Sample records for coordinates synaptonemal complex

  1. HTP-1 coordinates synaptonemal complex assembly with homolog alignment during meiosis in C. elegans. (United States)

    Couteau, Florence; Zetka, Monique


    During meiosis, the mechanisms responsible for homolog alignment, synapsis, and recombination are precisely coordinated to culminate in the formation of crossovers capable of directing accurate chromosome segregation. An outstanding question is how the cell ensures that the structural hallmark of meiosis, the synaptonemal complex (SC), forms only between aligned pairs of homologous chromosomes. In the present study, we find that two closely related members of the him-3 gene family in Caenorhabditis elegans function as regulators of synapsis. HTP-1 functionally couples homolog alignment to its stabilization by synapsis by preventing the association of SC components with unaligned and immature chromosome axes; in the absence of the protein, nonhomologous contacts between chromosomes are inappropriately stabilized, resulting in extensive nonhomologous synapsis and a drastic decline in chiasma formation. In the absence of both HTP-1 and HTP-2, synapsis is abrogated per se and the early association of SC components with chromosomes observed in htp-1 mutants does not occur, suggesting a function for the proteins in licensing SC assembly. Furthermore, our results suggest that early steps of recombination occur in a narrow window of opportunity in early prophase that ends with SC assembly, resulting in a mechanistic coupling of the two processes to promote crossing over.

  2. Meiosis in mice without a synaptonemal complex.

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    Anna Kouznetsova

    Full Text Available The synaptonemal complex (SC promotes fusion of the homologous chromosomes (synapsis and crossover recombination events during meiosis. The SC displays an extensive structural conservation between species; however, a few organisms lack SC and execute meiotic process in a SC-independent manner. To clarify the SC function in mammals, we have generated a mutant mouse strain (Sycp1(-/-Sycp3(-/-, here called SC-null in which all known SC proteins have been displaced from meiotic chromosomes. While transmission electron microscopy failed to identify any remnants of the SC in SC-null spermatocytes, neither formation of the cohesion axes nor attachment of the chromosomes to the nuclear membrane was perturbed. Furthermore, the meiotic chromosomes in SC-null meiocytes achieved pre-synaptic pairing, underwent early homologous recombination events and sustained a residual crossover formation. In contrast, in SC-null meiocytes synapsis and MLH1-MLH3-dependent crossovers maturation were abolished, whereas the structural integrity of chromosomes was drastically impaired. The variable consequences that SC inactivation has on the meiotic process in different organisms, together with the absence of SC in some unrelated species, imply that the SC could have originated independently in different taxonomic groups.

  3. Covariation of synaptonemal complex length and mammalian meiotic exchange rates. (United States)

    Lynn, Audrey; Koehler, Kara E; Judis, LuAnn; Chan, Ernest R; Cherry, Jonathan P; Schwartz, Stuart; Seftel, Allen; Hunt, Patricia A; Hassold, Terry J


    Analysis of recombination between loci (linkage analysis) has been a cornerstone of human genetic research, enabling investigators to localize and, ultimately, identify genetic loci. However, despite these efforts little is known about patterns of meiotic exchange in human germ cells or the mechanisms that control these patterns. Using recently developed immunofluorescence methodology to examine exchanges in human spermatocytes, we have identified remarkable variation in the rate of recombination within and among individuals. Subsequent analyses indicate that, in humans and mice, this variation is linked to differences in the length of the synaptonemal complex. Thus, at least in mammals, a physical structure, the synaptonemal complex, reflects genetic rather than physical distance.

  4. Solving a meiotic LEGO puzzle: transverse filaments and the assembly of the synaptonemal complex in Caenorhabditis elegans. (United States)

    Hawley, R Scott


    The structure of the meiosis-specific synaptonemal complex, which is perhaps the central visible characteristic of meiotic prophase, has been a matter of intense interest for decades. Although a general picture of the interactions between the transverse filament proteins that create this structure has emerged from studies in a variety of organisms, a recent analysis of synaptonemal complex structure in Caenorhabditis elegans by Schild-Prüfert et al. (2011) has provided the clearest picture of the structure of the architecture of a synaptonemal complex to date. Although the transverse filaments of the worm synaptonemal complex are assembled differently then those observed in yeast, mammalian, and Drosophila synaptonemal complexes, a comparison of the four assemblies shows that achieving the overall basic structure of the synaptonemal complex is far more crucial than conserving the structures of the individual transverse filaments.

  5. Hormad1 mutation disrupts synaptonemal complex formation, recombination, and chromosome segregation in mammalian meiosis.

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    Yong-Hyun Shin


    Full Text Available Meiosis is unique to germ cells and essential for reproduction. During the first meiotic division, homologous chromosomes pair, recombine, and form chiasmata. The homologues connect via axial elements and numerous transverse filaments to form the synaptonemal complex. The synaptonemal complex is a critical component for chromosome pairing, segregation, and recombination. We previously identified a novel germ cell-specific HORMA domain encoding gene, Hormad1, a member of the synaptonemal complex and a mammalian counterpart to the yeast meiotic HORMA domain protein Hop1. Hormad1 is essential for mammalian gametogenesis as knockout male and female mice are infertile. Hormad1 deficient (Hormad1(-/ (- testes exhibit meiotic arrest in the early pachytene stage, and synaptonemal complexes cannot be visualized by electron microscopy. Hormad1 deficiency does not affect localization of other synaptonemal complex proteins, SYCP2 and SYCP3, but disrupts homologous chromosome pairing. Double stranded break formation and early recombination events are disrupted in Hormad1(-/ (- testes and ovaries as shown by the drastic decrease in the γH2AX, DMC1, RAD51, and RPA foci. HORMAD1 co-localizes with γH2AX to the sex body during pachytene. BRCA1, ATR, and γH2AX co-localize to the sex body and participate in meiotic sex chromosome inactivation and transcriptional silencing. Hormad1 deficiency abolishes γH2AX, ATR, and BRCA1 localization to the sex chromosomes and causes transcriptional de-repression on the X chromosome. Unlike testes, Hormad1(-/ (- ovaries have seemingly normal ovarian folliculogenesis after puberty. However, embryos generated from Hormad1(-/ (- oocytes are hyper- and hypodiploid at the 2 cell and 8 cell stage, and they arrest at the blastocyst stage. HORMAD1 is therefore a critical component of the synaptonemal complex that affects synapsis, recombination, and meiotic sex chromosome inactivation and transcriptional silencing.

  6. Hormad1 mutation disrupts synaptonemal complex formation, recombination, and chromosome segregation in mammalian meiosis. (United States)

    Shin, Yong-Hyun; Choi, Youngsok; Erdin, Serpil Uckac; Yatsenko, Svetlana A; Kloc, Malgorzata; Yang, Fang; Wang, P Jeremy; Meistrich, Marvin L; Rajkovic, Aleksandar


    Meiosis is unique to germ cells and essential for reproduction. During the first meiotic division, homologous chromosomes pair, recombine, and form chiasmata. The homologues connect via axial elements and numerous transverse filaments to form the synaptonemal complex. The synaptonemal complex is a critical component for chromosome pairing, segregation, and recombination. We previously identified a novel germ cell-specific HORMA domain encoding gene, Hormad1, a member of the synaptonemal complex and a mammalian counterpart to the yeast meiotic HORMA domain protein Hop1. Hormad1 is essential for mammalian gametogenesis as knockout male and female mice are infertile. Hormad1 deficient (Hormad1(-/) (-)) testes exhibit meiotic arrest in the early pachytene stage, and synaptonemal complexes cannot be visualized by electron microscopy. Hormad1 deficiency does not affect localization of other synaptonemal complex proteins, SYCP2 and SYCP3, but disrupts homologous chromosome pairing. Double stranded break formation and early recombination events are disrupted in Hormad1(-/) (-) testes and ovaries as shown by the drastic decrease in the γH2AX, DMC1, RAD51, and RPA foci. HORMAD1 co-localizes with γH2AX to the sex body during pachytene. BRCA1, ATR, and γH2AX co-localize to the sex body and participate in meiotic sex chromosome inactivation and transcriptional silencing. Hormad1 deficiency abolishes γH2AX, ATR, and BRCA1 localization to the sex chromosomes and causes transcriptional de-repression on the X chromosome. Unlike testes, Hormad1(-/) (-) ovaries have seemingly normal ovarian folliculogenesis after puberty. However, embryos generated from Hormad1(-/) (-) oocytes are hyper- and hypodiploid at the 2 cell and 8 cell stage, and they arrest at the blastocyst stage. HORMAD1 is therefore a critical component of the synaptonemal complex that affects synapsis, recombination, and meiotic sex chromosome inactivation and transcriptional silencing.

  7. The diverse roles of transverse filaments of synaptonemal complexes in meiosis

    NARCIS (Netherlands)

    Boer, de E.; Heyting, C.


    In most eukaryotes, homologous chromosomes (homologs) are closely apposed during the prophase of the first meiotic division by a ladderlike proteinaceous structure, the synaptonemal complex (SC) [Fawcett, J Biophys Biochem Cytol 2:403-406, 1956; Moses, J Biophys Biochem Cytol 2:215-218, 1956]. SCs c

  8. SCP1, a major protein component of synaptonemal complexes of the rat.

    NARCIS (Netherlands)

    Meuwissen, R.L.J.


    Synaptonemal complexes (SCs) are structures that are formed between homologous chromosomes during meiotic prophase. SCs consist of two proteinaceous axes, one along each homologue, that are connected along their length by numerous transverse filaments (TFs). The assembly and disassembly of SCs close

  9. SUMO meets meiosis: an encounter at the synaptonemal complex: SUMO chains and sumoylated proteins suggest that heterogeneous and complex interactions lie at the centre of the synaptonemal complex. (United States)

    Watts, Felicity Z; Hoffmann, Eva


    Recent discoveries have identified the small ubiquitin-like modifier (SUMO) as the potential 'missing link' that could explain how the synaptonemal complex (SC) is formed during meiosis. The SC is important for a variety of chromosome interactions during meiosis and appears ladder-like. It is formed when 'axes' of the two homologous chromosomes become connected by the deposition of transverse filaments, forming the steps of the ladder. Although several components of axial and transverse elements have been identified, how the two are connected to form the SC has remained an enigma. Recent discoveries suggest that SUMO modification underlies protein-protein interactions within the SC of budding yeast. The versatility of SUMO in regulating protein-protein interactions adds an exciting new dimension to our understanding of the SC and suggests that SCs are not homogenous structures throughout the nucleus. We propose that this heterogeneity may allow differential regulation of chromosome structure and function.

  10. P31comet, a member of the synaptonemal complex, participates in meiotic DSB formation in rice. (United States)

    Ji, Jianhui; Tang, Ding; Shen, Yi; Xue, Zhihui; Wang, Hongjun; Shi, Wenqing; Zhang, Chao; Du, Guijie; Li, Yafei; Cheng, Zhukuan


    The human mitotic arrest-deficient 2 (Mad2) binding protein p31(comet) participates in the spindle checkpoint and coordinates cell cycle events in mitosis although its function in meiosis remains unknown in all organisms. Here, we reveal P31(comet) as a synaptonemal complex (SC) protein in rice (Oryza sativa L.). In p31(comet), homologous pairing and synapsis are eliminated, leading to the homologous nondisjunction and complete sterility. The failure in loading of histone H2AX phosphorylation (γH2AX) in p31(comet), together with the suppressed chromosome fragmentation in rice completion of meiotic recombination 1 (com1) p31(comet) and radiation sensitive 51c (rad51c) p31(comet) double mutants, indicates that P31(comet) plays an essential role in double-strand break (DSB) formation. Interestingly, the dynamic colocalization pattern between P31(comet) and ZEP1 (a transverse filament protein of SC) by immunostaining, as well as the interaction between P31(comet) and CENTRAL REGION COMPONENT 1 (CRC1) in yeast two-hybrid assays, suggests possible involvement of P31(comet) in SC installation. Together, these data indicate that P31(comet) plays a key role in DSB formation and SC installation, mainly through its cooperation with CRC1.

  11. Synaptonemal complex components persist at centromeres and are required for homologous centromere pairing in mouse spermatocytes.

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    C Gaston Bisig


    Full Text Available Recent studies in simple model organisms have shown that centromere pairing is important for ensuring high-fidelity meiotic chromosome segregation. However, this process and the mechanisms regulating it in higher eukaryotes are unknown. Here we present the first detailed study of meiotic centromere pairing in mouse spermatogenesis and link it with key events of the G2/metaphase I transition. In mouse we observed no evidence of the persistent coupling of centromeres that has been observed in several model organisms. We do however find that telomeres associate in non-homologous pairs or small groups in B type spermatogonia and pre-leptotene spermatocytes, and this association is disrupted by deletion of the synaptonemal complex component SYCP3. Intriguingly, we found that, in mid prophase, chromosome synapsis is not initiated at centromeres, and centromeric regions are the last to pair in the zygotene-pachytene transition. In late prophase, we first identified the proteins that reside at paired centromeres. We found that components of the central and lateral element and transverse filaments of the synaptonemal complex are retained at paired centromeres after disassembly of the synaptonemal complex along diplotene chromosome arms. The absence of SYCP1 prevents centromere pairing in knockout mouse spermatocytes. The localization dynamics of SYCP1 and SYCP3 suggest that they play different roles in promoting homologous centromere pairing. SYCP1 remains only at paired centromeres coincident with the time at which some kinetochore proteins begin loading at centromeres, consistent with a role in assembly of meiosis-specific kinetochores. After removal of SYCP1 from centromeres, SYCP3 then accumulates at paired centromeres where it may promote bi-orientation of homologous centromeres. We propose that, in addition to their roles as synaptonemal complex components, SYCP1 and SYCP3 act at the centromeres to promote the establishment and/or maintenance of

  12. Synaptonemal Complex Components Persist at Centromeres and Are Required for Homologous Centromere Pairing in Mouse Spermatocytes (United States)

    Kouznetsova, Anna; Scherthan, Harry; Höög, Christer; Dawson, Dean S.; Pezza, Roberto J.


    Recent studies in simple model organisms have shown that centromere pairing is important for ensuring high-fidelity meiotic chromosome segregation. However, this process and the mechanisms regulating it in higher eukaryotes are unknown. Here we present the first detailed study of meiotic centromere pairing in mouse spermatogenesis and link it with key events of the G2/metaphase I transition. In mouse we observed no evidence of the persistent coupling of centromeres that has been observed in several model organisms. We do however find that telomeres associate in non-homologous pairs or small groups in B type spermatogonia and pre-leptotene spermatocytes, and this association is disrupted by deletion of the synaptonemal complex component SYCP3. Intriguingly, we found that, in mid prophase, chromosome synapsis is not initiated at centromeres, and centromeric regions are the last to pair in the zygotene-pachytene transition. In late prophase, we first identified the proteins that reside at paired centromeres. We found that components of the central and lateral element and transverse filaments of the synaptonemal complex are retained at paired centromeres after disassembly of the synaptonemal complex along diplotene chromosome arms. The absence of SYCP1 prevents centromere pairing in knockout mouse spermatocytes. The localization dynamics of SYCP1 and SYCP3 suggest that they play different roles in promoting homologous centromere pairing. SYCP1 remains only at paired centromeres coincident with the time at which some kinetochore proteins begin loading at centromeres, consistent with a role in assembly of meiosis-specific kinetochores. After removal of SYCP1 from centromeres, SYCP3 then accumulates at paired centromeres where it may promote bi-orientation of homologous centromeres. We propose that, in addition to their roles as synaptonemal complex components, SYCP1 and SYCP3 act at the centromeres to promote the establishment and/or maintenance of centromere pairing and

  13. SOHLH2 is essential for synaptonemal complex formation during spermatogenesis in early postnatal mouse testes. (United States)

    Park, Miree; Lee, Youngeun; Jang, Hoon; Lee, Ok-Hee; Park, Sung-Won; Kim, Jae-Hwan; Hong, Kwonho; Song, Hyuk; Park, Se-Pill; Park, Yun-Yong; Ko, Jung Jae; Choi, Youngsok


    Spermatogenesis- and oogenesis-specific helix-loop-helix transcription factor 2 (SOHLH2) is exclusively expressed in germ cells of the gonads. Previous studies show that SOHLH2 is critical for spermatogenesis in mouse. However, the regulatory mechanism of SOHLH2 during early spermatogenesis is poorly understood. In the present study, we analyzed the gene expression profile of the Sohlh2-deficient testis and examined the role of SOHLH2 during spermatogenesis. We found 513 genes increased in abundance, while 492 genes decreased in abundance in 14-day-old Sohlh2-deficient mouse testes compared to wildtype mice. Gene ontology analysis revealed that Sohlh2 disruption effects the relative abundance of various meiotic genes during early spermatogenesis, including Spo11, Dmc1, Msh4, Prdm9, Sycp1, Sycp2, Sycp3, Hormad1, and Hormad2. Western blot analysis and immunostaining showed that SYCP3, a component of synaptonemal complex, was significantly less abundant in Sohlh2-deficient spermatocytes. We observed a lack of synaptonemal complex formation during meiosis in Sohlh2-deficient spermatocytes. Furthermore, we found that SOHLH2 interacted with two E-boxes on the mouse Sycp1 promoter and Sycp1 promoter activity increased with ectopically expressed SOHLH2. Taken together, our data suggest that SOHLH2 is critical for the formation of synaptonemal complexes via its regulation of Sycp1 expression during mouse spermatogonial differentiation.

  14. The effect of tequila in the synaptonemal complex structure of mouse spermatocytes. (United States)

    Tapia, F; Madrigal-Bujaidar, E; Aguirre, S


    The effect of tequila in the synaptonemal complex (SC) of mouse spermatocytes was determined. We tested 3 dosages (2.1, 4.2 and 8.4 g/kg) administered in a single intraperitoneal inoculation. The frequency of SC alterations was established in pachytenic nuclei 5 days after the administration using a silver impregnation technique. Three types of alterations were observed (desynapses, breaks and multiaxials) and the rate of each alteration was compared with that obtained with appropriate controls, including cyclophosphamide (CP) (150 mg/kg). The results showed a significant increase induced by tequila only in the frequency of desynapses. This damage began at the second highest dose (4.2 g/kg). The other SC alterations were in the control range. CP, however, induced a significant increase in all 3 types of SC alterations.

  15. Sex-specific differences in the synaptonemal complex in the genus Oreochromis (Cichlidae). (United States)

    Campos-Ramos, Rafael; Harvey, Simon C; Penman, David J


    Total synaptonemal complex (SC) lengths were estimated from Oreochromis aureus Steindachner (which has a WZ/ZZ sex determination system), O. mossambicus Peters and O. niloticus L. (both of which have XX/XY sex determination systems). The total SC length in oocytes was greater than that in spermatocytes in all three species (194 +/- 30 microm and 134 +/- 13 microm, 187 +/- 22 microm and 127 +/- 17 microm, 193 +/- 37 microm and 144 +/- 19 microm, respectively). These sex-specific differences did not appear to be influenced by the type of sex determination system (the female/male total SC length ratio was 1.45 in O. aureus, 1.47 in O. mossambicus and 1.34 in O. niloticus) and do not correlate with the lack of any overall sex-specific length differences in the current Oreochromis linkage map. Although based on data from relatively few species, there appears to be no consistent relationship between sex-specific SC lengths and linkage map lengths in fish. Neomale (hormonally masculinized genetic female) O. aureus and O. mossambicus had total SC lengths of 138 +/- 13 microm and 146 +/- 13 microm respectively, more similar to normal males than to normal females. These findings agree with data from other vertebrate species that suggest that phenotypic sex, rather than genotype, determines traits such as total SC length, chiasmata position and recombination pattern, at least for the autosomes.

  16. The synaptonemal complex of basal metazoan hydra: more similarities to vertebrate than invertebrate meiosis model organisms. (United States)

    Fraune, Johanna; Wiesner, Miriam; Benavente, Ricardo


    The synaptonemal complex (SC) is an evolutionarily well-conserved structure that mediates chromosome synapsis during prophase of the first meiotic division. Although its structure is conserved, the characterized protein components in the current metazoan meiosis model systems (Drosophila melanogaster, Caenorhabditis elegans, and Mus musculus) show no sequence homology, challenging the question of a single evolutionary origin of the SC. However, our recent studies revealed the monophyletic origin of the mammalian SC protein components. Many of them being ancient in Metazoa and already present in the cnidarian Hydra. Remarkably, a comparison between different model systems disclosed a great similarity between the SC components of Hydra and mammals while the proteins of the ecdysozoan systems (D. melanogaster and C. elegans) differ significantly. In this review, we introduce the basal-branching metazoan species Hydra as a potential novel invertebrate model system for meiosis research and particularly for the investigation of SC evolution, function and assembly. Also, available methods for SC research in Hydra are summarized.

  17. Synaptonemal complex damage in mouse spermatocytes exposed to tequila and brandy. (United States)

    Piña-Calva, A; Quezada-Medina, R; Madrigal-Bujaidar, E


    We evaluated the capacity of tequila and brandy to induce synaptonemal complex (SC) breaks in mouse spermatocytes. The alcoholic beverages were 20% diluted in distilled water and administered daily by oral intubation for 21 days (1, 2, and 3 g/kg, six animals per group). A positive control group was administered cyclophosphamide (CP) (20 mg/kg), and another group of mice was treated with distilled water. The results indicated the following: (i) tequila induced a statistically significant increase in SC damage with 2 g/kg and 3 g/kg, and brandy was genotoxic only with 3 g/kg, (ii) CP induced almost a duplication of the total number of breaks produced by tequila or brandy; (iii) the average weight increase in the animals was 3.3 g, but the group treated with the highest dose of tequila showed a slight weight decrease; (iv) the weight of the testes did not show any significant difference among groups of animals; and (v) there were no significant differences between groups with respect to the frequency of pachytenes (mean number: 195 in 1000 cells).

  18. The synaptonemal complex and meiotic recombination in humans: new approaches to old questions. (United States)

    Vallente, Rhea U; Cheng, Edith Y; Hassold, Terry J


    Meiotic prophase serves as an arena for the interplay of two important cellular activities, meiotic recombination and synapsis of homologous chromosomes. Synapsis is mediated by the synaptonemal complex (SC), originally characterized as a structure linked to pairing of meiotic chromosomes (Moses (1958) J Biophys Biochem Cytol 4:633-638). In 1975, the first electron micrographs of human pachytene stage SCs were presented (Moses et al. (1975) Science 187:363-365) and over the next 15 years the importance of the SC to normal meiotic progression in human males and females was established (Jhanwar and Chaganti (1980) Hum Genet 54:405-408; Pathak and Elder (1980) Hum Genet 54:171-175; Solari (1980) Chromosoma 81:315-337; Speed (1984) Hum Genet 66:176-180; Wallace and Hulten (1985) Ann Hum Genet 49(Pt 3):215-226). Further, these studies made it clear that abnormalities in the assembly or maintenance of the SC were an important contributor to human infertility (Chaganti et al. (1980) Am J Hum Genet 32:833-848; Vidal et al. (1982) Hum Genet 60:301-304; Bojko (1983) Carlsberg Res Commun 48:285-305; Bojko (1985) Carlsberg Res Commun 50:43-72; Templado et al. (1984) Hum Genet 67:162-165; Navarro et al. (1986) Hum Reprod 1:523-527; Garcia et al. (1989) Hum Genet 2:147-53). However, the utility of these early studies was limited by lack of information on the structural composition of the SC and the identity of other SC-associated proteins. Fortunately, studies of the past 15 years have gone a long way toward remedying this problem. In this minireview, we highlight the most important of these advances as they pertain to human meiosis, focusing on temporal aspects of SC assembly, the relationship between the SC and meiotic recombination, and the contribution of SC abnormalities to human infertility.

  19. Analysis of the synaptonemal complex of the nine-banded armadillo, Dasypus novemcinctus

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    Márcia Denise da Paixão Scavone


    Full Text Available The synaptonemal complex (SC of three specimens of the nine-banded armadillo (Dasypus novemcinctus was analyzed. Thirty-two bivalents (2n = 64 were observed, 31 of them being autosomes and one an XY sexual bivalent. Chromosome synapsis processes and nucleolus structure changes were analyzed in zygotene and pachytene cells, allowing a detailed description of the beginning of meiotic prophase in this species. There was complete synapsis of X and Y chromosomes. Some abnormalities in SC were observed in cells during zygotene and at the beginning of pachytene, but not in cells in the middle and late pachytene, suggesting the occurrence of synaptic adjustments in their SC.Foi analisado o complexo sinaptonêmico (SC de três espécimens de tatu galinha (Dasypus novemcinctus. Foi observada a ocorrência de 32 bivalentes (2n = 64, 31 dos quais correspondiam aos autossomos e um ao bivalente sexual XY. Os processos de sinapse cromossômica e transformação na estrutura do nucléolo foram analisados em células em zigóteno e paquíteno, permitindo uma detalhada descrição do início da prófase meiótica dessa espécie. Uma característica importante observada foi o completo emparelhamento dos cromossomos X e Y. Algumas anormalidades do SC foram observadas em células em zigóteno e no início de paquíteno, porém essas anormalidades não foram observadas em células no meio e fim de paquíteno, sugerindo a ocorrência de ajustamentos sinápticos no SC.

  20. Mutation of the mouse Syce1 gene disrupts synapsis and suggests a link between synaptonemal complex structural components and DNA repair.

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    Ewelina Bolcun-Filas


    Full Text Available In mammals, the synaptonemal complex is a structure required to complete crossover recombination. Although suggested by cytological work, in vivo links between the structural proteins of the synaptonemal complex and the proteins of the recombination process have not previously been made. The central element of the synaptonemal complex is traversed by DNA at sites of recombination and presents a logical place to look for interactions between these components. There are four known central element proteins, three of which have previously been mutated. Here, we complete the set by creating a null mutation in the Syce1 gene in mouse. The resulting disruption of synapsis in these animals has allowed us to demonstrate a biochemical interaction between the structural protein SYCE2 and the repair protein RAD51. In normal meiosis, this interaction may be responsible for promoting homologous synapsis from sites of recombination.

  1. Structural analysis of the human SYCE2-TEX12 complex provides molecular insights into synaptonemal complex assembly. (United States)

    Davies, Owen R; Maman, Joseph D; Pellegrini, Luca


    The successful completion of meiosis is essential for all sexually reproducing organisms. The synaptonemal complex (SC) is a large proteinaceous structure that holds together homologous chromosomes during meiosis, providing the structural framework for meiotic recombination and crossover formation. Errors in SC formation are associated with infertility, recurrent miscarriage and aneuploidy. The current lack of molecular information about the dynamic process of SC assembly severely restricts our understanding of its function in meiosis. Here, we provide the first biochemical and structural analysis of an SC protein component and propose a structural basis for its function in SC assembly. We show that human SC proteins SYCE2 and TEX12 form a highly stable, constitutive complex, and define the regions responsible for their homotypic and heterotypic interactions. Biophysical analysis reveals that the SYCE2-TEX12 complex is an equimolar hetero-octamer, formed from the association of an SYCE2 tetramer and two TEX12 dimers. Electron microscopy shows that biochemically reconstituted SYCE2-TEX12 complexes assemble spontaneously into filamentous structures that resemble the known physical features of the SC central element (CE). Our findings can be combined with existing biological data in a model of chromosome synapsis driven by growth of SYCE2-TEX12 higher-order structures within the CE of the SC.

  2. Complex relationship between meiotic recombination frequency and autosomal synaptonemal complex length per cell in normal human males. (United States)

    Pan, Zhenzhen; Yang, Qingling; Ye, Nan; Wang, Liu; Li, Jianhua; Yu, Dexin; Cooke, Howard J; Shi, Qinghua


    Although the relationship between meiotic recombination frequency and synaptonemal complex (SC) length has been of interest for a long time, how recombination frequency is related to SC length has not been carefully explored. To address this question, we have measured the meiotic recombination frequency as represented by MLH1 foci in 889 pachytene spermatocytes and measured the length of 19,558 autosomal SCs from 10 human males. A complex relationship between the number of MLH1 foci and total autosomal SC length per cell was observed. A positive correlation with significant correlation coefficients between the two variables was found in eight of the ten donors examined, with three donors showing weak correlation, and five showing moderate correlation. Two donors who did not show any correlation between the two variables were identified for the first time. Moreover, most cells with similar total autosomal SC length showed very different numbers of MLH1 foci both between individuals and even within an individual, and vice versa. Our data provide the first evidence for a complex relationship between the recombination frequency and total length of autosomal SCs per cell in human males.

  3. Sme4 coiled-coil protein mediates synaptonemal complex assembly, recombinosome relocalization, and spindle pole body morphogenesis. (United States)

    Espagne, Eric; Vasnier, Christelle; Storlazzi, Aurora; Kleckner, Nancy E; Silar, Philippe; Zickler, Denise; Malagnac, Fabienne


    We identify a large coiled-coil protein, Sme4/PaMe4, that is highly conserved among the large group of Sordariales and plays central roles in two temporally and functionally distinct aspects of the fungal sexual cycle: first as a component of the meiotic synaptonemal complex (SC) and then, after disappearing and reappearing, as a component of the spindle pole body (SPB). In both cases, the protein mediates spatial juxtaposition of two major structures: linkage of homolog axes through the SC and a change in the SPB from a planar to a bent conformation. Corresponding mutants exhibit defects, respectively, in SC and SPB morphogenesis, with downstream consequences for recombination and astral-microtubule nucleation plus postmeiotic nuclear migration. Sme4 is also required for reorganization of recombination complexes in which Rad51, Mer3, and Msh4 foci relocalize from an on-axis position to a between-axis (on-SC) position concomitant with SC installation. Because involved recombinosome foci represent total recombinational interactions, these dynamics are irrespective of their designation for maturation into cross-overs or noncross-overs. The defined dual roles for Sme4 in two different structures that function at distinct phases of the sexual cycle also provide more functional links and evolutionary dynamics among the nuclear envelope, SPB, and SC.

  4. Phylogenies of central element proteins reveal the dynamic evolutionary history of the mammalian synaptonemal complex: ancient and recent components. (United States)

    Fraune, Johanna; Brochier-Armanet, Céline; Alsheimer, Manfred; Benavente, Ricardo


    During meiosis, the stable pairing of the homologous chromosomes is mediated by the assembly of the synaptonemal complex (SC). Its tripartite structure is well conserved in Metazoa and consists of two lateral elements (LEs) and a central region (CR) that in turn is formed by several transverse filaments (TFs) and a central element (CE). In a previous article, we have shown that not only the structure, but also the major structural proteins SYCP1 (TFs) and SYCP3 (LEs) of the mammalian SC are conserved in metazoan evolution. In continuation of this work, we now investigated the evolution of the mammalian CE-specific proteins using phylogenetic and biochemical/cytological approaches. In analogy to the observations made for SYCP1 and SYCP3, we did not detect homologs of the mammalian CE proteins in insects or nematodes, but in several other metazoan clades. We were able to identify homologs of three mammalian CE proteins in several vertebrate and invertebrate species, for two of these proteins down to the basal-branching phylum of Cnidaria. Our approaches indicate that the SC arose only once, but evolved dynamically during diversification of Metazoa. Certain proteins appear to be ancient in animals, but successive addition of further components as well as protein loss and/or replacements have also taken place in some lineages.

  5. Identification of all pachytene bivalents in the common shrew using DAPI-staining of synaptonemal complex spreads. (United States)

    Belonogova, N M; Karamysheva, T V; Biltueva, L S; Perepelov, E A; Minina, J M; Polyakov, A V; Zhdanova, N S; Rubtsov, N B; Searle, J B; Borodin, P M


    A major problem in studies of synaptonemal complexes (SC) is the difficulty in distinguishing individual chromosomes. This problem can be solved combining SC immunostaining with FISH of chromosome-specific sequences. However, this procedure is expensive, time-consuming and applicable only to a very limited number of species. In this paper we show how a combination of SC immunostaining and DAPI staining can allow identification of all chromosome arms in surface-spreads of the SC of the common shrew (Sorex araneus L.). Enhancement of brightness and contrast of the images with photo editing software allowed us to reveal clear DAPI-positive and negative bands with relative sizes and positions similar to DAPI landmarks on mitotic metaphase chromosomes. Using FISH with DNA probes prepared from chromosome arms m and n we demonstrated correct recognition of the chromosomes mp and hn on the basis of their DAPI pattern. We show that the approach we describe here may be applied to other species and can provide an important tool for identification of individual bivalents in pachytene surface-spreads.

  6. Meiosis gene inventory of four ciliates reveals the prevalence of a synaptonemal complex-independent crossover pathway. (United States)

    Chi, Jingyun; Mahé, Frédéric; Loidl, Josef; Logsdon, John; Dunthorn, Micah


    To establish which meiosis genes are present in ciliates, and to look for clues as to which recombination pathways may be treaded by them, four genomes were inventoried for 11 meiosis-specific and 40 meiosis-related genes. We found that the set of meiosis genes shared by Tetrahymena thermophila, Paramecium tetraurelia, Ichthyophthirius multifiliis, and Oxytricha trifallax is consistent with the prevalence of a Mus81-dependent class II crossover pathway that is considered secondary in most model eukaryotes. There is little evidence for a canonical class I crossover pathway that requires the formation of a synaptonemal complex (SC). This gene inventory suggests that meiotic processes in ciliates largely depend on mitotic repair proteins for executing meiotic recombination. We propose that class I crossovers and SCs were reduced sometime during the evolution of ciliates. Consistent with this reduction, we provide microscopic evidence for the presence only of degenerate SCs in Stylonychia mytilus. In addition, lower nonsynonymous to synonymous mutation rates of some of the meiosis genes suggest that, in contrast to most other nuclear genes analyzed so far, meiosis genes in ciliates are largely evolving at a slower rate than those genes in fungi and animals.

  7. The Pch2 AAA+ ATPase promotes phosphorylation of the Hop1 meiotic checkpoint adaptor in response to synaptonemal complex defects. (United States)

    Herruzo, Esther; Ontoso, David; González-Arranz, Sara; Cavero, Santiago; Lechuga, Ana; San-Segundo, Pedro A


    Meiotic cells possess surveillance mechanisms that monitor critical events such as recombination and chromosome synapsis. Meiotic defects resulting from the absence of the synaptonemal complex component Zip1 activate a meiosis-specific checkpoint network resulting in delayed or arrested meiotic progression. Pch2 is an evolutionarily conserved AAA+ ATPase required for the checkpoint-induced meiotic block in the zip1 mutant, where Pch2 is only detectable at the ribosomal DNA array (nucleolus). We describe here that high levels of the Hop1 protein, a checkpoint adaptor that localizes to chromosome axes, suppress the checkpoint defect of a zip1 pch2 mutant restoring Mek1 activity and meiotic cell cycle delay. We demonstrate that the critical role of Pch2 in this synapsis checkpoint is to sustain Mec1-dependent phosphorylation of Hop1 at threonine 318. We also show that the ATPase activity of Pch2 is essential for its checkpoint function and that ATP binding to Pch2 is required for its localization. Previous work has shown that Pch2 negatively regulates Hop1 chromosome abundance during unchallenged meiosis. Based on our results, we propose that, under checkpoint-inducing conditions, Pch2 also possesses a positive action on Hop1 promoting its phosphorylation and its proper distribution on unsynapsed chromosome axes.

  8. Differential distribution and association of repeat DNA sequences in the lateral element of the synaptonemal complex in rat spermatocytes. (United States)

    Hernández-Hernández, Abrahan; Rincón-Arano, Héctor; Recillas-Targa, Félix; Ortiz, Rosario; Valdes-Quezada, Christian; Echeverría, Olga M; Benavente, Ricardo; Vázquez-Nin, Gerardo H


    The synaptonemal complex (SC) is an evolutionarily conserved structure that mediates synapsis of homologous chromosomes during meiotic prophase I. Previous studies have established that the chromatin of homologous chromosomes is organized in loops that are attached to the lateral elements (LEs) of the SC. The characterization of the genomic sequences associated with LEs of the SC represents an important step toward understanding meiotic chromosome organization and function. To isolate these genomic sequences, we performed chromatin immunoprecipitation assays in rat spermatocytes using an antibody against SYCP3, a major structural component of the LEs of the SC. Our results demonstrated the reproducible and exclusive isolation of repeat deoxyribonucleic acid (DNA) sequences, in particular long interspersed elements, short interspersed elements, long terminal direct repeats, satellite, and simple repeats. The association of these repeat sequences to the LEs of the SC was confirmed by in situ hybridization of meiotic nuclei shown by both light and electron microscopy. Signals were also detected over the chromatin surrounding SCs and in small loops protruding from the lateral elements into the SC central region. We propose that genomic repeat DNA sequences play a key role in anchoring the chromosome to the protein scaffold of the SC.

  9. Maize meiotic mutants with improper or non-homologous synapsis due to problems in pairing or synaptonemal complex formation (United States)

    Golubovskaya, Inna N.; Wang, C. J. Rachel; Timofejeva, Ljudmilla; Cande, W. Zacheus


    During meiotic prophase homologous chromosomes find each other and pair. Then they synapse, as the linear protein core (axial element or lateral element) of each homologous chromosome is joined together by a transverse central element, forming the tripartite synaptonemal complex (SC). Ten uncloned Zea mays mutants in our collection were surveyed by transmission electron microscopy by making silver-stained spreads of SCs to identify mutants with non-homologous synapsis or improper synapsis. To analyse the mutants further, zyp1, the maize orthologue of the Arabidopsis central element component ZYP1 was cloned and an antibody was made against it. Using antibodies against ZYP1 and the lateral element components AFD1 and ASY1, it was found that most mutants form normal SCs but are defective in pairing. The large number of non-homologous synapsis mutants defective in pairing illustrates that synapsis and pairing can be uncoupled. Of the ten mutants studied, only dsy2 undergoes normal homologous chromosome recognition needed for homologous pairing. The dsy2 mutation fails to maintain the SC. ZYP1 elongation is blocked at zygotene, and only dots of ZYP1 are seen at prophase I. Another mutant, mei*N2415 showed incomplete but homologous synapsis and ASY1 and AFD1 have a normal distribution. Although installation of ZYP1 is initiated at zygotene, its progression is slowed down and not completed by pachytene in some cells and ZYP1 is not retained on pachytene chromosomes. The mutants described here are now available through the Maize Genetics Cooperation Stock Center ( PMID:20926553

  10. Phosphorylation of the Synaptonemal Complex Protein Zip1 Regulates the Crossover/Noncrossover Decision during Yeast Meiosis. (United States)

    Chen, Xiangyu; Suhandynata, Ray T; Sandhu, Rima; Rockmill, Beth; Mohibullah, Neeman; Niu, Hengyao; Liang, Jason; Lo, Hsiao-Chi; Miller, Danny E; Zhou, Huilin; Börner, G Valentin; Hollingsworth, Nancy M


    Interhomolog crossovers promote proper chromosome segregation during meiosis and are formed by the regulated repair of programmed double-strand breaks. This regulation requires components of the synaptonemal complex (SC), a proteinaceous structure formed between homologous chromosomes. In yeast, SC formation requires the "ZMM" genes, which encode a functionally diverse set of proteins, including the transverse filament protein, Zip1. In wild-type meiosis, Zmm proteins promote the biased resolution of recombination intermediates into crossovers that are distributed throughout the genome by interference. In contrast, noncrossovers are formed primarily through synthesis-dependent strand annealing mediated by the Sgs1 helicase. This work identifies a conserved region on the C terminus of Zip1 (called Zip1 4S), whose phosphorylation is required for the ZMM pathway of crossover formation. Zip1 4S phosphorylation is promoted both by double-strand breaks (DSBs) and the meiosis-specific kinase, MEK1/MRE4, demonstrating a role for MEK1 in the regulation of interhomolog crossover formation, as well as interhomolog bias. Failure to phosphorylate Zip1 4S results in meiotic prophase arrest, specifically in the absence of SGS1. This gain of function meiotic arrest phenotype is suppressed by spo11Δ, suggesting that it is due to unrepaired breaks triggering the meiotic recombination checkpoint. Epistasis experiments combining deletions of individual ZMM genes with sgs1-md zip1-4A indicate that Zip1 4S phosphorylation functions prior to the other ZMMs. These results suggest that phosphorylation of Zip1 at DSBs commits those breaks to repair via the ZMM pathway and provides a mechanism by which the crossover/noncrossover decision can be dynamically regulated during yeast meiosis.

  11. Organization, function and genetic controlling of synaptonemal complex%联会复合体的组成、功能及遗传控制

    Institute of Scientific and Technical Information of China (English)

    谢文军; 史典义; 蔡泽熙; 陈晓阳; 金危危


    在多数有性生殖生物中,减数分裂第一次分裂前期同源染色体间会形成一种复杂的超级蛋白结构——联会复合体(Synaptonemal complex,SC).该结构与同源染色体间的配对、联会、交换、分离等过程密切相关.若其出现异常,将可导致性母细胞大量凋亡,宏观上即表现为生物个体不育.近年来,该结构已成为减数分裂研究领域的一个热点,但其控制机理至今所知还十分有限.文章对联会复合体的组成、功能及其遗传控制等情况进行概述,并对其未来的研究进行探讨和展望.%The synaptonemal complex (SC) is a super protein lattice that connects paired homologous chromosomes in most meiotic systems. This special organization is related to the meiosis processes such as homologous chromosomes pairing, synapsis, recombination, segregation, etc. Flaws of it would lead the meiocytes to apoptosis, which contributes to sterility. In recent years, the study of this complex has been a hotspot in meiosis research, but little was known about its exact mechanism. This review summarized the organization, function, and genetics of this complex with recent advances. Prospects of its further study were also briefly discussed.


    Lovinskaya, A V; Kolumbayeva, S Zh; Abilev, S K; Kolomiets, O L


    There was performed an assessment of genotoxic effects of rocket fuel component--unsymmetrical dimethylhydrazine (UDMH, heptyl)--on forming germ cells of male mice. Immunocytochemically there was studied the structure of meiotic nuclei at different times after the intraperitoneal administration of UDMH to male mice. There were revealed following types of disturbances of the structure of synaptonemal complexes (SCs) of meiotic chromosomes: single and multiple fragments of SCs associations of autosomes with a sex bivalent, atypical structure of the SCs with a frequency higher than the reference level. In addition, there were found the premature desinapsis of sex bivalents, the disorder offormation of the genital corpuscle and ring SCs. Established disorders in SCs of spermatocytes, analyzed at 38th day after the 10-days intoxication of animal by the component of rocket fuel, attest to the risk of permanent persistence of chromosomal abnormalities occurring in the pool of stem cells.

  13. A yeast two-hybrid screen for SYP-3 interactors identifies SYP-4, a component required for synaptonemal complex assembly and chiasma formation in Caenorhabditis elegans meiosis.

    Directory of Open Access Journals (Sweden)

    Sarit Smolikov


    Full Text Available The proper assembly of the synaptonemal complex (SC between homologs is critical to ensure accurate meiotic chromosome segregation. The SC is a meiotic tripartite structure present from yeast to humans, comprised of proteins assembled along the axes of the chromosomes and central region (CR proteins that bridge the two chromosome axes. Here we identify SYP-4 as a novel structural component of the SC in Caenorhabditis elegans. SYP-4 interacts in a yeast two-hybrid assay with SYP-3, one of components of the CR of the SC, and is localized at the interface between homologs during meiosis. SYP-4 is essential for the localization of SYP-1, SYP-2, and SYP-3 CR proteins onto chromosomes, thereby playing a crucial role in the stabilization of pairing interactions between homologous chromosomes. In the absence of SYP-4, the levels of recombination intermediates, as indicated by RAD-51 foci, are elevated in mid-prophase nuclei, and crossover recombination events are significantly reduced. The lack of chiasmata observed in syp-4 mutants supports the elevated levels of chromosome nondisjunction manifested in high embryonic lethality. Altogether our findings place SYP-4 as a central player in SC formation and broaden our understanding of the structure of the SC and its assembly.

  14. FISH and DAPI staining of the synaptonemal complex of the Nile tilapia (Oreochromis niloticus) allow orientation of the unpaired region of bivalent 1 observed during early pachytene. (United States)

    Ocalewicz, Konrad; Mota-Velasco, Jose C; Campos-Ramos, Rafael; Penman, David J


    Bivalent 1 of the synaptonemal complex (SC) in XY male Oreochromis niloticus shows an unpaired terminal region in early pachytene. This appears to be related to recombination suppression around a sex determination locus. To allow more detailed analysis of this, and unpaired regions in the karyotype of other Oreochromis species, we developed techniques for FISH on SC preparations, combined with DAPI staining. DAPI staining identified presumptive centromeres in SC bivalents, which appeared to correspond to the positions observed in the mitotic karyotype (the kinetochores could be identified only sporadically in silver-stained EM SC images). Furthermore, two BAC clones containing Dmo (dmrt4) and OniY227 markers that hybridize to known positions in chromosome pair 1 in mitotic spreads (near the centromere, Flpter 0.25, and the putative sex-determination locus, Flpter 0.57, respectively) were used as FISH probes on SCs to verify that the presumptive centromere identified by DAPI staining was located in the expected position. Visualization of both the centromere and FISH signals on bivalent 1 allowed the unpaired region to be positioned at Flpter 0.80 to 1.00, demonstrating that the unpaired region is located in the distal part of the long arm(s). Finally, differences between mitotic and meiotic measurements are discussed.

  15. Coordination Control Of Complex Machines

    NARCIS (Netherlands)

    J.C.M. Baeten; B. van Beek; J. Markovski; L.J.A.M. Somers


    Control and coordination are important aspects of the development of complex machines due to an ever-increasing demand for better functionality, quality, and performance. In WP6 of the C4C project, we developed a synthesis-centric systems engineering framework suitable for supervisory coordination o

  16. Analysis of the Relationships between DNA Double-Strand Breaks, Synaptonemal Complex and Crossovers Using the Atfas1-4 Mutant.

    Directory of Open Access Journals (Sweden)

    Javier Varas


    Full Text Available Chromatin Assembly Factor 1 (CAF-1 is a histone chaperone that assembles acetylated histones H3/H4 onto newly synthesized DNA, allowing the de novo assembly of nucleosomes during replication. CAF-1 is an evolutionary conserved heterotrimeric protein complex. In Arabidopsis, the three CAF-1 subunits are encoded by FAS1, FAS2 and MSI1. Atfas1-4 mutants have reduced fertility due to a decrease in the number of cells that enter meiosis. Interestingly, the number of DNA double-strand breaks (DSBs, measured by scoring the presence of γH2AX, AtRAD51 and AtDMC1 foci, is higher than in wild-type (WT plants, and meiotic recombination genes such AtCOM1/SAE2, AtBRCA1, AtRAD51 and AtDMC1 are overexpressed. An increase in DSBs in this mutant does not have a significant effect in the mean chiasma frequency at metaphase I, nor a different number of AtMLH1 nor AtMUS81 foci per cell compared to WT at pachytene. Nevertheless, this mutant does show a higher gene conversion (GC frequency. To examine how an increase in DSBs influences meiotic recombination and synaptonemal complex (SC formation, we analyzed double mutants defective for AtFAS1 and different homologous recombination (HR proteins. Most showed significant increases in both the mean number of synapsis initiation points (SIPs and the total length of AtZYP1 stretches in comparison with the corresponding single mutants. These experiments also provide new insight into the relationships between the recombinases in Arabidopsis, suggesting a prominent role for AtDMC1 versus AtRAD51 in establishing interhomolog interactions. In Arabidopsis an increase in the number of DSBs does not translate to an increase in the number of crossovers (COs but instead in a higher GC frequency. We discuss different mechanisms to explain these results including the possible existence of CO homeostasis in plants.

  17. Metallogels from Coordination Complexes, Organometallic, and Coordination Polymers. (United States)

    Dastidar, Parthasarathi; Ganguly, Sumi; Sarkar, Koushik


    A supramolecular gel results from the immobilization of solvent molecules on a 3D network of gelator molecules stabilized by various supramolecular interactions that include hydrogen bonding, π-π stacking, van der Waals interactions, and halogen bonding. In a metallogel, a metal is a part of the gel network as a coordinated metal ion (in a discrete coordination complex), as a cross-linking metal node with a multitopic ligand (in coordination polymer), and as metal nanoparticles adhered to the gel network. Although the field is relatively new, research into metallogels has experienced a considerable upsurge owing to its fundamental importance in supramolecular chemistry and various potential applications. This focus review aims to provide an insight into the development of designing metallogelators. Because of the limited scope, discussions are confined to examples pertaining to metallogelators derived from discrete coordination complexes, organometallic gelators, and coordination polymers. This review is expected to enlighten readers on the current development of designing metallogelators of the abovementioned class of molecules. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Coordination Approaches for Complex Software Systems

    NARCIS (Netherlands)

    Bosse, T.; Hoogendoorn, M.; Treur, J.


    This document presents the results of a collaboration between the Vrije Universiteit Amsterdam, Department of Artificial Intelligence and Force Vision to investigate coordination approaches for complex software systems. The project was funded by Force Vision.

  19. Wave propagation in complex coordinates

    CERN Document Server

    Horsley, S A R; Philbin, T G


    We investigate the analytic continuation of wave equations into the complex position plane. For the particular case of electromagnetic waves we provide a physical meaning for such an analytic continuation in terms of a family of closely related inhomogeneous media. For bounded permittivity profiles we find the phenomenon of reflection can be related to branch cuts in the wave that originate from poles of the permittivity at complex positions. Demanding that these branch cuts disappear, we derive a large family of inhomogeneous media that are reflectionless for a single angle of incidence. Extending this property to all angles of incidence leads us to a generalized form of the Poschl Teller potentials. We conclude by analyzing our findings within the phase integral (WKB) method.

  20. Deriving force field parameters for coordination complexes

    DEFF Research Database (Denmark)

    Norrby, Per-Ola; Brandt, Peter


    The process of deriving molecular mechanics force fields for coordination complexes is outlined. Force field basics are introduced with an emphasis on special requirements for metal complexes. The review is then focused on how to set up the initial model, define the target, refine the parameters,...

  1. Seventeen-coordinate actinide helium complexes

    Energy Technology Data Exchange (ETDEWEB)

    Kaltsoyannis, Nikolas [School of Chemistry, The University of Manchester (United Kingdom)


    The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe{sub 17}{sup 3+}, ThHe{sub 17}{sup 4+}, and PaHe{sub 17}{sup 4+} are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe{sub n}{sup 3+} (n=1-17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge-induced dipole bonding. Excellent correlations (R{sup 2}>0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac-He distances, and also with the incremental He binding energies. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Novel Intramolecular Coordination Chemistry of Some New Metallocene Complexes

    Institute of Scientific and Technical Information of China (English)

    钱延龙; 黄吉玲


    This article summarizes the recent results of systematic study on the novel intramolecular cordination chemistry of some new substituted metallocene complexes made by our research group.It deals with the syntheses,reactions,structures of 65 new substituted metallocene complexes and some application of such coordination in homogeneous ctalysis,especially the structural chemistry of such novel intramolecular coordination complexes,and the mechanism of elimination and cyclization of such coordination compounds,as well as their control action in catalytic reactions.

  3. Transition Metal Complexes Coordinated by Water Soluble Phosphane Ligands: How Cyclodextrins Can Alter the Coordination Sphere?

    Directory of Open Access Journals (Sweden)

    Michel Ferreira


    Full Text Available The behaviour of platinum(II and palladium(0 complexes coordinated by various hydrosoluble monodentate phosphane ligands has been investigated by 31P{1H} NMR spectroscopy in the presence of randomly methylated β-cyclodextrin (RAME-β-CD. This molecular receptor can have no impact on the organometallic complexes, induce the formation of phosphane low-coordinated complexes or form coordination second sphere species. These three behaviours are under thermodynamic control and are governed not only by the affinity of RAME-β-CD for the phosphane but also by the phosphane stereoelectronic properties. When observed, the low-coordinated complexes may be formed either via a preliminary decoordination of the phosphane followed by a complexation of the free ligand by the CD or via the generation of organometallic species complexed by CD which then lead to expulsion of ligands to decrease their internal steric hindrance.

  4. PT Metamaterials via Complex-Coordinate Transformation Optics

    CERN Document Server

    Castaldi, Giuseppe; Galdi, Vincenzo; Alu', Andrea; Engheta, Nader


    We extend the transformation-optics paradigm to a complex spatial coordinate domain, in order to deal with electromagnetic metamaterials characterized by balanced loss and gain, giving special emphasis to parity-time (PT) symmetry metamaterials. We apply this general theory to complex-source-point radiation and unidirectional invisibility, illustrating the capability and potentials of our approach in terms of systematic design, analytical modeling and physical insights into complex-coordinate wave-objects and resonant states.

  5. Phase diagram of coacervate complexes containing reversible coordination

    NARCIS (Netherlands)

    Wang, J.; Cohen Stuart, M.A.; Gucht, van der J.


    Phase separation of coacervate complexes from cationic PDMAEMA [poly(N,N-dimethylaminoethyl methacrylate)] and anionic reversible coordination polymers are studied in the present work. The coordination polymers are formed from zinc and a bis-ligand L2EO4 [1,11-bis(2,6-dicarboxypyridin-4-yloxy)-3,6,9

  6. New polypyridine anchoring ligands for coordination complexes and surface functionalization


    Müller, Steffen


    This PhD thesis focuses on the synthesis of new polypyridine anchoring ligands and several dfferent applications. The ligands consist of a coordinating part, a flexible linker and an anchoring group. Due to the fact that different anchoring groups were used, the ligands can be applied for several types of surface-materials. Using these anchoring ligands, several coordination complexes were synthesized. Ruthenium-based complexes, bearing an ion-sensitive ligand, were tested towards...

  7. On the π Coordination of Organometallic Fullerene Complexes

    Directory of Open Access Journals (Sweden)

    Bertha Molina


    Full Text Available Novel organometallic complexes of fullerene C80 and aryl ligands were simulated. The nature and characteristics of this family of complexes involving π coordination between the fullerene and a metal centre have been studied from a theoretical point of view. We are particularly interested in complexes where η6 coordination is present, this being the strangest manifestation of known coordinations, and thus we have studied several known and simulated compounds of this kind in order to understand the lack of examples. The presence of other η6 or η5 ligands on the opposite side seems to be an important element aiding the stabilization of these complexes, also inducing the conductive and semiconductive behaviour of the studied species.

  8. The stochastic separatrix and the reaction coordinate for complex systems. (United States)

    Antoniou, Dimitri; Schwartz, Steven D


    We present a new approach to the identification of degrees of freedom which comprise a reaction coordinate in a complex system. The method begins with the generation of an ensemble of reactive trajectories. Each trajectory is analyzed for its equicommittor position or transition state; then the transition state ensemble is identified as the stochastic separatrix. Numerical analysis of the points along the separatrix for variability of coordinate location correctly identifies the components of the reaction coordinate in a test system of a double well coupled to a promoting vibration and a bath of linearly coupled oscillators.

  9. Link power coordination for energy conservation in complex communication networks

    CERN Document Server

    Zhang, Guo-Qiang


    Communication networks consume huge, and rapidly growing, amount of energy. However, a lot of the energy consumption is wasted due to the lack of global link power coordination in these complex systems. This paper proposes several link power coordination schemes to achieve energy-efficient routing by progressively putting some links into energy saving mode and hence aggregating traffic during periods of low traffic load. We show that the achievable energy savings not only depend on the link power coordination schemes, but also on the network topologies. In the random network, there is no scheme that can significantly outperform others. In the scale-free network, when the largest betweenness first (LBF) scheme is used, phase transition of the networks' transmission capacities during the traffic cooling down phase is observed. Motivated by this, a hybrid link power coordination scheme is proposed to significantly reduce the energy consumption in the scale-free network. In a real Internet Service Provider (ISP)'...

  10. Coordination field analysis of rare earth complexes with triangular symmetry

    Institute of Scientific and Technical Information of China (English)

    范英芳; 潘大丰; 杨频


    The calculation of the complex matrixes in odd triangular symmetry was accomplished.The configurations of the coordination unit with various triangular symmetries and different ligand numbers were discussed.On the basis of the double-sphere coordination point-charge (DSCPCF) model,the detailed forms of the DSCPCF parameters Bmk and the expressions of the perturbation matrix elements in triangular field (D3,D3h,D3d) were derived.Thereby,the calculation scheme of coordination field perturbation energy of the rare earth complexes with triangular symmetry was constructed After the calculation scheme was programmed,the Stark energies of the crystalline TbAl3(BO3)4 were calculated The results were considerably close to the experimental values

  11. Memory for Negation in Coordinate and Complex Sentences (United States)

    Harris, Richard J.


    Two experiments were run to test memory for the negation morpheme "not" in coordinate sentences (e.g., The ballerina had twins and the policewoman did not have triplets) and complex sentences (e.g., The ghost scared Hamlet into not murdering Shakespeare). (Editor)

  12. Microporous coordination complex and method of making the same (United States)

    Matzger, Adam J.; Koh, Kyoungmoo


    Disclosed herein is a three-dimensional coordination complex that includes a plurality of inorganic centers; a plurality of a first bis(bidentate) linker; and a plurality of a second bis(bidentate) linker, where the first and the second bis(bidentate) linkers are have different lengths, and the bidentate binding sites on each linker face in opposite directions on an axis.

  13. Coordinating complex problem-solving among distributed intelligent agents (United States)

    Adler, Richard M.


    A process-oriented control model is described for distributed problem solving. The model coordinates the transfer and manipulation of information across independent networked applications, both intelligent and conventional. The model was implemented using SOCIAL, a set of object-oriented tools for distributing computing. Complex sequences of distributed tasks are specified in terms of high level scripts. Scripts are executed by SOCIAL objects called Manager Agents, which realize an intelligent coordination model that routes individual tasks to suitable server applications across the network. These tools are illustrated in a prototype distributed system for decision support of ground operations for NASA's Space Shuttle fleet.

  14. Automated recognition and post-coordination of complex clinical terms. (United States)

    Gooch, Philip; Roudsari, Abdul


    One of the key tasks in integrating guideline-based decision support systems with the electronic patient record is the mapping of clinical terms contained in both guidelines and patient notes to a common, controlled terminology. However, a vocabulary of pre-coordinated terms cannot cover every possible variation - clinical terms are often highly compositional and complex. We present a rule-based approach for automated recognition and post-coordination of clinical terms using minimal, morpheme-based thesauri, neoclassical combining forms and part-of-speech analysis. The process integrates MetaMap with the open-source GATE framework.

  15. Actinide coordination sphere in various U, Np and Pu nitrato coordination complexes

    Energy Technology Data Exchange (ETDEWEB)

    Auwer, C. Den; Revel, R.; Charbonnel, M.C.; Presson, M.T. [CEA, DCC/DRRV/SEMP, Lab. de Chimie Theorique et Structurale, Bagnols sur Ceze (France); Conradson, S.D. [Los Alamos National Lab., Materials Science and Technology Div., Los Alamos, NM (United States); Simoni, E.; Du, J.F. Le [Centre Univ. Paris Sud, IPN, Orsay CEDEX (France); Madic, C. [CEA, DCC Saclay, Gif sur Yvete (France)


    Waste management of nuclear fuel represents one of the major environmental concerns of the decade. To recycle fissile valuable materials, intimate knowledge of complexation mechanisms involved in the solvent extraction processes is indispensable. Evolution of the actinide coordination sphere of AnO{sub 2}(NO{sub 3}){sub 2}TBP-type complexes (an = U, Np, Pu; TBP = tributylphosphate) with the actinide valence state have been probed by XAS at the metal L{sub III} edge. Dramatic changes in the actinide coordination sphere appeared when the An(VI) metal is reduced to An(IV). However, no significant evolution in the actinide environment has been noticed across the series UO{sub 2}{sup 2+}, NpO{sub 2}{sup 2+} and PuO{sub 2}{sup 2+}. (au)

  16. Energetic lanthanide complexes: coordination chemistry and explosives applications (United States)

    Manner, V. W.; Barker, B. J.; Sanders, V. E.; Laintz, K. E.; Scott, B. L.; Preston, D. N.; Sandstrom, M.; Reardon, B. L.


    Metals are generally added to organic molecular explosives in a heterogeneous composite to improve overall heat and energy release. In order to avoid creating a mixture that can vary in homogeneity, energetic organic molecules can be directly bonded to high molecular weight metals, forming a single metal complex with Angstrom-scale separation between the metal and the explosive. To probe the relationship between the structural properties of metal complexes and explosive performance, a new series of energetic lanthanide complexes has been prepared using energetic ligands such as NTO (5-nitro-2,4-dihydro-1,2,4-triazole-3-one). These are the first examples of lanthanide NTO complexes where no water is coordinated to the metal, demonstrating novel control of the coordination environment. The complexes have been characterized by X-ray crystallography, NMR and IR spectroscopies, photoluminescence, and sensitivity testing. The structural and energetic properties are discussed in the context of enhanced blast effects and detection. Cheetah calculations have been performed to fine-tune physical properties, creating a systematic method for producing explosives with 'tailor made' characteristics. These new complexes will be benchmarks for further study in the field of metalized high explosives.

  17. Coordinated aggregation in complex systems:. an interdisciplinary approach (United States)

    Basios, V.; Nicolis, S. C.; Deneubourg, J. L.


    The study of the topic of guided aggregation in biology brings together decision making, collective motion and the dynamical interplay between individuals and groups. At the same time it meets statistical mechanics and the physics of complex systems in a new paradigmatic thinking. We propose a research platform for implementation and for undertaking systematic studies of coordinated aggregation, in a truly multi- and inter-disciplinary fashion.

  18. Design, synthesis and study of coordination complexes for quantum computing


    Aguilà Avilés, David


    This thesis presents different strategies for the design of molecular complexes with the requirements to be used as two-qubit quantum gates. The approaches followed towards the preparation of potential qubit systems have been carried out focusing on the synthesis of ligands with β-diketone coordination units, which are very versatile for the design of metallocluster assemblies. One of the main advantages of using this kind of ligands is that they can be easily prepared through simple Claisen ...

  19. Modulation of the coordination environment: a convenient approach to tailor magnetic anisotropy in seven coordinate Co(II) complexes. (United States)

    Dey, Mamon; Dutta, Snigdha; Sarma, Bipul; Deka, Ramesh Ch; Gogoi, Nayanmoni


    The possibility of controlling magnetic anisotropy by tuning contribution of second order perturbation to spin-orbit coupling through modulation of the coordination environment is investigated. Subtle variation of the coordination environment triggers a remarkable deviation in the axial zero field splitting parameter of seven coordinate Co(II) complexes.


    Directory of Open Access Journals (Sweden)

    Vasile Lozan


    Full Text Available The steric protection offered by the macrobinucleating hexaazaditiophenolate ligand (L allows for the preparation of the first stable dinuclear nickel(II borohydride bridged complex, which reacts rapidly with elemental sulphur producing a tetranuclear nickel(II complex [{(LNi2}2(μ-S6]2+ bearing a helical μ4-hexa- sulfide ligand. The [(LCoII 2]2+ fragment have been able to trap a monomethyl orthomolybdate in the binding pocket. Unusual coordination modes of substrate in dinuclear macrocyclic compounds was demonstrated.

  1. Isocyanide and Phosphine Oxide Coordination in Binuclear Chromium Pacman Complexes. (United States)

    Stevens, Charlotte J; Nichol, Gary S; Arnold, Polly L; Love, Jason B


    The new binuclear chromium Pacman complex [Cr2(L)] of the Schiff base pyrrole macrocycle H4L has been synthesized and structurally characterized. Addition of isocyanide, C≡NR (R = xylyl, (t)Bu), or triphenylphosphine oxide donors to [Cr2(L)] gives contrasting chemistry with the formation of the new coordination compounds [Cr2(μ-CNR)(L)], in which the isocyanides bridge the two Cr(II) centers, and [Cr2(OPPh3)2(L)], a Cr(II) phosphine oxide adduct with the ligands exogenous to the cleft.

  2. Design of magnetic coordination complexes for quantum computing. (United States)

    Aromí, Guillem; Aguilà, David; Gamez, Patrick; Luis, Fernando; Roubeau, Olivier


    A very exciting prospect in coordination chemistry is to manipulate spins within magnetic complexes for the realization of quantum logic operations. An introduction to the requirements for a paramagnetic molecule to act as a 2-qubit quantum gate is provided in this tutorial review. We propose synthetic methods aimed at accessing such type of functional molecules, based on ligand design and inorganic synthesis. Two strategies are presented: (i) the first consists in targeting molecules containing a pair of well-defined and weakly coupled paramagnetic metal aggregates, each acting as a carrier of one potential qubit, (ii) the second is the design of dinuclear complexes of anisotropic metal ions, exhibiting dissimilar environments and feeble magnetic coupling. The first systems obtained from this synthetic program are presented here and their properties are discussed.

  3. Two-body coordinate system generation using body-fitted coordinate system and complex variable transformation. M.S. Thesis (United States)

    Long, W. S.


    Attempts are made to generate acceptable coordinate systems for two-body configurations. The first method to be tried was to use the body-fitted coordinate system technique to obtain the best system. This technique alone did not produce very good results, so another approach was investigated. This new approach involved using a combination of the body fitted coordinate system procedure and a complex variable transformation method that was used successfully in conformal mapping.

  4. Ytterbium Coordination Polymer with Four Different Coordination Numbers: The First Structural Characterization of Lanthanide Phthalate Complex

    Institute of Scientific and Technical Information of China (English)

    WAN,Yong-Hong(万永红); JIN,Lin-Pei(金林培); WANG,Ke-Zhi(王科志)


    The novel ytterbium coordination polymer is a two-dimensional framework in which the central metal ions have four different coordination numhers and form four kinds of coordination polyhedra. The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms

  5. Similarities between GCS and human motor cortex: complex movement coordination (United States)

    Rodríguez, Jose A.; Macias, Rosa; Molgo, Jordi; Guerra, Dailos


    The "Gran Telescopio de Canarias" (GTC1) is an optical-infrared 10-meter segmented mirror telescope at the ORM observatory in Canary Islands (Spain). The GTC control system (GCS), the brain of the telescope, is is a distributed object & component oriented system based on RT-CORBA and it is responsible for the management and operation of the telescope, including its instrumentation. On the other hand, the Human motor cortex (HMC) is a region of the cerebrum responsible for the coordination of planning, control, and executing voluntary movements. If we analyze both systems, as far as the movement control of their mechanisms and body parts is concerned, we can find extraordinary similarities in their architectures. Both are structured in layers, and their functionalities are comparable from the movement conception until the movement action itself: In the GCS we can enumerate the Sequencer high level components, the Coordination libraries, the Control Kit library and the Device Driver library as the subsystems involved in the telescope movement control. If we look at the motor cortex, we can also enumerate the primary motor cortex, the secondary motor cortices, which include the posterior parietal cortex, the premotor cortex, and the supplementary motor area (SMA), the motor units, the sensory organs and the basal ganglia. From all these components/areas we will analyze in depth the several subcortical regions, of the the motor cortex, that are involved in organizing motor programs for complex movements and the GCS coordination framework, which is composed by a set of classes that allow to the high level components to transparently control a group of mechanisms simultaneously.

  6. Stability of complex coacervate core micelles containing metal coordination polymer. (United States)

    Yan, Yun; de Keizer, Arie; Cohen Stuart, Martien A; Drechsler, Markus; Besseling, Nicolaas A M


    We report on the stability of complex coacervate core micelles, i.e., C3Ms (or PIC, BIC micelles), containing metal coordination polymers. In aqueous solutions these micelles are formed between charged-neutral diblock copolymers and oppositely charged coordination polymers formed from metal ions and bisligand molecules. The influence of added salt, polymer concentration, and charge composition was investigated by using light scattering and cryo-TEM techniques. The scattering intensity decreases strongly with increasing salt concentration until a critical salt concentration beyond which no micelles exist. The critical micelle concentration increases almost exponentially with the salt concentration. From the scattering results it follows that the aggregation number decreases with the square root of the salt concentration, but the hydrodynamic radius remains constant or increases slightly. It was concluded that the density of the core decreases with increasing ionic strength. This is in agreement with theoretical predictions and is also confirmed by cryo-TEM measurements. A complete composition diagram was constructed based on the composition boundaries obtained from light scattering titrations.

  7. Complex coacervate core micelles from iron-based coordination polymers. (United States)

    Wang, Junyou; de Keizer, Arie; Fokkink, Remco; Yan, Yun; Cohen Stuart, Martien A; van der Gucht, Jasper


    Complex coacervate core micelles (C3Ms) from cationic poly(N-methyl-2-vinyl-pyridinium iodide)-b-poly(ethylene oxide) (P2MVP(41)-b-PEO(205)) and anionic iron coordination polymers are investigated in the present work. Micelle formation is studied by light scattering for both Fe(II)- and Fe(III)-containing C3Ms. At the stoichiometric charge ratio, both Fe(II)-C3Ms and Fe(III)-C3Ms are stable for at least 1 week at room temperature. Excess of iron coordination polymers has almost no effect on the formed Fe(II)-C3Ms and Fe(III)-C3Ms, whereas excess of P2MVP(41)-b-PEO(205) copolymers in the solution can dissociate the formed micelles. Upon increasing salt concentration, the scattering intensity decreases. This decrease is due to both a decrease in the number of micelles (or an increase in CMC) and a decrease in aggregation number. The salt dependence of the CMC and the aggregation number is explained using a scaling argument for C3M formation. Compared with Fe(II)-C3Ms, Fe(III)-C3Ms have a lower CMC and a higher stability against dissociation by added salt.

  8. Cytotoxicity of cyclometalated platinum complexes based on tridentate NCN and CNN-coordinating ligands: remarkable coordination dependence. (United States)

    Vezzu, Dileep A K; Lu, Qun; Chen, Yan-Hua; Huo, Shouquan


    A series of cyclometalated platinum complexes with diverse coordination patterns and geometries were screened for their anticancer activity. It was discovered that the N^C^N-coordinated platinum complex based on 1,3-di(pyridyl)benzene displayed much higher cytotoxicity against human lung cancer cells NCI-H522, HCC827, and NCI-H1299, and human prostate cancer cell RV1 than cisplatin. In a sharp contrast, the C^N^N-coordinated platinum complex based on 6-phenyl-2,2'-bipyridine was ineffective on these cancer cells. This remarkable difference in cytotoxicity displayed by N^C^N- and C^N^N-coordinated platinum complexes was related to the trans effect of the carbon donor in the cyclometalated platinum complexes, which played a crucial role in facilitating the dissociation of the chloride ligand to create an active binding site. The DNA binding was studied for the N^C^N-coordinated platinum complex using electrophoresis and emission titration. The cellular uptake observed by fluorescent microscope showed that the complex is largely concentrated in the cytoplasm. The possible pathways for the cell apoptosis were studied by western blot analysis and the activation of PARP via caspase 7 was observed.

  9. X-ray Emission Spectroscopy of Biomimetic Mn Coordination Complexes. (United States)

    Jensen, Scott C; Davis, Katherine M; Sullivan, Brendan; Hartzler, Daniel A; Seidler, Gerald T; Casa, Diego M; Kasman, Elina; Colmer, Hannah E; Massie, Allyssa A; Jackson, Timothy A; Pushkar, Yulia


    Understanding the function of Mn ions in biological and chemical redox catalysis requires precise knowledge of their electronic structure. X-ray emission spectroscopy (XES) is an emerging technique with a growing application to biological and biomimetic systems. Here, we report an improved, cost-effective spectrometer used to analyze two biomimetic coordination compounds, [Mn(IV)(OH)2(Me2EBC)](2+) and [Mn(IV)(O)(OH)(Me2EBC)](+), the second of which contains a key Mn(IV)═O structural fragment. Despite having the same formal oxidation state (Mn(IV)) and tetradentate ligands, XES spectra from these two compounds demonstrate different electronic structures. Experimental measurements and DFT calculations yield different localized spin densities for the two complexes resulting from Mn(IV)-OH conversion to Mn(IV)═O. The relevance of the observed spectroscopic changes is discussed for applications in analyzing complex biological systems such as photosystem II. A model of the S3 intermediate state of photosystem II containing a Mn(IV)═O fragment is compared to recent time-resolved X-ray diffraction data of the same state.

  10. Attributes of advanced practice registered nurse care coordination for children with medical complexity. (United States)

    Cady, Rhonda G; Kelly, Anne M; Finkelstein, Stanley M; Looman, Wendy S; Garwick, Ann W


    Care coordination is an essential component of the pediatric health care home. This study investigated the attributes of relationship-based advanced practice registered nurse care coordination for children with medical complexity enrolled in a tertiary hospital-based health care home. Retrospective review of 2,628 care coordination episodes conducted by telehealth over a consecutive 3-year time period for 27 children indicated that parents initiated the majority of episodes and the most frequent reason was acute and chronic condition management. During this period, care coordination episodes tripled, with a significant increase (p care coordination model has potential for changing the health management processes for children with medical complexity.

  11. Two new coordination polymers, a trinuclear metal complex and their interconversion depending on the solvent. (United States)

    Koike, Shiori; Hirakawa, Takeshi; Yamanishi, Katsunori; Kondo, Mitsuru


    Two new 1-D coordination polymers and a discrete trinuclear complex with a double-ring framework were synthesized and structurally characterized. The unique irreversible conversion from one of the 1-D coordination polymers to the trinuclear complex by contact with MeCN is described.

  12. [Complex chronic care situations and socio-health coordination]. (United States)

    Morilla Herrera, Juan Carlos; Morales Asencio, José Miguel; Kaknani, Shakira; García Mayor, Silvia


    Patient-centered healthcare is currently one of the most pursued goals in health services. It is necessary to ensure a sufficient level of cooperative and coordinated work between different providers and settings, including family and social and community resources. Clinical integration occurs when the care provided by health professionals and providers is integrated into a single coherent process through different professions using shared guidelines and protocols. Such coordination can be developed at three levels: macro, which involves the integration of one or more of the three basic elements that support health care (the health plan, primary care and specialty care), with the aim of reducing fragmentation of care; meso, where health and social services are coordinated to provide comprehensive care to elderly and chronic patients; and micro, aimed to improve coordination in individual patients and caregivers. The implementation of new roles, such as Advanced Practice Nursing, along with improvements in family physicians' problem-solving capacity in certain processes, or modifying the place of provision of certain services are key to ensure services adapted to the requirements of chronic patients.

  13. Identification of different coordination geometries by XAFS in copper(II) complexes with trimesic acid (United States)

    Gaur, A.; Klysubun, W.; Soni, Balram; Shrivastava, B. D.; Prasad, J.; Srivastava, K.


    X-ray absorption spectroscopy (XAS) is very useful in revealing the information about geometric and electronic structure of a transition-metal absorber and thus commonly used for determination of metal-ligand coordination. But XAFS analysis becomes difficult if differently coordinated metal centers are present in a system. In the present investigation, existence of distinct coordination geometries around metal centres have been studied by XAFS in a series of trimesic acid Cu(II) complexes. The complexes studied are: Cu3(tma)2(im)6 8H2O (1), Cu3(tma)2(mim)6 17H2O (2), Cu3(tma)2(tmen)3 8.5H2O (3), Cu3(tma) (pmd)3 6H2O (ClO4)3 (4) and Cu3(tma)2 3H2O (5). These complexes have not only Cu metal centres with different coordination but in complexes 1-3, there are multiple coordination geometries present around Cu centres. Using XANES spectra, different coordination geometries present in these complexes have been identified. The variation observed in the pre-edge features and edge features have been correlated with the distortion of the specific coordination environment around Cu centres in the complexes. XANES spectra have been calculated for the distinct metal centres present in the complexes by employing ab-initio calculations. These individual spectra have been used to resolve the spectral contribution of the Cu centres to the particular XANES features exhibited by the experimental spectra of the multinuclear complexes. Also, the variation in the 4p density of states have been calculated for the different Cu centres and then correlated with the features originated from corresponding coordination of Cu. Thus, these spectral features have been successfully utilized to detect the presence of the discrete metal centres in a system. The inferences about the coordination geometry have been supported by EXAFS analysis which has been used to determine the structural parameters for these complexes.

  14. Coordinating complex decision support activities across distributed applications (United States)

    Adler, Richard M.


    Knowledge-based technologies have been applied successfully to automate planning and scheduling in many problem domains. Automation of decision support can be increased further by integrating task-specific applications with supporting database systems, and by coordinating interactions between such tools to facilitate collaborative activities. Unfortunately, the technical obstacles that must be overcome to achieve this vision of transparent, cooperative problem-solving are daunting. Intelligent decision support tools are typically developed for standalone use, rely on incompatible, task-specific representational models and application programming interfaces (API's), and run on heterogeneous computing platforms. Getting such applications to interact freely calls for platform independent capabilities for distributed communication, as well as tools for mapping information across disparate representations. Symbiotics is developing a layered set of software tools (called NetWorks! for integrating and coordinating heterogeneous distributed applications. he top layer of tools consists of an extensible set of generic, programmable coordination services. Developers access these services via high-level API's to implement the desired interactions between distributed applications.

