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Scientific Research at Department of Chemistry University of Tartu www.chem.ut.ee. World-famous chemists who have worked at UT. Herman Hess (1821-1825) one of the founders of thermochemistry Moritz Hermann Jacobi (1835-1837) the inventor of galvanoplastics Wilhelm Ostwald (1871-1881) - PowerPoint PPT Presentation
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Scientific Research at Scientific Research at Department of ChemistryDepartment of Chemistry
University of TartuUniversity of Tartuwww.chem.ut.eewww.chem.ut.ee
February 2006 Tartu
World-famous chemists who World-famous chemists who have worked at UThave worked at UT
• Herman Hess (1821-1825)– one of the founders of thermochemistry
• Moritz Hermann Jacobi (1835-1837)– the inventor of galvanoplastics
• Wilhelm Ostwald (1871-1881)– one of the founders of physical chemistry– Nobel prize 1909, for his contributions in the field of
rates and equilibria of chemical reactions– first pKa values of acids
• Gustav Tammann (1879-1902)– milestone works on solid-liquid phase equilibria
February 2006 Tartu
PersonnelPersonnel
• Ca 72 teaching and research staff– Incl 3 members of Estonian Academy of
Sciences
• Ca 50 Doctoral Students (chemistry PhD curriculum)
• Ca 60 Master Students (chemistry master curricula)
February 2006 Tartu
Grants, ProjectsGrants, Projects
• During the period 1999-2005 the participants of DoC have had or have:– 17 targeted financing or postdoctoral projects
from the Ministry of Education and Science or ESTAG
– over 50 grants from Estonian Science Foundation
– 36 different other contracts from Estonia and 24 grants or contracts from abroad (FW5, FW6, etc) respectively
February 2006 Tartu
Grants, ProjectsGrants, Projects
• Among them– Numerous contracts and other support from
Estonian Private sector (e.g., AS Silmet, AS Elcogen, etc.)
– or foreign private sector (e.g. Schenten Glasgroap, Bruker AXJ, Aqua Consult GmbH, Svenska Superfarad AB, Toyota Motor Inc., Dow Chemical Co., etc.).
February 2006 Tartu
PublicationsPublications
• During the period 1998-2005– 345 ISI-referenced publications,
– 6 monographs or their parts
– 10 patent applications filed (or approved)
– Three co-workers of DoC (I.Koppel, J.Järv, M.Karelson) have been awarded the Estonian State Prize
– 38 Ph.D. dissertations defended
February 2006 Tartu
Main research directionsMain research directions
Chemical synthesis
Physical and Electrochemistry
Materials science and
nanotechnology
Analytical chemistry
Computational Chemistry
Bioorganic chemistry
February 2006 Tartu
Computational chemistryComputational chemistry• Computational studies of reactions
between Lewis bases and alkali metal cations, Prof. P. Burk
JPC A, 2000, 104, 2824
Computational Chemistry
February 2006 Tartu
Material science and nanotechnologyMaterial science and nanotechnology
• Computational studies of zeolites and reactions catalyzed by zeolites (Prof. P. Burk)
February 2006 Tartu
Design and studies of superacids ...Design and studies of superacids ...
• Design and studies of novel superacids and superbases (I.Leito, I.Koppel, P.Burk)
JACS, 2000, 122, 5114
JACS, 2002, 124, 5594
February 2006 Tartu
... and Superbases... and Superbases
(imme)3P=NH
GPB = 280.8 kcal/mol
PN
N
N
NH
N
NN
N
N
N
JACS, 2005, 127, 17656
February 2006 Tartu
Analytical ChemistryAnalytical Chemistry
• Applied research in analytical chemistry, measurement uncertainty, interlaboratory comparison measurements and providing related services to the community (I.Leito, K.Herodes)
200
250
300
350
400
450
500
0 1 2 3 4 5 6 7 8 9 10
Laboratory Number
Mo
istu
re c
on
ten
t (p
pm
)
Analytical chemistry
February 2006 Tartu
Environmental AnalysisEnvironmental Analysis
• Development and mathematical modelling of biosensors for environmental monitoring.
