Contribution to the phase diagram of the system PbCl2-AgCI

The side parts of the phase diagram of the binary system PbCl₂-AgCl were studied by using DTA. The only miscibility was found on the silver chloride side up to a concentration of 1.5±0.5 mole% PbCl₂. No solid solution of AgCl in PbCl₂ was observed on the lead chloride side.

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Zusammenfassung Mittels DTA wurden die Randzonen des Phasendiagrammes des binären Systemes PbCl₂-AgCl untersucht. Mischbarkeit konnte lediglich auf der Silberchloridseite bis zu einer Konzentration von 1.5±0.5 mol% mol% PbCl₂ festgestellt werden. Auf der Bleichloridseite konnten keinerlei Mischkristalle zwischen AgCl und PbCl₂ beobachtet werden.

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PbCl₂-AgCl. 1,5±0,5 %. .

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We are very grateful to our colleagues Dr E. Krová and Dr Z. Pokorná for the preparation of the single-crystals and for the chemical analysis.     

The phase diagram of the system Na2SO4 - CaSO4

Quenching of Na₂SO₄ - CaSO₄ melts down to room temperature results in different forms of metastable solid solutions dependent on the CaSO₄ content. The transformation of these solid solutions into stable phases were investigated after various times and temperatures by X-ray powder diffraction and thermal analyses. An equilibrium phase diagram is derived, which is in accordance with all experimental facts.     

Rhodium-catalyzed selective [2+2+2] cyclizations of 1,6-diynes with monoynes leading to isoindolines and isobenzofurans

<正>A highly efficient and selective[2+2+2]cyclization of diynes and monoalkynes was catalyzed by rhodium under room temperature in water/THF mixed solvent,affording isoindolines and isobenzofurans in good to excellent yields.The center atoms (N,O) in the diynes showed a significant effect for the cyclization.     

A novel reaction of 2-(arylamino)-1-(methylthio)-1-tosylethenes with hydrogen iodide leading to quinoline derivatives

The reaction of 2-(arylamino)-1-(methylthio)-1-tosylethenes (4) with hydrogen iodide in refluxing toluene gave 3-tosyl-2-(tosylmethyl)quinoline derivatives (6) in good yields. In this reaction, hydrogen iodide dose not only reductively removes the methylthio group of 4 to form an intermediary 1-(arylamino)-2-tosylethene (5), but also serves as a protic catalyst for the subsequent dimeric cyclization of 5 to lead to the quinoline derivatives (6).     

Successful screening of large encoded combinatorial libraries leading to the discovery of novel p38 MAP kinase inhibitors

Screening of more than 2 million compounds comprising 41 distinct encoded combinatorial libraries revealed a novel structural class of p38 mitogen-activated protein (MAP) kinase inhibitors. The methodology used for screening large encoded combinatorial libraries combined with the statistical interpretation of screening results is described. A strong preference for a particular triaminotriazine aniline amide was discovered based on biological activity observed in the screening campaign. Additional screening of a focused follow-up combinatorial library yielded data expanding the unique combinatorial SAR and emphasizing an extraordinary preference for this particular building block and structural class. The preference is further highlighted when the p38 inhibitor data set is compared to data obtained for a panel of other kinases.     

Contribution to the study of the Al-Zn phase diagram

Calorimetric measurements in the AI-Zn system rule out the existence of anα″-phase and of a second monotectoid reaction at 340?.     

Convenient synthesis of 4H-chromenyl-tetrahydro-2H-pyrancarboxylates and cleavage of chromone and pyran rings leading to 5-(2-hydroxybenzoyl)-2-(trifluoromethyl)-1,2-dihydropyridine-3-carboxylates

4H-Chromenyl-tetrahydro-2H-pyrancarboxylates 3a–k have been conveniently prepared by the reaction of 3-formylchromones 1a–k and ethyl 4,4,4-trifluoro-3-oxobutanoate 2a with good yields. Thus obtained 4H-chromenyl-tetrahydro-2H-pyrancarboxylates 3a–k were reacted with amines 4a–e to provide series of 5-(2-hydroxybenzoyl)-2-(trifluoromethyl)-1,2-dihydropyridine-3-carboxylates 5a–o. The reaction proceeded via Michael addition (C-N bond formation) and followed by cleavage of chromone and pyran rings (C-O bond cleavage) in one pot.     

A new cascade reaction: concurrent construction of six and five membered rings leading to novel fused quinazolinones

A one-pot cascade reaction has been developed leading to the concurrent construction of six and five membered fused N-heterocyclic rings of indazolo[3,2-b]quinazolinones. The methodology involved the reaction of isatoic anhydride, a hydrazine and o-iodo benzaldehyde in the presence of Pd(PPh(3))(4) and BINAP in MeCN. The mechanism of this cascade reaction is discussed. A variety of indazolo[3,2-b]quinazolinone derivatives were prepared by using this methodology in good yields, some of which were tested for their PDE4 inhibitory properties in vitro. The dose response and docking study performed using a representative compound is presented.     

