Study on the occurrence state of main components of phosphogypsum dihydrate and its impurity distribution.

The dihydrate phosphoric acid process is the mainstream technique. However, the phosphogypsum (PG) produced contains high levels of impurities such as phosphorus and fluorine, severely constraining its valorization. In order to elucidate the occurrence patterns of phosphorus and fluorine impurities in PG, this study employed analytical methods including XRF, XRD, AMICS (Automated Mineralogy Integrated with Chemistry System), XPS, and chemical element balance analysis. We investigated the occurrence states of phosphorus, fluorine, silicon, iron, and aluminum elements in PG from wet-process phosphoric acid production, as well as the distribution characteristics of phosphorus and fluorine impurities. Additionally, we utilized Density Functional Theory (DFT) calculations to determine the binding energies of major minerals with water-soluble phosphate and fluoride groups, and analyzed the zeta potentials of gypsum and quartz mineral surfaces. The results indicate that the main mineral phases in PG are gypsum, quartz, potassium silicate minerals, aluminosilicate minerals, and hematite, predominantly occurring in monomineralic forms. Phosphorus impurities primarily exist in calcium silicate and hematite minerals, while fluorine is mainly associated with gypsum and potassium silicate minerals. DFT calculations demonstrate strong binding energies between calcium silicate and hematite minerals with PO4 3-, as well as between gypsum and quartz minerals with F-. The acidic conditions in the separation tank during wet-process phosphoric acid production may contribute to the distinctive distribution characteristics of phosphorus and fluorine impurities in PG.

In situ SEM fatigue testing technology for metallic materials: a review.

Fatigue failure is one of the most common fracture modes of structural materials in the industrial field. The study of material fatigue mechanisms and methods for predicting fatigue life has always been of significant interest to researchers due to the abrupt and catastrophic failure mode. In recent decades, the performance and functionality of scanning electron microscopy (SEM) have been continuously improved and expanded. Based on this, the development of in situ fatigue testing in SEM has been rapidly developed. This technology plays a crucial role in providing insights into the deformation behavior of materials under fatigue. Keeping this in view, a comprehensive review of the development and application methods of in situ SEM fatigue testing technology is provided here. The development of in situ SEM fatigue testing devices is provided in brief overview, and the application and research progress of this technology in some representative metal structural materials (nickel-based single-crystal superalloys, steel, aluminum alloys and additive manufacturing materials) are analyzed in detail. Moreover, the perspectives on evaluating fatigue damage, particularly about small cracks and the plastic accumulations fatigue behavior, are presented in this study, utilizing the latest advancements in in situ SEM fatigue testing. Remarks about the present and outlook for future work to be done are then provided.

Epoxidized Soybean Oleic Acid/Oligomeric Poly(lactic acid)-Grafted Nano-Hydroxyapatite and Its Role as a Filler in Poly(L-lactide) for Potential Bone Fixation Application.

One of the most effective strategies for modifying the surface properties of nano-fillers and enhancing their composite characteristics is through polymer grafting. In this study, a coprecipitation method was employed to modify hydroxyapatite (HAP) with epoxidized soybean oleic acid (ESOA), resulting in ESOA-HAP. Subsequently, oligomeric poly(lactic acid) (OPLA) was grafted onto the surface of ESOA-HAP, yielding OPLA-ESOA-HAP. HAP, ESOA-HAP, and OPLA-ESOA-HAP were comprehensively characterized. The results demonstrate the progressive grafting of ESOA and OPLA onto the surface of HAP, resulting in enhanced hydrophobicity and improved dispersity in organic solvent for OPLA-ESOA-HAP compared to HAP. The vitality and adhesion of Wistar rat mesenchymal stem cells (MSCs) were assessed using HAP and modified HAP materials. Following culture with MSCs for 72 h, the OPLA-ESOA-HAP showed an inhibition rate lower than 23.0% at a relatively high concentration (1.0 mg/mL), which is three times lower compared to HAP under similar condition. The cell number for OPLA-ESOA-HAP was 4.5 times higher compared to HAP, indicating its superior biocompatibility. Furthermore, the mechanical properties of the OPLA-ESOA-HAP/PLLA composite almost remained unaltered ever after undergoing two stages of thermal processing involving melt extrusion and inject molding. The increase in the biocompatibility and relatively high mechanical properties render OPLA-ESOA-HAP/PLLA a potential material for the biodegradable fixation system.

