Molecular Imprinting-Based SERS Detection Strategy for the Large-Size Protein Quantitation and Curbing Non-Specific Recognition.

Molecular imprinting-based surface-enhanced Raman scattering (MI-SERS) sensors have shown remarkable potential from an academic standpoint. However, their practical applications, especially in the detection of large-size protein (≥10 nm), face challenges due to the lack of versatile sensing strategies and nonspecific fouling of matrix species. Herein, we propose a Raman reporter inspector mechanism (RRIM) implemented on a protein-imprinted polydopamine (PDA) layer coated on the SERS active substrate. In the RRIM, after large-size protein recognition, the permeability of the PDA imprinted cavities undergoes changes that are scrutinized by Raman reporter molecules. Target proteins can specifically bind and fully occupy the imprinted cavities, whereas matrix species cannot. Then, Raman reporter molecules with suitable size are introduced to serve as both inspectors of the recognition status and inducers of the SERS signal, which can only penetrate through the vacant and nonspecifically filled cavities. Consequently, changes in the SERS signal exclusively originate from the specific binding of target proteins, while the nonspecific recognition of matrix species is curbed. The RRIM enables reproducible quantitation of the large-size cyanobacteria-specific protein model (≥10 nm), phycocyanin, at the level down to 2.6 × 10-3 µg L-1. Finally, the practical applicability of the RRIM is confirmed by accurately analyzing crude urban waterway samples over 21 min without any pretreatment.

Molecular imprinting-based indirect fluorescence detection strategy implemented on paper chip for non-fluorescent microcystin.

Fluorescence analysis is a fast and sensitive method, and has great potential application in trace detection of environmental toxins. However, many important environmental toxins are non-fluorescent substances, and it is still a challenge to construct a fluorescence detection method for non-fluorescent substances. Here, by means of charge transfer effect and smart molecular imprinting technology, we report a sensitive indirect fluorescent sensing mechanism (IFSM) and microcystin (MC-RR) is selected as a model target. A molecular imprinted thin film is immobilized on the surface of zinc ferrite nanoparticles (ZnFe2O4 NPs) by using arginine, a dummy fragment of MC-RR. By implementation of IFSM on the paper-based microfluidic chip, a versatile platform for the quantitative assay of MC-RR is developed at trace level (the limit of detection of 0.43 µg/L and time of 20 min) in real water samples without any pretreatment. Importantly, the proposed IFSM can be easily modified and extended for the wide variety of species which lack direct interaction with the fluorescent substrate. This work offers the potential possibility to meet the requirements for the on-site analysis and may explore potential applications of molecularly imprinted fluorescent sensors.

Assessing the greenification potential of cyclodextrin-based molecularly imprinted polymers for pesticides detection.

Cyclodextrins, with their unparalleled attributes of eco-friendliness, natural abundance, versatile utility, and facile functionalization, make a paramount contribution to the field of molecular imprinting. Leveraging the unique properties of cyclodextrins in molecularly imprinted polymers synthesis has revolutionized the performance of molecularly imprinted polymers, resulting in enhanced adsorption selectivity, capacity, and rapid extraction of pesticides, while also circumventing conventional limitations. As the concern for food quality and safety continues to grow, the need for standard analytical methods to detect pesticides in food and environmental samples has become paramount. Cyclodextrins, being non-toxic and biodegradable, present an attractive option for greener reagents in imprinting polymers that can also ensure environmental safety post-application. This review provides a comprehensive summary of the significance of cyclodextrins in molecular imprinting for pesticide detection in food and environmental samples. The recent advancements in the synthesis and application of molecularly imprinted polymers using cyclodextrins have been critically analyzed. Furthermore, the current limitations have been meticulously examined, and potential opportunities for greenification with cyclodextrin applications in this field have been discussed. By harnessing the advantages of cyclodextrins in molecular imprinting, it is possible to develop highly selective and efficient methods for detecting pesticides in food and environmental samples while also addressing the challenges of sustainability and environmental impact.

