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IFN-I is the key regulatory component activating and modulating the response of innate and adaptive immune system to bacterial as well as viral pathogens. IFN-I promotes the expression of IFN-induced genes (ISG) and, consequently, the production of chemokines, e.g., CXCL10. Those chemokines control migration and localization of immune cells in tissues, and, thus, are critical to the function of the innate immune system during infection. Consequently, the regulation of IFN-I signaling is essential for the proper induction of an immune response. Our previous study has shown that E3 ubiquitin ligase Pellino3 positively regulates IFNβ expression and secretion. Herein, we examined the role of Pellino3 ligase in regulating

Epilobium angustifolium L. is a popular medicinal plant found in many regions of the world. This plant contains small amounts of essential oil whose composition and properties have not been extensively investigated. There are few reports in the literature on the antioxidant and antifungal properties of this essential oil and the possibility of applying it as a potential promoter of the skin penetration of drugs. The essential oil was obtained by distillation using a Clavenger type apparatus. The chemical composition was analyzed by the GC-MS method. The major active compounds of E. angustifolium L. essential oil (EOEa) were terpenes, including α-caryophyllene oxide, eucalyptol, β-linalool, camphor, (S)-carvone, and β-caryophyllene. The analyzed essential oil was also characterized by antioxidant activity amounting to 78% RSA (Radical Scavenging Activity). Antifungal activity against the strains Aspergillus niger, A. ochraceus, A. parasiticum, and Penicillium cyclopium was also determined. The largest inhibition zone was observed for strains from the Aspergillus group. The EOEa enhanced the percutaneous penetration of ibuprofen and lidocaine. After a 24 h test, the content of terpene in the skin and the acceptor fluid was examined. It has been shown that the main compounds contained in the essential oil do not penetrate through the skin, but accumulate in it. Additionally, FTIR-ATR analysis showed a disturbance of the stratum corneum (SC) lipids caused by the essential oil application. Due to its rich composition and high biological activity, EOEa may be a potential candidate to be applied, for example, in the pharmaceutical or cosmetic industries. Moreover, due to the reaction of the essential oil components with SC lipids, the EOEa could be an effective permeation enhancer of topically applied hydrophilic and lipophilic drugs.

Epilobium angustifolium L. is a popular medicinal plant found in many regions of the world. This plant contains small amounts of essential oil whose composition and properties have not been extensively investigated. There are few reports in the literature on the antioxidant and antifungal properties of this essential oil and the possibility of applying it as a potential promoter of the skin penetration of drugs. The essential oil was obtained by distillation using a Clavenger type apparatus. The chemical composition was analyzed by the GC-MS method. The major active compounds of E. angustifolium L. essential oil (EOEa) were terpenes, including α-caryophyllene oxide, eucalyptol, β-linalool, camphor, (S)-carvone, and β-caryophyllene. The analyzed essential oil was also characterized by antioxidant activity amounting to 78% RSA (Radical Scavenging Activity). Antifungal activity against the strains Aspergillus niger, A. ochraceus, A. parasiticum, and Penicillium cyclopium was also determined. The largest inhibition zone was observed for strains from the Aspergillus group. The EOEa enhanced the percutaneous penetration of ibuprofen and lidocaine. After a 24 h test, the content of terpene in the skin and the acceptor fluid was examined. It has been shown that the main compounds contained in the essential oil do not penetrate through the skin, but accumulate in it. Additionally, FTIR-ATR analysis showed a disturbance of the stratum corneum (SC) lipids caused by the essential oil application. Due to its rich composition and high biological activity, EOEa may be a potential candidate to be applied, for example, in the pharmaceutical or cosmetic industries. Moreover, due to the reaction of the essential oil components with SC lipids, the EOEa could be an effective permeation enhancer of topically applied hydrophilic and lipophilic drugs.

