Organosulfur Materials with High Photo- and Photo-Oxidation Stability: 10-Anthryl Sulfoxides and Sulfones and Their Photophysical Properties Dependent on the Sulfur Oxidation State.

While few studies show only symmetrical and poorly mono-SOn (n = 0-2) substituted acenes, in this study, we present a synthesis of a new group of unsymmetrical, significantly substituted derivatives, which revealed unique photophysical properties. Both sulfides (S), sulfoxides (SO) and sulfones (SO2) showed very high photochemical stabilities, unusual for these groups, during UV-irradiation at 254/365 nm (air O2 and Ar), which was higher than any found in the literature. For the (S)/(SO) series (254 nm), the stabilities of 80-519 min. (air O2 and Ar) were found. At 365 nm, stabilities of 124-812 min./(air O2) for (S)/(SO) and higher for (SO2) were observed. Photoluminescence lifetimes of (SOn) of the lower anthryl symmetry remained in the following order: (SO2) < (S) < (SO); those with full symmetry were in the following order: (S) < (SO) < (SO2). The enhanced photostability was explained with DFT/MS/Hammett's constants, which showed the leading role of the SOn groups in stabilization of HOMO/LUMO frontier orbitals. The SOn (n = 0-2) substituted acenes turned out to be tunable violet/blue/green emitters by oxidation of S atoms and the introduction of rich substitution.

Egg quality depending on the diet with different sources of protein and age of the hens.

Due to the planned limitations in the use of genetically modified soybean meal, the search for alternative sources of protein in animal nutrition is ongoing, which also supports the consumers' expectations of good quality products, such as eggs. The aim of the study was to assess and compare morphological traits of eggs, fatty acid composition in yolk lipids, and the content and activity of lysozyme in thick and thin albumen in eggs from hens fed a diet based on legume seeds as a substitute for soybean meal depending on the hens age. Analyses were carried out for 300 eggs on dates I-V (19-39 weeks age of hens), obtained from Rosa 1 hens managed in the semi-intensive system. Quality analysis was performed for 30 eggs from each group at a time. The control group of hens (A) was fed a diet based on soybean meal (SBM) and the treatment group (B) was fed a diet based on seeds from narrow-leaved lupin (Boruta), yellow lupin (Mister), and pea (Muza). Eggs were analysed for morphological traits (egg weight, the weight and density of egg components, egg shape index and egg surface area), parameters of albumen (height, Haugh units), yolk colour (La Roche, colorimetry in the CIE Lab system), lysozyme content and activity in albumen, and fatty acids composition in yolk lipids. In group B the egg shape index was higher (p = 0.002), and the eggshell colour index was lower (p = 0.007), as well as the height of thick albumen, Haugh score, and yolk colour (La Roche) were higher in group B (p < 0.05), while redness of yolk was significantly lower (p < 0.001) than in group A. Lower content of C15:0 and C18:1n9 and higher content of C18:2n6 and C18:3n3, (p < 0.05), as well as lower content of MUFA and OMEGA 9, but higher content of PUFA, OMEGA 3, OMEGA 6, PUFA/SFA, OMEGA 9/6 and OMEGA 9/3 were found in group B compared to group A (p < 0.05). There were significant differences in traits between age of hens (p < 0.05). Egg weight, yolk weight and its proportion in egg, as well as shell weight, its strength and thickness increased with the age of hens (p < 0.05). The content of lysozyme and its activity were also higher in eggs from older hens (p < 0.05). Fatty acids composition was beneficial at the beginning and end of the analysed egg production period. The proposed feed mixture based on legume seeds had no negative effect on the quality of eggs, and had a positive effect on yolk colour, the quality of albumen. There was no detrimental effect of diet and age of hens on fatty acid composition of eggs from both groups throughout the study period. To sum up, diet with legume seeds could be accepted as a substitute for soybean meal, due to the beneficial effects for some mentioned traits of eggs. Use of legumes could give a partial self-sufficient for producers from small farms, where is not possible to produce soybean meal. At the same time, the level of anti-nutrients in legumes should be considered.

Effects of legume-diet and sex of ducks on the growth performance, physicochemical traits of meat and fatty acid composition in fat.

