Agronomic Investigation of Spray Dispersion of Metal-Based Nanoparticles on Sunflowers in Real-World Environments.

In environmental and agronomic settings, even minor imbalances can trigger a range of unpredicted responses. Despite the widespread use of metal-based nanoparticles (NPs) and new bio-nanofertilizers, their impact on crop production is absent in the literature. Therefore, our research is focused on the agronomic effect of spray application of gold nanoparticles anchored to SiO2 mesoporous silica (AuSi-NPs), zinc oxide nanoparticles (ZnO-NPs), and iron oxide nanoparticles (Fe3O4-NPs) on sunflowers under real-world environments. Our findings revealed that the biosynthetically prepared AuSi-NPs and ZnO-NPs were highly effective in enhancing sunflower seasonal physiology, e.g., the value of the NDVI index increased from 0.012 to 0.025 after AuSi-NPs application. The distribution of leaf trichomes improved and the grain yield increased from 2.47 t ha-1 to 3.29 t ha-1 after ZnO-NPs application. AuSi-NPs treatment resulted in a higher content of essential linoleic acid (54.37%) when compared to the NPs-free control (51.57%), which had a higher determined oleic acid. No NPs or residual translocated metals were detected in the fully ripe sunflower seeds, except for slightly higher silica content after the AuSi-NPs treatment. Additionally, AuSi-NPs and NPs-free control showed wide insect biodiversity while ZnO-NPs treatment had the lowest value of phosphorus as anti-nutrient. Contradictory but insignificant effect on physiology, yield, and insect biodiversity was observed in Fe3O4-NPs treatment. Therefore, further studies are needed to fully understand the long-term environmental and agricultural sustainability of NPs applications.

Profiling and imaging of forensic evidence - A pan-European forensic round robin study part 1: Document forgery.

The forensic scenario, on which the round robin study was based, simulated a suspected intentional manipulation of a real estate rental agreement consisting of a total of three pages. The aims of this study were to (i) establish the amount and reliability of information extractable from a single type of evidence and to (ii) provide suggestions on the most suitable combination of compatible techniques for a multi-modal imaging approach to forgery detection. To address these aims, seventeen laboratories from sixteen countries were invited to answer the following tasks questions: (i) which printing technique was used? (ii) were the three pages printed with the same printer? (iii) were the three pages made from the same paper? (iv) were the three pages originally stapled? (v) were the headings and signatures written with the same ink? and (vi) were headings and signatures of the same age on all pages? The methods used were classified into the following categories: Optical spectroscopy, including multispectral imaging, smartphone mapping, UV-luminescence and LIBS; Infrared spectroscopy, including Raman and FTIR (micro-)spectroscopy; X-ray spectroscopy, including SEM-EDX, PIXE and XPS; Mass spectrometry, including ICPMS, SIMS, MALDI and LDIMS; Electrostatic imaging, as well as non-imaging methods, such as non-multimodal visual inspection, (micro-)spectroscopy, physical testing and thin layer chromatography. The performance of the techniques was evaluated as the proportion of discriminated sample pairs to all possible sample pairs. For the undiscriminated sample pairs, a distinction was made between undecidability and false positive claims. It was found that none of the methods used were able to solve all tasks completely and/or correctly and that certain methods were a priori judged unsuitable by the laboratories for some tasks. Correct results were generally achieved for the discrimination of printer toners, whereas incorrect results in the discrimination of inks. For the discrimination of paper, solid state analytical methods proved to be superior to mass spectrometric methods. None of the participating laboratories deemed addressing ink age feasible. It was concluded that correct forensic statements can only be achieved by the complementary application of different methods and that the classical approach of round robin studies to send standardised subsamples to the participants is not feasible for a true multimodal approach if the techniques are not available at one location.

Discovering the potential of an nZVI-biochar composite as a material for the nanobioremediation of chlorinated solvents in groundwater: Degradation efficiency and effect on resident microorganisms.

