Staff Publications

Staff Publications

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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

    Full text documents are added when available. The database is updated daily and currently holds about 240,000 items, of which 72,000 in open access.

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    The effect of me-substituents of 1,4-butanediol analogues on the thermal properties of biobased polyesters
    Klis, Frits van der; Knoop, Rutger J.I. ; Bitter, Johannes H. ; Broek, Lambertus A.M. van den - \ 2018
    Journal of Polymer Science. Part A, Polymer Chemistry 56 (2018)17. - ISSN 0887-624X - p. 1903 - 1906.
    biobased-building blocks - glass transition - polyesters - structure–property relations
    Biobased 1,4‐butanediol analogues are used to tune the glass transition temperature and crystallization in a series of polyesters, and allow for the formation of stereocomplexes.
    Isohexide hydroxy esters: synthesis and application of a new class of biobased AB-type building blocks
    Thiyagarajan, S. ; Wu, J. ; Knoop, J.R.I. ; Haveren, J. van; Lutz, M. ; Es, D.S. van - \ 2014
    RSC Advances : An international journal to further the chemical sciences 4 (2014)89. - ISSN 2046-2069 - p. 47937 - 47950.
    isosorbide - polyesters - derivatives - acid
    Here we present the synthesis of a new family of sugar derived 1,4: 3,6-dianhydrohexitol based AB-type monomers, containing one methyl ester group and a secondary hydroxyl group in all four possible stereo isomers (RR, RS, SR, SS). Structural characterization of the monomers (5a-d) was established by 1D and 2D NMR analysis, which was further confirmed by single-crystal X-ray structure determination. The application of these monomers in step-growth polymerization afforded fully isohexide based stereo-regular polyesters. Homo polyesters based on the RR and RS monomers were obtained with reasonable molecular weights by melt polymerization (Mn 2400 and 2500 resp.). These materials showed unexpectedly low glass-transition temperatures of 20 degrees C and 15 degrees C respectively. In contrast, the monomers with SR and SS configuration yielded only low molecular weight oligomers. Surprisingly, copolymerization of the RR and SR monomers gave a polyester with higher molecular weight (Mn 4100) and a high T-g of 80 degrees C. These preliminary results show that isohexide hydroxyesters are an intriguing new class of biobased building blocks with many potential applications.
    Waste Not, Want Not: Mild and Selective Catalytic Oxidation of Uronic Acids
    Klis, F. van der; Frissen, A.E. ; Haveren, J. van; Es, D.S. van - \ 2013
    ChemSusChem 6 (2013)9. - ISSN 1864-5631 - p. 1640 - 1645.
    acetalized galactaric acid - sugar-beet pulp - renewable resources - gold catalysts - polyesters - decarboxylation - glucose - chemicals - pectin - fdca
    And isn't it uronic: A mild, highly efficient and selective catalytic oxidation of pectin-derived uronic acids to the corresponding aldaric acids is reported. Fast, quantitative conversions (>99%) of the starting materials are achieved with high selectivity (>97%) at room temperature, using supported gold catalysts and air as oxidizing agent
    Synthesis of Isoidide through Epimerization of Isosorbide using Ruthenium on Carbon
    Notre, J.E.L. le; Haveren, J. van; Es, D.S. van - \ 2013
    ChemSusChem 6 (2013)4. - ISSN 1864-5631 - p. 693 - 700.
    dynamic kinetic resolution - chiral building-blocks - renewable resources - biodegradable polymers - secondary alcohols - catalytic isomerization - coating applications - succinic acid - polyesters - derivatives
    A highly efficient procedure for obtaining resin-grade isoidide through catalytic epimerization of isosorbide using a ruthenium-on-carbon (Ru/C) catalyst is reported. A comprehensive reaction-parameter variation study involving substrate concentration, catalyst (type of metal, support, and loading), initial pH value, hydrogen pressure, solvent, and reaction temperature demonstrates that superior performance and high selectivity can be achieved. Epimerization of isosorbide in water (pH 8) at 220¿°C, under 40 bar of hydrogen, and using a Ru/C catalyst (5¿% Ru) for 2 h results in a thermodynamic equilibrium mixture containing 55¿% isoidide, 40¿% isosorbide, and 5¿% isomannide. In comparison with previously reported nickel-based catalysts, the Ru/C catalyst is advantageous because it is highly active (as low as 360 ppm Ru) and recyclable. High purity isoidide is obtained by high-vacuum distillation of an equilibrium mixture on a 200 g scale. The high substrate loading (50 wt¿% in water), high selectivity, and the possibility for substrate reuse makes this procedure highly atom efficient and therefore, highly attractive for industrial use
    Green building blocks for biobased plastics: biobased processes and market development
    Harmsen, P.F.H. ; Hackmann, M.M. - \ 2013
    Wageningen : Wageningen UR - Food & Biobased Research (Green raw materials ) - ISBN 9789461736109 - 77
    bioplastics - biopolymeren - chemie op basis van biologische grondstoffen - biobased economy - materialen uit biologische grondstoffen - vinylkunststoffen - polyesters - amiden - polyurethanen - rubber - chemicaliën uit biologische grondstoffen - bioplastics - biopolymers - biobased chemistry - biobased economy - biobased materials - vinyl plastics - polyesters - amides - polyurethanes - rubber - biobased chemicals
