Chiral hydroxyl-controlled covalent organic framework-modified stationary phase for chromatographic enantioseparation.

Chiral covalent organic frameworks (CCOFs) possess a superior chiral recognition environment, abundant pore configuration, and favorable physicochemical stability. In the post-synthetic chiral modification of COFs, research usually focused on increasing the density of chiral sites as much as possible, and little attention has been paid to the influence of the density of chiral sites on the spatial structure and chiral separation performance of CCOFs. In this article, 1,3,5-tris(4-aminophenyl) benzene (TPB), 2,5-dihydroxyterephthalaldehyde (DHTP), and 2,5-dimethoxyterephthalaldehyde (DMTP) served as the platform molecules to directly establish hydroxyl-controlled COFs through Schiff base condensation reactions. Then the novel chiral selectors 6-deoxy-6-[1-(2-aminoethyl)-3-(4-(4-isocyanatobenzyl)phenyl)urea]-ß-cyclodextrin (UB-ß-CD) were pended into the micropore structures of COFs via covalent bond for further construction the [UB-ß-CD]x-TPB-DMTP COFs (x represents the density of chiral sites). The chiral sites density on [UB-ß-CD]x-TPB-DMTP COFs was regulated by changing the construction proportion of DHTP to obtain a satisfactory CCOFs and significantly improve the ability of chiral separation. [UB-ß-CD]x-TPB-DMTP COFs were coated on the inner wall of a capillary via a covalently bonding strategy. The prepared open tubular capillary exhibited strong and broad enantioselectivity toward a variety of chiral analytes, including sixteen racemic amino acids and six model chiral drugs. By comparing the outcomes of chromatographic separation, we observed that the density of chiral sites in CCOFs was not positively correlated with their enantiomeric separation performance. The mechanism of chiral recognition [UB-ß-CD]x-TPB-DMTP COFs were further demonstrated by molecular docking simulation. This study not only introduces a new high-efficiency member of the COFs-based CSPs family but also demonstrates the enantioseparation potential of CCOFs constructed with traditional post-synthetic modification (PSM) strategy by utilizing the inherent characteristics of porous organic frameworks.

Zeolitic imidazolate framework-67-modified open-tubular column with cyclodextrin for enantioseparation in capillary electrochromatography.

The histidine-modified zeolitic imidazolate framework [His-ZIF-67] was prepared with the histidine, 2-methylimidazole, and Co2+ under ambient temperature. His-ZIF-67 was bonded via a glycidyl methacrylate copolymer to the internal surface of capillary and then functionalized with the NH2 -ß-cyclodextrin (NH2 -ß-CD). The materials were characterized by field emission scanning electron microscopy, high-resolution transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, N2 adsorption-desorption isotherm, X-ray diffraction, and X-ray photoelectron spectroscopy. In comparison with the NH2 -ß-CD@capillary, the NH2 -ß-CD@His-ZIF-67@capillary-coated column shows significantly enhanced resolution for chiral molecules. The NH2 -ß-CD@His-ZIF-67@capillary column achieved the baseline separation of amlodipine and metoprolol (the resolution of amlodipine: 1.70; metoprolol: 1.50) and the partial separation of atenolol and propranolol (the resolution of atenolol: 1.03; propranolol: 0.60). These were attributed to the histidine modification and the features of ZIF-67, including an excellent surface area and the abundant porosity. The pH and proportion of organic modifier in the buffer were crucial for enantioseparation performance and were evaluated in detail. The fabricated NH2 -ß-CD@His-ZIF-67@capillary-coated column showed good stability and repeatability (relative standard deviation <6.3%). The molecular modeling with AutoDock and grand canonical ensemble was carried out to evaluate the interactions between chiral stationary phase and racemic drugs.

Carboxymethyl-ß-cyclodextrin and histidine-zeolitic imidazolate framework-8 used for enantioseparation of three basic drugs in open-tubular capillary electrochromatography.

