"Isocyanates and isocyanides - life-threatening toxins or essential compounds?"

Isocyanides and isocyanates are some of the most reactive compounds in organic chemistry, making them perceived as compounds with high potential for use in both the laboratory and industry. With their high reactivity also comes several disadvantages, most notably their potentially high toxicity. The following article is a collection of information on the toxic effects of the isocyanide group on the human body and the environment. Information on the mechanism of how these harmful substances affect living tissues and the environment, worldwide information on how to protect against these chemicals, current regulations, and exposure limits for specific countries is compiled. The latest research on the application uses of isocyanates and isocyanides is also outlined, as well as the latest safer and greener methods and techniques to work with these compounds. Additionally, the presented article can serve as a brief guide to the organic toxicity of a group of isocyanates and isocyanates.

Clean production of geopolymers as an opportunity for sustainable development of the construction industry.

Large-scale cement production generates significant amounts of carbon dioxide from the breakdown of limestone, contributing to environmental pollution. Clean production of eco-friendly three-dimensional geopolymers can be used as environmentally friendly building materials. Replacing Portland cement with eco-friendly materials correlates with reduced energy consumption, costs, and negative environmental impact. In addition, geopolymer cement has above-average physical and chemical properties, which in many cases exceed conventional Portland cement. The literature review summarizes the latest research in the production of geopolymers following the principles of green chemistry and sustainable development goals. Examples of upcycling of construction waste, industrial waste (fly ash, silica fume, slag, tailing), demolition waste, agriculture solid waste (rice husk, palm oil), and mining waste into functional geopolymer materials will be discussed. Additionally, the review focused on innovative applications and physicochemical properties of functional geopolymer materials.

Correction: Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine.

Correction for 'Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine' by Kacper Poblocki et al., Dalton Trans., 2024, 53, 4194-4203, https://doi.org/10.1039/D3DT04091G.

Analysis of the Model of Atherosclerosis Formation in Pig Hearts as a Result of Impaired Activity of DNA Repair Enzymes.

Excessive consumption of food rich in saturated fatty acids and carbohydrates can lead to metabolic disturbances and cardiovascular disease. Hyperlipidemia is a significant risk factor for acute cardiac events due to its association with oxidative stress. This leads to arterial wall remodeling, including an increase in the thickness of the intima media complex (IMT), and endothelial dysfunction leading to plaque formation. The decreased nitric oxide synthesis and accumulation of lipids in the wall result in a reduction in the vasodilating potential of the vessel. This study aimed to establish a clear relationship between markers of endothelial dysfunction and the activity of repair enzymes in cardiac tissue from a pig model of early atherosclerosis. The study was conducted on 28 female Polish Landrace pigs, weighing 40 kg (approximately 3.5 months old), which were divided into three groups. The control group (n = 11) was fed a standard, commercial, balanced diet (BDG) for 12 months. The second group (n = 9) was fed an unbalanced, high-calorie Western-type diet (UDG). The third group (n = 8) was fed a Western-type diet for nine months and then switched to a standard, balanced diet (regression group, RG). Control examinations, including blood and urine sampling, were conducted every three months under identical conditions with food restriction for 12 h and water restriction for four hours before general anesthesia. The study analyzed markers of oxidative stress formed during lipid peroxidation processes, including etheno DNA adducts, ADMA, and NEFA. These markers play a crucial role in reactive oxygen species analysis in ischemia-reperfusion and atherosclerosis in mammalian tissue. Essential genes involved in oxidative-stress-induced DNA demethylation like OGG1 (8-oxoguanine DNA glycosylase), MPG (N-Methylpurine DNA Glycosylase), TDG (Thymine-DNA glycosylase), APEX (apurinic/apirymidinic endodeoxyribonuclease 1), PTGS2 (prostaglandin-endoperoxide synthase 2), and ALOX (Arachidonate Lipoxygenase) were measured using the Real-Time RT-PCR method. The data suggest that high oxidative stress, as indicated by TBARS levels, is associated with high levels of DNA repair enzymes and depends on the expression of genes involved in the repair pathway. In all analyzed groups of heart tissue homogenates, the highest enzyme activity and gene expression values were observed for the OGG1 protein recognizing the modified 8oxoG. Conclusion: With the long-term use of an unbalanced diet, the levels of all DNA repair genes are increased, especially (significantly) Apex, Alox, and Ptgs, which strongly supports the hypothesis that an unbalanced diet induces oxidative stress that deregulates DNA repair mechanisms and may contribute to genome instability and tissue damage.

