Custom and definitive screening designs for evaluating multiple adsorbents: bisphenol-A adsorption onto villi-structured polyaniline/carboxymethyl cellulose composites.

Polyaniline composites consisting of carboxymethyl cellulose (CMC) have enhanced adsorption properties, but recent studies indicate that the oxidised species - dialdehyde carboxymethyl cellulose (DCMC) - outperforms CMC-based composites. However, these studies fail to study the effect of DCMC's aldehyde content and compare the composites with CMC-based composites; numerous experiments required to investigate each adsorbent for each factor limit such studies. We explored a way to study whether villi-structured polyaniline (VSPANI), its CMC composite (CMC/PANI), and its DCMC composites with 35% (DCMC(A)/PANI) and 77% (DCMC(B)/PANI) aldehyde content would be great adsorbents for removing bisphenol-A (BPA). We first customised a D-optimal screening design to alleviate the pitfalls of definitive screening design (DSD), hence estimating all the main effects: initial concentration, pH, flow rate, adsorbent amount, sample volume and type of adsorbent. We excluded CMC/PANI and DCMC(A)/PANI composites, both with low adsorption capacities of 56.57 and 57.27 mg/g from further investigation. The DSD followed to estimate all second-order effects through which we projected a response surface method (RSM) to optimise and model the active factors. Increasing the aldehyde content on the composites favoured adsorption, but there lacked evidence to suggest VSPANI and DCMC(B)/PANI differed significantly in performance. The models were numerically and graphically proven adequate, explaining 80% and 99% of the variation when predicting removal efficiency and adsorption capacity. VSPANI showed potential as an adsorbent for BPA removal with 85% removal efficiency and 129 mg/g adsorption capacity. This comprehensive approach, combining both designs, allows for sustainable investigation of multiple adsorbents and factors, minimising experimental waste.

Simple methods for measuring milk exosomes using fluorescent compound GIF-2250/2276.

Exosomes are small extracellular vesicles (EVs) found in culture supernatants, blood, and breast milk. The size of these nanocomplexes limits the methods of EV analyses. In this study, nitrobenzoxadiazole (NBD), a fluorophore, conjugated endosome-lysosome imager, GIF-2250 and its derivative, GIF-2276, were evaluated for exosome analyses. A correlation was established between GIF-2250 intensity and protein maker levels in bovine milk exosomes. We found that high-temperature sterilization milk may not contain intact exosomes. For precise analysis, we synthesized GIF-2276, which allows for the covalent attachment of NBD to the Lys residue of exosome proteins, and labeled milk exosomes were separated using a gel filtration system. GIF-2276 showed chromatographic peaks of milk exosomes containing >3 ng protein. The area (quantity) and retention time (size) of the exosome peaks were correlated to biological activity (NO synthesis suppression in RAW264.7 murine macrophages). Heat denaturation of purified milk-derived exosomes disrupted these indicators. Proteome analyses revealed GIF-2276-labeled immunomodulators, such as butyrophilin subfamily 1 member A1 and polymeric immunoglobulin receptor. The immunogenicity and quantity of these factors decreased by heat denaturation. When milk exosomes were purified from market-sourced milk we found that raw and low-temperature sterilization milk samples, contained exosomes (none in high-temperature sterilization milk). These results were also supported by transmission electron microscopy analyses. We also found that GIF-2276 could monitor exosome transportation into HEK293 cells. These results suggested that GIF-2250/2276 may be helpful to evaluate milk exosomes.

Mixed-mode chromatographic performance using nicotinic acid-functionalized chito-oligosaccharide-bonded Ti/Si hybrid monolithic capillary columns.

This article describes the fabrication of porous nicotinic acid-functionalized chito-oligosaccharide-bonded titania/silica hybrid monoliths (TiO2/SiO2@ChO-N) through a co-gelation sol-gel process. A capillary monolith with a well-defined and homogeneous structure was obtained by controlling the hydrolysis speed of titanium alkoxides in a sol mixture by using glycerol and acetylacetone. As a result of the functionalization with chito-oligosaccharides (ChO)-modified nicotinic acid, the obtained stationary phase provides superior physiochemical properties, such as a cationic hydrophilic surface, porosity, and mechanical strength. Scanning electron microscope and attenuated total reflectance-infrared spectroscopy were used to characterize the functionalized monolithic columns. The produced capillary columns showed high chromatographic performance with acceptable selectivity for charged analytes as well as organic polar compounds such as nucleic bases, nucleosides, carbamate pesticides, and strobilurin fungicides. The obtained results also indicated that the functionalized ChO's amino, amide, hydroxyl, and pyridinium ring moieties served as hydrophilic electrostatic traps for charged substances, in addition to stroing π-π interaction with the carbamate pesticides and strobilurin fungicides analytes via hydrogen bonding.

