Molecularly imprinted polymers for the selective extraction of tiliroside from the flowers of Edgeworthia gardneri (wall.) Meisn.

Nano-sized molecularly imprinted polymers for tiliroside were successfully prepared by a precipitation polymerization method. Acrylamide, ethylene glycol dimethacrylate, azobisisobutyronitrile, and acetonitrile/dimethyl sulfoxide were used as functional monomer, cross-linker, initiator, and porogen, respectively. The structural features and morphological characterization of tiliroside-imprinted polymers were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The adsorption experiments indicated that the tiliroside-imprinted polymers exhibited high selective recognition property to tiliroside. Scatchard analysis indicated that the homogeneous-binding sites were formed in the polymers. The selectivity test revealed that the adsorption capacity and selectivity of polymers to tiliroside was significantly higher than that of rutin, astragalin, and kaempferol. Finally, the tiliroside-imprinted polymers were employed as adsorbents in solid-phase extraction for the extraction of tiliroside from the ethyl acetate extract of the flowers of Edgeworthia gardneri (wall.) Meisn. The results demonstrated that the extraction recoveries of tiliroside ranged from 69.3 to 73.5% by using tiliroside-imprinted polymers coupled with solid-phase extraction method. These results indicated that the tiliroside-based molecularly imprinted solid-phase extraction method was proven to be an effective technique for the separation and enrichment of tiliroside from natural medicines.

Molecularly imprinted polymer for the selective extraction of luteolin from Chrysanthemum morifolium Ramat.

In this work, luteolin-imprinted polymers were prepared by noncovalent precipitation polymerization for the first time. Their structural features and morphologies were analyzed by using Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The adsorption experiments revealed that the luteolin-imprinted polymers presented high selective recognition property to luteolin. The selectivity experiment showed that the adsorption capacity and selectivity of polymers to luteolin was higher than that of three structural analogs, including quercetin, isorhamnetin, and ombuin. Furthermore, an efficient method based on luteolin-imprinted polymers coupled with solid-phase extraction was developed for the pretreatment of luteolin from Chrysanthemum morifolium Ramat. The results demonstrated that the luteolin-imprinted polymers coupled with solid phase extraction method was proven to be a potentially competitive technique for the separation and enrichment of luteolin in complex samples such as Chinese patent medicines and biological samples.

MXene/ZnS/chitosan-cellulose composite with Schottky heterostructure for efficient removal of anionic dyes by synergistic effect of adsorption and photocatalytic degradation.

Nowadays, dye water pollution is becoming increasingly severe. Composite of MXene, ZnS, and chitosan-cellulose material (MX/ZnS/CC) was developed to remove anionic dyes through the synergistic effect of adsorption and photocatalytic degradation. MXene was introduced as the cocatalyst to form Schottky heterostructure with ZnS for improving the separation efficiency of photocarriers and photocatalytic performance. Chitosan-cellulose material mainly served as the dye adsorbent, while also could improve material stability and assist in generation of free radicals for dye degradation. The physics and chemistry properties of MX/ZnS/CC composite were systematically inspected through various characterizations. MX/ZnS/CC composite exhibited good adsorption ability to anionic dyes with adsorption capacity up to 1.29 g/g, and excellent synergistic effects of adsorption and photodegradation with synergistic removal capacity up to 5.63 g/g. MX/ZnS/CC composite performed higher synergistic removal ability and better optical and electrical properties than pure MXene, ZnS, chitosan-cellulose material, and MXene/ZnS. After compounding, the synergistic removal percentage of dyes increased by a maximum of 309 %. MX/ZnS/CC composite mainly adsorbs anionic dyes through electrostatic interactions and catalyzes the generation of •O2-, h+, and •OH to degrade dyes, which has been successfully used to remove anionic dyes from environmental water, achieving a 100 % removal of 50 mg/L dye.

Magnetic porous cellulose surface-imprinted polymers synthetized with assistance of deep eutectic solvent for specific recognition and purification of bisphenols.

