Tumor necrosis factor (TNF) can drive inflammation, cell survival, and death. While ubiquitylation-, phosphorylation-, and nuclear factor κB (NF-κB)-dependent checkpoints suppress the cytotoxic potential of TNF, it remains unclear whether ubiquitylation can directly repress TNF-induced death. Here, we show that ubiquitylation regulates RIPK1’s cytotoxic potential not only via activation of downstream kinases and NF-kB transcriptional responses, but also by directly repressing RIPK1 kinase activity via ubiquitin-dependent inactivation. We find that the ubiquitin-associated (UBA) domain of cellular inhibitor of apoptosis (cIAP)1 is required for optimal ubiquitin-lysine occupancy and K48 ubiquitylation of RIPK1. Independently of IKK and MK2, cIAP1-mediated and UBA-assisted ubiquitylation suppresses RIPK1 kinase auto-activation and, in addition, marks it for proteasomal degradation. In the absence of a functional UBA domain of cIAP1, more active RIPK1 kinase accumulates in response to TNF, causing RIPK1 kinase-mediated cell death and systemic inflammatory response syndrome. These results reveal a direct role for cIAP-mediated ubiquitylation in controlling RIPK1 kinase activity and preventing TNF-mediated cytotoxicity.  •Ubiquitylation directly controls RIPK1 kinase activity in TNF signaling•UBA-dependent ubiquitylation of RIPK1 represses its kinase activity and cell death•The UBA contributes to optimal occupancy of ubiquitin-acceptor lysines in RIPK1•UBA-dependent ubiquitylation of RIPK1 also targets it for proteasomal degradation Annibaldi et al. show that cIAP-mediated ubiquitylation of RIPK1 kinase suppresses its auto-activation and, in addition, marks it for proteasomal degradation. These results reveal a direct role for ubiquitin in controlling RIPK1 kinase activity and suppressing TNF-mediated cytotoxicity. Inflammation and cell death are ancient processes of fundamental biological importance that enable survival and adaptation during infection and injury. Tumor necrosis factor (TNF) is a potent inflammatory cytokine that triggers, through its type 1 receptor (TNF-R1), either pro-survival/inflammatory or pro-death signaling pathways in a ubiquitin (Ub)- and phosphorylation-dependent manner . TNF canBinding of TNF to TNF-R1 results in the formation of two signaling complexes . Upon TNTNF-induced cell death is mediated by an RIPK1-containing secondary complex that is frequently referred to as complex-II or necrosome . It is tcIAP1UBAmut cells. Our data demonstrate that cIAP-mediated ubiquitylation of RIPK1 directly regulates its kinase activity, independently of the recruitment of IKK and TAK1 kinase complexes.While it is beyond doubt that cIAPs suppress TNF-induced cell death, how this is achieved remains unclear. The main problem in dissecting cIAP-mediated regulation of TNF-induced cell death has been the fact that the signaling aspect of Ub  and the direct Ub-dependent anti-apoptotic function of cIAPs cannot be separated. We now identified a point mutation in cIAP1 that selectively sensitizes cells to TNF-induced cell death, without interfering with TNF-mediated activation of NF-κB, and IKK- and MK2-mediated phosphorylation of RIPK1. This mutation affects the evolutionarily conserved ubiquitin-associated (UBA) domain of cIAP1. Mice with a knockin mutation in the UBA domain develop normally but are acutely sensitive to TNF-induced systemic inflammatory response syndrome (SIRS), which is caused by enhanced sensitivity to TNF-mediated cell death. Our data are consistent with the notion that the UBA domain is required for Ub-mediated regulation of RIPK1 kinase activity. We find that cIAP1 represses RIPK1 kinase auto-activation via UBA-dependent ubiquitylation of an expanded repertoire of Ub-acceptor lysines of RIPK1. In addition, we find that cIAP1 with a functional UBA domain increases the number of ubiquitylation sites on RIPK1. Moreover, it enhances K48-linked poly-ubiquitylation of RIPK1. Together, this destabilizes active RIPK1 via proteasomal degradation. In the absence of a functional UBA domain, fewer K residues are ubiquitylated and fewer K48-linked chains are present on RIPK1. Together, this causes lethal accumulation of active RIPK1 kinase in response to TNF in U/C/R) to establish a UBA interactome of cIAP1  in the TRAF-N domain, which is required for TRAF2 to interact with the BIR1 of cIAP1 , was alsTo independently corroborate the interaction, we performed isothermal titration calorimetry (ITC) using recombinant cIAP2. cIAP2 was used instead of cIAP1 because structural information of TRAF2/cIAP2 is available, and previous ITC measurements indicate that the BIR1 domains of cIAP1 and cIAP2 bind TRAF2 equivalently . Of noteFlp-InTM-RexTM-HEK293 (referred to as Flp-In) cells. Prior to transgene insertion, isogenic parental HEK293Flp-In;shcIAP1 cells bearing a doxycycline-inducible mir30-based short hairpin RNA (shRNA) against the 3′ UTR of endogenous cIAP1 were generated and reconstituted with either wild-type (WT) cIAP1 or the indicated mutants (Flp-In cells do not express detectable levels of cIAP2 (data not shown), this system ensures single-copy insertion and equal expression levels of untagged cIAP1 proteins without interference from endogenous cIAPs. Expression of the doxycycline-inducible cIAP1 shRNA in parental cells reduced cIAP1 to an almost undetectable level and resulted in concomitant activation of the non-canonical NF-κB pathway  almost completely abolished the binding of cIAP1 to TRAF2  completely abrogated the interaction between cIAP1 and TRAF2  clone that previously had been targeted at the cIAP2 locus (cIAP2−/−cIAP1UBAmut) are subsequently referred to as cIAP1UBAmut. cIAP1UBAmut mice were weaned at the expected Mendelian ratio (cIAP1UBAmut embryonic day 13.5 (E13.5) embryos exhibited the same cIAP1 protein levels  cells  cells E. Moreovut cells F. In conctivated  non-canoctivated F. As TRAof MAPKs G and S2Fof MAPKs H–3K. TakcIAP1UBAmut mice to TNF challenge. Injection of TNF provokes systemic inflammation that is driven by RIPK1 kinase-dependent cell death , alanine transaminase (ALT), and lactate dehydrogenase (LDH) in the plasma, indicating liver and tissue damage , and MEFs. TNF treatment did not induce substantial cell death in either WT or cIAP2-deficient cells; however, it was a potent cell death stimulus in ut cells  suppress animals A. Consis animals B. Primarmut MEFs D. Indeedactivity E, which activity D and 5F,activity F. Importe manner A–S3C. TocIAP2−/−, but cIAP1-deficient MEFs had significantly lower molecular weight-modified forms of RIPK1 and substantial levels of non-modified RIPK1. cIAP1UBAmut cells, however, displayed a marked and reproducible decrease in the extent of high molecular weight RIPK1 ubiquitylation (red arrows) in complex-I in both MEFs and MDFs -based mass spectrometry analysis of Ub chain composition   Figure B. To thicIAP2−/− B. The recIAP1UBAmut cells compared to WT cells over a 6-hr time period following TNF treatment  did not result in a further increase in RIPK1 accumulation .Further information and requests for reagents may be directed to and will be fulfilled by the Lead Contact, Pascal Meier  in a volume of 0.2 ml. Rectal body temperature was recorded with a digital thermometer . Plasma samples and tissue samples of liver were collected at designated times after injection. Blood was obtained by cardiac puncture.Flp-InTM-RexTM-HEK293 cells were cultured in Dulbecco’s modified Eagle’s Medium (DMEM) supplemented with 10% Fetal Bovine Serum (FBS), penicillin and streptomycin under 10% CO2.Primary and immortalized MEFs, primary MDFs and Primary Mouse Embryonic Fibroblasts (MEFs) were generated from E13.5 embryos. After removing the placenta, yolk sac, head and the dark red organs, embryos were finely minced and digested for 20 min in 0.25% trypsin. Single cell suspension was then obtained by pipetting up and down the digested embryos. Mouse Dermal Fibroblasts (MDFs) were isolated as described in 5 splenocytes were resuspended in 500 μL of cold PBS and stained with DAPI (1/5000) for 20 min on ice. Cells were then washed with cold PBS and resuspended in 50 μL Staining Buffer. 2 μL of blocking antibody (Anti-Mouse CD16/CD32) were added, and cells were kept on ice for 10 min. 50 μL of Staining Buffer containing the desired antibodies were then added and cells were kept on ice for 30 min. Cells were washed in cold PBS, resuspended in 1 mL of cold PBS and analyzed by FACS.5 × 10Flp-InTM T-RExTM HEK293shcIAP1 cells were created. First Flp-InTMT-RExTM-HEK293 cells (Invitrogen) were transduced with lentiviral particles targeting the 3′ UTR of the cIAP1 mRNA. To this end, we used pTRIPZ-shcIAP1 (Open Biosystems), which allows Doxocycline-inducible expression of a miR30-based shcIAP1 RNA. After puromycin selection, individual clones were tested for cIAP1 knockdown efficiency. Such cells were further tested functionally using TNF signaling and NIK activation as readouts. Next, the respective cIAP1 constructs were cloned into pcDNA5.1/FRT/TO (Invitrogen). The empty pcDNA5.1/FRT/TO-2HA-Strep plasmid was used as a control. To generate site-specific single copy insertions, pcDNA5.1FRT/TO-based plasmids were co-transfected with pOG44 into Flp-InTMT-RExTM-HEK293shcIAP1 cells. After selection with hygromycin, stable cells were selected. Endogenous cIAP1 suppression and expression of WT or mutant versions of cIAP1 were simultaneously induced by treating cells with 100 ng/ml Doxycycline for at least 48 hours.For the generation of the 293 stable cell lines, where endogenous cIAP1 was reconstituted with WT and mutant cIAP1, The GSK’963 RIPK1 kinase inhibitor was provided by GSK. The following antibodies were used: α-RIPK1 , α-HOIL , α-cIAP1 , α-TNFR1 , α-Actin , α-P-p65 , α-p65 , α-IkBα , α-P-p38 , α-p38 , α-P-JNK , α-JNK , α-P-ERK , α-ERK  α-caspase-8 , α-FLAG [M2] , α-Ub , α-FLIP , α-FADD , α-RIPK3 , α-Tubulin , α-SHARPIN , α-TRAF2 , α-CD8-PE-Cy7, GR-1-PE-Cy7, CD11c-FITC, CD4-FITC, CD11b-Cy5, B220-FITC , α-CD69-PE , α-CD3-APC , and α-CD16 .The UbiCRest analysis with linkage selective DUBs was performed essentially as described in Cells were lysed in DISC lysis buffer  supplemented with protease inhibitors, 1 mM DTT, PR619 (10 μM) and GST-TUBE . Cell lysates were rotated at 4°C for 20 min then clarified at 4°C at 14,000 rpm for 10 min. 20 μL GST beads were added and immunoprecipitations were performed overnight. Beads were washed 4x in wash buffer  + PR619 (10 μM), and bound proteins eluted by boiling in 50 μ l 1x SDS loading dye.Cells were seeded in 15 cm dishes and treated as indicated with 3x FLAG-hTNF (5 μg/ml). To terminate stimulation, media was removed and plates were washed with 50 mL of ice cold PBS. Plates were frozen at −80°C until all time points were acquired. Plates were thawed on ice and cells were lysed in 1% Triton X-100 lysis buffer . Cell lysates were rotated at 4°C for 20 mins then clarified at 4°C at 14,000 rpm for 30 mins. Proteins were immunoprecipitated from cleared protein lysates with 20 μL of α-FLAG M2 beads (SIGMA) with rotation overnight at 4°C. For the 0 hr sample 5 μg/ml of FLAG-TNF were added post-lysis. 