Ownership-attributing intuitions are cross-culturally shared.

This study tested intuitions about ownership in children of Dani people, an indigenous Papuan society (N = 79, Mage = 7, 49.4% females). The results show that similar to studies with children from Western societies, children infer ownership from (1) control of permission, (2) ownership of the territory the object is located in, and (3) manmade versus natural origins of the object. By contrast, they did not (4) infer ownership from the first observed possession of an object. Additionally, Papuan children showed (5) an absolute first possession heuristic, whereby they assigned ownership to a person who achieved a goal, in contrast to a person who was first to pursue this goal but failed to be the first to claim it.

Organometallic chemistry confined within a porphyrin-like framework.

The world of modified porphyrins changed forever when an N-confused porphyrin (NCP), a porphyrin isomer, was first published in 1994. The replacement of one inner nitrogen with a carbon atom revolutionised the chemistry that one is able to perform within the coordination cavity. One could explore new pathways in the organometallic chemistry of porphyrins by forcing a carbon fragment from the ring or an inner substituent to sit close to an inserted metal ion. Since the NCP discovery, a series of modifications became available to tune the coordination properties of the cavity, introducing a fascinating realm of carbaporphyrins. The review surveys all possible carbatetraphyrins(1.1.1.1) and their spectacular coordination and organometallic chemistry.

21-Carba-23-selenaporphyrinoid Dyads-An Azepine Unit as a Merging Motif.

The oxidation of 10,15-diaryl-21-carba-23-selenaporphyrinoids resulted in the creation of dyads. The dimerization process follows a [5+2] cycloaddition path with the formation of an azepine unit. The arrays display two direct bonds between the peripheral carbocyclic carbon atoms of one carbaselenaporphyrinic subunit and the central carbon and nitrogen atoms of the second subunit. This results in a unique canted arrangement of two carbaporphyrinoid planes resembling an open seashell-like motif.

Guest Encapsulation Alters the Thermodynamic Landscape of a Coordination Host.

The architecture of self-assembled host molecules can profoundly affect the properties of the encapsulated guests. For example, a rigid cage with small windows can efficiently protect its contents from the environment; in contrast, tube-shaped, flexible hosts with large openings and an easily accessible cavity are ideally suited for catalysis. Here, we report a "Janus" nature of a Pd6L4 coordination host previously reported to exist exclusively as a tube isomer (T). We show that upon encapsulating various tetrahedrally shaped guests, T can reconfigure into a cage-shaped host (C) in quantitative yield. Extracting the guest affords empty C, which is metastable and spontaneously relaxes to T, and the T⇄C interconversion can be repeated for multiple cycles. Reversible toggling between two vastly different isomers paves the way toward controlling functional properties of coordination hosts "on demand".

Illusory intuitions: Challenging the claim of non-exclusivity.

A person who arrives at correct solutions via false premises is right and wrong simultaneously. Similarly, a person who generates "logical intuitions" through superficial heuristics can likewise be right and wrong at the same time. However, heuristics aren't guaranteed to deliver the logical solution, so the claim that system 1 can routinely produce the alleged system 2 response is unfounded.

Bispalladium(II) Complexes of di-p-Pyrirubyrin Derivatives as Promising Near-Infrared Photoacoustic Dyes.

The insertion of palladium(II) into di-p-pyrirubyrin results in mutually convertible bimetallic complexes. Post-synthetic functionalization of one of them yielded bispalladium(II) dioxo-di-p-pyrirubyrin and, after demetallation, dioxo-di-p-pyrirubyrin, introducing for the first time the α,ß'-pyridin-2-one unit into the macrocyclic frame. Bispalladium(II) di-p-pyrirubyrin 6, bispalladium(II) dioxo-di-p-pyrirubyrin 9, and dioxo-di-p-pyrirubyrin 10 absorb and emit light around 1000 nm and are characterized by high photostability. Thus, they are promising candidates for near-infrared photoacoustic dyes, ideally targeting (9) the wavelength of Yb-based fiber lasers. The incorporation of an α,ß'-pyridine moiety into expanded porphyrins opens a highly interesting area of research due to the attractive optical and coordination properties of the resulting molecules.

