Artificial Photosynthases: Single-Chain Nanoparticles with Manifold Visible-Light Photocatalytic Activity for Challenging "in Water" Organic Reactions.

Photocatalyzed reactions of organic substances in aqueous media are challenging transformations, often because of scarce solubility of substrates and catalyst deactivation. Herein, we report single-chain nanoparticles, SCNPs, capable of efficiently catalyzing four different "in water" organic reactions by employing visible light as the only external energy source. Specifically, we decorated a high-molecular-weight copolymer, poly(OEGMA300-r-AEMA), with iridium(III) cyclometalated complex pendants at varying content amounts. The isolated functionalized copolymers demonstrated self-assembly into noncovalent, amphiphilic SCNPs in water, which enabled efficient visible-light photocatalysis of two reactions unprecedentedly reported in water, namely, [2 + 2] photocycloaddition of vinyl arenes and α-arylation of N-arylamines. Additionally, aerobic oxidation of 9-substituted anthracenes and ß-sulfonylation of α-methylstyrene were successfully carried out in aqueous media. Hence, by merging metal-mediated photocatalysis and SCNPs for the fabrication of artificial photoenzyme-like nano-objects─i.e., artificial photosynthases (APS)─our work broadens the possibilities for performing challenging "in water" organic transformations via visible-light photocatalysis.

Enantiopure [6]-Azairidahelicene by Dynamic Kinetic Resolution of a Configurationally Labile [4]-Helicene.

A pair of enantiopure [6]-azairidahelicenes incorporating chirality at the metal center and on the helicenic ligand were synthesized by dynamic kinetic resolution (dkr) of a configurationally labile [4]-helicenic ligand (4-(2-pyridyl)-benzo[g]phenanthrene, L1H) using bis-cyclometalated chiral-at-metal only iridium(III) precursors as chiral inductors. The origin of the observed dkr is attributed to the different conformation and stability of diastereomeric reaction intermediates formed during the cyclometalation process. The isolated enantiomers exhibited circularly polarized phosphorescence (CPP), with |gphos| values of 1.8×10-3.

Upgrading Polyurethanes into Functional Ureas through the Asymmetric Chemical Deconstruction of Carbamates.

The importance of systematic and efficient recycling of all forms of plastic is no longer a matter for debate. Constituting the sixth most produced polymer family worldwide, polyurethanes, which are used in a broad variety of applications (buildings, electronics, adhesives, sealants, etc.), are particularly important to recycle. In this study, polyurethanes are selectively recycled to obtain high value-added molecules. It is demonstrated that depolymerization reactions performed with secondary amines selectively cleave the C-O bond of the urethane group, while primary amines unselectively break C-O and C-N bonds. The selective cleavage of C-O bonds, catalyzed by an acid:base mixture, led to the initial polyol and a functional diurea in several hours to a few minutes for both model polyurethanes and commercial polyurethane foams. Different secondary amines were employed as nucleophiles to synthesize a small library of diureas obtained in good to excellent yields. This study not only targets the recovery of the initial polyol but also aims to form new diureas which are useful building blocks for the polymerization of innovative materials.

Optimization of Ultrasound Assisted Extraction of Bioactive Compounds from Apple Pomace.

In the present work, the optimization of the extraction of antioxidant compounds from apple pomace using ultrasound technology as an environmentally friendly and intensification process was developed. Different sonication powers, extraction temperatures and extraction times were studied and their influence on extraction yield and characteristics of the extracted samples (total phenolic compounds, flavonoid content and antioxidant capacity) are presented. The elaborated experimental design and the analysis of Pareto and response surface diagrams allowed us to determine the optimal extraction conditions. The conditions that allow the maximum extraction of phenolic compounds were found at 20 min, 90 °C and 50% ultrasound amplitude. Nevertheless, at these conditions, the antioxidant capacity measured by DPPH decreased in the extracted samples.

Bicolour fluorescent molecular sensors for cations: design and experimental validation.

