2,6-Bis(2-hydroxy­ethyl)-8b,8c-diphenyl­perhydro-2,3a,4a,6,7a,8a-hexa­azacyclo­penta­[def]fluorene-4,8-dithione

In the title mol­ecule, C24H28N6O2S2, the dihedral angle between the aromatic ring planes is 42.2 (1)°. In the crystal structure, the hydr­oxy groups are involved in O—H⋯S hydrogen bonding, which links the mol­ecules into corrugated layers propagating parallel to the bc plane

A mechanistic study of the acid and base catalysed reactions of thiourea, 1-substituted thioureas and 1,3 -disubstituted thioureas with 1,2-diketones

Thiourea, 1-substituted thioureas and 1,3-disubstituted thioureas react under acidic or basic catalysis with 1,2-diketones to give a wide variety of products. The nature of the product or products depends on the conditions used, the degree of substitution of the thiourea and on the nature of the aromatic or aliphatic groups attached to the dicarbonyl unit of the diketone. The mechanisms of formation of the various products have been investigated by a variety of techniques, including the determination of rate equations by ultraviolet spectroscopy, the influence of side group substituents on the rate and course of the reactions and the synthesis of putative Intermediates on the reaction pathway. The single most informative technique used was, without a doubt, the detection of low concentrations of transient intermediates and side products by the application of carbon-13 nmr spectroscopy to the reaction as it progressed using carbon-13 labelled di ketones to enhance the detection of low level intermediates. It has been shown convincingly that some organic reactions proceed via a small number of irreversible processes amongst a very complex set of more rapid equilibrium processes

1953 Sept. 13, Dear Carol and all:

Carolyn Dodge resided in Ellensburg, Washington, in the Badger Pocket area on a farm with her family and her letters describe her daily life as a farm wife and later as the wife of a potato broker in the Quincy Basin. Dodge also wrote letters to her cousin at her residences in Kittitas and Quincy, Washington, following her time in Ellensburg.https://digitalcommons.cwu.edu/dodge_letters/1083/thumbnail.jp

8b,8c-Diphenyl-2,6-bis(4-pyridyl­meth­yl)­perhydro-2,3a,4a,6,7a,8a-hexa­aza­cyclo­penta­[def]fluorene-4,8-dithione chloro­form solvate

In the thio­glycoluril system of the title compound, C32H30N8S2·CHCl3, the two pyridine rings are roughly parallel, forming a dihedral angle of 7.2 (1)°, and the distance between the centroids of the two phenyl rings is 3.951 (5) Å. The chloro­form solvent mol­ecule is linked to the main mol­ecule via a weak C—H⋯N hydrogen bond

3,6,14,17-Tetramethoxy-22,23-diphenyl-1,10,12,21-tetraazahexacyclo[19.2.1.02,7.010,23.012,22.013,18]tetracosa-2(7),3,5,13(18),14,16-hexaene-11,24-di­thione

The title compound, C36H34N4O4S2, is a thio­glycoluril derivative, which bears two phenyl substituents on its convex face and two meth­oxy substituted o-xylylenes as sidewalls of the molecular clip. There is one half-mol­ecule in the asymmetric unit: a crystallographic twofold axis generates the complete molecule. The non-planar seven-membered rings adopt chair conformations, while the two five-membered rings exhibit envelope conformations and make a dihedral angle of 68.46 (12)°. The O atoms of the meth­oxy groups are coplanar with the six-membered o-xylylene sidewalls

Panchromatic Imaging of a Transitional Disk: The Disk of GM Aur in Optical and FUV Scattered Light

