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In the context of the global increase in pesticide applications, aquatic animals are constantly subjected to their action in natural reservoirs. Our research sought to determine the molecular and biochemical effects of an environmental exposure to commonly used chloro-s-triazine herbicide terbuthylazine and organophosphate insecticide malathion on zebrafish. To this aim, mature zebrafish were exposed to 2 and 30 µg L−1 terbuthylazine and 5 and 50 µg L−1 malathion alone and in combination for 14 days. Following exposure, induction of reactive oxygen and nitrogen species, lipid peroxidation, and protein carbonylation in the liver of treated zebrafish have been registered. Aside from the accumulation of oxidative lesions, a decrease in antioxidants and succinate dehydrogenase activity, an increase in oxidized glutathione, and enhanced apoptosis via Caspase-3 and BAX overexpression (in the case of terbuthylazine) were observed. Furthermore, terbuthylazine and malathion induced mitochondrial swelling and lactate dehydrogenase leakage in a concentrationdependent manner. Significant upregulation of ubiquitin expression and increasing cathepsin D activity were characteristics that appeared only upon terbuthylazine exposure, whereas induction of IgM was identified as the specific characteristic of malathion toxicity. Pesticides in the studied concentration didn’t provoke significant alterations in the hypothalamic-pituitary-thyroid axis in zebrafish. Co-exposure increased adverse effects of individual pesticides to zebrafish. This study should improve understanding of the mechanisms of pesticide toxicity that leads to fish impairment and biodiversity decline, as well as emphasize the importance of paying attention to pesticide traces in the environment and fish, which can have devastating effects on biota even at low concentrations.

The aim of the study is an ecotoxicological assessment of magnetite iron oxide-based nanoparticles (NPs), which have risen in popularity in the last decade, on selected terrestrial and aquatic organisms from various levels of the food chain. In the presented study various organisms, from both the terrestrial and aquatic environment, were used as targets for the assessment of NPs ecotoxicity. Plants (radish, oat), marine bacteria (A. fischeri) and crustacean (H. incongruens) were used to represent producers, decomposers, and consumers, respectively. It was found that examined NPs were harmful (to a different degree) to biota from three different trophic levels. Physicochemical characterization (size/morphology, crystallinity, composition, and magnetic properties) of the tested nanoparticles was performed by: transmission electron microscopy, X-ray diffraction, energy dispersive spectroscopy, and Mossbauer spectroscopy, respectively. Phytotoxicity was evaluated according to the OECD 208 Guideline, while acute and chronic toxicity of NPs was conducted using bioassays employing bacteria and crustacea, respectively. The phytotoxicity of all investigated iron oxide-based NPs was dependent on concentration and type of NPs formulation and was measured via biomass, seed germination, root length, shoot height, and content of plant pigments. Increasing the concentration of NPs increased phytotoxicity and mortality of aquatic organisms. Ecotoxicity of iron oxide/silver was dependent on the size and content of silver. Iron oxide NPs coated with nanosilver in a percentage ratio of 69/31 were found to be the most toxic on tested terrestrial and aquatic biota.

Antibiotic resistance is one of the greatest threats to global health and food security today. It becomes increasingly difficult to treat infectious disorders because antibiotics, even the newest ones, are becoming less and less effective. One of the ways taken in the Global Plan of Action announced at the World Health Assembly in May 2015 is to ensure the prevention and treatment of infectious diseases. In order to do so, attempts are made to develop new antimicrobial therapeutics, including biomaterials with antibacterial activity, such as polycationic polymers, polypeptides, and polymeric systems, to provide non-antibiotic therapeutic agents, such as selected biologically active nanoparticles and chemical compounds. Another key issue is preventing food from contamination by developing antibacterial packaging materials, particularly based on degradable polymers and biocomposites. This review, in a cross-sectional way, describes the most significant research activities conducted in recent years in the field of the development of polymeric materials and polymer composites with antibacterial properties. We particularly focus on natural polymers, i.e., polysaccharides and polypeptides, which present a mechanism for combating many highly pathogenic microorganisms. We also attempt to use this knowledge to obtain synthetic polymers with similar antibacterial activity.

This work presents the results of research on the preparation of bioresorbable functional polyestercarbonates containing side carboxyl groups. These copolymers were synthesized in two ways: the classic two-step process involving the copolymerization of l-lactide and a cyclic carbonate containing a blocked side carboxylate group in the form of a benzyl ester (MTC-Bz) and its subsequent deprotection, and a new way involving the one-step copolymerization of l-lactide with this same carbonate, but containing an unprotected carboxyl group (MTC-COOH). Both reactions were carried out under identical conditions in the melt, using a specially selected zinc chelate complex, with Zn[(acac)(L)H2O] (where: L—N-(pyridin-4-ylmethylene) phenylalaninate ligand) as an initiator. The differences in the kinetics of both reactions and their courses were pictured. The reactivity of the MTC-COOH monomer without a blocking group in the studied co-polymerization was much higher, even slightly higher than l-lactide, which allowed the practically complete conversion of the comonomers in a much shorter time. The basic final properties of the obtained copolymers and the microstructures of their chains were determined. The single-step synthesis of biodegradable polyacids was much simpler. Contrary to the conventional method, this made it possible to obtain copolymers containing all carbonate units with carboxyl groups, without even traces of the heavy metals used in the deprotection of the carboxyl groups, the presence of which is known to be very difficult to completely remove from the copolymers obtained in the two-step process.

