Spectroscopic Symposium 2018

Symposium on Advanced Spectroscopic Techniques
Institute of Mathematical Sciences and Physics

University of the Philippines Los Baños, September 18-21, 2018
SCIENTIFIC PROGRAMME
Moderator: Arvin Lester C. Jusi

Day 1 ( September 18, 2018 –Tuesday, Chancellor’s Hall, UPLB Main Library, UP Los Baños, Los Baños,
Laguna, Philippines)
13:00-13:30 Symposium and Workshop Registration

13:30-13:40 IMSP,
Welcome Remarks Dr. Chrysline Margus N. Piñol
UPLB
13:40-14:00 Overview of DOST-JSPS program and IMSP,
Dr. Alvin Karlo G. Tapia
Symposium UPLB
14:00-14:30 MPRC,
Terahertz Spectroscopy of
Dr. Keisuke Tominaga KOBE
Condensed Matter
Univ.
14:30-15:00 Development of THz
spectrometers for materials
Dr. Jessica Afalla FIR, Univ.
characterization and
of FUKUI
semiconductor carrier dynamics
studies
15:00-15:30 Polyacrylonitrile-Kapok Fiber
Nanocomposite for Adsorptive DMMME,
Dr. Mary Donnabelle Balela
Removal of Methyl Orange and Cu(II) UPD
Ions in Aqueous Solution
15:30-16:00 Break
16:00 – 16:30 Synchrotron-based Nano-
IMSP,
resolved photoelectron Dr. Ivy R. Colambo
UPLB
spectroscopy
16:30-17:00 Current progress on the
development of photoconductive
Dr. Elmer Estacio NIP, UPD
antenna devices for terahertz
applications
17:00-17:10 Announcements and Group Photo
17:10 UPLB Walking Tour
Moderator: Prof. Lou Serafin Lozada

Day 2 ( September 19, 2018 –Wednesday, Chancellor’s Hall, UPLB Main Library, UP Los Baños, Los Baños,
8:30-9:00 Registration
9:00-9:05 Introduction and Announcements
9:05-9:35 JICHI
Broadband dielectric spectroscopy on
Dr. Naoki Yamamoto Medical
hydrated proteins
Univ.
9:35-10:05 Temperature dependence of
IMSP,
terahertz conductivity of polyaniline Prof. Lou Serafin Lozada
UPLB
clay composite
10:05-10:20 Break
10:20-10:35 Quantum states and vibrational IMSP,
Dr. Allan B. Padama
properties of H on Pd(110) surface UPLB
10:35-10:50 Materials discovery for important
catalytic applications: Linking IMSP,
Dr. Darwin Putungan
vibrational spectroscopy and phonon UPLB
dispersion calculations.
10:50-11:05 Conductivity of Polyaniline
Emeraldine Salt (PAni-ES) - and Zinc IMSP,
Dr. Marvin U. Herrera
Oxide-Embedded Paper using UPLB
Impedance Spectroscopy.
11:05-11:20 Synthesis and Characterizations of IMSP,
Prof. Armida Gillado
Conducting Polymer-Nanoclay Films UPLB
11:20-11:35 Effects of Hydration in the Low-
IMSP,
Frequency Dielectric Constant of Dustin Loren V. Almanza
UPLB
Casein
11:35-11:50 IMSP,
Study of SRO properties using THz-TDS Arvin Lester C. Jusi
UPLB
12:00 –13:00 Lunch Break
13:00-14:30 MPRC,
Ultrafast Spectroscopy Workshop I Dr. Keisuke Tominaga KOBE
Univ.
14:30-15:45 Break
SPECIAL SESSION ON BIOCHEMISTRY
15:45-16:15 Characterization of precursor aggregates JICHI
accumulated prior to an amyloid fibril Dr. Naoki Yamamoto Medical
formation. Univ.
16:15-16:45 Iron metabolism in C. elegans: Cecytb-2,
a homologue of cytochrome b561, KOBE
Prof. Motonari Tsubaki
functions as a ferric-chelate reductase in Univ.
C. elegans.
16:45-17:15 Kobe University Graduate School Forum
16:45 UPLB Walking Tour
Day 3 ( September 20, 2018 –Thursday, Chancellor’s Hall, UPLB Main Library, UP Los Baños, Los Baños,
13:00-14:30 MPRC,
Ultrafast Spectroscopy Workshop II Dr. Keisuke Tominaga KOBE
Univ.
15:00-17:00 UPLB Walking Tour
 Molecular Photoscience Research Center,  National Institute of Physics, University of

Kobe University (MPRC, KOBE Univ.) the Philippines Diliman (NIP, UPD)
 Research Center for the Development of  Jichi Medical University (JICHI Med. Univ.)
Far-Infrared Region, University of Fukui (FIR,  Institute of Mathematical Sciences and
FUKUI Univ.) Physics, University of the Philippines Los Baños
 Department of Mining, Metallurgical, and (IMSP, UPLB)
Materials Engineering, University of the
Philippines Diliman (DMMME, UPD)
Overview of the DOST-JSPS Joint Scientific

Research Program and the Symposium
The Department of Science and Technology-Japan Society for the Promotion of Science Joint
Scientific Research Program (DOST-JSPS JSRP) involves the cooperation of Philippine and
Japanese Universities to develop THz technologies for various applications. THz is a
submillimeter radiation that overlaps with different dynamics in materials. Also, THz
technologies extend to making electronics and communications faster in the future. This
program began with the initiatives of the group from the National Institute of Physics to develop
THz technologies for generation and detection in collaboration with leading THz research centers
in Japan and scientists from De La Salle University. In Japan, the Molecular Photoscience
Research Center of Kobe University thru the years developed THz spectroscopic set-ups to study
the dynamics in condensed phases while the Research Center for the Development of Far-
Infrared Region does cutting-edge research on THz generation and detection. In recent years,
more and more Filipino scientists are becoming part of this field that has wide-range of
applications. THz spectroscopies can be used to characterize charge and molecular dynamics.
Also, it is very promising in agricultural, biochemical, drugs and security applications. The
Institute of Mathematical Sciences and Physics has started forming a group in UPLB to utilize THz
technologies to characterize materials.
Acknowledging the use of THz technologies in spectroscopy for materials characterization, there
are speakers from the fields of materials science and spectroscopy using advanced light sources.
Also, speakers doing calculations in the low-frequency range will also discuss probing and
discovering new materials. The very wide array of disciplines contributes highly to the field of
advanced spectroscopic techniques as we probe more complex structures and faster dynamics.
This symposium aims to kick-off the DOST-JSPS JSRP, to strengthen research linkages between
Philippines and Japan and to inspire collaborative works among young researchers and scientists.
Terahertz Spectroscopy on the Condensed Matter