One-pot alkanolamines-assisted synthesis of magnetic mesoporous silica for synthetic dye adsorption.

Magnetic mesoporous silica (MMS) was synthesized in a one-pot system using various alkanolamines (triethanolamine, diethanolamine, tris (hydroxymethyl)aminomethane) as a basic catalyst. The characterization of the composites was conducted using scanning electron microscope, transmission electron microscope, X-ray diffractometer, surface area analyzer, and X-ray photoelectros spectroscopy. The MMS synthesized with tris(hydroxymethyl)aminomethane (MMSTRIS) showed the highest specific surface area, pore volume, and average pore diameter. However, when the composites were applied as adsorbents for brilliant green (BG) dye, MMS synthesized with diethanolamine (MMSDEA) showed the highest maximum adsorption capacity of 339.7 mg g-1. The fastest adsorption rate constant of 1.57 × 10-2 g mg-1 min-1 was obtained for MMSTRIS, which has the largest average pore size among all composites. The adsorption kinetic study suggested that the adsorption of BG onto the prepared MMS composites was mainly chemisorption process, which most likely involves electrostatic interaction and hydrogen bonding between BG molecule and the surface of the composites.

Separation of Inorganic Anions Using an 18-Crown-6-ether-modified Organic Polymer Monolithic Stationary Phase in Capillary Ion Chromatography.

In this study, a monolithic organic polymer stationary phase was modified using 18-crown-6-ether for use in capillary ion chromatography. Its use in the separation of inorganic anions was investigated. The monolithic stationary phase was obtained by chemically bonding 2-aminomethyl-18-crown-6-ether to a polymer skeleton comprising glycidyl methacrylate and ethylene glycol dimethacrylate. The optimum level of the loading of 2-aminomethyl-18-crown-6-ether onto the stationary phase was investigated. The resulting stationary phase was used to investigate the influence of the eluent cation, the concentration of the eluent, and the pH of the eluent on the separation of inorganic anions.

Poly(ethylene glycol) Methyl Ether Methacrylate-bonded Stationary Phase in Ion Chromatography and Its Application to Seawater Samples.

A fast and simple ion chromatographic method for the determination of iodide in seawater is reported using poly(ethylene glycol) methyl ether methacrylate-bonded stationary phase. Poly(ethylene glycol) methyl ether methacrylate was reacted with primary amino groups of aminopropylsilica in N,N-dimethylformamide at 80°C. The prepared stationary phases were evaluated by analyzing several inorganic anions and the retention behavior was observed. Various chromatographic parameters were optimized for the separation of these anions. Although there were no ion-exchange sites on the resulted stationary phases, the results obtained suggested that an ion-exchange mechanism was involved in the retention of analyte anions. With 0.15 µL injection, the limit of quantitation of iodide was 26 µg L-1 when 200 mM NaCl was selected as the eluent. This stationary phase was applied to the analysis of direct and fast determination of iodide in real seawater samples successfully with the recovery rates of 98.1 and 104.9%.

Retention Behavior of Inorganic Anions in Hydrophilic Interaction Chromatography.

The retention behavior of inorganic anions was studied in hydrophilic interaction chromatography (HILIC). In this study, five kinds of HILIC stationary phases (amino, imidazole, amide, pyridine and zwitterionic) were investigated. It was found that only amino and imidazole columns exhibited the separation of inorganic anions under HILIC conditions. The retention mechanism was further investigated under both columns. A reversed elution order of inorganic anions was observed under the HILIC condition compared with those observed under the ion-exchange chromatography mode (IEC). The effect of salt species and their concentration in the eluent were investigated under constant acetonitrile (ACN) content. Sodium chloride and sodium perchlorate were chosen as the salt, and the salt (sodium perchlorate) concentration was varied from 10 to 40 mM to confirm the effect of the electrostatic interaction. The slope values of the plots of the log retention factor (k) versus the log eluent concentration were calculated to be between -0.43 and -0.45 for the amino column, while those obtained on the imidazole column were between -0.68 and -0.73. Various concentrations of ACN were also examined with 20 mM sodium perchlorate, and the typical HILIC retention behavior was observed on both amino and imidazole columns. Due to the obtained results, it is considered that the separation of inorganic anions under the HILIC condition was achieved by both electrostatic interaction and partition.

