Facile preparation of a high‐capacity boronate‐affinity adsorbent based on low‐cost commercial supports for selective enrichment of cis‐diol‐containing biomolecules

Boronate‐affinity adsorbents have been regarded as favorable extraction adsorbents for the pretreatment of cis‐diol‐containing biomolecules owning to their specific selectivity, but most of them have low adsorption capacity and a tedious synthesis methods. In this study, a new boronate‐affinity material (PGMA@FPBA) with high adsorption capacity was synthesized via a “one‐pot” method based on a low‐cost commercial support. The PGMA@FPBA was characterized by Fourier transform infrared spectroscopy (FT‐IR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and nitrogen adsorption/desorption measurements. The as‐prepared adsorbent showed good selectivity, high adsorption capacity (448 μmol/g for catechol), and fast adsorption equilibration (1 min) for cis‐diol‐containing biomolecules. Subsequently, as an example for application, the obtained PGMA@FPBA was used as a dispersive solid‐phase extraction (d‐SPE) adsorbent for enrichment of quercetin in red wine. The results indicated that the facile‐prepared boronate‐affinity adsorbent has great potential application for separation and enrichment of cis‐diol‐containing biomolecules in complex samples.     

The influence of mercury(II) on the extraction efficiency of herbicides from water

In this work, the effect of Hg(II) on the extraction efficiency of triazine and phenylurea herbicides from water samples was tested. The results showed that in the presence of Hg(II), the recoveries of the s-triazine herbicides (except hexazinon) from styrene divinylbenzene (SDVB) cartridges were significantly reduced using acetonitrile as the elution solvent, whereas acidified methanol quantitatively eluted all the herbicides. Consequently, the loss in the recoveries was not due to degradation of the compounds but rather due to irreversible adsorption onto the resin. The adsorption is probably due to ternary complex formation between the compounds, Hg(II) and the polymeric resin. The chemical structure and the basicity of the compounds affected their interaction with Hg(II). When using octadecyl (C18) cartridges, only atraton was affected. Mercury did not affect the liquid–liquid extraction of the herbicides. The findings suggest that acidic methanol is a suitable elution solvent of s-triazines from mercury-loaded water samples.     

Separation of capsaicin from capsaicinoids by simulated moving bed chromatography

Capsaicinoids were separated from capsicum oleoresin by solvent extraction and adsorption separation on macropore resin, and used directly as the feed of simulated moving bed. Using a mobile phase of methanol/water (75/25, v/v) and ODS columns, the two key components, capsaicin and dihydrocapsaicin, were separated completely, while part of minor weak impurities were discarded by forcing them to leak into zone I. The amount of discarded impurities increases with decreasing flow rate in zone I so that the purity of capsaicin in raffinate stream could be improved.     

Neutron activation analysis in forensic investigations: Trace elements characterization of cigarettes

A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO₂-P, was prepared by impregnating a crown ether derivative, 4,4￠,(5￠)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO₂-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO₃ This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics of the adsorption of strontium(II) by a novel silica-based 4,4'',(5'')-di(tert-butylcyclohexano)-18-crown-6 extraction resin in nitric acid medium

A new type of silica-based chelating extraction resin, DtBuCH18C6/SiO₂-P, was prepared by impregnating a crown ether derivative, 4,4,(5)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6), into the porous silica/polymer composite particles (SiO₂-P). The adsorption of Sr(II) and some other fission product elements was investigated by a batch adsorption experiment in HNO₃ medium. It was found that Sr(II) exhibits a strong adsorption onto the extraction resin, while the other fission product elements show almost no or only weak adsorption. The adsorption kinetics of Sr(II) was explained by assuming as the rate-controlling step the complex-formation reaction between Sr(II) and DtBuCH18C6 contained in the extraction resin. The rate equation of Sr(II) adsorption was determined as:-d[Sr(II)]/dt = k[Sr(II)][DtBuCH18C6][NO₃ ^–]^0.5.     