Keisuke Tominaga
Molecular Photo science Research Center, Kobe University, Kobe, Japan
[email protected]
ABSTRACT
There has been considerable interest in both the experimental and theoretical investigation of the low-frequency
motion associated with molecules and molecular aggregates in condensed phases. Vibrational motions with
resonance frequencies in the terahertz (THz; 1 THz = 1012 Hz) frequency range are characterized by weaker potential
forces and/or larger reduced masses, which are in sharp contrast to vibrations localized within a molecule with
resonance frequencies in the mid infrared (IR) region. Dramatic progress has been made in the generation and
detection techniques of freely propagating THz radiation based on femtosecond pulsed laser in the past two decades.
Because the pulse duration of the THz radiation is in a sub-picosecond time region, it is possible to measure the
electric field of the radiation by coherent detection methods, which consequently allows us to conduct THz time-
domain spectroscopy (TDS). By THz-TDS we can obtain the refractive index and extinction coefficient of a medium
by measuring the phase and amplitude of the THz radiation. THz-TDS is an attractive method for studying dynamics
in condensed phases with time scales of sub-picoseconds and picoseconds. In this talk I summarize our recent
activities on the application of pulsed THz radiation spectroscopy to condensed phases such as biomolecules,
solutions, and liquids.
The spectroscopic fingerprint modes of molecular solids, phonons, are largely found in terahertz (THz) region.
Phonons directly arise from the intermolecular interactions determined by the molecular configuration in solid phase.
Similar molecular structures (even isomers) may possess distinct intermolecular connections, and consequently give
rise to distinct absorption feature in THz spectra. This advantage will give THz spectroscopy bright further in the
application of molecular identification in the pharmaceutical and bioproduction industries. Moreover, to understand
the nature of molecular phonons, accurate normal mode simulations can be achieved using solid-state density
functional theory (DFT) [1, 2]. In this work we preformed the structural and frequency calculations for several
molecular crystals including biologically important molecules such as polypeptides and polysaccharides by the
CRYSTAL14 software package. Accurate structural and frequency calculations have been obtained. Herein, we report
an analytical mode-decoupling method that allows decomposition of a normal mode of interest into intermolecular
translation, libration, and intramolecular vibration motions.
It is well known that liquid water interacts with electromagnetic waves over a broad frequency range. For example,
the collective rotational relaxation has its dielectric spectra from MHz to GHz frequency region, and the spectral
component in the THz region is suggested to be due to fluctuation of the hydrogen bonding network. These spectral
components in the different frequency regions overlap with each other. Therefore, it is necessary to perform
dielectric spectroscopic measurements in a broad frequency region. In this study, we chose H2O, H218O, and D2O as
samples. We also measure the dielectric spectra by changing temperature from 273 K to 353 K. In the microwave
region (200 MHz~20 GHz), the complex dielectric constants were measured by a vector network analyzer. In the sub-
THz region (40 GHz~300 GHz) and THz region (300 GHz~2.5 THz), a pair of spiral and dipole type photoconductive
antenna were used for generation and detection of the electromagnetic waves, respectively.
References
[1] O. Kambara, C. S. Ponseca, K. Tominaga, J. Nishizawa, T. Sasaki, H. W. Wang and M. Hayashi, Bull. Chem. Soc. Jpn., 2013, 86,
714-720.
[2] F. Zhang, O. Kambara, K. Tominaga, J.-i. Nishizawa, T. Sasaki, H.-W. Wang and M. Hayashi, RSC Advances, 2014, 4, 269-278
Synchrotron-based nano-resolved photoelectron spectroscopy

I. Razado-Colambo,1 J. Avila, 2 C. Chen, 2 J.-P. Nys, 3 X. Wallart, 3 M.-C. Asensio, 2 and D. Vignaud3
1 Instituteof Mathematical Sciences and Physics, University of the Philippines Los Baños, College, Laguna, Philippines
2 Synchrotron SOLEIL, L’Orme des Merisiers, Saint Aubin-BP 48, 91192 Gif sur Yvette Cedex, France
3 I.E.M.N., UMR CNRS 8520, Av. Poincar´e CS 60069, 59652 Villeneuve d’Ascq Cedex, France
[email protected]
ABSTRACT
During the last few decades, many scientific research areas have experienced remarkable progress in nanoscience
and nanotechnology. In an even rather wider field, complex and smart materials are also often isolated as small
crystallites, and they present serious difficulties in terms of being synthesized without fluctuations of their
compositions or crystalline orientations. This particular interest in material characterization at rather small scales
has considerably affected the design, manufacturing, and performance of advanced scientific instruments. In fact,
when characterizing advanced materials, progress frequently refers to a new area of knowledge, to the need of
seeing, measuring, and understanding objects at the nano- and mesoscopic scale.
Recently, a tremendous and fast expansion in modern spectroscopic and microscopic methods has been realized.
However, beyond the achievement of Angstrom spatial resolution, the challenge still remains in order to consolidate
energy-resolved spectroscopic methods with lateral nanometric resolution. A fine chemical and electronic analysis
with submicron spatial discrimination has been revealed to be indispensable for many scientific problems. X-ray
scanning spectromicroscopy, is a technique based on high brilliant tunable synchrotron radiation sources,
particularly well-positioned to provide both spatial resolution and chemical sensitivity.
In this talk, the complete electronic characterization of graphene films down to submicrometer grains obtained using
synchrotron-based conventional and nano-resolved photoelectron spectroscopies will be discussed. By probing
exactly the same region of the samples using angular-resolved and core-level photoelectron spectroscopy imaging
and point modes, we were able to identify two types of grains constituting the graphene films with radically different
thickness, stacking and orientation. The size, distribution, and registry with the substrate for each type of grain were
determined. Most interestingly, we have evidenced that multilayer graphene grains with Bernal stacking coexist with
areas composed of twisted bilayer graphene grains.
References
[1] J. Avila, I.C. Razado-Colambo, Stephane Lorcy, Bruno Lagarde, Francois Polack, and Maria C. Asensio, ANTARES, a scanning
photoemission microscopy beamline at SOLEIL, Journal of Physics Conferences Series 425 (2013) 192023
[2] I. Razado-Colambo, J. Avila, C. Chen, J.-P. Nys, X. Wallart, M.C. Asensio and D. Vignaud, Probing the electronic properties of
graphene on SiC(000-1) down to single domains by nanoresolved photoelectron spectroscopies , Physical Review B 92 (2015)
035105
Polyacrylonitrile-Kapok Fiber Nanocomposite for Adsorptive Removal of Methyl Orange and