Molecular entities whose fluorescence spectra are different when they bind metal cations are termed bicolour fluorescent molecular sensors. The basic design criteria of this kind of compound are presented and the different fluorescent responses are discussed in terms of their chemical behaviour and electronic features. These latter elements include intramolecular charge transfer (ICT), formation of intramolecular and intermolecular excimer/exciplex complexes and Förster resonance energy transfer (FRET). Changes in the electronic properties of the fluorophore based on the decoupling between its constitutive units upon metal binding are also discussed. The possibility of generating fluorescent bicolour indicators that can capture metal cations in the gas phase and at solid-gas interfaces is also discussed.

The Role of Experience, Perceived Match Importance, and Anxiety on Cortisol Response in an Official Esports Competition.

The aim of the present study was to analyse the neuroendocrine stress response, psychological anxiety response, and perceived match importance (PMI) between expert and non-expert control gamers in an official competitive context. We analyzed, in 25 expert esports players and 20 control participants, modifications in their somatic anxiety, cognitive anxiety, self-confidence, PMI, and cortisol in a League of Legends competition. We found how expert esports players presented higher cortisol concentrations (Z = 155.5; p = 0.03; Cohen's d = -0.66), cognitive anxiety (Z = 99.5; p = 0.001), and PMI (Z = 50.5; p < 0.001) before the competition than non-experts participants. We found a greater statistical weight in the cognitive variables than in the physiological ones. The results obtained suggest that real competitive context and player's expertise were factors associated with an anticipatory stress response. The PMI proved to be a differentiating variable between both groups, highlighting the necessity to include subjective variables that contrast objective measurements.

Zinc oxide nanostructures and stearic acid as surface modifiers for flax fabrics in polylactic acid biocomposites.

Different surface treatments including mercerization, stearic acid and growth of zinc oxide nanorods as well as their combinations were exploited to address their effects on the properties of green composites based on polylactic acid (PLA) and flax fabrics. The resulting fabrics were morphologically (SEM), crystallographically (XRD) and thermally (TGA) characterized, showing no significant changes with respect to the untreated samples. In contrast, tensile and flexural properties of composites produced by compression moulding were significantly influenced. A combination of mercerization and environmentally friendly stearic acid treatment turned the character of the flax fabric from hydrophilic to hydrophobic, and led to improved bending and tensile strengths by 20% and 12%, respectively, compared to untreated composites. The presence of ZnO nanorods promoted an increase in flexural and tensile stiffness by 58% and 31%, respectively, but at the expense of strength, with reductions ascribed to the degradation of polylactic acid under high-temperature conditions favoured by ZnO, as confirmed by a reduction in the initial thermal degradation temperature up to 26%. These latter composites can be suggested in those applications where a suitable combination of flexural properties and a shorter persistence in the environment is desired.

Synthetic Conjugates of Ursodeoxycholic Acid Inhibit Cystogenesis in Experimental Models of Polycystic Liver Disease.

BACKGROUND AND AIMS: Polycystic liver diseases (PLDs) are genetic disorders characterized by progressive development of symptomatic biliary cysts. Current surgical and pharmacological approaches are ineffective, and liver transplantation represents the only curative option. Ursodeoxycholic acid (UDCA) and histone deacetylase 6 inhibitors (HDAC6is) have arisen as promising therapeutic strategies, but with partial benefits. APPROACH AND RESULTS: Here, we tested an approach based on the design, synthesis, and validation of a family of UDCA synthetic conjugates with selective HDAC6i capacity (UDCA-HDAC6i). Four UDCA-HDAC6i conjugates presented selective HDAC6i activity, UDCA-HDAC6i #1 being the most promising candidate. UDCA orientation within the UDCA-HDAC6i structure was determinant for HDAC6i activity and selectivity. Treatment of polycystic rats with UDCA-HDAC6i #1 reduced their hepatomegaly and cystogenesis, increased UDCA concentration, and inhibited HDAC6 activity in liver. In cystic cholangiocytes UDCA-HDAC6i #1 restored primary cilium length and exhibited potent antiproliferative activity. UDCA-HDAC6i #1 was actively transported into cells through BA and organic cation transporters. CONCLUSIONS: These UDCA-HDAC6i conjugates open a therapeutic avenue for PLDs.

