The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64 (16)°. In the crystal, molecules are linked by O—-H⋯O and N—H⋯O hydrogen bonds, forming chains along [010]. In addition, weak C—H⋯O, C—H⋯π and π–π interactions further link the structure into a three-dimensional network.The title molecule adopts an  17H12N2O3·H2O comprises two molecules of (E)-3-(1H-indol-2-yl)-1-(4-nitrophenyl)prop-2-en-1-one and a water molecule. The main molecule adopts an s-cis configuration with respect to the C=O and C=C bonds. The dihedral angle between the indole ring system and the nitro-substituted benzene ring is 37.64 (16)°. In the crystal, molecules are linked by O—-H⋯O and N—H⋯O hydrogen bonds, forming chains along [010]. In addition, weak C—H⋯O, C—H⋯π and π–π interactions further link the structure into a three-dimensional network. The optimized structure was generated theoretically via a density functional theory (DFT) approach at the B3LYP/6–311 G++ basis level and the HOMO–LUMO behaviour was elucidated to determine the energy gap. The obtained values of 2.70 eV  and 2.80 eV (DFT) are desirable for optoelectronic applications. The intermolecular interactions were quantified and analysed using Hirshfeld surface analysis.The asymmetric unit of the title compound, 2C In addition, the chalcone bridge consists of two different double bonds, C=C and C=O, which contribute to the conjugation of charge transfer, leading to their excellent structural and spectroscopic properties  group as an acceptor group because the decrease of the resonance effect leads to substantial changes in π-electron delocalization in the ring  level, providing information about the geometry of the molecule. The optimized structure is shown in Fig. 1b. The geometrical parameters are mostly within normal ranges, the slight deviations from the experimental values are due to the fact that the optimization is performed in isolated conditions, whereas the crystal environment and hydrogen-bonding interactions affect the results of the X-ray structure  Å] and C9=C10 [1.310 (5) Å] bonds. The compound is twisted about the C10—C11 bond with C9—C10—C11—O1 torsion angle of −21.9 (6)°. The corresponding torsion angle obtained from the DFT study is 0.08°. In addition, the molecule is twisted about the C11—C12 bond with an O1—C11—C12—C13 torsion angle of 167.7 (4)° . The differences between the experimental and calculated values show that the intermolecular hydrogen bond involving the water molecule does not affect the planarity of the compound. A previous study  adopts an c). The enone group (O1/C9–C11) with maximum deviation of 0.082 (3) Å at C11 forms dihedral angles of 21.5 (2) and 16.3 (2)° with the indole ring system and the nitro-substituted benzene ring, respectively.The overall conformation of the molecule can be described by the dihedral angle formed by the indole ring system (N1/C1–C8) and the nitro-substituted benzene (C12–C17) ring with a value of 37.64 (16)° Fig. 1c. The evia O—H⋯O and N—H⋯O hydrogen bonds involving the solvent water molecule. The water molecule is connected to the carbonyl group and indole ring system by intermolecular O1W—H1OW⋯O1i and N1—H1A⋯O1W hydrogen bonds . Furthermore, C9—H9A⋯Cg1 interactions  are observed along the a-axis direction, completing the three-dimensional structure. Two of the anti-parallel molecules are linked by π–π stacking interactions  involving the centroids (Cg2 and Cg3) of the C1–C6 and C12–C17 rings with a centroid–centroid distance Cg2⋯Cg3  of 3.534 (3) Å. These π–π interactions further stabilize the crystal structure.In the crystal, four symmetry-related molecules are connected to each other s Table 1, formingon Fig. 2. In addis Table 1 link thene Fig. 3a. Furthns Fig. 3a involvCrystalExplorer3.1  pair and the full fingerprint is outlined in grey  plots were generated with ds Fig. 4. The finds Fig. 4. The H⋯Hde in . With the shape-indexed mapping, the C—H⋯π interactions can be observed as a bright-red spot identified with black arrows in Fig. 6b. The blue spots near the ring represent the reciprocal C—H⋯π interactions.The presence of the C—H⋯π interactions can be seen in the pale-orange spot inside the circle of black arrows on the Hirshfeld surface mapped over in Fig. 6a. With Eg) between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) is a crucial factor in elucidating the molecular electrical transport properties. In the present study, the HOMO and LUMO were computed at the DFT/B3LYP/6-311G++ theoretical level and the respective plots of the frontier molecular orbital are illustrated in Fig. 7et al., 2014et al., 2015et al., 2018Frontier molecular orbital analysis is a vital tool in the development of molecular electronic properties. The energy gap -3-(2-methylphenyl)-1-(4-nitrophenyl)prop-2-en-1-one ethanone (0.5 mmol) and indole-2-carboxaldehyde (0.5 mmol) was dissolved in methanol (20 mL). Sodium hydroxide (NaOH) solution was then added dropwise under vigorous stirring. The reaction mixture was stirred for 5–6 h at room temperature. The final precipitate was filtered, washed with distilled water and recrystallized by slow evaporation from acetone solution to obtain orange plate-shaped crystals.The title compound was synthesized Uiso(H) = 1.2Ueq(C). The water O atom was refined with half-occupancy. The O- and N-bound H atoms were located from difference-Fourier maps and refined freely.Crystal data collection and structure refinement details are summarized in Table 210.1107/S2056989018014329/lh5883sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018014329/lh5883Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018014329/lh5883Isup3.cmlSupporting information file. DOI: 1846181CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecules are connected  N,N-dimethylformamide (1/1/1), C14H10O4S2·C7H5ClO2·C3H7NO, contains a molecule each of 2,2′-dithiodibenzoic acid (DTBA), 2-chlorobenzoic acid (2CBA) and dimethylformamide (DMF). The DTBA molecule is twisted [the C—S—S—C torsion angle is 88.37 (17)°] and each carboxylic group is slightly twisted from the benzene ring to which it is connected [CO2/C6 dihedral angles = 7.6 (3) and 12.5 (3)°]. A small twist is evident in the molecule of 2CBA [CO2/C6 dihedral angle = 4.4 (4)°]. In the crystal, the three molecules are connected by hydrogen bonds with the two carboxylic acid residues derived from DTBA and 2CBA forming a non-symmetric eight-membered {⋯HOCO}2 synthon, and the second carboxylic acid of DTBA linked to the DMF molecule via a seven-membered {⋯HOCO⋯HCO} heterosynthon. The three-molecule aggregates are connected into a supramolecular chain along the a axis via DTBA-C—H⋯O(hydroxyl-2CBA), 2CBA-C—H⋯O(hydroxyl-DTBA) and DTBA-C—H⋯S(DTBA) interactions. Supramolecular layers in the ab plane are formed as the chains are linked via DMF-C—H⋯S(DTBA) contacts, and these inter-digitate along the c-axis direction without specific points of contact between them. A Hirshfeld surface analysis points to additional but, weak contacts to stabilize the three-dimensional architecture: DTBA-C=O⋯H(phenyl-DTBA), 2CBA-Cl⋯H(phenyl-DTBA), as well as a π–π contact between the delocalized eight-membered {⋯HOC=O}2 carboxylic dimer and the phenyl ring of 2CBA. The latter was confirmed by electrostatic potential (ESP) mapping.The asymmetric unit of the three-component title compound, 2,2′-dithiodibenzoic acid–2-chlorobenzoic acid– In this three-component crystal, one of the carboxylic acid groups of the DTBA molecule forms hydrogen bonds to DMF rather than to 2CBA. Herein, the crystal and molecular structures of the title co-crystal solvate are described along with an analysis of the calculated Hirshfeld surfaces and a computational chemistry study.Recent bibliographic reviews have highlighted the rich coordination chemistry based on ligands derived from 2-mercaptobenzoic acid (2-MBA) . The asymmetric unit comprises 2,2′-dithiodibenzoic acid (DTBA), 2-chlorobenzoic acid (2CBA) and a dimethylformamide (DMF) solvent molecule in a stoichiometric 1:1:1 ratio, as illustrated in Fig. 1The title compound, (I)et al., 2007As anticipated, crystallography reveals that the original 2-mercaptobenzoic acid underwent oxidation to yield a molecule of DTBA, with the benzoic acid moieties being bridged through a disulfide bond [S1—S2 = 2.053 (1) Å]. The presence of carboxylic acid groups is confirmed by the disparity in the bond lengths for C8—O4, O3 [1.317 (4) and 1.229 (4) Å] and C21—O6, O5 [1.326 (4) and 1.209 (4) Å]. Both carboxylic acid groups (O3—C8—O4 and O5—C21—O6) are slightly twisted from the benzene rings (C9/C14 and C15/C20) to which they are bonded with the corresponding dihedral angles being 7.6 (3) and 12.5 (3)°, respectively. The C14—S1—S2—C15 torsion angle is 88.37 (17)°, indicating an almost orthogonal disposition between the benzene rings. The carbonyl-O3 and O5 atoms are oriented towards the disulfide-S1 and S2 atoms with S1⋯O3 and S2⋯O5 distances of 2.713 (2) and 2.661 (3) Å, respectively, and are indicative of hypervalent S←O interactions  and 1.320 (4), respectively. The carboxylic acid group is almost co-planar with the phenyl ring (C2–C7) as seen in the dihedral angle of 4.4 (4)° between their planes. Similarly, co-planarity is also noted between the chloride atom and benzene ring plane with the r.m.s deviation from the least-squares plane through the seven non-hydrogen atoms being 0.027 Å.PLATON .The geometric parameters characterizing the interatomic contacts in the crystal of (I)2 homosynthon, as well as discrete DTBA-C11—H11⋯S1(DTBA) interactions. These lead to a supramolecular chain along the crystallographic a direction, as indicated in Fig. 2b). Interactions between the chains leading to a layer in the ab plane occur through DMF-C24—H24C⋯S2(DTBA) contacts, Fig. 2c). The layers inter-digitate along the c-axis direction with only weak contacts between them as detailed in the next section.The resultant three-molecule aggregates are connected by DTBA-C10—H10⋯O2(hydroxyl-2CBA) and 2CBA-C3—H3⋯O4(hydroxyl-DTBA) interactions to form a non-symmetric, ten-membered {⋯OCCCH}Crystal Explorer 17 dnorm maps of the respective molecules in the aggregates are shown in Fig. 3dnorm map signifying close contacts which originate from DTBA-O—H⋯O(carbonyl-2CBA), DTBA-O—H⋯O(carbonyl-DMF), DTBA-C=O⋯H(hydroxyl-2CBA) and DTBA-C=O⋯H(DMF). Other red spots are observed through the dnorm map, albeit with relatively weak intensity. The contacts are consistent with those identified above except for some additional interactions such as DTBA-C=O⋯H(phenyl-DTBA), 2CBA-Cl⋯H(phenyl-DTBA) as well as a π–π contact between the delocalized eight-membered {⋯HOC=O}2 carboxylic dimer and the phenyl ring of 2CBA, Fig. 3b). To validate the non-conventional π–π contact, the interacting molecules were subjected to electrostatic potential (ESP) mapping using Spartan’16  level of theory. The ESP mapping shows that the dimeric ring ranges from electropositive to neutral within the centre of the ring while the phenyl ring of 2CBA is mainly neutral indicating that the interaction is mainly diffusive in nature, Fig. 3c) and (d). As for the 2CBA and DMF molecules, the corresponding dnorm maps (not shown) are reflective of their interactions with the DTBA molecule.The di + de ∼2.20 Å), O⋯H/H⋯O , C⋯H/H⋯C , S⋯H/H⋯S , Cl⋯H/H⋯Cl  and other contacts (14.0%). Almost all of these contacts are shorter than their corresponding sum van der Waals radii, with H⋯H, O⋯H, C⋯H, S⋯H and Cl⋯H being ∼2.4, ∼2.72, ∼2.9, ∼3.0 and ∼2.95 Å, respectively.The two-dimensional fingerprint plots were generated to quantify the close contacts identified on the Hirshfeld surfaces. The overall fingerprint plot of (I)di + de contact distance of ∼2.18 and ∼2.24 Å for DTBA and 2CBA, respectively. The O⋯H/H⋯O contacts are the second most dominant contact for the individual molecules which lead to the distinctive spikes in the corresponding decomposed fingerprint plots with a contribution of 26.4% for DTBA and 22.2% for 2CBA. Further delineation of the contact shows that DTBA possesses about 11.1% of -H⋯O- and 15.3% -O⋯H- compared to 2CBA with 10.9 and 11.2% of the equivalent contacts, both