Abiotic and biotic remediation of chlorinated ethenes (CEs) in groundwater from a real contaminated site was studied using biochar-based composites containing nanoscale zero-valent iron (nZVI/BC) and natural resident microbes/specific CE degraders supported by a whey addition. The material represented by the biochar matrix decorated by isolated iron nanoparticles or their aggregates, along with the added whey, was capable of a stepwise dechlorination of CEs. The tested materials (nZVI/BC and BC) were able to decrease the original TCE concentration by 99% in 30 days. Nevertheless, regarding the transformation products, it was clear that biotic as well as abiotic transformation mechanisms were involved in the transformation process when nonchlorinated volatiles (i.e., methane, ethane, ethene, and acetylene) were detected after the application of nZVI/BC and nZVI/BC with whey. The whey addition caused a massive increase in bacterial biomass in the groundwater samples (monitored by 16S rRNA sequencing and qPCR) that corresponded with the transformation of trichloro- and dichloro-CEs, and this process was accompanied by the formation of less chlorinated products. Moreover, the biostimulation step also eliminated the adverse effect caused by nZVI/BC (decrease in microbial biomass after nZVI/BC addition). The nZVI/BC material or its aging products, and probably together with vinyl chloride-respiring bacteria, were able to continue the further reductive dechlorination of dichlorinated CEs into nonhalogenated volatiles. Overall, the results of the present study demonstrate the potential, feasibility, and environmental safety of this nanobioremediation approach.

Cotton Textile/Iron Oxide Nanozyme Composites with Peroxidase-like Activity: Preparation, Characterization, and Application.

At present, both native and immobilized nanoparticles are of great importance in many areas of science and technology. In this paper, we have studied magnetic iron oxide nanoparticles and their aggregates bound on woven cotton textiles employing two simple modification procedures. One modification was based on the treatment of textiles with perchloric-acid-stabilized magnetic fluid diluted with methanol followed by drying. The second procedure was based on the microwave-assisted conversion of ferrous sulfate at high pH followed by drying. The structure and functional properties of these modified textiles were analyzed in detail. Scanning electron microscopy of native and modified textiles clearly showed the presence of iron oxide nanoparticles on the surface of the modified cotton fibers. All of the modified textile materials exhibited light to dark brown color depending on the amount of the bound iron oxide particles. Magnetic measurements showed that the saturation magnetization values reflect the amount of magnetic nanoparticles present in the modified textiles. Small-angle X-ray and neutron scattering measurements were conducted for the detailed structural characterization at the nanoscale of both the native and magnetically modified textiles, and different structural organization of nanoparticles in the two kinds of textile samples were concluded. The textile-bound iron oxide particles exhibited peroxidase-like activity when the N,N-diethyl-p-phenylenediamine sulfate salt was used as a substrate; this nanozyme activity enabled rapid decolorization of crystal violet in the presence of hydrogen peroxide. The deposition of a sufficient amount of iron oxide particles on textiles enabled their simple magnetic separation from large volumes of solutions; if necessary, the magnetic response of the modified textiles can be simply increased by incorporation of a piece of magnetic iron wire. The simplicity of the immobilized nanozyme preparation and the low cost of all the precursors enable its widespread application, such as decolorization and degradation of selected organic dyes and other important pollutants. Other types of textile-bound nanozymes can be prepared and used as low-cost catalysts for a variety of applications.

Miniaturized analytical methods for determination of environmental contaminants of emerging concern - A review.

The determination of contaminants of emerging concern (CECs) in environmental samples has become a challenging and critical issue. The present work focuses on miniaturized analytical strategies reported in the literature for the determination of CECs. The first part of the review provides brief overview of CECs whose monitoring in environmental samples is of particular significance, namely personal care products, pharmaceuticals, endocrine disruptors, UV-filters, newly registered pesticides, illicit drugs, disinfection by-products, surfactants, high technology rare earth elements, and engineered nanomaterials. Besides, an overview of downsized sample preparation approaches reported in the literature for the determination of CECs in environmental samples is provided. Particularly, analytical methodologies involving microextraction approaches used for the enrichment of CECs are discussed. Both solid phase- and liquid phase-based microextraction techniques are highlighted devoting special attention to recently reported approaches. Special emphasis is placed on newly developed materials used for extraction purposes in microextraction techniques. In addition, recent contributions involving miniaturized analytical flow techniques for the determination of CECs are discussed. Besides, the strengths, weaknesses, opportunities and threats of point of need and portable devices have been identified and critically compared with chromatographic methods coupled to mass chromatography. Finally, challenging aspects regarding miniaturized analytical methods for determination of CECs are critically discussed.

Urease-immobilized magnetic microparticles in urine sample preparation for metabolomic analysis by gas chromatography-mass spectrometry.

