Description
Vibha Vinayakumar Bhat¹ and P. R. Chetana²¹Department of Chemistry, M S Ramaiah College of Arts, Science and Commerce, MSR Nagar, Bengaluru, Karnataka, India²Department of Chemistry, Central College Campus, Bengaluru City University, Bengaluru, IndiaPart of the book: What to Know about LanthanumAbstractThe rise of applications of lanthanum (III) metal ions in inorganic and bioinorganic fields are tremendous in recent years. The geometrical diversities due to variable coordination number, high Lewis acidity, and higher charge make La(III) ion bind to hard bases such as O, and N donor ligands making the complexes very beneficial in the field of luminescence, diagnostics and therapeutical agents. In recent years, rapid and continued interests have emerged in investigating and designing new molecules and metal complexes containing La(III) metal ion and other lanthanides in the field of medicine, MRI technology, immunoassays, separation techniques, etc. La(III)-complexes have been investigated for their applications as nucleic acid and protein binding agents, chemical nucleases, antiproliferative agents, antioxidants as well as antimicrobial agents. The stability induced by La(III) metal ion to the organic, bulkier ligands could be successfully utilized as a drug transport vehicle toward the target site in the biological systems. Here in this chapter, we would like to explain the synthetic methods of various La(III) complexes, their variable coordination geometry, applications in the field of luminescence, binding abilities towards nucleic acids and proteins, and cytotoxic activities against various cancerous cell lines, antimicrobial activities and antioxidant activities. The structural and application diversities of La(III)-complexes are graphically shown below.Keywords: Lanthanum(III) complex, DNA binder, chemical nuclease, antimicrobial, photoluminescentReferences[1] Periodic Table: History, (n.d.). https://www.rsc.org/periodic-table/history(accessed May 7, 2022).[2] IYPT promotional pack, Royal Society of Chemistry. (n.d.). https://www.rsc.org/iypt/iypt-elements/ (accessed May 7, 2022).[3] Yerly, F., F.A. Dunand, E. Tóth, A. Figueirinha, Z. Kovács, A.D. Sherry, C.F.G.C.Geraldes, A.E. Merbach, Spectroscopic Study of the Hydration Equilibria andWater Exchange Dynamics of Lanthanide(III) Complexes of 1,7-Bis(carboxymethyl)-1,4,7,10-tetraazacyclododecane (DO2A), European Journal ofInorganic Chemistry. 2000 (2000) 1001–1006. https://doi.org/10.1002/(SICI)1099-0682(200005)2000:5<1001::AID-EJIC1001>3.0.CO;2-J.[4] Cotton, S.A. Establishing coordination numbers for the lanthanides in simplecomplexes, Comptes Rendus Chimie. 8 (2005) 129–145. https://doi.org/10.1016/j.crci.2004.07.002.[5] Wang, C., X. Leng, Y. Chen, Tris(boratabenzene) Lanthanum Complexes:Synthesis, Structure, and Reactivity, Organometallics. 34 (2015) 3216–3221.https://doi.org/10.1021/acs.organomet.5b00262.[6] Zhao, G., F. Li, H. Lin, H. Lin, Synthesis, characterization and biological activityof complexes of lanthanum(III) with 2-(1′-phenyl- 2′-carboxyl-3′-aza-n-butyl)-1,10-phenanthroline and 2-(1′-p-phenol-2′-carboxyl-3′-aza-n-butyl)-1,10-phenan throline, Bioorganic & Medicinal Chemistry. 15 (2007) 533–540. https://doi.org/10.1016/j.bmc.2006.09.032.