Response of Galium species (cleavers) to herbicides

Non-Peer Reviewe

The horizon and its charges in the first order gravity

In this work the algebra of charges of diffeomorphisms at the horizon of generic black holes is analyzed within first order gravity. This algebra reproduces the algebra of diffeomorphisms at the horizon, (Diff(S^1)), without central extension

Pd@UiO-66-Type MOFs Prepared by Chemical Vapor Infiltration as Shape-Selective Hydrogenation Catalysts

[EN] Host-guest inclusion properties of UiO-66 and UiO-67 metal-organic frameworks have been studied using ferrocene (FeCp2) as probe molecule. According to variable-temperature solid-state H-1 and C-13 CP-MAS-NMR, two different environments exist for adsorbed FeCp2 inside UiO-66 and UiO-67, which have been assigned to octahedral and tetrahedral cavities. At room temperature, a rapid exchange between these two adsorption sites occurs in UiO-67, while at -80 degrees C the intracrystalline traffic of FeCp2 through the triangular windows is largely hindered. In UiO-66, FeCp2 diffusion is already impeded at room temperature, in agreement with the smaller pore windows. Palladium nanoparticles (Pd NPs) encapsulated inside UiO-66 and UiO-67 have been prepared by chemical vapor infiltration of (allyl)Pd(Cp) followed by UV light irradiation. Infiltration must be carried out at low temperature (-10 degrees C) to avoid uncontrolled decomposition of the organometallic precursor and formation of Pd NPs at the external surface of the MOF. The resulting Pd-MOFs are shape selective catalysts, as shown for the hydrogenation of carbonyl compounds with different steric hindrance.Financial support from the Consolider-Ingenio 2010 (project MULTICAT), the Severo Ochoa program, and the Spanish Ministry of Science and Innovation (project MAT2011-29020-C02-01) is gratefully acknowledged. C. R. is grateful for a graduate student fellowship awarded by the Cluster of Excellence RESOLV (EXC 1069) funded by the German Deutsche Forschungsgemeinschaft (DFG). This project has further received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skolodowska-Curie grant agreement, number 641887.Luz Mínguez, I.; Roesler, C.; Epp, K.; Llabrés I Xamena, FX.; Fischer, RA. (2015). Pd@UiO-66-Type MOFs Prepared by Chemical Vapor Infiltration as Shape-Selective Hydrogenation Catalysts. European Journal of Inorganic Chemistry. 23:3904-3912. https://doi.org/10.1002/ejic.201500299S3904391223Corma, A., García, H., & Llabrés i Xamena, F. X. (2010). Engineering Metal Organic Frameworks for Heterogeneous Catalysis. Chemical Reviews, 110(8), 4606-4655. doi:10.1021/cr9003924Farrusseng, D., Aguado, S., & Pinel, C. (2009). Metal-Organic Frameworks: Opportunities for Catalysis. Angewandte Chemie International Edition, 48(41), 7502-7513. doi:10.1002/anie.200806063Gascon, J., Corma, A., Kapteijn, F., & Llabrés i Xamena, F. X. (2013). Metal Organic Framework Catalysis: Quo vadis? ACS Catalysis, 4(2), 361-378. doi:10.1021/cs400959kLlabres i Xamena, F., & Gascon, J. (Eds.). (2013). Metal Organic Frameworks as Heterogeneous Catalysts. Catalysis Series. doi:10.1039/9781849737586Li, B., Wang, H., & Chen, B. (2014). Microporous Metal-Organic Frameworks for Gas Separation. Chemistry - An Asian Journal, 9(6), 1474-1498. doi:10.1002/asia.201400031Li, J.-R., Kuppler, R. J., & Zhou, H.-C. (2009). Selective gas adsorption and separation in metal–organic frameworks. Chemical Society Reviews, 38(5), 1477. doi:10.1039/b802426jKreno, L. E., Leong, K., Farha, O. K., Allendorf, M., Van Duyne, R. P., & Hupp, J. T. (2011). Metal–Organic Framework Materials as Chemical Sensors. Chemical Reviews, 112(2), 1105-1125. doi:10.1021/cr200324tEsken, D., Turner, S., Lebedev, O. I., Van Tendeloo, G., & Fischer, R. A. (2010). Au@ZIFs: Stabilization and Encapsulation of Cavity-Size Matching Gold Clusters inside Functionalized Zeolite Imidazolate Frameworks, ZIFs. Chemistry of Materials, 22(23), 6393-6401. doi:10.1021/cm102529cHermes, S., Schröter, M.