New Silver(I) Coordination Polymer with Fe4 Single-Molecule Magnets as Long Spacer

In continuation of our work on supramolecular architectures of single-molecule magnets (SMMs) as a promising strategy in developing their magnetic performance, in this paper we report the synthesis and single crystal X-ray structure of the centered triangular tetrairon(III) SMM, [Fe4(PhpPy)2(dpm)6], Fe4 (Hdpm = dipivaloylmethane, H3PhpPy = 2-(hydroxymethyl)- 2-(4-(pyridine-4-yl)phenyl)propane-1,3-diol), and its assembly in the coordination polymer {[Fe4(PhpPy)2(dpm)6Ag](ClO4)}n, Fe4Ag, upon reaction with silver(I) perchlorate. Thanks to the presence of the pyridyl rings on the two tripodal ligands, Fe4 behaves as divergent ditopic linker, and due to the Fe4:AgClO4 1:1 ratio, Fe4Ag probably possesses a linear arrangement in which silver(I) ions are linearly coordinated by two nitrogen atoms, forming 1D chains whose positive charge is balanced by the perchlorate anions. The stabilization of such a polymeric structure can be ascribed to the long distance between the two donor nitrogen atoms (23.4 \uc5) and their donor power. Fe4Ag shows slow relaxation of the magnetization which follows a thermally activated process with Ueff/kB = 11.17(18) K, t0 = 2.24(17) 107 s in zero field, and Ueff/kB = 14.49(5) K, t0 = 3.88(8) 107 s in 1-kOe applied field, in line with what reported for tetrairon(III) SMMs acting as building blocks in polymeric structures

From red to blue shift: switching the binding affinity from the acceptor to the donor end by increasing the π-bridge in push–pull chromophores with coordinative ends

A series of homologous push–pull compounds, in which identical donor (a dimethylamino) and acceptor (a malonate ester) functionalities endcap crescent PPV fragments, exhibit striking differences in their supramolecular recognition of cations acting as Lewis acids. The shorter conjugated compound (one phenyl ring) coordinates a wide variety of lanthanide cations (Eu3+, Yb3+ and Er3+) in MeCN solutions to the 1,3-dicarbonyl acceptor end, resulting in an overall supramolecular polarization of the system (red shift of the intramolecular charge-transfer ICT band). With the “hard” cation Sc3+, recognition switches to the tertiary amine donor end, turning the conjugated system from D–π–A to A–π–A, and resulting in a blue shift of the ICT band upon complexation. Interestingly, increasing the conjugation by means of the insertion of sequential p-phenylenevinylene units into the ligand results in coordination to the donor end regardless of cation “hardness” (Sc3+, Eu3+ and Er3+), suggesting a relative change in the nucleophilicity of the two coordinating ends when increasing the length of the conjugated π-bridge. Such a hypothesis is supported by quantum chemical calculations on the ligands and subsequent atomic charges determination using two independent approaches (QTAIM and CHelpG). The characterization of the thermodynamic stabilities and the dimensionalities of the ligand–cation complexes in solution reveals striking differences from case to case, yet increasing affinities (from log Kav = 2.5 to log Kav = 4.9) are recorded with the increase of the π-conjugated bridge