    From a chemical perspective, nearly all building blocks for plastics can be made using renewable raw materials. However, not every process is commercially feasible. Processes often remain inefficient, products have insufficient purity or the raw materials are simply too expensive. This publication provides more insight into the processes that are currently under development and the companies involved, as well as the current development stage (from R&D to commercial production).
    Groene bouwstenen voor biobased plastics : biobased routes en marktontwikkeling
    Harmsen, P.F.H. ; Hackmann, M.M. - \ 2012
    Wageningen : Wageningen UR - Food & Biobased Research (Groene grondstoffen ) - ISBN 9789461734822 - 80
    bioplastics - biopolymeren - chemie op basis van biologische grondstoffen - biobased economy - materialen uit biologische grondstoffen - vinylkunststoffen - polyesters - amiden - polyurethanen - rubber - chemicaliën uit biologische grondstoffen - bioplastics - biopolymers - biobased chemistry - biobased economy - biobased materials - vinyl plastics - polyesters - amides - polyurethanes - rubber - biobased chemicals
    Chemisch gezien kunnen vrijwel alle bouwstenen voor plastics uit hernieuwbare grondstoffen worden gemaakt, maar niet elke route is commercieel haalbaar. Processen zijn vaak (nog) niet efficiënt genoeg, producten hebben een te lage zuiverheid of de grondstoffen zijn te duur. Deze uitgave geeft meer inzicht in de routes waar momenteel aan gewerkt wordt en door welk bedrijf, en in welk ontwikkelingsstadium de processen momenteel zijn (van R&D tot commerciële productie).
    Renewable Rigid Diamines: Efficient, Stereospecific Synthesis of High Purity Isohexide Diamines
    Thiyagarajan, S. ; Gootjes, L. ; Vogelzang, W. ; Haveren, J. van; Lutz, M. ; Es, D.S. van - \ 2011
    ChemSusChem 4 (2011)12. - ISSN 1864-5631 - p. 1823 - 1829.
    chiral building-blocks - polyesters - polycondensation - derivatives - polyamides - resources
    We report an efficient three-step strategy for synthesizing rigid, chiral isohexide diamines derived from 1,4:3,6-dianhydrohexitols. These biobased chiral building blocks are presently the subject of several investigations (in our and several other groups) because of their application in high-performance biobased polymers, such as polyamides and polyurethanes. Among the three possible stereo-isomers, dideoxy-diamino isoidide and dideoxy-diamino isosorbide can be synthesized from isomannide and isosorbide respectively in high yield with absolute stereo control. Furthermore, by using this methodology dideoxy-amino isomannide—a tricyclic adduct—was obtained starting from isoidide in high yield. Our improved synthetic route is a valuable advance towards meeting scale and purity demands for evaluating the properties of new biobased performance materials, which will benefit the development of these plastics.
    Novel Enzymatic Synthesis of 3-hydroxybutyric Acid Oligomerswith Inserted Lactobionic Acid Moieties
    Kakasi-Zsurka, S. ; Todea, A. ; But, A. ; Paul, C. ; Boeriu, C.G. ; Nagv, A. ; Davidescu, C.M. ; Peter, F. - \ 2011
    Revista de Chimie 62 (2011)10. - ISSN 0034-7752 - p. 958 - 963.
    polymerization - lipase - polyesters
    3-Hydroxybutyric acid and lactobionic acid yielded linear and cyclic oligomers in a lipase-catalyzedcondensation polymerization reaction, performed at 80°C in bulk and organic solvent systems. Novozyme435 was the most efficient biocatalyst, and a mixture of t-butanol and dimethylsulfoxide in 80:20 (v/v) ratioprovided the highest copolymer conversions. The highest degree of polymerization reached 7 in case ofcopolymers with inserted lactobionic acid moiety and 11 for the 3-hydroxybutyric acid homopolymer by-product.
    Biocatalytic synthesis of cyclic ester oligomers from biobased building blocks
    Habeych Narvaez, D.I. - \ 2011
    Wageningen University. Promotor(en): Gerrit Eggink, co-promotor(en): Carmen Boeriu. - [S.l.] : S.n. - ISBN 9789085859888
    polyesters - chemicaliën uit biologische grondstoffen - chemie op basis van biologische grondstoffen - bioraffinage - biokatalyse - candida - triacylglycerol lipase - industriële enzymen - biobased economy - polyesters - biobased chemicals - biobased chemistry - biorefinery - biocatalysis - candida - triacylglycerol lipase - industrial enzymes - biobased economy
    The general conclusion of this thesis is that CEOs from biobased building blocks can be synthesized by CALB‐catalyzed reaction and the bioreactor operation leads to successful increase on CEOs synthesis. In addition, the spatial configuration of the substrates influences not only the reaction yield, but also the possibility to form CEOs in reactions catalyzed by CALB.
    Biocatalytic synthesis of new copolymers from 3-hydroxybutyric acid and a carbohydrate lactone
    Kakasi-Zsurka, S. ; Todea, A. ; But, A. ; Paul, C. ; Boeriu, C.G. ; Davidescu, C. ; Nagy, L. ; Kuki, A. ; Keki, S. ; Peter, F. - \ 2011
    Journal of Molecular Catalysis. B, Enzymatic 71 (2011)1-2. - ISSN 1381-1177 - p. 22 - 28.
    ring-opening polymerization - lipase-catalyzed synthesis - enzymatic-synthesis - ionic liquids - polyesters
    Lipase-catalyzed reaction of 3-hydroxybutyric acid with d-glucono-d-lactone at 5:1 molar ratio and 80 °C yielded a mixture of moderate molecular weight linear and cyclic oligomers. The most efficient biocatalyst, Candida antarctica B lipase (Novozyme 435), allowed the synthesis of new oligomeric compounds with ring-opened gluconolactone units included in the oligomeric chain, without previous derivatization of the sugar, or activation of the acid monomer. The reaction medium nature had an important influence on the product composition. Although the main copolymer amount was synthesized in tert-butanol/dimethylsulfoxide medium, the highest polymerization degrees, up to 9 for the copolymer, and 10 for the 3-hydroxybutyric acid homopolymer co-product, were achieved in solventless conditions.
