Molecular imprinting technology (MIT), often described as a method of making a molecular lock to match a molecular key, is a technique for the creation of molecularly imprinted polymers (MIPs) with tailor-made binding sites complementary to the template molecules in shape, size and functional groups. Owing to their unique features of structure predictability, recognition specificity and application universality, MIPs have found a wide range of applications in various fields. Herein, we propose to comprehensively review the recent advances in molecular imprinting including versatile perspectives and applications, concerning novel preparation technologies and strategies of MIT, and highlight the applications of MIPs. The fundamentals of MIPs involving essential elements, preparation procedures and characterization methods are briefly outlined. Smart MIT for MIPs is especially highlighted including ingenious MIT (surface imprinting, nanoimprinting, etc.), special strategies of MIT (dummy imprinting, segment imprinting, etc.) and stimuli-responsive MIT (single/dual/multi-responsive technology). By virtue of smart MIT, new formatted MIPs gain popularity for versatile applications, including sample pretreatment/chromatographic separation (solid phase extraction, monolithic column chromatography, etc.) and chemical/biological sensing (electrochemical sensing, fluorescence sensing, etc.). Finally, we propose the remaining challenges and future perspectives to accelerate the development of MIT, and to utilize it for further developing versatile MIPs with a wide range of applications (650 references).

http://ir.yic.ac.cn/bitstream/133337/17045/1/Molecular%20imprinting%20perspectives%20and%20applications.pdf

Molecular imprinting: perspectives and applications

Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables.

Mycotoxins are toxic secondary metabolites produced by certain filamentous fungi (molds). These low molecular weight compounds (usually less than 1000 Daltons) are naturally occurring and practically unavoidable. They can enter our food chain either directly from plant-based food components contaminated with mycotoxins or by indirect contamination from the growth of toxigenic fungi on food. Mycotoxins can accumulate in maturing corn, cereals, soybeans, sorghum, peanuts, and other food and feed crops in the field and in grain during transportation. Consumption of mycotoxin-contaminated food or feed can cause acute or chronic toxicity in human and animals. In addition to concerns over adverse effects from direct consumption of mycotoxin-contaminated foods and feeds, there is also public health concern over the potential ingestion of animal-derived food products, such as meat, milk, or eggs, containing residues or metabolites of mycotoxins. Members of three fungal genera, Aspergillus, Fusarium, and Penicillium, are the major mycotoxin producers. While over 300 mycotoxins have been identified, six (aflatoxins, trichothecenes, zearalenone, fumonisins, ochratoxins, and patulin) are regularly found in food, posing unpredictable and ongoing food safety problems worldwide. This review summarizes the toxicity of the six mycotoxins, foods commonly contaminated by one or more of them, and the current methods for detection and analysis of these mycotoxins.

Occurrence, Toxicity, and Analysis of Major Mycotoxins in Food

Populations of honey bees and other pollinators have declined worldwide in recent years. A variety of stressors have been implicated as potential causes, including agricultural pesticides. Neonicotinoid insecticides, which are widely used and highly toxic to honey bees, have been found in previous analyses of honey bee pollen and comb material. However, the routes of exposure have remained largely undefined. We used LC/MS-MS to analyze samples of honey bees, pollen stored in the hive and several potential exposure routes associated with plantings of neonicotinoid treated maize. Our results demonstrate that bees are exposed to these compounds and several other agricultural pesticides in several ways throughout the foraging period. During spring, extremely high levels of clothianidin and thiamethoxam were found in planter exhaust material produced during the planting of treated maize seed. We also found neonicotinoids in the soil of each field we sampled, including unplanted fields. Plants visited by foraging bees (dandelions) growing near these fields were found to contain neonicotinoids as well. This indicates deposition of neonicotinoids on the flowers, uptake by the root system, or both. Dead bees collected near hive entrances during the spring sampling period were found to contain clothianidin as well, although whether exposure was oral (consuming pollen) or by contact (soil/planter dust) is unclear. We also detected the insecticide clothianidin in pollen collected by bees and stored in the hive. When maize plants in our field reached anthesis, maize pollen from treated seed was found to contain clothianidin and other pesticides; and honey bees in our study readily collected maize pollen. These findings clarify some of the mechanisms by which honey bees may be exposed to agricultural pesticides throughout the growing season. These results have implications for a wide range of large-scale annual cropping systems that utilize neonicotinoid seed treatments.

https://www.panna.org/sites/default/files/Krupke_journal.pone_.0029268.pdf

Multiple routes of pesticide exposure for honey bees living near agricultural fields.