This work presents the results of research on the preparation of bioresorbable functional polyestercarbonates containing side carboxyl groups. These copolymers were synthesized in two ways: the classic two-step process involving the copolymerization of l-lactide and a cyclic carbonate containing a blocked side carboxylate group in the form of a benzyl ester (MTC-Bz) and its subsequent deprotection, and a new way involving the one-step copolymerization of l-lactide with this same carbonate, but containing an unprotected carboxyl group (MTC-COOH). Both reactions were carried out under identical conditions in the melt, using a specially selected zinc chelate complex, with Zn[(acac)(L)H

Purpose The aim of the present study was to evaluate the toxicity and biodegradation potential of oil hydrocarbons contaminated soil samples obtained from different depths at an oil refinery station area. An approach involving chemical, microbiological, respirometry and ecotoxicity assessment of soil polluted by oil hydrocarbons was adopted, in order to determine the biodegradability of pollutants and ecotoxicological effects of natural attenuation strategy. Methods The ecotoxicity of soil samples was evaluated using an ostracod test kit and a seed germination test. The results of the phytotoxicity assay were expressed as a percentage of seedling emergence and as the relative yield of fresh and dry biomass compared to control plants. The intrinsic biodegradation potential of the contaminated soil was examined using a Micro-Oxymax respirometer. Intrinsic biodegradation rates were estimated from the slopes of linear regressions curves plotted for cumulative O2 uptake. The obtained values were then entered in the mass balance equation for the stoichiometric reaction of hydrocarbon decomposition and converted per kg of soil per day. Results Although the tested contaminants were biodegradable in the respirometric assay, they were slightly to moderately toxic to plants and extremely toxic to ostracods. The noxious effects raised with the increased concentration of contaminants. The monocotyledonous oat was more tolerant to higher concentrations of oil hydrocarbons than the other test plants, indicating its greater suitability for soil reclamation purposes. Conclusion By assessing phytotoxicity and effect on ostracod mortality and progress of soil self-decontamination process, proper approach of reclamation of demoted area can be provided.

Poly(methylene-co-cyanoguanidine), PMCG, is an oligomeric polycation that has found its application in the waste-water treatment as well as in preparation of polyelectrolyte complex microcapsules for biomedical purposes. Considering the nitrogen-rich composition of repeating unit, PMCG may be a valuable polycation utilized as a novel slow-release fertilizer. The aim of this study was to evaluate the potential of PMCG as a nitrogen fertilizer during its 6-month incubation in the soil. Monocotyledonous oat (Avena sativa) and dicotyledonous radish (Raphanus sativus L.) were selected as representative model plants for plant growth test. The effect of PMCG on plant growth and development was dependent on both the PMCG concentration and time of incubation. An increase in the nitrogen amount in green parts of plants demonstrated the uptake of the plant-available form of nitrogen released from PMCG incubated in the soil. This resulted in an increased percentage of fresh matter and shoot height of the tested plants during their exposure to PMCG. Ecotoxicological impact of PMCG in the soil during incubation period against bacteria Allivibrio fischeri and crustacean Heterocypris incongruens was also assessed. PMCG was found as the potential polymer fertilizer that does not require special treatment and can be used as it is for the prolonged release of nitrogen in agriculture.

Nowadays, researchers in the field of agrochemicals are trying to find effective methods to limit the excessive usage of pesticides and protect the environment. One of the most popular and promising techniques is the immobilization of pesticides using environment-friendly polymers. In the conducted research, it was demonstrated that the family of lactide/glycolide copolymers are unsuitable for this purpose due to very slow degradation in the soil. We examined influence of relatively small content of PEG blocks in newly synthesized poly( l -lactide-co-glycolide)-poly(ethylene glycol)–poly( l -lactide-co-glycolide) (PLGA–PEG–PLGA) on the degradation in soil, in activated sludge and usefulness of this terpolymers as a biodegraded carrier for the controlled release of two commonly used herbicides (Metazachlor and Pendimethalin). Presence of even small amount of PEG block in the terpolymer chain increases slightly the hydrophilicity of the polymeric chain, thereby increasing its susceptibility to hydrolytic and unexpectedly strongly to enzymatic degradation in soil environment. The amorphism of used as a carriers PLGA-PEG-PLGA terpolymers and the lack of the phenomenon of increasing the degree of crystallinity during degradation allow to achieve uniform progress of degradation, and thus is obtained a relatively constantly release of tested herbicides. In this way, it is possible to determine the optimal profile of degradation of polymer in soil and proper rate of diffusion and leaching of active agents which allows the release of herbicides in optimal and effective doses within 3–4 months of its application.

