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