Search

This study successfully prepared different loading levels of cyano-functionalized RCC3 molecular cage silica gel stationary phase (RCC3-CN@SiO 2 ) through aldehyde-amine condensation reaction and subsequent modification strategies. Fourier transform infrared spectroscopy, thermogravimetric analysis, nitrogen adsorption-desorption, and scanning electron microscopy confirmed the successful synthesis of RCC3-CN@SiO 2 chromatographic stationary phase. The research demonstrates that due to hydrophobic/hydrophilic interactions, π-π interactions, hydrogen bonding, and size-selective porous structure, the stationary phase effectively separates moderately polar and weakly polar compounds in reversed-phase liquid chromatography (RPLC) mode, exhibiting hydrophobic selectivity comparable to the commercial DaisoC18-RP columns. Additionally, the tertiary amine and cyanogen groups on the molecular cage surface enhance the interaction with polar compounds, successfully separating nucleosides, sulfonamides, amino acids, and sugars in hydrophilic interaction chromatography (HILIC) mode. Further applications in the separation analysis of acidic drugs, alkaline drugs, cinnamic acid natural products, and chiral compounds demonstrate the multifunctional chromatographic capabilities for diverse compound types. Compared to Unitary Diol commercial columns, the prepared stationary phase showed significant advantages in wide polarity range separation performance. Moreover, through nucleoside compound separation mode switching analysis, RCC3-CN@SiO 2 stationary phase further validates its favorable performance in both RPLC and HILIC modes, demonstrating extensive potential applications in the field of analytical chemistry. Importantly, the stationary phase exhibits efficient separation of nucleoside compounds in pure water systems, aligning with the principles of green analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Water pollution caused by heavy metals is a major environmental problem, threatening water production, food safety, and human health. Cadmium (Cd) pollution is particularly serious because of food-chain biomagnification at toxic concentrations. Modified biochar is promising for heavy metal removal; however, efficient adsorbents for Cd removal are lacking. In the present study, a novel adsorbent, silica gel-modified biochar (SGB), was prepared and applied to treat sewage polluted by Cd. Through the batch adsorption experiments, it is known that SGB possessed outstanding Cd removal ability and recycleability. Furthermore, the adsorption behavior and mechanisms were analyzed by the application of kinetic and isotherm models. The maximum Cd 2+ adsorption capacity of SGB was 38.08 mg g -1 , and after five recycling processes, the Cd 2+ removal rate was still 86.89 %. When the pH of the solution was 7.0, SGB showed the strongest Cd 2+ adsorption capacity (29.06 mg g -1 ). When competitive ions existed, biochar also had high Cd removal efficiency, although the effect of Pb 2+ was greater than those of Cu 2+ and Zn 2+ , indicating that SGB was applicable to complex polluted water. Additionally, the main Cd 2+ adsorption mechanisms by SGB were electrostatic interactions, π-π interactions, complexation, and co-precipitation. These results showed that SGB can effectively treat Cd-contaminated wastewater as a new adsorbent., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Silica aerogels or xerogels are renowned dried gels with low density, high surface area, higher porosity, and better thermal stability which makes it suitable for aerospace, light weight structures, thermal insulation, and hydrophobic coatings. But brittle behaviour, low mechanical strength, and high manufacturing cost restrict its usage. Recently, the addition of various fibres like glass or carbon fiber is one of the best reinforcement methods to minimize the brittle behaviour. Supercritical drying technique usually used to develop aerogel that is expensive and difficult to produce in bulk quantities. Higher cost obstacle can be tackled by applying ambient pressure drying technique to develop xerogel. But researcher observed cracks in samples prepared through the ambient pressure drying technique is still a major shortcoming. The aim of this study is to systematically analyze the influence of silica gel fiber reinforcement on silica xerogels, encompassing morphology, mechanics, thermal behaviour, compression test, and thermogravimetric characteristics. The research used a low-cost precursor named Tetraethyl orthosilicate to synthesize low-cost composite Silica xerogel and glass and carbon fiber added to provide strength and flexibility to the overall composite. Silica gel works as binder in strengthening the xerogel network. The investigation employs scanning electron microscopy (SEM) to examine the morphology of the composites, Fourier Transform Infrared (FTIR) analysis to affirm hydrophobic characteristics, compression tests to assess mechanical strength, and thermogravimetric tests to study weight loss under different conditions. SEM results reveals that glass fibers exhibit lower adhesion to the xerogel network compared to carbon fibers. FTIR analysis confirms the hydrophobicity of the composite silica xerogel. Compression tests showed that, under a 48% strain rate, the carbon fiber composite demonstrates superior compressive stress endurance. Thermogravimetric tests revealed a 1% lower weight loss for the carbon fiber composite compared to the glass fiber composite. This work concludes that glass and carbon fiber together with silica gel particles successfully facilitated in developing flexible, less costly, hydrophobic, and crack-free silica xerogel composites by APD. These advancements have the potential to drive innovations in material science and technology across diverse industries., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Ammar et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

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.