The present study aimed to develop and prepare new polymer/herbicide formulations for their potential application in environment-friendly, controlled release systems of agrochemicals. Selected biodegradable polymers, including L-Lactide/Glycolide/PEG/Terpolymer (PLAGA-PEG-PLAGA) as well as oligosaccharide-based polymers and their blend with terpolymer, were used to prepare microspheres loaded with two soil-applied herbicides. The degradation process of the obtained polymeric microspheres was evaluated based on (1) their weight loss and surface erosion and (2) the release rate of loaded metazachlor and pendimethalin. The herbicidal effectiveness of the herbicides released to the soil from microspheres was evaluated using the European Weed Research Council (EWRC) rating scale. Moreover, the ecotoxicological effect of herbicide-loaded microspheres buried in soil on the marine bacterial species A. fischeri was assessed. It was found that the gradual degradation rate of microparticles led to the prolonged release of both herbicides that lasted for a few months, i.e., for the entire crop season, which is crucial in terms of agrochemical and environmental protection. Maltodextrin- and dextrin-based microspheres showed higher susceptibility to degradation than terpolymer-based microspheres. The microencapsulation of herbicides protected them from decomposition and excessive leaching into soil and maintained their activity for a longer period than that for non-immobilized herbicides. The ecotoxicological assessment on A. fischeri demonstrated that the proposed microsphere-encapsulated herbicides were less toxic than non-immobilized herbicides.

Packaging for fresh fruits and vegetables with additional properties such as inhibition of pathogens grown can reduce food waste. With its biodegradability, poly(ε-caprolactone) (PCL) is a good candidate for packaging material, especially in the form of an electrospun membrane. The preparation of nonwoven fabric of PCL loaded with food additive, antimicrobial nisin makes them an active packaging with antispoilage properties. During the investigation of the nonwoven fabric mats, different concentrations of nisin were obtained from the solution of PCL via the electrospinning technique. The obtained active porous PCL loaded with varying concentrations of nisin inhibited the growth of Staphylococcus aureus and Escherichia coli. Packages made of PCL and PCL/nisin fibrous mats demonstrated a prolongation of the fruits’ freshness, improving their shelf life and, consequently, their safety.

Application of new biodegradable polymer packaging based on polylactide (PLA), susceptible to organic recycling, can help in the waste reduction in landfills. In this paper, the results of the study on abiotic degradation of PLA and its blend containing 15 mol% of poly[(R,S)-3-hydroxybutyrate], as a model for the first step of organic recycling were presented. The samples used for this study have different shapes and thicknesses: rigid films and cuboid-bars. Particular emphasis was placed on determining the pattern of degradation products released into the medium. Originally, the results of present study revealed that the application of electrospray ionization mass spectrometry supported by high performance liquid chromatography allowed envisaging the differences in the degradation products pattern released from the studied PLA-based samples differing in thickness. The significant differences in degradation products pattern were predominately observed in the first steps of incubation process and are caused by an autocatalytic effect, which occurs mainly during degradation of the large size PLA samples. Although, the thickness of PLA-based packaging changes the degradation product patterns, however this does not increase the total amounts of acids released to the medium. Thus, it may be concluded that thickness should not affect significantly organic recycling of the packaging.

The synthesis of a series of N-sulfonylaminophosphonates 2aA-2dC and evaluation of their cytotoxicity and ecotoxicity is described. N-sulfonylaminophsophonates 2aA-2dC were obtained by addition of dialkyl phosphites to azomethine bonds of sulfonimines 1a-d in dichloromethane, and the reaction was mediated by potassium carbonate. Sulfonimines 1a-d were synthesized by direct condensation of selected aldehydes with p-toluenesulfonamide catalyzed by titanium(IV) ethoxide. The cytotoxicity of compounds 2aB-2cB, 2aC-2cC, 2bA and 2dA against normal primary human lymphocytes, non-small cell lung cancer cells A549, promyelocytic leukemia cells HL-60 and glioblastoma astrocytoma cells U87 was found to be very low. The phytotoxicity of 2dC against monocotyledonous oat (A. sativa) and dicotyledonous radish (R. sativus) was measured and the compound was found to be practically not toxic for two model plants. Lack of toxicity for marine bacteria A. fischeri has been also detected. However, the compound 2dC was found to be significantly toxic for freshwater, European crustaceans H. incongruens (ostracods).

Multifunctional nanocarriers are gaining increasing research interest as polymeric platforms for targeted drug delivery in cancer therapy and diagnosis. In this work, preparation and characterization of surfactant-free polyester nanoparticles (NPs) from a bio-based poly(butylene sebacate-co-butylene dilinoleate)s, poly(butylene sebacate) (PBSE)/poly(butylene dilinoleate) (PBDL), using nanoprecipitation, is reported. The polymeric nanoparticles (sizes narrowly distributed in a range less than 100 nm) were loaded with curcumin (CURC) with an encapsulation efficiency of 98% and drug loading (DL) content of 5–10% wtdrug/wtpolymer. The CURC-loaded nanoparticles were efficiently coated with a novel poly(sulfobetaine)-type zwitterionic polymer synthesized by nitroxide-mediated polymerization and postpolymerization functionalization step. Free and CURC formulated into noncoated and poly(sulfobetaine)-type zwitterionic polymer-coated nanoparticles were further investigated for cytotoxicity and antioxidant ...