with approximately the same di + de contact distance of ∼1.70 Å for DTBA and ∼1.62 Å for 2CBA. Additional contacts for DTBA and 2CBA are respectively dominated by C⋯H/H⋯C , S⋯H/H⋯S  and Cl⋯H/H⋯Cl . As for the DMF solvent molecule, this exhibits a relatively different claw-like profile with several disproportional spikes observed in the fingerprint plot mainly owing to the asymmetric interaction environment for the O⋯H/ H⋯O contact, in which the contribution of -O⋯H- contact to the Hirshfeld surfaces is about 14.6% (di + de ∼1.60 Å), while the -H⋯O- contact is about 11.2% (di + de ∼2.22 Å) that can be summed up to yield an overall 25.8%. The contribution of other short contacts is noted in decreasing order: H⋯H , C⋯H/ H⋯C  and H⋯S , respectively.The DTBA and 2CBA molecules display similar fingerprint patterns having a claw-like profile in the respective full fingerprint plots, implying the existence of nearly identical interactions between the molecules which is expected considering the similarity of their molecular structures. Detailed analysis of the decomposed fingerprint plots shows that H⋯H is the most prevalent contact for the molecules, with the percentage contribution to the overall contacts of 29.7 and 25.0% and minimum Crystal Explorer 17, Table 2Eint) of −73.2 kJ mol−1. This energy is about one and a half-fold greater than the second strongest interaction that occurs between DTBA-DMF [DTBA-O—H⋯O(carbonyl-DMF)/ DTBA=O⋯H—C-(DMF)] with an Eint = −45.9 kJ mol−1. The disparity in energy is likely due the replacement of one O—H⋯O hydrogen bond with a C—H⋯O interaction in the latter interaction.The energy calculations through 2 and the 2CBA-benzene ring gives an energy of −15.9 kJ mol−1 which is considered weak in nature. This indicates the energy is mainly dominated by dispersive forces, Table 2Eint for other interactions present in the crystal were also calculated and the results are summarized as in Table 2−1 which can be considered weak.On the other hand, the π–π interaction between the hydrogen bond-mediated dimer of (DTBA)c-axis direction. A relatively weaker dispersion force co-exists along with the main energy framework due to π–π interactions which help to sustain the overall molecular packing of (I)The energy frameworks of (I)ba), in (II) the two DTBA molecules (DTBA-IIa and DTBA-IIb) form hydrogen bonds with each other, to yield a non-symmetric homosynthon, and with the two remaining carboxylic acid groups being hydrogen bonded to two 3CBA molecules to give rise to a four-molecule aggregate.A structural analogue of (I)Mercury ca 12.4%) which is approximately 6% greater than 2CBA in (I)ca 6.3%).Both (I)et al., 2016et al., 20062 synthon in carboxylic acid structures, i.e. 33%, emphasizing that this particular synthon can be readily disrupted in the presence of competing synthons  solution of the ground mixture. M.p. 437.3–438.9 K. IR (cm−1): 3076 ν(C—H), 1678 ν(C=O), 1473 ν(C=C), 1426 δ(C—H), 736 δ(C—Cl).All chemical precursors were of reagent grade and used as received without further purification. 2-Mercaptobenzoic acid  was mixed with 2-chlorobenzoic acid  and ground for 15 mins in the presence of a few drops of methanol. The procedure was repeated three times. Colourless blocks were obtained through the careful layering of toluene (1 ml) on an Uiso(H) set to 1.2–1.5Ueq(C). The oxygen-bound H atoms were located from difference Fourier maps and refined without constraint. Owing to poor agreement, one reflection, i.e. (4 2 2), was omitted from the final cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S205698901900375X/hb7808sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901900375X/hb7808Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900375X/hb7808Isup3.cmlSupporting information file. DOI: 1903993CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the components are linked by Owater—H⋯N, N—H⋯Owater and N—H⋯N hydrogen bonds, forming chains along the [100] direction. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to the ab plane. Finally, the layers are linked by C—H⋯π interactions, forming a three-dimensional structure.The asymmetric unit of the title compound contains two independent organic molecules which differ primarily in the dihedral angle between the aromatic rings,  20H20N4O·0.5H2O, contains two independent organic molecules (1 and 2) and a water molecule of crystallization. The two molecules differ primarily in the dihedral angles between the aromatic rings, which are 7.79 (7) and 29.89 (7)° in molecules 1 and 2, respectively. In each molecule there is intramolecular C—H⋯O hydrogen bond forming an S(6) ring motif. In molecule 1 there is an intramolecular N—H⋯π(pyrazole) interaction and an intramolecular C—H⋯π(pyrazole) interaction present. Molecule 1 is linked to molecule 2 by a C—H⋯π(benzene ring) interaction. An intramolecular N—H⋯N hydrogen bond and an intramolecular C—H⋯N hydrogen bond are also present in molecule 2. In the crystal, the three components are linked by Owater—H⋯N, N—H⋯Owater and N—H⋯N hydrogen bonds, forming chains along the [100] direction. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to the ab plane. Finally, the layers are linked by C—H⋯π interactions, forming a three-dimensional structure.The asymmetric unit of the title compound, C We report herein on its crystal and molecular structures along with the Hirshfeld surface analysis.Pyrazole derivatives are biologically active heterocyclic compounds  ring motif  and 1.3596 (16) Å, respectively.The pyrazole ring (N1/N2/C2–C4) in molecule 1 is inclined to the benzene rings (C7–C12 and C14–C19) by 70.83 (8) and 76.79 (8)°, respectively. The corresponding dihedral angles in molecule 2, involving the N5/N6/C22–C24 pyrazole ring and the C27–C32 and C34–C39 benzene rings, are 68.47 (8) and 81.91 (8)°, respectively. In both molecules there is an intramolecular C—H⋯O hydrogen bond forming an if Fig. 1. In the In molecule 1, an intramolecular N—H⋯π(pyrazole) interaction and an intramolecular C—H⋯π(pyrazole) interaction are present Fig. 1. Molecuwater—H⋯N and N—H⋯Owater hydrogen bonds, and by N—H⋯N hydrogen bonds, forming chains propagating along the a-axis direction; see Fig. 3ab plane phenyl]acetamides gave many hits. A search for the substructure [2-(benzylideneamino)phenyl]acetamide gave 19 hits, some of which are metal complexes. The structures most similar to the title compound include: N-(2-{[(2-hydroxyphenyl)methylidene]amino}phenyl)-2,2-dimethylpropanamide aniline -N-(o-nitrobenzilidene)aniline -N-(m-nitrobenzilidene)aniline ° for POSPET, 16.2 (2)° for RIHHOF, 41.81 (14)° for RIHHUL and 11.2 (4)° in RIHJAT. The dihedral angles between the aromatic rings in the title compound are 7.79 (7) and 29.89 (7)° in molecules 1 and 2, respectively.A search of the Cambridge Structural Database -1-(2-hydroxyphenyl)ethylidene]amino}phenyl)-2-methoxyacetamide amino]phenyl}acetamides gave an interesting hit, namely that for CrystalExplorer17.5  to 1.583 (blue) Å. Fig. 6dnorm mapped on the Hirshfeld surface.The Hirshfeld surface analyse was carried out using a (H⋯H) illustrates the two-dimensional fingerprint of the  points associated with hydrogen atoms. It is characterized by an end point that points to the origin and corresponds to id = ed = 1.08 Å, which indicates the presence of the H⋯H contacts in this study (54%). Fig. 8b (C⋯H/H⋯C) shows the contacts between the carbon atoms inside the surface and the hydrogen atoms outside the surface of Hirshfeld and vice versa (24%). The O⋯H/H⋯O (11.5%) plot shows two symmetrical wings on the left and right sides . The N⋯H/H⋯N interactions (6.5%) are visualized in Fig. 8d.Fig. 7es Fig. 8c. The NN-2-aminophenyl-5-methylpyrazol-3-ylacetamide  with 4-methylbenzaldehyde  in acetone (50 ml) for 3 h. The solvent was evaporated under vacuum, and then water was added. The precipitate formed was filtered under vacuum and purified through silica gel column chromatography using hexane/ethyl acetate , yielding colourless rod-like crystals of the title compound (yield 63%).The title compound was prepared by stirring Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018017747/xu5954sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018017747/xu5954Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018017747/xu5954Isup3.cmlSupporting information file. DOI: 1885214CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, molecules form stacks along the [001] direction. The crystal packing is further stabilized by O—H⋯O and C—H⋯O hydrogen bonds and C—H⋯Cl and C—H⋯π contacts.The title compound, C 14H12ClNO3, is a Schiff base that exists in the keto–enamine tautomeric form and adopts a Z configuration. In the crystal, the dihedral angle between the planes of the benzene rings is 5.34 (15)°. The roughly planar geometry of the molecule is stabilized by a strong intramolecular N—H⋯O hydrogen bond. In the crystal, pairs of centrosymmetrically related molecules are linked by O—H⋯O hydrogen bonds, forming R22(10) rings. Besides this, the molecules form stacks along the [001] direction with C—H⋯π and C—H⋯Cl contacts between the stacks. The intermolecular interactions in the crystal were analysed using Hirshfeld surfaces. The most significant contribution to the crystal packing is from H⋯H contacts (30.8%).The title compound, C Such compounds can exist in two tautomeric forms, viz. keto–enamine (N—H⋯O) and phenol–imine (N⋯H—O) . The whole molecule is almost planar, with a dihedral angle of 5.34 (15)° between the benzene ring planes. The methoxy C14 atom deviates from the plane of the C1–C6 benzene ring by 0.038 (4) Å. The torsion angles C1—C6—N1—C7 and N1—C7—C8—C9 are 5.8 (5) and −0.6 (5)°, respectively. The planar molecular conformation is stabilized by the intramolecular N1—H2⋯O2 hydrogen bond -(phenylimino)methyl]-benzene-1,2-diol fragment revealed eight hits where this fragment adopts the keto–enamine tautomeric form and 21 hits where it exists as the phenol–imine tautomer. Distinctive bond lengths  in the title structure are the same within standard uncertainties as the corresponding bond lengths in the structures of 2-hydroxy-6-[(2-methoxyphenyl)aminomethylene]cyclohexa-2,4-dienone iminomethyl]benzene-1,2-diol  and 5-chloro-2-methoxyaniline , both in 15 mL of ethanol, with subsequent stirring for 5 h under reflux. Single crystals were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(C) for methyl H atoms. The O- and N-bound H atoms were located in a difference map and freely refined.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019002123/yk2119sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019002123/yk2119Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019002123/yk2119Isup3.cmlSupporting information file. DOI: 1886956CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Dear Editor,+ ROR‐gamma‐T+ innate lymphoid cell (ILC3) development.−/− mice,The BTB‐ZF  proteins play essential roles in the development of the immune system.−/− mouse. According to the surface maker expression by flow cytometry, D1 is a DN1‐like cell line, which is CD44+CD25−IL‐7Rα+. We sorted double positive (DP), CD4 single positive (SP) and CD8SP thymocytes from wild‐type C57BL/6 and IL‐7Rα mutant mice mentioned above ‐dependent thymic cell line derived from a p53α+Figure A. D1 cel+ cells to establish the stable cell line (Figure hi thymocytes in ScanT mice was also higher than that of their wild‐type littermates, although the percentage of TCRβhi thymocytes in ScanT mice was severely reduced (Figure Next we investigated the effect of Zbtb1 on IL‐7Rα expression. We transduced the D1 cells with either retroviral vector Mir‐CTR or Zbtb1‐overexpressing retrovirus, and sorted the GFPe Figure B. Consise Figure C. Interee Figure D. The ILd Figure E.Altogether, our results suggest that Zbtb1 and IL‐7Rα signalling can regulate each other during T‐cell development. IL‐7Rα signalling negatively regulate Zbtb1, and vice versa. Detailed molecular mechanisms by which Zbtb1 regulate IL‐7Rα expression in T cells are still under investigation.The authors confirm that there are no conflicts of interest. Click here for additional data file.


