"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.

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.

2-Methoxyestradiol and Hydrogen Peroxide as Promising Biomarkers in Parkinson's Disease.

Estrogens function in numerous physiological processes including controlling brain cell growth and differentiation. 2-Methoxestradiol (2-ME2), a 17ß-estradiol (E2) metabolite, is known for its anticancer effects as observed both in vivo and in vitro. 2-ME2 affects all actively dividing cells, including neurons. The study aimed to determine whether 2-ME2 is a potentially cancer-protective or rather neurodegenerative agent in a specific tissue culture model as well as a clinical setup. In this study, 2-ME2 activity was determined in a Parkinson's disease (PD) in vitro model based on the neuroblastoma SH-SY5Y cell line. The obtained results suggest that 2-ME2 generates nitro-oxidative stress and controls heat shock proteins (HSP), resulting in DNA strand breakage and apoptosis. On the one hand, it may affect intensely dividing cells preventing cancer development; however, on the other hand, this kind of activity within the central nervous system may promote neurodegenerative diseases like PD. Thus, the translational value of 2-ME2's neurotoxic activity in a PD in vitro model was also investigated. LC-MS/MS technique was used to evaluate estrogens and their derivatives, namely, hydroxy and methoxyestrogens, in PD patients' blood, whereas the stopped-flow method was used to assess hydrogen peroxide (H2O2) levels. Methoxyestrogens and H2O2 levels were increased in patients' blood as compared to control subjects, but hydoxyestrogens were simultaneously decreased. From the above, we suggest that the determination of plasma levels of methoxyestrogens and H2O2 may be a novel PD biomarker. The presented research is the subject of the pending patent application "The use of hydrogen peroxide and 17ß-estradiol and its metabolites as biomarkers in the diagnosis of neurodegenerative diseases," no. P.441360.

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.

Encapsulated Oxovanadium(IV) and Dioxovanadium(V) Complexes into Solid Lipid Nanoparticles Increase Cytotoxicity Against MDA-MB-231 Cell Line.

Introduction: Solid lipid nanoparticles (SLN) have been considered lately as promising drug delivery system in treatment of many human diseases including cancers. We previously studied potential drug compounds that were effective inhibitors of PTP1B phosphatase - possible target for breast cancer treatment. Based on our studies, two complexes were selected for encapsulation into the SLNs, the compound 1 ([VO(dipic)(dmbipy)] · 2 H2O) and compound 2 ([VOO(dipic)](2-phepyH) · H2O). Here, we investigate the effect of encapsulation of those compounds on cell cytotoxicity against MDA-MB-231 breast cancer cell line. The study also included the stability evaluation of the obtained nanocarriers with incorporated active substances and characterization of their lipid matrix. Moreover, the cell cytotoxicity studies against the MDA-MB-231 breast cancer cell line in comparison and in combination with vincristine have been performed. Wound healing assay was carried out to observe cell migration rate. Methods: The properties of the SLNs such as particle size, zeta potential (ZP), and polydispersity index (PDI) were investigated. The morphology of SLNs was observed by scanning electron microscopy (SEM), while the crystallinity of the lipid particles was analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The cell cytotoxicity of complexes and their encapsulated forms was carried out against MDA-MB-231 breast cancer cell line using standard MTT protocols. The wound healing assay was performed using live imaging microscopy. Results: SLNs with a mean size of 160 ± 25 nm, a ZP of -34.00 ± 0.5, and a polydispersity index of 30 ± 5% were obtained. Encapsulated forms of compounds showed significantly higher cytotoxicity also in co-incubation with vincristine. Moreover, our research shows that the best compound was complex 2 encapsulated into lipid nanoparticles. Conclusion: We observed that encapsulation of studied complexes into SLNs increases their cell cytotoxicity against MDA-MB-231 cell line and enhanced the effect of vincristine.

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.

Synthesis, In Vitro, and Computational Studies of PTP1B Phosphatase Inhibitors Based on Oxovanadium(IV) and Dioxovanadium(V) Complexes.

One of the main goals of recent bioinorganic chemistry studies has been to design and synthesize novel substances to treat human diseases. The promising compounds are metal-based and metal ion binding components such as vanadium-based compounds. The potential anticancer action of vanadium-based compounds is one of area of investigation in this field. In this study, we present five oxovanadium(IV) and dioxovanadium(V) complexes as potential PTP1B inhibitors with anticancer activity against the MCF-7 breast cancer cell line, the triple negative MDA-MB-231 breast cancer cell line, and the human keratinocyte HaCaT cell line. We observed that all tested compounds were effective inhibitors of PTP1B, which correlates with anticancer activity. [VO(dipic)(dmbipy)]·2 H2O (Compound 4) and [VOO(dipic)](2-phepyH)·H2O (Compound 5) possessed the greatest inhibitory effect, with IC50 185.4 ± 9.8 and 167.2 ± 8.0 nM, respectively. To obtain a better understanding of the relationship between the structure of the examined compounds and their activity, we performed a computer simulation of their binding inside the active site of PTP1B. We observed a stronger binding of complexes containing dipicolinic acid with PTP1B. Based on our simulations, we suggested that the studied complexes exert their activity by stabilizing the WPD-loop in an open position and limiting access to the P-loop.