Magnetic porous cellulose molecularly imprinted polymers-based bisphenols have been developed using Fe3O4 as the magnetic material, a deep eutectic solvent as the assisted solvent, and N-isopropylacrylamide as the functional monomer. The resulting magnetic porous cellulose molecularly imprinted polymers were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, vibrating sample magnetometry, thermal gravimetric analysis, and Brunauer-Emmett-Teller analysis. Moreover, the adsorption properties of the magnetic porous cellulose molecularly imprinted polymers toward bisphenol A, bisphenol F, and bisphenol AF were investigated using static, dynamic, and selective adsorption experiments. The introduction of porous cellulose materials significantly improves the capabilities of the material. The adsorption capacity, mass transfer efficiency, and selectivity of the magnetic porous cellulose molecularly imprinted polymers toward bisphenol A were 5.9, 4.0, and 4.4 times those of traditional molecularly imprinted polymers. Moreover, the adsorption stability of the magnetic porous cellulose molecularly imprinted polymers was investigated under different temperature and pH conditions. The adsorption characteristics of the magnetic porous cellulose molecularly imprinted polymers toward the target molecules were investigated using adsorption isotherm, kinetic, and thermodynamic models. Hydrogen bonding is the main interaction formed between the magnetic porous cellulose molecularly imprinted polymers and the target molecules. Magnetic porous cellulose molecularly imprinted polymers have great application value with excellent stability and reusability. Finally, the combination of the magnetic porous cellulose molecularly imprinted polymers and high-performance liquid chromatography or ultra-performance liquid chromatography-mass spectrometry was successfully used for the purification and detection of bisphenols in milk (1.349 ng/mL bisphenol F and 3.014 ng/mL bisphenol AF), canned fruits (1129 ng/mL bisphenol A, 10.11 ng/mL bisphenol F, and 91.87 ng/mL bisphenol AF), and fish (11.91 ng/mL bisphenol AF) samples. Furthermore, the magnetic porous cellulose molecularly imprinted polymer method is more selective, sensitive, and accurate than the traditional precipitation method.

Molecularly imprinted polymers based on magnetic metal-organic frameworks for surface-assisted laser desorption/ionization time-of-flight mass spectrometry analysis and simultaneous luteolin enrichment.

UiO-66(NH2), a metal-organic framework, exhibits excellent UV absorption and energy transfer performance and can be used as a substrate for surface-assisted laser desorption/ionization (SALDI) analysis of small molecules. Molecularly imprinted polymers (MIPs) exhibit outstanding selectivity toward certain targets. The complexes of UiO-66(NH2) and MIPs can be applied as both an adsorbent and substrate for SALDI-time-of-flight mass spectrometry (SALDI-TOF MS) analysis of small molecules. Herein, magnetic UiO-66(NH2)-molecularly imprinted polymers (MUMIPs) were prepared for the selective enrichment and detection of luteolin via SALDI-TOF MS. The amino group on UiO-66(NH2) were used as functional monomer to prepare MIPs that interact with luteolin via hydrogen bonding. The surface functional monomer can effectively control the coating thickness of the MIPs to avoid embedding template molecules and enhance adsorption performance. In addition, Fe3O4 particles were introduced for rapid magnetic separation. The physicochemical properties of the MUMIPs were characterized via scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, vibrating sample magnetometry, Brunauer-Emmett-Teller analysis, and X-ray photoelectron spectroscopy. Adsorption experiments and selectivity studies indicated that MUMIPs exhibited good adsorption capacity, fast adsorption rates, and excellent luteolin selectivity. MUMIPs are efficient substrates for the SALDI analysis of luteolin and its structural analogs. In addition, the MUMIPs-SALDI-TOF MS method successfully detected luteolin in rat plasma and urine after administration of oral Chrysanthemum morifolium Ramat extracts. This method possessed high sensitivity with a limit of detection of 0.5 ng/mL. The traditional precipitation method combined with high-performance liquid chromatography-mass spectrometry was also used to analyze luteolin in biological samples. Compared with the traditional method, the novel MUMIP-SALDI-TOF MS method can more effectively detect the target compounds in complex samples. Ultimately, the MUMIP-SALDI-TOF MS method was applied to detect luteolin and its metabolites in rat liver after oral luteolin treatment. Three luteolin metabolites (apigenin, chrysoeriol, and diosmetin) were analyzed using the newly developed MUMIP-SALDI-TOF MS method.

Deep eutectic solvent assisted synthesis of carbon dots using Sophora flavescens Aiton modified with polyethyleneimine: Application in myricetin sensing and cell imaging.

Here, an efficient method for synthesizing carbon dots (CDs) using a deep eutectic solvent (DES) was developed. To investigate the influence of different DESs on the quantum yield of CDs, different hydrogen-bonding acceptors (HBAs) and hydrogen-bonding donors (HBDs) were used to synthesize the DES and prepare CDs. Using Sophora flavescens Aiton as precursor, CDs were prepared using choline chloride (ChCl)/urea based DES as reaction media and doping agent in the presence of water. The CDs showed strong blue fluorescence and were further modified with polyethyleneimine (CDs@PEI). The fluorescence intensity of CDs@PEI was selectively quenched by myricetin with a limit of detection (LOD) of 10 nM. Furthermore, CDs@PEI was used to analyze myricetin in the extracts that were fluorescent by DES with satisfactory performance of Abelmoschus manihot (Linn.) Medicus flowers, vine teas and blueberries. Finally, the bio-imaging application of CDs@PEI was tested and the results confirmed its potential application in bio-imaging.