Fluorescent Imidazo[1,2-a]pyrimidine Compounds as Biocompatible Organic Photosensitizers that Generate Singlet Oxygen: A Potential Tool for Phototheranostics.

Photodynamic therapy has been used to treat a variety of diseases, however, there is continuing search for new biocompatible photosensitizers. Herein, we demonstrate for the first time that imidazo[1,2-a]pyrimidine compounds are able to generate singlet oxygen species and can act as photosensitizers in the intracellular environment. Our results show that this class of compounds absorb and emit in the 400-500 nm region, present low cytotoxicity in the dark, are efficiently uptaken by cells, are fluorescent in intracellular medium, and generate singlet oxygen upon irradiation, killing cancer cells within 2 h at low concentration (2.0 µm). The imidazo[1,2-a]pyrimidine compounds are a potential new tool for phototheranostics, because they can be simultaneously used for fluorescence imaging and photodynamic therapy.

Fluorescent bicolour sensor for low-background neutrinoless double ß decay experiments.

Observation of the neutrinoless double ß decay is the only practical way to establish that neutrinos are their own antiparticles1. Because of the small masses of neutrinos, the lifetime of neutrinoless double ß decay is expected to be at least ten orders of magnitude greater than the typical lifetimes of natural radioactive chains, which can mimic the experimental signature of neutrinoless double ß decay2. The most robust identification of neutrinoless double ß decay requires the definition of a signature signal-such as the observation of the daughter atom in the decay-that cannot be generated by radioactive backgrounds, as well as excellent energy resolution. In particular, the neutrinoless double ß decay of 136Xe could be established by detecting the daughter atom, 136Ba2+, in its doubly ionized state3-8. Here we demonstrate an important step towards a 'barium-tagging' experiment, which identifies double ß decay through the detection of a single Ba2+ ion. We propose a fluorescent bicolour indicator as the core of a sensor that can detect single Ba2+ ions in a high-pressure xenon gas detector. In a sensor made of a monolayer of such indicators, the Ba2+ dication would be captured by one of the molecules and generate a Ba2+-coordinated species with distinct photophysical properties. The presence of such a single Ba2+-coordinated indicator would be revealed by its response to repeated interrogation with a laser system, enabling the development of a sensor able to detect single Ba2+ ions in high-pressure xenon gas detectors for barium-tagging experiments.

Effect of Carbon Nanostructures and Fatty Acid Treatment on the Mechanical and Thermal Performances of Flax/Polypropylene Composites.

Four different strategies for mitigating the highly hydrophilic nature of flax fibers were investigated with a view to increase their compatibility with apolar polypropylene. The effects of two carbon nanostructures (graphene nanoplatelets (GNPs) and carbon nanotubes (CNTs)), of a chemical modification with a fatty acid (stearic acid), and of maleated polypropylene on interfacial adhesion, mechanical properties (tensile and flexural), and thermal stability (TGA) were compared. The best performance was achieved by a synergistic combination of GNPs and maleated polypropylene, which resulted in an increase in tensile strength and modulus of 42.46% and 54.96%, respectively, compared to baseline composites. Stearation proved to be an effective strategy for increasing the compatibility with apolar matrices when performed in an ethanol solution with a 0.4 M concentration. The results demonstrate that an adequate selection of surface modification strategies leads to considerable enhancements in targeted properties.

Challenging the Top Player: A Preliminary Study on Testosterone Response to An Official Chess Tournament.

