Integrated platforms for chemical synthesis

and crystallisation Victor Sans Cronin Lab http://www.chem.gla.ac.uk/cronin/

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• Polyoxometalates are anionic oxide molecules derived from partially reduced early transition metals, usually Mo, W and V formed by self-assembly under acidic conditions

• Vast range of potential applications in biology, electronics, magnetism, catalysis

• Extremely dependent on reaction conditions

[MoO4]2- {Mo154} {Mo132}

• pH • Temperature • ionic strength • reducing agent

One-pot

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• Difficult to synthesise/crystallise

• Low yields/poor reproducibility

• Labour intensive

• Harsh reaction conditions

• Discovery difficult and limited to specialised laboratories

Automated flow set-ups have the potential to overcome these limitations.

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The ‘CMAC’ experiment

Linear Flow System

5 Nature Chem., 2012, 4, 1037-1043

Polyoxometalate discovery and scale-up

6

Automated screening of reaction space

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• Highly reproducible results

• Rapid optimisation of reaction conditions

3D-printing, design and fabricate at home

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3D-printing chemical ‘reactionware’

9 Nature Chem., 2012, 4, 349-354

3D-print your own reactors

10 Lab Chip, 2012, 12, 3267-3271

R1 R2 R3

Printing Time (h) 2 4 4

Reactor Weight (g) 3.9 8.8 13.4

Printing Materials Cost (US$)

0.09 0.20 0.31

Dimensions (mm) 25x50x3 56x52x6 40x30x20

Inorganic chemistry in 3D-printed reactionware

11

{MoO4} HCl

Na2S2O4 {Mo36} {Mo154}

Organic Chemistry in 3D-printed devices

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• Continuous-flow synthesis of a simple imine. • Rapid and facile kinetic study possible. • Multi-step synthesis in one reactor.

Nanomaterials synthesis in 3D-printed reactionware

13 Synthesis of gold nanoparticles in flow mixing aqueous solutions of HAuCl4 with NABH4–citrate.

14 Beilstein J. Nanotechnol. 2013, 4, 285–291.

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• Automated flow array for discovery and scale-up of

inorganic clusters

• Flow chemistry in 3D-printed devices

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http://www.beilstein.tv/tvpost/3d-printed-millifluidic-reactionware-for-synthesis-and-analysis http://www.beilstein.tv/tvpost/3d-printed-reactionware/

Acknowledgements

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Prof. Lee Cronin

Dr. Craig J. Richmond

A. Ruiz de la Oliva

V. Dragone

Dr. Phil Kitson The Cronin Group 2012/13

Dr. Mali S. Rosnes

Dr. Jennifer Boyle

Dr. De-Liang Long

Cronin group

18

2. Chemical synthesis in 3D printed reactionware

19

Entry Product Yield (%)

1 78

2 99

3 96

4 97

HN

4a

NH

4b

CF3

NH

4c

Cl

HN

4d

Organic chemistry in 3D-printed reactionware