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 (R 2 ), i.e., 0.99, as compared to the Langmuir isotherm model.

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 (C 18 ) 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 C 18 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 C 18 column. SUBJECT CATEGORY: Chromatographic Technique., (Copyright © 2022 Elsevier Inc. All rights reserved.)

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 (CaCO 3 -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 CaCO 3 -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 CaCO 3 -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 CaCO 3 -PMAcO column had hydrophobic selectivity comparable to C 18 silica gel columns (α P/B ; CaCO 3 -PMAcO column: 1.53, C 18 column: 1.69), and higher shape/steric selectivity (α Tri/Ter ; CaCO 3 -PMAcO column: 1.56, C 18 column: 0.955). In practice, the CaCO 3 -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)., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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(NO 3 ) 6 2- and Pu(NO 3 ) 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.

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., (© 2021 Society of Chemical Industry.)

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 β-cyclodextrin (β-CD) derivatives grafted on silica gel to effectively extract NTBC from model physiological fluids. The inclusion complex formed between β-CD and NTBC was examined by proton nuclear magnetic resonance spectroscopy. The novel sorbents with derivatives of β-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.

Aflatoxin B 1 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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Position-specific isotope analysis by Nuclear Magnetic Resonance spectrometry was employed to study the 13 C 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 13 C and 15 N 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.., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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 SbCl 3 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 SbCl 3 (∼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.

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 (A T ) was maximized by the experimental design in function of the reaction pHs and temperatures. The A T 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.

Mesoporous silica has attracted significant attention in the drug delivery area; however, impurities can be a source of toxicity. The current study used commercial microparticles produced at large scale in a well-controlled environment. Micrometer sized mesoporous silica particles were acquired through a commercial vendor and pore structures were characterized by SEM. The three silica particle formulations had a diameter of 15 micrometers and three different pore sizes of 10 nm, 30 nm, and 100 nm. The fourth formulation had particle size of 20-40 micrometers with 50 nm pores. Before in vivo tests, an in vitro cytotoxicity test was conducted with silicic acid, derived from the sol-gel particles, on EA.hy926 cells. Low concentration (2.5 µg/mL) of silicic acid showed no cytotoxicity; however, high concentration (25 µg/mL) was cytotoxic. In vivo intravitreal injection demonstrated that 15 um silica particles with 10 nm pore were safe in both rabbit and guinea pig eyes and the particles lasted in the vitreous for longer than two months. Formulations of with larger pores demonstrated variable localized vitreous cloudiness around the sol-gel particle depot and mild inflammatory cells in the aqueous humor. The incidence of reaction trended higher with larger pores (10 nm: 0%, 30 nm: 29%, 50 nm: 71%, 100 nm: 100%, p  < .0001, Cochran Armitage Trend Test). Sol-gel mesoporous silica particles have uniform particle sizes and well-defined pores, which is an advantage for implantation via a fine needle. Selected formulations may be used as an intraocular drug delivery system with proper loading and encapsulation.

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.

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., (© 2020 Wiley Periodicals LLC.)

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]PF 6 -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]PF 6 -co-TDDM@SiO 2 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]PF 6 -co-TDDM@SiO 2 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]PF 6 -co-TDDM@SiO 2 composite microspheres by one-pot method can expand the application of OG as a functional additive on silica microspheres in LC., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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) N 2 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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financialinterestsor personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

A new class of chitosan derivatives with an isopropylthiourea at the 2-position and various carbamates at the 3,6-positions of the glucosamine skeleton was synthesized by the selective thiocarbamoylation of the 2-amino group. The chiral stationary phases (CSPs) were then prepared by coating the obtained chitosan 2-isopropylthiourea-3,6-dicarbamate derivatives onto silica gel. The enantioseparation property of the chitosan-based CSPs was assessed with twelve racemates by high-performance liquid chromatography (HPLC). The CSPs displayed a characteristic enantioseparation power, which seemed to be significantly affected by the 3,6-substituents of the glucosamine unit. The chitosan derivatives with the 3,6-diphenylcarbamate, except for 2-methylphenylcarbamate, possessed higher enantioseparation abilities than those with the 3,6-dicyclohexylcarbamate. Compared to other chitosan derivatives with 2-various substituents and commercialized Chiralcel OD, the chitosan 2-isopropylthiourea derivatives revealed a relatively higher enantioselectivity for some racemic compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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 (X 1 = silica-gel dosage, X 2 = adsorption temperature, and X 3 = 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 (Y 1 = phospholipid yield, Y 2 = ASG recovery, Y 3 = SG recovery, and Y 4 = 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 (Y 1 = 88.07%, Y 2 = 98.89%, Y 3 = 100%, and Y 4 = 49.03%) was acquired at X 1 = 3.54 g/g, X 2 = 26 °C, and X 3 = 43 mg/mL, whereas the PG product (Y 1 = 83.83%, Y 2 = 97.64%, Y 3 = 100%, and Y 4 = 59.21%) was obtained at X 1 = 2.00 g/g, X 2 = 28.38 °C, and X 3 = 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., (© 2020 Institute of Food Technologists®.)