Urea, as an end product of protein metabolism and an abundant polar compound, significantly complicates the metabolomic analysis of urine by GC-MS. We developed a sample preparation method removing urea from urine samples prior the GC-MS analysis. The method based on urease immobilized on magnetic microparticles was compared with the others that are conventionally used (liquid-liquid extraction, free urease protocol), and samples without any treatment. To study the impact of sample preparation approaches on the quality of analytical data, we employed comprehensive metabolomic analysis (using both GC-MS and LC-MS/MS platforms) of standard material based on human urine. Multivariate statistical analysis has shown that immobilized urease treatment provides similar results to a free urease approach. However, significant alterations in the profiles of metabolites were observed in the samples without any treatment and after the extraction. Compared to other approaches that were tested, the immobilization of urease on microparticles reduces both the number of artifacts and the variability of the metabolites (average CV of extraction 19.7%, no treatment 11.4%, free urease 5.0%, and immobilized urease 2.5%). The method that was developed was applied in a GC-MS metabolomic experiment of glutaric aciduria type I, where both known diagnostically important biomarkers and unknowns, as the most discriminating compounds, were found.

Semiquantitative determination of food acid dyes by magnetic textile solid phase extraction followed by image analysis.

Magnetic textile solid phase extraction, based on the use of magnetically modified non-woven textile impregnated with chitosan, was successfully employed for the preconcentration of acid food dyes from water solutions. The photos of textile squares with the adsorbed dye were taken with a mobile phone. The image analysis of the photos was performed using appropriate freeware. The values of saturation, obtained through the HSB color space, were proportional to the dye concentration in the analyzed samples. Described inexpensive, simple and elution free assay enables analysis of dyes concentration in various solutions. This novel method has a potential to be a useful alternative to existing semiquantitative determination procedures, especially for dyes analysis.

Smartphone-based image analysis for evaluation of magnetic textile solid phase extraction of colored compounds.

Novel modern easily feasible methods for direct evaluation of a new, simple preconcentration analytical procedure have been developed. Two types of smartphone image analysis applications (ON Color Measure and Color Lab) were evaluated to obtain RGB and HSV color spaces data for the quantification of Magnetic textile solid phase extraction of colored compounds (e.g. water-soluble organic dyes). Both direct measurement of color spaces values via the smartphone camera and image analysis of the photograph can be used successfully. The obtained data were similar to those obtained by previously examined professional ImageJ software. The saturation (S) values of the HSV color space are directly proportional to the concentrations of the analyzed dye.

Magnetization of active inclusion bodies: comparison with centrifugation in repetitive biotransformations.

BACKGROUND: Physiological aggregation of a recombinant enzyme into enzymatically active inclusion bodies could be an excellent strategy to obtain immobilized enzymes for industrial biotransformation processes. However, it is not convenient to recycle "gelatinous masses" of protein inclusion bodies from one reaction cycle to another, as high centrifugation forces are needed in large volumes. The magnetization of inclusion bodies is a smart solution for large-scale applications, enabling an easier separation process using a magnetic field. RESULTS: Magnetically modified inclusion bodies of UDP-glucose pyrophosphorylase were recycled 50 times, in comparison, inclusion bodies of the same enzyme were inactivated during ten reaction cycles if they were recycled by centrifugation. Inclusion bodies of sialic acid aldolase also showed good performance and operational stability after the magnetization procedure. CONCLUSIONS: It is demonstrated here that inclusion bodies can be easily magnetically modified by magnetic iron oxide particles prepared by microwave-assisted synthesis from ferrous sulphate. The magnetic particles stabilize the repetitive use of the inclusion bodies .

Magnetically Modified Agricultural and Food Waste: Preparation and Application.

The annual food and agricultural waste production reaches enormous numbers. Therefore, an increasing need to valorize produced wastes arises. Waste materials originating from the food and agricultural industry can be considered as functional materials with interesting properties and broad application potential. Moreover, using an appropriate magnetic modification, smart materials exhibiting a rapid response to an external magnetic field can be obtained. Such materials can be easily and selectively separated from desired environments. Magnetically responsive waste derivatives of biological origins have already been prepared and used as efficient biosorbents for the isolation and removal of both biologically active compounds and organic and inorganic pollutants and radionuclides, as biocompatible carriers for the immobilization of diverse types of (bio)molecules, cells, nano- and microparticles, or (bio)catalysts. Potential bactericidal, algicidal, or anti-biofilm properties of magnetic waste composites have also been tested. Furthermore, low cost and availability of waste biomaterials in larger amounts predetermine their utilization in large-scale processes.

Leptothrix sp. sheaths modified with iron oxide particles: Magnetically responsive, high aspect ratio functional material.

