Facile Preparation of Purified Sinapate Ethyl Ester from Rapeseed Meal Extracts Using Cation-exchange Resin in Dual Role as Adsorber and Catalyst.

In this study, cation-exchange resin was used to prepare an esterified antioxidant, sinapate ethyl ester (SE), using ethanolic extracts from rapeseed. A concentration of sinapic acid using the cation-exchange resin in 80% ethanol (aq) and subsequent interesterification of the extract in ethanol using the same resin afforded a product with a purity of 64 wt% and 100% of SE yield. Moreover, after purification using preparative thin-layer chromatography, almost 100 wt% purity was obtained. In an auto-oxidation test, purified SE conferred a much higher antioxidative effect on the bulk oil, emphasising the effectiveness of the protocol using cation-exchange resin for the purification.

Preparation of palm (Elaeis oleifera) pressed fibre cellulose nanocrystals via cation exchange resin: characterisation and evaluation as Pickering emulsifier.

BACKGROUND: Palm pressed fibre (PPF) is a cellulose-rich biomass residue produced during palm oil extraction. Its high cellulose content allows the isolation of cellulose nanocrystal (CNC). CNC has attracted scientific interest due to its biodegradability, biocompatibility and low cost. The present study isolated CNC from PPF using a cation exchange resin, which is an environmentally friendly and less harsh hydrolysis method than conventional mineral acid hydrolysis. Isolated CNC was used to stabilise an oil-in-water emulsion and the emulsion stability was evaluated in terms of droplet size, morphology and physical stability. RESULTS: PPF was subjected to alkali and bleach treatment prior to hydrolysis, which successfully removed 54% and 75% of non-cellulosic components (hemicellulose and lignin, respectively). Hydrolysis conditions of 5 h, 15:1 (w/w) resin-to-pulp ratio and 50 °C produced CNC particles of 50-100 nm in length. CNC had a crystallinity index of 42% and appeared rod-like morphologically. CNC-stabilised emulsion had better stability when used in combination with soy lecithin (SL), a well-established, commonly used food stabiliser. Emulsion stabilised by the binary mixture of CNC and SL had droplet size, morphology and physical stability comparable to those of emulsion stabilised using SL. CONCLUSIONS: CNC was successfully isolated from PPF through a cation exchange resin. This offers an alternative usage for the underutilised PPF to be converted into value-added products. Isolated CNC was also found to have promising potential in the stabilisation of Pickering emulsions. These results provide useful information indicating CNC as a natural and sustainable stabiliser for food, cosmeceutical and pharmaceutical applications. © 2021 Society of Chemical Industry.

Controlled methyl-esterification of pectin catalyzed by cation exchange resin.

This study developed a new method to methyl-esterify pectin using a cation exchange resin. Homogalacturonan (HG)-type pectin (WGPA-3-HG) and rhamnogalacturonan (RG)-I-type pectin (AHP-RG) obtained from the roots of Panax ginseng and sunflower heads, respectively, were used as models. Compared to commonly used methyl-esterification methods that use either methyl iodide or acidified methanol, the developed method can methyl-esterify both HG- and RG-I-type pectins without degrading their structures via ß-elimination or acid hydrolysis. In addition, by modifying reaction conditions, including the mass ratio of resin to pectin, reaction time, and temperature, the degree of esterification can be controlled. Moreover, the resin and methanol can be recycled to conserve resources, lower costs, and reduce environmental pollution. This new methodology will be highly useful for industrial esterification of pectin.

Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems.

Dissolution of synthetic uranium dibutyl phosphate deposits in oxidizing and reducing chemical formulations.

Permanganate and nitrilotriacetic acid (NTA) based dilute chemical formulations were evaluated for the dissolution of uranium dibutyl phosphate (U-DBP), a compound that deposits over the surfaces of nuclear reprocessing plants and waste storage tanks. A combination of an acidic, oxidizing treatment (nitric acid with permanganate) followed by reducing treatment (NTA based formulation) efficiently dissolved the U-DBP deposits. The dissolution isotherm of U-DBP in its as precipitated form followed a logarithmic fit. The same chemical treatment was also effective in dissolving U-DBP coated on the surface of 304-stainless steel, while resulting in minimal corrosion of the stainless steel substrate material. Investigation of uranium recovery from the resulting decontamination solutions by ion exchange with a bed of mixed anion and cation resins showed quantitative removal of uranium.