  15. A formula on linear complexity of highest coordinate sequences from maximal periodic sequences over Galois rings

    Institute of Scientific and Technical Information of China (English)

    HU Lei; SUN Nigang


    Using a polynomial expression of the highest coordinate map, we deduce an exact formula on the linear complexity of the highest coordinate sequence derived from a maximal periodic sequence over an arbitrary Galois ring of characteristic p2 , where p is a prime. This generalizes the known result of Udaya and Siddiqi for the case that the Galois ring is Z4.

  16. Coordination of cassava starch to metal ions and thermolysis of resulting complexes

    Directory of Open Access Journals (Sweden)

    Piotr Tomasik


    Full Text Available Cassava starch formed Werner-type complexes with ions of metals from the transition groups. This was proven by conductivity and electron paramagnetic resonance measurements. The coordination of starch to central metal ions influenced the thermal decomposition of starch. As a rule complexes started to decompose at lower temperature than did starch. On the other hand, the decomposition proceeded at a lower rate than the decomposition of non-coordinated starch.

  17. Coordination Chemistry of Homoleptic Actinide(IV)-Thiocyanate Complexes. (United States)

    Carter, Tyler J; Wilson, Richard E


    The synthesis, X-ray crystal structure, vibrational and optical spectroscopy for the eight-coordinate thiocyanate compounds, [Et4 N]4 [Pu(IV) (NCS)8 ], [Et4 N]4 [Th(IV) (NCS)8 ], and [Et4 N]4 [Ce(III) (NCS)7 (H2 O)] are reported. Thiocyanate was found to rapidly reduce plutonium to Pu(III) in acidic solutions (pHcoordination in acetonitrile based on the observation of intense ligand-to-metal charge-transfer bands. Spectroscopic and crystallographic data do not support the interaction of the metal orbitals with the ligand π system, but support an enhanced An(IV) -NCS interaction, as the Lewis acidity of the metal ion increases from Th to Pu.

  18. Coordination Complexes as Inorganic Explosives for Initiation Systems

    Institute of Scientific and Technical Information of China (English)

    依留申 M A; 泽林斯基 I V


    The study of the synthesis of coordination compounds in the series of perchlorates of d-metals containing polynitrogen heterocyclic ligands is presented in the following report. The major part of the report is also devoted to the investigations of properties of the compounds obtained and their applications in safe electric and laser detonators.%介绍了含多氮杂环配位体的过氯酸盐系列络合物的合成研究.主要对新合成的化合物进行了性能研究及在安全电雷管和激光雷管的应用研究.

  19. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex

    DEFF Research Database (Denmark)

    Hao, Xian; Zhu, Nan; Gschneidtner, Tina


    Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level...... remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold...

  20. A pentanuclear lead(II) complex based on a strapped porphyrin with three different coordination modes. (United States)

    Le Gac, Stéphane; Furet, Eric; Roisnel, Thierry; Hijazi, Ismail; Halet, Jean-François; Boitrel, Bernard


    We have previously described Pb(II) and Bi(III) bimetallic complexes with overhanging carboxylic acid strapped porphyrins in which one metal ion is bound to the N-core ("out-of-plane", OOP), whereas the second one is bound to the strap ("hanging-atop", HAT). In such complexes, the hemidirected coordination sphere of a HAT Pb(II) cation provides sufficient space for an additional binding of a neutral ligand (e.g., DMSO). Interestingly, investigations of the HAT metal coordination mode in a single strap porphyrin show that a HAT Pb(II) can also interact via intermolecular coordination bonds, allowing the self-assembly of two bimetallic complexes. In the pentanuclear Pb(II) complex we are describing in this Article, three different coordination modes were found. The OOP Pb(II) remains inert toward the supramolecular assembling process, whereas the HAT Pb(II) cation, in addition to its intramolecular carboxylate and regular exogenous acetate groups, coordinates an additional exogenous acetate. These two acetates are shared with a third lead(II) cation featuring a holo-directed coordination sphere, from which a centro-symmetric complex is assembled. Density functional theory calculations show some electron-density pockets in the vicinity of the hemidirected HAT Pb(II) atoms, which are associated with the presence of a stereochemically active lone pair of electrons. On the basis of the comparison with other HAT Pb(II) and Bi(III) systems, the "volume" of this lone pair correlates well with the bond distance distributions and the number of the proximal oxygen atoms tethered to the post-transition metal cation. It thus follows the order 6-coordinate Bi(III) > 6-coordinate Pb(II) > 5-coordinate Pb(II).

  1. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.


    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  2. Structure and Semiconducting Character of a Polymeric Iodoplumbate Coordination Complex

    Institute of Scientific and Technical Information of China (English)

    SONG De-Sheng; LIU Chang-Chun; CHEN Heng-Jun; SU Dong-Po; FU Zhi-Yong


    A new polymeric iodoplumbate complex [Zn(DMF)6][Pb2I6] 1 has been prepared and characterized by elemental analysis and single-crystal X-ray analysis. Its structure contains infinite iodoplumbate chains constructed by the [PbI5] subunit. EHT crystal orbital calculation and the experimental results show that this material is an unconventional semiconductor and the electrical character is associated with its structural feature.

  3. Biphenolate Iron (II) Complexes with Intramolecularly Coordinating Nitrogen Lewis Bases

    NARCIS (Netherlands)

    Koten, G. van; Brandts, J.A.M.; Janssen, M.D.; Hogerheide, M.P.; Boersma, J.; Spek, A.L.


    The synthesis and characterisation of a novel Fe(II) bisphenolate complex [Fe(OC{6}H{4}CH{2}NMe{2}-2){2}]{2} (1) from [Na(OC{6}H{4}CH{2}NMe{2}-2)] and anhydrous FeCl{2} is reported. The solid state structure has been elucidated by single crystal X-ray analysis and shows a dimeric structure with two

  4. Supramolecular coordination and antimicrobial activities of constructed mixed ligand complexes (United States)

    El-Sonbati, A. Z.; Diab, M. A.; El-Bindary, A. A.; Abou-Dobara, M. I.; Seyam, H. A.


    A novel series of copper(II) and palladium(II) with 4-derivatives benzaldehyde pyrazolone (Ln) were synthesized. The mixed ligand complexes were prepared by using 1,10-phenanthroline (Phen) as second ligand. The structure of these complexes was identified and confirm by elemental analysis, molar conductivity, UV-Vis, IR and 1H NMR spectroscopy and magnetic moment measurements as well as thermal analysis. The ligand behaves as a neutral bidentate ligand through ON donor sites. ESR spectra show the simultaneous presence of a planar trans and a nearly planar cis isomers in the 1:2 ratio for all N,O complexes [Cu(Ln)2]Cl2ṡ2H2O. Schiff bases (Ln) were tested against bacterial species; namely two Gram positive bacteria (Staphylococcus aureus and Bacillus cereus) and two Gram negative bacteria (Escherichia coli and Klebsiella pneumoniae) and fungal species (Aspergillus niger, Fusarium oxysporium, Penicillium italicum and Alternaria alternata). The tested compounds have antibacterial activity against S. aureus, B. cereus and K. pneumoniae.

  5. Metal ion coordination, conditional stability constants, and solution behavior of chelating surfactant metal complexes. (United States)

    Svanedal, Ida; Boija, Susanne; Almesåker, Ann; Persson, Gerd; Andersson, Fredrik; Hedenström, Erik; Bylund, Dan; Norgren, Magnus; Edlund, Håkan


    Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C12-DTPA were determined by competition measurements between 4-C12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu(2+) ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C12-DTPA could coordinate up to two Cu(2+) ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory.

  6. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex

    Energy Technology Data Exchange (ETDEWEB)

    Vlassa, Mihaela, E-mail: [' ' Babes-Bolyai' ' University, Raluca Ripan Institute of Research in Chemistry, 30 Fantanele Str., 400294 Cluj-Napoca (Romania); Bende, Attila, E-mail: [Molecular and Biomolecular Physics Department, National Institute for Research and Development of Isotopic and Molecular Technologies, Str. Donat 67-103, Cluj Napoca RO-400293 (Romania)


    Highlights: • Ni(II)- and Zn(II)-coordinated cyclam–azorubine complexes are described using DFT. • Ni(II) coordinated system shows a reasonably small singlet–triplet energy gap. • Intersystem crossing gives high barrier between singlet and triplet geometries. • For the Zn(II) case only the singlet state is energetically favorable. • The stability of a longer polymer (oligomer) chain was described using DFTB. - Abstract: Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet–triplet transition was studied in details and the corresponding spin–orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  7. Plutonium(IV) complexation by diglycolamide ligands - coordination chemistry insight into TODGA-based actinide separations

    NARCIS (Netherlands)

    Reilly, S.D.; Gaunt, A.J.; Scott, B.L.; Modolo, G.; Iqbal, M.; Verboom, W.; Sarsfield, M.J.


    Complexation of Pu(IV) with TMDGA, TEDGA, and TODGA diglycolamide ligands was followed by vis-NIR spectroscopy. A crystal structure determination reveals that TMDGA forms a 1:3 homoleptic Pu(IV) complex with the nitrate anions forced into the outer coordination sphere

  8. Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

    KAUST Repository

    Lamberti, Marina


    The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.

  9. Modeling and Simulation of Complex Network Attributes on Coordinating Large Multiagent System (United States)

    Li, Xiang; Liu, Ming


    With the expansion of distributed multiagent systems, traditional coordination strategy becomes a severe bottleneck when the system scales up to hundreds of agents. The key challenge is that in typical large multiagent systems, sparsely distributed agents can only communicate directly with very few others and the network is typically modeled as an adaptive complex network. In this paper, we present simulation testbed CoordSim built to model the coordination of network centric multiagent systems. Based on the token-based strategy, the coordination can be built as a communication decision problem that agents make decisions to target communications and pass them over to the capable agents who will potentially benefit the team most. We have theoretically analyzed that the characters of complex network make a significant difference with both random and intelligent coordination strategies, which may contribute to future multiagent algorithm design. PMID:24955399

  10. Role of the coordination center in photocurrent behavior of a tetrathiafulvalene and metal complex dyad. (United States)

    Sun, Yong-Gang; Ji, Shu-Fang; Huo, Peng; Yin, Jing-Xue; Huang, Yu-De; Zhu, Qin-Yu; Dai, Jie


    Small organic molecule-based compounds are considered to be promising materials in photoelectronics and high-performance optoelectronic devices. However, photoelectron conversion research based on functional organic molecule and metal complex dyads is very scarce. We design and prepare a series of compounds containing a tetrathiafulvalene (TTF) moiety substituted with pyridylmethylamide groups of formulas [Ni(acac)2L]·2CH3OH (1), [Cu2I2L2]·THF·2CH3CN (2), and [MnCl2L2]n·2nCH3CH2OH (3) (L = 4,5-bis(3-pyridylmethylamide)-4',5'-bimethylthio-tetrathiafulvalene, acac = acetylacetone) to study the role of the coordination center in photocurrent behavior. Complex 1 is a mononuclear species, and complex 2 is a dimeric species. Complex 3 is a two-dimensional (2-D) coordination polymer. Spectroscopic and electrochemical properties of these complexes indicate that they are electrochemically active materials. The tetrathiafulvalene ligand L is a photoelectron donor in the presence of electron acceptor methylviologen. The effect of metal coordination centers on photocurrent response behavior is examined. The redox-active metal coordination centers should play an important role in improvement of the photocurrent response property. The different morphologies of the electrode films reflect the dimensions in molecular structures of the coordination compounds.

  11. Surprising Coordination Geometry Differences in Ce(IV)- and Pu(IV)-Maltol Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Lawrence Berkeley National Laboratory; Raymond, Kenneth; Szigethy, Geza; Xu, Jide; Gorden, Anne E.V.; Teat, Simon J.; Shuh, David K.; Raymond, Kenneth N.


    As part of a study to characterize the detailed coordination behavior of Pu(IV), single crystal X-ray diffraction structures have been determined for Pu(IV) and Ce(IV) complexes with the naturally-occurring ligand maltol (3-hydroxy-2-methyl-pyran-4-one) and its derivative bromomaltol (5-bromo-3-hydroxy-2-methyl-pyran-4-one). Although Ce(IV) is generally accepted as a structural analog for Pu(IV), and the maltol complexes of these two metals are isostructural, the corresponding bromomaltol complexes are strikingly different with respect to ligand orientation about the metal ion: All complexes exhibit trigonal dodecahedral coordination geometry but the Ce(IV)-bromomaltol complex displays an uncommon ligand arrangement not mirrored in the Pu(IV) complex, although the two metal species are generally accepted to be structural analogs.

  12. Overcoming Statistical Complexity: Selective Coordination of Three Different Metal Ions to a Ligand with Three Different Coordination Sites. (United States)

    Akine, Shigehisa; Matsumoto, Takashi; Nabeshima, Tatsuya


    In general, it is difficult to selectively introduce different metal ions at specific positions of a cluster-like structure. This is mainly due to statistical problems as well as the reversibility of the formation of coordination bonds. To overcome this statistical problem, we used a carefully designed ligand, H6 L, which can accommodate three different kinds of metal ions in three types of coordination sites. The complex [LNiZn2La](3+), which contains three different metals, was quantitatively obtained by a stepwise procedure, but different products were obtained when the metal ions were added in a different order. However, equilibration studies indicated that this complex was almost solely formed among 54 (=3×3×3H2) possible products upon heating; the formation efficiency (ca. 100%) was significantly higher than the statistical probability (2.47%). Such carefully designed ligands should be useful for the synthesis multimetallic systems, which are of interest because of the interplay between the different metals.

  13. Scribble1/AP2 Complex Coordinates NMDA Receptor Endocytic Recycling

    Directory of Open Access Journals (Sweden)

    Nicolas H. Piguel


    Full Text Available The appropriate trafficking of glutamate receptors to synapses is crucial for basic synaptic function and synaptic plasticity. It is now accepted that NMDA receptors (NMDARs internalize and are recycled at the plasma membrane but also exchange between synaptic and extrasynaptic pools; these NMDAR properties are also key to governing synaptic plasticity. Scribble1 is a large PDZ protein required for synaptogenesis and synaptic plasticity. Herein, we show that the level of Scribble1 is regulated in an activity-dependent manner and that Scribble1 controls the number of NMDARs at the plasma membrane. Notably, Scribble1 prevents GluN2A subunits from undergoing lysosomal trafficking and degradation by increasing their recycling to the plasma membrane following NMDAR activation. Finally, we show that a specific YxxR motif on Scribble1 controls these mechanisms through a direct interaction with AP2. Altogether, our findings define a molecular mechanism to control the levels of synaptic NMDARs via Scribble1 complex signaling.

  14. Ion-polyether coordination complexes: crystalline ionic conductors for clean energy storage. (United States)

    Bruce, Peter G


    Ion-polyether complexes are the solid state analogues of crown ether and cryptand complexes. They represent a fascinating class of coordination compounds in their own right, with the ability to support ionic conductivity and the potential to be used as electrolytes in all-solid-state rechargeable lithium batteries. Here the recent discovery of ionic conductivity in crystalline ion-polyether complexes, when for 30 years such materials were considered to be insulators, is described, along with their closely related structural chemistry.

  15. Parent Perspective on Care Coordination Services for Their Child with Medical Complexity

    Directory of Open Access Journals (Sweden)

    Rhonda G. Cady


    Full Text Available The overarching goal of care coordination is communication and co-management across settings. Children with medical complexity require care from multiple services and providers, and the many benefits of care coordination on health and patient experience outcomes have been documented. Despite these findings, parents still report their greatest challenge is communication gaps. When this occurs, parents assume responsibility for aggregating and sharing health information across providers and settings. A new primary-specialty care coordination partnership model for children with medical complexity works to address these challenges and bridge communication gaps. During the first year of the new partnership, parents participated in focus groups to better understand how they perceive communication and collaboration between the providers and services delivering care for their medically complex child. Our findings from these sessions reflect the current literature and highlight additional challenges of rural families, as seen from the perspective of the parents. We found that parents appreciate when professional care coordination is provided, but this is often the exception and not the norm. Additionally, parents feel that the local health system’s inability to care for their medically complex child results in unnecessary trips to urban-based specialty care. These gaps require a system-level approach to care coordination and, consequently, new paradigms for delivery are urgently needed.

  16. Synthesis, complexation, and coordination oligomerization of 1,8-pyrazine-capped 5,12-dioxocyclams. (United States)

    Hegedus, Louis S; Sundermann, Michael J; Dorhout, Peter K


    (Methyl)(methoxy)-5,12-dioxocyclam 1 was alkylated on the secondary amines (capped) with 2,6-bis(bromomethyl)pyrazine. The resulting macrocycle was complexed to copper(II) to produce a five-coordinate complex 5a which was fully characterized by a range of spectroscopic methods (IR, UV-vis, ESR) as well as by X-ray crystallography. The structure of this complex is similar to the previously reported pyridine complex, with the five-coordinate copper having distorted square pyramidal geometry and a Cu-Pz bond length of 2.125 A. Attempts to prepare this same complex under microwave irradiation instead produced a trinuclear complex 6a having an octahedral copper(II) center complexed to two pyrazine-cyclam copper units through the amide carbonyl oxygen and the methoxyl group oxygen of the cyclam unit. The X-ray crystal structure of the trinuclear complex showed extensive distortion in the cyclam rings. The remote nitrogen of pyrazine-cyclam complex 5a was capable of coordinating an additional metal. Treatment with RuCl(2)(DMSO)(4) or Rh(2)(OAc)(4), respectively, produced trimetallic Cu-Ru-Cu complex 7 or tetrametallic Cu-Rh-Rh-Cu complex 8. The latter was fully characterized, including an X-ray crystal structure, and had two pyrazine-cyclam complexes bridged by a Rh(2)(OAc)(4) unit through the remote pyrazine nitrogens. There was little distortion in the pyrazine-cyclam copper units as compared to complex 5a: the four metals were collinear, and the two cyclam units were eclipsed. All of the copper complexes were subjected to cyclic voltametry measurements, and no reversible redox changes were observed. Magnetic measurements of 6a and 8 showed the copper atoms to be weakly antiferromagnetically coupled.

  17. Complex scaling of the hyper-spheric coordinates and Faddeev equations

    CERN Document Server

    Fedorov, D V; Jensen, A S


    We implement complex scaling of Faddeev equations using hyper-spheric coordinates and adiabatic expansion. Complex scaling of coordinates allows convenient calculations of three-body resonances. We derive the necessary equations and investigate the adiabatic spectrum at large distances. We illustrate the viability of the implementation by calculations of several three-body resonances: a $0^+$ resonance in a model benchmark system of three identical bosons; the $2^+$ resonance in the $^6$He nucleus within the $alpha+n+n$ model; and the two $0^+$ resonances in $^{12}$C within the three-$alpha$ model.

  18. Low-Complexity MMSE Precoding for Coordinated Multipoint with Per-Antenna Power Constraint

    DEFF Research Database (Denmark)

    Kim, Tae Min; Sun, Fan; Paulraj, Arogyaswami


    We propose a low-complexity minimum mean square error (MMSE) transmit filter design for the coordinated beamforming (CB) in the coordinated multipoint (CoMP) under the practical per-antenna power constraint (PAPC). The proposed design is based on the non-linear Gauss-Seidel type algorithm in which...... the transmit filters for given receive filters are computed by iteratively updating the beamformer of each transmit antenna using simple closed-form expressions. The proposed approach can significantly reduce the overall complexity of the alternating optimization while preserving the optimality in the MSE...

  19. Ytterbium Coordination Polymer with Four Different Coordination Numbers:The First Structural Characterization of Lanthanide Phthalate Complex

    Institute of Scientific and Technical Information of China (English)

    万永红; 金林培; 等


    The novel ytterbium coordination polymer is a t4wo-dimensional framework in which the central metal ions have four different coordination numbers and form four kinds of coordination poly-hedra,The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms.

  20. Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

    Institute of Scientific and Technical Information of China (English)

    ZHOU Nan; WAN ShiGang; ZHAO Jian; LIN YiJi; XUAN WeiMin; FANG XueMing; ZHANG Hui


    Eight-coordinate chiral lanthanide complexes[Eu(dbm)_3L~(RR)](1),[Eu(dbm)_3L~(SS)](2) and[Tb(dbm)_3L~(RR)](3)(L~(RR)/L~(SS)=(-)-1(+)-4,5-pineno-2,2'-bipyridine,Hdbm=dibenzoylmethane) were synthesized stereoselectively,which were characterized by UV-vis,CD spectra and X-ray single-crystal diffraction.The mirrorimage structure features of complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis.After further comparison with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectraabsolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The △ or Λ absolute configurations of complexes 1-3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.

  1. Stereochemistry and solid-state circular dichroism spectroscopy of eight-coordinate chiral lanthanide complexes

    Institute of Scientific and Technical Information of China (English)


    Eight-coordinate chiral lanthanide complexes [Eu(dbm)3LRR](1),[Eu(dbm)3LSS](2) and [Tb(dbm)3LRR](3)(LRR/LSS =(-)-/(+)-4,5-pineno-2,2’-bipyridine,Hdbm = dibenzoylmethane) were synthesized stereoselectively,which were characterized by UV-vis,CD spectra and X-ray single-crystal diffraction.The mirrorimage structure features of complexes 1 and 2 were obtained by combination of the solid-state CD spectra and the crystal structure analysis.After further comparison with the solid-state CD spectra of six-coordinate and seven-coordinate metal complexes containing β-diketone ligands,the CD spectraabsolute configuration correlation rule for the eight-coordinate β-diketonate lanthanide complexes was proposed through the exciton chirality method for the first time.The △ or Λ absolute configurations of complexes 1―3 with the distorted square antiprism geometry were confirmed by the X-ray single-crystal analysis.

  2. Coordination mode of nitrate in uranyl(VI) complexes: a first-principles molecular dynamics study. (United States)

    Bühl, Michael; Diss, Romain; Wipff, Georges


    According to Car-Parrinello molecular dynamics simulations for [UO(2)(NO(3))(3)](-), [UO(2)(NO(3))(4)](2-), and [UO(2)(OH(2))(4-)(NO(3))](+) complexes in the gas phase and in aqueous solution, the nitrate coordination mode to uranyl depends on the interplay between ligand-metal attractions, interligand repulsions, and solvation. In the trinitrate, the eta(2)-coordination is clearly favored in water and in the gas phase, leading to a coordination number (CN) of 6. According to pointwise thermodynamic integration involving constrained molecular dynamics simulations, a change in free energy of +6 kcal/mol is predicted for eta(2)- to eta(1)-transition of one of the three nitrate ligands in the gas phase. In the gas phase, the mononitrate-hydrate complex also prefers a eta(2)-binding mode but with a CN of 5, one H(2)O molecule being in the second shell. This contrasts with the aqueous solution where the nitrate binds in a eta(1)-fashion and uranyl coordinates to four H2O ligands. A driving force of ca. -3 kcal/mol is predicted for the eta(2)- to eta(1)- transition in water. This structural preference is interpreted in terms of steric arguments and differential solvation of terminal vs uranyl-coordinated O atoms of the nitrate ligands. The [UO(2)(NO(3))(4)](2-) complex with two eta(2)- and two eta(1)- coordinated nitrates, observed in the solid state, is stable for 1-2 ps in the gas phase and in solution. In the studied series, the modulation of uranyl-ligand distances upon immersion of the complex in water is found to depend on the nature of the ligand and the composition of the complex.

  3. Determination of tetracycline in milk by using nucleotide/lanthanide coordination polymer-based ternary complex. (United States)

    Tan, Hongliang; Ma, Chanjiao; Song, Yonghai; Xu, Fugang; Chen, Shouhui; Wang, Li


    The meta-organic coordination polymers have been emerged as fascinating nanomaterials because of their tunable nature. In this work, we employed lanthanide coordination polymer self-assembled from adenosine monophosphate (AMP) and europium ion (Eu(3+)) as receptor reagent and citrate (Cit) as ancillary ligand to construct a fluorescent sensor for the detection of tetracycline (Tc) in milk. The co-coordination of Cit and Tc with Eu(3+) on the surface of the coordination polymer AMP/Eu leads to the formation of ternary complex which emitted strong fluorescence due to the removal of coordinated water molecules and an intramolecular energy transfer from Tc to Eu(3+). The fluorescent intensity of Eu(3+) displayed a good linear response to Tc concentrations in the range of 0.1-20 μM with a detection limit of 60 nM. This method was successfully applied to determine the levels of Tc in milk, which is the first application of coordination polymer as a fluorescent sensor in real sample. Compared with other Eu(3+)-based fluorescent methods for Tc detection, the presented method allows simple, direct analysis of Tc without requiring special reaction media or complicated prepreparation processes. This straightforward strategy could be extended to the preparation of other lanthanide coordination polymer-based fluorescent probes for applications in biosensing, imaging, drug delivery, and so on. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Multifunctionality of organometallic quinonoid metal complexes: surface chemistry, coordination polymers, and catalysts. (United States)

    Kim, Sang Bok; Pike, Robert D; Sweigart, Dwight A


    Quinonoid metal complexes have potential applications in surface chemistry, coordination polymers, and catalysts. Although quinonoid manganese tricarbonyl complexes have been used as secondary building units (SBUs) in the formation of novel metal-organometallic coordination networks and polymers, the potentially wider applications of these versatile linkers have not yet been recognized. In this Account, we focus on these diverse new applications of quinonoid metal complexes, and report on the variety of quinonoid metal complexes that we have synthesized. Through the use of [(η(6)-hydroquinone)Mn(CO)3](+), we are able to modify the surface of Fe3O4 and FePt nanoparticles (NPs). This process occurs either by the replacement of oleylamine with neutral [(η(5)-semiquinone)Mn(CO)3] at the NP surface, or by the binding of anionic [(η(4)-quinone)Mn(CO)3](-) upon further deprotonation of [(η(5)-semiquinone)Mn(CO)3] at the NP surface. We have demonstrated chemistry at the intersection of surface-modified NPs and coordination polymers through the growth of organometallic coordination polymers onto the surface modified Fe3O4 NPs. The resulting magnetic NP/organometallic coordination polymer hybrid material exhibited both the unique superparamagnetic behavior associated with Fe3O4 NPs and the paramagnetism attributable to the metal nodes, depending upon the magnetic range examined. By the use of functionalized [(η(5)-semiquinone)Mn(CO)3] complexes, we attained the formation of an organometallic monolayer on the surface of highly ordered pyrolitic graphite (HOPG). The resulting organometallic monolayer was not simply a random array of manganese atoms on the surface, but rather consisted of an alternating "up and down" spatial arrangement of Mn atoms extending from the HOPG surface due to hydrogen bonding of the quinonoid complexes. We also showed that the topology of metal atoms on the surface could be controlled through the use of quinonoid metal complexes. A quinonoid

  5. Detecting coordinated regulation of multi-protein complexes using logic analysis of gene expression

    Directory of Open Access Journals (Sweden)

    Yeates Todd O


    Full Text Available Abstract Background Many of the functional units in cells are multi-protein complexes such as RNA polymerase, the ribosome, and the proteasome. For such units to work together, one might expect a high level of regulation to enable co-appearance or repression of sets of complexes at the required time. However, this type of coordinated regulation between whole complexes is difficult to detect by existing methods for analyzing mRNA co-expression. We propose a new methodology that is able to detect such higher order relationships. Results We detect coordinated regulation of multiple protein complexes using logic analysis of gene expression data. Specifically, we identify gene triplets composed of genes whose expression profiles are found to be related by various types of logic functions. In order to focus on complexes, we associate the members of a gene triplet with the distinct protein complexes to which they belong. In this way, we identify complexes related by specific kinds of regulatory relationships. For example, we may find that the transcription of complex C is increased only if the transcription of both complex A AND complex B is repressed. We identify hundreds of examples of coordinated regulation among complexes under various stress conditions. Many of these examples involve the ribosome. Some of our examples have been previously identified in the literature, while others are novel. One notable example is the relationship between the transcription of the ribosome, RNA polymerase and mannosyltransferase II, which is involved in N-linked glycan processing in the Golgi. Conclusions The analysis proposed here focuses on relationships among triplets of genes that are not evident when genes are examined in a pairwise fashion as in typical clustering methods. By grouping gene triplets, we are able to decipher coordinated regulation among sets of three complexes. Moreover, using all triplets that involve coordinated regulation with the ribosome

  6. Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials. (United States)

    Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan


    Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability.

  7. Highly dynamic coordination behavior of Pn ligand complexes towards "naked" Cu(+) cations. (United States)

    Fleischmann, Martin; Welsch, Stefan; Peresypkina, Eugenia V; Virovets, Alexander V; Scheer, Manfred


    Reactions of Cu(+) containing the weakly coordinating anion [Al{OC(CF3 )3 }4 ](-) with the polyphosphorus complexes [{CpMo(CO)2 }2 (μ,η(2) :η(2) -P2 )] (A), [CpM(CO)2 (η(3) -P3 )] (M=Cr(B1), Mo (B2)), and [Cp*Fe(η(5) -P5 )] (C) are presented. The X-ray structures of the products revealed mononuclear (4) and dinuclear (1, 2, 3) Cu(I) complexes, as well as the one-dimensional coordination polymer (5 a) containing an unprecedented [Cu2 (C)3 ](2+) paddle-wheel building block. All products are readily soluble in CH2 Cl2 and exhibit fast dynamic coordination behavior in solution indicated by variable temperature (31) P{(1) H} NMR spectroscopy.

  8. Thiosemicarbazone complexes of the platinum metals. A story of variable coordination modes

    Indian Academy of Sciences (India)

    Indrani Pal; Falguni Basuli; Samaresh Bhattacharya


    Salicylaldehyde thiosemicarbazone (H2saltsc) reacts with [M(PPh3)3X2] (M = Ru, Os; X = Cl, Br) to afford complexes of type [M(PPh3)2(Hsaltsc)2], in which the salicylaldehyde thiosemicarbazone ligand is coordinated to the metal as a bidentate N,S-donor forming a four-membered chelate ring. Reaction of benzaldehyde thiosemicarbazones (Hbztsc-R) with [M(PPh3)3X2] also affords complexes of similar type, viz. [M(PPh3)2(bztsc-R)2], in which the benzaldehyde thiosemicarbazones have also been found to coordinate the metal as a bidentate N,S-donor forming a fourmembered chelate ring as before. Reaction of the Hbztsc-R ligands has also been carried out with [M(bpy)2X2] (M = Ru, Os; X = Cl, Br), which has afforded complexes of type [M(bpy)2(bztsc-R)]+, which have been isolated as perchlorate salts. Coordination mode of bztsc-R has been found to be the same as before. Structure of the Hbztsc-OMe ligand has been determined and some molecular modelling studies have been carried out determine the reason for the observed mode of coordination. Reaction of acetone thiosemicarbazone (Hactsc) has then been carried out with [M(bpy)2X2] to afford the [M(bpy)2(actsc)]ClO4 complexes, in which the actsc ligand coordinates the metal as a bidentate N,S-donor forming a five-membered chelate ring. Reaction of H2saltsc has been carried out with [Ru(bpy)2Cl2] to prepare the [Ru(bpy)2(Hsaltsc)]ClO4 complex, which has then been reacted with one equivalent of nickel perchlorate to afford an octanuclear complex of type [{Ru(bpy)2(saltsc-H)}4Ni4](ClO4)4.

  9. A Mobile Care Coordination System for the Management of Complex Chronic Disease. (United States)

    Haynes, Sarah; Kim, Katherine K


    There is global concern about healthcare cost, quality, and access as the prevalence of complex and chronic diseases, such as heart disease, continues to grow. Care for patients with complex chronic disease involves diverse practitioners and multiple transitions between medical centers, physician practices, clinics, community resources, and patient homes. There are few systems that provide the flexibility to manage these varied and complex interactions. Participatory and user-centered design methodology was applied to the first stage of building a mobile platform for care coordination for complex, chronic heart disease. Key informant interviews with patients, caregivers, clinicians, and care coordinators were conducted. Thematic analysis led to identification of priority user functions including shared care plan, medication management, symptom management, nutrition, physical activity, appointments, personal monitoring devices, and integration of data and workflow. Meaningful stakeholder engagement contributes to a person-centered system that enhances health and efficiency.

  10. Influence of topology in the evolution of coordination in complex networks under information diffusion constraints (United States)

    Kasthurirathna, Dharshana; Piraveenan, Mahendra; Harré, Michael


    In this paper, we study the influence of the topological structure of social systems on the evolution of coordination in them. We simulate a coordination game ("Stag-hunt") on four well-known classes of complex networks commonly used to model social systems, namely scale-free, small-world, random and hierarchical-modular, as well as on the well-mixed model. Our particular focus is on understanding the impact of information diffusion on coordination, and how this impact varies according to the topology of the social system. We demonstrate that while time-lags and noise in the information about relative payoffs affect the emergence of coordination in all social systems, some topologies are markedly more resilient than others to these effects. We also show that, while non-coordination may be a better strategy in a society where people do not have information about the payoffs of others, coordination will quickly emerge as the better strategy when people get this information about others, even with noise and time lags. Societies with the so-called small-world structure are most conducive to the emergence of coordination, despite limitations in information propagation, while societies with scale-free topologies are most sensitive to noise and time-lags in information diffusion. Surprisingly, in all topologies, it is not the highest connected people (hubs), but the slightly less connected people (provincial hubs) who first adopt coordination. Our findings confirm that the evolution of coordination in social systems depends heavily on the underlying social network structure.

  11. Synthesis,Structure and Luminescent Properties of a Nine-Coordinated Praseodymium Complex

    Institute of Scientific and Technical Information of China (English)

    孙丽宁; 张洪杰; 符连社; 刘丰一; 孟庆国; 彭春耘; 于江波; 王淑彬


    The Pr(TTA)3phen(C2H5OH)quarternary complex with 2-thenoyltrifluoro-acetone(TTA), 1,10-phenanthroline(phen)and ethanol were synthesized and characterized by single-crystal X-ray diffraction. The central Pr3+ ion is nine-coordinated. The infrared(IR)spectrum, diffuse reflectance(DR)spectrum and fluorescence measurements of the complex were investigated.

  12. Pyridinediimine Iron Complexes with Pendant Redox-Inactive Metals Located in the Secondary Coordination Sphere. (United States)

    Delgado, Mayra; Ziegler, Joshua M; Seda, Takele; Zakharov, Lev N; Gilbertson, John D


    A series of pyridinediimine (PDI) iron complexes that contain a pendant 15-crown-5 located in the secondary coordination sphere were synthesized and characterized. The complex Fe((15c5)PDI)(CO)2 (2) was shown in both the solid state and solution to encapsulate redox-inactive metal ions. Modest shifts in the reduction potential of the metal-ligand scaffold were observed upon encapsulation of either Na(+) or Li(+).

  13. XAFS study of copper(II) complexes with square planar and square pyramidal coordination geometries (United States)

    Gaur, A.; Klysubun, W.; Nitin Nair, N.; Shrivastava, B. D.; Prasad, J.; Srivastava, K.


    X-ray absorption fine structure of six Cu(II) complexes, Cu2(Clna)4 2H2O (1), Cu2(ac)4 2H2O (2), Cu2(phac)4 (pyz) (3), Cu2(bpy)2(na)2 H2O (ClO4) (4), Cu2(teen)4(OH)2(ClO4)2 (5) and Cu2(tmen)4(OH)2(ClO4)2 (6) (where ac, phac, pyz, bpy, na, teen, tmen = acetate, phenyl acetate, pyrazole, bipyridine, nicotinic acid, tetraethyethylenediamine, tetramethylethylenediamine, respectively), which were supposed to have square pyramidal and square planar coordination geometries have been investigated. The differences observed in the X-ray absorption near edge structure (XANES) features of the standard compounds having four, five and six coordination geometry points towards presence of square planar and square pyramidal geometry around Cu centre in the studied complexes. The presence of intense pre-edge feature in the spectra of four complexes, 1-4, indicates square pyramidal coordination. Another important XANES feature, present in complexes 5 and 6, is prominent shoulder in the rising part of edge whose intensity decreases in the presence of axial ligands and thus indicates four coordination in these complexes. Ab initio calculations were carried out for square planar and square pyramidal Cu centres to observe the variation of 4p density of states in the presence and absence of axial ligands. To determine the number and distance of scattering atoms around Cu centre in the complexes, EXAFS analysis has been done using the paths obtained from Cu(II) oxide model and an axial Cu-O path from model of a square pyramidal complex. The results obtained from EXAFS analysis have been reported which confirmed the inference drawn from XANES features. Thus, it has been shown that these paths from model of a standard compound can be used to determine the structural parameters for complexes having unknown structure.

  14. Chromogenic detection of Sarin by discolouring decomplexation of a metal coordination complex. (United States)

    Ordronneau, Lucie; Carella, Alexandre; Pohanka, Miroslav; Simonato, Jean-Pierre


    An innovative chromogenic sensing concept based on decomplexation of a tris-(bipyridine)iron(II) coordination complex has been developed for the detection of organophosphorus nerve agents. It was evaluated both on a simulant and real Sarin in vapour and liquid phases.

  15. Synthesis and crystal structure of a wheel-shaped supramolecular coordination complex

    Indian Academy of Sciences (India)

    Deepak Gupta; Palanisamy Rajakannu; Bhaskaran Shankar; Firasat Hussain; Malaichamy Sathiyendiran


    Supramolecular coordination complex (SCC) possessing spatially arranged three anthraquinone dimers in a slipped-cofacial orientation was achieved by the treatment of Re2(CO)10, 2-hydroxymethylanthraquinone and tritopic N-donor via fac-Re(CO)3-directed one pot approach. The off-set -stacking and C≡O…H bonding interactions stabilize the ring structure.

  16. Synthesis and Base Hydrolysis of a Cobalt(III) Complex Coordinated by a Thioether Ligand (United States)

    Roecker, Lee


    A two-week laboratory experiment for students in advanced inorganic chemistry is described. Students prepare and characterize a cobalt(III) complex coordinated by a thioether ligand during the first week of the experiment and then study the kinetics of Co-S bond cleavage in basic solution during the second week. The synthetic portion of the…

  17. Synthesis and Base Hydrolysis of a Cobalt(III) Complex Coordinated by a Thioether Ligand (United States)

    Roecker, Lee


    A two-week laboratory experiment for students in advanced inorganic chemistry is described. Students prepare and characterize a cobalt(III) complex coordinated by a thioether ligand during the first week of the experiment and then study the kinetics of Co-S bond cleavage in basic solution during the second week. The synthetic portion of the…

  18. Care coordination for patients with complex health profiles in inpatient and outpatient settings. (United States)

    Berry, Leonard L; Rock, Beth L; Smith Houskamp, Beth; Brueggeman, Joan; Tucker, Lois


    Patients with the most complex health profiles consume a disproportionate percentage of health care expenditures, yet often receive fragmented, suboptimal care. Since 2003, Wisconsin-based Gundersen Health has improved the quality of life and reduced the cost burden of patients with complex health profiles with an integrated care coordination program. Those results are consistent with data from the most successful care coordination demonstration projects funded by the Centers for Medicare and Medicaid Services. Specifically, Gundersen's program has been associated with reduced hospital stays, lower costs for inpatients, less use of inpatient services, and increased patient satisfaction. Gundersen's success is rooted in its team-based approach to coordinated care. Teams, led by a subspecialty-trained nurse, have regular, face-to-face contact with patients and their physicians in both inpatient and outpatient settings; involve patients deeply in care-related decisions; access a system-wide electronic medical record database that tracks patients' care; and take a macrolevel view of care-related factors and costs. Gundersen's model offers specific take-home lessons for institutions interested in coordinated care as they design programs aimed at improving quality and lowering costs. This institutional case study provides a window into well-executed care coordination at a large health care system in an era when major changes in health care provision and reimbursement mechanisms are on the horizon.


    Institute of Scientific and Technical Information of China (English)

    Peter B. LUH; Weidong FENG


    With time-based competition and rapid technology advancements, effective manufacturing scheduling and supply chain coordination are critical to quickly respond to changing market conditions. These problems, however, are difficult in view of inherent complexity and various uncertainties involved. Based on a series of results by the authors, decomposition and coordination by using Lagrangian relaxation is identified in this paper as an effective way to control complexity and uncertainty. A manufacturing scheduling problem is first formulated within the job shop context with uncertain order arrivals, processing times, due dates, and part priorities as a separable optimization problem. A solution methodology that combines Lagrangian relaxation, stochastic dynamic programming, and heuristics is developed. Method improvements to effectively solve large problems are also highlighted. To extend manufacturing scheduling within a factory to coordinate autonomic members across chains of suppliers, a decentralized supply chain model is established in the second half of this paper. By relaxing cross-member constraints, the model is decomposed into member-wise subproblems, and a nested optimization structure is developed based on the job shop scheduling results. Coordination is performed through the iterative updating of cross-member prices without accessing other members' private information or intruding their decision-making authorities, either with or without a coordinator. Two examples are presented to demonstrate the effectiveness of the method. Future prospects to overcome problem inseparability and improve computing efficiency are then discussed.

  20. Types of coordination and syntactic complexity in written discourse of younger school age children

    Directory of Open Access Journals (Sweden)

    IvanoviĆ Maja


    Full Text Available For a long time influential linguists considered language development to be basically completed by the age of five or six. Consequently, research on school age children and adolescents has been quite rare. However, during the last two decades, considerable effort has been made to understand the nature of writing processes among schoolchildren. The aim of this paper is to explore writing competence of younger school age children by investigating compound sentences and coordinating conjunctions during the production of a written text. The most important thing in learning how to write is the development of a child's ability to produce and understand complex sentences of various kinds. Coordinating conjunctions are useful for connecting sentences, but compound sentences are often overused and traditionally seem to implicate poor syntactic ability. The examinees were divided in 4 age groups (181 pupils. Each examinee wrote 3 essays, so the whole corpus consisted of 543 texts in total. The analysis of the collected material included two levels: first we identified compound sentences and the number of clauses, and then the type of coordination was determined. The obtained results show the number and type of coordinated constructions which pupils from the first to the fourth grade of primary school produce. Also, coordinating conjunctions indicate the higher level of syntactic complexity of the text they are produced in. This research provides a new insight into syntactic competence of younger pupils in primary school.

  1. The Role of Care Coordinator for Children with Complex Care Needs: A Systematic Review

    Directory of Open Access Journals (Sweden)

    Rowan Hillis


    Full Text Available Introduction: This systematic review seeks to identify the intended components of the role of care coordinator for children with complex care needs and the factors that determine its composition in practice. Theory and methods: The initial search identified 1,157 articles, of which 37 met the inclusion criteria. They were quality assessed using the SIGN hierarchy of evidence structure. Results: Core components of the role include: coordination of care needs, planning and assessment, specialist support, emotional support, administration and logistics and continuing professional development. Influencing factors on the role include the external environment (political and socio-economic, the internal environment (organisational structure and funding protocols, the skills, qualifications and experience of the coordinator, the family circumstances and the nature of the interaction between the care coordinator and the family. Discussion: The lack of consistent terminology creates challenges and there is a need for greater consensus on this issue. Organisations and healthcare professionals need to recognise the extent to which contextual factors influence the role of a care coordinator in practice and plan accordingly. Despite evidence that suggests that the role is pivotal in ensuring that care needs are sustained, there remains great variability in the understanding of the role of a care coordinator for this population. Conclusions: As the provision of care increasingly moves closer to home there is a need for greater understanding of the nature and composition of the interaction between care coordinators and families to determine the extent to which appropriate services are being provided. Further work in this area should take into consideration any potential variance in service provision, for example any potential inequity arising due to geographic location. It is also imperative, where appropriate, to seek the views of children with complex care

  2. Theoretical investigation of polymer chain stability in the metal coordinated azorubine and cyclam complex (United States)

    Vlassa, Mihaela; Bende, Attila


    Theoretical investigations have been performed for unit systems with Ni(II) and Zn(II) coordination between azorubine and 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes using the conventional DFT and the DFT-based tight binding (DFTB) methods. Two different geometries (short and long) and spin states (singlet and triplet) of the model system built by two mesylate groups and the cyclam ring together with Ni(II) and Zn(II) ions were energetically characterized. For the Ni(II) coordination complex the triplet geometry is preferred, but one could not exclude also the presence of the singlet spin configuration due to the huge energy barrier defined by the intersystem crossing. The intersystem crossing geometry of the singlet-triplet transition was studied in details and the corresponding spin-orbit couplings were discussed. For the Zn(II) coordination complex only the singlet state was found. Polymer chain build up from four unit systems presents irregular forms with strong coordination bonds between units.

  3. Evolutionary dynamics of the traveler's dilemma and minimum-effort coordination games on complex networks. (United States)

    Iyer, Swami; Killingback, Timothy


    The traveler's dilemma game and the minimum-effort coordination game are social dilemmas that have received significant attention resulting from the fact that the predictions of classical game theory are inconsistent with the results found when the games are studied experimentally. Moreover, both the traveler's dilemma and the minimum-effort coordination games have potentially important applications in evolutionary biology. Interestingly, standard deterministic evolutionary game theory, as represented by the replicator dynamics in a well-mixed population, is also inadequate to account for the behavior observed in these games. Here we study the evolutionary dynamics of both these games in populations with interaction patterns described by a variety of complex network topologies. We investigate the evolutionary dynamics of these games through agent-based simulations on both model and empirical networks. In particular, we study the effects of network clustering and assortativity on the evolutionary dynamics of both games. In general, we show that the evolutionary behavior of the traveler's dilemma and minimum-effort coordination games on complex networks is in good agreement with that observed experimentally. Thus, formulating the traveler's dilemma and the minimum-effort coordination games on complex networks neatly resolves the paradoxical aspects of these games.

  4. A Stable Coordination Complex of Rh(IV) in an N,O-Donor Environment. (United States)

    Sinha, Shashi B; Shopov, Dimitar Y; Sharninghausen, Liam S; Vinyard, David J; Mercado, Brandon Q; Brudvig, Gary W; Crabtree, Robert H


    We describe facial and meridional isomers of [Rh(III)(pyalk)3], as well as meridional [Rh(IV)(pyalk)3](+) {pyalk =2-(2-pyridyl)-2-propanoate}, the first coordination complex in an N,O-donor environment to show a clean, reversible Rh(III/IV) redox couple and to have a stable Rh(IV) form, which we characterize by EPR and UV-visible spectroscopy as well as X-ray crystallography. The unprecedented stability of the Rh(IV) species is ascribed to the exceptional donor strength of the ligands, their oxidation resistance, and the meridional coordination geometry.

  5. Low complexity non-iterative coordinated beamforming in 2-user broadcast channels

    KAUST Repository

    Park, Kihong


    We propose a new non-iterative coordinated beamforming scheme to obtain full multiplexing gain in 2-user MIMO systems. In order to find the beamforming and combining matrices, we solve a generalized eigenvector problem and describe how to find generalized eigenvectors according to the Gaussian broadcast channels. Selected simulation results show that the proposed method yields the same sum-rate performance as the iterative coordinated beamforming method, while maintaining lower complexity by non-iterative computation of the beamforming and combining matrices. We also show that the proposed method can easily exploit selective gain by choosing the best combination of generalized eigenvectors. © 2006 IEEE.

  6. Flaviviral Replication Complex: Coordination between RNA Synthesis and 5'-RNA Capping. (United States)

    Klema, Valerie J; Padmanabhan, Radhakrishnan; Choi, Kyung H


    Genome replication in flavivirus requires (-) strand RNA synthesis, (+) strand RNA synthesis, and 51-RNA capping and methylation. To carry out viral genome replication, flavivirus assembles a replication complex, consisting of both viral and host proteins, on the cytoplasmic side of the endoplasmic reticulum (ER) membrane. Two major components of the replication complex are the viral non-structural (NS) proteins NS3 and NS5. Together they possess all the enzymatic activities required for genome replication, yet how these activities are coordinated during genome replication is not clear. We provide an overview of the flaviviral genome replication process, the membrane-bound replication complex, and recent crystal structures of full-length NS5. We propose a model of how NS3 and NS5 coordinate their activities in the individual steps of (-) RNA synthesis, (+) RNA synthesis, and 51-RNA capping and methylation.

  7. Dispersion-Force-Assisted Disproportionation: A Stable Two-Coordinate Copper(II) Complex. (United States)

    Wagner, Clifton L; Tao, Lizhi; Thompson, Emily J; Stich, Troy A; Guo, Jingdong; Fettinger, James C; Berben, Louise A; Britt, R David; Nagase, Shigeru; Power, Philip P


    The synthesis of the first linear coordinated Cu(II) complex Cu{N(SiMe3 )Dipp}2 (1 Dipp=C6 H5 -2,6Pr(i) 2 ) and its Cu(I) counterpart [Cu{N(SiMe3 )Dipp}2 ](-) (2) is described. The formation of 1 proceeds through a dispersion force-driven disproportionation, and is the reaction product of a Cu(I) halide and LiN(SiMe3 )Dipp in a non-donor solvent. The synthesis of 2 is accomplished by preventing the disproportionation into 1 by using the complexing agent 15-crown-5. EPR spectroscopy of 1 provides the first detailed study of a two-coordinate transition-metal complex indicating strong covalency in the Cu-N bonds.

  8. Two organoantimony (V) coordination complexes modulated by isomers of trifluoromethylbenzoate ligands: Syntheses, crystal structure, photodegradation properties (United States)

    Zhang, Xiao-Yin; Cui, Lian-sheng; Zhang, Xia; Jin, Fan; Fan, Yu-Hua


    Two organoantimony (V) coordination complexes, namely Ph3Sb(2-tmbc) (1) and Ph3Sb(3-tmbc) (2) (2-tmbc = 2-(trifluoromethyl)benzoic carboxyl, 3-tmbc = 3-(trifluoromethyl)benzoic carboxyl) have been synthesized and characterized by IR spectra, elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Single-crystal X-ray diffraction analysis reveals that complexes 1 and 2 show different architectures by the intermolecular hydrogen bonds (Csbnd H⋯F), complex 1 displays an 1D straight chain structure, while complex 2 shows an 1D zigzag chain structure. The photodegradation properties of complexes 1 and 2 has been investigated in organic dyes (RhB, MV, MB) the results indicated that the two complexes are good candidates for the photocatalytic degradation of three dyes. The tentative photocatalytic degradations mechanism is discussed.

  9. New water soluble heterometallic complex showing unpredicted coordination modes of EDTA

    Energy Technology Data Exchange (ETDEWEB)

    Mudsainiyan, R.K., E-mail:; Jassal, A.K.; Chawla, S.K., E-mail:


    A mesoporous 3D polymeric complex (I) having formula ([Zr(IV)O-μ{sup 3}-(EDTA)Fe(III)OH]·H{sub 2}O){sub n} has been crystallized and characterized by various techniques. Single-crystal X-ray diffraction analysis revealed that complex (I) crystallized in chiral monoclinic space group Cc (space group no. 9) with unexpected coordination modes of EDTA and mixture of two transition metal ions. In this complex, the coordination number of Zr(IV) ion is seven where four carboxylate oxygen atoms, two nitrogen atoms, one oxide atom are coordinating with Zr(IV). Fe(III) is four coordinated and its coordination environment is composed of three different carboxylic oxygen atoms from three different EDTA and one oxygen atom of –OH group. The structure consists of 4-c and 16-c (2-nodal) net with new topology and point symbol for net is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern showed that the coordination polymer is quite stable even after losing water molecule and –OH ion. Quenching behavior in fluorescence of ligand is observed by complexation with transition metal ions is due to n–π⁎ transition. The SEM micrograph shows the morphology of complex (I) exhibits spherical shape with size ranging from 50 to 280 nm. The minimum N{sub 2} (S{sub BET}=8.7693 m{sup 2}/g) and a maximum amount of H{sub 2} (high surface area=1044.86 m{sup 2}/g (STP)) could be adsorbed at 77 K. From DLS study, zeta potential is calculated i.e. −7.94 shows the negative charges on the surface of complex. Hirshfeld surface analysis and fingerprint plots revealed influence of weak or non bonding interactions in crystal packing of complex. - Graphical abstract: The complex (I) crystallized with unexpected coordination modes of EDTA having 4-c, 16-c net with new topology and point symbol is (3{sup 36}·4{sup 54}·5{sup 30})·(3{sup 6}). TGA study and XRPD pattern proved its stability with high preference of H{sub 2} uptake by complex. - Highlights: • 3D complex

  10. Coordination functionalization of graphene oxide with tetraazamacrocyclic complexes of nickel(II): Generation of paramagnetic centers

    Energy Technology Data Exchange (ETDEWEB)

    Basiuk, Vladimir A., E-mail: [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Department of Chemistry,Tufts University, 62 Talbot Avenue, Medford, MA 02155 (United States); Alzate-Carvajal, Natalia [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Henao-Holguín, Laura V. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Rybak-Akimova, Elena V. [Department of Chemistry,Tufts University, 62 Talbot Avenue, Medford, MA 02155 (United States); Basiuk, Elena V., E-mail: [Department of Chemistry,Tufts University, 62 Talbot Avenue, Medford, MA 02155 (United States); Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico)


    Highlights: • [Ni(cyclam)]{sup 2+} and [Ni(tet b)]{sup 2+} cations coordinate to carboxylic groups of GO. • The coordination takes place under basic conditions in aqueous-based medium. • The coordination results in the conversion from low-spin to high-spin Ni(II). • Functionalized GO samples were characterized by various instrumental techniques. - Abstract: We describe a novel approach to functionalization of graphene oxide (GO) which allows for a facile generation of paramagnetic centers from two diamagnetic components. Coordination attachment of [Ni(cyclam)]{sup 2+} or [Ni(tet b)]{sup 2+} tetraazamacrocyclic cations to carboxylic groups of GO takes place under basic conditions in aqueous-based reaction medium. The procedure is very straightforward and does not require high temperatures or other harsh conditions. Changing the coordination geometry of Ni(II) from square-planar tetracoordinated to pseudooctahedral hexacoordinated brings about the conversion from low-spin to high-spin state of the metal centers. Even though the content of tetraazamacrocyclic complexes in functionalized GO samples was found to be relatively low (nickel content of ca. 1 wt%, as determined by thermogravimetric analysis, elemental analysis and energy dispersive X-ray spectroscopy), room temperature magnetic susceptibility measurements easily detected the appearance of paramagnetic properties in GO + [Ni(cyclam)] and GO + [Ni(tet b)] nanohybrids, with effective magnetic moments of 1.95 BM and 2.2 BM for, respectively. According to density functional theory calculations, the main spin density is localized at the macrocyclic complexes, without considerable extension to graphene sheet, which suggests insignificant ferromagnetic coupling in the nanohybrids, in agreement with the results of magnetic susceptibility measurements. The coordination attachment of Ni(II) tetraazamacrocycles to GO results in considerable changes in Fourier-transform infrared and X-ray photoelectron spectra

  11. Multiporphyrin coordination arrays based on complexation of magnesium(II) porphyrins with porphyrinylphosphine oxides. (United States)

    Atefi, Farzad; McMurtrie, John C; Arnold, Dennis P


    Di- and triporphyrin arrays consisting of 5,15-diphenylporphyrinatomagnesium(II) (MgDPP) coordinated to free-base and Ni(II) porphyrinyl mono- and bis-phosphine oxides, as well as the self-coordinating diphenyl[10,20-diphenylporphyrinatomagnesium(II)-5-yl]phosphine oxide [MgDPP(Ph(2)PO)], were synthesised in excellent yields and characterised by various spectroscopic techniques. Phosphine oxides stabilise Mg(II) coordination to porphyrins and the resulting complexes have convenient solubilities, while the Ni(II) complexes exhibit interesting intramolecular fluorescence quenching behaviour. The binding constant of MgDPP to triphenylphosphine oxide (5.3 +/- 0.1 x 10(5) M(-1)) and the very high self-association constant of [MgDPP(Ph(2)PO)] (5.5 +/- 0.5 x 10(8) M(-1)) demonstrate the strong affinity of phosphine oxides towards Mg(II) porphyrins. These complexes are the first strongly bound synthetic Mg(II) multiporphyrin complexes and could potentially mimic the "special pair" in the photosynthetic reaction centre.

  12. Social dilemmas and individual/group coordination strategies in a complex rural land-use game

    Directory of Open Access Journals (Sweden)

    Luis García-Barrios


    Full Text Available Strengthening ongoing bottom-up capacity building processes for local and sustainable landscape-level governance is a multi-dimensional social endeavor. One of the tasks involved – participatory rural land use planning – requires more understanding and more awareness among all stakeholders regarding the social dilemmas local people confront when responding to each other’s land-use decisions. In this paper we will analyze and discuss a version of our game SIERRA SPRINGS that is simple to play for any stakeholder that can count to 24, yet entails a complex-coordination land use game – with an extensive and yet finite set of solutions – which can mimic in a stylized form some of the dilemmas landowners could confront in a landscape planning process where there livelihoods are at stake. The game has helped researchers and players observe and reflect on the individual coordination strategies that emerge within a group in response to these stylized dilemmas. This paper (1 develops a game-theoretical approach to cooperation, competition and coordination of land uses in small rural watersheds, (2 describe the goal, rules and mechanics of the game, (3 analyzes the structure of each farms’ solution set vs. the whole watershed’s solution set, (4 derives from them the coordination dilemmas and the risk of coordination failure, (5 describes four individual coordination strategies consistently displayed by players; mapping them in a plane we have called Group-Level Coordination Space, and (6 discusses the strengths, limitations and actual and potential uses of the game both for research and as an introductory tool for stakeholders involved in participatory land use planning.

  13. An europium(III) diglycolamide complex: insights into the coordination chemistry of lanthanides in solvent extraction. (United States)

    Antonio, Mark R; McAlister, Daniel R; Horwitz, E Philip


    The synthesis, stoichiometry, and structural characterization of a homoleptic, cationic europium(III) complex with three neutral tetraalkyldiglycolamide ligands are reported. The tri(bismuth tetrachloride)tris(N,N,N',N'-tetra-n-octyldiglycolamide)Eu salt, [Eu(TODGA)3][(BiCl4)3] obtained from methanol was examined by Eu L3-edge X-ray absorption spectroscopy (XAS) to reveal an inner-sphere coordination of Eu(3+) that arises from 9 O atoms and two next-nearest coordination spheres that arise from 6 carbon atoms each. A structural model is proposed in which each TODGA ligand with its O=Ca-Cb-O-Cb-Ca=O backbone acts as a tridentate O donor, where the two carbonyl O atoms and the one ether O atom bond to Eu(3+). Given the structural rigidity of the tridentate coordination motif in [Eu(TODGA)3](3+) with six 5-membered chelate rings, the six Eu-Ca and six Eu-Cb interactions are readily resolved in the EXAFS (extended X-ray absorption fine structure) spectrum. The three charge balancing [BiCl4](-) anions are beyond the cationic [Eu(TODGA)3](3+) cluster in an outer sphere environment that is too distant to be detected by XAS. Despite their sizeable length and propensity for entanglement, the four n-octyl groups of each TODGA (for a total of twelve) do not perturb the Eu(3+) coordination environment over that seen from previously reported single-crystal structures of tripositive lanthanide (Ln(3+)) complexes with tetraalkyldiglycolamide ligands (of the same 1:3 metal-to-ligand ratio stoichiometry) but having shorter i-propyl and i-butyl groups. The present results set the foundation for understanding advanced solvent extraction processes for the separation of the minor, tripositive actinides (Am, Cm) from the Ln(3+) ions in terms of the local structure of Eu(3+) in a solid state coordination complex with TODGA.

  14. A Rac1-GDP Trimer Complex Binds Zinc with Tetrahedral and Octahedral Coordination, Displacing Magnesium

    Energy Technology Data Exchange (ETDEWEB)

    Prehna,G.; Stebbins, E.


    The Rho family of small GTPases represent well characterized signaling molecules that regulate many cellular functions such as actin cytoskeletal arrangement and the cell cycle by acting as molecular switches. A Rac1-GDP-Zn complex has been crystallized in space group P3{sub 2}21 and its crystal structure has been solved at 1.9 {angstrom} resolution. These trigonal crystals reveal the unexpected ability of Rac1 to coordinate Zn atoms in a tetrahedral fashion by use of its biologically relevant switch I and switch II regions. Upon coordination of zinc, the switch I region is stabilized in the GDP-bound conformation and contributes to a Rac1 trimer in the asymmetric unit. Zinc coordination causes switch II to adopt a novel conformation with a symmetry-related molecule. Additionally, zinc was found to displace magnesium from its octahedral coordination at switch I, although GDP binding remained stable. This structure represents the first reported Rac1-GDP-Zn complex, which further underscores the conformational flexibility and versatility of the small GTPase switch regions.

  15. A Rac1--GDP trimer complex binds zinc with tetrahedral and octahedral coordination, displacing magnesium

    Energy Technology Data Exchange (ETDEWEB)

    Prehna, G.; Stebbins, C


    The Rho family of small GTPases represent well characterized signaling molecules that regulate many cellular functions such as actin cytoskeletal arrangement and the cell cycle by acting as molecular switches. A Rac1-GDP-Zn complex has been crystallized in space group P3221 and its crystal structure has been solved at 1.9 {angstrom} resolution. These trigonal crystals reveal the unexpected ability of Rac1 to coordinate Zn atoms in a tetrahedral fashion by use of its biologically relevant switch I and switch II regions. Upon coordination of zinc, the switch I region is stabilized in the GDP-bound conformation and contributes to a Rac1 trimer in the asymmetric unit. Zinc coordination causes switch II to adopt a novel conformation with a symmetry-related molecule. Additionally, zinc was found to displace magnesium from its octahedral coordination at switch I, although GDP binding remained stable. This structure represents the first reported Rac1-GDP-Zn complex, which further underscores the conformational flexibility and versatility of the small GTPase switch regions.

  16. Prebiotic coordination chemistry: The potential role of transition-metal complexes in the chemical evolution (United States)

    Beck, M.


    In approaching the extremely involved and complex problem of the origin of life, consideration of the coordination chemistry appeared not only as a possibility but as a necessity. The first model experiments appear to be promising because of prebiotic-type synthesis by means of transition-metal complexes. It is especially significant that in some instances various types of vitally important substances (nucleic bases, amino acids) are formed simultaneously. There is ground to hope that systematic studies in this field will clarify the role of transition-metal complexes in the organizatorial phase of chemical evolution. It is obvious that researchers working in the fields of the chemistry of cyano and carbonyl complexes, and of the catalytic effect of transition-metal complexes are best suited to study these aspects of the attractive and interesting problem of the origin of life.

  17. Coordination diversity of new mononucleating hydrazone in 3d metal complexes: Synthesis, characterization and structural studies

    Directory of Open Access Journals (Sweden)



    Full Text Available The mononucleating hydrazone ligand LH3, a condensation product of salicyloylhydrazine and (2-formylphenoxyacetic acid, was synthesized and its coordination behavior with first row transition metal(II ions was investigated by isolating and elucidating the structure of the complexes using elemental analysis, conductivity and magnetic susceptibility measurements, as well as IR, 1H-NMR, electronic and EPR spectral techniques. The ligand forms mononuclear metal(II complexes of the type [CoLH(H2O2], [NiLH(H2O2, [CuLH] and [ZnLH]. The ligand field parameters, Dq, B and b values, in the case of the cobalt and nickel complexes support not only the octahedral geometry around the metal ion, but also imply the covalent nature of the bonding in the complexes. The EPR study revealed the presence of a spin exchange interaction in the solid copper complex and the covalent nature of the bonding. The 1H-NMR study of the zinc(II complex indicated the non-involvement of the COOH group in the coordination. The physico-chemical study supports for the presence of octahedral geometry around cobalt(II, nickel(II and tetrahedral geometry around copper(II and zinc(II ions.

  18. Synthesis, characterization and photochemistry of a new heptamolybdate supported magnesium-aqua coordination complex

    Indian Academy of Sciences (India)

    Savita S Khandolkar; Pallepogu Raghavaiah; Bikshandarkoil R Srinivasan


    The synthesis, crystal structure, redox characteristics and photochemistry of a new heptamolyb-date supported magnesium-aqua coordination complex viz. (hmtH)2 [{Mg(H2O)5}2 {Mo7O24}]·3H2O 1 (hmt = hexamethylenetetramine) is reported. The cyclic voltammogram reveals quasireversible redox behaviour while the degradation of rhodamine B (RhB) by 1 under sunlight irradiation indicates its photocatalytic activity. In the crystal structure of 1, two [Mg(H2O)5]2+ units are linked by a 2-bridging bidentate hepta-molybdate ligand resulting in a heptamolybdate supported magnesium-aqua coordinated dianionic complex [{Mg(H2O)5}2 {Mo7O24}]2− charge balanced by two (hmtH)+ cations. The cations, anions and the lattice water molecules are linked by several hydrogen bonding interactions.

  19. Fluorescent zinc-terpyridine complex containing coordinated peroxo counter ion in aqueous medium

    Indian Academy of Sciences (India)

    S Kapoor; M S Sastry


    We describe a mixed ligand-zinc (10) complex containing coordinated peroxo ion and 2,2'2"-terpyridine and exhibiting fluorescence in the visible region (473 nm) on excitation at 390 nm in aqueous medium at room temperature. We also discuss the unusual phenomenon of enhancement of this fluorescence intensity on addition of some transition metal ions (35, 310, 40 and 39 electronic configurations).

  20. Dipyridylamide ligand dependent dimensionality in luminescent zinc 2,4-pyridinedicarboxylate coordination complexes (United States)

    Wudkewych, Megan J.; LaDuca, Robert L.


    Zinc nitrate, 2,4-pyridinedicarboxylic acid (2,4-pdcH2), and a hydrogen-bonding capable dipyridylamide ligand were combined in aqueous solution and subjected to hydrothermal reaction conditions. Three new crystalline coordination complexes were generated; their dimensionality depends crucially on the dipyridylamide length and geometric disposition of the pyridyl nitrogen donors. The three new phases were structurally characterized via single-crystal X-ray diffraction. {[H23-pina][Zn(2,4-pdc)2(H2O)2]·H2O} (1, 3-pina = 3-pyridylisonicotinamide) is a salt with protonated dipyridylamide cations and coordination complex anions. {[Zn2(2,4-pdc)2(H2O)4(3-pna)]·3H2O}n (2, 3-pna = 3-pyridylnicotinamide) shows a system of two-fold interpenetrated ruffled (6,3) coordination polymer layers. {[Zn(2,4-pdc)(H2O)2(3-pmna)]n (3, 3-pmna = 3-pyridylmethylnicotinamide) manifests a simple 1D chain topology. Luminescence was observed for two of the zinc complexes; this behavior is attributed to π-π* or π-n molecular orbital transitions. Thermal decomposition properties of the new phases are also probed.

  1. Flexible and Asymmetric Ligand in Constructing Coordinated Complexes: Synthesis, Crystal Structures and Fluorescent Characterization

    Directory of Open Access Journals (Sweden)

    Jianhua Lin


    Full Text Available Flexible and asymmetric ligand L [L = 1-((pyridin-3-ylmethyl-1H-benzotriazole], is used as a basic backbone to construct complicated metal-organic frameworks. Two new polymers, namely, [Ag2(L2(NO32]n (1 and [Ag(L(ClO4]n (2, were synthesized and characterized by X-ray structure analysis and fluorescent spectroscopy. The complex 1 gives an “S” type double helical conformation, whereas complex 2 exhibits a 1D zigzag configuration. Different anions affect the silver coordination geometry and crystal packing topology.

  2. Coordination chemistry and reactivity of zinc complexes supported by a phosphido pincer ligand. (United States)

    D'Auria, Ilaria; Lamberti, Marina; Mazzeo, Mina; Milione, Stefano; Roviello, Giuseppina; Pellecchia, Claudio


    The preparation and characterization of new Zn(II) complexes of the type [(PPP)ZnR] in which R = Et (1) or N(SiMe(3))(2) (2) and PPP is a tridentate monoanionic phosphido ligand (PPP-H = bis(2-diphenylphosphinophenyl)phosphine) are reported. Reaction of ZnEt(2) and Zn[N(SiMe(3))(2)](2) with one equivalent of proligand PPP-H produced the corresponding tetrahedral zinc ethyl (1) and zinc amido (2) complexes in high yield. Homoleptic (PPP)(2) Zn complex 3 was obtained by reaction of the precursors with two equivalents of the proligand. Structural characterization of 1-3 was achieved by multinuclear NMR spectroscopy ((1)H, (13)C, and (31)P) and X-ray crystallography (3). Variable-temperature (1)H and (31)P NMR studies highlighted marked flexibility of the phosphido pincer ligand in coordination at the metal center. A DFT calculation on the compounds provided theoretical support for this behavior. The activities of 1 and 2 toward the ring-opening polymerization of ε-caprolactone and of L- and rac-lactide were investigated, also in combination with an alcohol as external chain-transfer agent. Polyesters with controlled molecular parameters (M(n), end groups) and low polydispersities were obtained. A DFT study on ring-opening polymerization promoted by these complexes highlighted the importance of the coordinative flexibility of the ancillary ligand to promote monomer coordination at the reactive zinc center. Preliminary investigations showed the ability of these complexes to promote copolymerization of L-lactide and ε-caprolactone to achieve random copolymers whose microstructure reproduces the composition of the monomer feed.

  3. Coordination Nature of 4-Mercaptoaniline to Sn(II Ion: Formation of a One Dimensional Coordination Polymer and Its Decomposition to a Mono Nuclear Sn(IV Complex

    Directory of Open Access Journals (Sweden)

    Eon S. Burkett


    Full Text Available The coordination of the bifunctional ligand 4-mercaptoaniline with aqueo us tin(II metal ion was studied. A coordination polymer was synthesized when an aqueous solution of SnCl2 was treated with 4-MA. The crystalline material is stable under atmospheric conditions retaining its oxidation state. However, when submerged in a solution saturated with oxygen, the compound oxidizes to a mononuclear tin(IV complex. Both the compounds were characterized by single crystal X-ray diffraction studies. Although the structure of the tin(IV complex was previously reported, crystal structure of this compound was redetermined.

  4. Kinetic and Thermodynamic Stabilization of Metal Complexes by Introverted Coordination in a Calix[6]azacryptand. (United States)

    Inthasot, Alex; Brunetti, Emilio; Lejeune, Manuel; Menard, Nicolas; Prangé, Thierry; Fusaro, Luca; Bruylants, Gilles; Reinaud, Olivia; Luhmer, Michel; Jabin, Ivan; Colasson, Benoit


    The Huisgen thermal reaction between an organic azide and an acetylene was employed for the selective monofunctionalization of a X6 -azacryptand ligand bearing a tren coordinating unit [X6 stands for calix[6]arene and tren for tris(2-aminoethyl)amine]. Supramolecular assistance, originating from the formation of a host-guest inclusion complex between the reactants, greatly accelerates the reaction while self-inhibition affords a remarkable selectivity. The new ligand possesses a single amino-leg appended at the large rim of the calixarene core and the corresponding Zn(2+) complex was characterized both in solution and in the solid state. The coordination of Zn(2+) not only involves the tren cap but also the introverted amino-leg, which locks the metal ion in the cavity. Compared with the parent ligand deprived of the amino-leg, the affinity of the new monofunctionalized X6 tren ligand 6 for Zn(2+) is found to have a 10-fold increase in DMSO, which is a very competitive solvent, and with an enhancement of at least three orders of magnitude in CDCl3 /CD3 OD (1:1, v/v). In strong contrast with the fast binding kinetics, decoordination of Zn(2+) as well as transmetallation appeared to be very slow processes. The monofunctionalized X6 tren ligand 6 fully protects the metal ion from the external medium thanks to the combination of a cavity and a closed coordination sphere, leading to greater thermodynamic and kinetic stabilities.

  5. Coordination geometry around copper in a Schiff-base trinuclear copper complex using EXAFS spectroscopy (United States)

    Gaur, Abhijeet; Shrivastava, B. D.; Gaur, D. C.; Prasad, J.; Srivastava, K.; Jha, S. N.; Bhattacharyya, D.; Poswal, A.


    In the present investigation, we have studied extended X-ray absorption fine structure (EXAFS) spectra of a trinuclear Schiff-base copper complex tetraaqua-di-μ3-(N-salicylidene-DL-glutamato)-tricopper(II)heptahydrate, [Cu3(C12H10NO5)2 (H2O)4]. 7H2O, in which three metal sites are present. One metal site is square-pyramidal (4+1) and other two similar metal sites are tetragonally distorted octahedral (4+2). EXAFS has been recorded at the K-edge of copper in the complex at the dispersive EXAFS beamline at 2 GeV Indus-2 synchrotron source at RRCAT, Indore, India. The analysis of EXAFS spectra of multinuclear metal complexes pose some problems due to the presence of many absorbing atoms, even when the absorbing atoms may be of the same element. Hence, using the available crystal structure of the complex, theoretical models have been generated for the different copper sites separately, which are then fitted to the experimental EXAFS data. The two coordination geometries around the copper sites have been determined. The contributions of the different copper sites to the experimental spectrum have been estimated. The structural parameters, which include bond-lengths, coordination numbers and thermal disorders, for the two types of copper sites have been reported. Further, copper has been found to be in +2 oxidation state at these metal sites.

  6. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination (United States)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-ichi


    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9]3−), tungsten ([WH9]3−), niobium ([NbH9]4−) and tantalum ([TaH9]4−) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature. PMID:28287143

  7. Formation of novel transition metal hydride complexes with ninefold hydrogen coordination. (United States)

    Takagi, Shigeyuki; Iijima, Yuki; Sato, Toyoto; Saitoh, Hiroyuki; Ikeda, Kazutaka; Otomo, Toshiya; Miwa, Kazutoshi; Ikeshoji, Tamio; Orimo, Shin-Ichi


    Ninefold coordination of hydrogen is very rare, and has been observed in two different hydride complexes comprising rhenium and technetium. Herein, based on a theoretical/experimental approach, we present evidence for the formation of ninefold H- coordination hydride complexes of molybdenum ([MoH9](3-)), tungsten ([WH9](3-)), niobium ([NbH9](4-)) and tantalum ([TaH9](4-)) in novel complex transition-metal hydrides, Li5MoH11, Li5WH11, Li6NbH11 and Li6TaH11, respectively. All of the synthesized materials are insulated with band gaps of approximately 4 eV, but contain a sufficient amount of hydrogen to cause the H 1s-derived states to reach the Fermi level. Such hydrogen-rich materials might be of interest for high-critical-temperature superconductivity if the gaps close under compression. Furthermore, the hydride complexes exhibit significant rotational motions associated with anharmonic librations at room temperature, which are often discussed in relation to the translational diffusion of cations in alkali-metal dodecahydro-closo-dodecaborates and strongly point to the emergence of a fast lithium conduction even at room temperature.

  8. Heterobimetallic coordination polymers involving 3d metal complexes and heavier transition metals cyanometallates

    Energy Technology Data Exchange (ETDEWEB)

    Peresypkina, Eugenia V. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Samsonenko, Denis G. [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Vostrikova, Kira E., E-mail: [Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk 630090 (Russian Federation); LMI, Université Claude Bernard Lyon 1, 69622 Villeurbanne Cedex (France)


    The results of the first steps in the design of coordination polymers based on penta- and heptacyanometallates of heavier d transitions metals are presented. The 2D structure of the coordination polymers: [(Mn(acacen)){sub 2}Ru(NO)(CN){sub 5}]{sub n} and two complexes composed of different cyanorhenates, [Ni(cyclam)]{sub 2}[ReO(OH)(CN){sub 4}](ClO{sub 4}){sub 2}(H{sub 2}O){sub 1.25} and [Cu(cyclam)]{sub 2}[Re(CN){sub 7}](H{sub 2}O){sub 12}, was confirmed by single crystal XRD study, the rhenium oxidation state having been proved by the magnetic measurements. An amorphism of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} (M=Ni, Cu) polymers does not allow to define strictly their dimensionality and to model anisotropic magnetic behavior of the compounds. However, with high probability a honey-comb like layer structure could be expected for [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2} complexes, studied in this work, because such an arrangement is the most common among the bimetallic assemblies of hexa- and octacyanometallates with a ratio [M(cyclam)]/[M(CN){sub n}]=3/2. For the first time was prepared and fully characterized a precursor (n-Bu{sub 4}N){sub 2}[Ru(NO)(CN){sub 5}], soluble in organic media. - Graphical abstract: The very first results in the design of 2D coordination polymers based on penta- and heptacyanometallates of 4d and5d transitions metals are presented. - Highlights: • Design of coordination polymers based on penta- and heptacyanometallates. • New Ru and Re cyanide based heterobimetallic coordination complexes. • Hydrolysis and ox/red processes involving [Re(CN){sub 7}]{sup 3+} during crystallization. • High magnetic anisotropy of [M(cyclam)]{sub 3}[Re(CN){sub 7}]{sub 2}(H{sub 2}O){sub n}, M=Cu, Ni, complexes.