Nitrogen-doped metal-organic framework derived porous carbon/polymer membrane for the simultaneous extraction of four benzotriazole ultraviolet stabilizers in environmental water.

Benzotriazole ultraviolet stabilizers (BUVSs) that are added to pharmaceutical and personal care products (PPCPs) have raised global concerns because of their high toxicity. An efficient method to monitor its pollution level is urgently imperative. Here, a nitrogen-doped metal-organic framework (MOF) derived porous carbon (UiO-66-NH2/DC) was prepared and integrated into polyvinylidene fluoride mixed matrix membrane (PVDF MMM) as an adsorbent for the first time. The hydrophobic UiO-66-NH2/DC with a pore size of 162 Å exhibited outstanding extraction performance for BUVSs, which solves the problem of difficult enrichment of large-size and hydrophobic targets. Notably, the density functional theory simulation was employed to reveal the structure of the derived carbon material and explored the recognition and enrichment mechanism (synergy of π-π conjugation, hydrogen bond, coordination, hydrophobic interaction and mesoporous channel) of BUVSs by UiO-66-NH2/DC-PVDF MMM. And then, an influential method based on dispersive membrane extraction (DME) coupled with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for the simultaneous analysis of four BUVSs in environmental water samples. The validated method benefited from the high sensitivity (the limits of detection within 0.25-1.40 ng/L), accuracy (recoveries of 71.9-102.8% for wastewater) and rapidity (50 min to enrich 9 samples). This study expands the application prospects of porous carbon derived from MOF for sample pretreatment of pollutants in water.

Chiral molecular imprinting-based SERS detection strategy for absolute enantiomeric discrimination.

Chiral discrimination is critical in environmental and life sciences. However, an ideal chiral discrimination strategy has not yet been developed because of the inevitable nonspecific binding entity of wrong enantiomers or insufficient intrinsic optical activities of chiral molecules. Here, we propose an "inspector" recognition mechanism (IRM), which is implemented on a chiral imprinted polydopamine (PDA) layer coated on surface-enhanced Raman scattering (SERS) tag layer. The IRM works based on the permeability change of the imprinted PDA after the chiral recognition and scrutiny of the permeability by an inspector molecule. Good enantiomer can specifically recognize and fully fill the chiral imprinted cavities, whereas the wrong cannot. Then a linear shape aminothiol molecule, as an inspector of the recognition status is introduced, which can only percolate through the vacant and nonspecifically occupied cavities, inducing the SERS signal to decrease. Accordingly, chirality information exclusively stems from good enantiomer specific binding, while nonspecific recognition of wrong enantiomer is curbed. The IRM benefits from sensitivity and versatility, enabling absolute discrimination of a wide variety of chiral molecules regardless of size, functional groups, polarities, optical activities, Raman scattering, and the number of chiral centers.

Greenificated Molecularly Imprinted Materials for Advanced Applications.

Molecular imprinting technology (MIT) produces artificial binding sites with precise complementarity to substrates and thereby is capable of exquisite molecular recognition. Over five decades of evolution, it is predicted that the resulting host imprinted materials will overtake natural receptors for research and application purposes, but in practice, this has not yet been realized due to the unsustainability of their life cycles (i.e., precursors, creation, use, recycling, and end-of-life). To address this issue, greenificated molecularly imprinted polymers (GMIPs) are a new class of plastic antibodies that have approached sustainability by following one or more of the greenification principles, while also demonstrating more far-reaching applications compared to their natural counterparts. In this review, the most recent developments in the delicate design and advanced application of GMIPs in six fast-growing and emerging fields are surveyed, namely biomedicine/therapy, catalysis, energy harvesting/storage, nanoparticle detection, gas sensing/adsorption, and environmental remediation. In addition, their distinct features are highlighted, and the optimal means to utilize these features for attaining incredibly far-reaching applications are discussed. Importantly, the obscure technical challenges of the greenificated MIT are revealed, and conceivable solutions are offered. Lastly, several perspectives on future research directions are proposed.

