Renewable Resources Robert-Jan van Putten,†,‡ Jan C. van der Waal,† Ed de Jong,*,† Carolus B. Rasrendra,‡,⊥ Hero J. Heeres,*,‡ and Johannes G. de Vries* †Avantium Chemicals, Zekeringstraat 29, 1014 BV Amsterdam, the Netherlands ‡Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, the Netherlands DSM Innovative Synthesis BV, P.O. Box 18, 6160 MD Geleen, the Netherlands Department of Chemical Engineering, Institut Teknologi Bandung, Ganesha 10, Bandung 40132, Indonesia

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources

Human skin is a remarkable organ. It consists of an integrated, stretchable network of sensors that relay information about tactile and thermal stimuli to the brain, allowing us to maneuver within our environment safely and effectively. Interest in large-area networks of electronic devices inspired by human skin is motivated by the promise of creating autonomous intelligent robots and biomimetic prosthetics, among other applications. The development of electronic networks comprised of flexible, stretchable, and robust devices that are compatible with large-area implementation and integrated with multiple functionalities is a testament to the progress in developing an electronic skin (e-skin) akin to human skin. E-skins are already capable of providing augmented performance over their organic counterpart, both in superior spatial resolution and thermal sensitivity. They could be further improved through the incorporation of additional functionalities (e.g., chemical and biological sensing) and desired properties (e.g., biodegradability and self-powering). Continued rapid progress in this area is promising for the development of a fully integrated e-skin in the near future.

25th Anniversary Article: The Evolution of Electronic Skin (E-Skin): A Brief History, Design Considerations, and Recent Progress

Micromachining technology was used to prepare chemical analysis systems on glass chips (1 centimeter by 2 centimeters or larger) that utilize electroosmotic pumping to drive fluid flow and electrophoretic separation to distinguish sample components. Capillaries 1 to 10 centimeters long etched in the glass (cross section, 10 micrometers by 30 micrometers) allow for capillary electrophoresis-based separations of amino acids with up to 75,000 theoretical plates in about 15 seconds, and separations of about 600 plates can be effected within 4 seconds. Sample treatment steps within a manifold of intersecting capillaries were demonstrated for a simple sample dilution process. Manipulation of the applied voltages controlled the directions of fluid flow within the manifold. The principles demonstrated in this study can be used to develop a miniaturized system for sample handling and separation with no moving parts.

Micromachining a miniaturized capillary electrophoresis-based chemical analysis system on a chip

5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications

http://alpha.chem.umb.edu/chemistry/ch612/documents/CastellanoCoordChemrev.pdf

Photon upconversion based on sensitized triplet-triplet annihilation

A highly elastic and stretchable conductive polymer material resulted from blending the conductive polymer poly(3,4-ethylenedioxythiophene):p-tosylate and an aliphatic polyurethane elastomer. The blend inherited advantageous properties from its constituents, namely high conductivity of 120 S cm–1 from its conductive polymer component, and elastomeric mechanical properties resembling those of the polyurethane, including good adhesion to various substrates. Stretching of the blend material by up to 50 % resulted in increased conductivity, while subsequent relaxation to the unstretched state caused a decrease of conductivity compared to the pristine blend. These initial changes in conductivity were reproducible on further cycling between 50 % stretching and the unstretched state for at least 10 cycles. Stretching beyond 50 % resulted in decreasing conductivity of the blend but with substantial conductivity remaining even when stretched by 200 %. Optical, mechanical, and thermal properties of the blend, as well as high resolution electron microscopy of bulk cross-sections, suggest that the system is a single phase and not two separate phases. Ageing experiments indicate that the material retains substantial conductivity for at least a few years at room temperature.

Highly Stretchable and Conductive Polymer Material Made from Poly(3,4-ethylenedioxythiophene) and Polyurethane Elastomers

The development of biorefineries means that a key feedstock for many new processes will be sugars in various forms, such as glucose or fructose. From these feedstocks a range of chemicals can be synthesized using heterogeneous catalysis, immobilized enzymes, homogeneous catalysts, soluble enzymes, fermentations or combinations thereof. This presents a particularly interesting process integration challenge since the optimal conditions for each conversion step will be considerably different from each other. Furthermore, compared to oil-based refineries the feedstock represents a relatively high proportion of the final product value and therefore yield and selectivity in these steps are of crucial importance. In this paper using the conversion of glucose to 2,5-furandicarboxylic acid and associated products as an example, alternative routes will be compared with respect to achievable selectivity, and achievable yield.

Process integration for the conversion of glucose to 2,5-furandicarboxylic acid

http://www.chtf.stuba.sk/~szolcsanyi/education/files/Chemia%20heterocyklickych%20zlucenin/Prednaska%207/Doplnkove%20studijne%20materialy/Hydroxymethylfurfural/Synergy%20of%20boric%20acid%20and%20added%20salts%20in%20the%20catalytic%20dehydration%20of%20hexoses%20to%20HMF%20in%20water.pdf

Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water

The renewable chemical building block 5-hydroxymethylfurfural (HMF) was oxidized to 2,5-diformylfuran by an oxidation system consisting of the radical 2,2,6,6-tetramethyl-piperidin-1-oxyl (TEMPO) and CuCl. The system was optimized by exploring several reaction conditions and by employing nitrogen containing promoters (NCPs) to obtain excellent yields. In acetonitrile a 95% DFF yield was obtained after 24 h with ambient pressure of dioxygen at room temperature in the presence of different NCPs, which – to our knowledge – is the best result reported thus far for this reaction. The use of NCPs made it further possible to apply various traditional solvents, e.g. acetone, methanol and methyl isobutyl ketone for the reaction. The latter can be used as extraction solvent for HMF synthesis in aqueous media and thus integrate the two processes. Additionally, HMF was oxidized to 2,5-furandicarboxylic acid by a modified oxidation protocol consisting of CuCl and t-BuOOH. In all the reactions, mild conditions, including room temperature were employed.

Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

Click chemistry is used to obtain new conductive polymer films based on poly(3,4-ethylenedioxythiophene) (PEDOT) from a new azide functional monomer. Postpolymerization, 1,3-dipolar cycloadditions in DMF, using a catalyst system of CuSO4 and sodium ascorbate, and different alkynes are performed to functionalize films of PEDOT-N3 and copolymers prepared from EDOT-N3 and 3,4-ethylenedioxythiophene (EDOT). This approach enables new functionalities on PEDOT that could otherwise not withstand the polymerization conditions. Reactions on the thin polymer films have been optimized using an alkynated fluorophore, with reaction times of ∼20 h. The applicability of the method is illustrated by coupling of two other alkynes: a short chain fluorocarbon and a MPEG 5000 to the conductive polymer; this alters the advancing water contact angle of the surface by +20° and −20°/−25°, respectively. The targeted chemical surface modifications have been verified by X-ray photoelectron spectroscopy analysis.

Thomas Steen Hansen

Papers

Highly Stretchable and Conductive Polymer Material Made from Poly(3,4-ethylenedioxythiophene) and Polyurethane Elastomers

Process integration for the conversion of glucose to 2,5-furandicarboxylic acid

Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water

Cu catalyzed oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid under benign reaction conditions

Conductive Polymer Functionalization by Click Chemistry