SAXS studies with SR at ELETTRA Semra Ide Hacettepe Univ' TURKEY

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SAXS studies with SR at ELETTRASemra Ide
Hacettepe Univ. TURKEY
-SAXS method -SAXS beamline and experimental
hutches -Training and research programme (TRIL-SES
AME) -Prepared and studied projects

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SAXS Method
The amplitudes of scattered waves are the same
but their phases are different. Phases depend on
positions of electrons in the space.
Scattering from a set of planes which are
perpendicular to the q are important in
crystallography. In SAXS method this is not
important. The important one is calculating total
wave amplitudes of all secondary waves.
q, x-ray scattering
vector q k-k q2 k sin? q 4? sin? / ?
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Interatomic planes
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Samples must include nanostructures.
Gels, liquid crystals, biopolymers, amorphous
materials, muscles etc.
There must be different electron density regions
which can be detected in the samples.
A multi-body system can be detected in different
solvents.
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A(q) Ae ? ?(r) exp(-iq.r) dr
Scattered wave amplitude
?(r) ? A(q)/Ae exp(iq.r)
dq Radial electron density
Fourier T.
I(q) A(q)2 Ae2 ? ?(r)
exp(-iq.r) dr 2 ? P(r) exp(-iq.r) dr
Scattered wave intensity
P(r) ? ?(ur) ?(u) du ?
I(q) exp(iq.r) dq Distance
distribution function
Fourier T.
Real space
Reciprocal space
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The followed process to determine structures is
used
Measuring data
In addition to SAXS technique other techniques
are SANS ( Small angle neutron
scattering) XAFS (X-ray Absorption
Fine structure), XRD
(X-ray Diff.) and Microscopy techniques. More
sensitive and recordable structural results can
be obtained by this combination .
Determining of structural parameters R, M, V etc.
Defining model structure in real space and for
this purpose using other collaborative techniques
Construction of the model in q space and fitting
of the experimental and theoretical results
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Samples and different nanostructural forms
Diluted systems -I
Densed systems-I
Lamellar systems
Diluted systems-II
Densed systems-II
Other Densed nano phased systems
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Diluted systems-I
Protein solutions, polymer solutions etc.
Information obtained by SAXS - Radius of
gyration - particle weight, volume and shape

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? r 2 (??r) d3r R2
?????? ? (??r) d3r
____________  R ?(a2b2c2)/5    
____ R ? (3/5) r 0.77 r
Radius of gyration
For ellipsoids a,b,c are semi-axis of
ellipsoids
Guiner Law (q?0)
For sphere r, radius

Porod Law (q??) lim I(q) q4 constant constant
2?(?1-?2)2 S S, surface area
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Kratky drawing
Q V lt?2gt invariant Multiply of
scattering volume and the average of squared
fluctuation in electron density.
Q has the dimension of a reciprocal volume
Sample For amorphous and crystalline (two)
phased polymer structure Q V (?c-?a)2 ?a?c V,
total scattering volume ?c , ?a densities of
crsytalline and amorphous parts ?a, ?k volume
fractions of amorphous and crystalline parts
Kratky drawing gives recordable results when it
was used together with Porod laws.
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For a diluted system of identical-spherical
particles
I(q)N P(q)2
P(q) 3V (?1-?2) sin(qR) qR cos(qR) / (qR)3
V (4/3) ? R3
Form factor (includes total amplitude of
scattered waves)
Par. Num. in unit volume
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Scattering equations defined for different systems
For a diluted system of identical particles
I(q) N P(q)2
For a diluted and two type particle system
I(q) N1 P1(q)2 N2 P2(q)2
Dilute and polydisperse set of particles
I(q) N ? g(R) P(q)2 dR
For a concentrated set of identical particles
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Lamellar Structures
The positions of Bragg peaks for h 1, 2, 3
give the lamellar distance (1/d)
If we look through the perpendicular direction of
the lamelar structure, we may define
crystallographic order in SAXS range. In this
case, by using scattering intensity ratios and
peak positions, some scattering rules ( for
hexagonal, cubic etc.) controlled and compaired
to obtain the real phases.
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Hexagonal Phase
For hexagonal structure, in S q/2? axis, for
observed (10), (11),(20) and (21) peaks the
following rules are valid S(11) /S(10) ?3 ,
S(20) /S(10) 2 , S(21) /S(10) ?7 Sgt
?(h2hkk2) For hexagonal structure a2/(?3
S(10) )
Figures, H. Amenitsch SR school-ICTP
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Some ordered cubic morphologies
Im3m
P-surface
Pn3m
D-surface
Ia3d
G-surface
Figures, H. Amenitsch, SR School-ICTP
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Concentrated set of centrosymmetric
fractal particles
I(q)N.I1(q). S(q)
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The fractal dimensions and SAXS curves
D
J. Teixeira J. Appl. Cryst. 21, 781-785 (1988)
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SUMMARY