Arising from M. A. Bakar et al. Nature Commun. 10.1038/s41467-017-00720-3 (2017)1 A number of X-ray studies have reported gold compounds with short AuI···H contacts, but solid spectroscopic evidence for AuI···H bonding has been missing.1 Notably, during the revision of this work, Bourissou et al.2 and Straka et al.3 have provided evidence of true intramolecular AuI···H hydrogen bonds in [Cl–Au–L]+ complexes, where L is a protonated N-heterocyclic carbene. The studied compounds feature intramolecular AuI···H+–N bonds detected by means of NMR2 and infrared spectroscopies.3Hydrogen bonding to gold(I) and its effect on the structure and dynamics of molecules have been a matter of long debate.4 reported compound 1  NMR resonances at respective H(C) nuclei in 1 highly deshielded with respect to precursor 2  auride-like···hydrogen bonding interaction. In addition, computational analysis of NMR chemical shifts reveals that the deshielding effects at respective hydrogen nuclei are not directly related to Au···H–C hydrogen bonding in 1. It is well known that interactions of hydrogen with transition metals compounds may influence the 1H NMR shifts in unexpected ways.5Here, we show that the Au1, which is one of the four Au···H–C contacts in the molecule  as proposed in ref. 4. The calculated minimum Au···H distances (2.61–2.62 Å) are in excellent agreement with the reported ones (2.61–2.65 Å). To afford computational analysis of NMR chemical shifts9 (δ), the P(Ph)2 groups in 1 and 2 were replaced by P(CH3)2 groups in model systems 1′ and 2′ .8 Notably, the absence of the bulky P(Ph)2 ligands causes rotation of the central phenyl groups away from the Au6 cluster. The Au···H distances increase from 2.6 Å to 2.77 Å and the Au–H2–C2 angles bend from 167° to 144° 2 ligands that potentially stabilize the whole cluster via dispersion interactions among themselves.10 To avoid these undesirable changes in calculations, we fixed the core of 1 and 2 in optimization of 1′ and 2′ and only methyl groups were optimized.In the following, we analyze Au2···H2–C2 contact in ule Fig. . Computa1′ shows a low ED (0.016 e.bohr−3) with positive Laplacian (0.037 e.bohr−5) at the line critical point (LCP) of Au2···H2 interaction. These values are less than a half of those for reported Au···H+–N bonds.6 Small electron exchange between Au2 and H2 of 0.07 e (e = electron) is consistent with a dispersive interaction.12 The direction of the charge transfer in Au2···H2 interaction is from Au2 to H2  in 1′ have negative charge, about −0.15 e  analysis of 13 analysis of 1′ reveals a weak Au2···H2–C2 interaction channel  is found between H2–C2 and Au3 6p orbitals . This further points to a minimal stabilization effect of Au···H–C bonding in 1.Extended transition state-natural orbitals for chemical valence (ETS-NOCV)als Fig. . Notablyals Fig.  is also 1H chemical shifts between 1 and 2 (1′ and 2′) are in excellent agreement with the experimental ones, for H2 Δ1–2 = 4.4 ppm, Δ1′−2′ = 3.6 ppm, and Δexp1–2 = 4.4 ppm  arises from the diamagnetic part of the NMR chemical shift, Δδdia, which can be rationalized only by a depletion of electron density (ED) at the H2 nuclei. Molecular orbital (MO) analysis of Δδdia identifies that main part Δδdia (1.3 of 1.6 ppm) originates from four Au–P π-back-bonding MOs  at H2, H4, and H6 nuclei4 given in brackets in Fig. The calculated differences in 1′−2′ deshielding difference at H2 nuclei (2 ppm) is dominated by local Ramsey-type paramagnetic couplings15 between H2–C2 σ-bond  with C2 2py* in 1′, which is not possible in 2′, increases the MO ↔ MO* overlap in orbital magnetic couplings.16 This leads to the ~0.5 ppm larger paramagnetic deshielding at H2 in 1′ in this particular coupling  in 2′ contributes only by 0.2 ppm. An analogous mechanism is likely to be responsible also for the deshielding resonance at C2. The paramagnetic part of the Δing Fig. . Overall1 are an example of a weak  auride-like···hydrogen interaction, with small overall  stabilizing effect on the cluster structure. Instead, the stabilizing effect can be attributed to the dispersion interactions among the P(Ph)2 groups, as documented previously.10 Distinct δ(1H) NMR deshielding of C–H groups in contact with Au6 cluster in 1 as compared with the precursor 2 is due to (a) the differential ED at the H2 atom in 1 as compared to precursor 2, and (b) side-on orbital interactions between nearby Au3 atom and H–C MOs that increase the efficiency of the local Ramsey-type deshielding paramagnetic couplings in molecule 1 as compared with corresponding couplings in precursor 2.We conclude that the short Au···H contacts in Supplementary Information


It crystallizes in the non-centrosymmetric space group Pna21, with one molecule in the asymmetric unit, and is constructed from a pair of aromatic rings [2-(trifluoromethyl)phenyl and tetrazole], which are twisted by 76.8 (1)° relative to each other because of significant steric hindrance of the trifluoromethyl group at the ortho position of the benzene ring. In the crystal, very weak C—H⋯N and C—H⋯F hydrogen bonds and aromatic π–π stacking interactions link the molecules into a three-dimensional network. To further analyse the intermolecular interactions, a Hirshfeld surface analysis, as well as interaction energy calculations, were performed.The title compound, C Their biological properties, including antiviral, anticancer, anti-tuberculosis, antifungal and antioxidant activities have been shown by numerous studies  π,σ-complexes possessing non-linear optical properties 2(CF3SO3)2] 2]BF4 and [Cu(C11H9F3N4S)(NH2SO3)(MeOH)] based on 5-[(prop-2-en-1-yl)sulfanyl]-1-[2-(trifluoromethyl)phenyl]-1H-tetrazole (I)11H9F3N4S) have been reported recently 2]BF4 [dihedral angle = 78.0 (1)°] and [Cu(C11H9F3N4S)(NH2SO3)(MeOH)] [85.5 (1)°]  as well as calculation of the interaction energies were performed using CrystalExplorer . Fingerprint plots were produced to show the intermolecular surface bond distances with the regions highlighted for C—H⋯F  and C—H⋯N  interactions. The contribution to the surface area for H⋯H contacts is 19.8%.To further analyse the intermolecular interactions between the molecules of (I)⋯F Fig. 5b and C—⋯N Fig. 5c interCrystalExplorer. The total intermolecular energy is the sum of energies of four main components, viz. electrostatic, polarization, dispersion and exchange-repulsion factors of 1.057, 0.740, 0.871 and 0.618, respectively  covers C—H⋯N and C—H⋯F interactions with the neighbouring molecule generated by the symmetry code −x + 1, −y + 1, z − −1 and are mainly dispersive in nature.The interaction energies in (I)et al., 2016H-tetrazoles are known only as ligands in the structures of copper(I) and silver(I) π-complexes. In the crystal structures of bis[μ2-η2-5--1-phenyl-1H-tetrazole]diaquadisilver bis(tetrafluoroborate) sulfanyl]-1H-tetrazole}diaquadicopper bis(tetrafluoroborate) -5-[(prop-2-en-1-yl)sulfanyl]-1H-tetrazole}diaquadicopper bis(tetrafluoroborate) ethanol solvate sulfanyl]-1-[2-(trifluoromethyl)phenyl]-1H-tetrazole}bis(trifluoromethanesulfonato)dicopper {η2-1--5-[(prop-2-en-1-yl)sulfanyl]-1H-tetrazole}copper(I)} sulfanyl group is slightly elongated to 1.35–1.38 Å, in comparison with noncoordinated olefin bond value. The other S-substituted 1-phenyl-1H-tetrazole-5-thiol structures in the Cambridge Structural Database have different alkyl substituents, such as 2-naphthyl benzene was distilled in vacuo.The title compound was synthesized from 2-(trifluoromethyl)aniline by a multi-step reaction. Commercially available 2-(trifluoromethyl)aniline  was dissolved in the minimum amount of benzene and treated with carbon disulfide  and triethylamine . The solution was cooled to 273 K and left for 5 d. After complete precipitation of the triethylammonium dithiocarbamate salt, the solution was filtered. The solid was washed with anhydrous ether and air-dried for about 10 min. The salt was then dissolved in about 7.5 ml of chloroform, treated with 1.4 ml of triethylamine and cooled to 273 K. To this solution was added ethyl chloroformate  dropwise over a 15 min period under intensive stirring. The resulting solution was stirred at 273 K for 10 min and allowed to warm to room temperature over 1 h. The chloroform solution was washed with 3 3  and refluxed under intensive stirring until the suspension disappeared. The solution was cooled to room temperature and washed with TBME. The water fraction was separated and acidified with 3 M HCl (Caution! During the acidification beware of toxic HN3 gas). The sediment of 1-[2-(trifluoromethyl)phenyl]-1H-tetrazole-5-thiol was separated by filtration and used for alkylation without further purification.The obtained isothiocyanate  was mixed with water (10 ml) and NaNH-tetrazole-5-thiol  was dissolved in a solution of KOH  in ethanol (10 ml). To the solution allyl bromide  was added and the mixture was heated at 323 K for 1 h. The solvent was removed in vacuo and to the residue was added water (5 ml) and dichloromethane (10 ml). The dichloromethane was separated and removed to give the title compound. Colourless blocks of (I)1-[2-(Trifluoromethyl)phenyl]-11H , δ, p.p.m. 8.03 , 7.98–7.88 , 7.71 , 5.94 , 5.36 , 5.18 , 3.98 . Analysis calculated for C11H9F3N4S: C, 46.15; H, 3.17; N, 19.57; S, 11.20; found: C, 45.97; H, 3.04; N, 19.49; S, 11.27.NMR Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019011459/hb7842sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019011459/hb7842Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019011459/hb7842Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019011459/hb7842Isup4.cmlSupporting information file. DOI: 1947200CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


H-imidazol-3-ium chloride (IOH·Cl) is a new imidazolium salt with a hydroxy functionality.The title compound, 1,3-bis(4-hydroxyphenyl)-1 H-imidazol-3-ium chloride (IOH·Cl), C15H13N2O2+·Cl−, is a new imidazolium salt with a hydroxy functionality. The synthesis of IOH·Cl was achieved in high yield via a two-step procedure involving a diazabutadiene precursor followed by ring closure using trimethylchlorosilane and paraformaldehyde. The structure of IOH·Cl consists of a central planar imidazolium ring (r.m.s. deviation = 0.0015 Å), with out-of-plane phenolic side arms. The dihedral angles between the 4-hydroxyphenyl substituents and the imidazole ring are 55.27 (7) and 48.85 (11)°. In the crystal, O—H⋯Cl hydrogen bonds connect the distal hydroxy groups and Cl− anions in adjacent asymmetric units, one related by inversion  and one by the n-glide  and ] counterparts, with interplanar distances of 3.560 (3) and 3.778 (3) Å. The only other noteworthy intermolecular interaction is an O⋯O (not hydrogen bonded) close contact of 2.999 (3) Å between crystallographically different hydroxy O atoms on translationally adjacent molecules .Imidazolium salts are common building blocks for functional materials and in the synthesis of N-heterocyclic carbene (NHC) as σ-donor ligands for stable metal complexes. The title salt, 1,3-bis(4-hydroxyphenyl)-1 NaOtBu and NaH)  represent a versatile class of ligand systems for metal-center activation or stabilization in modern organic synthesis (Arduengo para-phenol substituents (C4–C9/O1 and C10–C16/O2) bonded to the imidazolium N atoms [N1—C4 = 1.442 (3) Å and N2—C10 = 1.441 (3) Å]. The phenol groups are out-of-plane, forming dihedral angles with the imidazolium ring of 55.27 (7) and 48.85 (11)° for rings C4–C9 and C10–C15, respectively. The hydroxy H-atom coordinates were refined freely and are slightly out-of-plane of their respective phenolic groups; the torsion angles are 9.1 (19)° for C6—C7—O1—H1O and 11 (2)° for C12—C13—O2—H2O.In the structure of IOH·Cl Fig. 2, there a− anion at  to two different IOH·Cl molecules, one related by inversion and the other by the n-glide. These hydrogen bonds, viz. O1i—H1Oi⋯Cl1 and O2ii—H2Oii—Cl1  and 21-screw [C3—H3⋯Clv; symmetry code: (v) −x − y + z + b and Table 1a–f) quantify the majority of intermolecular contacts as H⋯H  and C⋯H . In these diagrams, the O—H⋯Cl hydrogen bonds are indicated by sharp diagonal jutting spikes , while C—H⋯O interactions give less-pronounced spikes . C⋯C contacts, which are all as a result of π–π stacking, account for 6.6% of the intermolecular contacts .The most prominent intermolecular interactions in the crystals of IOH·Cl are O—H⋯Cl hydrogen bonds. These link the Cls Table 1. Short ces Fig. 7d, whilees Fig. 7e. C⋯C cts Fig. 7f.et al., 2016) on the three-ring fragment of the title compound yielded over 600 hits, ranging from similar simple salts to metal complexes containing analogous NHC frameworks. A search with H atoms bonded to the three carbons of the imidazole ring gave 180 hits. Of these, 28 had mesityl substituents, including IHOQUS , and the unsubstituted phenyl analog IPh·ClO4 -1,4-diazabutadiene (1)Synthesis of the precursor : to a round-bottomed flask charged with 15 ml of methanol, 4-phenolaniline  was added and stirred until fully dissolved. Glyoxal  was added to the reaction solution with stirring. Upon addition of glyoxal solution, 40 wt.