Cu(II) Ions in Aqueous Solution
Mary Donnabelle L Balelaa,Apollo R. Agcaoilia, Marvin U. Herrerab, and Cybelle M. Futalanc
aSustainable Electronic Materials Group, Department of Mining, Metallurgical and Materials Engineering, University of the
Philippines-Diliman, 1101 Diliman, Quezon City, Philippines
bInstitute of Mathematical Sciences and Physics, College of Arts and Sciences, University of the Philippines-Los Baños, 4031 Los
Baños, Laguna, Philippines

cEnvironment Business Line, Aecom Philippines Consultants Corporation. Bonifacio Global City, Fort
Bonifacio, 1634 Taguig City, Philippines

[email protected]
ABSTRACT
Polyacrylonitrile (PAN)-kapok fiber nanocomposites were fabricated by in situ polymerization with the assistance of
cetyltrimethylammonium bromide (CTAB) as surfactant. FTIR analysis confirmed the deposition of PAN layer on the
surface of the kapok fibers as seen in Fig. 1, leading to a drastic decrease in water contact angle from 133.43 to 0 o.
Interestingly, the hollow
tubular structure of the fibers was retained after surface modification with PAN. Batch sorption experiments were
performed to investigate the removal efficiency of the PAN-kapok nanocomposites for methyl orange dye and Cu(II)
in aqueous solution. The adsorption performance of the PAN-kapok fibers was evaluated using Langmuir and
Freundlich isotherms and pseudo-order kinetics. Isotherm studies revealed that removal of methyl orange and Cu(II)
follow the Langmuir isotherm model, with maximum adsorption capacity of 34.72 and 90.09 mg/g, respectively. This
suggests that Cu(II) is preferentially adsorbed on the PAN-kapok fibers over methyl orange [1]. Kinetic studies show
that the adsorption of methyl orange and Cu(II) on PAN-kapok follow a pseudo-second order kinetic model,
indicating chemisorption as the rate-determining step.
Figure 2. FTIR spectra of a.) pristine kapok, b.) PAN-kapok composites fabricated using a.) 10, b.) 20, and d.) 40 mg
of CTAB. AN and KPS was kept constant at 1.5 mL and 60 mg, respectively.
References
[1] A.R. Agcaoili, M.U. Herrera, C.M. Futalan and M.D.L. Balela. Fabrication of Polyacrylonitrile-Coated Kapok Hollow Microtubes
for Adsorption of Methyl Orange and Cu(II) Ions in Aqueous Solution. Journal of Taiwan Institute of Chemical Engineers, 78 (2017)
359-369.
Development of THz spectrometers for materials characterization and semiconductor

