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Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
1
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
Warsaw, 29 October 2013
Report No. 8
NOBLESSE Project
July – September 2013
WP3. Chemo- and biosensors – molecular imprinting
Task Leader – Prof. Włodzimierz Kutner
Task Vice-Leader – Iwona Flis-Kabulska, D.Sc.
Task 3.1 Transfer of knowledge and experience through twinning and networking
During the period of 22nd
till 30 July, 2013, Dr. Agnieszka Pietrzyk-Le visited the Department of
Chemistry of the University of Milan, Milan (Italy), a partner of the NOBLESSE Project, Work
Package WP3 „Chemo- and Biosensors – molecular imprinting”. The purpose of the trip to Milan, was
to discuss possibilities of using most appropriate cross-linking monomers for molecular imprinting of
oligonucleotides. During her stay in Milan, Dr A. Pietrzyk-Le had a chance to meet several
researchers of this Department, and Prof. Patrizia R. Mussini, Prof. Emauela Licandro, Prof. Stefano
Maiorana, and Prof. Francesco Sannicolò among them. For Dr. A. Pietrzyk-Le, the discussions with
researchers of this Department provided valuable information on the latest trends in the field of
conducting polymers and their monomers.
Dr. Agnieszka Pietrzyk-Le giving the lecture
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
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NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
The research achievements of Dr. A. Pietrzyk-Le were appreciated by a number of researchers of
this Department and, therefore, she was invited to give a lecture. Accordingly, on July 26, 2013 Dr.
A. Pietrzyk-Le gave a lecture at a departmental seminar, entitled: "Molecularly imprinted polymers
for development of chemical sensors for the biological target determination".
After the lecture, the discussion was focused on preparation and characterization of molecularly
imprinted polymers (MIPs), as well as calculation of the stability constants of affinity complexes of
MIPs and analytes.
Within discussions, novel thiophene-based oligomer T8 was chosen as a cross-linking monomer
for the collaborative future research. This is an asymmetric multithiophene-based monomer, which
can act as an effective 3 D electropolymerisation promoter.
The Report of the visit to the University of Milan, Milan, Italy is enclosed (Enclosure No. 1).
During the period of 22nd
till 28th September, 2013, Prof. Tadeusz Zakroczymski, Dr. Iwona Flis-
Kabulska and Dr. Arkadiusz Gajek visited Dr. Yong Sun, the researcher employed by the School of
Engineering, Media, and Sustainable Development of the Faculty of Technology of De Montfort
University (DMFU), Leicester (United Kingdom). Dr. Yong Sun is a Partner in the NOBLESSE
Project, Work Package WP3, “Chemo- and Biosensors - molecular imprinting”.
The visit in DMFU was related to the Polish
project funded by the National Science Centre,
“Surface modification with carbon introduced by
plasma treatment and deposition from solution for
improvement of electrocatalytic properties of cathodes
for production of hydrogen” realized jointly by IPC
PAS and DMFU.
Dr. Y. Sun, Dr. A. Gajek, Dr. I. Flis-Kabulska and Prof. T.
Zakroczymski in front of the School of Engineering, Media
and Sustainable Development, Faculty of Technology,
DMFU.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
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NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
The visit enabled our group to get acquainted with the works carried out at the Faculty of
Technology, DMFU. Dr. Y. Sun gave us a tour over several laboratories of the DMFU campus.
Our delegates participated in the seminar of the School of Engineering, Media and Sustainable
Development. Prof. T. Zakroczymski presented our Institute including its historical and present
research activities, with particular reference to the Department of Electrochemistry, Corrosion and
Applied Surface Science of IPC PAS. Dr. I. Flis-Kabulska and Dr. A. Gajek gave lectures based on the
recent results obtained in our Corrosion and Hydrogen Group.
Lectures presented by a group of Doctors and PhD Students enabled us to become more familiar
with the variety of research topics studied at the Department, which we visited.
A large part of the visit was devoted to discussing our joint project with Dr. Yong Sun. Our
discussions allowed establishing conditions of preparation of the studied materials, as well as the
methods for their characterisation. We agreed on how to realize the project and on assigning the
research tasks.
The Report of the visit to the De Montfort University in Leicester, UK is enclosed (Enclosure No.