% in H2O, a brown precipitate formed and the solution turned orange. The reaction was further stirred at room temperature for 5 h and the solid was vacuum filtered and washed with cold methanol . Step 2, Synthesis of IOH·Cl: ethyl acetate (10 ml) was pre-heated to 343 K. To the hot solution was added (1)  and paraformaldehyde . The reaction mixture was stirred until all of the paraformaldehyde had dissolved. To this was added a solution of trimethylchlorosilane (TMSCl)  in ethyl acetate (0.15 ml) dropwise over 5 min while stirring. The solution was stirred for 2 h and then placed in a refrigerator (275 K) overnight. The precipitate was collected by vacuum filtration and washed with cold ethyl acetate and ether until the filtrate was colorless, yielding a dark-orange solid . Crystals were grown by slow evaporation of a concentrated solution in acetone.The overall reaction for the synthesis of the title compound is depicted in Fig. 1Uiso(H) = 1.5Ueq(O). Carbon-bound H atoms were included in calculated positions and refined using a standard riding model, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C). Refinement progress was checked using an R-tensor .Crystal data, data collection, and structure refinement details are given in Table 210.1107/S2056989019011058/su5504sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019011058/su5504Isup2.hklStructure factors: contains datablock(s) I. DOI: 1946122CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the heterocyclic portion of the dihydrobenzothiazine unit adopts a flattened-boat conformation, while the oxazolidine ring adopts an envelope conformation. The 2-carbon link to the oxazole ring is perpendicular to the best plane through the dihydrobenzothiazine unit. In the crystal, the molecules form stacks extending along the normal to (104) through π-stacking interactions between the two carbonyl groups and inversion-related oxazole rings. Aromatic rings from neighbouring stacks intercalate to form an overall layer structure. 20H16Cl2N2O3S, is built up from a dihydrobenzothiazine moiety linked by –CH– and –C2H4– units to 2,4-dichlorophenyl and 2-oxo-1,3-oxazolidine substituents, where the oxazole ring and the heterocyclic portion of the dihydrobenzothiazine unit adopt envelope and flattened-boat conformations, respectively. The 2-carbon link to the oxazole ring is nearly perpendicular to the mean plane of the dihydrobenzothiazine unit. In the crystal, the molecules form stacks extending along the normal to (104) with the aromatic rings from neighbouring stacks intercalating to form an overall layer structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (28.4%), H⋯Cl/Cl⋯H (19.3%), H⋯O/O⋯H (17.0%), H⋯C/C⋯H (14.5%) and C⋯C (8.2%) interactions. Weak hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/ 6–311 G level are compared with the experimentally determined molecular structure in the solid state. The HOMO—LUMO behaviour was elucidated to determine the energy gap.The title compound, C A puckering analysis of the heterocyclic portion  of the dihydrobenzothiazine unit gave the parameters QT = 0.1206 (14) Å, q2 = 0.1190 (14) Å, q3 = −0.0174 (16) Å, φ = 178.2 (8)° and θ = 98.4 (8)°, indicating a flattened-boat conformation. A similar analysis for the oxazolidine ring C (O2/N2/C11–C13) yielded q2 = 0.1125 (18) Å and φ2 = 45.7 (9)°, indicating an envelope conformation with atom C12 at the flap position and at a distance of 0.175 (2) Å from the best plane of the other four atoms. The C9/C10 chain C is essentially perpendicular to the dihydrobenzothiazine unit, as indicated by the C6—N1—C9—C10 torsion angle of 90.61 (19)°. In the heterocyclic ring B, the C1—S1—C8 [104.29 (8)°], S1—C8—C7 [121.39 (12)°], C8—C7—N1 [120.77 (14)°], C7—N1—C6 [126.86 (14)°], C6—C1—S1 [123.97 (13)°] and N1—C6—C1 [121.60 (15)°] bond angles are enlarged compared with the corresponding values in the closely related compounds (2Z)-2-(4-chlorobenzylidene)-4-[2-(2-oxooxazoliden-3-yl)ethyl]-3,4-dihydro-2H-1,4-benzothiazin-3-one, (II), -2-[(4-fluorobenzylidene]-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzothiazin-3-one, (III), -4-[2-ethyl]-2(phenylmethylidene)-3,4-dihydro-2H-1,4-benzothiazin-3-one, (IV), ly Fig. 1. The benC ring at −x + 1, −y + 1, −z + 1  and between C13=O3 and the C ring at −x + 1, −y + 1, −z   through π-stacking interactions between C7=O1 and the ] Figs. 2 and 3 ▸.CrystalExplorer17.5  analysis  have a nearly symmetrical distribution of points, Fig. 8c, with thin edges at de + di = 2.88 Å. The fingerprint plot delineated into H⋯O/O⋯H contacts (17.0%), Fig. 8d, has a pair of characteristic wings with a pair of spikes with the tips at de + di = 2.48 Å. In the absence of C—H⋯π interactions, the pair of wings in the fingerprint plot delineated into H⋯C/C⋯H contacts (14.5%) have a nearly symmetrical distribution of points, Fig. 8e, with thick edges at de + di ∼2.66 Å. The C⋯C contacts (8.2%), Fig. 8f, have an arrow-shaped distribution of points with the tip at de = di ∼1.68 Å. Finally, the H⋯S/S⋯H  and C⋯Cl/Cl⋯C  contacts , and are seen as pairs of wide and thin spikes with the tips at de + di = 3.30 and 3.60 Å, respectively.The overall two-dimensional fingerprint plot, Fig. 8H Table 1 contribu⋯H Fig. 8g and C⋯⋯C Fig. 8h contacdnorm plotted onto the surface are shown for the H⋯H, H⋯Cl/Cl⋯H, H⋯O/O⋯H, H⋯C/C⋯H, C⋯C and H⋯S/S⋯H interactions in Fig. 9a–f, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6–311 G basis-set calculations -2-[methylidene]-4-[2-ethyl]3,4-dihydro-2H-1,4- benzothiazin-3-one ring. The energy band gap [ΔE = ELUMO − EHOMO] of the molecule is about 3.42 eV, and the frontier molecular orbital energies, EHOMO and ELUMO are −5.44 and −2.02 eV, respectively.The optimized structure of the title compound, (I)et al., 2016II -one , 2.20 equiv. of bis(2-chloroethyl)amine hydrochloride and 2.00 equiv. of potassium carbonate were added to a solution of (Z)-2--2H-1,4-benzothiazin-3(4H)-one (1.5 mmol) in DMF (25 ml). The mixture was stirred at 353 K for 6 h. After removal of salts by filtration, the solution was evaporated under reduced pressure and the residue obtained was dissolved in dichloromethane. The remaining salts were extracted with distilled water. The residue obtained was chromatographed on a silica gel column (eluent: ethyl acetate/hexane: 3/2). The isolated solid was recrystallized from ethanol solution to afford colourless crystals [light yellow in CIF?] (yield: 67%).Tetra-Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019004250/lh5895sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019004250/lh5895Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019004250/lh5895Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019004250/lh5895Isup4.cmlSupporting information file. DOI: 1906476CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure determination of Na 10[Pd2Cl6](C4H9SO3)8·4H2O, were obtained from a water/2-propanol solution of sodium n-butanesulfonate and sodium tetrachloridopalladate(II). In the crystal, sodium n-butanesulfonate anions and water molecules are arranged in an amphiphilic inverse bilayered cationic array represented by the formula {[Na10(C4H9SO3)8(H2O)4]2+}n. Within this lamellar array: (i) a hydrophilic layer region parallel to the bc plane is established by the Na+ cations, the H2O molecules  and the O3S– groups of the sulfonate ions, and (ii) hydrophobic regions are present containing all the n-butyl groups in an almost parallel orientation, with the chain direction approximately perpendicular to the aforementioned hydrophilic layer. Unexpectedly, the flat centrosymmetric [Pd2Cl6]2− anion in the structure is placed between the butyl groups, within the hydrophobic regions, but due to its appropriate length primarily bonded to the hydrophilic ‘inorganic’ layer regions above and below the hydrophobic area via Pd—Clt⋯Na- and Pd—Clt⋯H—O(H)—Na-type  interactions. In addition to these hydrogen-bonding interactions, both aqua ligands are engaged in charge-supported S—O⋯H—O hydrogen bonds of a motif characterized by the D43(9) graph-set descriptor within the hydrophilic region. The crystal structure of the title compound is the first reported for a metal n-butanesulfonate.In the course of crystal-engineering experiments, crystals of the hydrated title salt, Na In contrast to methanesulfonates (n = 1) and ethanesulfonates (n = 2), there is only rare structure information for the next higher homologues   chemistry.Sodium alkanesulfonates are artificial soaps (anionic tensides) with a widespread use  having the typical brown colour of palladium complexes with a square-planar coordination environment. According to the results of elemental analysis and vibrational spectroscopic investigations, hydrated sodium cations, n-butanesulfonate and hexachloridodipalladate(II) anions are present in the solid. The crystal structure determination of this compound is the first of a metal n-butanesulfonate and eventually confirmed the composition Na10(C4H9SO3)8[Pd2Cl6]·4H2O and a lamellar amphiphilic structure.In the investigation described herein, the incorporation of hexachloridodipalladate(II) anions into the sodium n-butanesulfonate anions and, close to a center of inversion, one half of a hexachloridodipalladate anion. The five Na+ cations are in quite different coordination environments . Bond lengths and angles of the n-butanesulfonate anions are as expected (see supplementary Tables). All these anions are found with an entirely anti-periplanar conformation of the alkyl groups, without any disorder. Altogether, n-butanesulfonate anions, Na+ cations and water molecules form a tenside-like inverse bilayered cationic array, which can be described by the formula {[Na10(H2O)4(C4H9SO3)8]2+}n. In this arrangement, the layer-like regions are oriented parallel to the bc plane of the unit cell. As visualized by the blue and the red sections of the transparent background of Fig. 3+ cations, the H2O molecules serving as aqua ligands in μ bridging mode coordination, and the O3S– groups of the sulfonate ions. With all the C4-chains in an approximately parallel orientation, the butyl groups are arranged on both sides of the hydrophilic region to complete the amphiphilic double layer with an inverse bilayer thickness according to unit-cell parameter a. The centrosymmetric [Pd2Cl6]2− anions in the structure of 1 are placed between the n-butyl groups within the hydrophobic regions. In a first view, this position seems to be unexpected; however, the length of the dipalladate(II) anion is appropriate to allow for pronounced bonding to the hydrophilic ‘inorganic’ layered regions above and below the hydrophobic area  and 2.3212 (12) Å]. These geometric parameters, as well as the Cl—Pd—Cl bond angles of 86.20 (4) to 92.45 (4)° and the Pd—μ-Cl—Pd angle of 93.80 (4)°, are in good agreement with those found in Cs2[Pd2Cl6] : Na8(C4H9SO3)8·Na2Pd2Cl6·4H2O. This choice takes into account that the Na—Cl distance from the terminal chlorido ligand Cl2 of the hexachloridodipalladate(II) anion to the sodium cation Na1 [2.8560 (18) Å] is close to the