-K., Schmid, R., Khodeir, L., Muhler, M., Tissler, A., … Fischer, R. A. (2005). Metal@MOF: Loading of Highly Porous Coordination Polymers Host Lattices by Metal Organic Chemical Vapor Deposition. Angewandte Chemie International Edition, 44(38), 6237-6241. doi:10.1002/anie.200462515Meilikhov, M., Yusenko, K., Esken, D., Turner, S., Van Tendeloo, G., & Fischer, R. A. (2010). Metals@MOFs - Loading MOFs with Metal Nanoparticles for Hybrid Functions. European Journal of Inorganic Chemistry, 2010(24), 3701-3714. doi:10.1002/ejic.201000473Schröder, F., Esken, D., Cokoja, M., van den Berg, M. W. E., Lebedev, O. I., Van Tendeloo, G., … Fischer, R. A. (2008). Ruthenium Nanoparticles inside Porous [Zn4O(bdc)3] by Hydrogenolysis of Adsorbed [Ru(cod)(cot)]: A Solid-State Reference System for Surfactant-Stabilized Ruthenium Colloids. Journal of the American Chemical Society, 130(19), 6119-6130. doi:10.1021/ja078231uRösler, C., Esken, D., Wiktor, C., Kobayashi, H., Yamamoto, T., Matsumura, S., … Fischer, R. A. (2014). Encapsulation of Bimetallic Nanoparticles into a Metal-Organic Framework: Preparation and Microstructure Characterization of Pd/Au@ZIF-8. European Journal of Inorganic Chemistry, 2014(32), 5514-5521. doi:10.1002/ejic.201402409Müller, M., Hermes, S., Kähler, K., van den Berg, M. W. E., Muhler, M., & Fischer, R. A. (2008). Loading of MOF-5 with Cu and ZnO Nanoparticles by Gas-Phase Infiltration with Organometallic Precursors: Properties of Cu/ZnO@MOF-5 as Catalyst for Methanol Synthesis. Chemistry of Materials, 20(14), 4576-4587. doi:10.1021/cm703339hMüller, M., Zhang, X., Wang, Y., & Fischer, R. A. (2009). Nanometer-sized titania hosted inside MOF-5. Chem. Commun., (1), 119-121. doi:10.1039/b814241fRösler, C., & Fischer, R. A. (2015). Metal–organic frameworks as hosts for nanoparticles. CrystEngComm, 17(2), 199-217. doi:10.1039/c4ce01251hHermannsdörfer, J., Friedrich, M., Miyajima, N., Albuquerque, R. Q., Kümmel, S., & Kempe, R. (2012). Ni/Pd@MIL-101: Synergistic Catalysis with Cavity-Conform Ni/Pd Nanoparticles. Angewandte Chemie International Edition, 51(46), 11473-11477. doi:10.1002/anie.201205078Cirujano, F. G., Llabrés i Xamena, F. X., & Corma, A. (2012). MOFs as multifunctional catalysts: One-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst. Dalton Transactions, 41(14), 4249. doi:10.1039/c2dt12480gCirujano, F. G., Leyva-Pérez, A., Corma, A., & Llabrés i Xamena, F. X. (2013). MOFs as Multifunctional Catalysts: Synthesis of Secondary Arylamines, Quinolines, Pyrroles, and Arylpyrrolidines over Bifunctional MIL-101. ChemCatChem, 5(2), 538-549. doi:10.1002/cctc.201200878Guo, Z., Xiao, C., Maligal-Ganesh, R. V., Zhou, L., Goh, T. W., Li, X., … Huang, W. (2014). Pt Nanoclusters Confined within Metal–Organic Framework Cavities for Chemoselective Cinnamaldehyde Hydrogenation. ACS Catalysis, 4(5), 1340-1348. doi:10.1021/cs400982nLi, X., Guo, Z., Xiao, C., Goh, T. W., Tesfagaber, D., & Huang, W. (2014). Tandem Catalysis by Palladium Nanoclusters Encapsulated in Metal–Organic Frameworks. ACS Catalysis, 4(10), 3490-3497. doi:10.1021/cs5006635Zhang, W., Lu, G., Cui, C., Liu, Y., Li, S., Yan, W., … Huo, F. (2014). A Family of Metal-Organic Frameworks Exhibiting Size-Selective Catalysis with Encapsulated Noble-Metal Nanoparticles. Advanced Materials, 26(24), 4056-4060. doi:10.1002/adma.201400620Chen, L., Chen, H., Luque, R., & Li, Y. (2014). Metal−organic framework encapsulated Pd nanoparticles: towards advanced heterogeneous catalysts. Chem. Sci., 5(10), 3708-3714. doi:10.1039/c4sc01847hRamsahye, N. A., Gao, J., Jobic, H., Llewellyn, P. L., Yang, Q., Wiersum, A. D., … Maurin, G. (2014). Adsorption and Diffusion of Light Hydrocarbons in UiO-66(Zr): A Combination of Experimental and Modeling Tools. The Journal of Physical Chemistry C, 118(47), 27470-27482. doi:10.1021/jp509672cCatal. Today 2014Cirujano, F. G., Corma, A., & Llabrés i Xamena, F. X. (2015). Conversion of levulinic acid into chemicals: Synthesis of biomass derived levulinate esters over Zr-containing MOFs. Chemical Engineering Science, 124, 52-60. doi:10.1016/j.ces.2014.09.047Vermoortele, F., Ameloot, R., Vimont, A., Serre, C., & De Vos, D. (2011). An amino-modified Zr-terephthalate metal–organic framework as an acid–base catalyst for cross-aldol condensation. Chem. Commun., 47(5), 1521-1523. doi:10.1039/c0cc03038dVermoortele, F., Bueken, B., Le Bars, G., Van de Voorde, B., Vandichel, M., Houthoofd, K., … De Vos, D. E. (2013). Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr). Journal of the American Chemical Society, 135(31), 11465-11468. doi:10.1021/ja405078uVermoortele, F., Vandichel, M., Van de Voorde, B., Ameloot, R., Waroquier, M., Van Speybroeck, V., & De Vos, D. E. (2012). Electronic Effects of Linker Substitution on Lewis Acid Catalysis with Metal-Organic Frameworks. Angewandte Chemie International Edition, 51(20), 4887-4890. doi:10.1002/anie.201108565McClellan, W. R., Hoehn, H. H., Cripps, H. N., Muetterties, E. L., & Howk, B. W. (1961). π-Allyl Derivatives of Transition Metals. Journal of the American Chemical Society, 83(7), 1601-1607. doi:10.1021/ja01468a013Schaate, A., Roy, P., Godt, A., Lippke, J., Waltz, F., Wiebcke, M., & Behrens, P. (2011). Modulated Synthesis of Zr-Based Metal-Organic Frameworks: From Nano to Single Crystals. Chemistry - A European Journal, 17(24), 6643-6651. doi:10.1002/chem.20100321