Incorporation of copper ion promoted adsorption of anionic dye (Acid Yellow 36) by acrolein-crosslinked polyethyleneimine/chitosan hydrogel: Adsorption, dynamics, and mechanisms.

In this study, a novel adsorbent, A-PEI/CS-Cu2+, was developed by crosslinking polyethyleneimine/chitosan hydrogel with acrolein and loading it with copper ions. The adsorption process of A-PEI/CS-Cu2+ on the anionic dye acid yellow 36 (AY36) was investigated by kinetic, isothermal and thermodynamic modeling. It was noteworthy that A-PEI/CS-Cu2+ exhibited rapid adsorption with a 90 % removal rate achieved within just 5 min, which was much faster than the adsorption rate of A-PEI/CS without load of copper ions and showed its potential for rapid adsorption applications. The maximum adsorption capacity for AY36 could reach up to 3114 mg g-1. In addition, the high concentration of saline wastewater was found to have almost no effect on the adsorption reaction in the salt effect test experiment. In five desorption-regeneration cycle experiments, the sample exhibited good recyclability and regeneration performance. The driving force of the adsorption process mainly originated from the electrostatic interaction, hydrogen bonding, and intermolecular interaction, in which the addition of copper ions led to the enhancement of the electrostatic interaction and chelation between A-PEI/CS-Cu2+ and AY36. Overall, the findings suggest the excellent potential of A-PEI/CS-Cu2+ for rapid and efficient adsorption, as well as its suitability for practical applications in wastewater treatment.

Green synthesis of N-rich carbon dot-derived crosslinked covalent organic nanomaterial for multipurpose chromatographic applications.

Carbon dots (CDs) derived crosslinked covalent organic nanomaterials (CONs) possessing high specific surface area and abundant surface functional groups are considered to be potential candidates for multimodal chromatographic separations. Typically, the synthesis of CDs and CONs requires harsh reaction conditions and toxic organic solvents, hence, the pursuit of facile and mild preparation strategies is the goal of researchers. In this work, 3-aminopropyltriethoxysilane and D-glucose were used as nitrogen and carbon sources, respectively, to prepare amino-CDs (AmCDs) by rapid low-temperature polymerization rather than the common high-temperature and high-pressure reaction. Then, surface functionalization of the aminated silica gel was carried out in a deep eutectic solvent by using hydrophilic AmCDs and 1,3,5-triformylbenzene (TFB) as the functional monomers. Consequently, a novel N-rich CDs derived CON surface-functionalized silica gel (AmCDs-CON@SiO2) was obtained under mild reaction conditions. The combination of AmCDs and TFB created an ideal CON based chromatographic stationary phase. The incorporation of TFB not only contributed to the successful construction of a crosslinked CON, but also enhanced the interaction forces. The developed AmCDs-CON@SiO2 has a great potential for versatile applications in liquid chromatography. This study proposes a simple stationary phase preparation strategy by the surface modification of silica gel with CDs-based CON. Moreover, this study verified the application potential of CDs derived CON in chromatographic separation. This not only promotes the development of CDs in the field of liquid chromatographic stationary phase, but also provides some reference value for the wide application of cross-linked CON.

Surface molecularly imprinted polymer/covalent organic framework/silica composite material with specific recognition ability and excellent chromatographic performance.