Hybridization of Al2O3 microspheres and acrylic ester resins as a synergistic absorbent for selective oil and organic solvent absorption

In this study, we have focused on the synthesis, characterization, and oil absorption properties of Al₂O₃ microspheres/acrylic ester resin (AER) hybrids. The Al₂O₃ microspheres are prepared by a combined hydrothermal and sintering processes, followed by surface modification with silane coupling agent (KH 570). The Al₂O₃ microspheres/AER hybrids with a rough surface are synthesized by a microwave polymerization route by using modified Al₂O₃ microspheres as modifiers. In this hybrid materials system, the Al₂O₃ microspheres with porous structures may provide fast oil absorption due to the low oils absorption energy and short diffusion lengths. The resin hybrids exhibited reversible oils and organic solvents adsorption with maximum absorption capacities up to 29.85 g/g. This study suggests potential environmental advantage in using metal oxide microspheres in improving the oil absorption properties of oil‐absorbing resins as absorbents for recovering oil and organic solvent from water.     

Batch and dynamic extraction of uranium(VI) from nitric acid medium by commercial phosphinic acid resin,Tulsion CH-96

Batch and dynamic extractions of uranium(VI) in 10⁻³–10⁻²M concentrations in 3–4M nitric acid medium have been investigated using a commercially available phosphinic acid resin (Tulsion CH-96). The extraction of uranium(VI) has been studied as a function of time, batch factor (V/m), concentrations of nitric acid and uranium(VI) ion. Dual extraction mechanism unique to phosphinic acid resin has been established for the extraction of uranium(VI). Distribution coefficient (K _d ) of uranium(VI) initially decreases with increasing concentration of nitric acid, reaches a minimum value at 1.3M, followed by increases in K _d . A maximum K _d value of ∼2000 ml/g was obtained at 5.0M nitric acid. Batch extraction data has been fitted into the linearized Langmuir adsorption isotherm. The performance of the resin under dynamic extraction conditions was assessed by following the breakthrough behavior of the system. Effect of flow rate, concentrations of nitric acid and uranium ion in the feed on the breakthrough behavior of the system was studied and the data was fitted using Thomas model.     

Separation and purification of flavonoid from Taxus remainder extracts free of taxoids using polystyrene and polyamide resin

An efficient separation process of flavonoid from Taxus wallichiana var. mairei remainder extracts free of taxoids was developed in this study. AB‐8 macroporous resin and polyamide resin offered the fine adsorption capacity, and its adsorption rate at 30°C fitted well to the Langmuir and Freundich isotherms. Resin dynamic adsorption and desorption experiments were conducted to optimize the separation process of total flavonoids from T. wallichiana var. mairei remainder extracts free of taxoids. The optimum parameters for adsorption by AB‐8 resin were as follows: (1) the concentration of flavonoids in a sample solution of 5.61 mg/mL with a processing volume of 2 bed volume (BV) (60 mL); (2) for desorption, ethanol–water (80:20, v/v), with 6 BV as an eluent at a flow rate of 2 BV/h. After a one‐run treatment with AB‐8 resin, the content of flavonoids was increased 5.10‐fold from 4.05 to 20.65%. The optimum parameters for adsorption by polyamide resin were as follows: processing volume of 2 BV (30 mL); for desorption, ethanol–water (70:30, v/v), with 8 BV as an eluent at a flow rate of 2 BV/h. After one‐run treatment with polyamide resin, the content of total flavonoids increased from 20.65 to 65.21%. The method will provide a potential approach for large‐scale separation and purification of flavonoid for its wide pharmaceutical use.     