In situ one-pot synthesis of polydopamine/octadecylamine co-deposited coating in capillary for open-tubular capillary electrochromatography.

Mussel-inspired polydopamine (PDA) based materials are attractive as stationary phase for open-tubular capillary electrochromatography (OT-CEC) due to their many fascinating properties. However, all of the existing strategies for fabricating PDA based OT-CEC columns are limited in aqueous solutions. Consequently, it is a challenge work to directly immobilize the hydrophobic functional materials onto the inner wall of PDA modified capillary. Herein, by using the organic amine-inducing co-deposition strategy, a novel preparative method was developed for in situ one-pot synthesis of PDA/octadecylamine (ODA) co-deposited coating inside capillary as OT-CEC stationary phase. The formation and morphology of the PDA/ODA co-deposited coating were characterized by field emission scanning electron microscopy, atomic force microscope, attenuated total reflectance Fourier transform infrared spectroscopy and contact angle measurements. The separation performance of the fabricated PDA/ODA modified columns was validated by the separation of alkylbenzenes and steroids, which could achieve baseline separation with high separation efficiency. Their separation was found to follow the reversed phase chromatographic retention mechanism. The co-deposited column showed good stability and long lifetime. The repeatability of the PDA/ODA co-deposited column was also evaluated, with the relative standard deviations for intra-day and inter-day runs less than 5% and column-to-column runs less than 6%.

Thermoresponsive chiral stationary phase functionalized with the copolymer of ß-cyclodextrin and N-isopropylacrylamide for high performance liquid chromatography.

A novel chiral stationary phase (CSP) was prepared through the reaction of surface-initiated atom transfer radical polymerization (ATRP) by the copolymerization of thermoresponsive N-isopropylacrylamide (NIPAM) and ß-cyclodextrin (ß-CD) on the silica beads for high performance liquid chromatography (HPLC). X-ray photoelectron spectroscopy (XPS), elemental analysis (EA), Fourier transform infrared spectrometry (FT-IR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM) were applied to characterize the surface property of modified silica. Thermoresponsive modulation for the effect on enantioselectivity were investigated with chiral reagents including 1-phenyl-1-propanol, styrene oxide, 2-phenylpropionic acid and commercial chiral drugs comprising ibuprofen and labetalol hydrochloride. The column efficiency was evaluated by chromatographic parameters including retention factor (k), selective factor (α), resolution (Rs), plate number (N) and peak tailing factor (Tf). The results showed that five chiral solutes could be separated on the prepared smart column. And the selectivity of these compounds could be modulated by regulating the column temperature. It was contributed to the thermoresponsive NIPAM assisting ß-CD to separate these chiral compounds. These results indicated that the thermoresponsive CSP would be a potential tool for separation of hydrophilic and hydrophobic chiral drugs and this paper provided a novel method for chiral separation in the future.

Preparation of an aspartame and N-isopropyl acrylamide copolymer functionalized stationary phase with multi-mode and chiral separation abilities.

A novel multi-mode and chiral separation stationary phase co-modified with copolymer composed of N-isopropyl acrylamide (NIPAM) and aspartame was synthesized by atom transfer radical polymerization (ATRP) reaction. The synthetic material was evaluated using thermogravimetric analysis (TGA), Fourier transform infrared spectrometry (FT-IR) and elemental analysis (EA). Analytes including hydrophobic, hydrophilic, alkaline and acidic compounds were separated well using the prepared stationary phase named Sil-PPAM-NIPAM. Besides, the separation of chiral compounds proved that the developed column also has the potential of chiral separation ability. In summary, the prepared column possesses excellent hydrophilic interaction, ion exchange, reversed-phase and chiral separation modes during the separation of complex and chiral compounds.

Solvothermal-assisted in situ rapid growth of octadecylamine functionalized polydopamine-based permanent coating as stationary phase for open-tubular capillary electrochromatography.