Facing with the difficulty of specific chromatographic separation of nucleoside drugs, this study prepared a surface molecularly imprinted polymer (SMIP) modified covalent organic framework (COF) coated silica stationary phase based on the specificity of molecular imprinting technology and the powerful chromatographic separation performance of COF. This novel SMIP-COF@SiO2 stationary phase can not only specifically identify template molecule and structural analogs, but can also be used to separate multiple types of analytes, such as B vitamins, sulfonamides, alkylbenzenes, phenyl ketones, polycyclic aromatic hydrocarbons and environmental endocrine disruptors, which satisfies the need for complex sample separation. Various retention mechanisms have been investigated and multiple interactions between the SMIP-COF@SiO2 stationary phase and the analytes are discovered. The chromatographic performance of SMIP-COF@SiO2 is far superior to that of the SMIP@SiO2 and COF@SiO2. Furthermore, the SMIP-COF@SiO2 stationary phase can be successfully used to analyze polycyclic aromatic hydrocarbons in the environmental water sample and detect whitening ingredient in skincare product, indicating its great potential for application in various fields.

Design of smart temperature-sensitive terpolymeric hydrogel for multi-applications in liquid chromatography.

Hydrogels with a unique three-dimensional network structure have been widely used in a variety of fields. However, hydrogels are prone to swelling under water-rich conditions, which severely limits their application in liquid chromatography. Therefore, producing a hydrogel with reliable performance and good mechanical property is essential. Smart temperature-sensitive chromatographic packings have attracted extensive attentions in recent years. In this work, sodium 4-styrenesulfonate and 1-octadecene were introduced into the poly(N-isopropylacrylamide) hydrogel to improve mechanical property and separation performance. As a consequence, a smart temperature-sensitive terpolymeric hydrogel modified silica stationary phase (ION-hydrogel@SiO2) was synthesized for multimode liquid chromatographic separation. It was found that this new ION-hydrogel@SiO2 column exhibited excellent chromatographic separation ability for a wide range of analytes. To a certain extent, this new column has a higher chromatographic separation efficiency compared to the commercial C18 column and XAmide column. Moreover, the use of low proportion of organic phase in chromatographic separation is conducive to the realization of green chromatography. By investigating the chromatographic separation mechanism, it has been demonstrated that the hydrogen bonding interaction is primarily responsible for the temperature-sensitive behavior of the hydrogel. Finally, the ION-hydrogel@SiO2 column was used for the determination of pyridoxine in the commercially available tablet samples. In conclusion, this study presents a feasible idea for the development of novel copolymer hydrogels as liquid chromatographic stationary phases.

Exploring the potential applications of amphiphilic carbon dots based nanocomposite hydrogel in liquid chromatographic separations.

BACKGROUND: Due to their excellent stability, low toxicity, flexible modification and adjustable functionality, carbon dots (CDs) have a promising application prospect in the field of chromatographic stationary phases. Hydrogels are new functional polymer materials with three-dimensional network structure that have excellent hydrophilicity, high porosity and unique mechanical properties, which are also good candidate materials for liquid chromatography. Nevertheless, a review of the literature reveals that CDs based nanocomposite hydrogels have not yet been reported as HPLC stationary phases. RESULTS: In this work, amphiphilic CDs with multiple functional groups and polyacrylic acid hydrogel were grafted to the surface of silica gel by an in-situ polymerization method, and a CDs/polyacrylic acid nanocomposite hydrogel stationary phase (CDs/hydrogel@SiO2) was prepared. CDs act as the macroscopic cross-linking agents to form a cross-linked network with polyacrylic acid chains through physical cross-linking by hydrogen bonding and chemical cross-linking by amidation and esterification reactions, which not only improve the swelling property of the hydrogel but also increase its stability. Additionally, the introduction of CDs with multifunctional groups modulates the hydrophilic-hydrophobic balance of the hydrogel that also imparts good hydrophobicity to the composite hydrogel. Through the study of retention mechanism and influencing factors, it is certificate that the CDs/hydrogel@SiO2 has mixed-mode chromatographic performance. Furthermore, the CDs/hydrogel@SiO2 column shows great potential for the determination of organic contaminants in environmental water samples. SIGNIFICANCE: This work confirms the potential application of CDs/hydrogel composite for the separation of various samples and provides the possibility of developing CDs based nanocomposite hydrogel in the field of liquid chromatography. Introducing CDs into hydrogel can open up a new way for nanocomposite hydrogels to be used in HPLC, which expands the advance of hydrogel and CDs in separation field.