Preparation and characterization of molecularly‐imprinted polymers for extraction of sanshool acid amide compounds followed by their separation from pepper oil resin derived from Chinese prickly ash (Zanthoxylum bungeanum)

Molecularly imprinted polymers were prepared using the molecular structure analogs of sanshool as template molecule, 2‐vinylpyridine and β‐cyclodextrin as double functional monomers, ethylene dimethacrylate as cross linker, and azobisisobutyronitrile as initiator. The structural characteristics of the polymers were determined by Fourier‐transform infrared spectroscopy and scanning electron microscopy. Dynamic adsorption and isothermal adsorption were also investigated. The molecularly imprinted polymers were used to prepare a molecularly imprinted solid‐phase extraction column in order to separate acid amide components from pepper oil resin derived from Chinese prickly ash (Zanthoxylum bungeanum). After eluting, the percentage of acid amide components was enhanced to 92.40 ± 1.41% compared with 23.34 ± 1.21% in the initial pepper oil resin, indicating good properties of purification of molecularly imprinted polymers and potential industrial application.     

Extraction of palladium from nitric acid medium by commercial resins with phosphinic acid,methylene thiol and isothiouronium moieties attached to polystyrene-divinylbenzene

Summary Commercially available polystyrene-divinylbenzene (PS-DVB) resins functionalized with isothiouronium (Tulsion CH-95), phosphinic acid (Tulsion CH-96) and methylene thiol (Tulsion CH-97) moieties have been used for separating palladium from nitric acid medium. Extraction of palladium has been studied as a function of time, concentration of nitric acid and palladium. The distribution coefficients (K_d, ml/g) of palladium on sulfur based resins (Tulsion CH-95 and Tulsion CH-97) are higher (5000-10⁴ml/g in 0.1M nitric acid) than on Tulsion CH-96 resin and decrease with increasing concentration of nitric acid. The initial rate of extraction of palladium by Tulsion CH-95 and Tulsion CH-97 resins was very rapid and the time required for the establishment of equilibrium was a function of palladium concentration in the aqueous phase. The rate data could be fitted by a second order rate equation and the magnitude of rate constant for the extraction of palladium by these resins (~10²M^-1. min^-1) decreased in the order of: Tulsion CH-95 > Tulsion CH-97 > Tulsion CH-96. The extraction isotherms of Tulsion CH-95 were fitted by Langmuir adsorption model and the coefficients were obtained by regression. The extraction capacity of palladium on Tulsion CH-95 was found to be ~20 mg/g at 3M nitric acid. Column experiments have been conducted and the data were fitted using Thomas model. A column utilization of 75% was achieved for the extraction of palladium by Tulsion CH-95 resin.     

Adsorption of uranium ions by crosslinked polyester resin functionalized with acrylic acid from aqueous solutions

In this paper, the crosslinked polyester resin containing acrylic acid functional groups was used for the adsorption of uranium ions from aqueous solutions. For this purpose, the crosslinked polyester resin of unsaturated polyester in styrene monomer (Polipol 353, Poliya) and acrylic acid as weight percentage at 80 and 20%, respectively was synthesized by using methyl ethyl ketone peroxide (MEK_p, Butanox M60, Azo Nobel)-cobalt octoate initiator system. The adsorption of uranium ions on the sample (0.05 g copolymer and 5 mL of U(VI) solution were mixed) of the crosslinked polyester resin functionalized with acrylic acid was carried out in a batch reactor. The effects of adsorption parameters of the contact time, temperature, pH of solution and initial uranium(VI) concentration for U(VI) adsorption on the crosslinked polyester resin functionalized with acrylic acid were investigated. The adsorption data obtained from experimental results depending on the initial U(VI) concentration were analyzed by the Freundlich, Langmuir and Dubinin–Radushkevich (D–R) adsorption isotherms. The adsorption capacity and free energy change were determined by using D–R isotherm. The obtained experimental adsorption data depending on temperature were evaluated to calculate the thermodynamic parameters of enthalpy (ΔH°), entropy (ΔS°) and free energy change (ΔG°) for the U(VI) adsorption on the crosslinked polyester resin functionalized with acrylic acid from aqueous solutions. The obtained adsorption data depending on contact time were analyzed by using adsorption models such as the modified Freundlich, Elovich, pseudo-first order and pseudo-second-order kinetic models.     

