Hyatt Place – Riverhead, Long Island, New York

October 11th to 15th

PosterAbstracts

CHARACTERIZATION OF THE SOLID ELECTROLYTE INTERPHASE ON SILICON BY

SYNCHROTRON INFRARED NANOSPECTROSCOPY

M. AYACHE1, A. JARRY

1, H. A. BECHTEL

2, M. C. MARTIN

2, R. KOSTECKI

1

1) Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720

USA

2) Advanced Light Source Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 USA

The solid electrolyte interphase (SEI) layer is a critical aspect of Li-ion battery systems [1]. Composed

of reduction products of the electrolyte, it forms early in cycling on the negative electrode, and in

stable systems protects the electrolyte from further breakdown while conducting lithium ions. The

SEI is heterogeneous at the nanoscale, which has presented a barrier to characterization using

traditional diffraction-limited infrared techniques. Here we apply near-field synchrotron infrared

nanospectroscopy (SINS) [2] to characterize the SEI layer on a silicon electrode at 20 nm resolution.

This follows recent published work applying near-field imaging to the SEI layer on other Li-ion

negative electrodes [3]. Although the SEI layer on silicon tends to be unstable, use of lithium

bis(oxalato)borate (LiBOB) as an electrolyte additive improves performance.

A silicon anode was potentiostatically swept from open-circuit potential (2.9 V) to 1.5 V against a

metallic Li counter electrode, with 1 M LiPF6 +2% LiBOB in EC:DEC 1:2 electrolyte, then removed from

the cell and analyzed by SINS. Several peaks are visible in the near-field IR spectrum, shown in Figure

1(a), which correspond well to some of the peaks visible in a far-field FTIR spectrum of an identical

sample (Figure 1(b)). This same spectrum appears at several points along the surface, potentially

corresponding to the early formation of a protective layer by reduction of the LiBOB additive.

(a)

(b)

Figure 1. (a) Near-field spectrum of SEI layer on 1.5 V

silicon electrode using LiBOB additive. (b) Far-field

spectrum of SEI layer on 1.5 V silicon electrode using

LiBOB additive

ACKNOWLEDGMENTS

− This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office

of Vehicle Technologies of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231

under the Advanced Battery Materials Research (ABMR) Program

REFERENCES

[1] E. Peled, J. Electrochem. Soc., 126, 2047 [1979] [2] H. A. Bechtel, E. A. Muller, R. L. Olmon, M. C. Martin, and M. B. Raschke, Proc. Natl. Acad. Sci. U. S. A., 111,

7191 [2014]

[3] M. Ayache, S. F. Lux, and R. Kostecki, J. Phys. Chem. Lett., 6, 1126 [2015]

http://pubs.acs.org/doi/abs/10.1021/acs.jpclett.5b00263.

POSTER SESSION

LACTOSE - AN INACTIVE INGREDIENT OF THE PHARMACEUTICALS-

FINGERPRINTING BY ATR-FTIR SPECTROSCOPY AND CHEMOMETRICS

A.BANAS1, K. BANAS

1, B.PAWLICKI

2,M.B.H. BREESE

1

1) Singapore Synchrotron Light Source, 5 Research Link 117603 Singapore

2) Gabriel Narutowicz Hospital, Pradnicka 37, 31-202 Krakow, Poland

Lactose and saccharose have the same molecular formula however the arrangement of their atoms is

different. A major difference between lactose and saccharose with regard to digestion and

processing is that it's not uncommon for individuals to be lactose intolerant (approximately 65% of

the human population has a reduced ability to digest lactose after infancy), but it is rather unlikely to

be saccharose intolerant.

In the pharmaceutical industry, lactose or saccharose is used as an inactive ingredient of the drugs to

help form tablets because of their excellent compressibility properties. Some patients with severe

lactose intolerance may experience symptoms of many allergic reactions. People who are specifically

"allergic" to lactose (not just lactose intolerant) should not use tablets containing lactose.

Fourier Transform Infrared spectroscopy possessing a unique chemical fingerprinting capability play a

significant role in providing specific data on the identification and characterization of analyzed

samples and hence has been widely used in pharmaceutical science. However a typical FTIR spectrum

collected from tablets contains a myriad of valuable information hidden in a family of tiny peaks.

Only powerful multivariate spectral data processing can transform FTIR spectroscopy to an ideal tool

for large volume, rapid screening and characterization of minor pills components down to parts per

billion (ppb) level.

In this poster a method for distinction between FTIR spectra collected for tablets with or without

lactose is presented. The results proved that the success of identification in FTIR spectroscopy is

largely dependent on the chemometric technique applied for data evaluation.

POSTER SESSION

INVESTIGATION OF RESIDUES AFTER HIGH AND LOW ORDER EXPLOSIONS BY

MEANS OF FTIR SPECTROSCOPY AND MULTIVARIATE STATISTICAL ANALYSIS

K. BANAS1, A. BANAS

1, J. LOKE

2, M.B.H. BREESE

1,3

1) Singapore Synchrotron Light Source, National University of Singapore, 5 Research Link, 117603 Singapore

2) Forensic Management Branch, Criminal Investigation Department, Police Cantonment Complex 391 New

Bridge Road #20-04 CID Tower Block C, Singapore 088762

3) Department of Physics, National University of Singapore, 2 Science Drive 3, 117542 Singapore

Fourier Transform Infrared (FTIR) spectroscopy offers near real time detection of analysed samples,

shows extremely high sensitivity and selectivity. These features made it the method of choice for the

forensic science in case of the identification of unknown compounds. The amount of obtained

information due to complexity of the measured spectra requires the use of additional data

processing (dimensionality reduction). Application of the multivariate statistical techniques for the

analysis of the FTIR data seems to be necessary in order to enable feature extraction, proper

evaluation and identification of obtained spectra. In this poster we present the procedure for

characterization of spectroscopic signatures of the explosive materials (C-4, TNT and PETN) in the

remnants after explosions of low and high order. All spectra were pre-processed (baseline correction,

vector normalization and derivative calculation) in order to reduce the environmental and residue

specific influences. Subsequently performed principal component analysis (PCA) allows for successful

identification of the explosive material even after high order blast in more than 95% cases. Complete

data processing and visualisation was performed within R environment [1] for statistical analysis –

code-driven open source platform that enables high standards of reproducibility.

Fig 1: Distribution of points for first two principal

components. Each point represents one spectrum –

color-coded for explosive material. PCA was

performed on vector normalized, first derivative of the

spectra in the range 500-1500 cm-1

ACKNOWLEDGMENTS

− This research was partially performed under NUS Core Support C-380-003-003-001.

− Samples were provided by Advanced Material Engineering Pte Ltd, controlled explosions were

performed in frame of TEC Project P005800/1274 in collaboration with Singapore Police Force,

Criminal Investigation Department.

REFERENCES

[1] R Core Team, The Comprehensive R archive network, http://cran.rproject.org/ [2015]

POSTER SESSION

1 2

POSTER SESSION

A SPECTROSCOPIC APPROACH TO PROBING BIOGENIC SULFUR PRODUCTION IN PHAEOCYSTIS ANTARCTICA R.E. BARLETTA 1, O. SACKETT2, T. GOODIE1, A. Carlijn-Aldercamp3

1) Department of Chemistry, University of South Alabama, Mobile AL 11973 2) Centre for Biospectroscopy, School of Chemistry, Monash University, Melbourne, Victoria, Australia3) Department of Environmental Earth System Science, Stanford University, Stanford CA 94305Phaeocystis antarctica, a dominant species of Southern Ocean phytoplankton, is a major contributor tothe global sulfur cycle, producing biogenic sulfur in the form of dimethylsulfoxide [DMSO]and dimethylsulfoniopropionate [DMSP] and releasing these compounds into surface waters. Intra-cellular concentrations of these compounds in P. antarctica are believed to be high (on the order of200mM), however, there is some uncertainty associated with these estimates as they are the result ofindirect measurement techniques. The intracellular role of these chemicals is poorly understood, in partdue to technical challenges associated with determining intracellular concentrations and localisationwithin the cell. It is believed DMSO and DMSP are important osmoregulators and antoxidants. Suchroles imply that P. antarctica should produce substantial quantities of biogenic sulfur in response toenvironmental stresses such as salinity, nutrient concentration, light, etc.

Previous measurements of stress response in P. antarctica have been limited to determination of bulkaverage biogenic sulfur concentrations, since single-cell measurements have not been possible. Thesesame technical challenges have prevented the characterisation of intraspecific variability. Usingsynchrotron-based Fourier Transform Infrared (FTIR) Spectroscopy, we have been measured vibrationalspectra attributable to individual P. antarctica cells. Chemometric analysis of this FTIR spectroscopicdata enables one to measure changes in both bulk intracellular chemistry (protein, lipid andcarbohydrates) through principal component analysis (PCA), as well as the contribution of individualcompounds such as DMSO and DMSP through classical least squares analysis (CLS). To demonstrate this,we have looked at the effects of several environmental stresses on P. antarctica. These included theeffect of salinity, pH, nutrient level and light on cell chemistry. P. antarctica cells were cultured underphysicochemical conditions (salinity, pH, nutrient level and light) over a range of conditions includingthose characteristic of sea ice brine channels. Measurements were made on single cells suspended inisotonic saline solution or preserved in the original medium using formalin. The results of this work arepresented.