2).
Task 3.2 Recruitment of one experienced researcher
On 1 August 2012, Dr. Piotr Pięta filled the position of an Experienced Researcher as the Assistant
Professor (“adiunkt” in Polish) in the Laboratory of Molecular Films (LMF) of the IPC PAS headed
by Prof. Włodzimierz Kutner.
According to the earlier provisions, the employment of Dr. P. Pięta was extended for the next 12
months – from 1 August 2013 till 31 July 2014.
Between July and September 2013, Dr. P. Pięta published, as a co-author, the following articles:
1. P. Pieta, I. Obraztsov, F. D’Souza, W. Kutner, “Composites of Conducting Polymers and Various
Carbon Nanostructures for Electrochemical Supercapacitors”, Journal of Solid State Science and
Technology, 2 (10) (2013) M3120-M3134.
2. T.-P. Huynh, P. Pieta, F. D'Souza, W. Kutner, “Molecularly imprinted polymer for recognition of 5-
fluorouracil by RNA-type nucleobase pairing”, Analytical Chemistry 85 (17) (2013) 8304-8312.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
4
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
3. M. Sosnowska, P. Pieta, P.S. Sharma, R. Chitta, C.B. Kc, V. Bandi, F. D'Souza, W. Kutner,
“Piezomicrogravimetric and impedimetric oligonucleotide biosensors using conducting polymers of
biotinylated bis(2,2′-bithien-5-yl)methane as recognition units”, Analytical Chemistry 85 (15) (2013)
7454-7461.
Dr. P. Pięta as the Project Leader of two proposals, one funded by the Foundation for Polish
Science, FNP, (“Change of nanomechanical properties of phospholipid bilayers in the presence of
cholesterol and antimicrobial peptides”), and the other by the National Science Centre, NCN,
(“Nanomechanical, visco-elastic, and electrochemical properties of conducting composites for
supercapacitors”) is responsible for organizing a modern laboratory for a new research group.
The renovated lately laboratory has been equipped in new instrumentation, as follows:
1. A system for chemical synthesis, Büchi AG.
2. A scanner and bipotentiostat for electrochemical experiments to be conducted with our AFM/STM
microscope, Bruker/Vecoo.
3. A multichannel potentiostat/galvanostat, BioLogic.
Task 3.3 Formation of independent research groups by young leader researchers
For recruitment of new employees to the research group of Dr. P. Pięta – one PhD student and two
master students, Calls for Applications were posted on 5 August 2013 and 17 October 2013.
The following persons have been employed:
1. Kamila Łępicka (PhD student) involved in project financed by NCN (Sonata 4).
2. Marta Majewska (master student) involved in project financed by FNP (Homing Plus)
3. Letycja Barzyk (master student) involved in project financed by FNP (Homing Plus)
Besides a new research group of Dr. P. Pięta, establishing of another two new research groups is
envisioned. One group will be organized by Dr. Agnieszka Pietrzyk-Le based on her research project,
entitled: “Selective determination of chosen oligonucleotides by synthetic polymer systems of
molecular recognition” funded by the Foundation for Polish Science within POMOST Programme
(Parent/Bridge Programme). A Call for Applications for the position within the group was posted on
26 April 2013. The position was filled by a PhD student, Ms. Katarzyna Bartołd. She passed a job
interview on 7 October 2013 and was admitted for the International Doctoral Studies at IPC PAS.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
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NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
The other group will be organized by Dr. Krzysztof Noworyta based on his research project,
entitled: “Chemosensors for selective determination of renal dysfunction biomarkers using
molecularly imprinted polymers, deposited by electropolymerization, as recognition layers”, funded
by the National Science Centre. The position within the group was filled by a PhD student, Valeri
Malyshev. He passed the job interview on 7 October 2013 and was admitted for the International
Doctoral Studies at IPC PAS.
Task 3.4 Facilitation of participation of the LMF and CHG researchers of IPC PAS in
international scientific conferences
The NOBLESSE Project enabled us for participation in the following international scientific
meetings.
1. IUPAC 10th
International Conference on Advanced Polymers via Macromolecular
Engineering, 17 – 24 August 2013, Durham, UK
Dr. Krzysztof Noworyta actively participated in the IUPAC 10th
International Conference on
Advanced Polymers via Macromolecular Engineering held at the Durham University, Durham, UK,
August 18 to 22, 2013.