4x washes in 1% Triton X-100 buffer with PR619 (10 μM) were performed, and samples eluted by boiling in 60 μL 1x SDS loading dye. For complex-II purification cells were seeded in 10 cm dishes and treated as indicated using media containing 1x FLAG-TNF (100 ng/ml) and zVAD (10 μM). Cells were lysed on ice in 1% Triton X-100 lysis buffer . Cell lysates were rotated at 4°C for 20 mins then clarified at 4°C at 14,000 rpm for 10 mins. 20 μL of protein G Sepharose (SIGMA), blocked for 1 hr with lysis buffer containing 1% BSA, were bound with FADD antibody (1.5 μg antibody/mg protein lysate) and were rotated with cleared protein lysates 4 hr at 4°C. 4x washes in lysis buffer were performed, and samples eluted by boiling in 80 μL 1x SDS sample buffer.5 cells (MEFs and MDFs) were seeded in six well plates and 24 hr later they were treated as indicated for an additional 24 hr. Hoechst 33342 (10 μg/ml) and Propidium Iodide (PI) (1 μg/ml) were added. After 2 mins 10 to 15 images per well were taken with a fluorescent inverted microscope and the ration of dead/live cells were counted manually. 5 × 104 BMDMs were seeded in 96 well plates and 24 hr later they were treated as indicated for an additional 24 hr. Hoechst (0.5 μg/ml) and PI (1 μg/ml) were added and the ratio dead/live cells was measured using the Celigo imaging system.2 × 10cIAP2 and TRAF2 segments were cloned into pSUMO vector respectively to produce N-terminally His-SUMO tagged proteins. The constructs were then transformed into BL21 (DE3) cells and cultured in LB medium at 37°C, respectively. Protein expression was induced overnight at 20°C with 0.5 mM IPTG when OD600 reached 0.8. Cells were lysed in buffer containing 25 mM Tris-HCl at pH 8.0, 150 mM NaCl, 10 mM imidazole and 5 mM β-mercaptoethanol. The recombinant proteins were affinity-purified by Ni-Sepharose beads . The SUMO tag was removed by overnight digestion with homemade ULP1 protease at 4°C. The untagged proteins were further purified by HiTrap Q anion exchange and Superdex 200 gel filtration chromatography . Isothermal titration calorimetry measurements were performed at 16°C, using a MicroCal ITC200 microcalorimeter . For the TRAF2:cIAP2 interactions, the calorimetric titrations were performed by injecting 2 μL of cIAP2 protein solution (2–4 mM) into a sample cell containing 200 μl 0.20 mM TRAF2 protein in 25 mM Tris-HCl at pH 8.0, 150 mM NaCl. A total of 20 injections were performed with a spacing of 150 s and a reference power of 6 μcal/s. Binding isotherms were plotted and analyzed using Origin Software .Various human 5 cells (MEFs) were plated in 6-well plates and treated as indicated in 2 mL for the indicated times. After treatment, media was removed, and 300 μL 1% DISC lysis buffer  was added to each well, cells were scraped and lysates were left on ice for 5 min. 50 μL of lysate per condition were transferred into a 24 well plate and 450 μL DEVDase assay mix (20 mM Ac-DEVD-AMC (Sigma), 1 mM DTT, 50 mM Tris pH 7.5, 150 mM NaCl, 0.1% Triton X-100, and 5% glycerol) was added to each well (NB: cell lysates were not cleared). Plates were wrapped in foil and reactions allowed to proceed by incubation at room temperature for up to 24 hr. DEVDase activity was read at 380 nM excitation/460 nM emission.2 × 10The yeast strain Y2HGold (Clontech) was co-transformed with the respective bait and prey plasmids. Positive transformants were selected on minimal SD-Leu-Trp medium (Formedium). Three single colonies for each bait and prey co-transformation were patched out on fresh SD-Leu-Trp plates and grown for 2 days at 30°C. Each patch was resuspended in 180 μL of sterile water in a 96-well plate and replica plated onto non-selective (SD-Leu-Trp) or selective medium (SD-Leu-Trp-His), containing the indicated concentration of 3-amino-1,2,4-triazole . Yeast plates were incubated at 30°C for 1 week. UbcH5b prey vector was provided by Rachel Klevit.BL21 cells were transformed with pGEX6p-1-3XFLAG-TNF plasmid. One colony was picked and incubated o/n in 100 mL LB medium with 100 μg/ml ampicillin. Next day 900 mL of LB medium without AMP were added, cells were grown for 1 h at 37°C and then 0.5 mM IPTG was added for further 4 h. Bacteria were spun for 15 min at 4000 rpm, the supernatant was discarded and the pellet was lysed in 10 mL Triton X-100 lysis buffer . The lysate was sonicated and left for 15 min at 4°C and clarified for 30 min at 140,000 rpm at 4°C. Lysate was rotated with glutathione Sepharose beads for 4 hr at 4°C and 3x washed with IPPG150 buffer  were performed, followed by a final wash in PreScission cleavage buffer . For PreScission cleavage 500 μL cleavage buffer and 30 μL PreScission enzyme were added to the beads at 4°C o/n. The beads were spun, and supernatants were collected and passed through Thermo Scientific buffer exchange columns to remove bead contamination. Recombinant TNF concentration was determined on Coomassie Blue-stained polyacrylamide gel using known amount of BSA as standard, and quantitated using Image Lab software.PLA was performed according to the manufacturer’s protocol using the Duolink Detection Kit (SIGMA). Cells were examined with a confocal microscope .Ub chains were separated on a NuPAGE 4%–12% gradient gel (Invitrogen) before in-gel digestion with trypsin and the addition of Ub-AQUA peptide internal standards according to Kirkpatrick et al. (2006)https://doi.org/10.17632/f559yfv4h4.1.Raw data have been deposited to Mendeley Data and are available at


The synthesis and crystal structure of a potentially redox non-innocent pentafluorophenyl-substituted pyridine diimine ligand system are reported. 21H9F10N3, represents a potential redox non-innocent pyridine diimine ligand system. It consists of a central pyridine ring with two pentafluorophenyl substituted imine groups in positions 2 and 6. The whole molecule is generated by mirror symmetry, the mirror bisecting the N and para-C atom of the pyridine ring. The perfluorophenyl ring is inclined to the pyridine ring by 73.67 (8)°. In the crystal, molecules stack along the a axis, but there are no significant intermolecular interactions present.The title compound, C Thus, only half of the molecule is present in the asymmetric unit °. The imine nitrogen atom, N2, is oriented in an anti-conformation with respect to the pyridine nitrogen, N1. This orientation is in contrast with the molecule acting as a tridentate ligand coordinating to the chromium ion in complex trichloroethyl)pyridine-N,N′,N′′)chromium(III) acetonitrile monosolvate chromium(III) acetonitrile monosolvate  in toluene (100 ml) was refluxed for 30 h during which time water was removed by a Dean–Stark apparatus. The crude yellow product was washed with cold methanol and filtered producing a pure off-white solid . Colorless block-like crystals were obtained by vapor diffusion of hexanes into a saturated dichloromethane solution of the title compound. Spectroscopic data: 1H NMR : δ 8.6–7.8 , 2.5 , and MS (ESI): m/z 494 [C21H9F10N3]H+.A mixture of 2,6-diacetylpyridine , 2,3,4,5,6-pentafluoroaniline  and Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989017008040/su5374sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017008040/su5374Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017008040/su5374Isup3.cmlSupporting information file. DOI: 1553189CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S,5R,6S on the basis of the synthetic pathway, was confirmed by single-crystal X-ray diffraction. The molecule is formed by a substituted six-membered cyclohexene ring adopting an envelope conformation and substituted by carbonyl, methyl and hydroxyl groups. The supramolecular structure is mainly built by a combination of O—H⋯O and weaker C—H⋯O hydrogen bonds.The absolute configuration of the title compound, determined as 4 7H10O4, is formed by a cyclohexene skeleton with an envelope conformation, substituted by carbonyl, methyl and hydroxyl groups. The crystal structure is controlled mainly by a combination of strong O—H⋯O and weak C—H⋯O hydrogen bonds, forming nearly perpendicular chains running parallel to the [110] and [-110] directions. This perpendicularity is caused by a tetragonal pseudosymmetry influenced by the similarity between the a and b axes, the value of 90.9770 (10)° of the β angle and the action of a 21 screw axis, which transform each chain into its corresponding nearly orthogonal one.The molecule of the title keto carbasugar, C Streptomyces strains  in the molecule adopts an envelope conformation with atom C5 as the flap [deviating from the plane through the other ring atoms by 0.639 (2) Å] and puckering parameters Q = 0.4653 (19) Å, θ = 129.5 (2)° and φ = 66.7 (3)°.Fig. 1i  link the molecules into chains that run along the [110] direction (Table 1ii and C4—H4⋯O6iii  hydrogen bonds along the  to define a three-dimensional array along the [001] direction. These hydrogen bonds connect the orthogonal chains by pairs along [001]. Between these neighboring [001] sheets, weak dipolar or van der Waals forces stabilize the assembly along the c-axis direction.In the crystal structure, hydrogen bonds O4—H41⋯O1n Table 1. These cts Fig. 2. Conside0] Fig. 3. The ortet al., 2016R,5R,6R)-4,5,6-trihydroxy-2-methylcyclohex-2-enone -5-Acetoxy-4,5-dihydroxy-3-methylcyclohex-2-enone  and diisopropyl azodicarboxylate . The reaction mixture was stirred at room temperature for 6 h. The solvent was evaporated and the crude mass was used for the next reaction without further purification. The crude product was dissolved in MeOH (3.4 mL), a catalytic quantity of K2CO3 was added and the reaction mixture was stirred at room temperature for 5 min and filtered. Evaporation of the solvent from the filtrate afforded crude gabosine H, which was purified by column chromatography  to afford pure gabosine H as a white crystalline powder : 3400, 2875, 1660 cm−1. 