Adjustable chromatographic performance of silica-based mixed-mode stationary phase through the control of co-grafting amounts of imidazole and C18 chain.

In this paper, three imidazole- and C18- bifunctional silica stationary phases (Sil-Im-C18) were prepared by adjusting introduction interval of octadecyltrichlorosilane (ODS) and 3-imidazol-1-ylpropyl(trimethoxy)silane (TMPImS), which can be used for reversed-phase liquid chromatography (RPLC) and ion exchange chromatography (IEC) with adjustable performance. The successful preparation of Sil-Im-C18 were confirmed by the characterizations of elemental analysis, infrared spectroscopy (FTIR) and contact angle (CA). Chromatographic performance of Sil-Im-C18 were evaluated by the separation of Tanaka test mixture, alkylbenzenes, linear PAHs and a set of analytes with different properties (uracil, phenol, 1,2-dinitrobenzene and naphthalene), and compared with commonly used C18 column. It was found that the chromatographic performance of Sil-Im-C18 changed significantly with the difference in bonding amount of imidazole and C18. Sil-Im-C18 demonstrated the excellent separation performance towards polycyclic aromatic hydrocarbons (PAHs), phenylesters, phenylamines, phenols and inorganic anions, and notably, nucleobases and nucleosides can be separated using pure water as mobile phases. The van Deemter plot showed that the column efficiency of Sil-Im-C18-3 was 64,933 plate·m-1 for naphthalene, indicated that Sil-Im-C18 was reasonably chromatographic columns. The RSD values of retention time were 0.22 %-0.61 % for 10 needles alkylbenzenes injected continuously at 50 °C to investigate thermal stability and repeatability, all the fluctuations of k of naphthalene were less than 2.3 % for Sil-Im-C18-1 during flushing 24 h with the mobile phase at different pH values (pH = 3 and 8), the retention time of alkylbenzenes were almost same for Sil-Im-C18-1 at different time, the RSD values of retention time of alkylbenzenes were 0.45 %-2.28 % for two batches Sil-Im-C18-1, revealing the excellent repeatability, thermal stability, durability and reproducibility of Sil-Im-C18, and implying a commercial prospect.

Enantioselective Glutamic Acid Discrimination and Nanobiological Imaging by Chiral Fluorescent Silicon Nanoparticles.

Enantioselective discrimination of chiral molecules is essential in chemistry, biology, and medical science due to the configuration-dependent activities of enantiomers. Therefore, identifying a specific amino acid and distinguishing it from its enantiomer by using nanomaterials with outstanding performance are of great significance. Herein, blue- and green-emitting chiral silicon nanoparticles named bSiNPs and gSiNPs, respectively, with excellent water solubility, salt resistance, pH stability, photobleaching resistance, biocompatibility, and ability to promote soybean germination, were fabricated in a facile one-step method. Especially, chiral gSiNPs presented excellent fluorescence recognition ability for glutamic acid enantiomers within 1 min, and the enantiomeric recognition difference factor was as high as 9.0. The mechanism for enantiomeric fluorescence recognition was systematically explored by combining the fluorescence spectra with density functional theory (DFT) calculation. Presumably, the different Gibbs free energy and hydrogen-bonding interaction of the chiral recognition module with glutamic acid enantiomers mainly contributed to the difference in the fluorescence signals. Most noteworthy was the fact that the chiral gSiNPs can showcase not only the ability to recognize l- and d-glutamic acids in living cells but also the test strips fabricated by soaking gSiNPs can be applied for d-glutamic acid visual detection. As a result, this study provided insights into the design of multifunctional chiral sensing nanoplatforms for enantiomeric detection and other applications.

A C4-modified bipyridinium multi-mode stationary phase for reversed phase, hydrophilic interaction and ion exchange chromatography.

