The document provides an overview of the history and current state of crystallography in Brazil. It discusses key developments like the discovery of X-ray diffraction and its applications to crystallography. It highlights Brazilian scientists' early contributions and the establishment of Brazil's national committee for crystallography in 1952. It also describes current infrastructure like the Brazilian Synchrotron Light Laboratory and research conducted using synchrotron facilities on topics like new drugs and protein structures. It concludes by noting the importance of continued funding for science in Brazil to support human and technological development.

1. “Crystallography in Brazil:
Origin and Current
Perspective”
Yvonne P. Mascarenhas
Instituto de Física de São Carlos
Instituto de Estudos Avançados/Polo de S. Carlos
USP
22 a 26 de setembro 2019

2. What is Crystallography?
Crystallography is the branch of Science that has the
objective of determining the crystalline and molecular
structure. i.e., the positional and thermal vibration
parameters of all atoms in the sample.

3. Crystallography Main Objectives
• Qualitative or Quantitative Sample Characterization
• Determination of materials morphology from
macroscopic to atomic or molecular level.
• Determination of the relationship between crystalline
and molecular structure and properties.
• Modification of materials structure to improve
properties.

4. Seeing is Believing
A good picture is worth a thousand words!
Seeing the invisible!
Good Image Quality Requirements:
Amplification, Definition, Resolution, Depth
of Focus, etc

5. Microscopy
Antonie Van Leeuwenhoek invented the
simple microscope in 1674 with a 50 to
200 fold increase. He observed red blood
cells, sperm and microorganisms in
water. Later used the compound
microscope.

6. Hans and Zacharias Jansen and Robert Hook:
Invention of the Compound Microscope in 1690
J. Bras. Patol. Med. Lab. vol.45 no.2 Rio de Janeiro Apr. 2009

7. The quality of the optical system is the increase
in size of the image compared to the object.
Resolution is the capacity of separating
details of an optical system details.
Characteristics of an optical system
Resolution=ε=0,6λ/n(sinϴ) and small λ and large ϴ

8. Early Crystallography XVIII century
Main Instrument: Contact Goniometer
Abé Hauy fundamental ideas: Unit cell, lattice,
constancy of interface angles, faces rational
intercpts, and Symmetry.
Father of modern crystallography

9. Optical Instrumentation Before
X - ray Diffraction
‘
Due to the advances in many aspects of Physics and Chemistry during the XIX
century Crystallography evolved to the study of the morphology of crystals
and of the anisotropy of their physical properties. Steno Law and Hauy’s ideas fully
confirmed.
The first Brazilian scientist was José Bonifácio, a mineralogist.

10. Pasteur Crystallography and Stereochemistry
Pasteur's first major contribution to
science occurred when he was only
26 years old, working in
crystallography. Pasteur was both
fortunate and perceptive when
working with a compound called
tartaric acid—a chemical found in
the sediments of fermenting wine.

11. Theoretical Crystallography Before
X - ray Diffraction
Based on Group Theory:
Bravais discovered the 14 CrystalClasses
Shoenfliess derived the 32 Point groups of crystal symmetry
and, independently,
Shoenfliess and Fedorov determined the 230 space groups
Paul Heinrich von Groth (1843 –1927) was a german mineralogist
whose most important contribution to science was a monumental five-
volume collection entitled Chemische Kristallographie, which contained
crystalline morphology and physical property data on thousands of
substances.

12. Science on late XIX Century: Spectroscopy

13. Roentgen’s X-ray
Discovery
Röntgen, on November 8,1895, had set up a
fluorescent screen painted with barium
platinocyanide and a Crookes tube, wrapped in
black cardboard to cover its fluorescence - when,
all of a sudden, he noticed a green glow on the
screen about a meter away.

14. Nature and Application of X-rays
1912 – von Laue experiment
reveals X-rays wave nature.
1914 – W.L. Bragg applies
X-ray diffraction for the
determination of crystal
structure, founding X-ray
Crystallography. W.H. Bragg
X-ray Spectroscopy.

15. Dame Kathleen Lonsdale, FRS
Structure of hexa-methyl benzene. All carbon atoms were
on the same plane at equal distances and angles.

16. 1952 Crystallography in Brazil
•Fortieth Anniversary of the Discovery of X-ray
Diffraction
In 10th June 1952, a special meeting was promoted by
the Brazilian National Committee for Crystallography
and held under the sponsorship of the Brazilian
Academy of Sciences.
Dr Arthur Moses, President of the Academy, was in
the Chair, and after the presentation of a message
written for the occasion by Prof. von Laue the
following papers were read:
•Acta Crystallographica Section A: Foundations of
Crystallography (1953) 6, 108-109.

17. 'History of the Discovery of X-ray Diffraction with an Account of Forty Years
Progress in the Crystallographic Field' by E. Tavora, Secretary of the Braz.
National Committee for Crystallography and Prof. of Mineralogy at the University
of Brazil.
'Crystallography and Chemistry' by Admiral Alvaro Alberto, President of the
National Research Council and Professor of Chemistry at the Naval Academy of
Brazil.
'Crystallography and Physics' by Bernard Gross, Head of the Sector of Physical
Research of the National Research Council and student of Paul Ewald.
'Crystallography and Metallurgy' by E. Fonseca Costa, Director of the National
Institute of Technology and Professor of Metallurgy at the University of Brazil.
'Crystallography and Biology' by Carlos Chagas, Professor of Biophysics at the
University of Brazil.
•'Crystallography and Mineralogy' by E. Tavora.
•The proceedings of the meeting, which were widely reported in the public press,
will appear as a special publication of the Brazilian Academy of Sciences.

