Water-dispersable photoreactors based on core-shell mesoporous silica particles.

Robust solid-core silica particles with submicrometer size and anthracene-containing mesoporous shell were obtained and studied as model water-dispersable photoreactors. An anthracene derivative containing a triethoxysilyl group was synthesized and co-condensed with tetraethoxysilane in various ratios to form a photoactive mesoporous shell with a thickness up to approximately 80 nm on previously prepared solid silica particles. Mesopores of as-synthesized particles, without a commonly applied removal of the micellar templates, offered a confined space for solubilization of hydrophobic molecules. Efficient excitation energy transfer from anthracene chromophores to both hydrophobic (perylene) and hydrophilic (fluoresceine) encapsulated acceptors was observed in an aqueous dispersion of the particles. Photosensitized oxidation of encapsulated perylene was shown to proceed efficiently in such systems serving as water-dispersable photoreactors. Importantly, the designed core-shell systems were found to be stable for a long time (at least 24 months) and robust enough, thanks to the presence of solid cores, to be handled by centrifugation in aqueous dispersions. All these features make them promising candidates for reusable systems for the photosensitized degradation of water pollutants, especially hydrophobic pollutants.

Multicomponent Synthesis of 4-Aryl-4,9-dihydro-1H-pyrazolo[3,4-b]quinolines Using L-Proline as a Catalyst-Does It Really Proceed?

Looking for effective synthetic methods for 1H-pyrazolo[3,4-b]quinolines preparation, we came across a procedure where, in a three-component reaction catalysed by L-proline, 4-aryl-4,9-dihydro-1H-pyrazolo[3,4-b]quinolines are formed. These compounds can be easily oxidised to a fully aromatic system, which gives hope for a synthetic method that could replace, e.g., Friedländer condensation, often used for this purpose, even though severely limited by the availability of suitable substrates. However, after careful repetition of the procedures described in the publication, it turned out that the compounds described therein do not form at all. The actual compounds turned out to be 4,4-(phenyl-methylene)-bis-(3-methyl-1-phenylpyrazol-5-oles). Therefore, 4-Aryl-4,9-dihydro-1H-pyrazolo[3,4-b]quinolines were prepared by another method and used as standards to compare the products formed in the original procedure.

The link between emotion comprehension and cognitive perspective taking in theory of mind (ToM): a study of preschool children.

The study examined the relation between perspective taking embedded in theory of mind (ToM) and emotion comprehension (EC) in young children. Our study involved children from Poland aged 3-6 (N = 99; 54% boys) from public and private kindergartens residing mainly in urban areas, whose parents could mostly be classified as middle class. The children were examined with the Test of Emotion Comprehension (TEC) and three tasks targeting three aspects of ToM: a first-order false belief task, an appearance-reality test, and a mental states opacity task. The results showed similarities in performances between these different measures. However, only the opacity task predicted the emotion comprehension test results (η2 = 0.13). The results indicate that the key element of ToM that explains individual differences in children's emotion comprehension is the full-blown understanding of perspective taking, namely that having access to an object under one description does not ensure access to that object under all descriptions. In the research, we took also into account the linguistic side of such specific competences as ToM and EC, which allowed us to see the role of language in scaffolding the development of children's ability to handle such socially fundamental tasks as understanding emotions and epistemic states.

1H-Pyrazolo[3,4-b]quinolines: Synthesis and Properties over 100 Years of Research.

This paper summarises a little over 100 years of research on the synthesis and the photophysical and biological properties of 1H-pyrazolo[3,4-b]quinolines that was published in the years 1911-2021. The main methods of synthesis are described, which include Friedländer condensation, synthesis from anthranilic acid derivatives, multicomponent synthesis and others. The use of this class of compounds as potential fluorescent sensors and biologically active compounds is shown. This review intends to summarize the abovementioned aspects of 1H-pyrazolo[3,4-b]quinoline chemistry. Some of the results that are presented in this publication come from the laboratories of the authors of this review.

Near-Infrared fluorescent unsymmetrical aza-BODIPYs: Synthesis, photophysics and TD-DFT calculations.

In view of the ever-growing demand for efficient NIR fluorophores for biomedical applications, we herein report the synthesis and properties of four unsymmetrical aza-BODIPYs exhibiting NIR fluorescence. Highly desirable photophysical and photochemical properties were induced in these molecules due to the presence of both strongly electron-withdrawing p-nitrophenyl rings (p-NO2Ph-) and mildly electron-donating p-methoxyphenyl rings (p-MeOPh-) within the aza-BODIPY core. In particular, upon excitation with λabs the unsymmetrical aza-BODIPYs studied exhibited NIR emission with λf ranging from 699 nm to 718 nm in toluene. The fluorescence quantum yields (Φf), depending on the substitution pattern, ranged from Φf = 0.49 to Φf = 0.22 and the fluorescence lifetimes ranged from τf = 1.90 ns to τf = 3.59 ns. Aza-BODIPY with electron-donating substituent at 3 position and electron-withdrawing substituent at 5 position was identified as cell permeable, NIR emitting fluorophore suitable for bioimaging.

Cultural Management of Terror and Worry During the COVID-19 Pandemic: How Religiosity and a Dream of Human Solidarity Help the Polish People Cope.

The COVID-19 pandemic, which involves the threat of contracting a potentially fatal disease, can be understood as a source of terror. According to terror management theory, people shield themselves from terror by adopting culturally specific worldviews and protecting self-esteem. The study investigates the protective role of worldviews that are culturally specific to Poles: religiosity and social solidarity. The hypothesis was that Poles who tend to worry, entertain these worldviews and are more likely to maintain high self-esteem and concentrate on the current moment (carpe diem), which theoretically allows them to reduce future-related anxiety. Path analysis confirmed that self-esteem, the centrality of religiosity, and expectation of solidarity due to the COVID-19 pandemic mediate the relationship between the worry trait and carpe diem.