The Conference gathered ~ 400 participants from all over the world working in the field of polymer
and materials sciences. Among the invited speakers, there were such eminent scientists as prof. K.
Matyjaszewski from the Carnegie Mellon University, prof. M. Sawamoto from the Kyoto University,
and prof. K. Landfester from the Max Planck Institute for Polymer Research.
During this conference, Dr. K. Noworyta presented the poster, entitled: “Application of the
Electrochemically Deposited Conducting Polymers as Molecularly Imprinted Recognition Units for
Creatinine Chemosensors” by P. Bocian, K.R. Noworyta, J.W. Sobczak, Ch.B. KC, F. D’Souza and
W. Kutner.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
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NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
Dr. K. Noworyta presenting the poster.
Participation in this conference allowed Dr. K. Noworyta to present results of the work, performed
in the Laboratory of Molecular Films at the Institute of Physical Chemistry PAS, to the world-class
specialists in the field of polymer chemistry and physics. Moreover, participation in this event
permitted Dr. K. Noworyta to learn modern trends in methods of polymer synthesis, processing, and
their practical applications as well as new techniques of characterization of these materials.
The Report of the participation in the IUPAC 10th
International Conference on Advanced Polymers
via Macromolecular Engineering is enclosed (Enclosure No. 3).
2. The 64th
Annual Meeting of the International Society of Electrochemistry, 8-13 September
2013, Santiago de Queretaro, Mexico
The 64th
Annual Meeting of the International Society of Electrochemistry, entitled
“Electrochemistry for a New Era” was held on 8 through 13 September 2013 in Santiago de
Queretaro, Mexico. The conference brought together ~1000 scientists from around the world
(including ~40 from Poland). They presented the most recent achievements of electrochemistry and
challenges it faces now. Five distinguished electrochemists delivered plenary lectures reviewing and
giving the newest information on the intriguing themes of electrochemistry including
photoelectrochemical cells (M. Grätzel), molecular electronics (R. L. McCreery), ionic liquids in
electrochemical devices (D. R. MacFarlane), interaction of oxygen radicals with the electrode surface
(F. Schulz) and new advanced materials for fuel cells (M. Watanabe).
Topics discussed at the Meeting included a wide range of issues, including among others
Bioelectrochemistry and Biosensors applied to Medicine, Molecular Electrochemistry: from Single
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
7
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
Molecules to Conducting Polymers, Surface Treatment for Aerospace Applications and Corrosion
Protection, Industrial Electrolysis, Electrochemical Energy Conversion and Storage.
The European Project NOBLESSE was represented at the Meeting by four researchers of the
Work Package WP3 “Chemo- and Biosensors- molecular imprinting”. They delivered the following
presentations (names of the presenting authors are underlined):
1. W. Kutner, Tan-Phat Huynh, M. Sosnowska, C.
Bikram K.C., V. Nesterov, J. W. Sobczak, F. D'Souza,
A General Protocol of Designing and Fabricating
Thin Films of Conducting Molecularly Imprinted
Polymers for Application to Selective Sensing.
(Lecture; Symposium 3: New Concepts for Designing
Bioelectrochemical Interfaces)
2. K. R. Noworyta, W. Kutner, C. A. Wijesinghe, F.
D’Souza, Electrochemical and
Piezomicrogravimetric Detection of Selected
Alkaloids using a Zinc Porphyrin Polymer with
Controlled Porosity. (Lecture; Symposium 6:
Conducting Polymers, Inorganic Materials and
their Hybrids for Electrocatalysis and
Photoelectrochemical Energy Conversion)
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
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NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
3. M. Dąbrowski, P. S. Sharma, Z. Wróbel, W. Kutner, Electrochemically-induced mesoporous
molecularly imprinted organosilica film, deposited as recognition unit of chiral chemosensor for
selective detection and determination of L-arabitol.(Poster; Symposium 2: Sensing in Living Systems)
The poster has been awarded with the Best Poster Award presented at the 64th ISE Meeting.