New zwitterionic (ZIC) stationary phases (SPs) are synthesized with the click and conventional bonding of tyrosine to silica gel. Infrared spectra and elemental analysis demonstrate the successful click and conventional bonding of this ZIC group on silica particles by the surface coverage including 2.36 and 0.75 µm m -2 , respectively. Given the above-mentioned explanation, the present study evaluated the retention mechanism and chromatographic manners of polar compounds on these new materials under hydrophilic interaction liquid chromatography (HILIC) conditions. Based on the results, the Click-Tyrosine Stationary Phase provided good HILIC characteristics when it was applied to separate phenolic compounds, amino acids, alkaloids, and nucleobases compared to bare silica gel SP and even conventional tyrosine SPs. Further, this new Click-Tyrosine-SP represented appropriate HILIC features and column efficiency (the theoretical plate number was up to 50,000 plates m -1 for thebaine). Furthermore, the study investigated the effect of solute polarity (the number of the hydroxyl group of phenolic compounds) and hydrophobicity (the number of the side chain of aliphatic amino acids) on retention behaviors. Finally, some important factors were studied as the potential variables for guiding the retention behavior of the polar compound in HILIC condition including solvent composition, salt concentration, and the buffer pH of the mobile phase., Competing Interests: Declaration of Competing Interest The authors have no other relevant affiliations or financial involvement with any organization or entity with a financial interest in or financial conflict with the subject matter or materials discussed in the manuscript, apart from those disclosed. No writing assistance was utilized in the production of this manuscript. The authors declare no conflict of interest., (Copyright © 2020. Published by Elsevier B.V.)

The present work described two triacontyl-bonded silica adsorbents containing different polar embedded groups (i.e. amide- and carbamate-type) for high performance liquid chromatography, which were prepared by covalent surface modification of silica gel with respective pre-synthesized polar-embedded triacontyl (C30) silane. The acylimidazole-mediated method was used for the first time for the synthesis of amide-type alkyl silane, while the carbamate-type silane was obtained via an improved solvent-free procedure. A conventional C30 stationary phase was also developed on the same silica substrate in the similar manner, which was used as a reference column for comparison of the unique mechanisms facilitated and/or furnished by the polar groups. The successful immobilization of the designed C30 species was confirmed by infrared spectroscopy and elemental analysis. In further comparison with an amide-embedded octadecyl (C18) two other conventional C18 stationary phases of different surface chemistry, detailed chromatographic characterization of the C30 series stationary phases was performed in terms of surface density, hydrophobicity, aromatic selectivity, shape selectivity and water tolerance using a diversified range of analytes, including homologous alkylbenzenes, isomeric polycyclic aromatic hydrocarbons, carotenes, congeners of polychlorobiphenyls, aromatic amines, phenolic compounds, estrogens and nucleosides. A high resemblance between the chromatographic behaviors of the two polar-modified C30 stationary phases was observed, meanwhile they demonstrated noticeable differences from non-polar C30 stationary phase. The polar-embedded C30 phases showed satisfactory performance towards the solutes of interest in the studied conditions. The beneficial synergy of the polar groups and the triacontyl chains enabled these polar-enhanced C30 stationary phases to address challenging separation tasks with high selectivity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Silica aerogel, a kind of nanoporous material, is regarded as a desired drug carrier for its low toxicity, high specific surface area, and excellent biocompatibility. Using silica aerogel in a drug carrier may be an appropriate method to improve the performance of pure resveratrol. In this study, resveratrol-loaded silica aerogel (RSA) as a drug delivery system was prepared by the sol-gel method. Before gelling, resveratrol was added into the hydrolyzed tetraethyl orthosilicate (TEOS) ethanol solution then dispersed by stir and ultrasound. The results showed that RSA has a high loading rate of 19% with low cost and excellent biocompatibility. The SEM images showed that silica aerogel wraps up outside the resveratrol. Sustained releasing effect could be observed in RSA after 1 h, while pure resveratrol did not display this. The release of RSA lasted for over 6 h, and the release amount reached over 90% and 80% in either simulated gastric fluid (pH = 2.0) or phosphate-buffered saline (pH = 7.4) at 37 °C. Preliminary in vitro toxicity test revealed RSA to be biocompatible and stable; and when coupled with the anti-inflammatory effects of resveratrol, showed good potential for osteoarthritis treatment.