1H NMR : δ = 2.07 , 3.56 , 4.01 , 4.23 , 5.92 .The synthesis of gabosine H was achieved by inversion of the allylic –OH group using Mitsunobu conditions followed by deprotection. (4Ueq of the parent atom. Hydroxy H atoms were located in difference density maps and were refined with Uiso(H) = 1.5 Ueq(O). The absolute structure parameter y was calculated using PLATON  I. DOI: 10.1107/S2056989017004509/rz5209Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004509/rz5209Isup3.cmlSupporting information file. DOI: 1539327CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title biphenyl derivative, the dihedral angle between the benzene rings is 52.84 (10)°. In the crystal, molecules are linked by two pairs of N—H⋯O hydrogen bonds, forming chains propagating along [101]. 12H9N3O4, the dihedral angle between the benzene rings is 52.84 (10)°. The nitro group attached to the benzene ring is inclined to the ring by 4.03 (2)°, while the nitro group attached to the amino-substituted benzene ring is inclined to the ring by 8.84 (2)°. In the crystal, molecules are linked by two pairs of N—H⋯O hydrogen bonds, forming chains propagating along [101]. Within the chains, these N—H⋯O hydrogen bonds result in the formation of R22(20) and R22(14) ring motifs. The latter ring motif is reinforced by a pair of C—H⋯O hydrogen bonds, enclosing R21(6) ring motifs. The chains are linked by a second C—H⋯O hydrogen bond, forming a three-dimensional supramolecular structure.In the title biphenyl derivative, C Within the chains, these N—H⋯O hydrogen bonds result in the formation of s Table 1. The lats Table 1. The chas Table 1, forminget al., 2016viz 4′-nitro-2-biphenylamine (II) , and to 52.84 (2)° in the title compound (I)ca 3.55 and 10.14° in (III) and 8.3 (2)° in the title compound (I)A search of the Cambridge Structural Database Uiso(H) = 1.2Ueq(N). The C-bound H atoms were included in calculated positions and refined as riding: C—H = 0.93–0.96 Å with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901700408X/su5355sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S205698901700408X/su5355Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901700408X/su5355Isup3.cmlSupporting information file. DOI: 1537734CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound, epalerstat acetone monosolvate, is isotypic with the previously reported tetrahydrofuran solvate. Z)-5-[(2E)-2-methyl-3-phenylprop-2-en-1-ylidene]-4-oxo-2-sulfanylidene-1,3-thiazolidine-3-acetic acid} crystallized as an acetone monosolvate, C15H13NO3S2·C3H6O. In the epalerstat molecule, the methylpropylenediene moiety is inclined to the phenyl ring and the five-membered rhodamine ring by 21.4 (4) and 4.7 (4)°, respectively. In addition, the acetic acid moiety is found to be almost normal to the rhodamine ring, making a dihedral angle of 85.1 (2)°. In the crystal, a pair of O—H⋯O hydrogen bonds between the carboxylic acid groups of epalerstat molecules form inversion dimers with an R22(8) loop. The dimers are linked by pairs of C—H⋯O hydrogen bonds, enclosing R22(20) loops, forming chains propagating along the [101] direction. In addition, the acetone molecules are linked to the chain by a C—H⋯O hydrogen bond. Epalerstat acetone monosolvate was found to be isotypic with epalerstat tertrahydrofuran solvate .Epalerstat {systematic name: (5 al. 2017. Acta Cr Epalerstat acetone monosolvate appeared concomitantly with epalerstat Form I and they could be distinguished visually based on their crystal habit. In this case, the title compound, epalerstat acetone monosolvate, and Form I appeared as yellow blocks and orange needle-like crystals, respectively.Uiso(H) = 1.5Uiso(C-methyl) and 1.2Uiso(C) for other H atoms. Initially the site occupancy factor of the acetone molecule was refined and determined to be 1.005 (4). In the final cycles of refinement the occupancy of the acetone molecule was fixed at 1.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017010751/su5385sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989017010751/su5385Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017010751/su5385Isup3.cmlSupporting information file. DOI: 1563705CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the molecules are linked into [100] chains by way of C—H⋯O, C—H⋯N, C—H⋯S hydrogen bonds. The Hirshfeld surface analysis indicates that the most important contributions to the packing are H⋯H (19.5%), N⋯H (17.3%), C⋯H (15.5%), Br⋯H (11.7%), and O⋯H (11.0%) interactions. 15H10BrN3O2S, the dihedral angles between the 1,3,4-oxadiazole ring and the 3-pyridinyl and bromobenzene rings are 12.17 (15) and 18.74 (15)°, respectively. In the crystal, the molecules are linked into [100] chains by way of C—H⋯O, C—H⋯N, C—H⋯S hydrogen bonds. The Hirshfeld surface analysis indicates that the most important contributions to the packing are H⋯H (19.5%), N⋯H (17.3%), C⋯H (15.5%), Br⋯H (11.7%), and O⋯H (11.0%) interactions.In the title compound, C The inter-ring dihedral angles are A/B = 6.93 (15), A/C = 18.74 (15) and B/C = 12.17 (15)°. The C7—C8—S2—C9 torsion angle of 172.56 (17)° indicates approximate coplanarity of these atoms. Otherwise, geometrical data for (I)et al., 2011et al., 2005The structure of (I)B⋯O1, C1—H2B⋯S2 and C4—H4A⋯N2 hydrogen bonds, which form chains running along a-axis direction  and di (x axis) values are the closest external and internal distances (Å) from given points on the Hirshfeld surface on Fig. 2. The Hiron Fig. 2 of the cce Fig. 4.viz. 1,3-bis{sulfanyl}propan-2-one (II) -methyl]-1,3,4-oxadiazol-2-ylthio}-1-ethanone (III) , the molecules are linked into a three-dimensional network via weak C—H⋯N hydrogen bonds (H⋯N distances = 2.51 and 2.54 Å) In (III), the C—H⋯N hydrogen bonds are found to be slightly weaker in comparison with the first structure (H⋯N distances = 2.41 Å). The change in substituents also changes the packing pattern towards zigzag chains extending along the b-axis direction. In addition, both (II) and (III) feature aromatic π–π stacking interactions, which are not observed in (I)A database search disclosed a long list of compounds containing the 1,3,4-oxadiazole moiety; however, only two examples of sulfanylethanone-substituted 1,3,4-oxadiazole derivatives were found, 5-(3-Pyridyl)-1,3,4-oxadiazole-2-thiol  and triethyl amine (0.1 ml) were added in ethanol (10 ml) and stirred for 10 min in a round-bottomed flask. After 10 min, to the reaction mixture was slowly added 2 4-dibromacetophenone . The mixture was refluxed until complete consumption of starting materials, the progress of reaction being monitored by TLC. After 2 h, the precipitate that had formed was separated, washed with ethanol and recrystallized from methanol solution to afford colourless blocks .2) and constrained to ride on their parent atoms with Uiso(H)= 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017004819/hb7660sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017004819/hb7660Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004819/hb7660Isup3.cmlSupporting information file. DOI: 1540579CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-oxide (NMI-O) crystallizes as a monohydrate, in the monoclinic space group P21 with Z′ = 2 (molecules A and B). The imidazole rings display a planar geometry and are linked in the crystal structure into infinite zigzag strands of ⋯NMI-O(A)⋯OH2⋯NMI-O(B)⋯OH2⋯ units by O—H⋯O hydrogen bonds. These chains propagate along the b-axis direction of the unit cell.1-Methylimidazole 3- N-oxide (NMI-O) crystallizes as a monohydrate, C4H6N2O·H2O, in the monoclinic space group P21 with Z′ = 2 (molecules A and B). The imidazole rings display a planar geometry (r.m.s. deviations = 0.0008 and 0.0002 Å) and are linked in the crystal structure into infinite zigzag strands of ⋯NMI-O(A)⋯OH2⋯NMI-O(B)⋯OH2⋯ units by O—H⋯O hydrogen bonds. These chains propagate along the b-axis direction of the unit cell.1-Methylimidazole 3- N-oxides are an important class of materials acting as highly efficient catalysts for the phosphorylation of alcohols , has been shown to be a highly efficient catalyst for both sulfonylation and silylation procedures  Å; O1B, −0.008 (4) Å. The methyl groups lie somewhat farther outside the plane of the ring with displacements of −0.073 (5) Å for C4A and −0.116 (1) Å for C4B. The dihedral angle formed between the least-squares planes of the A and B NMI-O molecules is 12.96 (16)°. The present data were not of sufficient quality to determine the absolute structure.The asymmetric unit of the title compound is shown in Fig. 12⋯NMI-O⋯OH2⋯ chain propagating along the b-axis direction of the unit cell. Each water molecule forms two hydrogen bonds, one to each of the N+— O− groups of NMI-O molecules A and B with the oxygen atoms of these groups acting as double acceptors from both water molecules  and 1.348 (3)Å for molecules A and B, respectively. These values are within the range exhibited for the remaining 15 database entries (1.326–1.368 Å).A search of the Cambridge Structural Database  = 1.5Ueq(C-methyl) and Uiso(H) = 1.2Ueq(C) for other H atoms. The data were not of a sufficient quality to reliably determine the absolute structure.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017002079/hb7643sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017002079/hb7643Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017002079/hb7643Isup3.cmlSupporting information file. DOI: 1531714CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Tg) in the range of 257–281 °C. These results suggest that the incorporating pyridine, kinky and bulky substituents to polymer backbone can improve the optical transparency effectively without sacrificing the thermal properties.In order to obtain highly optical transparency polyimides, two novel aromatic diamine monomers containing pyridine and kinky structures, 1,1-bis[4-(5-amino-2-pyridinoxy)phenyl]diphenylmethane (BAPDBP) and 1,1-bis[4-(5-amino-2-pyridinoxy)phenyl]-1-phenylethane (BAPDAP), were designed and synthesized. Polyimides based on BAPDBP, BAPDAP, 2,2-bis[4-(5-amino-2-pyridinoxy)phenyl]propane (BAPDP) with various commercial dianhydrides were prepared for comparison and structure-property relationships study. The structures of the polyimides were characterized by Fourier transform infrared (FT-IR) spectrometer, wide-angle X-ray diffractograms (XRD) and elemental analysis. Film properties including solubility, optical transparency, water uptake, thermal and mechanical properties were also evaluated. The introduction of pyridine and kinky structure into the backbones that polyimides presented good optical properties with 91–97% transparent at 500 nm and a low cut-off wavelength at 353–398 nm. Moreover, phenyl pendant groups of the polyimides showed high glass transition temperatures ( Fully a3)2, –O–, –SO2–, –S–, –CO–, cyclohexane and biphenyl groups. These polyimides showed highly optical transparency, low dielectric constants, good thermal stability, excellent mechanical properties, respectively propane was supplied by Sunlight Pharmaceutical Company (BAPP). 