The effect of cream and gel vehicles containing clove water on skin permeability was compared for a new eugenol derivative (eugenyl dichloroacetate—EDChA) with antioxidant activity. In vitro permeation experiments were conducted in a Franz cell with porcine skin. The cumulative mass and skin accumulation of EDChA were investigated and compared. The antioxidative capacity of the studied vehicles was determined by using the diphenylpicrylhydrazyl (DPPH) free radical reduction method. The antioxidant activity (evaluated with DPPH, ABTS, and the Folin–Ciocalteu methods) of the fluid that penetrated through the pig skin and of the fluid obtained after the skin extraction, were also determined. For comparison, eugenol was also tested. The results of this work could contribute to the development of vehicles with antioxidant potential estimated after 24 h of conducting the experiment, which indicates long-term protection against reactive oxygen species (ROS) in the deeper layers of the skin. The waste water from the clove buds steam distillation -contains several valuable biologically active compounds, and its use is environmentally friendly. We observed that gel vehicles were the best enhancer of skin permeation for both eugenol and its derivative. In most cases, -similar cumulative masses of eugenol and its ester were found in the acceptor fluid. The accumulation of EDChA was higher for cream vehicles in relation to the parent eugenol when applied onto the skin. The greatest amounts of eugenol were accumulated in the skin when these compounds were used in gel vehicles.

Bacterial cellulose membranes (BCs) are becoming useful as a drug delivery system to the skin. However, there are very few reports on their application of plant substances to the skin. Komagataeibacter xylinus was used for the production of bacterial cellulose (BC). The BC containing 5% and 10% ethanolic extract of Epilobium angustifolium (FEE) (BC-5%FEE and BC-10%FEE, respectively) were prepared. Their mechanical, structural, and antioxidant properties, as well as phenolic acid content, were evaluated. The bioavailability of BC-FESs using mouse L929 fibroblasts as model cells was tested. Moreover, In Vitro penetration through the pigskin of the selected phenolic acids contained in FEE and their accumulation in the skin after topical application of BC-FEEs was examined. The BC-FEEs were characterized by antioxidant activity. The BC-5% FEE showed relatively low toxicity to healthy mouse fibroblasts. Gallic acid (GA), chlorogenic acid (ChA), 3,4-dihydroxybenzoic acid (3,4-DHB), 4-hydroxybenzoic acid (4-HB), 3-hydroxybenzoic acid (3-HB), and caffeic acid (CA) found in FEE were also identified in the membranes. After topical application of the membranes to the pigskin penetration of some phenolic acid and other antioxidants through the skin as well as their accumulation in the skin was observed. The bacterial cellulose membrane loaded by plant extract may be an interesting solution for topical antioxidant delivery to the skin.

This study investigated the antioxidant activity DPPH, ABTS, and Folin–Ciocalteu methods of betulin (compound 1) and its derivatives (compounds 2–11). Skin permeability and accumulation associated with compounds 1 and 8 were also examined. Identification of the obtained products (compound 2–11) and betulin isolated from plant material was based on the analysis of 1H- NMR and 13C-NMR spectra. The partition coefficient was calculated to determine the lipophilicity of all compounds. In the next stage, the penetration through pig skin and its accumulation in the skin were evaluated of ethanol vehicles containing compound 8 (at a concentration of 0.226 mmol/dm3), which was characterized by the highest antioxidant activity. For comparison, penetration studies of betulin itself were also carried out. Poor solubility and the bioavailability of pure compounds are major constraints in combination therapy. However, we observed that the ethanol vehicle was an enhancer of skin permeation for both the initial betulin and compound 8. The betulin 8 derivative showed increased permeability through biological membranes compared to the parent betulin. The paper presents the transformation of polycyclic compounds to produce novel derivatives with marked antioxidant activities and as valuable intermediates for the pharmaceutical industry. Moreover, the compounds contained in the vehicles, due to their mechanism of action, can have a beneficial effect on the balance between oxidants and antioxidants in the body, minimizing the effects of oxidative stress. The results of this work may contribute to knowledge regarding vehicles with antioxidant potential. The use of vehicles for this type of research is therefore justified.

