The double Smiles rearrangement in neutral conditions leading to one of 10-(nitropyridinyl)dipyridothiazine isomers

© 2016 Elsevier B.V.Phenothiazines are reported to exhibit very promising anticancer, antibacterial, antifungal, anti-inflammatory activities, reversal of multidrug resistance and many other actions. Synthesis of phenotiazines is mostly carried cyclization of o-aminodiphenyl sulfides proceeded through the Smiles rearrangement. The modifications of the phenothiazine structure via the substitution of the benzene ring with the pyridine ring gave various pyridobenzothiazines and dipyridothiazines. The reaction of 3-amino-3’-nitro-2,2’-dipyridinyl sulfide with 4-chloro-3-nitropyridine in sole DMF led to one of four possible isomeric nitropyridinyldipyridothiazines. Two-dimensional 1H and 13C NMR experiments (COSY, ROESY, HSQC and HMBC) were used to reveal the right product structure as 10-(3'-nitro-4'-pyridinyl)dipyrido[2,3-b; 2',3’-e] [1,4]thiazine (10-(3'-nitro-4'-pyridinyl)-1,6-diazaphenothiazine). The final structure confirmation came from a single crystal X-ray analysis. This structure is the result of very rare reaction mechanism involving the double Smiles rearrangement of the S[sbnd]N type. The tricyclic dipyridothiazine system is unexpectedly almost planar, with the butterfly angle of 176.39(4)° between two pyridine rings and 174.17(6)° between the halves of the thiazine ring (the NCCS) planes. The pyridinyl substituent is rotated about N10[sbnd]C11 bond and oriented almost perpendicularly to the tricyclic ring system with the dihedral angle between the two planar systems of 94.93(3)°. The nitropyridinyl substituent is located quasi-equatorially with the S⋯N10‒C11 angle of 176.92(8)°. The nitro group is tilted from the pyridine ring by 128.44(8)°

Using water-mimic organic compounds to activate guest inclusion by initially dry beta-cyclodextrin

© 2016 The Royal Society of Chemistry.Optimal conditions were found enabling anhydrous beta-cyclodextrin (bCD) to include target guests using small monofunctional organic compounds instead of water. Structural criteria were specified for organic substances with such water-mimic behavior. For this, a thermodynamic description of guest and water inclusion by initially dry bCD in binary systems was given using experimentally determined vapor sorption isotherms. These data perform a cooperative inclusion of each water-mimic guest and water with phase transition, and give the values of inclusion and hydration Gibbs energy, respectively. The observed inclusion cooperativity in binary systems with bCD defines a specific size-exclusion effect banning monofunctional organic compounds from entering the dry bCD phase if they exceed a threshold value of molecular size parameter near that of acetone. For larger guests, this threshold was shown to be removed in ternary systems by simultaneous inclusion with water-mimic guests or by solid-phase exchange of such guests. As well as water, water-mimic organic compounds activate the inclusion of target guests by initially dry bCD just by forming ternary clathrates, thus making all other hypotheses on the role of water and its mimics in this inclusion process excessive. These procedures may be useful for practical purposes when the presence of water does not give good results in clathrate preparation with bCD. This may provide a way for developing new techniques for the preparation of beta-cyclodextrin clathrates with various organic compounds

Pseudopolymorphs-a variety of self-organization of: Para -sulphonato-calix[8]arene and phenanthroline in the solid state

© 2016 The Royal Society of Chemistry.The paper presents results concerning construction of inclusion complexes of para-sulphonato-calix[8]arene with 1,10-phenanthroline. Structures of crystalline host-guest complexes were determined by means of X-ray diffraction. Intermolecular interactions were analyzed and the organization of ions and molecules in the crystal lattice was described

Study of β-cyclodextrin inclusion complexes with volatile molecules geraniol and α-terpineol enantiomers in solid state and in solution

© 2015 Elsevier B.V. All rights reserved. Geraniol and α-terpineol are insoluble in water volatile compounds. α-Terpineol is a potentially important agent for medical applications. Formation of molecular complexes with β-cyclodextrin would lead to the increase of water solubility and bioavailability. β-Cyclodextrin forms 2:2 inclusion complexes with both enantiomers of α-terpineol and their precursor geraniol. Solid state complexes are thoroughly characterized by single X-ray crystallography and their stability over vast range of temperatures is proven by TG analysis. Intermolecular host-guest, host-host and guest-guest interactions give good insight into the nature of formed inclusion complexes. Stability constants of the complexes in solution are determined by HPLC

31/Palliative effectiveness and tolerance of endobronchial HDR brachytherapy in patients with lung cancer -the preliminary experience of Oncology Centre in Gliwice, Department of Brachytherapy