• The immobilization of biological materials was optimized in order to improve the output performance of biosensors
• Mathematical modeling of amperometric biosensors
• Prof. T. Tenno, Dr. T. Rinken
February 2006 Tartu
Environmental ChemistryEnvironmental Chemistry
• Gas transfer through gas-water interface and implications for sewage treatment
• Anaerobic treatment of biological waste
• Biogas
• Taavo Tenno, Kristo Kärmas, Vallo Lemmiksoo, Prof. T. Tenno
February 2006 Tartu
RRadiation detectors and adiation detectors and luminescence materialsluminescence materials
• Theory, design and exploitation of radiation detectors and luminescent materials (Senior Researcher Dr. M.Danilkin)
Environmental monitoring CaSO4-Dy CaF2-Mn SrSO4-Eu Individual dosimetry Li2B4O7-Mn Li2B4O7-Cu, Ag
Environmental monitoring CaSO4-Dy CaF2-Mn SrSO4-Eu Individual dosimetry Li2B4O7-Mn Li2B4O7-Cu, Ag
February 2006 Tartu
Chemical SynthesisChemical Synthesis
• Peptides and modified peptides (CPP-s)
• Peptide-nucleoside conjugates (as ligands and inhibitors)
• Hydrazine derivatives with different substituents (including chiral compounds)
• Bioactive compounds, receptor ligands, PET tracer precursors
• Prof. Jaak Järv, Assoc. Prof. U. Mäeorg
• Superbasic phosphazenes (Dr. T. Rodima)
Chemical synthesis
February 2006 Tartu
Peptide-nucleoPeptide-nucleosside conjugateside conjugates
• Example of nucleside-peptide conjugate, containig PEG group and substituent R for providing enhanced specificity against its target site
OHHO
OO
NH(CH2)5C(O)Arg4NHCHC(O)NHCH2CH2(OCH2CH2)n-OCH3
NN
NN
NH2
CH2CH2CH2CH2NH
R
February 2006 Tartu
Selective deprotection-substitution Selective deprotection-substitution methods for substituted hydrazinesmethods for substituted hydrazines
N NP
2
P3
HN N
P2
P3
R1
N N
H
P3
R1
N NP
3R
1
R2
N NR
2
R3
R1
P 1 P 1 P 1 P 1 R4
February 2006 Tartu
Chemical SynthesisChemical Synthesis
• Selective DAT ligand, used for PET of dopaminergic brain regions (after labeling with 11CH3 - group)
Me
N
I
O
OMe
February 2006 Tartu
Investigations in physical organic Investigations in physical organic chemistrychemistry
• Solvation effects in Grignard reactions (with implication for new chemical technologies)
• Effect of ultrasound and the role of hydrophobic interactions in kinetics of chemical processes
• Prof. A. Tuulmets
February 2006 Tartu
Bioorganic chemistryBioorganic chemistry
• Biochemistry of G protein-coupled receptor signal transduction complexes (muscarinic, dopaminergic, serotonergic, melanocortin).
Generation and validation of MODELSMODELS and in vitro METHODSMETHODS for characterization of chemical and biological activity of ligands of these receptor systems.
Radioligand binding experiments.Activation of second messenger systems.Modelling of receptor activation systems.
Prof. A. Rinken, Prof. J. Järv
Bioorganic chemistry
February 2006 Tartu
Bioorganic chemistryBioorganic chemistry
Introduction of new radioligand for MC4R:
I-N
DP
HS
13
1
HL
I-T
HIQ
TH
IQ
MS
Y-3
MS
Y-6
-4
-3
-2
-1
0
1
po
ten
cy d
iffe
ren
ce
(KiT
HIQ
- K
iND
P)
Pharmacological profile of ligands depends on the radioligand used:
Pharmacology of melanocortin4 receptors:
[125I]THIQ
February 2006 Tartu
Bioorganic chemistryBioorganic chemistryPharmacology of melanocortin4 receptors:
Proposed complex ligand binding model of tandemly arranged binding sites of receptor dimer allows more correct estimation of ligand binding properties to MC4R.