Duck meat enjoys growing popularity among consumers. Alternative protein sources to soybean are being investigated to eliminate genetically modified components from the poultry' diet. The aim of this study was to compare growth performance, quality of meat, and fatty acid composition in subcutaneous and abdominal fat from ducks fed a diet based on yellow lupin and rapeseed meal, sources of protein alternative to soybean meal (SBM). Ducks were allocated to different dietary treatment groups and reared for 8 weeks (N = 102 per group). Group A received a diet based on SBM, while group B was fed a diet based on yellow lupin with the addition of rapeseed meal. Both groups were divided into two subgroups, of male and female birds. Growth performance parameters and zoometric traits of ducks were monitored during the growth period. After 8 weeks selected birds were slaughtered and dissected (N = 10 per group). Carcass composition was calculated and selected traits of meat quality important for further processing were analysed. Subcutaneous and abdominal fat were collected to analyse fatty acid composition. The alternative diet had no negative effect on ducks' growth performance parameters and dressing percentage. The replacement of SBM with yellow lupin and rapeseed meal increased n-3 fatty acid content, which is important for consumers. In conclusion, SBM can be replaced with feed containing 60.10% of yellow lupin and 14.00% of rapeseed meal in concentrate. These sources of protein are mainly recommended for small poultry farms, which do not always have access to SBM and prepare poultry feed from their own crops.

Quality of Eggs, Concentration of Lysozyme in Albumen, and Fatty Acids in Yolk in Relation to Blue Lupin-Rich Diet and Production Cycle.

In recent years, the interest in lupin seeds as a source of protein in poultry nutrition has increased. The aim of this study was to assess the quality of table eggs produced by hens that were fed diets containing pea seeds and various levels of narrow-leafed lupin as a substitute for soybean meal. The share of lupin seeds in the treatment groups was 10%, 15%, 20% and 25%. Egg morphology, the fatty acid profile in egg yolk and the amount and activity of lysozyme in egg white were analysed. Results show that using 10-20% lupin seeds in feed in the diet of laying hens in intensive farming does not result in a change in weight or egg structure, their physical properties or their morphological composition. Increasing the share of lupin seeds in feed for laying hens increases the saturation of the colour of egg yolks, which is a desirable feature among consumers. The use of lupin seeds in feed for laying hens does not adversely affect the chemical properties of egg proteins, as expressed by the amount and activity of lysozyme. In feed for laying hens, replacing soybean meal with lupin seeds has a positive effect on the fatty acid profile in egg yolk (omega-3 and -6 polyunsaturated acids and hypocholesterolemic acids).

Ultrasound-assisted synthesis of RO- and RS-substituted (hetero)acenes via oxo- and thio-Friedel-Crafts/Bradsher reactions.

Two heteroatom-variants of the Friedel-Crafts/Bradsher cyclization of o-acetalaryl(aryl)methyl ethers and o-dithioacetalaryl(aryl)methyl thioethers, have been realized with the ultrasound assistance. The environmentally friendly "oxo-variant" (Oxo-F-C/B), proceeding in a medium containing mineral acid and a large amount of water (HClaq/CH3CN) led to a very efficient formation of RO-substituted (hetero)acenes in less than 5 min. In the "thio-variant" (Thio-F-C/B), o-dithioacetalaryl(aryl)methyl thioethers underwent ultrasound-assisted cyclization in nonaqueous medium (FeCl3/KI/EtOH) in less than 25 min., in lower yields than in the "oxygen variant" to give RS-substituted (hetero)acenes. The RO-(hetero)acenes cyclized at 25-60 °C in aqueous media but did not cyclize in organic solvents while the RS-(hetero)acenes required higher temperatures 55-60 °C and cyclized in organic solvents but did not react in aqueous media. The acceleration of the ultrasound-assisted reactions compared to the reactions carried out under silent conditions exceeded 7500 times in the most effective example of the oxo-variant and on average 2 times for the thio-variant. The plausible reaction mechanisms under ultrasound and silent conditions have been proposed. The ultrasonic mechanism involves disturbing of solvation layers and formation of the reactive ("naked") carbocations upon operation of the shock wave produced by the bubble collapse. The o-acetalaryl(aryl)methyl ethers underwent a selective ultrasound-assisted deacetalization to give o-formylaryl(aryl)methyl ethers, without subsequent cyclization under the acidic reaction conditions.

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel-Crafts/Bradsher Cyclization Reaction.

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (Tdecomp. =331-354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60-70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel-Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S1 state by molecular oxygen.

A selective removal of the secondary hydroxy group from ortho-dithioacetal-substituted diarylmethanols.

We present a successful deoxygenation reaction of ortho-1,3-dithianylaryl(aryl)methanols which enables a selective removal of the secondary hydroxy group in presence of the 1,3-dithianyl moiety under reductive conditions. This reaction proceeds well with ZnI2/Na(CN)BH3 in dichloroethane or benzene for both unsubstituted and substituted aryls (by electron-rich groups). This is leading to formyl-protected diarylmethanes with potential application in the synthesis of new pharmaceuticals and optoelectronic materials. This synthetic approach gives an access to a wide variety of functionalized ortho-1,3-dithianylaryl(aryl)methanes in 26-95% yields and is recommended for the substrates containing sulfur atoms, for which transition metal-induced reactions fail.