2-Chloro-5-nitropyridine, 4,4′-diphenol (Acros), 4,4′-diphenol, 4,4′-(diphenylmethylene)diphenol, potassium carbonate diphenol , 2-chloro-5-nitropyridine , 80 mL DMF, and potassium carbonate  was fitted with a mechanical stirrer, condenser, nitrogen inlet and thermometer. After 30 min of stirring at room temperature, the mixture was continuously reacted at 75 °C for 6 h. Then, the reaction mixture was cooled and poured into 500 ml of distilled water. The precipitated product was filtered off and washed with water until it was neutral. The crude product was recrystallized from DMF/water and then dried under vacuum at 80 °C for 10 h to yield 8.8 g (71%).2.2.2.1,1′-bis[4-(5-nitro-2-pyridinoxy)phenyl]-1-phenylethane was prepared in the same way. Yield: 65%.2.2.3.The synthesis of 2,2′-bis[4-(5-nitro-2-pyridinoxy)phenyl]propane was conducted in the same way. Yield: 90%.2.2.4.Under nitrogen protection, a mixture of 7.5 g (12.57 mmol) of BNPDBP, 3 g of Pd/C catalyst, and 150 mL of dioxane was placed into a 250 mL three-necked flask equipped with a dropping funnel, and reflux condenser. The mixture was stirred under reflux for 30 min, and then 25 mL of hydrazine hydrate was added dropwise over 2 h, followed by 6 h of reflux. The resulting mixture was filtered while hot to remove the catalyst and the filtrate was subsequently concentrated and poured into 500 mL of deionized water to produce a precipitate, which was washed with water. After recrystallization from dioxane/water, the product was dried under vacuum at 80 °C for 10 h to yield 5.8 g (77%).2.2.5.The synthesis of 1,1-bis[4-(5-amino-2-pyridinoxy)phenyl]diphenylmethane was conducted in the same way. Yield: 80%.2.2.6.The synthesis of 2,2-bis[4-(5-amino-2-pyridinoxy)phenyl]propane was conducted in the same way. Yield: 85%.2.3.PI films were prepared via a traditional two-step method, as shown in Scheme 2.4.2.4.1.1H NMR) spectra were determined using a BRUKER-300 spectrometer  at 300 MHz in CDCl3 or DMSO-d6.Hydrogen nuclear magnetic resonance  and thin films (PIs).FT-IR measurements were performed using a Bruker Vector 22 spectrometer  at a resolution of 2 cmHigh resolution liquid chromatography-mass spectroscopy (HRLC-MS) data were obtained using an Agilent 1290-microTOF-QII  high resolution mass spectrometer.Elemental analysis was run on a Vario EL cube CHN recorder analysis instrument .2.4.2.ηinh) were measured using an Ubbelohde viscometer  with a 0.5 g/dL DMAc solution at 25 °C.Inherent viscosities (2.4.3.Ultraviolet-visible (UV-vis) spectra of the films were recorded on a Shimadzu UV-vis 2501 spectrometer  in transmittance mode at room temperature.2.4.4.Solubility was measured by 10 mg of polyimides in 1 mL of solvent at room temperature for 24 h.2.4.5.λ = 1.541 Å) to determine the morphology structures. Data were collected at 0.02° intervals over the range of 5–50°, and the scan speed was 0.5° (2θ)/min.Wide-angle X-ray diffraction (WAXD) analysis was conducted using a Rigaku Wide-angle X-ray diffractometer  .Dynamic mechanical analysis (DMA) was measured with a TA instrument, DMA Q800 , at a heating rate of 5 °C/min from 50 to 400 °C and a load frequency of 1 Hz in film tension geometry. Differential scanning calorimetric (DSC) analyses were performed using a TA instrument, DSC Q100 , at a scanning rate of 10 °C/min under a nitrogen flow of 50 mL/min. To investigate the glass transition temperature, the polyimides samples were heated to a temperature higher than the glass transition temperature to eliminate thermal and stress history.Thermo gravimetric analysis (TGA) was measured by a TA 2050 , with a heating rate of 10 °C/min under nitrogen and air atmosphere, respectively.2.4.7.Mechanical properties of the films were measured by a Shimadzu AG-I universal testing apparatus  with a load of 1 kN at a speed of 5 mm/min. Measurements were performed at 25 °C with film specimens of approximately 30–40 μm thick, 3–5 mm wide and 60 mm long, and an average of at least five individual determinations was used.2.4.8.Wwet−Wdry)/Wdry × 100%; where Wwet is the weight of the film samples after immersion in deionized water, and Wdry is the initial weight of the samples.Water uptake (WU) of the films was determined by the weight differences before and after immersion in deionized water at room temperature for 24 h, and calculated by the following equation: WU = . FT-IR(KBr): 1601, 1578, 1512, 1494, 1348, 1265, 1205, 1111 cm−1; 1H NMR : 9.05 , 8.48 , 7.33 , 7.30 , 7.27 , 7.08 , 7.02 ; HRLC-MS (ESI): 597.5 (M + H)+, Calcd 596.6 for C35H24N4O6.BAPDBP Melting point: 209 °C (DSC peak). FT-IR(KBr): 3439, 3340, 1599, 1578, 1504, 1479, 1244, 1171, 1014 cm−1; 1H NMR : 7.58 , 7.29 , 7.18 , 7.08 , 6.86 , 6.77 , 5.13 ; HRLC-MS (ESI): 537.5 (M + H)+, Calcd 536.6 for C35H28N4O2.BNPDAP Melting point: 141 °C (DSC peak). FT-IR(KBr): 2972, 1601, 1578, 1517, 1504, 1352, 1273, 1205, 1113 cm−1; 1H NMR : 9.04 , 8.46 , 7.29 , 7.24 , 7.21 , 7.18 , 7.08 ,7.03, 2.24 ; HRLC-MS (ESI): 535.4 (M + H)+, Calcd 534.5 for C30H22N4O6.BAPDAP Melting point: 139 °C (DSC peak). FT-IR(KBr): 3438, 3337, 2970, 1598, 1577, 1504, 1269, 1130, 1014 cm−1; 1H NMR : 7.65 , 7.24 , 7.19 , 7.10 , 7.04 , 6.98 , 6.90 , 6.71 , 3.48 , 2.11 ; HRLC-MS (ESI): 475.5 (M + H)+, Calcd 474.6 for C30H26N4O2.BNPDP Melting point: 157 °C (DSC peak). FT-IR(KBr): 3070, 2852, 1596, 1576, 1516, 1464, 1349, 1259, 1198, 1115 cm−1; HRLC-MS (ESI): 473.4 (M + H)+, Calcd 472.5 for C25H20N4O6.BAPDP Melting point: 181 °C (DSC peak). FT-IR(KBr): 3438, 3361, 3097, 2966, 1599, 1579, 1477, 1209, 1119 cm−1; HRLC-MS (ESI): 413.4 (M + H)+, Calcd 412.5 for C25H24N4O2.3.2.ηinh) tended to be lower than those of highly polymerized PAAs; however, tough and flexible polyimides have been prepared.Polyimides based on various diamine monomers  and three commercially available aromatic dianhydrides  were synthesized using a conventional two-step method, as shown in Scheme −1 and 1560–1680 cm−1 had disappeared after thermal imidization. The absorptions of the imide ring appeared at 1775–1780 cm−1 , 1720–1730 cm−1 , and 1385–1390 cm−1 (C–N stretching), which indicated the success of imidization. The elemental analysis data confirmed with the calculated values based on the polymer repeating units.The polymer structure is proved with FT-IR Figure  and elem3.3.λcut-off) in the range of 353–398 nm. The highly optical transparent are directly related to the kinky substituents which can improve the free volume and inhibited the formation of CTC.Polyimide films based on pyridine and kinky structure showed high optical transparency as presented in Figure 3 groups in the dianhydrides, which can reduce CT interactions [λcut-off and transmittance at 500 nm which should attribute to the long repeat units decreased the influence of phenyl or methyl groups.PI films with the same diamine, their optical properties depend on the chemical structures of the dianhydrides. As shown in Table ractions . P1-1, Pλcut-off and transmittance [PI-3(BAPDP/6FDA) and PI-6(BAPP/6FDA) were synthesized to investigate the effects of pyridine in the chain. PI-3 showed slightly higher transmittance and lower wavelength than PI-6 as listed in Table mittance .3.4.3 etc.(Table 3 groups, which increased disorder in the chains and inhibited dense chain packing, therefore, reducing the interchain interactions to enhance solubility [All the fluorinated polyimides showed good solubility in high boiling point polar aprotic solvents, such as NMP, DMAc, DMF etc. and even in low boiling point solvents, such as THF, CHCllubility . The kinlubility . However3.5.The wide-angle X-ray diffractograms of polyimides are shown in Figure 3.6.Tg of the polyimides in the range of 257–281 °C by DSC and 254–275 °C by DMA, as shown in Figures Tg values for BAPDBP based polyimides depending on the structure of the dianhydride component [Tg was observed for the PI-5 obtained from s-BPDA because of the presence of a rigid chain in the backbone. The lowest Tg of PI-4 can be correlated with the flexibility of ether groups.The thermal behavior of the PI films is shown in Table omponent  and the Tg values in the order of PI-1 > PI-2 > PI-3. This is, because the phenyl substituents are stiffer than the methyl substituents on the backbone. Thus the polyimides with a diphenylmethylene linkage have a higher Tg than polyimides with a phenylethane or methyl linkage.For the structure-property relationship comparison studies, PI-1, PI-2, and PI-3 were prepared from reacting 6FDA with BAPDBP, BAPDAP and BAPDP, respectively. The resulting polyimide film samples gave 2. TGA curves for the 6FDA based polyimides PI-1, PI-2, and PI-3 are shown in Figure T5% and T10% was observed from the TGA curves in N2, significant differences were observed from those acquired under air atmosphere. It can be argued that the methyl structure had poor thermal oxidative stability than phenyl pendant.The thermal stabilities of the PIs were evaluated by TGA under nitrogen and air atmosphere Table . All PI 3.7.The tensile properties of the PI films are summarized in Table Water uptake of the PI films was in the range of 0.56–0.76% at room temperature for 24 h (Table 4.Td5% at 516–530 °C and Td10% at 531–547 °C in nitrogen and high optical transparency which can be compared to the commercial colorless polyimides. The synergistic effects of kinky structure and pyridine of polyimides leading to high optical transparency without the sacrificing of thermal stability. This is, because the introduction of kinky and bulky substituents which increases the free volume and the pyridine which possess relatively high mole refraction as compared to phenyl unit gave a benefit to improve the optical properties. These properties of polyimides are desirable for application on space solar cells and thermal control coating systems.Two novel diamines containing kinky structure and pyridine were synthesized, characterized, and used for the preparation of a series of polyimides, via a traditional two-step method. All the PI-films showed high thermal stability with the No potential conflict of interest was reported by the authors.