distances of 2.809 (3) to 2.821 (2) Å in Na2PdCl4  and 2.2800 (10) Å] are slightly shorter than the Pd—+ cations , the two crystallographically independent water molecules O1 and O2 in 1 are engaged in non-covalent bonding within the hydrophilic region (Table 12Cl6]2− anion [D⋯A distance = 3.127 (3) Å] and a charge-supported weak O—H⋯O type hydrogen bond to an O atom of a sulfonate anion containing S4 [D⋯A = 2.879 (4) Å]. In contrast, the water molecule containing O2 is engaged in two O—H⋯O type hydrogen bonds to sulfonate ions, one of moderate strength to an O atom of the sulfonate ion containing S4 [D⋯A = 2.723 (4) Å] and a weak one to an O atom of the sulfonate ion containing S3 [D⋯A = 2.884 (4) Å]. Pd—Clterm⋯H—O(Na2)—H⋯O14(S4)⋯H—O(Na2)—H⋯O—S is the entire path of hydrogen bonding described by the D34(9) graph-set descriptor  with n = 1–4 gave three hits, viz. the structures of sodium methanesulfonate  anion results in 46 entries. However, from a structural point of view, the role of the [Pd2Cl6]2− ion in 1 is completely different from the role of this species in all the other compounds. In addition to the reports on these compounds having organic components, there is one report on an inorganic ternary chloride containing the [Pd2Cl6]2− ion  of sodium n-butanesulfonate and 1.177 g (4 mmol) of sodium tetrachloridopalladate(II). The evaporation temperature of the solution was adjusted to 288 K with a thermostat. After three days, crystals suitable for X-ray crystal structure determination could be harvested . A single crystal was selected directly from the mother liquor. Raman spectroscopy was done with a Bruker MultiRAM spectrometer, equipped with a Nd:YAG laser (1064 nm) and an InGaAs detector (4000–70 cm−1): ν(C—H): 2969 (m), 2920 (s), 2872 (m); δs(C—H): 1445 (w), 1412 (w); δas(C—H): 1306 (w); νas(S—O): 1071 (s); νs(C—S): 800 (m); δ(S—O): 551 (m), 536 (m); ν(Pd—Clterm): 343 (m), ν(Pd—μ-Cl): 305 (s); ν(Pd—μ-Cl): 273 (m). Band assignments were made according to Fujimori  and an universal ATR equipment: ν(O—H): 3503 (s), 3462 (sh), 3436 (s), 3367 (s); ν(C—H): 2967 (s), 2936 (s), 2872 (m); δ(O—H): 1662 (m), 1602 (m); δs(C—H) 1465 (m), 1412 (w), 1378 (w), δas(C—H): 1314 (w), 1286 (w); νas(C—H): 1241 (w); νs(S—O): 1190 (s), 1166 (s); νas(S—O): 1057 (s), 1044 (s); νs(C—S): 794 (m); δ(S—O): 555 (m), 534 (m); band assignment according to Fujimori (195932H80Cl6Na10O28Pd2S8 (1824.84 g mol−1): C 21.06, H 4.42, S 14.06; found: C 20.78, H 4.49, S 12.98.Thin brown platelets of mori 1959 and Geri al. 1997. An IR smori 1959. A CHS a3 groups were allowed to rotate around the neighboring C—C bonds. The Uiso(H) values were set to 1.5Ueq(Cmethyl) and 1.2Ueq(Cmethylene), respectively. H—O distances of the water molecules were restrained to 0.83 (3) Å.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019004201/wm5491sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019004201/wm5491Isup2.hklStructure factors: contains datablock(s) I. DOI: 1906335CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Furthermore, ADAM10 participates to spine shaping through the cleavage of adhesion molecules and its activity is under the control of synaptic plasticity events. In particular, long-term depression (LTD) promotes ADAM10 synaptic localization triggering its forward trafficking to the synapse, while long-term potentiation elicits ADAM10 internalization. Here, we show that a short-term in vitro exposure to Aβ1–42 oligomers, at a concentration capable of inducing synaptic depression and spine loss, triggers an increase in ADAM10 synaptic localization in hippocampal neuronal cultures. However, the Aβ1–42 oligomers-induced synaptic depression does not foster ADAM10 delivery to the synapse, as the physiological LTD, but impairs ADAM10 endocytosis. Moreover, Aβ1–42 oligomers-induced inhibition of ADAM10 internalization requires neuronal activity and the activation of the NMDA receptors. These data suggest that, at the synaptic level, Aβ1–42 oligomers trigger an aberrant plasticity mechanism according to which Aβ1–42 oligomers can downregulate Aβ generation through the modulation of ADAM10 synaptic availability. Moreover, the increased activity of ADAM10 towards its synaptic substrates could also affect the structural plasticity phenomena. Overall, these data shed new lights on the strict and complex relationship existing between synaptic activity and the primary mechanisms of AD pathogenesis.A disintegrin and metalloproteinase 10 (ADAM10) is a synaptic enzyme that has been previously shown to limit amyloid-βThe online version of this article (10.1007/s12035-019-1583-5) contains supplementary material, which is available to authorized users. Then, to induce chemical LTD, we applied NMDA (20 μM) and glycine  for 3 min at room temperature in MgQuantification of Western Blot analysis was performed by means of computer-assisted imaging . The levels of the proteins were expressed as relative optical density (OD) measurements and normalized on tubulin. Values are expressed as mean ± S.E.M. of at least three independent experiments.t test  or, when appropriate, by using one-way ANOVA followed by Bonferroni’s post hoc test or Kruskal-Wallis analysis of variance followed by Dunn’s post hoc test.Co-localization analysis was performed using Zeiss AIM 4.2 software and spines analysis was performed with ImageJ software . For co-localization, and morphological analysis, cells were chosen randomly for quantification from 4 different coverslips (2–3 independent experiments), images were acquired using the same settings/exposure times, and at least 10 cells for each condition were analyzed. Statistical evaluations were performed by using 2-tailed Student’s Suppl. Fig. 11–42 short exposure does not affect the expression and synaptic levels of GluN1, GluN2A, GluN2B and PSD-95. A) Quantitative analysis of Western Blot analysis of homogenate reported in Fig.42–1 70.59 ± 17.76%, oAβ1–42 109.3 ± 14.55%; GluN2A, CTRL 100 ± 24.25, Aβ 42–1 119.9 ± 34.25%, oAβ1–42 80.28 ± 8.62%; GluN2B, CTRL 100 ± 30.65%, Aβ 42–1 90.94 ± 16.17%, oAβ1–42 99.64 ± 45.05%; PSD-95, CTRL 100 ± 20.64%, Aβ 42–1 132.2 ± 6.41%, oAβ1–42 111 ± 28.41%; p > 0.05, one-way ANOVA, n = 5); B) Quantitative analysis of Western Blot analysis of TIF reported in Fig.42–1 = 83.29 ± 32.03%, oAβ1–42 72.32 ± 13.9%; GluN2A CTRL 100 ± 16.60%, Aβ42–1 106.9 ± 10.78%, oAβ1–42 104.9 ± 18.36%; GluN2B, CTRL 100 ± 25.43%, Aβ42–1 117.3 ± 19.03, oAβ1–42 102.0 ± 14.97%; PSD-95, CTRL 100 ± 8.03, Aβ42–1 106.2 ± 5.13, oAβ1–42 102 ± 5.84; p > 0.05, one-way ANOVA, n = 5). (PNG 43 kb)oAβHigh Resolution Image (TIF 130 kb)Suppl. Fig. 21–42 short exposure does not affect the synaptic localization of SAP97 and β2-adaptin. A) Quantitative analysis of Western Blot analysis of SAP97 levels in TIF reported in Fig. 42–1 123.6 ± 29.07%, oAβ1–42 96.75 ± 21.64%; p > 0.05, one-way ANOVA, n = 5); B) Quantitative analysis of Western Blot analysis of β2-adaptin in TIF reported in Fig.42–1 = 101.50 ± 9.20%, oAβ1–42 110.60 ± 8.35%; p > 0.05, one-way ANOVA, n = 5) (PNG 44 kb)oAβHigh Resolution Image (TIF 109 kb)Suppl. Fig. 31–42-induced increase in ADAM10 synaptic availability does not involve the activation of GluN2B-containing NMDA receptors. The presence of ifenprodil , an inhibitor of GluN2B-containing NMDA receptors, does not affect oAβ1–42-triggered augment in ADAM10 synaptic levels  (PNG 66 kb)oAβHigh Resolution Image (TIF 134 kb)


In comparison with previous determinations, the present redetermination results in improved precision of the structural parameters.Sr 2PdO3  was carried out using high-quality single-crystal X-ray data. The Sr2PdO3 structure has been described previously in at least three reports [Wasel-Nielen & Hoppe  as reported previously. The structure consists of infinite chains of corner-sharing PdO4 plaquettes interspersed by SrII atoms. A brief comparison of Sr2PdO3 with the related K2NiF4 structure type is given.The crystal structure redetermination of Sroppe 1970. Z. Anor Roy 1971. Adv. Ch al. 2002. J. Allo The PdII atom forms distorted PdO4 square planes, which are linked by sharing oxygen atoms in the trans-position to form infinite chains extending along the b-axis direction as shown in Fig. 1j Wyckoff site having mm2 site symmetry. It is seven-coordinate in a monocapped trigonal–prismatic fashion by oxygen with three different bond lengths  × 3.7887 (2) × 3.9822 (3) Å3  Å] and five SrII atoms with one short [2.474 (2) Å] and four long distances [2.6668 (2) Å]  Å] and two PdII atoms [1.9911 (2) Å]  I. DOI: 10.1107/S2056989018017176/wm5474Isup2.hklStructure factors: contains datablock(s) I. DOI: 1882781CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Kip1 and p21Cip1, effectively canceled the accelerated activation of NF‐κB, suggesting that oncogenic Ras‐induced cell cycle progression is essential for the hyperactivation of NF‐κB. Furthermore, we found that Ras (G12V) augmented the transcriptional activation of NF‐κB, and this activation required the p38 MAP kinase. We observed that a downstream kinase of p38 MAP kinase, MSK1, was activated by Ras (G12V) and catalyzed the phosphorylation of p65/RelA at Ser‐276, which is critical for its transcriptional activation. Significantly, phosphorylation of the p65/RelA subunit at Ser‐276 was elevated in patient samples of colorectal cancer harboring oncogenic mutations of the K‐Ras gene, and the expression levels of NF‐κB target genes were drastically enhanced in several cancer tissues. These observations strongly suggest that oncogenic signal‐induced acceleration of NF‐κB activation is caused by activation of the p38 MAP kinase–MSK1 signaling axis and by cell cycle progression in cancer cells.It is well established that nuclear factor κB (NF‐κB) acts as one of the most important transcription factors for tumor initiation and progression, as it both protects cells from apoptotic/necrotic signals and accelerates angiogenesis and tumor metastasis, which is mediated via the expression of target genes. However, it has not yet been clarified how oncogenic signals accelerate the activation of NF‐κB. In the current study, we utilized untransformed NIH‐3T3 cells stably harboring a κB‐driven luciferase gene to show that an oncogenic mutant of Ras GTPase augmented TNFα‐induced NF‐κB activation. Notably, enforced expression of cyclin‐dependent kinase inhibitors, such as p27 CDKcyclin‐dependent kinaseCHXcycloheximideCOX‐2cyclooxygenase 2CRCcolorectal cancerDMEMDulbecco's modified Eagle's mediumGAPGTPase‐activating proteinICAM‐1intercellular adhesion molecule‐1IκBαinhibitor of κBαMSK1/2mitogen and stress activated protein kinase 1/2NF‐κBnuclear factor κBNPMnucleophosminPI‐3 kinasephosphatidylinositol‐3 kinasePKAprotein kinase ARHDRel homology domainshRNAshort‐hairpin RNATNFαtumor necrosis factor αVEGFvascular endothelial growth factor1et al., Nuclear factor κB (NF‐κB) includes a family of transcription factors, which induce the expression of a number of target genes related to anti‐inflammation, development, and the apoptosis‐related responses  supplemented with 10% FBS, 2 m2.2Kip1, and p21Cip1 were amplified by PCR using PrimeSTAR GXL DNA polymerase  and inserted into EcoRI and XhoI sites of MSCV‐ires‐Puro retroviral vector.pBabePuro‐H‐Ras (G12V) was a kind gift from S. Lowe, Sloan Kettering Institute. pBabePuro‐B‐RAF (V600E) was a gift from W. Hahn (Addgene plasmid # 15269). cDNA of p16Ink4a, p272.3An anti‐FLAG antibody (M2) was purchased from Merck Millipore . Anti‐cyclin A (SC‐751), anti‐cyclin D1 (SC‐753), anti‐CDC2 (SC‐163), anti‐CDK4 (SC‐601), anti‐H‐Ras (SC‐520), and anti‐β‐actin (SC‐130301) antibodies were obtained from Santa Cruz Biotechnology . An anti‐phospho p65/RelA (S276) antibody was purchased from Rockland Immunochemicals . Anti‐MSK1 and anti‐MSK2 antibodies were purchased from Cell Signaling Technology  and BD Biosciences , respectively. TNFα and PDGF were purchased from PeproTech . LY294002, U0126, SP600125, and SB203580 were obtained from FUJIFILM Wako Pure Chemical . NOX inhibitor, VAS2870, was purchased from Merck Millipore .2.46 cells per 60‐mm‐diameter