We have imaged GM Aur with HST, detected its disk in scattered light at 1400A and 1650A, and compared these with observations at 3300A, 5550A, 1.1 microns, and 1.6 microns. The scattered light increases at shorter wavelengths. The radial surface brightness profile at 3300A shows no evidence of the 24AU radius cavity that has been previously observed in sub-mm observations. Comparison with dust grain opacity models indicates the surface of the entire disk is populated with sub-micron grains. We have compiled an SED from 0.1 microns to 1 mm, and used it to constrain a model of the star+disk system that includes the sub-mm cavity using the Monte Carlo Radiative Transfer code by Barbara Whitney. The best-fit model image indicates that the cavity should be detectable in the F330W bandpass if the cavity has been cleared of both large and small dust grains, but we do not detect it. The lack of an observed cavity can be explained by the presence of sub-microns grains interior to the sub-mm cavity wall. We suggest one explanation for this which could be due to a planet of mass <9 Jupiter masses interior to 24 AU. A unique cylindrical structure is detected in the FUV data from the Advanced Camera for Surveys/Solar Blind Channel. It is aligned along the system semi-minor axis, but does not resemble an accretion-driven jet. The structure is limb-brightened and extends 190 +/- 35 AU above the disk midplane. The inner radius of the limb-brightening is 40 +/- 10 AU, just beyond the sub-millimeter cavity wall.Comment: 40 pages, 11 figures, 4 tables, accepted to Ap

Synthesis and evaluation of a novel pyrenyl-appended triazole-based thiacalix[4]arene as a fluorescent sensor for Ag+ ion

New fluorescent chemosensors 1,3-alternate-1 and 2 with pyrenyl-appended triazole-based on thiacalix[4]arene were synthesized. The fluorescence spectra changes suggested that chemosensors 1 and 2 are highly selective for Ag+ over other metal ions by enhancing the monomer emission of pyrene in neutral solution. However, other heavy metal ions, such as Cu2+, and Hg2+ quench both the monomer and excimer emission of pyrene acutely. The 1H NMR results indicated that Ag+ can be selectively recognized by the triazole moieties on the receptors 1 and 2 together with the ionophoricity cavity formed by the two inverted benzene rings and sulfur atoms of the thiacalix[4]arene

Gallium(III) chelates of mixed phosphonate-carboxylate triazamacrocyclic ligands relevant to nuclear medicine: structural, stability and in vivo studies

Three triaza macrocyclic ligands, H6NOTP (1,4,7-triazacyclononane-N,N′,N″-trimethylene phosphonic acid), H4NO2AP (1,4,7-triazacyclononane-N-methylenephosphonic acid-N′,N″-dimethylenecarboxylic acid), and H5NOA2P (1,4,7-triazacyclononane-N,N′-bis(methylenephosphonic acid)-N″-methylene carboxylic acid), and their gallium(III) chelates were studied in view of their potential interest as scintigraphic and PET (Positron Emission Tomography) imaging agents. A 1H, 31P and 71Ga multinuclear NMR study gave an insight on the structure, internal dynamics and stability of the chelates in aqueous solution. In particular, the analysis of 71Ga NMR spectra gave information on the symmetry of the Ga3+ coordination sphere and the stability of the chelates towards hydrolysis. The 31P NMR spectra afforded information on the protonation of the non-coordinated oxygen atoms from the pendant phosphonate groups and on the number of species in solution. The 1H NMR spectra allowed the analysis of the structure and the number of species in solution. 31P and 1H NMR titrations combined with potentiometry afforded the measurement of the protonation constants (log KHi) and the microscopic protonation scheme of the triaza macrocyclic ligands. The remarkably high thermodynamic stability constant (log KGaL =34.44 (0.04) and stepwise protonation constants of Ga (NOA2P)2− were determined by potentiometry and 69Ga and 31P NMR titrations. Biodistribution and gamma imaging studies have been performed on Wistar rats using the radiolabeled 67Ga(NO2AP)− and 67Ga (NOA2P)2−chelates, having both demonstrated to have renal excretion. The correlation of the molecular properties of the chelates with their pharmacokinetic properties has been analysed.The authors thank the financial support from the Fundação para a Ciência e Tecnologia (F.C.T., Portugal, projects RREQ/481/QUI/2006 and RECI/QEQ-QFI/0168/2012), the Rede Nacional de RMN (RNRMN), the Hungarian Scientific Research Fund (OTKA grants K-109029 and K-120224), the János Bolyai Research Scholarship (Gy.T.) of the Hungarian Academy of Sciences and the EU COST Action TD1004 “Theragnostics Imaging and Therapy”. The research was also supported by the EU and co-financed by the European Regional Development Fund (FEDER) under the projects CENTRO-07-CT62-FEDER) and GINOP-2.3.2-15-2016-00008.info:eu-repo/semantics/publishedVersio