Tuning the Surface Properties of Poly(Allylamine Hydrochloride)-Based Multilayer Films.

The layer-by-layer (LbL) method of polyelectrolyte multilayer (PEM) fabrication is extremely versatile. It allows using a pair of any oppositely charged polyelectrolytes. Nevertheless, it may be difficult to ascribe a particular physicochemical property of the resulting PEM to a structural or chemical feature of a single component. A solution to this problem is based on the application of a polycation and a polyanion obtained by proper modification of the same parent polymer. Polyelectrolyte multilayers (PEMs) were prepared using the LbL technique from hydrophilic and amphiphilic derivatives of poly(allylamine hydrochloride) (PAH). PAH derivatives were obtained by the substitution of amine groups in PAH with sulfonate, ammonium, and hydrophobic groups. The PEMs were stable in 1 M NaCl and showed three different modes of thickness growth: exponential, mixed exponential-linear, and linear. Their surfaces ranged from very hydrophilic to hydrophobic. Root mean square (RMS) roughness was very variable and depended on the PEM composition, sample environment (dry, wet), and the polymer constituting the topmost layer. Atomic force microscopy (AFM) imaging of the surfaces showed very different morphologies of PEMs, including very smooth, porous, and structured PEMs with micellar aggregates. Thus, by proper choice of PAH derivatives, surfaces with different physicochemical features (growth type, thickness, charge, wettability, roughness, surface morphology) were obtained.

Encultured minds, not error reduction minds.

There are serious theoretical problems with the free-energy principle model, which are shown in the current article. We discuss the proposed model's inability to account for culturally emergent normativities, and point out the foundational issues that we claim this inability stems from.

The Development of Understanding Opacity in Preschoolers: A Transition From a Coarse- to Fine-Grained Understanding of Beliefs.

Intensionality (or opacity) is a core property of mental representations and sometimes understanding opacity is claimed to be a part of children's theory of mind (evidenced with the false belief task). Children, however, pass the false belief task and the intensionality tasks at different ages (typically 4 vs. 5;1-6;11 years). According to two dominant interpretations, the two tests either require different conceptual resources or vary only in their executive or linguistic load. In two experiments, involving 120 children aged 3-6 (Experiment 1) and 75 children aged 4-6 (Experiment 2), we tested two variants of the executive load hypothesis: The differential linguistic complexity of the two tests, and the dual-name problem of the intensionality task. The former was addressed by standardizing and minimizing the linguistic demands of both tasks (contrasted with the typical narrative intensionality task), and the latter by introducing the dual-name problem into the false belief task as well, so that it was present in both tasks. We found that (1) two structurally different intensionality tasks shared more variance with each other than with the structurally similar false belief task, and that (2) introducing a dual label problem into the false belief task did not reduce the developmental gap. Our results speak against interpreting the difference between the time children pass the two tests entirely in terms of performative issues, and support the conceptual enrichment hypothesis. We discuss the theoretical relevance of these results, suggesting that they are best explained by fine-grained increments within the concept of belief, rather than a radical conceptual change. We conclude that understanding opacity of minds - which emerges between age 5 and 6 - is an important step toward a more advanced form of ToM.

Visible-Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza-BODIPYs: Synthesis, Photophysics and Redox Properties.

A series of novel iodinated NO2 -substituted aza-BODIPYs have been synthesized and characterized. Highly desirable photophysical and photochemical properties were induced in NO2 -substituted aza-BODIPYs by iodination of the pyrrole rings. In particular, high values of singlet oxygen quantum yields (ΦΔ ) ranging from 0.79 to 0.85 were measured. The photooxygenation process proceeds via a Type II mechanism under the experimental conditions applied. The compounds studied exhibited an absorption band within the so-called "therapeutic window", with λmax located between 645 nm to 672 nm. They were non-fluorescent at room temperature with excited singlet-state lifetimes within the picosecond range as measured by femtosecond transient absorption. Nanosecond laser flash photolysis experiments revealed T1 →Tn absorption spanning from ca. 400 nm to ca. 500 nm and allowed determination of the triplet-state lifetimes. The estimated triplet lifetimes (τT ) in deaerated acetonitrile ranged between 2.74 µs and 3.50 µs. As estimated by CV/DPV measurements, all iodinated aza-BODIPYs studied exhibited one irreversible oxidation and two quasi-reversible reductions processes. Estimation of the EHOMO gave the value of -6.06 to -6.26 eV while the ELUMO was found to be located at ca. -4.6 eV. Thermogravimetric (TGA) analysis revealed that iodinated aza-BODIPYs were stable up to approximately 300 °C. All compounds studied exhibit high photostability in toluene solution.

Photoactive Surface-Grafted Polymer Brushes with Phthalocyanine Bridging Groups as an Advanced Architecture for Light-Harvesting.

Surface-grafted polymer brushes of novel ladder-like architecture were proposed for inducing ordering of chromophores embedded therein. The brushes with acetylene side groups were obtained by surface-initiated photoiniferter-mediated polymerization. The acetylene moieties reacted then through a "click" process with an axially azide-bifunctionalized silicon phthalocyanine bridging the neighboring chains that inherently adopt extended conformations in dense brushes. FTIR, quartz crystal microbalance, and atomic force microscopy were used to study formation and structure of the photoactive brushes varying in grafting densities. Importantly, photophysical properties of the chromophores were virtually unaffected upon embedding them into the brushes, as evidenced by UV/Vis absorption and emission spectroscopy. Owing to the unique ordering of the chromophores, the proposed method may open new opportunities for the fabrication of light-harvesting systems suitable for photovoltaic or sensing applications.