A novel and simple method was established for the extraction and determination of seven compounds in Anemarrhena asphodeloides Bge. using silica gel-based vortex-homogenized matrix solid-phase dispersion and ultra-high performance liquid chromatography quadrupole-time of-flight mass spectrometer. The conditions for the extraction were optimized. Silica gel was used as the dispersant, 50% methanol-water was selected as an elution solvent and the grinding time was 3 min. Compared with the traditional ultrasonic-assisted extraction, the developed method was rapid and efficient. In order to screen potential antioxidants, extract dealing with the optimized method was applied to a polyamide chromatography column and a D-101 macroporous resin column. Fr.2.2 showed the highest antioxidant activities with the most content of flavonoid. A total of 25 peaks were identified from the active fraction. A 2,2'-diphenyl-1-picrylhydrazyl ultra-high performance liquid chromatography coupled with mass spectrometry approach was adopted for the rapid and exact screening and identification of antioxidant compounds. It indicated that flavonoids exhibited potential antioxidant activities. The antioxidant activities of nine monomeric compounds in vivo were tested. Structure-activity relationships were discussed. Five flavonoids with the concentration of 500 µg/mL would reduce the oxidative stress of PC12 cells that were induced with 2,2'-azobis[2-methylpropionamidine] dihydrochloride., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The blood fraction most commonly used for the assessment of fatty acid status is the plasma or serum phospholipids, since these provide a measure of long term dietary intake. However, conventional assays of fatty acid status in human plasma and serum require labour intensive, multi-step approaches, which are impractical for high-throughput analyses. This study reports a system capable of selectively separating plasma phospholipids from other lipid classes in just a few minutes. We demonstrate that compositional analysis of the fatty acids in plasma phospholipids using our plasma spot method resulted in greater than 97% of neutral lipid standards had been eluted from the paper, whereas more than 96% of the PC remained on the paper. These results were almost identical to conventional methods involving liquid/liquid extraction and thin layer chromatography separation. Evaluation of our plasma spot fractionation and assay using plasma from 110 human subjects (75 males, 35 females), provides confirmation of significant correlations between the fatty acid measures and those obtained from conventional measures for all fatty acids (r > 0.97, P<0.0001), including the omega (n)-6 (r = 0.988, P<0.0001) and n-3 long chain polyunsaturated fatty acids (r = 0.997, P<0.0001). These results establish our newly developed plasma spot separation technique as a rapid and reliable method for the assessment of plasma phospholipid fatty acid composition., (Copyright © 2020. Published by Elsevier Ltd.)

Esters of fruit acids including acetic acid and mono- and diacylglycerols (MAG and DAG), also known as E 472 emulsifiers, are used in the food industry as food additives to adjust techno-functional properties like viscosity, emulsion stability and foaming stability in various products, mainly dairy products. Based on the respective acids, E 472 emulsifiers are classified in several categories with acetic acid esters (ACETEM, E 472a), lactic acid esters (LACTEM, E 472b), citric acid esters (CITREM, E 472c), and mono- and diacetyl tartaric acid esters (DATEM, E 472e) as the most prominent representatives. Besides fruit acid esters, E 472 emulsifiers mainly comprise MAG, DAG, triacylglycerols, free fatty acids, free fruit acids and free glycerol in different amounts. Here we present an innovative and sensitive method for the characterization of the composition of E 472 emulsifiers by high-performance thin-layer chromatography with fluorescence detection (HPTLC-FLD). For HPTLC-FLD, technical emulsifiers were simply dissolved and analyzed on HPTLC silica gel plates after a two-fold development and derivatization with primuline, enabling the easy characterization and direct visual comparison of the emulsifier pattern (fingerprint) through the fluorescent lipid components under UV 366 nm. Thus, the HPTLC-FLD fingerprint approach represents a simple tool for the comparison of different samples, batches and categories of E 472. Coupling of HPTLC to mass spectrometry moreover enabled the identification of constituents of interest., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Novel green nanocomposite from mesoporous MCM-41 and Co 3 O 4 was synthesized from rice husk based silica gel and using the green extract of Peach leaves as reducing reagent. The composite was labeled as RH-MCM-41/Co 3 O 4 and characterized by different techniques as green photocatalyst in the degradation of Acephate pesticide under visible light illumination. The composite showed well developed spherical MCM-41 particles decorated by nano Co 3 O 4 nanoparticles with stunning surface area and low bandgap energy (1.51 eV). The composite displayed superior photocatalytic activities in the oxidation of Acephate which reflected in a complete degradation of different concentrations of it after 40 min (50 mg/L), 60 min (100 mg/L), 100 min (150 mg/L) and 140 min (200 mg/L) using 0.25 g of the composite. The complete removal of the present TOC for treatment of 100 mg/L acephate was achieved using 0.25 g after 70 min reflecting the formation of intermediate compounds during the oxidation steps. The reported intermediate compounds are CH 3 C(O)NH 2 , CH 3 O(CH 3 S)P(O)NH 2 , (CH 3 O) 2 P(O)SCH 3 , CH 3 OP(O)(OH) 2 , CH 3 SS(O) 2 CH 3 , and (COOH) 2 . All the formed intermediate compounds were degraded under the visible light photocatalytic activity of RH-MCM-41/Co 3 O 4 into NO 3 - , SO 4 2- , PO 4 3- , and CO 2 as final products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