A novel C4-modified bipyridinium stationary phase (Sil-DPC4) was prepared and characterized by elemental analysis (EA) and Fourier transform infrared spectrometry (FT-IR) and further investigated for multi-mode liquid chromatography. The chromatographic performances of Sil-DPC4 were evaluated by reversed-phase chromatography using polycyclic aromatic hydrocarbons (PAHs), phenylamines and phenols, hydrophilic interaction chromatography using nucleosides and nucleobases, and ion exchange chromatography using inorganic ions and organic ions. The effects of the acetonitrile content, salt concentration and pH value of the mobile phase on the retention of Sil-DPC4 were also investigated. Sil-DPC4 showed multiple retention mechanisms including π-π, hydrophobic and electrostatic interactions for PAHs, phenylamines and phenols compared with a dipyridine modified silica stationary phase (Sil-DP) and C18 in RPLC, faster separation for nucleosides and nucleobases compared with Sil-DP, and higher hydrophilicity than HILIC in HILIC, and stronger retention and better separation ability for inorganic ions and organic ions in comparison to Sil-DP in IEC. Besides, Sil-DPC4 was used successfully to detect iodide in artificial seawater and had the potential to analyze radionuclide iodine-131 in seawater. In conclusion, multiple retention mechanisms of Sil-DPC4 could make it have potential applications in complex samples.

Chiral metal-organic frameworks and their composites as stationary phases for liquid chromatography chiral separation: A minireview.

Chiral metal organic frameworks (CMOFs) are a kind of crystal porous framework material that has attracted increasing attention due to the customizable combination of metal nodes and organic ligands. In particular, the highly ordered crystal structure and rich adjustable chiral structure make it a promising material for developing new chiral separation material systems. In this review, the progress of CMOFs and their different types of composites used as chiral stationary phases (CSPs) in liquid chromatography for enantioseparation are discussed. The characteristics of CMOFs and their composites are summarized, aiming to provide new ideas for the development of CMOFs with better performance and further promote the application of CMOFs materials in enantioselective high-performance liquid chromatography (HPLC).

Non-porous silica support covalent organic frameworks as stationary phases for liquid chromatography.

A new strategy using non-porous silica (NPS) spheres as the support and covalent organic frameworks (COFs) as the porous functional shell for liquid chromatography was developed to ensure the independent effect of the COFs on the separation. As a proof of concept, NPS@TPB-DMTP was prepared for liquid chromatographic analysis using 1,3,5-tris(4-aminophenyl)benzene (TPB) and 2,5-dimethoxy-1,4-benzenedicarboxaldehyde (DMTP) as monomers by in situ polymerisation on the surface of NPS. It is a new way of developing COF-based stationary phases, which will be helpful in understanding what effect the COFs will have on separation.

Phosphorus-doped deep eutectic solvent-derived carbon dots-modified silica as a mixed-mode stationary phase for reversed-phase and hydrophilic interaction chromatography.

In this work, phosphorus-doped carbon dots (P-DESCDs) were successfully prepared using choline chloride/lactic acid type deep eutectic solvent and phosphoric acid as ingredients, and (3-aminopropyl) trimethoxysilane was used as a bridge to graft P-DESCDs onto the silica surface to obtain a new mixed-mode stationary phase (Sil-P-DESCDs) for reversed-phase and hydrophilic interaction liquid chromatography. The successful preparation of the stationary phase was confirmed by laser scanning confocal microscopy, elemental analysis, and Fourier transform infrared spectrometry. Interestingly, the doping of phosphorus greatly improved the separation performance and hydrophilicity of the Sil-P-DESCDs column. The Sil-P-DESCDs column was found to have certain hydrophobicity, hydrogen bonding ability and shape selectivity by Tanaka and Engelhardt standard test mixtures, and a series of hydrophilic and hydrophobic compounds such as alkylbenzenes, polycyclic aromatic hydrocarbons, sulfonamides, aromatic amines, phenols, flavonoids, nucleoside bases, and alkaloids. In addition, the effects of mobile phase ratio, column temperature, flow rate, salt concentration, and pH on the retention of analytes on Sil-P-DESCDs columns were investigated. Finally, the Sil-P-DESCDs column was applied to the qualitative and quantitative analysis of calcein-7-glucoside in the real sample of medicinal Astragalus pellets, and it was found at a concentration of 0.02 mg/mL.