Metal organic frameworks (MOFs) have drawn broad attention as a novel stationary phase due to their highly porous structure, modifiable pores, large specific surface areas, and satisfactory stability. In this paper, histidine-zeolitic imidazolate framework-8 (His-ZIF-8) synthesized at room temperature was physically coated to the internal surface of the capillary column and the carboxymethyl-ß-cyclodextrin (CM-ß-CD) as the chiral selector was chemically bonded to the His-ZIF-8@capillary column. The prepared CM-ß-CD@His-ZIF-8@capillary column was used for the enantioseparation of amlodipine, propranolol, and atenolol in capillary electrochromatography. In contrast to the CM-ß-CD@capillary column without His-ZIF-8, the CM-ß-CD@His-ZIF-8@capillary column reveals significantly improved enantiodiscrimination performance for amlodipine (Rs : 0 → 2.29), propranolol (Rs : 0 → 1.69), and atenolol (Rs : 0 → 0.79). His-ZIF-8 concentration, buffer pH, buffer concentration, and the proportion of organic modifier were evaluated in detail with enantiomerically separating chiral molecules. The repeatability of intraday, day-to-day, and column-to-column have been discussed; the result was preferable, and the relative standard deviation (RSD) of separation parameters was <6.7%.

In-situ grown metal organic framework synergistic system for the enantioseparation of three drugs in open tubular capillary electrochromatography.

Metal organic frameworks have received great attention as the chiral stationary phase for racemic drug separation because of their fascinating structures and properties. However, the most homochiral metal organic frameworks were constructed by rare and precious chiral organic ligands. In this work, an achiral metal organic framework, together with a natural chiral selector carboxymethyl ß-cyclodextrin built a synergistic separation system in the open tubular capillary electrochromatography. The novel coated columns were developed by inducing metal organic framework nanoparticles to grow on the imidazolyl functional capillary inner wall. The baseline separations of hydroxychloroquine, ofloxacin, and atenolol were achieved in the synergistic separation system. The effects of the concentration of chiral selector, pH, voltage, and the concentration of organic additives were studied. Compared with chiral selector auxiliary bare capillary, the resolutions of three drugs were remarkably improved. The relative standard deviations for the retention time of intraday (n = 6), interday (n = 6), and column-to-column were less than 2.1, 2.6, and 5.2%, respectively. These results demonstrate that affordable synergistic separation systems are prospective for racemic drug enantioseparation in capillary electrochromatography.

Colorimetric recognition of aromatic amino acid enantiomers by gluconic acid-capped gold nanoparticles.

In this work, we prepared gold nanoparticles (AuNPs) by employing gluconic acid (GlcA) as reducing-cum-stabilizing agent. The proposed GlcA-AuNPs successfully worked as a colorimetric sensor for visual chiral recognition of aromatic amino acid enantiomers, namely tyrosine (D/L-Tyr), phenylalanine (D/L-Phe), and tryptophan (D/L-Trp). After adding L-types to GlcA-AuNPs solution, the color of the mixture changed from red to purple (or gray), while no obvious color change occurred on the addition of D-types. The effect can be detected by naked eyes. The particles have been characterized by transmission electron microscopy, Fourier-transform infrared spectroscopy, zeta potential, the dynamic light scattering analysis as well as UV-Vis spectroscopy. This assay can be used to determine the enantiomeric excess of L-Trp in the range from 0 to + 100%. The method has advantages in simplicity, sensitivity, fast response, and low cost.

Immobilization of cellulase on monolith supported with Zr(IV)-based metal-organic framework as chiral stationary phase for enantioseparation of five basic drugs in capillary electrochromatography.