Organo-Ptii Complexes for Potent Photodynamic Inactivation of Multi-Drug Resistant Bacteria and the Influence of Configuration.

PtII based organometallic photosensitizers (PSs) have emerged as novel potent photodynamic inactivation (PDI) reagents through their enhanced intersystem crossing (ISC) processes. Currently, few PtII PSs have been investigated as antibacterial materials, with relatively poor performances reported and with structure-activity relationships not well described. Herein, a pair of configurational isomers are reported of Bis-BODIPY (4,4-difluoro-boradizaindacene) embedded PtII PSs. The cis-isomer (cis-BBP) displayed enhanced 1O2 generation and better bacterial membrane anchoring capability as compared to the trans-isomer (trans-BBP). The effective PDI concentrations (efficiency > 99.9%) for cis-BBP in Acinetobacter baumannii (multi-drug resistant (MDR)) and Staphylococcus aureus are 400 nM (12 J cm-2) and 100 nM (18 J cm-2), respectively; corresponding concentrations and light doses for trans-BBP in the two bacteria are 2.50 µM (30 J cm-2) and 1.50 µM (18 J cm-2), respectively. The 50% and 90% minimum inhibitory concentration (MIC50 and MIC90) ratio of trans-BBP to cis-BBP is 22.22 and 24.02 in A. baumannii (MDR); 21.29 and 22.36 in methicillin resistant S. aureus (MRSA), respectively. Furthermore, cis-BBP displays superior in vivo antibacterial performance, with acceptable dark and photoinduced cytotoxicity. These results demonstrate cis-BBP is a robust light-assisted antibacterial reagent at sub-micromolecular concentrations. More importantly, configuration of PtII PSs should be an important issue to be considered in further PDI reagents design.

Chemomechanical Origins of the Dynamic Evolution of Isolated Li Filaments in Inorganic Solid-State Electrolytes.

The penetrating growth of Li into the inorganic solid-state electrolyte (SSE) is one key factor limiting its practical application. Research to understand the underlying mechanism of Li penetration has been ongoing for years and is continuing. Here, we report an in situ scanning electron microscopy methodology to investigate the dynamic behaviors of isolated Li filaments in the garnet SSE under practical cycling conditions. We find that the filaments tend to grow in the SSE, while surprisingly, those filaments can self-dissolve with a decrease in the current density without a reversal of the current direction. We further build a coupled electro-chemo-mechanical model to assess the interplay between electrochemistry and mechanics during the dynamic evolution of filaments. We reveal that filament growth is strongly regulated by the competition between the electrochemical driving force and mechanical resistive force. The numerical results provide rational guidance for the design of solid-state batteries with excellent properties.

The investigation of ion association characteristics in lanthanum sulfate solution by the density functional theory and molecular dynamics simulations.

The ion association behavior in aqueous lanthanum sulfate solutions was investigated using density functional theory (DFT). The structures and properties of [La(SO4)m·(H2O)n](3-2m) clusters, where m = 1 to 3 and n = 1 to 9, were examined at the PBE0/6-311+G(d, p) level. The results show that Lanthanum sulfate hydrated clusters exist in the aqueous solution's microscopic state of contact ion pairs (CIP). [La(SO4)(H2O)n]+ and [La(SO4)2·(H2O)n]-, and [La(SO4)3·(H2O)n]3- clusters approximately reach the saturation of the first water shell at n = 7 and 6 and 3. [La(SO4)2·(H2O)6]- and [La(SO4)3·(H2O)3]3- clusters have lower binding energy than [LaSO4·(H2O)n]+. This indicates that lanthanum sulfate tends to aggregate in an aqueous solution. Compared to the gas-phase cluster structures, the distance of R(La-O)H2O expands in the PCM solvent model, while R(La-O)SO4 contracts. The hydration energy of LaSO4·(H2O)7, La(SO4)2·(H2O)6, and La(SO4)3·(H2O)3 were -76.5, -54.1 and -332.0 kcal/mol, respectively. The molecular dynamics simulation results show that La is more inclined to coordinate with sulfate's oxygen than water's oxygen, and the coordination number of water around La3+ is 6.075. These results are consistent with the calculated results by DFT.