Defect-Engineered Ruthenium MOFs as Versatile Heterogeneous Hydrogenation Catalysts

[EN] Ruthenium MOF [Ru-3(BTC)(2)Y-y] . G(g) (BTC=benzene-1,3,5-tricarboxylate; Y=counter ions=Cl-, OH-, OAc-; G=guest molecules=HOAc, H2O) is modified via a mixed-linker approach, using mixtures of BTC and pyridine-3,5-dicarboxylate (PYDC) linkers, triggering structural defects at the distinct Ru-2 paddlewheel (PW) nodes. This defect-engineering leads to enhanced catalytic properties due to the formation of partially reduced Ru-2-nodes. Application of a hydrogen pre-treatment protocol to the Ru-MOFs, leads to a further boost in catalytic activity. We study the benefits of (1) defect engineering and (2) hydrogen pre-treatment on the catalytic activity of Ru-MOFs in the Meerwein-Ponndorf-Verley reaction and the isomerization of allylic alcohols to saturated ketones. Simple solvent washing could not avoid catalyst deactivation during recycling for the latter reaction, while hydrogen treatment prior to each catalytic run proved to facilitate materials recyclability with constant activity over five runs.Funding by the Spanish Government is acknowledged through projects MAT2017-82288-C2-1-P and Severo Ochoa (SEV-2016-0683). This project is further funded by the Deutsche Forschungsgemeinschaft grant no. FI-502/32-1 ("DEMOFs"). KE and WRH would like to thank TUM Graduate School and the Gesellschaft Deutscher Chemiker (GDCh) for financial support. KE gratefully acknowledges support from the colleagues Olesia Halbherr (nee Kozachuk) and Wenhua Zhang.Epp, K.; Luz, I.; Heinz, WR.; Rapeyko, A.; Llabrés I Xamena, FX.; Fischer, RA. (2020). Defect-Engineered Ruthenium MOFs as Versatile Heterogeneous Hydrogenation Catalysts. ChemCatChem. 12(6):1720-1725. https://doi.org/10.1002/cctc.201902079S17201725126Gascon, J., Corma, A., Kapteijn, F., & Llabrés i Xamena, F. X. (2013). Metal Organic Framework Catalysis: Quo vadis? ACS Catalysis, 4(2), 361-378. doi:10.1021/cs400959kHasegawa, S., Horike, S., Matsuda, R., Furukawa, S., Mochizuki, K., Kinoshita, Y., & Kitagawa, S. (2007). Three-Dimensional Porous Coordination Polymer Functionalized with Amide Groups Based on Tridentate Ligand:  Selective Sorption and Catalysis. Journal of the American Chemical Society, 129(9), 2607-2614. doi:10.1021/ja067374yWang, Z., & Cohen, S. M. (2009). Postsynthetic modification of metal–organic frameworks. Chemical Society Reviews, 38(5), 1315. doi:10.1039/b802258pVermoortele, F., Bueken, B., Le Bars, G., Van de Voorde, B., Vandichel, M., Houthoofd, K., … De Vos, D. E. (2013). Synthesis Modulation as a Tool To Increase the Catalytic Activity of Metal–Organic Frameworks: The Unique Case of UiO-66(Zr). Journal of the American Chemical Society, 135(31), 11465-11468. doi:10.1021/ja405078uZheng, J., Ye, J., Ortuño, M. A., Fulton, J. L., Gutiérrez, O. Y., Camaioni, D. M., … Lercher, J. A. (2019). Selective Methane Oxidation to Methanol on Cu-Oxo Dimers Stabilized by Zirconia Nodes of an NU-1000 Metal–Organic Framework. Journal of the American Chemical Society, 141(23), 9292-9304. doi:10.1021/jacs.9b02902Rogge, S. M. J., Bavykina, A., Hajek, J., Garcia, H., Olivos-Suarez, A. I., Sepúlveda-Escribano, A., … Gascon, J. (2017). Metal–organic and covalent