This study presented a HPTLC platformed luminescent biosensor system for screening captan residue. First, the potential bio-effects of layers materials on the detectability of a luminescent bacteria Photobacterium phosphoreum (ATCC 11040) as the sensor cell were assessed. From comparison, it was noteworthy that the combination of sensor cells with normal silica gel layer exclusively gave outstanding detectability (<10 ng/zone). On this basis, HPTLC mediated separation and biosensing was further optimized. Then, the obtained graphic results were digitally quantified via software processing, offering satisfactory selectivity, linearity (R 2  = 0.9901 within 10-80 ng/zone) and sensitivity (0.5 mg/kg against MRLs ≥ 6 mg/kg). Additionally, the performance of the established method was validated with different fruits (recover rates 75-96%, RSD < 11.8%). Meanwhile, it was demonstrated that detectability of this hybrid system would be tuneable by altering the combination of bacteria strains and layer materials, which was meaningful to strengthen the usability of microbial biosensors., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Diatomaceous earth or diatom (DE) are naturally available and low cost micro particles with distinct porous structure were used as an adsorbent for the removal of a hazardous dye, Eriochrome Black T (EBT). The surface modification of these DE were performed by sol-gel and hydrothermal methods to obtain a series of adsorbents such as diatom-ceria (DC), diatom-silica xerogel (DX), and diatom-silica xerogel-ceria (DXC). A cauliflower like morphology structure of ceria was observed on DE and DX. The adsorption performance of EBT was conducted by varying various parameters such as pH, adsorbent dosage, initial concentration, contact time and ionic strength. The materials DE, DC, DX and DXC showed the EBT removal efficiencies of 52, 77, 20, and 93%, respectively. The maximum adsorption capacity (qm) of DE, DC, DX and DXC was found to be 13.83, 23.64, 0.2 and 47.02 mgg -1 for the adsorption of EBT, respectively. The selectivity of EBT towards DXC was evaluated by treating a mixture of anionic dyes. The dye removal experiments was performed in presence of inorganic salts, however the presence of these salts did not affect the removal efficiency of DXC. Furthermore, the reusability of DXC was studied by recycling it up to 5 times and even at 5th cycle a removal efficiency of ∼66.8% was found. Thus, these studies demonstrate that the DXC material could be a promising candidate for the removal of EBT via adsorption for real time application in water treatment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

1-Phenylthiosemicarbazide bonded modified silica gel (PTC-SG) was synthesised and characterised by FTIR, SEM and elemental analysis for a novel separation/preconcentration of multiple elements based on solid phase extraction. The analytical parameters including pH of solutions, amounts of PTC-SG, flow rates of sample, eluent type and sample volume were optimised. The adsorption capacities of PTC-SG were found to be 7.9, 6.4, 6.3, 8.3, 7.2, 8.9 and 6.6 mg/g for Cu(II), Cd(II), Pb(II), Co(II), Cr(III), Ni(II) and Mn(II), respectively. The limit of detection (LOD) was calculated as 3x the standard deviation(s) of the reagent blank (k = 3, N = 21) and the LOD values were obtained to be 0.98 µg L -1 (Cu), 0.65 µg L -1 (Cd), 0.57 µg L -1 (Pb), 1.12 µg L -1 (Co), 1.82 µL -1 (Cr), 1.67 µg L -1 (Ni) and 0.55 µg L -1 (Mn). Certified reference materials were used to test the validation of the present method. The new solid phase extraction method was successfully applied to determination of the amount of multiple elements in food and beverage samples.

We study the interplay between a crack tip slowly propagating through a hydrogel and nanoparticles suspended in its liquid environment. Using a proteinic gel enables us to tune the electrostatic interaction between the network and silica colloids. Thereby, we unveil two distinct, local toughening mechanisms. The primary one is charge independent and involves the convective building of a thin particulate clog, hindering polymer hydration in the crack process zone. When particles and network bear opposite charges, transient adhesive bonding superimposes, permitting the remarkable pinning of a crack by a liquid drop.

Silica gel chitosan composite was prepared to perform adsorptive experiment of different heavy metal ion solutions. The characterization of chitosan + silica gel (Ch + Sg) composite was done by FTIR and SEM-EDS to understand the presence of active sites and to have an insight on the surface morphology. The adsorption study of heavy metal ions by Ch + Sg composite gives maximum removal percent for Cu, Pb and Ni which were obtained at pH 5 and for Hg at pH 6.The trend of removal by Ch + Sg signifies that maximum removal percent was attained at 120 min. The surface of Ch + Sg is heterogeneous for the adsorption of Hg, Ni and Cu and homogeneous for Pb adsorption. The values obtained for Pb signify that its adsorption best fitted to pseudo first order with the R 2 value of 0.986, whereas pseudo second order best fitted to the experimental data of Cu, Ni and Hg as R 2 values which are 0.983, 0.819 and 0.957 respectively. The values of change in entropy (⊿S) obtained for Pb, Cu, Ni and Hg are - 69.33, - 118, - 63.33 and - 98.52 J/mol K respectively. Negative values of change in enthalpy, ⊿H in (kJ/mol) are in the range of - 18.2 to - 37.66 which indicates both physical and chemical adsorption involves in the process of adsorption.