Metal-organic framework (UiO-66-NH2)-incorporated organic polymer monolith was prepared by thermal polymerization. By virtue of the superior physical and chemical properties, the UiO-66-NH2-modified organic monolith was then functionalized by chiral selector cellulase via the condensation reaction between the primary amino groups and aldehyde groups. The synthesized materials were characterized by Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectrometry, thermogravimetric analysis, and nitrogen sorption isotherm. The cellulase@poly(glycidyl methacrylate-UiO-66-NH2-ethylene glycol dimethacrylate) (cellulase@poly(GMA-UiO-66-NH2-EDMA)) monolith was applied to enantiomerically separate the basic racemic forms of metoprolol, atenolol, esmolol, bisoprolol, and propranolol. In contrast to the cellulase@poly(GMA-co-EDMA) monolith without UiO-66-NH2, the cellulase@poly(GMA-UiO-66-NH2-EDMA) monolith reveals significantly improved enantiodiscrimination performance for metoprolol (Rs: 0 → 1.67), atenolol (Rs: 0 → 1.50), esmolol (Rs: 0 → 1.52), bisoprolol (Rs: 0 → 0.36), and propranolol (Rs: 0 → 0.44). The immobilization pH of cellulase, buffer pH, UiO-66-NH2 concentration, and the proportion of organic modifier were evaluated in detail with enantiomerically separating chiral molecules. The intra-day, inter-day, column-to-column, and inter-batch precision have been discussed, the result was preferable, and the relative standard deviation (RSD) of separation parameters was <4.3%. Schematic representation of the preparation of a UiO-66-NH2-modified organic polymer monolith for enantioseparating five racemic ß-blockers. UiO-66-NH2 was synthesized and converted into a monolith as the stationary phase. Then, the modified monolith containing cellulase as the chiral selector was applied in a capillary electrochromatography system for enantioseparating chiral drugs.

A rapid enantioseparation system of capillary electrochromatography modified by electrostatic adsorption with transfersomes.

Transfersomes were a special kind of nanomaterials with higher deformability and flexibility. A rapid method for coated-column preparation using anionic transfersomes as a coating material by electrostatic adsorption was developed. With carboxymethyl-ß-cyclodextrin added in running buffer as the chiral selector, the capillary electrochromatography enantioseparation system based on the transfersomes-coated column modified by electrostatic adsorption was established for the first time. Propranolol and metoprolol acted as model drugs to evaluate the enantioseparation performance, these two basic drugs achieved baseline separation with satisfactory resolution and selection factor in this transfersomes-electrochromatography system but only partial separation in bare column system. In order to get the optimal separation condition, concentration of chiral selector, buffer pH, and applied voltage were systematically investigated. A rapid and efficient enantioseparation electrochromatography system was established and showed that transfersomes as the stationary phase could efficiently improve chiral separation effect.

Metal organic framework ZIF-90 modified with lactobionic acid for use in improved open tubular capillary electrochromatographic enantioseparation of five basic drugs.

An in situ zeolite imidazole metal organic framework-90 (ZIF-90) modified capillary was prepared via the method of solvothermal synthesis. The coating of ZIF-90 was characterized by scanning electron microscopy, energy-dispersive X-ray spectrometry, and EOF. Capillary electrochromatography-based enantioseparation of the basic drugs propranolol (PRO), metoprolol (MET), atenolol (ATE), bisoprolol (BIS), and sotalol (SOT) was performed using lactobionic acid (LA) as the chiral selector. Compared with an uncoated silica capillary, the resolutions are greatly improved (PRO 1.40 → 3.23; MET 1.07 → 3.19; ATE 1.07 → 3.15; BIS 1.16 → 3.41; SOT 1.00 → 2.79). Effects of buffer pH values, proportion of organic additives, concentration of lactobionic acid, and applied voltage were investigated. Graphical abstract Schematic presentation of the preparation of zeolitic imidazolate framework-90 (ZIF-90) modified capillary (ZIF-90@capillary) for enantioseparation of drug enantiomers. The capillary was applied to construct capillary electrochromatography system with lactobionic acid for enantioseparation of basic chiral drugs.

Gold nanoparticles-functionalized monolithic column for enantioseparation of eight basic chiral drugs by capillary electrochromatography.