    Polylactide microcapsules and films: preparation and properties
    Sawalha, H.I.M. - \ 2009
    Wageningen University. Promotor(en): Remko Boom, co-promotor(en): Karin Schroen. - [S.l. : S.n. - ISBN 9789085853152 - 219
    inkapselen - films - polyesters - vervangbare hulpbronnen - biodegradatie - membranen - emulgering - hardwording - mechanische eigenschappen - thermische eigenschappen - ultrageluid - kunstmatige membranen - encapsulation - films - polyesters - renewable resources - biodegradation - membranes - emulsification - solidification - mechanical properties - thermal properties - ultrasound - artificial membranes
    This thesis aims at preparation of hollow polylactide (PLA) microcapsules for use as ultrasound contrast agents with controlled size, structure and mechanical and thermal properties. The microcapsules were prepared with multistage premix membrane emulsification. The mechanical and thermal properties of the microcapsules, and of films that were prepared under similar conditions, were highly dependent on the non-solvent and the liquid used as a template for the hollow core of the microcapsule. The size and size distribution of the microcapsules could, amongst others, be controlled through the process conditions that were applied during preparation. The main conclusion of this thesis was that the nonsolvent properties and the template liquid, highly affect the solidification process of the polymer; and through these parameters, the properties of PLA microcapsules and films can be effectively fine-tuned for various applications.
    Incorporation of Isosorbide into Poly(butylene terephthalate) via Solid-State Polymerization
    Sablong, R.J. ; Duchateau, R. ; Konings, C.E. ; Wit, G. de; Es, D.S. van; Koelewijn, R. ; Haveren, J. van - \ 2008
    Biomacromolecules 9 (2008)11. - ISSN 1525-7797 - p. 3090 - 3097.
    thermal-degradation - c-13 nmr - polyesters - temperature - polymers - diols - units - acid - pet
    The biomass-based monomer isosorbide was incorporated into poly(butylene terephthalate) (PBT) by solid-state polymerization (SSP) using the macrodiol monomer BTITB-(OH)2, which consists of isosorbide (I), terephthalic acid (T), and 1,4-butandiol (B) residues. This macromonomer can be synthesized by a simple one-pot, two-step reaction. Polymers with number-average molecular weights up to 100 000 g·mol¿1 were readily synthesized from various ratios of PBT/BTITB-(OH)2. Their molecular weights, thermal properties, and colors were compared with corresponding copolyesters that were obtained by melt polycondensation. We found that Tm, Tc, and especially Tg were superior for materials that were obtained by SSP. This is ascribed to differences in the microstructures of both types of copolyesters; the SSP products exhibit a more blocky structure than do the more random melt-polymerized counterparts. The SSP method resulted in much higher molecular weights and much less colored polymers, and it seems to be the preferred route for incorporating biobased monomers that exhibit limited thermal stability into engineering plastics.
    Co- and Terpolyesters based on isosorbide and succinic acid for coating applications : synthesis and characterization
    Noordover, B.A.J. ; Staalduinen, V.G. van; Duchateau, R. ; Koning, C.E. ; Benthem, R.A.T.M. van; Mak, M. ; Heise, A. ; Frissen, A.E. ; Haveren, J. van - \ 2006
    Biomacromolecules 7 (2006)12. - ISSN 1525-7797 - p. 3406 - 3416.
    end-groups - polyesters - esterification - poly(ethylene-terephthalate) - 1,4/3,6-dianhydro-d-glucitol - 1,4-3,6-dianhydrosorbitol - blends - uv
    Co- and terpolyesters based on succinic acid and isosorbide in combination with other renewable monomers such as 2,3-butanediol, 1,3-propanediol, and citric acid were synthesized and characterized. Linear polyesters were obtained via melt polycondensation of nonactivated dicarboxylic acids with OH functional monomers. Polymer end functionality (i.e., hydroxyl or carboxylic acid) was controlled by adjusting the monomer stoichiometry. The glass transition temperatures of the resulting polyesters could be effectively adjusted by varying the polymer composition and molar mass. By adding polyfunctional monomers such as trimethylolpropane or citric acid, polyesters with enhanced functionality were obtained. These biobased polyesters displayed functionalities and Tg values in the appropriate range for (powder) coating applications. The polyesters were cross-linked using conventional curing agents. Coatings from branched polyesters-hydroxyl as well as acid functional-showed significantly improved mechanical and chemical resistance compared to those formulated from linear polymers. These renewable polyesters proved to be suitable materials for coating applications with respect to solvent resistance, impact resistance, and hardness.
    Production of polyhydroxyalkanoates (PHAs) in transgenic potato
    Romano, A. - \ 2002
    Wageningen University. Promotor(en): L.H.W. van der Plas; R.G.F. Visser; H. Mooibroek. - S.l. : [s.n.] - ISBN 9789058087263 - 149
    solanum tuberosum - polymeren - polyesters - transgene planten - genetische transformatie - genetische modificatie - gentransfer - polyhydroxyalkanoaten - solanum tuberosum - polymers - polyesters - transgenic plants - genetic transformation - genetic engineering - gene transfer - polyhydroxyalkanoates