• SAXS can provide information on
• Particle size and shape ( Large scale
  structures)
• crystalline/amorphous volume fractions
• average correlation distance ( Long range order,
  
• distances between similar structures)
• mean thickness of crystalline or amorphous
  layers
• the specific inner surface

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Why do we need SR?
Esspecially, foton flux is limited for
laboratory type SAXS cameras and SR sources are
more usefull for time resolved experiments. So by
using SR source we may reach high quality-more
sensitive data and in a short time range it is
possible to define dynamic structural changes and
phase transitions of samples.

Fratzl et.al., J. Appl.
Cryst. 30, 765-769 (1997)
Flux in the sample 1013 ph/s In
lab. type cameras, the flux in the sample is 108
ph/s
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A third generation Synchrotron Radiation Center
Beam energy 2.0 or 2.4 GeV Storage
ring circumference 259.2
m
20(6 future)
beamlines 4688 hours beamtime for SR users in
2002
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General view and front-end of SAXS beamline
(ELETTRA)Project H. Amenitsch, S.Bernstorff, M.
Kriechbaum, D. Lombardo, H. Mio, M. Rappolt P.
Laggner (1997) J. Appl. Cryst. 30, 872-876
Control room
57 pole wiggler, 1.25 mrad off-axis, 1 x 0.3
mrad2 (hor. x ver.), vertical source size 0.26
mm, horizontal source size3.9 mm
Optic hutch.I.
Optic hutch II.
Exp.hutch
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4-25 keV
Diffraction beamline
Sample beam size ? 5.4 mm x 1.7 mm (Hor. x
Ver.)
Resolution in real space 1-140 nm (small-angle)
0.1- 0.9 nm (wide-angle)
Detectors 1 D (SWAX-Delay Line) and 2 D- CCD
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? 0.077, 0.154, 0.230 nm
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Experimental Hutch (It is open to users)

