Application of molecularly imprinted polymers in an analytical chiral separation and analysis

Over the last two decades the process of development and application of a new types of molecular imprinted polymer (MIP) sorbents in the field of analytical chemistry have been widely described in the literature. One of the new trends in analytical chemistry practice is the use of new types of MIP sorbents as specific sorption materials constituting the stationary phase in advanced separation techniques. The following review paper contains comprehensive information about the application of a specific and well defined MIP sorbents (with the data base in the paper about the reagents used in MIP preparation process) as stationary phases in separation techniques including high performance liquid chromatography and capillary electrochromatography. Coverage includes newly created types of stationary phases (MIP sorbents) used for chiral recognition, with the focus on applications in enantioselective separation

The role of atmospheric precipitation in introducing contaminants to the surface waters of the Fuglebekken catchment, Spitsbergen

Although the Svalbard Archipelago is located at a high latitude, far from potential contaminant sources, it is not free from anthropogenic impact. Towards the Fuglebekken catchment, in the southern part of Spitsbergen, north of Hornsund fjord, contaminants can be transported from mainland pollution sources. In the precipitation and surface water collected in the catchment, the following elements were detected and quantified: Ag, Al, As, B, Ba, Bi, Ca, Cd, Co, Cr, Cu, Cs, Mo, Ni, Pb, Sb, Se, Sr, Tl, U, Vand Zn. Additionally, pH, electrical conductivity and total organic carbon (TOC) were determined in those samples. The acidic reaction of precipitation waters was identified as an important factor intensifying the metal migration in this Arctic tundra environment. The air mass trajectory, surprisingly, explained the variability of only a small fraction of trace elements in precipitation water. The air mass origin area was correlated only with the concentrations of As, V and Cr. Wind directions were helpful in explaining the variability of Mn, U and Ba concentrations (east north-easterly wind) and the contents of B, As, Rb, Se, Sr and Li in precipitation (south-westerly wind), which may indicate the local geological source of those. Atmospheric deposition was found to play a key role in the transport of contaminants into the Fuglebekken catchment; however, the surface water composition was modified by its pH and TOC content

POM/EVA Blends with Future Utility in Fused Deposition Modeling

Polyoxymethylene (POM) is one of the most popular thermoplastic polymers used in the industry. Therefore, the interest in its potential applications in rapid prototyping is understandable. Nevertheless, its low dimensional stability causes the warping of 3D prints, limiting its applications. This research aimed to evaluate the effects of POM modification with ethylene-vinyl acetate (EVA) (2.5, 5.0, and 7.5 wt.%) on its processing (by melt flow index), structure (by X-ray microcomputed tomography), and properties (by static tensile tests, surface resistance, contact angle measurements, differential scanning calorimetry, and thermogravimetric analysis), as well as very rarely analyzed emissions of volatile organic compounds (VOCs) (by headspace analysis). Performed modifications decreased stiffness and strength of the material, simultaneously enhancing its ductility, which simultaneously increased the toughness even by more than 50% for 7.5 wt.% EVA loading. Such an effect was related to an improved linear flow rate resulting in a lack of defects inside the samples. The decrease of the melting temperature and the slight increase of thermal stability after the addition of EVA broadened the processing window for 3D printing. The 3D printing trials on two different printers showed that the addition of EVA copolymer increased the possibility of a successful print without defects, giving space for further development

Green Chemistry Metrics with Special Reference to Green Analytical Chemistry

The concept of green chemistry is widely recognized in chemical laboratories. To properly measure an environmental impact of chemical processes, dedicated assessment tools are required. This paper summarizes the current state of knowledge in the field of development of green chemistry and green analytical chemistry metrics. The diverse methods used for evaluation of the greenness of organic synthesis, such as eco-footprint, E-Factor, EATOS, and Eco-Scale are described. Both the well-established and recently developed green analytical chemistry metrics, including NEMI labeling and analytical Eco-scale, are presented. Additionally, this paper focuses on the possibility of the use of multivariate statistics in evaluation of environmental impact of analytical procedures. All the above metrics are compared and discussed in terms of their advantages and disadvantages. The current needs and future perspectives in green chemistry metrics are also discussed

Multivariate Assessment of Procedures for Molecularly Imprinted Polymer Synthesis for Pesticides Determination in Environmental and Agricultural Samples