II complex cations, uncoordinated 4-hydroxybenzoate anions and water molecules of crystallization, the CuII ions are bridged by a 4-oxidobenzoate ligand, each metal ion is five-coordinated by two chelated 1,10-phenanthroline (phen) molecules and one anion O atom in distorted trigonal bipyramid geometry.In the hydrated complex composed of dinuclear Cu 2(C7H4O3)(C12H8N2)4](C7H5O3)2·7.5H2O, is composed of dinuclear CuII complex cations, noncoordinating 4-hydroxybenzoate anions and water molecules of crystallization. In the dinuclear complex cation, the CuII ions are bridged by a 4-oxidobenzoate ligand and thus each metal ion is five-coordinated by two chelating 1,10-phenanthroline (phen) molecules and one anionic O atom in a distorted trigonal-bipyramid geometry. In the crystal, aromatic π–π stacking occurs between phen rings of neighbouring dinuclear CuII complex cations, forming two-dimensional supramolecular systems parallel to (100).The title hydrated complex, [Cu In some biological systems, π–π stacking between aromatic rings is correlated with the elctron-transfer process  are bridged by one 4-oxidobenzoate anion through oxido and carboxy O atoms , with a Cu1—O53 bond length of 1.941 (3) Å and a Cu2—O51 bond length of 1.979 (3) Å. Each CuII atom is five-coordinated, displaying a distorted trigonal-bipyramidal geometry y Table 1. The Cu1vii-phen  suggest intermolecular hydrogen bonding between atoms O6W and O7W, and between O8W and O73.The molecular packing of (I)s Table 2. The H a2·2H2O , 4-hydroxybenzoic acid , 1,10-phenanthroline  and NaOH  were dissolved in 20 ml water. The resulting solution was refluxed for 4 h and was then cooled to room temperature and filtered. Dark-green single crystals were obtained from the filtrate after five weeks.Each reagent was available commercially and was of analytical grade. CuClW atom was refined isotropically with a fixed occupacy of 0.5. Aromatic and hydroxy H atoms were placed in calculated positions, with C—H = 0.93 Å and O—H = 0.82 Å, and were included in the final cycles of refinement in riding mode, with Uiso(H) = 1.2 and 1.5Ueq(parent), respectively. Water H atoms were located in difference Fourier map, and were refined with fixed positions and a fixed isotropic displacement parameter of 0.1 Å2. The H atoms of the water molecules O6W, O7W and O8W were not assigned. The peak corresponding to the maximum electron density in the difference Fourier map was close (1.01 Å) to atom O8W.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989016013943/hb7601sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016013943/hb7601Isup2.hklStructure factors: contains datablock(s) I. DOI: 1501982CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The damage parameter and hysteresis dissipated energy of C/SiC composite under low peak stress are higher than that of SiC/SiC composite; However, at high peak stress, the damage extent inside of cross-ply SiC/SiC composite is higher than that of C/SiC composite as more transverse cracks and matrix cracks connect together.In this paper, the comparison of cyclic hysteresis behavior between cross-ply C/SiC and SiC/SiC ceramic-matrix composites (CMCs) has been investigated. The interface slip between fibers and the matrix existed in the matrix cracking mode 3 and mode 5, in which matrix cracking and interface debonding occurred in the 0° plies are considered as the major reason for hysteresis loops of cross-ply CMCs. The hysteresis loops of cross-ply C/SiC and SiC/SiC composites corresponding to different peak stresses have been predicted using present analysis. The damage parameter,  However, due to demands for reduced fuel consumption, lighter and hotter engines are required, especially in aviation. Ceramic materials can operate at high temperature with creep resistance, at which metals cannot. However, their use as structural components is severely limited because of their brittleness. Continuous fiber-reinforced ceramic-matrix composites (CMCs), by incorporating fibers in ceramic matrices, however, can be made as strong as metal, yet are much lighter and can withstand much higher temperatures exceeding the capability of current nickel alloys typically used in high-pressure turbines, which can increase the efficiency of aero engines .Considering the effect of multiple matrix cracking modes on hysteresis loops of cross-ply CMCs, the unloading and reloading strains of the composite are :(9)(εu)i.e., applied loading divided by the specimen cross section. The basic material properties of cross-ply C/SiC composite are given by: Vf = 40%, Ef = 230 GPa, Em = 350 GPa, rf = 3.5 μm, τi = 6 MPa, ζd = 0.1 J/m2, αf = −0.38 × 10−6/°C, αm = 2.8 × 10−6/°C, ΔT = −1000 °C.The cyclic loading/unloading tensile behavior of cross-ply C/SiC composite at room temperature has been investigated. The specimen was unloading and subsequent reloading at the peak stress of 20, 40, 60, 80, 100, and 120 MPa, respectively. The peak stress represents the macroscopic stress, σmax = 60 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.3. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 2, as shown in i.e., y(σmin)/ld = 86.5%, as shown in i.e., z(σmax)/ld = 86.5%, as shown in σtr_pu = 45 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 15 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in For σmax = 80 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.35. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 2, as shown in i.e., y(σmin)/ld = 73.5%, as shown in i.e., z(σmax)/ld = 73.5%, as shown in σtr_pu = 24 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 56 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in For σmax = 100 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.4. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 4, as shown in σtr_fu = 70 MPa, i.e., 2y(σtr_fu)/lc = 1, as shown in σtr_fr = 30 MPa, the interface new-slip length approaches to matrix crack spacing, i.e., 2z(σtr_fr)/lc = 1, as shown in σtr_pu = 95 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 5 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in For σmax = 120 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.42. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 4, as shown in σtr_fu = 90 MPa, i.e., 2y(σtr_fu)/lc = 1, as shown in σtr_fr = 30 MPa, the interface new-slip length approaches to matrix crack spacing, i.e., 2z(σtr_fr)/lc = 1, as shown in i.e., y(σmin)/ld = 89.3%, as shown in σmax = 120 MPa, the interface new-slip length approaches to 89.3% of interface debonded length, i.e., z(σmax)/ld = 89.3%, as shown in For Vf = 30%, Ef = 420 GPa, Em = 364 GPa, rf = 7.5 μm, τi = 15 MPa, ζd = 1.5 J/m2, αf = 4.6 × 10−6/°C, αm = 4.38 × 10−6/°C, and ΔT = −1400 °C.Gordon  investigσmax = 190 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.35. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 1, as shown in σtr_pu = 9.5 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 180.5 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in σtr_pu = 161.5 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 28.5 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in For σmax = 200 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.45. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 4, as shown in σtr_fu = 120 MPa, i.e., 2y(σtr_fu)/lc = 1, as shown in σtr_fr = 80 MPa, the interface new-slip length approaches to matrix crack spacing, i.e., 2z(σtr_fr)/lc = 1, as shown in σtr_pu = 150 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 50 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in For σmax = 210 MPa, the experimental and theoretical hysteresis loops are shown in η = 0.7. For matrix cracking mode 3, the hysteresis loops correspond to interface slip case 4, as shown in σtr_fu = 147 MPa, i.e., 2y(σtr_fu)/lc = 1, as shown in σtr_fr = 63 MPa, the interface new-slip length approaches to matrix crack spacing, i.e., 2z(σtr_fr)/lc = 1, as shown in σtr_pu = 147 MPa, i.e., y(σtr_pu)/ld = 1, as shown in σtr_pr = 63 MPa, the interface new-slip length approaches to interface debonded length, i.e., z(σtr_pr)/ld = 1, as shown in For η vs. normalized stress σmax/σuts curves of cross-ply C/SiC and SiC/SiC composites are illustrated in η increases. At low peak stress, the damage parameter η of cross-ply C/SiC is higher than that of cross-ply SiC/SiC composite, i.e., η = 0.3 at σmax = 60 MPa or 48.2% σuts of C/SiC composite, and η = 0.35 at σmax = 190 MPa or 82.6% σuts of SiC/SiC composite. However, at high peak stress, the damage parameter η of cross-ply SiC/SiC is higher than that of cross-ply C/SiC composite, i.e., η = 0.7 at σmax = 210 MPa or 91.3% σuts of SiC/SiC composite, and η = 0.42 at σmax = 120 MPa or 96.3% σuts of C/SiC composite. The matrix crack density of cracking mode 3 in the 0° plies vs. normalized stress σ/σmax curves of cross-ply C/SiC and SiC/SiC composites can be used to show the damage extent inside of composites, as shown in i.e., σ/σmax < 0.8, and lower for C/SiC composite than that of SiC/SiC composite under higher peak stress, i.e., σ/σmax > 0.8.The damage parameter i.e., −0.38 × 10−6/°C vs. 2.8 × 10−6/°C, and the radial thermal residual tensile stress existed in the fiber/matrix interface due to the large mismatch of the radial thermal expansion coefficient between carbon fibers and silicon carbide matrix, i.e., 7 × 10−6/°C vs. 2.8 × 10−6/°C, there are unavoidable microcracks existing within the SiC matrix in the 90° and 0° plies when the composite was cooled down from high fabricated temperature to ambient temperature. These processing-induced microcracks propagated and, in conjunction with new microcracks during the loading process, formed mode 5 matrix cracks in the 90° plies. With increasing applied stress, some matrix cracks in the 90° plies connected with matrix cracks in the 0° plies forming mode 3 matrix cracks, which propagate through the 90° and 0° plies. For cross-ply SiC/SiC composite, the axial thermal residual compressive stress existed in SiC matrix due to the large mismatch of the axial thermal expansion coefficient between silicon carbide fibers and silicon carbide matrix, i.e., 5.1 × 10−6/°C vs. 3.5 × 10−6/°C, and the radial thermal residual compressive stress