Ionic Liquid-Based Dispersive Extraction and Separation of Phenolic Acids from Salicornia Herbacea L.

This study reports the application of a dispersive extraction method for the extraction and separation of phenolic acids from Salicornia Herbacea L. using silica-confined ionic liquids as the sorbent. A suitable sorbent for phenolic acid extraction and separation was first identified based on the adsorption behavior of phenolic acids on different silica-confined ionic liquids. The sample was then mixed with the optimized sorbent and solvent to achieve dispersive extraction. After transferring the supernatant to an empty cartridge, a solid phase extraction process was used to separate the three organic acids from other interferences. Through systematical optimization, the optimal conditions were obtained with high recovery rates of protocatechuic acid (98.1%), caffeic acid (89.4%), and ferulic acid (92.2%). Overall, the proposed method expected to have wide applicability.     

Effects of active carbon pore size distributions on adsorption of toxic organic compounds

The use of active carbons for the removal of toxic organic compounds, for example from air or smoke, is of significant interest. In this paper, the equilibrium and dynamic adsorption characteristics of two active carbons are explored; one microporous coconut based and the other micro-mesoporous derived from a synthetic resin. Benzene, acetaldehyde and acrylonitrile were chosen as the probe toxicant vapours and adsorption was measured at a temperature of 298 K. The nitrogen equilibrium data (at 77 K), analysed using the BET, Dubinin-Radushkevich equations and DFT models, showed a higher overall adsorption capacity, more supermicroporosity and a higher proportion of pores wider than 2 nm for the synthetic resin based material. A micropore distribution biased toward the ultramicropore width-range was observed for the nutshell material. As a consequence, the characteristic adsorption energies in micropores are higher for the nutshell material than the resin based carbon. The effect of these different pore size characteristics on the adsorption kinetics, obtained by fitting the data to the linear driving force (LDF) model, is that the resulting adsorption rate constants are higher across much of the relative pressure range (p/p ^s ) studied for the resin based carbon compared to the nutshell material. Significantly, the wider pores of the resin-based carbon result in higher rates of adsorption in the micropore filling domain. When evaluated under dynamic conditions in cigarette smoke, improved toxicant removal was observed using the resin based carbon.     

Evaluation study on properties of isohexyl-BTP/SiO2-P resin for direct separation of trivalent minor actinides from HLLW

In order to develop a direct separation process for trivalent minor actinides from fission products in high level liquid waste (HLLW) by extraction chromatography, a novel macroporous silica-based 2,6-bis(5,6-diisohexyl)-1,2,4-triazin-3-yl)pyridine resin (isohexyl-BTP/SiO₂-P resin) was prepared. The content of isohexyl-BTP extractant in the resin was as high as 33.3 wt%. The resin exhibited much higher adsorption affinity for Am(III) in 2–3 M (mol/L) HNO₃ solution over U and FP which are contained in HLLW. The kinetic data were analyzed using pseudo-second-order equation. The results suggested that the Eu(III), Gd(III), and Dy(III) adsorption was well explained by the pseudo-second-order equation. Quantitative desorption for adsorbed elements was achieved by using H₂O or thiourea as eluting agents. However, the kinetics of adsorption and desorption were rather slow and this drawback needs to be resolved. Stability of the resin against HNO₃ was also examined. It was found that the resin was considerably stable against ≤4 M HNO₃ solution for the reasons of an extremely small leakage of the extractant into the solution from the resin and the adsorption performance keeping for rare earths in 3 M HNO₃ solution.     