According to the Challenge Hypothesis, high levels of testosterone (T) are associated with status-seeking behaviors, especially in competitive situations. However, there have not been many studies about rivals' social status and pre-competition neuroendocrine responses. The aim of this study was to analyze whether the participants in a chess tournament showed different pre-match testosterone and cortisol levels depending on differences in ELO (i.e., the International Chess Federation rating to rank the competitive potential and social status between players). The sample was six male participants (mean ± SD) aged 25.5 ± 8.4 years with experience in official tournaments of 16.33 ± 5.72 years and an average ELO rating of 2217.67 ± 112.67. Saliva samples were collected before each round for hormonal determination when participants competed against a rival with a different ELO rating. After five competition rounds per participant, higher rival pre-competition T concentrations were shown when playing against the best-rated participant, but there were no differences in cortisol (C). The multilevel model confirmed rises in rivals' precompetitive T levels modulated by the difference in the opponent´s ELO rating. No significant changes were observed in C. The results suggest that the rival´s status can determine the opponent´s anticipatory neuroendocrine responses to an official chess tournament.

Competition Seriousness and Competition Level Modulate Testosterone and Cortisol Responses in Soccer Players.

This study aimed to analyze the modulating effect of competition seriousness and competition level in the testosterone and cortisol responses in professional soccer player. Ninety five (95) soccer players were included in this study (professional, n = 39; semiprofessional, n = 27; amateur, n = 29) before and after training, friendly game and official games. Repeated measures ANOVA showed higher testosterone levels (F(1,89) = 134, p < 0.0001, η2p = 0.75) in professional soccer players, when compared with semiprofessional (p < 0.0001) or amateur athletes (p < 0.0001). After winning a competition game an increase in testosterone levels was observed in professionals (t = -3.456, p < 0.001), semiprofessionals (t = -4.400, p < 0.0001), and amateurs (t = -2.835, p < 0.009). In contrast, this momentary hormonal fluctuation was not observed after winning a friendly game or during a regular training day. Additionally, statistical analysis indicated that cortisol levels were lower in professional (t = -3.456, p < 0.001) and semiprofessional athletes (t = -4.400, p < 0.0001) than in amateurs (t = -2.835, p < 0.009). In soccer players a rise in testosterone was only observable when the team was faced with an actual challenge but did not support a different response between categories. Thus, the desire to achieve a goal (and keep the social status) may be one of the key reasons why testosterone levels rise promptly. Conversely, testosterone did not change after friendly games, which suggests these situations are not real goals and the players do not perceive an actual threat (in terms of dominance) more than the preparation for their next competitive game.

Discovering Biomolecules with Huisgenase Activity: Designed Repeat Proteins as Biocatalysts for (3 + 2) Cycloadditions.

Designed repeat proteins catalyze the 1,3-dipolar reaction between an imine and a π-deficient dipolarophile in THF solution to form unnatural nitroproline esters, a reaction that no enzyme can catalyze. NMR studies and mutation experiments show that both acidic and basic residues can catalyze the reaction. The diastereocontrol of the reaction depends on the flexibility of the protein and on the number and location of the active lysine and glutamate residues, which can participate independently or forming dyads that promote the formation of unusual diastereomeric cycloadducts. QM/MM calculations permit one to rationalize the origins of this Huisgenase activity and of its diastereocontrol.

Differences in Psychoneuroendocrine Stress Responses of High-Level Swimmers Depending on Autocratic and Democratic Coaching Style.

The aim of the present study was to analyse differences in the psychoneuroendocrine stress responses of high-level, young swimmers depending on whether an autocratic and democratic coaching style was applied. Modifications in cortisol and the motivational climate of 18 young swimmers (15.3 ± 1.86 years, 10 females and 8 males) were analysed before and after two training sessions with equivalent training loads but directed by two coaches applying different approaches, i.e., autocratic (A) and democratic (D). The basal testosterone levels of the coaches were also assessed. The basal testosterone concentration was higher in coach A than in coach D; the athletes perceived them as autocratic and democratic, respectively. Swimmers under coach A's instructions showed higher cortisol levels, suggesting higher cortisol production related to coaching style. Furthermore, differences in the motivational climate concerning ego (i.e., athletes comparing their ability with that of other athletes) were observed with coach A, whereas differences in motivational climate concerning the task (i.e., athletes comparing their ability with their own past performance) were observed with coach D. Cognitive variables showed negative perceptions affecting athletes' training experience and performance when they were screamed at or insulted by coach A. There were no gender or age differences in cortisol production or motivational climate. In conclusion, this study suggests that an autocratic coaching style modulates cortisol release in both genders, affecting young elite swimmers' motivational climate and training experience.

