Pulse Radiolysis Laboratory pulselab@orange.ichtj.waw.pl

Head: Prof. Krzysztof Bobrowski

Pawel B. Wisniowski, Ph.D.
E-mail: cherry@orange.ichtj.waw.pl

PROFILE: Chemist EDUCATION: 1994   M.Sc.  Faculty of Chemistry, Warsaw University, Poland. 2001   Ph.D.  Department of Radiation Chemistry and Technology, Institute of Nuclear Chemistry and Technology, Warsaw, Poland. SKILLS: Computer / System environments: DOS - perfect UNIX (IRIX) - Silicon Graphics network administrator authorization paper Microsoft Windows- perfect Office tools: Excel - perfect Word for Windows- perfect

Programming tools: Visual Basic - v. good Turbo Basic - v. good Turbo Pascal - good Visual C++ - good Delphi -v. good HTML - perfect Java - good Drawing tools: CorelDRAW! - perfect ( with Photo PAINT!, .....) Autocad - perfect 3DStudio (MAX) - perfect QuarkXpress - v. good Adobe PhotoShop - perfect and others... .

Me .. and some nice fish

Chemical equipment and experimental:
HPLC,TR-ESR, Linear accelerators, GC, UV/VIS Spectrometers...

EMPLOYMENT:
93/94 Research Associate and Chemist,
Department of Chemistry, University of Warsaw, Poland.

This position involved teaching and research activity. Participation in the teaching process requires responsibility and self-control, as well as communicational skills in contacts with students. The research work gives a lot of independence. Non conventional thinking and activity were very useful, especially in experimental work.

94/- Institute of Chemistry and Nuclear Technology,
Department of Radiation Chemistry and Technology.
Dorodna 16, 03-195 Warszawa, Poland.
current position: Senior Researcher

99/- Member of Scientific Council in the Institute.

Area of interests focuses on radiation effects in aqueous media, with particular emphasis on the identities and molecular structure of short-lived transients and reaction mechanisms in sulfur-containing compounds. Topic involves application of radiation methods for the study of OH-induced oxidation of sulfur-containing alcohols, carboxylic acids, amino acids and their derivatives. It is concerned with the characterization and quantification of reactive intermediates, such as hydroxysulfuranyl radicals, radicals and radical cations with various 2-center/3-electron bonds, reaction kinetics and the measurement of absolute rate constants for elementary processes involving these reactive intermediates, such as intramolecular proton and electron transfer, beta-fragmentation, decarboxylation, and reaction with molecular oxygen. The sulfur intermediates can undergo a variety of subsequent reactions depending on conformational flexibility of molecules and functional neighboring groups present in molecules. Part of these studies is done in collaboration with Dr. G. L. Hug (Radiation Laboratory, USA) doing both the the laser flash photolysis and time resolved and steady-state ESR and Professor B. Marciniak (A. Mickiewicz University, Poznan) doing steady-state photolysis.
The second major area of interests is connected with using computers skills and programming (Delphi) in chemistry what is now the most important because the Lab is currently developing a new electron linear accelerator pulse radiolysis system with optical detection. Construction of pulse radiolysis provides an opportunity to delve more deeply into instrumentation and excellent cooperation with Dr. Jacek H. Mirkowski (Warsaw University of Technology / Institute of Nuclear Chemistry and Technology, Warsaw) and Dr. Z. Dzwigalski (Institute of Nuclear Chemistry and Technology, Warsaw) gives fair promise for long distance and succesful research.

99/00 Research Scholar (International Atomic Energy Agency Fellowship)
Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana, USA

Notre Dame is a perfect place for fishing, too.

This IAEA fellowship gave excellent advantage of ESR methodology in the period of the four months.
The Notre Dame Radiation Laboratory's unique equipment gives an opportunity to go more deeply into both time-resolved ESR and steady-state ESR theory and phenomena including mathematical approximation of radicals' kinetics and radicals' yields. A new program for Windows 95/98/NT (in cooperation with Dr. R.W. Fessenden and Dr. G. L. Hug) was written. This program includes some very significant procedures and can be used for time-resolved ESR and Pulse Radiolysis problems. Two of these (using a Gaussian weighting function to compensate for line inhomogeneity effects in kinetic traces and the simultaneous solution of the spin and chemical differential equations) are excellent examples of using computational methods in chemistry. The combination of time-resolved ESR and pulse radiolysis at Notre Dame Radiation Laboratory involves complications and opportunities not commonly encountered at other techniques because of using two very difficult methods in the same time.