Porous oligomeric materials synthesised using a new, highly active precatalyst based on ruthenium(III) and 2-phenylpyridine.

There are few literature reports on using precatalysts based on ruthenium(II/III) ions in the polymerization of olefins. Therefore, a new coordination compound was designed based on ruthenium(III) ion and 2-phenylpyridine. The resulting monocrystal was characterized by X-ray diffraction (XRD), solid-state (photo)IR spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The new ruthenium(III) complex compound was used as a precatalyst in the oligomerization reactions of ethylene, 2-propen-1-ol, 2-chloro-2-propen-1-ol, 3-butene-2-ol and 2,3-dibromo-2-propen-1-ol with methylaluminoxane and ethylaluminium dichloride as activators. The catalytic activity of the newly discovered ruthenium(III) complex compound ranges from 159.5 (for 2-chloro-2-propen-1-ol) to 755.6 (for ethylene) g mmol-1 h-1 bar-1, indicating that it is a chemical compound with high catalytic activity. In addition, the oligomerization reaction products were subjected to physicochemical characterization, using BET (Brunauer-Emmett-Teller isotherm), mass spectrometry (MALDI-TOF-MS), Fourier transform infrared (FT-IR) spectroscopy, NMR, TGA, differential scanning calorimetry (DSC), and the morphology of the porous polymeric materials was investigated by SEM. The distinguishing feature of the obtained precatalyst is its high catalytic activity under mild reaction conditions, a rare phenomenon. Compared with other precatalysts, it is the most active ruthenium(II/III) ion-based catalytic material used in oligo- and polymerization reactions of ethylene.

The Influence of Carbon Nanotubes on the Physical and Chemical Properties of Nanocomposites Based on Unsaturated Polyester Resin.

The new actual scientific direction is in the development of different nanocomposites and the study of their medical-biological, physicochemical, and physicomechanical properties. One way to expand the functionality of nanocomposites and nanomaterials is to introduce carbon nanostructures into the polymer matrix. This study presents the properties of unsaturated polyester resins (Estromal, LERG S.A.) based on PET recyclate with multi-walled carbon nanotubes (MWCNTs): their mechanical and thermomechanical characteristics, resistance to ultraviolet radiation (UV-vis), and chemical resistance properties. The properties of the obtained materials were characterized using physical-chemical research methods. The changes in the properties of the composites for MWCNT content of 0.1, 0.3, and 0.5 wt % were determined. The results showed positive influences on the thermomechanical and mechanical properties of nanocomposites without significant deterioration of their gloss. Too much CNT added to the resin leads to heterogeneity of the composite structure.

Chalcone-Derived Lactones: Synthesis, Whole-Cell Biotransformation, and Evaluation of Their Antibacterial and Antifungal Activity.

Four compounds with lactone moiety were synthesized from chalcone 1 in three- or four-step synthesis. γ-Bromo-δ-lactone 5 was the only product of bromolactonization of acid 4 whereas bromolactonization of ester 3, apart from lactone 5 also afforded its isomer 6 and two diastereoisomeric δ-hydroxy-γ-lactones 7 and 8. Lactone 8 was also obtained in 88% yield as a product of simultaneous dehalogenation and translactonization of γ-bromo-δ-lactone 5 by Penicillum frequentans AM 359. Chalcone-derived lactones 5-8 were subjected to the tests on antimicrobial activity and the results compared with activity of starting chalcone 1. Obtained lactones 5-8 in most cases limited the growth of tested bacterial and fungal strains. The highest activity was found for δ-hydroxy-γ-lactone 8 which completely inhibited the growth of Staphylococcus aureus, Fusarium graminearum, Aspergillus niger, and Alternaria sp. The introduction of lactone moiety into chalcone scaffold significantly improved antimicrobial activity of the compound: γ-bromo-δ-lactone 6 and δ-hydroxy-γ-lactone 8 were significantly stronger growth inhibitors of S. aureus and F. graminearum. In the case of the latter, a clear positive effect of the lactone function on the antifungal activity was also observed for γ-bromo-δ-lactone 5.