ACKNOWLEDGMENTS

This work was supported by the NSF Office of Polar Programs, contract number 0939628, and the USA College of Arts and Sciences Professional Development Fund.

Travel assistance for REB was provided in part by a grant for the Alabama EPSCOR program. We acknowledge the assistance of Dr. Lisa Miller (BNL) and Randy Smith (BNL) for their assistance in

performing measurements and Brookhaven National Laboratory for donation of beamtime at NSLS.

FLUIDICS FOR SR-FTIR: FROM LIQUID CELLS TO HYBRID MICROFLUIDIC

DEVICES

GIOVANNI BIRARDA1,2

, GIANLUCA GRENCI3, MONA SURYAMA

3, ANDREA RAVASIO

3 AND HOI-YING

N.HOLMAN2

1) Elettra Sincrotrone Trieste, S.S. 14 Km 163.5 34149 Trieste, ITALY

2) Berkeley Synchrotron Infrared Structural Biology Program, LBNL, Berkeley, CA 94720, USA

3) Mechanobiology Institute, National University of Singapore, 117411, SINGAPORE

Infrared Spectromicroscopy is a label-free chemical imaging technique widely used as a diagnostic

and research tool [1] to obtain information on classes of molecules in biological specimens [2].

However, its application as a diagnostic tool to characterize living cells or tissues has been limited

due to the strong absorbance of water in the mid-IR. For almost two decades researchers have tried

various microfluidic approaches [3-7] to overcome this barrier. In this presentation, we will first

highlight these approaches, from the commercially available liquid cells to more elaborate

microfluidics.[8-10] We will then evaluate their pros and cons, and discuss the new challenges which

arise from the emerging High-Resolution synchrotron radiation-based infrared focal plane array (SR-

IR-FPA) imaging, FTIR-Tomography or Near-Field SR-FTIR spectral microscopy. Finally, we will present

a new hybrid device capable of maintaining live cells for days, providing experimental flexibility to

meet the new challenges, and reducing production costs. We will demonstrate the device’s capability

by showing results from the real-time spectral profiling of migrating REF52 rat embryo fibroblasts

inside the device, and of U937 monocytes during their exposure to TiO2 nanoparticles.

Fig. 1 a. Single cell spectra from live REF52 cells inside the hybrid device. b. RGB composite IR image of the cells. c. Visible

image of the same cells. d.-e. Two time snapshots of the same area after 24h. Scale bars 25 µm.

References: 1. Baker, M.J., J. Trevisan, P. Bassan, R. Bhargava, H.J. Butler, K.M. Dorling, P.R. Fielden, S.W. Fogarty, N.J. Fullwood, and

K.A. Heys, Nature protocols, 9 p. 1771-1791,[2014].

2. Chen, L., H.Y. Holman, Z. Hao, H.A. Bechtel, M.C. Martin, C. Wu, and S. Chu, Analytical Chemistry, 84 p. 4118-25,[2012].

3. Moss, D., M. Keese, and R. Pepperkok, Vibrational Spectroscopy, 38 p. 185-191,[2005].

4. Tobin, M.J., L. Puskar, R.L. Barber, E.C. Harvey, P. Heraud, B.R. Wood, K.R. Bambery, C.T. Dillon, and K.L. Munro,

Vibrational Spectroscopy, 53 p. 34-38,[2010].

5. Holman, H.Y., H.A. Bechtel, Z. Hao, and M.C. Martin, Analytical Chemistry, [2010].

6. Miller, L.M., M.W. Bourassa, and R.J. Smith, Biochimica et Biophysica Acta (BBA) - Biomembranes, 1828 p. 2339-

2346,[2013].

7. Gelfand, P., R.J. Smith, E. Stavitski, D.R. Borchelt, and L.M. Miller, Analytical Chemistry, 2015].

8. Birarda, G., G. Grenci, L. Businaro, B. Marmiroli, S. Pacor, F. Piccirilli, and L. Vaccari, Vibrational Spectroscopy, 53 p. 6-

11,[2010].

9. Vaccari, L., G. Birarda, L. Businaro, S. Pacor, and G. Grenci, Analytical Chemistry, 84 p. 4768-4775,[2012].

10. Loutherback, K., L. Chen, and H.-Y.N. Holman, Analytical chemistry, [2015].

POSTER SESSION

1

2

THE NSLS-II INRFARED BEAMLINE FOR CONDENSED MATTER PHYSICS AND MATERIALS UNDER EXTREME CONDITIONS (FIS AND MET)

G.L. CARR,1 R.J. SMITH

1 AND ZHENXIAN LIU

2

1) NSLS-II,Brookhaven National Laboratory, Upton, NY 11973, USA 2) Carnegie Institution for Science and COMPRES, Washington DC USA

The first planned infrared beamline for the NSLS-II synchrotron light source will be devoted to the study of

materials under extreme conditions as well as for condensed matter physics systems. The beamline is being

designed to reach into the sub-THz spectral range to match various low energy phenomena associated with

magnetic resonance and superconductivity. Planned instruments include diamond anvil cells, a 10T magnet,

Mueller-matrix ellipsometer, and various laser systems for reaching high sample temperatures as well as for

pump-probe spectroscopies.

ACKNOWLEDGEMENTS

Research at the NSLS-II is supported by the U.S. Department of Energy, Office of Science, under contract DE-SC0012704 at Brookhaven National Laboratory.

POSTER SESSION

SYNCHROTRON INFRARED MEASUREMENTS OF LIPID AND PROTEIN

PHOSPHORYLATION DYNAMICS DURING HCE CELL ELECTROTAXIS

Liang Chen1, Zhiqiang Zhao2, Kevin Loutherback1, Yao-Hui Sun2, Kan Zhu1, Hoi-Ying N. Holman1, Min Zhao2

1) Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California, 94720, USA 2) Department of Dermatology, Institute for Regenerative Cures, University of California Davis, Sacramento,

California, 95817, USA

Physiological direct current (DC) electric field(EF) stimulates and guides migration, proliferation,

orientation of many types of cells [1-3]. These cellular responses to EF are critical for wound healing,

tissue regeneration and tumour development [4, 5]. Previous studies have suggested that changes of

lipid signalling, protein phosphorylation, and actin filament re-distribution are required for cell

electrotaxis [5, 6]. In this presentation, we will describe our application of synchrotron-FTIR

spectromicroscopy to record time courses of intercellular biochemical changes in human corneal

epithelial(HCE) cells during EF stimulation. Synchrotron-FTIR imaging revealed re-organization of cell

membrane structure and both whole-cell level increase and locally differential distribution of protein

phosphorylation before and after EF. We interpret our results as direct evidence of global and local

dynamics of lipid and protein phosphorylation in electrically guided living mammalian cells.

Fig 1: (A). Schematics of the

experimental setup. (B).

Time course of differential

spectral changes of the

leading and trailing edge of

the HCE cell in EF.

ACKNOWLEDGMENTS

This work was performed under the Berkeley Synchrotron Infrared Structural Biology (BSISB) Program

funded by the U.S. Department of Energy, Office of Science, and Office of Biological and Environmental

Research. The Advanced Light Source is supported by the Director, Office of Science, and Office of Basic Energy

Sciences. Both were supported through Contract DE-AC02-05CH11231.This work was also supported by the

National Institutes of Health (NIH) (Grant number: R21EB015737 to M.Z.) and the Scottish Universities Life

Sciences Alliance (SULSA)

REFERENCES

[1] X. Li, and J. Kolega, J Vasc Res, 39, 391-404 [2002].

[2] C. D. McCaig, A. M. Rajnicek, B. Song, and M. Zhao, Physiol Rev, 85, 943-78 [2005].

[3] M. E. Mycielska, and M. B. Djamgoz, J Cell Sci, 117, 1631-9 [2004].

[4] D. Wu, X. Ma, and F. Lin, Cell Biochem Biophys, 67, 1115-25 [2013].

[5] M. Zhao, B. Song, J. Pu, T. Wada, B. Reid, G. Tai, F. Wang, A. Guo, etc., Nature, 442, 457-60 [2006].

POSTER SESSION

OPTICAL SIMULATIONS VERSUS EXPERIMENTAL PERFORMANCES OF THE

MIRIAM BEAMLINE B22 AT DIAMOND LIGHT SOURCE

GIANFELICE CINQUE1, MARK D. FROGLEY

1, DAVID LAUNDY

1

1) Diamond Light Source, Harwell Science & Innovation Campus, Chilton-Didcot, Oxon OX11 0DE, UK

The Multimode InfraRed Imaging And Microspectroscopy (also known as B22) is the IR Beamline at

Diamond Light Source, the UK’s national Synchrotron Radiation facility located on the Harwell

Science and Innovation Campus in Oxfordshire. MIRIAM is a state of the art IR facility for molecular

microspectroscopy/imaging, mostly used for biomedical research but increasingly more in chemical-

physics and material sciences as broad as geology and archaeology [1]. It provides diffraction-limited

spatial resolution and high spectral quality (S/N>5000 rms in 20sec acquisition over >8x8 µm2 spot in

the mid-IR) optically attainable over the full IR range, including full field microscopy via 64x64 pixels

FPA, and excellent performances in THz spectroscopy [2].