existed in the fiber/matrix interface due to the large mismatch of the radial thermal expansion coefficient between silicon carbide fibers and silicon carbide matrix, i.e., 2.9 × 10−6/°C vs. 3.5 × 10−6/°C, which decreases matrix cracking evolution rate and also the damage parameter η at low peak stress. However, with increasing peak stress, the damage extent inside of cross-ply SiC/SiC composite, i.e., the damage parameter η, is much higher than that of C/SiC composite as more transverse cracks and matrix cracks connecting together.As the axial thermal residual tensile stress existed in SiC matrix due to the large mismatch of the axial thermal expansion coefficient between carbon fibers and silicon carbide matrix, vs. normalized stress σmax/σuts curves of cross-ply C/SiC and SiC/SiC composites are illustrated in i.e., from 3.7 kPa at σmax = 60 MPa or 48.2% σuts, to 15.2 kPa at σmax = 120 MPa or 96.3% σuts; and from 5.2 kPa at σmax = 190 MPa or 82.6% σuts, to 46.6 kPa at σmax = 210 MPa or 91.3% σuts. The hysteresis dissipated energy of C/SiC composite under low peak stress is higher than that of SiC/SiC composite due to a higher damage parameter η at low peak stress of C/SiC composite compared with that of SiC/SiC composite. However, at high peak stress, the damage parameter η of SiC/SiC composite is higher than that of C/SiC composite, leading to higher hysteresis dissipated energy compared with that of C/SiC composite.The hysteresis dissipated energy For C/SiC composite, the hysteresis loops of matrix cracking mode 3 and mode 5 correspond to interface slip case 2 and case 1, respectively, under low peak stresses of 60 and 80 MPa; when the peak stress is 100 MPa, the hysteresis loops of matrix cracking mode 3 transfers from case 2 to case 4; and when the peak stresses are 120 MPa, the hysteresis loops of matrix cracking mode 5 transfers from case 1 to case 2, as shown in The comparison of cyclic hysteresis behavior between cross-ply C/SiC and SiC/SiC CMCs has been investigated. The interface slip between fibers and the matrix existed in matrix cracking mode 3 and mode 5 are considered as the major reason for hysteresis loops of cross-ply CMCs. The hysteresis loops of cross-ply C/SiC and SiC/SiC composites corresponding to different peak stresses have been predicted using present analysis. The differences between C/SiC and SiC/SiC composite on damage parameters and hysteresis dissipated energy have been investigated.(1)i.e., the proportion of matrix cracking mode 3 in the entire matrix cracking modes of the composite, and the hysteresis dissipated energy both increase with increasing peak stress;The damage parameter, (2)i.e., the damage paramter η and hysteresis dissipated energy, is much higher than that of C/SiC composite as more transverse cracks and matrix cracks connecting together.The damage parameter and hysteresis dissipated energy of C/SiC composite under low peak stress are higher than those of SiC/SiC composite; However, with increasing peak stress, the damage extent inside of cross-ply SiC/SiC composite,


Crystal structure of O3- and P2-type NaxMO2 with various M against temperature (T) was systematically investigated by synchrotron x-ray diffraction mainly focusing on the T-dependences of a- and c-axis lattice constants (a and c) and z coordinate (z) of oxygen. Using a hard-sphere model with minimum Madelung energy, we confirmed that c/a and z values in O3-type NaxMO2 were reproduced. We further evaluated the thermal expansion coefficients (αa and αc) along a- and c-axis at 300 K. The anisotropy of the thermal expansion was quantitatively reproduced without adjustable parameters for O3-type NaxMO2. Deviations of z from the model for P2-type NaxMO2 are ascribed to Na vacancies characteristic to the structure.Layered oxide Na Due to large Clark number (=2.63) of Na compared with that (=0.006) of Li, SIBs can be a promising next-generation battery for storage of natural energy at a power plant and for a large-scale device such as electrical vehicle. Layered oxide NaxMO2  is a typical cathode material for SIBs3. Crystal structure of this material is categorized into two typical structures: O3 and P2 types4. Figure 2. Red, yellow, and blue spheres represent O, Na, and M, respectively. M is surrounded by six oxygens, and a MO6 octahedron is formed. The edge-sharing MO6 octahedra form a MO2 layer. Both O3- and P2-type NaMO2 exhibit alternately stacked MO2 layers and Na sheets. The sodium sheet, upper and lower oxygen sheets stack as BAC resulting in the octahedral Na site. In the P2-type NaMO2, the sodium and oxygen sheets stack as BAB resulting in the prismatic Na site. O3-type NaMO2  and P2-type NaxMO2 (M = Mn and Co) were found to exhibit Na+ intercalation/deintercalation in early 1980s9. Concerning the discovery of hard carbon (≥200 mAh/g) as anode material of SIB10, electrochemical properties of NaxMO2 are extensively reported20. Very recently, substitution effects on the battery properties in O3-type structure27 and P2-type structure45 were extensively studied to reduce expensive element and improve the cyclability and capacity.Sodium-ion-secondary battery (SIB) stores electrochemical energy through Na46, crystal structure57, magnetism61, thermoelectric effect63, and first-principle calculation67 of the end family are also studied. Fujita et al. found that NaxCoOδ2− single crystal shows a large dimensionless figure-of-merit of ZT = 1 at 800 K63, which has motivated practical use for waste heat recovery at high temperatures (T). An isostructural O3-type LiMO2 is widely used as a cathode material in lithium-ion-secondary battery (LIB)69. This family is also studied as a thermoelectric material70 and a cathode material of solid oxide fuel cell (SOFC)71. In particular, Lan and Tao found that LixAl0.5Co0.5O2 shows good proton conductivity of 0.1 Scm−1 at 773 K71, which is the highest among those of known polycrystalline proton-conducting materials. During operation of energy devices such as LIB(SIB), thermoelectric device, and SOFC, these materials are exposed to a variation and/or a gradient of temperature. A mismatch in thermal expansion coefficients in between the components can result in high stresses around the interface leading to deterioration of the device. Thus, evaluation and systematical comprehension of thermal expansion behaviors in this class of materials are important.Not only electrochemical properties but also superconductivityxMO2 samples against T (300 K ≤ T ≤ 800 K) performed by synchrotron x-ray diffraction focusing on thermal expansion. To understand the thermal expansion behavior, we constructed a hard-sphere model with constraint that M, upper and lower oxygens are connected each other. We confirmed that the calculated d/a  and z well reproduced the experimental values for O3-type NaxMO2. By introducing T-linear expansion of the hard sphere, the anisotropy of the thermal expansion was quantitatively reproduced without adjustable parameter for O3-type NaxMO2.In this paper, we report systematic structural analysis of four O3- and five P2-type Naa-axis lattice constant (a), and (b) c-axis lattice constant (c) of O3-type Na0.99CrO2, Na0.99FeO2, Na1.00CoO2, Na0.98Fe0.5Co0.5O2, Na0.99Fe0.5Ni0.5O2, and Na0.94Ti0.5Ni0.5O2 against T. With T, a and c monotonically increase. Raw x-ray diffraction data and results of Rietveld refinements at 300 K are shown in Figs a- and c-axis was evaluated. Figure a and c of P2-type Na0.52MnO2, Na0.59CoO2, Na0.50Mn0.5Co0.5O2, Na0.70Ni0.33Mn0.67O2, Na0.69Ni0.33Mn0.5Ti0.17O2, Na0.70Ni0.33Mn0.33Ti0.34O2, and Na0.48Mn0.5Fe0.5O2. The P2-type compounds also show monotonical T-dependences of a and c. In Table a, c at 300 K, αa, and αc of O3- and P2-type NaxMO2 at 300 K were listed.Figure z coordinate of oxygen for O3- and P2-type structure (zO3 and zP2) against a at 300 and 700 K. Blue and red circles represent zO3 at 300 and 700 K, respectively. Light green and pink triangles represent zP2 at 300 and 700 K, respectively. The values were almost independent of T. Figure d) to a against a at 300 K, where d is c/3 for O3-type and c/2 for P2-type structure. Light blue and purple circles represent d/a of O3-type compounds at 300 and 700 K, respectively. Green and yellow triangles represent d/a of P2-type compounds at 300 and 700 K, respectively. d/a slightly decreases with an increase in a.Figure αa, (b) αc, and (c) αc/αa against a. αa and αc of O3-type Na1.00CoO2 were 0.98 × 10−5 K−1 and 1.71 × 10−5 K−1, respectively. These values are comparable to those of inorganic compounds; αa = 1.44 × 10−5 K−1 for LiMn2O472, and αa(αc) = 0.85(2.5) × 10−5 K−1 for layered BaFe1.84Co0.16As273. αa(αc) in Fig. a around the averaged value of 0.92(1.96) × 10−5 K−1. The ratio αc/αa is also scattered around the averaged value (=2.30). However, the data point for P2-Na0.59CoO2 are seriously deviated from the average value. This is probably due to the Na ordering67.Figure 2 to reproduce the experimental results . Firstly, imagine a sheet consists of hard spheres that were arrayed on triangular lattice, and then the sheet is alternately stacked as shown in Fig. 74; RNa = 1.02 Å, RO = 1.40 Å, and RM is a variable parameter that takes 0.58–0.7 Å, respectively. Since the ionic radius of the hard sphere is different from one another, the structure can not be the hexagonal close-packed structure, and several structures with different a are possible for the unique value of RM. Here, we adopted a constraint that M, upper, and lower oxygens coroneted each other, because the constraint minimizes the Madelung energy against a (vide infra). For a calculation of thermal expansion coefficient, the hard sphere is assumed to expand in proportion to the temperature difference (ΔT). ΔT dependence of RNa is expressed as maN(=22.99) is atomic weight of Na atom. Similarly, ΔT dependences of RO and RM are expressed as mO(=16.00) and mM(=55.85)  are atomic weights of O and M, respectively.We have constructed a hard-sphere structural model for O3- and P2-type NaMOacalc) of a-axis lattice constant as a function of ΔT. Note that the in-plane nearest-neighbor oxygen distance is a for both the P2- and O3-structure. Considering the above-mentioned constraint, acalc(ΔT) for both O3- and