Epilobium angustifolium L. is a popular and well-known medicinal plant. In this study, an attempt to evaluate the possibility of using this plant in preparations for the care and treatment of skin diseases was made. The antioxidant, antiaging and anti-inflammatory properties of ethanolic extracts from Epilobium angustifolium (FEE) were assessed. Qualitative and quantitative evaluation of extracts chemically composition was performed by gas chromatography with mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC). The total polyphenol content (TPC) of biologically active compounds, such as the total content of polyphenols (TPC), flavonoids (TFC), and assimilation pigments, as well as selected phenolic acids, was assessed. FEE was evaluated for their anti-inflammatory and antiaging properties, achieving 68% inhibition of lipoxygenase activity, 60% of collagenase and 49% of elastase. FEE also showed high antioxidant activity, reaching to 87% of free radical scavenging using 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 59% using 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). Additionally, in vitro penetration studies were performed using two vehicles, i.e., a hydrogel and an emulsion containing FEE. These studies showed that the active ingredients contained in FEE penetrate through human skin and accumulate in it. The obtained results indicate that E. angustifolium may be an interesting plant material to be applied as a component of cosmetic and dermatological preparations with antiaging and anti-inflammatory properties.

In this work the studies on the antioxidative properties of extracts from various morphotic parts of the ground elder (leaves, rhizomes, seeds and flowers) were presented. Moreover, the effect of different extraction methods (ultrasonic assisted extractions, extraction in a Soxhlet apparatus, extraction at the boiling point of the solvent used), solvent and its amount, and extraction time on the antioxidative properties of the obtained extracts were tested. The studies showed that all parts of ground elder can show radical scavenging activity, and it depends mainly on the method of extraction and extraction time. But the most beneficial is ultrasonic assisted extraction which used lower amount of solvent (ethanol). In case of all parts of the ground elder (leaves, rhizomes, seeds and flowers) it allows to obtain very high values of the antioxidant capacity (above 90%) for very short extraction time amounted to 20–40 minutes.

Sensing of viral particles and elements that initiate mechanisms of immune response is an intrinsic ability of mammalian cells. Regulatory cytokines and antiviral mediators are released after triggering of complex signaling cascades in response to interaction of pathogen particles with pattern recognition receptors (PRRs) leading to the production of interferons (IFN) and proinflammatory cytokines. Viral RNA in the cytoplasm constitute a potent danger molecule that recognition is performed by RIG-I-like receptors, the most common group of receptors in mammalian cells, capable to recognize a foreign RNA. It is known that the E3 ubiquitin ligase Pellino3 plays an important role in antibacterial and antiviral response, but its involvement in the RLR pathways remains poorly understood. In this study, we investigate the molecular mechanisms of the innate immune response in BMDMs (immortalized macrophages from mouse bone marrow) during VSV infection. Here, we present evidence that the activation of the RIG-I/Pellino3/ERK1/2 pathway in BMDMs is crucial for the protection against VSV. We demonstrate that during infection, viral particles replicate in Pellino3 knockout BMDMs more effectively than in wild-type cells. Increased viral replication resulting in cell lysis and death is aid by impaired synthesis of IFN-I and inflammatory cytokines as a consequence of disturbances in the ERK1/2 pathway regulation.

Activation of TLR7 by small imidazoquinoline molecules such as R848 or R837 initiates signaling cascades leading to the activation of transcription factors, such as AP-1, NF-&kappa, B, and interferon regulatory factors (IRFs) and afterward to the induction of cytokines and anti-viral Type I IFNs. In general, TLRs mediate these effects by utilizing different intracellular signaling molecules, one of them is Mal. Mal is a protein closely related to the antibacterial response, and its role in the TLR7 pathways remains poorly understood. In this study, we show that Mal determines the expression and secretion of IFN&beta, following activation of TLR7, a receptor that recognizes ssRNA and imidazoquinolines. Moreover, we observed that R848 induces Mal-dependent IFN&beta, production via ERK1/2 activation as well as the transcription factor IRF7 activation. Although activation of TLR7 leads to NF-&kappa, B-dependent expression of IRF7, this process is independent of Mal. We also demonstrate that secretion of IFN&beta, regulated by TLR7 and Mal in macrophages and dendritic cells leads to the IP-10 chemokine expression. In conclusion, our data demonstrate that Mal is a critical regulator of the imidazoquinolinones-dependent IFN&beta, production via ERK1/2/IRF7 signaling cascade which brings us closer to understanding the molecular mechanism&rsquo, s regulation of innate immune response.