Since its start of operation, this is the first report of a complete set of simulations, for the whole

beamline optics up to the FTIR pupil, which have been run via SRW including the triple optics system

[3] used to compress the longitudinal extension of the IR source due to the large B22 front end

(20x50 mrad2). These findings are compared with measured performances, including experimental

images of across the IR foci acquired via bandpass filters and a microbolometer detector, and flux via

calibrated power meter.

Fig. 1: Scheme of MIRIAM beamline B22 at Diamond Light Source (BM on right, endstations on left).

1. G. Cinque, M. D. Frogley, R. Bartolini, “Far-IR/THz spectral characterization of the coherent synchrotron radiation emission at Diamond IR beamline B22”, Rendiconti Lincei 22 (2011) 33

2. G. Cinque, M. Frogley, K. Wehbe, J. Filik, J. Pijanka, “Multimode InfraRed Imaging and Microspectroscopy (MIRIAM) Beamline at Diamond” Synchrotron Radiation News 24 (2011) 24, DOI: 10.1080/08940886.2011.618093

3. M. Frogley and G. Cinque, “Multiple Element Infrared Synchrotron Mirrors”, AIP Conf. Proc. 1214 (2010) 29, DOI:10.1063/1.3326340

POSTER SESSION

INFRARED PLASMONS IN 3-DIMENSIONAL NANOPOROUS GRAPHENE

F. D'APUZZO1,2

, A. R. PIACENTI2, Y. ITO

3 , M. CHEN

3 AND S. LUPI

2,

1) Center for Life Nano Science@Sapienza, Istituto Italiano di Tecnologia, Roma, Italy

2) Department of Physics, University of Rome “Sapienza”, P.le Aldo Moro, 5, 00185, Rome, Italy

3) WPI Advanced Institute for Materials Research Tohoku University, Sendai 980-8577, Japan

Graphene Plasmons hold promise of wide applications due to low-losses, tunability and extreme

confinement at the nanoscale[1], and have been investigate in all sorts of nanostructures and hybrid

systems. Three-dimensional Nanoporous Graphene (NPG) has recently been obtained with a new

CVD-based fabrication process[2], obtaining to construct graphene in a 3D configuration (see Fig.1a)

while retaining the unique characteristics of mass-less Dirac fermions with high electron mobility.

While NPG is the object of ongoing studies to demonstrated its application such as energy

harvesting electrode [3], little is known about its optical properties.

We performed THz and Mid-Infrared optical conductivity measurements with a Michelson

Interferometer kept under vacuum at the infrared beamlines of Soleil, Paris and Bessy II, Berlin

Synchrotrons. The optical conductivity spectra, as in Fig.1b, exhibit, beside the typical interband

absorption of graphene above the threshold of 2EF (chemical potential of the system), a strong

plasmonic absorption at THz (for unintentionally doped samples) and Mid-Infrared (for EF=250 meV)

frequencies. These plasmonic excitations strongly depend on the chemical doping and pore-size,

following the behavior of 2D Dirac-Plasmons.

Fig 1: a) SEM image of

Nanoporous Graphene with

average pore size p=200 nm. b) A

typical Infrared absorption

spectrum for a doped sample

shows two absorption features:

interband transitions and a

plasmonic peak, at high and low

frequency, respectively.

ACKNOWLEDGMENTS

− This work was sponsored by "WPI Research Center Initiative for Atoms, Molecules and Materials", Japan.

REFERENCES

[1] Tony Low and Phaedon Avouris, ACS Nano, 8, 1086 [2014]

[2] Y. Ito, M. Chen et al., Angewandte Chemie, 126, 1 [2014]

[3] Y. Ito, M. Chen et al., Angewandte Chemie, 54, 2131 [2015]

POSTER SESSION

ACTIVITIES AT THE INFRARED MICROSPECTROSCOPY BEAMLINE D7 AT

THE MAX IV LABORATORY SWEDEN.

ANDERS ENGDAHL1

1) MAX IV laboratory, Lund University, P. O. Box 124, 22100 Lund Sweden.

MAX-lab in Lund, Sweden is closing down in December 2015 and is being replaced by the MAX IV

facility in Lund. There will be one 1.5 GeV and one 3 GeV ring at the new facility which will start

operating in June 2016.

Some recent projects: 1. Detection of pre-plaque amyloid aggregation using FTIR.

We use FTIRM to visualize secondary structure of proteins in their natural state. Spatial and spectral

resolutions allow distinguishing between spectral features of unfolded and β folded proteins by

analyzing the amide I region of the infrared spectrum. From the comparison of the spectral intensity

of the alpha and beta bands we deduce that overexpressed Aβ starts to misfold within neurons.

These data support the growing awareness that misfolded intraneuronal Aβ can be a key pathogenic

species which can be involved in causing synapse dysfunction in AD.

2. Interpreting melanin-based coloration through deep time.

The study of animal color through deep time is a fascinating new area of research, but still very much

in its infancy and with numerous experimental pitfalls. Caution should therefore be exercised in this

endeavor. Illuminating aspects of ancient organismal color is achievable only by thorough evaluation

of all plausible hypotheses.

3. Molecular composition and ultrastructure of Jurassic paravian feathers.

Feathers are amongst the most complex epidermal structures known, and they have a well-

documented evolutionary trajectory across non-avian dinosaurs and basal birds. Moreover,

melanosome-like microbodies preserved in association with fossil plumage have been used to

reconstruct original colour, behaviour and physiology.

4. Ultrastructural heterogeneity of carbonaceous material in ancient cherts:

investigating biosignature origin and preservation.

Opaline silica deposits on Mars may be good target sites where organic biosignatures could be

preserved. Potential analogues on the Earth are provided by ancient cherts containing carbonaceous

matter (CM) permineralized by silica. In this study we investigate the ultrastructure and chemical

characteristics of CM in the Rhynie Chert (c. 410 Ma, UK), Bitter Springs Formation (c. 850

Ma,Australia) and Wumishan Formation (c. 1485 Ma, China).

[1] O. Klementieva, K. Wille'n, A. Engdahl, P. uvdal, G. Gouras.Manuscript in preparation.

[2] J. Lindgren, A. Moyer, M. Schweitzer, P. Sjövall, P. Uvdal, J. Heimdal, A. Engdahl, D-E. Nilsson, J. Gren, B.

Schultz, B. Kear, Submitted to Proceedings of the Royal Society B

[3] J.Lindgren, P. Sjövall, R.M. Carney, A. Cincotta, P. Uvdal, S.W. Hutcheson, O.Gustafsson, U.Lefèvre, F.

Escuillié, J. Heimdal, A. Engdahl, J.A. Gren, B.P. Kear, K. Wakamatsu1, J. Yans, P, Godefroit

Submitted to Scientific Reports

[4] Y. Qu, A.Engdahl, S. Zhu, N. McLoughlin, Submitted to Astrobiology.

POSTER SESSION

INFRARED EXTRACTION FROM 4TH

GENERATION SYNCHROTRON STORAGE

RINGS

RAUL FREITAS AND PAUL DUMAS

1) Brazilian Synchrotron Light Laboratory, Campinas, Sao Paulo 13083-970 Brazil

2) SOLEIL Synchrotron, L'Orme des Merisiers 91190, Saint-Aubin, France

Infrared beamlines are versatile endstations present in the most of synchrotron storage rings

around the globe. The high spectral irradiance across the infrared range (from THz to near-IR), well

defined polarization, short time structure (hundreds of MHz) and low divergence compared

to thermal sources make these beamlines the ultimate tool for frontier research in vibrational

spectroscopy and imaging. With confirmed performance in interdisciplinary studies, infrared

endstations are among the most demanded beamlines in synchrotrons facilities serving a variety of

areas such as chemistry, physics, geology, paleontology, biology and many others. We present here

the first insights for the infrared beamline that will operate in the new Brazilian

synchrotron accelerator, the Sirius light source. IR extraction is one of the main issues in

this class of machines and we present the idea of using a pure edge source that, comparable

continuous radiation sources, has considerable low divergence, low aberration due to its sharp

depth and optimum shape for focusing. Moreover, optics layout for beam focalization and

collimation

and mirrors mechanics will be explained in details. The beamline will feed two endstations: a

nano-FTIR hutch that will be dedicated to experiments with spatial resolution beyond the

diffraction limit (better than 40 nm) and a second hutch dedicated to

mid-IR micro-spectroscopy. Finally, we discuss potential scientific cases for the two end

stations.