  9. Ligand design for site-selective metal coordination: synthesis of transition-metal complexes with η{sup 6}-coordination of the central ring of anthracene

    Energy Technology Data Exchange (ETDEWEB)

    Karslyan, Eduard E.; Borissova, Alexandra O.; Perekalin, Dmitry S. [Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow (Russian Federation)


    A polycyclic aromatic ligand for site-selective metal coordination was designed by using DFT calculations. The computational prediction was confirmed by experiments: 2,3,6,7-tetramethoxy-9,10-dimethylanthracene initially reacts with [(C{sub 5}H{sub 5})Ru(MeCN){sub 3}]BF{sub 4} to give the kinetic product with a [(C{sub 5}H{sub 5})Ru]{sup +} fragment coordinated at the terminal ring, which is then transformed into the thermodynamic product with coordination through the central ring. These isomeric complexes have markedly different UV/Vis spectra, which was explained by analysis of the frontier orbitals. At the same time, the calculations suggest that electrostatic interactions are mainly responsible for the site selectivity of the coordination. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Coordination field calculation for rare earth complexes in dihedral symmetry field

    Institute of Scientific and Technical Information of China (English)

    范英芳; 杨频; 潘大丰; 王越奎


    The coordination field perturbation matrix element expressions about D2-field of the terms 2S+1Lf (J=0 - 8 and 7=1/2 - 15/2) with fN (N=1 -13) configuration have been derived The concrete forms of the DSCPCF parameters Akm in the dihedral field (D2, C2v) for various ligand numbers (5 -12) and their reducing behavior in the higher symmetry fields (D4, C4v, D2d, D4d, D2k, D4h and Oh) are discussed with the double sphere coordination point charge field (DSCPCF) model and the irreducible operator tensor method. Besides, the corresponding computational schemes have been developed and the computer program DSF.D has been compiled, which is applicable for the spectral analysis of the rare earth ion complexes with arbitrary ligand numbers in the dihedral, tetragonal and cubical symmetry fields.

  11. Hardware Implementation of a Modified Delay-Coordinate Mapping-Based QRS Complex Detection Algorithm

    Directory of Open Access Journals (Sweden)

    Andrej Zemva


    Full Text Available We present a modified delay-coordinate mapping-based QRS complex detection algorithm, suitable for hardware implementation. In the original algorithm, the phase-space portrait of an electrocardiogram signal is reconstructed in a two-dimensional plane using the method of delays. Geometrical properties of the obtained phase-space portrait are exploited for QRS complex detection. In our solution, a bandpass filter is used for ECG signal prefiltering and an improved method for detection threshold-level calculation is utilized. We developed the algorithm on the MIT-BIH Arrhythmia Database (sensitivity of 99.82% and positive predictivity of 99.82% and tested it on the long-term ST database (sensitivity of 99.72% and positive predictivity of 99.37%. Our algorithm outperforms several well-known QRS complex detection algorithms, including the original algorithm.

  12. Functional cooperation between FACT and MCM is coordinated with cell cycle and differential complex formation

    Directory of Open Access Journals (Sweden)

    Lin Chih-Li


    Full Text Available Abstract Background Functional cooperation between FACT and the MCM helicase complex constitutes an integral step during DNA replication initiation. However, mode of regulation that underlies the proper functional interaction of FACT and MCM is poorly understood. Methods & Results Here we present evidence indicating that such interaction is coordinated with cell cycle progression and differential complex formation. We first demonstrate the existence of two distinct FACT-MCM subassemblies, FACT-MCM2/4/6/7 and FACT-MCM2/3/4/5. Both complexes possess DNA unwinding activity and are subject to cell cycle-dependent enzymatic regulation. Interestingly, analysis of functional attributes further suggests that they act at distinct, and possibly sequential, steps during origin establishment and replication initiation. Moreover, we show that the phosphorylation profile of the FACT-associated MCM4 undergoes a cell cycle-dependent change, which is directly correlated with the catalytic activity of the FACT-MCM helicase complexes. Finally, at the quaternary structure level, physical interaction between FACT and MCM complexes is generally dependent on persistent cell cycle and further stabilized upon S phase entry. Cessation of mitotic cycle destabilizes the complex formation and likely leads to compromised coordination and activities. Conclusions Together, our results correlate FACT-MCM functionally and temporally with S phase and DNA replication. They further demonstrate that enzymatic activities intrinsically important for DNA replication are tightly controlled at various levels, thereby ensuring proper progression of, as well as exit from, the cell cycle and ultimately euploid gene balance.

  13. Desymmetrization of an Octahedral Coordination Complex Inside a Self-Assembled Exoskeleton. (United States)

    Johnstone, Mark D; Schwarze, Eike K; Ahrens, Jennifer; Schwarzer, Dirk; Holstein, Julian J; Dittrich, Birger; Pfeffer, Frederick M; Clever, Guido H


    The synthesis of a centrally functionalized, ribbon-shaped [6]polynorbornane ligand L that self-assembles with Pd(II) cations into a {Pd2 L4 } coordination cage is reported. The shape-persistent {Pd2 L4 } cage contains two axial cationic centers and an array of four equatorial H-bond donors pointing directly towards the center of the cavity. This precisely defined supramolecular environment is complementary to the geometry of classic octahedral complexes [M(XY)6 ] with six diatomic ligands. Very strong binding of [Pt(CN)6 ](2-) to the cage was observed, with the structure of the host-guest complex {[Pt(CN)6 ]@Pd2 L4 } supported by NMR spectroscopy, MS, and X-ray data. The self-assembled shell imprints its geometry on the encapsulated guest, and desymmetrization of the octahedral platinum species by the influence of the D4h -symmetric second coordination sphere was evidenced by IR spectroscopy. [Fe(CN)6 ](3-) and square-planar [Pt(CN)4 ](2-) were strongly bound. Smaller octahedral anions such as [SiF6 ](2-) , neutral carbonyl complexes ([M(CO)6 ]; M=Cr, Mo, W) and the linear [Ag(CN)2 ](-) anion were only weakly bound, showing that both size and charge match are key factors for high-affinity binding.

  14. Talking about the institutional complexity of the integrated rehabilitation system – the importance of coordination

    Directory of Open Access Journals (Sweden)

    Sari Miettinen


    Full Text Available Rehabilitation in Finland is a good example of functions divided among several welfare sectors, such as health services and social services.  The rehabilitation system in Finland is a complex one and there have been many efforts to create a coordinated entity. The purpose of this study is to open up a complex welfare system at the upper policy level and to understand the meaning of coordination at the level of service delivery. We shed light in particular on the national rehabilitation policy in Finland and how the policy has tried to overcome the negative effects of institutional complexity. In this study we used qualitative content analysis and frame analysis. As a result we identified four different welfare state frames with distinct features of policy problems, policy alternatives and institutional failure. The rehabilitation policy in Finland seems to be divided into different components which may cause problems at the level of service delivery and thus in the integration of services. Bringing these components together could at policy level enable a shared view of the rights of different population groups, effective management of integration at the level of service delivery and also an opportunity for change throughout the rehabilitation system.

  15. An aqueous non-heme Fe(iv)oxo complex with a basic group in the second coordination sphere

    DEFF Research Database (Denmark)

    Vad, Mads Sørensen; Lennartson, Anders; Nielsen, Anne;


    The Fe(iv)oxo complex of a coordinatively flexible multidentate mono-carboxylato ligand is obtained by the one electron oxidation of a low spin Fe(iii) precursor in water.......The Fe(iv)oxo complex of a coordinatively flexible multidentate mono-carboxylato ligand is obtained by the one electron oxidation of a low spin Fe(iii) precursor in water....

  16. Synthesis and reactivity of a conveniently prepared two-coordinate bis(amido) nickel(II) complex. (United States)

    Lipschutz, Michael I; Tilley, T Don


    A strictly two-coordinate nickel(II) bis(amido) complex has been prepared and its reactivity towards a variety of small molecules is described. Ni[N(SiMe(3))(DIPP)](2) reacts with DMAP and acetonitrile to form T-shaped three-coordinate complexes, and preliminary results show that Ni[N(SiMe(3))(DIPP)](2) is a catalyst for the hydrosilation of olefins with secondary silanes at ambient temperature.

  17. Investigation on the Coordinate Structures of the Rare Earth Metal Complexes with Edta and Cydta Ligands

    Institute of Scientific and Technical Information of China (English)

    WangJun; ZhangXiang-dong; ZhangYang; LiuZhen-rong


    The crystal and molecular structures of cydta(trans-1, 2-cyclohexanediaminetetraacetic acid) have been determined by single-crystal X-ray structure analyses. The reasons that REⅢ-edta and REⅢ-cydta complexes select different coordinate structures were discussed and illustrated through the comparison of the molecular and crystal structures between edta and cydta, (NH4)[Ⅲ(edta) (H2O)3]·5H2O and (NH4)[YⅢ(cydta)(H2O)2]·5H2O as well as (NH4)[GdⅢ(edta)(H2O)3]·5H2O and (NH4)[GdⅢ(cydta)(H2O)2]·5H2O complexes.

  18. Investigation on the Coordinate Structures of the Rare Earth Metal Complexes with Edta and Cydta Ligands

    Institute of Scientific and Technical Information of China (English)

    Wang Jun; Zhang Xiang-dong; Zhang Yang; Liu Zhen-rong


    The crystal and molecular structures of cydta (trans-1, 2-cyclohexanediaminetetraacetic acid) have been determined by single-crystal X-ray structure analyses. The reasons that REⅢ-edta and REⅢ-cydta complexes select different coordinate structures were discussed and illustrated through the comparison of the molecular and crystal structures between edta and cydta, (NH4)[YⅢ(edta)(H2O)3]*5H2O and (NH4)[YⅢ(cydta)(H2O)2]*5H2O as well as (NH4)[GdⅢ(edta)(H2O)3]*5H2O and (NH4)[GdⅢ(cydta)(H2O)2]*5H2O complexes.

  19. Synthesis and Characterization of Metal-B-diketonate Coordination Complexes and Polymers

    Directory of Open Access Journals (Sweden)

    Mohammed A. Al-Anber


    Full Text Available A mononuclear [M(tba2(H2O2] (3: M = Mn, 4: M = Ni, 5: M = Zn; tba = deprotonated of 1 complexes have been prepared by the reaction of 3-benzoyl-1.1.1-trifluoro-acetone (H-tba: 1 with M(OAc2.nH2O (M = Mn, Ni, Zn; OAc = O2CMe in a 2:1 molar ratio. Complexes 3 - 5 can be extended to form a coordination polymers of general formula [M(tba2(4,4'-bipy]n (6: M = Mn, 7: M = Ni, 8: M = Zn; tba = 3-benzoyl-1.1.1-trifluoro-acetone; 4,4'-bipy = 4,4’-bipyridine by bridging the central metal atom with 4,4’-bipyridine (4,4'-bipy. The reaction progress was controlled via FTIR, UV-Vis spectroscopy and elemental analysis.

  20. Synthesis, characterization, and alkyne trimerization catalysis of a heteroleptic two-coordinate fe(i) complex. (United States)

    Lipschutz, Michael I; Chantarojsiri, Teera; Dong, Yuyang; Tilley, T Don


    The synthesis of the first heteroleptic, two-coordinate Fe(I) complex IPr-Fe-N(SiMe3)DIPP (1) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; DIPP = 2,6-(i)Pr2-C6H3) is reported. Protonation of the Fe(II) bis(amido) complex Fe[N(SiMe3)DIPP]2 followed by addition of IPr and reduction by potassium graphite in a one-pot reaction results in good yields of 1. The redox activity of 1 and comparison between 1 and its reduction product by (57)Fe Mössbauer spectroscopy are discussed, and the reduction was found to be metal-based rather than ligand-based. The activity of 1 toward the catalytic cyclotrimerization of terminal and internal alkynes is described.

  1. Antitumor properties of five-coordinate gold(III) complexes bearing substituted polypyridyl ligands. (United States)

    Sanghvi, Chinar D; Olsen, Pauline M; Elix, Catherine; Peng, Shifang Bruce; Wang, Dongsheng; Chen, Zhuo Georgia; Shin, Dong M; Hardcastle, Kenneth I; MacBeth, Cora E; Eichler, Jack F


    In an on-going effort to discover metallotherapeutic alternatives to the chemotherapy drug cisplatin, neutral distorted square pyramidal gold(III) coordination complexes possessing 2,9-disubstituted-1,10-phenanthroline ligands {[((R)phen)AuCl3]; R = n-butyl, sec-butyl} have been previously synthesized and characterized. A structurally analogous gold(III) complex bearing a 6,6'-di-methylbipyridine ligand ([((methyl)bipy)AuCl3]) has been synthesized and fully characterized to probe the effect of differing aromatic character of the ligand on solution stability and tumor cell cytotoxicity. The two compounds [((sec-butyl)phen)AuCl3] and [((methyl)bipy)AuCl3]) were subsequently assessed for their stability against the biological reductant glutathione, and it was found that the [((sec-butyl)phen)AuCl3] complex exhibits slightly enhanced stability compared to the [((methyl)bipy)AuCl3] complex and significantly higher stability than previously reported square planar gold(III) complex ions. Furthermore, these complexes were tested for cytotoxic effects against existing lung and head and neck cancer cell lines in vitro. The [((sec-butyl)phen)AuCl3] complex was found to be more cytotoxic than cisplatin against five different tumor cell lines, whereas [((methyl)bipy)AuCl3] had more limited in vitro antitumor activity. Given that [((sec-butyl)phen)AuCl3] had significantly higher antitumor activity, it was tested against an in vivo tumor model. It was found that this complex did not significantly reduce the growth of xenograft tumors in mice and initial model binding studies with bovine serum albumin indicate that interactions with serum albumin proteins may be the cause for the limited in vivo activity of this potential metallotherapeutic.

  2. Small molecule regulation of self-association and catalytic activity in a supramolecular coordination complex. (United States)

    McGuirk, C Michael; Stern, Charlotte L; Mirkin, Chad A


    Herein, we report the synthesis and characterization of the first weak-link approach (WLA) supramolecular construct that employs the small molecule regulation of intermolecular hydrogen bonding interactions for the in situ control of catalytic activity. A biaryl urea group, prone to self-aggregation, was functionalized with a phosphinoalkyl thioether (P,S) hemilabile moiety and incorporated into a homoligated Pt(II) tweezer WLA complex. This urea-containing construct, which has been characterized by a single crystal X-ray diffraction study, can be switched in situ from a rigid fully closed state to a flexible semiopen state via Cl(-) induced changes in the coordination mode at the Pt(II) structural node. FT-IR and (1)H NMR spectroscopy studies were used to demonstrate that while extensive urea self-association persists in the flexible semiopen complex, these interactions are deterred in the rigid, fully closed complex because of geometric and steric restraints. Consequently, the urea moieties in the fully closed complex are able to catalyze a Diels-Alder reaction between cyclopentadiene and methyl vinyl ketone to generate 2-acetyl-5-norbornene. The free urea ligand and the semiopen complex show no such activity. The successful incorporation and regulation of a hydrogen bond donating catalyst in a WLA construct open the doors to a vast and rapidly growing catalogue of allosteric catalysts for applications in the detection and amplification of organic analytes.

  3. Synthesis And Third-order Nonlinear Optical Studies of Four-Coordinated Copper(I) Complexes (United States)

    Kumar, H. C. Sampath; Rudresha, B. J.; Bhat, B. Ramachandra; Philip, Reji; Row, T. N. Guru


    Three Cu(I) halide complexes [Cu(L)(PPh3)X] (L = 1,10-phenanthroline, X = Cl (1), Br (2) and I (3), PPh3 = triphenylphosphine) have been synthesised and characterised by spectroscopic techniques. Further structure of the complex 1 was confirmed by single crystal X-ray diffraction analysis. The nonlinear optical properties of the complexes were investigated at 532 nm using single beam Z-scan technique with nanosecond laser pulses. The complexes showed strong optical limiting behavior due to effective three-photon absorption (3PA). The values of 3PA coefficients (γ) for 1, 2 and 3 were found to be 3.2×10-24 m3/W2, 6.0×10-25 m3/W2 and 1.2×10-23 m3/W2 respectively, which are comparable to good optical limiting materials. These studies demonstrate that the Ligand→copper coordinative bonds facilitate the polarization of the electronic π-system which optimizes the third-order NLO response in the reported complexes.

  4. Intramolecular substitutions of square planar rhodium(Ⅰ) catioriic complexes of ds-dicarbonyl nitrogen coordinated tridentate

    Institute of Scientific and Technical Information of China (English)

    袁国卿; 柳忠阳; 朱长城; 潘平来; 刘世宏


    Four kinds of square planar cis-dicarbonyl-N,N-bis(2-pyridylethyl)-p-substituted-phenylamino rhodium(Ⅰ) are reported.The changes of their structures were analyzed by XPS,IR and NMR spectroscopy The results show that the weak N→Rh coordinated bond can replace very soon the strong Rh-Cπ back donation bond to form tris-nitrogen coordinated complexes due to the steric effect when the temperature is over 50℃,This reaction is reversible.The bis-nitrogen coordinated structure of the complex recovered when put under the atmosphere of CO

  5. Triply-bridged Dicopper (Ⅰ) Complex of Bis(diphenylphosphino)acetylene with a Helical Coordination Cage

    Institute of Scientific and Technical Information of China (English)


    Self-organization of copper (Ⅰ) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper (Ⅰ) complex [Cu2(μ-Ph2PC≡CPPh2)3(MeCN)2](ClO4)2(Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (Ⅰ) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the Cu(Cu separation of 6.231(A). The copper (Ⅰ) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P ī with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3)(A), ( = 98.289(1), ( = 91.232(1), ( = 106.496(1)(, V = 4117.60(9) (A)3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr = 1659.37, Dc = 1.338 g/cm3, F(000) = 1708, ( = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I > 2((I).

  6. Core-Shell Coating Silicon Anode Interfaces with Coordination Complex for Stable Lithium-Ion Batteries. (United States)

    Zhou, Jinqiu; Qian, Tao; Wang, Mengfan; Xu, Na; Zhang, Qi; Li, Qun; Yan, Chenglin


    In situ core-shell coating was used to improve the electrochemical performance of Si-based anodes with polypyrrole-Fe coordination complex. The vast functional groups in the organometallic coordination complex easily formed hydrogen bonds when in situ modifying commercial Si nanoparticles. The incorporation of polypyrrole-Fe resulted in the conformal conductive coating surrounding each Si nanoparticle, not only providing good electrical connection to the particles but also promoting the formation of a stable solid-electrolyte-interface layer on the Si electrode surface, enhancing the cycling properties. As an anode material for Li-ion batteries, modified silicon powders exhibited high reversible capacity (3567 mAh/g at 0.3 A/g), good rate property (549.12 mAh/g at 12 A/g), and excellent cycling performance (reversible capacity of 1500 mAh/g after 800 cycles at 1.2 A/g). The constructed novel concept of core-shell coating Si particles presented a promising route for facile and large-scale production of Si-based anodes for extremely durable Li-ion batteries, which provided a wide range of applications in the field of energy storage of the renewable energy derived from the solar energy, hydropower, tidal energy, and geothermal heat.

  7. Meeting the needs of children with medical complexity using a telehealth advanced practice registered nurse care coordination model. (United States)

    Cady, Rhonda G; Erickson, Mary; Lunos, Scott; Finkelstein, Stanley M; Looman, Wendy; Celebreeze, Margaret; Garwick, Ann


    Effective care coordination is a key quality and safety strategy for populations with chronic conditions, including children with medical complexity (CMC). However, gaps remain in parent report of the need for care coordination help and receipt of care coordination help. New models must close this gap while maintaining family-centered focus. A three-armed randomized controlled trial conducted in an established medical home utilized an advanced practice registered nurse intervention based on Presler's model of clinic-based care coordination. The model supported families of CMC across settings using telephone only or telephone and video telehealth care coordination. Effectiveness was evaluated from many perspectives and this paper reports on a subset of outcomes that includes family-centered care (FCC), need for care coordination help and adequacy of care coordination help received. FCC at baseline and end of study showed no significant difference between groups. Median FCC scores of 18.0-20.0 across all groups indicated high FCC within the medical home. No significant differences were found in the need for care coordination help within or between groups and over time. No significant difference was found in the adequacy of help received between groups at baseline. However, this indicator increased significantly over time for both intervention groups. These findings suggest that in an established medical home with high levels of FCC, families of CMC have unmet needs for care coordination help that are addressed by the APRN telehealth care coordination model.

  8. Design and its limitations in the construction of bi- and poly-nuclear coordination complexes and coordination polymers (aka MOFs): a personal view. (United States)

    Robson, R


    This article, presented from a personal point of view, is concerned with the design of ligands intended to give specifically either binuclear or tetranuclear metal complexes or coordination polymers. No attempt is made to provide a comprehensive coverage of these topics, the focus being mainly upon results from our laboratory. Some emphasis is placed upon aspects of the historical development of the deliberate construction of coordination polymers (aka MOFs)--materials promising useful applications, the study of which continues to expand exponentially. Some of our recent research is described in which the carbonate ion and the tetracyanoquinodimethane dianion are used as bridging ligands to generate targeted coordination polymers. It is intended that Dalton Perspectives be easily comprehensible to non-specialists in the field; an average second year university chemistry student should be easily able to understand the present contribution.

  9. A monofunctional platinum complex coordinated to a rhodium metalloinsertor selectively binds mismatched DNA in the minor groove. (United States)

    Weidmann, Alyson G; Barton, Jacqueline K


    We report the synthesis and characterization of a bimetallic complex derived from a new family of potent and selective metalloinsertors containing an unusual Rh-O axial coordination. This complex incorporates a monofunctional platinum center containing only one labile site for coordination to DNA, rather than two, and coordinates DNA nonclassically through adduct formation in the minor groove. This conjugate displays bifunctional, interdependent binding of mismatched DNA via metalloinsertion at a mismatch as well as covalent platinum binding. DNA sequencing experiments revealed that the preferred site of platinum coordination is not the traditional N7-guanine site in the major groove, but rather N3-adenine in the minor groove. The complex also displays enhanced cytotoxicity in mismatch repair-deficient and mismatch repair-proficient human colorectal carcinoma cell lines compared to the chemotherapeutic cisplatin, and it triggers cell death via an apoptotic pathway, rather than the necrotic pathway induced by rhodium metalloinsertors.

  10. Integrated complex care coordination for children with medical complexity: A mixed-methods evaluation of tertiary care-community collaboration

    Directory of Open Access Journals (Sweden)

    Cohen Eyal


    Full Text Available Abstract Background Primary care medical homes may improve health outcomes for children with special healthcare needs (CSHCN, by improving care coordination. However, community-based primary care practices may be challenged to deliver comprehensive care coordination to complex subsets of CSHCN such as children with medical complexity (CMC. Linking a tertiary care center with the community may achieve cost effective and high quality care for CMC. The objective of this study was to evaluate the outcomes of community-based complex care clinics integrated with a tertiary care center. Methods A before- and after-intervention study design with mixed (quantitative/qualitative methods was utilized. Clinics at two community hospitals distant from tertiary care were staffed by local community pediatricians with the tertiary care center nurse practitioner and linked with primary care providers. Eighty-one children with underlying chronic conditions, fragility, requirement for high intensity care and/or technology assistance, and involvement of multiple providers participated. Main outcome measures included health care utilization and expenditures, parent reports of parent- and child-quality of life [QOL (SF-36®, CPCHILD©, PedsQL™], and family-centered care (MPOC-20®. Comparisons were made in equal (up to 1 year pre- and post-periods supplemented by qualitative perspectives of families and pediatricians. Results Total health care system costs decreased from median (IQR $244 (981 per patient per month (PPPM pre-enrolment to $131 (355 PPPM post-enrolment (p=.007, driven primarily by fewer inpatient days in the tertiary care center (p=.006. Parents reported decreased out of pocket expenses (p© domains [Health Standardization Section (p=.04; Comfort and Emotions (p=.03], while total CPCHILD© score decreased between baseline and 1 year (p=.003. Parents and providers reported the ability to receive care close to home as a key benefit. Conclusions Complex

  11. Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project (United States)

    Coe, Benjamin J.


    An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

  12. Coordination Complexes as Catalysts: The Oxidation of Anthracene by Hydrogen Peroxide in the Presence of VO(acac)[subscript 2 (United States)

    Charleton, Kimberly D. M.; Prokopchuk, Ernest M.


    A laboratory experiment aimed at students who are studying coordination chemistry of transition-metal complexes is described. A simple vanadyl acetylacetonate complex can be used as a catalyst in the hydrogen peroxide oxidation of anthracene to produce anthraquinone. The reaction can be performed under a variety of reaction conditions, ideally by…

  13. Low-Complexity Interference-Free Downlink Channel Assignment with Improved Performance in Coordinated Small Cells

    KAUST Repository

    Radaydeh, Redha M.


    This paper proposes a low-complexity interference-free channel assignment scheme with improved desired downlink performance in coordinated multi-antenna small-coverage access points (APs) that employ the open-access control strategy. The adopted system treats the case when each user can be granted an access to one of the available channels at a time. Moreover, each receive terminal can suppress a limited number of resolvable interfering sources via its highly-correlated receive array. On the other hand, the operation of the deployed APs can be coordinated to serve active users, and the availability of multiple physical channels and the use of uncorrelated transmit antennas at each AP are exploited to improve the performance of supported users. The analysis provides new approaches to use the transmit antenna array at each AP, the multiple physical channels, the receive antenna array at each user in order to identify interference-free channels per each user, and then to select a downlink channel that provides the best possible improved performance. The event of concurrent interference-free channel identification by different users is also treated to further improve the desired link associated with the scheduled user. The analysis considers the practical scenario of imperfect identification of interference-free channel by an active user and/or the imperfectness in scheduling concurrent users requests on the same channel. The developed formulations can be used to study any performance metric and they are applicable for any statistical and geometric channel models. © 2015 IEEE.

  14. [Complexity of social and healthcare coordination in addictions and the role of the nurse]. (United States)

    Molina Fernández, Antonio Jesús; González Riera, Javier; Montero Bancalero, Francisco José; Gómez-Salgado, Juan


    The present article discusses the psychosocial impact of basic and advanced concepts, such as social support and prevention, as well as to establish a link between theoretical models related to the social sphere on one side, and the health aspects on the other. This work is based on the context of the influence on health shared by community psychology and social psychology. Starting from the historical background of current approaches, a review is presented of those first actions focused on the care plan and they are framed in a reaction model to the drug problem, which progressed to the current healthcare network model, through the creation of Spanish National Action Plan on Drugs. The complexity of the problem is then broken down into the following key elements: Multifactorial Model of Drugs and Addictions, importance of prevention, and social support. Subsequently, a description is presented on the different levels of the healthcare network, with their different resources. This is also illustrated using a coordination protocol. Finally, it features the nursing approach to drugs, with its contributions, particularly as regards the coordination of resources, and aspects that must be developed for improvement in this area.

  15. Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid-Complex Tauto-Conformers. (United States)

    Schäfer, Bernhard; Greisch, Jean-François; Faus, Isabelle; Bodenstein, Tilmann; Šalitroš, Ivan; Fuhr, Olaf; Fink, Karin; Schünemann, Volker; Kappes, Manfred M; Ruben, Mario


    The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism-driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [Fe(II) 4 L4 ](8+) complexes were determined by X-ray diffraction, and the distinctness of the products was confirmed by ion-mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (Fe(II) spin crossover vs. a blocked Fe(II) high-spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology.

  16. Low-Complexity Scheduling and Power Adaptation for Coordinated Cloud-Radio Access Networks

    KAUST Repository

    Douik, Ahmed


    In practical wireless systems, the successful implementation of resource allocation techniques strongly depends on the algorithmic complexity. Consider a cloud-radio access network (CRAN), where the central cloud is responsible for scheduling devices to the frames’ radio resources blocks (RRBs) of the single-antenna base-stations (BSs), adjusting the transmit power levels, and for synchronizing the transmit frames across the connected BSs. Previous studies show that the jointly coordinated scheduling and power control problem in the considered CRAN can be solved using an approach that scales exponentially with the number of BSs, devices, and RRBs, which makes the practical implementation infeasible for reasonably sized networks. This paper instead proposes a low-complexity solution to the problem, under the constraints that each device cannot be served by more than one BS but can be served by multiple RRBs within each BS frame, and under the practical assumption that the channel is constant during the duration of each frame. The paper utilizes graph-theoretical based techniques and shows that constructing a single power control graph is sufficient to obtain the optimal solution with a complexity that is independent of the number of RRBs. Simulation results reveal the optimality of the proposed solution for slow-varying channels, and show that the solution performs near-optimal for highly correlated channels.

  17. Ipsilateral coordination at preferred rate: effects of age, body side and task complexity. (United States)

    Van Impe, Annouchka; Coxon, James P; Goble, Daniel J; Wenderoth, Nici; Swinnen, Stephan Patrick


    Functional imaging studies have shown that elderly individuals activate widespread additional brain networks, compared to young subjects, when performing motor tasks. However, the parameters that effect this unique neural activation, including the spatial distribution of this activation across hemispheres, are still largely unknown. Here, we examined the effect of task complexity and body side on activation differences between older and younger adults while performing cyclical flexion-extension movements of the ipsilateral hand and foot. In particular, easy (isodirectional) and more difficult (non-isodirectional) coordination patterns were performed with either the left or right body side at a self-selected, comfortable rate. Even in the absence of imposed pacing the older group activated a larger brain network, suggestive of increased attentional deployment for monitoring the spatial relationships between the simultaneously moving segments and enhanced sensory processing and integration. Evidence of age-dependent underactivation was also found in contralateral M1, SMA and bilateral putamen, possibly reflecting a functional decline of the basal ganglia-mesial cortex pathway in the older group. An ANOVA model revealed significant main effects of task complexity and body side. However the interaction of these factors with age did not reach significance. Consequently, we conclude that under self-paced conditions, task complexity and body side did not have a modulatory effect on age-related brain activation.

  18. Synthesis and characterization of three-coordinate Ni(III)-imide complexes. (United States)

    Iluc, Vlad M; Miller, Alexander J M; Anderson, John S; Monreal, Marisa J; Mehn, Mark P; Hillhouse, Gregory L


    A new family of low-coordinate nickel imides supported by 1,2-bis(di-tert-butylphosphino)ethane was synthesized. Oxidation of nickel(II) complexes led to the formation of both aryl- and alkyl-substituted nickel(III)-imides, and examples of both types have been isolated and fully characterized. The aryl substituent that proved most useful in stabilizing the Ni(III)-imide moiety was the bulky 2,6-dimesitylphenyl. The two Ni(III)-imide compounds showed different variable-temperature magnetic properties but analogous EPR spectra at low temperatures. To account for this discrepancy, a low-spin/high-spin equilibrium was proposed to take place for the alkyl-substituted Ni(III)-imide complex. This proposal was supported by DFT calculations. DFT calculations also indicated that the unpaired electron is mostly localized on the imide nitrogen for the Ni(III) complexes. The results of reactions carried out in the presence of hydrogen donors supported the findings from DFT calculations that the adamantyl substituent was a significantly more reactive hydrogen-atom abstractor. Interestingly, the steric properties of the 2,6-dimesitylphenyl substituent are important not only in protecting the Ni═N core but also in favoring one rotamer of the resulting Ni(III)-imide, by locking the phenyl ring in a perpendicular orientation with respect to the NiPP plane.

  19. Two-coordinate terminal zinc hydride complexes: synthesis, structure and preliminary reactivity studies. (United States)

    Dawkins, Michael J C; Middleton, Ewart; Kefalidis, Christos E; Dange, Deepak; Juckel, Martin M; Maron, Laurent; Jones, Cameron


    The first examples of essentially two-coordinate, monomeric zinc hydride complexes, LZnH (L = -N(Ar)(SiR3)) (Ar = C6H2{C(H)Ph2}2R'-2,6,4; R = Me, R' = Pr(i) (L'); R = Pr(i), R' = Me (L*); R = Pr(i), R' = Pr(i) (L(†))) have been prepared and shown by crystallographic studies to have near linear N-Zn-H fragments. The results of computational studies imply that any PhZn interactions in the compounds are weak at best. Preliminary reactivity studies reveal the compounds to be effective for the stoichiometric hydrozincation and catalytic hydrosilylation of carbonyl compounds.

  20. A novel decomposition and coordination algorithm for complex networks and its application to power grids

    Institute of Scientific and Technical Information of China (English)

    Xiangping NI; Shengwei MEI


    To analyze and control complex networks effectively, this paper puts forward a new kind of scheme, which takes control separately in each area and can achieve the network's coordinated optimality. The proposed algorithm is made up of two parts: the first part decomposes the network into several independent areas based on community structure and decouples the information flow and control power among areas; the second part selects the center nodes from each area with the help of the control centrality index. As long as the status of center nodes is kept on a satisfactory level in each area, the whole system is under effective control. Finally, the algorithm is applied to power grids, and the simulations prove its effectiveness.

  1. A Molecular Artisans Guide to Supramolecular Coordination Complexes and Metal Organic Frameworks (United States)

    Wu, Xialu; Young, David J.; Hor, T. S. Andy


    As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.

  2. Rheb may complex with RASSF1A to coordinate Hippo and TOR signaling (United States)

    Nelson, Nicholas; Clark, Geoffrey J.


    The TOR pathway is a vital component of cellular homeostasis that controls the synthesis of proteins, nucleic acids and lipids. Its core is the TOR kinase. Activation of the TOR pathway suppresses autophagy, which plays a vital but complex role in tumorigenesis. The TOR pathway is regulated by activation of the Ras-related protein Rheb, which can bind mTOR. The Hippo pathway is a major growth control module that regulates cell growth, differentiation and apoptosis. Its core consists of an MST/LATS kinase cascade that can be activated by the RASSF1A tumor suppressor. The TOR and Hippo pathways may be coordinately regulated to promote cellular homeostasis. However, the links between the pathways remain only partially understood. We now demonstrate that in addition to mTOR regulation, Rheb also impacts the Hippo pathway by forming a complex with RASSF1A. Using stable clones of two human lung tumor cell lines (NCI-H1792 and NCI-H1299) with shRNA-mediated silencing or ectopic overexpression of RASSF1A, we show that activated Rheb stimulates the Hippo pathway, but is suppressed in its ability to stimulate the TOR pathway. Moreover, by selectively labeling autophagic vacuoles we show that RASSF1A inhibits the ability of Rheb to suppress autophagy and enhance cell growth. Thus, we identify a new connection that impacts coordination of Hippo and TOR signaling. As RASSF1A expression is frequently lost in human tumors, the RASSF1A status of a tumor may impact not just its Hippo pathway status, but also its TOR pathway status. PMID:27034171

  3. Rheb may complex with RASSF1A to coordinate Hippo and TOR signaling. (United States)

    Nelson, Nicholas; Clark, Geoffrey J


    The TOR pathway is a vital component of cellular homeostasis that controls the synthesis of proteins, nucleic acids and lipids. Its core is the TOR kinase. Activation of the TOR pathway suppresses autophagy, which plays a vital but complex role in tumorigenesis. The TOR pathway is regulated by activation of the Ras-related protein Rheb, which can bind mTOR. The Hippo pathway is a major growth control module that regulates cell growth, differentiation and apoptosis. Its core consists of an MST/LATS kinase cascade that can be activated by the RASSF1A tumor suppressor. The TOR and Hippo pathways may be coordinately regulated to promote cellular homeostasis. However, the links between the pathways remain only partially understood. We now demonstrate that in addition to mTOR regulation, Rheb also impacts the Hippo pathway by forming a complex with RASSF1A. Using stable clones of two human lung tumor cell lines (NCI-H1792 and NCI-H1299) with shRNA-mediated silencing or ectopic overexpression of RASSF1A, we show that activated Rheb stimulates the Hippo pathway, but is suppressed in its ability to stimulate the TOR pathway. Moreover, by selectively labeling autophagic vacuoles we show that RASSF1A inhibits the ability of Rheb to suppress autophagy and enhance cell growth. Thus, we identify a new connection that impacts coordination of Hippo and TOR signaling. As RASSF1A expression is frequently lost in human tumors, the RASSF1A status of a tumor may impact not just its Hippo pathway status, but also its TOR pathway status.

  4. New class of scorpionate: tris(tetrazolyl)-iron complex and its different coordination modes for alkali metal ions. (United States)

    Park, Ka Hyun; Lee, Kang Mun; Go, Min Jeong; Choi, Sung Ho; Park, Hyoung-Ryun; Kim, Youngjo; Lee, Junseong


    We report formation of a new metallascorpionate ligand, [FeL3](3-) (IPtz), containing a Fe core and three 5-(2-hydroxyphenyl)-1H-tetrazole (LH2) ligands. It features two different binding sites, oxygen and nitrogen triangles, which consist of three oxygen or nitrogen donors from tetrazole. The binding affinities of the complex for three alkali metal ions were studied using UV spectrophotometry titrations. All three alkali metal ions show high affinities and binding constants (>3 × 10(6) M(-1)), based on the 1:1 binding isotherms to IPtz. The coordination modes of the alkali metals and IPtz in the solid were studied using X-ray crystallography; two different electron-donor sites show different coordination numbers for Li(+), Na(+), and K(+) ions. The oxygen triangles have the κ(2) coordination mode with Li(+) and κ(3) coordination mode with Na(+) and K(+) ions, whereas the nitrogen triangles show κ(3) coordination with K(+) only. The different binding affinities of IPtz in the solid were manipulated using multiple metal precursors. A Fe-K-Zn trimetallic complex was constructed by assembly of an IPtz ligand, K, and Zn precursors and characterized using X-ray crystallography. Oxygen donors are coordinated with the K ion via the κ(3) coordination mode, and nitrogen donors are coordinated with Zn metal by κ(3) coordination. The solid-state structure was confirmed to be a honeycomb coordination polymer with a one-dimensional infinite metallic array, i.e., -(K-K-Fe-Zn-Fe-K)n-.

  5. Pseudo-symmetry analysis of the d-block molecular orbitals in four-coordinate complexes. (United States)

    Falceto, Andrés; Casanova, David; Alemany, Pere; Alvarez, Santiago


    A rigorous definition of the concept of pseudo-symmetry, which is as important to chemistry as the concepts of symmetry implemented through group theory, should allow us to apply those group theoretical tools to molecules that are significantly distorted from those ideal symmetries best known and understood by the chemical community. In this paper, we consider four-coordinate transition-metal complexes with geometries along the interconversion path between the square and the tetrahedron and show how their molecular orbitals can be expressed in terms of either the tetrahedral or tetragonal symmetry groups. Furthermore, we analyze how the intensity of a d-d absorption band can be related to the degree of symmetry loss of the d-block molecular orbitals by means of their decomposition in terms of contributions from different pseudo-symmetry representations. As a final example, we also show how the substitution of a single ligand in a square planar complex affects the symmetry of the molecular orbitals and the absorption intensity associated to an electronic transition.

  6. Two-Coordinate Co(II) Imido Complexes as Outstanding Single-Molecule Magnets. (United States)

    Yao, Xiao-Nan; Du, Jing-Zhen; Zhang, Yi-Quan; Leng, Xue-Bing; Yang, Mu-Wen; Jiang, Shang-Da; Wang, Zhen-Xing; Ouyang, Zhong-Wen; Deng, Liang; Wang, Bing-Wu; Gao, Song


    The pursuit of single-molecule magnets (SMMs) with better performance urges new molecular design that can endow SMMs larger magnetic anisotropy. Here we report that two-coordinate cobalt imido complexes featuring highly covalent Co═N cores exhibit slow relaxation of magnetization under zero direct-current field with a high effective relaxation barrier up to 413 cm(-1), a new record for transition metal based SMMs. Two theoretical models were carried out to investigate the anisotropy of these complexes: single-ion model and Co-N coupling model. The former indicates that the pseudo linear ligand field helps to preserve the first-order orbital momentum, while the latter suggests that the strong ferromagnetic interaction between Co and N makes the [CoN](+) fragment a pseudo single paramagnetic ion, and that the excellent performance of these cobalt imido SMMs is attributed to the inherent large magnetic anisotropy of the [CoN](+) core with |MJ = ± 7/2⟩ ground Kramers doublet.

  7. Coordination versus coupling of dicyanamide in molybdenum and manganese pyrazole complexes. (United States)

    Arroyo, Marta; Gómez-Iglesias, Patricia; Martín-Alvarez, Jose Miguel; Alvarez, Celedonio M; Miguel, Daniel; Villafañe, Fernando


    The reactions of cis-[MoCl(η(3)-methallyl)(CO)(2)(NCMe)(2)] (methallyl = CH(2)C(CH(3))CH(2)) with Na(NCNCN) and pz*H (pzH, pyrazole, or dmpzH, 3,5-dimethylpyrazole) lead to cis-[Mo(η(3)-methallyl)(CO)(2)(pz*H)(μ-NCNCN-κ(2)N,N)](2) (pzH, 1a; dmpzH, 1b), where dicyanamide is coordinated as bridging ligand. Similar reactions with fac-[MnBr(CO)(3)(NCMe)(2)] lead to the pyrazolylamidino complexes fac-[Mn(pz*H)(CO)(3)(NH═C(pz*)NCN-κ(2)N,N)] (pzH, 2a; dmpzH, 2b), resulting from the coupling of pyrazol with one of the CN bonds of dicyanamide. The second CN bond of dicyanamide in 2a undergoes a second coupling with pyrazole after addition of 1 equiv of fac-[MnBr(CO)(3)(pzH)(2)], yielding the dinuclear doubly coupled complex [{fac-Mn(pzH)(CO)(3)}(2)(μ-NH═C(pz)NC(pz)=NH-κ(4)N,N,N,N)]Br (3). The crystal structure of 3 reveals the presence of two isomers, cis or trans, depending on whether the terminal pyrazoles are coordinated at the same or at different sides of the approximate plane defined by the bridging bis-amidine ligand. Only the cis isomer is detected in the crystal structure of the perchlorate salt of the same bimetallic cation (4), obtained by metathesis with AgClO(4). All the N-bound hydrogen atoms of the cations in 3 or 4 are involved in hydrogen bonds. Some of the C-N bonds of the pyrazolylamidino ligand have a character intermediate between single and double, and theoretical studies were carried out on 2a and 3 to confirm its electronic origin and discard packing effects. Calculations also show the essential role of bromide in the planarity of the tetradentate ligand in the bimetallic complex 3.

  8. X-ray Emission Spectroscopy to Study Ligand Valence Orbitals in Mn Coordination Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Smolentsev, Grigory; Soldatov, Alexander V; Messinger, Johannes; Merz, Kathrin; Weyhermuller, Thomas; Bergmann, Uwe; Pushkar, Yulia; Yano, Junko; Yachandra, Vittal K.; Glatzel, Pieter


    We discuss a spectroscopic method to determine the character of chemical bonding and for the identification of metal ligands in coordination and bioinorganic chemistry. It is based on the analysis of satellite lines in X-ray emission spectra that arise from transitions between valence orbitals and the metal ion 1s level (valence-to-core XES). The spectra, in connection with calculations based on density functional theory (DFT), provide information that is complementary to other spectroscopic techniques, in particular X-ray absorption (XANES and EXAFS). The spectral shape is sensitive to protonation of ligands and allows ligands, which differ only slightly in atomic number (e.g., C, N, O...), to be distinguished. A theoretical discussion of the main spectral features is presented in terms of molecular orbitals for a series of Mn model systems: [Mn(H2O)6]2+, [Mn(H2O)5OH]+, [Mn(H2O)5NH2]+, and [Mn(H2O)5NH3]2+. An application of the method, with comparison between theory and experiment, is presented for the solvated Mn2+ ion in water and three Mn coordination complexes, namely [LMn(acac)N3]BPh4, [LMn(B2O3Ph2)(ClO4)], and [LMn(acac)N]BPh4, where L represents 1,4,7-trimethyl-1,4,7-triazacyclononane, acac stands for the 2,4-pentanedionate anion, and B2O3Ph2 represents the 1,3-diphenyl-1,3-dibora-2-oxapropane-1,3-diolato dianion.

  9. Inducing porosity and growing carbon nanofibers in ferroin perchlorate: An example of morphological transitions in coordination complexes (United States)

    Avraham, Efrat Shawat; Fleker, Ohad; Benisvy, Laurent; Oakes, Landon; Pint, Cary L.; Nessim, Gilbert D.


    Inducing porosity in solid coordination complex crystals, which are an important class of catalysts, is critical for many applications where a high surface area is required. However, unlike metal organic frameworks (MOFs), fabrication of porous coordination crystals remains a significant challenge. Here we demonstrate a simple method to produce and modulate porosity in coordination complex crystals using ferroin perchlorate, a model system that combines a common ionic complex with a very reactive counter-ion. Using thermal chemical vapor deposition (CVD), we show that by annealing ferroin perchlorate crystals at 350 °C under a flow of ethylene, hydrogen, argon, and oxygen, we induced pores in the crystal. We demonstrate that small amounts of oxygen, which may combine with hydrogen to form water, are essential for pore formation. We also demonstrate that pore size and density can be easily controlled by varying the ethylene flow. Upon raising the annealing temperature to 500 °C, we observed a second transition in which carbon nanofibers (CNFs) grew from the porous crystal. This approach represents a simple and effective method for the synthesis of porous materials with good control over pore size and density. It also enables the synthesis of complex networks of nanostructures (in our case CNFs) by simply varying process parameters such as temperature and gas flows. This represents an important advance for the fabrication of porous coordination complex crystals.

  10. Trinuclear nickel coordination complexes of phenanthrene-9,10-dione dioxime

    Directory of Open Access Journals (Sweden)

    Owen M. Williams


    Full Text Available A trinuclear nickel complex of phenanthrene-9,10-dione dioxime (H2pqd, namely bis[μ2-9,10-bis(oxidoiminophenanthrene]bis[μ2-10-(oxidoiminophenanthrene-9-one oxime](phenanthrene-9,10-dione dioximetrinickel(II toluene disolvate, [Ni3(C14H8N2O22(C14H9N2O22(C14H10N2O2]·2C7H8, has been isolated and its crystal structure determined. This complex features three independent NiII atoms that are arranged in a triangular fashion along with five supporting ligands. There are two square-planar NiII atoms and a third pseudo-octahedral NiII atom. While the square-planar NiII atoms are stacked, there are no ligand bridges between them. Each square-planar NiII atom, however, bridges with the pseudo-octahedral NiII atom through Ni—N—O—Ni and Ni—O—Ni bonds. A fluoridoboration reaction of the proton-bridged species gave the analogous complex bis(μ2-bis{[10-(oxidoimino-9,10-dihydrophenanthren-9-ylidene]amino}difluoridoborato(phenanthrene-9,10-dione dioximetrinickel(II dichloromethane trisolvate, [Ni3(C28H16BF2N4O24(C14H10N2O2]·3CH2Cl2, which shows the same binding structure, but features a widened Ni—Ni interaction between the square-planar NiII atoms. The proton-bridged complex completes the macrocyclic coordination around the square-planar NiII atoms by means of an O—H...O hydrogen bond. Both compounds feature O—H...N hydrogen bonds between the oxime and the N atoms attached to square-planar nickel atom. The nickel units show no direct interaction with their nearest neighbors in the extended lattice. Two π-stacking interactions between adjacent molecules are found: one with a centroid–centroid distance of 3.886 (2 Å and the other with a centroid–centroid distance of 4.256 (3 Å. In the latter case, although not aromatic, the distance to the centroid of the central phenanthrene ring is shorter, with a distance of 3.528 (3 Å. Toluene molecules occupy the solvent channels that are oriented along the c axis. In the

  11. The complex coordinate scattering theory and the Kohn variational method: A general formulation and application to long range potentials (United States)

    Peskin, Uri; Moiseyev, Nimrod


    The complex coordinate scattering theory for the calculation of T-matrix elements, as was introduced by Engdahl, Moiseyev, and Maniv [J. Chem. Phys. 94, 1636 (1991)] and by Peskin and Moiseyev [J. Chem. Phys. 96, 2347 (1992)], is shown to satisfy the complex version of the Kohn variational principle introduced by Nuttall and Cohen [Phys. Rev. 188, 1542 (1969)]. This theory and the related S-matrix version of the Kohn variational principle, developed by Zhang, Chu, and Miller [J. Chem. Phys. 88, 6233, (1988)] are combined to formulate a generalized variational basis set approach for quantum scattering calculations. In this approach the Kohn variational procedure to optimize the linear parameters in the T matrix is followed by an optimization of the complex nonlinear parameters. This enables the application of the complex coordinate analytical continuation of the T matrix to the calculation of scattering probability amplitudes for long range potentials. Illustrating numerical applications to short and long range potentials are given.

  12. Theoretical study of the Pb(II)-catechol system in dilute aqueous solution: Complex structure and metal coordination sphere determination (United States)

    Lapouge, Christine; Cornard, Jean-Paul


    We investigated the unknown interaction of Pb(II) with catechol ligand in diluted aqueous solution by electronic spectroscopies combined with quantum chemical calculations. The aim of this work is the determination of the complete structure of the complex formed and particularly the metal coordination sphere. Three successive steps have been necessary to reach this goal: (i) the comparison of the experimental electronic absorption spectrum with theoretical spectra calculated from various hypothetical structures, (ii) complexation reaction pathways calculations in vacuum and with taking into account the solvent effects and finally (iii) the fluorescence emission wavelength calculations. All these investigations led to identify a monodentate complex with the monodeprotonated ligand, in which the Pb atom presents a coordination number of five. The formula of the complex is [Pb(Hcat)(HO)4]mono+.

  13. Mononuclear nickel (II) and copper (II) coordination complexes supported by bispicen ligand derivatives: Experimental and computational studies

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Nirupama; Niklas, Jens; Poluektov, Oleg; Van Heuvelen, Katherine M.; Mukherjee, Anusree


    The synthesis, characterization and density functional theory calculations of mononuclear Ni and Cu complexes supported by the N,N’-Dimethyl-N,N’-bis-(pyridine-2-ylmethyl)-1,2-diaminoethane ligand and its derivatives are reported. The complexes were characterized by X-ray crystallography as well as by UV-visible absorption spectroscopy and EPR spectroscopy. The solid state structure of these coordination complexes revealed that the geometry of the complex depended on the identity of the metal center. Solution phase characterization data are in accord with the solid phase structure, indicating minimal structural changes in solution. Optical spectroscopy revealed that all of the complexes exhibit color owing to d-d transition bands in the visible region. Magnetic parameters obtained from EPR spectroscopy with other structural data suggest that the Ni(II) complexes are in pseudo-octahedral geometry and Cu(II) complexes are in a distorted square pyramidal geometry. In order to understand in detail how ligand sterics and electronics affect complex topology detailed computational studies were performed. The series of complexes reported in this article will add significant value in the field of coordination chemistry as Ni(II) and Cu(II) complexes supported by tetradentate pyridyl based ligands are rather scarce.

  14. 2-D boundary-fitted coordinate grid generation for casting with complex shape

    Directory of Open Access Journals (Sweden)

    Wang Ye


    Full Text Available In order to overcome the zigzag grids generated by conventional finite difference method on complicated casting boundaries in the simulation of casting process, the generation program for 2-D boundary-fitted coordinate grid has been developed by solving a set of partial differential equations (PDE numerically. The STL format files were treated as input data for 2-D physical regions. The equipartition method for boundary points was used to improve the self-adaptability of grid according to the characteristic of the STL format files. The program was demonstrated through some examples. The comparison between the conventional finite difference method and the proposed method shows that this program is effective and flexible for generation of boundary-fitted grid in any arbitrary 2-D complex domain, and the grid is in accordance with the variety of boundary curvature finely. The program also provides two types of boundary-fitted grids for double-connected region, O-type and C-type. The limitation of the step-like boundary with the rectangle grid could be avoided effectively. Therefore, the computational accuracy and efficiency would be improved and the computational time would be saved significantly by the application of boundary-fitted grids.

  15. Distinct Structural Pathways Coordinate the Activation of AMPA Receptor-Auxiliary Subunit Complexes. (United States)

    Dawe, G Brent; Musgaard, Maria; Aurousseau, Mark R P; Nayeem, Naushaba; Green, Tim; Biggin, Philip C; Bowie, Derek


    Neurotransmitter-gated ion channels adopt different gating modes to fine-tune signaling at central synapses. At glutamatergic synapses, high and low activity of AMPA receptors (AMPARs) is observed when pore-forming subunits coassemble with or without auxiliary subunits, respectively. Whether a common structural pathway accounts for these different gating modes is unclear. Here, we identify two structural motifs that determine the time course of AMPAR channel activation. A network of electrostatic interactions at the apex of the AMPAR ligand-binding domain (LBD) is essential for gating by pore-forming subunits, whereas a conserved motif on the lower, D2 lobe of the LBD prolongs channel activity when auxiliary subunits are present. Accordingly, channel activity is almost entirely abolished by elimination of the electrostatic network but restored via auxiliary protein interactions at the D2 lobe. In summary, we propose that activation of native AMPAR complexes is coordinated by distinct structural pathways, favored by the association/dissociation of auxiliary subunits.

  16. Polyoxometalate coordinated transition metal complexes as catalysts: Oxidation of styrene to benzaldehyde/benzoic acid

    Indian Academy of Sciences (India)

    Srinivasa Rao Amanchi; Anjali Patel; Samar K Das


    Oxidation of styrene is carried out by using heptamolybdate coordinated transition metal (Co2+, Zn2+) complexes, [2-ampH]4[{Co(H2O)5}Mo7O24]·9H2O (1), [3-ampH]4[{Co(H2O)5}Mo7O24]·9H2O (2), [2-ampH]4[{Zn(H2O)5}Mo7O24]·4H2O (3) and [3-ampH]4[{Zn(3-ampy)(H2O)4}Mo7O24]·4H2O (4) as catalysts and H2O2 as an oxidant at 80°C. The leaching study has been carried out to check the quality of catalyst and it has been reused for three times with good percentage of conversion. For the first two catalysts (compounds 1 and 2), the major product obtained is benzaldehyde, and benzoic acid is the major product for next two catalysts (compounds 3 and 4). Stability of the catalysts has been analyzed by IR, UV-spectroscopy and powder X-ray crystallography.

  17. Exploration and characterisation of novel bronze patinas derived from simple coordination complexes. (United States)

    Devantier, Ashley E; Murch, Susan J; McNeil, W Stephen


    The chemical reactions of aqueous solutions containing simple transition-metal salts and bidentate nitrogen ligands on bronze surfaces results in a series of brightly coloured patinas. Chemically and physically robust patinas involve a chemical oxidation of the copper atoms within the bronze surface, either by an applied ferric salt or atmospheric dioxygen. The combination of Fe(NO(3))(3)·9H(2)O and 2,2'-bipyridine produces a coloured patina that is either red or blue, depending on whether oxygen was present during application, due to the presence of [Fe(bpy)(3)](2+) or [Fe(bpy)(3))](3+), respectively. Application of pyrazine produces a bright orange patina, due to the formation of Cu(i) coordination polymers on the bronze surface. Application of Fe(NO(3))(3)·9H(2)O and tetramethylethylenediamine (TMEDA) yields a forest green coloration, believed to be due to a bimetallic copper-iron complex, while TMEDA alone affords the sapphire blue of [Cu(TMEDA)(2)](2+). These patinas were characterized with ESI-TOF MS, UV-Vis spectrophotometry, and IR spectrophotometry, to determine the molecular basis for the patina chromophores.

  18. Vibrational spectra, normal coordinate treatment and simulation of the vibrational spectra of piperazine glyoxime and its Co(III) complex (United States)

    Özpozan, T.; Küçükusta, D.; Büyükmumcu, Z.


    Newly synthesized Co(III) complexes of piperazine glyoxime (PGO) are examined from the vibrational spectroscopy point of view. A complete interpretation of the vibrational spectra of both the ligand and the complex has been carried out on the basis of normal coordinate analysis. A valence force field has been developed for both of the compounds. The vibrational spectra of the compounds are simulated by a visual basic program prepared to run on an MS Excel data sheet.

  19. Electronic Transitions as a Probe of Tetrahedral versus Octahedral Coordination in Nickel(II) Complexes: An Undergraduate Inorganic Chemistry Experiment. (United States)

    Filgueiras, Carlos A. L.; Carazza, Fernando


    Discusses procedures, theoretical considerations, and results of an experiment involving the preparation of a tetrahedral nickel(II) complex and its transformation into an octahedral species. Suggests that fundamental aspects of coordination chemistry can be demonstrated by simple experiments performed in introductory level courses. (Author/JN)

  20. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes

    NARCIS (Netherlands)

    Wang, J.; Groeneveld, A.; Oikonomou, M.E.; Prusova, A.; As, van H.; Lent, van J.W.M.; Velders, A.H.


    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and

  1. Identification of Copper(II) Complexes in Aqueous Solution by Electron Spin Resonance: An Undergraduate Coordination Chemistry Experiment. (United States)

    Micera, G.; And Others


    Background, procedures, and results are provided for an experiment which examines, through electron spin resonance spectroscopy, complex species formed by cupric and 2,6-dihydroxybenzoate ions in aqueous solutions. The experiment is illustrative of several aspects of inorganic and coordination chemistry, including the identification of species…

  2. Five-coordinated oxovanadium(IV) complexes derived from amino acids and ciprofloxacin: synthesis, spectral, antimicrobial, and DNA interaction approach. (United States)

    Patel, M N; Patel, S H; Chhasatia, M R; Parmar, P A


    Five-coordinated oxovanadium(IV) complexes with ciprofloxacin and various uninegative bidentate amino acids have been prepared. The structure of complexes has been investigated using spectral, physicochemical, mass spectroscopy, and elemental analyses. The antimicrobial activities (MIC) of the complexes, ligands, metal salt, and some standard drugs have been evaluated using the doubling dilution technique against Staphylococcus aureus, Bacillus subtilis, Serratia marcescens (gram-positive), and Pseudomonas aeruginosa, and Escherichia coli (gram-negative) bacteria. The result shows the significant increase in the antibacterial activity of the ligand, metal, and ciprofloxacin on complexation. The interaction of the complexes with pBR322 DNA has been investigated using spectroscopic, gel electrophoresis, and viscometric techniques. This shows that the complexes can bind to pBR322 DNA by the intercalative mode. The superoxide dismutase-like activity of the complexes has been determined.

  3. Coordination and conformational isomers in mononuclear iron complexes with pertinence to the [FeFe] hydrogenase active site. (United States)

    Orthaber, Andreas; Karnahl, Michael; Tschierlei, Stefanie; Streich, Daniel; Stein, Matthias; Ott, Sascha


    A series of six mononuclear iron complexes of the type [Fe(X-bdt)(P(R)2N(Ph)2)(CO)] (P(R)2N(Ph)2 = 1,5-diaza-3,7-diphosphaoctane, bdt = benzenedithiolate with X = H, Cl2 or Me and R = Ph, Bn, Cyc or tert-Bu) was prepared. This new class of penta-coordinate iron complexes contains a free coordination site and a pendant base as essential structural features of the [FeFe]-hydrogenase active site. The bidentate nature of the P(R)2N(Ph)2 ligands was found to be crucial for the preferential formation of coordinatively unsaturated penta-coordinate complexes, which is supported by first principle calculations. IR-spectroscopic data suggest the presence of coordination isomers around the metal center, as well as multiple possible conformers of the P(R)2N(Ph)2 ligand. This finding is further corroborated by X-ray crystallographic and computational studies. (31)P{(1)H}-NMR- and IR-spectroscopic as well as electrochemical measurements show that the electronic properties of the complexes are strongly, and independently, influenced by the P-substituents at the P(R)2N(Ph)2 ligand as well as by modifications of the bdt bridge. These results illustrate the advantages of this modular platform, which allows independent and selective tuning through site specific modifications. Potential catalytic intermediates, namely singly reduced and protonated complexes, have been further investigated by spectroscopic methods and exhibit remarkable stability. Finally, their general capacity for electro-catalytic reduction of protons to molecular hydrogen was verified.

  4. Revealing and tuning the core, structure, properties and function of polymer micelles with lanthanide-coordination complexes. (United States)

    Wang, Junyou; Groeneveld, Andrea; Oikonomou, Maria; Prusova, Alena; Van As, Henk; van Lent, Jan W M; Velders, Aldrik H


    Controlling self-assembly processes is of great interest in various fields where multifunctional and tunable materials are designed. We here present the versatility of lanthanide-complex-based micelles (Ln-C3Ms) with tunable coordination structures and corresponding functions (e.g. luminescence and magnetic relaxation enhancement). Micelles are prepared by charge-driven self-assembly of a polycationic-neutral diblock copolymer and anionic coordination complexes formed by Ln(III) ions and the bis-ligand L2EO4, which contains two dipicolinic acid (DPA) ligand groups (L) connected by a tetra-ethylene oxide spacer (EO4). By varying the DPA/Ln ratio, micelles are obtained with similar size but with different stability, different aggregation numbers and different oligomeric and polymeric lanthanide(III) coordination structures in the core. Electron microscopy, light scattering, luminescence spectroscopy and magnetic resonance relaxation experiments provide an unprecedented detailed insight into the core structures of such micelles. Concomitantly, the self-assembly is controlled such that tunable luminescence or magnetic relaxation with Eu-C3Ms, respectively, Gd-C3Ms is achieved, showing potential for applications, e.g. as contrast agents in (pre)clinical imaging. Considering the various lanthanide(III) ions have unique electron configurations with specific physical chemical properties, yet very similar coordination chemistry, the generality of the current coordination-structure based micellar design shows great promise for development of new materials such as, e.g., hypermodal agents.

  5. Stability and Reactivity of Cyclometallated Naphthylamine Complexes in Pd-C Bond Insertion Reactions with Coordinated Alkynylphosphanes

    KAUST Repository

    Chen, Shuli


    Phenylbis(phenylethynyl)phosphane PhP(C≡CPh)2 coordinates regiospecifically to the α-methyl-chiral ortho-platinated and -palladated naphthylamine units at the positions trans to the nitrogen donors. The P→Pt coordination bond is kinetically inert, whereas the P→Pd bond is labile. Upon heating of these phosphane complexes at 70 °C, one of the C≡C bonds in the coordinated PhP(C≡CPh)2 was activated towards an intermolecular Pd-C bond insertion reaction with an external ortho-palladated naphthylamine ring. No intramolecular insertion reaction occurred. In contrast to its palladium analogue, the ortho-platinated ring is not reactive towards coordinated PhP(C≡CPh)2, although it can promote the Pd-C bond insertion reaction. However, despite the high kinetic stability of the P→Pt coordination, the organoplatinum unit is a noticeably weaker activator than its organopalladium counterpart. The chirality of the reacting ortho-metallated naphthylamine ligand exhibited high stereochemical influence on the formation of the new stereogenic phosphorus center during the course of these C-C bond-formation reactions. The coordination chemistry and the absolute stereochemistry of the dimetallic products were determined by single-crystal X-ray crystallographic analysis. The asymmetric monoinsertion of PhP(C≡CPh)2 coordinated to a cyclometallated N,N-dimethyl naphthyl/benzylamine template into the Pd-C bonds of N,N-dimethylnaphthylamine palladacycles has been demonstrated for the synthesis of a variety of new P-stereogenic homo- or heterodimetallic complexes. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Two Zn(II) coordination complexes assembled by trithiocyanuric acid and two different N-donor auxiliary ligands. (United States)

    He, Xiao Xiao; Guo, Ya Mei


    The dipyridyl-type building blocks 4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole (3-bpt) and 4,4'-bipyridine (bpy) have been used to assemble with Zn(II) in the presence of trithiocyanuric acid (ttcH3) to afford two coordination compounds, namely bis[4-amino-3,5-bis(pyridin-3-yl)-1,2,4-triazole-κN(3)]bis(trithiocyanurato-κ(2)N,S)zinc(II), [Zn(C3H2N3S3)2(C12H10N6)2]·2H2O, (1), and catena-poly[[[bis(trithiocyanurato-κ(2)N,S)zinc(II)]-μ-4,4'-bipyridine-κ(2)N:N'] 4,4'-bipyridine monosolvate], {[Zn2(C3H2N3S3)4(C10H8N2)3]·C10H8N2}n, (2). Single-crystal X-ray analysis indicates that complex (1) is a mononuclear structure, while complex (2) presents a one-dimensional chain coordination motif. In both complexes, the central Zn(II) cation adopts an octahedral geometry, coordinated by four N- and two S-donor atoms. Notably, trithiocyanurate (ttcH2(-)) adopts the same bidentate chelating coordination mode in each complex and exists in the thione tautomeric form. The 3-bpt co-ligand in (1) adopts a monodentate coordination mode and serves as a terminal pendant ligand, whereas the 4,4'-bipyridine (bpy) ligand in (2) adopts a bidentate-bridging coordination mode. The different coordination characters of the different N-donor auxiliary ligands lead to structural diversity for complexes (1) and (2). Further analysis indicates that the resultant three-dimensional supramolecular networks for (1) and (2) arise through intermolecular N-H...S and N-H...N hydrogen bonds. Both complexes have been further characterized by FT-IR spectroscopy and elemental analyses.

  7. Synthesis, crystal structure and spectroscopic properties of a supramolecular zinc(II) complex with N2O2 coordination sphere. (United States)

    Dong, Wen-Kui; Zhang, Li-Sha; Sun, Yin-Xia; Zhao, Meng-Meng; Li, Gang; Dong, Xiu-Yan


    A new hexa-coordinated zinc(II) complex, namely [ZnL(H2O)2]n, with N2O2 coordination sphere (H2L=4,4'-dibromo-6,6'-dichloro-2,2'-[ethylenedioxybis(nitrilomethylidyne)]diphenol) has been synthesized and structurally characterized by elemental analyses, IR, UV-vis spectra and TG-DTA analyses, etc. Crystallographic data are monoclinic, space group P2(1)/c, a=24.634(2)Å, b=10.144(1)Å, c=7.9351(6)Å, β=91.371(2)°, V=1982.4(3)Å(3), Dc=2.099 g/cm(3), Z=4. The zinc(II) complex exhibits a slightly distorted octahedral geometry with halogen-substituted Salen-type bisoxime forming the basal N2O2 coordination sphere and two oxygen atoms from two coordinated water molecules in the axial position. The hydrogen-bonding and π-π stacking interactions have stabilized the zinc(II) complex molecules to form a self-assembling infinite dual metal-water chain-like structure with the nearest Zn⋯Zn distance of 4.954(4)Å.

  8. Coordination kinetics of different metal ions with the amidoximated polyacrylonitrile nanofibrous membranes and catalytic behaviors of their complexes

    Energy Technology Data Exchange (ETDEWEB)

    Li, Fu; Dong, Yong Chun; Kang, Wei Min; Cheng, Bowen; Qu, Xiang; Cui, Guixin [School of Textiles, Tianjin Polytechnic University, Tianjin (China)


    Two transition metal ions (Fe{sup 3+} and Cu{sup 2+}) and a rare earth metal ion (Ce{sup 3+}) were selected to coordinate with amidoximated polyacrylonitrile (PAN) nanofibrous membrane for preparing three metal modified PAN nanofibrous membrane complexes (M-AO-n-PANs, M = Fe, Cu, or Ce) as the heterogeneous Fenton catalysts for the dye degradation in water under visible irradiation. The coordination kinetics of three metal ions with modified PAN nanofibrous membranes was studied and the catalytic properties of the resulting complexes were also compared. The results indicated that increasing metal ion concentrations in solution or higher coordination temperature led to a significant increase in metal content, particularly in Fe and Cu contents of the complexes. Their coordination process could be described using Langmuir isotherm and pseudo-second-order kinetic equations. Moreover, Fe-AO-n-PAN had the best photocatalytic efficiency for the dye degradation in acidic medium, but a lower photocatalytic activity than Cu-AO-n-PAN in alkali medium.

  9. [Economic evaluation of a program of coordination between levels for complex chronic patients' management]. (United States)

    Allepuz Palau, Alejandro; Piñeiro Méndez, Pilar; Molina Hinojosa, José Carlos; Jou Ferre, Victoria; Gabarró Julià, Lourdes


    The complex chronic patient program (CCP) of the Alt Penedès aims to improve the coordination of care. The objective was to evaluate the relationship between the costs associated with the program, and its results in the form of avoided admissions. Dost-effectiveness analysis from the perspective of the health System based on a before-after study. Alt Penedès. Health services utilisation (hospital [admissions, emergency visits, day-care hospital] and primary care visits). CCP Program results were compared with those prior to its implementation. The cost assigned to each resource corresponded to the hospital CatSalut's concert and ICS fees for primary care. A sensitivity analysis using boot strapping was performed. The intervention was considered cost-effective if the incremental cost-effectiveness ratio (ICER) did not exceed the cost of admission (€ 1,742.01). 149 patients were included. Admissions dropped from 212 to 145. The ICER was €1,416.3 (94,892.9€/67). Sensitivity analysis showed that in 95% of cases the cost might vary between €70,847.3 and €121,882.5 and avoided admissions between 30 and 102. In 72.4% of the simulations the program was cost-effective. Sensitivity analysis showed that in most situations the PCC Program would be cost-effective, although in a percentage of cases the program could raise overall cost of care, despite always reducing the number of admissions. Copyright © 2013 Elsevier España, S.L.U. All rights reserved.

  10. A Longitudinal Electromyography Study of Complex Movements in Poststroke Therapy. 2: Changes in Coordinated Muscle Activation

    Directory of Open Access Journals (Sweden)

    Negin Hesam-Shariati


    Full Text Available Fine motor control is achieved through the coordinated activation of groups of muscles, or “muscle synergies.” Muscle synergies change after stroke as a consequence of the motor deficit. We investigated the pattern and longitudinal changes in upper limb muscle synergies during therapy in a largely unconstrained movement in patients with a broad spectrum of poststroke residual voluntary motor capacity. Electromyography (EMG was recorded using wireless telemetry from 6 muscles acting on the more-affected upper body in 24 stroke patients at early and late therapy during formal Wii-based Movement Therapy (WMT sessions, and in a subset of 13 patients at 6-month follow-up. Patients were classified with low, moderate, or high motor-function. The Wii-baseball swing was analyzed using a non-negative matrix factorization (NMF algorithm to extract muscle synergies from EMG recordings based on the temporal activation of each synergy and the contribution of each muscle to a synergy. Motor-function was clinically assessed immediately pre- and post-therapy and at 6-month follow-up using the Wolf Motor Function Test, upper limb motor Fugl-Meyer Assessment, and Motor Activity Log Quality of Movement scale. Clinical assessments and game performance demonstrated improved motor-function for all patients at post-therapy (p < 0.01, and these improvements were sustained at 6-month follow-up (p > 0.05. NMF analysis revealed fewer muscle synergies (mean ± SE for patients with low motor-function (3.38 ± 0.2 than those with high motor-function (4.00 ± 0.3 at early therapy (p = 0.036 with an association trend between the number of synergies and the level of motor-function. By late therapy, there was no significant change between groups, although there was a pattern of increase for those with low motor-function over time. The variability accounted for demonstrated differences with motor-function level (p < 0.05 but not time. Cluster

  11. Role of Occupational Therapy in Case Management and Care Coordination for Clients With Complex Conditions. (United States)

    Robinson, Monica; Fisher, Thomas F; Broussard, Kim


    Specific aspects of the profession of occupational therapy support a distinct value for its practitioners participating fully in the development of case management and care coordination systems. The expectation in the 21st century is that the U.S. health care system must be transformed from one that promotes volume of service to one that promotes value of care. Case management and care coordination will be critical components of that transformation. Occupational therapy's principles, education, practice, approach, and perspective offer much to benefit this increased attention to case management and care coordination. Occupational therapy practitioners should promote themselves and their profession as these system changes develop.

  12. Solubilization of silica: Synthesis, characterization and study of penta-coordinated pyridine N-oxide silicon complexes

    Indian Academy of Sciences (India)

    Subramania Ranganathan; Ch Chandrashekhar Rao; Suvarchala Devi Vudayagiri; Y B R D Rajesh; B Jagadeesh


    In an effort to design agents that could solubilize silica in water, under ambient conditions and pH, as takes place in nature, novel zwitterionic, penta-oxo-coordinated silicon compounds with siliconate cores have been prepared from 4-substituted pyridine N-oxides (H, OMe, morpholino, NO2) as donor ligands, their structures established by 1H, 13C and MS, and the coordination number of silicon, by 29Si NMR. The formation of complexes from pyridine N-oxides is noteworthy since they arise from interaction with a weakly nucleophilic oxygen centre. The ability of the pyridine N-oxides to enhance the solubilization of silica in water has been experimentally demonstrated. Possible rationalization of this observation on the basis of O→Si coordination via the oxygen atom of pyridine N-oxide is suggested.

  13. Bis(2-acetylpyridine-κ2N,Osilver(I tetrafluoridoborate: a complex with silver in a seesaw coordination geometry

    Directory of Open Access Journals (Sweden)

    Michael A. O'Donnell


    Full Text Available The reaction of 2-acetylpyridine with silver(I tetrafluoridoborate leads to the discrete title complex, [Ag(C7H7NO2]BF4, in the cation of which the Ag atom is coordinated by two 2-acetylpyridine ligands, each of which is N,O-bidentate, albeit with stronger bonding to the N atoms [Ag—N = 2.2018 (15 and 2.2088 (14 Å; Ag—O = 2.5380 (13 and 2.5454 (13 Å]. The four-coordinate Ag atom has a seesaw coordination geometry with a τ4 index of 0.51. The tetrafluoridoborate anion is disordered over two orientations with 0.568 (10:0.432 (10 occupancies.

  14. A Highly Reactive Seven-Coordinate Osmium(V) Oxo Complex: [Os(V)(O)(qpy)(pic)Cl](2+). (United States)

    Liu, Yingying; Ng, Siu-Mui; Lam, William W Y; Yiu, Shek-Man; Lau, Tai-Chu


    Seven-coordinate ruthenium oxo species have been proposed as active intermediates in catalytic water oxidation by a number of highly active ruthenium catalysts, however such species have yet to be isolated. Reported herein is the first example of a seven-coordinate group 8 metal-oxo species, [Os(V)(O)(qpy)(pic)Cl](2+) (qpy = 2,2':6',2'':6'',2'''-quaterpyridine, pic = 4-picoline). The X-ray crystal structure of this complex shows that it has a distorted pentagonal bipyramidal geometry with an Os=O distance of 1.7375 Å. This oxo species undergoes facile O-atom and H-atom-transfer reactions with various organic substrates. Notably it can abstract H atoms from alkylaromatics with C-H bond dissociation energy as high as 90 kcal mol(-1). This work suggests that highly active oxidants may be designed based on group 8 seven-coordinate metal oxo species.

  15. Application of an electronic bulletin board, as a mechanism of coordination of actions in complex systems - reference model

    Directory of Open Access Journals (Sweden)

    Katarzyna Grzybowska


    Full Text Available Background: In her previous research, the author of this publication indicates that coordination is a dependent variable which has a great driving force and is a very unstable factor. This results in the fact that all of the actions connected with coordination have an impact on other factors of cooperation as well as the integration of the enterprises in the structures of a supply chain type structure. Material and methods:  The article has been divided into two basic parts. The first part regards the reference models in complex systems (supply chain systems. They can constitute a starting point for the modelling of target processes in the built supply chain structure. The second part presents template process models (Reference Models for selected action coordination mechanisms during enterprise cooperation. The aim of the article is the presentation the model an Electronic Bulletin Board (EBB, as a mechanism of coordination of actions in complex systems. Results: The article was prepared on the basis of literature from the researched area. The material was also prepared on the basis of interviews with practitioners. They have allowed for the preparation of template process models (Reference Models for selected action coordination methods in the supply chain. Conclusions: The result of the work is a prepared model as well as its description in the use of IDEF0. The presented model is a demonstrative model. The proposed reference model makes it possible to define the parameters of a selected mechanism of coordination of actions, and forms a basis for affecting the progression of the process through an analysis of values of identified parameters. The parameterization of elements constitutes the foundation for the monitoring of the process via 1 unambiguous identification of the object of monitoring and 2 analysis of different variants of the progression of the process.