In recent years, mussel-inspired polydopamine (PDA) based materials have been widely used as stationary phases for open-tubular capillary electrochromatography (OT-CEC) because of their various excellent properties. Nevertheless, the traditional synthesis routes of functionalized PDA-based capillary columns usually are time-consuming and limited in aqueous solutions. Herein, we report a facile and rapid route to prepare octadecylamine (ODA) functionalized PDA coated OT-CEC columns in organic solvents via a novel one-step in situ solvothermal-assisted coating strategy. Through this developed solvothermal-assisted approach, the growth rate of ODA/PDA coating was significantly speeded up and their hybrid coating process on the capillary inner surface could be rapidly completed in 60 min. The successful preparation of the solvothermal-assisted ODA/PDA hybrid coating were systematically characterized and confirmed by several methods. The influence of the preparation parameters on the formation of hybrid coating and the separation ability of the ODA/PDA modified columns were systematically explored. Consequently, the high-efficiency baseline separation of four kinds of neutral, acidic and basic analytes were achieved based on the ODA/PDA modified columns. The repeatability of the solvothermal-assisted ODA/PDA coated column was also studied, and the relative standard deviations for intra-day, inter-day and column-to-column were all less than 5%. Additionally, the solvothermal-assisted ODA/PDA modified column exhibited good stability and long lifetime.

Preparation of an aminophenylboronic acid and N-isopropyl acrylamide copolymer functionalized stationary phase for mixed-mode chromatography.

A novel stationary phase co-modified with N-isopropyl acrylamide (NIPAM) and 3-aminophenylboronic acid copolymer on the silica was synthesized through atom transfer radical polymerization (ATRP) reaction for performing mixed-mode and boronate affinity chromatography. The prepared functionalized silica was characterized using Fourier transform infrared spectrometry (FT-IR), elemental analysis (EA) and thermogravimetric analysis (TGA), scanning electron micrographs (SEM) and Brunauer-Emmett-Teller (BET) measurements. The prepared column named Sil-PBA-NIPAM showed great separation performance for hydrophobic, hydrophilic, positional isomer, acidic and alkaline compounds. Besides, the mixture of cis-diol and non-cis-diol compounds was used to prove that the developed column also has potential to capture and enrich cis-diol compounds. The prepared column possesses merits of time-saving, high selectivity to cis-diol compounds and molecular-planarity selectivity compared with two commercial single-mode columns. The theoretical plates of material can reach to 57472 and the column has good hydrolysis stability and batch-to-batch reproducibility. In summary, the prepared column possesses good hydrophilicity, hydrophobicity, molecular-planarity selectivity and boronate affinity abilities for the analysis of various compounds.

Preparation of restricted access molecularly imprinted polymers based fiber for selective solid-phase microextraction of hesperetin and its metabolites in vivo.

A novel restricted access molecularly imprinted polymers (RAMIPs) fiber was developed for solid-phase microextraction (SPME) of hesperetin and its metabolites in livers of live rats in vivo. Hesperetin as the template, N-isopropylacrylamide as the functional monomer, ethylene glycol dimethyl acrylate as the crosslinker, 2,2-azobisisobutyonnitrile as initiator and bovine serum albumin as the restricted access material were applied in the preparation process. Scanning electron microscopy and Fourier transform infrared spectroscopy were applied to characterize the polymers. The adsorption experiments indicated that RAMIPs-SPME fibers performed high selective recognition property to hesperetin. The selectivity experiment indicated that the adsorption capacity and selectivity of RAMIPs-SPME fibers to hesperetin was higher than that of quercetin, luteolin and baicalein. Macromolecules elimination test showed RAMIPs-SPME fibers could eliminate 94.80%-98.96% of macromolecules, which indicated that RAMIPs-SPME fibers can be used to extract analytes directly from complex biological samples. Furthermore, RAMIPs-SPME sampling combined to ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was applied to capture and identify hesperetin and its metabolites in rat livers in vivo. Finally, hesperetin-7-O-glucuronide, hesperetin-3'-O-glucuronide, eriodictyol and homoeriodictyol were identified as the metabolites of hesperetin. In comparison with the MIPs fibers, commercial PDMS and DVB fibers, RAMIPs-SPME fibers possessed better exclusion effect to macromolecules and higher selectivity to hesperetin and its metabolites. The results demonstrated that the prepared RAMIPs-SPME fiber were proven to be effective tool for the selective adsorption and enrichment of hesperetin and its metabolites from the complex biological fluids.

Magnetic molecularly imprinted polymer for the selective extraction of hesperetin from the dried pericarp of Citrus reticulata Blanco.

In present study, novel magnetic molecularly imprinted polymers for hesperetin were successfully prepared by surface molecular imprinting method using functionalized Fe3O4 particles as the magnetic cores. Hesperetin as the template, N-Isopropylacrylamide as the functional monomer, ethylene glycol dimethyl acrylate as the crosslinker, 2,2-azobisisobutyonnitrile as initiator and acetonitrile-methanol (3:1, v/v) as the porogen were applied in the preparation process. Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscope, x-ray diffraction and vibrating sample magnetometry were applied to characterize the magnetic molecularly imprinted polymers. The adsorption experiments indicated that the magnetic molecularly imprinted polymers performed high selective recognition property to hesperetin. The selectivity experiment indicated that the adsorption capacity and selectivity of polymers to hesperetin was higher than that of luteolin, baicalein and ombuin. Furthermore, the magnetic molecularly imprinted polymers were employed as adsorbents for extraction and enrichment of hesperetin from the dried pericarp of Citrus reticulata Blanco. The recoveries of hesperetin in the dried pericarp of Citrus reticulata Blanco ranged from 90.5% to 96.9%. The linear range of 0.15-110.72 µg/mL was obtained with correlation coefficient of greater than 0.9991. The limit of detection and quantification of the proposed method was 0.06 µg/mL and 0.15 µg/mL, respectively. Based on three replicate measurements, intra-day RSD was 0.71% and inter-day RSD was 2.31%. These results demonstrated that the prepared magnetic molecularly imprinted polymers were proven to be an effective material for the selective adsorption and enrichment of hesperetin from natural medicines, fruits and et al.

Redox modulation of polydopamine surface chemistry: a facile strategy to enhance the intrinsic fluorescence of polydopamine nanoparticles for sensitive and selective detection of Fe3.

In recent years, polydopamine (PDA) nanoparticles have attracted considerable attention in different research fields because of their many fascinating physicochemical properties. However, as an analogue of naturally occurring melanin, PDA nanoparticles (PDANPs) typically exhibit weak fluorescence properties. Herein, we report a facile one-pot method for synthesizing bright blue luminescent PDANPs through the redox modulation of PDA surface chemistry. The composition and morphology of the resultant NPs were systematically characterized by transmission electron microscopy and several spectroscopy methods, which verified the successful fabrication of PDANPs. More importantly, comparative chemical analysis of dopamine polymerization revealed the significant impacts of synthesis conditions and PDA surface chemistry on the luminescence properties of PDANPs. Remarkably, in addition to their excellent water-solubility, salt-tolerance and high photostability under extreme pH conditions, the as-prepared PDANPs possess the highest quantum yield (5.1%) among all the reported intrinsic fluorescent PDANPs. Moreover, based on the coordination interaction between phenolic hydroxyl groups of PDANPs and ferric ions (Fe3+), the synthesized PDANPs were successfully utilized as a turn-off sensing platform for sensitive and selective detection of Fe3+ without using any additional targeting molecules. Upon increasing the Fe3+ concentration in the range from 0.5 to 20 µM, the fluorescence intensity of PDANPs decreased linearly. The detection limit of Fe3+ was 0.15 µM. Finally, this fluorescent sensor was successfully used to determine Fe3+ in natural water samples, showing good prospects for practical applications and may pave the way for the development of new rational methodologies for further enhancing the intrinsic fluorescence of PDA and fabricating other novel fluorescent organic nanoparticles.

Preparation and evaluation of magnetic molecularly imprinted polymers for the specific enrichment of phloridzin.

In present study, magnetic molecularly imprinted polymers (MMIPs) were successfully prepared for specific recognition and selective enrichment of phloridzin from the leaves of Malus doumeri (Bois) A. Chev and rats' plasma. The magnetic Fe3O4 were prepared by the solvothermal reaction method and followed by the modification of TEOS and functionalization with APTES. Using functionalized Fe3O4 particles as the magnetic cores, phloridzin as template, ethylene glycol dimethacrylate (EGDMA) as cross-linker and 2,2-azobisisobutyonnitrile (AIBN) as initiator, the MMIPs were prepared through APTES to associate the template on the surface of the magnetic substrate. The structural features and morphological characterizations of MMIPs were performed by FT-IR, SEM, TEM, XRD, TGA and VSM. The adsorption experiments revealed that the MMIPs presented high selective recognition property to phloridzin. The selectivity experiment indicated that the adsorption capacity and selectivity of polymers to phloridzin was higher than that of baicalin and 2,3,5,4'-ttrahydroxy stilbene-2-O-ß-D-glucoside. Furthermore, the MMIPs were employed as adsorbents for extraction and enrichment of phloridzin from the leaves of M. doumeri and rats' plasma. The recoveries of phloridzin in the leaves of M. doumeri ranged from 81.45% to 90.27%. The maximum concentration (Cmax) of phloridzin in rats' plasma was detected as 12.19 ± 0.84µg/mL at about 15min after oral administration of phloridzin (200mg/kg). These results demonstrate that the prepared MMIPs are suitable for the selective adsorption of phloridzin from complex samples such as natural medical plants and biological samples.