Grafting of Tetraphenylethylene on Silica Surface, Characterizations, and Their Chromatographic Performance as Reversed-Phase Stationary Phases.

Surface modification is an effective way to functionalize the materials so as to get some special properties. Tetraphenylethylene (TPE) has been widely investigated as a well-known reagent which has the nature of aggregation-induced emission (AIE), but has never been reported in the liquid chromatography stationary phase. In this work, TPE-grafted silica (Sil-TPE) was obtained successfully using the derivative of 1-(4-hydroxyphenyl)-1,2,2-triphenylethylene as a ligand, and then characterized by elemental analysis, Fourier transform infrared spectra, thermogravimetric analysis, and so forth. Laser scanning confocal microscopy images reflected the AIE phenomenon of grafted TPE because the internal vibration and rotation of TPE molecules were restrained in the confined silica space. The contact angle test showed superhydrophobic properties of Sil-TPE. In order to understand thoroughly the mechanism of chromatographic performance and retention behavior for Sil-TPE, Tanaka test mixture, alkylbenzenes, polycyclic aromatic hydrocarbons (PAHs), and phenols were separated. This reveals that Sil-TPE has strong aromaticity and certain shape selectivity, especially, has excellent separation performance for PAHs and phenols. The thermodynamic properties and repeatability of Sil-TPE were further studied, which showed the stability of Sil-TPE. This work shows that TPE can be successfully grafted on silica surface and it has the potential to be a new kind of promising stationary phases in the future.

Synthesis of chiral functionalized UiO-66-NH2@SiO2 and use of its domain-limiting effect for separating small enantiomers.

Herein, to overcome the challenges of enantiomerically separating small chiral molecules, UiO-66-NH2@SiO2 was synthesized and samples of it were functionalized using a simple post-synthetic modification strategy with (+)-diacetyl-L-tartaric anhydride (DATA) and dibenzoyl-(+)-tartaric acid (DBTA), respectively. Then, based on the domain-limiting effect from the regular micropore structure of the included metal organic frameworks, the obtained UiO-66-DATA@SiO2 and UiO-66-DBTA@SiO2 each exhibited enhanced stereoselectivity for small enantiomers and successfully achieved the separation of α-amino acid and small alkaline enantiomers. This study has provided a new concept for the design and synthesis of chiral materials for separating small-molecule enantiomers.

Preparation and evaluation of two silica-based hydrophilic-hydrophobic and acid-base balanced stationary phases via in-situ surface polymerization.

Two new hydrophilic-hydrophobic and acid-base balanced liquid chromatographic stationary phases were obtained by using two long-chain monomers including undecylenic acid (UA) and oleic acid (OA) combined with short-chain 4-vinyl pyridine (Py) in-situ polymerized on silica microspheres surfaces, respectively. These two stationary phases can be used for reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC) modes. Hydrophilic, hydrophobic, acidic and basic analytes can be separated on two new stationary phases in RPLC or HILIC mode. Compared with commercial hydrophobic C18 columns and other HILIC columns, two new stationary phases have excellent selectivity and separation performance in the separation of 9 polycyclic aromatic hydrocarbons, 10 aromatic acids, 10 anilines and 5 oxazolidinones, respectively. This novel polymer-functionalized silica design strategy has opened up new ideas for the future of mixed-mode stationary phases with multiple functions and specificity.

Comparison of chromatographic performance of co-grafted silica using octadecene respectively with vinylpyrrolidone, vinylimidazole and vinylpyridine.