Smart materials of biological origin are attracting a lot of attention nowadays, especially as catalysts, carriers or adsorbents. Among them, magnetically modified biomaterials are especially important due to their response to external magnetic field. This report demonstrates that naturally occurring micrometer sized, high aspect ratio material (native and autoclaved Leptothrix sp. sheaths) efficiently bind synthetically prepared magnetite and maghemite nanoparticles and their aggregates. Magnetic modification of Leptothrix sheaths enables to prepare a promising material for advanced biotechnology and environmental technology applications. The prepared magnetically responsive sheaths were tested as inexpensive adsorbent for crystal violet removal from aqueous solutions. The observed maximum adsorption capacity was 243.1mg of dye per 1g of adsorbent.

Magnetically modified bacterial cellulose: A promising carrier for immobilization of affinity ligands, enzymes, and cells.

Bacterial cellulose (BC) produced by Komagataeibacter sucrofermentans was magnetically modified using perchloric acid stabilized magnetic fluid. Magnetic bacterial cellulose (MBC) was used as a carrier for the immobilization of affinity ligands, enzymes and cells. MBC with immobilized reactive copper phthalocyanine dye was an efficient adsorbent for crystal violet removal; the maximum adsorption capacity was 388mg/g. Kinetic and thermodynamic parameters were also determined. Model biocatalysts, namely bovine pancreas trypsin and Saccharomyces cerevisiae cells were immobilized on MBC using several strategies including adsorption with subsequent cross-linking with glutaraldehyde and covalent binding on previously activated MBC using sodium periodate or 1,4-butanediol diglycidyl ether. Immobilized yeast cells retained approximately 90% of their initial activity after 6 repeated cycles of sucrose solution hydrolysis. Trypsin covalently bound after MBC periodate activation was very stable during operational stability testing; it could be repeatedly used for ten cycles of low molecular weight substrate hydrolysis without loss of its initial activity.

Microscale magnetic microparticle-based immunopurification of cytokinins from Arabidopsis root apex.

Cytokinins (CKs) are pivotal plant hormones that have crucial roles in plant growth and development. However, their isolation and quantification are usually challenging because of their extremely low levels in plant tissues (pmol g-1 fresh weight). We have developed a simple microscale magnetic immunoaffinity-based method for selective one-step isolation of CKs from very small amounts of plant tissue (less than 0.1 mg fresh weight). The capacity of the immunosorbent and the effect of the complex plant matrix on the yield of the rapid one-step purification were tested using a wide range of CK concentrations. The total recovery range of the new microscale isolation procedure was found to be 30-80% depending on individual CKs. Immunoaffinity extraction using group-specific monoclonal CK antibodies immobilized onto magnetic microparticles was combined with a highly sensitive ultrafast mass spectrometry-based method with a detection limit close to one attomole. This combined approach allowed metabolic profiling of a wide range of naturally occurring CKs (bases, ribosides and N9 -glucosides) in 1.0-mm sections of the Arabidopsis thaliana root meristematic zone. The magnetic immunoaffinity separation method was shown to be a simple and extremely fast procedure requiring minimal amounts of plant tissue.

Magnetically modified biochar for organic xenobiotics removal.

Large amounts of biochar are produced worldwide for potential agricultural applications. However, this material can also be used as an efficient biosorbent for xenobiotics removal. In this work, biochar was magnetically modified using microwave-synthesized magnetic iron oxide particles. This new type of a magnetically responsive biocomposite material can be easily separated by means of strong permanent magnets. Magnetic biochar has been used as an inexpensive magnetic adsorbent for the removal of water-soluble dyes. Five dyes (malachite green, methyl green, Bismarck brown Y, acridine orange and Nile blue A) were used to study the adsorption process. The dyes adsorption could be usually described with the Langmuir isotherm. The maximum adsorption capacities reached the value 137 mg of dye per g of dried magnetically modified biochar for Bismarck brown Y. The adsorption processes followed the pseudo-second-order kinetic model and the thermodynamic studies indicated spontaneous and endothermic adsorption. Extremely simple magnetic modification of biochar resulted in the formation of a new, promising adsorbent suggested for selected xenobiotics removal.

Composite particles formed by complexation of poly(methacrylic acid) - stabilized magnetic fluid with chitosan: Magnetic material for bioapplications.

A simple procedure for the synthesis of magnetic fluid (ferrofluid) stabilized by poly(methacrylic acid) has been developed. This ferrofluid was used to prepare a novel type of magnetically responsive chitosan-based composite material. Both ferrofluid and magnetic chitosan composite were characterized by a combination of microscopy (optical microscopy, TEM, SEM), scattering (static and dynamic light scattering, SANS) and spectroscopy (FTIR) techniques. Magnetic chitosan was found to be a perspective material for various bioapplications, especially as a magnetic carrier for immobilization of enzymes and cells. Lipase from Candida rugosa was covalently attached after cross-linking and activation of chitosan using glutaraldehyde. Baker's yeast cells (Saccharomyces cerevisiae) were incorporated into the chitosan composite during its preparation; both biocatalysts were active after reaction with appropriate substrates.