carrier dynamics studies
Jessica Afalla1, Hideaki Kitahara1, Valynn Mag-usara1, Hiroyuki Kato1, Masaki Shiihara1, Takashi Furuya1,
Yusuke Akamine1, Shoji Hayashi1, Miezel Talara1, Kazuko Mizuno1, Mary Clare Escaño1, Armando
Somintac2, Arnel Salvador2, Elmer Estacio2, Masahiko Tani1
1Research Center for Development of Far Infrared Region, University of Fukui, Fukui, Japan
2National Institute of Physics, University of the Philippines Diliman, Quezon City, Philippines
[email protected]
ABSTRACT
Terahertz spectroscopy has gained popularity as a characterization tool in the fields of medicine, chemistry and
physics. Terahertz time-domain spectroscopy (THz-TDS) can be used to obtain the absorption coefficients, indices of
refraction and dielectric constants of different materials; while time-resolved terahertz spectroscopy (TRTS) can be
used to elucidate ultrafast electron dynamics in semiconductors. The activities of our group include designing
terahertz spectrometers for specific applications such as these, and finding ways to improve existing THz emission
and detection schemes. Our recent work includes the use of a “polarization filter” technique which has increased
the detection sensitivity of a THz-TDS set-up with electro-optic sampling detection scheme [1]. We also continually
test the emission and detection efficiencies of photoconductive antennas designed, grown and fabricated in the
National Institute of Physics in UP Diliman (NIP-UPD). We have also developed two TRTS systems for different
semiconductor studies. The first system is a “double optical pump” THz-time domain emission spectrometer (DOP
THz TDES) [2] which can measure carrier lifetime from the THz emission of semiconductor surfaces. And recently,
we have also developed an optical pump terahertz probe (OPTP) set-up that uses a broadband air plasma THz source,
and a wavelength-tunable laser pump in order to study carrier lifetime and photoconductivity in different
semiconductors (LT-GaAs [3], GaAs on Si [4], GaN, ZnO), some of which are also designed and grown in NIP-UPD.
Figure 1. left: schematic of the DOP THz TDES system which measures carrier lifetime from the THz emission of
semiconductor surfaces right: schematic of the OPTP spectrometer, which measures carrier lifetime and
photoconductivity from terahertz transmission
References
[1] H. Kitahara, T. Yasumoto, D. Goto, H. Kato, M. Shiihara, J. Afalla, V. Mag-usara, K. Yamamoto, T. Furuya, A. Tapia, C. Que, E.
Estacio, M. Bakunov, K. Tominaga, and M. Tani. Sensitivity improvement of electro-optic sampling. Proceedings of the Samahang
Pisika ng Pilipinas 36th Physics Congress (Puerto Princesa City, Philippines, 2018), SPP-2018-EA-06 (manuscript in preparation)
[2]V. Mag-usara, S. Funkner, G. Niehues, E. A. Prieto, M. H. Balgos, A. Somintac, E. Estacio, A. Salvador, K. Yamamoto, M. Hase
and M. Tani. Low temperature-grown GaAs carrier lifetime evaluation by double optical pump terahertz time-domain emission
spectroscopy. Opt. Express 24 (23). 2016
[3] J. P. Afalla, V. K. Mag-usara, T. Moriyasu, H. Kitahara, and M. Tani. LT-GaAs carrier lifetime evaluation using THz and optical
probe techniques at different carrier injection levels. in JSAP-OSA Joint Symposia 2017 Abstracts, (Optical Society of America,
2017), paper 7a_A409_8.
[4] J. Afalla, K. C. Gonzales, J. Muldera, E. A. Prieto, G. Catindig, J. D. Vasquez, H. Husay, T. Moriyasu, H. Kitahara, D. Bulgarevich,
V. Mag-usara, T. Furuya, A. Somintac, A. Salvador, E. Estacio, and M. Tani. Photo-carrier Dynamics of MBE-grown GaAs On Silicon
Studied by Optical-pump Terahertz-Probe. Ext. Abstr. 43rd Int. Conf. IRMMW-THz 2018. We-P1-R1-5 (manuscript to be submit
Current progress on the development of photoconductive antenna devices for

terahertz applications
Elmer S. Estacio, Armando S. Somintac, and Arnel A. Salvador
National Institute of Physics, University of the Philippines Diliman, Quezon City, Philippines
[email protected]
ABSTRACT
Terahertz waves span the 0.3 to 3 mm-wavelength region of the electromagnetic radiation spectrum and promise a
wealth of applications from far-infrared spectroscopy to real-world utilization such as semiconductor and
pharmaceutical product testing and monitoring. The advent of THz science-based industry is expected to be brought
forward with advances in the generation and detection of THz radiation. As such, there is a pressing need to design
and fabricate intense terahertz sources and sensitive detectors. At the National Institute of Physics, University of the
Philippines, we have embarked on a terahertz photonics-based research thrust. A molecular beam epitaxy machine
is used to deposit GaAs thin films at relatively low-temperatures. These thin films are used as substrates for GaAs
photoconductive antenna devices. Our current research activities include the growth-design of a thin, n-doped GaAs
buffer layer prior to the deposition of the low temperature GaAs film. This is expected to modify the built-in electric
field of the semiconductor. This technique is intended to improve the drift transport of photoelectrons in the
material; thereby increasing terahertz generation efficiency. Some initial results on the successful fabrication of
photoconductive antenna devices using in-house grown low-temperature GaAs films will be presented.
.
(a) (b) (c)
Figure 1. (a) Wyko interferometry images of fabricated in-house PCAs with different patterns
(b) THz emission and (c) THz detection characteristics of the PCAs.
References
[1] E.A. Prieto, S.A. Vizcara, A. Somintac, A. Salvador, E. Estacio, C. Que, K. Yamamoto and M. Tani, “Terahertz emission
enhancement in low-temperature grown GaAs with an n-GaAs buffer in reflection and transmission excitation geometries”,
Journal of the Optical Society of America B, Volume 31 No.2. February 2014 pp 291-295,
[2] A. Tuico, J.P. Ferrolino, G. Catindig, M.H. Balgos, C. Yu, E.A. Prieto, J. Muldera, A. Somintac, A. Salvador, and E. Estacio,
“Prototype terahertz photoconductive antenna detector based on a low-temperature-grown gallium arsenide substrate”,
Proceedings of the 33rd Physics Congress of the Samahang Pisika ng Pilipinas, University of Northern Philippines, Vigan City, June
2015.
[3]. V.K. Mag-usara, A. Tuico, J.P. Ferrolino, G. Catindig, C> Yu, E.A. Prieto, T. Furuya, H. Kitahara, A. Somintac, A. Salvador, E.
Estacio, and M. Tani, “Photoconductive antenna prototypes as terahertz detectors”, Proceedings of the 34th Physics Congress of
the Samahang Pisika ng Pilipinas, University of the Philippines Visayas, Iloilo City, August 2016.
Broadband dielectric spectroscopy on hydrated proteins