organic frameworks as single-site catalysts. Chemical Society Reviews, 46(11), 3134-3184. doi:10.1039/c7cs00033bFarrusseng, D., Aguado, S., & Pinel, C. (2009). Metal-Organic Frameworks: Opportunities for Catalysis. Angewandte Chemie International Edition, 48(41), 7502-7513. doi:10.1002/anie.200806063Valvekens, P., Vermoortele, F., & De Vos, D. (2013). Metal–organic frameworks as catalysts: the role of metal active sites. Catalysis Science & Technology, 3(6), 1435. doi:10.1039/c3cy20813cDoonan, C. J., & Sumby, C. J. (2017). Metal–organic framework catalysis. CrystEngComm, 19(29), 4044-4048. doi:10.1039/c7ce90106bDhakshinamoorthy, A., Li, Z., & Garcia, H. (2018). Catalysis and photocatalysis by metal organic frameworks. Chemical Society Reviews, 47(22), 8134-8172. doi:10.1039/c8cs00256hWang, Y., & Wöll, C. (2018). Chemical Reactions at Isolated Single-Sites Inside Metal–Organic Frameworks. Catalysis Letters, 148(8), 2201-2222. doi:10.1007/s10562-018-2432-2Genna, D. T., Pfund, L. Y., Samblanet, D. C., Wong-Foy, A. G., Matzger, A. J., & Sanford, M. S. (2016). Rhodium Hydrogenation Catalysts Supported in Metal Organic Frameworks: Influence of the Framework on Catalytic Activity and Selectivity. ACS Catalysis, 6(6), 3569-3574. doi:10.1021/acscatal.6b00404Chen, H., He, Y., Pfefferle, L. D., Pu, W., Wu, Y., & Qi, S. (2018). Phenol Catalytic Hydrogenation over Palladium Nanoparticles Supported on Metal-Organic Frameworks in the Aqueous Phase. ChemCatChem, 10(12), 2558-2570. doi:10.1002/cctc.201800211Marx, S., Kleist, W., Huang, J., Maciejewski, M., & Baiker, A. (2010). Tuning functional sites and thermal stability of mixed-linker MOFs based on MIL-53(Al). Dalton Transactions, 39(16), 3795. doi:10.1039/c002483jFang, Z., Bueken, B., De Vos, D. E., & Fischer, R. A. (2015). Defect-Engineered Metal-Organic Frameworks. Angewandte Chemie International Edition, 54(25), 7234-7254. doi:10.1002/anie.201411540Dissegna, S., Epp, K., Heinz, W. R., Kieslich, G., & Fischer, R. A. (2018). Defective Metal-Organic Frameworks. Advanced Materials, 30(37), 1704501. doi:10.1002/adma.201704501Zhang, Y.-B., Furukawa, H., Ko, N., Nie, W., Park, H. J., Okajima, S., … Yaghi, O. M. (2015). Introduction of Functionality, Selection of Topology, and Enhancement of Gas Adsorption in Multivariate Metal–Organic Framework-177. Journal of the American Chemical Society, 137(7), 2641-2650. doi:10.1021/ja512311aDrache, F., Cirujano, F. G., Nguyen, K. D., Bon, V., Senkovska, I., Llabrés i Xamena, F. X., & Kaskel, S. (2018). Anion Exchange and Catalytic Functionalization of the Zirconium-Based Metal–Organic Framework DUT-67. Crystal Growth & Design, 18(9), 5492-5500. doi:10.1021/acs.cgd.8b00832Zhang, W., Kauer, M., Halbherr, O., Epp, K., Guo, P., Gonzalez, M. I., … Fischer, R. A. (2016). Ruthenium Metal-Organic Frameworks with Different Defect Types: Influence on Porosity, Sorption, and Catalytic Properties. Chemistry - A European Journal, 22(40), 14297-14307. doi:10.1002/chem.201602641Kozachuk, O., Yusenko, K., Noei, H., Wang, Y., Walleck, S., Glaser, T., & Fischer, R. A. (2011). Solvothermal growth of a ruthenium metal–organic framework featuring HKUST-1 structure type as thin films on oxide surfaces. Chemical Communications, 47(30), 