  16. New class of phosphine oxide donor-based supramolecular coordination complexes from an in situ phosphine oxidation reaction or phosphine oxide ligands. (United States)

    Shankar, Bhaskaran; Elumalai, Palani; Shanmugam, Ramasamy; Singh, Virender; Masram, Dhanraj T; Sathiyendiran, Malaichamy


    A one-pot, multicomponent, coordination-driven self-assembly approach was used to synthesize the first examples of neutral bridging phosphine oxide donor-based supramolecular coordination complexes. The complexes were self-assembled from a fac-Re(CO)3 acceptor, an anionic bridging O donor, and a neutral soft phosphine or hard phosphine oxide donor.

  17. Superchiral Pd3 L6 Coordination Complex and Its Reversible Structural Conversion into Pd3 L3 Cl6 Metallocycles. (United States)

    Jurček, Ondřej; Bonakdarzadeh, Pia; Kalenius, Elina; Linnanto, Juha Matti; Groessl, Michael; Knochenmuss, Richard; Ihalainen, Janne A; Rissanen, Kari


    Large, non-symmetrical, inherently chiral bispyridyl ligand L derived from natural ursodeoxycholic bile acid was used for square-planar coordination of tetravalent Pd(II) , yielding the cationic single enantiomer of superchiral coordination complex 1 Pd3 L6 containing 60 well-defined chiral centers in its flower-like structure. Complex 1 can readily be transformed by addition of chloride into a smaller enantiomerically pure cyclic trimer 2 Pd3 L3 Cl6 containing 30 chiral centers. This transformation is reversible and can be restored by the addition of silver cations. Furthermore, a mixture of two constitutional isomers of trimer, 2 and 2', and dimer, 3 and 3', can be obtained directly from L by its coordination to trans- or cis-N-pyridyl-coordinating Pd(II) . These intriguing, water-resistant, stable supramolecular assemblies have been thoroughly described by (1) H DOSY NMR, mass spectrometry, circular dichroism, molecular modelling, and drift tube ion-mobility mass spectrometry.

  18. Thermochemical Study on Coordination Complex of Samarium with Salicylic Acid and 8-Hydroxyquinoline

    Institute of Scientific and Technical Information of China (English)


    The coordination complex Sm(C7H5O3)2·(C9H6NO), synthesized from the reaction of samarium chloride six-hydrate with salicylic acid and 8-hydroxyquinoline, was characterized with IR, elemental analysis, molar conductance, and thermogravimatric analysis. The standard molar enthalpies of solution of [SmCl3·6H2O(s)], [2C7H6O3(s)], [C9H7NO(s)] and [Sm(C7H5O3)2·(C9H6NO)(s)] in the calorimetric solvent were determined with the solution-reaction isoperibol calorimeter at 298.15 K to be ΔsHΘm[SmCl3·6H2O (s), 298.15 K]=-103.98±0.04 kJ·mol-1, ΔsHΘm[2 C7H6O3 (s), 298.15 K]=16.35±0.14 kJ·mol-1, ΔsHΘm[C9H7NO (s), 298.15 K]=-6.11±0.08 kJ·mol-1 and ΔsHΘm[Sm(C7H5O3)2·(C9H6NO) (s), 298.15 K]=-130.08±0.04 kJ·mol-1, respectively. The enthalpy was determined to be ΔrHΘm=89.59±0.18 kJ·mol-1 for the reaction SmCl3·6H2O(s)+2C7H6O3(s)+C9H7NO(s)=Sm(C7H5O3)2·(C9H6NO)(s)+3HCl(g)+6H2O(l). According to the above results and the data given in literature and through Hess' law, the standard molar enthalpy of formation of Sm(C7H5O3)2·(C9H7NO)(s) was estimated to be ΔrHΘm[Sm(C7H5O3)2·(C9H6NO)(s), 298.15 K]=-2055.9±3.03 kJ·mol-1.

  19. Structural insights into complete metal ion coordination from ternary complexes of B family RB69 DNA polymerase. (United States)

    Xia, Shuangluo; Wang, Mina; Blaha, Gregor; Konigsberg, William H; Wang, Jimin


    We have captured a preinsertion ternary complex of RB69 DNA polymerase (RB69pol) containing the 3' hydroxyl group at the terminus of an extendable primer (ptO3') and a nonhydrolyzable 2'-deoxyuridine 5'-α,β-substituted triphosphate, dUpXpp, where X is either NH or CH(2), opposite a complementary templating dA nucleotide residue. Here we report four structures of these complexes formed by three different RB69pol variants with catalytically inert Ca(2+) and four other structures with catalytically competent Mn(2+) or Mg(2+). These structures provide new insights into why the complete divalent metal-ion coordination complexes at the A and B sites are required for nucleotidyl transfer. They show that the metal ion in the A site brings ptO3' close to the α-phosphorus atom (Pα) of the incoming dNTP to enable phosphodiester bond formation through simultaneous coordination of both ptO3' and the nonbridging Sp oxygen of the dNTP's α-phosphate. The coordination bond length of metal ion A as well as its ionic radius determines how close ptO3' can approach Pα. These variables are expected to affect the rate of bond formation. The metal ion in the B site brings the pyrophosphate product close enough to Pα to enable pyrophosphorolysis and assist in the departure of the pyrophosphate. In these dUpXpp-containing complexes, ptO3' occupies the vertex of a distorted metal ion A coordination octahedron. When ptO3' is placed at the vertex of an undistorted, idealized metal ion A octahedron, it is within bond formation distance to Pα. This geometric relationship appears to be conserved among DNA polymerases of known structure.

  20. Eddy-correlation measurements of benthic fluxes under complex flow conditions: Effects of coordinate transformations and averaging time scales

    DEFF Research Database (Denmark)

    Lorke, Andreas; McGinnis, Daniel F.; Maeck, Andreas


    hours of continuous eddy-correlation measurements of sediment oxygen fluxes in an impounded river, we demonstrate that rotation of measured current velocities into streamline coordinates can be a crucial and necessary step in data processing under complex flow conditions in non-flat environments...... in the context of the theoretical concepts underlying eddy-correlation measurements and a set of recommendations for planning and analyses of flux measurements are derived....

  1. Synthesis, crystal structure and spectral characterization of the first Ag+ complex compounds involving O,N,O-coordinated N-acylhydrazones of salicylaldehyde (United States)

    Repich, H. H.; Orysyk, S. I.; Orysyk, V. V.; Zborovskii, Yu. L.; Pekhnyo, V. I.; Vovk, M. V.


    N-acylhydrazones of salicylaldehyde is a well known class of ligands bearing O,N,O tridentate chelate coordination site. But up to now no structurally characterized Ag+ complexes with O,N,O coordinated N-acylhydrazones of salicylaldehyde were known. Therefore three Ag+ coordination compounds with functionally substituted N-acylhydrazones of salicylaldehyde were synthesized and characterized by X-ray diffraction, IR spectroscopy and thermogravimetric studies. In solutions the complexes were studied by 1H NMR and UV-Vis spectroscopy. The influence of the presence and location of additional nitrogen donor atoms in N-acylhydrazones of salicylaldehyde on their coordination modes was investigated. Ligand N'-salicylidenephenylacetohydrazide (contains no additional donor atoms) coordinates to Ag+ in classical O,N,O tridentate chelate manner. Ligand N‧-salicylidene-3-pyridinecarbohydrazide (contains β-N additional donor atom in acyl moiety) involves mixed O,N,O + β-N coordination. Whereas N'-salicylidene-4-pyridinecarbohydrazide (contains γ-N additional donor atom) coordinates to Ag+ in monodentate manner only via γ-N atom of heterocyclic substituent. All the complexes provide high coordination numbers of Ag+ and irregular shapes of coordination polyhedra which are not consistent with classical concepts of Ag+ coordination chemistry. However all the complexes are not thermally stable and easily undergo solvolysis upon dissolution.

  2. Molecular orbital study of coordinated dioxygen. I. Structure and bonding of model monomeric Co(II) complexes (United States)

    Boča, R.


    The CNDO—UHF type of MO—LCAO—SCP calculation is carried out for model systems of dioxygen fixation: O 2 CoCl 4L 2- complexes in which L = none and L = NH 3. A geometry variation is performed with respect to 5 internal coordinates describing the degrees of freedom of the Co—O 2 group. The calculated geometry, spin densities and atomic charges agree with available data based on X-ray and ESR measurements of real dioxygen carriers. Structure and bonding of complexes are discussed in more detail.

  3. Redox cycling of copper-amyloid β 1-16 peptide complexes is highly dependent on the coordination mode. (United States)

    Trujano-Ortiz, Lidia G; González, Felipe J; Quintanar, Liliana


    Copper (Cu)-amyloid β (Aβ) interactions play a role in the etiology of Alzheimer's disease. This work presents a spectroscopic and electrochemical study of two physiologically relevant Aβ-Cu(II) complexes, as a function of pH and relative Cu-Aβ(1-16) concentrations. Our results reveal that these coordination modes display distinct redox behaviors and provide experimental evidence for the existence of an intermediate Cu(I) species. A mechanism for the redox cycling of these complexes is proposed, providing further insight into the redox relevance of Aβ-Cu interactions.

  4. Analysis of Heme Iron Coordination in DGCR8: The Heme-Binding Component of the Microprocessor Complex. (United States)

    Girvan, Hazel M; Bradley, Justin M; Cheesman, Myles R; Kincaid, James R; Liu, Yilin; Czarnecki, Kazimierz; Fisher, Karl; Leys, David; Rigby, Stephen E J; Munro, Andrew W


    DGCR8 is the RNA-binding partner of the nuclease Drosha. Their complex (the "Microprocessor") is essential for processing of long, primary microRNAs (pri-miRNAs) in the nucleus. Binding of heme to DGCR8 is essential for pri-miRNA processing. On the basis of the split Soret ultraviolet-visible (UV-vis) spectrum of ferric DGCR8, bis-thiolate sulfur (cysteinate, Cys(-)) heme iron coordination of DGCR8 heme iron was proposed. We have characterized DGCR8 heme ligation using the Δ276 DGCR8 variant and combined electron paramagnetic resonance (EPR), magnetic circular dichroism (MCD), electron nuclear double resonance, resonance Raman, and electronic absorption spectroscopy. These studies indicate DGCR8 bis-Cys heme iron ligation, with conversion from bis-thiolate (Cys(-)/Cys(-)) axial coordination in ferric DGCR8 to bis-thiol (CysH/CysH) coordination in ferrous DGCR8. Pri-miRNA binding does not perturb ferric DGCR8's optical spectrum, consistent with the axial ligand environment being separated from the substrate-binding site. UV-vis absorption spectra of the Fe(II) and Fe(II)-CO forms indicate discrete species exhibiting peaks with absorption coefficients substantially larger than those for ferric DGCR8 and that previously reported for a ferrous form of DGCR8. Electron-nuclear double resonance spectroscopy data exclude histidine or water as axial ligands for ferric DGCR8 and favor bis-thiolate coordination in this form. UV-vis MCD and near-infrared MCD provide data consistent with this conclusion. UV-vis MCD data for ferrous DGCR8 reveal features consistent with bis-thiol heme iron coordination, and resonance Raman data for the ferrous-CO form are consistent with a thiol ligand trans to the CO. These studies support retention of DGCR8 cysteine coordination upon reduction, a conclusion distinct from those of previous studies of a different ferrous DGCR8 isoform.

  5. Deciphering the Conformational Choreography of Zinc Coordination Complexes with Standard and Novel Proton NMR Techniques Combined with DFT Methods. (United States)

    Pucheta, Jose Enrique Herbert; Prim, Damien; Gillet, Jean Michel; Farjon, Jonathan


    The presence of water has been shown to deeply impact the stability and geometry of Zn complexes in solution. Evidence for tetra- and penta-coordinated species in a pyridylmethylamine-Zn(II) model complex is presented. Novel (1) H NMR tools such as T1 -filtered selective exchange spectroscopy and pure shifted gradient-encoded selective refocusing as well as classical 2D ((1) H-(1) H) exchange spectroscopy, diffusion-ordered spectroscopy and T1 ((1) H) measurements, in combination with density functional theory methods allow the full conformational dynamics of a pyridylmethylamine-Zn(II) complex to be revealed. Four conformers and two families of complexes depending on the hydration states are elucidated.

  6. Cu(II) complexation by "non-coordinating" N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid (HEPES buffer). (United States)

    Sokołowska, Magdalena; Bal, Wojciech


    The combined potentiometric and spectroscopic studies of interactions of N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid (HEPES) with Cu(II) demonstrated that this popular buffer, commonly labelled as "non-coordinating" forms a CuL+ complex, with the logbeta(CuL) value of 3.22. This complex undergoes alkaline hydrolysis above pH 6, resulting in Cu(OH)2 precipitation. However, the presence of HEPES at a typical concentration of 100 mM at pH 7.4 elevates the apparent binding constant, being determined for a complex of another ligand, by a factor of 80. HEPES does not form ternary complexes with aminoacids Ala, Trp, and His, but may do so with other bioligands, such as nucleotides. Therefore, HEPES can still be recommended for Cu(II) studies in place of other common buffers, such as Tris and phosphate, but appropriate corrections and precautions should be applied in quantitative experiments.

  7. New insights into the coordination chemistry and molecular structure of copper(II) histidine complexes in aqueous solutions. (United States)

    Mesu, J Gerbrand; Visser, Tom; Soulimani, Fouad; van Faassen, Ernst E; de Peinder, Peter; Beale, Andrew M; Weckhuysen, Bert M


    Aqueous solutions of Cu2+/histidine (his) (1:2) have been analyzed in parallel with infrared, Raman, ultraviolet/visible/near-infrared, electron spin resonance, and X-ray absorption spectroscopy in the pH range from 0 to 10. Comprehensive interpretation of the data has been used to extract complementary structural information in order to determine the relative abundance of the different complexes. The formation of six different, partly coexisting species is proposed. Structural proposals from literature have been unambiguously confirmed, refined, or, in several cases, corrected. At highly acidic conditions, Cu2+ and his are present as free ions, but around pH = 2, coordination starts via the deprotonated carboxylic acid group. This results in the intermediate species Cu2+[H3his+(Oc)] and Cu2+[H3his+(Oc)]2. The coordination via Oc is attended with a drop in the pKa value of the other receptor groups resulting in a concomitant conversion to the bidentates Cu2+[H2his0(Oc,Nam)] and Cu2+[H2his0(Oc,Nam)]2, with the latter being dominant at pH = 3.5. Coordination of the imidazole ring begins around pH = 3 and leads to the formation of the mixed ligand complexes Cu2+[H2his0(Oc,Nam)][Hhis-(Oc,Nam,Nim)] and Cu2+[Hhis-(Nam,Nim)][Hhis-(Oc,Nam,Nim)] around pH = 5. It is demonstrated that coordination of the imidazole ring occurs predominantly via the N(pi) atom. At pH > 7, the double-tridentate ligand complex Cu2+[Hhis-(Oc,Nam,Nim)]2 is the major species with the N atoms in the equatorial plane and the O atoms in the axial position. This complex decomposes at pH > 10 into a copper oxide/hydroxide precipitate. The overall results provide a consistent picture of the mechanism that drives the coordination and complex formation of the Cu2+/his system.

  8. Heterotopic silver-NHC complexes: from coordination polymers to supramolecular assemblies

    NARCIS (Netherlands)

    Rubio, M.; Siegler, M. A.; Spek, A.L.; Reek, J.N.H.


    New coordination polymers based on different combinations of silver atoms and pyridyl-substituted N-heterocyclic carbene moieties are described. The addition of Zn(ii) templates leads to Ag-Zn supramolecular assemblies via selective ZnN interactions; a process that can be reverted.

  9. Heterotopic silver-NHC complexes: from coordination polymers to supramolecular assemblies

    NARCIS (Netherlands)

    Rubio, M.; Siegler, M.A.; Spek, A.L.; Reek, J.N.H.


    New coordination polymers based on different combinations of silver atoms and pyridyl-substituted N-heterocyclic carbene moieties are described. The addition of Zn(II) templates leads to Ag-Zn supramolecular assemblies via selective Zn⋯N interactions; a process that can be reverted.

  10. Complex

    African Journals Online (AJOL)


    Schiff bases and their complex compounds have been studied for their .... establishing coordination of the N–(2 – hydroxybenzyl) - L - α - valine Schiff base ..... (1967); “Spectrophotometric Identification of Organic Compounds”, Willey, New.

  11. Synthesis, spectroscopy, thermal studies and supramolecular structures of two new alkali-earth 4-nitrobenzoate complexes containing coordinated imidazole

    Indian Academy of Sciences (India)

    Bikshandarkoil R Srinivasan; Jyoti V Sawant; Pallepogu Raghavaiah


    The reaction of hydrated magnesium or calcium 4-nitrobenzoate (4-nba) generated in situ, with imidazole (Im) results in the formation of the complexes [Mg(H2O)2(Im)2(4-nba)2] 1 and [Ca(H2O)3(Im)(4-nba)2]$\\cdot$Im 2, which exhibit the same metal:4-nba:Im ratio but different degrees of hydration. Complex 1 crystallizes in the triclinic $_{\\bar{i}}$ space group and the Mg atom is located on an inversion centre, while 2 crystallizes in the monoclinic 21/ space group and all atoms are located in general positions. In 1 the Im ligands, which are trans to each other, are coordinated to Mg, while 2 contains coordinated as well as free Im. The monodentate 4-nba ligands are disposed trans to each other in 1, while they adopt a cis orientation in 2 resulting in different supramolecular structures. Complex 1 exhibits two types of H-bonding interactions namely O-HO and N-HO, while in 2 three varieties of H-bond, viz. O-HO, N-HO and O-HN are observed. The Im ligand functions as a bifurcated H-bond donor in 1 while the O atom of the nitro group functions as a H-bond acceptor. In contrast, the nitro group in 2 is not involved in any H-bonding interactions. The free Im in 2 functions as a bifurcated acceptor and forms an extended chain linking adjacent complex molecules. The chains thus formed are further cross-linked with the aid of H-donor bonds from both the free as well as the coordinated Im. Both 1 and 2 exhibit - stacking interactions. Complex 1 is thermally more stable as compared to 2, and both complexes can be dehydrated to the corresponding anhydrous complexes by heating at 140 and 100°C respectively. At elevated temperatures, both the complexes can be pyrolysed to the corresponding oxide. The anhydrous complexes can be rehydrated to obtain the starting hydrated materials.

  12. Shapiro's plane waves in spaces of constant curvature and separation of variables in real and complex coordinates

    CERN Document Server

    Ovsiyuk, E M; Red'kov, V M


    The aim of the article to clarify the status of Shapiro plane wave solutions of the Schr\\"odinger's equation in the frames of the well-known general method of separation of variables. To solve this task, we use the well-known cylindrical coordinates in Riemann and Lobachevsky spaces, naturally related with Euler angle-parameters. Conclusion may be drawn: the general method of separation of variables embraces the all plane wave solutions; the plane waves in Lobachevsky and Riemann space consist of a small part of the whole set of basis wave functions of Schr\\"odinger equation. In space of constant positive curvature $S_{3}$, a complex analog of horospherical coordinates of Lobachevsky space $H_{3}$ is introduced. To parameterize real space $S_{3}$, two complex coordinates $(r,z)$ must obey additional restriction in the form of the equation $r^{2} = e^{z-z^{*}} - e^{2z} $. The metrical tensor of space $S_{3}$ is expressed in terms of $(r,z)$ with additional constraint, or through pairs of conjugate variables $(...

  13. Synthesis of a base-stabilized silanone-coordinated complex by oxygenation of a (silyl)(silylene)tungsten complex. (United States)

    Muraoka, Takako; Abe, Keisuke; Haga, Youhei; Nakamura, Tomoko; Ueno, Keiji


    Base-stabilized silanone complex Cp*(OC)(2)W(SiMe(3)){O═SiMes(2)(DMAP)} (2) was synthesized by the reaction of (silyl)(silylene)tungsten complex Cp*(OC)(2)W(SiMe(3))(═SiMes(2)) (1) with 1 equiv of pyridine-N-oxide (PNO) in the presence of 4-(dimethylamino)pyridine (DMAP). Further oxygenation of 2 with 3 equiv of PNO at 80 °C resulted in the formation of a W-O-Si-O-Si framework to give disiloxanoxy complex Cp*(O)(2)W{OSiMes(2)(OSiMe(3))} (3). Complex 3 was also obtained by the direct reaction of complex 1 with 4 equiv of PNO at 80 °C.

  14. Synthesis, structural, thermal and optical studies of rare earth coordinated complex: Tb(Sal){sub 3}Phen

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Gagandeep; Dwivedi, Y. [Laser and Spectroscopy Laboratory, Department of Physics, Banaras Hindu University, Varanasi 221005 (India); Rai, S.B., E-mail: [Laser and Spectroscopy Laboratory, Department of Physics, Banaras Hindu University, Varanasi 221005 (India)


    Highlights: {yields} RE coordinated complex of Tb(Sal){sub 3}Phen in crystalline phases were synthesized. {yields} Enhancement in luminescence of Tb{sup 3+} was observed in complex on 355 nm excitation. {yields} Fluorescence enhancement is due to the efficient energy transfer from Sal to Tb{sup 3+}. {yields} An observed increase in lifetime of Tb{sup 3+} is due to encapsulation in Sal/Phen network. {yields} The present system is a deserving candidate for LSC when coupled with solar cells. - Abstract: Complexes of salicylic acid (Sal) and 1,10-phenanthroline (Phen) were synthesized coordinated with terbium ion (Tb{sup 3+}) in crystalline phases. The structural characterizations of the lanthanide complex were made using FT-IR, NMR ({sup 1}H and {sup 13}C) and XRD techniques. These measurements confirm the formation of Tb(Sal){sub 3}Phen complex structure. The thermal aspects of the complex were examined using DTA and TGA techniques. An enhancement in luminescence intensity of Tb{sup 3+} ion bands were observed in Tb(Sal){sub 3}Phen complex as compared to TbCl{sub 3} crystals on 355 nm laser excitation. Enhancement is reported due to the efficient energy transfer process from Sal to Tb{sup 3+} ions. This is also confirmed by the time resolved photoluminescence spectroscopy with increase in lifetime of Tb{sup 3+} ions due to encapsulation in Sal/Phen network. Our system in itself can be a deserving candidate for luminescent solar collector material when coupled with solar cells.

  15. Titanium coordination compounds: from discrete metal complexes to metal–organic frameworks

    KAUST Repository

    Assi, Hala


    Owing to their promise in photocatalysis and optoelectronics, titanium based metal–organic frameworks (MOFs) are one of the most appealing classes of MOFs reported to date. Nevertheless, Ti-MOFs are still very scarce because of their challenging synthesis associated with a poor degree of control of their chemistry and crystallization. This review aims at giving an overview of the recent progress in this field focusing on the most relevant existing titanium coordination compounds as well as their promising photoredox properties. Not only Ti-MOFs but also Ti-oxo-clusters will be discussed and particular interest will be dedicated to highlight the different successful synthetic strategies allowing to overcome the still “unpredictable” reactivity of titanium ions, particularly to afford crystalline porous coordination polymers.

  16. Titanium coordination compounds: from discrete metal complexes to metal-organic frameworks. (United States)

    Assi, Hala; Mouchaham, Georges; Steunou, Nathalie; Devic, Thomas; Serre, Christian


    Owing to their promise in photocatalysis and optoelectronics, titanium based metal-organic frameworks (MOFs) are one of the most appealing classes of MOFs reported to date. Nevertheless, Ti-MOFs are still very scarce because of their challenging synthesis associated with a poor degree of control of their chemistry and crystallization. This review aims at giving an overview of the recent progress in this field focusing on the most relevant existing titanium coordination compounds as well as their promising photoredox properties. Not only Ti-MOFs but also Ti-oxo-clusters will be discussed and particular interest will be dedicated to highlight the different successful synthetic strategies allowing to overcome the still "unpredictable" reactivity of titanium ions, particularly to afford crystalline porous coordination polymers.

  17. Anion coordination complex [ClPt(bpt)4]Cl (bpt= N,N’-bis(3-pyridylmethyl)-2-thiourea)

    Institute of Scientific and Technical Information of China (English)


    The anion coordination complex,[ClPt(bpt)4]Cl (bpt=N,N’-bis(3-pyridylmethyl)-2-thiourea),was synthesized and studied by X-ray crystal structure analysis,NMR and FAB mass spectra. In the solid state,the Pt(bpt)4 anion receptor adopts a cone conformation to bind the chloride anion through hydrogen bonds and electrostatic interaction in which the four branches of the thiourea ligands bind the chloride anion to form N-H…Cl-hydrogen bonds (3.49-3.81). The entraped chloride anion is situated above the Pt(Ⅱ) center at 3.52 . Further second-sphere coordination assemby from the Pt(bpt)4 core with 8 zinc(Ⅱ) tetraphenylporphyrins (ZnPr) is discussed.

  18. Anion coordination complex [Cl Pt(bpt)4]Cl (bpt=N,N'- bis(3-pyridylmethyl)-2-thiourea)

    Institute of Scientific and Technical Information of China (English)

    LI Xin; LI Hui; YU ShuYan; LI YiZhi


    The anion coordination complex, [Cl Pt(bpt)4]Cl (bpt=N,N'-bis(3-pyridylmethyl)-2-thiourea), was synthesized and studied by X-ray crystal structure analysis, NMR and FAB mass spectre. In the solid state, the Pt(bpt)4 anion receptor adopts a cone conformation to bind the chloride anion through hydrogen bonds and electrostatic interaction in which the four branches of the thiourea ligands bind the chloride anion to form N-H...Cl- hydrogen bonds (3.49--3.81 A). The entraped chloride anion is situated above the Pt(Ⅱ) center at 3.52 A. Further second-sphere coordination assemby from the Pt(bpt)4 core with 8 zinc(Ⅱ) tetraphenylporphyrins (ZnPr) is discussed.

  19. Dance choreography is coordinated with song repertoire in a complex avian display. (United States)

    Dalziell, Anastasia H; Peters, Richard A; Cockburn, Andrew; Dorland, Alexandra D; Maisey, Alex C; Magrath, Robert D


    All human cultures have music and dance, and the two activities are so closely integrated that many languages use just one word to describe both. Recent research points to a deep cognitive connection between music and dance-like movements in humans, fueling speculation that music and dance have coevolved and prompting the need for studies of audiovisual displays in other animals. However, little is known about how nonhuman animals integrate acoustic and movement display components. One striking property of human displays is that performers coordinate dance with music by matching types of dance movements with types of music, as when dancers waltz to waltz music. Here, we show that a bird also temporally coordinates a repertoire of song types with a repertoire of dance-like movements. During displays, male superb lyrebirds (Menura novaehollandiae) sing four different song types, matching each with a unique set of movements and delivering song and dance types in a predictable sequence. Crucially, display movements are both unnecessary for the production of sound and voluntary, because males sometimes sing without dancing. Thus, the coordination of independently produced repertoires of acoustic and movement signals is not a uniquely human trait.

  20. Making oxidation potentials predictable: Coordination of additives applied to the electronic fine tuning of an iron(II) complex

    KAUST Repository

    Haslinger, Stefan


    This work examines the impact of axially coordinating additives on the electronic structure of a bioinspired octahedral low-spin iron(II) N-heterocyclic carbene (Fe-NHC) complex. Bearing two labile trans-acetonitrile ligands, the Fe-NHC complex, which is also an excellent oxidation catalyst, is prone to axial ligand exchange. Phosphine- and pyridine-based additives are used for substitution of the acetonitrile ligands. On the basis of the resulting defined complexes, predictability of the oxidation potentials is demonstrated, based on a correlation between cyclic voltammetry experiments and density functional theory calculated molecular orbital energies. Fundamental insights into changes of the electronic properties upon axial ligand exchange and the impact on related attributes will finally lead to target-oriented manipulation of the electronic properties and consequently to the effective tuning of the reactivity of bioinspired systems.

  1. Pendant—armed Unsymmetrical Aza—macrocycles:Syntheses,Coordination Behavior and Crystal Structure of a Dinuclear Cadmium Complex

    Institute of Scientific and Technical Information of China (English)

    陶京朝; 廖新成; 等


    Two unsymmetridcal tetradentate aza-macrocycles with side arms attached to whte Nsp3 atoms ,L1 and L2 ,as well as their complexes with different metal cations were synthesized and characterized by EA,UV IR ,1H NMR and MS spectra ,Both the two ligands can efficiently transport alkai and transition metal cations across an organic membrane with high selectivity ratio.The structure of a dinuclear Cd(Ⅱ) complex [L1.(CdCl2)2] was elucidated by X-ray crystallography and was solved by the heavy-atom method to a final R value of 0.029 for 3084 reflections with |F|>3σ(I), In the exo-structure of the dinuclear complex each cadmium atom is five-coordinated,bonding to three N atoms and two chlorine atoms.

  2. Pendant-armed Unsymmetrical Aza-macrocycles: Syntheses,Coordination Behavior and Crystal Structure of a Dinuclear Cadmium Complex

    Institute of Scientific and Technical Information of China (English)

    TAO,Jing-Chao(陶京朝); LIAO,Xin-Cheng(廖新成); WANG,Xing-Wang(王兴旺); DU,Chen-Xia(杜晨霞)


    Two nsymmetrical tetradentate aza-macrocycles with side arms attached to the N3sp atoms, L1 and L2, as well as their complexes with different metal cations were synthesized and characterized by EA, UV, IR, 1H NMR and MS spectra. Both the two ligands can efficiently transport alkali and transition metal cations across an organic membrane with high selectivity ratio. The structure of a dinuclear Cd(Ⅱ)complex [L1@(CdCl2)2] was elucdated by X-ray crystallography and was solved by the heavy-atom method to afinal R value of 0.029 for 3084reflections with |F| >3σ(I). In the exo-structore of the dinuclear complex each cadmium atom is five-coordinated, bonding to three N atoms and two chlorine atoms.

  3. Systematic coordination chemistry and cytotoxicity of copper(II) complexes with methyl substituted 4-nitropyridine N-oxides. (United States)

    Puszko, Aniela; Brzuszkiewicz, Anna; Jezierska, Julia; Adach, Anna; Wietrzyk, Joanna; Filip, Beata; Pełczynska, Marzena; Cieslak-Golonka, Maria


    Three new nitrato copper(II) complexes of dimethyl substituted 4-nitropyridine N-oxide were synthesized and characterized by elemental analysis, magnetic, spectroscopic, thermal and X-ray methods, respectively. They were isolated as trans isomers, mononuclear (μ=1.70-1.88 BM), five (1-2) and four (3) coordinate species of general formula [Cu(NO3)2(H2O)L2] where L=2,3-dimethyl-, 2,5-dimethyl-4-nitropyridine N-oxide and [Cu (NO3)2L2], L=3,5-dimethyl-4-nitropyridine N-oxide, respectively. The X-ray crystal structure of (1) (L=2,3-dimethyl-4-nitropyridine N-oxide) was determined. The organic ligands, the complexes and copper hexaqua ion as a reference were tested in vitro on the cytotoxic activity against human cancer cell lines: MCF-7 (breast), SW-707 (colon) and P-388 (murine leukemia). The complexes are relatively strong cytotoxic agents towards P-388 cell line. Comparative analysis was performed for all known copper(II) complexes containing methyl derivatives of the 4-nitropyridine N-oxide on the basis of their composition, structure and cytotoxic activities. To obtain the typical structure for these species (i.e., 4-coordinate mononuclear of the type trans-[Cu(inorganic anion)2L2]), two methyl groups must be situated on both sides of nitrogen atom(s) (i.e., NO and NO2) in the ligand. The biological activity was found to be strongly dependent upon the number of the methyl groups and the type of cell line. The best cytotoxic results were found for the complexes without substituents or with one methyl group. Generally, for all cell lines, the complexation increased cytotoxicity when compared with the free ligands.

  4. Dipyridyl β-diketonate complexes and their use as metalloligands in the formation of mixed-metal coordination networks. (United States)

    Burrows, Andrew D; Mahon, Mary F; Renouf, Catherine L; Richardson, Christopher; Warren, Anna J; Warren, John E


    The iron(III) and aluminium(III) complexes of 1,3-di(4-pyridyl)propane-1,3-dionato (dppd) and 1,3-di(3-pyridyl)propane-1,3-dionato (dmppd), [Fe(dppd)(3)] 1, [Fe(dmppd)(3)] 2, [Al(dppd)(3)] 3 and [Al(dmppd)(3)] 4 have been prepared. These complexes adopt molecular structures in which the metal centres contain distorted octahedral geometries. In contrast, the copper(II) and zinc(II) complexes [Cu(dppd)(2)] 5 and [Zn(dmppd)(2)] 6 both form polymeric structures in which coordination of the pyridyl groups into the axial positions of neighbouring metal centres links discrete square-planar complexes into two-dimensional networks. The europium complex [Eu(dmppd)(2)(H(2)O)(4)]Cl·2EtOH·0.5H(2)O 7 forms a structure containing discrete cations that are linked into sheets through hydrogen bonds, whereas the lanthanum complex [La(dmppd)(3)(H(2)O)]·2H(2)O 8 adopts a one-dimensional network structure, connected into sheets by hydrogen bonds. The iron complexes 1 and 2 act as metalloligands in reactions with silver(I) salts, with the nature of the product depending on the counter-ions present. Thus, the reaction between 1 and AgBF(4) gave [AgFe(dppd)(3)]BF(4)·DMSO 9, in which the silver centres link the metalloligands into discrete nanotubes, whereas reactions with AgPF(6) and AgSbF(6) gave [AgFe(dppd)(3)]PF(6)·3.28DMSO 10 and [AgFe(dppd)(3)]SbF(6)·1.25DMSO 11, in which the metalloligands are linked into sheets. In all three cases, only four of the six pyridyl groups present on the metalloligands are coordinated. The reaction between 2 and AgNO(3) gave [Ag(2)Fe(dmppd)(3)(ONO(2))]NO(3)·MeCN·CH(2)Cl(2)12. Compound 12 adopts a layer structure in which all pyridyl groups are coordinated to silver centres and, in addition, a nitrate ion bridges between two silver centres. A similar structure is adopted by [Ag(2)Fe(dmppd)(3)(O(2)CCF(3))]CF(3)CO(2)·2MeCN·0.25CH(2)Cl(2)13, with a bridging trifluoroacetate ion playing the same role as the nitrate ion in 12.

  5. Impact of the equatorial coordination sphere on the rate of reduction, lipophilicity and cytotoxic activity of platinum(IV) complexes. (United States)

    Höfer, Doris; Varbanov, Hristo P; Hejl, Michaela; Jakupec, Michael A; Roller, Alexander; Galanski, Markus; Keppler, Bernhard K


    The impact of the equatorial coordination sphere on the reduction behavior (i.e. rate of reduction) of platinum(IV) complexes with axial carboxylato ligands was studied. Moreover, the influence of equatorial ligands on the stability, lipophilicity and cytotoxicity of platinum(IV) compounds was evaluated. For this purpose, a series of platinum(IV) complexes featuring axial carboxylato ligands (succinic acid monoesters) was synthesized; anionic carboxylato (OAc(-), oxalate) and halido (Cl(-), Br(-), I(-)) ligands served as leaving groups and am(m)ine carrier ligands were provided by monodentately (isopropylamine, ammine+cyclohexaneamine) or bidentately (ethane-1,2-diamine) coordinating am(m)ines. All platinum(IV) products were fully characterized based on elemental analysis, high resolution mass spectrometry and multinuclear ((1)H, (13)C, (15)N, (195)Pt) NMR spectroscopy as well as by X-ray diffraction in some cases. The rate of reduction in the presence of ascorbic acid was determined by NMR spectroscopy and the lipophilicity of the complexes was investigated by analytical reversed phase HPLC measurements. Cytotoxic properties were studied by means of a colorimetric microculture assay in three human cancer cell lines derived from cisplatin sensitive ovarian teratocarcinoma (CH1/PA-1) as well as cisplatin insensitive colon carcinoma (SW480) and non-small cell lung cancer (A549). Copyright © 2017 Elsevier Inc. All rights reserved.

  6. A new role for RINT-1 in SNARE complex assembly at the trans-Golgi network in coordination with the COG complex. (United States)

    Arasaki, Kohei; Takagi, Daichi; Furuno, Akiko; Sohda, Miwa; Misumi, Yoshio; Wakana, Yuichi; Inoue, Hiroki; Tagaya, Mitsuo


    Docking and fusion of transport vesicles/carriers with the target membrane involve a tethering factor-mediated initial contact followed by soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE)-catalyzed membrane fusion. The multisubunit tethering CATCHR family complexes (Dsl1, COG, exocyst, and GARP complexes) share very low sequence homology among subunits despite likely evolving from a common ancestor and participate in fundamentally different membrane trafficking pathways. Yeast Tip20, as a subunit of the Dsl1 complex, has been implicated in retrograde transport from the Golgi apparatus to the endoplasmic reticulum. Our previous study showed that RINT-1, the mammalian counterpart of yeast Tip20, mediates the association of ZW10 (mammalian Dsl1) with endoplasmic reticulum-localized SNARE proteins. In the present study, we show that RINT-1 is also required for endosome-to-trans-Golgi network trafficking. RINT-1 uncomplexed with ZW10 interacts with the COG complex, another member of the CATCHR family complex, and regulates SNARE complex assembly at the trans-Golgi network. This additional role for RINT-1 may in part reflect adaptation to the demand for more diverse transport routes from endosomes to the trans-Golgi network in mammals compared with those in a unicellular organism, yeast. The present findings highlight a new role of RINT-1 in coordination with the COG complex.

  7. Nitrite reduction by a pyridinediimine complex with a proton-responsive secondary coordination sphere. (United States)

    Kwon, Yubin M; Delgado, Mayra; Zakharov, Lev N; Seda, Takele; Gilbertson, John D


    The proton-responsive pyridinediimine ligand, (DEA)PDI (where (DEA)PDI = [(2,6-(i)PrC6H3)(N[double bond, length as m-dash]CMe)(N(Et)2C2H4)(N[double bond, length as m-dash]CMe)C5H3N]) was utilized for the reduction of NO2(-) to NO. Nitrite reduction is facilitated by the protonated secondary coordination sphere coupled with the ligand-based redox-active sites of [Fe(H(DEA)PDI)(CO)2](+) and results in the formation of the {Fe(NO)2}(9) DNIC, [Fe((DEA)PDI)(NO)2](+).

  8. Catalytic dioxygen activation by Co(II) complexes employing a coordinatively versatile ligand scaffold. (United States)

    Sharma, Savita K; May, Philip S; Jones, Matthew B; Lense, Sheri; Hardcastle, Kenneth I; MacBeth, Cora E


    The ligand bis(2-isobutyrylamidophenyl)amine has been prepared and used to stabilize both mononuclear and dinuclear cobalt(II) complexes. The nuclearity of the cobalt product is regulated by the deprotonation state of the ligand. Both complexes catalytically oxidize triphenylphosphine to triphenylphosphine oxide in the presence of O(2).

  9. Synthesis, spectroscopic, coordination and biological activities of some organometallic complexes derived from thio-Schiff base ligands (United States)

    Abou-Hussein, Azza A.; Linert, Wolfgang


    Two series of mono- and binuclear complexes cyclic or acyclic thio-ferocine Schiff base ligands, derived from the condensation of 2-aminobenzenthiol (L) with monoacetyl ferrocene in the molar ratio 1:1 or in the molar ratio 1:2 for diacetyl ferocine have been prepared. The condensation reactions yield the corresponding Schiff Base ligands, HLa-Maf and H2Lb-Daf. The chelation of the ligands to metal ions occurs through the sulfur of the thiol group as well as the nitrogen atoms of the azomethine group of the ligands. HLa-Maf acts as monobasic bidentate or dibasic tetradentate, while H2Lb-Daf behaves as twice negatively cargend tetradentate ligand. The structures of these ligands were elucidated by elemental analysis, infrared, ultraviolet-visible spectra, as well as 1H NMR spectra. Reactions of the Schiff bases ligands with ruthenium(III), oxovanadium(IV) and dioxouranium(VI) afforded the corresponding transition metal complexes. The properties of the newly prepared complexes were analyse by elemental analyses, infrared, electronic spectra, 1H NMR as well as the magnetic susceptibility and conductivity measurement. The metal complexes exhibits different geometrical arrangements such as octahedral and square pyramidal coordination. Schiff base ligands and their metal complexes were tested against two pathogenic bacteria as Gram-positive and Gram-negative bacteria as well as one kind of fungi to study their biological activity. All the complexes exhibit antibacterial and antifungal activities against these organisms.

  10. Coordination chemistry of sugar-phosphate complexes with palladium(II), rhenium(V) and zinc(II)

    Energy Technology Data Exchange (ETDEWEB)

    Steinborn, Christian Martin


    As described before, some studies dealing with coordination chemistry of sugar phosphates are available but no analogous complexes of Zn{sup II} have been investigated yet. The primary goal of this work is, therefore, to fill this gap. In order to stay close to the active sites of enzymes such as class-II-aldolase, the simple metal fragment Zn{sup II}(dien) is used. NMR spectroscopy is used primarily as analytical method since it enables the investigation of both complex equilibria in solution and pH dependence of metal-binding sites. Since this approach is challenging due to the fast metal-ligand exchange and the absence of CIS values, it is necessary to improve the significance of NMR data collected from sugar-phosphate complexes with Zn{sup II}. Hence, further experiments are performed with molecules similar to sugar phosphates such as reducing and methylated sugars or polyols. Beside NMR spectroscopy, crystal-structure analysis will be used to get more detailed information about the binding pattern of the complexes. Additionally, sugar-phosphate complexes of Pd{sup II} are investigated. Further experiments are conducted, on the one hand, to synthesise more sugarphosphate complexes with ReVON2 fragments, and, on the other hand, to grow crystals confirming the theory about mixed sugar-core-phosphate chelation.

  11. Modeling the magnetic properties of lanthanide complexes: relationship of the REC parameters with Pauling electronegativity and coordination number. (United States)

    Baldoví, José J; Gaita-Ariño, Alejandro; Coronado, Eugenio


    In a previous study, we introduced the Radial Effective Charge (REC) model to study the magnetic properties of lanthanide single ion magnets. Now, we perform an empirical determination of the effective charges (Zi) and radial displacements (Dr) of this model using spectroscopic data. This systematic study allows us to relate Dr and Zi with chemical factors such as the coordination number and the electronegativities of the metal and the donor atoms. This strategy is being used to drastically reduce the number of free parameters in the modeling of the magnetic and spectroscopic properties of f-element complexes.

  12. Spin crossover in Fe(II) complexes with N4S2 coordination

    DEFF Research Database (Denmark)

    Arroyave, Alejandra; Lennartson, Anders; Dragulescu-Andrasi, Alina;


    A systematic study of a series of Fe(II) complexes with the tetradentate N2S2-binding ligand and NCX− coligands (X = S, Se, BH3) conclusively demonstrates the occurrence of temperature-driven spin crossover (SCO), which is rarely observed for the Fe(II) ion in the N4S2 coordination environment....... The SCO is confirmed by crystallography, magnetic measurements, and Mössbauer spectroscopy. The last two methods also reveal a light-induced excited spin state trapping (LIESST) effect at low temperatures....

  13. Expanding the steric coverage offered by bis(amidosilyl) chelates: isolation of low-coordinate N-heterocyclic germylene complexes. (United States)

    Liew, Sean K; Al-Rafia, S M Ibrahim; Goettel, James T; Lummis, Paul A; McDonald, Sean M; Miedema, Leah J; Ferguson, Michael J; McDonald, Robert; Rivard, Eric


    The synthesis and coordination chemistry of a series of dianionic bis(amido)silyl and bis(amido)disilyl, [NSiN] and [NSiSiN], chelates with N-bound aryl or sterically modified triarylsilyl (SiAr(3)) groups is reported. In order to provide a consistent comparison of the steric coverage afforded by each ligand construct, various two-coordinate N-heterocyclic germylene complexes featuring each ligand set were prepared and oxidative S-atom transfer chemistry was explored. In the cases where clean oxidation transpired, sulfido-bridged centrosymmetric germanium(IV) dimers of the general form [LGe(μ-S)](2) (L = bis(amidosilyl) ligands) were obtained in lieu of the target monomeric germanethiones with discrete Ge═S double bonds. These results indicate that the reported chelates possess sufficient conformational flexibility to allow for the dimerization of LGe═S units to occur. Notably, the new triarylsilyl groups (4-RC(6)H(4))(3)Si- (R = (t)Bu and (i)Pr) still offer considerably expanded degrees of steric coverage relative to the parent congener, -SiPh(3,) and thus the use of substituted triarylsilyl groups within ligand design strategies should be a generally useful concept in advancing low-coordination main group and transition-metal chemistry.

  14. Dynamic Resectorization and Coordination Technology: An Evaluation of Air Traffic Control Complexity (United States)

    Brinton, Christopher R.


    The work described in this report is done under contract with the National Aeronautics and Space Administration (NASA) to support the Advanced Air Transportation Technology (AATR) program. The goal of this program is to contribute to and accelerate progress in Advanced Air Transportation Technologies. Wyndemere Incorporated is supporting this goal by studying the complexity of the Air Traffic Specialist's role in maintaining the safety of the Air Transportation system. It is envisioned that the implementation of Free Flight may significantly increase the complexity and difficulty of maintaining this safety. Wyndemere Incorporated is researching potential methods to reduce this complexity. This is the final report for the contract.

  15. Synthesis, Spectral and Thermal Behavior of Some New Four Coordinated Complexes


    Montazerozohori,M.; Khani, S.; S. Joohari; Musavi, S. A.


    A new symmetric bidentate Schiff base N, N′ bis(4-fluorobenzal-dehydene)-1,2-diaminoethane(L) and its complexes with general formula MLX2 (M= Zn(II), Cd(II) and Hg(II) and X=chloride, bromide, iodide, thiocyanate and azide) have been prepared. The ligand and complexes have been established by microanalysis, electronic, FT-IR, 1H and 13C NMR spectra, and by molar conductivity measurements. All compounds are non-electrolytes in chloroform or DMSO-d6. The thermal behavior of the complexes shows ...

  16. A New Polynuclear Coordination Type for (Salicylaldoxime)copper(II) Complexes: Structure and Magnetic Properties of an (Oxime)Cu6 Cluster

    DEFF Research Database (Denmark)

    Wenzel, Marco; Forgan, Ross S.; Faure, Anaëlle;


    A previously unseen coordination mode is reported for (salicylaldoxime)copper complexes utilising a linked zwitterionic NO22- donor set. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)......A previously unseen coordination mode is reported for (salicylaldoxime)copper complexes utilising a linked zwitterionic NO22- donor set. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)...

  17. HTP-1-dependent constraints coordinate homolog pairing and synapsis and promote chiasma formation during C. elegans meiosis. (United States)

    Martinez-Perez, Enrique; Villeneuve, Anne M


    Synaptonemal complex (SC) assembly must occur between correctly paired homologous chromosomes to promote formation of chiasmata. Here, we identify the Caenorhabditis elegans HORMA-domain protein HTP-1 as a key player in coordinating establishment of homolog pairing and synapsis in C. elegans and provide evidence that checkpoint-like mechanisms couple these early meiotic prophase events. htp-1 mutants are defective in the establishment of pairing, but in contrast with the pairing-defective chk-2 mutant, SC assembly is not inhibited and generalized nonhomologous synapsis occurs. Extensive nonhomologous synapsis in htp-1; chk-2 double mutants indicates that HTP-1 is required for the inhibition of SC assembly observed in chk-2 gonads. htp-1 mutants show a decreased abundance of nuclei exhibiting a polarized organization that normally accompanies establishment of pairing; analysis of htp-1; syp-2 double mutants suggests that HTP-1 is needed to prevent premature exit from this polarized nuclear organization and that this exit stops homology search. Further, based on experiments monitoring the formation of recombination intermediates and crossover products, we suggest that htp-1 mutants are defective in preventing the use of sister chromatids as recombination partners. We propose a model in which HTP-1 functions to establish or maintain multiple constraints that operate to ensure coordination of events leading to chiasma formation.

  18. Diverse CdII coordination complexes derived from bromide isophthalic acid binding with auxiliary N-donor ligands (United States)

    Tang, Meng; Dong, Bao-Xia; Wu, Yi-Chen; Yang, Fang; Liu, Wen-Long; Teng, Yun-Lei


    The coordination characteristics of 4-bromoisophthalic acid (4-Br-H2ip) have been investigated in a series of CdII-based frameworks. Hydrothermal reactions of CdII salts and 4-Br-H2ip together with flexible or semiflexible N-donor auxiliary ligands resulted in the formation of four three-dimensional coordination complexes with diverse structures: {Cd(bix)0.5(bix)0.5(4-Br-ip)]·H2O}n (1), [Cd(bbi)0.5(bbi)0.5(4-Br-ip)]n (2), {[Cd(btx)0.5(4-Br-ip)(H2O)]·0.5CH3OH·H2O}n (3) and {[Cd(bbt)0.5(4-Br-ip)(H2O)]·3·5H2O}n (4). These compounds were characterized by elemental analyses, IR spectra, single-crystal and powder X-ray diffraction. They displayed diverse structures depending on the configuration of the 4-connected metal node, the coordination mode of the 4-Br-H2ip, the coordination ability and conformationally flexibility of the N-donor auxiliary. Compound 1 exhibits 3-fold interpenetrated 66 topology and compound 2 has a 412 topology. Compounds 3-4 have similar 3D pillar-layered structures based on 3,4-connected binodal net with the Schläfli symbol of (4·38). The thermal stabilities and photoluminescence properties of them were discussed in detail.

  19. Characteristic differences in the formation of complex coacervate core micelles from neodymium and zinc-based coordination polymers. (United States)

    Yan, Yun; Besseling, Nicolaas A M; de Keizer, Arie; Stuart, Martien A Cohen


    In this paper we compare the formation of complex coacervate core micelles (C3Ms) from two different tricompontent mixtures, namely neodymium, the bisligand L2EO4 and the poly(cation)-block-poly(neutral) diblock copolymer P2MVP41-b-PEO205, and zinc, L2EO4 and P2MVP41-b-PEO205 mixed systems. Three sets of titration experiments were carried out for each system: (i) titration of diblock copolymer P2MVP41-b-PEO205 with the stoichiometric mixture of metal ions and bisligands, (ii) titration of a mixture of diblock copolymer and bisligand with metal ions, and (iii) titration of a mixture of diblock copolymer and metal ions with bisligands. In all the above three cases, micelles are found to form either in a broad range of charge ratios or in a broad range of metal/bisligand ratios. Upon addition of Nd2-(L2EO4)3 coordination polymer to P2MVP41-b-PEO205 solution, and upon addition of Nd3+ to a mixture of L2EO4 and P2MVP41-b-PEO205, micelles are found to form immediately after the first addition, whereas micelles show up in the similar zinc system only after a certain threshold Zn-(L2EO4) or Zn2+ concentration. This difference can be traced to the different structures of the Nd2-(L2EO4)3 and Zn-(L2EO4) coordination compounds. At very low concentrations, Zn-(L2EO4) are ring-like oligomers, but Nd2-(L2EO4)3 are larger networks. The network structure favors the formation of coacervate micellar core with P2MVP41-b-PEO205. Moreover, excess of Nd3+ ions will break up the C3Ms, while the same amount of Zn2+ has hardly any effect on the C3Ms. The breakdown of C3Ms by Nd3+ is due to the charge inversion of the coordination complex with increasing [Nd3+]/[L2EO4] ratio, which results in repulsive interaction between the coordination complex and the diblock copolymer, whereas no such interaction can occur in the zinc system.

  20. Coordination of 1,4-Diazabutadiene Ligands to Decamethylytterbocene: Additional Examples of Spin Coupling in Ytterbocene Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, Richard; Walter, Marc D.; Berg, David J.; Andersen, Richard A.


    The paramagnetic 1:1 coordination complexes of (C5Me5)2Yb with a series of diazabutadiene ligands, RN=C(R')C(R')=NR, where R= CMe3, CHMe2, adamantyl, p-tolyl, p-anisyl, and mesityl when R'=H, and R= p-anisyl when R'= Me, have been prepared. The complexes are paramagnetic, but their magnetic moments are less than expected for the two uncoupled spin carriers, (C5Me5)2Yb(III, 4f13) and the diazabutadiene radical anions (S=1/2), which implies exchange coupling between the spins. The variable temperature 1H NMR spectra show that rotation about the R-N bond is hindered and these barriers are estimated. The barriers are largely determined by steric effects but electronic effects are not unimportant.

  1. Field-induced slow magnetic relaxation in a six-coordinate mononuclear cobalt(II) complex with a positive anisotropy. (United States)

    Vallejo, Julia; Castro, Isabel; Ruiz-García, Rafael; Cano, Joan; Julve, Miguel; Lloret, Francesc; De Munno, Giovanni; Wernsdorfer, Wolfgang; Pardo, Emilio


    The novel mononuclear Co(II) complex cis-[Co(II)(dmphen)(2)(NCS)(2)]·0.25EtOH (1) (dmphen = 2,9-dimethyl-1,10-phenanthroline) features a highly rhombically distorted octahedral environment that is responsible for the strong positive axial and rhombic magnetic anisotropy of the high-spin Co(II) ion (D = +98 cm(-1) and E = +8.4 cm(-1)). Slow magnetic relaxation effects were observed for 1 in the presence of a dc magnetic field, constituting the first example of field-induced single-molecule magnet behavior in a mononuclear six-coordinate Co(II) complex with a transverse anisotropy energy barrier.

  2. Structures, Photophysical Properties, and Growth Patterns of Methylurea Coordinated Ni(II and Mn(II Complexes

    Directory of Open Access Journals (Sweden)

    Wenting Wang


    Full Text Available Four coordinated complexes MnxNi(1−x(C2H6N2O6SO4 (x=0, 0.33, 0.75, 0.90 were synthesized and characterized. Single-crystal X-ray analysis revealed that the complexes belong to the trigonal crystal family, R-3c space group. Spiral and terraced nucleus growth modes were observed by atomic force microscopy (AFM in the crystals. Thermogravimetric analysis (TGA and differential thermal analysis (DTA measurements showed their excellent thermostability until 200 °C. UV–vis spectra revealed that the transmission peaks of these crystals have a slight bathochromic shift compared to nickel sulfate hexahydrate (NSH, and the transmittance in the UV range increased as the proportion of Mn2+ increased. With their photophysical properties remaining similar, the much higher heat endurance is rendering these crystals better suitable for UV light filter (ULF applications.

  3. Coordination of 1,4-Diazabutadiene Ligands to Decamethylytterbocene: Additional Examples of Spin Coupling in Ytterbocene Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, Richard; Walter, Marc D.; Berg, David J.; Andersen, Richard A.


    The paramagnetic 1:1 coordination complexes of (C5Me5)2Yb with a series of diazabutadiene ligands, RN=C(R')C(R')=NR, where R= CMe3, CHMe2, adamantyl, p-tolyl, p-anisyl, and mesityl when R'=H, and R= p-anisyl when R'= Me, have been prepared. The complexes are paramagnetic, but their magnetic moments are less than expected for the two uncoupled spin carriers, (C5Me5)2Yb(III, 4f13) and the diazabutadiene radical anions (S=1/2), which implies exchange coupling between the spins. The variable temperature 1H NMR spectra show that rotation about the R-N bond is hindered and these barriers are estimated. The barriers are largely determined by steric effects but electronic effects are not unimportant.

  4. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with α-hydroxyisobutyric acid. (United States)

    Chen, Xiao-Yan; Goff, George S; Ewing, William C; Scott, Brian L; Runde, Wolfgang


    Despite the wide range of applications of α-hydroxyisobutyric acid (HIBA) in biochemical processes, pharmaceutical formulations, and group and elemental separations of lanthanides and actinides, the structures and geometries of lanthanide-HIBA complexes are still not well understood. We reacted HIBA with lanthanides in aqueous solution at pH = 5 and synthesized 14 lanthanide-HIBA complexes of the formula [Ln(HIBA)(2)(H(2)O)(2)](NO(3))·H(2)O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14)), isolating single crystals (1-7, 10, and 11) and powders (8, 9, and 12-14). Both single-crystal and powder X-ray diffraction studies reveal a two-dimensional extended structure across the entire lanthanide series. The environment around the eight-coordinated Ln(III) atom is best described as a distorted dodecahedron, where HIBA acts as a monoanionic tridentate ligand with one carboxylato oxygen atom and one hydroxyl oxygen atom chelating to one Ln(III) center. The carboxylato oxygen atom from a second HIBA ligand bridges to a neighboring Ln(III) atom to form a two-dimensional extended structure. While the coordination mode for HIBA is identical across the lanthanide series, three different structure types are found for La, Ce-Ho, and Er-Lu. Solution characterization using (13)C NMR further confirmed a single solution complex under the crystallization conditions. Raman and UV-vis-NIR absorbance and diffuse reflectance spectra of HIBA-Ln(III) complexes were also measured.

  5. Hetero-bimetallic Complex of a 2D Coordination Network Constructed by Sodium Ion and p-Sulfonatothiacalix[4]arene

    Institute of Scientific and Technical Information of China (English)


    A 2D coordination polymer built by sodium ion and water-soluble p-sulfonato thiacalix(4)arene of trivalent yttrium complex [Na(H2O)2Y(H2O)6(DMF) (p-sulfonatothiaca lix(4)arene)]·9H2O is reported.The complex belongs to the monoclinic system, space group P21/c, with a =16.703(3),b = 17.819(4), c = 17.357(4)(A), β= 106.23(3)°,Z= 4,V= 4960.0(17)(A)3, Mr = 1304.08,Dc = 1.746 g/cm3,μ= 1.624 mm-1, F(000) = 2688, the final R = 0.0398 and wR = 0.1132 for 7534 observed reflections with I>2σ(I).One yttrium(Ⅲ) ion is coordinated by the thiacalixarene ligand via the sulfonato group, and also ligated by an oxygen atom of a DMF molecule occupying the cavity of thiacalixarene and six aqua ligands.

  6. "Attention on the flight deck": what ambulatory care providers can learn from pilots about complex coordinated actions. (United States)

    Frankel, Richard M; Saleem, Jason J


    Technical and interpersonal challenges of using electronic health records (EHRs) in ambulatory care persist. We use cockpit communication as an example of highly coordinated complex activity during flight and compare it with providers' communication when computers are used in the exam room. Maximum variation sampling was used to identify two videotapes from a parent study of primary care physicians' exam room computer demonstrating the greatest variation. We then produced and analyzed visualizations of the time providers spent looking at the computer and looking at the patient. Unlike the cockpit which is engineered to optimize joint attention on complex coordinated activities, we found polar extremes in the use of joint focus of attention to manage the medical encounter. We conclude that there is a great deal of room for improving the balance of interpersonal and technical attention that occurs in routine ambulatory visits in which computers are present in the exam room. Using well-known aviation practices can help primary care providers become more aware of the opportunities and challenges for enhancing the physician patient relationship in an era of exam room computing. Published by Elsevier Ireland Ltd.

  7. Hydrogen Bonds Dictate the Coordination Geometry of Copper: Characterization of a Square-Planar Copper(I) Complex. (United States)

    Dahl, Eric W; Szymczak, Nathaniel K


    6,6''-Bis(2,4,6-trimethylanilido)terpyridine (H2Tpy(NMes)) was prepared as a rigid, tridentate pincer ligand containing pendent anilines as hydrogen bond donor groups in the secondary coordination sphere. The coordination geometry of (H2 Tpy(NMes))copper(I)-halide (Cl, Br and I) complexes is dictated by the strength of the NH-halide hydrogen bond. The Cu(I)Cl and Cu(II)Cl complexes are nearly isostructural, the former presenting a highly unusual square-planar geometry about Cu(I) . The geometric constraints provided by secondary interactions are reminiscent of blue copper proteins where a constrained geometry, or entatic state, allows for extremely rapid Cu(I)/Cu(II) electron-transfer self-exchange rates. Cu(H2 Tpy(NMes))Cl shows similar fast electron transfer (≈10(5)  m(-1)  s(-1)) which is the same order of magnitude as biological systems.

  8. Multidisciplinary management of pregnancy in complex congenital heart disease: a model for coordination of care. (United States)

    Harris, Rachel C; Fries, Melissa H; Boyle, Annelee; Adeniji-Adele, Hassan; Cherian, Zacharia; Klein, Nancy; John, Anitha S


    With advancements in medical care, many women with complex congenital heart disease (CHD) are now living into adulthood and childbearing years. The strains of pregnancy and parturition can be dangerous in such patients, and careful interdisciplinary plans must be made to optimize maternal and fetal health through this process. Several large studies have been published regarding risk prediction and medical management of pregnancy in complex CHD, though few case studies detailing clinical care plans have been published. The objective of this report is to describe the process of developing a detailed pregnancy and delivery care plan for three women with complex CHD, including perspectives from the multidisciplinary specialists involved in the process. This article demonstrates that collaboration between specialists in the fields of cardiology, anesthesiology, high-risk obstetrics, maternal fetal medicine, and neonatology results in clinically successful individualized treatment plans for the management of pregnancy in complex CHD. Multidisciplinary collaboration is a crucial element in the management of pregnancy in complex CHD. We provide a template used in three cases which can serve as a model for the design of future care plans.

  9. The coordination structure of the extracted copper(II) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and n-hexyl 3-pyridinecarboxylate ester (United States)

    Zhu, Shan; Hu, Huiping; Hu, Jiugang; Li, Jiyuan; Hu, Fang; Wang, Yongxi


    In continuation of our interest in the coordination structure of the nickel(II) complex with dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC), it was observed that the coordination sphere was completed by the coordination of two N atoms of pyridine rings in ligands 4PC and four water molecules while no direct interaction between Ni(II) and deprotonated HDNNS was observed. To investigate whether the coordination structure of nickel(II) with the synergistic mixture containing HDNNS and 4PC predominates or not in the copper(II) complex with the synergistic mixtures containing HDNNS and pyridinecarboxylate esters, a copper(II) synergist complex with n-hexyl 3-pyridinecarboxylate ester (L) and naphthalene-2-sulfonic acid (HNS, the short chain analogue of HDNNS), was prepared and studied by X-ray single crystal diffraction, elemental analyses and thermo gravimetric analysis (TGA), respectively. It was shown that the composition of the copper(II) synergist complex was [Cu(H2O)2(L)2(NS)2] and formed a trans-form distorted octahedral coordination structure. Two oxygen atoms of the two coordinated water molecules and two N atoms of the pyridine rings in the ligands L defined the basal plane while two O atoms from two sulfonate anions of the deprotonated HNS ligands occupied the apical positions by direct coordination with Cu(II), which was distinguished from the coordination structure of the nickel(II) synergist complex as reported in our previous work. In the crystal lattice, neighboring molecules [Cu(H2O)2L2(NS)2] were linked through the intermolecular hydrogen bonds between the hydrogen atoms of the coordinated water molecules and the oxygen atoms of the sulfonate anions in the copper(II) synergist complex to form a 2D plane. In order to bridge the gap between the solid state structure of the copper(II) synergist complex and the solution structure of the extracted copper(II) complex with the actual synergistic mixture containing

  10. Tracking excited-state charge and spin dynamics in iron coordination complexes

    DEFF Research Database (Denmark)

    Zhang, Wenkai; Alonso-Mori, Roberto; Bergmann, Uwe


    to spin state, can elucidate the spin crossover dynamics of [Fe(2,2'-bipyridine)(3)](2+) on photoinduced metal-to-ligand charge transfer excitation. We are able to track the charge and spin dynamics, and establish the critical role of intermediate spin states in the crossover mechanism. We anticipate......Crucial to many light-driven processes in transition metal complexes is the absorption and dissipation of energy by 3d electrons(1-4). But a detailed understanding of such non-equilibrium excited-state dynamics and their interplay with structural changes is challenging: a multitude of excited...... states and possible transitions result in phenomena too complex to unravel when faced with the indirect sensitivity of optical spectroscopy to spin dynamics(5) and the flux limitations of ultrafast X-ray sources(6,7). Such a situation exists for archetypal poly-pyridyl iron complexes, such as [Fe(2...

  11. Theoretical Studies on the Spin Exchange Interaction in Copper(II) Complexes Coordinated with Nitronyl Nitroxide

    Institute of Scientific and Technical Information of China (English)

    Jie REN; Hai Yan WEI; Qi Hua ZHAO; Zhi Da CHEN


    Nitronyl nitroxide radical 1, NIT (4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide) and copper(II) chloride complexes with nitronyl nitroxide 2, [Cu(NITPh)2Cl2] (NITPh=2-phenyl-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) were studied with density functional theory (DFT). The magnetic orbital analysis reveals that the antiferromagnetic coupling for complex 2 is due to the antibonding σ*-orbital overlap between (Cu) and π* (NO) orbitals. Also, spin population and atomic charge distribution analysis suggest that for AFS of complex 2 the antiferromagnetic coupling between the radical ligands and the copper(II) ion originates from the spin delocalization induced by the α electron transfer from π*(NO) to (Cu) orbital.

  12. Control of size in losartan/copper(II) coordination complex hydrophobic precipitate. (United States)

    Denadai, Ângelo M L; Da Silva, Jeferson G; Guimarães, Pedro P G; Gomes, Leonardo Bertolini S; Mangrich, Antonio S; de Rezende, Edivaltrys I P; Daniel, Izabela M P; Beraldo, Heloísa; Sinisterra, Rubén D


    Reaction of highly soluble orally active, non-peptide antihypertensive drug losartan with copper(II) leads to the spontaneous formation of a very insoluble 2:1 covalent complex, which self assembles in a hydrophobic supramolecular structure of nanometric dimensions. Thermal analysis showed that Los/Cu(II) complex presents intermediate stability in comparison with its precursors KLos and Cu(OAc)2·H2O. Isothermal titration calorimetry indicated complexation to be a stepwise process, driven by enthalpy and entropy. Zeta potential and DLS measurements showed that it is possible to control the size and charge of nanoprecipitates by adjusting the relative concentration of Los(-) and Cu(II). Copyright © 2013 Elsevier B.V. All rights reserved.

  13. School Nurses and Care Coordination for Children with Complex Needs: An Integrative Review (United States)

    McClanahan, Rachel; Weismuller, Penny C.


    Health care for students with chronic needs can be complex and specialized, resulting in fragmentation, duplication, and inefficiencies. Students who miss school due to chronic conditions lose valuable educational exposure that contributes to academic success. As health-related disabilities increase in prevalence so does the need for the…

  14. Structures of the m(6)A Methyltransferase Complex: Two Subunits with Distinct but Coordinated Roles. (United States)

    Zhou, Katherine I; Pan, Tao


    In this issue of Molecular Cell, Wang et al. (2016a) report crystal structures of the core of the METTL3/METTL14 m(6)A methyltransferase complex and propose how the two subunits interact and cooperate to bind and methylate RNA.

  15. Condition-based maintenance for complex systems : Coordinating maintenance and logistics planning for the process industries

    NARCIS (Netherlands)

    Olde Keizer, Minou Catharina Anselma


    Maintenance planning in the process industries is extremely complex for various reasons. Plants often run nonstop, allowing little time for performing preventive maintenance. Failures should be prevented, however, as they can lead to system downtime and high losses of revenue. Corrective maintenance

  16. Crystal structures of bis- and hexakis[(6,6′-dihydroxybipyridinecopper(II] nitrate coordination complexes

    Directory of Open Access Journals (Sweden)

    Deidra L. Gerlach


    Full Text Available Two multinuclear complexes synthesized from Cu(NO32 and 6,6′-dihydroxybipyridine (dhbp exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6′-dihydroxybipyridine-2κ2N,N′[μ-6-(6-hydroxypyridin-2-ylpyridin-2-olato-1:2κ3N,N′:O2](μ-hydroxido-1:2κ2O:O′(μ-nitrato-1:2κ2O:O′(nitrato-1κOdicopper(II, [Cu2(C10H7N2O2(OH(NO32(C10H8N2O2] or [Cu(6-OH-6′-O-bpy(NO3(μ-OH(μ-NO3Cu(6,6′-dhbp], (I, with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water–ethanol mixture at neutral pH. The hexanuclear complex bis(μ3-bipyridine-2,2′-diolato-κ3O:N,N′:O′tetrakis(6,6′-dihydroxybipyridine-κ2N,N′tetrakis(μ-hydroxido-κ2O:O′bis(methanol-κOtetrakis(μ-nitrato-κ2O:O′hexacopper(II, [Cu6(C10H6N2O22(CH4O2(OH4(NO34(C10H8N2O24] or [Cu(6,6′-dhbp(μ-NO32(μ-OHCu(6,6′-O-bpy(μ-OHCu(6,6′dhbp(CH3OH]2, (II, with a 1:1 NO3–OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II lies across an inversion center. Complexes (I and (II both display intramolecular O—H...O hydrogen bonding. Intermolecular O—H...O hydrogen bonding links symmetry-related molecules forming chains along [100] for complex (I with π-stacking along [010] and [001]. Complex (II forms intermolecular O—H...O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].

  17. Osmium and cobalt complexes incorporating facially coordinated N,N,O donor azo-imine ligands: Redox and catalytic properties

    Indian Academy of Sciences (India)

    Poulami Pattanayak; Debprasad Patra; Jahar Lal Pratihar; Andrew Burrows; Mary F Mahon; Surajit Chattopadhyay


    Reactions of 1-{[2-(arylazo)phenyl]iminomethyl}-2-phenol, HL [where H represents the dissociable phenolic protons of ligands and aryl groups of HL are C6H5 (HL1), -CH3C6H5 (HL2), -ClC6H5 (HL3)] with Os(H)(CO)(Br)(PPh3)3 in toluene and with Co(ClO4)3.6H2O in methanol afforded new facially coordinated complexes of composition [(L)Os(CO)(Br)(PPh3)] and [(L)2Co]ClO4. The anionic ligand (L)−, binds the metal in tridentate (N, N, O) manner in [(L)Os(CO)(Br)(PPh3)] and [(L)2Co]ClO4 complexes. All the Os(II) and Co(III) complexes are diamagnetic and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. The cyclic voltammograms exhibited one quasi reversible oxidative response near 0.10 V vs SCE for [(L)Os(CO)(Br)(PPh3)] and [(L)2Co]ClO4 complexes displayed serial reductive responses within −0.06 to −1.61 V vs SCE. Single point DFT calculation was carried out to examine the nature of redox orbitals. Conversion of ketones to corresponding alcohols has been studied using [(L)Os(CO)(Br)(PPh3)] as catalyst.

  18. Synthesis and characterization of oxo-bridged, trinuclear, six-coordinate mixed-carboxylato complexes of chromium (III) (United States)

    Baranwal, B. P.; Fatma, Talat


    Mixed-carboxylato β-diketonato complexes of chromium (III) (R=C13H27, C15H31 or C17H35 and L=CH3OH) [Cr3O(OOCR)3(dike)3L3]+ have been synthesized by enforced substitution reactions of [Cr3O(OOCCH3)7(H2O)] first with straight chain fatty acids (myristic, palmitic or stearic acid) and then with β-diketones (Hβ-dike) like acetylacetone(Hacac) or benzoylacetone(Hbzac) in toluene under reflux. These are new type of oxo-bridged chromium(III) complexes in which one ligand is a fatty acid while the other one is a β-diketone. The complexes were characterized by elemental analyses, spectral (infrared, electronic, FAB mass and powder XRD) studies, molar conductance and magnetic susceptibility measurements. Bridging coordination modes for both carboxylate and β-diketonate anions were indicated by presence of νasym(Cr3O) vibrations in the infrared spectra. Trinuclear nature of the complexes and their structural features have been discussed on the basis of physicochemical studies.

  19. Synthesis, Structure, and Photophysical Properties of Two Four-Coordinate Cu(I)-NHC Complexes with Efficient Delayed Fluorescence. (United States)

    Wang, Zhiqiang; Zheng, Caijun; Wang, Weizhou; Xu, Chen; Ji, Baoming; Zhang, Xiaohong


    Two luminescent cationic heteroleptic four-coordinate Cu(I) complexes supported by N-heterocyclic carbene ligand and diphosphine ligand were successfully prepared and characterized. These complexes adopt typical distorted tetrahedral configuration and have high stability in solid state. Quantum chemical calculations show carbene units have contributions to both highest occupied molecular orbitals and lowest unoccupied molecular orbitals of these Cu(I)-NHC complexes, the lowest-lying singlet and triplet excitations (S0 → S1 and S0 → T1) of [Cu(Pyim)(POP)](PF6) are dominated by metal-to-ligand charge transfer (MLCT) transition, while the S0 → S1 and S0 → T1 excitations of [Cu(Qbim)(POP)](PF6) are mainly MLCT and ligand-centered transitions, respectively. These Cu(I)-NHC complexes show efficient long-lifetime emissions (λem = 520 nm, τ = 79.8 μs, Φ = 0.56 for [Cu(Pyim)(POP)](PF6), λem = 570 nm, τ = 31.97 μs (78.99%) and 252.2 μs (21.01%), Φ = 0.35 for [Cu(Qbim)(POP)](PF6)) in solid state at room temperature, which are confirmed as delayed fluorescence by investigating the emissions at 77 K.

  20. Evolving dynamics of trading behavior based on coordination game in complex networks (United States)

    Bian, Yue-tang; Xu, Lu; Li, Jin-sheng


    This work concerns the modeling of evolvement of trading behavior in stock markets. Based on the assumption of the investors' limited rationality, the evolution mechanism of trading behavior is modeled according to the investment strategy of coordination game in network, that investors are prone to imitate their neighbors' activity through comprehensive analysis on the risk dominance degree of certain investment behavior, the network topology of their relationship and its heterogeneity. We investigate by mean-field analysis and extensive simulations the evolution of investors' trading behavior in various typical networks under different risk dominance degree of investment behavior. Our results indicate that the evolution of investors' behavior is affected by the network structure of stock market and the effect of risk dominance degree of investment behavior; the stability of equilibrium states of investors' behavior dynamics is directly related with the risk dominance degree of some behavior; connectivity and heterogeneity of the network plays an important role in the evolution of the investment behavior in stock market.

  1. Thermochemical Study on Coordination Complex of Neodymium Trichloroacetic Acid with 8-Hydroxyquinoline

    Institute of Scientific and Technical Information of China (English)

    李强国; 屈松生; 刘义


    Two coordinate reactions, NdCl3*6H2O(s) +3CCl3COOH(s)( or TCA) =Nd(TCA)3*3H2O(s) +3HCl(g) +3H2O(l) and Nd(TCA)3*3H2O(s) +2C9H7NO(s)= Nd(TCA)(C9H6NO)2 (s) +2CCl3COOH(s) +3H2O(l), were studied by the classical solution calorimetry at 298.15K. The molar dissolution enthalpies of the reactants and the products in certain solvent (the first reaction in 1 mol*L-1 HCl, the second in a mixed solution consisting of absolute ethyl alcohol, dimethyl sulfoxide and 4 mol*L-1 HCl ) were measured by using an isoperibol calorimeter at 298.15K . From the results and other auxiliary quantities, the standard molar formation enthalpies of [Nd(TCA)3*3H2O,s,298.15K] and [Nd(TCA) (C9H6NO)2 ,s, 298.15K] are determined as ΔfHm°[Nd(TCA)3*3H2O,s,298.15K]= -3053.3 kJ*mol-1 and ΔfHm°[Nd(TCA) (C9H6NO)2 ,s, 298.15K] = -1355.6 kJ*mol-1.

