Fabrication of UMCM-1 based monolithic and hollow fiber - Metal-organic framework deep eutectic solvents/molecularly imprinted polymers and their use in solid phase microextraction of phthalate esters in yogurt, water and edible oil by GC-FID.

In this study, for the first time, hollow fiber and monolithic fiber were fabricated based on metal-organic framework deep eutectic solvents/molecularly imprinted polymers (MOF- DES/MIPs) and were used for microextraction of phthalate esters under termed hollow fiber liquid membrane-protected solid-phase microextraction (HFLMP-SPME) followed by gas chromatography- flame ionization detection. Several parameters influencing extraction recoveries of phthalate esters including adsorption and desorption parameters were investigated and optimized using fabricated MOF- DES/MIPs monolithic fiber. Under optimal conditions, detection limits (S/N = 3) of the method were in a range of 0.008-0.03 µg L-1 and limits of quantification (S/N = 10) were between 0.028 and 0.12 µg L-1. RSD (%) for intra-day and inter-day precisions were between 2.4-4.7% and 2.6-3.4%, respectively. Subsequently, this procedure was successfully applied with satisfactory results in the determination of phthalate esters in yogurt, water, and soybean oil samples. The R (%) ranged from 95.5 to 100.0% in different samples.

Fully automated method based on on-line molecularly imprinted polymer solid-phase extraction for determination of lovastatin in dietary supplements containing red yeast rice.

A fully automated method for the determination of lovastatin in dietary supplements containing red yeast rice has been developed. It uses a sequential injection analysis system combined with solid-phase extraction applying highly selective molecularly imprinted polymer sorbent. A miniaturized column for on-line extraction was prepared by packing 4.5 mg of the sorbent in a 5.0 × 2.5-mm-i.d. cartridge, which was used in the flow manifold. Sequential injection analysis manifold enabled all steps of lovastatin extraction and continuous spectrophotometric detection at 240 nm. A limit of detection of 60 µg g-1, a limit of quantitation of 200 µg g-1, and a linear calibration range of 200-2000 µg g-1 were achieved. Intra-day and inter-day precision values (RSD) were ≤ 6.7% and ≤ 4.9%, respectively, and method recovery values of spiked red yeast rice extracts at 200, 1000, and 2000 µg g-1 concentration levels were 82.9, 95.2, and 87.7%. Our method was used for determination of lovastatin lactone in four dietary supplements containing red yeast rice as a natural source of lovastatin, also known as monacolin K. The extracted samples were subsequently analyzed by the reference UHPLC-MS/MS method. Statistical comparison of results (F test, t test, α = 0.05) obtained by both methods did not reveal significant difference. A substantial advantage of the new automated approach is high sample throughput thanks to the analysis time of 7.5 min, miniaturization via down-scaling the extraction column, and smaller sample and solvent consumption, as well as reduced generation of waste. Graphical abstract ᅟ.

Molecularly imprinted solid phase extraction in a syringe filter for determination of triazine herbicides in Radix Paeoniae Alba by ultra-fast liquid chromatography.

A novel, cost-effective and simple solid phase extraction (SPE) method, by using a syringe connected with a nylon membrane filter as the adsorbent container, was developed for the extraction of triazine herbicides from Radix Paeoniae Alba (RPA) samples. The selective molecularly imprinted polymers (MIPs) synthesized with the template of atrazine were employed as the adsorbents for the enrichment and purification of analytes. The extraction parameters, including the volume and type of loading solvent, the type of washing solvent and eluting solvent, were investigated. Under the optimized conditions, the final extracts were analyzed by ultra-fast liquid chromatography (UFLC). Recoveries of the developed method range from 92.4% to 107.3% with intra- and inter-day relative standard deviations (RSDs) lower than 8.2%. The calibration curve is linear in the concentration range of 0.005-2.4 µg g(-1) for desmetryn, atrazine and terbumeton, and 0.005-1.5 µg g(-1) for dimethametryn and dipropetryn, with the correlation coefficient (R(2)) higher than 0.9995. The limits of detection (LODs) of five triazine herbicides are in the range of 0.09-0.39 ng g(-1), which are lower than the maximum residue levels (MRLs) established by various official organizations. Analytical results of three real Radix Paeoniae Alba samples indicate that the proposed method is cost-effective and easy-to-use than other routine pretreatment methods.

Nanomoulding of functional materials, a versatile complementary pattern replication method to nanoimprinting.

We describe a nanomoulding technique which allows low-cost nanoscale patterning of functional materials, materials stacks and full devices. Nanomoulding combined with layer transfer enables the replication of arbitrary surface patterns from a master structure onto the functional material. Nanomoulding can be performed on any nanoimprinting setup and can be applied to a wide range of materials and deposition processes. In particular we demonstrate the fabrication of patterned transparent zinc oxide electrodes for light trapping applications in solar cells.

Development of sample preparation method for auxin analysis in plants by vacuum microwave-assisted extraction combined with molecularly imprinted clean-up procedure.

A novel sample preparation method for auxin analysis in plant samples was developed by vacuum microwave-assisted extraction (VMAE) followed by molecularly imprinted clean-up procedure. The method was based on two steps. In the first one, conventional solvent extraction was replaced by VMAE for extraction of auxins from plant tissues. This step provided efficient extraction of 3-indole acetic acid (IAA) from plant with dramatically decreased extraction time, furthermore prevented auxins from degradation by creating a reduced oxygen environment under vacuum condition. In the second step, the raw extract of VMAE was further subjected to a clean-up procedure by magnetic molecularly imprinted polymer (MIP) beads. Owing to the high molecular recognition ability of the magnetic MIP beads for IAA and 3-indole-butyric acid (IBA), the two target auxins in plants can be selectively enriched and the interfering substance can be eliminated by dealing with a magnetic separation procedure. Both the VMAE and the molecularly imprinted clean-up conditions were investigated. The proposed sample preparation method was coupled with high-performance liquid chromatogram and fluorescence detection for determination of IAA and IBA in peas and rice. The detection limits obtained for IAA and IBA were 0.47 and 1.6 ng/mL and the relative standard deviation were 2.3% and 2.1%, respectively. The IAA contents in pea seeds, pea embryo, pea roots and rice seeds were determined. The recoveries were ranged from 70.0% to 85.6%. The proposed method was also applied to investigate the developmental profiles of IAA concentration in pea seeds and rice seeds during seed germination.

Pollen-imprinted polyurethanes for QCM allergen sensors.

Molecularly imprinted polymers for detecting plant pollen were designed as artificial recognition materials for quartz crystal microbalances in the gaseous phase. Imprints of birch (diameter, 25 mum) and nettle (diameter, 15 mum) pollen can be generated by polydimethylsiloxane stamping technique as proven by atomic force microscopy. If pollen grains are able to access the cavities and thus are incorporated, the resulting sensors display Sauerbrey-like negative frequency shifts. Non-Sauerbrey behaviour can be observed as soon as pollen is prevented from entering the selective hollows: this results in grain mobility on the electrode surface leading to frequency increases. Access to the cavities is determined by the diameter ratio between pollen grains and imprints as can be revealed during cross-selectivity measurements of nettle and birch pollen imprinted layers. When the amount of pollen grains on the electrode surface exceeds the number of available imprints, the excess particles move freely, resulting in positive, non-Sauerbrey frequency shifts.

Ultratrace analysis of uracil and 5-fluorouracil by molecularly imprinted polymer brushes grafted to silylated solid-phase microextraction fiber in combination with complementary molecularly imprinted polymer-based sensor.

Main inborn errors of metabolism diagnosable through uracil (Ura) analysis and the therapeutic monitoring of toxic 5-fluorouracil (5FU) in dihydro pyrimidine dehydrogenase (DPD) deficient patients require a sensitive, reproducible, selective and accurate method. In this work, an artificial receptor in the format of molecularly imprinted polymer (MIP) brush 'grafted to' the surface of sol-gel immobilized on cost-effective homemade solid-phase microextraction (SPME) fibers, individually imprinted with either of Ura and 5FU, was used in combination with a voltammetric sensor duly modified with the same MIP. This combination provided up to 10- and 8.4-fold preconcentrations of Ura and 5FU, respectively, which was more than sufficient for achieving stringent detection limits in the primitive diagnosis of uracil disorders and fluoropyrimidine toxicity in DPD-deficient patients. The proposed method permits the assessment of Ura and 5FU plasma concentrations with detection limits pf 0.0245 and 0.0484 ng mL(-1) (RSD = 1.0-2.5%, S/N = 3), respectively, without any problems of non-specific false-positives and cross-reactivities in complicated matrices of biological samples.