February 2006 Tartu
Materials science and Materials science and nanotechnologynanotechnology
• Synthesis of nanoporous carbon and solid oxide fuel cell cathodes and anodes and electrochemical applications (supercapacitors, medium temperature solid oxide fuel cells)
• Thin inorganic, organic and hybrid films for novel applications.
• Development of new preparation, characterization, and analysis methods for nanoscale materials and devices
• Prof. E, Lust, prof. V. Sammelselg
Materials science and
nanotechnology
February 2006 Tartu
Electrochemical characteristics of different nanoporous carbons in 1M(C2H5)3CH3NBF4 acetonitrile solution
Nanoporous
carbon
min
V vs
SCE
Cs/ F cm-2 Cs/ F g-1 Cs/ F cm-3 fmax / Hz
C(TiC) 0.310.02 0.690.05 98.30.8 62.20.5 1990 0.95
C(-SiC) 0.300.02 0.140.03 16.30.4 12.80.3 630 0.73
C(Mo2C) 0.310.02 0.630.05 120.00.8 52.00.5 790 0.99
C(Al4C3) 0.300.02 0.600.05 82.30.5 53.00.5 1255 0.86
C(B4C) 0.240.02 0.470.04 70.90.5 41.80.4 1255 0.82
Emin — minimum potential in C,E -curvesCs — series differential capacitance at E= -1.4 V (vs SCE) and at f= 10 mHzfmax — characteristic frequency — fractional exponent obtained from the slope of the Z”,Z’ plots in the region offrequencies 0.005 Hz< f <1.0 Hz
Materials for supercapacitors AS Tartu Tehnoloogiad
A. Jänes, M. Arulepp, J. Leis, M. Lätt, E. Lust
Institute of Physical Chemistry
February 2006 Tartu
0
0.5
1
1.5
2
2.5
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0E / V
Et /
eV
Ce0.8Gd0.2O1.9 | La0.6Sr0.4CoO3- Ce0.8Gd0.2O1.9 | Pr0.6Sr0.4CoO3- Ce0.8Gd0.2O1.9 | Gd0.6Sr0.4CoO3- Ce0.8Gd0.2O1.9 | La0.6Sr0.4CoO3 + Ag Ce0.8Gd0.2O1.9 | La0.6Sr0.4CoO3 + (30%) Ce0.8Gd0.2O1.9 Ce0.8Gd0.2O1.9 | La0.6Sr0.4Co0.8Fe0.2O3 + (30%) Ce0.8Gd0.2O1.9
Materials for solid oxide fuel cells
G. Nurk, I. Kivi, P. Möller, E. Lust
AS Elcogen
Institute of Physical Chemistry
February 2006 Tartu
Material science and nanotechnologyMaterial science and nanotechnologySynthesis of metal oxide based nanofibers and other low dimentional materials. Investigation of sol-gel nano-jet physics and chemistry. Smooth surfaces.
Sn-oxide nanofiber for SPM(about 20 nm)
Sm3+doped TiO2 sol-gel fiber radiated by 355 nm laser
The surface of mica treated with linearly polymerized APTMS solution in methanol (a) and the corresponding surface with immobilized DNA molecules (b)
Hafniumoxide self-assemblingmicrotubes
February 2006 Tartu
Physical and electro-Physical and electro-chemistrychemistry
• Influence of the structure and chemical composition of electrode on the mechanism of heterogeneous charge transfer reactions (E. Lust, K. Tammeveski)
• In situ STM characterisation of inorganic and organic ions and 2D-condensation (E. Lust)
• Syntesis of electrically conducting polymers and physical and electrochemical characterisation (J. Tamm, V. Sammelselg)
Physical and Electrochemistry
February 2006 Tartu
In situ STM results for cut Bi(111)
in 0.1M LiClO4+ 110-4M HClO4 solution
S. Kallip, V. Grozovski, E. Lust
Institute of Physical Chemistry
February 2006 Tartu
In situ STM results for cut Bi(111) in 0.1M LiClO4+ 110-4M HClO4 solution
S. Kallip, V. Grozovski, E. Lust
Institute of Physical Chemistry
February 2006 Tartu
International Collaboration, International Collaboration, exchange of studentsexchange of students
• Over 100 Partners all around the World