POSTER SESSION

FTIR IMAGING OF COPPER ZINC SUPEROXIDE DISMUTASE AGGREGATION IN

LIVING CELLS FOR THE STUDY OF FAMILIAL ALS

P. GELFAND1, L. MILLER

1,2, R. SMITH

2,

ELI STAVITSKI

2, AND DAVID R. BORCHELT

3

1) Department of Chemistry, Stony Brook University, Stony Brook NY 11794 USA

2) NSLS-II Photon Sciences, Brookhaven National Laboratory, Upton NY 11973 USA

3) Department of Neuroscience, Center for Translational Research in Neurodegenerative Disease, Santa Fe

HealthCare Alzheimer’s Disease Research Center, McKnight Brain Institute, University of Florida, Gainesville, Fl

32611 USA

Amyotrophic Lateral Sclerosis (ALS) is a debilitating neurological disease affecting the motor neurons

of the spinal cord. The discovery of novel effective treatments for ALS is made difficult from by the

lack of known pathologies for sporadic cased of the disease, and a poor understanding of the

mechanisms causing inherited or familial ALS (FALS). The most prevalent form of familial ALS,

accounting for 20% of known cases, is caused by mutations in the anti-oxidant metalloprotein

copper-zinc superoxide dismutase 1 (SOD1) resulting in the formation of SOD1 aggregates within

spinal cord tissue. Through development and application of in vivo time resolved Fourier transform

infrared (FTIR) imaging, we are elucidating secondary structural changes to FALS-SOD1 during

aggregation as a function of time. Our data studying the D125H SOD1 mutation suggests a

unidirectional aggregation pathway for this variant, involving the formation of parallel β-sheet rich

fibrils. In combination with prior studies of the G36R mutation, this data suggests multiple pathways

for SOD1 aggregation exist in vivo.

Fig 1: Visible, Fluorescent, and overlay of antiparallel

to parallel β-sheet ratio (1695/1630 cm-1

) color map

(left to right) for aggregation of D125H SOD1 mutant

after 12 (top) and 24 hours (bottom). Scale bar is 10

microns.

ACKNOWLEDGMENTS

− This research, performed at the National Synchrotron Light Source beamline U10, was supported by the

National Institutes of Health grant RR23782.

REFERENCES

[1] L.M. Miller, M.W. Bourassa, R.J. Smith, Biochim. Biophys. Acta Biomembr. 1828, 2339 [2013].

[2] P. Gelfand, R.J. Smith, E. Stavitski, D.R. Borchelt, L.M. Miller, Anal. Chem. 87, 6025 [2015].

POSTER SESSION

ANTI-CANCER EFFECTS OF NITRIC OXIDE RELEASE FROM TDODSNO, A

PHOTOACTIVATED DONOR DRUG

G.I. GILES, F.A. DEUSS, A.F. NIELD-PATTERSON

Department of Pharmacology & Toxicology, University of Otago, Dunedin, Otago 9054, New Zealand

We have developed a photoactivated nitric oxide (NO) donor drug tDodSNO [1]. We have shown that

light can be used as a means of selectively killing cancer cells following exposure to tDodSNO (1-100

µM), however little is known about its mechanism of action. We therefore used single cell infrared

spectroscopy to investigate the effects of NO release on MDA-MB-231 triple negative breast cancer

cells. Photoactivation predominantly induced structural changes to cellular proteins, as evidenced by

variance within the amide I and II regions of the spectrum. Protein changes corresponded to a

significant increase in cellular oxidation, indicating that NO chemically reacted with cellular targets.

These mechanistic insights reinforce the potential use of tDodSNO as a targeted NO donor molecule

for cancer chemotherapy.

Cell infrared (A) and second derivative (B) spectra, fluorescence images (x4) of cells labelled with oxidation

sensitive probe DCFDA (C) and quantification of oxidative damage (D).

ACKNOWLEDGMENTS

- This work was supported by the Otago Medical Research Foundation, the New Zealand Synchrotron

Group and the Australian Synchrotron.

REFERENCES

[1] Giles et al. The Molecular Design of S-Nitrosothiols as Photodynamic Agents for Controlled Nitric Oxide

Release. Chem Biol Drug Des 80, 471-478 [2012].

POSTER SESSION

PRODUCTION OF Z-POLARIZED COHERENT CHERENKOV LIGHT IN THZ REGION

H. HAMA1, K. NANBU

1, F. HINODE

1, S. KASHIWAGI

1, T. MUTO

1, H. SAITO

1, T. ABE

1, Y. SHIBASAKI

1, I.

NAGASAWA1, K. TAKAHASHI

1, C. TOKOKU

1, E. KOBAYASHI

1

1) Research Center for Electron Photon Science Center, Tohoku University, Sendai Miyagi 982-0826 Japan

Longitudinally (z) polarized light is powerful tool in photo reaction and imaging, it enables us to

obtain new information such as 3D orientation of molecules, unlike transversely polarized light.

Cherenkov radiation can be generated by relativistic electron beam which propagates in medium,

whose refractive index is different with vacuum, and it is perfectly radial polarization light.

Cherenkov radiation via extremely short electron bunch, whose bunch length is much shorter than a

radiation wavelength, will be coherent. At the focus point, z-polarization will be created by using an

optical lens resulting from interference of radial polarization (Fig.1). An accelerator test facility, t-

ACTS [1], constructed at Electron Photon Science Center, Tohoku University. Test accelerator is

consisted of a thermionic cathode RF gun together with 3m-long accelerating structure and

maximum beam energy is 50 MeV. Production of z-polarized coherent Cherenkov light in THz

wavelength region will be demonstrated at t-ACTS. According to numerical simulation, approximately

50 ps (30 µm) electron bunch can be produced by using the t-ACTS accelerator configuration. In the

experiment, an aerogel with 1mm thickness and 1.05 of refractive index will be used as radiator and

an opening of Cherenkov light is 17.8°. As the Cherenkov ring is focused using a lens, radial

polarization is converted to z-polarization at focal point. In this workshop, the results of numerical

study and test experiment of Cherenkov light production will be described.

Fig 1: Conversion from radial polarization to z-

polarization.

ACKNOWLEDGMENTS

− This work is supported by Grant-in-Aid for Challenging Exploratory Research 15K13394, JSPS, Japan.

REFERENCES

[1] H. Hama et al., Energy Procedia 9 (2011) 391-397.

POSTER SESSION

DEVELOPMENT OF THZ SOURCE AT KEK CERL

Y. HONDA1,

, A. ARYSHEV1, M. SHEVELEV

1 , M. SHIMADA

1

1) Accelerator Department, High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801

Japan

At KEK, a test accelerator of energy recovery linac (ERL) scheme, called cERL, has been constructed

and under commissioning since 2013. One of the feature of ERL is that it can realize a short bunched

and low emittance beam as it is a linac based accelerator, and it can operate a high averaged current

because of the energy recovery scheme. Especially in a bunch compression mode, which compresses

the bunch in time at the downstream of the dispersion controlled arc section, it will be able to

produce bunch length shorter than 100 fs at the repetition rate of 162.5 MHz continuously. Coherent

radiation from this beam is expected to be a powerful source in THz regime. As a test accelerator, we

propose to develop a resonant coherent diffraction radiation (rCDR) system at cERL. It is an optical

cavity formed on the beam orbit to build-up CDR. If the fundamental frequency matches to the

bunch repetition rate, the stored radiation from the preceding bunches will stimulate the radiation in

the following bunches, resulting in a much stronger power extracted from the beam. We will show an

estimation of this scheme based on a simple model.

Fig 1: Layout of cERL. At downstream of

the arc, a high repetition rate and short

bunched beam is available. We propose

to develop a rCDR system in the straight

section.

ACKNOWLEDGMENTS

− This work is partially supported by Photon and Quantum Basic Research Coordinated Development

Program from the Ministry of Education, Culture, Sports, Science and Technology, Japan.

REFERENCES

[1] A. Aryshev et al. Nucl. Instr. Meth. A 763 , pp 424-432[2014].

POSTER SESSION

OPTICAL SPECTROSCOPY OF THE INSULATING PHASES OF VANADIUM

DIOXIDE

T.J. HUFFMAN1, PENG XU

1, M.M. QAZILBASH

1, C. HENDRIKS

1, E.J. WALTER

1, H. KRAKAUER

1, JIANG WEI

2,

D.H. COBDEN3, HONGLYOUL JU

4, H.A. BECHTEL

5, M.C. MARTIN

5,R. SMITH

6, G. L. CARR

6, AND D.N. BASOV

7

1) Department of Physics, College of William and Mary, Williamsburg VA 23187 USA

2) Department of Physics and Engineering Physics, Tulane University, New Orleans, Louisiana 70118, USA

3) Department of Physics, University of Washington, Seattle, Washington 98195, USA

4) Department of Physics, Yonsei University, Seoul 120-749, Republic of Korea

5) Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

6) Photon Sciences, Brookhaven National Laboratory, Upton, New York 11973, USA

7) Department of Physics, University of California, San Diego, La Jolla, California 92093, USA

Bulk, crystalline vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340K. This

thermally-driven MIT is accompanied by a structural phase transition that results in pairing of all

vanadium ions in the insulating, monoclinic M1 phase. While a complete explanation of the MIT has

proven elusive, this pairing has long been thought to be critical to the emergence of insulating

behavior in VO2. However, there exist two additional insulating VO2 crystal structures, the

monoclinic M2 and triclinic (T) phases, which exhibit distinctly different vanadium-vanadium pairing.