The main focus of this work is to extend the knowledge about the complexity of issues of oxidative stress. Natural compounds play a serious role in multiple aspects of both human, leading to clear health-promoting effects. This work is focused on the potential application cosmetic formulations containing including but not limited to of clove water and isolated clove oils on their aid in the control of the diseases. The aim of our work was to prepare to evaluate cosmetic formulations containing clove oil, eugenol or new eugenol ester derivative (eugenyl dichloroacetate - EDChA) but also cosmetic formulations containing the aqueous phase obtained after separation of essential oil following the clove buds steam distillation. To evaluate the antioxidants transdermal delivery system, in vitro permeation experiments in a Franz diffusion cell were performed using pig skin. The antioxidative capacity of the cosmetic formulations obtained was determined by the DPPH free radical reduction method. In the next stage, the antioxidant activity (DPPH, ABTS, and Folin–Ciocalteu methods) of the fluid that penetrated through pig skin and of the fluid obtained after skin extraction, were also evaluated. For comparison, studies of cosmetic formulation containing alone dichloroacetic acid (DChAA) were as well carried out. The obtained cosmetic formulations were characterized by of antioxidant activity estimated after 24 hours of conducting the experiment, which indicates long-term protection against reactive oxygen species (ROS) in the deeper layers of the skin. The results of this work contribute to the development of cosmetic formulations with antioxidant potential, emphasizing that the water phases are waste from the process of cloves steam distillation and are not used to prepare cosmetic formulations. The use of waste water from the clove buds steam distillation process is environmentally friendly and not allows us to waste, containing however valuable biologically active compounds (furfural, methyl salicylate, 4-allilofenol, eugenol, α- and β-caryophyllene, eugenyl acetate, β-caryophyllene oxide). Together, these results suggest that cosmetic formulations may be potential drug candidates for chemopreventive, antineoplastic and antimutagenic therapy.

A new method of the oxidation of natural limonene, obtained from waste orange peels, using relatively inexpensive MoO2-containing activated carbon catalysts is presented. The contents of molybdenum in the catalysts were equal to 0.68, 1.32, and 2.64 wt%, and these new materials were investigated using various instrumental methods (ICP-AES, XRD, SEM, and GC), as well as liquid nitrogen sorption. The oxidation of limonene was performed separately with H2O2 and t-butyl hydroperoxide (TBHP) as the oxidants under the following conditions: temperature of 70 °C, molar ratio of limonene/oxidant = 1:2, methanol concentration 95 wt%, catalyst content 2.45 wt%, and reaction times of 0.5–72 h. All catalysts were active in the oxidation of limonene. With H2O2 as the oxidant, carveol (selectivity of 42–65 mol%) and perillyl alcohol (selectivity of 10–30 mol%) were the main products of the limonene oxidation, and carvone and 1,2-epoxylimonene diol were by-products. For the oxidations with TBHP, the conversion of limonene was lower than with hydrogen peroxide. This new environmentally friendly method allows for the transformation of organic waste material into industrially important value-added products.

The paper presents the oxidation of natural limonene (extracted from waste orange peels) by 60 wt% hydrogen peroxide, in the presence of Ti-MCM-41 catalyst and in methanol as the solvent. The aim of the research was to develop the most favorable technological parameters for the process of limonene oxidation (temperature, molar ratio of limonene to hydrogen peroxide, methanol concentration, Ti-MCM-41 catalyst content and reaction time) by analyzing changes in the main functions describing this process: the conversion of limonene, selectivities of appropriate products, the conversion of hydrogen peroxide and the effective conversion of hydrogen peroxide. The process is environmentally friendly process and it uses renewable raw material - limonene and a safe oxidant -hydrogen peroxide. During the study, very valuable oxygenated derivatives of limonene were obtained: 1,2-epoxylimonene, its diol, carvone, carveol, and perillyl alcohol. These compounds are used in medicine, cosmetics, perfumery, food and polymers industries.