8509. doi:10.1039/c1cc11107hKozachuk, O., Luz, I., Llabrés i Xamena, F. X., Noei, H., Kauer, M., Albada, H. B., … Fischer, R. A. (2014). Multifunctional, Defect-Engineered Metal-Organic Frameworks with Ruthenium Centers: Sorption and Catalytic Properties. Angewandte Chemie International Edition, 53(27), 7058-7062. doi:10.1002/anie.201311128Agirrezabal-Telleria, I., Luz, I., Ortuño, M. A., Oregui-Bengoechea, M., Gandarias, I., López, N., … Soukri, M. (2019). Gas reactions under intrapore condensation regime within tailored metal–organic framework catalysts. Nature Communications, 10(1). doi:10.1038/s41467-019-10013-6Zhang, W., Kozachuk, O., Medishetty, R., Schneemann, A., Wagner, R., Khaletskaya, K., … Fischer, R. A. (2015). Controlled SBU Approaches to Isoreticular Metal-Organic Framework Ruthenium-Analogues of HKUST-1. European Journal of Inorganic Chemistry, 2015(23), 3913-3920. doi:10.1002/ejic.201500478Heinz, W. R., Kratky, T., Drees, M., Wimmer, A., Tomanec, O., Günther, S., … Fischer, R. A. (2019). Mixed precious-group metal–organic frameworks: a case study of the HKUST-1 analogue [RuxRh3−x(BTC)2]. Dalton Transactions, 48(32), 12031-12039. doi:10.1039/c9dt01198fBäckvall, J.-E. (2002). Transition metal hydrides as active intermediates in hydrogen transfer reactions. Journal of Organometallic Chemistry, 652(1-2), 105-111. doi:10.1016/s0022-328x(02)01316-5Chowdhury, R. L., & Bäckvall, J.-E. (1991). Efficient ruthenium-catalysed transfer hydrogenation of ketones by propan-2-ol. J. Chem. Soc., Chem. Commun., 0(16), 1063-1064. doi:10.1039/c39910001063Ahlsten, N., Bartoszewicz, A., & Martín-Matute, B. (2012). Allylic alcohols as synthetic enolate equivalents: Isomerisation and tandem reactions catalysed by transition metal complexes. Dalton Transactions, 41(6), 1660. doi:10.1039/c1dt11678aAhlsten, N., Lundberg, H., & Martín-Matute, B. (2010). Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature. Green Chemistry, 12(9), 1628. doi:10.1039/c004964fCahard, D., Gaillard, S., & Renaud, J.-L. (2015). Asymmetric isomerization of allylic alcohols. Tetrahedron Letters, 56(45), 6159-6169. doi:10.1016/j.tetlet.2015.09.098Xia, T., Wei, Z., Spiegelberg, B., Jiao, H., Hinze, S., & de Vries, J. G. (2018). Isomerization of Allylic Alcohols to Ketones Catalyzed by Well-Defined Iron PNP Pincer Catalysts. Chemistry - A European Journal, 24(16), 4043-4049. doi:10.1002/chem.201705454Scalambra, F., Lorenzo-Luis, P., de los Rios, I., & Romerosa, A. (2019). Isomerization of allylic alcohols in water catalyzed by transition metal complexes. Coordination Chemistry Reviews, 393, 118-148. doi:10.1016/j.ccr.2019.04.012Yamaguchi, K., Koike, T., Kotani, M., Matsushita, M., Shinachi, S., & Mizuno, N. (2005). Synthetic Scope and Mechanistic Studies of Ru(OH)x/Al2O3-Catalyzed Heterogeneous Hydrogen-Transfer Reactions. Chemistry - A European Journal, 11(22), 6574-6582. doi:10.1002/chem.200500539Mitchell, R. W., Spencer, A., & Wilkinson, G. (1973). Carboxylato-triphenylphosphine complexes of ruthenium, cationic triphenylphosphine complexes derived from them, and their behaviour as homogeneous hydrogenation catalysts for alkenes. Journal of the Chemical Society, Dalton Transactions, (8), 846. doi:10.1039/dt973000084