Synthesis of Sultones from Chlorosulfates by a Complex Cascade Reaction Occurring under Mild Thermal Conditions.

Chlorosulfate derivatives are interesting reagents that have been traditionally used to get other sulfur-containing compounds by formal nucleophilic substitution of the chlorine atom. This work describes a different mode of reactivity of alkyne-containing chlorosulfates to get sultones, the sulfur analogues of lactones. The complex skeletal rearrangement observed in this transformation is comparable to those intricate processes promoted or catalyzed by organometallic compounds. However, the reaction here described does not require any reagent or additive, being just a thermal process. Computational calculations support a mechanism based on a series of cascade reactions where almost every step is counterintuitive. Some of these steps include original processes related to classical reactions, thus adding complementary views to traditional organic chemistry.

Lanthanum-Catalyzed Enantioselective Trifluoromethylation by Using an Electrophilic Hypervalent Iodine Reagent.

A highly enantioselective catalytic method for the synthesis of quaternary α-trifluoromethyl derivatives of 3-oxo esters is described. The reaction uses lanthanum(III) triflate and chiral PyBOX-type C2 -symmetric ligands to generate intermediate LaIII complexes that incorporate an enolate moiety of the starting 3-oxo ester and the trifluoromethylation transfer reagent. The enantioselectivity of the reaction stems from the efficient blockage of one of the prochiral faces of the LaIII enolate by one unit of the C2 -symmetric ligand.

Chirality-Induced Electron Spin Polarization and Enantiospecific Response in Solid-State Cross-Polarization Nuclear Magnetic Resonance.

NMR-based techniques are supposed to be incapable of distinguishing pure crystalline chemical enantiomers. However, through systematic studies of cross-polarization magic angle spinning (CP-MAS) NMR in a series of amino acids, we have found a rather unexpected behavior in the intensity pattern of optical isomers in hydrogen/nitrogen nuclear polarization transfer that would allow the use of CP NMR as a nondestructive enantioselective detection technique. In all molecules considered, the d isomer yields higher intensity than the l form, while the chemical shift for all nuclei involved remains unchanged. We attribute this striking result to the onset of electron spin polarization, accompanying bond charge polarization through a chiral center, a secondary mechanism for polarization transfer that is triggered only in the CP experimental setup. Electron spin polarization is due to the chiral-induced spin selectivity effect (CISS), which creates an enantioselective response, analogous to the one involved in molecular recognition and enantiospecific separation with achiral magnetic substrates. This polarization influences the molecular magnetic environment, modifying the longitudinal relaxation time T1 of 1H, and ultimately provoking the observed asymmetry in the enantiomeric response.

1,3-Dioxa-[3,3]-sigmatropic Oxo-Rearrangement of Substituted Allylic Carbamates: Scope and Mechanistic Studies.

An unexpected 1,3-dioxa-[3,3]-sigmatropic rearrangement during the treatment of aryl- and alkenyl-substituted allylic alcohols with activated isocyanates is reported. The reorganization of bonds is highly dependent on the electron density of the aromatic ring and the nature of isocyanate used. This metal-free tandem reaction from branched allyl alcohols initiated by a carbamoylation reaction and followed by a sigmatropic rearrangement thus offers a new access to ( E)-cinnamyl and conjugated ( E, E)-diene carbamates, such as N-acyl and N-sulfonyl derivatives. A computational study was conducted in order to rationalize this phenomenon, and a rearrangement progress kinetic analysis was performed.