Le Corbusier Roof-Spaces

[EN] From technical solution, the roof-garden became a key spatial theme within Le Corbusier’s work and creativity, evolving to become a fundamental component of his vision for the contemporary city. The roof garden is an open space in which to cultivate both the mind and body, and to experience a direct relationship with nature; through plants, the sky, and the sun, the urban and the natural world are combined together in the surroundings. This article follows the principal steps of Le Corbusier’s research, starting with his initial experimentation in his own apartment studio in rue Nungesser-et-Coli, through to the complex development at the Unité. It follows how the roof garden becomes an optical device toward the horizon and a strong evocative instrument. The relationship with the nature and the horizon are the key of readings of several selected design projects which demonstrate at the same time the continuity of the research and the richness of the variations on the theme itself. The roof garden is one of the most fertile topics of Le Corbusier’s legacy, evident in contemporary architectural developments.[ES] A partir de una solución técnica, el roof-garden se convierte en el tema central del trabajo y de la poética de Le Corbusier, evolucionando para convertirse en un componente fundamental de su visión de la ciudad contemporánea. El roofgarden es un espacio abierto en el que el hombre puede cultivar la mente y el cuerpo, donde se puede experimentar una relación directa con la naturaleza -la vegetación, a través de las plantas, el cielo, el sol, el urbano -y el mundo natural se combinan juntos en los alrededores. Este texto sigue los pasos principales de la investigación de Le Corbusier , partiendo de las experimentaciones iniciales -en su apartamento-estudio en la rue Nungesser-et-Coli- hasta el complejo desarrollado en la Unité. El texto sigue como el roof garden se convierte en un dispositivo óptico hacia el horizonte y en un gran instrumento evocativo. La relación con la naturaleza y el horizonte son las claves de lectura de varios proyectos seleccionados que muestran a la vez la continuidad de la investigación y la riqueza de las variaciones sobre el tema. El roof garden es uno de los temas más vivos del legado de Le Corbusier, también de gran importancia hoy en la arquitectura contemporánea.Como, A.; Smeragliuolo Perrotta, L.; Forni, I. (2016). Le Corbusier Roof-Spaces. En LE CORBUSIER. 50 AÑOS DESPUÉS. Editorial Universitat Politècnica de València. 441-460. https://doi.org/10.4995/LC2015.2015.960OCS44146

Vitamin K Vitamers Differently Affect Energy Metabolism in IPEC-J2 Cells

The fat-soluble vitamin K (VK) has long been known as a requirement for blood coagulation, but like other vitamins, has been recently recognized to play further physiological roles, particularly in cell development and homeostasis. Vertebrates cannot de novo synthesize VK, which is essential, and it can only be obtained from the diet or by the activity of the gut microbiota. The IPEC-J2 cell line, obtained from porcine small intestine, which shows strong similarities to the human one, represents an excellent functional model to in vitro study the effect of compounds at the intestinal level. The acute VK treatments on the bioenergetic features of IPEC-J2 cells were evaluated by Seahorse XP Agilent technology. VK exists in different structurally related forms (vitamers), all featured by a naphtoquinone moiety, but with distinct effects on IPEC-J2 energy metabolism. The VK1, which has a long hydrocarbon chain, at both concentrations (5 and 10 \u3bcM), increases the cellular ATP production due to oxidative phosphorylation (OXPHOS) by 5% and by 30% through glycolysis. The VK2 at 5 \u3bcM only stimulates ATP production by OXPHOS. Conversely, 10 \u3bcM VK3, which lacks the long side chain, inhibits OXPHOS by 30% and glycolysis by 45%. However, even if IPEC-J2 cells mainly prefer OXPHOS to glycolysis to produce ATP, the OXPHOS/glycolysis ratio significantly decreases in VK1-treated cells, is unaffected by VK2, and only significantly increased by 10 \u3bcM VK3. VK1, at the two concentrations tested, does not affect the mitochondrial bioenergetic parameters, while 5 \u3bcM VK2 increases and 5 \u3bcM VK3 reduces the mitochondrial respiration (i.e., maximal respiration and spare respiratory capacity). Moreover, 10 \u3bcM VK3 impairs OXPHOS, as shown by the increase in the proton leak, namely the proton backward entry to the matrix space, thus pointing out mitochondrial toxicity. Furthermore, in the presence of both VK1 and VK2 concentrations, the glycolytic parameters, namely the glycolytic capacity and the glycolytic reserve, are unaltered. In contrast, the inhibition of glycoATP production by VK3 is linked to the 80% inhibition of glycolysis, resulting in a reduced glycolytic capacity and reserve. These data, which demonstrate the VK ability to differently modulate IPEC-J2 cell energy metabolism according to the different structural features of the vitamers, can mirror VK modulatory effects on the cell membrane features and, as a cascade, on the epithelial cell properties and gut functions: balance of salt and water, macromolecule cleavage, detoxification of harmful compounds, and nitrogen recycling