Konjac glucomannan-based aerogels with excellent thermal stability and flame retardancy for thermal insulation application.

Biomass aerogels are a promising kind of environment-friendly thermal insulation material. However, the flammability, poor water resistance, and thermal instability of biomass aerogels limit their applications. Herein, freeze-drying and thermal imidization were used to create konjac glucomannan (KGM), boron nitride (BN), and polyimide (PI)-based aerogels with a semi-interpenetrating network structure. The introduction of BN was beneficial to improve the mechanical properties and thermal stability of aerogels. The imidization process of PI improved the hydrophobicity, mechanical property, and flame retardancy of the aerogels. The synergistic effect of PI and BN reduced the peak heat release rate and total heat release rate of KGM-based aerogel by 55.8 % and 35 %, respectively, and endowed aerogel with good self-extinguishing performance. Moreover, the results of thermal conductivity and infrared thermal imaging demonstrated that the aerogels had excellent thermal insulation properties, and could effectively manage thermal energy over a wide range of temperatures. This study provides a simple method for the preparation of heat-insulating aerogel with high fire safety, which has broad application prospects in the field of energy saving and emission reduction.

Efficient treatment of palladium from wastewater by acrolein cross-linked chitosan hydrogels: Adsorption, kinetics, and mechanisms.

Herein we present a study on the preparation and properties of a hydrogel adsorbent for treatment of wasted palladium souring from actial petrochemical industrial wastewater. Chitosan was used as the raw material and acrolein as the cross-linking agent for the hydrogel (A/CS). The adsorption behaviors of the hydrogel for Pd(II) ions were characterized and analyzed. The effect of pH, temperature, adsorption kinetics, and thermodynamics were investigated. Langmuir models were employed to describe the adsorption isotherms, while the pseudo-second-order equation was applied to describe the adsorption kinetics. The experimental results demonstrated that the adsorption was a monolayer chemical adsorption, and the adsorption capacity was found to reach 505.05 mg/g under optimal conditions. In addition, FT-IR and XPS analyses, combined with MS calculations confirmed that chelation and electrostatic attraction were dominated in the adsorption process. Overall, the development of this hydrogel adsorbent will provide a practical approach to the treatment of industrial wastewater containing palladium and have great potential for practical applications.

Facile synthesis of a novel polymer/covalent organic framework@silica composite material in deep eutectic solvent for mixed-mode liquid chromatographic separation.

The solvothermal synthesis of covalent organic framework (COF) modified silica gel usually requires the use of harmful organic solvents, tedious steps, and harsh reaction conditions. In pursuit of green chemistry, a new strategy for the facile preparation of COF@SiO2 composite material was realized in this work by using a low-toxicity and low-cost deep eutectic solvent as the reaction medium. Additionally, a flexible polyacrylic acid (PAA) was introduced for the purpose of improving the hydrophilic selectivity and separation efficiency of COF@SiO2. Based on the above ideas, a novel PAA/COF@SiO2 composite was successfully developed as a liquid chromatographic packing material. Performance evaluation of the slurry-packed PAA/COF@SiO2 column showed that diverse types of analytes were effectively separated, and the retention behavior of polar nucleosides showed a U-shaped trend, indicating mixed-mode of hydrophobic/hydrophilic retention mechanisms. Thermodynamic studies revealed that the separation mechanism was largely independent of temperature. This work verifies the feasibility of synthesizing polymer/COF@SiO2 composite material in the deep eutectic solvent. This strategy provides a theoretical reference for the green and facile preparation of COF@SiO2 as an efficient liquid chromatographic stationary phase.

Ionic liquid/covalent organic framework/silica composite material: Green synthesis and chromatographic evaluation.