Determination of anionic perfluorinated compounds in water samples using cationic fluorinated metal organic framework membrane coupled with UHPLC-MS/MS.

Global concerns stem from the environmental crisis have compelled researchers to develop selective and sensitive methods for the identification and measurement of emerging pollutants in the environmental matrices. The cationic F-TMU-66+Cl-/polyvinylidene fluoride metal-organic frameworks (MOFs) mixed matrix membrane (F-TMU-66+Cl-/PVDF MMM) was synthesized and used as a versatile adsorbent with multiple binding sites for the simultaneous extraction of twelve anionic perfluorinated compounds (PFCs) from reservoir water samples. The physical and chemical characteristics of the materials, as well as adsorption mechanism were fully surveyed by various instrumental techniques. Important extraction parameters, including amount of MOFs, pH, desorption conditions, and salinity were systematically investigated and optimized. The combination of dispersive membrane solid extraction based on F-TMU-66+Cl-/PVDF MMM with ultra-high performance liquid chromatography-tandem mass spectrometry provided ultra-low limit of detections within the range of 0.03-0.48 ng/L. By virtue of the simplicity and robustness of the extraction procedure, high sensitivity of detection scheme, good stability and selectivity of the F-TMU-66+Cl-/PVDF MMM, the developed method exhibits excellent practicability for ultra-trace analysis of anionic PFCs in water samples.

Molecular Imprinting: Green Perspectives and Strategies.

Advances in revolutionary technologies pose new challenges for human life; in response to them, global responsibility is pushing modern technologies toward greener pathways. Molecular imprinting technology (MIT) is a multidisciplinary mimic technology simulating the specific binding principle of enzymes to substrates or antigens to antibodies; along with its rapid progress and wide applications, MIT faces the challenge of complying with green sustainable development requirements. With the identification of environmental risks associated with unsustainable MIT, a new aspect of MIT, termed green MIT, has emerged and developed. However, so far, no clear definition has been provided to appraise green MIT. Herein, the implementation process of green chemistry in MIT is demonstrated and a mnemonic device in the form of an acronym, GREENIFICATION, is proposed to present the green MIT principles. The entire greenificated imprinting process is surveyed, including element choice, polymerization implementation, energy input, imprinting strategies, waste treatment, and recovery, as well as the impacts of these processes on operator health and the environment. Moreover, assistance of upgraded instrumentation in deploying greener goals is considered. Finally, future perspectives are presented to provide a more complete picture of the greenificated MIT road map and to pave the way for further development.

Label-free SERS detection of Raman-Inactive protein biomarkers by Raman reporter indicator: Toward ultrasensitivity and universality.

It is still challenging to sensitively detect protein biomarkers via surface-enhanced Raman scattering (SERS) technique owing to their low Raman activity. SERS tag-based immunoassay is usually applied; however, it is laborious and needs specific antibodies. Herein, an ultrasensitive and universal "Raman indicator" sensing strategy is proposed for protein biomarkers, with the aid of a glass capillary-based molecularly imprinted SERS sensor. The sensor consists of an inner SERS substrate layer for signal enhancement and an outer mussel-inspired polydopamine imprinted layer as a recognition element. Imprinted cavities have two missions: first, selectively capturing the target protein, and second, the only passageway of Raman indicator to access SERS substrate. Specific protein recognition means filling imprinted cavities and blocking Raman indicator flow. Thus, the quantity of captured protein can be reflected by the signal decrease of ultra-Raman active indicator molecule. The capillary sensor exhibited specific and reproducible detection at the level down to 4.1 × 10-3 µg L-1, for trypsin enzyme in as-received biological samples without sample preparation. The generality of the mechanism is confirmed by using three different protein models. This platform provides a facile, fast and general route for sensitive SERS detection of Raman inactive biomacromolecules, which offers great promising utility for in situ and fast point-of-care practical bioassay.

Hydrophilic molecularly imprinted nanospheres for the extraction of rhodamine B followed by HPLC analysis: A green approach and hazardous waste elimination.