Our research focused on applying microextraction by packed sorbent to extracting antisense oligonucleotides from serum samples. The tested sorbents included poly(styrene-co-divinylbenzene), octyl, octadecyl, and unmodified silica gel. As nonpolar sorbents were used for highly-polar molecules, this required ion-pair mode. Comprehensive optimization of extraction conditions was performed for 20-mer phosphorothioate oligonucleotide. Several parametres - the number of "draw-eject" cycles during the conditioning and load step, the amine type and concentration, and the volume of elution mixture - and the influence they had on recovery were studied for nonpolar sorbents, which made it possible to obtain high (ca. 90%) recovery values. The most influential parameter turned out to be the volume of elution mixture. Similar optimization was performed for silica sorbents; however, despite optimization of various parameters, the recovery values stayed relatively low. The optimized procedures for nonpolar sorbents were applied in extraction of six different oligonucleotides of various length and with different structure modifications. The highest recoveries were obtained for octyl and octadecyl sorbents, ranging between 80-99%. The developed microextraction method was used to extract phosphorothioate and 2'-O-(2-methoxyethyl) oligonucleotides and their two synthetic metabolites from enriched human plasma, with recoveries around 70-80%.

Pluchea indica Less. is a medicine and food dual-use plant, which belongs to the Pluchea genus, Asteraceae family. Its main constituents are quinic acids, flavonoids, thiophenes, phenolic acids, as well as sesquiterpenes. In order to provide a comprehensive chemical profiling of P. indica , an orthogonal chromatography combining reverse-phase chromatography BEHC18 column with a normal-phase chromatography silica column as the separation system and a ESI-Q-Orbitrap MS as the detector in both positive and negative ion modes were used. According to the retention time ( t R ) and the exact mass-to-charge ratio ( m/z ), 67 compounds were unambiguously identified by comparing to the standard references. Moreover, 47 compounds were tentatively speculated on the basis of the rules of MS/MS fragmentation pattern and chromatographic elution order generalized from the above-mentioned reference standards. Among them, 10 of them were potentially novel.

Bioactive peptides have a positive impact on body functions and conditions and may influence health. However, peptides are degraded by digestive enzymes, such as pepsin in the stomach when ingested orally. In order to solve this problem, we previously focused on porous silica gel and found that by using calcined silica gel, hydrophobic and negatively charged peptides could be efficiently delivered into the intestine, because peptides adsorbed on the cavity of the silica gel could be protected from enzymatic degradation. Therefore, in this study, we attempted to develop peptides whose physicochemical properties were suitable for intestinal delivery without lowering their activity. We also proposed guidelines of predictive selection of such peptides. For that purpose, we selected hypercholesterolemic peptides as a model and re-designed the peptides based on the previously reported color map, in which intestinal delivery degree was predictively depicted as contour lines. As a result, we succeeded in getting five different re-designed peptides from 1265 substituted peptide derivatives. These peptides showed a dual function of being suitable for intestinal delivery with silica gel and for disruption of bile acid micelles. The release amount of IYEYMY was 2.09 times the parent peptide, which was the highest., (Copyright © 2019 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.)

Background: Soybean lecithin powders are good sources of phytosterol glucosides (PGs) containing acyl-sterylglycosides (ASGs) and sterylglucosides (SGs), but PG extraction from soybean lecithin powder is difficult due to the solubilizing property of phospolipids. To comprehensively utilize soybean lecithin resources, an evaluation system construction and factor impact analysis of PG extraction by silica-gel adsorption was investigated in this article., Results: With high-performance liquid chromatography (HPLC) as the main experimental analysis method, software such as SIMICA and SPSS were applied to construct an evaluation system of PG extraction. Different from scores plot in SIMICA for distinguishing samples in chloroform from others, the loading plot and binary variant correlation analysis of all indicators in PG extraction were brought to confirm four evaluation indicators containing PG purity, ASG recovery, SG recovery and phospholipid recovery. In the factor impact analysis, four times elution from silica-gel sediment was enough to achieve a PG product with least reagent waste, while SPW in petroleum ether at 50 mg mL -1 with 1:3 silica-gel dosage (lecithin/silica-gel, w/w) was then determined as the optimum of single factors., Conclusion: All studies in this article were of great significance, as they laid foundations for research of PG extraction procedure, as well as PG industrial production, facilitating the comprehensive utilization of lecithin resources. © 2019 Society of Chemical Industry., (© 2019 Society of Chemical Industry.)