  2. Coordination modes, spectral, thermal and biological evaluation of hetero-metal copper containing 2-thiouracil complexes. (United States)

    Masoud, Mamdouh S; Soayed, Amina A; El-Husseiny, Amel F


    Mononuclear copper complex [CuL(NH(3))(4)]Cl(2)·0.5H(2)O and three new hetero-metallic complexes: [Cu(2)Ni(L)(2)(NH(3))(2)Cl(2)·6H(2)O] 2H(2)O(,) [Cu(3)Co(L)(4)·8H2O]Cl·4(·)5H(2)O, and [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2)O]4H(2)O where L is 2-thiouracil, were prepared and characterized by elemental analyses, molar conductance, room-temperature magnetic susceptibility, spectral (IR, UV-Vis and ESR) studies and thermal analyses techniques (TG, DTG and DTA). The molar conductance data revealed that [CuL(NH(3))(4)]Cl(2)·0.5H(2)O and [Cu(3)Co(L)(4)·8H2O]Cl·4.5H(2)O are electrolytes, while, [Cu(2)Ni(L)(2)(NH(3))(2)Cl(2·)6H(2)O]·2H(2)O and [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2)O]4H(2)O are non-electrolytes. IR spectra showed, that 2-thiouracil ligand behaves as a bidentate or tetradentate ligand. The geometry around the metal atoms is octahedral in all the prepared complexes except in [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2)O]4H(2)O complex where square planar environment around Co(II), Ni(II) and Cu(II) were suggested. Thermal decomposition study of the prepared complexes was monitored by TG, DTG and DTA analyses under N(2) atmosphere. The decomposition course and steps were analyzed. The order of chemical reactions (n) was calculated via the peak symmetry method and the activation parameters of the non- isothermal decomposition were computed from the thermal decomposition data. The negative values of ΔS(∗) deduced the ordered structures of the prepared complexes compared to their starting reactants. The antimicrobial activity of the prepared complexes were screened in vitro against a Gram positive, a Gram negative bacteria, a filamentous fungi and a yeast. The antimicrobial screening data showed that the studied compounds exhibited a good level of activity against Escherichia coli, Staphylococcus aureus and Candida albicans but have no efficacy against Aspergillus flavus. It was observed that [Cu(4)Co(2)Ni(L)(3)(OH)(4)(NH(3))Cl(4)·3H(2

  3. Luminescent platinum complexes with terdentate ligands forming 6-membered chelate rings: advantageous and deleterious effects in N--N--N and N--C--N-coordinated complexes. (United States)

    Garner, Katherine L; Parkes, Louise F; Piper, Jason D; Williams, J A Gareth


    Platinum(II) complexes of the form [PtL(n)Cl](+) are reported, containing the N--N--N-coordinating ligands 2,6-di(8-quinolyl)pyridine (L(1)), 2,6-di(8-quinolyl)-4-methoxypyridine (L(2)), or 2,6-di(7-aza-indolyl)-pyridine (L(3)). Metathesis of the chloride co-ligand in [PtL(1)Cl](+) can be accomplished under mild conditions, as exemplified by the formation of the complexes [PtL(1)OMe](+) and [PtL(1)(C[triple bond]C-tfp)](+), in which L(1) remains bound as a terdentate ligand {HC[triple bond]C-tfp = 3,5-bis(trifluoromethyl)-phenylacetylene}. An N--C--N-coordinated, cyclometalated analogue of [PtL(1)Cl](+) has also been prepared, namely, PtL(4)Cl where HL(4) is 1,3-di(8-quinolyl)benzene. The common feature among the six new complexes described here is that they contain 6-membered chelate rings, rather than the usual 5-membered rings that form when more common N--N--N ligands, such as 2,2':6',2''-terpyridine (tpy), bind to Pt(II). All the quinolyl-based complexes are phosphorescent in solution at room temperature, with quantum yields up to 4%. This contrasts with the well-established lack of emission from [Pt(tpy)Cl](+) under these conditions. Density functional theory calculations suggest that the improvement may stem, at least in part, from the relief of ring strain associated with the larger chelate ring size, leading to a more optimal bite angle at the metal, close to 180 degrees , and hence to a stronger ligand field. Consideration of the luminescence parameters, including data at 77 K, together with absorption and electrochemical data and the results of TD-DFT calculations, suggests that the lowest-lying singlet states have metal-to-ligand charge-transfer (MLCT) character, but that the triplet state from which emission occurs has more predominant ligand-centered character. The azaindolyl complex [PtL(3)Cl](+) is not emissive at room temperature, apparently owing to a particularly small radiative rate constant. The cyclometalated complex PtL(4)Cl emits at lower

  4. Uranyl-glycine-water complexes in solution: comprehensive computational modeling of coordination geometries, stabilization energies, and luminescence properties. (United States)

    Su, Jing; Zhang, Kai; Schwarz, W H Eugen; Li, Jun


    Comprehensive computational modeling of coordination structures, thermodynamic stabilities, and luminescence spectra of uranyl-glycine-water complexes [UO(2)(Gly)(n)aq(m)](2+) (Gly = glycine, aq = H(2)O, n = 0-2, m = 0-5) in aqueous solution has been carried out using relativistic density functional approaches. The solvent is approximated by a dielectric continuum model and additional explicit water molecules. Detailed pictures are obtained by synergic combination of experimental and theoretical data. The optimal equatorial coordination numbers of uranyl are determined to be five. The energies of several complex conformations are competitively close to each other. In non-basic solution the most probable complex forms are those with two water ligands replaced by the bidentate carboxyl groups of zwitterionic glycine. The N,O-chelation in non-basic solution is neither entropically nor enthalpically favored. The symmetric and antisymmetric stretch vibrations of the nearly linear O-U-O unit determine the luminescence features. The shapes of the vibrationally resolved experimental solution spectra are reproduced theoretically with an empirically fitted overall line-width parameter. The calculated luminescence origins correspond to thermally populated, near-degenerate groups of the lowest electronically excited states of (3)Δ(g) and (3)Φ(g) character, originating from (U-O)σ(u) → (U-5f)δ(u),ϕ(u) configurations of the linear [OUO](2+) unit. The intensity distributions of the vibrational progressions are consistent with U-O bond-length changes around 5 1/2 pm. The unusually high intensity of the short wavelength foot is explained by near-degeneracy of vibrationally and electronically excited states, and by intensity enhancement through the asymmetric O-U-O stretch mode. The combination of contemporary computational chemistry and experimental techniques leads to a detailed understanding of structures, thermodynamics, and luminescence of actinide compounds, including

  5. Chelate-Thiolate-Coordinate Ligands Modulating the Configuration and Electrochemical Property of Dinitrosyliron Complexes (DNICs). (United States)

    Yeh, Shih-Wey; Lin, Chih-Wei; Liu, Bai-Heng; Tsou, Chih-Chin; Tsai, Ming-Li; Liaw, Wen-Feng


    As opposed to the reversible redox reaction ({Fe(NO)2 }(10) reduced-form DNIC [(NO)2 Fe(S(CH2 )3 S)](2-) (1)⇌{Fe(NO)2 }(9) oxidized-form [(NO)2 Fe(S(CH2 )3 S)](-) ), the chemical oxidation of the {Fe(NO)2 }(10) DNIC [(NO)2 Fe(S(CH2 )2 S)](2-) (2) generates the dinuclear {Fe(NO)2 }(9) -{Fe(NO)2 }(9) complex [(NO)2 Fe(μ-SC2 H4 S)2 Fe(NO)2 ](2-) (3) bridged by two terminal [SC2 H4 S](2-) ligands. On the basis of the Fe K-edge pre-edge energy and S K-edge XAS, the oxidation of complex 1 yielding [(NO)2 Fe(S(CH2 )3 S)](-) is predominantly a metal-based oxidation. The smaller S1-Fe1-S2 bond angle of 94.1(1)° observed in complex 1 (S1-Fe1-S2 88.6(1)° in complex 2), compared to the bigger bond angle of 100.9(1)° in the {Fe(NO)2 }(9) DNIC [(NO)2 Fe(S(CH2 )3 S)](-) , may be ascribed to the electron-rich {Fe(NO)2 }(10) DNIC preferring a restricted bite angle to alleviate the electronic donation of the chelating thiolate to the electron-rich {Fe(NO)2 }(10) core. The extended transition state and natural orbitals for chemical valence (ETS-NOCV) analysis on the edt-/pdt-chelated {Fe(NO)2 }(9) and {Fe(NO)2 }(10) DNICs demonstrates how two key bonding interactions, that is, a FeS covalent σ bond and thiolate to the Fe d z 2 charge donation, between the chelating thiolate ligand and the {Fe(NO)2 }(9/10) core could be modulated by the backbone lengths of the chelating thiolate ligands to tune the electrochemical redox potential (E1/2 =-1.64 V for complex 1 and E1/2 =-1.33 V for complex 2) and to dictate structural rearrangement/chemical transformations (S-Fe-S bite angle and monomeric vs. dimeric DNICs).

  6. Allosteric interactions coordinate catalytic activity between successive metabolic enzymes in the tryptophan synthase bienzyme complex. (United States)

    Brzović, P S; Ngo, K; Dunn, M F


    Tryptophan synthase from enteric bacteria is an alpha 2 beta 2 bienzyme complex that catalyzes the final two reactions in the biosynthesis of L-tryptophan (L-Trp) from 3-indole-D-glycerol 3'-phosphate (IGP) and L-serine (L-Ser). The bienzyme complex exhibits reciprocal ligand-mediated allosteric interactions between the heterologous subunits [Houben, K., & Dunn, M. F. (1990) Biochemistry 29, 2421-2429], but the relationship between allostery and catalysis had not been completely defined. We have utilized rapid-scanning stopped-flow (RSSF) UV-visible spectroscopy to study the relationship between allostery and catalysis in the alpha beta-reaction catalyzed by the bienzyme complex from Salmonella typhimurium. The pre-steady-state spectral changes that occur when L-Ser and IGP are mixed simultaneously with the alpha 2 beta 2 complex show that IGP binding to the alpha-site accelerates the formation of alpha-aminoacrylate [E(A-A)] from L-Ser at the beta-site. Through the use of L-Ser analogues, we show herein that the formation of the E(A-A) intermediate is the chemical signal which triggers the conformational transition that activates the alpha-subunit. beta-subunit ligands, such as L-Trp, that react to form covalent intermediates at the beta-site, but are incapable of E(A-A) formation, do not stimulate the activity of the alpha-subunit. Titration experiments show that the affinity of G3P and GP at the alpha-site is dependent upon the nature of the chemical intermediate present at the beta-active site.(ABSTRACT TRUNCATED AT 250 WORDS)

  7. Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Cary, Samantha K.; Silver, Mark A.; Liu, Guokui; Wang, Jamie C.; Bogart, Justin A.; Stritzinger, Jared T.; Arico, Alexandra A.; Hanson, Kenneth; Schelter, Eric J.; Albrecht-Schmitt, Thomas E.


    The reaction of 248CmCl3 with excess 2,6-pyridinedicarboxylic acid (DPA) under mild solvothermal conditions results in crystallization of the tris-chelate complex Cm(HDPA)3·H2O. Approximately half of the curium remains in solution at the end of this process, and evaporation of the mother liquor results in crystallization of the bis-chelate complex [Cm(HDPA)- (H2DPA)(H2O)2Cl]Cl·2H2O. 248Cm is the daughter of the α decay of 252Cf and is extracted in high purity from this parent. However, trace amounts of 249,250,251Cf are still present in all samples of 248Cm. During the crystallization of Cm(HDPA)3·H2O and [Cm(HDPA)(H2DPA)(H2O)2Cl]Cl·2H2O, californium(III) spontaneously separates itself from the curium complexes and is found doped within crystals of DPA in the form of Cf(HDPA)3. These results add to the growing body of evidence that the chemistry of californium is fundamentally different from that of earlier actinides.

  8. Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

    Energy Technology Data Exchange (ETDEWEB)

    Fang, Ming; Wiedner, Eric S.; Dougherty, William G.; Kassel, W. S.; Liu, Tianbiao L.; DuBois, Daniel L.; Bullock, R. Morris


    A series of heteroleptic 17e- cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), [CpC5F4NCoII(PtBu2NPh2)](BF4), [where P2tBuN2Ph = 1,5-diphenyl-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)] were synthesized, and structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)] as a result of the strongly electron-withdrawing perfluorpyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e- complexes CpICo(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the cobalt hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4). The cobalt hydride with the most electron-withdrawing Cp ligand, [CpC5F4NCoIII(PtBu2NPh2)H]+ is an electrocatalyst for production of H2 using 4-MeOC6H4NH3BF4 (pKaMeCN = 11.86) with a turnover frequency of 350 s-1 and an overpotential of 0.75 V. Experimental measurement of thermochemical data provided further insights into the thermodynamics of H2 elimination. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  9. System Coordination of Survivability and Safety of Complex Engineering Objects Operation

    Directory of Open Access Journals (Sweden)

    Nataliya Pankratova


    Full Text Available A system strategy to estimation the guaranteed survivability and safety of complex engineering objects (CEO operation is proposed. The principles that underlie the strategy of the guaranteed safety of CEO operation provide a flexible approach to timely detection, recognition, forecast, and system diagnostics of risk factors and situations, to formulation and implementation of a rational decision in a practicable time within an unremovable time constraint. Implementation of the proposed strategy is shown on example of diagnostics of electromobile-refrigerator functioning in real mode.

  10. Complex Coordination of Cell Plasticity by a PGC-1α-controlled Transcriptional Network in Skeletal Muscle. (United States)

    Kupr, Barbara; Handschin, Christoph


    Skeletal muscle cells exhibit an enormous plastic capacity in order to adapt to external stimuli. Even though our overall understanding of the molecular mechanisms that underlie phenotypic changes in skeletal muscle cells remains poor, several factors involved in the regulation and coordination of relevant transcriptional programs have been identified in recent years. For example, the peroxisome proliferator-activated receptor γ coactivator-1α (PGC-1α) is a central regulatory nexus in the adaptation of muscle to endurance training. Intriguingly, PGC-1α integrates numerous signaling pathways and translates their activity into various transcriptional programs. This selectivity is in part controlled by differential expression of PGC-1α variants and post-translational modifications of the PGC-1α protein. PGC-1α-controlled activation of transcriptional networks subsequently enables a spatio-temporal specification and hence allows a complex coordination of changes in metabolic and contractile properties, protein synthesis and degradation rates and other features of trained muscle. In this review, we discuss recent advances in our understanding of PGC-1α-regulated skeletal muscle cell plasticity in health and disease.

  11. Complex coordination of cell plasticity by a PGC-1α-controlled transcriptional network in skeletal muscle

    Directory of Open Access Journals (Sweden)

    Barbara eKupr


    Full Text Available Skeletal muscle cells exhibit an enormous plastic capacity in order to adapt to external stimuli. Even though our overall understanding of the molecular mechanisms that underlie phenotypic changes in skeletal muscle cells remains poor, several factors involved in the regulation and coordination of relevant transcriptional programs have been identified in recent years. For example, the peroxisome proliferator-activated receptor γ coactivator-1α (PGC-1α is a central regulatory nexus in the adaptation of muscle to endurance training. Intriguingly, PGC-1α integrates numerous signaling pathways and translates their activity into various transcriptional programs. This selectivity is in part controlled by differential expression of PGC-1α variants and post-translational modifications of the PGC-1α protein. PGC-1α-controlled activation of transcriptional networks subsequently enables a spatio-temporal specification and hence allows a complex coordination of changes in metabolic and contractile properties, protein synthesis and degradation rates and other features of trained muscle. In this review, we discuss recent advances in our understanding of PGC-1α-regulated skeletal muscle cell plasticity in health and disease.

  12. Carboxylate-bridged Cu(II) coordination polymeric complex: synthesis, crystal structure, magnetic properties, DNA binding and electrochemical studies

    Indian Academy of Sciences (India)



    A novel water-soluble carboxylate-bridged copper(II) coordination polymer,Cu-BIG was formed by the reaction of Cu(ClO₄)₂ ·6H₂O and tridentate benzimidazole-glycine conjugate ligand, 2-((1H-benzimidazol- 2-yl)methylamino) acetic acid, BIGH and its structure has been determined by IR, UV, powder XRD, VSM, CV, TGA, DTA, EPR and single crystal X-ray diffraction. Crystallographic studies indicate it to be a coordination polymer with P¯ı Space group. The asymmetric unit of complex contains two Cu(II) ions with elongated square pyramid geometry.The axial positions of theCu(II) atoms are occupied by the carbonyl oxygen of the carboxylate group with the bond distances Cu(1)–O(5)axial , 2.28Å, and Cu(2)–O(2)axial , 2.26Å. The two Cu(II) are connected through the carboxylic group present in BIGH, which provides electron mobilisation in the molecule and hence results in the soft ferromagnetic polymer. An in vitro antibacterial activity study of BIGH and Cu-BIG showed moderate activity against Bacillus subtilis. The DNA binding studies showed the interaction of Cu-BIG with CT-DNA.

  13. A new hybrid optimization algorithm CRO-DE for optimal coordination of overcurrent relays in complex power systems

    Directory of Open Access Journals (Sweden)

    Mohamed Zellagui


    Full Text Available The paper presents a new hybrid global optimization algorithm based on Chemical Reaction based Optimization (CRO and Di¤erential evolution (DE algorithm for nonlinear constrained optimization problems. This approach proposed for the optimal coordination and setting relays of directional overcurrent relays in complex power systems. In protection coordination problem, the objective function to be minimized is the sum of the operating time of all main relays. The optimization problem is subject to a number of constraints which are mainly focused on the operation of the backup relay, which should operate if a primary relay fails to respond to the fault near to it, Time Dial Setting (TDS, Plug Setting (PS and the minimum operating time of a relay. The hybrid global proposed optimization algorithm aims to minimize the total operating time of each protection relay. Two systems are used as case study to check the effeciency of the optimization algorithm which are IEEE 4-bus and IEEE 6-bus models. Results are obtained and presented for CRO and DE and hybrid CRO-DE algorithms. The obtained results for the studied cases are compared with those results obtained when using other optimization algorithms which are Teaching Learning-Based Optimization (TLBO, Chaotic Differential Evolution Algorithm (CDEA and Modiffied Differential Evolution Algorithm (MDEA, and Hybrid optimization algorithms (PSO-DE, IA-PSO, and BFOA-PSO. From analysing the obtained results, it has been concluded that hybrid CRO-DO algorithm provides the most optimum solution with the best convergence rate.

  14. Two lanthanum(III) complexes containing η2-pyrazolate and η2-1,2,4-triazolate ligands: intramolecular C-H...N/O interactions and coordination geometries. (United States)

    Wang, Yu-Long; Feng, Meng; Tao, Xian; Tang, Qing-Yun; Shen, Ying-Zhong


    The lanthanum(III) complexes tris(3,5-diphenylpyrazolato-κ(2)N,N')tris(tetrahydrofuran-κO)lanthanum(III) tetrahydrofuran monosolvate, [La(C(15)H(11)N(2))(3)(C(4)H(8)O)(3)]·C(4)H(8)O, (I), and tris(3,5-diphenyl-1,2,4-triazolato-κ(2)N(1),N(2))tris(tetrahydrofuran-κO)lanthanum(III), [La(C(14)H(10)N(3))(3)(C(4)H(8)O)(3)], (II), both contain La(III) atoms coordinated by three heterocyclic ligands and three tetrahydrofuran ligands, but their coordination geometries differ. Complex (I) has a mer-distorted octahedral geometry, while complex (II) has a fac-distorted configuration. The difference in the coordination geometries and the existence of asymmetric La-N bonding in the two complexes is associated with intramolecular C-H...N/O interactions between the ligands.

  15. Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands (United States)

    Moreno, Virtudes; Lorenzo, Julia; Aviles, Francesc X.; Garcia, M. Helena; Ribeiro, João P.; Morais, Tânia S.; Florindo, Pedro; Robalo, M. Paula


    Four cationic ruthenium(II) complexes with the formula [Ru(η5-C5H5)(PPh3)2]+, with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b;4,3-b′] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells). PMID:20689715

  16. A new arene-Ru based supramolecular coordination complex for efficient binding and selective sensing of green fluorescent protein. (United States)

    Mishra, Anurag; Ravikumar, Sambandam; Song, Young Ho; Prabhu, Nadarajan Saravanan; Kim, Hyunuk; Hong, Soon Ho; Cheon, Seyeon; Noh, Jaegeun; Chi, Ki-Whan


    A new dipyridyl ligand is encoded with 120° angularity between its coordination vectors by using a central pyridine carboxamide scaffold to orient two 4-(pyridin-4-ylethynyl)phenyl moieties. The N,N'-bis(4-(pyridin-4-ylethynyl)phenyl)pyridine-2,6-dicarboxamide ligand undergoes self-assembly with a diruthenium arene complex to furnish a [2 + 2] metallacycle with a wedge-like structure. The metallacycle binds to the enhanced green fluorescent protein (EGFP) variant of GFP, resulting in steady-state spectral changes in UV-Vis absorption and emission experiments. These studies indicate that the metallacycle induces conformation changes to the EGFP, disrupting the tripeptide chromophore. Furthermore, gel electrophoresis, circular dichroism and atomic force microscopy studies indicate that binding ultimately leads to aggregation of the protein. Computational investigations indicate a favorable interaction, predominantly between the metallacycle and the Arg168 residue of the EGFP. An interaction with Arg168 and related residues was previously observed for an emission-attenuating antibody, supporting that these interactions induce changes to the photophysical properties of EGFP by disrupting the tripeptidechromophore in a similar manner. Additionally, we have also described the quenching study of the reporter GFP protein in vivo by a new metal complex using reflected fluorescence microscopy. We anticipate that such metal complexes which can passively diffuse into the cells in vivo can serve as potential tools in molecular and drug targeting based biological studies.

  17. Effect of pH on complex coacervate core micelles from Fe(III)-based coordination polymer. (United States)

    Wang, Junyou; de Keizer, Arie; van Leeuwen, Herman P; Yan, Yun; Vergeldt, Frank; van As, Henk; Bomans, Paul H H; Sommerdijk, Nico A J M; Cohen Stuart, Martien A; van der Gucht, Jasper


    The effect of pH on iron-containing complex coacervate core micelles [Fe(III)-C3Ms] is investigated in this paper. The Fe(III)-C3Ms are formed by mixing cationic poly(N-methyl-2-vinylpyridinium iodide)-b-poly(ethylene oxide) [P2MVP(41)-b-PEO(205)] and anionic iron coordination polymers [Fe(III)-L(2)EO(4)] at stoichiometric charge ratio. Light scattering and Cryo-TEM have been performed to study the variations of hydrodynamic radius and core structure with changing pH. The hydrodynamic radius of Fe(III)-C3Ms is determined mainly by the corona and does not change very much in a broad pH range. However, Cryo-TEM pictures and magnetic relaxation measurements indicate that the structure of the micellar cores changes upon changing the pH, with a more crystalline, elongated shape and lower relaxivity at high pH. We attribute this to the formation of mixed iron complexes in the core, involving both the bis-ligand and hydroxide ions. These complexes are stabilized toward precipitation by the diblock copolymer.

  18. Restoring Lands - Coordinating Science, Politics and Action Complexities of Climate and Governance

    CERN Document Server

    Scarlett, Lynn; Vargas-Moreno, Juan; Flaxman, Michael


    Environmental issues, vast and varied in their details, unfold at the confluence of people and place. They present complexities in their biophysical details, their scope and scale, and the dynamic character of human action and natural systems. Addressing environmental issues often invokes tensions among battling interests and competing priorities. Air and water pollution, the effects of climate change, ecosystem transformations—these and other environmental issues involve scientific, social, economic, and institutional challenges. This book analyzes why tackling many of these problems is so difficult and why sustainability involves more than adoption of greener, cleaner technologies. Sustainability, as discussed in this book, involves knowledge flows and collaborative decision processes that integrate scientific and technological methods and tools, political and governance structures and regimes, and social and community values. The authors synthesize a holistic and adaptive approach to rethinking the frame...

  19. Freeze-drying synthesis of an amorphous Zn(2+) complex and its transformation to a 2-D coordination framework in the solid state. (United States)

    Itakura, T; Horike, S; Inukai, M; Kitagawa, S


    An amorphous and metastable precursor for a Zn two-dimensional coordination framework was synthesised via freeze drying. The precursor comprises randomly packed discrete clusters of a Zn complex. The amorphous-to-crystalline framework transformation, which was triggered by the gentle application of heat or pressure, was accompanied by a change in the coordination geometry of the Zn(2+) ions from tetrahedral to octahedral symmetry.

  20. Two mechanisms coordinate replication termination by the Escherichia coli Tus–Ter complex

    KAUST Repository

    Pandey, Manjula


    The Escherichia coli replication terminator protein (Tus) binds to Ter sequences to block replication forks approaching from one direction. Here, we used single molecule and transient state kinetics to study responses of the heterologous phage T7 replisome to the Tus–Ter complex. The T7 replisome was arrested at the non-permissive end of Tus–Ter in a manner that is explained by a composite mousetrap and dynamic clamp model. An unpaired C(6) that forms a lock by binding into the cytosine binding pocket of Tus was most effective in arresting the replisome and mutation of C(6) removed the barrier. Isolated helicase was also blocked at the non-permissive end, but unexpectedly the isolated polymerase was not, unless C(6) was unpaired. Instead, the polymerase was blocked at the permissive end. This indicates that the Tus–Ter mechanism is sensitive to the translocation polarity of the DNA motor. The polymerase tracking along the template strand traps the C(6) to prevent lock formation; the helicase tracking along the other strand traps the complementary G(6) to aid lock formation. Our results are consistent with the model where strand separation by the helicase unpairs the GC(6) base pair and triggers lock formation immediately before the polymerase can sequester the C(6) base.

  1. Investigation on Inter-Limb Coordination and Motion Stability, Intensity and Complexity of Trunk and Limbs during Hands-Knees Crawling in Human Adults. (United States)

    Ma, Shenglan; Chen, Xiang; Cao, Shuai; Yu, Yi; Zhang, Xu


    This study aimed to investigate the inter-limb coordination pattern and the stability, intensity, and complexity of the trunk and limbs motions in human crawling under different speeds. Thirty healthy human adults finished hands-knees crawling trials on a treadmill at six different speeds (from 1 km/h to 2.5 km/h). A home-made multi-channel acquisition system consisting of five 3-axis accelerometers (ACC) and four force sensors was used for the data collection. Ipsilateral phase lag was used to represent inter-limb coordination pattern during crawling and power, harmonic ratio, and sample entropy of acceleration signals were adopted to depict the motion intensity, stability, and complexity of trunk and limbs respectively. Our results revealed some relationships between inter-limb coordination patterns and the stability and complexity of trunk movement. Trot-like crawling pattern was found to be the most stable and regular one at low speed in the view of trunk movement, and no-limb-pairing pattern showed the lowest stability and the greatest complexity at high speed. These relationships could be used to explain why subjects tended to avoid no-limb-pairing pattern when speed was over 2 km/h no matter which coordination type they used at low speeds. This also provided the evidence that the central nervous system (CNS) chose a stable inter-limb coordination pattern to keep the body safe and avoid tumbling. Although considerable progress has been made in the study of four-limb locomotion, much less is known about the reasons for the variety of inter-limb coordination. The research results of the exploration on the inter-limb coordination pattern choice during crawling from the standpoint of the motion stability, intensity, and complexity of trunk and limbs sheds light on the underlying motor control strategy of the human CNS and has important significance in the fields of clinical diagnosis, rehabilitation engineering, and kinematics research.

  2. Engineering and Coordination of Regulatory Networks and Intracellular Complexes to Maximize Hydrogen Production by Phototrophic Microorganisms

    Energy Technology Data Exchange (ETDEWEB)

    James C. Liao


    This project is a collaboration with F. R. Tabita of Ohio State. Our major goal is to understand the factors and regulatory mechanisms that influence hydrogen production. The organisms to be utilized in this study, phototrophic microorganisms, in particular nonsulfur purple (NSP) bacteria, catalyze many significant processes including the assimilation of carbon dioxide into organic carbon, nitrogen fixation, sulfur oxidation, aromatic acid degradation, and hydrogen oxidation/evolution. Our part of the project was to develop a modeling technique to investigate the metabolic network in connection to hydrogen production and regulation. Organisms must balance the pathways that generate and consume reducing power in order to maintain redox homeostasis to achieve growth. Maintaining this homeostasis in the nonsulfur purple photosynthetic bacteria is a complex feat with many avenues that can lead to balance, as these organisms possess versatile metabolic capabilities including anoxygenic photosynthesis, aerobic or anaerobic respiration, and fermentation. Growth is achieved by using H{sub 2} as an electron donor and CO{sub 2} as a carbon source during photoautotrophic and chemoautotrophic growth, where CO{sub 2} is fixed via the Calvin-Benson-Bassham (CBB) cycle. Photoheterotrophic growth can also occur when alternative organic carbon compounds are utilized as both the carbon source and electron donor. Regardless of the growth mode, excess reducing equivalents generated as a result of oxidative processes, must be transferred to terminal electron acceptors, thus insuring that redox homeostasis is maintained in the cell. Possible terminal acceptors include O{sub 2}, CO{sub 2}, organic carbon, or various oxyanions. Cells possess regulatory mechanisms to balance the activity of the pathways which supply energy, such as photosynthesis, and those that consume energy, such as CO{sub 2} assimilation or N{sub 2} fixation. The major route for CO{sub 2} assimilation is the CBB

  3. Photoinduced intercalation and coordination of a dirhodium complex to DNA: dual DNA binding. (United States)

    Palmer, Alycia M; Burya, Scott J; Gallucci, Judith C; Turro, Claudia


    Two new complexes, cis-H,H-[Rh2 (OCCH3 NH)2 (LL)(CH3 CN)2 ](2+) , where LL=bpy (2, bpy=2,2'-bipyridine) and dppz (3, dppz=dipyrido[3,2-a:2',3'-c]phenazine), were prepared from the reaction of cis-H,H-[Rh2 (OCCH3 NH)2 (CH3 CN)6 ](2+) (1) with the corresponding bidentate ligand. The bpy and dppz ligands chelate to the same rhodium atom and are positioned trans to the amidato N atoms, as determined by the single crystal X-ray structure of 2. Irradiation of 2 and 3 with visible light in water results in the exchange of one CH3 CNeq ligand for an H2 O molecule with quantum yields, Φ400 , of 0.040 and 0.044, respectively (λirr =400 nm). The identities of the photoproducts of 2 and 3 were determined to be cis-H,H-[Rh2 (OCCH3 NH)2 (L)(H2 O)(CH3 CN)](2+) , where L is bpy (4) and dppz (5), respectively. Mobility shift assays show that 4 crosslinks double-stranded DNA, and ESI-MS experiments indicate that both 4 and 5 form covalent adducts with single-stranded DNA. In addition, relative viscosity and 2D NMR experiments show that the dppz ligand of 5 also intercalates into DNA upon irradiation, making 3 a dual-binding agent that both intercalates and covalently binds to DNA upon the absorption of visible light.

  4. [trans-en2Os(η-H2)]2+ as an 1H NMR probe for the coordination of some anticancer metal complexes to deoxyguanotide

    Institute of Scientific and Technical Information of China (English)

    杨频; 郭茂林; 李青山; 田燕妮; Henry TAUBE


    The molecular hydrogen complex of osmium,[trans-en2Os(η-H2)]2+(en,entlylendediamine) is a new 1H NMR recognition probe for biomolecules.By using this probe,the coordination between deoxyguanylic acid (dGMP) and four metal anticancer complexes,titanocene dichloride,(C2H5)2SnCl2(phen),(C2H5)2SnCl2 and cis-piatm are studied in D2O under the condition near the physiological one.The results show that the former three complexes mainly and strongly coordinate with the phosphate oxygen of dGMP,while cisplatin mainly coordinates with N(7) of dGMP

  5. Analysis of unsaturated compounds by Ag+ coordination ionspray mass spectrometry: studies of the formation of the Ag+/lipid complex. (United States)

    Seal, Jennifer R; Havrilla, Christine M; Porter, Ned A; Hachey, David L


    Coordination ionspray mass spectrometry (CIS-MS) is a useful tool in the detection and identification of cholesterol ester and phospholipid hydroperoxides and diacyl peroxides. Extensive studies of a series of cholesterol esters using CIS-MS revealed the following: (1) Cholesterol esters with equal number of double bonds as the internal standard showed a linear relative response in the mass spectrometer while compounds with non-equal numbers of double bonds gave a nonlinear relative response. (2) Complex adducts containing cholesterol ester, silver ion, AgF, AgBF(4), and 2-propanoxide form when silver is in molar excess of cholesterol esters, reducing the [M + Ag](+) signal. (3) In a mixture of cholesterol esters where silver is limiting, Ch22:6 and Ch20:4 bind to silver at the expense of Ch18:2 and have a higher signal in the mass spectrometer. (4) In a mixture of cholesterol esters where silver concentration is twofold greater than total cholesterol ester concentration, Ch22:6 and Ch20:4 form large complex adducts more frequently than Ch18:2 and have a lower signal in the mass spectrometer.

  6. Coordination Complexes of Decamethylytterbocene with4,4'-Disubstituted Bipyridines: An Experimental Study of Spin Coupling inLanthanide Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Walter, Marc D.; Berg, David J.; Andersen, Richard A.


    The paramagnetic 1:1 coordination complexes of (C5Me5)2Ybwith a series of 4,4'-disubstituted bipyridines, bipy-X, where X is Me,tert-Bu, OMe, Ph, CO2Me, and CO2Et have been prepared. All of thecomplexes are paramagnetic and the values of the magnetic susceptibilityas a function of temperature show that these values are less thanexpected for the cation, [(C5Me5)2Yb(III)(bipy-X)]+, which have beenisolated as the cation-anion ion-pairs[(C5Me5)2Yb(III)(bipy-X)]+[(C5Me5)2YbI2]f fnfn where X is CO2Et, OMe andMe. The 1H NMR chemical shifts (293 K) for the methine resonances locatedat the 6,6' site in the bipy-X ring show a linear relationship with thevalues of chiT (300 K) for the neutral complexes which illustrates thatthe molecular behavior does not depend upon the phase with one exception,viz., (C5Me5)2Yb(bipy-Me). Single crystals of the 4,4'-dimethylbipyridinecomplex undergo an irreversible, abrupt first order phase change at 228 Kthat shatters the single crystals. The magnetic susceptibility,represented in a delta vs. T plot, on this complex, in polycrystallineform undergoes reversible abrupt changes in the temperature regime 205 -212 K, which is suggested to be due to the way the individual molec ularunits pack in the unit cell. A qualitative model is proposed thataccounts for the sub-normal magnetic moments in theseytterbocene-bipyridine complexes.

  7. Solvent-mediated crystal-to-crystal interconversion between discrete lanthanide complexes and one-dimensional coordination polymers and selective sensing for small molecules. (United States)

    Wu, Jin-Ji; Ye, Yu-Xin; Qiu, Ying-Yu; Qiao, Zheng-Ping; Cao, Man-Li; Ye, Bao-Hui


    Two isostructural 1D coordination polymers {[Ln(OAc)2(H2O)(OBPT)]·3H2O}n (HOBPT = 4,6-bis(2-pyridyl)-1,3,5-triazin-2-ol, Ln = Eu(3+), 1; Tb(3+), 3) and two discrete complexes [Ln(OAc)2(DMF)2(OBPT)] (Ln = Eu(3+), 2; Tb(3+), 4) have been synthesized in H2O-MeOH or DMF solvents, respectively. Their structures were identified by powder X-ray diffraction. Single-crystal X-ray studies for complexes 1 and 2 revealed that the coordination geometries of the Eu(3+) ions are similar and can be described as a distorted tricapped trigonal prism with six oxygen atoms and three nitrogen atoms. The difference between them is that one aqua ligand and one oxygen atom from the OBPT ligand complete the coordination sphere in complex 1, whereas two DMF molecules complete the coordination sphere in complex 2. Interestingly, the solvent-mediated, reversible crystal-to-crystal transformation between them was achieved by immersing the crystalline samples in the corresponding solvent (H2O or DMF) or by exposing them to solvent vapor. Complex 1 shows a highly selective luminescence enhancement in response to DMF in comparison to that observed in response to other examined solvents such as acetone, ethyl acetate, ethanol, acetonitrile, methanol, and THF.

  8. Tunable N-substitution in zwitterionic benzoquinonemonoimine derivatives: metal coordination, tandemlike synthesis of zwitterionic metal complexes, and supramolecular structures. (United States)

    Yang, Qing-Zheng; Siri, Olivier; Braunstein, Pierre


    Full details on a very efficient transamination reaction for the synthesis of zwitterionic N,N-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives [C6H2(=NHR)2(=O)2] 5-16 are reported. The molecular structures of zwitterions 5 (R=CH3) in 5.H2O, 13 (R=CH2CH2OMe), 15 (R=CH2CH2NMe2), and of the parent, unsubstituted system [C6H2(=NH2)2(=O)2] 4 in 4.H2O have been established by single-crystal X-ray diffraction. This one-pot preparation can be carried out in water, MeOH, or EtOH and allows access to new zwitterions with N-substituents bearing functionalities such as -OMe (13), -OH (9-12), NR1R2 with R1 = or not equal R2 (14-16) or an alkene (8), leading to a rich coordination chemistry and allowing fine-tuning of the supramolecular arrangements in the solid state. As previously described for 15, which reacted with Zn(acac)2 to afford the octahedral Zn(II) complex [Zn[C6H2(NCH2CH2NMe2)O(O)(NHCH2CH2NMe2)]2] (20), ligands 13 and 16 with coordinating "arms" afforded with Zn(acac)2 the 2:1 adducts [Zn[C6H2(NCH2CH2X)O(=O)(NHCH2CH2NX)]2] 19 (X=OMe) and 21 (X=NHEt), with N2O4 and N4O2 donor sets around the octahedral Zn(II) center, respectively. Furthermore, zwitterions 15 and 16 reacted with ZnCl2 to give the stable, crystallographically characterized Zn(II) zwitterionic complexes [ZnCl2[C6H2(NCH2CH2NR1R2)O(=O)(NHCH2CH2NHR1R2)

  9. Simultaneous end-on/side-on coordination modes of a diphosphorus tetrahedral complex imposed by pre-organization of oligometallic Cu(I) acceptors. (United States)

    Welsch, Stefan; Lescop, Christophe; Balazs, Gabor; Réau, Régis; Scheer, Manfred


    The reaction of the [{CpMo(CO)(2)}(2)(μ,η(2):η(2)-P(2))] (Cp=cyclopentadienyl) metallo-ligand 2 with pre-organized Cu(I) bi- and trimetallic precursors afforded new coordination complexes with unprecedented coordination modes for a Mo(2)P(2) complex. Variable-temperature solution and solid-state (31)P NMR spectroscopy measurements were performed and X-ray diffraction studies revealed an η(2):η(1) coordination mode for the Mo(2)P(2) unit of 2 in the Cu(I) bimetallic complexes 3 and 4. DFT calculations were carried out to highlight the bonding situation of this unprecedented coordination mode in the Cu(I) bimetallic compound 3. It is built up from a side-on coordination of the P-P σ bond to one copper ion and from the interaction of the lone pair of one phosphorus atom with the second copper ion. The remaining available lone pair of the second phosphorus atom can be involved as well to interact with an additional metal centre, as evidenced in the Cu(I) trimetallic compound 5 in which an η(2):η(1):η(1) coordination mode of the ligand 2 is observed. Derivative 3 can be used as a molecular clip to obtain discrete π-stacked dimers through a ligand exchange reaction between acetonitrile ligands and cyano-capped π-conjugated systems, indicating the stability of the new η(2):η(1) coordination mode. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Syntheses and Structural Researches of Yb3+ Complexes with Nitrilotriacetic Acids--Nine-coordinate K3[Yb(nta)2(H2O)]·5H2O and Eight-coordinate Na3[Yb(nta)2]·6H2O Complexes

    Institute of Scientific and Technical Information of China (English)


    Yb3+ complexes with two nitrilotriacetic acid molecules were prepared and their compositions were determined as K3[Yb(nta)2(H2O)]*5H2O and Na3[Yb(nta)2]*6H2O by elemental analyses. Their structures were characterized by single-crystal X-ray diffraction analyses. In complex K3[Yb(nta)2(H2O)]*5H2O, the YbN2O7 part forms a nine-coordinate monocapped square antiprismatic structure. In complex Na3[Yb(nta)2]*6H2O, the YbN2O6 part forms an eight-coordinate square antiprismatic structure. It can be seen that the outer cations (K+ and Na+) greatly affect the coordination number and coordinate structure from these results.

  11. 从配位体到配位络合物结构:扫描隧道显微学的分子工程%From ligands to coordinated complex architectures:a molecular engineering with scanning tunneling microscopy

    Institute of Scientific and Technical Information of China (English)



    @@ With the development of modem coordination chemistry,various metal-ligand complexes with elaborate structures have been synthesized.[1]The structural complexities as well as the coordination processes of these metal-ligand complexes can be partially comparable to those in biology system formed by self-assembling with the weak intermolecular or intramolecular interactions.

  12. Identification of Second Shell Coordination in Transition Metal Species Using Theoretical XANES: Example of Ti-O-(C, Si, Ge) Complexes. (United States)

    Spanjers, Charles S; Guillo, Pascal; Tilley, T Don; Janik, Michael J; Rioux, Robert M


    X-ray absorption near-edge structure (XANES) is a common technique for elucidating oxidation state and first shell coordination geometry in transition metal complexes, among many other materials. However, the structural information obtained from XANES is often limited to the first coordination sphere. In this study, we show how XANES can be used to differentiate between C, Si, and Ge in the second coordination shell of Ti-O-(C, Si, Ge) molecular complexes based on differences in their Ti K-edge XANES spectra. Experimental spectra were compared with theoretical spectra calculated using density functional theory structural optimization and ab initio XANES calculations. The unique features for second shell C, Si, and Ge present in the Ti K pre-edge XANES are attributed to the interaction between the Ti center and the O-X (X = C, Si, or Ge) antibonding orbitals.

  13. Separation performance of cucurbit[8]uril and its coordination complex with cadmium (II) in capillary gas chromatography. (United States)

    Sun, Tao; Ji, Ningning; Qi, Meiling; Tao, Zhu; Fu, Ruonong


    Here we report the investigation of using cucurbit[8]uril (CB8) and its coordination complex with cadmium (II) (CB8-Cd) as stationary phases for capillary gas chromatography (GC). The prepared capillary columns of CB8 and CB8-Cd stationary phases achieved column efficiency of 2200plates/m and 1508plates/m, respectively, and showed weak polarity based on the measured McReynolds constants. Their separation performance was investigated by GC separation of mixtures of different types while a commercial column was used for comparison. The CB8 stationary phase achieved high resolution for a wide range of analytes from nonpolar to polar while the CB8-Cd stationary phase exhibited good separation mainly for nonpolar to weak polar analytes. The CB stationary phases differ from the commercial one in terms of retention behaviors and resolving ability due to their different molecular interactions with analytes. Moreover, energy effect on the retention of analytes on CB8 and CB8-Cd stationary phases was examined, showing that retention on CB8 column was determined mainly by enthalpy change for polar analytes and by both enthalpy change and entropy change for weak polar analytes whereas retention on CB8-Cd column was mainly controlled by entropy change. This work demonstrates the great potential of CB8 and CB8-Cd stationary phases as a new type of GC stationary phases in GC analysis.

  14. Nonrelativistic Compton scattering in Furry's picture: Beyond the sudden impulse approximation by means of the complex coordinate method (United States)

    Froelich, P.; Weyrich, Wolf


    Basic electrodynamical and collision theory presumptions related to Compton scattering are critically reconsidered (with particular emphasis on identifying the proper transition matrix element effectively controlling the process, and on framing it within time dependent perturbation theory and scattering theory) in order to indicate the main features and the validity of the proposed method. The on-energy-shell transition matrix element governing the cross-sectional formula is obtained from Furry's two-potential formalism, which makes possible a treatment of the primary electron-photon interaction to first order while incorporating the effects of the final state Coulombic interaction to all orders. Furry's procedure, in addition to defining clearly which initial and final states should enter the transition matrix element, also brings additional insight into the nature of the so-called ``sudden impulse approximation.'' A treatment is proposed in which the decisive transition matrix element is obtained without explicit calculation of the distorted continuum solutions implied by Furry's procedure, but is instead extracted from the dispersion relations of the ``beat-frequency'' dependent generalized polarizability by means of the L2 treatment based on the complex-coordinate method. The practical advantage of the method will be its ability to incorporate correlation between the ejected electron and the electrons remaining in the ion.

  15. Arf6 coordinates actin assembly through the WAVE complex, a mechanism usurped by Salmonella to invade host cells (United States)

    Humphreys, Daniel; Davidson, Anthony C.; Hume, Peter J.; Makin, Laura E.; Koronakis, Vassilis


    ADP ribosylation factor (Arf) 6 anchors to the plasma membrane, where it coordinates membrane trafficking and cytoskeleton remodelling, but how it assembles actin filaments is unknown. By reconstituting membrane-associated actin assembly mediated by the WASP family veroprolin homolog (WAVE) regulatory complex (WRC), we recapitulated an Arf6-driven actin polymerization pathway. We show that Arf6 is divergent from other Arf members, as it was incapable of directly recruiting WRC. We demonstrate that Arf6 triggers actin assembly at the membrane indirectly by recruiting the Arf guanine nucleotide exchange factor (GEF) ARNO that activates Arf1 to enable WRC-dependent actin assembly. The pathogen Salmonella usurped Arf6 for host cell invasion by recruiting its canonical GEFs EFA6 and BRAG2. Arf6 and its GEFs facilitated membrane ruffling and pathogen invasion via ARNO, and triggered actin assembly by generating an Arf1–WRC signaling hub at the membrane in vitro and in cells. This study reconstitutes Arf6-dependent actin assembly to reveal a mechanism by which related Arf GTPases orchestrate distinct steps in the WRC cytoskeleton remodelling pathway. PMID:24085844

  16. Tetrapositive plutonium, neptunium, uranium, and thorium coordination complexes: chemistry revealed by electron transfer and collision induced dissociation. (United States)

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K


    The Pu(4+), Np(4+), and U(4+) ions, which have large electron affinities of ∼34.6, ∼33.6, and ∼32.6 eV, respectively, were stabilized from solution to the gas phase upon coordination by three neutral tetramethyl-3-oxa-glutaramide ligands (TMOGA). Both collision induced dissociation (CID) and electron transfer dissociation (ETD) of Pu(TMOGA)3(4+) reveal the propensity for reduction of Pu(IV) to Pu(III), by loss of TMOGA(+) in CID and by simple electron transfer in ETD. The reduction of Pu(IV) is in distinct contrast to retention of Th(IV) in both CID and ETD of Th(TMOGA)3(4+), where only the C-Oether bond cleavage product was observed. U(TMOGA)3(4+) behaves similarly to Th(TMOGA)3(4+) upon CID and ETD, while the fragmentation patterns of Np(TMOGA)3(4+) lie between those of Pu(TMOGA)3(4+) and U(TMOGA)3(4+). It is notable that the gas-phase fragmentation behaviors of these exceptional tetrapositive complexes parallel fundamental differences in condensed phase chemistry within the actinide series, specifically the tendency for reduction from the IV to III oxidation states.

  17. Steric, electronic, and secondary effects on the coordination chemistry of ionic phosphine ligands and the catalytic behavior of their metal complexes

    NARCIS (Netherlands)

    Snelders, D.J.M.; van Koten, G.; Klein Gebbink, R.J.M.


    The effects of introducing ionic functionalities in phosphine ligands on the coordination chemistry of these ligands and the catalytic behavior of the corresponding metal complexes are reviewed. The steric and electronic consequences of such functionalizations are discussed. Apart from these steric

  18. Steric, electronic, and secondary effects on the coordination chemistry of ionic phosphine ligands and the catalytic behavior of their metal complexes

    NARCIS (Netherlands)

    Snelders, D.J.M.; van Koten, G.; Klein Gebbink, R.J.M.


    The effects of introducing ionic functionalities in phosphine ligands on the coordination chemistry of these ligands and the catalytic behavior of the corresponding metal complexes are reviewed. The steric and electronic consequences of such functionalizations are discussed. Apart from these steric

  19. Synthesis, crystal structures, and urease inhibition of an acetohydroxamate-coordinated oxovanadium(V) complex derived from N'-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide. (United States)

    Qu, Dan; Niu, Fang; Zhao, Xinlu; Yan, Ke-Xiang; Ye, Yu-Ting; Wang, Jia; Zhang, Mei; You, Zhonglu


    A new benzohydrazone compound N'-(3-bromo-2-hydroxybenzylidene)-4-methoxybenzohydrazide (H₂L) was prepared. Reaction of H₂L and acetohydroxamic acid (HAHA) with VO(acac)₂ in methanol gave the complex [VOL(AHA)]. Both H₂L and the oxovanadium complex were characterized by elemental analysis, IR, UV-vis and (1)H NMR spectra, and single crystal X-ray diffraction. H₂L was also characterized by high-resolution mass spectrum. Thermal analysis of the oxovanadium complex was carried out. The benzohydrazone ligand, in its dianionic form, coordinates to V atom through the phenolate oxygen, imino nitrogen and enolate oxygen. The acetohydroxamic acid coordinates to V atom through the carbonyl oxygen and deprotonated hydroxyl oxygen. The V atom is in octahedral coordination. H₂L, HAHA and the oxovanadium complex were tested for their urease inhibitory activities. The percent inhibition at concentration of 100 μmol·L(-1) on Helicobacter pylori urease is 78% for the oxovanadium complex. The IC₅₀ value for the complex is 36.5 μmol·L(-1). Molecular docking study was performed to study the inhibition. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. The coordination structure of the extracted nickel(ii) complex with a synergistic mixture containing dinonylnaphthalene sulfonic acid and 2-ethylhexyl 4-pyridinecarboxylate ester. (United States)

    Li, Jiyuan; Hu, Huiping; Zhu, Shan; Hu, Fang; Wang, Yongxi


    In this paper, a synergist complex of Ni(ii) with naphthalene-2-sulfonic acid (HNS) and n-hexyl 4-pyridinecarboxylate ester (L(I)), which are corresponding short chain analogues of active synergistic extractants dinonylnaphthalene sulfonic acid (HDNNS) and 2-ethylhexyl 4-pyridinecarboxylate ester (4PC, L(II)), was prepared and characterized by Nuclear Magnetic Resonance ((1)H-NMR), elemental analyses, Fourier Transform Infrared Spectroscopy (FT-IR) and Electrospray Ionization Mass Spectrometry (ESI-MS) spectroscopic studies. Single crystals of the nickel synergist complex have been grown from a methanol/water (10/1) solution and analyzed by single crystal X-ray diffraction. The crystal structure of the nickel synergist complex shows that Ni(ii) is coordinated by four water molecules and two monodentate L(I) ligands and there is no direct interaction of the Ni(ii) with sulfonic oxygen atoms of naphthalene-2-sulfonic acid anions, while hydrogen-bonded interactions of the coordinated water molecules with sulfonic oxygen atoms of naphthalene-2-sulphate anions were observed. In addition, in order to provide parallels to solvent extraction, the extracted Ni(ii) complex with HDNNS and 4PC is also prepared and studied using FT-IR and ESI-MS technology. Compared with their corresponding free ligand, similar shifts assigned to the stretching vibration of the pyridine ring and S[double bond, length as m-dash]O in both the nickel synergist complex and the extracted Ni(ii) complex suggest that in the non-polar organic phase, Ni(ii) is also coordinated by L(II) ligands, while the sulfonic oxygen atoms of dinonylnaphthalene sulfonate anions not directly bonded to Ni(ii) form hydrogen bonds with water molecules (coordinated with Ni(ii) or/and solubilized in the non-polar organic phase). For the ESI-MS spectrum of the extracted Ni(ii) complex in non-polar organic phase, there exists a peak at m/z values of 1058.76, which indicates that the extracted Ni(ii) complex in the non

  1. Variable coordinating activity of sulfur in silver(I) complexes with thiophene based N¹ -substituted thiosemicarbazones: First case of thiopheneyl-thione sulfur bridging in a dinuclear complex

    Indian Academy of Sciences (India)



    Thiophene-2-carbaldehyde / acetaldehyde-N¹-substituted thiosemicarbazones {R¹R²C² = N³ - N(H)- C¹(=S)N¹HR; R¹, R², R : C₄H₃S, H, Me, Httsc- NMe; C₄H₃S, H, Et, Httsc-NEt; C₄H₃S, H, Ph, Httsc-NPh; C₄H₃S, Me, Et, Hattsc-NEt} and furan-2-carbaldehyde-N-ethyl thiosemicarbazone (C₄H₃O, H, Et, Hftsc-NEt) were reacted with silver(I) halides/silver(I) acetate in presence of triphenylphosphine in organic solvents. These reactions yielded a series of dinuclear [Ag₂(μ-Br)₂ (κ-S-Httsc-NEt)2(PPh3)2]·2MeOH 1, [Ag2Cl2(κ1-SHttsc-NPh)2(μ-S,S-Httsc-NPh)2] 2, [Ag2Cl2(μ-S-Hftsc-NEt)2(κ1-S-Hftsc-NEt)2] 4, [Ag2(μ3-N3,S-ttsc-NMe)2 (Ph3P)2]·2(CH3)2CO 5, [Ag2 (μ3-N3,S-attsc-NEt)2(Ph3P)2]·0.5(CH3)2CO 6 and mononuclear [AgBr(κ1-SHttsc-NPh)(PPh3)2]· MeCN 3 complexes, all of which have been characterized using analytical techniques, IRand NMR spectroscopy, and X-ray crystallography. Thio-ligands bind in neutral form in complexes 1-4 and in anionic form in complexes 5-6. Further, the sulfur donor atoms have shown variable coordination modes incomplexes, namely, κ1-S in 1 and 3; κ1-S, μ-S in 4; κ1-S, μ-S,S (thiopheneyl-thione) in 2 and μ3- N3, S in 5 and 6. Tertiary-phosphine (PPh3) showed dual function of ligation/de-ligation towards silver(I) chloride during the synthesis of complexes 2 and 4. The bridge bonding of Httsc-NPh in 2 through thiopheneyl ring sulfur andthione sulfur is unprecedented in metal-thiosemicarbazone chemistry.

  2. A novel binuclear copper complex incorporating a nalidixic acid derivative displaying a one-dimensional coordination polymeric structure. (United States)

    Bergamini, F R G; Ribeiro, M A; Miranda, P C M L; Formiga, A L B; Corbi, P P


    The identification of the antibacterial action of nalidixic acid (nx) was central to the development of the quinolone antibacterial compounds. The ability of the nx naphthyridyl ring to interact with and inhibit some proteins has encouraged the investigation of similar structures in the search for more active compounds with less adverse effects. The possibility of structural modification by attachment of other biologically active moieties to the naphthyridyl ring of nx allowed the development of new active antimicrobial molecules. Hydrazone derivatives of nx can be synthesized easily based on the condensation of the hydrazide derivative of nx with the desired aldehyde or ketone. Only a few complexes with nx hydrazone derivatives have been described but for none were the crystal structures elucidated. The synthesis of a new one-dimensional Cu(II) coordination polymer, namely catena-poly[[copper(II)-di-μ-chlorido-copper(II)-{μ-1-ethyl-N'-[(1H-imidazol-4-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}-[dimethanolcopper(II)]-{μ-1-ethyl-N'-[(1H-imidazol-3-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}] dichloride methanol tetrasolvate], {[Cu3(C16H15N6O2)2Cl2(CH3OH)2]Cl2·4CH3OH}n, with the (1H-imidazol-4-yl)methylidene carbohydrazide derivative of nalidixic acid (denoted h4imi), is presented and its structure is compared to the density functional theory (DFT) optimized structure of free h4imi. The title structure presents an octahedral Cu(II) ion on an inversion centre alternating along a polymer chain with a square-pyramidal Cu(II) ion, with the two Cu(II) centres bridged by two chloride ligands. Hydrogen bonds involving chloride counter-ions and methanol solvent molecules mediate the three-dimensional packing of the polymer. Comparison of the geometrical results from the structure analysis with those derived from a DFT study of the free ligand reveal the differences that arise upon coordination.

  3. Solid-state and solution-state coordination chemistry of lanthanide(III) complexes with (pyrazol-1-yl)acetic acid. (United States)

    Chen, Xiao-Yan; Goff, George S; Scott, Brian L; Janicke, Michael T; Runde, Wolfgang


    As a precursor of carboxyl-functionalized task-specific ionic liquids (TSILs) for f-element separations, (pyrazol-1-yl)acetic acid (L) can be deprotonated as a functionalized pyrazolate anion to coordinate with hard metal cations. However, the coordination chemistry of L with f-elements remains unexplored. We reacted L with lanthanides in aqueous solution at pH = 5 and synthesized four lanthanide complexes of general formula [Ln(L)3(H2O)2]·nH2O (1, Ln = La, n = 2; 2, Ln = Ce, n = 2; 3, Ln = Pr, n = 2; 4, Ln = Nd, n = 1). All complexes were characterized by single crystal X-ray diffraction analysis revealing one-dimensional chain formations. Two distinct crystallographic structures are governed by the different coordination modes of carboxylate groups in L: terminal bidentate and bridging tridentate (1-3); terminal bidentate, bridging bidentate, and tridentate coordination in 4. Comparison of the solid state UV-vis-NIR diffuse reflectance spectra with solution state UV-vis-NIR spectra suggests a different species in solution and solid state. The different coordination in solid state and solution was verified by distinctive (13)C NMR signals of the carboxylate groups in the solid state NMR.

  4. Preparation and Reactions of the 1,1-Dithiolato Complexes of Ni(II). An Undergraduate Coordination Chemistry Experiment. (United States)

    Ballester, L.; Perpinan, M. F.


    Described is an undergraduate coordination chemistry experiment that enables students to relate concepts developed in class about the stereochemistry and coordination numbers to the interpretation of the electronic and infrared spectra and their magnetic behavior. Indicates that thermal decomposition and x-ray diffraction studies can also be…

  5. Methylresorcinarene: a reaction vessel to control the coordination geometry of copper(II) in pyridine N-oxide copper(II) complexes. (United States)

    Beyeh, Ngong Kodiah; Puttreddy, Rakesh


    Pyridine and 2-picolinic acid N-oxides form 2 : 2 and 2 : 1 ligand : metal (L : M) discrete L2M2 and polymeric complexes with CuCl2 and Cu(NO3)2, respectively, with copper(ii) salts. The N-oxides also form 1 : 1 host-guest complexes with methylresorcinarene. In combination, the three components form a unique 2 : 2 : 1 host-ligand-metal complex. The methylresorcinarene acts as a reaction vessel/protecting group to control the coordination of copper(ii) from cis-see-saw to trans-square planar, and from octahedral to square planar coordination geometry. These processes were studied in solution and in the solid state via(1)H NMR spectroscopy and single crystal X-ray diffraction.

  6. Solution chemistry of a water-soluble eta2-H2 ruthenium complex: evidence for coordinated H2 acting as a hydrogen bond donor. (United States)

    Szymczak, Nathaniel K; Zakharov, Lev N; Tyler, David R


    The ability of an eta2-H2 ligand to participate in intermolecular hydrogen bonding in solution has long been an unresolved issue. Such species are proposed to be key intermediates in numerous important reactions such as the proton-transfer pathway of H2 production by hydrogenase enzymes. We present the synthesis of several new water-soluble ruthenium coordination complexes including an eta2-H2 complex that is surprisingly inert to substitution by water. The existence of dihydrogen hydrogen bonding (DHHB) was experimentally probed by monitoring the chemical shift of H-bonded Ru-(H2) complexes using NMR spectroscopy, by UV-visible spectroscopy, and by monitoring the rotational dynamics of a hydrogen-bonding probe molecule. The results provide strong evidence that coordinated H2 can indeed participate in intermolecular hydrogen bonding to bulk solvent and other H-bond acceptors.

  7. Design and structure analysis of artificial metalloproteins: selective coordination of His64 to copper complexes with square-planar structure in the apo-myoglobin scaffold. (United States)

    Abe, Satoshi; Ueno, Takafumi; Reddy, Pattubala A N; Okazaki, Seiji; Hikage, Tatsuo; Suzuki, Atsuo; Yamane, Takashi; Nakajima, Hiroshi; Watanabe, Yoshihito


    apo-Myoglobin (apo-Mb) was reconstituted with three copper complexes: CuII(Sal-Phe) (1; Sal-Phe = N-salicylidene-L-phenylalanato), CuII(Sal-Leu) (2; Sal-Leu = N-salicylidene-L-leucinato), and CuII(Sal-Ala) (3; Sal-Ala = N-salicylidene-L-alanato). The crystal structures of 1.apo-Mb (1.65 Angstrom resolution) and 2.apo-Mb (1.8 Angstrom resolution) show that the coordination geometry around the CuII atom in apo-Mb is distorted square-planar with tridentate Sal-X and a Nepsilon atom of His64 in the apo-Mb cavity and the plane of these copper complexes is perpendicular to that of heme. These results suggest that the apo-Mb cavity can hold metal complexes with various coordination geometries.

  8. Hybrid scorpionate/cyclopentadienyl magnesium and zinc complexes: synthesis, coordination chemistry, and ring-opening polymerization studies on cyclic esters. (United States)

    Garcés, Andrés; Sánchez-Barba, Luis F; Alonso-Moreno, Carlos; Fajardo, Mariano; Fernández-Baeza, Juan; Otero, Antonio; Lara-Sánchez, Agustín; López-Solera, Isabel; Rodríguez, Ana María


    The reaction of the hybrid scorpionate/cyclopentadienyl lithium salt [Li(bpzcp)(THF)] [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] with 1 equiv of RMgCl proceeds cleanly to give very high yields of the corresponding monoalkyl kappa(2)-NN-eta(5)-C(5)H(4) magnesium complexes [Mg(R)(kappa(2)-eta(5)-bpzcp)] (R = Me 1, Et 2, (n)Bu 3, (t)Bu 4, CH(2)SiMe(3) 5, CH(2)Ph 6). Hydrolysis of the hybrid lithium salt [Li(bpzcp)(THF)] with NH(4)Cl/H(2)O in ether cleanly affords the two previously described regioisomers: (bpzcpH) 1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (a) and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethyl]-1,3-cyclopentadiene (b). Subsequent reaction of the bpzcpH hybrid ligand with ZnR(2) quantitatively yields the monoalkyl kappa(2)-NN-eta(1)(pi)-C(5)H(4) zinc complexes [Zn(R){kappa(2)-eta(1)(pi)-bpzcp}] (R = Me 7, Et 8, (t)Bu 9, CH(2)SiMe(3) 10). Additionally, magnesium alkyls 1, 2, 4, and 5 can act as excellent cyclopentadienyl and alkyl transfers to the zinc metal center and yield zinc alkyls 7-10 in good yields. The single-crystal X-ray structures of the derivatives 4, 5, 7, and 10 confirm a 4-coordinative structure with the metal center in a distorted tetrahedral geometry. Interestingly, whereas alkyl magnesium derivatives 4 and 5 present a eta(5) coordination mode for the cyclopentadienyl fragment, zinc derivatives 7 and 10 feature a peripheral eta(1)(pi) arrangement in the solid state. Furthermore, the reaction of the hybrid lithium salt [Li(bpzcp)(THF)] with 1 equiv of ZnCl(2) in tetrahydrofuran (THF) affords very high yields of the chloride complex [ZnCl{kappa(2)-eta(1)(pi)-bpzcp}] (11). Compound 11 was used as a convenient starting material for the synthesis of the aromatic amide zinc compound [Zn(NH-4-MeC(6)H(4)){kappa(2)-eta(1)(pi)-bpzcp}] (12), by reaction with the corresponding aromatic primary amide lithium salt. Alternatively, aliphatic amide and alkoxide derivatives were

  9. Syntheses and Structural Researches of Yb3+ Complexes with Nitrilotriacetic Acids—Nine—coordinate K3[Yb(nta)2(H2O)]·5H2O and Eight—coordinate Na3[Yb(nta)2]·6H2O complexes

    Institute of Scientific and Technical Information of China (English)

    WANGJun; ZHANGXiang-dong; JIAWei-guo; LIHui-fang


    Yb3+ complexes with two nitrilotriacetic acid molecules were prepared and their compositions were determined as K3[Yb(nta)2(H2O)]·5H2O and Na3[Yb(nta)2]·6H2O by elemental analyses.Their structures were characterized by single-crystal X-ray diffraction analyses.In complex K3[Yb(nta)2(H2O)]·5H2O,the YbN2O7 part forms a nine-coordinate monocapped square antiprismatic structure.In comples Na3[Yb(nta)2]·6H2O,the YbN2O6 part forms an eight-coordinate square antiprismatic structure.It can be seen that the outer cations(K+ and Na+)greatly affect the coordination number and coordinate structure from these results.

  10. Thiocyanate-Ligated Heterobimetallic {PtM} Lantern Complexes Including a Ferromagnetically Coupled 1D Coordination Polymer. (United States)

    Guillet, Jesse L; Bhowmick, Indrani; Shores, Matthew P; Daley, Christopher J A; Gembicky, Milan; Golen, James A; Rheingold, Arnold L; Doerrer, Linda H


    A series of heterobimetallic lantern complexes with the central unit {PtM(SAc)4(NCS)} have been prepared and thoroughly characterized. The {Na(15C5)}[PtM(SAc)4(NCS)] series, 1 (Co), 2 (Ni), 3 (Zn), are discrete compounds in the solid state, whereas the {Na(12C4)2)}[PtM(SAc)4(NCS)] series, 4 (Co), 5 (Ni), 6 (Zn), and 7 (Mn), are ion-separated species. Compound 7 is the first {PtMn} lantern of any bridging ligand (carboxylate, amide, etc.). Monomeric 1-7 have M(2+), necessitating counter cations that have been prepared as {(15C5)Na}(+) and {(12C4)2Na}(+) variants, none of which form extended structures. In contrast, neutral [PtCr(tba)4(NCS)]∞ 8 forms a coordination polymer of {PtCr}(+) units linked by (NCS)(-) in a zigzag chain. All eight compounds have been thoroughly characterized and analyzed in comparison to a previously reported family of compounds. Crystal structures are presented for compounds 1-6 and 8, and solution magnetic susceptibility measurements are presented for compounds 1, 2, 4, 5, and 7. Further structural analysis of dimerized {PtM} units reinforces the empirical observation that greater charge density along the Pt-M vector leads to more Pt···Pt interactions in the solid state. Four structural classes, one new, of {MPt}···{PtM} units are presented. Solid state magnetic characterization of 8 reveals a ferromagnetic interaction in the {PtCr(NCS)} chain between the Cr centers of J/kB = 1.7(4) K.

  11. Polycations XX: New Monodentate Cationic Ligands and Their Coordination with Ruthenium for the Construction of Complexes Expressing Enhanced Interaction with DNA

    Directory of Open Access Journals (Sweden)

    Leslie Babukutty


    Full Text Available Prior investigations from this laboratory concerned with the preparation of new types of organic cations for a variety of biological and nonbiological applications have been extended to the preparation of cation-bearing ligands with nitrogen coordinating sites for use in complexation reactions with ruthenium cores. The syntheses of new cationic ligands as well as ruthenium complexes bearing them are reported here. The introduction of these new types of ligands is intended to provide to the complexes an enhanced ability to interact with DNA, and thereby to have the potential to be enhanced antitumor agents. Preliminary observations of their interactions with DNA are presented.

  12. Coordination of complex bimanual multijoint movements under increasing cycling frequencies: the prevalence of mirror-image and translational symmetry. (United States)

    Li, Yong; Levin, Oron; Forner-Cordero, Arturo; Ronsse, Renaud; Swinnen, Stephan P


    The present study examined the principles underlying inter and intralimb coordination constraints during performance of bimanual elbow-wrist movements at different cycling frequencies (from 0.75 Hz to 2.50 Hz). Participants performed eight coordination tasks that consisted of a combination of in-phase (IN) and/or anti-phase (AN) coordination modes between both elbows and wrists (interlimb), with isodirectional (Iso) or non-isodirectional (NonI) coordination modes within each limb (intralimb). As expected, the principle of muscle homology (in-phase coordination), giving rise to mirror symmetrical movements with respect to the mid-sagittal plane, had a powerful influence on the quality of global coordinative behavior both between and within limbs. When this principle was violated (i.e., when the anti-phase mode was introduced in one or both joint pairs), the non-isodirectional intralimb mode exhibited a (de)stabilizing role in coordination, which became more pronounced at higher cycling frequencies. However, pattern loss with increasing cycling frequency resulted not only in convergence toward the more stable in-phase patterns with the elbows and wrists but also to the anti-phase patterns (which were associated with directional compatibility of within-limb motions). Moreover, participants generally preserved their initial mode of coordination (either in-phase or anti-phase) in the proximal joints (i.e., elbows) while shifting from anti-phase to in-phase (or vice versa) with their distal joint pair (i.e., wrists). Taken together, these findings reflect the impact of two immanent types of symmetry in bimanual coordination: mirror-image and translational symmetry.

  13. Nonoxido V(IV) Complexes: Prediction of the EPR Spectrum and Electronic Structure of Simple Coordination Compounds and Amavadin. (United States)

    Sanna, Daniele; Sciortino, Giuseppe; Ugone, Valeria; Micera, Giovanni; Garribba, Eugenio


    Density functional theory (DFT) calculations of the (51)V hyperfine coupling (HFC) tensor A have been completed for 20 "bare" V(IV) complexes with different donor sets, electric charges, and coordination geometries. Calculations were performed with ORCA and Gaussian software, using functionals BP86, TPSS0, B1LYP, PBE0, B3LYP, B3P, B3PW, O3LYP, BHandHLYP, BHandH, and B2PLYP. Among the basis sets, 6-311g(d,p), 6-311++g(d,p), VTZ, cc-pVTZ, def2-TZVPP, and the "core properties" CP(PPP) were tested. The experimental Aiso and Ai (where i = x or z, depending on the geometry and electronic structure of V(IV) complex) were compared with the values calculated by DFT methods. The results indicated that, based on the mean absolute percentage deviation (MAPD), the best functional to predict Aiso or Ai is the double hybrid B2PLYP. With this functional and the basis set VTZ, it is possible to predict the Aiso and Az of the EPR spectrum of amavadin with deviations of -1.1% and -2.0% from the experimental values. The results allowed us to divide the spectra of nonoxido V(IV) compounds in three types-called "type 1", "type 2", and "type 3", characterized by different composition of the singly occupied molecular orbital (SOMO) and relationship between the values of Ax, Ay, and Az. For "type 1" spectra, Az ≫ Ax ≈ Ay and Az is in the range of (135-155) × 10(-4) cm(-1); for "type 2" spectra, Ax ≈ Ay ≫ Az and Ax ≈ Ay are in the range of (90-120) × 10(-4) cm(-1); and for the intermediate spectra of "type 3", Az > Ay > Ax or Ax > Ay > Az, with Az or Ax values in the range of (120-135) × 10(-4) cm(-1). The electronic structure of the V(IV) species was also discussed, and the results showed that the values of Ax or Az are correlated with the percent contribution of V-dxy orbital in the SOMO. Similarly to V(IV)O species, for amavadin the SOMO is based mainly on the V-dxy orbital, and this accounts for the large experimental value of Az (153 × 10(-4) cm(-1)).

  14. Fac-mer equilibria of coordinated iminodiacetate (ida2-) in ternary CuII(ida)(H-1B)- complex formation (B = imidazole, benzimidazole) in aqueous solution

    Indian Academy of Sciences (India)

    Susmita Bandyopadhyay; G N Mukherjee


    pH potentiometric and spectrophotometric investigations on the complex formation equilibria of CuII with iminodiacetate (ida2-) and heterocyclic N-bases, viz. imidazole and benzimidazole (B), in aqueous solution in binary and ternary systems using different molar ratios of the reactants indicated the formation of complexes of the types, Cu(ida), Cu(ida)(OH)-, (ida)Cu(OH)Cu(ida)-, Cu(B)2+, Cu(H-1B)+, Cu(ida)(H-1B)-, (ida)Cu(B)Cu(ida) and (ida)Cu(H-1B)Cu(ida)-. Formation constants of the complexes at 25 ± 1° at a fixed ionic strength, = 0.1 mol dm-3 (NaNO3) in aqueous solution were evaluated and the complex formation equilibria were elucidated with the aid of speciation curves. Departure of the experimental values of the reproportionation constants (log Cu) of ternary Cu(ida)(H-1B)- complexes from the statistically expected values, despite their formation in appreciable amounts at equilibrium, were assigned to fac(f)-mer(m) equilibria of the ida2- ligand coordinated to CuII, as the N-heterocyclic donors, (H-1B)-, coordinate trans- to the N-(ida2-) atom in the binary Cu(ida) complex to form the ternary Cu(ida) (H-1B)- complexes.

  15. Synthesis and Crystal Structure of a Mn(Ⅱ) Complex with Thiosemicarbazone Derivative of Pyridine-3-carbaldehyde Showing Unusual Coordination Mode of Tridentate Thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    LI Ming-Xue; ZHOU Jing; WANG Jing-Ping; WANG Zi-Liang


    The title complex Mn(HL)4(NCS)2(CH3CH2OH)2 has been achieved via selfassembly by incorporating manganese(Ⅱ) into pyridine-3-carbaldehyde thiosemicarbazonate ligand,and characterized by elemental analysis and single-crystal X-ray diffraction study. The crystal crystallizes in triclinic, space group P1 with a = 8.896(2), b = 9.530(2), c = 14.520(4) (A), α =87.035(4), β= 88.112(4), γ= 69.434(4)°, V= 1150.9(5) (A)3, Z = 1, Mr = 984.17, Dc = 1.420 g/cm3,μ(MoKα) = 0.612 mm-1, F(000) = 511, the final R = 0.0574 and wR = 0.1547 for 2855 observed reflections with I > 2σ(I). The complex contains one six-coordinated manganese ion connected by two thiosemicarbazide ligands, in which the thiosemicarbazone ligand acts as a monodentate ligand and coordinates to the center metal atoms via the pyridyl nitrogen atoms, two ethanol molecules and two isothiocyanic anions to give rise to a mononuclear structure. The coordination of a potentially tridentate thiosemicarbazone in manganese(Ⅱ) complex without using its sulfur and imine nitrogen sites is unusual. Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure.

  16. Higher coordinate gold(I) complexes with the weak Lewis base tri(4-fluorophenyl) phosphine. Synthesis, structural, luminescence, and DFT studies (United States)

    Agbeworvi, George; Assefa, Zerihun; Sykora, Richard E.; Taylor, Jared; Crawford, Carlos


    The structures and spectroscopic properties of two high coordinate gold(I) phosphine complexes with the TFFPP=tri(4-fluorophenyl)phosphine ligand are reported. Synthesis in a 1:3 metal to ligand ratio provided the compound [AuCl(TFFPP)3] (2) that crystallize in the P 1 bar space group, where the asymmetric unit consists of three independent molecules. In all three sites, two sets of bond angles display distinctly different ranges. The three P-Au-P angles have average values of 117.92°, 117.57°, and 114.78° for sites A, B, and C, with the corresponding P-Au-Cl angles of 98.31°, 99.05°, and 103.38°, respectively. The chloride ion coordinates as the fourth ligand, at the corresponding Au-Cl distance of 2.7337, 2.6825, and 2.6951 Å for the three sites. This distance is longer by 0.40-0.45 Å than the Au-Cl distance found in the mono TFFPP complex 1 (2.285 Å) indicating a weakening of the Au-Cl interaction as the coordination number increases. In compound 3, [Au(TFFPP)3]Cl·½CH2Cl2·H2O, the structure consists of three phosphine ligands bound to the gold(I) atom, but the Cl- exists as uncoordinated counter anion. The structural differences observed in the two complexes are attributable to crystal-packing effects caused by the introduction of H-bonding as well as enhanced intra and inter-molecular π-interaction in 3. The photoluminescence of the complexes compared with that of the ligand show ligand centered emission perturbed by the metal coordination. Theoretical DFT studies conducted on these complexes supports assignments of the electronic transitions observed in these systems.

  17. Increasingly complex bimanual multi-frequency coordination patterns are equally easy to perform with on-line relative velocity feedback. (United States)

    Boyles, Jason; Panzer, Stefan; Shea, Charles H


    An experiment was conducted to determine whether multi-frequency continuous bimanual circling movements of varying difficulty (1:2, 2:3, 3:4, and 4:5) could be effectively performed following relatively little practice when on-line continuous relative velocity feedback is provided. The between-subjects results indicate extremely effective bimanual multi-frequency performance for all coordination patterns with relatively stable and continuous movements of both limbs. The findings suggest that the previous performance effects using Lissajous feedback with reciprocal movement can be extended to circling movements using on-line relative velocity feedback. Contrary to the long-held position that these coordination patterns result in increasing difficulty, we failed to find systematic relative velocity error, variability, or bias differences between the participants performing the various multi-frequency coordination patterns. Indeed, coordination error, variability, and biases were remarkably low for each of the tasks. The results clearly indicate the ease with which participants are able to produce bimanual coordination patterns typically considered difficult if not impossible when salient visual information is provided that allows the participants to detect and correct their coordination errors.