In the M2 phase, only half of the vanadium ions exhibit pairing while the other half carry spin 1/2

magnetic moments and are equally spaced in quasi-one dimensional chains. The triclinic phase can

be viewed as a superposition of the M1 and M2 phases.

By studying the three insulating phases with optical spectroscopy, we investigate how changes to the

VO2 crystal structure, particularly the vanadium-vanadium pairing, affect the properties of the VO2

insulating state. Such experiments could lead to insight into the connection between crystal

structure and electronic properties in this material. Photon spectroscopy is an ideal experimental

probe for this investigation, as it is able to access the crystal structure through the infrared active

phonons, and the electronic structure through the inter-band transitions.

There is significant experimental challenge in that these crystals are quite small, on the order of 50 or

60 micrometers. To extract optical constants from these small crystals, we performed confocal

infrared transmission and reflectance micro-spectroscopy with polarized light at U12IR beam line at

NSLS to study the M1, M2 and T phase VO2 crystals at photon energies between 20 meV to 0.8 eV. To

extend the spectral range up to 5.5 eV, spectroscopic micro-ellipsometry has been performed at the

College of William and Mary. With these experiments, we are able to extract the infrared

“fingerprint” of these three phases, as well as the optical conductivity in the vicinity of the band gap.

Changes in the infrared active phonon features provide clear evidence of a structural transition.

However, the higher frequency electronic properties differ only in detail. The gross electronic

structure, specifically the band gap, remain largely unchanged. Hence, we deduce that vanadium-

vanadium pairing is not critical to the emergence of insulating behavior in VO2.

POSTER SESSION

TOWARDS CONTACTLESS THERMOGRAPHY AT THE NANOSCALE USING

SYNCHROTRON RADIATION BASED NANO-FTIR SPECTROSCOPY

B. KÄSTNER1, P. HERMANN

1, A. HOEHL1, P. KRZYSTECZKO

2, H. W. SCHUMACHER2, G. ULRICH

3, P. PATOKA3,

B. BECKHOFF1, E. RÜHL

3, AND G. ULM1

1) Physikalisch-Technische Bundesanstalt (PTB), 10587 Berlin, Germany

2) Physikalisch-Technische Bundesanstalt (PTB), 38116 Braunschweig, Germany

3) Physical and Theoretical Chemistry, Institute for Chemistry and Biochemistry, Freie Universität Berlin, 14195

Berlin, Germany

Measuring temperatures at the nanoscale is a key issue in many technologies and remains

challenging [1]. Self-heating in integrated electronics, for example, causes hot spots influencing

device performance and reliability. In this work we demonstrate a novel method for contactless

thermography at the nanoscale. It is based on a scanning near-field infrared microscopy system

coupled to ultrabroadband synchrotron radiation [2, 3]. Evaluating temperature induced shifts of

characteristic phonon modes is proposed to determine the local temperature. The method is

demonstrated by scanning the SiO2 surface within a distance of 500 nm of a 200 nm wide Pt wire

used as a heater. The second order scattering signal s2, as function of frequency and heater current,

has been recorded (Fig. 1) for local temperature evaluation. One may deduce from this

demonstration experiment that temperature changes smaller than 10 K should be resolvable over a

length scale of less than 100 nm.

Fig 1: Imaginary part of the second order scattering

amplitude from the SiO2 surface s2(SiO2), normalized

by the scattering amplitude from the Pt-heater s2(Pt).

The peak near 1130 cm-1

results mainly from surface

phonon excitations. Evaluating the resistance change

of the heater wire a temperature difference of ∆T <

100 K is deduced between the shown ON and OFF

state.

ACKNOWLEDGMENTS

− The authors acknowledge financial support by the European Metrology Research Programme (EMRP). This

work was funded through the EMRP projects IND54 Nanostrain, IND56 Q-AIMDS and EXL04. The EMRP is

jointly funded by the EMRP participating countries within EURAMET and the European Union.

REFERENCES

[1] S. Gomes, A. Assy, P.-O- Chapuis, Physica Status Solidi (A) 212, 477 [2015].

[2] P. Hermann, A. Hoehl, P. Patoka, F. Huth, E. Rühl, and G. Ulm, Opt. Express 21, 2913 [2013].

[3] P. Hermann, et al., Opt. Express 22, 17948 [2014].

POSTER SESSION

PHASE TRANSITIONS IN THE SYSTEM CaCO3 AT HIGH P AND T DETERMINED BY

IN-SITU VIBRATIONAL SPECTROSCOPY IN DIAMOND-ANVIL CELLS

MONIKA KOCH-MÜLLER1, SANDRO JAHN

1, 2, NATALIE BIRKHOLZ1, 3, EGLOF RITTER

4, ULRICH SCHADE5

1) Deutsches GeoForschungsZentrum GFZ, Sektion 3.3, Telegrafenberg, 14473 Potsdam, Germany 2) Universität zu Köln, Institut für Geologie und Mineralogie, 50939 Köln, Germany

3) Institut für Angewandte Geowissenschaften, Technische Universität Berlin, Germany

4) Experimentelle Biophysik, Humboldt-Universität zu Berlin, 10115 Berlin, Germany

5) Methoden der Materialentwicklung, Helmholtz-Zentrum Berlin, 12489 Berlin, Germany

Carbonates are the most abundant carbon-bearing minerals on Earth. They can be transported into

the upper and lower mantle via subduction processes. Evidence for the presence of carbonates in the

mantle comes from carbonate inclusions in diamonds from the lower mantle [1]. Knowledge of the

stability of solid carbonates adapting different structures with increasing pressure and temperature is

therefore of great importance to understand the structure and dynamics of the Earth. The high-

pressure CaCO3-polymorphs (cc-III and cc-VI) are studied by conventional and synchrotron (SR) mid-

infrared spectroscopy, by SR far-infrared and Raman spectroscopy to explore the P/T stability in the

carbon bearing system. It can be assumed from our study that under the P/T-conditions of the

Earth's mantle cc-VI may be stabilized towards lower pressure replacing aragonite in some parts of

the mantle.

REFERENCES

[1] Brenker F. E. et al. (2007) Earth and Planetary Science Letters, 260: 1-9

POSTER SESSION

Fig. 1: Selected spectra of the CaCO3

polymorphs.

a, b: Raman-spectra,

c: synchrotron MIR spectra,

d: synchrotron FIR spectra

P was determined in-situ in all

experiments by laser-induced

fluorescence of Cr3+

R1-line in Ruby. To

do so a green laser and an Ocean Optics

USB-spectrometer was installed into

the optical path of the Nicolet

microscope at the IRIS beamline of

BESSY II.

CHANGE IN THE MICROENVIRONMENT OF BREAST CANCER STUDIED BY FTIR

MICROSPECTROSCOPY

S. KUMAR1, X. LIU

1, F.BORONDICS

2, E. GOORMAGHTIGH

3, AND T. ELLIS

1

1) Canadian Lightsource, Saskatoon, Canada

2) SOLEIL synchrotron, Gif-sur-Yvette, Ile-de-France, France

3) SFMB, Université Libre de Bruxelles, Belgium

Background: Breast cancer is a global public health issue. It is the second cause of mortality in

western women. Surgery is the primary treatment in the majority of cases, however around 50% of

these cases will develop metastatic disease (incurable). The mechanism involved in the progression

towards metastasis remains elusive. The understanding of invasion of cancer could be significantly

improved if cancer cell interaction with the microenvironment were better known. Current interest is

to understand the difference between normal and reactive stroma especially the role of fibroblast.

FTIR imaging technique could be able to distinguish these two different types of stroma due to its

potential to probe tissues and cells at the molecular level.

Methods: The spectroscopic imaging data on breast cancer samples were acquired in transmission

on deparaffined 3 µm thick tissue slices deposited on 40x26 mm2 BaF2 slides. For cells, the fibroblasts

were grown on CaF2 window and directly used for FTIR measurements. We used a Hyperion imaging

system (Bruker) equipped with a 64*64 MCT (Mercury-Cadmium-Telluride) FPA (Focal Plane Array)

detector.

Results: Using infrared imaging together with multivariate statistical tools we attempted to in a first

step to discriminate the reactive stroma in contact with the diseased epithelium on one side and the

normal stroma on the other side. A subsequent analysis of the spectra assigned to collagen was then

performed to identify any potential influence of the tumors. An initial work on 8 patients with

different tumor grades has shown promising findings [1]. In a second step we collected infrared

spectra of fibroblasts growing in culture on CaF2 windows in order to evaluate the impact of the

different shapes encountered in fibroblasts. This investigation shows a significant separation could

though be observed that the fibroblasts stimulated by these cancer cell lines grouped together and

remained distinctly separated from normal fibroblasts indicating a modified different chemical

composition in the cancer-stimulated fibroblasts [2].

ACKNOWLEDGMENTS

We are grateful to CIHR-THRUST, Canadian light source (for project initiation), Brain back to Brussels and

Swedish research for postdoctoral fellowships.

REFERENCES

[1] S. Kumar et al., Analyst, 138, 4058-65, 2013.

[2] S. Kumar et al., Plos One, 9, 1-8, 2014.