4. I. Flis-Kabulska, J. Flis, T. Zakroczymski, Antimony Microelectrode for Facile Measurements of
the Near-Surface pH. Identification of Electrode Processes Involving Protons. (Poster; Symposium
5: Corrosion Processes at the Nanoscale; Surface
Treatments)
5. J. Flis, I. Flis-Kabulska, Determination of
Hydrogen Absorption in Iron Cathodes for Alkaline
Water Electrolysis by Anodic Discharging and
Electrochemical Permeation Technique. (Poster;
Symposium 12: Tradition to Modernity: Challenges at
the Electrochemical Interface; Electrocatalysis)
Vivid discussions with the authors of the lectures and of the above-mentioned posters indicated
that there was a significant interest in the research results presented by the researchers from the IPS
PAS.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
9
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
The active participation of the researchers from the IPC PAS
in the 64th Annual Meeting of ISE was extremely useful because it
gave us this opportunity of both getting acquainted with most
recent achievements in selected fields of electrochemistry and to
confront our own research achievements with opinions of the
world electrochemistry community.
The 64th Annual Meeting of ISE gave us also opportunity to
promote the Institute of Physical Chemistry PAS. Books and
leaflets presenting IPC PAS captured participants’ attention and
were quickly distributed.
The Report of the participation in the 64th Annual Meeting of the International Society of
Electrochemistry is enclosed (Enclosure No. 4).
3. The 6th
Kurt Schwabe Symposium, 16-19 September, 2013, Cracow, Poland
The 6th Kurt Schwabe Symposium was organized in Cracow (Poland) on 16 through 19
September, 2013, as continuation of the Kurt Schwabe Symposia organized previously in various
towns of Europe. These symposia bring together researchers from all over the world who focus their
scientific interests on new materials and new electrochemical techniques in electrochemical
technologies, corrosion science, and corrosion engineering. There were 6 plenary lectures and 9
invited lectures delivered. Moreover, 38 communications and 22 posters were presented.
Three researchers of the European Project NOBLESSE, Work Package WP3 “Chemo- and
Biosensors- molecular imprinting”, of the Corrosion and Hydrogen Group actively participated in the
Meeting. They delivered the following presentations (names of the presenting authors are underlined):
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
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NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
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1. T. Zakroczymski, “Stress corrosion cracking
and hydrogen embrittlement” (invited lecture;
Session 8 – Hydrogen in metals)
2. A. Gajek, I. Flis-Kabulska, T. Zakroczymski,
Cheng-Hsien Yang, Jeng-Kuei Chang, Wen-Ta
Tsai, “Diffusion of hydrogen in magnesium
studied by the electrochemical permeation
metod” (Lecture; Session 8 – Hydrogen in
metals)
3. I. Flis-Kabulska, J. Flis, T. Zakroczymski,
“Hydrogen permeation measurements for
evaluation of absorbed hydrogen and of
surface changes on iron cathodes during
alkaline water electrolysis”(Lecture; Session 8
– Hydrogen in metals)
4. I. Flis-Kabulska, J. Flis, Y. Sun, T. Zakroczymski, “Measurement of pH at the electrode
surface for better understanding the corrosion behaviour of low-temperature plasma
nitrided stainless steel” (Lecture; Session 10 – Corrosion resistant alloys)
Organizing of small international conferences, which bring together less than ~100 participants,
gives the unique opportunity to meet world renowned researchers in the area of our interest, to listen to
their lectures and to discuss with them.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
11
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
The Report of the participation in the 6th Kurt Schwabe Symposium is enclosed (Enclosure No. 5).
For the WP3 researchers, participation in the Scientific Meetings allowed to present their results to
the international electrochemistry community. The scientists of IPC PAS could discuss their research
with a large group of electrochemists that allowed them to look at their own research from different
perspectives. The Meetings gave us this opportunity to learn new research topics and to make new
acquaintances with foreign researchers of similar or complementary scientific interest for future
collaborative twinning.
Task 3.5 Organization of the 6th
International Workshop on Surface Modification for
Chemical and Biochemical Sensing (SMCBS’2013)
The SMCBS’2013 Workshop will be organized in Lochow (Pol. Łochów) near Warsaw on 8 till
12 November 2013. Information on the SMCBS’2013 Workshop is available on the website at
http://smcbs2013.pl.