Six new dimethyl N-arylamino(2-pyrrolyl)methylphosphonates 2a-f were synthesized by the modified aza-Pudovik reaction. Their ecotoxicological impact using battery of bioassay was assessed using Microtox and Ostracodtoxit tests as well as phytotoxicity towards two plants, dicotyledonous radish (Raphanus sativus) and monocotyledonous oat (Avena sativa) following the OECD 208 Guideline. Ecotoxicological properties of compounds 2a-f in aspect of acute and chronic toxicity were evaluated using Heterocypris incongruens and Aliivibrio fisheri tests. The obtained results showed that tested aminophosphonates 2a-f have moderate-to-high phyto- and ecotoxicological impact. They are toxic for both plants but more toxic against dicotyledonous. The investigated compounds showed important ecotoxicity against Heterocypris incongruens crustaceans and Aliivibrio fisheri bacteria. It was found that the substituents of the phenyl ring plays a key role in the degree of toxicity. Results showed that investigated compounds are ecologically toxic and that any of their application should be implemented with care.

The presented work aimed to test influence of poly(L-lactide-co-glycolide)-block-poly (ethylene oxide) copolymer modification by blending with grafted dextrin or maltodextrin on the course of degradation in soil and the usefulness of such material as a matrix in the controlled release of herbicides. The modification should be to obtain homogenous blends with better susceptibility to enzymatic degradation. Among all tested blends, which were proposed as a carrier for potential use in the controlled release of plant protection agents, PLGA-block-PEG copolymer blended with grafted dextrin yielded very promising results for their future applications, and what is very importantly proposed formulations provide herbicides in unchanged form into soil within few months of release. The modification PLAGA/PEG copolymer by blending with modificated dextrins affects the improvement of the release profile. The weekly release rates for both selected herbicides (metazachlor and pendimethalin) were constant for a period of 12 weeks. Enzymatic degradation of modified dextrin combined with leaching of the degradation products into medium caused significant erosion of the polymer matrix, thereby leading to acceleration of water diffusion into the polymer matrix and allowing for easier leaching of herbicides outside the matrix.

In this paper, comparison of ecotoxicological and herbicidal effect of newly synthesized N‑[(phosphono)(aryl)methyl]glycines 1a-g (C-substituted glyphosate derivatives) with pure glyphosate (N-phosphonomethylglycine) (2) was demonstrated. All of tested glyphosate derivatives (1a-g) in contrast to glyphosate, were found to be completely safe for oat (Avena sativa) and classified as not harmful for marine bacteria Aliivibrio fischeri. Compounds 1a-g were also found rather harmless to radish (Raphanus sativus) as compared to N-phosphonomethylglycine, but they were moderately toxic against freshwater crustaceans Heterocypris incongruens. One of synthesized compounds, namely N-[(phosphono)(4-hydroxyphenyl)methyl]glycine (1f) was found to possess stronger herbicidal properties against gallant soldier (Galinsoga parviflora) and common sorrel (Rumex acetosa) when compared to pure glyphosate and demonstrated total death of these weeds being ranked 1 in the European Weed Research Council (EWRC) scale. Considering lower phytotoxicity of compound 1f against cultivated plants and tested microorganisms when compared to pure glyphosate, this aminophosphonate may be good candidate for further, more comprehensive study toward its agrochemical application, especially that this active agent demonstrated much stronger herbicidal properties than N-phosphonomethylglycine.

Although there are many reports on the dangers posed by glyphosate, this herbicide is still one of the most popular and widely used total weed killers. Therefore, great effort should be made to minimize exposure to this herbicide and limit its losses into the environment. The aim of this study was to prepare a new formulation consisted of various molecular weight chitosans with glyphosate and their evaluation toward active substance release, phytotoxicity, and preliminary herbicidal efficiency. The phytotoxicity study of the obtained chitosan/glyphosate formulations was determined based on the Organisation for Economic Co-operation and Development 208 guideline. Among all tested formulations evaluated for phytotoxicity, that containing the highest molecular weight of chitosan was found to be the least toxic, showing simultaneously the most effective herbicidal activity against selected weeds. The release rate of glyphosate from the obtained formulations was dependent on the molecular weight and viscosity of chitosan.

In modern society, it is impossible to imagine life without polymeric materials. However, managing the waste composed of these materials is one of the most significant environmental issues confronting us in the present day. Recycling polymeric waste is the most important action currently available to reduce environmental impacts worldwide and is one of the most dynamic areas in industry today. Utilizing this waste could not only benefit the environment but also promote sustainable development and circular economy management. In its program statement, the European Union has committed to support the use of sorted polymeric waste. This study reviews recent attempts to recycle this waste and convert it by alternative technologies into fine, nano-, and microscale fibers using electrospinning, blowing, melt, or centrifugal spinning. This review provides information regarding applying reprocessed fine fibers in various areas and a concrete approach to mitigate the threat of pollution caused by polymeric materials.

The paper presents a synthesis of poly(l-lactide) with bacteriostatic properties. This polymer was obtained by ring-opening polymerization of the lactide initiated by selected low-toxic zinc complexes, Zn[(acac)(L)H2O], where L represents N-(pyridin-4-ylmethylene) tryptophan or N-(2-pyridin-4-ylethylidene) phenylalanine. These complexes were obtained by reaction of Zn[(acac)2 H2O] and Schiff bases, the products of the condensation of amino acids and 4-pyridinecarboxaldehyde. The composition, structure, and geometry of the synthesized complexes were determined by NMR and FTIR spectroscopy, elemental analysis, and molecular modeling. Both complexes showed the geometry of a distorted trigonal bipyramid. The antibacterial and antifungal activities of both complexes were found to be much stronger than those of the primary Schiff bases. The present study showed a higher efficiency of polymerization when initiated by the obtained zinc complexes than when initiated by the zinc(II) acetylacetonate complex. The synthesized polylactide showed antibacterial properties, especially the product obtained by polymerization initiated by a zinc(II) complex with a ligand based on l-phenylalanine. The polylactide showed a particularly strong antimicrobial effect against Pseudomonas aeruginosa, Staphylococcus aureus, and Aspergillus brasiliensis. At the same time, this polymer does not exhibit fibroblast cytotoxicity.

Due to the fact that α-aminophosphonates are structurally analogous to α-amino acids, the search for new biologically active agents based on the chemistry of these compounds has stimulated growing interest. Although there is increasing attention focused on the various applications of these compounds, there is poor information about their ecotoxicological impact on the environment. In this study, ferrocene-derived aminophosphonates have been synthesized and their environmental impact on selected plants, namely Avena sativa and Raphanus sativus as well as on the bacteria Vibrio fischeri, and the crustacean Heterocypris inconguens, has been assessed and their ecotoxicological profile determined.

Poly(2-oxazoline) polymers have found extensive application in the preparation of microcapsules for biomedical purposes. However, there is a scarcity of information related to their ecotoxicological assessment. Therefore, in this study, we focused on the ecotoxicity of selected polyethylenimines (PEIs) including poly(2-ethyl-2-oxazoline) (PEtOx) as an N-acyl-substituted PEI, linear polyethylenimine (LPEI) and branched polyethylenimine (BPEI). Oat (a monocotyledon) (Avena sativa) and radish (a dicotyledon) (Raphanus sativus) were selected as the representative plants, which are recommended by the Organization for Economic Cooperation and Development (OECD) 208 as the standard to test for plant growth. Shoot and root length, fresh and dry matter, level of total nitrogen in green parts of the plants, as well as total chlorophyll and carotenoids were determined. Phytotoxicity of all the tested parameters was dependent on the concentration of the examined polymers in the soil as well as on the time of their incubation in the soil. According to our results, the amount of nitrogen in green parts of the plants was increased compared to the control plants, which revealed the uptake of the plant-available form of nitrogen released from the tested PEIs. This was especially true for the plants treated with LPEI. Ecotoxicological impact of the incubated polymers in the soil against marine bacteria Allivibrio fischeri proved that, the all tested polyethylenimines may be classified as not harmful to aquatic microorganisms.

This paper discusses the impact of two nitrofuran-derived drugs, namely furazolidone and nitrofurantoin on growth of oat and common radish as well as their impact on bacteria Allivibrio fischeri and crustaceans Heterocypris incongruens. Results indicated that both compounds were highly phytotoxic for radish (R. sativus) being simultaneously nearly not harmful for oat (A. sativa). Growing inhibition of shoots, roots, fresh matter and photosynthetic pigments is correlated with growing concentration of drugs in soil. Ecotoxicological impact of both compounds on model luminescence bacteria Aliivibrio fischeri and freshwater crustaceans Heterocypris incongruens as a representative organisms of two different level of food chain, is also reported herein, and the obtained data show significant toxicity against these two organisms. Basing on obtained results, it was concluded that both nitrofuran drugs in case of distribution through environment, by improper utilisation after use or unplanned environmental intoxication with unused drugs may cause serious environmental problems and therefore both should be handled with a reasonable care at any step of their production or utilisation.

The aim of the presented study was preparation, analysis of properties, and in vitro characterization of porous shape-memory scaffolds, designed for large bone defects treatment using minimally invasive surgery approach. Biodegradable terpolymers of l-lactide/glycolide/trimethylene carbonate (LA/GL/TMC) and l-lactide/glycolide/e-caprolactone (LA/GL/Cap) were selected for formulation of these scaffolds. Basic parameters of shape memory behavior (i.e. recovery ratio, recovery time) and changes in morphology (SEM, average porosity) and properties (surface topography, water contact angle, compressive strength) during shape memory cycle were characterized. The scaffolds preserved good mechanical properties (compressive strength about 0.7 to 0.9 MPa) and high porosity (more than 80%) both in initial shape as well as after return from compressed shape. Then the scaffolds in temporary shape were inserted into the model defect of bone tissue at 37°C. After 12 min the defect was filled completely as a result of shape recovery process induced by body temperature. The scaffold obtained from LA/GL/TMC terpolymer was found the most prospective for the planned application thanks to its appropriate recovery time, high recovery ratio (more than 90%), and cytocompatibility in contact with human osteoblasts and chondrocytes.

Since aminophosphonate-based herbicides like glyphosate are currently one of the most popular and widely applied active agent in agrochemistry, there is an urgent need for searching new compounds among this family with potential herbicidal activity, but exhibiting low toxicity against surrounding environment. Six new (5-nitrofurfuryl)-derived aminophosphonates were synthesized for the first time and apart from the only one example of N-benzylamino(5-nitrofuryl)-methylphosphonic acid, it was the first time in the history, when this class of compounds was prepared. Their prospective and real biological properties have been followed up by evaluation of their preliminary ecotoxicology. They have been then investigated in aspect of their phytotoxicity against oat (A. sativa) and common radish (R. sativus) exhibiting moderate-to-severe toxicity for these plants. The significant selectivity towards radish (up to 3 times greater toxicity against radish) was observed in some cases. Title compounds were also tested in terms of their toxicity for freshwater crustaceans H. incongruens (ostracods) and marine luminescent bacteria A. fischeri. Although their harmful action on ostracods was not too much elevated, they were found to be highly toxic for bacteria. Various aspects of their ecotoxicity are discussed in this paper.

We report the forensic engineering study on the non-woven fabrics made from poly(lactide-co-glycolide), PLGA, with low toxicity. The comprehensive degradation investigations were conducted under abiotic conditions. The extent of degradation was monitored by weight loss, composition and molar mass changes of the copolymer and by macro- and microscopic observations of the sample surfaces. The structure of the degradation products was evaluated at the molecular level by electrospray ionization mass spectrometry and high-performance liquid chromatography analysis. The degradation process takes place predominantly by the bulk erosion mechanism and rate of release of lactic and glycolic acids from the non-woven fabrics is dependent on their formation method. Described solvent-free formation method of nonwovens from the tin-free PLGA results in biomaterials with higher biocompatibility, what is particularly important for their applications. Moreover, the continuous release of lactic and glycolic acids from the PLGA biomaterials studied allows their gradual removal via biochemical processes and prevents local acidification of the body.

Ionic liquids have attracted considerable interest in various areas as new, non-volatile and non-flammable organic solvents, catalysts, reaction additives, ligands, drugs and other dedicated materials etc. Their general use, sometimes in bulky quantities, requires determination of their potential ecotoxicity on selected organisms. In the present work, influence of triphenylmethylphosphonium iodide (1) and triphenylhexadecylphosphonium iodide (2), introduced to soil, on germination and early stages of growth and development of superior plants was investigated using the plant growth test based on the OECD/OCDE 208/2006. In this test, the seeds of selected species, i.e. land superior plants - spring barley (Hordeum vulgare) and common radish (Raphanus sativus L. subvar. radicula Pers.) were planted in pots containing soil to which a test chemical compound had been added and in pots with control soil. To evaluate the phytotoxicity of ionic liquids 1 and 2 germination and weight (dry and fresh) of control plant seedlings were determined and compared with the germination and weight (dry and fresh) of the seedlings of plants grown in the soil watered with appropriate amounts of the test chemicals. The visual assessment of any types of damage to the test species, such as growth inhibition, chlorosis and necrosis, was also carried out and documented by digital photographs. Based on the obtained results, magnitudes of the LOEC - the lowest concentration causing observable effects in the form of reduction in growth and germination compared with the control and the NOEC - the highest concentration not causing observable, toxic effects - were also determined.

From the environmental protection point of view, the growing interest of ionic liquids in various industrial branches has raised concerns for the toxicity assessment of these compounds. The paper discusses the effect of salts containing the shared 1-ethyl-3-methylimidazolium [EMIM] cation as coupled with five different anions: bromide [Br], nitrate [NO3], p-toluenesulfonate (tosylate) [Ts], dimethylphosphate [dMP] and methanesulfonate [MS] on the growth and development of higher land plants - spring barley and common radish. The experiment was done according to the ISO Standard 11269-2:1995 and the OECD/OCDE Guide 208/2006. As the indications of phytotoxicity, the percentage of sprouts and the level of dry and fresh plant mass were used; in addition, the visual assessment of any signs of damage to the examined plant species, such as growth inhibition and chlorotic changes, was also made. Results of our study has proved the negative impact of ILs on the tested plants and the toxic effect of imidazolium salts was dependent primarily on the applied ionic liquids concentration. The common radish revealed the higher tolerance to the imidazolium as compared to spring barley. The anion type of ionic liquid was crucial for the toxicity against common radish.

Studies were conducted using a 10-chamber Micro-Oxymax (Columbus, OH, USA) respirometer to determine the effect of bioaugmentation, biostimulation and combination of them on enhancing intrinsic biodegradation of oil hydrocarbons in soil. Contaminated soil was collected from a former military airport in Kluczewo, Poland. Bioaugmentation was realized by addition of indigenous or exogenous bacteria to soil. Biostimulation was done by aerated water supply and surfactant addition. Bioaugmentation + addition of a surfactant was applied as the combined treatment. The intrinsic and enhanced hydrocarbons biodegradation rates were estimated from the slopes of linear regressions of cumulative curves of O2 uptake. Pertinent biodegradation rates were recalculated on the basis of the stoichiometric reaction (mass balance equation) and conversion equation. The results showed that combined treatment (indigenous bacteria bioaugmentation + addition of a surfactant) was the most effective method of biodegradation enhancement as the 20-fold increase of biodegradation rate was observed.

The aim of this work was to synthesize selected furaldimines and their aminophosphonic derivatives and evaluation the phytotoxicity of new obtained products according to OECD 208 Guideline. Four Schiff bases, N-furfurylidene-p-anisidine (1a), N-furfurylidene-p-toluidine (1b), N-furfurylidene-benzhydrylamine (1c), and N-(2-nitrofurfurylidene)-p-toluidine (1d) were synthesized and three new furan-derived N-substituted aminomethylphosphonic acids, namely: 2-furyl N-(p-methoxyphenyl)-aminomethylphosphonic acid (2a), 2-furyl N-(p-methylphenyl)-aminomethylphosphonic acid (2b) and 2-furyl N-(diphenylmethyl)-aminomethylphosphonic acid (2c) were synthesized by the addition of in situ generated bis-(trimethylsilyl) phosphite to azomethine bond of corresponding Schiff bases 1a-c. Three Schiff bases 1a-b and 1d as well as all three aminophosphonic acids 2a-c were analyzed in regard with their phytotoxicity toward two plants, radish (Raphanus sativus) and oat (Avena sativa). It has been found that tested N-furfurylidene-p-anisidine (1a), N-(2-nitrofurfurylidene)-p-toluidine (1d) and aminophosphonic acids 2a-c are toxic for selected plants. N-furfurylidene-p-toluidine (1b) did not show any ecotoxicological impact in used plant growth test.

Four diphenyl pyrene-derived aminophosphonates were synthesized. Attempts were made to synthesize diphenyl N-(R)-α-methylbenzylamino(pyren-1-yl)methylphosphonate (3e) in order to obtain the chiral aminophosphonate bearing a pyrene moiety. Because these attempts failed, dimethyl and dibenzyl N-(R)-α-methylbenzyl substituted aminophosphonates 4 and 5 were synthesized and the predominant diastereoisomer of dimethyl aminophosphonate 4 was isolated. The resolution of the diastereomeric mixture of 5 failed. Aminophosphonates 3a–d and the predominant diastereoisomer of 4 were investigated in terms of their ecotoxicity using tests performed on the ostracode Heterocypris incongruens and the fluorescent bacterium Vibrio fisheri. The tests confirmed the moderate-to-high ecotoxicity of aminophosphonates 3a–d and 4, but no evident correlation between the structure and toxicity has been found.

A new amphoteric biopolymer carrier based on alginate and aminated chitosan coated microbeads (Alg/AmCS) was developed and characterized for bovine serum albumin (BSA) protein delivery. The amphoteric character was investigated through studying the swelling and in vitro BSA release behaviors of the developed microbeads in simulated gastric (SGF; pH1.2), intestinal (SIF; pH6.8), and colonic (SCF; pH7.4) fluids. The pH sensitivity was found to depend on the amount of AmCS in the coating medium. The results were interpreted from the view of the individual pH sensitivity of alginate and aminated chitosan in addition to the ionic interaction between them under the studied pHs. Besides; it was found that the BSA loading efficiency (LE) exceeded 82% regardless of the initial concentration of BSA. The released amount of BSA reached approximately 63% and 86% in SIF and SCF, respectively, using 0.25% AmCS. The stability of alginate microbeads in SCF was improved with increasing AmCS concentration in the coating medium up to 2%. Furthermore, the developed microbeads demonstrated their ability for biodegradation in addition to their antibacterial activities against selected bacterial strains. The results clearly suggested that Alg/AmCS coated microbeads could be suitable carriers for site-specific protein delivery in the intestinal and colon tracts.

The design of proteins whose structure and function can be manipulated by binding with specific ligands such as cyclodextrins, has been of great interest in the field of protein engineering and also could be used as drug delivery systems in targeted cancer therapy (Loftsson and Duchene, Int. J. Pharm. 329:1–11, 1; Loftsson et al., Expert. Opin. Drug Deliv. 2:335–351, 2). CD/proteins conjugates are synthesized using original high temperature method in which mono-6-O-formyl-β-CD reacts with two proteins: basic pancreatic trypsin inhibitor and lysozyme. The proposed synthesis method has a high reproducibility which makes it useful for pharmaceutical purposes. That method allows to obtain the conjugate without losing protein’s biological and enzymatic activity which will used in the reaction, and without violating the chemical structure of cyclodextrin molecules.

The aim of the study was the evaluation of gamma irradiation and electron beams for sterilization of porous scaffolds with shape memory behavior obtained from biodegradable terpolymers: poly(l-lactide-co-glycolide-co-trimethylene carbonate) and poly(l-lactide-co-glycolide-co-ɛ-caprolactone). The impact of mentioned sterilization techniques on the structure of the scaffolds before and after the sterilization process using irradiation doses ranged from 10 to 25 kGy has been investigated. Treatment of the samples with gamma irradiation at 15 kGy dose resulted in considerable drop in glass transition temperature (Tg) and number average molecular weight (Mn). For comparison, after irradiation of the samples using an electron beam with the same dose, no significant changes in structure or properties of examined scaffolds have been noticed. Higher doses of irradiation via electron beam caused essential changes of the scaffolds’ pores resulting in partial melting of their surface. Nevertheless, obtained results have revealed that sterilization with electron beam, when compared to gamma irradiation, is a better method because it does not affect significantly the physicochemical properties of the scaffolds. Both used methods of sterilization did not influence the shape memory behavior of the examined materials.