Optimization and Investigation of Zwitterionic Monolithic Stationary Phases for Capillary Ion Chromatography.

Zwitterionic monolithic columns were synthesized by a one-pot reaction using [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, ethylene dimethacrylate, methanol and 2,2'-azobis(isobutyronitrile) as the monomer, cross-linker, porogen and initiator, respectively. The optimum conditions for polymerization and the efficiency of the prepared columns were examined for ion chromatography. The separation of five kinds of inorganic anions was achieved. The back pressures were monitored as increasing flow-rate, and the resulting plate heights (i.e. height equivalent of a theoretical plate, HETP) of SCN- were calculated at the inspected flow-rates. It was found that the increment rates of both the back pressure and HETP were rather slight. Mobile phases containing various cations or acid increased the retention times of the anions. Divalent cations could be separated, while monovalent cations could not be resolved due to their weak retention on the stationary phases.

Evaluation of column carryover of phosphorylated peptides and fumonisins by duplicated solvent gradient method in liquid chromatography/tandem mass spectrometry.

Columns made of three different materials were evaluated with regard to the carryover of phosphorylated peptides and fumonisins in liquid chromatography/tandem mass spectrometry (LC/MS/MS). In order to eliminate carryover caused by the injection operation in the autosampler, the column carryover was calculated using the duplicated solvent gradient method. A column made of a glass-lined stainless-steel tube and polyethylene frits (GL-PE column) yielded the most significant improvements in the peak shape and the carryover as compared to the other columns. The carryover of fumonisin B1 (FB1) and HLADLSpK (T19p) in the GL-PE column could be reduced; the lower limit of quantitation of T19p, and the range of the calibration curve were also improved. Since carryover peaks with the GL-PE column were symmetrical peaks of the samples, carryover in the column did not occur. The carryover calculated by the duplicated solvent gradient method corresponded to those in the flow path from the injection port to the inlet frit of the column. The carryover value of FB1 in the column with a stainless-steel tube and stainless-steel frits (S-S column) was 1.70%, and that of the flow path was 0.23%. We found that the majority of the carryover in our system occurred in the S-S column.

Evaluation of column hardware on liquid chromatography-mass spectrometry of phosphorylated compounds.

The influences of column hardware, such as chromatographic tubes and frits, on liquid chromatography-mass spectrometry (LC-MS) analysis of phosphorylated compounds were evaluated. The signal to noise ratio (S/N) and the intensity of flavin adenine dinucleotide (FAD) using a glass lined tube and polyethylene frit (GL-PE) column was approximately 170 and 90 times higher, respectively, than those using conventional stainless steel tube and stainless steel frit (S-S) column. In addition, the retention time of FAD using GL-PE column was the shortest compared to other columns. Interaction between phosphorylated compounds and metal ions in the flow path in the S-S column was stronger than that between them and the GL-PE column. Thus, the metal ions in the flow path in GL-PE column were low. Since the specific surface area of a pair of frits was 70 times larger than that of a chromatographic tube (150 mm×2.1 mm), the frits were found to have more effective improvement of the S/N as well as the intensity than the chromatographic tubes, when phosphorylated compounds were analyzed by LC-MS. When the evaluated phosphorylated compounds were analyzed by LC-MS(/MS) using a GL-PE column, the intensity and S/N were increased.

Polymer monolithic methacrylate base modified with tosylated-polyethylene glycol monomethyl ether as a stationary phase for capillary liquid chromatography.

A polyethylene glycol (PEG) monolithic column was successfully prepared in situ for the separation of inorganic anions in ion exchange capillary chromatography. By attaching PEG-groups into the methacrylate-based polymer, the number of theoretical plates was improved from 1433 to 3346 plates/m (when nitrate was used as the analyte). The retention behavior of iodate, bromate, nitrite, bromide and nitrate was observed under various salt aqueous solutions. The retention was based on cations trapped among PEG chain and the positively charged pyridine that work as the anion exchange sites in the PEG monolith. The relative standard deviations (RSDs, for n=7) of retention time, peak height and peak area were less than 2.27% for all the analyte anions. The PEG monoliths showed satisfactory mechanical stability and did not swell or shrink significantly with swelling propensity value of 0.34 and 0.64 for methanol and THF, respectively. This stationary phase was successfully applied to the determination of these anions in seawater as well as public drinking water samples.

Preparation of a hybrid monolithic stationary phase with allylsulfonate for the rapid and simultaneous separation of cations in capillary ion chromatography.