In this work, hydrophilic molecularly imprinted nanospheres (MINs) were synthesized via surface imprinting technology and subsequently utilized as dispersant sorbent in matrix solid phase dispersion (MSPD) for the extraction of rhodamine B (RhB) as the illogical food additive dye from different foodstuffs, followed by HPLC analysis. By considering hydrophilicity of target analyte, the sol-gel route was chosen for the preparation of MINs in aqueous media at mild conditions. Most importantly, both synthesis and extraction steps were designed and performed in the line of green chemistry and hazardous waste was eliminated to minimize detrimental impact on the operator health and the environment. The reputable experimental design methodology was adopted to assist the condition optimization of MSPD, which comprehends the significance of the factors and their interactions with the least experimental runs. Under optimized MINs-MSPD-HPLC conditions, the detection limit of RhB was down to 0.14 µg kg-1 and excellent linearity over the wide range of 0.5-10000 µg kg-1 was attained. Furthermore, endogenous RhB was found in the tested food samples with relative standard deviations (RSDs) of ≤4.6%, and satisfactory recoveries were from 83.6 to 96.9%. The simple green MINs-MSPD method holds great potential for determination of trace RhB in complicated solid/semi-solid samples, showing rapidity, accuracy and reliability.

Cationic metal-organic framework based mixed-matrix membrane for extraction of phenoxy carboxylic acid (PCA) herbicides from water samples followed by UHPLC-MS/MS determination.

A novel kind of cationic metal-organic framework(MOF) based mixed-matrix membrane(MMM) namely cationic MOF-MMM was firstly designed and used for simultaneous dispersive membrane extraction(DME) of six phenoxy carboxylic acid(PCA) herbicides from water samples followed by determination using ultrahigh-performance liquid chromatography tandem mass spectrometry. The cationic MOF-MMM was synthesized by soaking the zirconium-based MOFs in a polyvinylidene fluoride(PVDF) solution and further functionalization with quaternary amine groups, viz., UiO-66-NMe3+ MMM. The well-prepared UiO-66-NMe3+ MMM was characterized by FT-IR, SEM, XRD, XPS, NMR and etc. Several main variables influencing the MMM based DME efficiency were investigated and optimized in detail, such as dosage ratio of MOF/PVDF, solution pH, extraction time, coexistent anions and ionic strength. Electrostatic interactions dominated adsorption mechanism between anionic PCAs and cationic UiO-66-NMe3+ MMM, along with ππ conjugation and cation-π bonding, leading to better adsorption performance. Low limits of detection in the range of 0.03-0.59 ng/L and satisfactory recoveries within 80.06-117.40 % for all the PCAs are a reliable witness to demonstrate supreme sensitivity and the applicability of the developed method. By relying on the obtained results, the present work implied cationic MOF-MMM based DME can be a versatile and worthy utility for extraction of pollutants from different water samples with high throughput.

Preparation of hollow porous molecularly imprinted and aluminum(III) doped silica nanospheres for extraction of the drugs valsartan and losartan prior to their quantitation by HPLC.

Water compatible hollow porous molecularly imprinted nanospheres (HP-MINs) have been prepared for specific recognition and extraction of the blood pressure regulating drugs valsartan (VAL) and losartan (LOS). All synthetic steps were performed in aqueous medium and without consumption of organic solvents. The morphology and functionality of the materials were characterized by FT-IR, FE-SEM, and TEM techniques. The adsorption and selectivity experiments demonstrate that the HP-MINs possess a high binding capacity, fast kinetics, excellent water dispersibility and remarkable selectivity for VAL and LOS. The HP-MINs were utilized for dispersive solid phase extraction of VAL and LOS prior to their determination by HPLC-UV. Main variables and their interactions on extraction yield were optimized by multivariate analysis with least amount of experiments. Under optimized conditions, the method has a linear response in the 5-2000 µg L-1 concentration range of both VAL and LOS. The limits of detection are 1.5 µg L-1 for VAL and 1.4 µg L-1 for LOS. Graphical abstract Schematic representation of dispersive solid phase extraction (d-SPE) of valsartan (VAL) and losartan (LOS) from urine sample by hollow porous molecularly imprinted nanospheres (HP-MINs).