POSTER SESSION

Oxidative Damage and Pathological Heterogeneity of Active Lesions in

Multiple Sclerosis

SAROJ KUMAR1, MYLYNE THAM

2,4, CLAUDIA LUCCHINETTI

3, BOGDAN POPESCU

2,4

1) Canadian Lightsource, Saskatoon, Canada

2) Cameco MS Neuroscience Research Centre, University of Saskatchewan, Canada

3) Department of Neurology, Mayo Clinic, Rochester, MN, USA

4) Department of Anatomy and Cell Biology, University of Saskatchewan, Canada

Background: Multiple sclerosis is a neuro-degenerative disease where insulating covers (myelin) of

nerve cell damaged which disrupts the communication between the brain and the rest of the body.

Due to disease heterogeneity in nature emphasis on identifying a single cause and therapy effective

for all multiple sclerosis (MS) patients not get success due to the clinical, pathologic, genetic and

radiographic heterogeneity that underlies the variable response of MS patients to any given

treatment. Four distinct MS patterns have been described pathologically, suggesting that targets of

injury and mechanisms of demyelination are different in different patient subgroups. Current

research suggests a significant role of oxidative stress in the process of demyelination and

neurodegeneration of MS active lesions. The human brain is highly susceptible to oxidative damage

due to high concentrations of lipids and unsaturated fatty acids. Oxidative damage can lead to

impaired cellular functions and generation of toxic reactive oxygen species, which can cause

significant damage to macromolecules, such as lipids and proteins.

Objectives: To use Fourier-transform infrared microspectroscopy, immunohistochemistry, and X-ray

fluorescence (XRF) imaging to analyze the metal distribution and oxidative changes to proteins and

lipids in demyelinated and non-demyelinated areas of biopsy specimens. Methods: Formalin-fixed,

paraffin-embedded 5 µm-thick tissue sections were stained histochemically and

immunohistochemically to characterize active lesions. 15 µm-thick sections were mapped for iron

using Rapid Scan XRF at beamline 10-2 at the Stanford Synchrotron Radiation Lightsource. 5 µm-thick

sections were collected on CaF2 slides and FT-IR spectra were acquired using a Hyperion 3000 FTIR

imaging system at the Canadian LightSource.

Results: Demyelinated active MS lesions had prominent lipid oxidation, protein aggregation,

phosphate reduction, and lower levels of sulfur and phosphorous, compared to the non-

demyelinated tissue. Iron distribution did not change remarkably between demyelinated and non-

demyelinated areas. Initial observations suggest there is a profound pathological heterogeneity in

active MS lesions and proposes that tissue injury through metal dysregulation and oxidative damage

have an important role in the pathogenesis and evolution of lesions.

ACKNOWLEDGMENTS

We are grateful to CIHR-THRUST, Canadian light source and University of Saskatchewan, Canada.

POSTER SESSION

MYSTERIES OF POLAR BEAR HAIR REVEALED BY MORPHOLOGY AND

RADIATIVE STUDIES

XIA LIU1, S. KUMAR

1, N. SYLVAIN

2, N. ZHU, G. BELEV

1, A. DUFFY

1, C. KARUNAKARAN

1, F. BORONDICS

3

1) Science division, Canadian Light Source, Saskatoon, SK S7N2V3 Canada

2) Department of surgery, University of Saskatchewan, Saskatoon, SK S7N5E5 Canada

3) SMIS Beamline, Soleil Synchrotron, BP48, L’Orme des Merisiers, 91192 Gif sur Yvette Cédex, France

A number of mysteries of polar bears attracted attention from scientists. How they survive in

extremely weather conditions in the arctic; whether the hair can be used as fibre-optic or solar

energy collector [1]; why they are invisible except their face and nose for infrared camera; what

makes them such good swimmers [2]. These mysteries remain unsolved, with some controversial

results reported in the literature [3]. Information on morphology and radiative properties of polar

bear hair is essential to better understand its natural functionality and possibly answer some of these

questions. However there is little information available to date [4,5]. In this project, we investigated

polar bear hair using synchrotron based computed x-ray micro-tomography imaging and FTIR

microspectroscopy. Our results allow a better understanding of the natural functionality of polar

bear hair and the key roles it plays in heat insulation as well as long-distance swimming. The findings

can provide insight and inspiration for producing new bioinspired materials with similar functionality

and properties as polar bear hair.

ACKNOWLEDGMENTS

− This work supported by Canadian Light Source, which is supported by the Canada Foundation for

Innovation. Natural Sciences and Engineering Research Council of Canada, the University of Saskatchewan,

The Government of Saskatchewan, Western Economic Diversification Canada, the National Research

Council Canada, and the Canadian Institutes of Health Research.

− We would sincerely acknowledge Dr. David Cooper from Department of Anatomy and Cell Biology of the

University of Saskatchewan for the use of micro-computed tomography system setup at BMIT beamline at

CLS.

REFERENCES

[1] T. Stegmaier, M. Linke, H. Planck, Bionics in textiles: flexible and translucent thermal insulations for solar

thermal applications, Phil.Trans. R. Soc. A 367, 1749 [2009].

[2] G.M. Durner, J.P. Whiteman, H.J. Harlow, S.C. Amstrup, E.V. Regehr, M. Ben-David, Consequences of long-

distance swimming and travel over deep-water pack ice for a female polar bear during a year of extreme sea

ice retreat, Polar Biol. 34, 975[2011].

[3] D.W. Koon, Is polar bear hair fiber optic? Applied Optics 37, 3198 [1998].

[4] M. Rattal, A. Balhamri, Y. Bahou, A. Deraoui, A. Mouhsen, M. Harmouchi, A. Tabyaoui, El M. Oualim, Study

of the optical properties of polar bear hair in the infrared range and their microscopic structures for passive

control of temperature, Journal of science and arts, 2, 217[2011].

[5] J.A. Preciado, B. Rubinsky, D. Otten, B. Nelson, M.C. Martin, R. Greif, Radiative properties of polar bear hair,

Advances in Bioengineering 53, 1[2002].

POSTER SESSION

SYNCHROTRON INFRARED NANOSPECTROSCOPY USING LOW-ABERRATION

BEAMLINE OPTICS

Francisco C. B. Maia1, Christoph Deneke

2, Thierry Moreno

2, Paul Dumas

2 and Raul O. Freitas

1

1) Brazilian Synchrotron Light Laboratory, Campinas, SP, 13083-970, Brazil

2) SOLEIL Synchrotron, Gif Sur Yvette Cedex, 91192, France

3) Brazilian Nanotechnology National Laboratory, Campinas, SP, 13083-970, Brazil

Scattering-type Scanning Near-Field Optical Microscopy (s-SNOM) has recently taken advantage of

the outperforming properties of the Synchrotron's broadband infrared radiation to allow high

performance Synchrotron Nanoinfrared Spectroscopy (SINS)1,2

. As s-SNOM, SINS breaks the Abbe's

diffraction limit, but, additionally has succeeded in recovering the vibrational molecular fingerprints

at nanometer scale. Here, we describe SINS experiments accomplished with the use of an aberration-

less optics for the extraction of the infrared radiation at the storage ring. Firstly, we detail the

tailored extraction optics designed upon theoretical simulations. Notably, the well agreement

between calculations and measured beam profiles at each optical element shows the powerful

capability of the developed modeling of beam propagation for projecting complex optical setups. Our

setup provided deep-in analysis at near-field regime of a patterned sample of SiO2 on Au substrate.

We present, for the first time to our knowledge, a near-field hyper-spectral image of a SiO2 structure

obtained in Synchrotrons. Such result clearly demonstrates the potential of attaining the long-

pursued chemical images. We also image and retrieve the vibrational molecular signature, spanning

through an extended spectral range, of Poly(methyl methacrylate) (PMMA), which falls in the

challenging branch of weak oscillator molecules. Summarily, this work brings the whole description

for attaining high-performance SINS experiments which can be steadfastly ranked among the probes

of excellence for nanoscopy.

[1] H. A. Bechtel, E. A. Muller; R. L. Olmon, M. C. Martin, M. B. Raschke, Proceedings of the National Academy

of Science 111, 7191 [2014].

[2] P. Hermann, A. Hoehl; G. Ulrich, C. Fleischmann, A. Hermelink, B. Kästner, P. Patoka, A. Hornemann, B.

Beckhoff, E. Rühl, G. Ulm, Optics Express, 22, 17948 [2014].

POSTER SESSION

1

2

FTIR SPECTRO-TOMOGRAPHY USING AN FPA DETECTOR

MARTIN ASHFORD,1,2 MICHAEL TANG, 1

DILWORTH Y. PARKINSON, 1 HANS A. BECHTEL, 1

MICHAEL C. MARTIN1

1) Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA 2) ENSICAEN, France

Two-dimensional (2D) FTIR spectromicroscopy has recently become substantially faster via the use of

focal plane array (FPA) detectors. We now use the rapid 2D spectral image acquisition capability of

the Agilent 620 FTIR microscope coupled to a 128 x 128 FPA detector to measure a large number of

projected transmission images as a sample is precisely rotated. A 3D representation of the sample at

every wavelength is reconstructed via computed tomography back projection algorithms. We

produce 4D reconstructions: three spatial dimensions plus a full mid-IR spectral dimension for every

voxel. This method, Fourier transform infrared (FTIR) spectro-microtomography, provides rich

spectral information and chemical fingerprinting, including 3D distributions of these signatures

throughout the sample. To make FTIR spectro-microtomography possible, we developed a motorized

sample mount capable of precisely rotating a sample on a pin mount while holding it at the focus of

an IR microscope. Data collection of 2D spectral transmission images as a function of sample angle

was automated, and we modified computed tomography reconstruction algorithms to make them

spectrally aware, meaning to allow the reconstruction of integrated absorption intensities of

specified spectral regions with and without baseline subtractions, differences between spectral

regions and full reconstructions for every wave number measured, which are reassembled into a

complete spectrum for every voxel.