Enhanced catalysis of Yarrowia lipolytica lipase LIP2 immobilized on macroporous resin and its application in enrichment of polyunsaturated fatty acids.

An immobilization strategy was employed to improve activity and operational stability of Yarrowia lipolytica lipase LIP2 (YlLIP2) by using macroporous resins as carrier. D152H, a cation-exchange resin, was the best support. Under the optimized conditions, the immobilization efficiency was 89.81% and the specific activity was 809,751 U/g, being 2.1-fold higher than that of the free lipase. Bioimprinting and interfacial activation were used to further boost the catalytic activity of YlLIP2, respectively enhanced 21.5-fold, 231.2% and 107.2% compared to the free, non-bioimprinted and non-interfacial-activated lipases. The immobilized lipase exhibited much better thermal and pH stability and broader substrate specificity; when used to enrich docosahexaenoic acid (DHA) from Chlorella protothecoides oil, it could increase 1.66-fold of DHA content and show good operational stability. These indicate that the immobilized YlLIP2 offers a promising approach for the enrichment of DHA.

Microwave assisted esterification of acidified oil from waste cooking oil by CERP/PES catalytic membrane for biodiesel production.

The traditional heating and microwave assisted method for biodiesel production using cation ion-exchange resin particles (CERP)/PES catalytic membrane were comparatively studied to achieve economic and effective method for utilization of free fatty acids (FFAs) from waste cooking oil (WCO). The optimal esterification conditions of the two methods were investigated and the experimental results showed that microwave irradiation exhibited a remarkable enhanced effect for esterification compared with that of traditional heating method. The FFAs conversion of microwave assisted esterification reached 97.4% under the optimal conditions of reaction temperature 60°C, methanol/acidified oil mass ratio 2.0:1, catalytic membrane (annealed at 120°C) loading 3g, microwave power 360W and reaction time 90min. The study results showed that it is a fast, easy and green way to produce biodiesel applying microwave irradiation.

Separation of patatins and protease inhibitors from potato fruit juice with clay minerals as cation exchangers.

Potato fruit juice as a by-product of the starch industry contains proteins with interesting functionalities such as protease inhibitors or patatin with its high nutritional value. Due to their functional properties, these proteins are principally of industrial interest. A drawback for the application of these potato proteins is the separation and isolation under maintenance of the biological activity. So far, there are no methods in literature, which are satisfying concerning the costs or the separation performance. In this study, we show a chromatographic approach using natural clay minerals as cation exchangers to separate two protein fractions in potato fruit juice. Additionally, the content of glycoalkaloids naturally occurring in potatoes is significantly reduced in a single step together with the separation of the patatins and the protease inhibitors.

Synthesis, characterization and applications of a new cation exchanger tamarind sulphonic acid (TSA) resin.

A new composite cation exchanger, tamarind sulphonic acid (TSA) resin has been synthesized. The chemically modified TSA ion exchange resin has been used for the removal and preconcentration of Zn2+, Cd2+, Fe2+, Co2+ and Cu2+ ions in aqueous solution and effluent from the Laxmi steel plant in Jodhpur, India. This type of composite represents a new class of hybrid ion exchangers with good ion exchange capacity, stability, reproducibility and selectivity for toxic metal ions found in effluent from the steel industry. The characterization of the resin was carried out by determining the ion-exchange capacity, elemental analysis, pH titration, Fourier transform infrared spectra and thermal analysis. The distribution coefficients (K(d)) of toxic metal ions were determined in a reference aqueous solution and the steel plant effluent at different pH values; the absorbency of different metal ions on the TSA resin was studied for up to 10 cycles. The adsorption of different metal ions on TSA resin follows the order: Co2+ > Cu2+ > Zn2+ > Fe2+ > Cd2+. The ion exchange capacity of TSA resin is 2.87%.

Simultaneous isolation of lactoferrin and lactoperoxidase from bovine colostrum by SPEC 70 SLS cation exchange resin.