A hybrid monolithic column with sulfonate functionality was successfully prepared for the simultaneous separation of common inorganic cations in ion-exchange chromatographic mode through a simple and easy single-step preparation method. The strong cation-exchange moieties were provided directly from allylsulfonate, which worked as an organic monomer in the single-step reaction. Inorganic cations (Li(+), Na(+), K(+), NH4(+), Cs(+), Rb(+), Mg(2+), Ca(2+), and Sr(2+)) were separated satisfactorily by using CuSO4 as the eluent with indirect UV detection. The allysulfonate hybrid monolith showed a better performance in terms of speed and pressure drop than the capillary packed column. The number of theoretical plates achieved was 19,017 plates/m (in the case of NH4(+) as the analyte). The relative standard deviations (n = 6) of both retention time and peak height were less than 1.96% for all the analyte cations. The allysulfonate hybrid monolithic column was successfully applied for the rapid and simultaneous separation of inorganic cations in groundwater and the effluent of onsite domestic wastewater treatment system.

Capillary liquid chromatographic fingerprint used for discrimination of Zingiber montanum from related species.

Fingerprint analysis using capillary liquid chromatography (CLC) has been developed for discrimination of Zingiber montanum (ZM) from related species, for example Z. americans (ZA) and Z. zerumbet (ZZ). By comparing the fingerprint chromatograms of ZM, ZA, and ZZ we could identify ZM samples and discriminate them from ZA and ZZ by using their marker peaks. We also combined CLC fingerprint with multivariate analysis, including principal-component analysis (PCA) and canonical variate analysis (CVA); all three species were discriminated successfully. This result indicates that CLC fingerprint analysis in combination with PCA and CVA can be used for discrimination of ZM samples from samples of related species.

Methacrylate-based diol monolithic stationary phase for the separation of polar and non-polar compounds in capillary liquid chromatography.

A monolithic capillary column prepared with glycidyl methacrylate (GMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) was investigated and used in capillary liquid chromatography. The polymer monolith was synthesized in the presence of methanol and decanol as the biporogenic solvents by in situ polymerization of GMA and PEGDMA, and the optimum composition of monomer and porogen was investigated. After polymerization, glycidyl groups were hydrolyzed with sulfuric acid to produce diol groups at the surface of the porous monolith via epoxy-ring-opening. The GMA content in the polymerization mixture affected the hydrophilicity of the monolith. The separation capability was evaluated by separation of phenol compounds, phthalic acids, and polycyclic aromatic hydrocarbons. The poly(GMA-PEGDMA) monolithic capillary column exhibited satisfactory stability.

Poly(ethylene oxide)-bonded stationary phase for separation of inorganic anions in capillary ion chromatography.

A tosylated-poly(ethylene oxide) (PEO) reagent was reacted with primary amino groups of an aminopropylsilica packing material (TSKgel NH2-60) in acetonitrile to form PEO-bonded stationary phase. The reaction was a single and simple step reaction. The prepared stationary phase was able to separate inorganic anions. The retention behavior of six common inorganic anions on the prepared stationary phase was examined under various eluent conditions in order to clarify its separation/retention mechanism. The elution order of the tested anions was iodate, bromate, bromide, nitrate, iodide, and thiocyanate, which was similar as observed in common ion chromatography. The retention of inorganic anions could be manipulated by ion exchange interaction which is expected that the eluent cation is coordinated among the PEO chains and it works as the anion-exchange site. Cations and anions of the eluent therefore affected the retention of sample anions. We demonstrated that the retention of the analyte anions decreased with increasing eluent concentration. The repeatability of retention time for the six anions was satisfactory on this column with relative standard deviation values from 1.1 to 4.3% when 10mM sodium chloride was used as the eluent. Compared with the unmodified TSKgel NH2-60, the prepared stationary phase retained inorganic anions more strongly and the selectivity was also improved. The present stationary phase was applied for the determination of inorganic anions contained in various water samples.

Separation of inorganic anions on a chemically bonded 18-crown-6 ether stationary phase in capillary ion chromatography.

Inorganic anions were separated on a chemically bonded 18-crown-6 ether (18C6E) stationary phase in capillary ion chromatography. In this study 18C6E groups were chemically bonded on silica gel via reaction with 3-glycidyloxypropyltrimethoxysilane, followed by reaction with 2-aminomethyl-18C6E. Analyte anions were separated in the ion-exchange mode based on the fact that the eluent cation was trapped on the 18C6E and it worked as the anion-exchange site. The eluent cation and eluent anion as well as the eluent concentration affected the retention of the analyte anions. Different selectivity was achieved by using an acetonitrile-rich eluent. The present stationary phase was applied for the determination of UV-absorbing anions contained in saliva samples.

