7 research outputs found
1H CSA parameters by ultrafast MAS NMR: measurement and applications to structure refinement
A 1H anisotropic-isotropic chemical shift correlation experiment which employs symmetry-based recoupling sequences to reintroduce the chemical shift anisotropy in ν1 and ultrafast MAS to resolve 1H sites in ν2 is described. This experiment is used to measure 1H shift parameters for L-ascorbic acid, a compound with a relatively complex hydrogen-bonding network in the solid. The 1H CSAs of hydrogen-bonded sites with resolved isotropic shifts can be extracted directly from the recoupled lineshapes. In combination with DFT calculations, hydrogen positions in crystal structures obtained from X-ray and neutron diffraction are refined by comparison with simulations of the full two-dimensional NMR spectrum. The improved resolution afforded by the second dimension allows even unresolved hydrogen-bonded sites 1H to be assigned and their shift parameters to be obtained
Ectopic callose deposition into woody biomass modulates the nano-architecture of macrofibrils
Plant biomass plays an increasingly important role in the circular bioeconomy, replacing non-renewable fossil resources. Genetic engineering of this lignocellulosic biomass could benefit biorefinery transformation chains by lowering economic and technological barriers to industrial processing. However, previous efforts have mostly targeted the major constituents of woody biomass: cellulose, hemicellulose and lignin. Here we report the engineering of wood structure through the introduction of callose, a polysaccharide novel to most secondary cell walls. Our multiscale analysis of genetically engineered poplar trees shows that callose deposition modulates cell wall porosity, water and lignin contents and increases the lignin-cellulose distance, ultimately resulting in substantially decreased biomass recalcitrance. We provide a model of the wood cell wall nano-architecture engineered to accommodate the hydrated callose inclusions. Ectopic polymer introduction into biomass manifests in new physico-chemical properties and offers new avenues when considering lignocellulose engineering.Bourdon et al. demonstrate the possibility to ectopically synthesize callose, a polymer restricted to primary cell walls, into Arabidopsis and aspen secondary cell walls to manipulate their ultrastructure and ultimately reduce their recalcitrance
Importance of Water in Maintaining Softwood Secondary Cell Wall Nanostructure.
Water is one of the principal constituents by mass of living plant cell walls. However, its role and interactions with secondary cell wall polysaccharides and the impact of dehydration and subsequent rehydration on the molecular architecture are still to be elucidated. This work combines multidimensional solid-state 13C magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) with molecular dynamics modeling to decipher the role of water in the molecular architecture of softwood secondary cell walls. The proximities between all main polymers, their molecular conformations, and interaction energies are compared in never-dried, oven-dried, and rehydrated states. Water is shown to play a critical role at the hemicellulose-cellulose interface. After significant molecular shrinkage caused by dehydration, the original molecular conformation is not fully recovered after rehydration. The changes include xylan becoming more closely and irreversibly associated with cellulose and some mannan becoming more mobile and changing conformation. These irreversible nanostructural changes provide a basis for explaining and improving the properties of wood-based materials.New Zealand Ministry of Business, Innovation and Employment
(MBIE) Endeavour Fund (Contract No. C04X1707, Fibre
Grand Design)
The European Research
Council (ERC Starting Grant 639907 awarded to Józef
Lewandowski) and the University of Warwick funded the
700 MHz Bruker Avance III spectromete
NMR Data files "Eudicot primary cell wall glucomannan is related in synthesis, structure, and function to xyloglucan"
Zip files contain unprocessed data of solid-state NMR on Arabidopsis wild-type callus and mutant calli, irx9l xxt1 xxt2, csla2 xxt1 xxt2, which were described in the paper published in The Plant Cell. Each zip file contains a different experiment. Microsoft Word file describes the keys for each experiment. Zip file no. 10, 30, and 1000 contain the data of 2D CP-INADEQUATE of irx9l xxt1 xxt2, wild-type, and csla2 xxt1 xxt2, which detect immobile components in the samples. Zip file no. 20 contains 2D DP-INADEQUATE of irx9l xxt1 xxt2, which detects mobile components in the sample. See the main manuscript for more details on sample collection, data acquisition, and interpretation of the data
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Research data supporting “Ectopic callose deposition into woody biomass modulates the nano-architecture of macrofibrils”
The repository is divided in distinct folders which contain the raw data necessary to produce each figure of the “Ectopic callose deposition into woody biomass modulates the nano-architecture of macrofibrils” manuscript. As such, each folder is named after the figure it is referring to, and often contains several subfolders distinguishing the different data sets necessary to produce each figure. Each subfolder name ends up with the initials of the main co-author(s) originating the data they contain.