In this work, simultaneous isolation of lactoferrin (Lf) and lactoperoxidase (Lp) from defatted bovine colostrum by one-step cation exchange chromatography with SPEC 70 SLS ion-exchange resin was investigated. A RP-HPLC method for Lf and Lp determination was developed and optimized as the following conditions: detection wavelength of 220 nm, flow rate of 1 mL/min and acetonitrile concentration from 25% to 75% within 20 min. The adsorption process of Lf on SPEC 70 SLS resin was optimized using Lf standard as substrate. The maximum static binding capacity of SPEC 70 SLS resin was of 22.0 mg/g resin at 15 °C, pH 7.0 and adsorption time 3 h. The Lf adsorption process could be well described by the Langmuir adsorption isotherm model, with a maximum adsorption capacity of 21.73 mg/g resin at 15 °C. In batch fractionation of defatted colostrum, the binding capacities of SPEC 70 SLS resin for adsorbing Lf and Lp simultaneously under the abovementioned conditions were 7.60 and 6.89 mg/g resin, respectively, both of which were superior to those of CM Sepharose F.F. or SP Sepharose F.F. resins under the same conditions. As a result, SPEC 70 SLS resin was considered as a successful candidate for direct and economic purification of Lf and Lp from defatted colostrum.

Two-dimensional strong cation-exchange liquid chromatography/reversed-phase pressurized capillary electrochromatography for separation of complex samples.

A 2-D separation platform was constructed using micro strong cation-exchange liquid chromatography (µ-SCXLC) and reversed-phase pressurized capillary electrochromatography (RP-pCEC) for the analysis of complex samples. Samples were fractionated by the first-dimension µ-SCXLC with a linear solvent gradient and then injected into the second-dimension RP-pCEC for further separation. The µ-SCXLC/RP-pCEC 2-D system with three separation mechanisms, namely strong cation-exchange, reversed-phase chromatography and electrophoresis, provided high selectivity, high resolution and high peak capacity compared to one-dimensional chromatographic approaches. Separation effectiveness of this 2-D system was demonstrated by the analysis of different kinds of complex samples, such as traditional Chinese medicine Cortex Phellodendri, bovine serum albumin (BSA) tryptic digest and real serum tryptic digest. A theoretical peak capacity of approximately 1200 was achieved, which proves its promising potential for the separation and analysis of complex samples.

Esterification of oleic acid in a three-phase, fixed-bed reactor packed with a cation exchange resin catalyst.

Esterification of oleic acid was performed in a three-phase fixed-bed reactor with a cation exchange resin catalyst (Amberlyst-15) at high temperature, which was varied from 80 to 120 °C. The fatty acid methyl ester (FAME) yields in the fixed-bed reactor were increased with increases in the reaction temperature, methanol flow rate and bed height. Moreover, the FAME yields were higher than those obtained using a batch reactor due to an equilibrium shift toward the product that resulted from continuous evaporation of the produced water. In addition, there was no catalyst deactivation during the esterification of oleic acid. However, addition of sunflower oil to the oleic acid reduced the FAME yield obtained from simultaneous esterification and transesterification. The FAME yield was 97.5% at a reaction temperature of 100 °C in the fixed-bed with a height of 5 cm when the methanol and oleic acid feed rates were 8.6 and 9.0 mL/h, respectively.

Application of calcined waste fish (Labeo rohita) scale as low-cost heterogeneous catalyst for biodiesel synthesis.

This paper explores the feasibility of converting waste Rohu fish (Labeo rohita) scale into a high-performance, reusable, low-cost heterogeneous catalyst for synthesis of biodiesel from soybean oil. The thermo-gravimetric analysis (TGA) and X-ray diffraction (XRD) analysis revealed that a significant portion of the main component of fish scale i.e. HAP (hydroxyapatite) could be transformed into ß-tri-calcium phosphate when calcined above 900°C for 2 h. Scanning Electron Microscopy (SEM) morphology studies of the calcined scale depicted a fibrous layer of porous structure; while a BET surface area of 39 m(2)/g was measured. Response surface methodology (RSM) was employed to determine the optimal parametric conditions viz. methanol/oil molar ratio, 6.27:1, calcination temperature, 997.42°C and catalyst concentration, 1.01 wt.% of oil corresponding to a maximum FAME yield of 97.73%. Reusability results confirmed that the prepared catalyst could be reemployed up to six times, procreating a potentially applicable avenue in biodiesel synthesis.

A continuous process for biodiesel production in a fixed bed reactor packed with cation-exchange resin as heterogeneous catalyst.