2,2'-diidrossi-3,3'-dimetossi-5,5'-dimetil-6,6'-dibromo-1,1'-bifenile: preparazione, risoluzione, struttura e attività biologica

Nell'ambito dei nostri studi riguardanti la sintesi di nuovi sistemi idrossilati bifenilici come builing blocks per la preparazione sia di potenziali agenti farmaceutici che di nuovi leganti, abbiamo individuato nel 2,2'-diidrossi-3,3'-dimetossi-5,5'-dimetil-1,1'- bifenile (deidrodicreosolo) un possibile precursore di derivati 6,6'-dibromo disostituiti conformazionalmente stabili

In Vivo Effects of Einkorn Wheat (Triticum monococcum) Bread on the Intestinal Microbiota, Metabolome, and on the Glycemic and Insulinemic Response in the Pig Model

Einkorn wheat (Triticum monococcum) is characterized by high content of proteins, bioactive compounds, such as polyunsaturated fatty acids, fructans, tocols, carotenoids, alkylresorcinols, and phytosterols, and lower α-, β-amylase and lipoxygenase activities compared to polyploid wheat. These features make einkorn flour a good candidate to provide healthier foods. In the present study, we investigated the effects of einkorn bread (EB) on the intestinal physiology and metabolism of the pig model by characterizing the glycemic and insulinemic response, and the microbiota and metabolome profiles. Sixteen commercial hybrid pigs were enrolled in the study; four pigs were used to characterize postprandial glycemic and insulinemic responses and twelve pigs underwent a 30-day dietary intervention to assess microbiota and metabolome changes after EB or standard wheat bread (WB) consumption. The postprandial insulin rise after an EB meal was characterized by a lower absolute level, and, as also observed for glucose, by a biphasic shape in contrast to that in response to a WB meal. The consumption of EB led to enrichment in short-chain fatty acid producers (e.g., Blautia, Faecalibacterium, and Oscillospira) in the gut microbiota and to higher metabolic diversity with lower content of succinate, probably related to improved absorption and therefore promoting intestinal gluconeogenesis. The observed changes, at both a compositional and metabolic scale, strongly suggest that EB consumption may support a health-promoting configuration of the intestinal ecosystem

Роль семьи в процессе первичной социализации в отечественной и зарубежной литературе

A series of 5,15 push–pull <i>meso</i>-diarylzinc­(II) porphyrinates, carrying one or two −COOH or −COOCH₃ acceptor groups and a −OCH₃ or a −N­(CH₃)₂ donor group, show in <i>N</i>,<i>N</i>-dimethylformamide and CHCl₃ solutions a negative and solvent-dependent second-order nonlinear-optical (NLO) response measured by the electric-field-induced second-harmonic generation (EFISH) technique, different from the structurally related zinc­(II) porphyrinate carrying a −N­(CH₃)₂ donor group and a −NO₂ acceptor group, where a still solvent-dependent but positive EFISH second-order response was previously reported. Moreover, when a −N­(CH₃)₂ donor group and a −COOH acceptor group are part of a sterically hindered 2,12 push–pull β-pyrrolic-substituted tetraarylzinc­(II) porphyrinate, the EFISH response is positive and solvent-independent. In order to rationalize these rather intriguing series of observations, EFISH measurements have been integrated by electronic absorption and IR spectroscopic investigations and by density functional theory (DFT) and coupled-perturbed DFT theoretical and ¹H pulsed-gradient spin-echo NMR investigations, which prompt that the significant concentration effects and the strong influence of the solvent nature on the NLO response are originated by a complex whole of different aggregation processes induced by the −COOH group