    Polyhydroxyalkanoates (PHAs) represent a large class of microbial polyesters which are widely distributed in prokaryotes. Because of the current environmental concerns related to the use of mineral-oil-based plastics, PHAs gained a considerable interest for their possible use as biodegradable polymers. In recent years the possible fields of application for PHAs have broadened and a considerable number of novel uses of PHAs as rubber material, coating material, binder in paints and several medical applications have been developed. However, high costs related to the fermentative production of PHAs in natural or recombinant microorganisms hampered the production of PHAs on large scale and the expansion of the utilisation of PHAs into society. The use of transgenic plants for the production of PHAs has been considered an excellent and elegant strategy to accumulate bulk amounts of PHAs at low costs. In this thesis, the possibility to produce PHAs in transgenic potato was investigated. A number of metabolic engineering strategies has been considered and the accumulation of low amounts of PHAs in transgenic potato lines has been achieved.

    PHA production is one of those traits that require the coordinate expression of several genes. Because the minimum gene set required for PHA accumulation was not completely known at the beginning of the experiments described in this thesis, a flexible system was required for gene-transfer into the potato genome in order to avoid time-consuming or technically difficult approaches (multiple genes plant vector construction, crossing, re-transformation). It was advantageous to introduce simultaneously into the potato genome all the genes of interest delivered via separate DNA molecules. This allowed the easy combination of different sets of genes to establish the minimum gene-set required for PHA accumulation in potato. Although Agrobacterium -mediated transformation is a well established technique to deliver alien genes into potato, our preliminary analyses showed that it was not suitable for simultaneous co-transformation using separate plasmids. Thus, we developed a particle bombardment-mediated procedure to introduce simultaneously into the potato genome several genes from separate plasmids or separate linear DNA fragments. The particle bombardment protocol established during the course of this project proved to be very efficient and comparable with Agrobacterium -mediated transformation. We observed that transgenic potato plants obtained by particle bombardment showed relatively simple patterns of integration of the transgenes and integration of different transgenes at independent sites into the plant genome. The system also proved applicable for co-transformation of potato using gene cassettes, i.e. DNA fragments comprising promoter - gene - terminator.