  18. Synaptonemal complex karyotyping in spermatocytes of the Chinese hamster (Cricetulus griseus). I. Morphology of the autosomal complement in spread preparations. (United States)

    Moses, M J


    Using the Counce-Meyer spreading technique, in over 70 spermatocytes it was possible consistently to obtain whole, flattened nuclei containing complete sets of pachytene SCs. The SCs are visible in both the phase and electron microscopes. Each SC is morphologically intact, preferentially stained, and attached to the nuclear envelope by a dense, terminal plaque. It is thus possible to trace each SC for its entire length. Also, a structure representing the kinetochore is clearly visible in each autosomal SC. Karyotypes comparable to the somatic karyotype can be constructed by arranging SCs according to length and kinetochore position. The observed regularity of SC morphology implies structural stability sufficient to withstand the stresses imposed by the procedure.--A coarse network of closely packed nuclear annuli connecting SC attachment plaques often provides end-to-end associations and may tend to immobilize SCs during processing.--Three kinds of perturbation of SC structure are encountered. Twists in the SC frequently occur, but no regular pattern or correspondence with chiasma distribution is observed. SCs occasionally hook around each other without disruption, but in two instances the unpaired axis of the X apparently was interlocked within an autosomal SC. Streching of the SC is infrequent; it is conspicous when it occurs and is usaully associated with other obvious distortions of the nucleus.--Distinctive morphologies of the X and Y chromosomes facilitate their identification inall preparations.--During zygotene, autosomal synapsis, i.e., the formation of SCs from the pairing of single axial elements, initiates at distal ends and terminates at the kinetochore region; neither initiation nor termination is synchronous among all autosomes.

  19. Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes. (United States)

    Matveeva, Anna G; Vologzhanina, Anna V; Goryunov, Evgenii I; Aysin, Rinat R; Pasechnik, Margarita P; Matveev, Sergey V; Godovikov, Ivan A; Safiulina, Alfiya M; Brel, Valery K


    Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.

  20. Importance of the C-H...N weak hydrogen bonding on the coordination structures of manganese(III) porphyrin complexes. (United States)

    Ikezaki, Akira; Nakamura, Mikio


    The reactions between Mn(Por)Cl and Bu(4)N(+)CN(-) have been examined in various solvents by UV-vis and (1)H NMR spectroscopy, where Por's are dianions of meso-tetraisopropylporphyrin (T(i)PrP), meso-tetraphenylporphyrin (TPP), meso-tetrakis(p-(trifluoromethyl)phenyl)porphyrin (p-CF(3)-TPP), meso-tetramesitylporphyrin (TMP), and meso-tetrakis(2,6-dichlorophenyl)porphyrin (2,6-Cl(2)-TPP). Population ratios of the reaction products, Mn(Por)(CN) and [Mn(Por)(CN)(2)](-), have been sensitively affected by the solvents used. In the case of Mn(T(i)PrP)Cl, the following results are obtained: (i) The bis-adduct is preferentially formed in dipolar aprotic solvents such as DMSO, DMF, and acetonitrile. (ii) Both the mono- and bis-adduct are formed in the less polar solvents such as CH(2)Cl(2) and benzene though the complete conversion to the bis-adduct is achieved with much smaller amount of the ligand in benzene solution. (iii) Only the mono-adduct is formed in CHCl(3) solution even in the presence of a large excess of cyanide. (iv) Neither the mono- nor the bis-adduct is obtained in methanol solution. The results mentioned above have been explained in terms of the C-H.N and O-H.N hydrogen bonding in chloroform and methanol solutions, respectively, between the solvent molecules and cyanide ligand; hydrogen bonding weakens the coordination ability of cyanide and reduces the population of the bis-adduct. The importance of the C-H.N weak hydrogen bonding is most explicitly shown in the following fact: while the starting complex is completely converted to the bis-adduct in CH(2)Cl(2) solution, the conversion from the mono- to the bis-adduct is not observed even in the presence of 7000 equiv of Bu(4)N(+)CN(-) in CHCl(3) solution. The effective magnetic moments of the bis-adduct has been determined by the Evans method to be 3.2 micro(B) at 25 degrees C, suggesting that the complex adopts the usual (d(xy))(2)(d(xz), d(yz))(2) electron configuration despite the highly ruffled

  1. A redox-active porous coordination network film based on a Ru complex as a building block on an ITO electrode. (United States)

    Shinomiya, Takuya; Ozawa, Hiroaki; Mutoh, Yuichiro; Haga, Masa-Aki


    The combination of self-assembled monolayer (SAM) and layer-by-layer (LbL) growth methods for the construction of a surface porous film has the potential to incorporate a wide range of chemical functionalities on a solid surface. A novel redox-active Ru complex with 2,6-bis(N-pyridylbenzimidazolyl)-pyridine ligands (Ru complex 1), in which four peripheral pyridine groups act as coordination sites, was used as a building block for a porous coordination network film. By using (4-pyridyl)phenylphosphonic acid as a SAM primer layer on an ITO surface, the Ru complex 1 was immobilized by the successive reaction of PdCl2 on the ITO electrode in the LbL growth method. Multilayer growth was monitored by UV-vis spectra and cyclic voltammetry, in which the linear increases of both absorbance and the peak current were observed. This result indicated that the regular accumulation of Ru complex 1 onto the ITO surface took place. The permselectivity of the present porous coordination network structure was examined using redox-active molecular probes with different sizes and charges such as ferrocene, trimethylaminomethylferrocene, the Os bis(2,6-bis(N-methylbenzimidazolyl)-pyridine) complex, and tetrathiofulvarene (TTF). With the Os complex and cationic ferrocene, only the catalytic peak was observed as a prewave of the adsorbed Ru(II/III) peak at +0.73 V. On the other hand, the oxidation peak of ferrocene was observed around 0 V vs. Fc(+)/Fc even for nine-layered films in addition to the adsorbed Ru(II/III) peak. From these results, not only molecular size but also electrostatic interaction plays an important role in the permeation into the Ru complex 1 porous network film.

  2. Bowl adamanzanes--bicyclic tetraamines: syntheses and crystal structures of complexes with cobalt(III) and chelating coordinated oxo-anions. (United States)

    Broge, Louise; Søtofte, Inger; Jensen, Kristian; Jensen, Nicolai; Pretzmann, Ulla; Springborg, Johan


    Seven cobalt(III) complexes of the macrobicyclic tetraamine ligand [2(4).3(1)]adamanzane ([2(4).3(1)]adz) are reported along with the crystal structure of six of these complexes. The solid state and solution structures are discussed, and a detailed assignment of the NMR spectra of the sulfato complex is provided. Four of the seven complexes contain a chelate coordinating oxo-anion (sulfate, formiate, nitrate, carbonate). Equilibration of these species with the corresponding diaqua complex is generally slow. The rates of equilibration in 5 mol dm(-3) perchloric acid at 25 degrees C have been measured, yielding half lives of 20 min, 10 min and 3 h for the sulfato, formiato and carbonato species respectively. The corresponding reaction for the nitrato complex occurs with a half life of less than 3 min. The concentration acid dissociation constant for the Co([2(4).3(1)]adz)(HCO(3))(2+) ion has been measured to K(a) = 0.33 mol dm(-3) [25 degrees C, I = 2 mol dm(-3)] and K(a) = 0.15 mol dm(-3) [25 degrees C, I = 5 mol dm(-3)]. The propensity for coordination of sulfate was found to be large enough for a quantitative conversion of the carbonato complex to the sulfato complex to occur in 3 mol dm(-3) triflic acid containing a small sulfate contamination. On this basis the decarboxylation in 5 mol dm(-3) triflic acid of the corresponding cobalt(III) carbonato complex of the larger macrobicyclic tetraamine ligand [3(5)]adz was reinvestigated and found to lead to the sulfato complex as well. The difference in exchange rate of the oxo-anion ligands for the cobalt(III) complexes of the two adamanzane ligands is discussed and attributed to fundamental differences in the molecular structure where an inverted configuration of the secondary non-bridged amine groups is seen for the complexes of the larger [3(5)]adz ligand. The high affinity for chelating coordination of oxo-anions for these two cobalt(iii)-adamanzane-moieties is rationalised on basis of the N-Co-N angles. N

  3. Excited state intramolecular proton transfer (ESIPT) in six-coordinated zinc(ii)-quinoxaline complexes with ligand hydrogen bonds: their fluorescent properties sensitive to axial positions. (United States)

    Sakai, Ken-Ichi; Takahashi, Sami; Kobayashi, Ataru; Akutagawa, Tomoyuki; Nakamura, Takayoshi; Dosen, Masaaki; Kato, Masako; Nagashima, Umpei


    Zinc(ii)-quinoxaline complexes, [Zn(hqxc)(2)(py)(2)] and [Zn(hqxc)(2)(DMSO)(2)] (hqxc = 3-hydroxy-2-quinoxalinecarboxylate, py = pyridine, DMSO = dimethyl sulfoxide), were prepared and characterized by X-ray crystallography and fluorescence spectroscopy. In both complexes, the zinc ion is six-coordinated by two equatorial bidentate hqxc ligands with an intramolecular hydrogen bond and two axial monodentate ligands such as pyridine or DMSO. In spite of similar coordination geometries, there is a remarkable difference between their solid-state fluorescent properties. The pyridine complex is strongly fluorescent (fluorescence quantum yield Phi = 0.22), giving rise to a significantly Stokes-shifted spectrum. From its thin film photopumped by a nitrogen gas laser, amplified spontaneous emission was observed. These results suggest that the fluorescence occurs by way of excited-state intramolecular proton-transfer (ESIPT) in the hydrogen bond of hqxc. On the other hand, the DMSO complex shows fluorescent intensity (Phi = 0.08) lower than that of the pyridine complex, and shows normal emission in addition to ESIPT emission. From IR measurements for these complexes, it is concluded that axial ligands influence the hydrogen bond strength of the equatorial hqxc ligand via zinc and thus the ESIPT efficiency.

  4. Extremely bulky amido first row transition metal(II) halide complexes: potential precursors to low coordinate metal-metal bonded systems. (United States)

    Hicks, Jamie; Jones, Cameron


    Reactions of the extremely bulky potassium amide complexes, [KL'(η(6)-toluene)] or [KL"] (L'/L" = N(Ar*)(SiR3), Ar* = C6H2{C(H)Ph2}2Me-2,6,4; R = Me (L') or Ph (L")), with a series of first row transition metal(II) halides have yielded 10 rare examples of monodentate amido first row transition metal(II) halide complexes, all of which were crystallographically characterized. They encompass the dimeric, square-planar chromium complexes, [{CrL'(THF)(μ-Cl)}2] and [{CrL"(μ-Cl)}2], the latter of which displays intramolecular η(2)-Ph···Cr interactions; the dimeric tetrahedral complexes, [{ML'(THF)(μ-Br)}2] (M = Mn or Fe), [{ML"(THF)(μ-X)}2] (M = Mn, Fe or Co; X = Cl or Br) and [{CoL"(μ-Cl)}2] (which displays intramolecular η(2)-Ph···Co interactions); and the monomeric zinc amides, [L'ZnBr(THF)] (three-coordinate) and [L"ZnBr] (two-coordinate). Solution state magnetic moment determinations on all but one of the paramagnetic compounds show them to be high-spin systems. Throughout, comparisons are made with related bulky terphenyl transition metal(II) halide complexes, and the potential for the use of the prepared complexes as precursors to low-valent transition metal systems is discussed.

  5. Variation of the coordination environment and its effect on the white light emission properties in a Mn-doped ZnO-ZnS complex structure. (United States)

    Cheng, Yan; Chen, Rui; Feng, Haifeng; Hao, Weichang; Xu, Huaizhe; Wang, Yu; Li, Jiong


    Mn-doped ZnO-ZnS complex nanocrystals were fabricated through coating of dodecanethiol on Mn-doped ZnO nanocrystals. The relationship between the component of white light emission and the coordination environments of Mn-dopants were experimentally investigated. It was shown that Mn ions mainly formed Mn(3+)O6 octahedra in as prepared Mn-doped ZnO, while the Mn(3+) ions on the surface of ZnO transferred into Mn(2+) ions at the interface between ZnO and ZnS after dodecanethiol coating. The Mn(2+)S4 tetrahedron density and the orange emission intensity increased upon enhancing the dodecanethiol content. These results provide an alternative way to optimize the white emission spectrum from nanocrystals of Mn-doped ZnS-ZnO complex structures through modulation of the coordination environment of Mn ions.

  6. Coordinated leading and lagging strand DNA synthesis by using the herpes simplex virus 1 replication complex and minicircle DNA templates. (United States)

    Stengel, Gudrun; Kuchta, Robert D


    The origin-specific replication of the herpes simplex virus 1 genome requires seven proteins: the helicase-primase (UL5-UL8-UL52), the DNA polymerase (UL30-UL42), the single-strand DNA binding protein (ICP8), and the origin-binding protein (UL9). We reconstituted these proteins, excluding UL9, on synthetic minicircular DNA templates and monitored leading and lagging strand DNA synthesis using the strand-specific incorporation of dTMP and dAMP. Critical features of the assays that led to efficient leading and lagging stand synthesis included high helicase-primase concentrations and a lagging strand template whose sequence resembled that of the viral DNA. Depending on the nature of the minicircle template, the replication complex synthesized leading and lagging strand products at molar ratios varying between 1:1 and 3:1. Lagging strand products (∼0.2 to 0.6 kb) were significantly shorter than leading strand products (∼2 to 10 kb), and conditions that stimulated primer synthesis led to shorter lagging strand products. ICP8 was not essential; however, its presence stimulated DNA synthesis and increased the length of both leading and lagging strand products. Curiously, human DNA polymerase α (p70-p180 or p49-p58-p70-p180), which improves the utilization of RNA primers synthesized by herpesvirus primase on linear DNA templates, had no effect on the replication of the minicircles. The lack of stimulation by polymerase α suggests the existence of a macromolecular assembly that enhances the utilization of RNA primers and may functionally couple leading and lagging strand synthesis. Evidence for functional coupling is further provided by our observations that (i) leading and lagging strand synthesis produce equal amounts of DNA, (ii) leading strand synthesis proceeds faster under conditions that disable primer synthesis on the lagging strand, and (iii) conditions that accelerate helicase-catalyzed DNA unwinding stimulate decoupled leading strand synthesis but not

  7. Seven-coordinate anion complex with a tren-based urea: binding discrepancy of hydrogen sulfate in solid and solution states. (United States)

    Pramanik, Avijit; Thompson, Bethtrice; Hayes, Trina; Tucker, Kimberly; Powell, Douglas R; Bonnesen, Peter V; Ellis, Erick D; Lee, Ken S; Yu, Hongtao; Hossain, Md Alamgir


    Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with six NH···O bonds (d(N···O) = 2.857 (3) to 3.092 (3) Å) and one OH···O bond (d(O···O) = 2.57 (2) Å) from three receptors; however, in solution the anion is bound within the pseudo-cavity of one receptor.

  8. Crystal growth of semiorganic complex- samarium chloride coordinated thiourea-L-tartaric acid and its studies on structure and optical characteristics (United States)

    Slathia, Goldy; Singh, Harjinder; Ramya, E.; Rao, D. Narayana; Bamzai, K. K.


    The semi-organic complex of samarium chloride coordinated thiourea-L-tartaric acid (SCTLT) has been grown as a single crystal by slow evaporation technique at room temperature. For structural studies, the grown crystal was subjected to single crystal X-ray diffraction and Fourier transform infra-red (FTIR) spectroscopy. Low cut off wavelength and transparent characteristics were explored by UV-VIS optical characterization. Third-order nonlinear optical properties of grown crystal were investigated by Z-scan technique.

  9. Extending the NIF DISCO framework to automate complex workflow: coordinating the harvest and integration of data from diverse neuroscience information resources


    Marenco, Luis N.; Wang, Rixin; Anita E. Bandrowski; Grethe, Jeffrey S.; Shepherd, Gordon M.; Miller, Perry L.


    This paper describes how DISCO, the data aggregator that supports the Neuroscience Information Framework (NIF), has been extended to play a central role in automating the complex workflow required to support and coordinate the NIF’s data integration capabilities. The NIF is an NIH Neuroscience Blueprint initiative designed to help researchers access the wealth of data related to the neurosciences available via the Internet. A central component is the NIF Federation, a searchable database that...

  10. Seven-coordinate anion complex with a tren-based urea: Binding discrepancy of hydrogen sulfate in solid and solution states

    Energy Technology Data Exchange (ETDEWEB)

    Pramanik, Avijit [Jackson State University; Thompson, Bethtrice [Jackson State University; Hayes, Trina [Jackson State University; Tucker, Kimberly [Jackson State University; Powell, Douglas R. [University of Oklahoma, Norman; Bonnesen, Peter V [ORNL; Ellis, Erick D [Jackson State University; Lee, Ken S. [Jackson State University; Yu, Hongtau [Jackson State University; Hossain, Md. Alamgir [Jackson State University


    Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with sixNH Obonds (dN O = 2.857 (3) to 3.092 (3)A ) and one OH O bond (dO O = 2.57 (2) A ) from three receptors; however, in solution the anion is bound within the pseudocavity of one receptor.

  11. Synthesis and crystal structures of two coordination polymers and a binuclear cadmium(II) complex containing 3- and 4-aminobenzoate ligands. (United States)

    Zhou, Dong-Mei; Zhao, Xiao-Lan; Liu, Feng-Yi; Kou, Jun-Feng


    Due to their wide range of coordination modes and versatile conformations when binding to metal atoms, multicarboxylate ligands are of interest in the design of metal-organic frameworks (MOFs). Three Cd(II) complexes, namely catena-poly[diammonium [[chloridocadmium(II)]-di-μ-chlorido-[chloridocadmium(II)]-bis(μ-3-aminobenzoato)-κ(3)N:O,O';κ(3)O,O':N

  12. Novel Ni(II) and Zn(II) complexes coordinated by 2-arylaminomethyl-1H-benzimidazole: Molecular structures, spectral, DFT studies and evaluation of biological activity (United States)

    Abdel-Ghani, Nour T.; Abo El-Ghar, Maha F.; Mansour, Ahmed M.


    [NiL1,2Cl2(OH2)3]·zH2O and [ZnL1,2(CH3CO2)2] (L1 = (1H-benzimidazol-2-ylmethyl)-N-phenyl amine, z = 0 and L2 = 2-[(1H-Benzimidazol-2-ylmethyl)-amino]-benzoic acid methyl ester, z = 1) complexes have been synthesized and characterized by a variety of physico-chemical techniques. The central Ni(II) ion is coordinated by only the pyridine-type nitrogen (Npy) of benzimidazole ring, three water molecules and two chlorido ligands forming a distorted octahedral geometry. Five coordinated zinc complexes were obtained, where the coordination sphere of zinc ion is made up of secondary amino group (NHsec), Npy and two acetate groups, one acts as a unidentate and the other as a bidentate. A theoretical DFT/UB3LYP method combined with LANL2DZ basis set shows that all the metal-ligand bonds are of the L → M type. Electronic structures have been calculated using TD-DFT method. The antibacterial activity of NiL2 complexes decreases by the introduction of COOCH3 group in the ortho-position of the aniline moiety.

  13. Bulky N-Phosphino-Functionalized N-Heterocyclic Carbene Ligands: Synthesis, Ruthenium Coordination Chemistry, and Ruthenium Alkylidene Complexes for Olefin Metathesis. (United States)

    Brown, Christopher C; Rominger, Frank; Limbach, Michael; Hofmann, Peter


    Ruthenium chemistry and applications in catalytic olefin metathesis based on N-phosphino-functionalized N-heterocyclic carbene ligands (NHCPs) are presented. Alkyl NHCP Ru coordination chemistry is described, and access to several potential synthetic precursors for ruthenium alkylidene complexes is outlined, incorporating both trimethylsilyl and phenyl alkylidenes. The Ru alkylidene complexes are evaluated as potential olefin metathesis catalysts and were shown to behave in a latent fashion. They displayed catalytic activity at elevated temperatures for both ring closing metathesis and ring opening metathesis polymerization.

  14. Coordination behavior of N-benzoylamino acids: Synthesis and structure of mixed-ligand complexes of palladium(Ⅱ) with N-benzoylamino acid dianion and diamine

    Institute of Scientific and Technical Information of China (English)

    龚钰秋; 陈耀峰; 顾建明; 胡秀荣


    Four new mixed-ligand complexes of pailadiumt(Ⅱ) with L1(N-benzoyl-α-amino acid dianion) and L2[ethyldiamine (en),2,2’-bipyridine (Bpy) and 1,10-phenanthroline (Phen)] were synthesized.Ail the complexes have been characterized by elemental analyses,molar conductance,infrared and 1H NMR spectra and therme-gravimetric analyses.Crystal structures of [Pd(Bpy)(Bzval-N,O)] and [Pd(en) (Bzphe-N,O)] H2O have been do termmed by X-ray diffraction analysis.The results indicate that in all the complexes hgand L1 coordinates to palladium (Ⅱ) through deprotonated amide nitrogen and carboxylic oxygen,and there are some intramolecular nonrovalent in teractions in the complexes.

  15. Genetic effects of some platinum co-ordination complexes on E.coli DNA as revealed by transformation studies

    NARCIS (Netherlands)

    Hoekstra, W.P.M.; Daemen, Toos


    E. coli chromosomal DNA was treated with various Pt co-ordination compounds and then used as donor DNA in E. coli transformation. Genetic analysis of transformants obtained with Pt-treated DNA showed effects of cis-diamminedichloroplatinum(II) (cis-Pt(II)) and cis-Pt-dimethyl-1,3-diaminopropane Cl4

  16. Synthesis, Coordination Chemistry, and Cooperative Activation of H2 with Ruthenium Complexes of ProtonResponsive METAMORPhos Ligands

    NARCIS (Netherlands)

    F.G. Terrade; M. Lutz; J.I. van der Vlugt; J.N.H. Reek


    The synthetic scope of proton-responsive sulfonamidophosphorus (METAMORPhos) ligands is expanded and design principles for the selective formation of particular tautomers, ion pairs, or double condensation products are elucidated. These systems have been introduced in the coordination sphere of Ru f

  17. Synthesis, coordination chemistry, and cooperative activation of H 2 with ruthenium complexes of proton-responsive METAMORPhos ligands

    NARCIS (Netherlands)

    Terrade, Frédéric G.; Lutz, Martin; Van Der Vlugt, Jarl Ivar; Reek, Joost N H


    The synthetic scope of proton-responsive sulfonamidophosphorus (METAMORPhos) ligands is expanded and design principles for the selective formation of particular tautomers, ion pairs, or double condensation products are elucidated. These systems have been introduced in the coordination sphere of Ru f


    Directory of Open Access Journals (Sweden)

    M. O. Fomina


    Full Text Available The aim of work was to elucidate the mechanisms of bioaccumulation of copper leached from minerals by fungus Aspergillus niger with great bioremedial potential due to its ability to produce chelating metabolites and transform toxic metals and minerals. The special attention was paid to the chemical speciation of copper bioaccumulated within fungal colony in the process of fungal transformation of copper-containing minerals. Chemical speciation of copper within different parts of the fungal colony was studied using solid-state chemistry methods such as synchrotron-based X-ray absorption spectroscopy providing information about the oxidation state of the target element, and its coordination environment. The analysis of the obtained X-ray absorption spectroscopy spectra was carried out using Fourier transforms of Extended X-ray Absorption Fine Structure regions, which correspond to the oscillating part of the spectrum to the right of the absorption edge. Results of this study showed that fungus A. niger was involved in the process of solubilization of copper-containing minerals resulted in leaching of mobile copper and its further immobilization by fungal biomass with variable coordination of accumulated copper within fungal colony which depended on the age and physiological/reproductive state of fungal mycelium. X-ray absorption spectroscopy data demonstrated that copper accumulated within outer zone of fungal colony with immature vegetative mycelium was coordinated with sulphur–containing ligands, in contrast to copper coordination with phosphate ligands within mature mycelium with profuse conidia in the central zone of the colony. The findings of this study not only broaden our understanding of the biogeochemical role of fungi but can also be used in the development of various fungal-based biometallurgy technologies such as bioremediation, bioaccumulation and bioleaching and in the assessment of their reliability. The main conclusion is that

  19. Nickel(II) complexes having Imidazol-2-ylidene-N′-phenylurea ligand in the coordination sphere – syntheses and solid state structures

    Indian Academy of Sciences (India)

    Kishor Naktode; Abhinanda Kundu; Sudeshna Saha; Hari Pada Nayek; Tarun K Panda


    We report the syntheses and structural studies of two nickel(II) complexes of imidazol-2-ylidene- N'-phenylureate ligand of composition [{ImBu NCON(H)Ph}2 Ni(acac)2] (1) and [(C6H5NH2)2 Ni(acac)2] [ImMes NCON(H)Ph] (2). The nickel complex 1 was readily prepared by the reaction of nickel(II) acetylacetonate [Ni(acac) 2 ] with imidazol-2-ylidene-N'-phenylureate ligand [ImBu NCON(H)Ph] (L1) in THF under reflux condition for 72 h. The nickel complex 2 was obtained by the reaction of [Ni(acac)2], mesityl derivative of imidazol-2-ylidene-N′-phenylureate ligand [ImMes NCON(H)Ph] (L2) in the presence of aniline as base under reflux condition in THF. Both the paramagnetic complexes have been characterized by FT-IR spectroscopy and elemental analyses. Solid-state structures of both the new complexes were established by single crystal X-ray diffraction analysis. In the molecular structures of complexes 1 and 2, each nickel(II) ion is six fold coordinated and form a distorted octahedral geometry. The optical properties of both complexes have been explored. The Hirshfeld surfaces are used to view and analyze the intermolecular contacts in crystalline state for complex 2.

  20. One-pot synthesis of four-coordinate boron(III) complexes by the ligand-promoted organic group migration between boronic acids. (United States)

    Sadu, Venkata S; Bin, Hye-Rin; Lee, Do-Min; Lee, Kee-In


    Multidisciplinary applications of four-coordinate boron(III) complexes make them very attractive and challenging research field in chemistry, biology and material sciences. The dual role played by boron atom in stabilising the chelate ligand and enhancing the π-conjugation makes them very useful as luminescent materials for organic electronics and photonics, and sensing and imaging probes for biomedical purposes. The conventional methods involve the use of diarylborinic acids or anhydrides and triaryl boranes, which are made from organometallic reagents. The strong nucleophilicity of these reagents limits the peripheral modifications onto the boron cores. Here, we report a metal-free one-pot synthesis of four-coordinate organoborons using boronic acids, which represents the first instance of ligand assisted organic group migration between boronic acids. A tetrahedral boron 'ate' complex capable of transferring an organic group to the adjacent sp(2) boron within a boronic anhydride intermediate is proposed and preliminary mechanistic studies by MALDI-TOF and (11)B NMR support this proposal. The products are available from a series of N,O-, N,N- and O,O-bidentate ligands upon a wide array of boronic acids. We anticipate that this reaction will impact the way of producing the four-coordinate organoborons, and propel a new discovery of such materials for optoelectronic and biomedical applications.

  1. Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

    KAUST Repository

    Vidal, Fernando


    The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

  2. Mixed-valence copper(I,II) complexes with 4-(1H-pyrazol-1-yl)-6-R-pyrimidines: from ionic structures to coordination polymers. (United States)

    Vinogradova, Katerina A; Krivopalov, Viktor P; Nikolaenkova, Elena B; Pervukhina, Natalia V; Naumov, Dmitrii Yu; Boguslavsky, Evgenii G; Bushuev, Mark B


    Two pyrimidine-based ligands, 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-(morpholino)pyrimidine () and 4-(3,5-diphenyl-1H-pyrazol-1-yl)-6-phenoxypyrimidine (), and a series of mixed-valence copper(i,ii) halide complexes, [Cu(L(2))2Br]2[Cu2Br4] (), [Cu(L(2))2Cl][CuCl2] (), and [Cu2L(3)Br3]n (), have been synthesized. The complex [Cu(L(2))2Br]2[Cu2Br4] was prepared by the reaction of with CuBr2 in a 1 : 1 molar ratio in MeCN. Its chlorido-analogue, the complex [Cu(L(2))2Cl][CuCl2], was synthesized by the reaction between , CuCl2 and CuCl in a 2 : 1 : 1 molar ratio in MeCN. The ligand acts as a chelating one. In the structures of the complexes [Cu(L(2))2Br]2[Cu2Br4] and [Cu(L(2))2Cl][CuCl2] the Cu(2+) ion is in the cationic part of the complex whereas the Cu(+) ion is located in the anionic part. The best way to synthesize the mixed-valence 1D coordination polymer [Cu2L(3)Br3]n is to react CuBr2 with in a 2 : 1 molar ratio in the MeCN/CHCl3 mixture on heating. In the structure of [Cu2L(3)Br3]n the ligand shows chelating/bridging tridentate coordination. This is the first example of the tridentate coordination of 4-(1H-pyrazol-1-yl)-6-R-pyrimidines. The striking difference between the coordination behavior of and (chelating bidentate vs. chelating/bridging coordination) is related with the possibility of rotation of the 6-phenoxy group around the C-O bond which makes the N(1) pyrimidine atom less sterically hindered, enabling it to participate in metal ion binding. Importantly, all copper ions in [Cu2L(3)Br3]n show similar tetrahedral environments, CuNBr3 and CuN2Br2, which is extremely rare for mixed-valence copper(i,ii) compounds. The ligands and show blue emission which is quenched upon their coordination to copper ions. The 1D coordination polymer [Cu2L(3)Br3]n shows high thermal stability and unusual solvent-occlusion properties. The role of the substituents favoring the formation of the mixed-valence copper(i,ii) complexes with 4-(1H-pyrazol-1-yl)-6-R

  3. Versatile structures of group 13 metal halide complexes with 4,4'-bipy: from 1D coordination polymers to 2D and 3D metal-organic frameworks. (United States)

    Sevastianova, Tatiana N; Bodensteiner, Michael; Maulieva, Albina F; Davydova, Elena I; Virovets, Alexander V; Peresypkina, Eugenia V; Balázs, Gábor; Graßl, Christian; Seidl, Michael; Scheer, Manfred; Frenking, Gernot; Berezovskaya, Ekaterina A; Kazakov, Igor V; Khoroshilova, Olesya V; Timoshkin, Alexey Y


    A systematic structural study of complexes formed by aluminium and gallium trihalides with 4,4'-bipyridine (bipy) in 2 : 1, 1 : 1, and 1 : 2 stoichiometric ratios has been performed. Molecular structures of 11 complexes in the solid state have been determined for the first time. Complexes of 2 : 1 composition are molecular, while complexes of 1 : 1 composition form metal-organic frameworks of different kinds: an ionic 3D network (three interpenetrated lvt nets for AlCl3bipy), an ionic 2D network for AlBr3bipy and GaBr3bipy and a 1D coordination polymer in the case of GaCl3bipy. Thus, the nature of the Lewis acid plays a critical role in the structural type of the complex in the solid state. Incorporation of excess bipy molecules into (GaCl3bipy)∞ (formation of crystallosolvate) leads to an unprecedented change of the molecular structure from a non-ionic 1D coordination polymer to an ionic 2D metal organic framework [GaCl2bipy2](+)[GaCl4](-)·2bipy. As indicated by the temperature-dependent XRD study, removal of bipy by heating in a vacuum restores the non-ionic 1D structure. Quantum chemical computations for simple cluster model systems (up to eight Al and Ga atoms) reveal that ionic forms are slightly favourable, although the energy differences between the ionic and non-ionic structures are not large. These theoretical predictions are in good agreement with experimental findings. Thus, even relatively simple cluster models may be used to indicate the structural preferences in the solid state. Both experimental and computational IR frequency shifts of the in-plane ring bending mode of bipy upon complexation correlate well with the M-N bond distances in the complexes.

  4. Square-Planar Alkylidyne-Osmium and Five-Coordinate Alkylidene-Osmium Complexes: Controlling the Transformation from Hydride-Alkylidyne to Alkylidene. (United States)

    Buil, María L; Cardo, Juan J F; Esteruelas, Miguel A; Oñate, Enrique


    Square-planar alkylidyne and five-coordinate alkylidene mixed (i)Pr3P-Os-IPr (IPr = 1,3-bis(diisopropylphenyl)imidazolylidene) complexes have been discovered and characterized, and their formation has been rationalized. The cationic five-coordinate hydride-alkylidyne compounds [OsHX(≡CPh)(IPr)(P(i)Pr3)]OTf (X = Cl (1), F (4); OTf = CF3SO3) undergo deprotonation with KO(t)Bu to afford the trans-halide-alkylidyne square-planar derivatives OsX(≡CPh)(IPr)(P(i)Pr3) (X = Cl (2), F (5)). Oxidative addition of the C(sp)-H bond of phenylacetylene and methyl propiolate along the Cl-Os-CPh axis of 2 with the hydrogen atom directed to the alkylidyne leads to alkynyl-cis-hydride-alkylidyne intermediates, which rapidly evolve into the five-coordinate alkylidene complexes Os(C≡CR)Cl(═CHPh)(IPr)(P(i)Pr3) (R = Ph (6), CO2Me (7)) as a consequence of the migration of the hydride from the metal center to the Cα atom of the alkylidyne. Oxidative addition of the C(sp)-H bond of methyl propiolate along the X-Os-CPh axis of 2 and 5 with the hydrogen atom directed to the halide gives the alkynyl-trans-hydride-alkylidyne derivatives OsH(C≡CCO2Me)X(≡CPh)(IPr)(P(i)Pr3) (X = Cl (8), F (9)). Complex 8 evolves into 7. However, complex 9 containing the stronger π-donor fluoride is stable. The oxidative addition of HCl to 2 selectively yields the cis-hydride-alkylidyne compound OsHCl2(≡CPh)(IPr)(P(i)Pr3) (10), which is also stable.

  5. Exploratory studies on coordination chemistry of a redox-active bridging ligand: synthesis, properties and solid state structures of the complexes. (United States)

    Ran, Ying-Fen; Liu, Shi-Xia; Sereda, Olha; Neels, Antonia; Decurtins, Silvio


    The explorative coordination chemistry of the bridging ligand TTF-PPB is presented. Its strong binding ability to Co(II) and then to Ni(II) or Cu(II) in the presence of hexafluoroacetylacetonate (hfac(-)), forming new mono- and dinuclear complexes 1-3, is described. X-ray crystallographic studies have been conducted in the case of the free ligand TTF-PPB as well as its complexes [Co(TTF-PPB)(hfac)(2)] (1) and [Co(hfac)(2)(μ-TTF-PPB)Ni(hfac)(2)] (2). Each metal ion is bonded to two bidentate hfac(-) anions through their oxygen atoms and two nitrogen atoms of the PPB moiety with a distorted octahedral coordination geometry. Specifically, nitrogen donor atoms of TTF-PPB adopt a cis-coordination but not in the equatorial plane, which is quite rare. Electronic absorption, photoinduced intraligand charge transfer ((1)ILCT), and electrochemical behaviour of 1-3 have been investigated. UV-Vis spectroscopy shows very strong bands in the UV region consistent with ligand centred π-π* transitions and an intense broad band in the visible region corresponding to a spin-allowed π-π* (1)ILCT transition. Upon coordination, the (1)ILCT band is bathochromically shifted by 3100, 6100 and 5900 cm(-1) on going from 1 to 3. The electrochemical studies reveal that all of them undergo two reversible oxidation and one reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the PPB unit, respectively. This journal is © The Royal Society of Chemistry 2011

  6. 城市综合体建设工作协同关系研究%Research on coordinative relationship in construction of city complexes

    Institute of Scientific and Technical Information of China (English)

    金巍; 张洪波


    针对城市综合体投资规模大、建设周期长、参与建设单位多的特点,深入研究了城市综合体建设工作的协同关系,对城市综合体项目工作流程及各科目的注意事项进行了论述,以取得良好的经济效益。%According to the features of city complexes with large investment scales,long construciton cycle,and various participations of con-struction parties,the paper researches the coordinative relationship in the construction of the city complexes,and indicates the precautions for the construction procedure and precautions of each part of the complex construction,so as to achieve better economic benefits.

  7. Coordination Chemistry of Polyaromatic Thiosemicarbazones 2: Synthesis and Biological Activity of Zinc, Cobalt, and Copper Complexes of 1-(Naphthalene-2-ylethanone Thiosemicarbazone

    Directory of Open Access Journals (Sweden)

    Marc-Andre LeBlanc


    Full Text Available A novel thiosemicarbazone from 2-acetonaphthone (represented as acnTSC has been synthesized and its basic coordination chemistry with zinc(II, cobalt(II, and copper(II explored. The complexes were characterized by elemental analysis and various spectroscopic techniques and are best formulated as [M(acnTSC2Cl2] with the metal likely in an octahedral environment. The anticancer activity of the complexes was determined against a panel of human colon cancer cells (HCT-116 and Caco-2. The compounds bind to DNA via an intercalative mode with binding constants of 9.7×104 M-1, 1.8×105 M-1, and 9.5×104 M-1 for the zinc, cobalt, and copper complexes, respectively.

  8. Some metal complexes of three new potentially heptadentate (N4O3) tripodal Schiff base ligands; synthesis, characterizatin and X-ray crystal structure of a novel eight coordinate Gd(III) complex (United States)

    Golbedaghi, Reza; Moradi, Somaeyh; Salehzadeh, Sadegh; Blackman, Allan G.


    The symmetrical and asymmetrical potentially heptadentate (N4O3) tripodal Schiff base ligands (H3L1-H3L3) were synthesized from the condensation reaction of three tripodal tetraamine ligands tpt (trpn), tris (3-aminopropyl) amine; ppe (abap), (2-aminoethyl)bis(3-aminopropyl)amine, and tren, tris(2-aminoethyl)amine, with 5-methoxysalicylaldehyde. Then, the reaction of Ln(III) (Ln = Gd, La and Sm), Al(III), and Fe(III) metal ions with the above ligands was investigated. The resulting compounds were characterized by IR, mass spectrometry and elemental analysis in all cases and NMR spectroscopy in the case of the Schiff base ligands. The X-ray crystal structure of the Gd complex of H3L3 ligand showed that in addition to all donor atoms of the ligand one molecule of H2O is also coordinated to the metal ion and a neutral eight-coordinate complex is formed.

  9. Zirconium and hafnium complexes containing N-alkyl substituted amine biphenolate ligands: coordination chemistry and living ring-opening polymerization catalysis. (United States)

    Liang, Lan-Chang; Lin, Sheng-Ta; Chien, Chia-Cheng; Chen, Ming-Tsz


    The coordination chemistry of zirconium and hafnium complexes containing the tridentate amine biphenolate ligands [RN(CH2-2-O-3,5-C6H2(tBu)2)2](2-) ([R-ONO](2-); R = tBu (1a), iPr (1b), nPr (1c)) featuring distinct N-alkyl substituents is described. Alcoholysis of Zr(OiPr)4(HOiPr) or Hf(OiPr)4(HOiPr) with H2[1a] in diethyl ether solutions at -35 °C generates the corresponding five-coordinate [1a]M(OiPr)2 (M = Zr (2a), Hf (3a)) in high isolated yield. Similar reactions employing H2[1b] produce six-coordinate [1b]M(OiPr)2(HOiPr) (M = Zr (2b·HOiPr), Hf (3b·HOiPr)) as an isopropanol adduct. Repetitive trituration of 2b·HOiPr and 3b·HOiPr with diethyl ether gives five-coordinate 2b and 3b, respectively. Treatment of M(OiPr)4(HOiPr) with H2[1c] under similar conditions affords six-coordinate [1c]M(OiPr)2(HOiPr) (M = Zr (2c·HOiPr), Hf (3c·HOiPr)), subsequent recrystallization of which from acetonitrile-diethyl ether solutions leads to acetonitrile adducts 2c·MeCN and 3c·MeCN. Reactivity studies of these zirconium and hafnium complexes revealed that they are all active catalysts for ring-opening polymerization of ε-caprolactone. Among them, the N-isopropyl derived complexes are most reactive. Polymerizations catalyzed by 2b, 3b and 3c·MeCN were proved to be living. The X-ray structures of 2a·HOiPr, 2a·MeCN, 2c·HOiPr, 2c·MeCN, and 3c·MeCN are presented.

  10. Synthesis of monomeric and polymeric alkali and alkaline earth metal complexes using a phosphinoselenoic amide ligand in metal coordination sphere

    Indian Academy of Sciences (India)

    Jayeeta Bhattacharjee; Ravi K Kottalanka; Harinath Adimulam; Tarun K Panda


    We report the monomeric complexes of magnesium and calcium of composition [M(THF){2-Ph2P(Se)N(CMe3)}2] [M= Mg (3), n = 1 andM = Ca (4), n = 2)] and polymeric complexes of potassium and barium of composition [K(THF)2{Ph2P(Se)N(CMe3)}] (2) and [K(THF)Ba{Ph2P(Se)N(CMe3)}3](5) respectively. The potassium complex 2 was readily prepared by the reaction of potassium bis(trimethylsilyl)amide with phosphinoselenoic amide ligand (1) at ambient temperature. The calcium complex 4 was prepared by two synthetic routes: in the first method, commonly known as salt metathesis reaction, the potassium complex 2 was made to react with alkaline earth metal diiodide at room temperature to afford the corresponding calcium complex. The metal bis(trimethylsilyl)amides were made to react with protic ligand 1 in the second method to eliminate the volatile bis(trimethyl)silyl amine. The magnesium complex 3 and barium complex 5 were prepared only through the first method. Solid-state structures of all the new complexes were established by single crystal X-ray diffraction analysis. The smaller ionic radii of Mg2+ (0.72Å) and Ca2+ (0.99Å) ions form the monomeric complex, whereas the larger ions K+ (1.38Å) and Ba2+ (1.35Å) were found to form onedimensional polymeric complexes with monoanionic ligand 1. Compound 2 serves an example of magnesium complex with a Mg-Se direct bond.

  11. Synthesis, characterisation and catalytic activity of 4, 5-imidazoledicarboxylate ligated Co(II) and Cd(II) metal-organic coordination complexes (United States)

    Gangu, Kranthi Kumar; Maddila, Suresh; Mukkamala, Saratchandra Babu; Jonnalagadda, Sreekantha B.


    Two mono nuclear coordination complexes, namely, [Co(4,5-Imdc)2 (H2O)2] (1) and [Cd(4,5-Imdc)2(H2O)3]·H2O (2) were constructed using Co(II) and Cd(II) metal salts with 4,5-Imidazoledicarboxylic acid (4,5-Imdc) as organic ligand. Both 1, 2 were structurally characterized by single crystal XRD and the results reveal that 1 belongs to P21/n space group with unit cell parameters [a = 5.0514(3) Å, b = 22.5786(9) Å, c = 6.5377(3) Å, β = 111.5°] whereas, 2 belongs to P21/c space group with unit cell parameters [a = 6.9116(1) Å, b = 17.4579(2) Å, c = 13.8941(2) Å, β = 97.7°]. While Co(II) in 1 exhibited a six coordination geometry with 4,5-Imdc and water molecules, Cd(II) ion in 2 showed a seven coordination with the same ligand and solvent. In both 1 and 2, the hydrogen bond interactions with mononuclear unit generated 3D-supramolecular structures. Both complexes exhibit solid state fluorescent emission at room temperature. The efficacy of both the complexes as heterogeneous catalysts was examined in the green synthesis of six pyrano[2,3,c]pyrazole derivatives with ethanol as solvent via one-pot reaction between four components, a mixture of aromatic aldehyde, malononitrile, hydrazine hydrate and dimethyl acetylenedicarboxylate. Both 1 and 2 have produced pyrano [2,3,c]pyrazoles in impressive yields (92-98%) at room temperature in short interval of times (<20 min), with no need for any chromatographic separations. With good stability, ease of preparation and recovery plus reusability up to six cycles, both 1 and 2 prove to be excellent environmental friendly catalysts for the value-added organic transformations using green principles.

  12. Pt(II) coordination complexes as visible light photocatalysts for the oxidation of sulfides using batch and flow processes


    Casado-Sánchez, A.; Gómez-Ballesteros, R.; Tato, F.; Soriano, F.J.; Pascual-Coca, G.; Cabrera, S.; J. Alemán


    A new catalytic system for the photooxidation of sulfides based on Pt(ii) complexes is presented. The catalyst is capable of oxidizing a large number of sulfides containing aryl, alkyl, allyl, benzyl, as well as more complex structures such as heterocycles and methionine amino acid, with complete chemoselectivity. In addition, the first sulfur oxidation in a continuous flow process has been developed

  13. Controlling proton movement: electrocatalytic oxidation of hydrogen by a nickel(II) complex containing proton relays in the second and outer coordination spheres. (United States)

    Das, Parthapratim; Ho, Ming-Hsun; O'Hagan, Molly; Shaw, Wendy J; Bullock, R Morris; Raugei, Simone; Helm, Monte L


    A nickel bis(diphosphine) complex containing proton relays in the second and outer coordination spheres, Ni(P(Cy)2N((CH2)2OMe))2, (P(Cy)2N((CH2)2OMe) = 1,5-di(methoxyethyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex results in rapid formation of three isomers of the doubly protonated Ni(0) complex, [Ni(P(Cy)2N((CH2)2OMe)2H)2](2+). The three isomers show fast interconversion at 40 °C, unique to this complex in this class of catalysts. Under conditions of 1.0 atm H2 using H2O as a base, catalytic oxidation proceeds at a turnover frequency of 5 s(-1) and an overpotential of 720 mV, as determined from the potential at half of the catalytic current. Compared to the previously reported Ni(P(Cy)2N(Bn))2 complex, the new complex operates at a faster rate and at a lower overpotential.

  14. Synthesis and Coordination Mechanism of Complex of Troxerutin and Lanthanum%曲克芦丁镧配合物的制备和机理探讨

    Institute of Scientific and Technical Information of China (English)

    尹慧; 徐启杰; 时文中; 刘大勇; 左春山; 许丹丽


    In order to research the prepared conditions of the complex of troxerutin and lanthanum and its coordination mechanism, the ultraviolet absorption of the complex in different reaction conditions were measured by using spetrophotometry, and the complex of troxerutin and lanthanum was characterized by ultraviolet visible spectrophotometer (UV), infrared spectrometer (IR), and high performance liquid chromatograph (HPLC). The results show that the coordination reaction occurred between the groups containing oxygen and Laa+ , coordination mechanism is that the carbonyl oxygen on 4th position of troxerutin and the hydroxyl oxygen on 5th position reacts with La3+ , and then forms coordination bond~ the optimum conditions for preparing the complex of troxerutin with lanthanum are the ratio of troxerutin and lanthanum 2 : 1, the reaction time 4 h, temperature 55 ℃, and the solution pH 7.0.%为了探讨曲克芦丁镧配合物的形成条件及配位作用机理,利用分光光度法测定了不同反应条件对曲克芦丁镧配合物的紫外吸收的影响,并通过紫外-可见分光光度计、红外光谱仪和液相色谱仪对配合物的结构进行表征.研究结果表明,曲克芦丁结构中的氧与镧离子发生配位作用,推测曲克芦丁结构中4位上的羰基氧和5位上的羟基氧参与配位反应形成配合物;制备曲克芦丁镧配合物的适宜条件为:曲克芦丁与镧的物质的量比为2∶1、反应时间4h、反应温度55℃和反应体系pH值为7.

  15. Synthesis, electronic structure, and magnetism of [Ni(6-Mes)2]+: a two-coordinate nickel(I) complex stabilized by bulky N-heterocyclic carbenes. (United States)

    Poulten, Rebecca C; Page, Michael J; Algarra, Andrés G; Le Roy, Jennifer J; López, Isidoro; Carter, Emma; Llobet, Antoni; Macgregor, Stuart A; Mahon, Mary F; Murphy, Damien M; Murugesu, Muralee; Whittlesey, Michael K


    The two-coordinate cationic Ni(I) bis-N-heterocyclic carbene complex [Ni(6-Mes)2]Br (1) [6-Mes =1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene] has been structurally characterized and displays a highly linear geometry with a C-Ni-C angle of 179.27(13)°. Density functional theory calculations revealed that the five occupied metal-based orbitals are split in an approximate 2:1:2 pattern. Significant magnetic anisotropy results from this orbital degeneracy, leading to single-ion magnet (SIM) behavior.

  16. The Diphosphorus Complex [Cp2Mo2(CO)4(η(2)-P2)] as a Building Block for the Synthesis of Mixed-Hybrid Coordination Polymers. (United States)

    Moussa, Mehdi Elsayed; Attenberger, Bianca; Fleischmann, Martin; Schreiner, Andrea; Scheer, Manfred


    The three-component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η(2)-P2)] (1), with Ag[BF4] (2) in the presence of 2,2'-bipyrimidine (3) leads to the formation of the two novel two-dimensional networks 4 and 5. Compound 4 is a new two-dimensional organometallic-organic hybrid polymer, while derivative 5 represents a unique two-dimensional organometallic-inorganic-organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two-component reactions with organic molecules in addition of metal ions.

  17. Construction of metal-organic frameworks through coordination and hydrogen bonding interactions: Syntheses, structures and photoluminescent properties of metal complexes with macrocyclic ligand (United States)

    Ouyang, Xing-Mei; Li, Zhen-Wu; Okamura, Taka-aki; Li, Yi-Zhi; Sun, Wei-Yin; Tang, Wen-Xia; Ueyama, Norikazu


    A macrocyclic ligand L with two diethylenetriamine units linked by two rigid biphenylene spacers was used as building block for construction of metal-organic frameworks. A silver(I) complex with macrocyclic and open-chain mix-type ligands [Ag 2( L)( L')](ClO 4) 2 ( 1) [ L'=1,6-bis(4-imidazol-1'-ylmethylphenyl)-2,5-diazahexane] was obtained by reaction of L and L' together with AgClO 4·H 2O. It is interesting that the open-chain tetradentate ligand L' only served as a bidentate ligand to bridge the Ag 2L units into an infinite one-dimensional (1D) cationic chain. Neutral 1D chain coordination polymer [Cu 2( L)( μ-SO 4) 2]·3H 2O·3MeOH ( 2) is formed by sulfate bridges between the neighboring Cu 2L units. When L reacted with nickel(II) sulfate instead of copper(II) sulfate, a monomacrocycle molecular complex [Ni 2( L)(H 2O) 4(SO 4) 2] ( 3) was obtained in which the sulfate anion acts as monodentate ligands rather than as bridges. When Cd(II) salts were used for the reactions with L, another two neutral 1D coordination polymers, [Cd 2( L)( μ-Cl) 2Cl 2]·2H 2O ( 4) and [Cd 2( L)( μ-Br) 2Br 2] ( 5), with the same structure were isolated. All the synthesized complexes exhibit three-dimensional framework structures linked by various hydrogen bonds. The photoluminescent properties of the synthesized complexes were studied in the solid state at room temperature, and the Ag(I) and Cd(II) complexes were found to show strong blue luminescence.

  18. Intramolecular N-H···Cl hydrogen bonds in the outer coordination sphere of a bipyridyl bisurea-based ligand stabilize a tetrahedral FeLCl2 complex. (United States)

    Gavette, Jesse V; Klug, Christina M; Zakharov, Lev N; Shores, Matthew P; Haley, Michael M; Johnson, Darren W


    A bipyridyl-based anion receptor is utilized as a ligand in a tetrahedral FeCl2 complex and demonstrates secondary coordination sphere influence through intramolecular hydrogen bonding to the chloride ligands as evidenced by X-ray crystallography.

  19. 4th July 2011 - Russian Deputy Director-General Director of Directorate for Scientific and Technical Complex ROSATOM V. Pershukov in the ATLAS underground experimental area with Adviser T. Kurtyka, ATLAS Technical Coordinator M. Nessi and ATLAS Russian users.

    CERN Multimedia

    Maximilien Brice


    4th July 2011 - Russian Deputy Director-General Director of Directorate for Scientific and Technical Complex ROSATOM V. Pershukov in the ATLAS underground experimental area with Adviser T. Kurtyka, ATLAS Technical Coordinator M. Nessi and ATLAS Russian users.

  20. Coordination of degrees of freedom and stabilization of task variables in a complex motor skill: expertise-related differences in cello bowing. (United States)

    Verrel, Julius; Pologe, Steven; Manselle, Wayne; Lindenberger, Ulman; Woollacott, Marjorie


    Stringed instrument bowing is a complex sensorimotor skill, involving fine regulation of bow orientation and motion relative to the string. In this study, we characterize this skill in terms of stabilization of specific bow parameters as well as the underlying use and coordination of the degrees of freedom (DOF) of the right bowing arm. Age-matched samples of 10 advanced cellists and 10 cello novices took part in the study. Kinematic bow movement data were analyzed with respect to task variables suggested by the cello teaching literature: position and orientation of the bow relative to the string, bow velocity, and timing. Joint motion of the bowing arm was analyzed in terms of movement amplitude and inter-joint coordination (principal component analysis). As expected, novices showed poorer control of bowing parameters. In addition, novices differed markedly from advanced players in the use and coordination of the DOF of the bowing arm, with the elbow and wrist showing less overall movement and a reduced proportion of variance explained by the first principal component (PC1). In contrast, larger amounts of shoulder variance were explained by PC1 in novices compared to experts. Our findings support Bernstein's theory of graded skill acquisition, according to which early stages of motor skill learning are characterized by a "freezing" of movement DOF, while later learning stages exploit the DOF, possibly following a proximal-to-distal sequence, for improved task performance.

  1. Copper(II)-bis-histidine coordination structure in a fibrillar amyloid β-peptide fragment and model complexes revealed by electron spin echo envelope modulation spectroscopy. (United States)

    Hernández-Guzmán, Jessica; Sun, Li; Mehta, Anil K; Dong, Jijun; Lynn, David G; Warncke, Kurt


    Truncated and mutated amyloid-β (Aβ) peptides are models for systematic study-in homogeneous preparations-of the molecular origins of metal ion effects on Aβ aggregation rates, types of aggregate structures formed, and cytotoxicity. The 3D geometry of bis-histidine imidazole coordination of Cu(II) in fibrils of the nonapetide acetyl-Aβ(13-21)H14A has been determined by powder (14) N electron spin echo envelope modulation (ESEEM) spectroscopy. The method of simulation of the anisotropic combination modulation is described and benchmarked for a Cu(II) -bis-cis-imidazole complex of known structure. The revealed bis-cis coordination mode, and the mutual orientation of the imidazole rings, for Cu(II) in Ac-Aβ(13-21)H14A fibrils are consistent with the proposed β-sheet structural model and pairwise peptide interaction with Cu(II) , with an alternating [-metal-vacancy-]n pattern, along the N-terminal edge. Metal coordination does not significantly distort the intra-β-strand peptide interactions, which provides a possible explanation for the acceleration of Ac-Aβ(13-21)H14A fibrillization by Cu(II) , through stabilization of the associated state and low-reorganization integration of β-strand peptide pair precursors.

  2. A series of Zn-4f heterometallic coordination polymers and a zinc complex containing a flexible mixed donor dicarboxylate ligand. (United States)

    Feng, Xun; Feng, Yu-Quan; Liu, Lang; Wang, Li-Ya; Song, Hong-Liang; Ng, Seik-Weng


    A new zinc compound, together with a corresponding series of Zn-4f heterometallic coordination polymers, namely, [Zn(H2PBDA)(PBDA)]n (1), {[Ln2(PBDA)2·2H2O] [Zn2(PBDA)2Cl2]}n [H2PBDA = 3-(pyridin-3-yl-oxy) benzene-1,2-dicarboxylic acid, and Ln = Pr(2), Nd(3), Eu(4), Gd(5), Dy(6), Ho(7), Er(8)] have been hydrothermally synthesized and characterized systematically. Polymers 2-8 feature two-dimensional (2D) 4,4 networks, containing the original 1D heterometallic double stranded chains composed of [Ln2Zn2(PBDA)2] entities. The extensive hydrogen bonding and π-π stacking interactions were observed to stabilize the extended architectures. The luminescence emission spectra of the polymers vary depending on the lanthanide(III) ion present. Informative magnetic susceptibility measurements show that the same carboxylate bridging fashion of the PBDA ligand results in the different magnetic properties occurring within the heterometallic coordination polymers. In addition, polymer 6 exhibits an interesting slow magnetic relaxation behavior at lower temperatures.

  3. Synthesis, spectroscopic, coordination and biological activities of some transition metal complexes containing ONO tridentate Schiff base ligand. (United States)

    Belal, A A M; El-Deen, I M; Farid, N Y; Zakaria, Rosan; Refat, Moamen S


    The main target of this paper is to get an interesting data for the preparation and characterizations of metal oxide (MO) nanoparticles using H2L Schiff base complexes as precursors through the thermal decomposition procedure. Five Schiff base complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) metal ions were synthesized from 2-[(2-hydroxy-naphthalen-1-ylmethylene)-amino]-benzoic acid new adduct (H2L). Theses complexes were characterized using infrared, electronic, mass and (1)H NMR spectroscopic techniques. The elemental analysis data was confirmed that the stoichiometry of (metal:H2L) is 1:1 molar ratio. The molar conductance indicates that all of complexes are non electrolytic. The general chemical formulas of these complexes is [M(L)(NH3)]·nH2O. All complexes are tetrahedral geometry. The thermal decomposition behavior of H2L hydrated and anhydrous complexes has been discussed using thermogravimetric analysis (TG/DTG) and differential thermal analyses (DTA) under nitrogen atmosphere. The crystalline phases of the reaction products were checked using X-ray diffractometer (XRD) and scanning electron microscopy (SEM).

  4. Synthesis and Reactivity of Four- and Five-Coordinate Low-Spin Cobalt(II) PCP Pincer Complexes and Some Nickel(II) Analogues. (United States)

    Murugesan, Sathiyamoorthy; Stöger, Berthold; Carvalho, Maria Deus; Ferreira, Liliana P; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Kirchner, Karl


    Anhydrous CoCl2 or [NiCl2(DME)] reacts with the ligand PCP(Me)-iPr (1) in the presence of nBuLi to afford the 15e and 16e square planar complexes [Co(PCP(Me)-iPr)Cl] (2) and [Ni(PCP(Me)-iPr)Cl] (3), respectively. Complex 2 is a paramagnetic d(7) low-spin complex, which is a useful precursor for a series of Co(I), Co(II), and Co(III) PCP complexes. Complex 2 reacts readily with CO and pyridine to afford the five-coordinate square-pyramidal 17e complexes [Co(PCP(Me)-iPr)(CO)Cl] (4) and [Co(PCP(Me)-iPr)(py)Cl] (5), respectively, while in the presence of Ag(+) and CO the cationic complex [Co(PCP(Me)-iPr)(CO)2](+) (6) is afforded. The effective magnetic moments μeff of all Co(II) complexes were derived from the temperature dependence of the inverse molar magnetic susceptibility by SQUID measurements and are in the range 1.9 to 2.4 μB. This is consistent with a d(7) low-spin configuration with some degree of spin-orbit coupling. Oxidation of 2 with CuCl2 affords the paramagnetic Co(III) PCP complex [Co(PCP(Me)-iPr)Cl2] (7), while the synthesis of the diamagnetic Co(I) complex [Co(PCP(Me)-iPr)(CO)2] (8) was achieved by stirring 2 in toluene with KC8 in the presence of CO. Finally, the cationic 16e Ni(II) PCP complex [Ni(PCP(Me)-iPr)(CO)](+) (10) was obtained by reacting complex 3 with 1 equiv of AgSbF6 in the presence of CO. The reactivity of CO addition to Co(I), Co(II), and Ni(II) PCP square planar complexes of the type [M(PCP(Me)-iPr)(CO)] (n) (n = +1, 0) was investigated by DFT calculations, showing that formation of the Co species, 6 and 8, is thermodynamically favorable, while Ni(II) maintains the 16e configuration since CO addition is unfavorable in this case. X-ray structures of most complexes are provided and discussed. A structural feature of interest is that the apical CO ligand in 4 deviates significantly from linearity, with a Co-C-O angle of 170.0(1)°. The DFT-calculated value is 172°, clearly showing that this is not a packing but an electronic effect.

  5. A spectroscopic study on the coordination and solution structures of the interaction systems between biperoxidovanadate complexes and the pyrazolylpyridine-like ligands. (United States)

    Yu, Xian-Yong; Deng, Lin; Zheng, Baishu; Zeng, Bi-Rong; Yi, Pinggui; Xu, Xin


    In order to understand the substitution effects of pyrazolylpyridine (pzpy) on the coordination reaction equilibria, the interactions between a series of pzpy-like ligands and biperoxidovanadate ([OV(O2)2(D2O)](-)/[OV(O2)2(HOD)](-), abbrv. bpV) have been explored using a combination of multinuclear ((1)H, (13)C, and (51)V) magnetic resonance, heteronuclear single quantum coherence (HSQC), and variable temperature NMR in a 0.15 mol L(-1) NaCl D2O solution that mimics the physiological conditions. Both the direct NMR data and the equilibrium constants are reported for the first time. A series of new hepta-coordinated peroxidovanadate species [OV(O2)2L](-) (L = pzpy-like chelating ligands) are formed due to several competitive coordination interactions. According to the equilibrium constants for products between bpV and the pzpy-like ligands, the relative affinity of the ligands is found to be pzpy > 2-Ester-pzpy ≈ 2-Me-pzpy ≈ 2-Amide-pzpy > 2-Et-pzpy. In the interaction system between bpV and pzpy, a pair of isomers (Isomers A and B) are observed in aqueous solution, which are attributed to different types of coordination modes between the metal center and the ligands, while the crystal structure of NH4[OV(O2)2(pzpy)]·6H2O (CCDC 898554) has the same coordination structure as Isomer A (the main product for pzpy). For the N-substituted ligands, however, Isomer A or B type complexes can also be observed in solution but the molar ratios of the isomer are reversed (i.e., Isomer B type is the main product). These results demonstrate that when the N atom in the pyrazole ring has a substitution group, hydrogen bonding (from the H atom in the pyrazole ring), the steric effect (from alkyl) and the solvation effect (from the ester or amide group) can jointly affect the coordination reaction equilibrium.

  6. Low-dimensional coordination polymeric structures in alkali metal complex salts of the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D). (United States)

    Smith, Graham


    The Li, Rb and Cs complexes with the herbicide (2,4-dichlorophenoxy)acetic acid (2,4-D), namely poly[[aqua[μ3-(2,4-dichlorophenoxy)acetato-κ(3)O(1):O(1):O(1')]lithium(I)] dihydrate], {[Li(C8H5Cl2O3)(H2O)]·2H2O}n, (I), poly[μ-aqua-bis[μ3-(2,4-dichlorophenoxy)acetato-κ(4)O(1):O(1'):O(1'),Cl(2)]dirubidium(I)], [Rb2(C8H5Cl2O3)2(H2O)]n, (II), and poly[μ-aqua-bis[μ3-(2,4-dichlorophenoxy)acetato-κ(5)O(1):O(1'):O(1'),O(2),Cl(2)]dicaesium(I)], [Cs2(C8H5Cl2O3)2(H2O)]n, (III), respectively, have been determined and their two-dimensional polymeric structures are described. In (I), the slightly distorted tetrahedral LiO4 coordination involves three carboxylate O-atom donors, of which two are bridging, and a monodentate aqua ligand, together with two water molecules of solvation. Conjoined six-membered ring systems generate a one-dimensional coordination polymeric chain which extends along b and interspecies water O-H...O hydrogen-bonding interactions give the overall two-dimensional layers which lie parallel to (001). In hemihydrate complex (II), the irregular octahedral RbO5Cl coordination about Rb(+) comprises a single bridging water molecule which lies on a twofold rotation axis, a bidentate O(carboxy),Cl-chelate interaction and three bridging carboxylate O-atom bonding interactions from the 2,4-D ligand. A two-dimensional coordination polymeric layer structure lying parallel to (100) is formed through a number of conjoined cyclic bridges, including a centrosymmetric four-membered Rb2O2 ring system with an Rb...Rb separation of 4.3312 (5) Å. The coordinated water molecule forms intralayer aqua-carboxylate O-H...O hydrogen bonds. Complex (III) comprises two crystallographically independent (Z' = 2) irregular CsO6Cl coordination centres, each comprising two O-atom donors (carboxylate and phenoxy) and a ring-substituted Cl-atom donor from the 2,4-D ligand species in a tridentate chelate mode, two O-atom donors from bridging carboxylate groups and one from a

  7. Synthesis and characterization of Eu(III)-based coordination complexes of modified D-glucosamine and poly(N-isopropylacrylamide) (United States)

    Cui, Guihua; Zhao, Dehai; Lv, Peng; Gao, Zhengguo; Chen, Shuiying; Qiu, Nannan; Satoh, Toshifumi; Kakuchi, Toyoji; Duan, Qian


    A series of novel fluorescent complexes was formed by chelation of the thermosensitive polymers with europium(III) ions. The polymers was synthesized via atom transfer radical polymerization (ATRP), which composed of poly(N-isopropyl acrylamide) (PNIPAM) and 2-amino-2-deoxy-D-glucopyranose(D-glucosamine, GA). The aqueous solutions of the polymers and its Eu(III) complexes exhibited a lower critical solution temperatures (LCSTs), and which were approximately equal to body temperature. The maximum emission intensity of the complexes at 613 nm was enhanced by a factor of approximately 10 relative to that of the corresponding Eu(III) chloride. Cell viability assays suggested that these thermosensitive polymers and Eu(III) complexes showed excellent biocompatibility in vitro.

  8. Examination of the coordination sphere of Al(III) in trifluoromethyl-heteroarylalkenolato complex ions by gas-phase IRMPD spectroscopy and computational modelling. (United States)

    Brückmann, Lisa; Tyrra, Wieland; Mathur, Sanjay; Berden, Giel; Oomens, Jos; Meijer, Anthony J H M; Schäfer, Mathias


    A series of aluminium complex ions with trifluoromethyl-heteroarylalkenolato (TMHA) ligands are studied by gas-phase infrared multiphoton-dissociation (IRMPD) spectroscopy and computational modelling. The selected series of aluminium TMHA complex ions are promising species for the initial study of intrinsic binding characteristics of Al(III) cations in the gas phase as corresponding molecular ions. They are readily available for examination by (+) and (-) electrospray ionization mass spectrometry (ESI-MS) by spraying of [Al(3+)⋅(L(-))(3)] solutions. The complex ions under investigation contain trivalent Al(3+) cations with two chelating anionic enolate ligands, [Al(3+)⋅(L(-))(2)](+), providing insights in the nature of the heteroatom-Al bonds. Additionally, the structure of a deprotonated benzimidazole ligand, L(-,) and an anionic complex ion of Al(III) with two doubly deprotonated benzimidazole ligands, [Al(3+)⋅(L(2-))(2)](-), are examined by (-)ESI-IRMPD spectroscopy. Experimental and computational results are highly consistent and allow a reliable identification of the ion structures. In all complex ions examined the planar TMHA ligands are oriented perpendicular to each other around the metal ion, leading to a tetrahedral coordination sphere in which aluminium interacts with the enolate oxygen and heteroaryl nitrogen atoms available in each of the bidentate ligands.

  9. Synthesis, Crystal Structures and Catalysis of Dinuclear Cd(Ⅱ) Complexes Bridged by Unusual (N,O,O')-Coordinated a-Amino Acids

    Institute of Scientific and Technical Information of China (English)

    DENG Dong-sheng; WANG Li; PEI Ya-mei; FENG Lu; LIU Chang-lin


    Four dinuclear amino acid cadmium(Ⅱ) complexes [Cd2(tren)2(dl-alaninato)](ClO4)3·H2O(Ⅰ),[Cd2(tren)2·(l-alaninato)](ClO4)3·H2O(Ⅱ),[Cd2(tren)2(dl-phenylalaninato)](ClO4)3(Ⅲ) and [Cd2(tren)2(l-phenylalaninato)]·(ClO4)3(Ⅳ),constructed from mixed ligands of tris(2-aminoethyl)amine(tren) and racemic or natural amino acids(amino acids=dl- or l-alanine,and dl- or l-phenylalanine),have been synthesized and characterized by X-ray crystallography.The structural analysis of complexes Ⅰ and Ⅲ reveals that the cadmium centers are coordinated by one tren ligand and one amino acid molecule with the unusual (N,O,O')-bridged mode,resulting in asymmetric chromophores of CdN4O and CdN5O in complex Ⅰ,CdN4O2 and CdN5O in complex Ⅲ,respectively.The utility of the four complexes as efficient water-compatible Lewis acid catalysts for the direct aldol reaction in water was examined.The reaction proceeded smoothly to afford the corresponding β-hydroxy ketones in up to 99% yield.Moreover,the diastereoselectivity of the reaction favors the formation of the syn-isomers.

  10. Electronic structures and properties of eight-coordinate metal-polyarsenic complexes MAs8n- (M = V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re). (United States)

    Li, J; Wu, K


    The eight-coordinate early transition metal polyarsenic complexes, MAs(8)3- (M = V, Nb, Ta), MAs(8)2- (M = Cr, Mo, W), and MAs8- (M = Mn, Tc, Re), have been studied using density functional theory (DFT). The geometry optimizations of these complexes indicate that in the most stable structures the transition metal atoms are trapped in a crownlike cavity consisting of a zigzag eight-membered ring of As8 cluster. The scalar-relativistic effects and spin-orbit coupling effects on the electronic structures and energy levels were taken into account. The stabilities of gas-phase MAs8n- ions and bonding between the As8 ring and early transition metals are discussed on the basis of population analysis, atomization energies, and decomposition reaction energies. All these complex ions are found to be diamagnetic with notable HOMO-LUMO energy gaps. The vibrational frequencies and infrared absorption intensities of the MAs8n- series are predicted theoretically. Brief theoretical calculations of the similar MoA(8)2- pnictide ions indicate that the analogous P, Sb, and even Bi complexes are likely to be stable, whereas the crownlike MoN(8)2- is not a stable complex.

  11. Potentiometric and spectroscopic studies on the copper(II) complexes of rat amylin fragments. The anchoring ability of specific non-coordinating side chains. (United States)

    Dávid, Ágnes; Kállay, Csilla; Sanna, Daniele; Lihi, Norbert; Sóvágó, Imre; Várnagy, Katalin


    Copper(ii) complexes of peptides modelling the sequence of the 17-22 residues of rat amylin have been studied by potentiometric, UV-Vis, CD and ESR spectroscopic methods. The peptides were synthesized in N-terminally free forms, NH2-VRSSNN-NH2, NH2-VRSSAA-NH2, NH2-VRAANN-NH2, NH2-VRSS-NH2, NH2-SSNN-NH2, NH2-SSNA-NH2 and NH2-AANN-NH2, providing a possibility for the comparison of the metal binding abilities of the amino terminus and the -SSNN- domain. The amino terminus was the primary ligating site in all cases and the formation of only mononuclear complexes was obtained for the tetrapeptides. The thermodynamic stability of the (NH2, N(-), N(-)) coordinated complexes was, however, enhanced by the asparaginyl moiety in the case of NH2-SSNN-NH2, NH2-SSNA-NH2 and NH2-AANN-NH2. Among the hexapeptides the formation of dinuclear complexes was characteristic for NH2-VRSSNN-NH2 demonstrating the anchoring ability of the -SSNN- (SerSerAsnAsn) domain. The complexes of the heptapeptide NH2-GGHSSNN-NH2 were also studied and the data supported the above mentioned anchoring ability of the -SSNN- site.

  12. Crystal structure of yeast monothiol glutaredoxin Grx6 in complex with a glutathione-coordinated [2Fe–2S] cluster (United States)

    Abdalla, Mohnad; Dai, Ya-Nan; Chi, Chang-Biao; Cheng, Wang; Cao, Dong-Dong; Zhou, Kang; Ali, Wafa; Chen, Yuxing; Zhou, Cong-Zhao


    Glutaredoxins (Grxs) constitute a superfamily of proteins that perform diverse biological functions. The Saccharomyces cerevisiae glutaredoxin Grx6 not only serves as a glutathione (GSH)-dependent oxidoreductase and as a GSH transferase, but also as an essential [2Fe–2S]-binding protein. Here, the dimeric structure of the C-terminal domain of Grx6 (holo Grx6C), bridged by one [2Fe–2S] cluster coordinated by the active-site Cys136 and two external GSH molecules, is reported. Structural comparison combined with multiple-sequence alignment demonstrated that holo Grx6C is similar to the [2Fe–2S] cluster-incorporated dithiol Grxs, which share a highly conserved [2Fe–2S] cluster-binding pattern and dimeric conformation that is distinct from the previously identified [2Fe–2S] cluster-ligated monothiol Grxs. PMID:27710937

  13. MALDI-TOFMS analysis of coordination and organometallic complexes: a nic(h)e area to work in. (United States)

    Wyatt, Mark F


    A mini-review of the characterisation of metal-containing compounds by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is presented. Organometallic and coordination compounds have many varied applications, most notably in industrial catalytic processes and also in the electronics and healthcare sectors. In general, the compounds discussed, be they small or large molecules, have a high percentage metal content, rather than simply containing 'a metal atom'. A brief history of the field is given, but the main scope over the last 5 years is covered in some detail. How MALDI-TOFMS compliments electrospray for metal-containing compounds is highlighted. Perspectives on recent advances, such as solvent-free and air/moisture-sensitive sample preparation, and potential future challenges and developments, such as nanomaterials and metallodrug/metallometabolite imaging, are given.

  14. Conformation driven complexation of two analogous benzimidazole based tripodal ligands with Ag(I) resulting in a trigonal prism and a coordination polymer

    Indian Academy of Sciences (India)

    Suman Bhattacharya; Binoy K Saha


    Two analogous tripodal ligands, namely, 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-triethylbenzene (1-Et) and 1,3,5-tris(benzimidazol-1-ylmethyl)-2,4,6-trimethoxybenzene (1-OMe) have been used for complexation with silver(I) tetrafluoroborate. A trinuclear Ag(I) salt, formulated as $\\mathbf{[Ag_3(1-Et)_2]^{3+}(BF_4){}^{−}_{3}\\bullet 7CH_3CN\\bullet yH_2O}$ was formed in the complexation reaction of 1-Et with silver(I) tetrafluoroborate, which consists of a trigonal prismatic cation formed by three bicoordinated Ag(I) coordinated with two 1-Et ligands. In case of the 1-OMe ligand, however, a one dimensional ladder, formulated as $\\mathbf{[(Ag(1-OMe)OH_2)^{+}(BF_4)^{−}\\bullet MeOH]_{\\infty}}$ was obtained which is constituted of a tetracoordinated Ag(I) center in a distorted tetrahedral environment. The crystal structures of the ligand hydrates namely $\\mathbf{1-Et\\bullet H_2O}$ and $\\mathbf{1-OMe\\bullet 3.6H_2O}$ have been discussed along with the structure of methanol solvate-hydrate of 1-Et. The imidazole rings of the Bim groups in 1-Et in the crystal structures of the ligand as well as in its coordination complex with the Ag(I) are pointed inward with respect to the central ring, whereas it is pointed outwards in the crystal structures of 1-OMe as well as its Ag(I) complex.

  15. Reversible switching of coordination mode of ansa bis(amidinate) ligand in ytterbium complexes driven by oxidation state of the metal atom. (United States)

    Tolpygin, Aleksei O; Cherkasov, Anton V; Fukin, Georgii K; Trifonov, Alexander A


    Reaction of bisamidine C6H4-1,2-{NC(t-Bu)NH(2,6-Me2C6H3)}2 (1) and [(Me3Si)2N]2Yb(THF)2 (THF = tetrahydrofuran) (toluene; room temperature) in a 1:1 molar ratio afforded a bis(amidinate) Yb(II) complex [C6H4-1,2-{NC(t-Bu)N(2,6-Me2C6H3)}2]Yb(THF) (2) in 65% yield. Complex 2 features unusual κ(1)amide, η(6)-arene coordination of both amidinate fragments to the ytterbium ion, resulting in the formation of a bent bis(arene) structure. Oxidation of 2 by Ph3SnCl (1:1 molar ratio) or (PhCH2S)2 (1:0.5) leads to the Yb(III) species [C6H4-1,2-{NC(t-Bu)N(2,6-Me2C6H3)}2]YbCl(1,2-dimethoxyethane) (3) and {[C6H4-1,2-{NC(t-Bu)N(2,6-Me2C6H3)}2]Yb(μ-SCH2Ph)}2 (4), performing "classic" κ(2)N,N'-chelating coordination mode of ansa bis(amidinate) ligand. By the reduction of 3 with equimolar amount of sodium naphthalide [C10H8(•-)][Na(+)] in THF, complex 2 can be recovered and restored to a bent bis(arene) structure. Complex 3 was also synthesized by the salt metathesis reaction of equimolar amounts of YbCl3 and the dilithium derivative of 1 in THF.