[7] Bradley, D.C., J.S. Ghotra, F.A. Hart, M.B. Hursthouse, P.R. Raithby, Low co ordination numbers in lanthanoid and actinoid compounds. Part 2. Syntheses,properties, and crystal and molecular structures of triphenylphosphine oxide andperoxo-derivatives of [bis(trimethylsilyl)-amido]lanthanoids, J. Chem. Soc., DaltonTrans. (1977) 1166–1172. https://doi.org/10.1039/DT9770001166.[8] Deacon, G.B., B.M. Gatehouse, Q. Shen, G.N. Ward, E.R.T. Thiekink,Organoamido- and aryloxo-lanthanides—VII. The x-ray structure of five coordinate [La(OC6H6Ph2-2,6)3(THF)2]·THF, Polyhedron. 12 (1993) 1289–1294.https://doi.org/10.1016/S0277-5387(00)84318-1.[9] Clark, D.L., R.V. Hollis, B.L. Scott, J.G. Watkin, Alkali Metal Induced StructuralChanges in Complexes Containing Anionic Lanthanum Aryloxide Moieties. X-rayCrystal Structures of (THF)La(OAr)2(μ-OAr)2Li(THF), (THF)La(OAr)2(μ OAr)2Na(THF)2, and CsLa(OAr)4 (Ar = 2,6-i-Pr2C6H3), Inorg. Chem. 35 (1996)667–674. https://doi.org/10.1021/ic9510472.[10] Siddappa, K., S.B. Mane, D. Manikprabhu, La(III) complex involving the O,N donor environment of quinazoline-4(3H)-one Schiff’s base and their antimicrobialattributes against methicillin-resistant Staphylococcus aureus (MRSA),Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 130(2014) 634–638. https://doi.org/10.1016/j.saa.2014.03.115.[11] Aguiari, A., S. Tamburini, P. Tomasin, P.A. Vigato, Lanthanide(III) macroacyclicand macrocyclic Schiff base complexes containing oxamidic groups, InorganicaChimica Acta. 256 (1997) 199–210. https://doi.org/10.1016/S0020-1693(96)05441-2.[12] Kulkarni, A., S.A. Patil, P.S. Badami, Synthesis, characterization, DNA cleavageand in vitro antimicrobial studies of La(III), Th(IV) and VO(IV) complexes withSchiff bases of coumarin derivatives, European Journal of Medicinal Chemistry.44 (2009) 2904–2912. https://doi.org/10.1016/j.ejmech.2008.12.012.[13] Starynowicz, P., J. Lisowski, Monomeric, dimeric and polymeric lanthanide(III)complexes of a hexaazamacrocyclic imine derived from 2,6-diformylpyridine andethylenediamine, Polyhedron. 85 (2015) 232–238. https://doi.org/10.1016/j.poly.2014.08.032.[14] Chetana, P., V. Bhat, M. Dhale, Hetero-Binuclear Complexes of Lanthanum (III)Using Bridging N,N′-Bis(2-Pyridylmethyl)Oxamide and Terminal 1,10-Phenanthroline: Synthesis, Characterization and Biological Evaluation,International Journal of Pharmaceutical Sciences and Drug Research. 10 (2018).https://doi.org/10.25004/IJPSDR.2018.100606.[15] Barta, C.A., K. Sachs-Barrable, J. Jia, K.H. Thompson, K.M. Wasan, C. Orvig,Lanthanide containing compounds for therapeutic care in bone resorption disorders,Dalton Trans. (2007) 5019–5030. https://doi.org/10.1039/B705123A.[16] Mawani, Y., J.F. Cawthray, S. Chang, K. Sachs-Barrable, D.M. Weekes, K.M.Wasan, C. Orvig, In vitro studies of lanthanide complexes for the treatment ofosteoporosis, Dalton Trans. 42 (2013) 5999–6011. https://doi.org/10.1039/C2DT32373G.[17] Fryzuk, M.D., T.S. Haddad, S.J. Rettig, Phosphine complexes of yttrium,lanthanum, and lutetium. Synthesis, thermolysis, and fluxional behavior of thehydrocarbyl derivatives MR[N(SiMe2CH2PMe2)2]2. X-ray crystal structure of[cyclic] Y[N(SiMe2CHPMe2)(SiMe2CH2PMe2)][N(SiMe2CH2PMe2)2], Orga nometallics. 10 (1991) 2026–2036. https://doi.org/10.1021/om00052a059.[18] Roitershtein, D., Â. Domingos, L.C.J. Pereira, J.R. Ascenso, N. Marques,Coordination of 2,2‘-Bipyridyl and 1,10-Phenanthroline to Yttrium and LanthanumComplexes Based on a Scorpionate Ligand, Inorg. Chem. 42 (2003) 7666–7673.https://doi.org/10.1021/ic034838+.