18. My internship in Pittsburgh 1959-60
For approximately 18 months I had the privilege to begin my
training in Structural Crystallography at the X-ray
crystallography Depart. directed by G. A. Jeffrey, English
crystallographer whose laboratory was considered one of the
best of USA. Brian Craven was my supervisor and I started
my job participating in the determination of the crystal
structure of violuric acid, a barbiturate, one of his research
projects. Luckily the structure presented a bifurcated
hydrogen bond for the first time experimentally observed.

19. Grupos de cristalografia e produção científica
Glaucius Oliva, at his
presentation at UNESCO in
2014, reported that the
following results had been
obtained in Brazil
≈ 400 estruturas de proteínas
≈ 3000 estruturas de pequenas
moléculas

20. How to obtain the image of the crystal structure:
the phase problem

21. Experimental X-ray Crystallography Methods
Low resolution - SAXS suitable for systems with
electron density discontinuity between medium and
the scattering particle.
Powder diffractometry - Poly or semi-crystalline
samples. Material identification and structure
determination.
Single crystall diffractometry – Single crystalline
samples of small molecules and macromolecules.

22. Applications of X-ray diffraction in various
fields.
Aitipamula, S. & Vangala, V.R. J Indian Inst Sci (2017) 97:
227. https://doi.org/10.1007/s41745-017-0026-4

23. Sources and registration devices for
X-ray diffraction
Sources of X-ray:
Vacuum tubes and synchrotron radiation.
How to register the difratogram?
Up to early 1960: Cameras and fotographic
films.
After mid 1960: Automatic difractometers
using scintilation counters or image plates.

24. Sample types
Amorphous samples - short range order which restricts
measured data to small 2  values  low resolution.
Semicrystalline samples - coexistence of amorphous and
polycrystalline regions.
Polycrystalline Samples - Randomly distributed micro crystals 
circular diffracted beans. Possible overlap of diffracted beans.
Single crystalline samples - ideal for obtaining molecular and
crystallographic structure.

25. The Relation between Structure and Function
Physical Properties
1) Structure of pure material.
2) Structural modifications aimed at improving
properties
3) Changing properties through physical parameters:
temperature, pressure, radiation.
4) Changes in properties due to chemical composition.
5) Influence of structural defects.
Usually large number of polycrystalline samples.

26. The Relation between Structure and Function
Chemical and biological Properties
Small and macromolecules
1) Pure singlecrystalline material
2) Structural modifications aimed at improving
properties (Catalysis, Solubility, Biological
action,...)
3) Change of properties through
physicochemical parameters: temperature,
pressure, solvent, pH etc.

27. When is synchrotron radiation required?
Need of high intensity X-ray beam
a) low intensity diffracting samples (amorphous, semicrystalline,
macromolecules, thin films).
b) Measurement of large quantity of samples.
c) Determination of structural variations with temporal
resolution.

28. O Centro Nacional de Pesquisas em Materiais
(CNPM)
The Sincrotron National Light Laboratory operates Latin America's only
Synchrotron light source and is building Sirius, the new fourth-generation Brazilian
accelerator for analysis of various types of materials, organic and inorganic;
The National Bioscience Laboratory (LNBio) conducts research in frontier areas
of Bioscience, focusing on biotechnology and drugs;
The National Biorenewables Laboratory (LNBR) researches biotechnological
solutions for the sustainable development of advanced biochemical, biochemical
and biomaterials, employing Brazilian biomass and biodiversity; and
The National Nanotechnology Laboratory (LNNano) conducts research with
advanced materials with great economic potential for the country.

29. World Synchrotron Light Sources

30. Synchrotron radiation spectra

31. XRD1 PGM XPD XRD2 XR
XDS XAFS2 SGM IMX DXAS
TGM XAS1 SXS IR1 SAXS2
SAX1 MX2
Energia=1.37 GEV
7 estações de difração
SIRIUS Energia= 3.2 GEV
Lines of Light of UVsynchrotron and SIRIUS

32. Examples of work done by IFSC-USP
researchers on LNLS UVsynchrotron
Discovery of new drugs for the treatment of
endemic infectious diseases in Brazil ( Oliva, G. et al)
and
Characterization of Protein in solution
Mario de (Oliveira Neto, M. et al)

33. 2015-16

34. Elucidation of Zika virus protein structure
responsible for its replication in infected
persons
New Anti-Zika
Drug Candidates

35. FERREDOXIN--NADP+ REDUCTASE
MONÔMERO - PDB 1OGJ
FERREDOXIN:NADP+ REDUCTASE
DIMERO – PDB 1QGO

38. Number of papers from UV synchrotron
(A.F. Craievich. Radiation Physics and Chemistry. In press (2019))

39. Periods of operation of the 18 beamlines of the
UVX synchrotron

40. Number of indexed papers associated
to LNLS data.

41. Sirius Predicted Year to start operation: 2020!

42. Current perspectives for science in Brazil
Unfortunately, the successive budget cuts suffered by the federal
science funding agencies are extremely worrying, especially
with regard to graduate and postgraduate scholarships
and the discontinuity of funding for research centers and
university research groups.
Consequences: loss of human resources formed or in formation
with inevitable and practically unrecoverable interruption of
Brazil’s technological development...
The Building of the Synchrotron involved strong
colaboration with brazilian industryies.

43. My sincere thanks:
To the organizers of the VIII Congress of SBPMAT
for the honorable invitation to deliver this Memorial Lecture.
To Glaucius Oliva, Aldo Craievich and Ricardo D. Rodrigues
for the great suggestions and excellent material I used to
prepare this conference.
And to the audience for their attention,
wishing you will make excellent use of SIRIUS!