Column packing elimination in matrix solid phase dispersion by using water compatible magnetic molecularly imprinted polymer for recognition of melamine from milk samples.

This paper reports a new variant of sample clean-up procedure based on miniaturized matrix solid phase dispersion (MSPD) combining with water compatible magnetic molecularly imprinted polymers (MMIP) for preconcentration of melamine from milk samples prior high-performance liquid chromatography with UV detection. By employing MMIP as dispersant sorbent matrix interferences could be eliminated completely and the column packing step was interestingly omitted that decreasing in glassware expenditure, labor effort and extraction time which cause improvement of the method performance. In order to investigate the functionality, morphology and magnetic properties of the prepared MMIP, it was fully characterized by FT-IR, VSM, SEM, and TEM. Multivariate optimization was applied as a versatile statistical approach for evaluating the influence of the main variables and their interactions on extraction efficiency. Under optimized conditions, the proposed method exhibited a wide linear response in the concentration range of 250.0-5000.0 µg L-1, satisfactory recoveries for all samples (86.6% ≤), and supreme repeatability (RSD less than 6.3%) were achieved as well. The low limit of detection close to 67.0 µg L-1 implied high ability of proposed method for isolation of melamine from complicate milk sample. These befitting results demonstrated that the developed method is unique in terms of the facility, rapidly and least solvent consumption as well as accurate analysis of melamine at trace levels.

Dummy molecularly imprinted polymers based on a green synthesis strategy for magnetic solid-phase extraction of acrylamide in food samples.

In this work, novel dummy molecularly imprinted polymers (DMIP) with propanamide as a dummy template molecule were prepared based on a green synthesis strategy of less consumption of hazardous/organic reagents and at mild conditions for magnetic solid-phase extraction (MSPE) of acrylamide in biscuit samples, followed by high performance liquid chromatography (HPLC) determination. The resultant DMIP was well characterized by FT-IR, SEM, TEM and VSM, exhibiting uniform nanoscale coreshell structure and good magnetic property in favor of simple rapid separation. Several main variables influencing MSPE efficiency were investigated, including DMIP dosage, sample solution pH, extraction time and desorption solvent; central composite design (CCD) and response surface methodology (RSM) were employed to assist in the MSPE condition optimization with rapidity and reliability. Under optimized conditions, excellent linearity for acrylamide was obtained in the range of 5.0-5000.0 µg kg-1, and low detection and quantification limits were 1.3 µg kg-1 and 4.4 µg kg-1, respectively. The method recoveries at five spiked concentrations were found within 86.0-98.3% with relative standard deviations (RSDs) of 1.2-4.1%. Furthermore, endogenous acrylamide was detected in five different biscuit samples and the RSDs values were lower than 3.3%. The present study suggested promising perspectives of water-compatible eco-friendly DMIP based MSPE-HPLC method for highly effective sample pretreatment and targeted analytes determination in complicated matrices.

Ultrasonically synthesis of Mn- and Cu- @ ZnS-NPs-AC based ultrasound assisted extraction procedure and validation of a spectrophotometric method for a rapid preconcentration of Allura Red AC (E129) in food and water samples.

