE | ID: mdl-32823098

RESUMEN

The selective extraction and column separation rear earth elements (REEs) were investigated in the present work. Herein, the functional ligand of N, N-dioctyldiglycolic acid (DODGA) was synthesized and chemically grafted on the silica gel (SG) particles to give the novel material SG@DODGA. The obtained SG@DODGA was fully characterized by NMR, BET (Brunauer-Emmett-Teller) N2 physisorption analysis, atom force microscopy (AFM), scanning electronic microscopy (SEM), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). After investigating the adsorption capability of the SG@DODGA towards 16 kinds of REEs (La, Ce, Pr, Nd, Sm, Eu, Gd, Td, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc), the results showed that the adsorption kinetic data was better fitted with pseudo-second-order model and Elovich model, the adsorption isotherms data was suitable for Freundlich model. The above result also indicated that the adsorption mechanism between the SG@DODGA and REEs was chemical ion exchange. Moreover, choose SG@DODGA as the column chromatography stationary phase and packed in a glass column for the column studies to obtain breakthroughs profile of each REEs. Furthermore, the column was used to try to separate the mixed 16 kinds of REEs. The first attempt to preliminary separate REEs result showed that this column could be applied for simply separating REEs. The light REEs La, Ce, Pr, Nd exhibited better separation effect than the other REEs.


Asunto(s)
Glicolatos/química , Metales de Tierras Raras/aislamiento & purificación , Gel de Sílice/química , Adsorción , Concentración de Iones de Hidrógeno , Iones , Cinética , Ligandos , Nitrógeno/química , Espectroscopía de Fotoelectrones , Espectroscopía Infrarroja por Transformada de Fourier , Temperatura , Termogravimetría
16.
J Chromatogr A ; 1626: 461366, 2020 Aug 30.
Artículo en Inglés | MEDLINE | ID: mdl-32797845

RESUMEN

An alternative method for efficient synthesis of urea-functionalized silanes was proposed on the basis of an N, N'-carbonyldiimidazole-mediated acyl-transfer reaction between various amino-containing building blocks. The employment of different parent aminosilanes and alkylamines afforded an array of urea-containing silanes, which were subsequently immobilized onto silica gel to form corresponding urea-embedded alkyl stationary phases for high-performance liquid chromatography. The different substituents on the silicon core of the derivatized silane were found to significantly influence the final chromatographic behaviors. The comparative chromatographic characterization of thus-prepared silica packings with conventional octadecyl (C18) stationary phases revealed that the urea group was beneficial to suppress silanol activity towards basic probes, as well as to increase the water-compatibility of the alkyl stationary phases. The combination of a polar urea moiety and a non-polar long alkyl chain was favorable for an enhanced steric selectivity towards shape-constrained isomers. The polarizability-sensitive feature of such stationary phases made them good candidates for efficient separation of nitro-containing polar substances.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Silanos/química , Urea/química , Isomerismo , Silanos/síntesis química , Gel de Sílice/química , Dióxido de Silicio/química
17.
J Chromatogr A ; 1625: 461277, 2020 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-32709329

RESUMEN

The influence of impregnation the chromatographic plate adsorbent layer, silica, with hen's egg white albumin (OVA) or bovine serum albumin (BSA) on the retention of some popular medicines (paracetamol, aminophenazone, theophylline, caffeine, acetanilide, ciprofloxacin, tramadol, acetylsalicylic acid, acebutolol) is investigated. The effect of composition and buffer pH of the mobile phase on solute separation selectivity is also studied. The chromatographic systems with and without above mentioned albumins and their influence on investigated drug retention are compared. In general, it has been turned out that retention of tested medicines in systems with the sorbent impregnated with albumin significantly increase relative to those with non-impregnated.


Asunto(s)
Cromatografía en Capa Delgada/métodos , Clara de Huevo/química , Preparaciones Farmacéuticas/análisis , Albúmina Sérica Bovina/química , Gel de Sílice/química , Adsorción , Animales , Bovinos , Pollos , Femenino , Concentración de Iones de Hidrógeno , Metanol/química , Compuestos Orgánicos/química , Solventes/química , Espectroscopía Infrarroja por Transformada de Fourier , Tolueno/química
18.
J Chromatogr A ; 1625: 461282, 2020 Aug 16.
Artículo en Inglés | MEDLINE | ID: mdl-32709333

RESUMEN

In recent years, core-shell silica particles (CSSPs) have been increasingly used for highly efficient separation at fast flow rates and relatively low back pressures in high-performance liquid chromatography (HPLC). However, material synthesis techniques for producing CSSPs economically in batch processes remain elusive. In this report, a practical and straightforward method for the preparation of CSSPs is presented. By refluxing freshly prepared nonporous silica particles in ammonia-water solution in the presence of poly(diallyldimethylammonium chloride) at 70-100 °C, CSSPs with shell thicknesses of up to 300 nm and pore sizes from 8 to 25 nm were easily prepared. The effects of the synthetic conditions on the shell thickness, surface area, and pore size were investigated in detail, and the method reproducibility was evaluated in scale-up experiments. A mechanism of CSSP formation is also proposed. The CSSPs were characterized via scanning electron microscopy, transmission electron microscopy, laser particle size (dynamic light scattering) analysis, and nitrogen adsorption and desorption experiments. The synthesized 3.4-µm CSSPs were functionalized with dimethyloctadecylchlorosilane and used as an HPLC packing material, exhibiting excellent separation performance for both small molecules and large biomolecules. In summary, we report the simplest method developed thus far for the preparation of monodisperse core-shell silica particles suitable for HPLC column packing.