The waste from industrial fruits processing is utilized for the extraction of limonene, a renewable terpene biomass compound obtained from orange peels. This was followed by limonene oxidation, which produces highly useful oxygenated derivatives (carveol, and perillyl alcohol, 1,2-epoxylimonene and its diol). New catalysts were obtained by treating relatively inexpensive commercially available EuroPh and FPV activated carbons with plasma. These catalysts were characterized by the following instrumental methods XRD, sorption of N 2 and CO 2 , SEM, EDS, TEM, XPS, and Raman spectroscopy. The activities of the plasma-treated catalysts were measured in the oxidation of limonene by means of either hydrogen peroxide or t-butyl hydroperoxide as the oxidizing agents. During the oxidation with hydrogen peroxide the new plasma-treated catalysts were more active than their untreated counterparts. This effect was noticeable in the considerable increase in the conversion of limonene. The mechanism explaining this property is proposed, and it takes into account the role of the appropriate functional groups on the surface of the catalysts. This work has shown for the first time that the commercial EuroPh and FPV activated carbons, after having been treated by plasma, are active catalysts for the selective limonene oxidation for the production of value-added industrial products.

In this work the application of Ti-SBA-16 catalysts for eugenol isomerization is described for the first time. These materials were produced by the impregnation method using titanium(IV) chloride acetone solutions. The Ti-SBA-16 catalysts were characterized by means of the following instrumental methods: N2 adsorption at 77 K, XRD, UV, SEM, X-ray microanalysis, and sorption studies. Ti-SBA-16 is a stable material and it has been shown that no deterioration of the catalyst will occur during the reaction and thus the liquid environment will not be contaminated. It was shown that catalysts with the highest titanium content were more active in the eugenol isomerization process. The highest activity, with regards to the eugenol conversion, was for the Ti-SBA-16 catalyst containing 22.28 wt% of titanium. In addition, we present non-solvent heterogeneous catalysis for this process under atmospheric pressure. The main products of the isomerization reaction were cis- and trans-isoeugenol, while the latter isomer had the higher selectivity.

Epilobium angustifolium L. is applied as an antiseptic agent in the treatment of skin diseases. However, there is a lack of information on human skin penetration of active ingredients with antioxidative potential. It seems crucial because bacterial infections of skin and subcutaneous tissue are common and partly depend on oxidative stress. Therefore, we evaluated in vitro human skin penetration of fireweed ethanol-water extracts (FEEs) by determining antioxidant activity of these extracts before and after penetration study using 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2&rsquo, azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), and Folin&ndash, Ciocalteu methods. Microbiological tests of extracts were done. The qualitative and quantitative evaluation was performed using gas chromatography-mass spectrometry (GC-MS) and high-performance liquid chromatography (HPLC-UV) methods. The in vitro human skin penetration using the Franz diffusion chamber was assessed. The high antioxidant activity of FEEs was found. Gallic acid (GA), chlorogenic acid (ChA), 3,4-dihydroxybenzoic acid (3,4-DHB), 4-hydroxybenzoic acid (4-HB), and caffeic acid (CA) were identified in the extracts. The antibacterial activities were found against Serratia lutea, S. marcescens, Bacillus subtilis, B. pseudomycoides, and B. thuringiensis and next Enterococcus faecalis, E. faecium, Streptococcus pneumoniae, Pseudomonas aeruginosa, and P. fluorescens strains. In vitro penetration studies showed the penetration of some phenolic acids and their accumulation in the skin. Our results confirm the importance of skin penetration studies to guarantee the efficacy of formulations containing E. angustifolium extracts.