Preparation and evaluation of a molecularly imprinted sol–gel material as the solid‐phase extraction adsorbents for the specific recognition of cloxacilloic acid in cloxacillin

Highly selective molecularly imprinted polymers on the surface of silica gels were prepared by a sol–gel process and used as solid‐phase extraction adsorbents for the specific recognition, enrichment and detection of cloxacilloic acid in cloxacillin. The obtained polymers were characterized by scanning electron microscopy, FTIR spectroscopy, nitrogen adsorption and desorption, elemental analysis and thermogravimetric analysis. The imprinted polymers not only possessed high adsorption capacity (6.5 μg/mg), but also exhibited fast adsorption kinetics (they adsorb 80% of the maximum amount within 20 min) and excellent selectivity (the imprinted factor was 3.6). A method using the imprinted polymers as solid‐phase extraction adsorbents coupled with high‐performance liquid chromatography was established with good specificity, linearity (r = 0.9962), precision (ranging from 0.5 to 6.7%), accuracy (ranging from 93.9 to 97.7%) and extraction recoveries (ranging from 78.8 to 89.8%). The limits of detection and quantification were 0.07 and 0.25 mg/g, respectively. This work could provide a promising method in the enrichment, extraction and detection of allergenic impurities in the manufacture, storage and application of cloxacillin.     

Neutron irradiation in activation analysis: A new rabbit for the NBSR

Two radiochemical separation methods were developed for the separation of ⁸⁸Y from a SrS target (3.2 g, pressed into a 19 mm disc) and Al (2.5 g, the capsule contained the target). The first method was based on solvent extraction technique using undiluted TBP/HNO₃ system and the second was an extraction chromatography using a column packed with TBP-impregnated Amberlite XAD-4 resin. A simple procedure was used for the impregnation of the XAD-4 resin with TBP. For both methods concentrated nitric acid was used for extraction/adsorption and 2M HCl for back extraction/elution of ⁸⁸Y. In terms of recovery of ⁸⁸Y, the solvent (TBP)-impregnated resin showed better results (average 91.2% compared to 88.9% with extraction).     

Extraction and preconcentration of toxic metal ions from aqueous solution using benzothiazole-based chelating resins

Polystyrene-divinylbenzene resin (PS-DVB) was functionalized with a benzothiazole group. PS-DVB with amino group was initially prepared by nitration and reduction reactions and subsequently treated with ethyl 2-benzothiazolylacetate (BA) to obtain the chelating resin with an amide linkage (BA-PS-DVB). Meanwhile, the amino-PS-DVB was diazotized and coupled with BA to obtain the chelating resin with an azo linkage (azo-BA-PS-DVB). The resins were characterized by elemental analysis and infrared spectroscopy and evaluated for their extraction of Cd(II), Cu(II) and Pb(II) ions in water before their determinations by flame atomic absorption spectrometry (FAAS). Extraction conditions were optimized for batch method such as the pH of the solution, the extraction time and the adsorption isotherm. The optimum pH for the extraction of Cd(II), Cu(II) and Pb(II) are 8.0, 7.0 and 6.0, respectively, while the equilibrium time of all ions was reached within 10-20 min. The adsorption behavior of all the metal ions followed the Langmuir adsorption isotherm. In the column method, the optimum flow rates of metal sorption onto BA-PS-DVB and azo-BA-PS-DVB columns were 2.5 and 4.0 mL min^− 1. Metal ions sorbed onto columns were eluted by 0.5 to 2.0 M HNO₃. The preconcentration factors of Cd(II) and Cu(II) on azo-BA-PS-DVB and Cu(II) on BA-PS-DVB were 50, 50, and 20, respectively. The present column method gave acceptable validation results: 71.2 and 74.0% recovery for Cd(II) and Cu(II) and an overall relative standard deviation (R.S.D) less than 10% (n = 15). The proposed method was applicable for determining Cu(II) in drinking water.     