The final List of Participants includes 114 scientists from all over the world. The total number of
submitted abstracts was 104. Oral presentations will include 19 keynote lectures, 14 tutorial lectures,
and 13 short communications. Moreover, fifty eight posters will be presented.
The Book of Abstracts with an ISBN number assigned will be published and distributed to all
participants at the Workshop.
Miscellaneous issues:
Articles published with acknowledgement to NOBLESSE Project.
1. P. Pieta, I. Obraztsov, F. D’Souza, W. Kutner, “Composites of Conducting Polymers and
Various Carbon Nanostructures for Electrochemical Supercapacitors”, Journal of Solid State Science
and Technology, 2 (10) (2013) M3120-M3134.
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
12
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
2. T.-P. Huynh, P. Pieta, F. D'Souza, W. Kutner, “Molecularly imprinted polymer for recognition
of 5-fluorouracil by RNA-type nucleobase pairing”, Analytical Chemistry 85 (17) (2013) 8304-8312.
3. M. Sosnowska, P. Pieta, P.S. Sharma, R. Chitta, C.B. Kc, V. Bandi, F. D'Souza, W. Kutner,
“Piezomicrogravimetric and impedimetric oligonucleotide biosensors using conducting polymers of
biotinylated bis(2,2′-bithien-5-yl)methane as recognition units”, Analytical Chemistry 85 (15) (2013)
7454-7461.
4. I. Flis-Kabulska, Y. Sun, J. Flis “Monitoring the near-surface pH to probe the role of nitrogen in
corrosion behaviour of low-temperature plasma nitrided 316L stainless steel”, Electrochimica Acta
104 (2013) 208– 215.
5. I. Flis-Kabulska, Y. Sun, J. Flis “ Corrosion Characteristics of Low Temperature Plasma
Carburised and Nitrocarburised 316L Stainless Steel in Sulphate-Chloride Solution” Zeitschrift Fur
Physikalische Chemie - International Journal Of Research In Physical Chemistry & Chemical
Physics 227 (8) (2013) 1105-1119.
6. P. S. Sharma, M. Dabrowski, F. D’Souza, W. Kutner “Surface development of
molecularly imprinted polymer films to enhance sensing signals“ TrAC Trends in Analytical
Chemistry 51 (2013) 146-157.
7. Tan-Phat Huynh, Chandra Bikram K.C., Wojciech Lisowski, Francis D'Souza,
Wlodzimierz Kutner “Molecularly imprinted polymer of bis(2,2′-bithienyl)methanes for
selective determination of adrenaline“ Bioelectrochemistry 93 (2013) 37-45.
8. Piotr Pieta, Ievgen Obraztsov, Janusz W. Sobczak, Olga Chernyayeva, Sushanta K.
Das, Francis D’Souza, Wlodzimierz Kutner “A Versatile Material for a Symmetrical Electric
Energy Storage Device: A Composite of the Polymer of the Ferrocene Adduct of C60 and
Single-Wall Carbon Nanotubes Exhibiting Redox Conductivity At Both Positive and
Negative Potentials“ Journal of Physical Chemistry C 2013, 117, 1995-2007.
Enclosures
1. The Report of the visit to the University of Milan, Milan, Italy is enclosed
(APietrzykLe_WP3_staż.doc).
2. The Report of the visit to the De Montfort University in Leicester, UK (Report_TZ AG IFK.doc)
Institute of Physical Chemistry Polish Academy of Sciences
address: M. Kasprzaka 44/52, PL-01-224 Warsaw, Poland website: http://ichf.edu.pl phone: 48 22 3433109 fax: 48 22 3433333
13
NanOtechnology, Biomaterials and aLternative Energy Source for ERA integration
FP7–REGPOT–CT–2011–285949-NOBLESSE
EUROPEAN
UNION
3. The Report of the participation in the IUPAC 10th
International Conference on Advanced Polymers
via Macromolecular Engineering (KNoworyta_APME_2013_sprawozdanie_1.doc)
4. The Report of the participation in the 64th Annual Meeting of the International Society of
Electrochemistry (WP3 Meksyk ISE_report_2013.doc)
5. The Report of the participation in the The 6th Kurt Schwabe Symposium (KSS
Krakow_report_2013 IFKphoto.doc)