Hairy Canola (Brasssica napus) re-visited: Down-regulating TTG1 in an AtGL3-enhanced hairy leaf background improves growth, leaf trichome coverage, and metabolite gene expression diversity

Primer sequences used in the construction and analysis of B. napus transgenic lines. Table S1B. Blast of batch leaf Q-PCR primers to the B. rapa, B. oleracea, and B. napus genomes for five trichome regulatory genes and two control genes in B. napus. Table S1C. “Detectable” B. napus homologues of five trichome regulatory genes in first true leaves (from RNA sequencing). Table S1D. BlastP for five Arabidopsis trichome regulatory genes against the Brassica napus genome in NCBI. Table S2A. Differentially expressed leaf trichome ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy line K-5-8 relative to semi-glabrous cv. Westar. Table S2B. Leaf trichome genes with no significant expression differences (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy line K-5-8 relative to semi-glabrous cv. Westar. Table S3. Differentially expressed leaf flavonoid ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S4. Differentially expressed leaf phenylpropanoid and lignin ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S5. Differentially expressed leaf phenolic ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S6. Differentially expressed leaf shikimate ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S7. Differentially expressed leaf isoprenoid and terpene ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S8. Differentially expressed leaf glucosinolate-related and miscellaneous sulphur-related ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S9. Differentially expressed leaf alkaloid-related and miscellaneous N-metabolizing ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S10. Differentially expressed leaf cell wall structural carbohydrate ESTs ((p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S11. Differentially expressed leaf mucilage ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S12. Differentially expressed leaf wax ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S13. Differentially expressed leaf hormone ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S14. Differentially expressed leaf secondary metabolism ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S15. Differentially expressed leaf redox-related ESTs (p < 0.05)) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S16. Differentially expressed leaf protein modification ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S17. Differentially expressed leaf protein degradation ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. Table S18. Differentially expressed leaf transcription factor ESTs (p < 0.05) in hairy AtGL3+ B. napus or ultra-hairy K-5-8 relative to semi-glabrous cv. Westar. (XLSX 400 kb