See the 'Repository_readme' file for a detailed description of this dataseto The UK High-Field Solid-State NMR Facility used in this research was funded by EPSRC and BBSRC (EP/T015063/1) as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). We thank the Cambridge Advanced Imaging Center (CAIC) for providing access to their TEM resources and for technical assistance in imaging. The lignin analysis was supported by the Soluserre funding (Région Pays de la Loire, France). The authors acknowledge the funding received from the New Zealand Ministry of Business, Innovation, and Employment (MBIE) Strategic Science Investment Fund (Contract No. C0X41703, High-Value Biorefineries Portfolio) for supporting this work. FV acknowledges support from the Swedish Research Council (grants 621-2014-5295 and 2020-04720) and from the Knut and Alice Wallenberg Foundation (through the Wallenberg Wood Science Centre). Work in the YBA lab is supported by the Leverhulme Trust (Grant RPG-2016-136) which funded S.A. and C.P. and the UKRI Future Leader Fellowship program (MR/T04263X/1). Work in the JJL lab is supported by a grant from the National Science Centre Poland awarded to JJL as part of the SONATINA 3 programme (project number 2019/32/C/NZ3/00392) and a grant from National Science Centre Poland awarded as part of SONATA 17 programme (project number 2021/43/D/NZ9/01978). MB was supported by the ERC Proof of Concept APPLICAL (2020-2022) and the HiLife Proof of Concept APPLICAL (2020-2021) grants. L.K. received funding from the SNSF (P2LAP3_178062) and a Marie Curie IEF (No. 795250). Work in the YH lab was supported by the Finnish CoE in Molecular Biology of Primary Producers (Academy of Finland CoE programme 2014–2019) decision n°. 271832, the Gatsby Foundation (GAT3395/PR3), the University of Helsinki (award 799992091) and the ERC Advanced Investigator Grant SYMDEV (No. 323052)
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Ectopic callose deposition into woody biomass modulates the nano-architecture of macrofibrils.
Acknowledgements: We thank G. Evans for technical support with microscopy experiments; L. Wang for statistical analysis assistance; G. Hindle, J. Salmon and S. Ward for media preparation; K. Blajecka for technical assistance; J. Daff, L. Tully, B. Fidget, A. Jootoo and G. Porteous for Horticulture assistance; M. Calatraba for lignin analysis; T. Weber from the ETH X-Ray Service Platform for technical support with the SAXS equipment; and K. Kainulainen for in vitro maintenance and horticulture assistance. R.C. was supported by UK BBSRC (Grant BB/R015783/1) to R.D. The UK High-Field Solid-State NMR Facility used in this research was funded by EPSRC and BBSRC (EP/T015063/1) as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF). We thank the Cambridge Advanced Imaging Centre (CAIC) for providing access to their TEM resources and for technical assistance in imaging. Lignin analysis was supported by the Soluserre funding (Région Pays de la Loire, France). The authors acknowledge the funding received from the New Zealand Ministry of Business, Innovation, and Employment (MBIE) Strategic Science Investment Fund (Contract No. C0X41703, High-Value Biorefineries Portfolio). Part of this research was conducted as part of the Scion-INRAE-U Montpellier–Institut Agro Associated International Laboratory BIOMATA. F.V. acknowledges support from the Swedish Research Council (grants 621-2014-5295 and 2020-04720) and from the Knut and Alice Wallenberg Foundation (through the Wallenberg Wood Science Centre). Work in the Y.B.