[19] Kretschmer, W.P., A. Meetsma, B. Hessen, N.M. Scott, S. Qayyum, R. Kempe,Lanthanum Dibromide Complexes of Sterically Demanding Aminopyridinato andAmidinate Ligands, Journal of inorganic and general chemistry. 632 (2006) 1936–1938. https://doi.org/10.1002/zaac.200600142.[20] Neelima, K. Poonia, S. Siddiqui, M. Arshad, D. Kumar, In vitro anticancer activitiesof Schiff base and its lanthanum complex, Spectrochimica Acta Part A: Molecularand Biomolecular Spectroscopy. 155 (2016) 146–154. https://doi.org/10.1016/j.saa.2015.10.015.[21] Al-Karaghouli, A.R., R.O. Day, J.S. Wood, Crystal structure of tetrakis(2,2’-bipyridine dioxide)lanthanum perchlorate: an example of cubic eight-coordination,Inorg. Chem. 17 (1978) 3702–3706. https://doi.org/10.1021/ic50190a076.[22] Al-Karaghouli, A.R., J.S. Wood, Crystal and molecular structures of theoctakis(pyridine N-oxide) lanthanide complexes M(PyO)8(ClO4)3, M = lanthanumand neodymium, Inorg. Chem. 18 (1979) 1177–1184. https://doi.org/10.1021/ic50195a001.[23] Morrow, J.R., S. Amin, C.H. Lake, M.R. Churchill, Synthesis, structure, anddynamic properties of the lanthanum(III) complex of 1,4,7,10-tetrakis(2-carbamoylethyl)-1,4,7,10-tetraazacyclododecane, ACS Publications. (2002).https://doi.org/10.1021/ic00073a017.[24] Zipp, A.P., S.G. Zipp, Disulfoxide complexes with lanthanum perchlorate, Journalof Inorganic and Nuclear Chemistry. 42 (1980) 395–397. https://doi.org/10.1016/0022-1902(80)80013-3.[25] Lescop, C., E. Belorizky, D. Luneau, P. Rey, Synthesis, Structures, and MagneticProperties of a Series of Lanthanum(III) and Gadolinium(III) Complexes withChelating Benzimidazole-Substituted Nitronyl Nitroxide Free Radicals. Evidencefor Antiferromagnetic GdIII−Radical Interactions, Inorg. Chem. 41 (2002) 3375–3384. https://doi.org/10.1021/ic0200038.[26] Kay, J., J.W. Moore, M.D. Glick, Structural studies of bridged lanthanide(III)complexes. Diaquotri(nicotinic acid)holmium(III) hexa(isothiocyanato)chromate(III) dihydrate and diaquotris(isonicotinato)lanthanum(III), Inorg. Chem. 11 (1972)2818–2827. https://doi.org/10.1021/ic50117a047.[27] Shi, T., A.C. Hopkinson, K.W.M. Siu, Coordination of Triply Charged Lanthanumin the Gas Phase: Theory and Experiment, Chemistry – A European Journal. 13(2007) 1142–1151. https://doi.org/10.1002/chem.200601074.[28] Shavaleev, N.M., S.V. Eliseeva, R. Scopelliti, J.-C.G. Bünzli, Influence ofSymmetry on the Luminescence and Radiative Lifetime of Nine-CoordinateEuropium Complexes, Inorg. Chem. 54 (2015) 9166–9173. https://doi.org/10.1021/acs.inorgchem.5b01580.[29] Hussain, A., K. Somyajit, B. Banik, S. Banerjee, G. Nagaraju, A.R. Chakravarty,Enhancing the photocytotoxic potential of curcumin on terpyridyl lanthanide(III)complex formation, Dalton Trans. 42 (2012) 182–195. https://doi.org/10.1039/C2DT32042H.[30] Feng, R., F.-L. Jiang, M.-Y. Wu, L. Chen, C.-F. Yan, M.-C. Hong, Structures andPhotoluminescent Properties of the Lanthanide Coordination Complexes withHydroxyquinoline Carboxylate Ligands, Crystal Growth & Design. 10 (2010)2306–2313. https://doi.org/10.1021/cg100026d.[31] Vasilescu, I.M., M. Taş, P.C. Junk, Structural diversity of lanthanum saccharinatesinduced by 1,10-phenanthroline: A synthetic and X-ray crystallographic study,Polyhedron. 87 (2015) 259–267. https://doi.org/10.1016/j.poly.2014.11.009.