AlmEndobronchial HDR brachytherapy (E-HDR-BT) is a well-established method of palliative treatment in patients with lung cancer. There is, however, no consensus on optimal radiation and the rate of complications. The aim of the work is to evaluate early effectiveness and tolerance of E-HDR-BT in palliative treatment of patients with lung cancer treated in Oncology Centre in Gliwice.Material and methodsSince 2000 in Oncology Centre in Gliwice HDR (Ir192) E-HDR-BT is used in palliative treatment of patients with bronchial obturation due to lung cancer. Regression of bronchial obturation and improvement in dyspnoea, cough and haemoptysis after therapy was analyzed for the first thirty patients. The total dose was 18 Gy, calculated at 1cm from the source, in 3 fraction (of 6 Gy) given everyweek.ResultsTwenty-five patients finished therapy as planned. Five patients didn’t complete treatment: two of them (6.6%) died because of massive haemoptysis; one patients suffered from exaggeration of angina pectoris, one patients developed high hectic fever not responding for antibacterial treatment, one suffered from exaggeration of their symptoms prohibiting continuation of the treatment. Changes in obturation of the bronchi and in patient's symptoms are shown in Table 1.Table 1Changes in obturation of the bronchi and in patient's symptom.SymptomsImprovementNochangesExaggerationObturation #/%22/88%3/12%0Dyspnoea #/%15/54%11/40%2/7%Cough #/%4/27%10/67%2/7%Haemoptysis #/%2/14%10/72%2/14%More detailed analysis of improvements in symptoms has been carried out according to own scoring system for dyspnoea, cough and haemoptysis. Mean duration of palliative response was 55 days (1–405). Mean survival time was 114 days (2–406).ConclusionE-HOR-BT is an effective method of palliation of symptoms related to bronchial obturation in course of lung cancer. The most frequent serious treatment complication of E-HOR-BTwas massive haemoptysis

Smart Polymorphism of Thiacalix[4]arene with Long-Chain Amide Containing Substituents

© 2017 American Chemical Society.A problem of controlled (smart) formation of polymorphs was solved for a set of tert-butylthiacalix[4]arene derivatives with four N-(2-acetoxyethyl)carbamoylmethoxy substituents at the lower rim with 1,3-alternate, cone, and partial cone conformations. For this, an effective polymorph screening with a reproducible influence of preparation history was achieved using guest vapor inclusion and a standard state of host glass powder. By this procedure with consequent guest release and heating, the ability of the studied calixarenes for polymorphism was investigated and compared as a function of their macrocycle conformation. The data of simultaneous thermogravimetry and differential scanning calorimetry with mass spectrometry of evolved vapors were determined together with the data of powder X-ray diffraction for the initial host samples, intermediate clathrates, and final polymorphs. In addition, single crystal X-ray diffraction data were obtained for four crystalline forms of the studied calixarenes. The results yielded a structure-property relationship, where 1,3-alternate calixarene without an extended H-bonded supramolecular network at least in one crystalline form has a much higher ability for polymorphism than the other two conformations. Thus, 10 polymorphs with essentially different crystal packing were found for this calixarene including a unique tetramorphism with four consecutive melting points of guest-free polymorph and corresponding three crystallization ranges. This ability of 1,3-alternate calixarene is linked with its other smart property: selective crystallization of its compact glass in vapors of binary liquid mixtures, which can be used for visual detection of very small benzene impurities (0.5% (v/v)) in cyclohexane

Molecular cloning and transcriptional activity of a new Petunia calreticulin gene involved in pistil transmitting tract maturation, progamic phase, and double fertilization

Calreticulin (CRT) is a highly conserved and ubiquitously expressed Ca2+-binding protein in multicellular eukaryotes. As an endoplasmic reticulum-resident protein, CRT plays a key role in many cellular processes including Ca2+ storage and release, protein synthesis, and molecular chaperoning in both animals and plants. CRT has long been suggested to play a role in plant sexual reproduction. To begin to address this possibility, we cloned and characterized the full-length cDNA of a new CRT gene (PhCRT) from Petunia. The deduced amino acid sequence of PhCRT shares homology with other known plant CRTs, and phylogenetic analysis indicates that the PhCRT cDNA clone belongs to the CRT1/CRT2 subclass. Northern blot analysis and fluorescent in situ hybridization were used to assess PhCRT gene expression in different parts of the pistil before pollination, during subsequent stages of the progamic phase, and at fertilization. The highest level of PhCRT mRNA was detected in the stigma–style part of the unpollinated pistil 1 day before anthesis and during the early stage of the progamic phase, when pollen is germinated and tubes outgrow on the stigma. In the ovary, PhCRT mRNA was most abundant after pollination and reached maximum at the late stage of the progamic phase, when pollen tubes grow into the ovules and fertilization occurs. PhCRT mRNA transcripts were seen to accumulate predominantly in transmitting tract cells of maturing and receptive stigma, in germinated pollen/growing tubes, and at the micropylar region of the ovule, where the female gametophyte is located. From these results, we suggest that PhCRT gene expression is up-regulated during secretory activity of the pistil transmitting tract cells, pollen germination and outgrowth of the tubes, and then during gamete fusion and early embryogenesis

Colombo Focus City Project : data brief; 2009 quarter 1

This Data Brief focuses on perceptions of wellbeing of Under-served Settlement (USS) households as well as income and expenditure patterns, and satisfaction regarding access to existing service provision. It provides an introduction to the Baseline Survey sampling, providing information on environmental burdens that are linked to limited service provision, including sewerage and solid waste management facilities and their impact on poverty. The Colombo (Sri Lanka) study uses water and sanitation as an entry-point to develop a model of participatory service provision that addresses how best to deliver different types of urban services to the urban poor