Determination of iodide in seawater by capillary ion chromatography using hexadimethrine bromide modified C30 stationary phases.

A novel and simple capillary ion chromatographic method for the determination of iodide is reported. Separation was achieved on a laboratory-made packed capillary column (100 mm × 0.32 mm i.d.) packed with triacontyl-functionalized silica, followed by a modification with hexadimethrine bromide, where 1 mM sodium chloride-acetonitrile (95:5, v/v) was used as the eluent and UV-absorbing analyte anions were detected at 225 nm. The effects of the eluent composition on the retention behavior of inorganic anions were investigated. The addition of a small amount of an organic substance in an eluent such as acetonitrile increased the retention of iodide, while the addition of methanol decreased its retention. The present analytical method was successfully applied to the rapid and direct determination of iodide in seawater without any preconcentration. Also, this modified column could be used for about two months (6 h operation per day) without hexadimethrine bromide being contained in the eluent.

Simultaneous determination of gingerols and shogaol using capillary liquid chromatography and its application in discrimination of three ginger varieties from Indonesia.

A new method using reversed phase capillary liquid chromatography was developed for simultaneous determination of four bioactive compounds found in ginger (Zingiber officinale) namely, 6-, 8-, 10-gingerol, and 6-shogaol. The separation of these four compounds was performed using C30 as the stationary phase and 60% acetonitrile as the mobile phase in isocratic elution mode with a flow rate of 5 µL/min. All four compounds were separated within 25 min with good resolution. As the evaluation of method validation, a linear regression of the four compounds was obtained within the tested range with correlation coefficients ≥ 0.9995. The limits of detection and quantitation were between 0.034-0.039 µg/mL and 0.112-0.129 µg/mL, respectively. Intra- and inter-day precision expressed as relative standard deviations (RSD) were less than 3.1%, and the accuracy based on recovery test was ranging from 97% to 105%. Stability of the analytes within 1 day was found in the range between 1.34% and 2.93% (RSD). In addition, based on the amount of these four compounds combining with the discriminant analysis, a reliable and accurate method was developed for discrimination of three ginger varieties found in Indonesia. The results indicated that the developed method could be used as quality control for ginger raw material and its related products.

Simultaneous determination of inorganic cations by capillary ion chromatography with a non-suppressed contactless conductivity detector.

A non-suppressed capillary ion chromatographic method with a laboratory-made packed cation-exchange column (100 mm × 0.32 mm i.d.) was developed for the separation and simultaneous determination of five common inorganic cations (sodium, ammonium, potassium, magnesium and calcium). Cation exchangers were prepared by the reaction of the hydroxyl group on the surface of diol-group bonded silica gel with 1,3-propanesultone in methanol. Simultaneous separation of these five common inorganic cations were achieved within 17 min using 1 mM methanesulfonic acid and 0.1 mM 15-crown-5 ether in methanol-water (8:2, v/v) as the eluent. The effects of organic solvents and crown ethers in the eluent on the retention of analytes were investigated. The limits of detection (S/N = 3) of the cations were in the range of 18-124 µg/l, the linear correlation coefficients were 0.9991-0.9998, and the RSD values of retention time and peak height were all smaller than 2.1%. The present analytical method was successfully applied to the rapid and direct determination of inorganic cations in samples of river water and commercial drinks, with satisfactory results.

Polyoxyethylene as the stationary phase in ion chromatography.

The present article reviews the use of polyethylene glycol (PEG) or polyoxyethylene (POE) as the stationary phase for the separation of inorganic anions in ion chromatography and discusses about the retention mechanisms involved in the separation of anions on the novel stationary phases. PEG permanently coated on a hydrophobic stationary phase retained anions in the partition mode and allowed us to use high-concentration eluents because the retention of anions increased with increasing eluent concentration for most of the eluents. This situation was convenient to determine trace anions contained in seawater samples without any disturbance due to matrices. Chemically bonded POE stationary phases retained not only anions but also cations. Anions were retained in the ion-exchange mode, although POE chains possess no ion exchange sites. The retention behavior suggested that eluent cations could be trapped among multiple POE chains via ion-dipole interaction, and that the trapped cations worked as the anion-exchange sites. Anions could be separated using crown ether, i.e., cyclic POE, as the eluent additive with a hydrophobic stationary phase, where analyte anions were retained via electrostatic interaction with the eluent cation trapped on the crown ether.