In the case of quantitative and qualitative analysis of pesticides in environmental and food samples, it is required to perform a sample pre-treatment process. It allows to minimalize the impact of interferences on the final results, as well as increase the recovery rate. Nowadays, apart from routinely employed sample preparation techniques such as solid-phase extraction (SPE) or solid-phase microextraction (SPME), the application of molecularly imprinted polymers (MIPs) is gaining greater popularity. It is mainly related to their physicochemical properties, sorption capacity and selectivity, thermo-mechanical resistance, as well as a wide range of polymerization techniques allowing to obtain the desired type of sorption materials, adequate to a specific type of pesticide. This paper targets to summarize the most popular and innovative strategies since 2010, associated with the MIPs synthesis and analytical procedures for pesticides determination in environmental and food samples. Application of multi-criteria decision analysis (MCDA) allows for visualization of the most beneficial analytical procedures in case of changing the priority of each step of analysis (MIPs synthesis, sample preparation process—pesticides extraction, chromatographic analysis) bearing in mind metrological and environmental issues

Emission Profiles of Volatiles during 3D Printing with ABS, ASA, Nylon, and PETG Polymer Filaments

In this short communication we characterize the emission of volatile organic compounds (VOCs) from fused filament fabrication (FFF) 3D printing using four polymer materials, namely polyethylene terephthalate glycol-modified (PETG), acrylonitrile styrene acrylate (ASA), Nylon, and acrylonitrile butadiene styrene (ABS). Detailed emission profiles are obtained during thermal degradation of the polymers as a function of temperature and also in real-time during 3D printing. Direct quantitative measurement was performed using proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Qualitative determination of the volatiles emitted from the printed elements at various temperatures was accomplished using gas chromatography-mass spectrometry (GC-MS). The emission rates of VOCs differ significantly between the different polymer filaments, with the emission from Nylon and PETG more than an order of magnitude lower than that of ABS

Insights into the Thermo-Mechanical Treatment of Brewers’ Spent Grain as a Potential Filler for Polymer Composites

This paper investigated the impact of twin-screw extrusion parameters on the properties of brewers’ spent grain. The chemical structure, antioxidant activity, particle size, and color properties, as well as the emission of volatile organic compounds during extrusion, were investigated. The main compounds detected in the air during modifications were terpenes and terpenoids, such as α-pinene, camphene, 3-carene, limonene, or terpinene. They could be considered as a potential threat to human health and the environment. Changes in the chemical structure, antioxidant activity, and color of materials after modification indicated the Maillard reactions during extrusion, which resulted in the generation of melanoidins, especially at higher temperatures. This should be considered an exciting feature of this treatment method because modified brewers’ spent grain may improve the thermooxidative stability of polymer materials. Moreover, the impact of the brewers’ spent grain particle size on color and browning index used to determine the melanoidins content was investigated. The presented results show that proper adjustment of extrusion parameters enables the preparation of brewers’ spent grain with the desired appearance and chemical properties, which could maximize the efficiency of the modification process

Ground Tire Rubber Modified by Elastomers via Low-Temperature Extrusion Process: Physico-Mechanical Properties and Volatile Organic Emission Assessment

In this paper, low-temperature extrusion of ground tire rubber was performed as a pro-ecological waste tires recycling method. During this process, ground tire rubber was modified with constant content of dicumyl peroxide and a variable amount of elastomer (in the range: 2.5–15 phr). During the studies, three types of elastomers were used: styrene-butadiene rubber, styrene-ethylene/butylene-styrene grafted with maleic anhydride and ethylene-octene copolymer. Energy consumption measurements, curing characteristics, physico-mechanical properties and volatile organic compounds emitted from modified reclaimed GTR were determined. The VOCs emission profile was investigated using a passive sampling technique, miniature emission chambers system and static headspace analysis and subsequently quantitative or qualitative analysis by gas chromatography. The VOCs analysis showed that in the studied conditions the most emitted volatile compounds are dicumyl peroxide decomposition by-products, such as: α-methylstyrene, acetophenone, α-cumyl alcohol, methyl cumyl ether, while the detection level of benzothiazole (devulcanization “marker”) was very low. Moreover, it was found that the mechanical properties of the obtained materials significantly improved with a higher content of styrene-butadiene rubber and styrene-ethylene/butylene-styrene grafted with maleic anhydride while the opposite trend was observed for ethylene-octene copolymer content