Poly(glycidyl methacrylate)-co-(ethylene dimethacrylate) [poly(GMA-co-EDMA)] monoliths were prepared, and used as a support to attach gold nanoparticles (AuNP) via Au-S bond. Pepsin, acting as a chiral selector, was linked to the surface of the carboxyl-modified AuNP through a hydrochloride/N-hydroxysuccinimide coupling reaction. The material was characterized by scanning electron microscopy, energy dispersive X-ray spectrometry, transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy and N2 adsorption-desorption isotherm. The pepsin@AuNP@poly(GMA-co-EDMA) monolith showed preferable enantioselectivity for hydroxychloroquine (HCQ), chloroquine (CHQ), hydroxyzine (HXY), labetalol (LAB), nefopam (NEF), clenbuterol (CLE), amlodipine (AML) and chlorpheniramine (CHL) in capillary electrochromatography (CEC). These racemic drugs were monitored at the maximum absorption wavelength (220 nm for HXQ, CHQ, HXY, LAB, NEF; 240 nm for AML; 215 nm for CLE, CHL). In comparison with the pepsin@poly(GMA-co-EDMA) monolith loaded with 5 nm AuNP, the pepsin@poly(GMA-co-EDMA) monolith loaded with 13 nm AuNP shows significantly enhanced enantiomeric resolution (HCQ: 0.62 → 3.45; CHQ: 0.60 → 2.11; HXY: 0.49 → 2.30; LAB: 1.03 → 2.45, 1.45 → 3.46, 0 → 0.67; NEF: 0.53 → 1.29; CLE: 0.42 → 0.56; AML: 0 → 0.83; CHL: 0.24 → 0.55). Pepsin concentration, buffer pH value, buffer concentration and applied voltage were investigated in detail with (±) HCQ and (±) HXY as model analytes. The reproducibility of intra-day, inter-day and column-to-column were explored, and found to be satisfactory. Graphical abstractSchematic presentation of the preparation of gold nanoparticles (AuNP) modified.

ß-Cyclodextrin covalent organic framework-modified organic polymer monolith as a stationary phase for combined hydrophilic and hydrophobic aqueous capillary electrochromatographic separation of small molecules.

A ß-Cyclodextrin covalent organic framework (ß-CD COF) was successfully prepared under ambient temperature with a mild chemistry strategy from heptakis(6-amino-6-deoxy)-ß-cyclodextrin and terephthalaldehyde. It was embedded into the poly[(glycidyl methacrylate)-co-(ethylene dimethacrylate)] [poly(GMA-co-EDMA)] monolith and served as the ß-CD COF material-incorporated monolith. The synthetic materials were characterized by field emission scanning electron microscopy, energy-dispersive X-ray mapping analysis, transmission electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, and N2 adsorption-desorption isotherm. The ß-CD COF material-incorporated monolith achieved baseline separation in capillary electrochromatographic separation of three amides, three amino acids, three nucleosides, four aromatic acids, and three positional isomers (with resolution values of three amides, 1.75 and 1.54; three amino acids, 5.24 and 1.75; three nucleosides, 2.56 and 1.77; four aromatic acids, 6.96, 2.74, and 1.64; three positional isomers, 1.61 and 1.50). In comparison with the original monolith, the ß-CD COF material-incorporated monolith shows significantly enhanced resolution for mixed molecules. The effect of pH and concentration of buffer and applied voltage were discussed in detail. The fabricated monolith showed good stability and reproducibility (relative standard deviation (RSD) < 6.9%). Molecular modeling illuminated the interactions between the small molecules and stationary phase, and provided a sufficient theoretical basis for experimental data. Graphical abstract Schematic presentation of the preparation of ß-cyclodextrin covalent organic framework (ß-CD COF) material-incorporated organic polymer monolith for separating the amides, amino acids, nucleosides, aromatic acids, and positional isomers. ß-CD COF materials were synthesized and incorporated into the monolith as the stationary phase. Then, the incorporated monolith was applied in the capillary electrochromatography system for separating small molecules.

Maltodextrin-modified graphene oxide for improved enantiomeric separation of six basic chiral drugs by open-tubular capillary electrochromatography.