Asunto(s)
Cromatografía Líquida de Alta Presión/métodos , Gel de Sílice/química , Adsorción , Amoníaco/análisis , Dispersión Dinámica de Luz , Microesferas , Peso Molecular , Nanopartículas/química , Nanopartículas/ultraestructura , Tamaño de la Partícula , Polietilenos/química , Porosidad , Compuestos de Amonio Cuaternario/química , Reproducibilidad de los Resultados , Temperatura , Factores de Tiempo
19.
J Food Sci ; 85(7): 1971-1982, 2020 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-32529719

RESUMEN

Phytosterol glycosides (PGs), comprising both acylated steryl glycosides (ASGs) and steryl glycosides (SGs), are active ingredients with benefits for human use. Here, we aimed to optimize the silica-gel adsorption technique for the extraction of PGs from soybean lecithin powder, which contains 5 to 10% of these glycolipids. Both response surface methodology (RSM) and artificial neural networks (ANNs) were applied to optimize the PG extraction parameters (X1 = silica-gel dosage, X2 = adsorption temperature, and X3 = lecithin concentration) for high-purity phospholipid and PG production, and their prediction and optimization accuracies were compared. Although both models fitted well with the experimental data, the ANN model demonstrated better accuracy for predicting and optimizing the conditions using four interrelated dependent variables (Y1 = phospholipid yield, Y2 = ASG recovery, Y3 = SG recovery, and Y4 = PG purity) and had a higher coefficient of determination and lower root mean square error and absolute average deviation. After digitally setting the percentages of the four dependent variables for phospholipid and PG production, the ANN-optimized phospholipid product (Y1 = 88.07%, Y2 = 98.89%, Y3 = 100%, and Y4 = 49.03%) was acquired at X1 = 3.54 g/g, X2 = 26 °C, and X3 = 43 mg/mL, whereas the PG product (Y1 = 83.83%, Y2 = 97.64%, Y3 = 100%, and Y4 = 59.21%) was obtained at X1 = 2.00 g/g, X2 = 28.38 °C, and X3 = 41 mg/mL. In conclusion, the ANN method was better than RSM for the optimization of the silica-gel adsorption technique for PG extraction from soybean lecithin powder. PRACTICAL APPLICATION: This paper lays a theoretical foundation for the optimization of the industrial production of phytosterol glycosides and the comprehensive utilization of lecithin resources.


Asunto(s)
Glycine max/química , Glicósidos/aislamiento & purificación , Lecitinas/química , Fitosteroles/aislamiento & purificación , Extractos Vegetales/aislamiento & purificación , Gel de Sílice/química , Extracción en Fase Sólida/métodos , Adsorción , Glicósidos/análisis , Redes Neurales de la Computación , Fitosteroles/análisis , Extractos Vegetales/análisis , Polvos/química , Extracción en Fase Sólida/instrumentación
20.
Biotechnol Bioeng ; 117(10): 3066-3080, 2020 10.
Artículo en Inglés | MEDLINE | ID: mdl-32589792

RESUMEN

Around 20-30% of ovarian cancer patients exhibit chemoresistance, but there are currently no methods to predict whether a patient will respond to chemotherapy. Here, we discovered that chemoresistant ovarian cancer cells exhibit enhanced survival in a quiescent state upon experiencing the stress of physical confinement. When immobilized in stiff silica gels, most ovarian cancer cells die within days, but surviving cells exhibit hallmarks of single-cell dormancy. Upon extraction from gels, the cells resume proliferation but demonstrate enhanced viability upon reimmobilization, indicating that initial immobilization selects for cells with a higher propensity to enter dormancy. RNA-seq analysis of the extracted cells shows they have signaling responses similar to cells surviving cisplatin treatment, and in comparison to chemoresistant patient cohorts, they share differentially expressed genes that are associated with platinum-resistance pathways. Furthermore, these extracted cells demonstrate greater resistance to cisplatin and paclitaxel, despite being proliferative. In contrast, serum starvation and hypoxia could not effectively select for chemoresistant cells upon removal of the environmental stress. These findings demonstrate that ovarian cancer chemoresistance and the ability to enter dormancy are linked, and immobilization rapidly distinguishes chemoresistant cells. This platform could be suitable for mechanistic studies, drug development, or as a clinical diagnostic tool.


Asunto(s)
Bioensayo/métodos , Supervivencia Celular , Cisplatino/farmacología , Resistencia a Antineoplásicos , Neoplasias Ováricas/tratamiento farmacológico , Paclitaxel/farmacología , Gel de Sílice/química , Antineoplásicos/farmacología , Antineoplásicos Fitogénicos/farmacología , Línea Celular Tumoral , Proliferación Celular , Femenino , Humanos , Neoplasias Ováricas/genética , Neoplasias Ováricas/metabolismo , Neoplasias Ováricas/patología , Transducción de Señal
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