Continuous esterification of free fatty acids (FFA) from acidified oil with methanol was carried out with NKC-9 cation-exchange resin in a fixed bed reactor with an internal diameter of 25 mm and a height of 450 mm to produce biodiesel. The results showed that the FFA conversion increased with increases in methanol/oil mass ratio, reaction temperature and catalyst bed height, whereas decreased with increases in initial water content in feedstock and feed flow rate. The FFA conversion kept over 98.0% during 500 h of continuous esterification processes under 2.8:1 methanol to oleic acid mass ratio, 44.0 cm catalyst bed height, 0.62 ml/min feed flow rate and 65°C reaction temperature, showing a much high conversion and operational stability. Furthermore, the loss of sulfonic acid groups from NKC-9 resin into the production was not found during continuous esterification. In sum, NKC-9 resin shows the potential commercial applications to esterification of FFA.

New resin gel for uranium determination by diffusive gradient in thin films technique.

A new resin gel based on Spheron-Oxin(®) chelating ion-exchanger with anchored 8-hydroxyquinoline functional groups was tested for application in diffusive gradient in thin film technique (DGT) for determination of uranium. Selectivity of uranium uptake from model carbonate loaded solutions of natural water was studied under laboratory conditions and compared with selectivity of the conventional Chelex 100 based resin gel. The affinity of Spheron-Oxin(®) functional groups enables determination of the overall uranium concentration in water containing carbonates up to the concentration level of 10(2) mg L(-1). The effect of uranium binding to the polyacrylamide (APA) and agarose diffusive gels (AGE) was also studied. Uranium is probably bound in both gels by a weak interaction with traces of acrylic acid groups in the structure of APA gel and with pyruvic and sulfonic acid groups in the AGE gel. These sorption effects can be eliminated to the negligible level by prolonged deployment of DGT probes or by disassembling probes after the 1-2 days post-sampling period that is sufficient for release of uranium from diffusive gel and its sorption in resin gel.

Improved performance of a biomaterial-based cation exchanger for the adsorption of uranium(VI) from water and nuclear industry wastewater.

The amine-modified polyhydroxyethylmethacrylate (poly(HEMA))-grafted biomaterial (tamarind fruit shell, TFS) carrying carboxyl functional groups at the chain end (PGTFS-COOH) was prepared and used as an adsorbent for the removal of uranium(VI) from water and nuclear industry wastewater. FTIR spectral analysis revealed that U(VI) ions and PGTFS-COOH formed a chelate complex. The adsorption process was relatively fast, requiring only 120 min to attain equilibrium. The adsorption kinetic data were best described by the pseudo-second-order equation. The equilibrium adsorption data were correlated with the Sips isotherm model. The maximum U(VI) ions uptake with PGTFS-COOH was estimated to be 100.79 mg/g. The complete removal of 10mg/L U(VI) from simulated nuclear industry wastewater was achieved by 3.5 g/L PGTFS-COOH. The reusability of the adsorbent was demonstrated over 4 cycles using NaCl (1.0M)+HCl (0.5M) solution mixture to de-extract the U(VI). The results show that the PGTFS-COOH tested is very promising for the recovery of U(VI) from water and wastewater.

Optimization of a new resin, Amberlyst 36, as a solid-phase extractor and determination of copper(II) in drinking water and tea samples by flame atomic absorption spectrometry.

A new simple and reliable method has been developed to separate and preconcentrate trace copper ion in drinking water and tea samples for subsequent measurement by flame atomic absorption spectrometry (FAAS). The copper ions are adsorbed quantitatively during passage of aqueous solutions through Amberlyst 36 cation exchange resin. After the separation and preconcentration stage, the analyte was eluted with a potassium cyanide solution and determined by FAAS. Different factors including pH of sample solution, sample volume, amount of resin, flow rate of aqueous solution, volume and concentration of eluent, and matrix effects for preconcentration were examined. The analytical figures of merit for the determination of copper are as follows: analytical detection limit (3 sigma), 0.26 microg/L; precision (RSD), 3.1% for 100 microg/L; enrichment factor, 200 (using 1000 mL of sample solution and 5 mL of eluent); time of analysis, 3.5 h (for obtaining enrichment factor of 200); capacity of resin, 125 mg/g. The method was applied for copper determination by FAAS in tap water, commercial natural spring water, commercial treated drinking water, and commercial tea bag sample. The accuracy of the method is confirmed by analyzing tea leaves (GBW 07605). The results demonstrated good agreement with the certified values.

