Sinteze, fizičke, strukturne i biološke karakteristike novih kompleksnih jedenjenja

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Sinteze, fizičke, strukturne i biološke karakteristike novih kompleksnih jedenjenja (en)
Синтезе, физичке, структурне и биолошке карактеристике нових комплексних једењења (sr)
Sinteze, fizičke, strukturne i biološke karakteristike novih kompleksnih jedenjenja (sr_RS)
Authors

Publications

Molecular Structure of Metal Enolates

(Wiley, 2009)

TY  - CHAP
PY  - 2009
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/3673
AB  - Ligand properties such as coordination activity, bond length and orientation of donor atoms are among the key functions in designing organic structures. β-Diketones and their metal complexes are among the first groups studied. Numerous classes of various metal complexes are the product of their versatility and flexibility to adopt different coordination modes. They typically act in monoanionic form as bidentate oxygen donor in enol form or in keto form as neutral molecule. In that form ligand coordination can take place through the carbon atom or as a monodentate oxygen donor in enol form, or as bridging ligand donor.
PB  - Wiley
T2  - PATAI'S Chemistry of Functional Groups
T1  - Molecular Structure of Metal Enolates
DO  - 10.1002/9780470682531.pat0418
ER  - 
@inbook{
year = "2009",
abstract = "Ligand properties such as coordination activity, bond length and orientation of donor atoms are among the key functions in designing organic structures. β-Diketones and their metal complexes are among the first groups studied. Numerous classes of various metal complexes are the product of their versatility and flexibility to adopt different coordination modes. They typically act in monoanionic form as bidentate oxygen donor in enol form or in keto form as neutral molecule. In that form ligand coordination can take place through the carbon atom or as a monodentate oxygen donor in enol form, or as bridging ligand donor.",
publisher = "Wiley",
journal = "PATAI'S Chemistry of Functional Groups",
booktitle = "Molecular Structure of Metal Enolates",
doi = "10.1002/9780470682531.pat0418"
}
(2009). Molecular Structure of Metal Enolates. in PATAI'S Chemistry of Functional Groups
Wiley..
https://doi.org/10.1002/9780470682531.pat0418
Molecular Structure of Metal Enolates. in PATAI'S Chemistry of Functional Groups. 2009;.
doi:10.1002/9780470682531.pat0418 .
"Molecular Structure of Metal Enolates" in PATAI'S Chemistry of Functional Groups (2009),
https://doi.org/10.1002/9780470682531.pat0418 . .
2

Synthesis, characterization and antitumor activity of novel N-substituted α-amino acids containing ferrocenyl pyrazole-moiety

Joksović, M.D.; Marković, V.; Juranić, Zorica; Stanojković, Tatjana; Jovanović, L.S.; Damljanović, I.S.; Szécsényi, K.M.; Todorović, Nina; Trifunović, Snežana; Vukićević, Rastko

(2009)

TY  - JOUR
AU  - Joksović, M.D.
AU  - Marković, V.
AU  - Juranić, Zorica
AU  - Stanojković, Tatjana
AU  - Jovanović, L.S.
AU  - Damljanović, I.S.
AU  - Szécsényi, K.M.
AU  - Todorović, Nina
AU  - Trifunović, Snežana
AU  - Vukićević, Rastko
PY  - 2009
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/619
AB  - A series of new N-[(3-ferrocenyl-1-phenylpyrazol-4-yl)methyl] α-amino acids were prepared and characterized by a range of spectroscopic techniques and cyclic voltammetry. The in vitro antitumor activity of all synthesized compounds was investigated against cervix adenocarcinoma HeLa, melanoma Fem-x and myelogenous leukemia K562 cell lines using the MTT method. Tryptophan derivative 1l exhibited the highest cytotoxic activity in the cell growth inhibition of all three types of cell lines.
T2  - Journal of Organometallic Chemistry
T1  - Synthesis, characterization and antitumor activity of novel N-substituted α-amino acids containing ferrocenyl pyrazole-moiety
VL  - 694
IS  - 24
SP  - 3935
EP  - 3942
DO  - 10.1016/j.jorganchem.2009.08.013
ER  - 
@article{
author = "Joksović, M.D. and Marković, V. and Juranić, Zorica and Stanojković, Tatjana and Jovanović, L.S. and Damljanović, I.S. and Szécsényi, K.M. and Todorović, Nina and Trifunović, Snežana and Vukićević, Rastko",
year = "2009",
abstract = "A series of new N-[(3-ferrocenyl-1-phenylpyrazol-4-yl)methyl] α-amino acids were prepared and characterized by a range of spectroscopic techniques and cyclic voltammetry. The in vitro antitumor activity of all synthesized compounds was investigated against cervix adenocarcinoma HeLa, melanoma Fem-x and myelogenous leukemia K562 cell lines using the MTT method. Tryptophan derivative 1l exhibited the highest cytotoxic activity in the cell growth inhibition of all three types of cell lines.",
journal = "Journal of Organometallic Chemistry",
title = "Synthesis, characterization and antitumor activity of novel N-substituted α-amino acids containing ferrocenyl pyrazole-moiety",
volume = "694",
number = "24",
pages = "3935-3942",
doi = "10.1016/j.jorganchem.2009.08.013"
}
Joksović, M.D., Marković, V., Juranić, Z., Stanojković, T., Jovanović, L.S., Damljanović, I.S., Szécsényi, K.M., Todorović, N., Trifunović, S.,& Vukićević, R.. (2009). Synthesis, characterization and antitumor activity of novel N-substituted α-amino acids containing ferrocenyl pyrazole-moiety. in Journal of Organometallic Chemistry, 694(24), 3935-3942.
https://doi.org/10.1016/j.jorganchem.2009.08.013
Joksović M, Marković V, Juranić Z, Stanojković T, Jovanović L, Damljanović I, Szécsényi K, Todorović N, Trifunović S, Vukićević R. Synthesis, characterization and antitumor activity of novel N-substituted α-amino acids containing ferrocenyl pyrazole-moiety. in Journal of Organometallic Chemistry. 2009;694(24):3935-3942.
doi:10.1016/j.jorganchem.2009.08.013 .
Joksović, M.D., Marković, V., Juranić, Zorica, Stanojković, Tatjana, Jovanović, L.S., Damljanović, I.S., Szécsényi, K.M., Todorović, Nina, Trifunović, Snežana, Vukićević, Rastko, "Synthesis, characterization and antitumor activity of novel N-substituted α-amino acids containing ferrocenyl pyrazole-moiety" in Journal of Organometallic Chemistry, 694, no. 24 (2009):3935-3942,
https://doi.org/10.1016/j.jorganchem.2009.08.013 . .
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A study of novel cobalt(II) octaazamacrocyclic complexes with aminocarboxylates or their derivatives

Vučković, Gordana; Tanasković, Slađana B.; Antonijević-Nikolić, Mirjana; Živković-Radovanović, Vukosava; Gojgić-Cvijović, Gordana

(Serbian Chemical Society, 2009)

TY  - JOUR
AU  - Vučković, Gordana
AU  - Tanasković, Slađana B.
AU  - Antonijević-Nikolić, Mirjana
AU  - Živković-Radovanović, Vukosava
AU  - Gojgić-Cvijović, Gordana
PY  - 2009
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/504
AB  - Four new air-stable mixed-ligand Co(II) complexes having the general formula [Co2(Y)tpmc]Z3×q(H2O/CH3CN) (HY = N-methylglycine/N,N-dimethylglycine, Z = - 4BF , qH2O=4 or 3; HY=S-norvaline/S-valine Z=-ClO4 , qCH3CN = 0.5; qH2O = 0.5; tpmc = N,N',N'',N'''-tetrakis(2-pyridylmethyl)- -1,4,8,11-tetraazacyclotetradecane) were prepared. The composition, some physical and chemical properties and their tentative geometries were evaluated based on elemental analysis (C, H, N), conductometric and magnetic measurements, spectroscopic data (UV/Vis, IR) and cyclic voltammetry. The data were compared with earlier described analogous complexes containing the macrocyclic ligand and aliphatic aminocarboxylates. It is assumed that all complexes are binuclear with an exo coordination mode of the octaazamacrocyclic pendant ligand in the boat conformation. In addition, two -N-(CH2)2-N- portions of the cyclam ring within the tpmc ligand and Co(II) ions in the high-spin state are most probably bridged via oxygen atoms from the anion of the aminocarboxylate/derivatives, whereas nitrogen atoms rest uncoordinated. In all cases, a combined chelate-bridged coordination is proposed as the most probable. The complexes were electrochemically stable in the potential range -1.0 to 1.0 V. They were also preliminary assayed toward some microorganisms together with the ligands, starting simple salts and solvents as test substances. In some cases, certain antimicrobial activity of the complexes was detected.
AB  - Dobijena su četiri nova mešovito-ligandna kompleksa Co(II), stabilna na vazduhu, opšte formule [Co2(Y)tpmc]Z3×q(H2O/CH3CN) (HY = N-metilglicin/N,N-dimetilglicin, Z=-4BF , qH2O=4 ili 3); HY = S-norvalin/S-valin, Z=-ClO4, qCH3CN=0,5; qH2O=0,5; tpmc= N,N',N'',N'''-tetrakis(2-piridilmetil)-1,4,8,11-tetraazaciklotetradekan). Sastav, neka fizička i hemijska svojstva i njihove približne geometrije su izvedene na osnovu elementalne analize (C, H, N), konduktometrijskih i magnetnih merenja, spektroskopskih podataka (UV/Vis, IR) odnosno ciklične voltametrije. Podaci su upoređeni sa ranije opisanim analogim kompleksima koji sadrže makrociklični ligand i alifatične aminokarboksilate. Pretpostavljeno je da su svi kompleksi dinuklearni sa egzo koordinacijom pendantnog oktaazamakrocikla u konformaciji lađe. Pored dva -N-(CH2)2-N- dela ciklamovog prstena unutar tpmc-a, joni visoko-spinskog Co(II) su najverovatnije premošćeni angažovanjem kiseonikovih atoma sa anjona aminokarboksilata/derivata, dok atomi azota ostaju nekoordinovani. Za sve komplekse predložen je kombinovani helatno-mostovni način vezivanja. Kompleksi su bili elektrohemijski stabilni u opsegu potencijala -1,0 do 1,0 V. Oni su preliminarno testirani na mikroorganizme zajedno sa ligandima, polaznim prostim solima i rastvaračima kao test supstancama. U nekim slučajevima je nađena izvesna antimikrobna aktivnost kompleksa.
PB  - Serbian Chemical Society
T2  - Journal of the Serbian Chemical Society
T1  - A study of novel cobalt(II) octaazamacrocyclic complexes with aminocarboxylates or their derivatives
T1  - Proučavanje novih kompleksa kobalta(II) sa oktaazamakrociklom i aminokarboksilatima ili njihovim derivatima
VL  - 74
IS  - 6
SP  - 629
EP  - 640
DO  - 10.2298/JSC0906629V
ER  - 
@article{
author = "Vučković, Gordana and Tanasković, Slađana B. and Antonijević-Nikolić, Mirjana and Živković-Radovanović, Vukosava and Gojgić-Cvijović, Gordana",
year = "2009",
abstract = "Four new air-stable mixed-ligand Co(II) complexes having the general formula [Co2(Y)tpmc]Z3×q(H2O/CH3CN) (HY = N-methylglycine/N,N-dimethylglycine, Z = - 4BF , qH2O=4 or 3; HY=S-norvaline/S-valine Z=-ClO4 , qCH3CN = 0.5; qH2O = 0.5; tpmc = N,N',N'',N'''-tetrakis(2-pyridylmethyl)- -1,4,8,11-tetraazacyclotetradecane) were prepared. The composition, some physical and chemical properties and their tentative geometries were evaluated based on elemental analysis (C, H, N), conductometric and magnetic measurements, spectroscopic data (UV/Vis, IR) and cyclic voltammetry. The data were compared with earlier described analogous complexes containing the macrocyclic ligand and aliphatic aminocarboxylates. It is assumed that all complexes are binuclear with an exo coordination mode of the octaazamacrocyclic pendant ligand in the boat conformation. In addition, two -N-(CH2)2-N- portions of the cyclam ring within the tpmc ligand and Co(II) ions in the high-spin state are most probably bridged via oxygen atoms from the anion of the aminocarboxylate/derivatives, whereas nitrogen atoms rest uncoordinated. In all cases, a combined chelate-bridged coordination is proposed as the most probable. The complexes were electrochemically stable in the potential range -1.0 to 1.0 V. They were also preliminary assayed toward some microorganisms together with the ligands, starting simple salts and solvents as test substances. In some cases, certain antimicrobial activity of the complexes was detected., Dobijena su četiri nova mešovito-ligandna kompleksa Co(II), stabilna na vazduhu, opšte formule [Co2(Y)tpmc]Z3×q(H2O/CH3CN) (HY = N-metilglicin/N,N-dimetilglicin, Z=-4BF , qH2O=4 ili 3); HY = S-norvalin/S-valin, Z=-ClO4, qCH3CN=0,5; qH2O=0,5; tpmc= N,N',N'',N'''-tetrakis(2-piridilmetil)-1,4,8,11-tetraazaciklotetradekan). Sastav, neka fizička i hemijska svojstva i njihove približne geometrije su izvedene na osnovu elementalne analize (C, H, N), konduktometrijskih i magnetnih merenja, spektroskopskih podataka (UV/Vis, IR) odnosno ciklične voltametrije. Podaci su upoređeni sa ranije opisanim analogim kompleksima koji sadrže makrociklični ligand i alifatične aminokarboksilate. Pretpostavljeno je da su svi kompleksi dinuklearni sa egzo koordinacijom pendantnog oktaazamakrocikla u konformaciji lađe. Pored dva -N-(CH2)2-N- dela ciklamovog prstena unutar tpmc-a, joni visoko-spinskog Co(II) su najverovatnije premošćeni angažovanjem kiseonikovih atoma sa anjona aminokarboksilata/derivata, dok atomi azota ostaju nekoordinovani. Za sve komplekse predložen je kombinovani helatno-mostovni način vezivanja. Kompleksi su bili elektrohemijski stabilni u opsegu potencijala -1,0 do 1,0 V. Oni su preliminarno testirani na mikroorganizme zajedno sa ligandima, polaznim prostim solima i rastvaračima kao test supstancama. U nekim slučajevima je nađena izvesna antimikrobna aktivnost kompleksa.",
publisher = "Serbian Chemical Society",
journal = "Journal of the Serbian Chemical Society",
title = "A study of novel cobalt(II) octaazamacrocyclic complexes with aminocarboxylates or their derivatives, Proučavanje novih kompleksa kobalta(II) sa oktaazamakrociklom i aminokarboksilatima ili njihovim derivatima",
volume = "74",
number = "6",
pages = "629-640",
doi = "10.2298/JSC0906629V"
}
Vučković, G., Tanasković, S. B., Antonijević-Nikolić, M., Živković-Radovanović, V.,& Gojgić-Cvijović, G.. (2009). A study of novel cobalt(II) octaazamacrocyclic complexes with aminocarboxylates or their derivatives. in Journal of the Serbian Chemical Society
Serbian Chemical Society., 74(6), 629-640.
https://doi.org/10.2298/JSC0906629V
Vučković G, Tanasković SB, Antonijević-Nikolić M, Živković-Radovanović V, Gojgić-Cvijović G. A study of novel cobalt(II) octaazamacrocyclic complexes with aminocarboxylates or their derivatives. in Journal of the Serbian Chemical Society. 2009;74(6):629-640.
doi:10.2298/JSC0906629V .
Vučković, Gordana, Tanasković, Slađana B., Antonijević-Nikolić, Mirjana, Živković-Radovanović, Vukosava, Gojgić-Cvijović, Gordana, "A study of novel cobalt(II) octaazamacrocyclic complexes with aminocarboxylates or their derivatives" in Journal of the Serbian Chemical Society, 74, no. 6 (2009):629-640,
https://doi.org/10.2298/JSC0906629V . .
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A Cu2+ probe over nizatidine and ranitidine, or in Silico vs. experimentally obtained complexatlon of drugs

Drakulić, Branko; Sovilj, Sofija P.

(Switzerland : Trans Tech Publications LTD, 2007)

TY  - JOUR
AU  - Drakulić, Branko
AU  - Sovilj, Sofija P.
PY  - 2007
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/4308
AB  - In silico model of title drugs mode of interaction with Cu2+ ion was proposed. A hundred conformations of each drug are used in this study. Examination of drugs interactions with Cu2+ ion were conducted using GRID package. The Cu2+ probe was used. The two favorable regions of interactions were detected: a) the nitro group and terminal imino nitrogen in a γ position from it, as proposed from the experimental data, b) the region of heterocyclic ring (tiazoline and furan from Nizatidine and Ranitidine, respectively) as the most favorable one. Therefore, the present study identifies the second region of the molecule that is able to strongly interact with the Cu2+ ion, The position and energies of obtained molecular interaction fields (MIF) are discussed. The results support the fact that the properties, which express recognition forces of the molecules, are strongly dependent on 3D geometry.
PB  - Switzerland : Trans Tech Publications LTD
T2  - Materials Science Forum
T1  - A Cu2+ probe over nizatidine and ranitidine, or in Silico vs. experimentally obtained complexatlon of drugs
VL  - 555
SP  - 435
EP  - 439
DO  - 10.4028/0-87849-441-3.435
ER  - 
@article{
author = "Drakulić, Branko and Sovilj, Sofija P.",
year = "2007",
abstract = "In silico model of title drugs mode of interaction with Cu2+ ion was proposed. A hundred conformations of each drug are used in this study. Examination of drugs interactions with Cu2+ ion were conducted using GRID package. The Cu2+ probe was used. The two favorable regions of interactions were detected: a) the nitro group and terminal imino nitrogen in a γ position from it, as proposed from the experimental data, b) the region of heterocyclic ring (tiazoline and furan from Nizatidine and Ranitidine, respectively) as the most favorable one. Therefore, the present study identifies the second region of the molecule that is able to strongly interact with the Cu2+ ion, The position and energies of obtained molecular interaction fields (MIF) are discussed. The results support the fact that the properties, which express recognition forces of the molecules, are strongly dependent on 3D geometry.",
publisher = "Switzerland : Trans Tech Publications LTD",
journal = "Materials Science Forum",
title = "A Cu2+ probe over nizatidine and ranitidine, or in Silico vs. experimentally obtained complexatlon of drugs",
volume = "555",
pages = "435-439",
doi = "10.4028/0-87849-441-3.435"
}
Drakulić, B.,& Sovilj, S. P.. (2007). A Cu2+ probe over nizatidine and ranitidine, or in Silico vs. experimentally obtained complexatlon of drugs. in Materials Science Forum
Switzerland : Trans Tech Publications LTD., 555, 435-439.
https://doi.org/10.4028/0-87849-441-3.435
Drakulić B, Sovilj SP. A Cu2+ probe over nizatidine and ranitidine, or in Silico vs. experimentally obtained complexatlon of drugs. in Materials Science Forum. 2007;555:435-439.
doi:10.4028/0-87849-441-3.435 .
Drakulić, Branko, Sovilj, Sofija P., "A Cu2+ probe over nizatidine and ranitidine, or in Silico vs. experimentally obtained complexatlon of drugs" in Materials Science Forum, 555 (2007):435-439,
https://doi.org/10.4028/0-87849-441-3.435 . .

Preparation, characterization and X-ray analysis of [Co2(Cl)2tpmc](BF4)2. Comparative structural analysis with the complexes having analogous geometries and ligands

Vučković, Gordana; Tanasković, Slađana B.; Rychlewska, Urszula; Radanović, Dušanka; Mroziñski, Jerzy; Korabik, Maria

(Elsevier, 2007)

TY  - JOUR
AU  - Vučković, Gordana
AU  - Tanasković, Slađana B.
AU  - Rychlewska, Urszula
AU  - Radanović, Dušanka
AU  - Mroziñski, Jerzy
AU  - Korabik, Maria
PY  - 2007
UR  - https://cer.ihtm.bg.ac.rs/handle/123456789/4250
AB  - A novel binuclear Co(II) complex, [Co2(Cl)2tpmc](BF4)2 (tpmc = N,N′,N″,N‴-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraaz acyclotetradecane), was prepared and structurally characterized by X-ray diffraction analysis at low temperature. The complex crystallizes in P21/c space group of the monoclinic crystal system, and its crystals are isomorphic with those of [Cu2(Br)2tpmc](ClO4)2 complex. In the crystal structure the complex cations [Co2(Cl)2tpmc]2+ are settled around the inversion centres. Cobalt(II) is exo coordinated with four macrocyclic N atoms, and Cl- supplements the fifth coordination site. Based on the index of trigonality, the coordination polyhedron formed around Co(II) ion is described as distorted trigonal bipyramid. Two metal centres are at a distance of 5.710 Å. This is the first Co(II) complex for which X-ray analysis confirmed a chair conformation of tpmc ligand. IR, EPR (X-band) and UV/VIS absorption and reflectance spectra, molar conductivities and magnetic measurements (SQUID) are used to study the investigated complex. A comparative structural analysis with some of the described Co(II) and Cu(II) complexes of analogous geometries and type of pendant azamacrocyclic ligands was also done.
PB  - Elsevier
T2  - Journal of Molecular Structure
T1  - Preparation, characterization and X-ray analysis of [Co2(Cl)2tpmc](BF4)2. Comparative structural analysis with the complexes having analogous geometries and ligands
VL  - 827
IS  - 1-3
SP  - 80
EP  - 87
DO  - 10.1016/j.molstruc.2006.05.009
ER  - 
@article{
author = "Vučković, Gordana and Tanasković, Slađana B. and Rychlewska, Urszula and Radanović, Dušanka and Mroziñski, Jerzy and Korabik, Maria",
year = "2007",
abstract = "A novel binuclear Co(II) complex, [Co2(Cl)2tpmc](BF4)2 (tpmc = N,N′,N″,N‴-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraaz acyclotetradecane), was prepared and structurally characterized by X-ray diffraction analysis at low temperature. The complex crystallizes in P21/c space group of the monoclinic crystal system, and its crystals are isomorphic with those of [Cu2(Br)2tpmc](ClO4)2 complex. In the crystal structure the complex cations [Co2(Cl)2tpmc]2+ are settled around the inversion centres. Cobalt(II) is exo coordinated with four macrocyclic N atoms, and Cl- supplements the fifth coordination site. Based on the index of trigonality, the coordination polyhedron formed around Co(II) ion is described as distorted trigonal bipyramid. Two metal centres are at a distance of 5.710 Å. This is the first Co(II) complex for which X-ray analysis confirmed a chair conformation of tpmc ligand. IR, EPR (X-band) and UV/VIS absorption and reflectance spectra, molar conductivities and magnetic measurements (SQUID) are used to study the investigated complex. A comparative structural analysis with some of the described Co(II) and Cu(II) complexes of analogous geometries and type of pendant azamacrocyclic ligands was also done.",
publisher = "Elsevier",
journal = "Journal of Molecular Structure",
title = "Preparation, characterization and X-ray analysis of [Co2(Cl)2tpmc](BF4)2. Comparative structural analysis with the complexes having analogous geometries and ligands",
volume = "827",
number = "1-3",
pages = "80-87",
doi = "10.1016/j.molstruc.2006.05.009"
}
Vučković, G., Tanasković, S. B., Rychlewska, U., Radanović, D., Mroziñski, J.,& Korabik, M.. (2007). Preparation, characterization and X-ray analysis of [Co2(Cl)2tpmc](BF4)2. Comparative structural analysis with the complexes having analogous geometries and ligands. in Journal of Molecular Structure
Elsevier., 827(1-3), 80-87.
https://doi.org/10.1016/j.molstruc.2006.05.009
Vučković G, Tanasković SB, Rychlewska U, Radanović D, Mroziñski J, Korabik M. Preparation, characterization and X-ray analysis of [Co2(Cl)2tpmc](BF4)2. Comparative structural analysis with the complexes having analogous geometries and ligands. in Journal of Molecular Structure. 2007;827(1-3):80-87.
doi:10.1016/j.molstruc.2006.05.009 .
Vučković, Gordana, Tanasković, Slađana B., Rychlewska, Urszula, Radanović, Dušanka, Mroziñski, Jerzy, Korabik, Maria, "Preparation, characterization and X-ray analysis of [Co2(Cl)2tpmc](BF4)2. Comparative structural analysis with the complexes having analogous geometries and ligands" in Journal of Molecular Structure, 827, no. 1-3 (2007):80-87,
https://doi.org/10.1016/j.molstruc.2006.05.009 . .
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