culture dish) with helpers such as pE‐Eco and pGP (TAKARA‐Bio). Twenty‐four hours later, culture medium was replaced with 1.5 mL fresh culture medium. Secreted retroviruses were harvested every 4–6 h during 24–60 h post‐transfection, pooled, and stored on ice. Exponentially growing cells (1 × 105 cells per 60‐mm‐diameter culture dish) were infected several times at 2‐h intervals with 2 mL of virus‐containing conditioned medium with 1.0 µg·mL−1 polybrene (Merck Millipore). Twenty‐four hours later, the infected cells were cultured in completed medium including suitable concentrations of puromycin  for 3 days. Then, selected cells were utilized for the experiments.To obtain retroviruses, MSCV‐ires‐GFP or MSCV‐ires‐Puro encoding the cDNA of the indicated proteins was transfected into HEK293T cells  against murine MSK1/2 and human K‐Ras gene products were inserted into pSUPER‐retro‐puro retroviral plasmid . The sequences of oligonucleotides used for constructing the shRNA retroviral vector against each gene product were described as below: For sh‐mMSK1#1; GATCCCCGTGATTTACCAGAGAGAAATTCAAGAGATTTCTCTCTGGTAAATCACTTTTTA and AGCTTAAAAAGTGATTTACCAGAGAGAAATCTCTTGAATTTCTCTCTGGTAAATCACGGG, For sh‐mMSK1#2; GATCCCCGCCAATACTCAGAAAGAAATTCAAGAGATTTCTTTCTGAGTATTGGCTTTTTA and AGCTTAAAAAGCCAATACTCAGAAAGAAATCTCTTGAATTTCTTTCTGAGTATTGGCGGG, For sh‐MSK2#1; GATCCCCGCGGAGAGCTATTGGAACATTCAAGAGATGTTCCAATAGCTCTCCGCTTTTTA and AGCTTAAAAAGCGGAGAGCTATTGGAACATCTCTTGAATGTTCCAATAGCTCTCCGCGGG, For sh‐MSK2#2; GATCCCCGGGCATGAGGAGAAGGTGATTCAAGAGATCACCTTCTCCTCATGCCCTTTTTA and AGCTTAAAAAGGGCATGAGGAGAAGGTGATCTCTTGAATCACCTTCTCCTCATGCCCGGG, For sh‐K‐Ras#1; GATCCCCCGAATATGATCCAACAATATTCAAGAGATATTGTTGGATCATATTCGTTTTTA and AGCTTAAAAACGAATATGATCCAACAATATCTCTTGAATATTGTTGGATCATATTCGGGG, For sh‐K‐Ras#2; GATCCCCGGACGAATATGATCCAACATTCAAGAGATGTTGGATCATATTCGTCCTTTTTA and AGCTTAAAAAGGACGAATATGATCCAACATCTCTTGAATGTTGGATCATATTCGTCCGGG.Infection with retroviruses, including these shRNA, into NIH‐3T3 cells was performed at the same time with a retrovirus harboring oncogenic Ras.2.6−1 TNFα for 16 h. Cells were lysed with passive lysis buffer , and the activity of expressed luciferase was measured by using a Luciferase Assay kit (Promega). The specific activity of luciferase was calculated by normalizing with protein concentration of each cell lysate, and data were shown in the graph as relative amount. To observe the effect of each kinase inhibitor on the NF‐κB activation, cells were treated with the inhibitors 15 min prior to stimulation with TNFα. To analyze the transcriptional activation of NF‐κB, parental NIH‐3T3 cells were transfected with pFR‐luciferase containing the sequence of a GAL4‐responsive element with the indicated combination of plasmids. Cells were cultured in serum‐free DMEM for 24 h, and then, the cells were harvested, and luciferase activity was assayed as described above.KF‐8 cells infected with indicated retroviruses were re‐plated on a 24‐well plate and then cultured in serum‐starved medium for 24 h. Then, the cells were stimulated with 10 ng·mL2.7et al., m HEPES–KOH pH7.5 including 1 μg·μL−1 poly‐dIdC for 30 min at 25 °C. Then, the binding mixtures were pulled down using streptavidin‐conjugated agarose . The samples were analyzed by immunoblotting analysis as described below.Nuclear extracts were prepared as reported previously  supplemented with protease inhibitors. FLAG‐MSK1 and FLAG‐PKAc were purified by immunoprecipitation using an M2 antibody attached to protein G‐sepharose , and they were utilized for in vitro kinase assays. For these assays, purified kinases were incubated with 2 μg GST‐p65/RelA and 100 μm ATP for 30 min at 30 °C. The reaction was terminated by the addition of Laemmli sample buffer, and then, phosphorylated samples were resolved by SDS/PAGE and immunoblotting analysis with an anti‐phospho p65/RelA (S276) antibody .HEK293T cells were transfected with the indicated combinations of plasmids harboring cDNA of FLAG‐MSK1, FLAG‐PKAc, or H‐Ras (G12V). Twenty‐four hours later, the transfected cells were cultured in serum‐free DMEM for 24 h. Then, cells were harvested, and cell lysates were prepared with Nonidet P‐40 (NP‐40) lysis buffer (50 m2.9m sodium phosphate (pH 7.2), 150 mm NaCl, 3 mm MgCl2, 2 mm EDTA, 1% NP‐40, 1% sodium deoxycholate, 0.2 U·mL−1 aprotinin, and phosphatase inhibitors] and briefly sonicated on ice. Then, debris were removed by sedimentation in a microcentrifuge at 16 400 g for 10 min, and cleared cell lysates were harvested and mixed with Laemmli sample buffer. Twenty‐five microgram of protein of whole cell lysates was loaded in each lane of an SDS‐polyacrylamide gel, and each protein was separated by the electrophoresis. Then, the separated proteins were transferred onto a polyvinylidene difluoride membrane (Merck Millipore). Proteins were visualized by immunoblotting analysis with the indicated antibodies and a chemical luminescence reagent, ECL . In some case such as the in vitro kinase assay, cells were lysed with NP‐40 lysis buffer as described above.For usual immunoblotting analysis, cells were lysed with RIPA buffer without SDS [10 m2.10m dNTPs, and 5 pmol oligo (dT)20 primer , and then, cDNA synthesis was performed for 60 min at 42 °C. The reaction was terminated by heating at 95 °C for 5 min and diluted with 80 μL TE buffer. One microlitre of synthesized cDNA was used for quantitative PCR in a 20 μL volume with the KAPA SYBR® FAST qPCR Kit , and the reaction was analyzed by a LightCycler 96 . The PCR primer sequences used are shown in Table Total RNA was extracted using TRIzol . To synthesize the single‐strand cDNA, 2 μg of total RNA was added into 20 μL reaction mixture including 100 units ReverTra Ace, 1 m2.114 cells per 35‐mm‐diameter dish, and grown for 2–3 weeks. The visible colonies showing a diameter of 1.0 mm or more were counted using nih imagej software, freely provided from Dr. Wayne Rasband in NIH (https://imagej.nih.gov/ij/), and results were shown in the graph.For the colony formation assay, infected NIH‐3T3 cells were seeded onto soft agar at 1 × 102.12To detect K‐Ras mutations by quantitative PCR for the human colorectal tumor samples, and perform further experiments using them, we obtained informed consent forms from each patient. All experiments were undertaken with the understanding and written consent of each subject. The methodologies for experiments conformed to the standards set by the Declaration of Helsinki. The methodologies of current study were approved by the ethics committee in Jichi medical university.2.13et al., From tumor tissues of each patient, genomic DNA was extracted using a NucleoSpin Tissue XS Genomic DNA Purification kit  in accordance with the manufacturer's instructions. The prepared genomic DNA was utilized for quantitative PCR analysis to detect K‐Ras mutations. Hydrolysis probes were designed in accordance with a previous report  patients, and samples were fixed with formaldehyde. Among them, seven samples were selected for further analysis, because the tumor tissues in these samples harbored an oncogenic point mutation in exon 2 of the K‐Ras gene. The formalin‐fixed paraffin‐embedded sections were pretreated in a microwave oven for 15 min. First, H&E staining of each tumor tissue was performed to differentiate between tumor cell areas and normal tissues. Then, immunohistochemical staining was performed using anti‐p65/RelA or anti‐phospho p65/RelA (Ser‐276) as a primary antibody. As a secondary antibody, HRP‐conjugated anti‐rabbit IgG antibody (donkey) was used. Then, the sections were incubated with Envision  and stained with DAB  for the visualization of signals.2.15n = 3), and the results of calculations of independent t‐tests are shown.All experiments were performed individually three times, and representative data shown. In graphs, error bars indicate standard deviation  drastically enhanced the expression of cyclin A and cyclin D1, while the expression of p27Kip1 was markedly diminished.Previously, we established KF‐8 cells, a subline of NIH‐3T3 cells stably harboring κB‐responsive elements‐driven luciferase gene  caused the hyperacceleration of NF‐κB activation  on TNF‐α‐induced signal transduction pathways for NF‐κB activation. As shown in Fig. V on TNF‐3.3Ink4a but not p27Kip1 suppressed TNFα‐induced NF‐κB activation in HEK293 and HeLa cells  and TNFα. Unexpectedly, we observed that the enforced expression of p16Ink4a could not inhibit the hyperactivation of NF‐κB  is a marker protein in the nucleolus, and some studies reported that NPM antagonizes p19ARF  inhibitor p163.4m), U0126 (20 μm), and SP600125 (50 μm), slightly suppressed the hyperactivation of NF‐κB, suggesting the partial involvement of the PI‐3 kinase, ERK, and JNK pathways. Mitsushita et al. (m), an inhibitor for NOX1, exhibited slight inhibitory effect on NF‐κB. Notably, treatment with 10 μm of SB203580, an inhibitor of p38 MAP kinase, exhibited drastic inhibitory effects on the oncogenic hyperactivation of NF‐κB. These observations suggested the functional involvement of p38 MAP kinase in the H‐Ras (G12V)‐provoked oncogenic hyperactivation of NF‐κB. As shown in Fig. m of SB203580 effectively suppressed the hyperactivation of NF‐κB induced by co‐stimulation with B‐Raf (V600E) and TNFα  and MSK1, a downstream protein kinase of p38 MAP kinase, were reported to be protein kinases for the phosphorylation of p65/RelA at Ser‐276 , which catalyzes monomethylation of p65/RelA at Lys‐310 and suppresses the expression of NF‐κB target genes. Additionally, several studies reported the importance of the phosphorylation of p65/RelA at Ser‐536 for the nuclear translocation or transcriptional activation of NF‐κB  KF‐8 cells were infected with control retroviruses or retroviruses harboring K‐Ras (G12V) or c‐Myc. After puromycin selection, cells were stimulated with 10 μg/ml TNFa for indicated periods. Then, cells were lysed, and the luciferase assay was performed. (B) Using KF‐8 cells infected with control retroviruses or retroviruses harboring K‐Ras mutants including G12V, K117N and A146T, the luciferase assay was performed as shown in (A). In the graph, error bars = SD .Fig. S2. (A) HEK293T cells were transfected with a luciferase vector including κB‐responsive element with/without FLAG‐PKAc, a catalytic subunit of PKA. Then, using the transfected cells, luciferase assays were performed. In graph, error bars indicate standard deviation , and the results of calculations of independent t‐tests are shown (*P < 0.005). (B) The expression of FLAG‐MSK1 and H‐Ras (G12V) in cells analyzed for in vitro kinase assay  was analyzed by immunoblotting analysis using antibodies against FLAG‐tag (M2) and H‐Ras. (C) KF‐8 cells were infected with retroviruses harboring scrambled short‐hairpin RNA, sh‐MSK1 (1A or 1B) or sh‐MSK2 (2A or 2B). After puromycin selection, cells were lysed, and immunoblotting analysis was performed to evaluate the knockdown efficiency of MSK1 and MSK2. β‐actin was used as a loading control.Fig. S3. (A) NIH‐3T3 cells were infected with indicated retroviruses as described in Figure 5B. After puromycin selection, cells (1 × 104 cells) were seeded on soft agar media in 35 mm dishes. After 3 weeks, the number of colonies were counted and shown in graph as shown in (B). In the graph, error bars = SD . In the photograph, 500 μm scale bar was shown.Fig. S4. SW620, a colorectal cancer‐derived cell line was transfected with siRNAs against both MSK1 and MSK2.Fig. S5. Genomic DNA was extracted from tumor tissues of 30 colorectal cancer patients (designated as T001 to T030).Fig. S6. Utilizing paired samples of tumor and normal tissues from K‐Ras (+) patients, immunohistochemical analyses were performed to detect total p65/RelA and phosphorylated p65/RelA (Ser276).Fig. S7. Total RNA was extracted from normal and tumor tissues from each patient harboring KRas mutations.Click here for additional data file.Table S1. Primers used in quantitative PCR for NF‐kB target genes.Click here for additional data file.Table S2. Primers used for genotyping of KRas gene.Click here for additional data file.