Ultrasound assisted Bradsher reaction in aqueous and non-aqueous media: First use of ultrasounds in electrophilic aromatic cyclisation leading to polyacenes.

The present work describes the first use of ultrasounds in the Bradsher cyclisation of activated and non-activated ortho-formyl diarylmethanes. This reaction is also the first example of electrophilic, aromatic cyclisation assisted by ultrasounds which leads to pure polycyclic, fused aromatic hydrocarbons containing 3 and 4 fused rings in excellent yields. The reaction proceeds not only in aqueous but also in non-aqueous media at milder conditions (room temperature) and in much shorter reaction times than in conventional protocols.

Is there a decline in cognitive functions after combined electroconvulsive therapy and antipsychotic therapy in treatment-refractory schizophrenia?

An analysis of literature shows that there is still little evidence concerning the efficacy of electroconvulsive therapy (ECT) combined with antipsychotic therapy in a group of treatment-resistant schizophrenia patients. More precisely, its influence on cognitive functions is still equivocal. The aim of this study was to assess the influence of ECT combined with antipsychotic therapy on working memory, attention, and executive functions in a group of treatment-refractory schizophrenia patients. Twenty-seven patients completed the study: 14 men and 13 women, aged 21 to 55 years (mean age, 32.8 years), diagnosed with treatment-resistant schizophrenia. Each patient underwent a course of ECT sessions and was treated with antipsychotic medications. Before the ECT and within 3 days after the last ECT session, the participants were assessed with the following neuropsychological tests: Trail Making Test (TMT) and Wisconsin Cart Sorting Test (WCST). There were no significant differences in the TMT and WCST results after combined ECT and antipsychotic therapy in treatment-refractory schizophrenia patients. According to the results of the neuropsychological tests, there was no decline in attention, executive functions, or working memory. The current study shows no significant difference in attention, working memory, or executive functions after treatment with a combination of electroconvulsive and antipsychotic therapy. This suggests that combined electroconvulsive therapy may not have a negative influence on the neuropsychological functioning of patients with treatment resistant schizophrenia.

Augmentation of antipsychotics with electroconvulsive therapy in treatment-resistant schizophrenia patients with dominant negative symptoms: a pilot study of effectiveness.

OBJECTIVES: The aim of the study was to determine the effectiveness of the augmentation of antipsychotics (AP) with electroconvulsive therapy (ECT) in treatment-resistant schizophrenia (TRS) patients with dominant negative symptoms. METHODS: The study encompassed 34 patients aged 21-55 years, 47.1% of whom were female, who were diagnosed with TRS. Each patient underwent a course of ECT sessions combined with AP medications which had previously been found to be ineffective. Prior to ECT and within 3 days after the final ECT session, the participants were evaluated on the Positive and Negative Syndrome Scale (PANSS), the Calgary Depression Scale for Schizophrenia and the Clinical Global Impression scales. RESULTS: Augmentation of AP therapy with ECT led to a significant decrease in symptom severity in TRS patients with dominant negative symptoms, 58.8% of whom demonstrated at least a 25% decrease in the total PANSS score. The greatest reductions were observed in the general and positive PANSS subscales (mean ± SD: 11.35 ± 7.43 and 6.79 ± 5.23 patients), and the least significant in the negative symptoms subscale (5.03 ± 4.36 patients). CONCLUSION: Augmentation of AP therapy with ECT in a group of TRS patients with dominant negative symptoms induced a significant decrease in symptom severity. The greatest reductions were obtained in general and positive symptoms and the least in negative symptoms.

Effectiveness and clinical predictors of response to combined ECT and antipsychotic therapy in patients with treatment-resistant schizophrenia and dominant negative symptoms.

The effectiveness and predictors of response to electroconvulsive therapy (ECT) combined with antipsychotics (AP) in treatment-resistant schizophrenia patients with the dominance of negative symptoms (TRS-NS) have not been studied systematically so far. 29 patients aged 21-55 years diagnosed with TRS-NS underwent ECT combined with antipsychotics (ECT+AP). Prior to the ECT, the symptom profile and severity were evaluated using Positive and Negative Syndrome Scale (PANSS). Demographic and medical data was collected; ECT parameters and pharmacotherapy results were evaluated. After the combined ECT+AP therapy a significant decrease in symptom severity was found. A response to treatment was achieved by 60% of patients. The greatest reductions were obtained in general and positive PANSS subscale (median change: 11 and 7 pts.) and the smallest, but still significant, ones in negative symptoms subscale (median: 3.5 pts.). Patients who responded to ECT+AP demonstrated a significantly shorter duration of the current episode in comparison with patients who did not experience at least a 25% reduction in symptom severity (median: 4 vs. 8 months). A combination of ECT and antipsychotic therapy can provide a useful treatment option for patients with TRS-NS. The only significant predictor of response to treatment was a shorter duration of the current episode.