Altering the Properties of Spiropyran Switches Using Coordination Cages with Different Symmetries.

Molecular confinement effects can profoundly alter the physicochemical properties of the confined species. A plethora of organic molecules were encapsulated within the cavities of supramolecular hosts, and the impact of the cavity size and polarity was widely investigated. However, the extent to which the properties of the confined guests can be affected by the symmetry of the cage─which dictates the shape of the cavity─remains to be understood. Here we show that cage symmetry has a dramatic effect on the equilibrium between two isomers of the encapsulated spiropyran guests. Working with two Pd-based coordination cages featuring similarly sized but differently shaped hydrophobic cavities, we found a highly selective stabilization of the isomer whose shape matches that of the cavity of the cage. A Td-symmetric cage stabilized the spiropyrans' colorless form and rendered them photochemically inert. In contrast, a D2h-symmetric cage favored the colored isomer, while maintaining reversible photoswitching between the two states of the encapsulated spiropyrans. We also show that the switching kinetics strongly depend on the substitution pattern on the spiropyran scaffold. This finding was used to fabricate a time-sensitive information storage medium with tunable lifetimes of the encoded messages.

Cementless femoral neck endoprosthesis SPIRON in men in aspects of clinical status and quality of life in an average 7-year follow-up.

BACKGROUND: We report the clinical evaluation, quality of life and pain assessment in patients who had a femoral neck SPIRON endoprosthesis. METHODS: The study group consisted of 27 men in whom 35 femoral neck endoprosthesis were implanted (8 on the left side, 12 on the right side and 7 bilateral) due to idiopathic osteoarthritis of the hip (20 patients) or avascular femoral osteonecrosis (7 patients) in a mean 7-year follow-up. RESULTS: The median pre-operative Harris Hip score (HHS) was 35.5 and post-operative 98.5 (p < 0.001). The median WOMAC HIP score was pre-operatively 57 and post-operatively 0 (p < 0.001). The median SF-12 score was pre-operatively 4 and post-operatively 33 (p < 0.001). The median pain assessment in VAS scale was 7 pre-operatively and 0 post-operatively (p < 0.001). CONCLUSIONS: The results of all examined patients have changed significantly in every category showing that SPIRON endoprosthesis improved their quality of life and statistically reduced pain ailments. Moreover we have proved that higher BMI (> 30) is associated with worse operation outcomes.

Social bias insights concern judgments rather than real-world decisions.

Judgments differ from decisions. Judgments are more abstract, decontextualized, and bear fewer consequences for the agent. In pursuit of experimental control, psychological experiments on bias create a simplified, bare-bone representation of social behavior. These experiments resemble conditions in which people judge others, but not how they make real-world decisions.

Explaining bias with bias.

Bermúdez argues that a framing effect is rational, which will be true if one accepts that the biased editing phase is rational. This type of rationality was called procedural by Simon. Despite being procedurally rational in the evaluation phase framing effect stems from biased way we set a reference point against which outcomes are compared.

Tibiotalocalcaneal Arthrodesis in Osteoarthritis Deformation of Ankle and Subtalar Joint: Evaluation of Treatment Results.

Tibiotalocalcaneal arthrodesis (TTCA) is an increasingly used method of stiffening the ankle and subtalar joints in advanced degenerative deformities. The study group consisted of 19 men who were subjected to intramedullary and intraosseous arthrodesis using an intramedullary nail. The average age of patients was 46 (range 19-68) years. The main indication for surgical treatment was post-traumatic arthrosis 11 (58%). In the studied group, clinical condition was assessed using the American Orthopedic Foot and Ankle Score (AOFAS) classification, quality of life using the SF-12 scale, and assessment of pain intensity using the visual-analog scale (VAS) scale. The above parameters were evaluated before surgery (under 2 years), intermediate (from 2 to 5 years), and late (over 5 years) postoperative period. The clinical condition on the AOFAS scale improved from an average of 20.6 points before tibiotalocalcaneal arthrodesis to 63.5 after the procedure. The result was statistically significant (p < .0001). Analyzing the results using the SF-12 scale, a statistically significant increase was found. In the physical sphere of Physical Health Component Score-12 (p = .0004) and in the mental sphere of Mental Health Component Score-12 (p = .030). The intensity of pain assessed in the VAS scale, decreased in all three periods-p < .05. The strongest analgesic effect was observed in the early postoperative follow-up period. Tibiotalocalcaneal arthrodesis using an intramedullary nail causes a significant improvement in the clinical condition according to the AOFAS classification, enabling most patients to move independently, a significant improvement quality of life assessed in the SF-12 scale and a significant reduction of pain ailments assessed in the VAS scale, especially in the early postoperative period.