MecAAC (E=S (1); Se (2); Te (3); L=PhC(NtBu)2; MecAAC=C(CH2)(CMe2)2N‐2,6‐iPr2C6H3)) were synthesized from the reactions of silylene–phosphinidene LSi−P−MecAAC (A) with elemental chalcogens. All the compounds reported herein have been characterized by multinuclear NMR, elemental analyses, LIFDI‐MS, and single‐crystal X‐ray diffraction techniques. Furthermore, the regeneration of silylene–phosphinidene (A) was achieved from the reactions of 2–3 with L′Al (L′=HC{(CMe)}2). Theoretical studies on chalcogen‐bonded silicon phosphinidenes indicate that the Si−E  bond can be best represented as charge‐separated electron‐sharing σ‐bonding interaction between [LSi−P−MecAAC]+ and E−. The partial double‐bond character of Si−E is attributed to significant hyperconjugative donation from the lone pair on E− to the Si−N and Si−P σ*‐molecular orbitals.Chalcogen‐bonded silicon phosphinidenes LSi(E)−P− A, Scheme B, Scheme C, Scheme CycAAC)SiCl2→P−Tip .CycAAC)SiCl2→P−Tip Si(P−Tip)]2  reacts smoothly with elemental chalcogens to form the chalcogen‐bonded silicon phosphinidenes LSi(E)−P−MecAAC (E=S (1); Se (2); Te (3)).Phosphinidenes (R−P) are phosphorus analogues of carbenes and nitrenes.2, which is the only example of a compound with a silicon–chalcogen double bond and a phosphine functionality.MecAAC (E=S (1); Se (2); Te (3)) with phosphinidene functionality. Compounds 1–3 were characterized by single‐crystal X‐ray structural investigation and multinuclear NMR spectroscopy. An equimolar reaction of compound A with elemental sulfur and selenium at room temperature in toluene afforded compounds 1 and 2 in 68 % and 75 % yield, respectively −P−MecAAC (3) in 79 % yield }2) at room temperature as well as at elevated temperature, but no chalcogen transfer occurred. Nonetheless, 2 and 3 react with L′Al at 60 °C, resulting in the formation of parent silylene–phosphinidene ; Te ) with ph1–3 are thermally stable with melting points over 200 °C, but they are sensitive towards moisture. They are fully characterized by NMR spectroscopy, elemental analyses, LIFDI‐MS, and X‐ray single‐crystal structure analysis. The 31P{1H} NMR spectra of 1–3 exhibit a singlet at δ=+2.33, +9.37, and +21.67 ppm, respectively, which are highfield shifted compared with the starting material, silylene–phosphinidene (A). In the 29Si{1H} NMR spectra, 1–3 display doublets at δ=+20.48 (1JSi−P=107 Hz), +16.96 (1JSi−P=117 Hz), and −10.94 ppm (1JSi−P=127 Hz), respectively, due to the coupling with the phosphorus atom. The difference of the chemical shift between 1–3 and A in the 29Si{1H} NMR spectra is due to the different silicon oxidation states (+4 and +2). The 77Se{1H} NMR spectrum of 2 shows a doublet at δ=−286.13 ppm (2JSe−P=18 Hz) due to the coupling with the phosphorus atom. For the same reason the 125Te{1H} NMR spectrum of 3 exhibits a doublet at δ=−835.45 ppm (2JTe−P=38 Hz). The LIFDI mass spectra of 1–3 in toluene exhibit molecular‐ion peaks at 607.4, 655.3, and 705.4, respectively.Compounds 1–3 suitable for X‐ray structural analysis were obtained from toluene solution either at 0 °C or at room temperature (for details see the Supporting Information). Compounds 1–3 crystallize in the monoclinic space group P21/c. All three structures are isostructural, whereas 1 and 2 are even isomorphous. Compound 3 crystallizes as a pseudo‐merohedral twin with two molecules in the asymmetric unit. As a representative for all the molecular structure of 1 is depicted in Figure 1, 2, and 3 are about 3 pm shorter than in A 2}Si(S)N(SiMe3)2] and [{PhC(NtBu)2}Si(Se)N(SiMe3)2] (1.987(8) and 2.136(9) Å, respectively).3 is similar to the one observed in [{PhC(NtBu)2}Si(Te)N(SiMe3)2], (2.3720(15) Å).1–3 are well within the range of previous reported Si−E double bond lengths.Single crystals of A as well as chalcogen‐bonded silicon phosphinidenes 1, 2, and 3.A is given in Figure S2.3a (Supporting Information). The ESP value in the direction of the lone pair at P  is slightly higher than that in the direction of the lone pair at Si . This indicates a slightly higher nucleophilicity of the first than the second (Table S2.1). The occupancy of the P (1.943 e) and Si (1.925 e) lone pair in A are well corroborated with ESP values (Table S2.2). This is in accordance with our previous theoretical study on silylene–phosphinidenes.Quantum‐mechanical calculations were performed at the M06/def2‐TZVPP//BP86/def2‐SVP level of theory to understand the electronic structure and reactivity of silylene–phosphinidene A, the reactions of silylene–phosphinidene A with chalcogens result in silicon bonded chalcogens in the phosphinidenes 1, 2, and 3. To account for this observation, we have calculated the reaction energies for the formation of chalcogen‐bonded silicon phosphinidenes 1, 2, and 3 as well as hypothetical chalcogen‐bonded phosphorus phosphinidenes 1′, 2′, and 3′ . All the reaction energies are exothermic, and the energies become more positive with the descent from sulfur to tellurium. The reaction energies for the formation of silicon‐bonded chalcogen phosphinidenes 1 (−107.3), 2 (−88.2), and 3  are much higher than chalcogen‐bonded phosphorus phosphinidenes 1′ (−77.0), 2′ (−59.4), and 3′ . Hence the formation of the P−E bond is less favorable than the formation of a Si−E bond. Note that our calculated reaction energies are comparable to the previously reported bond‐dissociation energies for Si=S (112.8), Si=Se (95.5), and Si=Te  bonds in CH3Si(=E)OH compounds  at the MP2/6–311++G//MP2/6–311+G level of theory.1–3, which is in accordance with the experimental observation that the regeneration of parent molecule A could not be achieved when 1 is treated with the L′Al (L′=HC{(CMe)}2) . The Si−E bond lengths in 1 (2.019), 2 (2.160), and 3 (2.398 Å) in turn are close to those of previously reported Si=E double bond lengths.1 is comparable to those in the amidinate stabilized siladithiocarboxylate (2.030 Å),1–3 is in agreement with the Wiberg bond index of Si−E bond , −36.1(2), and −32.0 kcal mol−1 (3).The calculated geometrical parameters of 19), 2 2.0, and 3 MecAAC]+ and E−. The second bonding interaction represents donor–acceptor interaction between [LSi−P−MecAAC] and E. The best bonding representation is the one having the least value for orbital stabilization energy ΔEorb.Eorb for the charge separated electron sharing interaction in 1, 2, and 3 are −215.8, −189.1, and −159.6 kcal mol−1, respectively. The ΔEorb for the donor–acceptor interaction in 1, 2, and 3 are −265.2, −214.7, and −164.9 kcal mol−1, respectively. Hence the best bonding description for the Si−E bond in 1–3 is the charge‐separated electron‐sharing interaction between the fragments. However, the difference in the ΔEorb between the two bonding models in 3 is only 5.3 kcal mol−1. Hence, the donor–acceptor interaction also contributes towards the ground electronic structure of Si−Te bond in 3.The EDA‐NOCV analysis was carried out to further shed light on the nature of the Si−E bond. Two different bonding situations were analyzed, and the results are given in Table S2.5 (Supporting Information). The first bonding interaction represents charge separated electron‐sharing interaction between , wR2=0.0973 , res. density peaks: 0.324 to −0.251 e Å−3; Crystal data for 2: C35H54N3PSeSi, rM=654.83 g mol−1, 0.351×0.257×0.145 mm, monoclinic, P21/c, a=13.903(2), b=10.077(2), c=26.651(3) Å, β=102.18(3)°, V=3649.8(11) Å3, Z=4, μ (Mo Kα)=1.131 mm−1, θmax=28.34°, 125 128 reflections measured, 9105 independent (int=R0.0424), R1=0.0252 [I>2σ(I)], wR2=0.0640 , res. density peaks: 0.406 to −0.182 e Å−3; Crystal data for 3: C35H54N3PTeSi, rM=703.47 g mol−1, 0.254×0.119×0.082 mm, monoclinic, P21/c, a=35.937(3), b=9.237(2), c=23.498(3) Å, β=109.09(2)°, V=7371(2) Å3, Z=8, μ (Mo Kα)=0.909 mm−1, θmax=25.32°, 120 742 reflections measured, 13 421 independent (int=R0.0522), R1=0.0259 [I>2σ(I)], wR2=0.0500 , res. density peaks: 0.570 to −0.559 e Å−3.The datasets were collected on an Incoatec Mo Microsource1), 1891854 (2), and 1891855 (3)1891853  should be addressed to the authors.SupplementaryClick here for additional data file.