[32] Lu, Y., G. Deng, F. Miao, Z. Li, Metal-ion interactions with sugars. Crystalstructures and FT-IR studies of the LaCl3–ribopyranose and CeCl3–ribopyranosecomplexes, Carbohydrate Research. 339 (2004) 1689–1696. https://doi.org/10.1016/j.carres.2004.04.009.[33] Hussain, A., D. Lahiri, M.S. Ameerunisha Begum, S. Saha, R. Majumdar, R.R.Dighe, A.R. Chakravarty, Photocytotoxic Lanthanum(III) and Gadolinium(III)Complexes of Phenanthroline Bases Showing Light-Induced DNA CleavageActivity, Inorg. Chem. 49 (2010) 4036–4045. https://doi.org/10.1021/ic901791f.[34] Clapp, L.A., C.J. Siddons, J.R. Whitehead, D.G. VanDerveer, R.D. Rogers, S.T.Griffin, S.B. Jones, R.D. Hancock, Factors Controlling Metal-Ion Selectivity in theBinding Sites of Calcium-Binding Proteins. The Metal-Binding Properties ofAmide Donors. A Crystallographic and Thermodynamic Study, Inorg. Chem. 44(2005) 8495–8502. https://doi.org/10.1021/ic050632s.[35] Jiang, B., M. Wang, C. Li, J. Xie, DNA-binding and hydrolytic cleavage promotedby tetraazamacycle La(III) and Ce(III) complexes, Med Chem Res. 22 (2013) 3398–3404. https://doi.org/10.1007/s00044-012-0357-7.[36] Chetana, P.R., D.R. Navya, V.V. Bhat, B.S. Srinatha, M.A. Dhale, Studies on DNAInteractions and Biological Activities of Lanthanum(III) Complexes with 4-Quinoline Terpyridine and 1,10-Phenanthroline, Asian Journal of Chemistry. 31(2019) 1265–1274.[37] Premkumar, T., S. Govindarajan, N.P. Rath, V. Manivannan, New nine and tencoordinated complexes of lanthanides with bidentate 2-pyrazinecarboxylatecontaining hydrazinium cation, Inorganica Chimica Acta. 362 (2009) 2941–2946.https://doi.org/10.1016/j.ica.2008.12.014.[38] Yang, L., X. Hua, J. Xue, Q. Pan, L. Yu, W. Li, Y. Xu, G. Zhao, L. Liu, K. Liu, J.Chen, J. Wu, Interactions between Metal Ions and Carbohydrates. SpectroscopicCharacterization and the Topology Coordination Behavior of Erythritol withTrivalent Lanthanide Ions, Inorg. Chem. 51 (2012) 499–510. https://doi.org/10.1021/ic2019605.[39] Li, X.D., Gan, M. Tan, X. Wang, Synthesis and characterization of lanthanidecomplexes of 1,4,7,10,13-pentaazacyclopentadecane, Polyhedron. 16 (1997) 3991–3995. https://doi.org/10.1016/S0277-5387(97)00181-2.[40] Bray, D.J., J.K. Clegg, L.F. Lindoy, D. Schilter, Self-assembled Metallo supramolecular Systems Incorporating β-Diketone Motifs as Structural Elements,in: R. van Eldik, K. Bowman-James (Eds.), Advances in Inorganic Chemistry,Academic Press, 2006: pp. 1–37. https://doi.org/10.1016/S0898-8838(06)59001-4.[41] Patil, S., V. Naik, D. Bilehal, N. Mallur, Synthesis, Spectral and AntimicrobialStudies of Lanthanide (III) Nitrate Complexes with Terdentate ONO DonorHydrazones, Journal of Experimental Sciences 2011, 2(7): 15-20. 2 (2011) 15–20.[42] Casotto, G., B. Zarli, G. Faraglia, L. Sindellari, N-substituted ethylcarbamatecomplexes of thorium(IV) and lanthanum(III) nitrates, Inorganica Chimica Acta.95 (1984) 247–250. https://doi.org/10.1016/S0020-1693(00)84892-6.[43] Yan, C., Y. Zhang, S. Gao, B. Li, C. Huang, G. Xu, Synthesis and structure oftributylammonium hexanitrate lanthanum, Journal of Alloys and Compounds. 225(1995) 385–389. https://doi.org/10.1016/0925-8388(94)07043-1.[44] Perdih, F., A. Demšar, A. Pevec, S. Petriček, I. Leban, G. Giester, J. Sieler, H.W.Roesky, Synthesis and the crystal structures of a monoanionic tetrafluorodentateligand and its complex with lanthanum ion, Polyhedron. 20 (2001) 1967–1971.https://doi.org/10.1016/S0277-5387(01)00789-6.