Three reversed-phase liquid chromatography (RPLC) stationary phases were obtained by using long-chain 1-octadecene (OD) co-grafted with three short-chain monomers, including N-vinylpyrrolidone (NVP), 1-vinylimidazole (VIm) and 4-vinylpyridine (VPy), respectively (noted as Sil@ODNVP, Sil@ODVIm and Sil@ODVPy). Peak broadening phenomenon in RPLC mode which resulted by short-chain was examined carefully. Compared with Sil@ODNVP, both of Sil@ODVIm and Sil@ODVPy had smaller peak width and higher column efficiency in the separation of 10 polycyclic aromatic hydrocarbons (PAHs), 7 alkyl benzenes, 7 aromatic acids, 7 aromatic esters and 9 phenols. In addition, VPy has the strongest ion exchange capacity than other two short-chains. In this case, we can see that VPy and VIm maybe more suitable to be used as functional monomeric modifiers of new chromatographic stationary phases.

N-Vinyl pyrrolidone and undecylenic acid copolymerized on silica surface as mixed-mode stationary phases for reversed-phase and hydrophilic interaction chromatography.

In this work, three new mixed-mode stationary phases were prepared, based on different ratio of N-vinyl pyrrolidone (NVP) copolymerized together with undecylenic acid (UA) on silica microspheres surface without silanization, which named Sil@NVPUA series. The combination of NVP and UA rendered the Sil@NVPUA suitable for reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), and shown excellent methyl, planar, isomers and ion selectivity. Five types of model analytes including eight polycyclic aromatic hydrocarbons, six alkylbenzenes, eight nucleosides and nucleobases, seven ginsenosides and five oxazolidinones can be well separated on this stationary phase. The preparation method of NVP and UA modified silica-based stationary phase is simple, and it also provides a new idea for the design of synthetic polymers to develop mixed-mode chromatography.

Anhydride-linked ß-cyclodextrin-bonded silica stationary phases with enhanced chiral separation ability in liquid chromatography.

ß-Cyclodextrin can be functionalized by derivation of reactive hydroxyl on the ring due to its special chiral environment and structural characteristics, which can be used to identify or separate a variety of chiral substance. In this manuscript, a series of excellent chiral stationary phases for high-performance liquid chromatography were developed for enantioseparation by using anhydride modified ß-cyclodextrin bearing chiral (R/S)-α-phenethylamine or (S)-(+)-2-amino-1-propanol. They were characterized by elemental analysis, Fourier transform infrared spectra (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and BET. These chiral stationary phases presented good resolution and repeatability, about 17 kinds of enantiomers were effectively separated. And most of enantiomers were separated better than those reported in the literature in the same both normal and reversed phase modes. The RSD values of Rs for repeatability and column-to-column were below 0.44% and 2.83%, respectively. All results revealed that these new CSPs show great prospect for chiral separation in actual applications.

Preparation and applications of cellulose-functionalized chiral stationary phases: A review.

Separation and identification of chiral enantiomers play an increasingly important role in many fields like pharmaceutical production, preparation of chemical intermediates and biochemistry. Although there are multiple methods for obtaining a single enantiomer, chiral chromatographic separation is still considered to be one of the most efficient methods. Among the numerous chiral separation materials, cellulose and its derivatives, with strong chiral recognition ability, large loading capacity and easy to functionalization, have been presented excellent enantioseparation performance, which reveals their great prospect in chiral separation. In this review, the types of cellulose derivatives, preparation of cellulose-functionalized chiral stationary phases and their application in chiral chromatographic separation in recent years were systematically summarized, and we hope to provide a useful reference for researchers working in chiral separation and inspire new discoveries in the field of cellulose-functionalized chiral separation materials.

Recovery and recycling of solvent of counter-current chromatography: The sample of isolation of zeaxanthin in the Lycium barbarum L. fruits.

An efficient method of recovering and recycling solvent for counter-current chromatography was established by which zeaxanthin was separated from Lycium barbarum L. fruits. A column with activated carbon combined with high performance counter-current chromatography formed the recovering and recycling solvent system. Using the solvent system of n-hexane-ethyl acetate-ethanol-water (8:2:7:3, v/v) from the references, five injections were performed with an almost unchanged purity of zeaxanthin (80.9, 81.2, 81.5, 81.3, and 80.2% respectively) in counter-current chromatography separation. Meanwhile, the mobile phase reduced by half than conventional counter-current chromatography. By this present method, an effective improvement of counter-current chromatography solvent utilization was achieved.