Dicarba[26]hexaporphyrinoids(1.1.1.1.1.1) with an Embedded Cyclopentene Moiety-Conformational Switching.

Invited for the cover of this issue is Lechoslaw Latos-Grazynski and co-workers at University of Wroclaw. The image depicts two essential conformations of 31,34-dicarba[26]hexachlorins: dumbbell and rectangular with regular or doubly inverted carbocyclic rings, respectively. Read the full text of the article at 10.1002/chem.202002603.

Dicarba[26]hexaporphyrinoids(1.1.1.1.1.1) with an Embedded Cyclopentene Moiety-Conformational Switching.

Incorporation of cyclopentene fragments into a skeleton of parental [26]hexaphyrin(1.1.1.1.1.1) afforded extended carbaporphyrinoids: 31,34-dicarbahexa[26]chlorin and its derivatives: the first externally substituted by ethoxy and 2,4,6-trimethylbenzylidene groups and the second one formed by selective oxidation of one cyclopentene ring. Macrocycles adopt dumbbell-shaped conformations with two meso hydrogen atoms located inside the macrocyclic cavity. Protonation of 31,34-dicarba[26]hexachlorins provided dications existing in dumbbell-shaped and rectangular conformations.

Conformation-Dependent Response to the Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): A Route to Pseudorotaxane-Like Structures.

Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0), an expanded carbaporphyrinoid incorporating two phenanthrenylene moieties, exists as two separate, yet interconvertible, locked stereoisomers. These species demonstrate complex dynamic behavior upon protonation, consisting in multiple conformational rearrangements and anion-binding events. The formation of one of the final dicationic forms is accompanied by the inclusion of a complex anion(s) within the macrocyclic cavity yielding a pseudorotaxane-like host-guest complex. Protonation with trifluoroacetic or dichloroacetic acids followed by neutralization afforded a conformation-switching cycle, which involves six structurally different species. Analogous acidification with chiral 10-camphorsulfonic acid and subsequent neutralization generated one of the free base stereoisomers with enantiomeric excess. Therefore, it was shown that the simple acid-base chemistry of diphenanthrioctaphyrin can act as stimulus, inducing chirality into the system, allowing for the manipulation of the stereochemical information imprinted into the enantiomers of the macrocycle.

Foreign Language does not Affect Gambling-Related Judgments.

Previous work has demonstrated that peoples' gambling-related judgments (e.g., perceived likelihood of winning) are often biased by non-diagnostic unclaimed prize information (i.e., the number of prizes still available to be won) resulting in non-optimal scratch card preferences. Another line of research suggests that people make less biased decisions (e.g., are less affected by the framing of a gamble) when using a foreign language. In the current study, we investigated whether using a foreign language (as opposed to one's native language) reduced the biasing effects of unclaimed prize information and consequently led to more optimal scratch card preferences. Across three experiments (N = 409), we found that people were equally biased by unclaimed prize information regardless of whether they completed our scratch card gambling task in their native (Polish) or foreign (English) language. In conclusion, it appears that using a foreign language does not help people be less biased in utilizing gambling-related information, and consequently does not lead to more optimal scratch card preferences.

Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): Conformational Switching Controls the Stereochemical Dynamics of the Topologically Chiral System.