[45] Deng, Y.-H., G.-R. Gao, J. Liu, H. Liy. Synthesis and Crystal Structure of anUnusual Dodecacoordinated Lanthanum Complex by Phenanthroline and Nitrate(phenH)_2[La(NO_3)_5(phen)]·CH_3OH, Chinese Journal of StructuralChemistry 30 (2011) 690–696.[46] Pandey, O.P. Mononuclear and binuclear lanthanum(III) complexes of macrocyclicligands derived from 2,6-diacetylpyridine, Polyhedron. 6 (1987) 1021–1025.https://doi.org/10.1016/S0277-5387(00)80948-1.[47] Fedushkin, I.L., M.N. Bochkarev, H. Schumann, L. Esser, Binuclear complexes ofLa(III) and Eu(II) with the bridging naphthalene dianion. Synthesis and X-raycrystallographic analysis of [μ2-η4:η4-C10H8][LaI2(THF)3]2 and [μ2-η4:η4-C10H8][EuI(DME)2]2, Journal of Organometallic Chemistry. 489 (1995) 145–151. https://doi.org/10.1016/0022-328X(94)05145-2.[48] Guerriero, P., P.A. Vigato, J.-C.G. Bünzli, E. Moret, Macrocyclic complexes withlanthanoid salts part 38. Synthesis and luminescence study of homo- and hetero binuclear complexes of lanthanides with a new cyclic compartmental Schiff base,J. Chem. Soc., Dalton Trans. (1990) 647–655. https://doi.org/10.1039/DT9900000647.[49] Yang, E.-C., P.-X. Dai, X.-G. Wang, X.-J. Zhao, Two Discrete Lanthanum(III)Complexes with Bulky Aromatic Mixed Ligands: Syntheses, Crystal Structures andFluorescent Properties, Journal of inorganic and general chemistry. 635 (2009)346–350. https://doi.org/10.1002/zaac.200800392.[50] Inoue, M.B., M. Inoue, Q. Fernando, Yttrium(III) and lanthanum(III) complexes ofa 15-membered macrocycle with three pendant carboxymethyl groups, Acta CrystC. 50 (1994) 1037–1040. https://doi.org/10.1107/S0108270193011151.[51] Ma, S.-L., W.-X. Zhu, G.-H. Huang, D.-Q. Yuan, X. Yan, Novel three-dimensionalnetwork of lanthanum(III) complex {[La2(BTA)6(4,4′-bpdo)1.5]·1.5H2O}n (BTA= benzoyltrifluoroacetone; 4,4′-bpdo=4,4′-bipyridine dioxide), Journal ofMolecular Structure. 646 (2003) 89–94. https://doi.org/10.1016/S0022-2860(02)00617-8.[52] Zheng, K., L. Zhu, Y.-T. Li, Z.-Y. Wu, C.-W. Yan, Synthesis and crystal structureof new dicopper(II) complexes having asymmetric N,N′-bis(substituted)oxamideswith DNA/protein binding ability: In vitro anticancer activity and moleculardocking studies, Journal of Photochemistry and Photobiology B: Biology. 149(2015) 129–142. https://doi.org/10.1016/j.jphotobiol.2015.05.014.[53] Hall, J., D. Hüsken, R. Häner, Sequence-Specific Cleavage of RNA UsingMacrocyclic Lanthanide Complexes Conjugated to Oligonucleotides: A StructureActivity Study, Nucleosides and Nucleotides. 16 (1997) 1357–1368.https://doi.org/10.1080/07328319708006187.[54] Liu, X., Y. Li, Y. Ci, Interaction of the La3+-Morin Complex with DNA, AnalyticalSciences. 13 (1997) 939–944. https://doi.org/10.2116/analsci.13.939.[55] Branum, M.E., L. Que Jr., Double-strand DNA hydrolysis by dilanthanidecomplexes, JBIC. 4 (1999) 593–600. https://doi.org/10.1007/s007750050382.[56] Zhou, J., L. Wang, J. Wang, N. Tang, Synthesis, characterization, antioxidative andantitumor activities of solid quercetin rare earth(III) complexes, Journal ofInorganic Biochemistry. 83 (2001) 41–48. https://doi.org/10.1016/S0162-0134(00)00128-8.[57] Zhou, J.-H., S.-Q. Xia, J.-R. Chen, X.-S. Wang, B.-W. Zhang, H.-J. Zhang, P. Zou,X.-C. Ai, J.-P. Zhang, Surface binding and improved photodamage of thelanthanum ion complex of hypocrellin A to calf thymus DNA, Journal ofPhotochemistry and Photobiology A: Chemistry. 