This study is devoted on Allura Red as food colorant preconcentration and determination in beverage, fruit juice and drink water samples is based on usage of Mn- and Cu- @ ZnS-NPs-AC as new sorbent for ultrasound-assisted-dispersive solid-phase microextraction (UA-DSPME) combined with ultraviolet-visible spectrophotometric based method (UV-Vis). Contribution of volume of eluent, pH, sorbent mass and sonication time on response following conduction of 28 experiments were optimized and investigated while their significantly justified according to p-value. Values of "Prob > F" less than 0.0500 is proportional with their significant influence on recovery of analyte. Under the optimum conditions 0.14 mL of THF; pH of 2.5; 8 mg of sorbent and 3 min sonication time guide and help achievement of limit of quantification (LOQ) and limit of detection (LOD) of 6.08 and 20.26 ng mL-1, respectively. The accuracy of method was validated according to calculation of recovery following spiking 400 and 600 ng mL-1 to blank solution and recovery as more reliable indication of accuracy 93.41 and 102.17% recoveries with RSD < 3.5%, which demonstrate the successful applicability of present method for real sample analysis. The maximum sorbent capacity was 50.0 mg g-1 based on Langmuir isotherm as best model with high correlation coefficient. Combination of UA-DSPME and UV-Vis lead to higher sensitivity and lower cost for accurate and repeatable monitoring of Allura Red level in beverage, fruit juice and drink water samples with acceptable recovery and reasonable RSD%.

Fabrication of water-compatible superparamagnetic molecularly imprinted biopolymer for clean separation of baclofen from bio-fluid samples: A mild and green approach.

A superparamagnetic molecularly imprinted biopolymer (SMIBP) was utilized as an eco-friendly and worth welting bio-sorbent and subsequently was applied for selective dispersive solid phase extraction (d-SPE) and selective separation of baclofen from urine samples. This effective solid phase was biopolymer network with imprinted cavities grafted on the surface of Fe3O4 cores possessing an influential SiO2 layer. The present sorbent easily achieved via co-precipitation and sol-gel processes followed by impressive bio-polymerization route under green and mild reaction conditions. The prepared SMIBP was subsequently characterized by different techniques including SEM, VSM, FT-IR, XRD, TEM and TGA verifying high suitability of the proposed solid phase for trapping and accumulation of target compound. Under optimized conditions recommended by experimental design, understudy SMIBP-d-SPE procedure supplied linear response over 1.0-2500.0µgL-1 with a satisfactory detection limit close to 0.26µgL-1, while repeatability assign to intra-day and inter-day precision as coefficients of variation was lower than 3.9% in both case. These appropriate validation imply high ability of proposed microextraction procedure for clean and effective enrichment of target analyte in complex human urine sample cause consequently leading to accurate analyses at ultra-trace levels.

Hydrophilic Multitemplate Molecularly Imprinted Biopolymers Based on a Green Synthesis Strategy for Determination of B-Family Vitamins.

A novel green synthesis strategy was proposed for preparation of multitemplate molecularly imprinted biopolymers (mt-MIBP) in aqueous media with less consumption of organic solvents, which were subsequently used as sorbents of ultrasound-assisted dispersive solid-phase extraction (d-SPE) for simultaneous recognition and efficient separation of B-family vitamins in juice samples, followed by high performance liquid chromatography (HPLC) determination. The obtained mt-MIBP was fully characterized by SEM, FT-IR, TEM, and BET. It offered high binding capacity, good selectivity, and fast dynamics toward all the templates. Involved parameters in the d-SPE efficiency such as mt-MIBP mass, sonication time, and eluting/washing solvents' types and volumes were concurrently investigated by central composite design with rapidity and reliability. Under the optimum conditions, the developed mt-MIBP-d-SPE-HPLC method exhibited wide linear range, low limits of detection and quantification (LOQs) within 1.2-5.5 µg L-1 and 4.0-18.4 µg L-1, respectively, and appropriate repeatability (relative standard deviation values below 4.2%, n = 4). The high selectivity of this method makes it suitable for successful monitoring of vitamins in juice samples with satisfactory recoveries of 75.8-92.7%, 81.1-92.5%, and 84.7-93.8% for vitamins riboflavin (B2), nicotinamide (B3), and pyridoxine (B6), respectively. The present study implied highly promising perspectives of water-compatible eco-friendly mt-MIBP for highly effective multiresidue analysis in complicated matrixes.

A facile and selective approach for enrichment of l-cysteine in human plasma sample based on zinc organic polymer: Optimization by response surface methodology.