BACKGROUND: Due to their large surface area and distinctive adsorption affinity, covalent organic frameworks (COFs) appear to be good candidates as liquid chromatographic separation materials with good application prospect. The development of COF materials in chromatographic science is currently in an exploratory stage. Especially, the practicability of COF@silica composite materials as liquid chromatographic stationary phases needs further exploration. Reasonably integrating a functional component such as ionic liquid (IL) into the COF@silica composite materials may provide customized functionality to achieve the purpose of synthesizing multi-functional COF based stationary phases. RESULTS: In this study, an IL modified COF bonded silica composite material (IL-COF@SiO2) was successfully synthesized by using an environmentally friendly deep eutectic solvent as the reaction medium instead of the frequently-used organic solvent. The synthesized IL-COF@SiO2 composite material combines the excellent separation ability of COF and the excellent mass transfer function of spherical porous silica microsphere, and meanwhile, the introduction of IL endows COF@SiO2 with preferable separation performance. The slurry-packed IL-COF@SiO2 liquid chromatographic column could be applied to effectively separate hydrophobic and hydrophilic compounds with preferable separation selectivity and high column efficiency. By investigating the retention behavior and influencing factors, a mixed-mode retention mechanism was found. Multiple interaction forces endow the IL-COF@SiO2 with a hydrophilic-hydrophobic balance performance, demonstrating a good application prospect as a versatile liquid chromatographic separation material. SIGNIFICANCE: In this study, a new strategy is proposed for greenly synthesizing a novel IL-COF@SiO2 composite material under mild conditions, which expands the potential application of COF materials in chromatographic science. One particular point to note is that the reaction medium in each step of the preparation process is low toxic and degradable deep eutectic solvent, which conforms to the concept of green chemistry.

Diazotization-Enabled Deaminative Late-Stage Functionalization of Primary Sulfonamides.

We, for the first time, disclosed a simple and efficient strategy for the late-stage functionalization of primary sulfonamides by diazotization, leading to sulfonyl chlorides, sulfonates, and complex sulfonamides. This protocol obviates the requirement for the prefunctionalization of sulfonamides. Its applicability is exemplified by the late-stage functionalization of sulfonamide-type drugs.

Synthesis and Micellization of Carbosilane Sulfonate Surfactants with Short Alkyl Chains.

Carbosilane surfactants, consisting of carbosilane as a hydrophobic group linked to hydrophilic groups, are one kind of silicone surfactants. In this paper, a series of carbosilane sulfonate surfactants with short alkyl chains (Cn-Si2C-SO3Na (n = 1-6)), Me-Si2C-SO3Na, Et-Si2C-SO3Na, Pr-Si2C-SO3Na, Bu-Si2C-SO3Na, Pen-Si2C-SO3Na, and Hex-Si2C-SO3Na, were prepared and characterized by 29 Si NMR, 1H NMR, and FT-IR spectroscopies. The influence of the alkyl chain length on their micellization was studied using surface tension, dynamic light scattering, conductivity, and transmission electron microscopy. The CMC value decreases with increasing length of the short alkyl group. The γCMC value of Cn-Si2C-SO3Na (n = 1-6) increases as the alkyl chain increases from methyl to propyl, while the γCMC value gradually decreases as the alkyl chain increases from propyl to hexyl. The larger and rigid tetramethyldicarbosilane group functioned synergistically with a short alkyl chain, resulting in carbosilane sulfonate surfactants adsorbing at the air/water interface with a rugby ball shape; accordingly, the Amin values of the investigated carbosilane sulfonate surfactants increase with increasing length of the alkyl chain. The micellization process of carbosilane sulfonate surfactants is enthalpy-driven at lower temperatures and entropy-driven at high temperatures. The ΔHm0 values became more negative and ΔSm0 values more positive as the alkyl chain length increased. Aggregates in the range of 10-800 nm were observed for Cn-Si2C-SO3Na (n = 1-6) in an aqueous solution, and the hydrodynamic diameter (Dh) decreased with increasing length of the short alkyl group.

Routine Workflow of Spatial Proteomics on Micro-formalin-Fixed Paraffin-Embedded Tissues.

In the era of single-cell biology, spatial proteomics has emerged as an important frontier. However, it still faces several challenges in technology. Formalin-fixed paraffin-embedded (FFPE) tissues are an important material in spatial proteomics, in which fixed tissues are excised using laser capture microdissection (LCM), followed by protein identification with mass spectrometry. For a satisfied spatial proteomics upon FFPE tissues, the excision area is expected to be as small as possible, and the identified proteins are countered upon as much as possible. For a general laboratory for spatial proteomics, a routine workflow is required, not relying on any special device, and is easily operating. In view of these challenges in technology, we initiated a technology evaluation throughout the entire procedure of proteomic analysis with micro-FFPE tissues. In contrast to the protocols reported previously, several innovations in technology were proposed and conducted, such as removal of destaining, decross-linking with "hang-down", solution simplification for peptide generation and balancing to excision area, and capture rate of micro-FFPE tissues. After optimization of all the necessary steps, a routine workflow was established, in which the minimized area for protein identification was 0.002 mm2, while the excision area for a consistent proteomic analysis was 0.05 mm2. Using the developed workflow and collecting the micro-FFPE tissues continuously, for the first time, a spatial proteomic atlas of mouse brain was preliminarily constructed, which exhibited the typical characteristics of spatial-dependent protein abundance and functional enrichment.

Chitosan/polyacrylic acid/octadecene double-crosslinked network hydrogel functionalized porous silica microspheres for multimode liquid chromatographic separation.

In this study, chitosan (CS) and polyacrylic acid (PAA) were used to construct a double-crosslinked network hydrogel, which was employed as the functional material for silica microspheres to prepare a CS/PAA hydrogel modified liquid chromatographic stationary phase. During preparation, octadecene (ODE) was introduced into the CS/PAA hydrogel to improve its hydrophobicity and separation ability. The electrostatic interaction between the amino group of CS and the carboxyl group of PAA effectively prevented the swelling of the CS/PAA hydrogel, which ensured the successful application of the obtained CS/PAA hydrogel@SiO2 in chromatographic analysis. Polar nucleosides/bases and B-vitamins were selectively separated using hydrophilic interaction liquid chromatography. Hydrophobic polycyclic aromatic hydrocarbons and alkylphenols were effectively separated through reversed-phase liquid chromatography. Moreover, the effective separation of aromatic positional isomers and chiral enantiomers was achieved. This study confirms the potential application of the CS/PAA hydrogel in chromatographic separation. What is noteworthy is that the method developed in this study also provides a feasible strategy to solve the swelling issue associated with the hydrogel-based liquid chromatographic stationary phase.

Preparation and application of a novel imine-linked covalent organic framework@silica composite for reversed-phase and hydrophilic interaction chromatographic separations.

The composites of covalent organic frameworks (COFs) and silica gel have been considered to be promising chromatographic separation materials due to the distinct advantages such as large specific surface area, good mechanical strength and high porosity. In the present study, a novel imine-linked COF@silica composite was prepared by in-situ growth of 2,4,6-tris(4-aminophenyl)-1,3,5-triazine (TAPT) and 2,5-dihydroxyterephthalaldehyde (DHTA) monomers on the surface of aminated silica gel (SiO2-NH2). The successful surface-modification of TAPT-DHTA-COF distinctly enhanced the separation selectivity and efficiency of SiO2-NH2. Multiple types of analyte-stationary phase interactions contributed to the selective retention of structurally similar analytes. The designed TAPT-DHTA-COF@SiO2 was observed to effectively separate hydrophobic phenyl ketones, phthalate esters and steroid hormones. Moreover, the polar amino and hydroxyl groups of TAPT-DHTA-COF facilitated the selective determination of hydrophilic nucleosides/bases. The kinetic performance and thermodynamic behavior of TAPT-DHTA-COF@SiO2 column were particularly explored. It was found that column efficiency was mainly affected by the mass transfer resistance, and the retention of nucleosides/bases on the TAPT-DHTA-COF@SiO2 column was temperature dependent. The developed versatile TAPT-DHTA-COF@SiO2 column was finally applied for detecting environmental hormones as well as water-soluble nicotinamide in real samples. In summary, the potential application of TAPT-DHTA-COF@SiO2 composite material for liquid chromatographic separations was first explored and verified. The TAPT-DHTA-COF@SiO2 was proved to be a promising chromatographic separation material.