An electrochromatographic capillary was modified with graphene oxide (GO), and the coating was characterized by scanning electron microscopy, energy dispersive X-ray spectrometry, and Fourier transform infrared spectra. By utilizing maltodextrin (MD) as the chiral selector, the basic chiral drugs nefopam (NEF), amlodipine (AML), citalopram hydrobromide (CIT), econazole (ECO), ketoconazole (KET) and cetirizine hydrochloride (CET) can be enantiomerically separated on this CEC. Compared with an uncoated silica capillary, the resolutions are markedly improved (AML: 0.32 → 1.45; ECO: 0.55 → 1.89; KET: 0.88 → 4.77; CET: 0.81 → 2.46; NEF: 1.46 → 2.83; CIT: 1.77 → 4.38). Molecular modeling was applied to demonstrate the mechanism of enantioseparation, which showed a good agreement with the experimental results. Graphical abstractSchematic representation of the preparation of graphene oxide-modified capillary (GO@capillary) for enantioseparation of drug enantiomers. The monolayered GO was used as the coating of the GO@capillary. Then the capillary was applied to construct capillary electrochromatography system with maltodextrin for separation of basic chiral drugs.

A metal organic framework-functionalized monolithic column for enantioseparation of six basic chiral drugs by capillary electrochromatography.

Poly(glycidyl methacrylate)-co-(ethylene dimethacrylate) [poly(GMA-co-EDMA)] monoliths were used as a support to grow a zeolitic imidazolate framework-8 (ZIF-8) via layer-by-layer self-assembly. Pepsin, acting as as chiral selector, was covalently linked to the surface of the amino-modified ZIF-8 through the Schiff base method. The material was characterized by scanning electron microscopy, thermogravimetric analysis, X-ray diffraction, Fourier transform infrared spectroscopy and elemental analysis. The pepsin-ZIF-8-poly(GMA-co-EDMA) column was utilized to the enantioseparation of the racemic forms of hydroxychloroquine (HCQ), chloroquine (CHQ), hydroxyzine (HXY), nefopam (NEF), clenbuterol (CLE) and amlodipine (AML). In comparison with a pepsin-poly(GMA-co-EDMA) monolithic column (without self-assembled ZIF-8 nanoparticles), the resolution is strongly enhanced (HCQ: 0.34 → 2.50; CHQ: 0.45 → 1.97; HXY: 0.39 → 1.43; NEF: 0.27 → 0.81; CLE: 0 → 0.81; AML: 0.16 → 0.72). Effects of self-assembly layers of ZIF-8, pepsin concentration, buffer pH values and applied voltage were investigated with hydroxychloroquine as the model analyte. The reproducibility of run-to-run, day-to-day and column-to-column were explored, and found to be satisfactory. Graphical abstractSchematic representation of capillary electrochromatography (CEC) systems with a pepsin-zeolitic imidazolate framework-8 (ZIF-8) modified poly(glycidyl methacrylate)-co-(ethylene dimethacrylate) [poly(GMA-co-EDMA)] monolithic column as stationary phases for separation of basic racemic drugs. ZIF-8 modified column was prepared via layer-by-layer self-assembly.

Recent progress in the synthesis and applications of covalent organic framework-based composites.

Covalent organic frameworks (COFs) have historically been of interest to researchers in different areas due to their distinctive characteristics, including well-ordered pores, large specific surface area, and structural tunability. In the past few years, as COF synthesis techniques developed, COF-based composites fabricated by integrating COFs and other functional materials including various kinds of metal or metal oxide nanoparticles, ionic liquids, metal-organic frameworks, silica, polymers, enzymes and carbon nanomaterials have emerged as a novel kind of porous hybrid material. Herein, we first provide a thorough summary of advanced strategies for preparing COF-based composites; then, the emerging applications of COF-based composites in diverse fields due to their synergistic effects are systematically highlighted, including analytical chemistry (sensing, extraction, membrane separation, and chromatographic separation) and catalysis. Finally, the current challenges associated with future perspectives of COF-based composites are also briefly discussed to inspire the advancement of more COF-based composites with excellent properties.