This year was good, too.

Most of the scientific aspects were in the chemistry of free radicals formed in the radiolytic oxidation of simple amino acids, in particular glycine and its alkyl substituents. Glycine and multiple carboxylic acids are models for organic complexants found in nuclear waste tanks. The mechanism of the radiolytic oxidation of these complexants and their fragments are of concern in the nuclear clean-up effort. The chemistry of the carbon- and nitrogen-centered radicals formed in the radiolysis of glycine is distinct from the sulfur-centered radicals that it is main point of interest in maternal lab in Poland.
In the domain of pure chemistry, a new carbon-centered radical was observed. A little-used method of collecting data was used, and this allowed to observe the short-lived radical that had previously escaped the observation in steady-state radiolysis. Both new method for determining the yield of radicals and observation of the new radical will be published.
Special thanks Dr. G. L. Hug for being excellent supervisor.

01 Research Associate, Chemist.
Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana, USA
Subject: Wasting of nuclear tanks. Supported by the Office of Basic Energy Sciences of the U.S. Department of Energy (Document No. NDRL-4344 from the Notre Dame Radiation Laboratory).

The oxidation of simple amino acids by the •OH radical has turned out to be quite complicated. This finding is of significance to questions of how aminopolycarboxylic acids degrade (organic aging) in nuclear waste storage tanks. The precise chemical mechanisms of amino acid oxidation are also of interest to understanding the fate of proteins under oxidative stress in biological systems.

2002   1^st Institute of Nuclear Chemistry and Technology Director's Award

!!! Under Construction

Specialization:
1. Main fields: radiation chemistry, organic chemistry;
2. Other fields: pulse radiolysis, time resolved ESR, dosimetry, analytical methods, scientific information;
3. Current research interests: computer skills in chemistry, electron transfer reactions in organic and mixed organic-aqueous systems, charge transfer processes in organo-sulphur compounds, ionic liquids.

INTERESTS:
Programming and computer systems, travelling, foreign cultures, art, entomology, projecting architecture, DTP, fishing, skiing, projecting (making) jewelry, writing, collecting insects (Member of Polish Academy of Sciences).

SELECTED PUBLICATIONS:

Pawel Wisniowski, Krzysztof Bobrowski, Piotr Filipiak, Ian Carmichael, and Gordon L. Hug “Reactions of hydrogen atoms with a-(alkylthio) carbonyl compounds. Time-resolved ESR detection and DFT calculations”, Res. Chem. Intermed., (2005), accepted.

Pawel Wisniowski, Krzysztof Bobrowski, Ian Carmichael, and Gordon L. Hug. "Bimolecular homolytic substitution (S_H2) reaction with hydrogen atoms. Time-resolved ESR detection in the pulse radiolysis of a-(methylthio)acetamide", J.Am.Chem.Soc.(2004), 126, 14468-14474.

Pawel B. Wisniowski, Ian Carmichael, Richard W. Fessenden, and Gordon L. Hug "Evidence for b-Scission in the Oxidation of Amino Acids", J. Phys. Chem. A. (2002), 106, 4573-4580.

N. Varmenot, S. Remita, Z. Abedinzadeh, P. Wiśniowski, G. Strzelczak, K. Bobrowski "Oxidation processes of N,S-diacetyl-L-cysteine ethylester: influence of S-acetylation" J. Phys. Chem. A. (2001), 105, 6867.

Christian Schöneich, D. Pogocki, P. Wisniowski, Gordon L. Hug and K. Bobrowski, "Intramolecular Sulfur-Oxygen Bond Formation in Radical Cations of N-acetylmethionine Amide", J. Am. Chem. Soc., 122, p.10224-10225 (2000).

K.Bobrowski, G.L.Hug, B.Marciniak, C.Schöneich, P.Wiśniowski "Intramolecular Hydrogen Transfer During Oxidation of b-Hydroxysulfides and a-(Methyl)thioacetamide. Pulse Radiolysis and Flash Photolysis Studies", Res. Chem. Intermed., vol. 25, No. 3, pp. 285-297 (1999).

SELECTED PROGRAMS:

DECOM 2004 - deconvolution of the spectra
TRESR 2002 - TR ESR simulation

E-mail: cherry@orange.ichtj.waw.pl