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X-ray crystallography is an imaging scientific technique using solid crystals to acquire a molecular image

of micro- and macro- molecules with different complexities. +

' Th" dir"onery, as well as the development, of x-ray has been one of the greatest discoveries man has

- in the last century which has impacted not only advanced countries, but has shaped the course
made of

human history.

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Like many inventions, the discovery of the existence of X-rays was first notably observed by Wilhelm

Conrad Rdentgen of Germany in late 1895 (l). While working with different cathode tubesn in a dark

room, from makes such as Tesla and Edison, he noticed that a barium platinocyanide screen was emitting

a florescence after applying a discharge on a tube ( 1 ). The interesting part of this however, is that the

fluorescence was observed after an electrical discharge had taken on a tube. This led to the discovery of a

type of similar radiation like light existed. (1)'

- I To not give credit to any cathode tube for the discovery of this new type of radiation, Roentgen never
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\nentioned which tube he first observed his findings (1). After considering many names from this type of

radiation, and to not second guess himself in front of the scientific community, he simply named this

radiation, radiation x, as x is an indeteminate variable in mathematics (1).

From this discovery Roentgen discovered that if objects were placed in

front of the rays, a dark outline was acquired when photographic plates

were used to receive the radiation- To protect his reputation and the new

discovery, he continued his work in secrecy for two weeks until his

results were conclusive. The most important image acquired from his

finding was that of his wife's image (fig.l), also known as a hand x-ray
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Figure 1. X-ray of Wilhelm's wife Anna on' 5' l{e decideo to1tf'lnt
Bertha Ludwig taken November 8, 1895(2)
present his findings in a medical symposium in December 1895(1). The
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news in the medical community spread like wild fne and now doctors and surgeons alike used the visual

benefits from these images to treat sicknesses and to know what parts of the body in better detail could be

operated on, with less hassle. This breakthrough could not have come at a better time since in WWI was

around the corner and x-ray was essential in saving thousands of lives on the field (2). For his discovery,

Riientgen received the firstNobel Prize in history in the field of physic in 1901. As a gift to humanity he

decided not to patent his discoveryo as his discovery helped furlher the science of X-ray imaging (1).

X-ray diffraction

In lg12 Max Laue with the aid of technicians Paul Knipping and Walter Frie-drich, placed a photographic
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plate behind a copper sulphate crystal and obtained u d1fft*IlggLtgnr (3). The diffraction spots were

explained by Laue as interference pattern due to the crystal's space lattice (3, fig. 2)' ln l9l4 they

received the Nobel Prize in physics for their "discovery of the diffraction of X-rays by crystals" (3)
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Miller indices and Bragg)s Law,

Using earlier theoretical work by Auguste Bravais in 1848 that 'shouJed

"there are 14 unique lattices in three-dimensional crystalline

systems" of a unit cell, Miller indices and Bragg's law were

devised (4). Miller indices are planes in which atoms may

occupy space in a unit cell (fig 3). A crystal system is a

uniform repeating unit cell. Depending on the size of the atoms

Figure 2. First X-ray diffraction photograph of copper
and their location l4 possible unit cells are possible, which
sulphate. Copper ion surrounded bv four sulphates tfie2)

Bravais derived mathematically (fig. a)

Bragg's law (Eq. 1) is a result ofjoining Bravais lattices and Miller indices using findings from observed

Laue diffraction patterns as well as Laue equations. Father and son team Lawrence and William Henry

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Bragg in 1915 received a Nobel Prize "for their services in the analysis of crystal structure by means of

X-rays" (3). YqP+4h'rc

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Figure 3. Miller indices, numbering used to determine

Figure 4. 14 possible unit cells in a crystal system (fig 4).

location of atom plane in a unit cell (fig 3).