Naoki Yamamoto1*, Shota Ito2, Kaoru Ohta3, Masahiro Nakanishi4, Atsuo Tamura1, Eri Chatani1, Hideki
Kandori2, Keisuke Tominaga3
1Graduate School of Science, Kobe University, Kobe City, Japan
2Graduate School of Engineering, Nagoya Institute of Technology, Nagoya City, Japan
3Molecular Photoscience Research Center, Kobe University, Kobe City, Japan
4Department of Electrical Engineering, Fukuoka Institute of Technology, Fukuoka City, Japan
*Present affiliation; School of Medicine, Jichi Medical University, Shimotsuke City, Japan
[email protected]
ABSTRACT
Various kinds of protein functions are indispensable for life activity. These protein functions are exhibited in the
thermal fluctuation of solvent, water. Therefore, for the understanding of the protein functional mechanisms, it is
essential to clarify how protein dynamics are related to those of water. Especially, water molecules proximal to a
protein surface, or hydration water molecules, are assumed to be strongly coupled to protein dynamics. Thus a few
layers of hydration water on the protein surface should be specifically focused on. In this line, we have studied
temperature and hydration dependence of globular and membrane proteins using dielectric spectroscopy from
gigahertz (GHz) to terahertz (THz) regions. These frequency regions are known to be rich in dynamics such as the
rotational relaxation of hydration water and low-frequency vibrations of protein and hydration water. In the case of
a typical globular protein, lysozyme, it was revealed that a large spectral component of the rotational relaxational
mode originating from protein-water coupling dominated in the frequency regions [1]; the relaxational mode
experienced a blue-shift as temperature increased, and started to overlap with the THz region from ~230 K. A similar
tendency was also observed in the temperature-dependent spectra of purple membrane, which is a lipid-protein
complex [2]. These results imply that the energy transfer from the rotational relaxational mode to protein low-
frequency vibrational modes is important for a large structural change and a resultant functional expression.
However, the relaxation time of the relaxational mode of lysozyme was ~3 times faster than that of purple
membrane [1,2]. The difference might be due to the difference in the chemical properties of these proteins and also
the difference in the shapes of the surfaces.
References
[1] N. Yamamoto, K. Ohta, A. Tamura, K. Tominaga (2016) Broadband Dielectric Spectroscopy on Lysozyme in the Sub-Gigahertz
to Terahertz Frequency Regions: Effects of Hydration and Thermal Excitation. J. Phys. Chem. B, 120, 4743.
[2] N. Yamamoto, S. Ito, M. Nakanishi, E. Chatani, K. Inoue, H. Kandori, K. Tominaga (2018) Effect of Temperature and Hydration
Level on Purple Membrane Dynamics Studied Using Broadband Dielectric Spectroscopy from Sub-GHz to THz Regions. J. Phys.
Chem. B, 122, 1367.
Temperature dependence of terahertz conductivity of polyaniline clay composite

Lou Serafin M. Lozada1, Alvin Karlo G. Tapia1 and Keisuke Tominaga2
1Institute
of Mathematical Sciences and Physics, University of the Philippines Los Baños, College, Laguna, Philippines
2MolecularPhotoscience Research Center, Kobe University, Kobe, Japan
[email protected]
ABSTRACT
This work focuses on the complex conductivity of polyaniline composite with bentonite and polyacrylic acid at the
terahertz range. Here, we report the temperature dependence of complex conductivity of the composite measured
using terahertz-time domain spectroscopy (THz-TDS). The conductivity spectra (Figure 1) were fitted against Drude-
Smith model. Results show that conduction parameters from both models describe charge transport properties
found in disordered systems. Usually, for disordered systems, variable range hopping (VRH) models are used to
describe the transport mechanism. Common models for this are the Mott VRH model and the Efros-Shklovskii VRH
model. In this presentation, we will discuss how these models are differentiated against each other especially in
fitting against experimental data.
The effects of polyacrylic acid and bentonite on the conduction properties of polyaniline composites are
differentiated from conductivity and structural measurements. Polyacrylic acid generally increased conduction
parameters of the composite through structural (colloidal) stabilization and electron donating ability. On the other
hand, bentonite may have provided additional scattering sources and promoted an even more percolating system.
Figure 1. Temperature dependence of terahertz conductivity from terahertz-time domain spectroscopy of

polyaniline/polyacrylic acid/bentonite composite
References
[1] T. Unuma, N. Yamada, A. Nakamura, H. Kishida, S. C. Lee,E. Y. Hong,S. H. Lee, and O. P. Kwon, “Direct observation of carrier
delocalization in highly conducting polyaniline”, Appl. Phys. Lett. 103, 053303 (2013).
[2] T. Unuma, K. Fujii, H. Kishida, and A. Nakamura, “Terahertz complex conductivities of carriers with partial localization in doped
polythiophenes”, Appl. Phys. Lett. 97, 033308 (2010).
[3] A. K. G. Tapia and K. Tominaga, “Conduction in polyaniline emeraldine salt in the terahertz region: A temperature dependence
study”, Chem. Phys. Lett. 598, 39-42 (2014).
[4] T. Homma, M. Kondo, T. Kuwahara, and M. Shimomura, “Polyaniline/poly(acrylic acid) composite film: A promising material
for enzyme-aided electrochemical sensors”, Eur. Poly. J. 62, 139-144 (2015).
Quantum states and vibrational properties of H on Pd(110) surface

Allan Abraham B. Padama
Institute of Mathematical Sciences and Physics, University of the Philippines Los Baños, College, Laguna, Philippines
[email protected]
ABSTRACT
The interaction of hydrogen (H) on Palladium (Pd) and Pd based surfaces is important in hydrogen-based technology
due to the good properties of the metal surfaces in facilitating reactions that involve H [1]. Pd based materials allow
the dissociation of H2 molecules and the diffusion of H atoms [2-4], thus, the are usually employed as hydrogen
electrodes, separation membranes and storage materials. Understanding the mechanisms of these processes are
relevant to maximize the use of Pd and Pd based materials for various applications.
In this work, the quantum states and vibrational properties of adsorbed hydrogen atom on the (110) surface facet
of Pd are investigated by employing first principles calculations based on density functional theory (DFT) [5]. The
potential energy surface (PES) of H atom on Pd(110) is calculated to obtain the stable position of H and to determine
its diffusion path on the surface. Using the PES, the wave functions and eigenenergies in the ground and few excited
states of H are then identified. It was observed that localized wave functions of hydrogen atom exist on pseudo-
threefold and long bridge sites of Pd(110). From the PES, the short bridge site of the surface is also determined as a
local minimum. However, incorporating quantum effect depicted that H will not stay on the site but is a part of the
diffusion path from pseudo-threefold to pseudo-threefold site. The vibrational properties and diffusion of H on the
surface are described based from the calculated eigenenergies,and are found to be in good agreement with
experimental findings.
References
[1] B.D. Adams, A. Chen, The role of palladium in a hydrogen economy, Mater.Today 2011, 14, 282–289.
[2] K. Shimizu, W.A. Dino, H. Kasai, Dynamics of Mu, H, D, and T absorption into Pd(111): isotope effects, J. Phys. Soc. Jpn. 2014,
83, 013601.
[3] A. Groß, A. Dianat, Hydrogen dissociation dynamics on precovered Pd surfaces: Langmuir is still right, Phys. Rev. Lett. 2007,
98, 206107.
[4] V.R. Fernandes, J. Gustafson, M.H. Farstad, L.E. Walle, S. Blomberg, E.Lundgren, H.J. Venvik, A. Borg, H 2 reduction of surface
oxides on Pd-based membrane model systems – the case of Pd(100) and Pd75Ag25(100), Appl. Surf. Sci. 2014, 313, 794–803.
[5] A.A.B. Padama, H. Nakanishi, H. Kasai, Quantum states of hydrogen atom on Pd(1 1 0) surface, Appl. Surf. Sci. 2015, 359,
687–691.
Materials discovery for important catalytic applications: Linking vibrational