The utilization of starch films, obtained by extrusion of potato starch with urea as plasticizer, for the fertilization of plants has been undertaken. Release rate of urea from the starch films was conducted in water conditions. The molecular weight distribution, surface erosion and weight loss of the starch samples have been determined. The evaluation of efficiency of urea as a fertilizer in the process of release from the starch films was performed under laboratory conditions based on the plant growth test proposed by OECD 208 Guideline and the PN-ISO International Standard using oat and common radish. Although among extruded starch-based films, those that contain the highest amount of fertilizer hold the most promise for a delayed release system, the time of release of fertilizer from obtained films in undertaken study was not satisfactory. All the same, in the present study effort has been made to utilize extruded samples as a fertilizer for agriculture or horticulture purposes. Urea-plasticized starch was successfully used as a fertilizer. Plant growth assessment, including determination of such parameters as fresh and dry matter of plants and their visual evaluation, has proved the stimulating effect of using extruded films on the growth and development of cultivated plants.

The criteria for the diagnosis of HNPCC established by the ICG-HNPCC are very restrictive as they do not allow for the diagnosis of a large number of "suspected HNPCC" cases - these are families which do no fulfill the strict diagnostic "Amsterdam criteria", but do present with several pedigree and clinical features characteristic for HNPCC. Several series of families suspected of harboring germline mutations in DNA mismatch repair genes have been studied for germline changes in DNA mismatch repair genes and a mutation rate of somewhere between 8-60% was found. Therefore a subgroup of members of the ICG-HNPCC has been working on pedigree/clinical diagnostic criteria for suspected HNPCC. Materials and methods Part I The study was based on two series of colorectal cancer (CRC) cases: 1) HNPCC - this group comprised 190 patients affected by CRC from randomly selected families which fulfilled the Amsterdam II criteria registered in Düsseldorf, Germany (102 cases of CRC), Denmark (18 CRCs), Leiden, Holland (23 CRCs) and Szczecin, Poland (47 CRCs). 2) Consecutive CRCs - this group comprised 629 (78.0%) of 806 individuals with CRC diagnosed in 1991-1997 in the city of Szczecin (ca. 400,000 of inhabitants), Poland. Nuclear pedigrees in both groups were compared for frequency of occurrence of clinical features, that have been shown to be associated with HNPCC. Part II 52 consecutive CRC cases from Szczecin, matching the criteria recognized in part I as appropriate for diagnosis of cases "suspected of HNPCC" were studied for the occurrence of germline hMSH2/hMLH1 constitutional mutations using "exon by exon" sequencing. Results The combination of features - i.e. the occurrence of an HNPCC associated cancer (CRC or cancer of the endometrium, small bowel or urinary tract) in a 1st degree relative of a CRC patient; at least one of the patients being diagnosed under age of 50 - appeared to be strongly associated to HNPCC with an OR - 161. Constitutional mutations were identified in 18 (10 MLH1 and 8 MSH2 mutations) of 52 (34%) cases matching the above features. Conclusions The results of our studies strongly suggest that it is possible to diagnose HNPCC with a high degree of accuracy on the basis of nuclear pedigree data and clinical features.

A preliminary study of the degradation of selected commercial packaging materials in compost and aqueous environments The paper presents the results of the degradation of two commercial packaging materials CONS-PET and BioPlaneta in the compost and distilled water at 70°C. The materials containing polylactide (PLA), CONS-PET 13% and BioPlaneta 20%, aliphatic-aromatic copolyester terephthalic acid/adipic acid/1,4-butanediol (BTA) and commercial additives degraded under the industrial composting conditions (composting pile or container) and in distilled water at 70°C in the laboratory holding oven. Distilled water provided the conditions for the hydrolytic (abiotic) degradation of the materials. Weight loss, changes of molecular weight, dispersity monitored via the GPC technique and the macroscopic surface changes of the tested materials were monitored during the experiments. The investigated systems show similar trends of degradation, however on the last day of the incubation the decrease of the molecular weight was higher in water than under the industrial composting conditions. The results indicate that commercial packaging materials can be degraded both while composting ((bio)degradation) and during the incubation in distilled water at 70°C (abiotic hydrolysis).

Degradation of poly[(1,4-butylene terephthalate)-co-(1,4-butylene adipate)] (Ecoflex, BTA) monofilaments (rods) in standardized sandy soil was investigated. Changes in the microstructure and chemical composition distribution of the degraded BTA samples were evaluated and changes in the pH and salinity of postdegradation soil, as well as the soil phytotoxicity impact of the degradation products, are reported. A macroscopic and microscopic evaluation of the surface of BTA rod samples after specified periods of incubation in standardized soil indicated erosion of the surface of BTA rods starting from the fourth month of their incubation, with almost total disintegration of the incubated BTA material observed after 22 months. However, the weight loss after this period of time was about 50% and only a minor change in the M(w) of the investigated BTA samples was observed, along with a slight increase in the dispersity (from an initial 2.75 up to 4.00 after 22 months of sample incubation). The multidetector SEC and ESI-MS analysis indicated retention of aromatic chain fragments in the low molar mass fraction of the incubated sample. Phytotoxicity studies revealed no visible damage, such as necrosis and chlorosis, or other inhibitory effects, in the following plants: radish, cres, and monocotyledonous oat, indicating that the degradation products of the investigated BTA copolyester are harmless to the tested plants.