Catalytic Properties of Two Complexes of chromium(III) and cobalt(II) with Nitrilotriacetate, Dipicolinate, and 4-Acetylpyridine.

In this paper, a synthesis of two innovative coordination compounds, based on chromium(III) and cobalt(II) ions with N,O-donor ligands (nitrilotriacetate, dipicolinate) and 4-acetylpyridine, is reported. The obtained metal-organic compounds were structurally characterized using the single-crystal X-ray diffraction (XRD) method. The well-defined chromium(III) and cobalt(II) complexes were used as precatalysts in the oligomerization reaction of 2-chloro-2-propen-1-ol and 2-propen-1-ol with methylaluminoxane (MMAO) as an activator. The products of the oligomerization reaction were subjected to full physicochemical characteristics, i.e., time-of-flight mass spectrometry (MALDI-TOF-MS), TGA, and differential scanning calorimetry (DSC) methods. The catalytic activity of the precatalysts in both reactions was calculated and compared with other catalysts known in the literature.

Aluminium(III) Oxide-The Silent Killer of Bacteria.

In this article, we describe the antimicrobial properties of pristine anodised aluminium oxide matrices-the material many consider biologically inert. During a typical anodisation process, chromium and chlorine compounds are used for electropolishing and the removal of the first-step aluminium oxide. Matrices without the use of those harmful compounds were also fabricated and tested for comparison. The antibacterial tests were conducted on four strains of Escherichia coli: K12, R2, R3 and R4. The properties of the matrices were also compared to the three types of antibiotics: ciprofloxacin, bleomycin and cloxacillin using the Minimal Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) tests. Moreover, DNA was isolated from the analysed bacteria which was additionally digested with formamidopyrimidine-DNA glycosylase (Fpg) protein from the group of repair glycosases. These enzymes are markers of modified oxidised bases in nucleic acids produced during oxidative stress in cells. Preliminary cellular studies, MIC and MBC tests and digestion with Fpg protein after modification of bacterial DNA suggest that these compounds may have greater potential as antibacterial agents than the aforementioned antibiotics. The described composites are highly specific for the analysed model Escherichia coli strains and may be used in the future as new substitutes for commonly used antibiotics in clinical and nosocomial infections in the progressing pandemic era. The results show much stronger antibacterial properties of the functionalised membranes on the action of bacterial membranes in comparison to the antibiotics in the Fpg digestion experiment. This is most likely due to the strong induction of oxidative stress in the cell through the breakdown of the analysed bacterial DNA.

A Series of Green Oxovanadium(IV) Precatalysts with O, N and S Donor Ligands in a Sustainable Olefins Oligomerization Process.

Designing catalyst systems based on transition metal ions and activators using the principles of green chemistry is a fundamental research goal of scientists due to the reduction of poisonous solvents, metal salts and organic ligands released into the environment. Urgent measures to reduce climate change are in line with the goals of sustainable development and the new restrictive laws ordained by the European Union. In this report, we attempted to use known oxovanadium(IV) green complex compounds with O, N and S donor ligands, i.e., [VO(TDA)phen] • 1.5 H2O (TDA = thiodiacetate), (phen = 1,10-phenanthroline), oxovanadium(IV) microclusters with 2-phenylpyridine (oxovanadium(IV) cage), [VOO(dipic)(2-phepyH)] • H2O (dipic = pyridine-2,6-dicarboxylate anion), (2-phepyH = 2-phenylpyridine), [VO(dipic)(dmbipy)] • 2H2O (dmbipy = 4,4'-dimethoxy-2,2'-dipyridyl) and [VO(ODA)(bipy)] • 2 H2O (ODA = oxydiacetate), (bipy = 2,2'-bipyridine), as precatalysts in oligomerization reactions of 3-buten-2-ol, 2-propen-1-ol, 2-chloro-2-propen-1-ol and 2,3-dibromo-2-propen-1-ol. The precatalysts, in most cases, turned out to be highly active because the catalytic activity exceeded 1000 g mmol-1·h-1. In addition, the oligomers were characterized by Fourier-transform infrared spectroscopy (FTIR), matrix-assisted laser desorption/ionization (MALDI-TOF-MS), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques.