spectroscopy and phonon dispersion calculations
Darwin Barayang Putungan1
1Institute
[email protected]
ABSTRACT
In this talk, I will give a bird’s eye view of how new materials could be fabricated and therefore, be discovered, via
an understanding of the link between first-principles calculations results such as phonon dispersion relation and
experimental data such as vibrational spectroscopy. The talk will give emphasis on newly discovered and synthesized
2D materials and their potential applications. Finally, I will briefly share some of our success stories with 2D transition
metal dichalcogenides (TMDs), such as our prediction of certain 1T’ phase TMD [1] and potentially new 2D transition
metal hallides [2].
J. Am. Chem. Soc. 2013, 135, 10274−10277

Phys. Chem. Chem. Phys., 2015,17, 21702-21708
Figure 1. A link between phonon dispersion curve and Raman spectra
References
[1] Phys. Chem. Chem. Phys., 2015,17, 21702-21708
[2] Phys. Chem. Chem. Phys., 2014, 16, 20763--20771
Conductivity of Polyaniline Emeraldine Salt (PAni-ES)- and Zinc Oxide-Embedded

Paper using Impedance Spectroscopy
Ana Rose Ramos1, Genne Patt Samar1, Chrysline Margus N. Piñol1, Nacita B. Lantican2,
Ronniel D. Manalo3, Alvin Karlo G. Tapia1 and Marvin U. Herrera1,*
1Instituteof Mathematical Sciences and Physics,
2Instituteof Biological Sciences,
3Department of Forest Products and Paper Science,
University of the Philippines Los Baños, College, Laguna, 4031

[email protected]
ABSTRACT
Polyaniline (PAni) has been the focus of various researches involving the development of sensors, capacitors,
circuit boards, and other technological advancements. This is due to its interesting electrical and optical properties,
and stability in doped state. By acid doping PAni-emeraldine base (PAni-EB) to yield a green PAni-emeraldine salt
(PAni-ES), it can increase the conductivity of PAni. In this study, PAni-ES molecules were deposited onto cellulose
paper via the successive ionic layer adsorption and reaction (SILAR) technique. It uses aniline as the monomer, HCl
as the acid dopant, and ammonium peroxydisulfate (APS) as oxidant. The conductivity of the PANI-deposited paper
was determined using an impedance analyzer from 20Hz to 20MHz. Results showed that increasing the dipping
cycles leads to an increase in the conductivity of the material until it reaches a saturation point. Also, a transition
from frequency-independent to frequency-dependent conductivity regions was seen at some critical frequency. By
Fourier Transform Infrared (FTIR) analysis, it proved the embedment of PANI-ES on paper. Moreover, the ability of
polyaniline-embedded paper in suspension showed reduction in bacterial populations when tested against
Staphylococcus aureus and Escherichia coli.
On the other hand, zinc oxide (ZnO) is promising material for diodes as well as wearable devices due to its
high conductivity. In addition, the morphology of ZnO nanostructures can be varied which makes it useful in gas
sensors, transducers and actuator. The study dealt with the in situ embedment of ZnO on paper. Filter paper
(Whatman No. 1) was soaked sequentially in various concentrations of zinc sulfate heptahydrate (ZnSO 4∙7H2O) and
sodium hydroxide (NaOH) solutions. The samples were then exposed to microwave irradiation at 540 Watts and
varying exposure times (0-10 minutes) to hasten the formation of ZnO particles. ZnO embedded-filter paper was
characterized using x-ray diffraction and impedance spectroscopy. The antibacterial activity was tested against
Staphylococcus aureus and Escherichia coli. XRD analysis confirmed the formation of zinc oxide with two-theta peaks
at around 32, 34 and 36 degrees which correspond to (100), (201) and (101) structural planes of ZnO, respectively.
Impedance spectroscopy at 20 Hz to 20 MHz showed that the electrical conductivity increased with NaOH
concentration. On the other hand, prolonged microwave exposure time negatively effected the electrical
conductivity of the embedded material in filter paper. No definite trend was observed with increasing ZnSO 4∙7H2O
concentration. Antibacterial activity of ZnO-embedded filter paper showed higher activity against S. aureus than E.
coli.
Synthesis and Characterizations of Conducting Polymer-Nanoclay Films

