Integrated 3D-printed reactionware for chemical synthesis and analysis

Journal name:
Nature Chemistry
Volume:
4,
Pages:
349–354
Year published:
DOI:
doi:10.1038/nchem.1313
Received
Accepted
Published online

Abstract

Three-dimensional (3D) printing has the potential to transform science and technology by creating bespoke, low-cost appliances that previously required dedicated facilities to make. An attractive, but unexplored, application is to use a 3D printer to initiate chemical reactions by printing the reagents directly into a 3D reactionware matrix, and so put reactionware design, construction and operation under digital control. Here, using a low-cost 3D printer and open-source design software we produced reactionware for organic and inorganic synthesis, which included printed-in catalysts and other architectures with printed-in components for electrochemical and spectroscopic analysis. This enabled reactions to be monitored in situ so that different reactionware architectures could be screened for their efficacy for a given process, with a digital feedback mechanism for device optimization. Furthermore, solely by modifying reactionware architecture, reaction outcomes can be altered. Taken together, this approach constitutes a relatively cheap, automated and reconfigurable chemical discovery platform that makes techniques from chemical engineering accessible to typical synthetic laboratories.

At a glance

Figures

  1. The Fab@Home Version 0.24 RC6 freeform fabricator.
    Figure 1: The Fab@Home Version 0.24 RC6 freeform fabricator.

    a, The fabricator viewed from the front, with a single syringe of acetoxysilicone polymer loaded in the printing head. The white area below the printing head is a square of ordinary paper onto which the reactionware was printed. b, The fabricator printing one of the devices used in this work. c, Schematic of the as-printed multipurpose reactionware used in the synthesis of compounds 13, which shows the key features of the design.

  2. The synthesis and crystallization of polyoxometalates in the 3D-printed reactionware.
    Figure 2: The synthesis and crystallization of polyoxometalates in the 3D-printed reactionware.

    a, Photographs of the crystallization of (C2H8N)7Na4[W19Co2O61Cl(SeO3)2(H2O)2]Cl2·6H2O at various times after the initial mixing. b, Synthesis and ball-and-stick representation of the structure of ((C2H8N)3[W19M2O61Cl(SeO3)2(H2O)2])6− (M = Co(II) or Mn(II)). Protons are omitted for clarity. Black, teal, cyan, green, violet, dark blue and red represent C, N, O, Se, Cl, W and M, respectively.

  3. The synthesis of heterocycle 3 in 3D-printed reactionware.
    Figure 3: The synthesis of heterocycle 3 in 3D-printed reactionware.

    a, Synthetic scheme with a ball-and-stick representation of the crystal structure of the organic phenanthridine-based heterocycle 3. Grey, black, light blue and pink represent protons, C, N and O, respectively. b, The partial 1H NMR spectrum (400 MHz, d6-DMSO, 298 K) of heterocycle 3.

  4. The 3D-printed reactionware used for in situ spectroscopies.
    Figure 4: The 3D-printed reactionware used for in situ spectroscopies.

    a, The reactionware as a cell for electrochemistry in a three-electrode configuration. b,c, The reactionware used for spectroelectrochemistry. d, Cyclic voltammetry, as recorded using the set-up shown in (a–c), for PMA (5 mM in 0.1 M H2SO4) at a scan rate of 0.1 V s−1. e, Partial UV-vis spectrum obtained during the electrochemical cycling of the PMA solution. Relative absorbances are normalized at 500 nm. The active surface area of the ITO working electrode was 2.0 cm2. Black dashed line = before reduction, red solid line = after partial reduction.

  5. The 3D-printed electrochemical cell and electrodes.
    Figure 5: The 3D-printed electrochemical cell and electrodes.

    a, The reactionware used for in situ spectroscopies showing the two conductive electrodes based on carbon black. The working electrode (upper line) had an area exposed to the reaction medium of approximately 0.8 × 0.1 cm2 and the reference/counter electrode rail (lower line) had an exposed area of 1.0 × 0.2 cm2. b, The connected cell filled with 1 ml of 5 mM PMA in 0.1 M H2SO4 before electrochemical reduction. c, The same cell after reduction at −2.5 V for 4,500 seconds. d, The charge passed versus time curve for the reduction process shows that the current was constant over the time course of the experiment.

  6. The 3D-printed reactionware-assisted selective syntheses of C22H20N2O (4) and C22H19BrN2O (5).
    Figure 6: The 3D-printed reactionware-assisted selective syntheses of C22H20N2O (4) and C22H19BrN2O (5).

    The outcome of the reaction can be switched between these two products by simply altering the reactor architecture. For Reactor A, both reagents flow completely into the lower reaction chamber, but for Reactor B some 5-(2-bromoethyl)phenanthridinium bromide solution remains unreacted after mixing because of the smaller volume of the reaction chamber. Hence, the dimensions of the reactionware control the outcome of the reaction.

Compounds

3 compounds View all compounds
  1. 1-(4-Hydroxyphenyl)-2,3-dihydro-1H-imidazo[1,2-f]phenanthridin-4-ylium bromide
    Compound 3 1-(4-Hydroxyphenyl)-2,3-dihydro-1H-imidazo[1,2-f]phenanthridin-4-ylium bromide
  2. 1-(4-Methoxyphenyl)-1,2,3,12b-tetrahydroimidazo[1,2-f]phenanthridine
    Compound 4 1-(4-Methoxyphenyl)-1,2,3,12b-tetrahydroimidazo[1,2-f]phenanthridine
  3. 1-(4-Methoxyphenyl)-2,3-dihydro-1H-imidazo[1,2-f]phenanthridin-4-ylium bromide
    Compound 5 1-(4-Methoxyphenyl)-2,3-dihydro-1H-imidazo[1,2-f]phenanthridin-4-ylium bromide

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Author information

  1. These authors contributed equally to this work

    • Mark D. Symes,
    • Philip J. Kitson &
    • Jun Yan

Affiliations

  1. WestCHEM, School of Chemistry, The University of Glasgow, University Avenue, Glasgow G12 8QQ, UK

    • Mark D. Symes,
    • Philip J. Kitson,
    • Jun Yan,
    • Craig J. Richmond,
    • Geoffrey J. T. Cooper &
    • Leroy Cronin
  2. School of Physics & Astronomy, Kelvin Building, The University of Glasgow, University Avenue, Glasgow G12 8QQ, UK

    • Richard W. Bowman
  3. Uformia AS, Industriveien 6, 9062 Furuflaten, Norway

    • Turlif Vilbrandt

Contributions

L.C. conceived the idea and the organized the fabricator assembly, M.D.S., P.J.K., T.V., G.J.T.C. and R.W.B. designed the reactionware, M.D.S. and P.J.K. printed the devices, M.D.S., P.J.K., J.Y. and C.J.R. performed the experiments, L.C., M.D.S, P.J.K., J.Y. and C.J.R. analysed the results and M.D.S. and L.C. co-wrote the paper.

Competing financial interests

The authors declare no competing financial interests.

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