P2-structures is expressed asNow, let us derive the expression , minimum value of acalc is 2.80 Å. At acalc = 2.80 Å, RM is evaluated to be ≈0.5799 Å using Eq. RM, the oxygen triangular lattice expands in order to keep the connection between M, upper and lower oxygens.This equation is easily derived using Pythagorean theorem. As shown in Eq. gen RO = .40 Å, mi2 layers as BAC (BAB) in the O3-type (P2-type) structure. We noted that the expression  of interlayer distance is independent of the stacking manner, and the ΔT-dependence of dcalc for O3- and P2-type structure is expressed as,Na sheet is sandwiched by the MO2 and NaO2 layers, respectively. A relationship between dcalc and the expression of c  is expressed as z  for O3- and P2-type structures are derived asThe first and the second terms correspond to entclass1pt{minimaRM (=0.65 Å) against a. We show that this model exhibits minimum Madelung energy (EME). Figure EME of O3- and P2-type NaMO2 against a. Our constraint gives acalc ≈ 2.995 Å [Eq. RM = 0.65 Å. With the O3 structure, the acalc value corresponds to the minimum position of EME (−8.67 eV). With an increase in a from 2.995 Å, M becomes isolated from the surrounding oxygens . Similar results are obtained for the P2 structure. Thus, our model is energetically stable against the variation of a. Our constraint that M, upper and lower oxygens connected to each other causes the compact layered structure and minimized the long-range Coulomb energy between the layers. We call our model “hard-sphere model with minimum Madelung energy”.Now, let us consider the stability of the hard-sphere model with the constraint that M, upper and lower oxygens coroneted to each other. For this purpose, we calculated the Madelung energy at a specific RM =0.6 Å agains95 Å Eq.  at RM = d/a based on the hard-sphere model with minimum Madelung energy  was chosen to fit the average value of αa (=0.92 × 10−5 K−1). Using the same value of A, αc for the P2 materials is possibly due to Na vacancies except for the data point of Na0.59CoO2. We note that A,75, S76, 4d transition metals78, Os78, MgO79, CaO79, and ZnO80, which is beyond the scope of this paper.The broken lines in Fig. z-coordinates of P2- and O3-type NaMO2. We proposed a simple hard-sphere model with constraint that M, upper and lower oxygens are coroneted to each others. The model quantitatively reproduced a, c, z, αa and αc for O3-type NaxMO2. On the other hand, z coordinate of P2-type NaxMO2 deviates from the hard-sphere model possibly due to Na vacancies. This simple model can be easily applied for the other layered compounds to intuitively understand and design the thermal expansion behaviors.We systematically determined the temperature dependent lattice constant and xMO2  were synthesized by using conventional solid state reaction. For O3-Na1.00CoO2, Na2O2 and Co3O4 were mixed under the molar ratio of Na:Co = 1.1:1, and calcined at 550°C in O2 for 16 h. Then, the product was finely ground, and again calcined in the same condition (this process was repeated once again.). For O3-Na0.98Fe0.5Co0.5O2, Na2CO3, Fe3O4 and Co3O4 were mixed under the molar ratio of Na:Fe:Co = 1.05:0.5:0.5, and calcined at 900 °C in air for 15 h. For O3-Na0.99Fe0.5Ni0.5O2, Na2O2, Fe2O3 and NiO were mixed under the molar ratio of Na:Fe:Ni = 1.2:0.5:0.5, and calcined at 650°C in O2 for 15 h. Then the product was finely ground and again calcined in the same condition. For O3-Na0.94Ti0.5Ni0.5O2, Na2CO3, TiO2 and NiO were mixed under the molar ratio of Na:Ti:Ni = 1.05:0.5:0.5, and calcined at 900°C in air for 15 h. Then the product was finely ground and again calcined in the same condition.Powders of O3- and P2-Na0.50Mn0.5Co0.5O2, Na2CO3, MnCO3 and Co3O4 were mixed under the molar ratio of Na:Mn:Co = 0.7:0.5:0.5, and calcined at 900°C in air for 12 h, Then, the product was finely ground and again calcined in the same condition. For P2-Na0.70Ni0.33Mn0.67O2, Na2CO3, NiO and Mn2O3 were mixed in ethanol under the molar ratio of Na:Ni:Mn = 0.7:0.33:0.67, and calcined at 900°C in air for 24 h. Then, the product was finely ground and again calcined in the same condition. For P2-Na0.69Ni0.33Mn0.5Ti0.17O2, Na2CO3, NiO, Mn2O3 and TiO2 were mixed under the molar ratio of Na:Ni:Mn:Ti = 0.7:0.33:0.5: 0.17, and calcined at 900°C in air for 18 h. For P2-Na0.70Ni0.33Mn0.33Ti0.34O2, Na2CO3, NiO, Mn2O3 and TiO2 were mixed under the molar ratio of Na:Ni:Mn:Ti = 0.7:0.33:0.33:0.34, and calcined at 900°C in air for 12 h. For P2-Na0.48Mn0.5Fe0.5O2, Na2O2, Mn2O3 and Fe2O3 were mixed under the molar ratio of Na:Mn:Fe = 0.7:0.5:0.5, and calcined at 900°C in air for 12 h. Then, the product was finely ground and again calcined in the same condition. All the samples were taken out from the hot furnace (>200°C), and then immediately transferred into a vacuum desiccator to avoid moisture in air.For P2-Na81 at SPring-8. The capillary was placed on the Debye-Scherrer camera at the beamline. The sample temperature was controlled by blowing a hot N2 in the temperature range of 300 K ≤ T ≤ 800 K. The XRD patterns were detected with an imaging plate (IP). The exposure time was 5 min. The wavelength of the x-ray was 0.499420 Å for P2-Na0.48Mn0.5Fe0.5O2 and P2-Na0.50Mn0.5Co0.5O2, and 0.499892 Å for O3-Na0.98Fe0.5Co0.5O2 and Na0.94Ti0.5Ni0.5O2, and 0.499838 Å for the others. The wavelengths are calibrated by the cell parameter of standard CeO2 powders. Crystal structure was analyzed by RIETAN-FP program82. Schematic figure of the crystal structure were drawn by VESTA program83. All the reflections can be indexed with the O3-type (P63/mmc) structures except for a tiny amount of impurity of O3-type Fe-rich phase for Na0.99Fe0.5Ni0.5O2 and NiO for Na0.94Ti0.5Ni0.5O2. All the structural parameters against T (300 K ≤ T ≤ 800 K) were listed in Tables The synchrotron radiation x-ray diffraction (XRD) patterns were measured at BL02B2 beamline45 reported a consistency of Na contents determined by ICP-AES (Inductively Coupled Plasma Atomic Emission Spectroscopy) and Rietveld refinement using synchrotron x-ray diffraction for P2-NaxMn1/2Fe1/2O2 phase.The actual Na concentrations in the compound were determined by the Rietveld refinement based on the synchrotron XRD patterns at 300 K. We note that ref.EME) was computed by the MADEL program in the VESTA software using the Fourier method83. The site potential ϕi is calculated by the formula gj is the occupancy of the j th ion, Zi is the valence of the j th ion, ε0 is the vacuum permittivity, and lij is the distance between ions i and j. EME is calculated by using the formula Wi is a factor depending on gi and the number of equivalent atomic positions at the site i in the unit cell. For O3-type structure , 3b M  sites in stoichiometric NaMO2. In the calculation of the P2-type structure (P63/mmc), we assume a stoichiometric NaMO2 with fully occupied 2d Na site. We put +e, +3e, and −2e charges on 2d Na a M , and 4f O s) of the hard sphere was set to 0.3 Å, and Fourier coefficients are summed up to 10 Å−1 in the reciprocal space.Madelung energy (Supplementary information


II atom is coordinated by four pyrrole N atoms of the porphyrin core and one O atom of the crown ether. Intramolecular N—H⋯O and intermolecular C—H⋯π interactions are observedIn the title compound, the central Co 57H52N6O6)], the central CoII atom is coordinated by four pyrrole N atoms of the porphyrin core and one O atom of the crown ether. The complex has a distorted porphyrin core, with mean absolute core-atom displacements of 0.14 (10) (Ca), 0.20 (10) (Cb), 0.24 (4) (Cm) and 0.18 (10) Å (Cav), respectively. The axial Co—O bond length is 2.3380 (15) and the average Co—Np bond length is 1.968 (5) Å. Intramolecular N—H⋯O and intermolecular C—H⋯π interactions are observed.In the title compound, [Co(C There have been some reports on the single-crystal structures of crown ether-porphyrinates, including chloridoiron(III)  bond length is 1.968 (5), in the narrow range of 1.958 (2)–1.969 (2) Å reported by Dey & Rath (2014II(TDPMP)(CH3OH)] 2 . The title compound shows a distorted porphyrin core conformation. The mean absolute core-atom displacements Ca, Cb, Cm and Cav are 0.14 (10), 0.20 (10), 0.24 (4) and 0.18 (10) Å, respectively.The cobalt(II) cation is displaced slightly from the porphyrin core to the axial ligand, as illustrated by the displacement of the metal atom from the 24-atom mean plane  of the crown ether and the nitrogen atom (N5) of the amide linker. The distance between O2 and N5 is 2.886 (2) Table 1, consistA, H31A, H32A, H33A) of the crown ether and the plane of the neighbouring porphyrin core are 2.52, 2.57, 2.71 and 2.34 Å, all of which are smaller than 2.9 Å, a limit suggested for the existence of C—H⋯π interactions  over calcium hydride. 52-Aminophenyl-5,10,15,20-tetraphenylporphyrin was prepared according to the reported method  was distilled over sodium/benzophenone, hexanes over potassium-sodium alloy and dichloromethane carbonylamino]phenyl}-10,15,20-triphenylporphyrin was prepared according to a modification of the reported methods  and triethylamine  at 273 K. The mixture was stirred for 1 h and evaporated to dryness under vacuum. A CH2Cl2 (150 mL) solution of 1-aza-18-crown-6  and Et3N (0.3 mL) was added to the resulting solid stepwise. After overnight stirring, the solution was evaporated. The porphyrin product  was obtained by chromatography on a silica gel column (CH2Cl2).Triphosgene  was added to a THF (150 mL) solution of 5et al., 1970carbonylamino]phenyl}-10,15,20-triphenylporphyrinato)cobalt(II) was prepared according to a modification of the reported method  was added to a THF (150 mL) solution of 52-N-(4-aza-18-crown-6)acylamino-5,10,15,20-tetraphenylporphyrin . The mixture was refluxed for 3 h until the reaction was complete (monitored by TLC). The solution was extracted with CH2Cl2, washed with distilled water 2–3 times. After drying over Na2SO4 and filtration, the solvent was removed by rotoevaporation. The cobalt porphyrin product  was obtained by chromatography on a silica gel column . The title crystal was obtained in a THF solution with hexanes as non-solvent.Dried CoClUiso(H) = 1.2Ueq(C). One outlier was omitted in the last cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017007745/qm2115sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017007745/qm2115Isup2.hklStructure factors: contains datablock(s) I. DOI: 1552184CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