Iron/nanoporous carbon catalysts (Fe/NPC) were used in the studies on limonene oxidation employing methanol as a solvent and aqueous hydrogen peroxide as an oxidizing agent. The nanoporous carbon support of the catalyst was produced from molasses, a sugar refinery waste product. To the best of our knowledge, there are no reports on the preparation of nanoporous carbon from molasses. The content of iron in the Fe/NPC catalysts studied included 0.68, 1.32 and 2.64 wt% Fe. The products of the limonene oxidation process were 1,2-epoxylimonene and its diol, carveol and perillyl alcohol, which are compounds with a large number of applications. The conversion of limonene reached 60 mol%. The “pure” NPC material was also active in the oxidation process. The utilized catalytic system is simple and cheap, and the use of environmentally-friendly H2O2 and the natural product limonene signify that this process can be considered as a “green process”. The results of the current research indicate that the utilization of molasses for the preparation of the carbonaceous catalysts active in the limonene oxidation is feasible, and these catalysts could be used in numerous industrial oxidation processes.

The Ti-SBA-15 catalyst, which was prepared according to the literature by the hydrothermal method, was used in the isomerization of α-pinene to: camphene and limonene. In this work, the influence of: Ti-SBA-15 catalyst content (5–15 wt%), temperature (80–140 °C), and reaction time (5–48 h) was studied. The most beneficial conditions were determined on the basis of the following functions: the conversion of α-pinene, and the selectivities of camphene and limonene. The most beneficial conditions were taken as: the temperature of 140 °C, the reaction time 48 h and the amount of the catalyst 15 wt%. Under these conditions, the conversion of α-pinene amounted to 60 mol%, and the selectivities of camphene and limonene amounted to 51 and 19 mol%, respectively.

The studies on the oxidation of limonene with 60 wt% hydrogen peroxide over the titanium silicalite TS-1 catalyst were carried out. The influence of the following parameters was examined: the temperature 0–120 °C, the molar ratio of limonene/H2O2 = 1:2–5:1, methanol concentration 60–95 wt%, TS-1 content 0.25–8 wt% and the reaction time 15 min to 11 days. The studies showed that the most beneficial conditions for the obtaining of high selectivity of 1,2-epoxylimonene, at simultaneously high values of the conversion of reactants and the efficiency of hydrogen peroxide, are as follows: the temperature 80 °C, the molar ratio of limonene/H2O2 = 1:1, the methanol concentration 80 wt%, the TS-1 content 3 wt% and the reaction time 10 days. Moreover, the research showed that the process of limonene oxidation is very complicated, because during this process also other very useful oxygenated derivatives of limonene can be obtained, for example: perillyl alcohol, carveol, carvone and 1,2-epoxylimonene diol. The studies on the reuse of the TS-1 catalyst showed that it is very stable catalyst at the studied conditions and it can be recycled to the oxidation process at least three times.

This work presents the studies on the optimization the process of allyl alcohol epoxidation over the Ti-SBA-15 catalyst. The optimization was carried out in an aqueous medium, wherein water was introduced into the reaction medium with an oxidizing agent (30 wt% aqueous solution of hydrogen peroxide) and it was formed in the reaction medium during the processes. The main investigated technological parameters were: the temperature, the molar ratio of allyl alcohol/hydrogen peroxide, the catalyst content and the reaction time. The main functions the process were: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, the selectivity of transformation to diglycidyl ether in relation to allyl alcohol consumed, the conversion of allyl alcohol and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The analysis of the layer drawings showed that in water solution it is best to conduct allyl alcohol epoxidation in direction of glycidol (selectivity of glycidol 54 mol%) at: the temperature of 10–17°C, the molar ratio of reactants 0.5–1.9, the catalyst content 2.9–4.0 wt%, the reaction time 2.7–3.0 h and in direction of diglycidyl ether (selectivity of diglycidyl ether 16 mol%) at: the temperature of 18–33°C, the molar ratio of reactants 0.9–1.65, the catalyst content 2.0–3.4 wt%, the reaction time 1.7–2.6 h. The presented method allows to obtain two very valuable intermediates for the organic industry.