The analogue of octaphyrin(1.1.1.0.1.1.1.0) bearing two dimethoxyphenanthrene units was synthesized and characterized in solution and solid state. The macrocycle was demonstrated to exist as two locked conformers that can be easily separated and handled individually. The conversion of conformers was proven to be facilitated by the presence of hydrogen-bond acceptors, such as amines. The bis-boron(III) complex of diphenanthrioctaphyrin has been obtained, proving that the metalloid center acts as the topology selector stabilizing only one conformation of the macrocycle, irrespective of the stereoisomer used for the insertion. Both conformers of diphenanthrioctaphyrin, as well as the boron complex formed from them, have been separated into enantiomers using HPLC with a chiral stationary phase. All of these systems have shown strikingly different stereodynamic behavior.

C-H and C-M Activation, Aromaticity Tuning, and Co⋠⋠⋠Ru Interactions Confined in the Azuliporphyrin Framework.

Invited for the cover of this issue is Lechoslaw Latos-Grazynski and co-workers at University of Wroclaw. The image depicts cobalt(II) azuliporphyrin as a magical organometallic platform to perform other types of chemistry, that is, dioxygen activation, aromaticity control, and construction of intermetallic communication motifs. Read the full text of the article at 10.1002/chem.201903215.

C-H and C-M Activation, Aromaticity Tuning, and Co⋠⋠⋠Ru Interactions Confined in the Azuliporphyrin Framework.

Taking advantage of the specific properties of azuliporphyrin and the reactivity of cobalt(II), activation of an azulene C(sp2 )-H bond occurred and organometallic complexes with Co-C bonding were formed. The system allowed for macrocyclic aromaticity tuning through metal coordination and oxidation. Thanks to the CoII -C and parallel tested CuII -C reactivity and the affinity of metal centers to dioxygen, oxygen atom insertion into the M-C bond could be investigated. Insertion starts with an oxygen molecule coordination and leads to monomeric and dimeric complexes of specific electronic structures. Formation of unique paramagnetic σ/π-hybrid bimetallic complexes enabled spectroscopic and theoretical investigations of peculiar CoII ⋅⋅⋅Ru0 interactions.

Oxygenation of Phenanthriporphyrin and Copper(III) Phenanthriporphyrin: An Efficient Route to Phenanthribilinones.

Photooxidation of copper(III) 5,6-dimethoxyphenathriporphyrin and copper(III) 5,6-dioxophenanthriporphyrin, which contain phenanthrene or dioxophenathrene moieties built into the macrocyclic frameworks, resulted in the regioselective cleavage that afforded organometallic copper(III) complexes of open-chain phenanthribilinone-type acyclic ligands terminated by carbonyl groups. The copper(III) coordinates two carbon atoms of phenantherene (dioxophenanthrene) and two nitrogen atoms of pyrrole and pyrrolone units, preserving the donor sets of the paternal complexes. The primary dioxygen attack is located at the meso carbon atom adjacent to the phenanthrene moiety. Demetalation of copper(III) 21-benzoyl-phenanthribilin-1-one and copper(III) 21-benzoyl-dioxophenanthribilin-1-one yielded mainly two diastereomers [15Z, 20E] and [15Z, 20Z], which differ in the configurations at two Cα-Cmeso double bonds. The regioselectivity of the cleavage, detected in the course of experimental studies, has been substantiated by DFT investigations. The regioselective cleavage of 5,6-dimethoxyphenanthriporphyrin in reaction with basic iron(III) acetate was detected, providing the synthetically efficient methodology to produce 21-benzoyl-dioxophenanthribilin-1-one.

Organocopper(III) Phenanthriporphyrin-Exocyclic Transformations.

5,6-Dimethoxyphenanthriporphyrin 1 and 5,6-dioxophenanthriporphyrin 2 act as suitable organometallic ligands for copper(III), adopting trianionic [CCNN] coordination cores. Under oxidizing conditions, in the presence of methanol, copper(III) phenanthriporphyrin 1-Cu undergoes transformation to copper(III) phenanthriporphodimethene with methoxy substituents attached to two trans meso positions. Addition of acids to 1-Cu yields two isomeric copper(III) isophenanthriporphyrins protonated on one of the meso carbon atoms. Protonation of copper(III) 5,6-dioxophenanthriporphyrin 2-Cu yields the aromatic diprotonated complex 2-Cu-H22+. In the presence of HBF4 2-Cu undergoes borylation at the carbonyl oxygen atoms, forming an aromatic exocyclic boron(III) complex.