Functionalised Anodised Aluminium Oxide as a Biocidal Agent.

In this article, we describe the antimicrobial properties of a new composite based on anodic aluminium oxide (AAO) membranes containing propyl-copper-phosphonate units arranged at a predetermined density inside the AAO channels. The samples were prepared with four concentrations of copper ions and tested as antimicrobial drug on four different strains of Escherichia coli (K12, R2, R3 and R4). For comparison, the same strains were tested with three types of antibiotics using the minimal inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) tests. Moreover, DNA was isolated from the analysed bacteria which was additionally digested with formamidopyrimidine-DNA glycosylase (Fpg) protein from the group of repair glycosases. These enzymes are markers of modified oxidised bases in nucleic acids produced during oxidative stress in cells. Preliminary cellular studies, MIC and MBC tests and digestion with Fpg protein after modification of bacterial DNA suggest that these compounds may have greater potential as antibacterial agents than antibiotics such as ciprofloxacin, bleomycin and cloxacillin. The described composites are highly specific for the analysed model Escherichia coli strains and may be used in the future as new substitutes for commonly used antibiotics in clinical and nosocomial infections in the progressing pandemic era. The results show much stronger antibacterial properties of the functionalised membranes on the action of bacterial membranes in comparison to the antibiotics in the Fpg digestion experiment. This is most likely due to the strong induction of oxidative stress in the cell through the breakdown of the analysed bacterial DNA. We have also observed that the intermolecular distances between the functional units play an important role for the antimicrobial properties of the used material. Hence, we utilised the idea of the 2D solvent to tailor them.

Regiospecific Hydrogenation of Bromochalcone by Unconventional Yeast Strains.

This research aimed to select yeast strains capable of the biotransformation of selected 2'-hydroxybromochalcones. Small-scale biotransformations were carried out using four substrates obtained by chemical synthesis (2'-hydroxy-2″-bromochalcone, 2'-hydroxy-3″-bromochalcone, 2'-hydroxy-4″-bromochalcone and 2'-hydroxy-5'-bromochalcone) and eight strains of non-conventional yeasts. Screening allowed for the determination of the substrate specificity of selected microorganisms and the selection of biocatalysts that carried out the hydrogenation of tested compounds in the most effective way. It was found that the position of the bromine atom has a crucial influence on the degree of substrate conversion by the tested yeast strains. As a result of the biotransformation of the 2'-hydroxybromochalcones, the corresponding 2'-hydroxybromodihydrochalcones were obtained. The products obtained belong to the group of compounds with high potential as precursors of sweet substances.

Promiscuous Lipase-Catalyzed Markovnikov Addition of H-Phosphites to Vinyl Esters for the Synthesis of Cytotoxic α-Acyloxy Phosphonate Derivatives.

An enzymatic route for phosphorous-carbon- bond formation is developed by discovering new promiscuous activity of lipase. This biocatalytic transformation of phosphorous-carbon- bond addition leads to biologically and pharmacologically relevant α-acyloxy phosphonates with methyl group in α-position. A series of target compounds were synthesized with yields ranging from 54% to 83% by enzymatic reaction with Candida cylindracea (CcL) lipase via Markovnikov addition of H-phosphites to vinyl esters. We carefully analyzed the best conditions for the given reaction such as the type of enzyme, temperature, and type of solvent. The developed protocol is applicable to a range of H-phosphites and vinyl esters significantly simplifying the preparation of synthetically challenging α-pivaloyloxy phosphonates. Further, the obtained compounds were validated as new potential antimicrobial drugs with characteristic E. coli bacterial strains and DNA modification recognized by the Fpg protein, N-methyl purine glycosylases as new substrates. The impact of the methyl group located in the α-position of the studied α-acyloxy phosphonates on the antimicrobial activity was demonstrated. The pivotal role of this group on inhibitory activity against selected pathogenic E. coli strains was revealed. The observed results are especially important in the case of the increasing resistance of bacteria to various drugs and antibiotics.

The Evaluation of DHPMs as Biotoxic Agents on Pathogen Bacterial Membranes.

Herein, we present biological studies on 3,4-dihydropyrimidin-2(1H)-ones (DHPMs) obtained via Biginelli reaction catalyzed by NH4Cl under solvent-free conditions. Until now, DHPMs have not been tested for biological activity against pathogenic E. coli strains. We tested 16 newly synthesized DHPMs as antimicrobial agents on model E. coli strains (K12 and R2-R4). Preliminary cellular studies using MIC and MBC tests and digestion of Fpg after modification of bacterial DNA suggest that these compounds may have greater potential as antibacterial agents than typically used antibiotics, such as ciprofloxacin (ci), bleomycin (b) and cloxacillin (cl). The described compounds are highly specific for pathogenic E. coli strains based on the model strains used and may be engaged in the future as new substitutes for commonly used antibiotics in clinical and nosocomial infections in the pandemic era.

Investigation of Degradation of Composites Based on Unsaturated Polyester Resin and Vinyl Ester Resin.

This study compares the degradation process of unsaturated polyester resin (UPR) and vinyl ester resin (VER) and their biocomposites with kraft lignin. In order to study their degradation, accelerated aging, immersion in different solvents, microwave radiation and high temperature were applied. The results show that, depending on the conditions, the degradation assumes a different course. The VER resin is more chemically resistant than the UPR resin. In the case of the composites immersed in an aggressive solvent (acetone), it can be observed that the polymer matrix is degraded, whereas in water only a small increase of weight takes place. Immersion in NaOH initiates the degradation process consisting in the hydrolysis of ester bonds, which are especially observed for pure resins. Under the influence of UV radiation and microwaves, the resins are additionally cross-linked. Thermogravimetric analysis shows that in the case of composites heated to 1000 °C, a residual mass remains, which is carbonized with lignin. In turn, composites treated with microwaves lost weight.

Dipicolinate Complexes of Oxovanadium(IV) and Dioxovanadium(V) with 2-Phenylpyridine and 4,4'-Dimethoxy-2,2'-bipyridyl as New Precatalysts for Olefin Oligomerization.

Polyolefins are used in everyday life, including in the production of many types of plastic. In addition, polyolefins account for over 50% of the polymers produced in the world. After conducting the oligomerization reactions of 2-propen-1-ol, 2-chloro-2-propen-1-ol, and norborene, polyolefins are obtained. In this report, two complexes of oxovanadium(IV) and dioxovanadium(V) with dipicolinate, 2-phenylyridine, and 4,4'-dimethoxy-2,2'-bipyridyl as precatalysts for 2-propen-1-ol, 2-chloro-2-propen-1-ol, and norborene oligomerizations are prepared. We present for the first time the new dipicolinate complex compound of oxovanadium(IV) with 4,4'-dimetoxy-2,2'-bipyridyl. Both complexes were tested for catalytic activity in the oligomerization reactions of 2-propen-1-ol, 2-chloro-2-propen-1-ol, and norbornene. Both synthesized complexes showed high catalytic activity in these oligomerization reactions, except for the oligomerization of norbornene.

Bis(5-chloroquinolin-8-olato)-bis(pyridine)-cobalt(II) as new catalytic material.

Nowadays, studies are carried out on the design and synthesis of new catalysts for olefin oligomerization and polymerization, which would contain non-toxic metals and at the same time show high catalytic activities. Complex compounds of transition metal ions such as Fe(II), Cr(III) and Zr(II) containing pyridine or quinoline as ligands show at least moderate catalytic activity in ethylene and propylene polymerizations. To investigate the catalytic activity of the complex containing pyridine ligands and quinoline derivatives, here we have synthesized the crystals of new bis(5-chloroquinolin-8-olato)-bis(pyridine)-cobalt(II) solvate. The synthesized cobalt(II) complex compound was tested in reactions of 2-chloro-2-propen-1-ol and norbornene oligomerizations. Our studies showed that bis(5-chloroquinolin-8-olato)-bis(pyridine)-cobalt(II) after activation by MMAO-12 catalyzes the formation of oligomers in nitrogen atmosphere, under atmospheric pressure and at room temperature. Bis(5-chloroquinolin-8-olato)-bis(pyridine)-cobalt(II) possesses moderate catalytic activity in the formation of norbornene oligomers process and low catalytic activity in 2-chloro-2-propen-1-ol oligomerization.