165 (2004) 143–147.https://doi.org/10.1016/j.jphotochem.2004.03.015.[58] Rittich, B., A. Španová, M. Falk, M.J. Beneš, M. Hrubý, Cleavage of doublestranded plasmid DNA by lanthanide complexes, Journal of Chromatography B.800 (2004) 169–173. https://doi.org/10.1016/j.jchromb.2003.09.011.[59] Qin, D., G. Qi, Z. Yang, J. Wu, Y. Liu, Fluorescence and Biological Evaluation ofthe La(III) and Eu(III) Complexes with 7-methoxychromone-3-carbaldehydeBenzoyl Hydrazone Schiff Base, J Fluoresc. 19 (2009) 409–418.https://doi.org/10.1007/s10895-008-0427-x.[60] Ansari, A.A., R.K. Sharma, Synthesis and Characterization of a Biologically ActiveLanthanum(III)–Catechin Complex and DNA Binding Spectroscopic Studies,Spectroscopy Letters. 42 (2009) 178–185. https://doi.org/10.1080/00387010902827718.[61] Mohanan, K., R. Aswathy, L.P. Nitha, N.E. Mathews, B.S. Kumari, Synthesis,spectroscopic characterization, DNA cleavage and antibacterial studies of a noveltridentate Schiff base and some lanthanide(III) complexes, Journal of Rare Earths.32 (2014) 379–388. https://doi.org/10.1016/S1002-0721(14)60081-8.[62] Asadi, Z., H. Mosallaei, M. Sedaghat, R. Yousefi, Competitive binding affinity oftwo lanthanum(III) macrocycle complexes toward DNA and bovine serum albuminin water, J Iran Chem Soc. 14 (2017) 2367–2385. https://doi.org/10.1007/s13738-017-1172-3.[63] Asadi, Z., N. Nasrollahi, H. Karbalaei-Heidari, V. Eigner, M. Dusek, N. Mobaraki,R. Pournejati, Investigation of the complex structure, comparative DNA-bindingand DNA cleavage of two water-soluble mono-nuclear lanthanum(III) complexesand cytotoxic activity of chitosan-coated magnetic nanoparticles as drug deliveryfor the complexes, Spectrochimica Acta Part A: Molecular and BiomolecularSpectroscopy. 178 (2017) 125–135. https://doi.org/10.1016/j.saa.2017.01.037.[64] Kostova, I., I. Manolov, S. Konstantinov, M. Karaivanova, Synthesis,physicochemical characterisation and cytotoxic screening of new complexes ofcerium, lanthanum and neodymium with Warfarin and Coumachlor sodium salts,European Journal of Medicinal Chemistry. 34 (1999) 63–68. https://doi.org/10.1016/S0223-5234(99)80041-5.[65] Manolov, I., I. Kostova, S. Konstantinov, M. Karaivanova, Synthesis,physicochemical characterization and cytotoxic screening of new complexes ofcerium, lanthanum and neodymium with Niffcoumar sodium salt, EuropeanJournal of Medicinal Chemistry. 34 (1999) 853–858. https://doi.org/10.1016/S0223-5234(99)00207-X.[66] Kostova, I., R. Kostova, G. Momekov, N. Trendafilova, M. Karaivanova,Antineoplastic activity of new lanthanide (cerium, lanthanum and neodymium)complex compounds, Journal of Trace Elements in Medicine and Biology. 18(2005) 219–226. https://doi.org/10.1016/j.jtemb.2005.01.002.[67] Kostova, I., G. Momekov, T. Tzanova, M. Karaivanova, Synthesis,Characterization, and Cytotoxic Activity of New Lanthanum(III) Complexes of Bis Coumarins, Bioinorganic Chemistry and Applications. 2006 (2006) e25651.https://doi.org/10.1155/BCA/2006/25651.[68] Kostova, I., V.K. Rastogi, W. Kiefer, A. Kostovski, New Lanthanum (III) Complex– Synthesis, Characterization, and Cytotoxic Activity, Archiv Der Pharmazie. 339(2006) 598–607. https://doi.org/10.1002/ardp.200600077.[69] Kostova, I., G. Momekov, Synthesis, characterization and cytotoxicity evaluationof new cerium(III), lanthanum(III) and neodymium(III) complexes, AppliedOrganometallic Chemistry. 