    Particle bombardment-mediated co-transformation was subsequently used to introduce the genes involved in the PHA biosynthetic pathways. Four methods were considered for the production of PHAs in potato.

    Method 1. The accumulation of the homopolymer polyhydroxybutyrate (PHB) was achieved after Ralstonia eutrophaphb B and phb C genes coding for an NADPH-dependent acetoacetyl-CoA reductase and for the PHB-polymerase, respectively, were expressed in transgenic potato lines. Because the minimum gene set for PHB production in plants was well documented when this project started, the possible production of PHB seemed to be the simplest model to test the ability of potato to accumulate PHAs. Indeed, PHB formation in small amounts was observed.

    Subsequently, we attempted the production of the heteropolymer medium-chain-length (mcl)-PHA in potato.

    Method 2. To study the expression of the Pseudomonas oleovorans mcl-PHA-polymerase in potato, the polymerase was first expressed in the cytoplasm, where no post-transcriptional modification of the polypeptide is needed. Proper expression of the mcl-PHA polymerase was indeed observed in selected transgenic lines. However, because the cytoplasm of potato does not contain suitable substrates for the polymerase (mcl-hydroxy fatty acids), substrate feeding experiments were performed. These experiments resulted in the accumulation of low amounts of mcl-PHA.

    Methods 3 and 4. Afterwards, mcl-PHA accumulation was attempted in plastids, by re-directing hydroxy fatty acid precursors from FAB to mcl-PHA biosynthesis. A truncated form of E. coli thioesterase-I ( tes A gene. Method 3) and P. putida ACP-CoA-transacylase ( pha G gene. Method 4) were expressed in combination with the Pha-C1 polymerase. All heterologous proteins were targeted to the plastid by N terminal fusion with the Rubisco transit peptide. The two combinations of genes (Pha-C1 plus thioesterase, and Pha-C1 plus transacylase) represent theoretically the minimum gene set for mcl-PHA accumulation deriving precursors from FAB. The double transformants which expressed the Pha-C1 polymerase and the thioesterase-I did not accumulate mcl-PHA because a fewb-oxidation steps may be required to provide the proper precursor to the polymerase. However, simultaneous expression of the Pha-C1 polymerase and the ACP-CoA-transacylase did result in the synthesis of low amounts of mcl-PHA in leaves of intact plants.

    We established several possible routes to achieve the accumulation of PHAs in transgenic potato, based on the use of the endogenous pool of acetyl-CoA, on feeding approaches of cell suspension cultures or on using precursors derived from de novo FAB. Although improvements in these systems are still required in order to increase the yields of PHAs, the results open new prospects for the accumulation of PHAs in potato. Final conclusions on the future development of production of PHAs in plants are overviewed. Advantages and disadvantages of fermentation-based-PHAs, plant-based-PHAs, other biodegradable polymers and oil-based-plastics are compared. Novel and future possible interesting applications of PHAs not based on bulk productions, are also described.

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