Application of DTA and TG to studies of the CaCO3-CaF2 phase diagram

A new method (based on DTA and TG) for the determination of the eutectic composition is proposed for systems in which one of the components is unstable in the vicinity of the eutectic melting temperature. The eutectic composition established by means of this method for the CaCO₃-CaF₂ system is in very good agreement with the results obtained in a classical way.

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Zusammenfassung Eine neue Methode zur Bestimmung der eutektischen Zusammensetzung von Systemen, deren eine Komponente in der Nähe der eutektischen Temperatur instabil ist, beruht auf der simultanen TG-Messung. Mit der vorgeschlagenen Methode wird die eutektische Zusammensetzung des Systems CaF₂-CaCO₃ in sehr guter Übereinstimmung mit den Ergebnissen klassischer Untersuchungen gefunden.

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, . , CaCO₃-CaF₂, , .

     

Temperature-pressure phase diagram of a D2O-D2 system at pressures to 1.8 kbar

Using a volumetric technique, the deuterium solubility, X, in heavy water (L), low-pressure hexagonal ice (I h), and high-pressure cubic clathrate ice (sII) is studied at deuterium pressures up to 1.8 kbar and temperatures from -40 to +5 degrees C. The triple point of the L + I(h) + sII equilibrium is located at P = 1.07(3) kbar and T = -4.5(8) degrees C. The molar ratios D2/D2O of phases at the triple point are X(L) = 0.020(5), X(Ih) = 0.012(5), and X(sII) = 0.207(5).     

Ab initio study of the high‐temperature phase transition in crystalline GeO2

Germanium dioxide (GeO₂) takes two forms at ambient pressure: a thermodynamically stable rutile‐type structure and a high‐temperature quartz‐type polymorph. Here, we investigate the phase stability at finite temperatures by ab initio phonon and thermochemical computations. We use gradient‐corrected density‐functional theory (PBE‐GGA) and pay particular attention to the modeling of the “semicore” germanium 3d orbitals (ascribing them either to the core or to the valence region). The phase transition is predicted correctly in both cases, and computed heat capacities and entropies are in excellent agreement with thermochemical database values. Nonetheless, the computed formation energies of α‐quartz‐type GeO₂ (and, consequently, the predicted transition temperatures) differ significantly depending on theoretical method. Remarkably, the simpler and cheaper computational approach produces seemingly better results, not worse. In our opinion, GeO₂ is a nice test case that illustrates both possibilities and limitations of modern ab initio thermochemistry. © 2013 Wiley Periodicals, Inc.     

Binary solid-liquid phase diagram of the two diastereomer racemates of triglycidyl isocyanurate (TGIC)

Triglycidyl isocyanurate [2451-62-9] as a trifunctional epoxy monomer is mostly used as curing agent. It exists in the form of two diastereomer racemates according to the configuration of the three chiral carbon atoms in the molecule, i.e. beta- or RRR/SSS and alpha- or RRS/SSR. The binary solid-liquid phase diagram of the two diastereomer racemates has been determined by differential scanning calorimetry (DSC). The two diastereomer racemates have different crystalline structures and are physical mixtures with an eutectic phase diagram. The eutectic mixture melts at 92.3 ± 1.0 °C and has alpha-TGIC content of 93.44% by mass or mole. With the help of the phase diagram the ratio of the two diastereomer racemates in TGIC may be determined. The binary phase diagram shows that beta-TGIC can be separated with efficiency from the mixture and may serve for enantiomer synthesis of high optical activity giving rise to the development of novel polymers.     

Chemical investigation of Cannabis sativa leading to the discovery of a prenylspirodinone with anti-microbial potential

The discovery of a new spiran based natural product, prenylspirodinone (1), together with six known cannabinoids (2–7) from the leaves of Cannabis sativa (Marijuana) is reported. All compounds were screened for antifungal and antibacterial activity against a panel of microbial pathogens and exhibited antimicrobial activities with IC₅₀ values ranging from 2.6 to 49.6?µM. Compound 2, a propyl substituted cannabidiol, was determined to be a specific inhibitor against C. albicans (IC₅₀ 11.9?µM) and can be considered as a new lead against Candidiasis.     

Hydrothermal synthesis and structural characterizations of two new germanates with a novel topological framework and unusual Ge4(OH)4 cubane

Two new germanates, Ge7O12(OH)4 (C4N3H13)(0.5)(H2O)5 (1) and Ge7O12(OH)4(H2O)6 (2) have been synthesized under hydrothermal conditions and characterized by IR spectroscopy, powder XRD, TG, and single-crystal X-ray diffraction. Compound 1 crystallizes in cubic space group P3m (No. 215) with a = b = c = 7.7119(5) A, v = 458.65(5) A(3), z = 1. Compound 2: cubic, P3m, a = b = c = 7.7653(17) A, v = 457.48(17) A(3), z = 1. Both germanates keep the same topological novel inorganic framework, which is assembled from Ge4(OH)4 cubane and chiral intertwined Ge-O double helices.     

