Size-dependent electrocatalytic reduction of nitrite at nanostructured films of hollow polyaniline spheres and polyaniline–polystyrene core–shells

Nanostructured films of the conducting polymer polyaniline (PANI) were prepared by its potentiostatic polymerization in the presence of thin polystyrene (PS) nanoparticle templates. Two sizes of PS nanoparticles were used (50 and 100 nm) and electron microscopic analysis showed that core–shell composite films of PANI (PANI–PS₅₀ and PANI–PS₁₀₀) and, following removal of the PS, hollow structures (PANI₅₀ and PANI₁₀₀) were formed due to the growth mechanism of PANI around the PS templates. The electrochemical behaviour of the PANI-modified electrodes was studied by cyclic voltammetry, chronocoulometry and amperometry in the presence of nitrite and it was found that nitrite reduction was enhanced by the nanostructuring of the films. The electrocatalysis was dependent on the size of the template, being more pronounced at 50 nm than at 100 nm. The hollow PANI₅₀ film was also a better catalyst than PANI–PS₅₀, whereas for structures based on 100 nm templates, the composite film was better. Such behaviour could be explained in terms of larger surface area and surface concentration of PANI₅₀ and PANI–PS₅₀ films on the electrodes and by higher differential capacitance of those films.     

Green TPUs from Prepolymer Mixtures Designed by Controlling the Chemical Structure of Flexible Segments

This study concerns green thermoplastic polyurethanes (TPU) obtained by controlling the chemical structure of flexible segments. Two types of bio-based polyether polyols—poly(trimethylene glycol)s—with average molecular weights ca. 1000 and 2700 Da were used (PO3G1000 and PO3G2700, respectively). TPUs were prepared via a two-step method. Hard segments consisted of 4,4′-diphenylmethane diisocyanates and the bio-based 1,4-butanodiol (used as a chain extender and used to control the [NCO]/[OH] molar ratio). The impacts of the structure of flexible segments, the amount of each type of prepolymer, and the [NCO]/[OH] molar ratio on the chemical structure and selected properties of the TPUs were verified. By regulating the number of flexible segments of a given type, different selected properties of TPU materials were obtained. Thermal analysis confirmed the high thermal stability of the prepared materials and revealed that TPUs based on a higher amount of prepolymer synthesized from PO3G2700 have a tendency for cold crystallization. An increase in the amount of PO3G1000 at the flexible segments caused an increase in the tensile strength and decrease in the elongation at break. Melt flow index results demonstrated that the increase in the amount of prepolymer based on PO3G1000 resulted in TPUs favorable in terms of machining.     

The Effect of Castration on Peripheral Autonomic Neurons Supplying Mammalian Male Genitourinary System

This review paper deals with the influence of androgens (testosterone) on pelvic autonomic pathways in male mammals. The vast majority of the relevant information has been gained in experiments involving castration (testosterone deprivation) performed in male rats, and recently, in male pigs. In both species, testosterone significantly affects the biology of the pathway components, including the pelvic neurons. However, there are great differences between rats and pigs in this respect. The most significant alteration is that testosterone deprivation accomplished a few days after birth results some months later in the excessive loss (approximately 90%) of pelvic and urinary bladder trigone intramural neurons in the male pig, while no changes in the number of pelvic neurons are observed in male rats (rats do not have the intramural ganglia). In the castrated pigs, much greater numbers of pelvic neurons than in the non-castrated animals express CGRP, GAL, VIP (peptides known to have neuroprotective properties), and caspase 3, suggesting that neurons die due to apoptosis triggered by androgen deprivation. In contrast, only some morpho-electrophysiological changes affecting neurons following castration are found in male rats. Certain clinicopathological consequences of testosterone deprivation for the functioning of urogenital organs are also discussed.     

Evaluation of QuEChERS method for the determination of organochlorine pesticide residues in selected groups of fruits

This paper reports a method for organochlorine pesticide determination in selected fruit species where pesticide residues were extracted and cleaned using a buffered QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, followed by GC–MS analysis. The method results showed the matrix-matched calibration curve linearity was >0.99 for all target analytes. With pesticide recovery rates (spiked at 0.008 mg kg⁻¹) ranging from 70% to 120%, and RSD values <17% for most compounds, the limit of quantification ranged from 0.001–0.013 mg kg⁻¹. Finally, the method ruggedness was further demonstrated by analysis of actual commercial fruits and baby food samples.     

Peritoneal Fluid from Patients with Ovarian Endometriosis Displays Immunosuppressive Potential and Stimulates Th2 Response