Hairy Canola (Brasssica napus) re-visited: Down-regulating TTG1 in an AtGL3-enhanced hairy leaf background improves growth, leaf trichome coverage, and metabolite gene expression diversity

Background Through evolution, some plants have developed natural resistance to insects by having hairs (trichomes) on leaves and other tissues. The hairy trait has been neglected in Brassica breeding programs, which mainly focus on disease resistance, yield, and overall crop productivity. In Arabidopsis, a network of three classes of proteins consisting of TTG1 (a WD40 repeat protein), GL3 (a bHLH factor) and GL1 (a MYB transcription factor), activates trichome initiation and patterning. Introduction of a trichome regulatory gene AtGL3 from Arabidopsis into semi-glabrous Brassica napus resulted in hairy canola plants which showed tolerance to flea beetles and diamondback moths; however plant growth was negatively affected. In addition, the role of BnTTG1 transcription in the new germplasm was not understood. Results Here, we show that two ultra-hairy lines (K-5-8 and K-6-3) with BnTTG1 knock-down in the hairy AtGL3+ B. napus background showed stable enhancement of trichome coverage, density, and length and restored wild type growth similar to growth of the semi-glabrous Westar plant. In contrast, over-expression of BnTTG1 in the hairy AtGL3+ B. napus background gave consistently glabrous plants of very low fertility and poor stability, with only one glabrous plant (O-3-7) surviving to the T3 generation. Q-PCR trichome gene expression data in leaf samples combining several leaf stages for these lines suggested that BnGL2 controlled B. napus trichome length and out-growth and that strong BnTTG1 transcription together with strong GL3 expression inhibited this process. Weak expression of BnTRY in both glabrous and trichome-bearing leaves of B. napus in the latter Q-PCR experiment suggested that TRY may have functions other than as an inhibitor of trichome initiation in the Brassicas. A role for BnTTG1 in the lateral inhibition of trichome formation in neighbouring cells was also proposed for B. napus. RNA sequencing of first leaves identified a much larger array of genes with altered expression patterns in the K-5-8 line compared to the hairy AtGL3+ B. napus background (relative to the Westar control plant). These genes particularly included transcription factors, protein degradation and modification genes, but also included pathways that coded for anthocyanins, flavonols, terpenes, glucosinolates, alkaloids, shikimates, cell wall biosynthesis, and hormones. A 2nd Q-PCR experiment was conducted on redox, cell wall carbohydrate, lignin, and trichome genes using young first leaves, including T4 O-3-7-5 plants that had partially reverted to yield two linked growth and trichome phenotypes. Most of the trichome genes tested showed to be consistant with leaf trichome phenotypes and with RNA sequencing data in three of the lines. Two redox genes showed highest overall expression in K-5-8 leaves and lowest in O-3-7-5 leaves, while one redox gene and three cell wall genes were consistently higher in the two less robust lines compared with the two robust lines. Conclusion The data support the strong impact of BnTTG1 knockdown (in the presence of strong AtGL3 expression) at restoring growth, enhancing trichome coverage and length, and enhancing expression and diversity of growth, metabolic, and anti-oxidant genes important for stress tolerance and plant health in B. napus. Our data also suggests that the combination of strong (up-regulated) BnTTG1 expression in concert with strong AtGL3 expression is unstable and lethal to the plant