Predicting the phase diagram of two-dimensional colloidal systems with long-range interactions

The phase diagram of a two-dimensional model system for colloidal particles at the air-water interface was determined using Monte Carlo computer simulations in the isothermic-isobaric ensemble. The micrometer-range binary colloidal interaction has been modeled by hard disklike particles interacting via a secondary minimum followed by a weaker longer-range repulsive maximum, both of the order of kBT. The repulsive part of the potential drives the clustering of particles at low densities and low temperatures. Pinned voids are formed at higher densities and intermediate values of the surface pressure. The analysis of isotherms, translational and orientational correlation functions as well as structure factor gives clear evidence of the presence of a melting first-order transition. However, the melting process can be also followed by a metastable route through a hexatic phase at low surface pressures and low temperatures, before crystalization occurs at higher surface pressure.     

Down to the quantum limit at the neutral-to-ionic phase transition of (BEDT-TTF)-(ClMe-TCNQ): symmetry analysis and phase diagram

We report on the neutral-to-ionic (N-I) phase transition in the one-dimensional organic complex (BEDT-TTF)-(ClMeTCNQ). The X-ray studies at room temperature show that the neutral phase of (BEDT-TTF)-(ClMeTCNQ) is already characterized by a polar long-range ordering, at variance with other charge-transfer compounds comprising noncentrosymmetric molecules. From a detailed neutron diffraction study of this complex under high pressure, we present the phase diagram of the N-I transition down to the quantum limit. We discuss the symmetry breaking associated with the transition and the evolution of its first-order character under pressure.     

Vibron frequencies of solid H2 and D2 to 200 GPa and implications for the P-T phase diagram

Vibrational spectroscopy of the intramolecular stretching mode (vibron) of the hydrogen isotopes has been used for the past 20 years in different laboratories using various techniques to probe phase diagrams of this system under extreme conditions. Available vibrational spectroscopy data in hydrogen and deuterium to 200 GPa at 10-300 K are analyzed and reassessed to identify the existence of an additional molecular phase (I') to phases I, II, and III previously identified at megabar pressures. The results do not support the existence of phase I' in the pressure-temperature range studied. Previously proposed boundaries between phases I, II, and III are re-examined and updated phase diagrams of hydrogen and deuterium are proposed.     

Transition from the layered Sr2RhO4 to the monodimensional Sr4RhO6 phase

Study of the structural changes occurring during the reduction process of the Sr2RhO4+delta, (214), n=1 term of the Ruddlesden and Popper series, shows that for delta <0.02 values, this material dissociates into the Sr4RhO6 (416) monodimensional phase, alpha = infinity, beta = 0 compound of the (A3B2O6)alpha-(A3B3O9)beta family, and Rh metal. During the first stage, this process occurs by the formation of an intergrowth between the (214) and (416) materials which can be only detected by high resolution electron microscopy and is easily interpreted on the basis of the structural relationship established between them. Further reduction allows the segregation of both phases as separated entities, which coexist with Rh metal. The dissociation process is reversible and, under oxidizing conditions, a layered material with anionic composition delta =0.06 is always obtained. This behaviour seems to be a general way of accommodating the compositional changes in layered A2BO4 phases where the B cation is always in a octahedral environment. The structural mechanism of this transformation is proposed, and the structural relationship between these two low-dimensional oxides is established.     

Interference between the hydrogen bonds to the two rings of nicotine

The biochemical transport and binding of nicotine depends on the hydrogen bonding between water and binding site residues to the pyridine ring and the protonated pyrrolidinium ring. To test the independence of these two moderately separated hydrogen-bonding sites, we have calculated the structures of clusters of protonated nicotine with water and a bicarbonate anion, benzene, indole, or a second water molecule. Unprotonated nicotine-water clusters have also been studied for contrast. The potential energy surfaces are first explored with an intermolecular anisotropic atom-atom model potential. Full geometry optimizations are then carried out using density functional theory to include nonadditive terms in the interaction energies. The presence of the charge on the pyrrolidine nitrogen removes the conventional hydrogen-bonding site on the pyridine ring. The hydrogen-bond ability of this site is nearly recovered when the protonated pyrrolidinium ring is bound to a bicarbonate anion, whereas its interaction with benzene shows a much smaller effect. Indole appears to partially restore the hydrogen-bond ability of the pyridine nitrogen, although indole and benzene both pi-bond to the pyrrolidinium ring. A second hydrogen-bonding water produces a significant conformational distortion of the nicotine. This demonstrates the limitations of the conventional qualitative predictions of hydrogen bonding based on the independence of molecular fragments. It also provides benchmarks for the development of atomistic modeling of biochemical systems.