Armida V. Gillado1, Reynaldo Pareja Jr.1, Alvin Karlo G. Tapia1, Chelo S. Pascua2, and Keisuke Tominaga
1Institute
2Institute
of Environmental Science and Meteorology, University of the Philippines Diliman, Quezon City, Philippines
3Molecular Photoscience Research Center, Kobe University, Kobe, Japan
[email protected]
ABSTRACT
Films based on electrically-conductive polymers and nanoparticles of clays have attracted interest in the field of
research and engineering due to their potential novel use in nanotechnology. This includes applications in energy
storage, electronic and optical devices, sensors, electrochromic displays, microelectronic devices, corrosion inhibitor,
and electromagnetic shielding [1]. Thus, understanding the properties of these films opens a way for more specific
application of these films in electronic industry. In this study, nanocomposites were synthesized via hydrothermal
treatment of solutions of nontronite clay nanoparticles collected using sedimentation techniques and polyaniline-
emeraldine salt (PAni-ES) powder synthesized via standard polymerization technique. The homogenized mixture was
vacuum-filtered and then dried to form the nanocomposite films. Figure 1 shows both the DC conductivities and the
low-frequency conductivities of the polyaniline-nontronite nanocomposite films. The DC conductivities of
nanocomposite films increases then decreases upon increasing of PAni loadings. These values are lower than that
described in other studies [2,3] but of similar trend. The same conductivity trend (i.e., increases and decreases upon
increasing of PAni loadings) was observed at frequency range of 1kHz to 1MHz. The conductivity is found to be
almost constant up to 100kHz and thereafter increases exponentially. A similar study showing a strong contribution
of PAni to the overall frequency-dependent conductivities was also reported [4]. However, THz conductivities
increased with increasing nontronite composition which implies that the nontronite has a larger effect on the THz
conductivities of the nanocomposites.
Figure 1. Conductivities of Polyaniline-Nontronite Nanocomposites: (a) DC Conductivities and (b) conductivities at

different frequencies.
References
[1] R.B Valapa, S. Loganathan, G. Pugaszhenthi, S. Thomas and T.O. Varghese, Chapter 2 - An Overview of Polymer–Clay, Clay-
polymer Nanocomposites, 2017, pp. 29-81.
[2] S. Kazim, and S. Ahmad, J. Pfleger, J. Plestil and Y.M. Joshi, Y.M. Polyaniline–sodium montmorillonite clay nanocomposites:
effect of clay concentration on thermal, structural, and electrical properties. Journal of Materials Science, 2011.
[3]M.A. Abd El-Ghaffar,A.M.Youssef,and A.A.Abd El-Hakim, Polyaniline nanocomposites via in situ emulsion polymerization based
on montmorillonite: Preparation and characterization, Arabian Journal of Chemistry, Elseveir, 2015, 8(6),pp.771-779.
[4] A. K. G. Tapia and Keisuke Tominaga, Conduction Properties in Polyaniline-Polyethylene Composites in the Terahertz Region,
Infrared, Millimeter Waves and THz 2012, IEEE Conference, University of Wollongong, Australia, September 23-28, 2012
Effects of Hydration in the Low-Frequency Dielectric Constant of Casein

Dustin Loren V. Almanza1, Reynaldo B. Pareja, Jr. 1, Mariam Recuenco2, and Alvin Karlo G. Tapia1
1Institute
2Institute
of Chemistry, University of the Philippines Los Baños, College, Laguna, Philippines
[email protected]
ABSTRACT
Casein is the main protein (80%) that can be found in milk [1]. It has a variety of uses in medicine, supplements,
additives in food and paint among many others. Hydration or rehydration of casein is relevant for industrial purposes.
Conductivity measurements aid in the evaluation of the release of minerals or ionic strength of a protein-containing
solution [1]. Conductivities can be derived from imaginary dielectric constant (”) which vary dynamically in different
frequency ranges. Low-frequency dielectric measurements were conducted on a pelletized casein at different
hydration levels (13%, 20%, 30%, 35%, 40%) using an impedance analyzer. The Nyquist plots of the different samples
were fitted using Zfit-function of the Electrochemical Impedance Spectroscopy (EIS). Initial results show that as the
hydration of the pelletized casein increases, the conductivity also increases. Literature suggests that hydrated
proteins are separated into distinct hydrophobic regions and proton-conducting hydrophilic water channels, which
probably can serve as proton transport networks [2]. The Nyquist plots display semicircle in the high-frequency
region and an inclined spur in the low-frequency region. These results are similar with the description of the Nyquist
plots by the EIS data of Ordinario et al.
Figure 1. Conductivities at different frequencies of pelletized Casein at various hydration levels.
(a) (b) (c)

Figure 2. Nyquist plots of pelletized Casein at (a) 30% hydration level, (b) 35% hydration level and (c) 40%
hydration level.
References
[1] Denise Felix da Silva, Lilia Ahrné, Richard Ipsen and Anni Bygvraa Hougaard, Casein‐Based Powders: Characteristics and
Rehydration Properties, Comprehensive Reviews in Food Science and Food Safety, 13 November 2017.
[2] David D. Ordinario, Long Phan, Ward G. Walkup IV, Jonah-Micah Jocson, Emil Karshalev, Nina Hu ̈sken and Alon A.
Gorodetsky, Bulk protonic conductivity in a cephalopod structural protein, July 2014.
Study of SRO properties using THz-TDS

Arvin Lester C. Jusi1,2, Der-jun Jang2,and Chou Hsiung2
1Institute
2Department of Physics, National Sun Yat-sen University, Kaohsiung City, Taiwan
[email protected]
ABSTRACT
Because of the diverse properties exhibited by Strontium ruthenate (SRO), like superconductivity and
semiconductivity, its applications are very promising suggesting the importance of studying the properties of SRO.
In this study, SRO samples were grown on sapphire and fused quartz (FQ) substrates. The properties of the SRO
samples were studied using Terahertz Time-domain Spectroscopy (THZ-TDS). The transmittance, index of refraction,
absorption coefficient, and complex conductivity in the THz range were reported. The conductivities were fitted by
simple Drude model to obtain the carrier concentration and mobility in the THz regime. The effect of using different
substrates in growing SRO were also investigated. Generally, the conductivities of SRO grown on FQ substrate were
larger compared to those grown on sapphire. This behavior can be accounted to the larger lattice mismatch between
SRO and sapphire compared to the lattice mismatch between SRO and FQ. Larger lattice mismatch is being linked to
the reduction of carrier mobility, and, consequently, to the decrease in conductivity.
References
[1] R. Kinjo, X. Weiming, I. Kawayama, H. Murakami and M. Tonouchi. Strain induced conductivity change of SrRuO3 thin films
observed by terahertz time-domain spectroscopy. 2011 International Conference on Infrared, Millimeter, and Terahertz Waves,
Houston, TX, pp. 1-2 doi: 10.1109/irmmw-THz.2011.6104855 (2011)
[2] J. S. Dodge, C. P. Weber, J. Corson, J. Orenstein, Z. Schlesinger, J. W. Reiner, and M. R. Beasley. Low-Frequency Crossover of
the Fractional Power-Law Conductivity in SrRuO3. Phys. Rev. Lett. 85, 4932 doi: 10.1103/PhysRevLett.85.4932 (2000)
[3] Yoshiteru Maeno, T. Maurice Rice, and Manfred Sigrist. The Intriguing Superconductivity of Strontium Ruthenate. Physics
Today 54, 1, 42 doi: 10.1063/1.1349611 (2001)
Characterization of precursor aggregates accumulated prior to an amyloid fibril formation