XRD,XRR,GISAXS,SAXS measurements
different sample manuplations ( Static and
dynamic measurements)
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Subjects of performed experiments
CdSe/ZnSSe quantum dot stacks, CdS,ZnTe
nanocrystals in SiO2, nanocrystallization in
amorphous alloys Some ionic liquids, phase
diagrams
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GISAXS SETUP
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GISAXS
2D detector
z
Scattering by particles in substrate Coherent
scattering from surface Incoherent surface
scattering
Incident beam
acrit
SiO2
y
CdS, CdSe, ZnTe
O
Reference P. Dubcek , et.al.
Elettra Research Highlight 2000-2001, p.33
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What did we do during the training and research
programme at ELETTRA-SAXS beamline
Five projects were prepared and some pre-studies
have been done.
1. SAXS Studies of Some Novel Boron- and
Nitrogen- Containing Bioengineering Functional
Copolymers (
Proposal number 2003427)  Semra Ide, Yusuf
Ozcan, Zakir. M.O. Rzaev, Sigrid Bernstorff 2.
SAXS studies of some anhydride containing co- and
terpolymers (Proposal number 2003516)  
Sigrid Bernstorff, Semra Ide, Ömer Çelik, Ali
Güner, Hatice K. Can 3. SWAXS measurements on
DEVIT-3 and UVEDOSE Semra Ide, Levent Çidik,
Barbara Sartori, Sigrid Bernstorff 4. SAXS
Studies on Resistant Starch (RS) formation
effected by different parameters (level of
acid modification, autoclaving, storing
temperature and time)   Semra Ide, Hamit
Koksel, Sueda Çelik, M.ichael Rappolt 5.
Structural investigation on Lipase (EC 3.1.1.3)
Semra Ide, Yusuf Ozcan, Elif Sarikaya, Nilufer
Cihangir, Sigrid Bernstorff
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SAXS Studies of Some Novel Boron- and Nitrogen-
Containing Bioengineering Functional Copolymers
Boron- and nitrogen- containing polymers
are widely used in medical and chemical
applications. Beside of their opto-electronic
properties, these type polymers are very
important for boron neutron capture therapy
(BNCT) as effective tumour targeting agents
possesing low toxicities and very suitable for
brain tumour
( W. Siebert, Advanges in Boron Chemistry
1987). We would like to investigate the
possibility H-bonded side formation between
ethylene oxide and primary amine groups. This
possibility play an important role in formation
of compact supramolacular chains and cause to
rich bioactive properties. To reach this,
information about macromolecular structure, we
used SWAXS method as a collaborative technique.
Especially, determining the molecular
conformations and examining pH and temperature
effects in the polymer structures were our
fundamental purposes.
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These polymers have vinylphenylboronic acid in
their structure
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SAXS studies of some anhydride containing co-
and terpolymers In this project we have
six samples which have antitumour activity.These
are Poly(MA-alt-AA) copolymer,
Poly(AA-co-MA-co-VA )terpolymer,Poly( Maleic
Anhydride-alt-Acrylamide),Poly (Maleic Anhydride
-co-Acrylamide-co-Vinyl acetate),Poly( Citraconic
Anhydride-alt-Acrylamide) ve Poly (Citraconic
anhydride-co-Acrylamide-co-Vinyl acetate)
In the first phase of the studies, we tried to
increase the crystallinity percentage of the
polymers by using some chemical methods. The
crystallinities were determined after x-ray
powder diffraction studies. Poly(MA-alt-AA)
copolymer was chosen for SWAXS measurements as a
most stable structure. In the powder form we
could not determine a nanostructural formation.
We would like to continue this project, by
measuring the other samples in different
solutions (pH 5) and different temperature
especialy in the range of 20-60 C.
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SWAXS measurements on DEVIT-3 and UVEDOSE
In clinic studies, two medicines including
vitamine-D3 were used for a kind of epilepsy
illness. Different results were observed in a
group of patients.We prepared this project to
investigate and compare the structures. Two
different medicine company are producing these
two medicines. These medicine substances can be
found as ingredient of ampul in oil form . They
have used different oil solvents to solve Vit-D3
compound in these products.In this research, we
want to give answers to these questions. Are
molecular structures are the stable in the
solutions? Are nanosized structures the same in
the solutions? Can different solutions cause to
different biological activities and clinical
observations? Firstly we defined some molecular
differencies in IR studies. After that we
obtained, different sized micelle forms in the
solutions. These structural differencies will be
investigated by using different solutions with
different surfactant ratios. At the same time we
wonder about time resolved experiments to explain
the dynamic behaviour of the nanosized
aggregations.
Uvedose
Vitamine-D3
Devit-3
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SAXS Study on Resistant Starch (RS) formation
effected by different parameters (level of acid
modification, autoclaving, storing temperature
and time)
2-100 ?m
Crystalline
Amorphous
Amylopectin (Branched shapes)
Amylose (parallel helical shapes)
Unit repeated molecular structure is glucose
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Structural investigation of Lipase (EC 3.1.1.3)
and its molecular interaction with some
phospholipid structures
Lipases are enzyme with general interest
within many industrial applications e.g.,
detergent,oil and fats, baking, organic
synthesis, hard surface cleaning, leather
industry and paper industry. Bornscheuer,
U.T. 1999.Recent Res.Dev.Oil.Chem.393-106 In
this project we would like to determine
structural parameters and behaviours of the
lipase (EC 3.1.1.3 ) by using SAXS method. This
lipase sample was obtained from novel Aspergillus
sp. by N. Cihangir and E. Sarikaya. In these
days, we are also investigate some phosholipid
samples which can interact with this enzyme to
explain biological interaction between enzymes
and membraines. This project is under
preperation.
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Phospholipid structures and modelling
studies (Dr. M. Rappolts research)
Sodium- N-dodecanoyl-l-prolinate in D2O
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GENERAL RESULTS

• At the end of this program at ELETTRA,
  theoretical and experimental knowledge about this
  method was tried to learn.
• International scientific collaboration about
  SAXS with SR experimental technique was
  constructed among ITALY-AUSTRIA-TURKEY. This
  colloboration will be able to principally
  continue during the construction of SAXS beamline
  at SESAME and in the future.
• we began to evaluate data and as soon as
  possible we will develope our studies.
• I defined two research subjects for my PhD
  students, The titles of these researches will
  be,
• An investigation of the affects of
  intramolecular hydrogen bonds and chiral centers
  in the scattering models of phospholipid
  structures
• Relative Guinier drawings for protein
  structures more sensitive Rg values and larger
  effective Guinier range