Successful application of aminolevulinic acid/photodynamic therapy in the treatment of giant condyloma acuminatum in an 87-year-old patient.

Condyloma acuminatum is a common sexually transmitted disease caused by human papillomavirus infection and is a benign hyperplastic lesion of the genital and perianal areas. The principle of its treatment is to remove the visible warts as much as possible and to prevent recurrence. Traditional treatment methods of condyloma acuminatum, such as CO2 laser, liquid nitrogen freezing, surgery, and topical medications, can remove warts. However, these methods have disadvantages such as pain, high recurrence rates, long treatment cycles, and scarring. Aminolevulinic acid/photodynamic therapy (ALA-PDT), a safe and effective method, has been widely used to treat condyloma acuminatum in recent years. Condyloma acuminatum occurs relatively rarely in elderly patients, in whom treatment is difficult owing to poorer physiological function. We successfully treated an 87-year-old patient with a giant condyloma acuminatum of the glans penis using six sessions of ALA-PDT at 7-day intervals and obtained satisfactory results. No recurrence was observed during a 6-month follow-up. Therefore, ALA-PDT is worth popularizing in clinical practice.

Polydopamine Coating Doped with Graphene Oxide Enhances Enantioseparation of Capillary Column.

How to improve the enantiomer separation efficiency of drugs is a hot topic. In this paper, polydopamine (PDA) coating doped with graphene oxide (GO) by physical adsorption was used to modify the capillary column to enhance the enantioseparation efficiency of the drugs. In the capillary electrochromatography (CEC) system, the novel capillary column with carboxymethyl-ß-cyclodextrin (CM-ß-CD) as a chiral selector has completed the enantioseparation of four basic drugs (propranolol, metoprolol, amlodipine and chlorpheniramine). The optimum separation conditions were obtained by optimizing the pH of the buffer, the concentration of organic modifier, the concentration of the chiral selector and the voltage, and the resolution and peak shape were significantly improved compared with uncoated bare-fused column. The stability and reproducibility of the new capillary column were satisfactory and the relative standard deviation of intra-day and inter-day was <3.2%, and of column-to-column was <4.8%. The rich functional groups of GO are key factors to improve the enantioseparation efficiency, which also indicates that nanomaterials with easy modification of functional groups and large specific surface area are excellent resources for capillary modification applications.

Metal organic framework- modified monolithic column immobilized with pepsin for enantioseparation in capillary electrochromatography.

Metal-organic frameworks (MOFs), defined as a class of microporous hybrid materials, are established by coordination of metal cations with functional organic ligands. In addition to outstanding porosity and large surface area, the structures and functions of MOFs can be designed and adjusted based on different destinations, which would be employed as stationary phases in various chromatographic modes. Pepsin, a class of protein, has been investigated as chiral selector owing to their unique interactions with analytes based on chiral or affinity selectivity. In this work, MOF-5 was exploited to grow on the support of poly (glycidyl methacrylate)-co-(ethylene dimethacrylate) [poly(GMA-co-EDMA)] monoliths by layer-by-layer self-assembly method. Pepsin was subsequently bonded with the carboxyl group of MOF-5 through amidation reaction. The ultimate pepsin@MOF-5@poly(GMA-co-EDMA) column was applied for enantioseparation of six basic chiral drugs by capillary electrochromatography with good resolution and repeatability. Compared with the pepsin modified monolithic column, the newly prepared column with MOF-5 shows significantly enhanced enantiomeric resolution, which reveals that MOFs-modified capillary monolithic columns lead a promising road to separation of racemates by chromatography.

A review on chiral metal-organic frameworks: synthesis and asymmetric applications.