Preliminary extraction of tannins by 1‐butyl‐3‐methylimidazole bromide and its subsequent removal from Galla chinensis extract using macroporous resins

In recent years, ionic liquids have become increasingly attractive as ‘green solvents’ used in the extraction of bioactive compounds from natural plant. However, the separation of ionic liquid from the target compounds was difficult, due to their low vapour pressure and high stabilities. In our study, ionic liquid‐based ultrasonic and microwave‐assisted extraction was used to obtain the crude tannins, then the macroporous resin adsorption technology was further employed to purify the tannins and remove the ionic liquid from crude extract. The results showed that XDA‐6 had higher separation efficiency than other tested resins, and the equilibrium experimental data were well fitted to Langmuir isotherms. Dynamic adsorption and desorption were performed on XDA‐6 packed in glass columns to optimise the separation process. The optimum conditions as follows: the ratio of column height to diameter bed was 1:8, flow rate 1 BV/h (bed volume per hour), 85% ethanol was used as eluant while the elution volume was 2 BV. Under the optimised conditions, the adsorption and desoption rate of tannins in XDA‐6 were 94.81 and 91.63%, respectively. The content of tannins was increased from 70.24% in Galla chinensis extract to 85.12% with a recovery of 99.06%. The result of ultra‐performance liquid chromatography (UPLC)‐MS/MS analysis showed that [bmim]Br could be removed from extract.     

Application of anion‐exchange imidazolium silica for the multiphase dispersive extraction of phenolic acids

This paper reports the application of a multiphase dispersive extraction method to the extraction, separation, and determination of the phenolic acids from Salicornia herbacea L. using silica‐confined ionic liquids as sorbents. A suitable sorbent for phenolic acid extraction and separation was first identified based on the adsorption behavior of the phenolic acids on different silica‐confined ionic liquids. The sample was then mixed with the optimized sorbent and solvent to achieve multiphase dispersive extraction. The sample/sorbent ratio was optimized using theoretical calculations from the adsorption isotherm and experiments. After transferring the supernatant to an empty cartridge, an SPE process was used to separate the three phenolic acids from the other interference. Through systematic optimization, the optimal conditions produced high recovery rates of protocatechuic acid (91.20%), caffeic acid (94.03%), and ferulic acid (91.33%). Overall, the proposed method is expected to have wide applicability.     

Binding of Cd2+ to self-assembled bilayers bearing pyridine terminal groups: attenuated total reflection Fourier transform infrared spectroscopic studies

Various aspects of the adsorption of Cd2+ on self-assembled monolayers (SAMs) of 4-heptadecylpyridine (HDpy) and 7-tridecyl-4-methyl-1,10-bipyridine (TMbipy) supported on an octadecylsilane (ODS)-modified Ge prism have been examined both ex situ (dry) and in situ (in the presence of aqueous solutions) using attenuated total reflection Fourier transform infrared spectroscopy. In direct analogy with the behavior found for a variety of genuine pyridine (py) and bipyridine (bipy) metal ion complexes, Cd2+ binding to both SAMs led to shifts in the skeletal vibrational modes of the corresponding uncoordinated ligands in the region 1650-1400 cm(-1), toward higher energies. Analysis of spectra acquired ex situ for HDpy/ODS/Ge and TMbipy/ODS/Ge before and after exposure to 0.1 mM [Cd2+] yielded values for the fraction of uncoordinated py, theta(py(un)), and uncoordinated bipy, theta(bipy(un)), of about 0.5 and about 0.1, respectively. The features attributed to the py(un) groups for spectra collected for HDpy/ODS/Ge in situ and ex situ were found to be virtually identical, making it possible to isolate by graphical means the most prominent band of py(co) centered at about 1615 cm(-l) for HDpy/ODS/Ge collected in situ. The resulting bands for pure py(co) and pyun in situ were then used to deconvolute spectra recorded in situ for HPpy/ODS/Ge in contact with Cd2+containing solutions in the range 10 nM < [Cd2+] < 0.1 mM, from which information regarding the adsorption isotherm was obtained.