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.

Catalytic Activity of New Oxovanadium(IV) Microclusters with 2-Phenylpyridine in Olefin Oligomerization.

So far, few microclusters containing vanadium have been described in the literature. In this report, the synthesis protocol for the preparation of oxovanadium (IV) microclusters with 2-phenylpyridine is shown for the first time. Moreover, the crystal structure of these microclusters is also studied through the use of X-rays. The morphology of the prepared crystals is investigated using a field-emission Scanning Electron Microscope (SEM). The new compound, after activation by modified methylaluminoxane as the catalytic system, is investigated regarding the oligomerizations of 3-buten-1-ol, 2-chloro-2-propen-1-ol, allyl alcohol, and 2,3-dibromo-2-propen-1-ol. The products of oligomerization are tested by the TG-FTIR and MALDI-TOF-MS methods. Moreover, the values of catalytic activities for the new oxovanadium(IV) microclusters with 2-phenylpyridine are determined for the 3-buten-1-ol, 2-chloro-2-propen-1-ol, allyl alcohol, and 2,3-dibromo-2-propen-1-ol oligomerizations. Oxovanadium(IV) microclusters with 2-phenylpyridine are shown to be very highly active precatalysts for the oligomerization of allyl alcohol, 2,3-dibromo-2-propen-1-ol, and 3-buten-1-ol. However, in the case of 2-chloro-2-propen-1-ol oligomerization, the new microclusters are seen as highly active precatalysts.

Curcumin and Its New Derivatives: Correlation between Cytotoxicity against Breast Cancer Cell Lines, Degradation of PTP1B Phosphatase and ROS Generation.

Breast cancer is the most common cancer of women-it affects more than 2 million women worldwide. PTP1B phosphatase can be one of the possible targets for new drugs in breast cancer therapy. In this paper, we present new curcumin derivatives featuring a 4-piperidone ring as PTP1B inhibitors and ROS inducers. We performed cytotoxicity analysis for twelve curcumin derivatives against breast cancer MCF-7 and MDA-MB-231 cell lines and the human keratinocyte HaCaT cell line. Furthermore, because curcumin is a known antioxidant, we assessed antioxidant effects in its derivatives. For the most potent cytotoxic compounds, we determined intracellular ROS and PTP1B phosphatase levels. Moreover, for curcumin and its derivatives, we performed real-time microscopy to observe the photosensitizing effect. Finally, computational analysis was performed for the curcumin derivatives with an inhibitory effect against PTP1B phosphatase to assess the potential binding mode of new inhibitors within the allosteric site of the enzyme. We observed that two tested compounds are better anticancer agents than curcumin. Moreover, we suggest that blocking the -OH group in phenolic compounds causes an increase in the cytotoxicity effect, even at a low concentration. Furthermore, due to this modification, a higher level of ROS is induced, which correlates with a lower level of PTP1B.

Relationship between Antioxidant Activity and Ligand Basicity in the Dipicolinate Series of Oxovanadium(IV) and Dioxovanadium(V) Complexes.

Oxidative stress plays an important role in the pathogenesis of many serious diseases, including cancer, atherosclerosis, coronary artery disease, Parkinson's disease, Alzheimer's disease, stroke and myocardial infarction. In the body's natural biochemical processes, harmful free radicals are formed, which can be removed with the help of appropriate enzymes, a balanced diet or the supply of synthetic antioxidant substances such as flavonoids, vitamins or anthocyanins to the body. Due to the growing demand for antioxidant substances, new complex compounds of transition metal ions with potential antioxidant activity are constantly being sought. In this study, four oxovanadium(IV) and dioxovanadium(V) dipicolinate (dipic) complexes with 1,10-phenanthroline (phen), 2,2'-bipyridyl (bipy) and the protonated form of 2-phenylpyridine (2-phephyH): (1) [VO(dipic)(H2O)2]·2 H2O, (2) [VO(dipic)(phen)]·3 H2O, (3) [VO(dipic)(bipy)]·H2O and (4) [VOO(dipic)](2-phepyH)·H2O were synthesized including one new complex, so far unknown and not described in the literature, i.e., [VOO(dipic)](2-phepyH)·H2O. The oxovanadium(IV) dipicolinate complexes with 1,10-phenanthroline and 2,2'-bipyridyl have been characterized by several physicochemical methods: NMR, MALDI-TOF-MS, IR, but new complex [VOO(dipic)](2-phepyH)·H2O has been examined by XRD to confirm its structure. The antioxidant activities of four complexes have been examined by the nitrotetrazolium blue (NBT) method towards superoxide anion. All complexes exhibit high reactivity with superoxide anion and [VOO(dipic)](2-phepyH)·H2O has higher antioxidant activity than L-ascorbic acid. Our studies confirmed that high basicity of the auxiliary ligand increases the reactivity of the complex with the superoxide radical.