A methionine methyl ester-modified coumarin derivative was designed and synthesized, which could discriminate Cu 2+ from other metal ions in HEPES buffer (10 mM, pH 7.4)/CH 3 CN (40:60, V/V). The detection limit of WM toward Cu 2+ was 1.84 × 10 -7  M, which was lower than the concentration of Cu 2+ in drinking water suggested by WHO and EPA. And the proposed coordination mode exhibiting the interaction between WM and Cu 2+ was studied by UV-Vis, fluorescence spectrum, ESI-MS and FT-IR. Based on the fluorescent reversibility of WM, WM was considered as a molecular logic gate and molecular keypad lock. In addition, the test strips and the silica gel plates prepared from the solution of WM also demonstrate the favorable selectivity toward Cu 2+ ., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Water pollution caused by Cr(III) is a serious environmental problem which bring adverse effect to environmental protection and public safety. Efficient removal of Cr(III) from aqueous solution is important for the remediation of Cr(III) pollution. Herein, a series of silica-gel/polyamidoamine (PAMAM) dendrimer hybrid materials (SG-G0~SG-G4.0) were used for the removal of Cr(III) from aqueous solution. The factors that affect the adsorption were extensively studied and the adsorption mechanism was demonstrated based on the experimental results and density functional theory (DFT) calculation. Result demonstrates the adsorption capacity of ester-terminated silica-gel/PAMAM dendrimers follow the order of SG-G2.5 > SG-G3.5 > SG-G1.5 > SG-G0.5, while that of amino-terminated ones decrease in the order of SG-G2.0 > SG-G4.0 > SG-G3.0 > SG-G1.0 > SG-G0. The highest adsorption is achieved at pH 4.0 for both ester- and amino-terminated materials. Adsorption kinetic indicates the adsorption equilibrium can be reached at about 240 and 180 min for amino- and ester-terminated hybrids, respectively. Adsorption kinetic can be well fitted by pseudo-second-order kinetic model with film diffusion process as the rate-limiting step. Adsorption isotherm follows Langmuir model with monolayer adsorption behavior. Fourier transform infrared spectra (FTIR) indicate the adsorption of Cr(III) by PAMAM dendrimer mainly involve the participation of N-H and C=O groups. DFT calculation demonstrates the uptake of Cr(III) by ester-terminated adsorbents mainly involves carbonyl oxygen and secondary amine nitrogen atoms to form tetra-coordinated chelate, while that of amino-terminated one tends to form hexa-coordinated chelates by carbonyl oxygen, primary and secondary amine nitrogen atoms.

Copper is an essential element in many biological processes and plays an important role in carbohydrate and lipid metabolism. Excess or deficiency of Cu ions can cause disturbances in cellular homeostasis and damage the central nervous system. Here, for the first time, two functionalized silica gel (SG-A and SG-B) adsorbents were prepared and tested for copper detection via the reactions of chlorinated silica gel with two novel D-π-A Schiff base compounds: 2-amino-3-(quinolin-2-ylmethyleneamino)maleonitrile (A) and 2-(4-(diethylamino)-2-hydroxybenzylideneamino)-3-aminomaleonitrile (B) in the thionyl chloride solution, respectively. SG-A and SG-B as adsorbents filled in a microcolumn were used to enrich trace Cu ions in foods and water with the detection of flame atomic absorption spectrometry. Because of the strong coordination between two D-π-A Schiff base compounds and Cu 2+ ions, the stable heterocyclic Cu 2+ -SG-A/B complex is formed. For a sample volume of 30 mL, detection limits of 0.09 μg L -1 and 0.15 μg L -1 have been achieved. The results of selectivity study show that the two adsorbents can selectively extract Cu 2+ in complex matrixes with other metal cations. The methods have been successfully applied to the determination of Cu 2+ content in various real samples, and the detection sensitivity that we report here is better than most results reported using modified silica gels.

This work describes the direct coupling of the in-tube solid-phase microextraction (in-tube SPME) technique to a tandem mass spectrometry system (MS/MS) to determine amino acids (AA) and neurotransmitters (NT) (alanine, serine, isoleucine, leucine, aspartic acid, glutamic acid, lysine, methionine, tyrosine, and tryptophan) in plasma samples from schizophrenic patients. An innovative organic-silica hybrid monolithic capillary with bifunctional groups (amino and cyano) was developed and evaluated as an extraction device for in-tube SPME. The morphological and structural aspects of the monolithic phase were evaluated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), nitrogen sorption experiments, X-ray diffraction (XRD) analyses, and adsorption experiments. In-tube SPME-MS/MS conditions were established to remove matrix, enrich analytes (monolithic capillary) and improve the sensitivity of the MS/MS system. The proposed method was linear from 45 to 360 ng mL -1 for alanine, from 15 to 300 ng mL -1 for leucine and isoleucine, from 12 to 102 ng mL -1 for methionine, from 10 to 102 ng mL -1 for tyrosine, from 9 to 96 ng mL -1 for tryptophan, from 12 to 210 ng mL -1 for serine, from 12 to 90 ng mL -1 for glutamic acid, from 12 to 102 ng mL -1 for lysine, and from 6 to 36 ng mL -1 for aspartic acid. The precision of intra-assays and inter-assays presented CV values ranged from 1.6% to 14.0%. The accuracy of intra-assays and inter-assays presented RSE values from -11.0% to 13.8%, with the exception of the lower limit of quantification (LLOQ) values. The in-tube SPME-MS/MS method was successfully applied to determine the target AA and NT in plasma samples from schizophrenic patients.