Endometriosis is a common gynaecological disorder characterized by the ectopic growth of endometrial tissue outside the uterine cavity. It is associated with chronic pelvic inflammation and autoimmune reactivity manifesting by autoantibody production and abrogated cellular immune responses. Endometriotic peritoneal fluid contains various infiltrating leucocyte populations and a bulk of proinflammatory and immunoregulatory cytokines. However, the nature and significance of the peritoneal milieu in women with endometriosis still remains obscure. Therefore, the aim of the present study was to investigate the immunoregulatory activity of the peritoneal fluid (PF) from women with endometriosis. The peritoneal fluid samples were collected during laparoscopic surgery from 30 women with and without endometriosis. Immunoregulatory cytokines (IL-2, IL-4, IL-6, IL-10, IL-17A, IFN-γ and TNF) and chemokines (CCL2, CCL5, CXCL8 and CXCL9) were evaluated in PF and culture supernatants generated by unstimulated and CD3/CD28/IL-2-stimulated CD4⁺ T cells cultured in the presence of PF. The effect of PF on the generation of Treg and Th17 cells in CD4⁺ T cell cultures, as well as the natural cytotoxic activity of peripheral blood mononuclear cells, was also investigated. Concentrations of IL-6, IL-10, CCL2, CXCL8 and CXCL9 were significantly upregulated in the PF from women with endometriosis when compared to control women, whereas concentrations of other cytokines and chemokines were unaffected. The culturing of unstimulated and CD3/CD28/IL-2-stimulated CD4⁺ T cells in the presence of endometriotic PF resulted in the downregulation of their IL-2, IFN-γ, IL-17A and TNF production as compared to culture medium alone. On the other side, endometriotic PF significantly stimulated the production of IL-4 and IL-10. Endometriotic PF also stimulated the release of CCL2 and CXCL8, whereas the production of CCL5 and CXCL9 was downregulated. Endometriotic PF stimulated the generation of Treg cells and had an inhibitory effect on the generation of Th17 cells in cultures of CD4⁺ T cells. It also inhibited the NK cell cytotoxic activity of the peripheral blood lymphocytes. These results strongly imply that the PF from patients with endometriosis has immunoregulatory/immunosuppressive activity and shifts the Th1/Th2 cytokine balance toward the Th2 response, which may account for deviation of local and systemic immune responses. However, a similar trend, albeit not a statistically significant one, was also observed in case of PF from women without endometriosis, thus suggesting that peritoneal milieu may in general display some immunoregulatory/immunosuppressive properties. It should be stressed, however, that our present observations were made on a relatively small number of PF samples and further studies are needed to reveal possible mechanism(s) responsible for this phenomenon.     

The influence of brewing method on bioactive compounds residues in spent coffee grounds of different roasting degree and geographical origin

The content of bioactive compounds in spent coffee grounds (SGC) was studied. SGC were obtained from Coffea arabica beans of different roasting degrees (light and dark) and different geographical origins (Nicaragua, Columbia and Mexico) processed using four brewing methods (mocha, filtered, drip and infusion). The highest caffeine and chlorogenic acid contents were determined in filtered spent coffee extracts. All extracts of light roasted spent coffee grounds showed lower browning index levels in comparison to that from dark roasted spent coffee grounds. Generally, the highest content of total polyphenolic compounds and highest antioxidant capacity were determined in extracts prepared in drip. In conclusion, the results obtained in this study indicate that the spent coffee grounds produced of domestic levels, especially those obtained from filter coffeemaker, could be considered as a good source of natural antioxidants.     

The Content of Polyphenolic Compounds in Cocoa Beans (Theobroma cacao L.), Depending on Variety,Growing Region,and Processing Operations: A Review

Polyphenols form the largest group of compounds among natural antioxidants, which largely affect the overall antioxidant and antifree radical activity of cocoa beans. The qualitative and quantitative composition of individual fractions of polyphenolic compounds, even within one species, is very diverse and depends on many factors, mainly on the area of cocoa trees cultivation, bean maturity, climatic conditions during growth, and the harvest season and storage time after harvest. Thermal processing of cocoa beans and cocoa derivative products at relatively high temperatures may in addition to favorable physicochemical, microbiological, and organoleptic changes result in a decrease of polyphenols concentration. Technological processing of cocoa beans negatively affects the content of polyphenolic compounds.     

Gas‐phase removal of indoor volatile organic compounds and airborne microorganisms over mono‐ and bimetal‐modified (Pt,Cu, Ag) titanium(IV) oxide nanocomposites

The photocatalytic deactivation of volatile organic compounds and mold fungi using TiO₂ modified with mono‐ and bimetallic (Pt, Cu, Ag) particles is reported in this study. The mono‐ and bimetal‐modified (Pt, Cu, Ag) titanium(IV) oxide photocatalysts were prepared by chemical reduction method and characterized using XRD, XPS, DR/UV‐Vis, BET, and TEM analysis. The effect of incident light, type and content of mono‐ and bimetallic nanoparticles deposited on titanium(IV) oxide was studied. Photocatalytic activity of as‐prepared nanocomposites was examined in the gas phase using LEDs array. High photocatalytic activity of Ag/Pt‐TiO₂ and Cu/Pt‐TiO₂ in the reaction of toluene degradation resulted from improved efficiency of interfacial charge transfer process, which was consistent with the fluorescence quenching effect revealed by photoluminescence (PL) emission spectra. The photocatalytic deactivation of Penicillium chrysogenum, a pathogenic fungi present in the indoor environment, especially in a damp or water‐damaged building using mono‐ and bimetal‐modified (Pt, Cu, Ag) titanium(IV) oxide was evaluated for the first time. TiO₂ modified with mono‐ and bimetallic NPs of Ag/Pt, Cu, and Ag deposited on TiO₂ exhibited improved fungicidal activity under LEDs illumination than pure TiO₂.