Decrease of Pseudomonas aeruginosa biofilm formation by food waste materials.

The formation of bacterial biofilm on various surfaces has significant negative economic effects. The aim of this study was to find a simple procedure to decrease the Pseudomonas aeruginosa biofilm formation in a water environment by using different food waste biological materials as signal molecule adsorbents. The selected biomaterials did not reduce the cell growth but affected biofilm formation. Promising biomaterials were magnetically modified in order to simplify manipulation and facilitate their magnetic separation. The best biocomposite, magnetically modified spent grain, exhibited substantial adsorption of signal molecules and decreased the biofilm formation. These results suggest that selected food waste materials and their magnetically responsive derivatives could be applied to solve biofilm problems in water environment.

Magnetically modified microalgae and their applications.

The majority of algal cells can interact with a wide range of nano- and microparticles. Upon interaction the modified cells usually maintain their viability and the presence of foreign material on their surfaces or in protoplasm can provide additional functionalities. Magnetic modification and labeling of microalgal biomass ensures a wide spectrum of biotechnological, bioanalytical and environmental applications. Different aspects of microalgal cell magnetic modification are covered in the review, followed by successful applications of magnetic algae. Modified cells can be employed during their harvesting and removal, applied in toxicity microscreening devices and also as efficient adsorbents of different types of xenobiotics.

Utilization of magnetically responsive cereal by-product for organic dye removal.

BACKGROUND: Barley straw, an agricultural by-product, can also serve as a low-cost and relatively efficient adsorbent of various harmful compounds. In this case, adsorption of four water-soluble dyes belonging to different dye classes (specifically Bismarck brown Y, representing the azo group; methylene blue, quinone-imine group; safranin O, safranin group; and crystal violet, triphenylmethane group) on native and citric acid-NaOH-modified barley straw, both in magnetic and non-magnetic versions, was studied. RESULTS: The adsorption was characterized using three adsorption models, namely Langmuir, Freundlich and Sips. To compare the maximum adsorption capacities (qmax), the Langmuir model was employed. The qmax values reached 86.5-124.3 mg of dye per g of native non-magnetic straw and 410.8-520.3 mg of dye per g of magnetic chemically modified straw. Performed characterization studies suggested that the substantial increase in qmax values after chemical modification could be caused by rougher surface of adsorbent (observed by scanning electron microscopy) and by the presence of higher amounts of carboxyl groups (detected by Fourier transform infrared spectroscopy). The adsorption processes followed the pseudo-second-order kinetic model and thermodynamic studies indicated spontaneous and endothermic adsorption. CONCLUSION: The chemical modification of barley straw led to a significant increase in maximum adsorption capacities for all tested dyes, while magnetic modification substantially facilitated the manipulation with adsorbent.

Chitinase III in Euphorbia characias latex: Purification and characterization.

This paper deals with the purification of a class III endochitinase from Euphorbia characias latex. Described purification method includes an effective novel separation step using magnetic chitin particles. Application of magnetic affinity adsorbent noticeably simplifies and shortens the purification procedure. This step and the subsequently DEAE-cellulose chromatography enable to obtain the chitinase in homogeneous form. One protein band is present on PAGE in non-denaturing conditions and SDS-PAGE profile reveals a unique protein band of 36.5 ± 2 kDa. The optimal chitinase activity is observed at 50 °C, pH 5.0. E. characias latex chitinase is able to hydrolyze colloidal chitin giving, as reaction products, N-acetyl-D-glucosamine, chitobiose and chitotriose. Moreover, we observed that calcium and magnesium ions enhance chitinase activity. Finally, we cloned the cDNA encoding the E. characias latex chitinase. The partial cDNA nucleotide sequence contains 762 bp, and the deduced amino acid sequence (254 amino acids) is homologous to the sequence of several plant class III endochitinases.

Magnetically responsive yeast cells: methods of preparation and applications.

Magnetically modified yeast cells represent an interesting type of biocomposite material, applicable in various areas of bioanalysis, biotechnology and environmental technology. In this review, typical examples of magnetic modifications of yeast cells of the genera Saccharomyces, Kluyveromyces, Rhodotorula and Yarrowia are presented, as well as their possible applications as biocatalysts, active part of biosensors and biosorbents for the separation of organic xenobiotics, heavy metal ions and radionuclides.