Mineral oil saturated and aromatic hydrocarbons (MOSH/MOAH) are food contaminants, mainly due migration from packaging materials made from recycled fibers, but other routes of entry into food have also been identified. Legal limits for MOSH and MOAH in food and food contact materials currently are not set, but are to be expected in the near future. For the analysis of MOSH and MOAH, the very well developed and highly automated on-line liquid chromatography-gas chromatography with flame ionization detection (LC-GC-FID) is commonly used. However, this approach is time-consuming, and data interpretation is a very challenging task. Therefore, a planar solid phase extraction (pSPE) method was developed for a rapid and efficient MOSH and MOAH screening in paper and cardboard. Based on high-performance thin-layer chromatography (HPTLC), pSPE offers the simultaneous clean-up and analysis of up to 20 samples in parallel, while MOSH and MOAH analytes were focused in two distinct target zones on silica gel HPTLC plates after a twofold development. Plate impregnation with primuline allowed the detection of MOSH by fluorescence, while MOAH were detected by UV light absorption. The pSPE screening approach provided limits of detection of 7.2 and 2.3 ng/zone for MOSH and MOAH, respectively, corresponding to 1.8 and 0.6 mg/kg paper. Coupling of pSPE with GC revealed the common MOSH and MOAH peak humps, while marker substances offered the identification of the mineral oil origin or information about recycled fiber materials. As compared to SPE-GC-FID analyses, the determined quantities of MOSH and MOAH in cardboard samples indicated pSPE as a rapid and suitable screening tool. The co-migration of polyolefin oligomeric saturated hydrocarbons, native n-alkanes, terpenes and possibly essential oils or sterol esters, however, can result in an overestimation of MOSH and MOAH. Hence, samples with pSPE results above a given limit are subsequently analyzed by GC (pSPE-GC) for confirmation and detailed evaluation., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The application of boronic acid affinity chromatography to glycoprotein/glycopeptide enrichment is increasingly maturing. The enrichment selectivity, biocompatibility, and facile operation protocol are key aspects in efficient enrichment methods. In this work, a novel triazo-cyanide boronic acid functionalized material (TCNBA) was prepared using triazo-cyanide click chemistry. The TCNBA was proved to be successfully synthesized through infrared ray (IR) characterization. Subsequently, the glycopeptide/glycoprotein enrichment selectivity of the TCNBA was evaluated. Matrix-assisted laser desorption/ionization time-of-flight mass (MALDI-TOF MS) was employed for the glycopeptide enrichment selectivity evaluation. Taking the digestion of horseradish peroxidase (HRP) and immunoglobulin G (IgG) as samples, 13 and 11 glycopeptides could be characterized with improved signals after TCNBA enrichment, respectively. High abundance non-glycopeptides could be removed effectively from the eluting fraction. This result indicates the high glycopeptide enrichment selectivity of TCNBA. In addition, a mixture of HRP and bovine serum albumin (BSA) enzymatic solution (1:10, amount of substance ratio) was utilized as a sample, and five glycopeptide signals could be identified following enrichment. To evaluate the glycoprotein enrichment selectivity, sodium salt-polyacrylamide gel electrophoresis (SDS-PAGE) was adopted as an evaluation method. Mixtures of HRP, IgG, BSA, and ribonuclease B (RNaseB) proteins were employed as samples, and the results demonstrated that TCNBA had a high glycoprotein enrichment selectivity. The application of TCNBA to the analysis of a real biosample was also evaluated using human plasma. The results indicated the TCNBA could be utilized in large-scale glycoprotein analysis.

Dopamine, norepinephrine, and epinephrine neurotransmitters can be detected by electrochemical oxidation in conventional electrodes. However, their similar chemical structure and electrochemical behavior makes a difficult selective analysis. In the present work, glassy carbon electrodes have been modified with silica layers, which were prepared by electroassisted deposition of sol⁻gel precursors. These layers were morphologically and compositionally characterized using different techniques, such as field emission scanning electron microscopy (FESEM), TEM, FTIR, or thermogravimetric analysis⁻mass spectrometry (TG-MS). The affinity of silica for neurotransmitters was evaluated, exclusively, by means of electrochemical methods. It was demonstrated that silica adsorbs dopamine, norepinephrine, and epinephrine, showing different interaction with silica pores. The adsorption process is dominated by a hydrogen bond between silanol groups located at the silica surface and the amine groups of neurotransmitters. Because of the different interaction with neurotransmitters, electrodes modified with silica films could be used in electrochemical sensors for the selective detection of such molecules.

The urgent demand for pure biological and pharmaceutical enantiomers has brought together great efforts in developing chiral techniques. High-performance liquid chromatography employing chiral stationary phases (CSPs) has evolved as a powerful tool for both chiral analysis and manufacture of pure enantiomers. Herein, we describe a facile method to prepare a phenylcarbamate cyclodextrin (CD)-based CSPs via azide/alkyne click chemistry. The functionalities of CD rims are altered to mediate the enantioseparation performance in multimode high-performance liquid chromatography.