Ionic Compounds

The use of X-ray was initially focused on determining the molecular structure of simple inorganic
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crystals. Lawrence Bragg et al., in 1914 determinedits molecular structure, using crystals, but also

disproved the need for covalent bonding in a compound, which therefore proved the existence of ionic

compounds (6).

Patterson Function P'$"*^'e

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\ To obtain a 3D model of a material under study,Patterson Functions are used. They consist of summing

Fourier series in two and three dimensions over time (Eq' 2\.By rotating the material, different intensities

Eq.ZPatterson Functions used to 1 *^k

'
c(r) : o*11*1y(*.*) :l#c(q)g'u'' obtain a 3D model from constructive \ 5vrzrat{e'z
f interference obtained from rotating a \
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of diffraction are obtained used to construct a Patterson Map and therefore a 3D model is obtained (fig

5b).

Globular proteins

Because of WWII, there was a dispersal of scientific knowledge which slowed the progress in the

development of X-rays. However, this changed in 1959 when Max Penftz and John Kendrew with the

support of the young professor Lawrence Brag, determined the structure of oxy- and deoxy- haemoglobin,

and myoglobin respectively, at high resolution (7)

Figure 5a. X-ray diffraction photograph of Figure 5b. Patterson Map of

of'Hemoglobn
Hemoglobin

oxyhemoglobin and the famous hemoglobin model.

DNA and the Double llelix

Rosalind Franklin which was a research associate in 1951, elucidated to the double helix structure of

DNA using x-ray crystallography with the help of colleagues in King's College London. Unforfurretg!*
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James Watson and Francis Crick, with the help of Maurice Wilkins used Franklinls crystallography
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results, to prove that DNA consisted of an antiparallel double stranded helix (7). ,/W^W- V-+t\P
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Literature Cited

l.Streller, E., Winau, R., Hermann, A. (1973) Wilhem Conrad Roentgen, 1845-1923. Bonn: Inter
Nationes

2.Lauer J, SchlagerN. Science And lts Times: UnderstandingThe Social Sigpificance Af Scientific
Discovery [e-book]. Farmington Hills, Mi: Gale Group; 2001. Available from: eBook Collection
(EBSCOhost), Ipswich, MA. Accessed February 14, 201 8.

3.Eckert, M. (2012), Max von Laue and the discovery of X-ray dffiaction in 1912. Ann. Phys., 524: A83-
A85. doi: I 0. 1 002/andp.2012007 24

4.Auguste Bravais, https://en.rvikipedia.org/wiki/Auguste:Bravais. Last accessed:2118/2018 10:15 PM

S.Bragg, W., James, R., & Bosanquet, C. (1921). XnX. The intensity oJ'reflexion of X-rays by rock-
sult.The London, Edinburgh, and Dublin PhilosophicalMagazine and Joumalof Science, 4l(243),3A9-
337.

6.lrttps://en.rvikipedia.org/rviki/X-ra.v:cr)'stallography#cite_ref-Ll9l2_16-1. Lastaccessed2120/2018
5:13 PM

7. Klug, Aaron. (20Aq, The Discovery of the DNA Double Helix. J. Mol. 8io.,335:3-26

Figures

l.https://en.rvikipedia.org/wikiiCr.v-stal*structure. Last accessed: 2/1812018 l0:16 PM

2.trttp:/ ierv. Lastaccessed:2/18/2018 10:35 PM

3.https /ien.wikiped ia.orglwiltiiCrystal*s,vstern. Last accessed 2/18/2018 10:18 PM

5.https://en.wikipedia.or#r.viki/Crystal:structure. Last accessed2/19/201810:06 AM

6.http://r,vrvw.mfpl.ac.ativips/rnax-f-perutz/ Last accessed2119/2018 3:56 PM

Equations

I. Bragg's Law, A Dictionary of Plrysics (6ed). Oxford University Press. Oxford. 2009.

S.https://en.lvikipedia.org/wiki/Arthur:Lindo_Patterson. Las accessed: 212012018 6:01 PM