Advances and prospects on acid phosphatase biosensor.

Acid phosphatase (ACP) is a lysosomal enzyme widely found in animals and plants. Particularly, abnormal ACP levels are often closely related to many diseases of the individual and are therefore widely used as biomarkers in clinical diagnosis. With the rapid development of precision medicine, the improvement or enhancement of the selectivity, sensitivity and broad target sample types of ACP biosensors based on the established methods has become an emerging demand for the treatment of diseases related to ACP levels. Therefore, a large number of ACP detection strategies have been used to improve these problems. In this review, the types and advantages/disadvantages of ACP detection methods were summarized and compared. According to the previous reports, the prospects and development trends of ACP detection were discussed. It was expected to provide some insights and inspiration for future research work.

Magnetic solid-phase extraction of triazole fungicides based on magnetic porous carbon prepared by combustion combined with solvothermal method.

A magnetic porous carbon (Fe3O4@PC) was successfully fabricated based on combustion combined with solvothermal method, and then used as magnetic solid-phase extraction absorbent for the determination of four triazole fungicides. The porous carbon was fabricated by imperfect combustion of filter paper loaded with zinc nitrate hexahydrate, which possessed extremely abundant pores, high specific surface area (908.05 m2 g-1) and large pore volume. Due to the introduction of solvothermal method used to prepare Fe3O4@PC, homogeneously distributed magnetic nanoparticles and high saturation magnetization were obtained. Compared with another magnetic porous carbon (Fe3O4@C), Fe3O4@PC obviously enhanced enrichment factors and extraction recoveries. Several key parameters influencing extraction efficiency were optimized. The satisfactory enrichment factors, low limits of detection of the method and good linearities were achieved under the optimal conditions. The relative recoveries ranged from 82.8% to 113.2% in three spiked real samples with relative standard deviations lower than 6.2%. The results indicated the great potential of the novel Fe3O4@PC as adsorbent for the extraction of triazole fungicides from complex real samples.

Imidazolium ionic liquid-enhanced poly(quinine)-modified silica as a new multi-mode chromatographic stationary phase for separation of achiral and chiral compounds.

In this work, a novel imidazolium ionic liquid-functionalized poly(quinine)-modified silica stationary phase (Sil-PQn-MIm) was successfully synthesized via surface radical chain transfer and nucleophilic substitution reaction. The modified silica was confirmed by series of characterizations including Fourier transform infrared spectroscopy (FT-IR), elemental analysis (EA), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The multi-mode chromatographic performances of the Sil-PQn-MIm column were investigated by anion-exchange mode for separation of aromatic acid samples, hydrophilic interaction mode for separation of nucleosides/nucleobases and sulfanilamides, and reversed-phase mode for separation of alkylbenzenes, benzene and polycyclic aromatic hydrocarbons (PAHs), and the Tanaka test mixtures, respectively. As expected, compared to the Sil-PQn column only with quinine as functional group, the Sil-PQn-MIm column further modified by imidazolium ionic liquid possessed higher separation performance, especially for the separation of nucleosides/nucleobases. The effects including buffer concentration, pH, organic solvent content and column temperature on chromatographic performance were studied, which proved that multiple interactions including electrostatic, hydrophobic and hydrophilic interactions can be simultaneously existed between the stationary phase and the analytes. In addition, reproducibility and efficiency of the Sil-PQn-MIm column were also investigated, the results illustrated that the stationary phase have good enough reproducibility (RSDs 0.15%-0.72%, n = 7) and high efficiency (plates per meter, ~90000 plates/m). In conclusion, the prepared stationary phase with multiple-mode retention capabilities could realize separation for various types of samples by optimizing chromatographic conditions, even for some chiral compounds.