  16. The loading of coordination complex modified polyoxometalate nanobelts on activated carbon fiber: a feasible strategy to obtain visible light active and highly efficient polyoxometalate based photocatalysts. (United States)

    Lu, Tingting; Xu, Xinxin; Li, Huili; Li, Zhenyu; Zhang, Xia; Ou, Jinzhao; Mei, Mingliang


    To enhance the photocatalytic properties of coordination complex modified polyoxometalates (CC/POMs) in the visible light region, its nanobelts (CC/POMNBs) were loaded on activated carbon fiber (ACF) through a simple colloidal blending process. The resulting coordination complex modified polyoxometalate nanobelts loaded activated carbon fiber composite materials (CC/POMNBs/ACF) exhibited dramatic photocatalytic activity for the degradation of rhodamine B (RhB) under visible light irradiation. Optical and electrochemical methods illustrated the enhanced photocatalytic activity of CC/POMNBs/ACF, which originates from the high separation efficiency of the photogenerated electrons and holes on the interface of the CC/POMNBs and ACF, which results from the synergistic effects between them. In the composite material, the role of ACF could be described as a photosensitizer and a good electron transporter. Furthermore, the influence of the mass ratio between the CC/POMNBs and ACF on the photocatalytic performance of the resulting composite material was discussed, and an ideal value to obtain highly efficient photocatalysts was obtained. The results suggested that the loading of CC/POMNBs on the surface of ACF would be a feasible strategy to enhance their photocatalytic activity.

  17. Purkinje-cell-restricted restoration of Kv3.3 function restores complex spikes and rescues motor coordination in Kcnc3 mutants. (United States)

    Hurlock, Edward C; McMahon, Anne; Joho, Rolf H


    The fast-activating/deactivating voltage-gated potassium channel Kv3.3 (Kcnc3) is expressed in various neuronal cell types involved in motor function, including cerebellar Purkinje cells. Spinocerebellar ataxia type 13 (SCA13) patients carrying dominant-negative mutations in Kcnc3 and Kcnc3-null mutant mice both display motor incoordination, suggested in mice by increased lateral deviation while ambulating and slips on a narrow beam. Motor skill learning, however, is spared. Mice lacking Kcnc3 also exhibit muscle twitches. In addition to broadened spikes, recordings of Kcnc3-null Purkinje cells revealed fewer spikelets in complex spikes and a lower intraburst frequency. Targeted reexpression of Kv3.3 channels exclusively in Purkinje cells in Kcnc3-null mice as well as in mice also heterozygous for Kv3.1 sufficed to restore simple spike brevity along with normal complex spikes and to rescue specifically coordination. Therefore, spike parameters requiring Kv3.3 function in Purkinje cells are involved in the ataxic null phenotype and motor coordination, but not motor learning.

  18. Extending the NIF DISCO framework to automate complex workflow: coordinating the harvest and integration of data from diverse neuroscience information resources. (United States)

    Marenco, Luis N; Wang, Rixin; Bandrowski, Anita E; Grethe, Jeffrey S; Shepherd, Gordon M; Miller, Perry L


    This paper describes how DISCO, the data aggregator that supports the Neuroscience Information Framework (NIF), has been extended to play a central role in automating the complex workflow required to support and coordinate the NIF's data integration capabilities. The NIF is an NIH Neuroscience Blueprint initiative designed to help researchers access the wealth of data related to the neurosciences available via the Internet. A central component is the NIF Federation, a searchable database that currently contains data from 231 data and information resources regularly harvested, updated, and warehoused in the DISCO system. In the past several years, DISCO has greatly extended its functionality and has evolved to play a central role in automating the complex, ongoing process of harvesting, validating, integrating, and displaying neuroscience data from a growing set of participating resources. This paper provides an overview of DISCO's current capabilities and discusses a number of the challenges and future directions related to the process of coordinating the integration of neuroscience data within the NIF Federation.

  19. Extending the NIF DISCO framework to automate complex workflow: coordinating the harvest and integration of data from diverse neuroscience information resources

    Directory of Open Access Journals (Sweden)

    Luis eMarenco


    Full Text Available This paper describes how DISCO, the data-aggregator that supports the Neuroscience Information Framework (NIF, has been extended to play a central role in automating the complex workflow required to support and coordinate the NIF's data integration capabilities. The NIF is an NIH Neuroscience Blueprint initiative designed to help researchers access the wealth of data related to the neurosciences available via the Internet. A central component is the NIF Federation, a searchable database that currently contains data from 231 data and information resources regularly harvested, updated, and warehoused in the DISCO system. In the past several years, DISCO has greatly extended its functionality and has evolved to play a central role in automating the complex, ongoing process of harvesting, validating, integrating, and displaying neuroscience data from a growing set of participating resources. This paper provides an overview of DISCO's current capabilities and discusses a number of the challenges and future directions related to the process of coordinating the integration of neuroscience data within the NIF Federation.

  20. Magnetic adsorbent constructed from the loading of amino functionalized Fe3O4 on coordination complex modified polyoxometalates nanoparticle and its tetracycline adsorption removal property study (United States)

    Ou, Jinzhao; Mei, Mingliang; Xu, Xinxin


    A magnetic polyoxometalates based adsorbent has been synthesized successfully through the loading of amino functionalized Fe3O4 (NH2-Fe3O4) on nanoparticle of a coordination complex modified polyoxometalates (CC/POMNP). FTIR illustrate there exist intense hydrogen bonds between NH2-Fe3O4 and CC/POMNP, which keep the stability of this adsorbent. At room temperature, this adsorbent exhibits ferromagnetic character with saturation magnetization of 8.19 emu g-1, which provides prerequisite for fast magnetic separation. Water treatment experiment illustrates this POM based magnetic adsorbent exhibits high adsorption capacity on tetracycline. The adsorption process can be described well with Temkin model, which illustrates the interaction between adsorbent and tetracycline plays the dominated role in tetracycline removal. The rapid, high efficient tetracycline adsorption ability suggests this POM based magnetic adsorbent exhibits promising prospect in medical and agriculture waste water purification. A magnetic polyoxometalates based adsorbent, which exhibits excellent tetracycline adsorption removal property has been synthesized through the loading of NH2-Fe3O4 on coordination complex modified polyoxometalates

  1. Extending the NIF DISCO framework to automate complex workflow: coordinating the harvest and integration of data from diverse neuroscience information resources (United States)

    Marenco, Luis N.; Wang, Rixin; Bandrowski, Anita E.; Grethe, Jeffrey S.; Shepherd, Gordon M.; Miller, Perry L.


    This paper describes how DISCO, the data aggregator that supports the Neuroscience Information Framework (NIF), has been extended to play a central role in automating the complex workflow required to support and coordinate the NIF’s data integration capabilities. The NIF is an NIH Neuroscience Blueprint initiative designed to help researchers access the wealth of data related to the neurosciences available via the Internet. A central component is the NIF Federation, a searchable database that currently contains data from 231 data and information resources regularly harvested, updated, and warehoused in the DISCO system. In the past several years, DISCO has greatly extended its functionality and has evolved to play a central role in automating the complex, ongoing process of harvesting, validating, integrating, and displaying neuroscience data from a growing set of participating resources. This paper provides an overview of DISCO’s current capabilities and discusses a number of the challenges and future directions related to the process of coordinating the integration of neuroscience data within the NIF Federation. PMID:25018728

  2. Five-Coordinate Zinc(II Complex: Synthesis, Characterization, Molecular Structure, and Antibacterial Activities of Bis-[(E-2-hydroxy-N′-{1-(4-methoxyphenylethylidene}benzohydrazido]dimethylsulfoxidezinc(II Complex

    Directory of Open Access Journals (Sweden)

    Zhi-Qiang Liu


    Full Text Available The titled Zn(II complex was synthesized by reacting the compound (E-2-hydroxy-N′-{1-(4-methoxyphenylethylidene}benzohydrazide with zinc(II acetate dihydrate in alkaline DMSO and ethanol solution under reflux condition for 28 hours. The resulting solid was filtered and recrystallized from the mixture of ethanol and DMSO. The hydrazone Schiff base and its Zn(II complex were characterized using 1H, 13C NMR, FTIR, UV-Vis spectroscopy, and single crystal X-ray diffraction analysis. Meanwhile, their antibacterial activities were examined using disc diffusion method. The spectral studies showed that the hydrazone Schiff base underwent keto-enol tautomerization, forming a bidentate ligand (N,O towards Zn(II ion. Surprisingly, on top of the two hydrazone Schiff base molecules which coordinated to the Zn metal center, an additional DMSO molecule was found attached to the Zn metal center in the crystal data, resulting in a 5-coordinate distorted trigonal bipyramidal Zn(II complex. Both hydrazone Schiff base and its Zn(II complexes were found to exhibit low antibacterial activity even when the concentrations were increased to 800 ppm.

  3. Coordinated regulation of transcriptional repression by the RBP2 H3K4 demethylase and Polycomb-Repressive Complex 2

    DEFF Research Database (Denmark)

    Pasini, Diego; Hansen, Klaus H; Christensen, Jesper;


    Polycomb group (PcG) proteins regulate important cellular processes such as embryogenesis, cell proliferation, and stem cell self-renewal through the transcriptional repression of genes determining cell fate decisions. The Polycomb-Repressive Complex 2 (PRC2) is highly conserved during evolution......, and its intrinsic histone H3 Lys 27 (K27) trimethylation (me3) activity is essential for PcG-mediated transcriptional repression. Here, we show a functional interplay between the PRC2 complex and the H3K4me3 demethylase Rbp2 (Jarid1a) in mouse embryonic stem (ES) cells. By genome-wide location analysis we...... found that Rbp2 is associated with a large number of PcG target genes in mouse ES cells. We show that the PRC2 complex recruits Rbp2 to its target genes, and that this interaction is required for PRC2-mediated repressive activity during ES cell differentiation. Taken together, these results demonstrate...

  4. New in situ generated acylhydrazidate-coordinated complexes and acylhydrazide molecules: Synthesis, structural characterization and photoluminescence property (United States)

    Wang, Yan-Ning; Huo, Qi-Sheng; Zhang, Ping; Yu, Jie-Hui; Xu, Ji-Qing


    By utilizing the hydrothermal in situ acylation of organic acids with N2H4, three acylhydrazidate-coordinated compounds [Mn(L1)2(H2O)2] (L1 = 2,3-quinolinedicarboxylhydrazidate; HL1 = 2,3-dihydropyridazino[4,5-b] quinoline-1,4-dione) 1, [Mn2(ox)(L2)2(H2O)6]·2H2O (L2 = benzimidazolate-5,6-dicarboxylhydrazide; HL2 = 6,7-dihydro-1H-imidazo[4,5-g]phthalazine-5,8-dione; ox = oxalate) 2, and [Cd(HL3)(bpy)] (L3 = 4,5-di(3‧-carboxylphenyl)phthalhydrazidate; H3L3 = 6,7-dihydro-1H-imidazo[4,5-g]phthalazine-5,8-dione; bpy = 2,2‧-bipyridine) 3, as well as two acylhydrazide molecules L4 (L4 = oxepino[2,3,4-de:7,6,5-d‧e‧]diphthalazine-4,10(5H,9H)-dione) 4 and L5 (L5 = 4,5-dibromophthalhydrazide; L5 = 6,7-dibromo-2,3-dihydrophthalazine-1,4-dione) 5 were obtained. X-ray single-crystal diffraction analysis reveals that (i) 1 only possesses a mononuclear structure, but it self-assembles into a 2-D supramolecular network via the Nhydrazinesbnd H ⋯ Nhydrazine and Owsbnd H ⋯ Ohydroxylimino interactions; (ii) 2 exhibits a dinuclear structure. Ox acts as the linker, while L2 just serves as a terminal ligand; (iii) In 3, L3 acts as a 3-connected node to propagate the 7-coordinated Cd2 + centers into a 1-D double-chain structure; (iv) 4 is a special acylhydrazide molecule. Two sbnd OH groups for the intermediates 3,3‧-biphthalhydrazide further lose one water molecule to form 4; (v) 5 is a common monoacylhydrazide molecule. Via the Nhydrazinesbnd H ⋯ Ohydrazine, Ohydroxyliminosbnd H ⋯ Oacylamino and the π ⋯ π interactions, it self-assembles into a 2-D supramolecular network. The photoluminescence analysis reveals that 4 emits light with the maxima at 510 nm.

  5. Coordination ligand exchange of a xanthene probe-Ce(III) complex for selective fluorescence sensing of inorganic pyrophosphate. (United States)

    Kittiloespaisan, Ekkachai; Takashima, Ippei; Kiatpathomchai, Wansika; Wongkongkatep, Jirarut; Ojida, Akio


    A fluorescence sensing system for inorganic pyrophosphate based on ligand exchange of the Ce(III) complex of a xanthene-type probe is developed. This sensing system is successfully applied to the fluorescence detection of polymerase-catalyzed DNA amplification using loop-mediated isothermal amplification.

  6. XRCC1 coordinates disparate responses and multiprotein repair complexes depending on the nature and context of the DNA damage

    DEFF Research Database (Denmark)

    Hanssen-Bauer, Audun; Solvang-Garten, Karin; Sundheim, Ottar


    XRCC1 is a scaffold protein capable of interacting with several DNA repair proteins. Here we provide evidence for the presence of XRCC1 in different complexes of sizes from 200 to 1500 kDa, and we show that immunoprecipitates using XRCC1 as bait are capable of complete repair of AP sites via both...

  7. Influence of the π-coordinated arene on the anticancer activity of ruthenium(II) carbohydrate organometallic complexes

    NARCIS (Netherlands)

    Hanif, Muhammad; Meier, Samuel M; Nazarov, Alexey A; Risse, Julie; Legin, Anton; Casini, Angela; Jakupec, Michael A; Keppler, Bernhard K; Hartinger, Christian G


    The synthesis and in vitro cytotoxicity of a series of Ru(II)(arene) complexes with carbohydrate-derived phosphite ligands and various arene co-ligands is described. The arene ligand has a strong influence on the in vitro anticancer activity of this series of compounds, which correlates fairly well

  8. Structure and Coordination Determination of Peptide-metal Complexes Using 1D and 2D 1H NMR


    Shoshan, Michal S.; Tshuva, Edit Y.; Shalev, Deborah E.


    Copper (I) binding by metallochaperone transport proteins prevents copper oxidation and release of the toxic ions that may participate in harmful redox reactions. The Cu (I) complex of the peptide model of a Cu (I) binding metallochaperone protein, which includes the sequence MTCSGCSRPG (underlined is conserved), was determined in solution under inert conditions by NMR spectroscopy.

  9. Influence of the π-coordinated arene on the anticancer activity of ruthenium(II) carbohydrate organometallic complexes

    NARCIS (Netherlands)

    Hanif, Muhammad; Meier, Samuel M; Nazarov, Alexey A; Risse, Julie; Legin, Anton; Casini, Angela; Jakupec, Michael A; Keppler, Bernhard K; Hartinger, Christian G


    The synthesis and in vitro cytotoxicity of a series of Ru(II)(arene) complexes with carbohydrate-derived phosphite ligands and various arene co-ligands is described. The arene ligand has a strong influence on the in vitro anticancer activity of this series of compounds, which correlates fairly well

  10. Zinc(II) and Cadmium(II) complexes with N4-coordinate pyrazole based ligand: Syntheses, characterization and structure (United States)

    Solanki, Ankita; Sadhu, Mehul H.; Kumar, Sujit Baran; Mitra, Partho


    A series of six new mononuclear zinc(II) complexes of the type [Zn(X)(dbdmp)]Y (1-6) (X = N3-/NCO-/NCS-, Y = ClO4-/PF6-, and dbdmp = N,N-diethyl-N‧,N‧-bis((3,5-dimethyl-1H-pyrazol-1-yl)methyl)ethane-1,2-diamine), two binuclear cadmium(II) complexes [{Cd(dbdmp)}2(μ-N3)2](Y)2 (7-8) and three mononuclear cadmium(II) complexes [Cd(NCO)(dbdmp)]Y (Y = ClO4-/PF6-) (9-10) and [Cd(NCS)2(dbdmp)] (11) have been synthesized and characterized by physico-chemical methods. Crystal structures of the complexes [Zn(N3)(dbdmp)]ClO4 (1), [{Cd(dbdmp)}2(μ-N3)2](ClO4)2 (7), [Cd(NCO)(dbdmp)]ClO4 (9) and [Cd(NCS)2(dbdmp)] (11) have been solved by single crystal X-ray diffraction studies and showed that [Zn(N3)(dbdmp)]ClO4 (1) and [Cd(NCO)(dbdmp)]ClO4 (9) have distorted trigonal bipyramidal geometry, [Cd(NCS)2(dbdmp)] (11) and [(dbdmp)Cd(μ-N3)]2(ClO4)2 (7) have distorted octahedral geometry.

  11. Managing interteam coordination within and between organizations

    NARCIS (Netherlands)

    de Vries, Thomas Arend


    To accomplish complex tasks and effectively respond to environmental contingencies, teams must coordinate task-related issues with other teams (i.e., interteam coordination). Regrettably, interteam coordination is often complicated by misunderstandings that can arise from differences in teams’

  12. Synthesis, structure and antifungal activity of thiophene-2,3-dicarboxaldehyde bis(thiosemicarbazone) and nickel(II), copper(II) and cadmium(II) complexes: unsymmetrical coordination mode of nickel complex. (United States)

    Alomar, Kusaï; Landreau, Anne; Allain, Magali; Bouet, Gilles; Larcher, Gérald


    The reaction of nickel(II), copper(II) chlorides and cadmium(II) chloride and bromide with thiophene-2,3-dicarboxaldehyde bis(thiosemicarbazone) (2,3BTSTCH2) leads to a series of new complexes: [Ni(2,3BTSTCH)]Cl, [Cu(2,3BTSTC)], [CdCl2(2,3BTSTCH2)] and [CdBr2(2,3BTSTCH2)]. The crystal structures of the ligand and of [Ni(2,3BTSTCH)]Cl complex have been determined. In this case, we remark an unusual non-symmetrical coordination mode for the two functional groups: one acting as a thione and the second as a deprotonated thiolate. All compounds have been tested for their antifungal activity against human pathogenic fungi: Candida albicans, Candida glabrata and Aspergillus fumigatus, the cadmium complexes exhibit the highest antifungal activity. Cytotoxicity was evaluated using two biological methods: human MRC5 cultured cells and brine shrimp Artemia salina bioassay.

  13. Crystal structures of bis- and hexakis[(6,6'-di-hydroxy-bipyridine)copper(II)] nitrate coordination complexes. (United States)

    Gerlach, Deidra L; Nieto, Ismael; Herbst-Gervasoni, Corey J; Ferrence, Gregory M; Zeller, Matthias; Papish, Elizabeth T


    Two multinuclear complexes synthesized from Cu(NO3)2 and 6,6'-di-hydroxy-bipyridine (dhbp) exhibit bridging nitrate and hydroxide ligands. The dinuclear complex (6,6'-di-hydroxy-bipyridine-2κ(2) N,N')[μ-6-(6-hy-droxy-pyridin-2-yl)pyridin-2-olato-1:2κ(3) N,N':O (2)](μ-hydroxido-1:2κ(2) O:O')(μ-nitrato-1:2κ(2) O:O')(nitrato-1κO)dicopper(II), [Cu2(C10H7N2O2)(OH)(NO3)2(C10H8N2O2)] or [Cu(6-OH-6'-O-bpy)(NO3)(μ-OH)(μ-NO3)Cu(6,6'-dhbp)], (I), with a 2:1 ratio of nitrate to hydroxide anions and one partially deprotonated dhbp ligand, forms from a water-ethanol mixture at neutral pH. The hexa-nuclear complex bis-(μ3-bi-pyridine-2,2'-diolato-κ(3) O:N,N':O')tetra-kis-(6,6'-di-hydroxy-bipyridine-κ(2) N,N')tetra-kis-(μ-hydroxido-κ(2) O:O')bis-(methanol-κO)tetra-kis-(μ-nitrato-κ(2) O:O')hexa-copper(II), [Cu6(C10H6N2O2)2(CH4O)2(OH)4(NO3)4(C10H8N2O2)4] or [Cu(6,6'-dhbp)(μ-NO3)2(μ-OH)Cu(6,6'-O-bpy)(μ-OH)Cu(6,6'dhbp)(CH3OH)]2, (II), with a 1:1 NO3-OH ratio and two fully protonated and fully deprotonated dhbp ligands, was obtained by methanol recrystallization of material obtained at pH 3. Complex (II) lies across an inversion center. Complexes (I) and (II) both display intra-molecular O-H⋯O hydrogen bonding. Inter-molecular O-H⋯O hydrogen bonding links symmetry-related mol-ecules forming chains along [100] for complex (I) with π-stacking along [010] and [001]. Complex (II) forms inter-molecular O-H⋯O hydrogen-bonded chains along [010] with π-stacking along [100] and [001].

  14. Molybdenum complexes of biochemical interest. New coordination complexes of oxomolybdenum(V) with the tridentate ONO donor Schiff bases derived from salicylaldehydes and ethanolamine

    Energy Technology Data Exchange (ETDEWEB)

    Syamal, A.; Niazi, M.A.B.


    New oxomolybdenum(V) complexes MoOClL (where LH/sub 2/ = Schiff base) derived from ethanolamine and salicylaldehyde, 5-chlorosalicylaldehyde, 5-bromosalicylaldehyde, 5-nitrosalicylaldehyde, 3-ethoxysalicylaldehyde and 2-hydroxy-1-naphthaldehyde have been synthesized and characterised by elemental analyses, conductance, molecular weight, I.R. and electronic spectra and magnetic measurements. The Schiff bases behave as dibasic tridentate ONO donor ligands. The complexes are non-electrolytes and dimers. The complexes exhibit subnormal magnetic moments and are involved in antiferromagnetic exchange with S = 0 ground state. The complexes exhibit electronic spectral bands at ca. 13000 and ca. 17000 cm/sup -1/ due to the transitions dsub(xy)- > dsub(xz,yz) (/sup 2/B/sub 2/- > /sup 2/E) and dsub(xy)- > dsub(x2-y2) (/sup 2/B/sub 2/- > /sup 2/B/sub 1/), respectively. The = O) frequency of the complexes is observed in the 900-970 cm/sup -1/ region. On the basis of the magnetic susceptibility, I.R. and molecular weight data a dimetallic structure with alcoholic oxygen atoms as the bridging atoms is suggested.

  15. Characterization of the TolB-Pal trans-envelope complex from Xylella fastidiosa reveals a dynamic and coordinated protein expression profile during the biofilm development process. (United States)

    Santos, Clelton A; Janissen, Richard; Toledo, Marcelo A S; Beloti, Lilian L; Azzoni, Adriano R; Cotta, Monica A; Souza, Anete P


    The intriguing roles of the bacterial Tol-Pal trans-envelope protein complex range from maintenance of cell envelope integrity to potential participation in the process of cell division. In this study, we report the characterization of the XfTolB and XfPal proteins of the Tol-Pal complex of Xylella fastidiosa. X. fastidiosa is a major plant pathogen that forms biofilms inside xylem vessels, triggering the development of diseases in important cultivable plants around the word. Based on functional complementation experiments in Escherichia coli tolB and pal mutant strains, we confirmed the role of xftolB and xfpal in outer membrane integrity. In addition, we observed a dynamic and coordinated protein expression profile during the X. fastidiosa biofilm development process. Using small-angle X-ray scattering (SAXS), the low-resolution structure of the isolated XfTolB-XfPal complex in solution was solved for the first time. Finally, the localization of the XfTolB and XfPal polar ends was visualized via immunofluorescence labeling in vivo during bacterial cell growth. Our results highlight the major role of the components of the cell envelope, particularly the TolB-Pal complex, during the different phases of bacterial biofilm development. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Using low-frequency IR spectra for the unambiguous identification of metal ion-ligand coordination sites in purpose-built complexes. (United States)

    Varga, Gábor; Csendes, Zita; Peintler, Gábor; Berkesi, Ottó; Sipos, Pál; Pálinkó, István


    One of the aims of our long-term research is the identification of metal ion-ligand coordination sites in bioinspired metal ion-C- or N-protected amino acid (histidine, tyrosine, cysteine or cystine) complexes immobilised on the surface of chloropropylated silica gel or Merrifield resin. In an attempt to reach this goal, structurally related, but much simpler complexes have been prepared and their metal ion-ligand vibrations were determined from their low-frequency IR spectra. The central ions were Mn(II), Co(II), Ni(II) or Cu(II) and the ligands (imidazole, isopropylamine, monosodium malonate) were chosen to possess only one-type of potential donor group. The low-frequency IR spectra were taken of the complexes for each ion-ligand combination and the typical metal ion-functional group vibration bands were selected and identified. The usefulness of the obtained assignments is demonstrated on exemplary immobilised metal ion-protected amino acid complexes.

  17. Competitive coordination aggregation for V-shaped [Co3] and disc-like [Co7] complexes: synthesis, magnetic properties and catechol oxidase activity. (United States)

    Singha Mahapatra, Tufan; Basak, Dipmalya; Chand, Santanu; Lengyel, Jeff; Shatruk, Michael; Bertolasi, Valerio; Ray, Debashis


    Unique dependence on the nature of metal salt and reaction conditions for coordination assembly reactions of varying architecture and nuclearity have been identified in V-shaped [Co3L4] and planar disc-like [Co7L6] compounds: [CoL2(μ-L)2(μ-OH2)2(CF3CO2)2] (1) and [Co(μ-L)6(μ-OMe)6]Cl2 (2) (HL = 2-{(3-ethoxypropylimino)methyl}-6-methoxyphenol). At room temperature varying reaction conditions, cobalt-ligand ratios and use of different bases allowed unique types of coordination self-assembly. The synthetic marvel lies in the nature of aggregation with respect to the two unrelated cores in 1 and 2. Complex 1 assumes a V-shaped arrangement bound to L(-), water and a trifluoroacetate anion, while 2 grows around a central Co(II) ion surrounded by a {Co} hexagon bound to methoxide and L(-). Magnetic measurements revealed that the intermetallic interactions are antiferromagnetic in nature in the case of complex 1 and ferromagnetic in the case of 2 involving high spin cobalt(ii) ions with stabilization of the high-spin ground state in the latter case. In MeCN solutions complexes 1 and 2 showed catalytic oxidation of 3,5-di-tert-butylcatechol (3,5-DTBCH2) to 3,5-di-tert-butylbenzoquinone (3,5-DTBQ) in air. The kinetic study in MeCN revealed that with respect to the catalytic turnover number (kcat) 2 is more effective than 1 for oxidation of 3,5-DTBCH2.

  18. Azadipyrromethene dye derivatives in coordination chemistry: the structure-property relationship in homoleptic metal(II) complexes. (United States)

    Bessette, André; Ferreira, Janaina G; Giguère, Martin; Bélanger, Francis; Désilets, Denis; Hanan, Garry S


    As a chromophore closely related to dipyrromethene (DPM), the azadipyrromethene (ADPM) family has attracted much interest in the life sciences and optoelectronic fields. A high-yielding microwave-assisted synthesis is reported for new homoleptic complexes of cobalt(II), nickel(II), copper(II) and zinc(II) based on the tetrakis(p-methoxyphenyl)azadipyrromethene ligand 1b. These complexes are compared with other homoleptic complexes of the same metal(II) series based on the tetraphenylazadipyrromethene 1a and also with related BF2(+) chelates (Aza-BODIPYs 6a and 6b) for a better understanding of trends arising from substitution of the chelate and/or the electron-donating effect of the p-methoxy substituents. The electrochemical behavior of the new compounds 2b, 3b, and 5b in dichloromethane revealed two pseudoreversible reductions (2b, -1.09 and -1.25 V vs SCE; 3b, -1.05 and -1.29 V; 5b, -1.13 and -1.25 V) followed by a third irreversible process (2b, -1.78 V; 3b, -1.80 V; 5b, -1.77 V) along with two pseudoreversible oxidations (2b, 0.55 and 0.80 V; 3b, 0.56 and 0.80 V; 5b, 0.55 and 0.80 V) followed by two closely spaced irreversible processes (2b, 1.21 and 1.27 V; 3b, 1.21 and 1.28 V; 5b, 1.22 and 1.25 V). On its side, copper(II) homoleptic complex 4b revealed only one pseudoreversible reduction at -0.59 V followed by three irreversible processes at -0.95, -1.54, and -1.74 V, respectively. The oxidation behavior of this complex exhibited two pseudoreversible processes (0.55 and 0.82 V) and two irreversible processes (1.19 and 1.25 V). The redox processes are assigned and discussed in relation to their photophysical properties. X-ray structures for 1b and related copper(II) complex 2b are also discussed.

  19. Computational insight into complex structures of thorium coordination with N, N'- bis(3-allyl salicylidene)-o-phenylenediamine. (United States)

    Lan, Wenbo; Gao, Sha; Lin, Ying-Wu; Liao, Lifu; Wang, Xiaofeng; Nie, Changming


    Theoretical calculations on the structure of Th(IV) complex containing N, N'- bis(3-allyl salicylidene)-o-phenylenediamine (BASPDA) were performed using density functional theory (DFT) at the B3LYP/6-311G** level. The geometrical structural parameters and infrared spectra results of the Th(BASPDA)2 from the calculation were compared with the parallel dislocated structure (PDS) obtained in laboratory. The calculated structural parameters were in good agreement with the experimental results. In addition, based on the calculations, a stereoisomer SFS (staggered finger " + " structure) of the Th(BASPDA)2 complex was forecasted by the analysis of a comprehensive method. The charge distribution, structural parameters, bond order indices, spectral properties and thermodynamic properties as well as the molecular orbitals of the two possible crystal structures of Th(BASPDA)2 were also systematically studied. It was expected that this work could provide insightful information for understanding the properties of Th (BASPDA)2 complex at the molecular level.

  20. Synthesis, spectroscopic, electrochemical and computational studies of rhenium(I) dicarbonyl complexes based on meridionally-coordinated 2,2':6',2''-terpyridine. (United States)

    Frenzel, Blaise A; Schumaker, Josh E; Black, Daniel R; Hightower, Sean E


    A homologous series of meridionally-coordinated tridentate 2,2':6',2''-terpyridine Re(I) dicarbonyl complexes have been prepared and investigated. The complexes mer,cis-[Re(tpy-κ(3)N)(CO)2(L)](n) (L = Cl(-) (1), OSO2CF3(-) (2), NCCH3 (3), CN(-) (4), NC5H5 (5), PMe3 (6), PEt3 (7), PPh3 (8), P(OMe)3 (9) and P(OEt)3 (10); n = 0 or +1) have been synthesized and characterized by elemental analysis, (1)H NMR and infrared spectroscopy. The electrochemistry of these compounds has been studied and compared to that of other known rhenium compounds using an electrochemical parameterization model. Cyclic voltammetry measurements have shown that the first oxidation of the complexes varies systematically in potential as the ligand L is altered. Many of these one-electron oxidations occur at lower potentials compared to more familiar bidentate diimine Re(I) tricarbonyl complexes. A correlation exists between CO, a strong π-acidic ligand, and deviations of the observed reduction potentials from the calculated values. Many of the complexes absorb light throughout a significant portion of the visible spectrum. Two of these complexes, mer,cis-Re(tpy-κ(3)N)(CO)2Cl (1) and mer,cis-Re(tpy-κ(3)N)(CO)2CN (4), absorb light throughout the entire visible spectrum. Low temperature emission spectra were obtained for the compounds mer,cis-Re(tpy-κ(3)N)(CO)2Cl (1) and mer,cis-[Re(tpy-κ(3)N)(CO)2(P(OEt)3)](+) (10) at 77 K in a 4 : 1 methanol-ethanol glass matrix and give metal-to-ligand charge transfer ((3)MLCT) luminescence. Density functional theory (DFT) calculations of the electronic structure are in good agreement with the experimental data.

  1. Fluorescent sensing and electrocatalytic properties of three Zn(II)/Co(II) coordination complexes containing two different dicarboxylates and two various bis(pyridyl)-bis(amide) ligands (United States)

    Lin, Hongyan; Rong, Xing; Liu, Guocheng; Wang, Xiang; Wang, Xiuli; Duan, Surui


    Three new transition metal(II) coordination complexes constructed from two different dicarboxylates (1,3-H2BDC = 1,3-benzenedicarboxylic acid, 1,4-H2NDC = 1,4-naphthalenedicarboxylic acid) and two bis(pyridyl)-bis(amide) ligands (3-bpcd = N,N‧-bis(3-pyridyl)cyclohexane-1,4-dicarboxamide, 3-bpod = N,N‧-bis(3-pyridyl)octandiamide), [Zn(1,3-BDC)(3-bpcd)0.5(H2O)]·H2O (1), [Zn(1,3-BDC)(3-bpod)0.5(H2O)] (2) and [Co(1,4-NDC)(3-bpod)1.5(H2O)] (3) have been synthesized in the hydrothermal environments and structurally characterized by IR, TG and single crystal X-ray diffraction. Complexes 1 and 2 possess the similar 1D ladder-like chain based on [Zn(1,3-BDC)]n zigzag chain and the bidentate ligands 3-bpcd/or 3-bpod. Complex 3 shows a 2D layered structure with a 5-connected {410} topology, which consists of 1D linear [Co(1,4-NDC)]n chain and [Co(3-bpod)1.5]n chain with alternating arrangement of 3-bpod ligands and Co2(3-bpod)2 dinuclear loops. The adjacent 1D chains for 1-2 or the 2D layers for 3 are further extended into 2D or 3D supramolecular frameworks through the hydrogen bonding interactions. Additionally, the solid state fluorescent properties for the title complexes 1-3, the fluorescent sensing behaviors of complexes 1-2 and the electrochemical behaviour of complex 3 have been investigated.

  2. Effect of heme structure on O(2)-binding properties of human serum albumin-heme hybrids: intramolecular histidine coordination provides a stable O(2)-adduct complex. (United States)

    Komatsu, Teruyuki; Matsukawa, Yasuko; Tsuchida, Eishun


    5,10,15,20-Tetrakis[(alpha,alpha,alpha,alpha-o-pivaloylamino)phenyl]porphinatoiron(II) and 5,10,15,20-tetrakis([alpha,alpha,alpha,alpha-o-(1-methylcyclohexanoylamino)]phenyl)porphinatoiron(II) complexes bearing a covalently bound 8-(2-methyl-1-imidazolyl)octanoyloxymethyl or 4-(methyl-L-histidinamido)butanoyloxymethyl side-chain [FeRP(B) series: R = piv or cyc, B = Im or His] have been synthesized. The histidine-bound derivatives [FepivP(His), FecycP(His)] formed five N-coordinated high-spin iron(II) complexes in organic solvents under an N(2) atmosphere and showed large O(2)-binding affinities in comparison to those of the 2-methylimidazole-bound analogues [FepivP(Im), FecycP(Im)] due to the low O(2)-dissociation rate constants. On the contrary, the difference in the fence groups around the O(2)-coordination site (pivaloyl or 1-methylhexanoyl) did not significantly influence to the O(2)-binding parameters. These four porphinatoiron(II)s were efficiently incorporated into recombinant human serum albumin (rHSA), thus providing the synthetic hemoprotein, the albumin-heme hybrid [rHSA-FeRP(B)]. An rHSA host absorbs a maximum of eight FeRP(B) molecules in each case. The obtained rHSA-FeRP(B) can reversibly bind and release O(2) under physiological conditions (in aqueous media, pH 7.3, 37 degrees C) like hemoglobin and myoglobin. As in organic solutions, the difference in the fence groups did not affect their O(2)-binding parameters, but the axial histidine coordination significantly increased the O(2)-binding affinity, which is again ascribed to the low O(2)-dissociation rates. The most remarkable effect of the heme structure appeared in the half-life (tau(1/2)) of the O(2)-adduct complex. The dioxygenated rHSA-FecycP(His) showed an unusually long lifetime (tau(1/2): 25 h at 37 degrees C) which is ca. 13-fold longer than that of rHSA-FepivP(Im).

  3. Anion-Directed Copper(II) Metallocages, Coordination Chain, and Complex Double Salt: Structures, Magnetic Properties, EPR Spectra, and Density Functional Study. (United States)

    Wu, Jing-Yun; Zhong, Ming-Shiou; Chiang, Ming-Hsi; Bhattacharya, Dibyendu; Lee, Yen-Wei; Lai, Long-Li


    A series of Cu(II) metallo-assemblies showing anion-directed structural variations, including five metallocages [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) (A(-) )8-n (G(n-) =NO3 (-) , ClO4 (-) , SiF6 (2-) , BF4 (-) , SO4 (2-) ; A(-) =NO3 (-) , ClO4 (-) , BF4 (-) , CH3 SO4 (-) ; Hdpma=bis(3-pyridylmethyl)ammonium cation), a complex double salt, namely, (H3 dpma)4 (CuCl4 )5 Cl2 , and a coordination chain, namely, [Cu2 (dpma)(OAc)4 ], are reported. The influence of the anion can be explained by its coordinating ability, the affinity of which for the Cu(II) center interferes significantly with metallocage formation, and its shape, which offers host-guest recognition ability to engage in weak metal-anion coordination and hydrogen bonding to the organic ligand, which are responsible for metallocage templation. EPR studies of these metallocages in the powder phase at room temperature and 77 K showed a trend of the g values (g|| >2.10>g⊥ >2.00) indicating a dx2-y2 -based ground state with square-pyramidal geometry for the Cu(II) centers. The magnetism of these metallocages can be interpreted as the result of a combination of relatively small magnetic coupling integrals and a substantial contribution of temperature-independent paramagnetism (TIP). The weak magnetic interaction is corroborated by the results of DFT calculations and the EPR spectra. Availability of the low-lying state for spin population was confirmed by a magnetization study, which revealed a magnetic moment approaching 2Nβ, which would explain the presence of the larger TIP term.

  4. Synthesis, Characterization, and Crystal Structure of a Novel Copper(II) Complex with an Asymmetric Coordinated 2,2'-Bipyridine Derivative: A Model for the Associative Complex in the Ligand-Substitution Reactions of [Cu(tren)L](2+)? (United States)

    Lu Zl, Zhong-lin; Duan Cy, Chun-ying; Tian Yp, Yu-peng; You Xz, Xiao-zeng; Huang Xy, Xiao-ying


    The titled compound, (tris(2-aminoethyl)amine)(4,5-diazafluoren-9-one) copper(II) perchlorate, [Cu(C(6)H(18)N(4))(C(11)H(6)N(2)O)(ClO(4))(2)], 1, has been designed, synthesized, and characterized. The electronic and ESR spectra are very different from those of [Cu(tren)L](2+) complexes where L is monodentate ligand. The X-ray analysis revealed that the complex crystallizes in the monoclinic space group P2(1)/c, with a = 10.726(6) Å, b = 14.921(7) Å, c = 14.649(4) Å, beta = 95.13(3) degrees, and Z = 4. The copper(II) ion is coordinated by four nitrogen atoms from tris(2-aminoethyl)amine (tren) and two nitrogen atoms from 4,5-diazafluoren-9-one (dzf) to form an unusual six-coordinate (4 + 1 + 1') geometry. The structure is very rare, and to our knowledge, it is the first example of an asymmetric bidentate phenanthroline derivative metal complex. The structure could be used as a model of the associative complex in the ligand-exchange and ligand-substitution reactions of [Cu(tren)L](2+) and the catalytic mechanisms of enzymes involving copper sites. From the electronic and variable-temperature ESR spectra in solution, the possible mechanism of these reactions has also been proposed. As a comparison, the complex [Cu(tren)(ImH)(ClO(4))(2)], 2, was also synthesized and characterized, where ImH is imidazole.

  5. Coordination equilibria in the complex formation of guanylurea with CuII: Formation and stability of binary CuII-guanylurea and ternary CuII-guanylurea-glycinate complexes

    Indian Academy of Sciences (India)

    Tannistha Roy Barman; G N Mukherjee


    Combined pH-metric and spectrophotometric investigations on the complex formation equilibria of CuII with guanylurea (H$_{2}^{1}$NC(=O) 2NH.C(=3NH) 4NH2), hereafter, GuH, in the absence and in the presence of glycine (GlyH), in aqueous solution indicates variety of binary and mixed-ligand complexes: Cu(Gu)+, Cu(Gu)(OH); Cu(Gu)2, Cu(Gu-H)(Gu)-, Cu(Gu-H)$_{2}^{2-}$, Cu(Gu-H)(Gu-2H)3-; Cu(Gly)+, Cu(Gly) (OH); Cu(Gly)(Gu); Cu(Gly)(Gu-H)-, Cu(Gly)(Gu-2H)2-; (Gly)Cu(Gu)Cu(Gly)+, (Gly)Cu(Gu-H)Cu(Gly) and (Gly)Cu(Gu-2H)Cu(Gly)-. At pH < 6, guanylurea anion (Gu-) acts as a [(C=O), 3N-] or [=1NH, 3N-] bidentate ligand and above pH 7 it is transformed through a coordination equilibrium into a (=1N-, =3N-) bidentate ligand, similar to biguanide dianion. Occurrence of dinuclear complex species, (Gly) Cu(Gu)Cu(Gly)+, in the complexation equilibria, indicates bridging double bidentate [(1NH2, 3N-), (C=O, 4NH2)] and/or [(1NH2, 4NH2), (C=O, 3N-)] chelation by Gu- ion in an isomeric equilibrium. Above pH 6.5, the dinuclear complex decomposes mostly to the mononuclear species, Cu(Gly)(OH) and Cu(Gu)(OH) and only partly deprotonates to (Gly)Cu(Gu-H)Cu(Gly) and (Gly)Cu(Gu-2H)Cu(Gly)-. Electronic spectral shifts, with change of pH have been correlated with the possible modes of coordination of guanylurea species.

  6. Structures and properties of 1,8,15,22-tetrasubstituted phthalocyaninato zinc and nickel complexes: substitution and axially coordination effects study based on density functional theory calculations. (United States)

    Wan, Liang; Zhang, Yuexing; Qi, Dongdong; Jiang, Jianzhuang


    On the basis of the density functional theory (DFT) calculation of ZnPc (1), Zn[Pc(alpha-OC(5)H(11))(4)] (2), Ni[Pc(alpha-OC(5)H(11))(4)] (3), and Zn[Pc(alpha-OC(5)H(11))(4)]xH(2)O (4), the effects of non-peripheral substitution, different transition metals, and axial water coordination on the molecular structure, molecular orbital, atomic charge, infrared (IR) spectrum, and electronic absorption spectrum were investigated. The calculation results reveal that bulky 3-pentyloxy groups at the non-peripheral positions of the phthalocyanine ring evince great changes in structure and properties: they deflect the isoindole units, lift the frontier molecular orbitals, alter the atomic charge distribution, shift the bands of IR and electronic absorption spectra, etc. Though the central metal can shorten or lengthen the bond length, its effect on the electronic structure and properties of the phthalocyanine complex is very limited. Axial coordination significantly enhances the non-planarity of the phthalocyanine ring and, thus, alters the electronic structure, which is important for the formation of novel dimeric supramolecular structures through intermolecular hydrogen bonds. In addition, the calculated structures of 3 as well as the simulated IR and electronic absorption spectra of 4 were compared with the experimental data and showed good agreement.

  7. Coordinated regulation of the ESCRT-III component CHMP4C by the chromosomal passenger complex and centralspindlin during cytokinesis (United States)

    Capalbo, Luisa; Mela, Ioanna; Abad, Maria Alba; Jeyaprakash, A. Arockia; Edwardson, J. Michael


    The chromosomal passenger complex (CPC)—composed of Aurora B kinase, Borealin, Survivin and INCENP—surveys the fidelity of genome segregation throughout cell division. The CPC has been proposed to prevent polyploidy by controlling the final separation (known as abscission) of the two daughter cells via regulation of the ESCRT-III CHMP4C component. The molecular details are, however, still unclear. Using atomic force microscopy, we show that CHMP4C binds to and remodels membranes in vitro. Borealin prevents the association of CHMP4C with membranes, whereas Aurora B interferes with CHMP4C's membrane remodelling activity. Moreover, we show that CHMP4C phosphorylation is not required for its assembly into spiral filaments at the abscission site and that two distinctly localized pools of phosphorylated CHMP4C exist during cytokinesis. We also characterized the CHMP4C interactome in telophase cells and show that the centralspindlin complex associates preferentially with unphosphorylated CHMP4C in cytokinesis. Our findings indicate that gradual dephosphorylation of CHMP4C triggers a ‘relay’ mechanism between the CPC and centralspindlin that regulates the timely distribution and activation of CHMP4C for the execution of abscission. PMID:27784789

  8. Novel bipyridinyl oxadiazole-based metal coordination complexes: High efficient and green synthesis of 3,4-dihydropyrimidin-2(1H)-ones through the Biginelli reactions (United States)

    Wang, Jin-Hua; Zhang, E.; Tang, Gui-Mei; Wang, Yong-Tao; Cui, Yue-Zhi; Ng, Seik Weng


    Three new metal coordination complexes, namely, [Co(BPO)2(H2O)4](BS)2(H2O)2 (1), [Co(BPO)2(H2O)4](ABS)2(H2O)2 (2), [Co(BPO)2(H2O)4](MBS)2(H2O)2 (3) [BPO=2,5-di(pyridin-4-yl)-1,3,4-oxadiazole, BS=benzenesulphonate, ABS=4-aminobenzenesulphonate, MBS=4-methylbenzenesulphonate] were obtained under hydrothermal conditions. Complexes 1-3 were structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR and thermogravimetric analyses (TGA). All of them display a zero-dimensional motif, in which strong intermolecular hydrogen bonding interactions (O-H···O/N) and packing interactions (C-H···π and π···π) make them achieve a three-dimensional supramolecular architecture. The primary catalytic results of these three complexes show that high efficiency for the green synthesis of a variety of 3,4-dihydropyrimidin-2(1H)-ones was observed under solvent free conditions through Biginelli reactions. The present catalytic protocols exhibit advantages such as excellent yield, easy isolation, eco-friendly conditions, and short reaction time.

  9. Complexation of Curium(III) with DTPA at 10–70 °C: Comparison with Eu(III)–DTPA in Thermodynamics, Luminescence, and Coordination Modes

    Energy Technology Data Exchange (ETDEWEB)

    Tian, Guoxin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhang, Zhiyong [Stanford Univ., CA (United States). Stanford Research Computing Center; Martin, Leigh R. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Rao, Linfeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)


    Separation of trivalent actinides (An(III)) from trivalent lanthanides (Ln(III)) is a challenging task because of their nearly identical chemical properties. Diethylenetriaminepentaacetate (DTPA), a key reagent used in the TALSPEAK process that effectively separates An(III) from Ln(III), is believed to play a critical role in the An(III)/Ln(III) separation. However, the underlying principles for the separation based on the difference in the complexation of DTPA with An(III) and Ln(III) remain unclear. In this work, the complexation of DTPA with Cm(III) at 10-70 ºC was investigated by spectrophotometry, luminescence spectroscopy, and microcalorimetry, in conjunction with computational methods. The binding strength, the enthalpy of complexation, the coordination modes, and the luminescence properties are compared between the Cm(III)-DTPA and Eu(III)-DTPA systems. The experimental and computational data have demonstrated that the difference between Cm(III) and Eu(III) in the binding strength with DTPA can be attributed to the stronger covalence bonding between Cm(III) and the nitrogen donors of DTPA.

  10. Complexation of curium(III) with DTPA at 10-70 °C: comparison with Eu(III)-DTPA in thermodynamics, luminescence, and coordination modes. (United States)

    Tian, Guoxin; Zhang, Zhiyong; Martin, Leigh R; Rao, Linfeng


    Separation of trivalent actinides (An(III)) from trivalent lanthanides (Ln(III)) is a challenging task because of the nearly identical chemical properties of these groups. Diethylenetriaminepentaacetate (DTPA), a key reagent used in the TALSPEAK process that effectively separates An(III) from Ln(III), is believed to play a critical role in the An(III)/Ln(III) separation. However, the underlying principles for the separation based on the difference in the complexation of DTPA with An(III) and Ln(III) remain unclear. In this work, the complexation of DTPA with Cm(III) at 10-70 °C was investigated by spectrophotometry, luminescence spectroscopy, and microcalorimetry, in conjunction with computational methods. The binding strength, the enthalpy of complexation, the coordination modes, and the luminescence properties are compared between the Cm(III)-DTPA and Eu(III)-DTPA systems. The experimental and computational data demonstrated that the difference between Cm(III) and Eu(III) in the binding strength with DTPA can be attributed to the stronger covalence bonding between Cm(III) and the nitrogen donors of DTPA.

  11. Synthesis, crystal structures and coordination modes of some triorganotin(IV) complexes with 2-N-propyl and 2-N-benzyl-amino-1-cyclopentene-1-dithiocarboxylates (United States)

    López-Cardoso, Marcela; Vargas-Pineda, Gabriela; Román-Bravo, Perla Patricia; Rodríguez-Narváez, Cristina; Rosas-Valdez, Elena; Cea-Olivares, Raymundo


    The syntheses and characterization of six new triorganotin(IV) complexes, Ph3Sn(PrACDA) (1), Bu3Sn(PrACDA) (2), Ph3Sn(BzACDA) (3), Bu3Sn(BzACDA) (4), Me3Sn(BzACDA) (5) and Cy3Sn(BzACDA) (6) (ACDA = 2-amino-1-cyclopentene-1-carbodithioate anion) are reported. Compounds 1-6 were synthesized by the reaction between the sodium salts of 2-N-propyl- or 2-N-benzyl-2-amino-1-cyclopentene-1-carbodithioate and R3SnCl (R = Ph, Bu, Me, Cy) in a 1:1 M ratio. The complexes were characterized by elemental analyses, IR and NMR (1H, 13C and 119Sn) spectroscopy and by FAB+ mass spectrometry. The experimental data reveal that the tin atom is coordinated to the ligand by means of the two sulfur atoms from the carbodithioate group in an anisobidentate mode, while the 119Sn{1H} NMR spectra suggest a pentacoordinate metal center in 1-4 and a tetracoordinate tin atom for 5 and 6. The molecular structures of complexes 1, 3 and 5 were confirmed by single crystal X-ray diffraction analysis showing the presence of N-H···S hydrogen bonding and a distorted trigonal bipyramid geometry for the tin atoms.

  12. Copper(II) complexes with peptides based on the second cell binding site of fibronectin: metal coordination and ligand exchange kinetics. (United States)

    Pizzanelli, Silvia; Forte, Claudia; Pinzino, Calogero; Magrì, Antonio; La Mendola, Diego


    Copper(ii) complexes with short peptides based on the second cell binding site of fibronectin, PHSFN and PHSEN, have been characterized by potentiometric, UV-vis, CD, EPR and NMR spectroscopic methods. The histidine imidazole nitrogen is the anchoring site for the metal ion binding. Thermodynamic and spectroscopic evidence is given that the side chain oxygen donor atom of glutamyl residue in Ac-PHSEN-NH2 is also involved in the binding up to physiological pH. To determine ligand exchange kinetic parameters after the imidazole nitrogen anchoring, proton relaxation enhancement NMR data have been collected for the two hydrogen atoms of the imidazole ring in the temperature range 293-315 K at pH 5.2 and globally treated within different kinetic models for ligand exchange. The best fitting model involves two steps. In the first one, which is slow, a water molecule disengages a carbonyl or a carboxylate group coordinated to the metal ion in the complex formed by PHSFN or PHSEN, respectively. This stage is one order of magnitude slower for PHSEN, due to entropic effects. In the second step, which is fast, the complex just formed exchanges with the ligand. In this step, no appreciable differences are found for the two cases examined.

  13. Open coordination sites-induced structural diversity of a new series of Cu(II) complexes with tridentate aroylhydrazone Schiff base (United States)

    Xu, Guohong; Tang, Beibei; Gu, Leilei; Zhou, Pei; Li, Hui


    Six Cu(II) complexes containing the NO2 donor tridentate asymmetrical aroylhydrazone ligand (E)-4-hydroxy-N‧-((2-hydroxynaphthalen-1-yl)methylene)benzohydrazide (HL), namely, [Cu(L)Cl]·2H2O (1), [Cu(L)(CH3OH)2]·NO3 (2), [Cu(L)(NO3)(H2O)]·H2O (3), [Cu(L)(CH3OH)Cl]·CH3OH (4), [Cu(L)(SCN)(DMF)]·DMF (5) and {[Cu(L)(4,4‧-bipy)]ClO4·4DMF}n (6) have been synthesized and analysized by X-ray singal crystal diffraction. The structures of 1-6 are varied from zero-dimensional (0D) mononuclear complex to one-dimensional (1D) polymer based on the control of solvents, anions or auxiliary ligands, which can occupy the open coordination sites of Cu(II). Different hydrogen bonding interactions can also be observed in these complexes.

  14. The First Homoleptic Complex of Seven-Coordinated Osmium: Synthesis and Crystallographical Evidence of Pentagonal Bipyramidal Polyhedron of Heptacyanoosmate(IV

    Directory of Open Access Journals (Sweden)

    Eugenia V. Peresypkina


    Full Text Available The ligand exchange in (n-Bu4N2OsIVCl6 (n-Bu4N = tetra-n-butylammonium leads to the formation of the osmium(IV heptacyanide, the first fully inorganic homoleptic complex of heptacoordinated osmium. The single-crystal X-ray diffraction (SC-XRD study reveals the pentagonal bipyramidal molecular structure of the [Os(CN7]3− anion. The latter being a diamagnetic analogue of the highly anisotropic paramagnetic synthon, [ReIV(CN7]3− can be used for the synthesis of the model heterometallic coordination compounds for the detailed study and simulation of the magnetic properties of the low-dimensional molecular nanomagnets involving 5d metal heptacyanides.

  15. Formation of diphenylphosphanylbutadienyl complexes by insertion of two P-coordinated alkynylphosphanes into a PtbondC6F5 bond: detection of intermediate and reaction products. (United States)

    Ara, Irene; Forniés, Juan; García, Ana; Gómez, Julio; Lalinde, Elena; Moreno, M Teresa


    The reactions between cis-[M(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (M=Pt, Pd; R=Ph, tBu, Tol 2, 3) or cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu)] (R=Ph 4, Tol 5) and cis-[Pt(C(6)F(5))(2)(thf)(2)] 1 have been investigated. Whereas [M](PPh(2)CtriplebondCtBu)(2) ([M]=cis-M(C(6)F(5))(2)) is inert towards 1, the analogous reactions starting from [M](PPh(2)CtriplebondCR)(2) or [Pt](PPh(2)CtriplebondCR)(PPh(2)CtriplebondCtBu) (R=Ph, Tol) afford unusual binuclear species [Pt(C(6)F(5))(S)mu-[C(R')dbondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]M(C(6)F(5))(2)] (R=R'=Ph, Tol, M=Pt 6 a,c, M=Pd 7 a,c; M=Pt, R'=tBu, R=Ph 8, Tol 9) containing a bis(diphenylphosphanyl)butadienyl bridging ligand formed by an unprecedented sequential insertion reaction of two P-coordinated PPh(2)CtriplebondCR ligands into a PtbondC(6)F(5) bond. Although in solution the presence of coordinated solvent S (S=(thf)(x)(H(2)O)(y)) in 6, 7 is suggested by NMR spectroscopy, X-ray diffraction analyses of different crystals of the mixed complex [Pt(C(6)F(5))mu-[C(tBu)doublebondC(PPh(2))C(PPh(2))doublebondC(Tol)(C(6)F(5))]Pt(C(6)F(5))(2)] 9 unequivocally establish that in the solid state the steric crowding of the new diphenylbutadienyl ligand formed stabilizes an unusual coordinatively unsaturated T-shaped 3-coordinated platinum(II) center. Structure determinations of the mononuclear precursors cis-[Pt(C(6)F(5))(2)(PPh(2)CtriplebondCR)(2)] (R=Ph, tBu, Tol) have been carried out to evaluate the factors affecting the insertion processes. The reactions of the platinum complexes 6 towards neutral ligands (L=CO, py, PPh(2)H, CNtBu) in a 1:1 molar ratio afford related diplatinum derivatives 10-13, whereas treatment with CNtBu (1:2 molar ratio) or 2,2'-bipy (1:1 molar ratio) results in the opening of the chelating ring to give cis,cis-[Pt(C(6)F(5))(L)(2)mu-[1-kappaC(1):2-kappaPP'-C(R)doublebondC(PPh(2))C(PPh(2))doublebondC(R)(C(6)F(5))]Pt(C(6)F(5))(2)] (14, 15). The unsaturated or solvento

  16. Binuclear Pt-Tl bonded complex with square pyramidal coordination around Pt: a combined multinuclear NMR, EXAFS, UV-Vis, and DFT/TDDFT study in dimethylsulfoxide solution. (United States)

    Purgel, Mihály; Maliarik, Mikhail; Glaser, Julius; Platas-Iglesias, Carlos; Persson, Ingmar; Tóth, Imre


    The structure and bonding of a new Pt-Tl bonded complex formed in dimethylsulfoxide (dmso), (CN)(4)Pt-Tl(dmso)(5)(+), have been studied by multinuclear NMR and UV-vis spectroscopies, and EXAFS measurements in combination with density functional theory (DFT) and time dependent density functional theory (TDDFT) calculations. This complex is formed following the equilibrium reaction Pt(CN)(4)(2-) + Tl(dmso)(6)(3+) ⇆ (CN)(4)Pt-Tl(dmso)(5)(+) + dmso. The stability constant of the Pt-Tl bonded species, as determined using (13)C NMR spectroscopy, amounts to log K = 2.9 ± 0.2. The (NC)(4)Pt-Tl(dmso)(5)(+) species constitutes the first example of a Pt-Tl bonded cyanide complex in which the sixth coordination position around Pt (in trans with respect to the Tl atom) is not occupied. The spectral parameters confirm the formation of the metal-metal bond, but differ substantially from those measured earlier in aqueous solution for complexes (CN)(5)Pt-Tl(CN)(n)(H(2)O)(x)(n-) (n = 0-3). The (205) Tl NMR chemical shift, δ = 75 ppm, is at extraordinary high field, while spin-spin coupling constant, (1)J(Pt-Tl) = 93 kHz, is the largest measured to date for a Pt-Tl bond in the absence of supporting bridging ligands. The absorption spectrum is dominated by two strong absorption bands in the UV region that are assigned to MMCT (Pt → Tl) and LMCT (dmso → Tl) bands, respectively, on the basis of MO and TDDFT calculations. The solution of the complex has a bright yellow color as a result of a shoulder present on the low energy side of the band at 355 nm. The geometry of the (CN)(4)Pt-Tl core can be elucidated from NMR data, but the particular stoichiometry and structure involving the dmso ligands are established by using Tl and Pt L(III)-edge EXAFS measurements. The Pt-Tl bond distance is 2.67(1) Å, the Tl-O bond distance is 2.282(6) Å, and the Pt-C-N entity is linear with Pt-C and Pt···N distances amounting to 1.969(6) and 3.096(6) Å, respectively. Geometry optimizations on

  17. Influence of the π-coordinated arene on the anticancer activity of ruthenium(II carbohydrate organometallic complexes

    Directory of Open Access Journals (Sweden)

    Muhammad eHanif


    Full Text Available The synthesis and in vitro cytotoxicity of a series of RuII(arene complexes with carbohydrate-derived phosphite ligands and various arene co-ligands is described. The arene ligand has a strong influence on the in vitro anticancer activity of this series of compounds, which correlates fairly well with cellular accumulation. The most lipophilic compound bearing a biphenyl moiety and a cyclohexylidene-protected carbohydrate is the most cytotoxic with unprecedented IC50 values for the compound class in three human cancer cell lines. This compound shows reactivity to the DNA model nucleobase 9-ethylguanine, but does not alter the secondary structure of plasmid DNA indicating that other biological targets are responsible for its cytotoxic effect.

  18. Seven-coordinate iron complex as a ditopic receptor for lithium salts: study of host-guest interactions and substitution behavior. (United States)

    Sarauli, David; Popova, Vesselina; Zahl, Achim; Puchta, Ralph; Ivanović-Burmazović, Ivana


    Interactions between the seven-coordinate tweezerlike [Fe(dapsox)(H2O)2]ClO4 complex (H2dapsox = 2,6-diacetylpyridine-bis(semioxamazide)) with different lithium salts (LiOTf, LiClO4, LiBF4, and LiPF6) in CH3CN have been investigated by electrochemical, spectrophotometric, 7Li and 19F NMR, kinetic, and DFT methods. It has been demonstrated that this complex acts as ditopic receptor, showing spectral and electrochemical ion-pair-sensing capability for different lithium salts. In general, the apparent binding constants for lithium salts increase in the order LiOTf LiBF4. From the electrochemical measurements, the apparent lithium salt binding constants for the Fe(III) and Fe(II) forms of the complex have been obtained, suggesting a stronger host-guest interaction with the reduced form of the complex. In the presence of LiPF6, the solution chemistry is more complex because of the hydrolysis of PF6-. The kinetics of the complexation of [Fe(dapsox)(CH3CN)2]+ by thiocyanate at -15 degrees C in acetonitrile in the presence of 0.2 M NBu4OTf shows two steps with the following rate constants and activation parameters: k(1) = 411 +/- 14 M(-1) s(-1); DeltaH(1) not equal = 9 +/- 2 kJ mol(-1); DeltaS1 not equal = -159 +/- 6 J K(-1) mol(-1); k(2) = 52 +/- 1 M(-1) s(-1); DeltaH(2) not equal = 4 +/- 1 kJ mol(-1); DeltaS(2) not equal = -195 +/- 3 J K(-1) mol(-1). The very negative DeltaS not equal values are consistent with an associative (A) mechanism. Under the same conditions but with 0.2 M LiOTf, k1Li and k2Li are 1605 +/- 51 and 106 +/- 2 M(-1) s(-1), respectively. The increased rate constants for the {[Fe(dapsox)(CH3CN)2] x LiOTf}+ adduct are in agreement with an associative mechanism. Kinetic and spectrophotometric titration measurements show stronger interaction between the lithium salt and the anion-substituted forms, [Fe(dapsox)(CH3CN)(NCS)] and [Fe(dapsox)(NCS)2]-, of the complex. These experiments demonstrate that in nonaqueous media lithium salts cannot be simply used as

  19. Coordinating Work with Groupware

    DEFF Research Database (Denmark)

    Pors, Jens Kaaber; Simonsen, Jesper


    One important goal of employing groupware is to make possible complex collaboration between geographically distributed groups. This requires a dual transformation of both technology and work practice. The challenge is to re­duce the complexity of the coordination work by successfully inte­grating...

  20. Sterically congested uranyl complexes with seven-coordination of the UO{sub 2} unit: the peculiar ligation mode of nitrate in [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] complexes

    Energy Technology Data Exchange (ETDEWEB)

    Berthet, J. C.; Thuery, P.; Dognon, J. P.; Ephritikhine, M. [CEA Saclay, DSM, Serv Chim Mol, CNRS, URA 331, F-91191 Gif Sur Yvette, (France); Guillaneux, D. [CEA VALRHO, DEN/VRH/DRCP/SCPS/LCAM, F-30207 Bagnols Sur Ceze, (France)


    Addition of 1 or 2 molar equiv of Rbtp [Rbtp 2,6-bis(5,6-dialkyl-1,2,4-triazin-3-yl)pyridine; R = Me, Pr{sup n} to UO{sub 2}(OTf){sub 2} in anhydrous acetonitrile gave the neutral compounds [UO{sub 2}(OTf){sub 2}(Rbtp)] [RMe (1), {sup n}Pr (2)] and the cationic complexes [UO{sub 2}(Rbtp){sub 2}][OTf]{sub 2} [R = Me (3), Pr{sup n} (4)], respectively. No equilibrium between the mono and bis(Rbtp) complexes or between [UO{sub 2}(Rbtp){sub 2}][OTf]{sub 2} and free Rbtp in acetonitrile was detected by NMR spectroscopy. The crystal structures of 1 and 3 resemble those of their ter-pyridine analogues, and 3 is another example of a uranyl complex with the uranium atom in the unusual rhombohedral environment. In the presence of 1 molar equiv of Rbtp in acetonitrile, UO{sub 2}(NO{sub 3}){sub 2} was in equilibrium with [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] and the formation of the bis adduct was not observed, even with an excess of Rbtp. The X-ray crystal structures of [UO{sub 2}(NO{sub 3}){sub 2}(Rbtp)] [R = Me (5), Pr{sup n} (6)] reveal a particular coordination geometry with seven coordinating atoms around the UO{sub 2} fragment. The large steric crowding in the equatorial girdle forces the bidentate nitrate ligands to be almost perpendicular to the mean equatorial plane, inducing bending of the UO{sub 2} fragment. The dinuclear oxo compound [U(CyMe{sub 4}btbp){sub 2}({mu}-O)UO{sub 2}(NO{sub 3}){sub 3}][OTf] (7), which was obtained fortuitously from a 1:21 mixture of U(OTf){sub 4}, CyMe{sub 4}btbp, and UO{sub 2}(NO{sub 3}){sub 2} [CyMe{sub 4}btbp6,6'-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2 = '-bipyridine] is a very rare example of a mixed valence complex involving covalently bound U(IV) and U(VI) ions; its crystal structure also exhibits a seven coordinate uranyl moiety, with one bidentate nitrate group almost parallel to the UO{sub 2} fragment. The distinct structural features of [UO{sub 2}(k{sup 2}-NO{sub 3}){sub 2}(Mebtp)], with its high

  1. Coordination Compounds of Niobium(IV) Oxide Dihalides Including the Synthesis and the Crystallographic Characterization of NHC Complexes. (United States)

    Bortoluzzi, Marco; Ferretti, Eleonora; Marchetti, Fabio; Pampaloni, Guido; Pinzino, Calogero; Zacchini, Stefano


    The 1:1 molar reactions of NbOX3 with SnBu3H, in toluene at 0 °C in the presence of oxygen/nitrogen donors, resulted in the formation of NbOX2L2 (X = Cl, L2 = dme, 2a; X = Br, L2 = dme, 2b; X = Cl, L = thf, 2c; X = Cl, L = NCMe, 2d; dme = 1,2-dimethoxyethane, thf = tetrahydrofuran), in good yields. The 1:2 reactions of freshly prepared 2d and 2b with the bulky NHC ligands 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, Imes, and 1,3-bis(2,6-dimethylphenyl)imidazol-2-ylidene, Ixyl, respectively, afforded the complexes NbOCl2(Imes)2, 3, and NbOBr2(Ixyl)2, 4, in 50-60% yields. The reactions of 2b with NaOR, in tetrahydrofuran, gave NbOCl(OR) (R = Ph, 5; R = Me, 6) in about 60% yields. All the products were characterized by analytical and spectroscopic techniques; moreover DFT calculations were carried out in order to shed light on synthetic and structural features. Compounds 3 and 4, whose molecular structures have been ascertained by X-ray diffraction, represent very rare examples of crystallographically characterized niobium-NHC systems.

  2. A series of novel 1D coordination polymers constructed from metal?quinolone complex fragments linked by aromatic dicarboxylate ligands (United States)

    He, Jiang-Hong; Xiao, Dong-Rong; Yan, Shi-Wei; Sun, Dian-Zhen; Chen, Hai-Yan; Wang, Xin; Yang, Juan; Ye, Zhong-Li; Yuan, Ruo; Wang, En-Bo


    Self-assembly of quinolones with metal salts in the presence of aromatic dicarboxylate ligands affords a series of novel 1D metal-quinolone complexes, namely [Mn(Hppa)(oba)]·3H2O (1), [Co(Hppa)(oba)]·3.25H2O (2), [Zn(Hppa)(sdba)]·1.5H2O (3), [Mn(Hcf)(bpda)(H2O)]·2H2O (4), [Mn(Hppa)2(bpdc)] (5) and [Mn(Hlome)2(bpdc)]·4H2O (6) (Hppa = Pipemidic acid, Hcf = ciprofloxacin, Hlome = lomefloxacin). The structures of compounds 1-3 consist of novel polymeric chains spanning two different directions, which display an intriguing 1D → 3D inclined polycatenation of supramolecular ladders. Compound 4 exhibits a chain compound formed from the interconnection of [Mn2(Hcf)2(μ-CO2)2] dimers with bpda ligands. Compounds 5 and 6 are similar chain compounds constructed from [Mn(Hppa)2] (or [Mn(Hlome)2]) fragments linked by bpdc ligands. The magnetic properties of 4 have been studied, which indicate the existence of antiferromagnetic interactions. Furthermore, the luminescent properties of compound 3 are discussed.

  3. Coordinated destruction of cellular messages in translation complexes by the gammaherpesvirus host shutoff factor and the mammalian exonuclease Xrn1. (United States)

    Covarrubias, Sergio; Gaglia, Marta M; Kumar, G Renuka; Wong, Wesley; Jackson, Andrew O; Glaunsinger, Britt A


    Several viruses encode factors that promote host mRNA degradation to silence gene expression. It is unclear, however, whether cellular mRNA turnover pathways are engaged to assist in this process. In Kaposi's sarcoma-associated herpesvirus this phenotype is enacted by the host shutoff factor SOX. Here we show that SOX-induced mRNA turnover is a two-step process, in which mRNAs are first cleaved internally by SOX itself then degraded by the cellular exonuclease Xrn1. SOX therefore bypasses the regulatory steps of deadenylation and decapping normally required for Xrn1 activation. SOX is likely recruited to translating mRNAs, as it cosediments with translation initiation complexes and depletes polysomes. Cleaved mRNA intermediates accumulate in the 40S fraction, indicating that recognition occurs at an early stage of translation. This is the first example of a viral protein commandeering cellular mRNA turnover pathways to destroy host mRNAs, and suggests that Xrn1 is poised to deplete messages undergoing translation in mammalian cells.

  4. Coordinated destruction of cellular messages in translation complexes by the gammaherpesvirus host shutoff factor and the mammalian exonuclease Xrn1.

    Directory of Open Access Journals (Sweden)

    Sergio Covarrubias


    Full Text Available Several viruses encode factors that promote host mRNA degradation to silence gene expression. It is unclear, however, whether cellular mRNA turnover pathways are engaged to assist in this process. In Kaposi's sarcoma-associated herpesvirus this phenotype is enacted by the host shutoff factor SOX. Here we show that SOX-induced mRNA turnover is a two-step process, in which mRNAs are first cleaved internally by SOX itself then degraded by the cellular exonuclease Xrn1. SOX therefore bypasses the regulatory steps of deadenylation and decapping normally required for Xrn1 activation. SOX is likely recruited to translating mRNAs, as it cosediments with translation initiation complexes and depletes polysomes. Cleaved mRNA intermediates accumulate in the 40S fraction, indicating that recognition occurs at an early stage of translation. This is the first example of a viral protein commandeering cellular mRNA turnover pathways to destroy host mRNAs, and suggests that Xrn1 is poised to deplete messages undergoing translation in mammalian cells.

  5. Integrating complex functions: coordination of nuclear pore complex assembly and membrane expansion of the nuclear envelope requires a family of integral membrane proteins. (United States)

    Schneiter, Roger; Cole, Charles N


    The nuclear envelope harbors numerous large proteinaceous channels, the nuclear pore complexes (NPCs), through which macromolecular exchange between the cytosol and the nucleoplasm occurs. This double-membrane nuclear envelope is continuous with the endoplasmic reticulum and thus functionally connected to such diverse processes as vesicular transport, protein maturation and lipid synthesis. Recent results obtained from studies in Saccharomyces cerevisiae indicate that assembly of the nuclear pore complex is functionally dependent upon maintenance of lipid homeostasis of the ER membrane. Previous work from one of our laboratories has revealed that an integral membrane protein Apq12 is important for the assembly of functional nuclear pores. Cells lacking APQ12 are viable but cannot grow at low temperatures, have aberrant NPCs and a defect in mRNA export. Remarkably, these defects in NPC assembly can be overcome by supplementing cells with a membrane fluidizing agent, benzyl alcohol, suggesting that Apq12 impacts the flexibility of the nuclear membrane, possibly by adjusting its lipid composition when cells are shifted to a reduced temperature. Our new study now expands these findings and reveals that an essential membrane protein, Brr6, shares at least partially overlapping functions with Apq12 and is also required for assembly of functional NPCs. A third nuclear envelope membrane protein, Brl1, is related to Brr6, and is also required for NPC assembly. Because maintenance of membrane homeostasis is essential for cellular survival, the fact that these three proteins are conserved in fungi that undergo closed mitoses, but are not found in metazoans or plants, may indicate that their functions are performed by proteins unrelated at the primary sequence level to Brr6, Brl1 and Apq12 in cells that disassemble their nuclear envelopes during mitosis.

  6. Coordination and processing of DNA ends during double-strand break repair: the role of the bacteriophage T4 Mre11/Rad50 (MR) complex. (United States)

    Almond, Joshua R; Stohr, Bradley A; Panigrahi, Anil K; Albrecht, Dustin W; Nelson, Scott W; Kreuzer, Kenneth N


    The in vivo functions of the bacteriophage T4 Mre11/Rad50 (MR) complex (gp46/47) in double-strand-end processing, double-strand break repair, and recombination-dependent replication were investigated. The complex is essential for T4 growth, but we wanted to investigate the in vivo function during productive infections. We therefore generated a suppressed triple amber mutant in the Rad50 subunit to substantially reduce the level of complex and thereby reduce phage growth. Growth-limiting amounts of the complex caused a concordant decrease in phage genomic recombination-dependent replication. However, the efficiencies of double-strand break repair and of plasmid-based recombination-dependent replication remained relatively normal. Genetic analyses of linked markers indicated that double-strand ends were less protected from nuclease erosion in the depleted infection and also that end coordination during repair was compromised. We discuss models for why phage genomic recombination-dependent replication is more dependent on Mre11/Rad50 levels when compared to plasmid recombination-dependent replication. We also tested the importance of the conserved histidine residue in nuclease motif I of the T4 Mre11 protein. Substitution with multiple different amino acids (including serine) failed to support phage growth, completely blocked plasmid recombination-dependent replication, and led to the stabilization of double-strand ends. We also constructed and expressed an Mre11 mutant protein with the conserved histidine changed to serine. The mutant protein was found to be completely defective for nuclease activities, but retained the ability to bind the Rad50 subunit and double-stranded DNA. These results indicate that the nuclease activity of Mre11 is critical for phage growth and recombination-dependent replication during T4 infections.

  7. Synthesis, Crystal Structure and Fluorescence Property of a Five- and Six-coordinated Trinuclear Zinc(II) Complex:{[ZnL(OAc)]2Zn}·CH3COCH3

    Institute of Scientific and Technical Information of China (English)

    DONG,Wen-Kui; ZHANG,Yan-Ping; ZHAO,Chun-Yu; TANG,Xiao-Lu; L(U),Zhong-Wu; ZOU,Zheng


    A novel linear trinuclear zinc(II) complex, {[ZnL(OAc)]2Zn}·CH3COCH3 (H2L: ethylenedioxybis(5-bromo-2-hydroxybenzylideneamino)), has been synthesized and structurally characterized. X-ray crystal structure of the complex reveals that three zinc(II) ions are coordinated by two tetradentate L2- units and two acetate ions acting as bridging groups. The coordination geometry around the terminal Zn(1) or Zn(1)#1 atom approaches a distorted square pyramid. The coordination sphere of the central Zn(2) atom constitutes a slightly distorted octahedral geometry. The blue-green emission from the zinc(II) complex can be observed, where the maximum emission wavelength is at 464 nm.

  8. Synthesis Characterization and Biological Activities of Coordination Compounds of 4-Hydroxy-3-nitro-2H-chromen-2-one and Its Aminoethanoic Acid and Pyrrolidine-2-carboxylic Acid Mixed Ligand Complexes (United States)

    Akinkunmi, Ezekiel; Obuotor, Efere; Olawuni, Idowu; Isabirye, David; Jordaan, Johan


    Coordination compounds of 4-hydroxy-3-nitro-2H-chromen-2-one and their mixed ligand complexes with aminoethanoic acid and pyrrolidine-2-carboxylic acid were synthesized by the reaction of Cu(II) and Zn(II) salts in molar ratio 1 : 2 for the coumarin complexes and 1 : 1 : 1 for the mixed ligand complexes, in basic media. The compounds formed were characterized using infrared, Uv-vis spectrophotometric analyses, mass spectrometry, magnetic susceptibility measurements, and EDX analyses. It was concluded that 4-hydroxy-3-nitro-2H-chromen-2-one coordinated as a monobasic ligand for all the complexes; it also coordinated via the carbonyl moiety in the case of the Cu(II) mixed ligand complexes. Similarly it was proposed that the amino acids also coordinated in a bidentate fashion via their amino nitrogen and carboxylate oxygen atoms. The synthesized compounds were screened for their antimicrobial and cytotoxic activities. The complexes exhibited marginal antimicrobial activity but good cytotoxic activity. PMID:28270743

  9. Uranyl ion coordination (United States)

    Evans, H.T.