In this research, a facile and selective method was described to extract l-cysteine (l-Cys), an essential α-amino acid for anti-ageing playing an important role in human health, from human blood plasma sample. The importance of this research was the mild and time-consuming synthesis of zinc organic polymer (Zn-MOP) as an adsorbent and evaluation of its ability for efficient enrichment of l-Cys by ultrasound-assisted dispersive micro solid-phase extraction (UA-DMSPE) method. The structure of Zn-MOP was investigated by FT-IR, XRD and SEM. Analysis of variance (ANOVA) was applied for the experimental data to reach the best optimum conditions. The quantification of l-Cys was carried out by high performance liquid chromatography with UV detection set at λ=230nm. The calibration graph showed reasonable linear responses towards l-Cys concentrations in the range of 4.0-1000µg/L (r2=0.999) with low limit of detection (0.76µg/L, S/N=3) and RSD≤2.18 (n=3). The results revealed the applicability and high performance of this novel strategy in detecting trace l-Cys by Zn-MOP in complicated matrices.

MOF-5(Zn)-Fe2O4 nanocomposite based magnetic solid-phase microextraction followed by HPLC-UV for efficient enrichment of colchicine in root of colchicium extracts and plasma samples.

In present work, facile method is developed for determination of colchicine in human plasma sample, autumn and spring root of colchicium extracts by ultrasound assisted dispersive magnetic solid phase microextraction followed by HPLC-UV method (UAD-MSPME-HPLC-UV). Magnetic (Fe2O4-nanoparticles) metal organic framework-5, (MOF-5(Zn)-Fe2O4NPs) was synthesized by dispersing MOF-5 and Fe(NO3)3.9H2O in ethylene glycol (as capping agent) and NaOH (pH adjustment agent) by hydrothermal method. The prepared sorbent was characterized via XRD and SEM analysis and applied as magnetic solid phase in UAD-MSPME-HPLC-UV method. In this method, colchicine molecules were sorbed on MOF-5(Zn)-Fe2O4NPs sorbent by various mechanisms like ion exchange, hydrogen bonding and electrostatic, á´¨-á´¨, hard-hard and dipole-ion interaction followed by exposing sonication waves as incremental mass transfer agent and then the sorbent was separated from the sample matrix by an external magnetic fields. Subsequently, accumulated colchicine were eluted by small volume of desorption organic solvent. Influence of operational variables such as MOF-5(Zn)-Fe2O4NPs mass, volume of extracting solvent and sonication time on response property (recovery) were studied and optimized by central composite design (CCD) combined with desirability function (DF) approach. Under optimum condition, the method has wide linear calibration rang (0.5-1700ngmL-1) with reasonable detection limit (0.13ngmL-1) and R2=0.9971. Finally, the UAD-MSPME-HPLC-UV method was successfully applied for determination of colchicine autumn and spring root of colchicium extracts and plasma samples.

Hollow porous molecularly imprinted polymer for highly selective clean-up followed by influential preconcentration of ultra-trace glibenclamide from bio-fluid.

In the present work, hollow porous molecularly imprinted polymer (HPMIP) was prepared via adopting a sacrificial support approach using glibenclamide (GB) as template, methacrylic acid (MAA) as functional monomer, ethylene glycol dimethacrylate as cross-linker (EGDMA) and mesoporous MCM-48 nanospheres as support. Owing to a short thickness of the foresaid HPMIP, a suitable steric structure was readily available that lead to fast and effective mass transfer of target analyte to sorbent and consequently supply high binding capacity. After ultrasonic-assisted dispersive solid phase extraction of urine sample, the analyte of interest was quantitatively pre-concentrated and determined by high performance liquid chromatography-ultraviolet detection (HPLC-UV). Influence of factors affecting the extraction efficiency such as sonication time, sample pH, sorbent dosage, and volumes of eluent and washing agents as well as their significant interactions were simultaneously optimized by experimental design methodology. Under optimized conditions, present method has linear response over concentration range of 10.0-3000.0µgL-1 in human urine samples with a satisfactory detection limit close to 3.5µgL-1. The inter-day precisions of the current method (coefficient of variation) are lower than 5%, while recoveries are more than 89.5%.