Performance of three resin-based materials for treating uranium-contaminated groundwater within a PRB.

Three materials that are designed to treat uranium-contaminated water were investigated. These are a cation exchange resin, IRN 77; an anion exchange resin, Varion AP; and a recently developed material called PANSIL (quartz sand coated with 2% amidoxime resin by weight). The reaction rate, capacity, and effective pH range of the three materials are reported. The capacity and conditional distribution coefficient in neutral, uranyl-contaminated synthetic groundwater containing carbonate are also reported. The suitability of each material for treating uranium-contaminated groundwater using a permeable reactive barrier (PRB) approach is then discussed. All three materials react rapidly in the pH range 5-7, reaching equilibrium in less than 4h at approximately 23 degrees C. The unconditioned cation exchange resin removed 8 g UO2 2+ per kg of resin from neutral synthetic groundwater containing 30 mg/l of UO2 2+, but a lower capacity is anticipated in groundwater with either higher ionic strength or lower UO2 2 concentrations. It operates by first acidifying the solution, then sorbing UO2 2, and can release UO2 2 when its buffering capacity has been exhausted. The anion exchange resin is very effective at removing anionic uranyl carbonate species from solutions with a pH above 5, with good specificity. Up to 50 g/kg of uranium is removed from contaminated groundwater at neutral pH. PANSIL is effective at sequestering cationic and neutral uranyl species from solutions in the pH range 4.5-7.5, with very good specificity. The capacity of PANSIL is pH-dependent, increasing from about 0.4 g/kg at pH 4.5, to about 1 g/kg at pH 6, and 1.5 g/kg around pH 7.5. In neutral groundwater containing carbonate, both the anion exchange resin and PANSIL exhibit conditional distribution coefficients exceeding 1470 ml/g, which is about an order of magnitude higher than comparable reactive barrier materials reported in the literature.

Thermodynamic and kinetic investigations of uranium adsorption on amberlite IR-118H resin.

The adsorption behavior of uranium(VI) on a strongly acidic cation exchanger amberlite IR-118H has been studied as a function of the solution concentration and temperature. Results have been analyzed by Langmuir and Dubinin-Radushkevich (D-R) adsorption isotherms. The mean energy of adsorption 7.14kJmol(-1) was calculated from the D-R adsorption isotherm. In order to understand the significance of the diffusion mechanisms and to accurately estimate the diffusivities inside the adsorbent particles, a model for uranium(VI) adsorption on amberlite IR-118H was used. The rate constants have been calculated for 293, 313 and 333K using Lagergren equation and the activation energy (E(a)) was derived using the Arhenius equation. The thermodynamic quantities for the process of adsorption have been estimated by plotting Ln K(D) versus 1/T. The DeltaH(o) and DeltaG(o) values of uranium(VI) adsorption on amberlite IR-118H show endothermic heat of adsorption; higher temperatures favor the process.

Ionic imbalance as a source of toxicity in an estuarine effluent.

A toxicity identification evaluation (TIE) was conducted on the effluent from a petrochemical plant which discharges into an estuary. The effluent had been consistently toxic to mysid shrimp (Mysidopsis bahia) but not toxic to sheepshead minnows (Cyprinodon variegatus). Phase I effluent toxicity characterization tests revealed that treatment of the effluent with a cation exchange resin (Amberlite(R) IR-120 Plus) was partially effective at reducing, but not removing, toxicity. Phase II characterization tests revealed that four cations varied with toxicity: Ca and Sn were positively correlated with increasing toxicity; Mg and K were negatively correlated with increasing toxicity. Toxicity tests with SnCl2 revealed that the toxicity threshold for Sn was far above the concentrations present in the raw effluent. Reduction of Ca was shown to result in a significant improvement in survival, but some toxicity still remained. Further augmentation of the treated effluent with CaCl2, MgCl2, and KBr to restore the concentrations of Ca, Mg, K, and Br to natural seawater concentrations resulted in survival of all exposed organisms. Repeated success of this treatment regime on additional samples of the effluent as well as "mock effluent" studies confirmed that ion imbalance was the sole source of toxicity in this effluent. Process source water composition and essential ion balance are discussed as important components of marine effluent TIEs.