II complex and a CuII open-cube complex were synthesized using the tridentate Schiff base ligand, {1-[1-(pyridyl)(2-ethoxyethylidene)]-2-[(pyridin-3-yl)carbonyl]}hydrazine and copper(II) acetate and their molecular and crystal structures determined.A linear polymeric Cu II complexes [Cu(C14H13N4O2)Cl]n, I, and [Cu4(C8H10NO2)4Cl4]n, II, have been synthesized. In the structure of the mononuclear complex I, each ligand is coordinated to two metal centers. The basal plane around the CuII cation is formed by one chloride anion, one oxygen atom, one imino and one pyridine nitrogen atom. The apical position of the distorted square-pyramidal geometry is occupied by a pyridine nitrogen atom from a neighbouring unit, leading to infinite one-dimensional polymeric chains along the b-axis direction. Each chain is connected to adjacent chains by intermolecular C—H⋯O and C—H⋯Cl interactions, leading to a three-dimensional network structure. The tetranuclear complex II lies about a crystallographic inversion centre and has one core in which two CuII metal centers are mutually interconnected via two enolato oxygen atoms while the other two CuII cations are linked by a chloride anion and an enolato oxygen. An open-cube structure is generated in which the two open-cube units, with seven vertices each, share a side composed of two CuII ions bridged by two enolato oxygen atoms acting in a μ3-mode. The CuII atoms in each of the two CuO3NCl units are connected by one μ2-O and two μ3-O atoms from deprotonated hydroxyl groups and one chloride anion to the three other CuII centres. Each of the pentacoordinated CuII cations has a distorted NO3Cl square-pyramidal environment. The CuII atoms in each of the two CuO2NCl2 units are connected by μ2-O and μ3-O atoms from deprotonated alcohol hydroxy groups and one chloride anion to two other CuII ions. Each of the pentacoordinated CuII cations has a distorted NO2Cl2 square-pyramidal environment. In the crystal, a series of intramolecular C—H⋯O and C—H⋯Cl hydrogen bonds are observed in each tetranuclear monomeric unit, which is connected to four tetranuclear monomeric units by intermolecular C—H⋯O hydrogen bonds, thus forming a planar two-dimensional structure in the (Two Cu It has been shown that the presence of metal ions promotes the hydrolysis of the ester function of the picolinic ester  ions. These ligands then coordinate to the copper(II) cations to yield the two complexes that are reported here.Picolinic acid esters methanol] and a condensation product [({1-[1-ethoxy-1-(pyridin-2-yl)methylene]}-2-(oxonicotinyl))hydrazine]. It has been shown (Papaefstathiou 14H13N4O2)]n, I, the repeat unit of which is shown in  Å, an O16 atom with a Cu1—O16 distance of 1.9808 (15) Å and the N11 and N22 atoms from the same ligand with a Cu—N distances of 1.9437 (17) and 2.0444 (17) Å –79.40 (7)°, which are slightly smaller than those found in similar compounds ° and 146.17 (6)° methanolate ligand coordinating to each Cu atom through its imine nitrogen atom and its alcoholate oxygen atom, forming five-membered chelate rings . Intramolecular C—H⋯O contacts are also found  −x + y − z + i, Cu2i atoms, μ3-bridging atoms O26, O26i, a μ2-bridging O15i atom and a μ2-bridging Cl3 ion. The result is a is a distorted open-cube, defined as a distorted cube missing one corner. This can be seen by considering that the range of Cu—O—Cu angles is [99.76 (6)–102.98 (6)°] and the Cu1—Cl3—Cu2i angle is 84.39 (2)°. These differ extensively from the 90° angles of an ideal cube. The two Cu3O3Cl open-cubes are joined by a perfectly rectangular side defined by the Cu1, O26, and Cui, O26i atoms. The values of the two different lengths of the edges of the rectangular sides are 2.4280 (14) and 1.9684 (13) Å. The other faces of the two open-cubes are irregular with different distances i.e. Cu1—O26i = 2.4280 (14) Å, Cu2—O26 = 1.9707 (14) Å, Cu1—Cl3 = 2.2181 (6) Å and Cu2—Cl3 = 2.8134 (6) Å. The Cu1 (Cu1i) atoms in each of the two CuO3NCl units are connected by one μ2-O and two μ3-O atoms from the deprotonated hydroxyl groups and one chloride ion to three other CuII cations. In the CuO2NCl2 units, the Cu2 (Cu2i) atoms are linked to one μ2-O and one μ3-O atoms from a deprotonated hydroxyl groups and one chloride ion to two other CuII cations with Cu1—Cu2 and Cu1—Cu2i distances of approximately 3.012 and 3.408 Å, respectively. These are in good agreement with literature values , 1.9684 (13), 1.9707 (14) Å, respectively, while Cu1—O15 and Cu2—O15 are 1.9170 (13) and 1.9324 (13) Å, respectively °], O26—Cu1—N10 [156.02 (7)°], O26—Cu2—Cl4 [170.05 (5)°] and O15—Cu2—N21 [157.61 (7)°] ° are different from those of ideal cube. This bridging angle is also smaller than those reported for similar complexes 2Cl2](DMF) where qsalBr = 8-aminoquinoline with 5-bromo-salicylaldehyde . These contacts combine with the C—H⋯O hydrogen bonds to stack the molecules in a three-dimensional network along the a-axis direction ]methylenehydrazine yielded no hits, indicating that compound I is reasonably unique. However, a search for ethoxy(pyridin-2-yl)methanolate, the ligand found in II gave ten hits, although none of these was closely related to II. The matches included the CuII complexes HAXBEN methyl]pyridin, has a central pyridine ring that is substituted by 1-ethoxy-1-hydroxy-1-(pyridin-2-yl)methyl fragments in the 2- and 6-positions.A search of the CSD database 2·H2O  in 5 ml of ethanol was added at room temperature. The initial yellow solution immediately turned deep blue and was stirred under reflux for 2 h. The mixture was filtered and the solution evaporated to near dryness. The solid was isolated by filtration and recrystallized from a minimum of ethanol. On standing for five days, two types of crystals suitable for X-ray analysis were formed, light-yellow blocks of I and light-green plates of II.To a solution of 2-pyridine carbaldehyde  in 30 ml of ethanol was added a solution of nicotinic hydrazide  in 10 ml of ethanol. The mixture was stirred for 5 min. A solution of Cu: 2982, 1628, 1583, 1423, 1343, 1245, 941, 816, 630. For II: analysis calculated: C16H20N2Cl2O4Cu2: C, 38.26; H, 4.01; N, 5.58; Cl; 14.12. Found: C, 38.23; H, 3.98; N, 5.55; Cl; 14.08. IR : 2982, 1585, 1423, 1243, 1145, 940, 812.For d(C—H) = 0.93 Å for aromatic, d(C—H) = 0.97 Å for methylene and d(C—H) = 0.98 Å for methine H atoms with Uiso(H) = 1.2Ueq(C) and d(C—H) = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms. One reflection with Fo <<< Fc that was likely to have been affected by the beamstop was omitted from the final refinement cycles.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989019008922/sj5575sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989019008922/sj5575Isup4.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019008922/sj5575IIsup5.hklStructure factors: contains datablock(s) II. DOI: 1935842, 1935841CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Hirshfeld surface analysis of both compounds have been carried out.The molecular and crystal structures of μ-aqua-κ 2O:O-di-μ-diphenylacetato-κ4O:O′-bis[(diphenylacetato-κO)bis(pyridine-κN)nickel(II)], [Ni2(C14H11O2)4(C5H5N)4(H2O)] (1) and μ-aqua-κ2O:O-di-μ-diphenylacetato-κ4O:O′-bis[(diphenylacetato-κO)nickel(II)]–acetonitrile–diphenylacetic acid (1/2.5/1), [Ni2(C14H11O2)4(C10H8N2)2(H2O)]·2.5CH3CN·C14H12O2 (2), the complex units are stabilized by a variety of intra- and intermolecular hydrogen bonds, as well as C—H⋯π and π–π contacts between the aromatic systems of the pyridine, dipyridyl and diphenylacetate ligands. Despite the fact that the diphenylacetate ligand is sterically bulky, this does not interfere with the formation of the described aqua-bridged dimeric core, even with a 2,2′-bipyridine ligand, which has a strong chelating effect.In the crystal structures of the title compounds, namely μ-aqua-κ They belong to the type of aqua-bridged dinickel(II) carboxylates with the general formula [MII2(μ-H2O)(μ-O2CR)2(O2CR)2nL] (n = 4 in the case of a monodentate ligand or 2 in the case of bidentate coordination), well known since the 1970s  (for 1) or one 2,2′-bipyridine (Bipy) ligand (for 2) and one O atom from a bridging aqua ligand in an octahedral geometry  and 3.4826 (5) Å (for 2). Each monodentate coordinated diphenylacetate ligand is involved in the formation of an intramolecular hydrogen bond with a bridging water molecule. Hydrogen-bond geometries are specified in Tables 1In the title binuclear complexes, y Figs. 1 and 2 ▸.1, molecules are combined into pairs connected by a centre of symmetry using offset face-to-face π–π stacking interactions, in which coordinated pyridine ligands of each complex  are involved. These pairs, which result from the intermolecular hydrogen bonds between Py ligands and O atoms of carbonyl groups of diphenylacetate ligands , form layered structures parallel to the (101) plane. The layers form a 3D supramolecular structure through intermolecular C—H⋯π contacts, as well as π–π stacking interactions between the phenyl substituents of diphenylacetate ligands .In the crystal packing of compound 2, each molecule of the complex is associated with two neighbouring molecules via π–π stacking interactions between Bipy ligands . As a result, polymer chains are formed along the , as well as N⋯H interactions involving acetonitrile solvent molecules .For compound ds Fig. 7. Other o1, close C⋯C interplanar contacts, responsible for π–π stacking interactions between Bipy ligands, are displayed as patches of combined blue and red triangles on the surface over shape index  fragment and no binuclear structures were found. A survey of the CSD reveals 46 related structures of NiII carboxylates with a similar structure fragment.A search in the Cambridge Structural Database , in acetonitrile (40 ml) was added to a solution of diphenylacetic acid  in 10 ml acetonitrile. After full conversion of hellyerite, pyridine  was added and the solution was refluxed for 15 min. The resulting pale-green–blue solution was cooled to room temperature and filtered. After a few days, blue crystals of 1 were collected by filtration (yield ∼70%).A suspension of synthetic hellyerite, NiCO2 was carried out in a similar manner to the synthesis of compound 1, but 2,2′-bipyridine  was added instead of pyridine. The resulting blue solution was cooled to room temperature and filtered. After a few days, blue crystals of 2 were collected by filtration (yield ∼60%).The synthesis of compound Uiso(H) = 1.2Ueq(C) for the tertiary C atoms, C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C atoms, and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019014063/su5519sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S2056989019014063/su55191sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989019014063/su55192sup3.hklStructure factors: contains datablock(s) 2. DOI: 1959435, 1959436, 1959435, 1959436CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-018-30356-2, published online 10 August 2018Correction to: This Article contains errors in the Methods under subheading ‘IBV protection experiment 2’.7 EID50 of rNDV and rNDV/codon optimized-S, respectively, via oculanasal route. Five chickens of group three were inoculated with 10 recommended doses of a commercial live attenuated Mass-type IBV vaccine via oculanasal route and chickens of group four were inoculated with PBS.”“A total of twenty 4-week-old SPF chickens were divided into four groups of five each. Five chickens of groups one and two were inoculated with 10should read:7 EID50 of rNDV/codon optimized-S and 10 recommended doses of a commercial live attenuated Mass-type IBV vaccine via oculanasal route, respectively. Chickens of group three were inoculated with PBS. Samples collected from five non-vaccinated SPF chickens involved in another IBV protection study also were used as control.”“A total of fifteen 4-week-old SPF chickens were divided into three groups of five each. Five chickens of groups one and two were inoculated with 10Furthermore, within the Methods under subheading ‘Quantitative reverse transcription-polymerase chain reaction (RT-qPCR)’“Forty cycles of PCR at 95 °C for 10 s (denaturation), 58 °C for 20 s , and 72 °C for 30 s (elongation) followed by melting curve analysis that consisted of 95 °C for 5 s and 65 °C for 60 s.”should read:“The thermal conditions of 50 °C for 10 min and 95 °C for 10 min, then forty-five cycles of PCR at 95 °C for 10 s (denaturation), 58 °C for 20 s  followed by 95 °C for 5 s and melting curve analysis that consisted of 65 °C to 95 °C for 5 s was carried out to amplify the 150 nt – N gene fragments.”


A new symmetrical thiocarbonohydrazone derivative with two similar benzoylthioureido functional groups has been prepared and characterized. 18H18N4O2S2, which consists of two benzoylthioureido moieties connected by an ethylene chain. The asymmetric unit consists of one half of the molecule, the complete molecule being generated by crystallographic inversion symmetry. Both thiourea moieties are in a trans conformation. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, C—H⋯S and C—H⋯O hydrogen bonds link the molecules, forming layers parallel to the ac plane.The reaction of benzoyl chloride and ethylendiamine in the presence of potassium thiocyanate yielded a white solid, C CuII, NiII and CoII) from acidic media. Thiourea derivatives have also been shown to possess antibacterial, antifungal, antitubercular, antithyroid and insecticidal properties  Å] and O1—C3 [1.2209 (16) Å] distances indicate that these correspond to double bonds and are comparable to those observed for 1,2-bis(N-benzoylthioureido)benzene [1.6574 (18) Å for S—C and 1.222 (2) Å for O7—C16]  rings  plane. Molecular layers running almost parallel to the ac plane are formed by intermolecular C—H⋯O and C—H⋯S interactions  Å; Cg1 is the centroid of ring C4–C9; symmetry code: (iv) −x + 1, y + z + In the crystal, the molecules, which feature an overall Z-form, have both halves roughly parallel to the s Table 1. These let al., 2016et al., 2016trans with respect to the thiono S atom across the C—N bond. The 1-benzoyl-3-ethylthiourea fragment adopts a cis conformation with respect to the thiono S atom across the respective C—N bond. Six structures in which the spacer is different from the spacer in the symmetrical bis(thioureido) molecule studied here appear in the literature. The angles between the phenyl rings are: 63.1° for DAVHOZ  was added and a white solid appeared after a few minutes. The compound was filtered off, washed with 3 × 50 ml of water and dried under vacuum. The solid product was washed with water and purified by recrystallization from an ethanol/dichloromethane mixture (1:1 v/v). 12.3 g of the title compound were obtained (yield 88.5%). A small quantity of powder was recrystallized from 5 ml of DMF. Colourless single crystals suitable to XRD grew within six days.All purchased chemicals and solvents were of reagent grade and were used without further purification. Melting points were determined with a Büchi 570 melting-point apparatus and were uncorrected. To a mixture of 7.02 g (72 mmol) of potassium thiocyanate and 100 ml of acetone was added dropwise a solution of 10.116 g (72 mmol) of benzoyl chloride in 50 ml of acetone. The resulting mixture was stirred under reflux for 1 h and cooled to room temperature. A solution of 2.2 g (36.6 mmol) of 1,2-ethylenediamine in 20 ml of acetone was added. The yellow solution obtained was stirred at room temperature during 2 h. Hydrochloric acid (0.1 arH) or 0.97 Å (CH2). The NH H atoms were located in a difference Fourier map and freely refined.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901900495X/vm2216sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901900495X/vm2216Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901900495X/vm2216Isup3.cmlSupporting information file. DOI: 1909438CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: