direct determination of heavy metals in plant solid samples using hr-cs aas

190 Pages·2013·8.27 MB·English

C O N T E N T S

Foreword ................................................................................................... 1

1. Sven STADLBAUER, René FRANK, Johannes KUNIG, Verena
ORTMANN, Annette G. BECK-SICKINGER, and Evamarie HEY-
HAWKINS (Leipzig - Germany) - Boron clusters in cancer therapy....... 3

2. Sergei V. MAKAROV (Ivanovo - Russia) - Comparative study of
catalytic activity of metallophthalocyanines and
metallotetrapyrazinoporphyrazines .......................................................... 11

3. Constantin-Horia BARBU, Bianca-Petronela PAVEL, Camelia
SAND, Mihai-Radu POP (Sibiu - Romania) – Miscanthus sinensis
gigantheus’ behaviour on soils polluted with heavy metals........................ 21

4. Angela-Nadia ALBETEL, Tamara A. DAILEY, Harry A. DAILEY,
Michael K. JOHNSON (Athens, GA - USA) – Properties and function of
[2Fe-2S] centers in ferrochelatases ........................................................... 25

5. Gabriela GARBAN, Zeno GARBAN, George–Daniel GHIBU,
Mihaela-Elisabeta MITROI (Timisoara – Romania) - Mineral
ingredients in food supplements used in the European Union – some
current aspects........................................................................................... 30

6. Yõldõz KALEBA I AKTA , Arõkan KOCABA (Edirne - Turkey) -
Arsenic pollution in some major roadside stations in Edirne city (Turkey).. 38

7. Zeno GARBAN, George-Daniel GHIBU, Adina AVACOVICI, Cornel
BALT!, Gabriela GARBAN, Mihaela-Elisabeta MITROI (Timisoara –
Romania) - Effects of sodium nitrate administration in drinking water of
leporides regarding zinc concentration in organs and tissues ................. 43

8. Bianca-Petronela PAVEL, Constantin-Horia BARBU, Camelia
SAND, Mihai-Radu POP (Sibiu - Roumania) - Direct determination of
heavy metals in plant solid samples using HR-CS AAS............................. 49

9. Maryam EIDI, Akram EIDI, Pouneh SHAHMOHAMMADI, Omid
POUYAN, Reza FAZAELI, Massih BAHAR (Varamin - Iran) - Toxic
effect of seminal plasma levels of copper on human semen parameters .. 53

10. Marilena ONETE, Mihaela PAUC!-COM!NESCU, Elisabeta BIANU,
Stelian ION (Bucure ti - Roumania) - Heavy metals content of soil and
plants from central parks (Bucharest, Romania)........................................ 58

11. Akram EIDI, Maryam EIDI, Mohammadhadi Givian RAD, Nasim
ABASPOUR (Teheran - Iran) - Effect of alcoholic extract of Eucalyptus
globulus labill. leaves on sodium and potassium levels in healthy and
diabetic rats ............................................................................................... 65
I
12. Claudiu-Nicolae IMONA"I (Arad – Romania) - Determination and
assessment of heavy metal content in fish in Mure river.......................... 70

13. Gulay SEREN, Ozan YORUK (Edirne - Turkey) - Determination of
manganese in soil and sunflower (Helianthus annuus L.) plant parts
after microwave-assisted digestions by ICP-OES...................................... 76

14. Anca HAINAL, Ioana IGNAT, Alina STINGU, Irina VOLF, Valentin I.
POPA (Iasi – Romania) - The influence of some natural polyphenols on
Rhodotorula spp. growth in the presence of copper ions........................... 79

15. Masoomeh SOHRABI-MOLLAYOUSEFI, Maryam SAHBA (Teheran -
Iran) - Effects of metals on benthic foraminiferal tests in Asalooye
(Persian Gulf) ...........................................................................................184

16. Alina STINGU, Ioana IGNAT, Anca HAINAL, Irina VOLF, Valentin I.
POPA (Iasi - Roumania) - Behaviour of tomato plant during cultivation
in the presence of copper in forest and sandy soils ................................... 90

17. Marija CIZLER, Dušan VELJKOVI#, Goran V. JANJI#, Snežana D.
ZARI# (Belgrade - Serbia) - Study of C-H...O interactions beetwen
coordinated water molecule and C6-aromatic group................................ 94

18. Mariann-Kinga ÁRKOSI, Florina DEAC, Radu SILAGHI-

DUMITRESCU (Cluj-Napoca - Roumania) - Hemoglobin as a
competitive pathway to liver in xenobiotic activation: peroxidase
reactivity towards anthracene and a protective role for hydroquinone ..... 99

19. Cornelia MAJDIK, Andrada M!IC!NEANU, Cerasella INDOLEAN,
Silvia BURCA, Maria STANCA (Cluj-Napoca - Roumania) - Cadmium
removal from wastewaters using Ca-alginate immobilized bentonite as
adsorbent.................................................................................................. 111

20. Eva FISCHER-FODOR, Rares BUIGA, Doris PELAU, Cosmin
LISENCU, Piroska VIRAG, Corina TATOMIR, Olga SORITAU (Cluj-
Napoca - Roumania) – In vitro chemosensitivity testing of tumor cells
treated with platin-based drugs................................................................. 116

21. Augustin MOT, Alina ROMAN, Radu SILAGHI-DUMITRESCU (Cluj-
Napoca – Roumania) - Blood substitutes: can we do without
hemoglobin?............................................................................................. 122

22. Béla MIHÁLY, Edit FORIZS, Ioan SILAGHI-DUMITRESCU (Cluj-
Napoca - Roumania) - Novel mixed ligand cadmium(II) theophyllinato
complexes with potential bioactivity .......................................................... 126

23. Vicentiu TACIUC, Cristina BISCHIN, Radu SILAGHI-DUMITRESCU
(Cluj-Napoca - Roumania) - A novel mechanism for platinum-based
drugs: cisplatin and related compounds as pro-oxidants in blood............. 130
II
24. Gheorghe TOMOAIA, Olga SORITAU, Maria TOMOAIA-COTISEL3,
Lacrimioara-Bianca POP, Alexandru POP, Aurora MOCANU, Ossi
HOROVITZ, Liviu-Dorel BOBOS (Cluj-Napoca - Roumania) - The
effect of self-assemblies based on nanostructured phosphates and
collagen mixtures on cell cultures .......................................................... 135

25. Valeria DI"OIU, Nina HOLBAN (Suceava - Roumania) – Study
regarding the characteristics and heavy metals content in the sludge in
the municipal wastewater treatment plants in the county of Suceava....... 141

26. Marioara MOLDOVAN, Cristina PREJMEREAN, Marcela TRIF,
Laura SILAGHI DUMITRESCU, Olga MUSAT, Doina PRODAN,
Codruta SAROSI, Gabriel FURTOS, Ioan ROMAN, Stanca BOBOIA
(Cluj-Napoca - Roumania) – Interaction between biocomposites and Co
alloys for dental crowns ........................................................................... 148

27. Claudiu T!N!SELIA, Stanko ILIK-POPOV, Dana POP, Bela
ABRAHAM, Cecilia ROMAN, Emil Cordo$, Tiberiu Fren%iu, Traj&e
STAFILOV, Leontin DAVID (Cluj-Napoca - Roumania) – Fast
measurement method of lead isotopic ratio in meteoritic material using
quadrupole ICP-MS................................................................................... 154

28. Marin ENIL!, L'crimioara ENIL!, Tiberiu FREN"IU, Michaela
PONTA, Emil CORDO , Lumini%a SILAGHI-DUMITRESCU (Cluj-
Napoca - Roumania) – Determination of dissolved metals in water
samples by diffusion gradients in thin films (DGT) method ...................... 157

29. Mirela MICLEAN, Marin ENIL!, Cecilia ROMAN, Tiberiu FREN"IU,
Emil CORDO (Cluj-Napoca - Roumania) – Plant uptake factors for 55
elements in a rural mining area, NW Romania ......................................... 162

30. Florina DEAC, Anamaria TODEA, Radu SILAGHI-DUMITRESCU
(Cluj-Napoca - Roumania) - Glutaraldehyde derivatization of
hemoglobin: a potential blood substitute................................................... 166

31. Radu SILAGHI-DUMITRESCU, Cristina BISCHIN, Florina DEAC,
Zoltan KIS, Augustin MOT, Sergei V. MAKAROV (Cluj-Napoca -
Roumania) – Unusual metal oxidation states in metalloproteins and
related complexes: from degenerate orbitals to apoptosis ....................... 174

Authors index................................................................................................... 183

III
C O N T E N T S

Foreword ................................................................................................... 1

1. Sven STADLBAUER, René FRANK, Johannes KUNIG, Verena
ORTMANN, Annette G. BECK-SICKINGER, and Evamarie HEY-
HAWKINS (Leipzig - Germany) - Boron clusters in cancer therapy ....... 3

2. Sergei V. MAKAROV (Ivanovo - Russia) - Comparative study of
catalytic activity of metallophthalocyanines and
metallotetrapyrazinoporphyrazines .......................................................... 11

3. Constantin-Horia BARBU, Bianca-Petronela PAVEL, Camelia
SAND, Mihai-Radu POP (Sibiu - Romania) – Miscanthus sinensis
gigantheus’ behaviour on soils polluted with heavy metals........................ 21

4. Angela-Nadia ALBETEL, Tamara A. DAILEY, Harry A. DAILEY,
Michael K. JOHNSON (Athens, GA - USA) – Properties and function of
[2Fe-2S] centers in ferrochelatases ........................................................... 25

5. Gabriela GARBAN, Zeno GARBAN, George–Daniel GHIBU,
Mihaela-Elisabeta MITROI (Timisoara – Romania) - Mineral
ingredients in food supplements used in the European Union – some
current aspects........................................................................................... 30

6. Yıldız KALEBAŞI AKTAŞ, Arıkan KOCABAŞ (Edirne - Turkey) -
Arsenic pollution in some major roadside stations in Edirne city (Turkey).. 38

7. Zeno GARBAN, George-Daniel GHIBU, Adina AVACOVICI, Cornel
BALTĂ, Gabriela GARBAN, Mihaela-Elisabeta MITROI (Timisoara –
Romania) - Effects of sodium nitrate administration in drinking water of
leporides regarding zinc concentration in organs and tissues ................. 43

8. Bianca-Petronela PAVEL, Constantin-Horia BARBU, Camelia
SAND, Mihai-Radu POP (Sibiu - Roumania) - Direct determination of
heavy metals in plant solid samples using HR-CS AAS............................. 49

9. Maryam EIDI, Akram EIDI, Pouneh SHAHMOHAMMADI, Omid
POUYAN, Reza FAZAELI, Massih BAHAR (Varamin - Iran) - Toxic
effect of seminal plasma levels of copper on human semen parameters .. 53

10. Marilena ONETE, Mihaela PAUCĂ-COMĂNESCU, Elisabeta BIANU,
Stelian ION (Bucureşti - Roumania) - Heavy metals content of soil and
plants from central parks (Bucharest, Romania)........................................ 58

11. Akram EIDI, Maryam EIDI, Mohammadhadi Givian RAD, Nasim
ABASPOUR (Teheran - Iran) - Effect of alcoholic extract of Eucalyptus
globulus labill. leaves on sodium and potassium levels in healthy and
diabetic rats ............................................................................................... 65
I
12. Claudiu-Nicolae ŞIMONAŢI (Arad – Romania) - Determination and
assessment of heavy metal content in fish in Mureş river.......................... 70

13. Gulay SEREN, Ozan YORUK (Edirne - Turkey) - Determination of
manganese in soil and sunflower (Helianthus annuus L.) plant parts
after microwave-assisted digestions by ICP-OES...................................... 76

14. Anca HAINAL, Ioana IGNAT, Alina STINGU, Irina VOLF, Valentin I.
POPA (Iasi – Romania) - The influence of some natural polyphenols on
Rhodotorula spp. growth in the presence of copper ions........................... 79

15. Masoomeh SOHRABI-MOLLAYOUSEFI, Maryam SAHBA (Teheran -
Iran) - Effects of metals on benthic foraminiferal tests in Asalooye
(Persian Gulf) ...........................................................................................184

16. Alina STINGU, Ioana IGNAT, Anca HAINAL, Irina VOLF, Valentin I.
POPA (Iasi - Roumania) - Behaviour of tomato plant during cultivation
in the presence of copper in forest and sandy soils ................................... 90

17. Marija CIZLER, Dušan VELJKOVIĆ, Goran V. JANJIĆ, Snežana D.
ZARIĆ (Belgrade - Serbia) - Study of C-H...O interactions beetwen
coordinated water molecule and C6-aromatic group................................ 94

18. Mariann-Kinga ÁRKOSI, Florina DEAC, Radu SILAGHI-

DUMITRESCU (Cluj-Napoca - Roumania) - Hemoglobin as a
competitive pathway to liver in xenobiotic activation: peroxidase
reactivity towards anthracene and a protective role for hydroquinone ..... 99

19. Cornelia MAJDIK, Andrada MĂICĂNEANU, Cerasella INDOLEAN,
Silvia BURCA, Maria STANCA (Cluj-Napoca - Roumania) - Cadmium
removal from wastewaters using Ca-alginate immobilized bentonite as
adsorbent.................................................................................................. 111

20. Eva FISCHER-FODOR, Rares BUIGA, Doris PELAU, Cosmin
LISENCU, Piroska VIRAG, Corina TATOMIR, Olga SORITAU (Cluj-
Napoca - Roumania) – In vitro chemosensitivity testing of tumor cells
treated with platin-based drugs................................................................. 116

21. Augustin MOT, Alina ROMAN, Radu SILAGHI-DUMITRESCU (Cluj-
Napoca – Roumania) - Blood substitutes: can we do without
hemoglobin?............................................................................................. 122

22. Béla MIHÁLY, Edit FORIZS, Ioan SILAGHI-DUMITRESCU (Cluj-
Napoca - Roumania) - Novel mixed ligand cadmium(II) theophyllinato
complexes with potential bioactivity .......................................................... 126

23. Vicentiu TACIUC, Cristina BISCHIN, Radu SILAGHI-DUMITRESCU
(Cluj-Napoca - Roumania) - A novel mechanism for platinum-based
drugs: cisplatin and related compounds as pro-oxidants in blood............. 130
II
24. Gheorghe TOMOAIA, Olga SORITAU, Maria TOMOAIA-COTISEL3,
Lacrimioara-Bianca POP, Alexandru POP, Aurora MOCANU, Ossi
HOROVITZ, Liviu-Dorel BOBOS (Cluj-Napoca - Roumania) - The
effect of self-assemblies based on nanostructured phosphates and
collagen mixtures on cell cultures .......................................................... 135

25. Valeria DIŢOIU, Nina HOLBAN (Suceava - Roumania) – Study
regarding the characteristics and heavy metals content in the sludge in
the municipal wastewater treatment plants in the county of Suceava....... 141

26. Marioara MOLDOVAN, Cristina PREJMEREAN, Marcela TRIF,
Laura SILAGHI DUMITRESCU, Olga MUSAT, Doina PRODAN,
Codruta SAROSI, Gabriel FURTOS, Ioan ROMAN, Stanca BOBOIA
(Cluj-Napoca - Roumania) – Interaction between biocomposites and Co
alloys for dental crowns ........................................................................... 148

27. Claudiu TĂNĂSELIA, Stanko ILIK-POPOV, Dana POP, Bela
ABRAHAM, Cecilia ROMAN, Emil Cordoş, Tiberiu Frenţiu, Trajče
STAFILOV, Leontin DAVID (Cluj-Napoca - Roumania) – Fast
measurement method of lead isotopic ratio in meteoritic material using
quadrupole ICP-MS................................................................................... 154

28. Marin ŞENILĂ, Lăcrimioara ŞENILĂ, Tiberiu FRENŢIU, Michaela
PONTA, Emil CORDOŞ, Luminiţa SILAGHI-DUMITRESCU (Cluj-
Napoca - Roumania) – Determination of dissolved metals in water
samples by diffusion gradients in thin films (DGT) method ...................... 157

29. Mirela MICLEAN, Marin ŞENILĂ, Cecilia ROMAN, Tiberiu FRENŢIU,
Emil CORDOŞ (Cluj-Napoca - Roumania) – Plant uptake factors for 55
elements in a rural mining area, NW Romania ......................................... 162

30. Florina DEAC, Anamaria TODEA, Radu SILAGHI-DUMITRESCU
(Cluj-Napoca - Roumania) - Glutaraldehyde derivatization of
hemoglobin: a potential blood substitute................................................... 166

31. Radu SILAGHI-DUMITRESCU, Cristina BISCHIN, Florina DEAC,
Zoltan KIS, Augustin MOT, Sergei V. MAKAROV (Cluj-Napoca -
Roumania) – Unusual metal oxidation states in metalloproteins and
related complexes: from degenerate orbitals to apoptosis ....................... 174

Authors index................................................................................................... 183

III
Foreword

The present volume hosts papers presented during the 9th edition of the „Metal
Elements in Environment, Medicine and Biology” (M.E.E.M.B.) symposium, organized
under the auspices of the Cluj-Napoca and Timisoara branches of the Romanian
Academy. While all previous editions have taken place in Timisoara, this year the
event has been organized at the „Babes-Bolyai” University in Cluj-Napoca, Romania.
This series of symposia was initiated in 1993 by the „Working Group for Metal
Research in Biological Systems”, founded by Timisoara researchers in 1979. Past
editions have allowed for inter-disciplinary interaction between researchers from
various parts of the world, interested in the importance of metals for various aspects of
our life. We thank this year’s participants for their valuable contributions, and look
forward for even more fruitful discussions during the future editions of this symposium.

THE ORGANIZING COMMITTEE

Acad. Ionel HAIDUC, PhD, Dr.h.c. - Honorary President
President of the Roumanian Academy

Prof. Ioan SILAGHI-DUMITRESCU, PhD, corresp. member Roum.Acad. – Chairman
„Babeş-Bolyai” University at Cluj-Napoca, Department of Chemistry and Chemical
Technology

Gabriela GÂRBAN, MD, PhD - Co-Chairman
Institute of Public Health Timişoara

Prof. Zeno GÂRBAN, PhD - Founding member of „Working Group for Metal
Research in Biological Systems” Timişoara (1979)
University of Agricultural Sciences and Veterinary Medicine Timişoara

Assoc. Prof. Radu SILAGHI-DUMITRESCU, Ph.D - Secretary of 9th MEEMB
Symposium
„Babeş-Bolyai” University at Cluj-Napoca, Department of Chemistry and Chemical
Technology

3
BORON CLUSTERS
IN CANCER THERAPY

Sven STADLBAUER,a René FRANK,a Johannes KUNIG,a Verena ORTMANN,b An-
nette G. BECK-SICKINGER,b and Evamarie HEY-HAWKINSa,*

a Universität Leipzig, Institute of Inorganic Chemistry, Johannisallee 29,
D-04103 Leipzig, Germany, fax: [phone]; phone: [phone]; email: [email protected]
leipzig.de
b Universität Leipzig, Institute of Biochemistry, Brüderstraße 34, D-04103 Leipzig, Germany

Abstract
High and selective accumulation in tumor cells is an important requirement for
a BNCT agent. Increasing the tumor selectivity of BNCT agents may be possible by
the use of carbaborane-containing bis-phosphonates and incorporation of carbabo-
rane-containing amino acids into breast cancer selective neuropeptide Y derivatives.

Keywords: BNCT, carbaboranes, phosphonates, tumor selectivity

INTRODUCTION
To date, the treatment of malignant tumors is always accompanied by ex-
tremely negative side effects. One potentially useful approach for selective destruc-
tion of tumor cells is boron neutron capture therapy (BNCT), a powerful form of radio-
therapy involving preferential incorporation of 10B-containing compounds into tumor
cells, followed by irradiation of the tumor with thermal neutrons. The high-energy fis-
sion products which are formed on absorption of a neutron allow selective destruction
of the tumor cells without affecting the surrounding healthy tissue. High and selective
accumulation in tumor cells is one important requirement for a BNCT agent.1 For
successful treatment, a concentration of 30 µg 10B per gram tumor must be achieved.
The main problem to date is the availability of boron compounds which exhibit the
necessary high selectivity, water solubility, and low toxicity in high concentrations.2
The synthesis of and bioactivity studies on the first phosphorus-containing bo-
ron cluster compounds bearing phosphate and pyrophosphate moieties were re-
ported by Kaczmarczyk and Bechtold in 1975.3 However, these compounds turned
out to be highly toxic. Interestingly, some simple carbaboranyl bis-phosphonates ex-
hibit high tumor selectivity and can be used in the treatment of calcifying tumors.4
Oligomeric phosphate diesters which contain closo- or nido-carbaboranes show high
accumulation in tumor tissue in BALB/c mice bearing EMT6 tumors.5 However, com-
prehensive biological assessments of boron-containing phosphonates as potential
tumor-targeting agents in BNCT are still rare.6

We have therefore devised efficient syntheses for novel boron compounds
which provide a combined tumor-targeting system: The use of phosphonato groups
as phosphate mimics and galactosyl groups for binding to lectins at the surface of a
tumor cell.7
Transformation from a normal to a malignant breast cell is accompanied by
overexpression of the Y1 receptor.8 Beck-Sickinger and co-workers developed a
modified neuropeptide Y derivative featuring high affinity for the Y1 receptor.9 There-

„Metal Elements in Environment, Medicine and Biology”, Tome IX, pp. 3 - 10, Cluj University Press,
„Babeş-Bolyai” University, Cluj-Napoca, 2009
Proc. of 9th Int. Symp. of Roumanian Academy - Branch Cluj-Napoca and Branch Timişoara,
2009, October 16-17, Cluj-Napoca, Roumania
4
fore, we synthesized carbaborane-containing amino acids for incorporation in neu-
ropeptide Y to selectively target breast cancer cells.

RESULTS AND DISCUSSION
The synthesis of sugar-containing carbaboranyl bis-phosphonates was at-
tempted starting from carbaboranyl bis(chlorophosphonates) and a protected sugar
(with one hydroxyl group still available). Thus, carbaboranyl bis(chlorophos-phonate)
2 was obtained from 1 by chlorination with sulfuryl chloride (Scheme 1).10

Scheme 1: Synthesis of 2
However, we were unable to convert compound 2 to the target compound by
reaction with 1,2:5,6-di-O-isopropylidene-α-D-glucofuranose (3) under different reac-
tion conditions; in all cases, only decomposition was observed (Scheme 2).

Scheme 2: Reaction of 2 with the sugar derivative 3 led to decomposition
As phosphorus(V) sub-stituents on ortho-
carbaborane exhibit only low reactivity, more
reactive phosphorus(III) deriva-tives were em-
ployed. However, no reaction occurred between
the dialkylamidohalophospho-nito-substituted
ortho-carbabo-ranes 1,2-{P(NR )X} C B H (R
2 2 2 10 10
B
= Me, iPr, X = Cl, Br) and isopropylidene-
protected galactose 5. Employing meta-
carbaborane instead of ortho-carbaborane was