-A. lab was supported by the Leverhulme Trust (Grant RPG-2016-136), which funded S.A., and the UKRI Future Leader Fellowship programme (MR/T04263X/1). Work in the J.J.L. lab was supported by a grant from the National Science Centre Poland awarded to J.J.L. as part of the SONATINA 3 programme (project number 2019/32/C/NZ3/00392) and a grant from the National Science Centre Poland awarded as part of the SONATA 17 programme (project number 2021/43/D/NZ9/01978). M.B. was supported by ERC Proof of Concept APPLICAL (2020-2022) and HiLife Proof of Concept APPLICAL (2020-2021) grants. L.K. received funding from the SNSF (P2LAP3_178062) and a Marie Curie IEF (No. 795250). Work in the Y.H. lab was supported by the Finnish CoE in Molecular Biology of Primary Producers (Academy of Finland CoE programme 2014–2019; decision no. 271832), the Gatsby Foundation (GAT3395/PR3), the University of Helsinki (award 799992091) and the ERC Advanced Investigator Grant SYMDEV (No. 323052).Funder: Matthieu Bourdon was supported by the ERC Proof of Concept APPLICAL (2020-2022) and the HiLife Proof of Concept APPLICAL (2020-2021) grantsFunder: Work in the Lyczakowski lab is supported by a grant from the National Science Centre Poland awarded to JJL as part of the SONATINA 3 programme (project number 2019/32/C/NZ3/00392) and a grant from National Science Centre Poland awarded as part of SONATA 17 programme (project number 2021/43/D/NZ9/01978)Funder: The UK High-Field Solid-State NMR Facility used in this research was funded by EPSRC and BBSRC (EP/T015063/1) as well as the University of Warwick including via part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF)Funder: Francisco Vilaplana acknowledges support from the Swedish Research Council (grants 621-2014-5295 and 2020-04720) and from the Knut and Alice Wallenberg Foundation (through the Wallenberg Wood Science Centre)Funder: funding received from the New Zealand Ministry of Business, Innovation, and Employment (MBIE) Strategic Science Investment Fund (Contract No. C0X41703, High-Value Biorefineries Portfolio)Funder: Lothar Kalmbach received funding from the SNSF (P2LAP3_178062) and a Marie Curie IEF (No. 795250)Funder: The lignin analysis was supported by the Soluserre funding (Région Pays de la Loire, France)Funder: Work in the Benitez-Alfonso lab is supported by the Leverhulme Trust (Grant RPG-2016-136) which funded S.A. and C.P. and the UKRI Future Leader Fellowship program (MR/T04263X/1)Funder: Work in the Helariutta lab was supported by the Finnish CoE in Molecular Biology of Primary Producers (Academy of Finland CoE programme 2014amp;#x2013;2019) decision n°. 271832, the Gatsby Foundation (GAT3395/PR3), the University of Helsinki (award 799992091) and the ERC Advanced Investigator Grant SYMDEV (No. 323052)Plant biomass plays an increasingly important role in the circular bioeconomy, replacing non-renewable fossil resources. Genetic engineering of this lignocellulosic biomass could benefit biorefinery transformation chains by lowering economic and technological barriers to industrial processing. However, previous efforts have mostly targeted the major constituents of woody biomass: cellulose, hemicellulose and lignin. Here we report the engineering of wood structure through the introduction of callose, a polysaccharide novel to most secondary cell walls. Our multiscale analysis of genetically engineered poplar trees shows that callose deposition modulates cell wall porosity, water and lignin contents and increases the lignin-cellulose distance, ultimately resulting in substantially decreased biomass recalcitrance. We provide a model of the wood cell wall nano-architecture engineered to accommodate the hydrated callose inclusions. Ectopic polymer introduction into biomass manifests in new physico-chemical properties and offers new avenues when considering lignocellulose engineering