    A review of the known crystal structures containing the uranyl ion shows that plane-pentagon coordination is equally as prevalent as plane-square or plane-hexagon. It is suggested that puckered-hexagon configurations of OH - or H2O about the uranyl group will tend to revert to plane-pentagon coordination. The concept of pentagonal coordination is invoked for possible explanations of the complex crystallography of the natural uranyl hydroxides and the unusual behavior of polynuclear ions in hydrolyzed uranyl solutions.

  10. Co(II), Ni(II), Cu(II) and Zn(II) complexes of a bipyridine bis-phenol conjugate: generation and properties of coordinated radical species. (United States)

    Arora, Himanshu; Philouze, Christian; Jarjayes, Olivier; Thomas, Fabrice


    Four bis-phenolate complexes [Zn(II)L], [Ni(II)L], [Cu(II)L] and [Co(II)L] (where [H(2)L = 2,2'-[2,2']bipyridinyl-6-yl-bis-4,6-di-tert-butylphenol] have been synthesized. The copper(II) and nickel(II) complexes have been characterized by X-ray diffraction, showing a metal ion within a square planar geometry, slightly distorted towards tetrahedral. The cyclic voltametry (CV) curve of [Zn(II)L] consists of a single bi-electronic reversible wave at 0.06 V vs. Fc/Fc(+). The electrochemically generated dication is a diradical species [Zn(II)L˙˙](2+) that exhibits the typical phenoxyl π-π* band at 395 nm. It is EPR-silent due to magnetic interactions between the phenoxyl moieties. The CV curves of [Ni(II)L] and [Cu(II)L] exhibit two distinct ligand-centred one-electron oxidation waves. The first one is observed at E(1/2)(1) = 0.38 and 0.40 V for the nickel and copper complex, respectively, and corresponds to the formation of M(II)-coordinated phenoxyl radicals. Accordingly, [Ni(II)L˙](+) exhibits a strong absorption band at 960 nm and an (S = ½) EPR signal centred at g(iso) = 2.02. [Cu(II)L˙](+) is EPR-silent, in agreement with a magnetic coupling between the metal and the radical spin. In contrast with the other complexes, [Co(II)L] was found to react with dioxygen (mostly in the presence of pyridine), giving rise to a stable (S = ½) superoxo radical complex [Co(III)L(Py)(O(2)˙)]. One-electron oxidation of [Co(II)L] at -0.01 V affords a diamagnetic cobalt(III) complex [Co(III)L](+) that is inert towards O(2) binding, whereas two-electron oxidation leads to the paramagnetic phenoxyl radical species [Co(III)L˙](+) whose EPR spectrum features an (S = ½) signal at g(iso) = 2.00.

  11. Structure, ligands and substrate coordination of the oxygen-evolving complex of photosystem II in the S2 state: a combined EPR and DFT study. (United States)

    Lohmiller, Thomas; Krewald, Vera; Navarro, Montserrat Pérez; Retegan, Marius; Rapatskiy, Leonid; Nowaczyk, Marc M; Boussac, Alain; Neese, Frank; Lubitz, Wolfgang; Pantazis, Dimitrios A; Cox, Nicholas


    The S2 state of the oxygen-evolving complex of photosystem II, which consists of a Mn4O5Ca cofactor, is EPR-active, typically displaying a multiline signal, which arises from a ground spin state of total spin ST = 1/2. The precise appearance of the signal varies amongst different photosynthetic species, preparation and solvent conditions/compositions. Over the past five years, using the model species Thermosynechococcus elongatus, we have examined modifications that induce changes in the multiline signal, i.e. Ca(2+)/Sr(2+)-substitution and the binding of ammonia, to ascertain how structural perturbations of the cluster are reflected in its magnetic/electronic properties. This refined analysis, which now includes high-field (W-band) data, demonstrates that the electronic structure of the S2 state is essentially invariant to these modifications. This assessment is based on spectroscopies that examine the metal centres themselves (EPR, (55)Mn-ENDOR) and their first coordination sphere ligands ((14)N/(15)N- and (17)O-ESEEM, -HYSCORE and -EDNMR). In addition, extended quantum mechanical models from broken-symmetry DFT now reproduce all EPR, (55)Mn and (14)N experimental magnetic observables, with the inclusion of second coordination sphere ligands being crucial for accurately describing the interaction of NH3 with the Mn tetramer. These results support a mechanism of multiline heterogeneity reported for species differences and the effect of methanol [Biochim. Biophys. Acta, Bioenerg., 2011, 1807, 829], involving small changes in the magnetic connectivity of the solvent accessible outer MnA4 to the cuboidal unit Mn3O3Ca, resulting in predictable changes of the measured effective (55)Mn hyperfine tensors. Sr(2+) and NH3 replacement both affect the observed (17)O-EDNMR signal envelope supporting the assignment of O5 as the exchangeable μ-oxo bridge and it acting as the first site of substrate inclusion.

  12. The physical chemistry of coordinated aqua-, ammine-, and mixed-ligand Co2+ complexes: DFT studies on the structure, energetics, and topological properties of the electron density. (United States)

    Varadwaj, Pradeep R; Marques, Helder M


    Spin-unrestricted DFT-X3LYP/6-311++G(d,p) calculations have been performed on a series of complexes of the form [Co(H(2)O)(6-n)(NH(3))(n)](2+) (n = 0-6) to examine their equilibrium gas-phase structures, energetics, and electronic properties in their quartet electronic ground states. In all cases Co(2+) in the energy-minimised structures is in a pseudo-octahedral environment. The calculations overestimate the Co-O and Co-N bond lengths by 0.04 and 0.08 A, respectively, compared to the crystallographically observed mean values. There is a very small Jahn-Teller distortion in the structure of [Co(H(2)O)(6)](2+) which is in contrast to the very marked distortions observed in most (but not all) structures of this cation that have been observed experimentally. The successive replacement of ligated H(2)O by NH(3) leads to an increase in complex stability by 6 +/- 1 kcal mol(-1) per additional NH(3) ligand. Calculations using UB3LYP give stabilisation energies of the complexes about 5 kcal mol(-1) smaller and metal-ligand bond lengths about 0.005 A longer than the X3LYP values since the X3LYP level accounts for the London dispersion energy contribution to the overall stabilisation energy whilst it is largely missing at the B3LYP level. From a natural population analysis (NPA) it is shown that the formation of these complexes is accompanied by ligand-to-metal charge transfer the extent of which increases with the number of NH(3) ligands in the coordination sphere of Co(2+). From an examination of the topological properties of the electron charge density using Bader's quantum theory of atoms in molecules it is shown that the electron density rho(c) at the Co-O bond critical points is generally smaller than that at the Co-N bond critical points. Hence Co-O bonds are weaker than Co-N bonds in these complexes and the stability increases as NH(3) replaces H(2)O in the metal's coordination sphere. Several indicators, including the sign and magnitude of the Laplacian of the

  13. Formation of a ruthenium(IV)-oxo complex by electron-transfer oxidation of a coordinatively saturated ruthenium(II) complex and detection of oxygen-rebound intermediates in C-H bond oxygenation. (United States)

    Kojima, Takahiko; Nakayama, Kazuya; Ikemura, Kenichiro; Ogura, Takashi; Fukuzumi, Shunichi


    A coordinatively saturated ruthenium(II) complex having tetradentate tris(2-pyridylmethyl)amine (TPA) and bidentate 2,2'-bipyridine (bpy), [Ru(TPA)(bpy)](2+) (1), was oxidized by a Ce(IV) ion in H(2)O to afford a Ru(IV)-oxo complex, [Ru(O)(H(+)TPA)(bpy)](3+) (2). The crystal structure of the Ru(IV)-oxo complex 2 was determined by X-ray crystallography. In 2, the TPA ligand partially dissociates to be in a facial tridentate fashion and the uncoordinated pyridine moiety is protonated. The spin state of 2, which showed paramagnetically shifted NMR signals in the range of 60 to -20 ppm, was determined to be an intermediate spin (S = 1) by the Evans' method with (1)H NMR spectroscopy in acetone-d(6). The reaction of 2 with various oraganic substrates in acetonitrile at room temperature afforded oxidized and oxygenated products and a solvent-bound complex, [Ru(H(+)TPA)(bpy)(CH(3)CN)], which is intact in the presence of alcohols. The oxygenation reaction of saturated C-H bonds with 2 proceeds by two-step processes: the hydrogen abstraction with 2, followed by the dissociation of the alcohol products from the oxygen-rebound complexes, Ru(III)-alkoxo complexes, which were successfully detected by ESI-MS spectrometry. The kinetic isotope effects in the first step for the reaction of dihydroanthrathene (DHA) and cumene with 2 were determined to be 49 and 12, respectively. The second-order rate constants of C-H oxygenation in the first step exhibited a linear correlation with bond dissociation energies of the C-H bond cleavage.

  14. Two pathways for electrocatalytic oxidation of hydrogen by a nickel bis(diphosphine) complex with pendant amines in the second coordination sphere. (United States)

    Yang, Jenny Y; Smith, Stuart E; Liu, Tianbiao; Dougherty, William G; Hoffert, Wesley A; Kassel, W Scott; Rakowski DuBois, M; DuBois, Daniel L; Bullock, R Morris


    A nickel bis(diphosphine) complex containing pendant amines in the second coordination sphere, [Ni(P(Cy)2N(t-Bu)2)2](BF4)2 (P(Cy)2N(t-Bu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex gives three isomers of the doubly protonated Ni(0) complex [Ni(P(Cy)2N(t-Bu)2H)2](BF4)2. Using the pKa values and Ni(II/I) and Ni(I/0) redox potentials in a thermochemical cycle, the free energy of hydrogen addition to [Ni(P(Cy)2N(t-Bu)2)2](2+) was determined to be -7.9 kcal mol(-1). The catalytic rate observed in dry acetonitrile for the oxidation of H2 depends on base size, with larger bases (NEt3, t-BuNH2) resulting in much slower catalysis than n-BuNH2. The addition of water accelerates the rate of catalysis by facilitating deprotonation of the hydrogen addition product before oxidation, especially for the larger bases NEt3 and t-BuNH2. This catalytic pathway, where deprotonation occurs prior to oxidation, leads to an overpotential that is 0.38 V lower compared to the pathway where oxidation precedes proton movement. Under the optimal conditions of 1.0 atm H2 using n-BuNH2 as a base and with added water, a turnover frequency of 58 s(-1) is observed at 23 °C.

  15. Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li(+)-, Na(+)- and K(+)-uranyl(VI)-peroxide-carbonate systems. (United States)

    Zanonato, Pier Luigi; Szabó, Zoltán; Vallet, Valerie; Di Bernardo, Plinio; Grenthe, Ingmar


    The constitution and equilibrium constants of ternary uranyl(vi) peroxide carbonate complexes [(UO2)p(O2)q(CO3)r](2(p-q-r)) have been determined at 0 °C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; (17)O NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O2)(CO3)]n", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li(+), Na(+), K(+) and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by μ-η(2)-η(2) bridged peroxide-ions. The templating effect is due to the coordination of the M(+)-ions to the uranyl oxygen atoms, where the coordination of Li(+) results in the formation of Li[(UO2)(O2)(CO3)]4(7-), Na(+) and K(+) in the formation of Na/K[(UO2)(O2)(CO3)]5(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-). The NMR spectra demonstrate that the coordination of Na(+) in the five- and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O2)(CO3)]5(9-) and TMA[(UO2)(O2)(CO3)]6(11-) is slow on the (17)O chemical shift time-scale, while the exchange between TMA[(UO2)(O2)(CO3)]6(11-) and Na[(UO2)(O2)(CO3)]6(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed.

  16. Versatile coordination modes of bis[5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl]alkanes in Cu(II) complexes. (United States)

    Gusev, Alexey N; Nemec, Ivan; Herchel, Radovan; Bayjyyev, Eziz; Nyshchimenko, Galyna A; Alexandrov, Grigory G; Eremenko, Igor L; Trávníček, Zdeněk; Hasegawa, Miki; Linert, Wolfgang


    Nine new mononuclear and polynuclear Cu(II) complexes [Cu(H2L(2))Cl]Cl·3H2O (1), [Cu(H2L(3))Cl]Cl·H2O (2), [Cu(H2L(4))Cl]Cl·2.5H2O (3), [Cu3(μ(3)-L(1))2(H2O)3](ClO4)2·H2O (4), [Cu4(μ-HL(1))4](ClO4)8·CH3OH·5H2O (5), [Cu2(HL(3))2](ClO4)2·2H2O (6a), [Cu2(μ-HL(3))2](ClO4)2·H2O (6b), [Cu2(μ-HL(3))(L(3))Cu(teta)](ClO4)3·2H2O (7) and [Cu2(H2L(3))2(ox)](ClO4)2·2H2O·2MeOH (8) containing [5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl]alkanes (H2L(n), n = 1-4) in combination with other ligands, such as chlorido, aqua, triethylenetetramine (teta) and/or oxalato (ox(2-)), were synthesized and characterized by various techniques such as elemental analysis, FTIR, NMR and UV-Vis spectroscopy. X-ray structures of H2L(3) and H2L(4) as well as complexes 1-8 were determined. The X-ray structures revealed that relatively small composition and structural changes in the H2L(n) ligands have a substantial impact on the coordination geometries of the complexes themselves as well as on their resulting magnetic properties. It has been found that the geometries of the complexes vary from square-pyramidal to trigonal-bipyramidal (with τ ranging from 0.00 to 0.96) and, moreover, that the trigonal bipyramidal geometry becomes more preferable with the increase in the length of the polymethylene chain within the corresponding H2L(n) ligand. The magnetic properties of the polynuclear compounds 4, 5, 6, 7 and 8 were analysed using the spin Hamiltonian formalism, which revealed the presence of antiferromagnetic exchange in the polynuclear systems mediated by the title ligands. The significant effect of the geometric parameters on the Cu···Cu exchange interactions in the polynuclear complexes is discussed.

  17. Comparative studies of mononuclear Ni(II) and UO2(II) complexes having bifunctional coordinated groups: synthesis, thermal analysis, X-ray diffraction, surface morphology studies and biological evaluation. (United States)

    Fahem, Abeer A


    Two Schiff base ligands derived from condensation of phthalaldehyde and o-phenylenediamine in 1:2 (L(1)) and 2:1 (L(2)) having bifunctional coordinated groups (NH(2) and CHO groups, respectively) and their metal complexes with Ni(II) and UO(2)(II) have been synthesized and characterized by elemental analysis, molar conductance, magnetic susceptibilities and spectral data (IR, (1)H NMR, mass and solid reflectance) as well as thermal, XRPD and SEM analysis. The formula [Ni(L(1))Cl(2)]·2.5H(2)O, [UO(2)(L(1))(NO(3))(2)]·2H(2)O, [Ni(L(2))Cl(2)]·1.5H(2)O and [UO(2)(L(2))(NO(3))(2)] have been suggested for the complexes. The vibrational spectral data show that the ligands behave as neutral ligands and coordinated to the metal ions in a tetradentate manner. The Ni(II) complexes are six coordinate with octahedral geometry and the ligand field parameters: D(q), B, β and LFSE were calculated while, UO(2)(II) complexes are eight coordinate with dodecahedral geometry and the force constant, F(U-O) and bond length, R(U-O) were calculated. The thermal decomposition of complexes ended with metal chloride/nitrate as a final product and the highest thermal stability is displayed by [UO(2)(L(2))(NO(3))(2)] complex. The X-ray powder diffraction data revealed the formation of nano sized crystalline complexes. The SEM analysis provides the morphology of the synthesized compounds and SEM image of [UO(2)(L(2))(NO(3))(2)] complex exhibits nano rod structure. The growth-inhibiting potential of the ligands and their complexes has been assessed against a variety of bacterial and fungal strains.

  18. Introduction to Coordination Chemistry

    CERN Document Server

    Lawrance, Geoffrey Alan


    Introduction to Coordination Chemistry examines and explains how metals and molecules that bind as ligands interact, and the consequences of this assembly process. This book describes the chemical and physical properties and behavior of the complex assemblies that form, and applications that may arise as a result of these properties. Coordination complexes are an important but often hidden part of our world?even part of us?and what they do is probed in this book. This book distills the essence of this topic for undergraduate students and for research scientists.

  19. Poisson Coordinates. (United States)

    Li, Xian-Ying; Hu, Shi-Min


    Harmonic functions are the critical points of a Dirichlet energy functional, the linear projections of conformal maps. They play an important role in computer graphics, particularly for gradient-domain image processing and shape-preserving geometric computation. We propose Poisson coordinates, a novel transfinite interpolation scheme based on the Poisson integral formula, as a rapid way to estimate a harmonic function on a certain domain with desired boundary values. Poisson coordinates are an extension of the Mean Value coordinates (MVCs) which inherit their linear precision, smoothness, and kernel positivity. We give explicit formulas for Poisson coordinates in both continuous and 2D discrete forms. Superior to MVCs, Poisson coordinates are proved to be pseudoharmonic (i.e., they reproduce harmonic functions on n-dimensional balls). Our experimental results show that Poisson coordinates have lower Dirichlet energies than MVCs on a number of typical 2D domains (particularly convex domains). As well as presenting a formula, our approach provides useful insights for further studies on coordinates-based interpolation and fast estimation of harmonic functions.

  20. Spectroscopic Studies of a Three-dimensional, Five-coordinated Copper(Ⅱ) Complex via Hydrogen Bonds: [Cu(PDA)(H2O)2](H2PDA=Pyridine-2,6-dicarboxylic Acid)

    Institute of Scientific and Technical Information of China (English)


    A new copper(Ⅱ) complex [Cu(PDA)(H2O)2] was synthesized and its structure was determined. Cu(Ⅱ) is five-coordinated in a tetragonal pyramid geometry. The two coordinating water molecules are different and the two Cu-O bond lengths differ by nearly 0.02 nm. The whole crystal is linked to form a three-dimensional network by means of hydrogen bonds. The X-band ESR spectrum shows three different g tensors with a well-resolved hyperfine structure in the gz signal, giving the ESR parameters gx=2.05, gy=2.065 and gz=2.29. The covalency of the coordinate bonds and the deviation from tetragonal pyramid geometry for the complex are discussed based on the ESR spectra.

  1. Six-coordinate high-spin iron(ii) complexes with bidentate PN ligands based on 2-aminopyridine - new Fe(ii) spin crossover systems. (United States)

    Holzhacker, Christian; Calhorda, Maria José; Gil, Adrià; Carvalho, Maria Deus; Ferreira, Liliana P; Stöger, Berthold; Mereiter, Kurt; Weil, Matthias; Müller, Danny; Weinberger, Peter; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl


    Several new octahedral iron(ii) complexes of the type [Fe(PN(R)-Ph)2X2] (X = Cl, Br; R = H, Me) containing bidentate PN(R)-Ph (R = H, Me) (1a,b) ligands based on 2-aminopyridine were prepared. (57)Fe Mössbauer spectroscopy and magnetization studies confirmed in all cases their high spin nature at room temperature with magnetic moments very close to 4.9μB reflecting the expected four unpaired d-electrons in all these compounds. While in the case of the PN(H)-Ph ligand an S = 2 to S = 0 spin crossover was observed at low temperatures, complexes with the N-methylated analog PN(Me)-Ph retain an S = 2 spin state also at low temperatures. Thus, [Fe(PN(H)-Ph)2X2] (2a,3a) and [Fe(PN(Me)-Ph)2X2] (2b,3b) adopt different geometries. In the first case a cis-Cl,P,N-arrangement seems to be most likely, as supported by various experimental data derived from (57)Fe Mössbauer spectroscopy, SQUID magnetometry, UV/Vis, Raman, and ESI-MS as well as DFT and TDDFT calculations, while in the case of the PN(Me)-Ph ligand a trans-Cl,P,N-configuration is adopted. The latter is also confirmed by X-ray crystallography. In contrast to [Fe(PN(Me)-Ph)2X2] (2b,3b), [Fe(PN(H)-Ph)2X2] (2a,3a) is labile and undergoes rearrangement reactions. In CH3OH, the diamagnetic dicationic complex [Fe(PN(H)-Ph)3](2+) (5) is formed via the intermediacy of cis-P,N-[Fe(κ(2)-P,N-PN(H)-Ph)2(κ(1)-P-PN(H)-Ph)(X)](+) (4a,b) where one PN ligand is coordinated in a κ(1)-P-fashion. In CH3CN the diamagnetic dicationic complex cis-N,P,N-[Fe(PN(H)-Ph)2(CH3CN)2](2+) (6) is formed as a major isomer where the two halide ligands are replaced by CH3CN.

  2. Peroxidase-benzhydroxamic acid complexes: spectroscopic evidence that a Fe-H2O distance of 2.6 A can correspond to hexa-coordinate high-spin heme. (United States)

    Smulevich, G; Feis, A; Indiani, C; Becucci, M; Marzocchi, M P


    Resonance Raman (RR) spectra have been obtained for single-crystal horseradish peroxidase isozyme C complexed with benzhydroxamic acid (BHA). The data are compared with those obtained in solution by both RR and electronic absorption spectroscopies at room and low (12-80 K) temperatures. Moreover, the analysis has been extended to Coprinus cinereus peroxidase complexed with BHA. The results obtained for the two complexes are very similar and are consistent with the presence of an aqua six-coordinate high-spin heme. Therefore it can be concluded that despite the rather long Fe-H2O distance of 2.6-2.7 A found by X-ray crystallography in both complexes, the distal water molecule can still coordinate to the heme iron.

  3. The coordination chemistry of boron porphyrin complexes B2OX2 (TYPP) (X = OH, F; Y = Cl, CH3) and their chemical reactivities

    Indian Academy of Sciences (India)

    G I Cárdenas-Jirón; F Espinoza-Leyton; T L Sordo


    The structure and coordination chemistry of boron porphyrin complexes B2OX2 (TYPP) (X = OH, F; Y = Cl, CH3) in connection with its chemical reactivity are analyzed at ab initio density functional theory B3LYP/6-31G∗ and restricted Hartree-Fock RHF/6-31G∗ levels of theory. Global reactivity and local selectivity descriptors are used as adequate tools to analyze the isomerism effect ( or isomer) and the substitution effect (X: in axial ligand; or Y: in porphyrin ligand). In all the cases, we find that the conformation is the most stable one, in agreement with X-ray results, and that a principle of maximum hardness in the isomerism analysis is fullfilled. In the substitution analysis, we find that the three global reactivity indexes (, , ) and the two local reactivity indexes (, electrostatic potential) used in this paper predict the same trend when an electron-withdrawing substituent is replaced by an electron donor. Finally, we show that substitution in the porphyrin ligand is slightly more significant than that in the axial ligand.

  4. Controlled synthesis, formation mechanism, and carbon oxidation properties of Ho2Cu2O5 nanoplates prepared with a coordination-complex method (United States)

    Guo, Rui; You, Junhua; Han, Fei; Li, Chaoyang; Zheng, Guiyuan; Xiao, Weicheng; Liu, Xuanwen


    Ho2Cu2O5 nanoplates with perovskite structures were synthesized via a simple solution method (SSM) and a coordination-complex method (CCM) using [HoCu(3,4-pdc)2(OAc)(H2O)3]·8H2O (L = 3,4-pyridinedicarboxylic acid) as a precursor. The CCM was also performed in an N2 environment (CCMN) under various calcination conditions. The crystallization processes were characterized using X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. Ho2Cu2O5 formed through the diffusion of CuO into Ho2O3 particles. Cu2+ diffused faster than Ho3+ during this process. The initial products of CCMN (along with the thermal decomposition products) were initially laminarized in the N2 atmosphere, which prevented the growth of CuO particles and decreased the size of the Ho2Cu2O5 particles. The final Ho2Cu2O5 particles from CCMN had a nanoplate morphology with an average thickness of 75 nm. The decomposition of organic molecules and protection from N2 played important roles in determining the morphology of the resulting Ho2Cu2O5. The catalytic oxidation activity of Ho2Cu2O5 samples for carbon was characterized using a specific surface area measurement and thermogravimetric analysis, which revealed that the samples produced by CCMN had the highest catalytic activity.

  5. Cyclic M2(RL)2 coordination complexes of 5-(3-[N-tert-Butyl-N-aminoxyl]phenyl)pyrimidine with paramagnetic transition metal dications. (United States)

    Baskett, Martha; Lahti, Paul M; Paduan-Filho, Armando; Oliveira, Nei F


    5-(3-(N-tert-Butyl-N-aminoxyl)phenyl)pyrimidine (RL = 3NITPhPyrim) forms isostructural cyclic M2(RL)2 cyclic dimers with M(hfac)2 (M = Mn, Co, Cu; hfac = hexafluoroacetylacetonate). Mn2(hfac)4(RL)2 exhibits strong antiferromagnetic Mn-RL exchange, with weak ferromagnetic exchange (0.7 cm(-1)) between Mn-RL units that is consistent with a spin polarization exchange mechanism. The magnetic moment of Co2(hfac)4(RL)2 at higher temperatures is consistent with strongly antiferromagnetic exchange within the Co-NIT units and tends toward zero below 50 K at lower magnetic fields. Cu2(hfac)4(RL)2 shows more complex behavior, with no high-temperature plateau in chiT(T) up to 300 K but a monotonic decrease down to about 100 K. The Cu(II)-nitroxide bonds decrease by 0.2-0.3 A over the same temperature range, corresponding to a change of nitroxide coordination from axial to equatorial. This thermally reversible Jahn-Teller distortion leads to a thermally induced spin state conversion from a high-spin, paramagnetic state at higher temperature to a low-spin state at lower temperature. This spin state conversion is accompanied by a reversible solid-state thermochromic change between dull yellow-brown at room temperature and green at 77 K.

  6. Cobalt(II), nickel(II) and copper(II) complexes of a hexadentate pyridine amide ligand. Effect of donor atom (ether vs. thioether) on coordination geometry, spin-state of cobalt and M(III)-M(II) redox potential. (United States)

    Pandey, Sharmila; Das, Partha Pratim; Singh, Akhilesh Kumar; Mukherjee, Rabindranath


    Using an acyclic hexadentate pyridine amide ligand, containing a -OCH(2)CH(2)O- spacer between two pyridine-2-carboxamide units (1,4-bis[o-(pyrydine-2-carboxamidophenyl)]-1,4-dioxabutane (H(2)L(9)), in its deprotonated form), four new complexes, [Co(II)(L(9))] (1) and its one-electron oxidized counterpart [Co(III)(L(9))][NO(3)]·2H(2)O (2), [Ni(II)(L(9))] (3) and [Cu(II)(L(9))] (4), have been synthesized. Structural analyses revealed that the Co(II) centre in 1 and the Ni(II) centre in 3 are six-coordinate, utilizing all the available donor sites and the Cu(II) centre in 4 is effectively five-coordinated (one of the ether O atoms does not participate in coordination). The structural parameters associated with the change in the metal coordination environment have been compared with corresponding complexes of thioether-containing hexadentate ligands. The μ(eff) values at 298 K of 1-4 correspond to S = 3/2, S = 0, S = 1 and S = 1/2, respectively. Absorption spectra for all the complexes have been investigated. EPR spectral properties of the copper(II) complex 4 have been investigated, simulated and analyzed. Cyclic voltammetric experiments in CH(2)Cl(2) reveal quasireversible Co(III)-Co(II), Ni(III)-Ni(II) and Cu(II)-Cu(I) redox processes. In going from ether O to thioether S coordination, the effect of the metal coordination environment on the redox potential values of Co(III)-Co(II) (here the effect of spin-state as well), Ni(III)-Ni(II) and Cu(II)-Cu(I) processes have been systematically analyzed.

  7. Elaboration de nouveaux complexes de coordination d'éléments de transititon d et f : synthèses, structures, propriétés magnétiques et optiques


    Petit, Sarah


    Coordination chemistry of transition metals gives an access to numerous molecular magnetic materials that exhibit varied properties. During this work, several ligands with intrinsic properties have been chosen and their chemistry has been developed in order to get specific magnetic behavior. Solvothermal syntheses allowed the characterization of several complexes based on macrocycles. Two dinuclear CoII and FeIII complexes were isolated. Their molecular structures are built from metal ions lo...

  8. Crystal structure and properties of complexes [Ln(Gly)4Im·(ClO4)4]n (Ln:Nd, Sm) constructed from eight-coordination containing square antiprism (United States)

    Pan, Lu; Gao, Xiao-han; Lv, Xue-chuan; Tan, Zhi-cheng; Cao, Hui


    Two eight-coordination containing square antiprism polyhedra, [Ln(Gly)4Im·(ClO4)4]n (Ln:Nd, Sm) were synthesized through the self-assembly of Ln3+ (Ln:Nd, Sm) ions, glycine and imidazole in aqueous solution and characterized by X-ray single crystal diffraction. Both of the complexes crystallized in the C2/c space group. In the cluster, each Ln3+ ions was eight-coordination by eight oxygen atoms of the glycine. The coordination sphere of each Ln3+ ions could be described as a distorted square antiprism. Two central Ln3+ ions were connected by four bridging carboxyl groups from four glycine molecules. The Ln-O bond distances were related to the coordination geometries of the ligands. The complexes had two special solid-solid phase transitions at 224 K and 248 K, which were interpreted as a freezing-in phenomenon of the reorientational motion of perchlorate ions ClO4- and the orientational order/disorder process of ClO4- ions. The decomposition mechanism of the complexes was deduced to be three stages from 300 to 700 K. The fluorescent excitation and emission spectra showed that the complexes had strong fluorescent property.

  9. Intercomparison of terrain-following coordinate transformation and immersed boundary methods in large-eddy simulation of wind fields over complex terrain (United States)

    Fang, Jiannong; Porté-Agel, Fernando


    Accurate modeling of complex terrain, especially steep terrain, in the simulation of wind fields remains a challenge. It is well known that the terrain-following coordinate transformation method (TFCT) generally used in atmospheric flow simulations is restricted to non-steep terrain with slope angles less than 45 degrees. Due to the advantage of keeping the basic computational grids and numerical schemes unchanged, the immersed boundary method (IBM) has been widely implemented in various numerical codes to handle arbitrary domain geometry including steep terrain. However, IBM could introduce considerable implementation errors in wall modeling through various interpolations because an immersed boundary is generally not co-located with a grid line. In this paper, we perform an intercomparison of TFCT and IBM in large-eddy simulation of a turbulent wind field over a three-dimensional (3D) hill for the purpose of evaluating the implementation errors in IBM. The slopes of the three-dimensional hill are not steep and, therefore, TFCT can be applied. Since TFCT is free from interpolation-induced implementation errors in wall modeling, its results can serve as a reference for the evaluation so that the influence of errors from wall models themselves can be excluded. For TFCT, a new algorithm for solving the pressure Poisson equation in the transformed coordinate system is proposed and first validated for a laminar flow over periodic two-dimensional hills by comparing with a benchmark solution. For the turbulent flow over the 3D hill, the wind-tunnel measurements used for validation contain both vertical and horizontal profiles of mean velocities and variances, thus allowing an in-depth comparison of the numerical models. In this case, TFCT is expected to be preferable to IBM. This is confirmed by the presented results of comparison. It is shown that the implementation errors in IBM lead to large discrepancies between the results obtained by TFCT and IBM near the surface

  10. Crystal structure of a pyrazine-2,3-dicarboxamide ligand and of its silver(I nitrate complex, a three-dimensional coordination polymer

    Directory of Open Access Journals (Sweden)

    Dilovan S. Cati


    Full Text Available The title ligand, C18H16N6O2·2H2O (L1 [N2,N3-bis(pyridin-4-ylmethylpyrazine-2,3-dicarboxamide], crystallized as a dihydrate. The molecule is U-shaped with the carboxamide groups being cis to one another, making a dihedral angle of 81.6 (5°. The terminal pyridine rings are inclined to one another by 58.5 (4°. There is an intramolecular N—H...Npyrazine hydrogen bond present, forming an S(5 ring motif. In the crystal, adjacent molecules are linked by N—H...Ocarboxamide hydrogen bonds, forming a chain along [001]. A chain of hydrogen-bonded water molecules is linked to the chain of (L1 molecules by O—H...N hydrogen bonds, forming columns propagating along the c axis. The columns are linked by C—H...O and C—H...N hydrogen bonds, forming a three-dimensional supramolecular structure. The reaction of ligand (L1 with silver(I nitrate led to the formation of a new three-dimensional coordination polymer, {[Ag(C18H16N6O2]NO3}n, poly[[[μ4-N2,N3-bis(pyridin-4-ylmethylpyrazine-2,3-dicarboxamide]silver(I] nitrate] (I. The asymmetric unit is composed of half of one silver ion, located on a twofold rotation axis, half a ligand molecule and half a positionally disordered nitrate anion located about a twofold rotation axis. The full molecule of the ligand is generated by twofold rotational symmetry, with this twofold axis bisecting the Car—Car bonds of the pyrazine ring and the Ag—Ag bond. The carboxamide groups are now trans to one another, making a dihedral angle of 65.8 (4°. The two terminal pyridine rings are inclined to one another by 6.6 (3°. Two ligands wrap around an Ag—Ag bond of 3.1638 (11 Å, forming a figure-of-eight-shaped complex molecule. Each silver ion is coordinated by two pyridine N atoms and by two carboxamide O atoms of neighbouring molecules, hence forming a three-dimensional framework. The nitrate anion is linked to the framework by N—H...O and C—H...O hydrogen bonds.

  11. Evans-Showell-Type Polyoxometalates Constructing High-Dimensional Inorganic-Organic Hybrid Compounds with Copper-Organic Coordination Complexes: Synthesis and Oxidation Catalysis. (United States)

    An, Haiyan; Hou, Yujiao; Wang, Lin; Zhang, Yumeng; Yang, Wei; Chang, ShenZhen


    Four new hybrid architectures containing a [Co2Mo10H4O38](6-) polyoxoanion, (en)[Cu3(ptz)4(H2O)4][Co2Mo10H4O38]·24H2O (1), (Hbim)2[{Cu(bim)2(H2O)2}2{Co2Mo10H4O38}]·5H2O (2), H2[Cu(dpdo)3(H2O)4][{Cu2(dpdo)3(H2O)4(CH3CN)}2{Co2Mo10H4O38}2]·9H2O (3), and (H2bpp)4[{Cu(H2O)2}{NaCo2Mo10H4O38}2]·10H2O (4), where ptz = 5-(4-pyridyl)-1H-tetrazole, en = ethylenediamine, bim = benzimidazole, dpdo = 4,4'-bipyridine-N,N'-dioxide, and bpp = 1,3-bis(4-pyridyl)propane, have been prepared and characterized through elemental analysis, thermogravimetric analysis, IR spectroscopy, and powder and single-crystal X-ray diffraction. Compound 1 shows a 3D host-guest framework composed of 3D Cu-ptz as the host and Evans-Showell-type polyoxoanion [Co2Mo10H4O38](6-) as the guest. Compound 2 is constructed from [Co2Mo10H4O38](6-) polyoxoanions and Cu-bim coordination complexes to form a 2D covalent layer. Compound 3 also exhibits a 2D hybrid network based on [Co2Mo10H4O38](6-) polyoxoanions linked by Cu-dpdo coordination groups. Compound 4 is a 1D double-chain structure composed of [Co2Mo10H4O38](6-) polyoxoanions joined together by Na(+) and Cu(2+) cations. As far as we know, compound 1 is the first host-guest compound with an Evans-Showell-type polyoxometalate as the guest, and compounds 2 and 3 are the first 2D inorganic-organic hybrid architectures constructed from Evans-Showell-type polyoxometalates. Compounds 1-4 are redox catalysts that heterogeneously prompt sulfide and alcohol oxidation with excellent efficiency.

  12. Complexation and coordination selectivities of the tetradentate ligand 7-[(2-hydroxy-5-sulfophenyl) azo]-8-hydroxyquinoline-5-sulfonic acid with Fe(II), Ni(II), Zn(II), Cd(II) and VO(IV)

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Hu; Kai, Fumiaki; Hirohata, Masaaki; Nakamura, Masaaki; Matsuzaki, Susumu; Komori, Kenji; Tsunematsu, Yuriko [Kumamoto Univ. (Japan)


    The new title tetradentate ligand (SPAHQS), containing both phenylazo and 8-quinolinol fragments, was prepared. Proton-dissociation processes of the ligand and complexing equilibria with Fe(II), Ni(II), Zn(II), Cd(II), and VO(IV) were analyzed spectrophotometrically. Coordination modes of SPAHQS with these metal ions have been investigated by means of polarography and Raman spectroscopy in aqueous solution. It was established that the coordination selectivity of SPAHQS for such metal ions is mainly dependent on steric factors in the chelate ring formed, not on HSAB properties. 18 refs., 6 figs., 2 tabs.

  13. Synthesis, magnetic and spectral studies on polystyrene-anchored coordination complexes of bi-, tri-, tetra- and hexavalent metal ions with unsymmetrical dibasic tetradentate ONNO donor Schiff base derived from 3-formylsalicylic acid, ethylenediamine and 2-benzoylacetanilide

    Indian Academy of Sciences (India)

    Dinesh Kumar; Arun Syamal; Jaipal; Lalit Kumar Sharma


    Polystyrene-anchored Cu(II), Zn(II), Cd(II), Ni(II), Mn(II), MoO2(II), UO2(II), Fe(III) and Zr(IV), complexes of the unsymmetrical dibasic tetradentate ONNO donor Schiff base derived from the condensation of chloromethylated polystyrene, 3-formylsalicylic acid, ethylenediamine and 2-benzoylacetanilide (PS-LH2) has been synthesized. The polystyrene anchored complexes have the formulae: PS-LM (where M = Cu, Zn, Cd, Ni, MoO2, UO2), PS-LFeCl.DMF, PS-LMn.2DMF and PS-LZr(OH)2.DMF. The polystyrene-anchored coordination compounds have been characterized by elemental analysis, IR, reflectance, ESR and magnetic susceptibility measurements. The per cent reaction conversion of polystyrene anchored Schiff base to polystyrene supported coordination compounds lies between 28.98 and 85.9. The coordinated dimethylformamide is completely lost on heating the complexes. The shifts of the ν(C=N)(azomethine) and ν(C-O)(phenolic) stretches have been monitored in order to find out the donor sites of the ligands. The Cu(II) complex is paramagnetic with square planar structure; the Ni(II) complex is diamagnetic with square planar structure; the Zn(II) and Cd(II) complexes are diamagnetic and have tetrahedral structure; the Mn(II) and Fe(III) complexes are paramagnetic and have octahedral structure; the MoO2(II) and UO2(II) complexes are diamagnetic and have octahedral structure and the Zr(IV) complexes are diamagnetic and have pentagonal bipyramidal structure.

  14. An elusive vinyl radical isolated as an appended unit in a five-coordinate Co(iii)-bis(iminobenzosemiquinone) complex formed via ligand-centered C-S bond cleavage. (United States)

    Sarkar, Prasenjit; Tiwari, Archana; Sarmah, Amrit; Bhandary, Subhrajyoti; Roy, Ram Kinkar; Mukherjee, Chandan


    Redox-active ligand H4Pra(edt(AP/AP)) experienced C-S bond cleavage during complexation reaction with Co(OAc)2·2H2O in the presence of Et3N in CH3OH in air. Thus, formed complex 1 was composed of two iminobenzosemiquinone radicals in its coordination sphere and an unprecedented stable tethered-vinyl radical. The complex has been characterized by mass, X-ray single crystal, X-band EPR, variable-temperature magnetic moment measurements and DFT based computational study.

  15. Coordination Between Complex Product Development and Organizational Design%基于多Agent模拟的产品开发与组织设计协同研究

    Institute of Scientific and Technical Information of China (English)

    胡斌; 王缓缓; 胡慕海; 牛飞


    The mathematical model for CoPS is proposed and quantitative study on such coordination is conducted with the agent-based simulation. Firstly the development of CoPS is modeled from two dimensions, complexity and the time pressure of development. Secondly the common organizational design elements of different type of organizational design are identified and modeled, the further quantitative study on the consistency or fit between the development of CoPS and organizational design is conducted based on the detailed simulation experiments and how the both are matched is given in details. The results indicate that the organization should configure the common organizational design elements according to the different product development identified by the combination of complexity and time pressure, which assures the organization high performance. Meanwhile how the development of CoPS is matched with design of PBO is given from the micro-level perspective.%建立产品开发的数学模型并采用多智能体模拟方法对复杂产品开发与组织设计的协同性进行了定量分析.首先,对产品和项目从复杂度和开发的时间压力进行了二维建模;然后对不同类型的组织设计所共同关注的组织要素进行识别和建模;通过一组模拟实验进一步对产品开发与组织设计之间的匹配和一致性关系进行了定量化研究,并总结出复杂产品开发与组织设计的协同关系.研究结果表明,组织应针对产品开发的不同特征对各组织要素进行与之相匹配的设计,产品开发与组织设计的良好的协同性是确保组织取得产品开发高绩效的重要因素,并从微观水平上给出复杂产品开发与基于项目的组织设计的协同方案.

  16. Comparative DNA binding abilities and phosphatase-like activities of mono-, di-, and trinuclear Ni(II) complexes: the influence of ligand denticity, metal-metal distance, and coordinating solvent/anion on kinetics studies. (United States)

    Bhardwaj, Vimal K; Singh, Ajnesh


    Six novel Ni(II) complexes, namely, [Ni2(HL(1))(OAc)2] (1), [Ni3L(1)2]·H2O·2CH3CN (2), [Ni2(L(2))(L(3))(CH3CN)] (3), [Ni2(L(2))2(H2O)2] (4), [Ni2(L(2))2(DMF)2]2·2H2O (5), and [Ni(HL(2))2]·H2O (6), were synthesized by reacting nitrophenol-based tripodal (H3L(1)) and dipodal (H2L(2)) Schiff base ligands with Ni(II) metal salts at ambient conditions. All the complexes were fully characterized with different spectroscopic techniques such as elemental analyses, IR, UV-vis spectroscopy, and electrospray ionization mass spectrometry. The solid-state structures of 2, 3, 5, and 6 were determined using single-crystal X-ray crystallography. The compounds 1, 3, 4, and 5 are dinuclear complexes where the two Ni(II) centers have octahedral geometry with bridging phenoxo groups. Compound 2 is a trinuclear complex with two different types of Ni(II) centers. In compound 3 one of the Ni(II) centers has a coordinated acetonitrile molecule, whereas in compound 4, a water molecule has occupied one coordination site of each Ni(II) center. In complex 5, the coordinated water of complex 4 was displaced by the dimethylformamide (DMF) during its crystallization. Complex 6 is mononuclear with two amine-bis(phenolate) ligands in scissorlike fashion around the Ni(II) metal center. The single crystals of 1 and 4 could not be obtained; however, from the spectroscopic data and physicochemical properties (electronic and redox properties) it was assumed that the structures of these complexes are quite similar to other analogues. DNA binding abilities and phosphatase-like activities of all characterized complexes were also investigated. The ligand denticity, coordinated anions/solvents (such as acetate, acetonitrile, water, and DMF), and cooperative action of two metal centers play a significant role in the phosphate ester bond cleavage of 2-hydroxypropyl-p-nitropenylphosphate by transesterification mechanism. Complex 3 exhibits highest activity among complexes 1-6 with 3.86 × 10(5) times

  17. Synthesis, structures and electrochemical properties of two novel metal-organic coordination complexes based on trimesic acid (H 3BTC) and 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (BPO) (United States)

    Wang, Xiu-Li; Li, Jin; Lin, Hong-Yan; Hu, Hai-Liang; Chen, Bao-Kuan; Mu, Bao


    Two novel metal-organic coordination complexes [Cu(HBTC)(BPO)]·H 2O ( 1) and [Co 3(BTC) 2(BPO) 3(H 2O) 2]·5.25H 2O ( 2), have been synthesized from hydrothermal reaction of metal chloride with the mixed ligands 1,3,5-benzenetricarboxylate (H 3BTC) and bent dipyridyl based ligand 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (BPO), and structurally characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction analysis. The results reveal that each dinuclear Cu II unit is bridged by two kinds of different ligands (H 3BTC and BPO) to form one-dimensional (1-D) chain structure in complex 1. The adjacent chains for 1 are further linked by π-π stacking interactions and hydrogen bonding interactions to form a three-dimensional (3-D) supramolecular framework. Complex 2 possesses a 3-D network composed of three different cobalt(II) centers [carboxylate-bridged dinuclear cobalt units and mononuclear cobalt ion] and bridging ligands BTC and BPO, which presents the first example of 3-D coordination polymer constructed from the BPO ligands simultaneously showing three different coordination modes. Moreover, the electrochemical behaviors of the two complexes bulk-modified carbon paste electrodes ( 1-CPE and 2-CPE) have been reported.

  18. Mechanochemical Synthesis of 3d Transition-Metal-1,2,4-Triazole Complexes as Precursors for Microwave-Assisted and Thermal Conversion to Coordination Polymers with a High Influence on the Dielectric Properties. (United States)

    Brede, Franziska A; Heine, Johanna; Sextl, Gerhard; Müller-Buschbaum, Klaus


    The complexes [MCl2 (TzH)4] (M=Mn (1), Fe (2); TzH=1,2,4-1H-triazole) and [ZnCl2 (TzH)2] (3) have been obtained by mechanochemical reactions of the corresponding divalent metal chloride and 1,2,4-1H-triazole. They were successfully used as precursors for the formation of coordination polymers either by a microwave-assisted reaction or by thermal conversion. For manganese, the conversion directly yielded 1∞ [MnCl2 TzH] (4), whereas for the iron-containing precursor, 1∞ [FeCl2 TzH] (6), was formed via the intermediate coordination polymer 1∞ [FeCl(TzH)2]Cl (5). For cobalt, the isotypic polymer 1∞ [CoCl(TzH)2]Cl (7) was obtained, but exclusively by a microwave-induced reaction directly from CoCl2 . The crystal structures were resolved from single crystals and powders. The dielectric properties were determined and revealed large differences in permittivity between the precursor complexes and the rigid chain-like coordination polymers. Whereas the monomeric complexes exhibit very different dielectric behaviour, depending on the transition metal, from "low-k" to "high-k" with the permittivity ranging from 4.3 to >100 for frequencies of up to 1000 Hz, the coordination polymers and complexes with strong intermolecular interactions are all close to "low-k" materials with very low dielectric constants up to 50 °C. Therefore, the conversion procedures can be used to deliberately influence the dielectric properties from complex to polymer and for different 3d transition-metal ions.

  19. Persistent coordination patterns in a complex task after 10 years delay: subtitle: how validate the old saying "once you have learned how to ride a bicycle, you never forget!". (United States)

    Nourrit-Lucas, Déborah; Zelic, Grégory; Deschamps, Thibault; Hilpron, Michael; Delignières, Didier


    Motor learning studies have for a long time focused on performance variables (in terms of speed or accuracy) in assessing learning, transfer and retention of motor skills. We argue, however, that learning essentially resides in changes in coordination variables (in terms of qualitative organization of behavior) and that relevant tests for assessing the effectiveness of learning and retention should consider these variables. The aim of this experiment was to test the retention of a complex motor skill, after a long-term delay. Ten years ago, five participants were involved in an experiment during which they practiced for 39 sessions of ten 1-min trials on a ski-simulator. All participants volunteered for a retention test, ten years after, for one session of ten 1-min trials. Analyses focused on the oscillations of the platform of the simulator. Performance was assessed in terms of amplitude and frequency. Coordination was accounted for by an analysis of dynamical properties of the motion of the platform, and especially the nature of the damping function that was exploited for sustaining the limit cycle dynamics. Results showed a significant decrement in performance variables. In contrast, all participants adopted from the first trial onwards the coordination mode they learned 10years ago. These results confirm the strong persistence of coordination modes, once acquired and stabilized in the behavioral repertoire. They also support the importance of coordination variables for a valid assessment of learning and retention.

  20. Electronic structure study of seven-coordinate first-row transition metal complexes derived from 1,10-diaza-15-crown-5: a successful marriage of theory with experiment. (United States)

    Platas-Iglesias, Carlos; Vaiana, Lea; Esteban-Gómez, David; Avecilla, Fernando; Real, José Antonio; de Blas, Andrés; Rodríguez-Blas, Teresa


    A detailed study of the electronic structure of seven-coordinate Mn(II), Co(II), and Ni(II) complexes with the lariat ether N,N'-bis(2-aminobenzyl)-1,10-diaza-15-crown-5 (L(1)) is presented. These complexes represent new examples of structurally characterized seven-coordinate (pentagonal bipyramidal) complexes for the Mn(II), Co(II), and Ni(II) ions. The X-ray crystal structures of the Mn(II) and Co(II) complexes show C(2) symmetries for the [M(L(1))](2+) cations, whereas the structures of the Ni(II) complexes show a more distorted coordination environment. The magnetic properties of the Mn(II) complex display a characteristic Curie law, whereas those of the Co(II) and Ni(II) ions show the occurrence of zero-field splitting of the S = 3/2 and 1 ground states, respectively. Geometry optimizations of the [M(L(1))](2+) systems (M = Mn, Co, or Ni) at the DFT (B3LYP) level of theory provide theoretical structures in good agreement with the experimental data. Electronic structure calculations predict a similar ordering of the metal-based beta spin frontier MO for the Mn(II) and Co(II) complexes. This particular ordering of the frontier MO leads to a pseudodegenerate ground state for the d(8) Ni(II) ion. The distortion of the C(2) symmetry in [Ni(L(1))](2+) is consistent with a Jahn-Teller effect that removes this pseudodegeneracy. Our electronic structure calculations predict that the binding strength of L(1) should follow the trend Co(II) approximately Mn(II) > Ni(II), in agreement with experimental data obtained from spectrophotometric titrations.

  1. Síntese e atividade citotóxica de alguns azido-ciclopaladados estabilizados com ligantes bifosfínicos Synthesis and cytotoxicity of some cyclometallated palladium (II complexes containing coordinated azide and diphosphines

    Directory of Open Access Journals (Sweden)

    Antonio Carlos Fávero Caires


    Full Text Available Some cyclopalladated compounds containing the azido group ligand and the (C-N ring of N,N-dimethylbenzylamine have been prepared by bridge opening reactions of dimmer azide complex precursor with some diphosphines in different stoichiometric quantities. The neutral or ionic, mono or binuclear complexes synthesized were characterized by elemental analyses, I. R. spectroscopy and NMR techniques. The series of complexes was screened for cytotoxicity against a panel three human tumour cells lines(C6,Hep-2,HeLa. All complexes were found to be cytotoxic (IC50 at µM concentrations while one complex having the coordination bond N-Pd ruptured also displayed some differential cytotoxicity.

  2. A seven-coordinated manganese(II) complex with V-shaped ligand bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine: synthesis, structure, DNA-binding properties and antioxidant activities. (United States)

    Wu, Huilu; Yuan, Jingkun; Bai, Ying; Wang, Hua; Pan, Guolong; Kong, Jin


    A manganese(II) complex of the type, [MnL(pic)(2)]·H(2)O, was obtained by the reaction of the V-shaped ligand bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine (L) with Mn(pic)(2) (pic=picrate). The ligand L and Mn(II) complex were confirmed on the basis of elemental analysis, molarconductivities, (1)H NMR, IR, UV-vis spectra and X-ray crystallography. Single-crystal X-ray revealed that central Mn(II) atom is seven-coordinate with a MnN(3)O(4) environment, in which ligand L acts as a tridentate N-donor. The remaining coordination sites were occupied by four O atoms afforded by two picrate anion. Interaction of the free ligand L and Mn(II) complex with DNA were investigated by spectrophotometric methods and viscosity measurements. The results suggested that both ligand L and Mn(II) complex bind to DNA in an intercalative binding mode, and DNA-binding affinity of the Mn(II) complex is stronger than that of ligand L. Moreover, antioxidant assay in vitro shows the Mn(II) complex possesses significant antioxidant activities.

  3. Coordinated Leading and Lagging Strand DNA Synthesis by Using the Herpes Simplex Virus 1 Replication Complex and Minicircle DNA Templates ▿ (United States)

    Stengel, Gudrun; Kuchta, Robert D.


    The origin-specific replication of the herpes simplex virus 1 genome requires seven proteins: the helicase-primase (UL5-UL8-UL52), the DNA polymerase (UL30-UL42), the single-strand DNA binding protein (ICP8), and the origin-binding protein (UL9). We reconstituted these proteins, excluding UL9, on synthetic minicircular DNA templates and monitored leading and lagging strand DNA synthesis using the strand-specific incorporation of dTMP and dAMP. Critical features of the assays that led to efficient leading and lagging stand synthesis included high helicase-primase concentrations and a lagging strand template whose sequence resembled that of the viral DNA. Depending on the nature of the minicircle template, the replication complex synthesized leading and lagging strand products at molar ratios varying between 1:1 and 3:1. Lagging strand products (∼0.2 to 0.6 kb) were significantly shorter than leading strand products (∼2 to 10 kb), and conditions that stimulated primer synthesis led to shorter lagging strand products. ICP8 was not essential; however, its presence stimulated DNA synthesis and increased the length of both leading and lagging strand products. Curiously, human DNA polymerase α (p70-p180 or p49-p58-p70-p180), which improves the utilization of RNA primers synthesized by herpesvirus primase on linear DNA templates, had no effect on the replication of the minicircles. The lack of stimulation by polymerase α suggests the existence of a macromolecular assembly that enhances the utilization of RNA primers and may functionally couple leading and lagging strand synthesis. Evidence for functional coupling is further provided by our observations that (i) leading and lagging strand synthesis produce equal amounts of DNA, (ii) leading strand synthesis proceeds faster under conditions that disable primer synthesis on the lagging strand, and (iii) conditions that accelerate helicase-catalyzed DNA unwinding stimulate decoupled leading strand synthesis but not

  4. Room-Temperature Energy-Sampling Kβ X-ray Emission Spectroscopy of the Mn4Ca Complex of Photosynthesis Reveals Three Manganese-Centered Oxidation Steps and Suggests a Coordination Change Prior to O2 Formation. (United States)

    Zaharieva, Ivelina; Chernev, Petko; Berggren, Gustav; Anderlund, Magnus; Styring, Stenbjörn; Dau, Holger; Haumann, Michael


    In oxygenic photosynthesis, water is oxidized and dioxygen is produced at a Mn4Ca complex bound to the proteins of photosystem II (PSII). Valence and coordination changes in its catalytic S-state cycle are of great interest. In room-temperature (in situ) experiments, time-resolved energy-sampling X-ray emission spectroscopy of the Mn Kβ1,3 line after laser-flash excitation of PSII membrane particles was applied to characterize the redox transitions in the S-state cycle. The Kβ1,3 line energies suggest a high-valence configuration of the Mn4Ca complex with Mn(III)3Mn(IV) in S0, Mn(III)2Mn(IV)2 in S1, Mn(III)Mn(IV)3 in S2, and Mn(IV)4 in S3 and, thus, manganese oxidation in each of the three accessible oxidizing transitions of the water-oxidizing complex. There are no indications of formation of a ligand radical, thus rendering partial water oxidation before reaching the S4 state unlikely. The difference spectra of both manganese Kβ1,3 emission and K-edge X-ray absorption display different shapes for Mn(III) oxidation in the S2 → S3 transition when compared to Mn(III) oxidation in the S1 → S2 transition. Comparison to spectra of manganese compounds with known structures and oxidation states and varying metal coordination environments suggests a change in the manganese ligand environment in the S2 → S3 transition, which could be oxidation of five-coordinated Mn(III) to six-coordinated Mn(IV). Conceivable options for the rearrangement of (substrate) water species and metal-ligand bonding patterns at the Mn4Ca complex in the S2 → S3 transition are discussed.

  5. 2-(Methylamido)pyridine-Borane: A Tripod κ(3)-N,H,H Ligand in Trigonal Bipyramidal Rhodium(I) and Iridium(I) Complexes with an Asymmetric Coordination of Its BH3 Group. (United States)

    Brugos, Javier; Cabeza, Javier A; García-Álvarez, Pablo; Kennedy, Alan R; Pérez-Carreño, Enrique; Van der Maelen, Juan F


    The complexes [M(κ(3)-N,H,H-mapyBH3)(cod)] (M = Rh, Ir; HmapyBH3 = 2-(methylamino)pyridine-borane; cod = 1,5-cyclooctadiene), which contain a novel anionic tripod ligand coordinated to the metal atom through the amido N atom and through two H atoms of the BH3 group, were prepared by treating the corresponding [M2(μ-Cl)2(cod)2] (M = Rh, Ir) precursor with K[mapyBH3]. X-ray diffraction studies and a theoretical Quantum Theory of Atoms in Molecules analysis of their electron density confirmed that the metal atoms of both complexes are in a very distorted trigonal bipyramidal coordination environment, in which two equatorial sites are asymmetrically spanned by the H-B-H fragment. While both 3c-2e BH-M interactions are more κ(1)-H (terminal σ coordination of the B-H bond) than κ(2)-H,B (agostic-type coordination of the B-H bond), one BH-M interaction is more agostic than the other, and this difference is more marked in the iridium complex than in the rhodium one. This asymmetry is not evident in solution, where the cod ligand and the BH3 group of these molecules participate in two concurrent dynamic processes of low activation energies (variable-temperature NMR and density functional theory studies), namely, a rotation of the cod ligand that interchanges its two alkene fragments (through a square pyramidal transition state) and a rotation of the BH3 group about the B-N bond that equilibrates the three B-H bonds (through a square planar transition state). While the cod rotation has similar activation energy in 2 and 3, the barrier to the BH3 group rotation is higher in the iridium complex than in the rhodium one.

  6. Mono- and binuclear tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate bismuth(III) dichloride complexes: a soft scorpionate ligand can coordinate to p-block elements. (United States)

    Fujisawa, Kiyoshi; Kuboniwa, Ayaka; Kiss, Mercedesz; Szilagyi, Robert K


    Tris(pyrazolyl)hydroborate ligands have been utilized in the fields of inorganic and coordination chemistry due to the ease of introduction of steric and electronic substitutions at the pyrazole rings. The development and use of the tris(pyrazolyl)hydroborate ligand, called a `scorpionate', were pioneered by the late Professor Swiatoslaw Trofimenko. He developed a second generation for his ligand system by the introduction of 3-tert-butyl and 3-phenyl substituents and this new ligand system accounted for many remarkable developments in inorganic and coordination chemistry in stabilizing monomeric species while maintaining an open coordination site. Bismuth is remarkably harmless among the toxic heavy metal p-block elements and is now becoming popular as a replacement for highly toxic metal elements, such as lead. Two bismuth(III) complexes of the anionic sulfur-containing tripod tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl)hydroborate ligand were prepared. By recrystallization from MeOH/CH2Cl2, orange crystals of dichlorido(methanol-κO)[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III), [Bi(C21H34BN6S3)Cl2(CH4O)], (I), were obtained, manifesting a mononuclear structure. By using a noncoordinating solvent, red crystals of the binuclear structure with bridging Cl atoms were obtained, namely di-μ-chlorido-bis{chlorido[tris(3-tert-butyl-2-sulfanylidene-1H-imidazol-1-yl-κS)hydroborato]bismuth(III)}, [Bi2(C21H34BN6S3)2Cl4], (II). These complexes show {Bi(III)S3Cl2O} and {Bi(III)S3Cl3} coordination geometries with average Bi(III)-S bond lengths of 2.73 and 2.78 Å in (I) and (II), respectively. The overall Bi(III) coordination geometry is distorted octahedral due to stereochemically active lone pairs. The three Bi(III)-S bond lengths are almost equal in (I) but show considerable differences in (II), with one long and two shorter distances that also correlate with changes in the UV-Vis and (1)H NMR spectra. For direct measurements

  7. Synthesis and characterization of new unsymmetrical 'side-off' tetra and hexa coordinate homobinuclear Cu(II) and heterobinuclear Cu(II)-Zn(II) complexes: Magnetic, electrochemical and kinetic studies (United States)

    Shanmuga Bharathi, K.; Sreedaran, S.; Kalilur Rahiman, A.; Narayanan, V.

    A new class of phenol based unsymmetrical side-off tetra and hexa coordinate homobinuclear Cu(II) and heterobinuclear Cu(II)-Zn(II) complexes have been synthesized and characterized by elemental and spectral analysis. The electronic spectra of all the complexes show "Red shift" in LMCT band, for the ligand H2L2 compared to that of the ligand H2L1 due to the relatively higher electron donating nature of their substitutents. The homobinuclear Cu(II) complexes (1 and 2) illustrate an antiferromagnetic interaction (μeff: 1.58 and 1.60 BM) at 298 K with a broad EPR signal. Variable temperature magnetic moment study of the binuclear copper (II) complexes shows that the extent of antiferromagnetic coupling is greater in the case of H2L2 complexes than H2L1 complexes (-2 J values: 192 cm-1 and 184 cm-1 respectively). The heterobinuclear Cu(II)-Zn(II) complexes (3 and 4) have a magnetic moment value close to the spin only value with four hyperfine EPR signals. Electrochemical studies of the complexes reveal that all the binuclear complexes show two irreversible one-electron transfer reduction waves in the cathodic region. There is an "anodic shift" in the first reduction potential of the complexes, of the ligand H2L1 when compared to that of the ligand H2L2 due to the presence of relatively higher electron donating N-substituents in the later case than in the former case. The catecholase activity of the complexes reveals that the homobinuclear Cu(II) complexes show higher catalytic activity than the corresponding heterobinuclear Cu(II)-Zn(II) complexes. In the hydrolysis of 4-nitrophenylphosphate, the heterobinuclear Cu(II)-Zn(II) complexes show better catalytic activity than the corresponding homobinuclear Cu(II) complexes.


    CERN Multimedia

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    Overview From a technical perspective, CMS has been in “beam operation” state since 6th November. The detector is fully closed with all components operational and the magnetic field is normally at the nominal 3.8T. The UXC cavern is normally closed with the radiation veto set. Access to UXC is now only possible during downtimes of LHC. Such accesses must be carefully planned, documented and carried out in agreement with CMS Technical Coordination, Experimental Area Management, LHC programme coordination and the CCC. Material flow in and out of UXC is now strictly controlled. Access to USC remains possible at any time, although, for safety reasons, it is necessary to register with the shift crew in the control room before going down.It is obligatory for all material leaving UXC to pass through the underground buffer zone for RP scanning, database entry and appropriate labeling for traceability. Technical coordination (notably Stephane Bally and Christoph Schaefer), the shift crew and run ...

  9. Influence of terminal acryloyl arms on the coordination chemistry of a ditopic pyrimidine-hydrazone ligand: comparison of Pb(II), Zn(II), Cu(II), and Ag(I) complexes. (United States)

    Hutchinson, Daniel J; Hanton, Lyall R; Moratti, Stephen C


    A new ditopic pyrimidine-hydrazone ligand, 6-hydroxymethylacryloyl-2-pyridinecarboxaldehyde, 2,2'-[2,2'-(2-methyl-4,6-pyrimidinediyl)bis(1-methylhydrazone)] (L2), was synthesized with terminal acryloyl functional groups to allow incorporation into copolymer gel actuators. NMR spectroscopy was used to show that L2 adopted a horseshoe shape with transoid-transoid pym-hyz-py linkages. Metal complexation studies were performed with L2 and salts of Pb(II), Zn(II), Cu(II), and Ag(I) ions in CH3CN in a variety of metal to ligand ratios. Reacting L2 with an excess amount of any of the metal ions resulted in linear complexes where the pym-hyz-py linkages were rotated to a cisoid-cisoid conformation. NMR spectroscopy showed that the acryloyl arms of L2 did not interact with the bound metal ions in solution. Seven of the linear complexes (1-7) were crystallized and analyzed by X-ray diffraction. Most of these complexes (4-7) also showed no coordination between the acryloyl arms and the metal ions; however, complexes 1-3 showed some interactions. Both of the acryloyl arms were coordinated to Pb(II) ions in [Pb2L2(SO3CF3)4] (1), one through the carbonyl oxygen donor and the other through the alkoxy oxygen donor. One of the acryloyl arms of [Cu2L2(CH3CN)3](SO3CF3)4 (2) was coordinated to one of the Cu(II) ions through the carbonyl oxygen donor. There appeared to be a weak association between the alkoxy donors of the acryloyl arms and the Pb(II) ions of [Pb2L2(ClO4)4]·CH3CN (3). Reaction of excess AgSO3CF3 with L2 was repeated in CD3NO2, resulting in crystals of {[Ag7(L2)2(SO3CF3)6(H2O)2] SO3CF3}∞ (8), the polymeric structure of which resulted from coordination between the carbonyl donors of the acryloyl arms and the Ag(I) ions. In all cases the coordination and steric effects of the acryloyl arms did not inhibit isomerization of the pym-hyz bonds of L2 or the core shape of the linear complexes.

  10. Carbon-carbon cross-coupling reactions catalyzed by a two-coordinate nickel(II)-bis(amido) complex via observable Ni(I) , Ni(II) , and Ni(III) intermediates. (United States)

    Lipschutz, Michael I; Tilley, T Don


    Recently, the development of more sustainable catalytic systems based on abundant first-row metals, especially nickel, for cross-coupling reactions has attracted significant interest. One of the key intermediates invoked in these reactions is a Ni(III) -alkyl species, but no such species that is part of a competent catalytic cycle has yet been isolated. Herein, we report a carbon-carbon cross-coupling system based on a two-coordinate Ni(II) -bis(amido) complex in which a Ni(III) -alkyl species can be isolated and fully characterized. This study details compelling experimental evidence of the role played by this Ni(III) -alkyl species as well as those of other key Ni(I) and Ni(II) intermediates. The catalytic cycle described herein is also one of the first examples of a two-coordinate complex that competently catalyzes an organic transformation, potentially leading to a new class of catalysts based on the unique ability of first-row transition metals to accommodate two-coordinate complexes.

  11. Theoretical studies in local coordination and vibrational spectra of M +CH 3O(CH 2CH 2O) nCH 3 ( n = 2-7) complexes (M = Na, K, Mg and Ca) (United States)

    Dhumal, Nilesh R.; Gejji, Shridhar P.


    Solid polymer electrolytes (SPE) comprised of poly(ethylene oxide) (PEO) oligomers complexed with alkali metal salt of weakly coordinating anions have been of a great interest due to their high ionic conductivity. Ion pair formation influence the number of charge carriers and is an important factor underlying the ion transport phenomenon. In this work, the electronic structure and vibrational spectra of the metal ion-PEO oligomer represented by M-CH 3O(CH 2CH 2O) nCH 3 ( n = 2-7) (M = Na +, K +, Mg 2+ and Ca 2+) are obtained by employing the ab initio and hybrid density functional methods. Structural and spectral consequences of PEO oligomers to the alkali- and alkaline earth-metal ion coordination in different chemical environments have been presented. In metal ion-PEO oligomer ion-pairs the Mg 2+ ion binds strongly to ether oxygens of polyether complexes. The density functional calculations predict the heptaglyme ( n = 7 in the above series) binds strongly to the metal ion. The frequency shifts of characteristics vibrations induced by the metal ion-coordination in CH 3O(CH 2CH 2O) nCH 3-M ( n = 2-7) complexes have been discussed.

  12. A ditopic O(4)S(2) macrocycle and its hard, soft, and hard/soft metal complexes exhibiting endo-, exo-, or endo/exocyclic coordination: synthesis, crystal structures, NMR titration, and physical properties. (United States)

    Ryu, Hyunsoo; Park, Ki-Min; Ikeda, Mari; Habata, Yoichi; Lee, Shim Sung


    A 20-membered O4S2 macrocycle (L(2)) was synthesized as a ditopic ligating system toward hard and soft metal ions simultaneously. Five complexes (3-7) of L(2) with different structures and coordination modes, including discrete to infinite forms, mono- to heteronuclear, and endo- to exo- and endo/exocoordination, were prepared and structurally characterized. First, the reaction of L(2) with Pb(ClO4)2·3H2O afforded a typical endocyclic mononuclear perchlorato complex [Pb(L(2))(ClO4)2] (3) in which one lead(II) is surrounded by the macrocycle adopting a "tight and bent" conformation. Meanwhile, the reaction with a softer metal salt AgNO3 resulted in the formation of the dinuclear bis(macrocycle) complex [Ag2(L(2))2(NO3)2] (4) in which two exocyclic silver(I) ions are doubly linked by two nitrate ions. The treatment of L(2) with CuI gave a mixture of the exocyclic monomer complex [Cu(L(2))I] (5) and the exocyclic dimer complex [(Cu2I2)(L(2))2] (6), which were separated manually because of their brick and rhomboid shapes of the crystals, respectively. Furthermore, the reaction of L(2) with a mixture of CuI and NaI afforded a photoluminescent heteronuclear complex [Na2(Cu6I8)(L(2))2(CH3CN)4]n (7) in the endo/exocyclic coordination mode. In this case, the endocyclic sodium(I) complex units are linked by the double-open cubanes-type cluster Cu6I8, yielding a two-dimensional network. The structural and binding properties of the complex of L(2) with silver(I) nitrate in solution were monitored by the NMR titration. Photophysical and thermal properties for complex 7 were also investigated and discussed.

  13. C -IBI: Targeting cumulative coordination within an iterative protocol to derive coarse-grained models of (multi-component) complex fluids (United States)

    de Oliveira, Tiago E.; Netz, Paulo A.; Kremer, Kurt; Junghans, Christoph; Mukherji, Debashish


    We present a coarse-graining strategy that we test for aqueous mixtures. The method uses pair-wise cumulative coordination as a target function within an iterative Boltzmann inversion (IBI) like protocol. We name this method coordination iterative Boltzmann inversion ( C -IBI). While the underlying coarse-grained model is still structure based and, thus, preserves pair-wise solution structure, our method also reproduces solvation thermodynamics of binary and/or ternary mixtures. Additionally, we observe much faster convergence within C -IBI compared to IBI. To validate the robustness, we apply C -IBI to study test cases of solvation thermodynamics of aqueous urea and a triglycine solvation in aqueous urea.

  14. Nitrate-Bridged One-Dimension Coordination Polymer Self-Assembled from a N4O2-Tetraiminodiphenolate Dicopper(II Macrocyclic Complex

    Directory of Open Access Journals (Sweden)

    Julio Cesar da Rocha


    Full Text Available Herein we report on the synthesis and single crystal X-ray structure characterization of [{Cu2(tidf(μ-NO3}∞]ClO4 (tidf = a Robson type macrocyclic ligand obtained upon condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane. The coordination geometry around the copper(II is square-pyramidal and has [Cu2(tidf]2+ units connected to each other through nitrate bridges extending as a one-dimension coordination polymer. The compound exhibits an extensive supramolecular structure supported by nonclassic hydrogen bonding between C-H⋯Operchlorate and C-H⋯Onitrate.

  15. Physico-chemical and biological studies of Cu(II, Co(II and Ni(II complexes of an N4 coordinating ligand derived from diacetylbisethylenediamine and benzoic acid

    Directory of Open Access Journals (Sweden)

    Singh Pal Netra


    Full Text Available Mononuclear metal complexes of the type [ML1]Cl2 (where, M = = Cu(II, Co(II or Ni(II and L1 = ligand were synthesized by the reaction of a new N4 coordinating ligand, derived from diacetylbisethylenediamine with benzoic acid, and the corresponding hydrated metal chloride salts. The metal complexes were characterized by elemental analysis, melting point determination, molar conductance and magnetic moment measurements, IR, UV-Vis, 1H- and 13C-NMR, and ESR spectroscopy. The ligand and all the metal complexes were stable in the solid state at room temperature. From the analytical and spectroscopic investigations, the stoichiometry of the complexes was found to be 1:1 (metal:ligand. Based on the electronic spectra and magnetic moment data, the metal complexes had a square planar geometry. The molar conductance values show the 1:2 electrolytic nature of the metal complexes. A cyclic voltammetric study of the Cu(II metal complex has also performed, which showed one electron quasi-reversible reduction around -0.92 to -1.10 V. In vitro biological activities of the ligand and metal complexes was checked against two bacteria Bacillus subtilis and Escherichia coli and two fungi Aspirgillus niger and A. flavus which showed the antibacterial and antifungal properties of the ligand and its metal complexes.

  16. Complexity

    CERN Document Server

    Gershenson, Carlos


    The term complexity derives etymologically from the Latin plexus, which means interwoven. Intuitively, this implies that something complex is composed by elements that are difficult to separate. This difficulty arises from the relevant interactions that take place between components. This lack of separability is at odds with the classical scientific method - which has been used since the times of Galileo, Newton, Descartes, and Laplace - and has also influenced philosophy and engineering. In recent decades, the scientific study of complexity and complex systems has proposed a paradigm shift in science and philosophy, proposing novel methods that take into account relevant interactions.

  17. 团体操复杂队形变化过程标示方法的研究%Study on the method of coordinate indication of the changing process of complex formation of group calisthenics

    Institute of Scientific and Technical Information of China (English)



    In order to meet the design of the changing process of complex formation of group calisthenics and the training needs,we put forward methods that make actors into groups,number,and coordinate the changing process after divided into several components.This method could reduce a large number of moving path coordinates,and it is convenient for us to find the changes of every actor's coordinate position and moving path,the coordinate is clear and easily understand.Not only could we convenient to communicate and research the complex formation changing skills,but also reduce the training difficulty of the changing process of complex formation.Practices prove that the method is scientific and effective.%为了满足团体操复杂队形变化过程设计和训练的需要,提出了将演员分组、编号、划分成若干元件后标示变化过程的方法。这种方法大量地减少了移动路径的标示数量,可以方便地查找变化前后每个演员的坐标位置及移动路径,标示图清晰易懂。这不仅方便了复杂队形变化技巧的交流与研究,而且还降低了复杂队形变化过程的训练难度。


    CERN Multimedia

    A. Ball


    Operational Experience At the end of the first full-year running period of LHC, CMS is established as a reliable, robust and mature experiment. In particular common systems and infrastructure faults accounted for <0.6 % CMS downtime during LHC pp physics. Technical operation throughout the entire year was rather smooth, the main faults requiring UXC access being sub-detector power systems and rack-cooling turbines. All such problems were corrected during scheduled technical stops, in the shadow of tunnel access needed by the LHC, or in negotiated accesses or access extensions. Nevertheless, the number of necessary accesses to the UXC averaged more than one per week and the technical stops were inevitably packed with work packages, typically 30 being executed within a few days, placing a high load on the coordination and area management teams. It is an appropriate moment for CMS Technical Coordination to thank all those in many CERN departments and in the Collaboration, who were involved in CMS techni...

  19. Managing interteam coordination within and between organizations

    NARCIS (Netherlands)

    de Vries, Thomas Arend


    To accomplish complex tasks and effectively respond to environmental contingencies, teams must coordinate task-related issues with other teams (i.e., interteam coordination). Regrettably, interteam coordination is often complicated by misunderstandings that can arise from differences in teams’ langu

  20. Synthesis and structural characterization of silver(I), copper(I) coordination polymers and a helicate palladium(II) complex of dipyrrolylmethane-based dipyrazole ligands: the effect of meso substituents on structural formation. (United States)

    Guchhait, Tapas; Barua, Bhagyasree; Biswas, Aritra; Basak, Biswanath; Mani, Ganesan


    A new class of multidentate dipyrrolylmethane based ditopic tecton, 1,9-bis(3,5-dimethylpyrazolylmethyl)dipyrrolylmethane, containing diethyl (L1) or cyclohexylidene (L2) substituents at the meso carbon atom were readily synthesized in 28-45% yields in two different ways starting from dipyrrolylmethanes. A one dimensional coordination polymer structure ([(L2)Ag][BF4])n was obtained when L2 was treated with AgBF4, whereas the analogous reaction between L1 and AgBF4 afforded the dicationic binuclear metallacycle complex [(L1)2Ag2][BF4]2. In addition, yet another coordination polymeric structure [(L1)CuI]n was obtained from the reaction between L1 and CuI. The analogous reaction of L1 with [Pd(PhCN)2Cl2] afforded the binuclear palladium complex [(L1)2Pd2Cl4] having a double-stranded helicate structure. The observed structural differences are attributed to the effects of the substituents present at the meso carbon atom of the ligand, in addition to the nature of the metal centre, coordination number and the preferred geometry.