Coordination Complexes as a New Generation Photosensitizer for Photodynamic Anticancer Therapy.

Photodynamic therapy (PDT) has become an alternative to standard cancer treatment methods such as surgery, chemotherapy and radiotherapy. The uniqueness of this method relies on the possibility of using various photosensitizers (PS) that absorb and convert light emission in radical oxygen-derived species (ROS). They can be present alone or in the presence of other compounds such as metal organic frameworks (MOFs), non-tubules or polymers. The interaction between DNA and metal-based complexes plays a key role in the development of new anti-cancer drugs. The use of coordination compounds in PDT has a significant impact on the amount ROS generated, quantum emission efficiency (Φem) and phototoxic index (PI). In this review, we will attempt to systematically review the recent literature and analyze the coordination complexes used as PS in PDT. Finally, we compared the anticancer activities of individual coordination complexes and discuss future perspectives. So far, only a few articles link so many transition metal ion coordination complexes of varying degrees of oxidation, which is why this review is needed by the scientific community to further expand this field worldwide. Additionally, it serves as a convenient collection of important, up-to-date information.

Cat-CrNP as new material with catalytic properties for 2-chloro-2-propen-1-ol and ethylene oligomerizations.

The contemporary search for new catalysts for olefin oligomerization and polymerization is based on the study of coordinating compounds and/or organometallic compounds as post-metallocene catalysts. However known catalysts are suffered by many flaws, among others unsatisfactory activity, requirement of high pressure or instability at high temperatures. In this paper, we present a new catalyst i.e. the crystalline complex compound possesing high catalytic activity in the oligomerization of olefins, such as 2-chloro-2-propen-1-ol and ethylene under very mild conditions (room temperature, 0.12 bar for ethylene oligomerization, atmospheric pressure for 2-chloro-2-propen-1-ol oligomerization). New material-Cat-CrNP ([nitrilotriacetato-1,10-phenanthroline]chromium(III) tetrahydrate) has been obtained as crystalline form of the nitrilotriacetate complex compound of chromium(III) with 1,10-phenanthroline and characterized in terms of its crystal structure by the XRD method and by multi-analytical investigations towards its physicochemical propeties The yield of catalytic oligomerization over Cat-CrNP reached to 213.92 g · mmol-1 · h-1· bar-1 and 3232 g · mmol-1 · h-1 · bar-1 for the 2-chloro-2-propen-1-ol and ethylene, respectively. Furthemore, the synthesis of Cat-CrNP is cheap, easy to perform and solvents used during preparation are environmentally friendly.

New chromium(III)-based catalysts for ethylene oligomerization.

The report focuses on the new precatalysts for ethylene oligomerization. The five chromium(III) complex compounds containing the following ligands: dipicolinate anion, oxalate anion, 5-aminopyridine-2-carboxylate anion, 2,2'-bipyridine and 4,4'-dimethoxy-2,2'-bipyridine have been examined towards catalytic activity for ethylene oligomerization. The chromium(III) complexes have been activated by modified methylaluminoxane. The obtained oligomers have been investigated by MALDI-TOF-MS, thermal analysis and infrared spectroscopy. The results revealed that the examined chromium(III) complexes are highly active catalysts for ethylene oligomerization. The values of catalytic activities of the examined complexes are in the range 1860 - 3798 g∙mmol-1∙h-1∙bar-1.

Application of Coordination Compounds with Transition Metal Ions in the Chemical Industry-A Review.

This publication presents the new trends and opportunities for further development of coordination compounds used in the chemical industry. The review describes the influence of various physicochemical factors regarding the coordination relationship (for example, steric hindrance, electron density, complex geometry, ligand), which condition technological processes. Coordination compounds are catalysts in technological processes used during organic synthesis, for example: Oxidation reactions, hydroformylation process, hydrogenation reaction, hydrocyanation process. In this article, we pointed out the possibilities of using complex compounds in catalysis, and we noticed what further research should be undertaken for this purpose.

The impact of environmental contamination on the generation of reactive oxygen and nitrogen species - Consequences for plants and humans.

Environmental contaminants, such as heavy metals, nanomaterials, and pesticides, induce the formation of reactive oxygen and nitrogen species (RONS). Plants interact closely with the atmosphere, water, and soil, and consequently RONS intensely affect their biochemistry. For the past 30 years researchers have thoroughly examined the role of RONS in plant organisms and oxidative modifications to cellular components. Hydrogen peroxide, superoxide anion, nitrogen(II) oxide, and hydroxyl radicals have been found to take part in many metabolic pathways. In this review the various aspects of the oxidative stress induced by environmental contamination are described based on an analysis of literature. The review reinforces the contention that RONS play a dual role, that is, both a deleterious and a beneficial one, in plants. Environmental contamination affects human health, also, and so we have additionally described the impact of RONS on the coupled human - environment system.