Preparation and evaluation of biselector bonded-type multifunctional chiral stationary phase based on dialdehyde cellulose and 6-monodeoxy-6-monoamino-ß-cyclodextrine derivatives.

A novel biselector bonded-type multifunctional chiral stationary phase (MCSP) was prepared by covalently crosslinking dialdehyde cellulose (DAC) with 6-monodeoxy-6-monoamino-ß-cyclodextrine (CD) via Schiff base reaction. The biselector bonded-type MCSP had good chiral and achiral chromatographic performance in normal phase (NP) and reversed phase (RP) modes. Seven and eight enantiomers were successfully separated on the prepared biselector bonded-type MCSP in NP and RP modes, respectively. The biselector bonded-type MCSP showed enhanced chiral resolution ability compared with single selector chiral stationary phases due to the simultaneous introduction of DAC and 6-monodeoxy-6-monoamino-ß-CD on the surface of silica gel. Aromatic compounds including polycyclic aromatic hydrocarbons, anilines, phenols, phenylates, and aromatic acids were choosed as analytes to investigate the achiral chromatographic performance of the biselector bonded-type MCSP in NP and RP modes. Chromatographic evaluation results showed that the above aromatic compounds were essentially capable of achieving baseline separation by hydrophobic interaction, π-π interaction, and π-π electron-donor-acceptor interaction. Moreover, the host-guest inclusion effect of 6-monodeoxy-6-monoamino-ß-CD and the multiple interactions made the biselector bonded-type MCSP have good steric selectivity. The preparation method of the biselector bonded-type MCSP was simple and provided a new idea and strategy for the preparation of the subsequent novel biselector MCSP.

Counter-current chromatography melamine-modified column and its separation mechanism.

In this work, to further verify and develop the novel counter-current chromatography modified column separate mode, a melamine modified counter-current chromatography column was prepared. Meanwhile, the modified counter-current chromatography column was used to separate stevioside and rebaudioside A with the same partition coefficient in chosen solvent system to evaluate its separation efficiency. The results show that because of the presence of intermolecular forces between melamine and model compounds, better separation could be achieved on the modified column while it's almost impossible to be separated on the unmodified column. So the results of this research further show that column modified method is a possible approach to further increase the separation ability of counter-current chromatography. Take advantage of large sample handing capacity of counter-current chromatography, the mothed may have great potential to be an efficient method of separation and preparation enantiomer compounds.

Isolation of high-purity peptide Val-Val-Tyr-Pro from Globin Peptide using MCI gel column combined with high-speed counter-current chromatography.

Peptides have gained increased interest over the past several decades because of their therapeutics. In this research, a strategy combining MCI gel column chromatography and high-speed countercurrent chromatography was developed for the separation of high-purity peptide Val-Val-Tyr-Pro from Globin Peptide. First, the fraction of Val-Val-Tyr-Pro mixtures with a purity of 15.8% was obtained by using MCI gel column with a mixture of ethanol/water (20:80, v/v/v). Then, the high-purity Val-Val-Tyr-Pro was separated by high-speed countercurrent chromatography with a aqueous two phase systems of ethanol/acetonitrile/iso-propyl alcohol/(NH4 )2 SO4 Saturated solution /H2 O (0.5:0.5:0.25:1.5:0.7,v/v). The ammonium sulfate from high-speed countercurrent chromatography fractions was removed from target compound by MCI gel column chromatography using ethanol/water in stepwise elution mode. A 78 mg of Val-Val-Tyr-Pro was successfully purified with the purities of 98.80% from 30 g crude Globin Peptide. The amino acid sequence of the Val-Val-Tyr-Pro was determined by electrospray ionization high resolution tandem mass spectrometry. The method presents a practical strategy for the large-scale separation of pure peptide Val-Val-Tyr-Pro from Globin Peptide, and provides a reference method for obtaining high-purity peptide from other polypeptide mixtures.