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 80 pesticides belonging to various chemical classes from various types of representative commodities with low lipid contents A mixture of 38 pesticides amenable to gas chromatography (GC) were quantitatively recovered from spiked lemon, raisins, wheat flour and cucumber, and determined using gas chromatography–tandem mass spectrometry (GC–MS/MS) An additional mixture of 42 pesticides were recovered from oranges, red wine, red grapes, raisins and wheat flour, using liquid chromatography–tandem mass spectrometry (LC–MS/MS) for determination The pesticides chosen for this study included many of the most frequently detected ones and/or those that are most often found to violate the maximum residue limit (MRL) in food samples, some compounds that have only recently been introduced, as well as a few other miscellaneous compounds The method employed involved initial extraction in a water/acetonitrile system, an extraction/partitioning step after the addition of salt, and a cleanup step utilizing dispersive solid-phase extraction (D-SPE); this combination ensured that it was a rapid, simple and cost-effective procedure The spiking levels for the recovery experiments were 0005, 001, 002 and 02 mg kg−1 for GC–MS/MS analyses, and 001 and 01 mg kg−1 for LC–MS/MS analyses Adequate pesticide quantification and identity confirmation were attained, even at the lowest concentration levels, considering the high signal-to-noise ratios, the very good accuracies and precisions, as well as the good matches between the observed ion ratios Mean recoveries mostly ranged between 70 and 110% (98% on average), and relative standard deviations (RSD) were generally below 10% (43% on average) The use of analyte protectants during GC analysis was demonstrated to provide a good alternative to the use of matrix-matched standards to minimize matrix-effect-related errors Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity/pesticide combinations

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection.

A simple, fast, and inexpensive method for the determination of pesticide residues in fruits and vegetables is introduced. The procedure involves initial single-phase extraction of 10 g sample with 10 mL acetonitrile, followed by liquid-liquid partitioning formed by addition of 4 g anhydrous MgSO4 plus 1 g NaCl. Removal of residual water and cleanup are performed simultaneously by using a rapid procedure called dispersive solid-phase extraction (dispersive-SPE), in which 150 mg anhydrous MgSO4 and 25 mg primary secondary amine (PSA) sorbent are simply mixed with 1 mL acetonitrile extract. The dispersive-SPE with PSA effectively removes many polar matrix components, such as organic acids, certain polar pigments, and sugars, to some extent from the food extracts. Gas chromatography/mass spectrometry (GC/MS) is then used for quantitative and confirmatory analysis of GC-amenable pesticides. Recoveries between 85 and 101% (mostly > 95%) and repeatabilities typically < 5% have been achieved for a wide range of fortified pesticides, including very polar and basic compounds such as methamidophos, acephate, omethoate, imazalil, and thiabendazole. Using this method, a single chemist can prepare a batch of 6 previously chopped samples in < 30 min with approximately 1 dollar (U.S.) of materials per sample.

Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and "Dispersive Solid-Phase Extraction" for the Determination of Pesticide Residues in Produce

http://www.superchrom.it/images/file/analprot_orig.pdf

Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides.

Analyte protectants were previously defined as compounds that strongly interact with active sites in the gas chromatographic (GC) system, thus decreasing degradation, adsorption, or both of coinjected analytes. In this study, we evaluated various combinations of promising analyte protectants for the volatility range of GC-amenable pesticides using GC/quadrupole mass spectrometry (MS) and 1-microL hot splitless injection for sample introduction. A mixture of ethylglycerol, gulonolactone, and sorbitol (at 10, 1, and 1 mg/mL, respectively, in the injected samples) was found to be the most effective in minimizing losses of susceptible analytes and significantly improving their peak shapes (due to reduction of peak tailing). When added to final sample extracts and matrix-free calibration standards alike, these analyte protectants induced a similar response enhancement in both instances, resulting in effective equalization of the matrix-induced response enhancement effect even after a large number of fruit and vegetable extract injections. As compared to matrix-matched standardization, the analyte protectant approach offers a more convenient solution to the problems associated with calibration in routine GC/MS analysis of pesticide residues and possibly other susceptible analyte types in diverse samples. Moreover, the use of analyte protectants also substantially reduced another adverse matrix-related effect caused by gradual build-up of nonvolatile matrix components in the GC system, thus improving ruggedness and, consequently, reducing need for frequent maintenance.

Michelangelo Anastassiades

Papers

Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/Partitioning and "Dispersive Solid-Phase Extraction" for the Determination of Pesticide Residues in Produce

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection.

Evaluation of analyte protectants to improve gas chromatographic analysis of pesticides.

Combination of analyte protectants to overcome matrix effects in routine GC analysis of pesticide residues in food matrixes.

Recent Developments in QuEChERS Methodology for Pesticide Multiresidue Analysis