This work presents the studies on the oxidation of limonene with hydrogen peroxide and tert-butyl hydroperoxide (TBHP) in the presence of : TS-2, Ti-Beta, Ti-MCM-41 and Ti-MWW catalysts, at the autogenic pressure and atmospheric pressure. The examination were performed at the following conditions: the temperature of 140°C (studies in the autoclave) and 80°C (studies in glass reactor), the molar ratio of limonene/oxidant (H2O2 or WNTB) = 1:1, the methanol concentration 80 wt%, the catalyst content 3 wt%, the reaction time 3 h and the intensity of stirring 500 rpm. The analysis of the results showed that in process not only 1,2-epoxylimonene was formed but also: 1,2-epoxylimonene diol, carveol, carvone and perillyl alcohol but for 1,2-epoxylimonene obtaining the better method was the method at the autogenic pressure and in the presence of TBHP.

Fe-carbon nanoreactors were prepared by the impregnation of carbon cages with iron nitrate. Carbon cages were obtained using molasses as a carbon precursor and silica spheres as a template. The porous structure of the carbon cages allows for uniform dispersion of Fe. Fe concentration was equal to 0.68, 1.32, and 2.64 wt% as Fe3O4. Obtained materials were characterized by nitrogen adsorption at 77 K, X-ray powder diffraction (XRD), and scanning electron microscope (SEM) method. Fe-carbon nanoreactors were very active in limonene oxidation. Fe-carbon nanoreactors were used as a catalyst in limonene oxidation by t-butyl hydroperoxide.

Adenosine induces expression of the tyrosine hydroxylase (TH) gene in PC12 cells. However, it is suggested that atrial natriuretic peptide (ANP) inhibits expression of this gene. Using real-time PCR and luciferase reporter assays we found that ANP significantly decreases the adenosine-induced transcription of the TH gene. Results of measurements of cyclic nucleotide concentrations indicated that ANP-induced accumulation of cGMP inhibits the adenosine-induced increase in cAMP level. Using selective phosphodiesterase 2 (PDE2) inhibitors and a synthetic cGMP analog activating PDE2, we found that PDE2 is involved in coupling the ANP-triggered signal to the cAMP metabolism. We have established that ANP-induced elevated levels of cGMP as well as cGMP analog stimulate hydrolytic activity of PDE2, leading to inhibition of adenosine-induced transcription of the TH gene. We conclude that ANP mediates negative regulation of TH gene expression via stimulation of PDE2-dependent cAMP breakdown in PC12 cells.

The synthesis of Ti-MCM-41 catalyst was performed. The obtained catalyst was characterized by the following instrumental methods: UV-vis, IR spectroscopy, XRD, and X-ray microanalysis. The activity of the obtained catalyst was tested in the process of allyl alcohol epoxidation with 30 wt.% hydrogen peroxide in methanol as a solvent and under atmospheric pressure. In the next stage, recovery of Ti-MCM-41 catalyst from the post-reaction mixture and its regeneration by washing with appropriate solvents and drying were conducted. In the case of total loss of the activity of the catalyst, calcination of the catalyst was also carried out. The loss of titanium from the structure of Ti-MCM-41 catalyst and a partial collapsing of the structure of this catalyst can be the main reason of the decrease the activity of the catalyst what was manly visible in the decrease of the values of two functions of this process: the allyl alcohol conversion and conversion of hydrogen peroxide to organic compounds.

The work presents the studies on the epoxidation of allyl-glycidyl ether (AGE) to digly‐ cidyl ether (DGE) over the mesoporous Ti-SBA-15 catalyst and with 60 wt% hydrogen peroxide. The influence of the following parameters was studied: the temperature 0– 100°C, the molar ratio of AGE/H2O2 = 0.03:1 – 4:1, the content of Ti-SBA-15 catalyst 0.0–0.5 wt%, and the reaction time 15–240 min. The studies showed that it is possible to obtain DGE with the selectivity of 100 mol% (for reaction time below 60 min) but at low conver‐ sion of AGE – about 4 mol%. The prolongation of the reaction time decreases the selectiv‐ ity of DGE because the following competitive reactions take place: (1) hydration of the epoxide ring in AGE and 3A12PD formation, (2) collapsing of the ethers by hydrolysis of the ether groups, and (3) the epoxidation and the hydration of the products of collapsing and obtaining glycerol. The explanation of the very high ineffective decomposition of hy‐ drogen peroxide and possible ways of increasing its efficiency of conversion are also pre‐ sented.