Chiral metal-organic frameworks (CMOFs) have the characteristics of framework structure diversity and functional tunability, and have important applications in the fields of chiral identification, separation of enantiomers and asymmetric catalysis. In recent years, the application of CMOFs has also been extended to other research fields, such as circularly polarized fluorescence and chiral ferroelectrics. Compared with achiral MOFs, the design of CMOFs only considers the modes of introduction of chirality, and also takes into account the crystallization and purification. Therefore, the synthesis and characterization of CMOFs face many difficult challenges. This review discusses three effective strategies for constructing CMOFs, including direct synthesis of chiral ligands, spontaneous resolution of achiral ligands or chiral template-induced synthesis, and post-synthetic chiralization of achiral MOFs. In addition, this review also discusses the recent application progress of CMOFs in chiral molecular recognition, enantiomer separation, asymmetric catalysis, circularly polarized fluorescence, and chiral ferroelectrics.

A porous layer open-tubular capillary column supported with pepsin and zeolitic imidazolate framework for enantioseparation of four basic drugs in capillary electrochromatography.

New material zeolitic imidazolate framework-4, 5-imidazoledicarboxylic acid (ZIF-IMD) located on the pore surface of porous layer open-tubular (PLOT) column previously functionalized with N-(3-aminopropyl)-imidazole have been prepared via a layer-by-layer self-assembly strategy. This new ZIF-IMD coating hybrids are used as solid-phase carriers for chiral selector pepsin immobilization. The ZIF-IMD material was characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscope and X-ray diffraction. The synthesized pepsin@ZIF-IMD@POLT column achieved the baseline separation of hydroxychloroquine (HCQ), chloroquine (CHQ) and hydroxyzine (HXY) (the resolution of HCQ: 2.19; CHQ: 1.84; HXY: 1.53). Compared with the pepsin@PLOT column (without ZIF-IMD material), the chiral separation capability of the pepsin@ZIF-IMD@POLT column can be remarkably improved. Several key parameters including concentration of chiral selector, buffer pH, applied voltage and buffer concentration were systematically evaluated to provide the optimal enantioseparation condition. The relative standard deviations (RSDs) of intra-day, inter-day, column-to-column and inter-batch of migration time and Rs of the HCQ were evaluated in detail, respectively (RSD < 7.21%). Additionally, the potential mechanism of increased resolution was discussed in the article.

Low Temperature NH3-SCR over Mn-Ce Oxides Supported on MCM-41 from Diatomite.

A series of MCM-41 molecular sieves with different molar ratio of template to silicon were synthesized through hydrothermal synthesis method by using cetyltrimethylammonium bromide (CTAB) as the template, diatomite as the silicon source. By using impregnation method, the Mn-Ce/MCM-41 SCR molecular sieve-based catalysts were prepared. The results observed that when the molar ratio of template to silicon was 0.2:1, the MCM-41 as catalyst carrier has the highest surface area and largest pore volume, it also presented typically ordered hexagonal arrays of uniform channels. The denitration catalytic material based on this carrier has a high number of Lewis acidic sites, and the denitration efficiency can reach more than 93%.

Structural, thermal, and hydrolysis properties of large and small granules from C-type starches of four Chinese chestnut varieties.

Large and small granules were separated from C-type starches of four Chinese chestnut varieties growing in the same environment. They had similar amylose contents from 17.7% to 20.2% and showed C-type crystallinity. The large granules had relative crystallinity from 19.2% to 20.3%, ordered degree from 0.672 to 0.706, and lamellar peak intensity from 233.2 to 267.1, but small granules had relative crystallinity from 16.2% to 18.2%, ordered degree from 0.635 to 0.663, and lamellar peak intensity from 201.6 to 213.1. The gelatinization peak temperatures ranged from 62.6 to 65.7 °C in large granules but from 60.3 to 61.7 °C in small granules, and enthalpy variation did from 12.5 to 13.7 J/g in large granules but from 10.1 to 11.7 J/g in small granules. Both large and small granules showed biphasic hydrolysis. Though small granules had significantly higher hydrolysis rate than large granules, but they had similar total hydrolysis extent during whole hydrolysis. The granule size had significantly positive relationships with relative crystallinity, ordered degree, lamellar peak intensity, and gelatinization temperature and enthalpy variation, but was negatively correlated to hydrolysis rate. The principal component analysis was conducted to reveal the interrelationships among different starch properties and the variations among different starches.