Fig 1: A human hair splitting into two. Left shows cuts

in the z, x, and y planes (top to bottom), and in color is a

3D IR intensity map where the split can be clearly seen.

ACKNOWLEDGEMENTS

The ALS is supported by the Director, Office of Science, Office of Basic Energy Sciences, and the BSISB is supported by the Office of Biological and Environmental Research, all through the U. S. Department of Energy (DOE) under Contract No. DE-AC02-05CH11231.

REFERENCES

[1] Michael C. Martin, Charlotte Dabat-Blondeau, Miriam Unger, Julia Sedlmair, Dilworth Y. Parkinson, Hans A. Bechtel, Barbara Illman, Jonathan M. Castro, Marco Keiluweit, David Buschke, Brenda Ogle, Michael J. Nasse, Carol J. Hirschmugl, Nature Methods, 10, 861-864 (2013).

POSTER SESSION

MID IR BEAM LINE REDESIGN FOR FOCAL PLANE ARRAY

T.E. MAY1, A. DUFFY

1, D. TRIVET

1, TH.MORENO

2

1) Canadian Light Source, Inc., Saskatoon, SK S7N2V3 Canada

2) SOLEIL Synchrotron, BP48, L'Orme des Merisier ,Gif sur Yvette Cédex 91192 France

The Mid Infrared beam line at Canadian Light Source was designed to illuminate a single element

detector in an IR microscope [1]. The addition of a Focal Plane Array detector provides a new user

experience with a large number of pixels illuminated [2]. Although functioning with a reduced array

size and large magnification, defocus is needed to make the beam more uniform on the array, which

loses brightness. Recent developments to better couple the extended synchrotron IR source, due to

large port angles, to the sample/detector prompts us to consider a new optical design to take

advantage of the array [3,4,5]. Ray-tracing is used to model a new layout in the existing space.

Synchrotron source generated in SHADOW can be imported into ZEMAX to simulate our beam [6].

Toroid mirrors replacing ellipsoids are simulated in SPOTX and transferred to Zemax. The

development is underway and current progress will be discussed.

Fig 1: Simple model to reshape the infrared beam

takes four points along electron orbit and reflects the

light from a conical mirror to form 4 beams. They are

reflected into a 2 x 2 array by pairs of flat mirrors

making the beam profile more “square”. A parabolic

mirror focusses the beams to an aperture in the

microscope.

ACKNOWLEDGMENTS

− Lively discussions, model assistance and great encouragement by Paul Dumas are gratefully acknowledged.

− Work supported by Canada Foundation for Innovation, Natural Sciences and Engineering Research Council

of Canada, National Research Council Canada, and Canadian Institutes of Health Research.

REFERENCES

[1] Tim May, Thomas Ellis, Ruben Reininger, Nucl. Instrum. Methods Phys. Res., Sect. A, 582, 111 [2007].

[2] Mark J. Hackett, Sally Caine, Xia Liu, Tim E. May, Ferenc Borondics, Vibrational Spectroscopy, 77, 51 [2015].

[3] Th. Moreno, H. Westfahl, R. de Oliveira Freitas, Y. Petroff, P. Dumas, J. of Physics: Conf. Series, 425, [2013].

[4] Michael J. Nasse, Michael J. Walsh, Eric C. Mattson, Ruben Reininger, André Kajdacsy-Balla,

Virgilia Macias, Rohit Bhargava, Carol J. Hirschmugl, Nature Methods, 8, 413 [2011].

[5] Mark Frogley and Gianfelice Cinque, AIP Conference Proceedings, 1214, 29 [2010].

[6] Timothy May and Alan Duffy, Vibrational Spectroscopy, 75, 123 [2014].

POSTER SESSION

1

2

CAPABILITIES OF FTIR MICROSPECTROSCOPY TO DISTINGUISH AMONG EACH CELL-CYCLE STAGE ACCORDING TO THE RELATIVE AMOUNT OF DNA AND RNA

E. MITRI1, P. ZUCCHIATTI

2, S. KENIG3, R. MENDOZA-MALDONADO

4, G.BIRARDA2, D.E. BEDOLLA

1, AND L. VACCARI

1

1) Elettra Sinctrotrone Trieste S.C.pA., Basovizza, Trieste, 34149 Italy 2) Università degli studi di Trieste, Trieste, 34126 Italy 3) Structural Biology Laboratory, Elettra-Sincrotrone Trieste S.C.pA., Basovizza, Trieste, 34149 Italy 4) National Laboratory CIB, Area Science Park, Padriciano, Trieste, 34149 Italy

Our group has already proposed the exploitation of Synchrotron Radiation (SR) FTIR Microscopy

(FTIRM) as a fast and totally label-free technique for assessing the cell cycle state of individual live

cells according to the total amount of Nucleic Acids (NAs), with an accuracy comparable to the one of

Flow Cytometry (FC) with Propidium Iodide staining (PI) [1]. Both techniques give classification into

three main classes, namely G1/G0, S and G2/M. We have also pointed out that a spectroscopic

continuum exists among the different phases, possibly due to the different RNA content that

characterizes the cellular stages [2]. In this contribution our recent results on the topic will be

presented. We will report on an optimized protocol for the digestion of cellular RNA, which minimally

affects the cell membrane integrity, maintaining unaltered the vibrational contribution of the other

macromolecules. The implementation of this protocol allowed us to collect the first FTIR spectra of

intact hydrated single cells deprived of RNA and to highlight in-cell diagnostic features of the two

types of NAs (See Fig. 1). We will also present the optimization of a FC assay based on Acridin Orange

(AO) fluorescent dye, which allowed the simultaneous evaluation of both DNA and RNA content,

permitting the determination of each stage of the cell cycle with a single analysis. FTIRM experiments

have been done in parallel on single hydrated cells. The spectral contributions of both NAs were

separately evaluated by deconvolving the symmetric and asymmetric stretching bands of phosphate

moieties. The good agreement among the techniques demonstrates the capability of FTIRM to assess

all the stages of the cell cycle at the level of a single live cell without the use of any label.

Fig 1: Second derivative of the spectra of a single

hydrated B16 cell obtained after the removal of RNA in

the region between 1480 and 900 cm-1

(red) compared

to the one obtained from a single B16 control cell

(blue). From the comparison of the two spectra it is

possible to establish that PhI band component at 1240

cm-1

as well as PhII components at 1120 and 996 cm-1

could be associated mainly to RNA contributions.

REFERENCES

[1] D.E. Bedolla, S. Kenig, E. Mitri, P. Ferraris, A. Marcello, G. Grenci and L. Vaccari, Analyst, 138, 4015 [2013] [2] D.E. Bedolla, S. Kenig, E. Mitri, P. Storici, L. Vaccari, Vibrational Spectroscopy, 75, 127 [2014]

POSTER SESSION

STUDY ON THZ IMAGING BY USING A COHERENT CHERENKOV RADIATION

M. NISHIDA1, M. MIZUGAKI

1, M. WASHIO

1, K. SAKAUE

2, R. KURODA

3, Y. TAIRA

3

1) Research Institute for Science and Engineering, Waseda University, Tokyo, Japan

2) Waseda Institute for Advanced Study, Waseda University, Tokyo, Japan

3) National Institute of Advanced Industrial Science and Technology, Ibaraki, Japan

THz frequency is a unique electromagnetic wave which is categorized between a radio wave and a

light wave. It can pass through various materials as a radio wave and can be transported with optical

components as a light wave[1]

. Thus, it is suitable for imaging application of materials. At Waseda

University, it is possible to generate a high-quality electron beam using Cs-Te photocathode RF-Gun

and the electron beam is applied to several application researches. As an application of this electron

beam, we observed a coherent Cherenkov radiation[2]

, and succeeded in generating a high power THz

light.

The successful results of high power THz radiation encourage us to perform the THz imaging with

both transmission and reflection imaging. Figure 1 shows the THz transmission image of the IC card.

It is clear that the THz image includes an internal structure of IC, antennas and circuits. On the other

hand, we also tried to obtain the THz reflection images. Figure 2 shows the reflection image of 10 yen

coin. As shown in Figure 2, the surface designs of 10 yen coin were observed with reflection image.

The horizontal size of THz image was smaller than the object. We think that it is because of the

discrepancy between the angle of the sample and the direction of scanning.

Figure 1: THz transmission image of IC card. Figure 2: THz reflection imaging of 10 yen coin.