Naoki Yamamoto
Molecular Physiology & Biophysics, Physiology, School of Medicine, Jichi Medical University
3311-1 Yakushiji Shimotsuke-shi, Tochigi 329-0498 JAPAN
[email protected]
ABSTRACT
Amyloid fibrils are abnormal protein aggregates possessing fibrous structures. Formation and accumulation of
amyloid fibrils usually lead to occurrences of intractable diseases such as Alzheimer’s disease. A large part of the
mechanism of the fibril formation is still hidden in a vail of mystery. Recently we declared that a specific prefibrillar
intermediate functioned as a precursor of the fibril formation in an in vitro system where a model peptide derived
from human insulin was used [1]. Furthermore, we found that the nucleation step requisite for the fibril formation
was prohibited in the presence of fibrinogen, a blood protein necessary for blood clotting [2]. A small-angle X-ray
scattering study revealed the structural basis of the prefibrillar intermediate as well as the inhibition mechanism by
fibrinogen [2]. Our findings provide a hint about how to treat and prevent amyloidoses by stabilizing prefibrillar
intermediates.
References
[1] N. Yamamoto, S. Tsuhara, A. Tamura, Eri Chatani; Sei. Rep. (2018) 8:62
[2] N. Yamamoto, T. Akai, R. Inoue, M. Sugiyama, A. Tamura, E. Chatani; Manuscript in preparation
Iron metabolism in C. elegans: Cecytb-2, a homologue of cytochrome b561, functions as a ferric-

chelate reductase in C. elegans
Tsubaki Motonari
Department of Chemistry, Graduate School of Science, Kobe University
1-1 Rokkodai-cho, Nada-ku, Kobe, Hyogo 657-8501, JAPAN
[email protected]
ABSTRACT
In the present study, we conducted analyses on the mechanism of ferric reductase activity of C. elegans Cecytb-2, a
homologue of human Dcytb. The purified Cecytb-2 protein by employing Pichia pastoris system showed a significant
ferric reductase activity in its reduced form, based on the acceleration of the heme oxidation upon addition of
various forms of ferric ion, particularly by a ferric-chelate complex. The nitroso-PSAP assay proved that reduced form
of Cecytb-2 could donate maximally two electron equivalents specifically to a ferric-chelate complexes rather than
to a “free ferric ion”. The photo-reduced form of Cecytb-2 prepared under a strict anaerobic condition provided
further evidence for the authenticity of the ferric reductase activity. Effects of the site-directed mutations on the
extracellular side of Cecytb-2 on the ferric reductase activity for Fe3+-EDTA were evaluated by a stopped-flow rapid-
scan method, showing that both Km and Vmax values were not much affected by the locations of site-directed
mutations. This unexpected observation seemed consistent with our proposal that Cecytb-2 protein is a ferric-
chelate reductase rather than a ferric reductase.

Spectroscopic Symposium 2018

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Spectroscopic Symposium 2018

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Symposium on Advanced Spectroscopic Techniques

Institute of Mathematical Sciences and Physics

Moderator: Arvin Lester C. Jusi

13:00-13:30 Symposium and Workshop Registration

Moderator: Prof. Lou Serafin Lozada

 Molecular Photoscience Research Center,  National Institute of Physics, University of

Overview of the DOST-JSPS Joint Scientific

Terahertz Spectroscopy on the Condensed Matter

Synchrotron-based nano-resolved photoelectron spectroscopy

Polyacrylonitrile-Kapok Fiber Nanocomposite for Adsorptive Removal of Methyl Orange and

Baños, Laguna, Philippines

Bonifacio, 1634 Taguig City, Philippines

Development of THz spectrometers for materials characterization and semiconductor

Current progress on the development of photoconductive antenna devices for

Broadband dielectric spectroscopy on hydrated proteins

Temperature dependence of terahertz conductivity of polyaniline clay composite

Figure 1. Temperature dependence of terahertz conductivity from terahertz-time domain spectroscopy of

Quantum states and vibrational properties of H on Pd(110) surface

Materials discovery for important catalytic applications: Linking vibrational

J. Am. Chem. Soc. 2013, 135, 10274−10277

Figure 1. A link between phonon dispersion curve and Raman spectra

Conductivity of Polyaniline Emeraldine Salt (PAni-ES)- and Zinc Oxide-Embedded

University of the Philippines Los Baños, College, Laguna, 4031

Synthesis and Characterizations of Conducting Polymer-Nanoclay Films

Figure 1. Conductivities of Polyaniline-Nontronite Nanocomposites: (a) DC Conductivities and (b) conductivities at

Effects of Hydration in the Low-Frequency Dielectric Constant of Casein

Figure 1. Conductivities at different frequencies of pelletized Casein at various hydration levels.

(a) (b) (c)

Study of SRO properties using THz-TDS

SPECIAL SESSION ON BIOCHEMISTRY

Characterization of precursor aggregates accumulated prior to an amyloid fibril formation

SPECIAL SESSION ON BIOCHEMISTRY

Iron metabolism in C. elegans: Cecytb-2, a homologue of cytochrome b561, functions as a ferric-

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