How crystals are made and why this really matters Mike Zaworotko

Bernal Professor of Crystal Engineering & SFI Research ProfessorUniversity of Limerick

23rd February 2015 1st Brasil-Ireland Science Week

Addressing human disease and environmental sustainability trump all else.

The “right chemistry” is at the heart of both matters.

Individual research groups and individual countries cannot solve the big problems alone – we are all “wearing the green”.

Being “competitive” is not enough – the rewards do not go to the runners-up.

Some immediate low cost, low risk but high reward opportunities are crystal clear.

My 2 cents worth

The vast majority of substances form one or more crystalline solids that exhibit a regular repeating array of molecules that extends in 3D.

This brings purity, consistency and easy processing.

solution supersaturated solution crystalThe Basics: Compounds form Crystals

First some ancient history – 2000+ years agoPasteur’s spontaneous resolution

experiment in 1848 started the field of stereochemistry

The original “crystal”, named after the Greek word κρύσταλλος (krystallos) meaning clear ice

(thought at time to be a hard version of ice)

D- and L- quartz: chiral crystals

Max von Laue discovered x-ray

diffraction (CuSO4, ZnS) in 1912: Nobel Prize for Physics in

1914

W.L. Bragg and W.H. Bragg, 1912: Nobel Prize

for Physics in 1915

J. WatsonF. Crick

R. FranklinD. Hodgkin

M. Perutz

More recently: the dawn of modern scienceThe discovery of x-ray diffraction?

J.D. BernalK. Lonsdale

John D. Bernal, 1901-1971Born Nenagh, Co. Tipperary, IrelandStudent of W.H. BraggStalin Peace Prize, 1953Determined structure of graphite, 1924Two students won Nobel Prizes(Hodgkin, Perutz), Crick was a Perutz studentCredited with idea of first database (CSD, 1950’s)Recognized CO2 and climate change (1950’s)

J.D. BernalProc. Royal Soc., 1924, 749-773.

“One of the continuing scandals in the physical sciences is that it remains in general impossible to predict the structure of even the simplest crystalline solids from a knowledge of their chemical composition”

John Maddox editorial, Nature, 1988, 335, 201.

But ... the situation in 1988Crystal engineering was an oxymoron

“… a large part of the scandal remains”Philip Ball editorial, Nature, 1996, 381, 648

“Whenever people agree with me I always feel I must be wrong” Oscar Wilde

Why does design of crystalline materials matter?

ForceFaithFinesse

Now for some geography: 11/2013-present

40 million Euro over 6 years30 PIs30 post docs60 Ph.D. studentsHosted by University of Limerick7 other Irish institutions17 industry partners12 international partners

“Starship Enterprise”

Courtesy SSPCAnthony Maher

Bernal BuildingUniversity of Limerick

Polymorph 1

Polymorph 2

A $30 billion patent

(Zantac®)

Form 2 is:• Novel• Not obvious• Has utility

Application 1: Pharmaceutical Materials

Medicinal Chemistry

Molecules

le

MedicinesDrug Product

APIActive Pharmaceutical

IngredientExcipients

Drug Substance(s)

Materials

Pre-formulation

Early Drug Discovery and Development3 stages: Molecules to Materials to Medicines

FormulationObjective

Instituto de Fisica de Sao

Carlos,Universidade de

Sao Paulo

Universidade Federal do Ceara

Alejandro Ayala, Beatriz Bezerra, Renato Carneiro, Javier Ellena, Pierre Fechine, Alcemira Oliveira

A Catch-22Why has the pharmaceutical

industry failed to address neglected diseases?

Financial incentives for the developed world

• Need high prices to cover development + provide profits

• Patent protection needed• Patient reimbursement

schemes needed

Financial incentives for the developing world

• High prices cannot be sustained

• Patent protection not enforced or discouraged

• Little or no reimbursement

See poster 7 for more details

15

• Desiccants

• Catalysts/Catalyst Supports

• Molecular Sieving

• Separation or Storage of Gases

• Purification of Liquids

• Drug Delivery

• Pollution Control

• Sensors

• Respiratory Protection

Application 2: Porous Materials

Industry uses around 1/3 of world energy production

Commodity purification uses >10% of world energy

Distillation alone uses >5% of world energy production

Porous sorbents also used in heat pumps

Why should we care?

WebofScience® search on “coordination polymers”

Publications, citations on coordination polymers

The main reason for the inflection point?

The most cited chemists in India both work in solid state chemistry:C.N.R. Rao (h-index = 110, about 40 chemists >100)G.R. Desiraju (h-index = 70)

India is also in on the act

Energy-related applications of CO2 capture

Natural gas (most abundant)

CO2 is an impurity in natural gas and NG storage

is a challenge

CO2 is a bye-product of coal combustion

Published November 2012

Relationship between cost of CO2 capture, CO2 selectivity, and working CO2 capacity for solid sorbents

Merel, J., Clausse, M. & Meunier, F. Ind. Eng. Chem. Res. 47, 209-215 (2008)

Selectivity is a critical parameter for CO2 capture

mmo-2: 298K single component isotherms + selectivity

mmo-2 11 cm3/g at 0.39 mbar45 cm3/g at 0.15 bar

Overall goal: task specific materials by design

ForceFaithFinesseThink Globally

Think Teamwork

The Right Chemistry

Thank you