Preparation of Allyl Alcohol Oligomers Using Dipicolinate Oxovanadium(IV) Coordination Compound.

Currently, new precatalysts for olefin oligomerization are being sought in the group of vanadium(IV) complexes. Thus, the aim of our research was to examine the catalytic activity of the oxovanadium(IV) dipicolinate complex [VO(dipic)(H2O)2] 2 H2O (dipic = pyridine-2,6-dicarboxylate anion) in 2-propen-1-ol oligomerization as well as to characterize oligomerization products using matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF-MS), infrared spectroscopy (IR) and nuclear magnetic resonance (NMR). The oligomerization process took place at room temperature, under atmospheric pressure and under nitrogen atmosphere to prevent oxidation of the activator MMAO-12-the modified methylaluminoxane (7 wt.%) aluminum in toluene. The last point was to determine the catalytic activity of the complex in the oligomerization reaction of 2-propen-1-ol. The aspect that enriches this work is the proposed mechanism of oligomerization of allyl alcohol based on the literature.

Assessment Study on the Solvent Resistance of Low-Density Polyethylene with Pumpkin Seed Hulls.

When designing products that are made of composite materials and that contain natural fillers, it is particularly important to consider the long-term exposure of these materials to caustic liquids and substances (concentrated acids, bases), and to ensure that these products meet strict requirements for reliability and operational safety. This study investigated the effects of different solvents on the mass, mechanical, thermal, surface, and structural properties of polymer composites containing natural fillers in the form of pumpkin seed hulls. Experiments were conducted using four different filler contents (5, 10, 15, and 20 wt%) and grain sizes ranging from 0.2 to 0.4 mm and 0.6 to 0.8 mm. Hybrid injection-moulded pieces were immersed in distilled water (H2O), 1% NaOH solution, acetone (C3H6O), and toluene (C7H8) for 84 days. After that, their mechanical and thermal properties as well as their structure geometries were analysed statistically. Changes in the properties of the tested composite materials were assessed depending on the solvent type, and the statistical significance of these changes were determined. The results showed that the nature of degradation depended on the applied solvent type. It was observed that the polymer matrix of the toluene-immersed samples absorbed the liquid to a significant extent first and then underwent a gradual degradation with time. In contrast, the samples immersed in water showed a slight increase in their mass. It was found that all tested properties of the composite samples deteriorated irrespective of the solvent type.

Synthesis and Characterization of Biodegradable Polymers Based on Glucose Derivatives.

Syntheses of two new monomers, namely the glucose derivatives 2,3,4,6-tetra-O-acetyl-1 methacryloyl-glucopyranose (MGlc) and 2,3,4,6 tetra-O-acetyl-1-acryloylglucopyranose (AGlc), are presented. Their chemical structures were determined by the FTIR, 1H and 13C NMR spectroscopies, the single-crystal X-ray analysis, supported by the powder X-ray diffraction, and the DSC analyses. Molecules of both monomers exist in the ß-anomeric form in the solid state. The variable temperature X-ray diffraction studies, supported by the DSC analyses, revealed AGlc's propensity for polymorphism and temperature-induced phase transitions. MGlc and AGlc crystallised from methanol were polymerized or copolymerized with methyl methacrylate and N-vinylpyrrolidone. The biodegradabilities of polymers as well as thermal and optical properties were studied. The results show that some properties of the obtained homopolymers and copolymers resemble those of PMMA. The main difference is that the AGlc and MGlc homopolymers are biodegradable while PMMA is not. The ternary copolymers, i.e., MGlc/AGlc-MMA-NVP lose more than 10% of their weight after six months.