PDGFRα+ cells directly interact with interstitial cells of Cajal (ICC) and smooth muscle cells (SMC) in gastrointestinal smooth muscle tissue. These three cell types, SMC, ICC, and PDGFRα+ cells (SIP cells), form an electrical syncytium, which dynamically regulates gastrointestinal motility. We have previously reported the transcriptomes of SMC and ICC. To complete the SIP cell transcriptome project, we obtained transcriptome data from jejunal and colonic PDGFRα+ cells. The PDGFRα+ cell transcriptome data were added to the Smooth Muscle Genome Browser that we previously built for the genome-scale gene expression data of ICC and SMC. This browser provides a comprehensive reference for all transcripts expressed in SIP cells. By analyzing the transcriptomes, we have identified a unique set of PDGFRα+ cell signature genes, growth factors, transcription factors, epigenetic enzymes/regulators, receptors, protein kinases/phosphatases, and ion channels/transporters. We demonstrated that the low voltage-dependent T-type Ca2+ channel Cacna1g gene was particularly expressed in PDGFRα+ cells in the intestinal serosal layer in mice. Expression of this gene was significantly induced in the hyperplasic PDGFRα+ cells of obstructed small intestine in mice. This gene was also over-expressed in colorectal cancer, Crohn’s disease, and diverticulitis in human patients. Taken together, our data suggest that Cacna1g exclusively expressed in serosal PDGFRα+ cells is a new pathological marker for gastrointestinal diseases.Platelet-derived growth factor receptor alpha (PDGFRα) These cells form an electrical syncytium, collectively known as the SIP  syncytium. Each type of SIP cell contributes unique behaviors and responses to neurotransmitters, and there may be many more unrecognized behaviors of SIP cells. Remodeling of these cells occurs in a variety of pathophysiological conditions, and the loss, or loss-of-function, of SIP cells can contribute to the development of motor dysfunction .(A) K(TIF)Click here for additional data file.S4 Fig(A) Hydrogen transporter isoforms enriched in JPαC and CPαC. (B) PαC-specific hydrogen transporter isoforms. Cell specificity was determined by comparative analysis of gene expression profiles among PαC, SMC, and ICC.(TIF)Click here for additional data file.S5 Fig(A) Growth factor isoforms enriched in JPαC and CPαC. (B) PαC-specific growth factor isoforms. (C) Receptor isoforms enriched in JPαC and CPαC. (D) PαC-specific receptor isoforms. (E) Transcription factor isoforms enriched in JPαC and CPαC. (F) PαC-specific transcription factor isoforms. Cell specificity was determined by comparative analysis of gene expression profiles among among PαC, SMC, and ICC.(TIF)Click here for additional data file.S6 FigDnmt1 and Dnmt3a), methylcytosine dioxygenases , and DNA oxidative demethylase (Alkbh1) enriched in JPαC and CPαC. (B) PαC-specific isoforms of DNA methylation and demethylation enzymes. (C) Methyl-CpG binding proteins enriched in JPαC and CPαC. (D) PαC-specific methyl-CpG binding proteins. Cell specificity was determined by comparative analysis of gene expression profiles among PαC, SMC, and ICC.(A) DNA methyltransferases ((TIF)Click here for additional data file.S7 Fig(A) Histone acetyltransferases enriched in JPαC and CPαC. (B) PαC-specific histone acetyltransferases. (C) Histone deacetylases enriched in JPαC and CPαC. (D) ICC-specific histone deacetylases. (E) Histone methyltransferases enriched in JPαC and CPαC. (F) PαC-specific histone methyltransferases. (G) Histone demethylases enriched in JPαC and CPαC. (H) PαC-specific histone demethylases. Cell specificity was determined by comparative analysis of gene expression profiles among PαC, SMC, and ICC.(TIF)Click here for additional data file.S8 Fig(A) Protein kinases enriched in JPαC and CPαC. (B) PαC-specific protein kinases. (C) Phosphatases enriched in JPαC and CPαC. (D) PαC-specific phosphatases. Cell specificity was determined by comparative analysis of gene expression profiles among PαC, SMC, and ICC.(TIF)Click here for additional data file.S1 Table(XLSX)Click here for additional data file.S2 Table(XLSX)Click here for additional data file.S3 Table(XLSX)Click here for additional data file.S4 Table(XLSX)Click here for additional data file.S5 Table(XLSX)Click here for additional data file.S6 Table(XLSX)Click here for additional data file.S7 Table(XLSX)Click here for additional data file.S8 Table(XLSX)Click here for additional data file.S9 Table(XLSX)Click here for additional data file.S10 Table(XLSX)Click here for additional data file.S11 Table(XLS)Click here for additional data file.


The copper(II) complex of the non-symmetric, bidentate ligand 2-{[6-(dimethylamino)pyrimidin-4-yl]sulfanyl}pyrimidine-4,6-diamine exhibits distorted square pyramidal geometry around the metal centre, with disorder in the axial position, occupied by chloride or water. The six-membered metal–chelate ring is in a boat-conformation, and short intermolecular S⋯S interactions are observed. L1) is reported. The single-crystal X-ray structure of aqua[aqua/chlorido(0.49/0.51)](2-{[6-(dimethylamino)pyrimidin-4-yl]sulfanyl}pyrimidine-4,6-diamine)copper(II) 0.49-chloride 1.51-hydrate, [CuCl1.51(C10H13N7S)(H2O)1.49]Cl0.49·1.51H2O or [(L1)Cl1.51(H2O)1.49Cu]0.49Cl·1.51H2O, exhibits distorted square-pyramidal geometry around the metal centre, with disorder in the axial position, occupied by chloride or water. The six-membered metal–chelate ring is in a boat conformation, and short intermolecular S⋯S interactions are observed. In addition to its capacity for bidentate metal coordination, the ligand has the ability to engage in further supramolecular interactions as both a hydrogen-bond donor and acceptor, and multiple interactions with lattice solvent water molecules are present in the reported structure.A copper(II) complex of the non-symmetric bidentate ligand 2-{[6-(dimethylamino)pyrimidin-4-yl]sulfanyl}pyrimidine-4,6-diamine ( Even upon metal coordination, the ligand can still serve as a hydrogen-bond donor to anions via the amine moieties. Alternatively, these free amines could also act as possible anchors for surface attachment, with a view towards future device applications.In the interest of exploring simultaneous coordination chemistry and anion–ligand affinity P21/c with one bidentate ligand bound to a copper(II) cation  or water  with occupancies of 0.511 (5) and 0.489 (5), respectively. The two largest ligand–metal–ligand bond angles  and the apical ligand (H2O)Cl2]·H2O .A simpler, symmetric bidentate ligand, di(pyridin-2-yl)sulfide (DPS), has been reported to exhibit a very similar metal coordination environment to the major component reported here, upon reaction with CuClb axis  Å; symmetry code: (i) −x + 1, y + z + In the crystal, molecules of the title complex pack in columns, parallel to the crystallographic is Fig. 3, with shet al., 2016ConQuest pyrimidin-4-yl]sulfanyl}pyrimidine-4,6-diamine (CL1): 0.972 g (7.03 mmol) of potassium carbonate and 1.000 g (6.24 mmol) of 4,6-diamino-2-mercaptopyrimidine hydrate were combined in 20 mL of dimethylformamide, and stirred at 333 K for 20 min, prior to the addition of 0.524 g (3.51 mmol) of 4,6-dichloropyrimidine (see reaction scheme). The resulting cloudy orange solution was refluxed for 24 h. It was then filtered, and the brown filtrate was reduced in vacuo to yield 0.387 g (1.47 mmol) of orange solid, after washing with ethanol (42% yield).1.51(C10H13N7S)(H2O)1.49]Cl0.49·1.51H2O:Aquachlorido(2-{[6-(dimethylamino)pyrimidin-4-yl]sulfanyl}pyrimidine-4,6-diamine)copper(II) chloride hydrate [CuCl 0.050 g (0.19 mmol) of L1 and 0.048 g (0.28 mmol) of CuCl2·2H2O were separately dissolved in 5 mL of 1:1 methanol/acetonitrile. The solution of CuCl2 was added dropwise to the solution of L1. The resulting cloudy brown solution was stirred vigorously with heating (333 K) for 20 min. This was filtered, yielding 0.007 g of brown, amorphous powder, and a clear green filtrate that was left for slow evaporation. Green, prismatic X-ray quality crystals grew from the filtrate over the course of six weeks. 3.6 mg (0.0080 mmol) of analytically pure crystals were harvested as soon as they formed, though the mother liquor was still highly coloured, accounting for the low (4.2%) yield. These crystals were analyzed via small molecule X-ray diffraction, and elemental analysis. Analysis calculated for [(C10H13N7S)CuCl2·3H2O: C, 26.58; H, 4.24; N, 21.7. Found: C, 26.26; H, 4.13; N, 21.31. Presence of copper confirmed via graphite furnace atomic absorption spectroscopy: calculated: 25 µg L−1; found: 31.0 ± 0.14 µg L−1 (n = 8).Uiso(H) 1.5 times that of the parent atoms and rotating geometry constraints (AFIX 7). Similar distance restraints  were applied for all water molecules.Crystal data, data collection and structure refinement details are summarized in Table 32 and Cu—Cl bonds; for each, one O atom (O1) and one Cl atom (Cl1) were fully occupied, while the other (O2 and Cl2) were at partial occupancy, occupying the same coordination site on Cu1, with a sum of their occupancy equal to one. Identical anisotropic displacement parameter (EADP) constraints were applied to Cl2 and O2. Finally, EADP constraints were also applied to a disordered water molecule (O4 and O5), with a sum occupancy of one.The structure exhibited significant disorder. This included main fragment disorder in the coordination sphere around Cu1. As such, similar distance restraints  were applied to the Cu—OHWhile the structure does exhibit significant disorder, careful consideration was given to ensure that: (i) charge balance was established; (ii) the model was consistent with a reasonable hydrogen-bonding network; and (iii) the next highest residual electron density peak was associated along a C—S bond.10.1107/S205698901701338X/zl2715sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901701338X/zl2715Isup2.hklStructure factors: contains datablock(s) I. DOI: 1575371CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: