Multifunctionalized Covalent Organic Frameworks for Broad-Spectrum Extraction and Ultrasensitive Analysis of Per- and Polyfluoroalkyl Substances.

The contamination of surface and ground water by per- and polyfluoroalkyl substances (PFASs) has become a growing concern, and the structural diversity of PFASs is the major challenge for their ubiquitous applications. Strategies for monitoring coexistent anionic, cationic, and zwitterionic PFASs even at trace levels in aquatic environments are urgently demanded for effective pollution control. Herein, novel amide group and perfluoroalkyl chain-functionalized covalent organic frameworks (COFs) named COF-NH-CO-F9 are successfully synthesized and used for highly efficient extraction of broad-spectrum PFASs, attributing to their unique structure and the multifunctional groups. Under the optimal conditions, a simple and high-sensitivity method is established to quantify 14 PFASs including anionic, cationic, and zwitterionic species by coupling solid-phase microextraction (SPME) with ultrahigh-performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS) for the first time. The established method displays high enrichment factors (EFs) of 66-160, ultrahigh sensitivity with low limits of detection (LODs) of 0.0035-0.18 ng L-1, a wide linearity of 0.1-2000 ng L-1 with correlation coefficient (R2) ≥0.9925, and satisfactory precision with relative standard deviations (RSDs) ≤11.2%. The excellent performance is validated in real water samples with recoveries of 77.1-108% and RSDs ≤11.4%. This work highlights the potential of rational design of COFs with the desired structure and functionality for the broad-spectrum enrichment and ultrasensitive determination of PFASs in real applications.

Developing a Noncontact Heating Matrix Spraying Apparatus with Controllable Matrix Film Formation for MALDI Mass Spectrometry Imaging.

Matrix deposition plays an important role in obtaining high-quality and reliable molecular spatial location information for matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-MSI). To control the matrix film formation, an automatic matrix spraying apparatus was developed with the introduction of a noncontact heating lamp. Compared with the unheated condition, the noncontact heating lamp suppressed the coffee-ring effect and the diffusion phenomenon of the analyte effectively by controllable matrix film formation. Meanwhile, the signal intensity was increased by 2-5 fold. To prove the ability of the matrix deposition apparatus, the apparatus combined with metabolomics analysis was used to show the spatial distribution of the substance in sprouted potato tubers. The potential biomarkers at m/z 868.5049 and m/z 852.5101 were identified as α-solanine and α-chaconine, and the synthesis pathways were further searched. To further demonstrate the quality of MALDI images including localization and spatial resolution, lipid distribution in rat brain tissue was investigated by the developed noncontact heating matrix spraying apparatus. An excellent match with distinguishable compartments of lipids in the rat brain was obtained between the H&E-stained sections and MALDI-MSI images. These results indicate that the developed noncontact heating matrix spraying apparatus is reliable and provides a low-cost, high-quality, rapid approach for MALDI-MSI.

Determination of oxalate and citrate in urine by capillary electrophoresis using solid-phase extraction and capacitively coupled contactless conductivity based on an improved mini-cell.

A new method for the rapid determination of the metabolites oxalate and citrate in urine samples was based on capillary electrophoresis and capacitively coupled contactless conductivity detection coupled with solid-phase extraction. The detection cell for capacitively coupled contactless conductivity detection was improved with a smaller inner volume (1.5 nL), reduced noise (0.2∼0.5 mV) and better reproducibility and durability. Under optimal conditions, oxalate and citrate can achieve baseline separation within 4 min and the detection limits (S/N = 3) for oxalate and citrate are about 44 and 244 ng/mL, respectively. The overall recovery is between 80.0 and 89.2%. This method offers a better choice for quantitative analysis of strong anions such as oxalate and citrate in diagnostic testing associated with human diseases.

Tetraazacalix[2]arence[2]triazine Coated Fe3O4/SiO2 Magnetic Nanoparticles for Simultaneous Dispersive Solid Phase Extraction and Determination of Trace Multitarget Analytes.

To satisfy the requirement of simultaneous extraction and characterization of diverse kinds of multitarget analytes, the preparation, characterization, and application of a novel tetraazacalix[2]arene[2]triazine (TCT) coated magnetic nanoparticle (TCT MNP) adsorbent are presented in this paper. TCT assembles two benzene rings and two triazines with nitrogen cross-bridging links, which exhibits a unique structural framework and versatile recognition features based on the multiple recognition sites. These include π electron stacking, charge transfer, hydrogen bonding, and ion-exchange. TCT MNPs acted as a dispersive SPE adsorbent showing strong interaction with and adsorption of polycyclic aromatic hydrocarbons (PAHs), nitroaromatics, and heavy metal ions. The dispersive magnetic nanoparticle solid phase extraction (d-MNSPE) strategy with the simultaneous extraction and stepwise elution (SESE) procedure was designed and optimized for the five PAHs (phenanthrene, anthracene, pyrene, chrysene, and benzo(a)pyrene), six nitroaromatics (4-nitrotoluene, 2,4-dinitrotoluene, 2,4,6-trinitrotoluene, 4-nitrophenol, 2,4-dinitrophenol, and 2,4,6-trinitrophenol), and four metal ions (Cu, Zn, Mn, Cd) in aqueous samples. Due to the high stability, desirable durability, larger saturation magnetization, reuse and distinct enrichment capacity of TCT MNPs, the d-MNSPE method with the SESE strategy provided high recovery (>90%) and good precision (relative standard deviations, RSD < 10%). Coupled with the commonly used HPLC-fluorescence detection, HPLC-UV detection, and atomic absorption spectrometry, these trace probes in tap water, river water, and lake water were determined with very low detection limits, in the range of 0.09-0.15 pg mL-1 for PAHs, 6-11 pg mL-1 for nitroaromatics, and 17-53 pg mL-1 for metal ions after being enriched by the d-MNSPE. The determination of trace PAHs in urine samples from smokers and nonsmokers was successfully carried out with this method, which implied that the versatile TCT MNPs and the robust method together represent a significant potential application in the analysis of body fluids and disease markers. Such methods for accurate quantification of trace components in water are very valuable as they fulfill an unmet need in environmental and medicinal chemistry.

Design of magnetic photonic crystal microdroplet for sensitive detection of cationic organic pollutants by the coupled resonance effect.

Photonic crystals (PCs), periodically arranged nanoparticles, have emerged with extraordinary optical properties for light manipulation owing to their photonic band gaps (PBGs). Here, a novel strategy and method was developed for efficient enrichment and sensitive detection of cationic organic pollutants in water. Size-controlled Fe3O4@poly (4-styrenesulfonic acid-co-maleic acid) (Fe3O4@PSSMA) was prepared, and high surface charge were formed with the coating of PSSMA layer on the surface of Fe3O4, which could be used for adsorption and removal of cationic organic pollutants. The Fe3O4@PSSMA after adsorbing cationic organic pollutant were assembled to magnetic photonic crystal microdroplet (MPCM) structure in an external magnetic field, which was used as surface-enhanced Raman scattering (SERS) substrate. By coupling the magnetically tuned PBGs with Raman laser wavelength, the light utilization efficiency can be improved and the coupled resonance effect was greatly enhanced. The enhancement factor (EF) of MB was more than 800 attributing to the dual function of enrichment and coupled resonance effect of MPCM. The developed analytical strategy is the first time to use MPCM as a SERS substrate to realize the sensitive detection of 10 nmol L-1 MB in real water, which greatly improves the application of MPCM in the field of contaminant analysis and detection in water.

A nitrogen-doped graphene tube composite based on immobilized metal affinity chromatography for the capture of phosphopeptides.

A novel immobilized metal affinity chromatography (IMAC) functional composite, mNi@N-GrT@PDA@Ti4+, was fabricated based on ultrathin magnetic nitrogen-doped graphene tube (mNi@N-GrT) after chelated Ti4+ with polydopamine, following as a magnetic solid-phase extraction sorbent for rapidly selective enrichment and mass spectrometry identification of phosphorylated peptides. After optimized, the composite exhibited high specificity in the enrichment of phosphopeptides from the digest mixture of ß-casein and bovine serum albumin (BSA). The robust method presented the low detection limits (1 fmol, 200 µL) and excellent selectivity (1:100) in the molar ration mixture of ß-casein and BSA digests. Furthermore, the selective enrichment of phosphopeptides in the complex bio-samples, was successfully carried out. The results showed that 28 phosphopeptides were finally detected in mouse brain, and 2087 phosphorylated peptides were identified in the HeLa cells extracts with specific selectivity of 95.6%. The enrichment performance of mNi@N-GrT@PDA@Ti4+ was satisfactory, suggesting that the functional composite provided a potential application in the enrichment of trace phosphorylated peptides from the complex biological matrix.

Preparation, characterization and application of a new 25,27-bis-[2-(5-methylthiadiazole)thioethoxyl]-26,28-dihydroxy-para-tert-butyl calix[4]arene stationary phase for HPLC.

A new para-tert-butylcalix[4]arene column containing thiadiazole functional groups was prepared and used for the separation of polycyclic aromatic hydrocarbons, phenolic compounds, aromatic amines, benzoic acid and its derivatives by high-performance liquid chromatography (HPLC). The effect of organic modifier content in the mobile phase on retention and selectivity of these compounds were investigated. The results indicate that the stationary phase behaves like reversed-phase packing. However, hydrogen bonding, π-π and inclusion interactions seem to be involved in the separation process. The column has been successfully employed for the analysis of clenbuterol in pork and pig casing; the limit of detection and the limit of quantitation for this method by HPLC-UV detection was 0.03 and 0.097 µg/mL, respectively; the method is demonstrated to be suitable and a competitive alternative analytical method for the determination of clenbuterol.

Crystal morphology tuning and green post-synthetic modification of metal organic framework for HPLC enantioseparation.

Chiral metal-organic frameworks (CMOFs) served as chiral stationary phases (CSPs) show great potential in enantioseparation field. However, their performance improvement are still hindered by the difficult column packed and high back pressure due to the irregular morphology and broad size scope of CMOF particles. Here, the size and morphology of achiral Co-MOF-74 were effectively adjusted by controlling the synthetic route, temperature, the ratio of reactants and the amount of 2-methylimidazole (2-MI) at first. As a result, the uniformly spherical crystals in size of about 5 µm with good dispersion were obtained. Subsequently, a simple, green post-synthetic modification strategy was proposed for the fabrication of l-tyrosine functionalized Co-MOF-74, namely Co-MOF-74-L-Tyr in H2O by incorporating l-tyrosine into the parent framework of Co-MOF-74 to construct chiral microenvironment. The homochiral Co-MOF-74-L-Tyr CSP gave superior enantioseparation performance for the eight chiral drugs and drug intermediates, such as nitrendipine, nimodipine, benzoin, 2,2'-furoin and bi-2-naphthol to the commercial columns under normal phase condition. The good repeatability and stability of this CSP was verified by the replicate enantioseparation for nimodipine and flavanone. Furthermore, the Co-MOF-74-L-Tyr packed column was successfully applied to detect the product N-1-(1-naphthyl)ethyltosylamide (HR-8) in the asymmetric reductive amination reaction. The size/morphology-controlled synthesis coupled with the green post-synthetic modification approach paves the way to fabricate target chiral MOFs with pre-designed functional groups, which is an effective complement for the preparation of CSPs in chiral chromatography.

A novel methodology and strategy to detect low molecular aldehydes in beer based on charged microdroplet driving online derivatization and high resolution mass spectrometry.

The concentration of aldehydes is one of the important indicators in the food quality and safety. To efficiently analyze the four aldehydes (methanal, ethanal, propanal and n-butanal) in beer, charged microdroplet driving online derivatization apparatus coupled with high resolution mass spectrometry was firstly developed. Utilizing the high-speed reaction accelerated by microdroplets, the offline derivative of aldehydes with 2,4-dinitrophenylhydrazine in bulk was transferred into online derivatization. The developed method featured acceptable linearities (R2 ≥ 0.95), high sensitivities (LODs at ng mL-1 level) and qualified precisions (RSDs ≤ 8.4 %) for target compounds. Four aldehydes with trace amount were successfully determined in beer. The results indicated that the novel online analytical strategy did not require complex sample preparation and could conduct simple, rapid, sensitive detection of small molecule aldehydes with high throughput in beer or even other food samples.

Decorated traditional cellulose with nanoscale chiral metal-organic frameworks for enhanced enantioselective capture.

Herein, a rapid approach toward the size/morphology-controlled synthesis of [Cu(L-mal)(bipy)·2H2O] (CuLBH) was developed by adjusting the concentrations of 2-methylimidazole (2-MI) and copper ions. The chiral separation efficiency test indicated that the nano-diameter CuLBH exhibited better selective potential towards (±)-1-(1-naphthyl)ethanol (NE) by providing more fully exposed recognition sites. In order to further improve the selectivity for NE enantiomers and avoid the aggregation of MOF nanoparticles, the nanosized CuLBH-decorated carboxylated cellulose (CC) composite CC-CuLBH was designed by controlling the ratio of the solvent and Cu2+, which exhibited much higher enantioselectivity than those of pristine CC and even nano CuLBH.

Targeting Enrichment and Correlation Studies of Glutathione and Homocysteine in IgAVN Patient Urine Based on a Core-Shell Zr-Based Metal-Organic Framework.

Aminothiols are closely related to chronic kidney disease, but little is known regarding levels of related aminothiols in the urine of immunoglobulin A vasculitis with nephritis (IgAVN) patients. Herein, a well-defined core-shell Zr-based metal-organic framework (Zr-MOF) composite SiO2@50Benz-Cys was constructed as a mercury ion affinity material via a solvent-assisted ligand exchange strategy for the selective extraction and enrichment of low-concentration aminothiols in IgAVN patient urine. SiO2@50Benz-Cys was competent to enrich the total glutathione (GSH) and total homocysteine (Hcy) in virtue of the excellent affinity after chelation with mercury ions. The extraction efficiencies were closely related to the pH, dithiothreitol amount, and the dose of functional Zr-MOF. Coupled with HPLC-MS/MS in optimized conditions, GSH and Hcy were determined with low detection limits of 0.5 and 1 nmol L-1, respectively. The recoveries of GSH and Hcy for the urine sample at three spiked levels were in the range of 85.3-105% and 79.5-103%, which showed good precision and accuracy. Benefiting from the matrix interference elimination in the process of extraction, the simultaneous detection of aminothiols in the urine of the healthy group and immunoglobulin A vasculitis (IgAV) and IgAVN patients was successfully carried out, suggesting that the Zr-MOF and the robust method together provided a potential application in the analysis of urinary biomolecules. The analysis of variance (ANOVA) showed that the levels of GSH and Hcy had significant differences between the patients and the control. This work is very valuable as it provides a better understanding of concentration alterations of GSH and Hcy in urine involved with IgAVN for clinical research.

Sheathed in-situ room-temperature growth covalent organic framework solid-phase microextraction fiber for detecting ultratrace polybrominated diphenyl ethers from environmental samples.

The extraction performance of solid-phase microextraction (SPME) fiber is significantly influenced by coating materials and fabricating process. It is urgently needed for fabricating robust SPME fiber with facile preparation methods. Herein, a novel polyimide (PI) @ covalent organic framework (COF) synthesized by 1,3,5-Tris (4-aminophenyl) benzene (TPB) and 2,5-dimethoxyterephthalaldehyde (DMTP) fiber, named PI@TPB-DMTP fiber, was successfully fabricated with facile method at room temperature. Firstly, a COF crystals TPB-DMTP was in situ grown on stainless steel fiber, where the COF crystals was synthesized by the Schiff-base reaction between TPB and DMTP. Subsequently, the COF coating was covered with an ultrathin layer of PI through a simple dip-coating method to improve the fiber stability. By coupled PI@TPB-DMTP SPME fiber with gas chromatography-negative chemical ion-mass spectrometry (GC-NCI-MS), a sensitive analytical method was established for the determination of ultratrace polybrominated diphenyl ethers (PBDEs) in water sample. To achieve the best efficiency and sensitivity for the analysis of PBDEs, six potential influencing factors in extraction step and desorption step were optimized. Under optimized conditions, the established method showed high enhancement factors of 1470-3555, wide linear range of 0.05-100 ng L-1, low detection limits of 0.0083-0.0190 ng L-1, good repeatability for intra-day in the range of 3.71%-7.62% and inter-day in the range of 5.12%-8.81%, good reproducibility in the range of 6.83%-9.21%. The satisfactory recovery was ranged from 79.2% to 117.3% in determining real water samples. The excellent experimental performance was mainly attributed to the large specific surface area of TPB-DMTP, as well as the high permeability of porous PI film. The results demonstrated that the COF-based fiber showed great potential for analysis of PBDEs in complex environmental samples.

Morphology-maintaining synthesis of copper hydroxy phosphate@metal-organic framework composite for extraction and determination of trace mercury in rice.

A novel copper hydroxy phosphate@MOF composite DMP-Cu decorated by 2, 5-dimercapto-1, 3, 4-thiadiazol was facilely prepared and characterized. A dispersive SPE strategy using DMP-Cu as adsorbent combined with atomic fluorescence spectroscopy was developed for the selective capture of trace total mercury in rice sample. The adsorption mechanism showed that the Hg2+ removal process was fitted with pseudo second-order kinetics and the Langmuir adsorption model. The adsorbent was easy to be regenerated and the maximum adsorption capacity for the removal of Hg2+ was 249.5 mg g-1 at the optimal pH of 4. X-ray photoelectron spectroscopy and Raman spectra verified the selective and strong interaction between Hg2+ and thiol/nitrogen-containing functional groups of DMTZ on DMP-Cu. The trace total mercury in rice samples was determined with detection limit of 0.0125 ng mL-1 and relative standard deviation below 6%. The high recoveries were obtained in range of 98.8-109% for the spiked rice samples.

Controlled fabrication of core-shell silica@chiral metal-organic framework for significant improvement chromatographic separation of enantiomers.

Chiral metal-organic frameworks (CMOFs) have been explored as potential chiral stationary phases (CSPs) for chiral high performance liquid chromatography (HPLC). However, their application is still hindered by the low column efficiency, high back pressure and the difficulty in column packing due to the irregular shapes and wide size distributions of CMOF particles. Here we report an efficient one-pot method for the immobilization of chiral MOF [Cu2((+)-Cam)2Dabco] (Cu2C2D) onto microspheric silica particles, generating a uniform core-shell microsphere with SiO2@CMOF@CMOF morphology as CSP packing material. Significantly, the shell thickness and the corresponding column efficiency could be rationally regulated by controlling the growth cycles of [Cu2((+)-Cam)2Dabco]. The structure of developed core-shell microspheres were characterized by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD), N2 adsorption experiments, infrared spectroscopy (FT-IR) and thermogravimetric analysis. Mechanism involved in the chromatographic separation is the multi-interactions including hydrophobic and hydrogen-bonding, etc. Based on these interactions, successful separation could be achieved among different types of racemic compounds such as carboxylic acid, ketones and phenols under normal phase liquid chromatography (NPLC) condition. In addition, the relative standard deviation (RSD%) value of the retention time for TNPTO was below 1.1% (n = 5), indicating the good repeatability and stability of the chiral SiO2@Cu2C2D-2 column for HPLC enantioseparation. The results reveal that the CMOF coating approach is convenient to fabricate CSP with pre-designed functions of good recognition performance and to facilitate the evolution of CSP in chiral HPLC. Furthermore, the SiO2@Cu2C2D-2 column was successfully employed for the determination of the enantiomeric excess value for TNPTO in the asymmetric Michael addition reaction.

[Synthesis of a chiral metal-organic framework using zinc oxide as zinc source for enantioselective adsorption of 2,2'-furoin racemate].

Chiral metal-organic frameworks (CMOFs),[Zn(L-mal)(H2O)2]n were prepared by using zinc oxide instead of the traditional metal inorganic salt as the zinc source, and their chiral separation performance was investigated. Equal amounts of ZnO and L-malic acid were dissolved in H2O, and[Zn(L-mal)(H2O)2]n were obtained by allowing the mixture to stand at room temperature for 24 h. Then, 100 mg[Zn(L-mal)(H2O)2]n as the adsorbent was added to 250 µL 1 g/L 2,2'-furoin racemate, and 4.5 mL isopropanol and 1 mL methanol were selected as the extraction solvent and elution solvent, respectively, for selective adsorption experiments. The final filtrate was analyzed by high performance liquid chromatography (HPLC). The results showed that[Zn(L-mal)(H2O)2]n exhibited better selective adsorption ability for R-2,2'-furoin with 20% enantiomeric excess (ee). This work provides a new method for the green preparation of CMOF and expands its application in the field of chiral separation.

Revelation of the chiral recognition of alanine and leucine in an l-phenylalanine-based metal-organic framework.

As a proof-of-concept, an l-phenylalanine-based metal-organic framework Zn-MOF, namely [Zn2(l-Phe)2(bpe)2]n, was designed for experimentally revealing the chiral recognition mechanism of alanine and leucine by means of 13C CP MAS NMR spectroscopy, X-ray photoelectron spectroscopy and control experiments.

Novel chiral metal organic frameworks functionalized composites for facile preparation of optically pure propranolol hydrochlorides.

Two novel sorbents based on polydopamine (PDA)-coated magnetic graphite oxide-metal organic frameworks nanoparticles [Cu(L-mal)(bpy)]·H2O (MGO-CuLBH) and [Cu(D-mal)(bpy)]·H2O (MGO-CuDBH) possessing of both magnetic property and excellent enantioselective ability were prepared and characterized. Solutions of racemic propranolol hydrochloride (Rac-PRO) were chosen to investigate the enantioselective performance of MGO-CuLBH and MGO-CuDBH by dispersive magnetic nanoparticle solid phase extraction (d-MNSPE). The results showed that the nanocomposites have excellent enantioselectivity to PROs with enantiomeric excess (ee) values reaching up to 98%. The entire process with PROs by the d-MNSPE method was fast, convenient and the collected composites could be easily recycled. Multi-stage operations using MGO-CuLBH and MGO-CuDBH were scaled up to obtain milligram quantities of R-propranolol hydrochloride (R-PRO) and S-propranolol hydrochloride (S-PRO). Furthermore, on the basis of the successful preparations, the differences in the cytotoxicity of Rac-PRO, R-PRO and S-PRO on A549 cells in vitro were all evaluated.

Functionalized metal-organic framework nanocomposites for dispersive solid phase extraction and enantioselective capture of chiral drug intermediates.

The facile preparation, characterization and application of a novel magnetic graphene oxide- metal organic framework [Zn2(d-Cam)2(4, 4'-bpy)]n (MGO-ZnCB) as a sorbent for fast, simple and enantioselective capture of chiral drug intermediates are presented in this paper. The MGO-ZnCB nanocomposite, developed by encapsulating MGO nanoparticles into the homochiral metal organic framework of ZnCB, can integrate the advantages from each component endowing the hybrids with improved synergystic effects. The enantioselective performance of MGO-ZnCB was evaluated by dispersive magnetic nanoparticle solid phase extraction (d-MNSPE) of 1, 1'-bi-2-naphthol (BN) and 2, 2'-furoin (Furoin) racemic solutions. Due to the excellent dispersive capability, high stability, relatively larger saturation magnetization and distinct enrichment capacity of MGO-ZnCB, the d-MNSPE method provids good enantioselective separation of these compounds with enantiomeric excess (ee) values as high as 74.8% and 57.4%, respectively. The entire process with BN or Furoin can be completed within 3 min or less. After washing with methanol, the host MGO-ZnCB can be easily recycled and reused six times without any apparent loss of performance. Furthermore, the adsorbed BN and Furoin in nanodomains of the MGO-ZnCB composite were directly investigated for the first time by atomic force microscopy-infrared (AFM-IR) technique.

Silica gel microspheres decorated with covalent triazine-based frameworks as an improved stationary phase for high performance liquid chromatography.

A new stationary phase for high performance liquid chromatography (HPLC) applications based on silica gel microspheres decorated with covalent triazine-based frameworks (CTF-SiO2) composite has been reported here. In this new hybrid material, sheet-like covalent triazine-based frameworks (CTF) were grown onto the supporting silica spheres, in order to achieve improved chromatographic separation and selectivity. The new material was characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. The chromatographic performance and retention mechanism of the new stationary phase were investigated in reversed-phase mode and compared against standard C18 and cyano-modified silica (CN-SiO2) columns. A variety of different probe molecules were analyzed, including mono-substituted benzenes, polycyclic aromatic hydrocarbons, phenols, anilines and bases. The synergism of triazine and aromatic moieties provided several different retention mechanisms, thus improving the selectivity in the CTF-SiO2 composite. The good column packing properties of the uniform silica microspheres combined with the separation ability of the CTF frameworks make the new CTF-SiO2 material a potentially useful stationary phase for the analysis of complex samples.

Synthesis and performance of chiral ferrocene modified silica gel for mixed-mode chromatography.

A brush-type chiral stationary phase, N-ferrocenyl benzoyl-(1S, 2R)-1, 2-diphenyl ethanol-bonded on the silica gel (NFcBEs) for high performance liquid chromatography (HPLC), was prepared using γ-glycidoxypropyltrimethoxysilane as coupling reagent. The structure of this novel material was characterized by infrared spectroscopy, elemental analysis and thermogravimetric analysis. Mechanism involved in the chromatographic separation is the multi-interaction including hydrophobic, π-π, hydrogen-bonding, π-charge transfer, dipole-dipole and acid-base equilibrium interactions. Based on these interactions, successful separation could be achieved among polycyclic aromatic hydrocarbons, mono-substituted benzenes, aromatic amines, quinolines, nucleosides, phenols and 5-nitroimidazoles drugs in reversed phase liquid chromatography (RPLC). Good resolutions for substituted amine isomers were also obtained with NFcBEs. Racemates of amino acids and drug carvedilol mixtures were well separated on NFcBEs in the normal phase liquid chromatography (NPLC) mode. Such stationary phase with characteristics of multi-interaction mechanism and mixed-mode separation is potential for the analysis of complex samples. The retention behaviors of R- and S-carvedilol on NFcBEs column were investigated with the assistance of quantum chemistry calculation using the density functional theory (DFT) B3LYP method.