In this experiment, we obtained high resolution images of both transmission image and reflection

image. As a result, we succeeded to analyze both internal structure of sample which can be passed

through by THz light and surface structure which can reflect it. As the future prospects, we will

optimize the THz radiation for improve the THz intensity and spatial resolution. Also, we will try to

obtain the cross-section images for measuring the 3-dimentional structure. .

REFERENCES

[1] J. Nishizawa, The basics and application of the Terahertz wave [2005].

[2] T.Takahashi, et al., Phys. Rev. E 62, 8606 [2000]

POSTER SESSION

UNDERSTANDING THE PROTON EXCHANGE MEMBRANES DYNAMICS

L. PUSKAR1, U. SCHADE

1, E. RITTER

2, E. F. AZIZ

1,3

1) Methods for Material Development, Helmholtz-Zentrum für Materialien und Energie GmbH, Berlin, 12489

Germany

2) Experimentelle Biophysik, Humboldt-Universität zu Berlin, Berlin, 10115, Germany

3) Fachbereich Physik, Freie Universität Berlin, Berlin, 14195, Germany

Light driven water oxidation is a vital step in harvesting the solar energy. In nature this is effectively

performed by photosystem II in plants and cyanobacteria. Catalysts that can oxidise water at

potentials close to thermodynamic limit are of special interest as they allow efficient utilization of the

light energy. The high proton conductivity of ionomer membranes (PEM-proton exchange

membranes) makes them ideal candidates for catalyst immobilization inside fuel cells. High proton

conductivity and good mechanical-chemical stability are essential performance parameters. Although

the most commonly used ionomer Nafion provides these properties there is further technological

demand for operation at higher temperatures and lower humidity. New multi acid side-chain

ionomers, such as 3M perfluoroimide acid (PFIA) are designed to meet these challenges. Nafion and

PFIA polymers consist of a hydrophobic tetrafluoroethylene (PTFE) backbone which provides the

stability and hydrophilic perfluorinated pendant chains terminating in sulfonate groups (SO3H+). The

3M-PFIA polymer has a sulfonyl imide group as an additional exchangeable cation site.

MIR and FIR spectroscopy was applied to investigate the nature of interactions in these films under

various environmental conditions.

Fig 1: Time-dependent transmission FTIR spectra of

water saturated perfluoroimide acid (PFIA polymer, 25

µm thickness) membrane at 120⁰ C. Inset showing the

chemical structure of the PFIA ionomer.

REFERENCES

A. D. O.Bawagan, S. J. Hamrock, M. Schaberg, I.Yousef, E.Ritter, and U. Schade, Vib. Spec. 75, 213 [2014].

K. Feng, L. Hou, B. Tang and P. Wu, PCCP 17, 9106 [2015].

R. K. Hocking, R. Brimblecombe, L-Y Chang, A. Singh, M. H. Cheah, C. Glover, W. H. Casey and L. Spiccia, Nat.

Chem. 3, 461 [2011].

POSTER SESSION

INTENSE THZ GENERATION BY A COHERENT CHERENKOV RADIATION

K. SAKAUE1, M. MIZUGAKI

2, M. NISHIDA

2, M. WASHIO

2, R. KURODA

3, Y. TAIRA

3

1) Waseda Inistitute for Advanced Study, Waseda University, Tokyo, Japan

2) Research Institute for Science and Engineering, Waseda University, Tokyo, Japan

3) National Institute of Advanced Industrial Science and Technology, Ibaraki, Japan

We have been studying about a coherent THz generation by an ultra-short pulse electron bunch via

the transition radiation[1]

, synchrotron radiation[2]

and so on. There are many well-known processes

to generate a radiation from the relativistic electrons. In these processes, we found that the

Cherenkov radiation is the most efficient process because the number of interacting atoms and/or

molecules is larger than the other processes.

As shown in Figure 1, however, the Cherenkov radiation is emitted at certain angle with electron

beam, which is determined by the refractive index of the radiator n and the Lorentz factor of β of

electrons. It makes difficult to achieve coherent radiation and collect whole radiation from the

radiator. In order to solve this problem, we used a hemispherical silicon target. As illustrated in Figure 2,

the electron bunch injects to the hemispherical silicon target and produces a coherent Cherenkov radiation

at the thin area near the surface. Whole radiation is collected by the hemispherical structure. For producing

coherent radiation, the electron bunch has to be focused less than the wave length of THz radiation. Also, by selecting suitable material, we found that coherent Cherenkov THz source will achieve more than

1mW average power.

We will report a principle of this coherent Cherenkov radiation, the experimental results by using our

electron gun at the energy of 5 MeV, and future prospective at the conference.

Figure 1: Schematic of Cherenkov radiation from

relativistic electron.

Figure 2: Cherenkov radiation from the

hemispherical target.

REFERENCES

[1] Y. Koshiba et al., Vibrational Spectroscopy, 75, 184 [2014].

[2] R. Kuroda et al., Nucl. Instrum. Meth., A637, S30 [2011].

POSTER SESSION

1

2

MID INFRARED TO THz SPECTROSCOPY WITHOUT CHANGIND OF OPTICAL

COMPONENTS. PIGMENTS IDENTIFICATION IN ART OBJECTS.

SEGREY V. SHILOV 1

1) Bruker Optics, 19 Fortune Dr. Billerica, MA,

Vibrational modes of infrared active molecules are manifest in the spectral range from 4000 down to

30 cm-1. While the mid-IR spectral range (4000-400 cm-1) is the standard range for a modern FTIR

spectrometer, changing of optical components are required to access the FIR/THz region below 400

cm-1. This inconvenience has been eliminated with the Bruker Vertex FM spectrometer. The Vertex

FM is a Fourier transform spectrometer which has been optimized to record spectra from 6500 cm-1

down to 50 cm-1 without needing to change any optical components. This saves an enormous

amount of time in acquiring the complete molecular spectral information and eliminates the risk of

breaking expensive optics during the exchange. All spectrometer parts are insensitive to humidity.

Identification of pigments in art paintings is highly demanded among art conservation community.

Comparison of infrared spectra of unknown paint against the spectral libraries is commonly used

technique for this application. Library of pigments in infrared spectral range are commercially

available. Paint that was used in art objects consist mostly of inorganic compounds. These

compounds have characteristics bands in the far IR range below 400 cm-1. For this reason extension

of spectral libraries to FIR spectral range is of general interest in art conservation community. The

major requirement in art conservation is that spectra of unknown paintings must be acquired

without touching of the object of art. To satisfy this requirement reflectance accessory was used to

acquire spectra for the library. Library of most common pigments in MIR-FIR spectral range will be is

presented methods of data pretreatment will be discussed in details.

POSTER SESSION

SYMBIOTIC CHANGES IN NUTRIENT DISTRIBUTION IN THE POPLAR

RHIZOSPHERE OBSERVED WITH FTIR IMAGING

T. VICTOR 1, L. MILLER

1,2, AND L.CSEKE

3

1) Department of Chemistry, Stony Brook University, Stony Brook NY 11794 USA

2) NSLS-II Photon Sciences, Brookhaven National Laboratory, Upton NY 11973 USA

3) University of Alabama-Huntsville, Huntsville, AL, 35899 USA

Symbiotic associations in the rhizosphere between plants and micro-organisms lead to an efficient

and sustainable distribution of nutrients that promotes growth for all organisms involved.

Understanding this nutrient flow provides insight into the molecular dynamics involved in nutrient

transport from one organism to the other. To study this nutrient flow, we developed an FTIR imaging

method that entailed growing poplar seedlings in a thin, nutrient enriched Phytagel matrix and then

measuring the distribution of key nutrients in the poplar rhizosphere, such as nitrogen, which is a

primary nutrient limiting plant growth. Spectra collected from ammonium nitrate in Phytagel indicate

the greatest changes in spectra at 1337 cm-1

due to nitrate’s asymmetric stretching vibrations. We

found that the limit of detection for nitrate falls between 0.035 mM and 0.07 mM, which is ~ 2.85%

of the total nitrate contained in the control media. Chemical images collected from the poplar

rhizosphere showed evidence for symbiotic sharing of nutrients between the plant and the fungi,

Laccaria bicolor, where the nitrate concentration was high around the fungi, suggesting

sequestration from the media toward the plant root. Similarly, the sucrose used in the growth media

as a carbon source was depleted around the fungi, suggesting its consumption. This ability to monitor

nutrient changes with other micro-orgasms in the rhizosphere is a key step for understanding

nutrient flow processes.

Acknowledgments

− This work was supported by the Genomics Science Program, U.S. Department of Energy Biological and

Environmental Sciences Division. Use of the National Synchrotron Light Source, Brookhaven National

Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy

Sciences, under Contract No. DE-AC02-98CH10886.

POSTER SESSION

Fig 1: A) Visible image of a Poplar plant

root embedded in Phytagel media. B)

FTIR image represents a principal

components analysis (PCA) of the

chemical composition of the

rhizosphere, where white indicates the

root, green indicates the largest fungus

colonization, magenta indicates a high

concentration of nitrate, and yellow

represents the sucrose in the media.

Scale bar is 1 mm.