PDE3 is a dual-substrate phosphodiesterase responsible for hydrolyzing both cAMP and cGMP whilst being simultaneously inhibited by cGMP. This feature is related to presence of the 44 amino acid insert in the catalytic domain, which determines the mechanism of introduction of the cyclic nucleotide into the catalytic pocket of the enzyme. Once bound in the catalytic site cGMP results in steric hindrance for cAMP to enter the site. The regulatory domain of PDE3 consists of two hydrophobic regions: NHR1 and NHR2. Their presence defines the enzyme’s intracellular localization, thus determining its participation in particular signaling cascades. Due to the properties of PDE3 this enzyme has exceptional importance for the cross-talk between cAMP-dependent signaling and other cascades. There are two different mechanisms of action of PDE3 enzymes in cell signaling pathways. In many signaling cascades assembly of a signalosome is necessary for phosphorylation and activation of the PDE3 proteins. In response to certain hormones and growth factors, PDE3 merges the metabolism of cAMP with protein kinase-dependent signaling pathways. PDE3 also controls the level of cAMP with regard to the alternating concentration of cGMP. This effect occurs in signaling cascades activated by natriuretic peptide.

Ti-SBA-15, one of the latest titanium silicalite catalysts, has been prepared according to the literature by the direct hydrothermal synthesis using Pluronic 123 as structure-directing agent. The characterization of the catalyst was performed by means of the following methods: XRD, IR, UV–Vis, X-ray microanalysis and SEM. The catalytic properties of the Ti-SBA-15 catalyst have been tested in the epoxidation of allyl alcohol, methallyl alcohol, crotyl alcohol and 1-butene-3-ol with hydrogen peroxide. The process has been described by the following main functions: the selectivity to epoxide compound in relation to allylic compound consumed and the conversion of allylic compound.

This work presents the results of phenol hydroxylation with hydrogen peroxide over the Ti-MWW catalyst. The studies were carried out under autogenic pressure and in the presence of acetonitrile as a solvent. The influence of the following technological parameters on the course of hydroxylation was examined: the temperature in the range of 100-150 °C, the molar ratio of phenol/H

Research studies on the epoxidation of allyl alcohol, methallyl alcohol, crotyl alcohol and 1-butene-3-ol over the titanosilicate catalysts—Ti-SBA-15 have been conducted. The studies were carried out in an acetonitrile medium and in water. However, water was introduced only with an oxidizing agent, which was a 30 wt% aqueous solution of hydrogen peroxide. When investigating the influence of chosen technological parameters, the most favorable conditions for conducting epoxidation for each of the allylic alcohols, both in the acetonitrile medium and in water, were determined. The obtained results were compared. The comparison showed that water may be a good solvent for the epoxidation of allylic alcohols. The phenomenon of epoxy ring hydration can be limited by choosing appropriate reaction conditions, when the reaction is performed only in an aqueous medium.

The catalysts in the form of an activated carbon EuroPh supported Fe were prepared and characterized structurally and chemically by XRD, nitrogen sorption, FESEM, EDX, and ICP-AES methods. The active phase was magnetite Fe 3 O 4 . The concentration of Fe in the catalysts was equal to 0.68, 1.32, 2.64 wt%. The catalytic activity of the obtained catalysts was examined in limonene oxidation with hydrogen peroxide and tert -butyl hydroperoxide as oxidants. The studies were carried out in a batch reactor. The catalytic activity of the recovered catalysts was also tested. The research showed that all from the studied catalysts were active in the limonene oxidation. As a result of limonene oxidation the following products were mainly obtained: 1,2-epoxylimonene diol, carveol, carvone and perillyl alcohol – products with a great importance. The reused catalysts were characterized by considerably lover activity in the limonene oxidation than in the first run, especially when the oxidation was performed with t -butyl hydroperoxide.