Back-to-back emission of the electrons in double photoionization of helium

We calculate the double differential distributions and distributions in recoil momenta for the high energy non-relativistic double photoionization of helium. We show that the results of recent experiments is the pioneering experimental manifestation of the quasifree mechanism for the double photoionization, predicted long ago in our papers. This mechanism provides a surplus in distribution over the recoil momenta at small values of the latter, corresponding to nearly "back-to-back" emission of the electrons. Also in agreement with previous analysis the surplus is due to the quadrupole terms of the photon-electron interaction. We present the characteristic angular distribution for the "back-to-back" electron emission. The confirmation of the quasifree mechanism opens a new area of exiting experiments, which are expected to increase our understanding of the electron dynamics and of the bound states structure. The results of this Letter along with the recent experiments open a new field for studies of two-electron ionization not only by photons but by other projectiles, e.g. by fast electrons or heavy ions.Comment: 10 pages, 2 figure

Selected Topics in High Energy Semi-Exclusive Electro-Nuclear Reactions

We review the present status of the theory of high energy reactions with semi-exclusive nucleon electro-production from nuclear targets. We demonstrate how the increase of transferred energies in these reactions opens a complete new window in studying the microscopic nuclear structure at small distances. The simplifications in theoretical descriptions associated with the increase of the energies are discussed. The theoretical framework for calculation of high energy nuclear reactions based on the effective Feynman diagram rules is described in details. The result of this approach is the generalized eikonal approximation (GEA), which is reduced to Glauber approximation when nucleon recoil is neglected. The method of GEA is demonstrated in the calculation of high energy electro-disintegration of the deuteron and A=3 targets. Subsequently we generalize the obtained formulae for A>3 nuclei. The relation of GEA to the Glauber theory is analyzed. Then based on the GEA framework we discuss some of the phenomena which can be studied in exclusive reactions, these are: nuclear transparency and short-range correlations in nuclei. We illustrate how light-cone dynamics of high-energy scattering emerge naturally in high energy electro-nuclear reactions.Comment: LaTex file with 51 pages and 23 eps figure

QED on Curved Background and on Manifolds with Boundaries: Unitarity versus Covariance

Some recent results show that the covariant path integral and the integral over physical degrees of freedom give contradicting results on curved background and on manifolds with boundaries. This looks like a conflict between unitarity and covariance. We argue that this effect is due to the use of non-covariant measure on the space of physical degrees of freedom. Starting with the reduced phase space path integral and using covariant measure throughout computations we recover standard path integral in the Lorentz gauge and the Moss and Poletti BRST-invariant boundary conditions. We also demonstrate by direct calculations that in the approach based on Gaussian path integral on the space of physical degrees of freedom some basic symmetries are broken.Comment: 29 pages, LaTEX, no figure

Model Calculations for the Two-Fragment Electro-Disintegration of 4^4He

Differential cross sections for the electro-disintegration process $e + {^4He} \longrightarrow {^3H}+ p + e'$ are calculated, using a model in which the final state interaction is included by means of a nucleon-nucleus (3+1) potential constructed via Marchenko inversion. The required bound-state wave functions are calculated within the integrodifferential equation approach (IDEA). In our model the important condition that the initial bound state and the final scattering state are orthogonal is fulfilled. The sensitivity of the cross section to the input $p{^3H}$ interaction in certain kinematical regions is investigated. The approach adopted could be useful in reactions involving few cluster systems where effective interactions are not well known and exact methods are presently unavailable. Although, our Plane-Wave Impulse Approximation results exhibit, similarly to other calculations, a dip in the five-fold differential cross-section around a missing momentum of $\sim 450 MeV/c$, it is argued that this is an artifact of the omission of re-scattering four-nucleon processes.Comment: 16 pages, 6 figures, accepted for publication by Phys.Rev.