21 (2007) 226–233. https://doi.org/10.1002/aoc.1205.[70] Kostova, I., N. Trendafilova, G. Momekov, Theoretical, spectral characterizationand antineoplastic activity of new lanthanide complexes, Journal of Trace Elementsin Medicine and Biology. 22 (2008) 100–111. https://doi.org/10.1016/j.jtemb.2007.10.005.[71] Yang, Z.-Y., B.-D. Wang, Y.-H. Li, Study on DNA-binding properties andcytotoxicity in L1210 of La(III) complex with PMBP-isonicotinoyl hydrazone,Journal of Organometallic Chemistry. 691 (2006) 4159–4166.https://doi.org/10.1016/j.jorganchem.2006.06.002.[72] Hussain, A., S. Gadadhar, T.K. Goswami, A.A. Karande, A.R. Chakravarty,Photoactivated DNA cleavage and anticancer activity of pyrenyl-terpyridinelanthanide complexes, European Journal of Medicinal Chemistry. 50 (2012) 319–331. https://doi.org/10.1016/j.ejmech.2012.02.011.[73] Wang, Z.-M., H.-K. Lin, S.-R. Zhu, T.-F. Liu, Y.-T. Chen, Spectroscopy,cytotoxicity and DNA-binding of the lanthanum(III) complex of an l-valinederivative of 1,10-phenanthroline, Journal of Inorganic Biochemistry. 89 (2002)97–106. https://doi.org/10.1016/S0162-0134(01)00395-6.[74] Biersack, B., R. Diestel, C. Jagusch, F. Sasse, R. Schobert, Metal complexes ofnatural melophlins and their cytotoxic and antibiotic activities, Journal of InorganicBiochemistry. 103 (2009) 72–76. https://doi.org/10.1016/j.jinorgbio.2008.09.005.[75] Durgo, K., I. Halec, I. Šola, J. Franekić, Genotoxic effect of quercetin andlanthanum complex on human cervical cancer cells, Archives for OccupationalHygiene and Toxicology. 62 (2011) 221–226. https://doi.org/10.2478/10004-1254-62-2011-2122.[76] Heffeter, P., M.A. Jakupec, W. Körner, S. Wild, N.G. von Keyserlingk, L. Elbling,H. Zorbas, A. Korynevska, S. Knasmüller, H. Sutterlüty, M. Micksche, B.K.Keppler, W. Berger, Anticancer activity of the lanthanum compound [tris(1,10-phenanthroline)lanthanum(III)]trithiocyanate (KP772; FFC24), BiochemicalPharmacology. 71 (2006) 426–440. https://doi.org/10.1016/j.bcp.2005.11.009.[77] Shahraki, S., F. Shiri, M. Heidari Majd, S. Dahmardeh, Anti-cancer study and wheyprotein complexation of new lanthanum(III) complex with the aim of achievingbioactive anticancer metal-based drugs, Journal of Biomolecular Structure andDynamics. 37 (2019) 2072–2085. https://doi.org/10.1080/07391102.2018.1476266.[78] Abo El-Maali, N., A.Y. Wahman, A.A.M. Aly, A.Y. Nassar, D.M. Sayed,Anticancer activity of lanthanum (III) and europium (III) 5-fluorouracil complexeson Caco-2 cell line, Applied Organometallic Chemistry. 34 (2020) e5594.https://doi.org/10.1002/aoc.5594.[79] Wang, B., Z.-Y. Yang, P. Crewdson, D. Wang, Synthesis, crystal structure andDNA-binding studies of the Ln(III) complex with 6-hydroxychromone-3-carbaldehyde benzoyl hydrazone, Journal of Inorganic Biochemistry. 101 (2007)1492–1504. https://doi.org/10.1016/j.jinorgbio.2007.04.007.[80] Zhou, J., L. Wang, J. Wang, N. Tang, Synthesis, characterization, antioxidative andantitumor activities of solid quercetin rare earth(III) complexes, Journal ofInorganic Biochemistry. 83 (2001) 41–48. https://doi.org/10.1016/S0162-0134(00)00128-8.[81] Hassan, S.S., E.F. Mohamed, Antimicrobial, antioxidant and antitumor activities ofNano-Structure Eu (III) and La (III) complexes with nitrogen donor tridentateligands, Applied Organometallic Chemistry. 34 (2020) e5258. https://doi.org/10.1002/aoc.5258.[82] Gonca, S., S. Özdemi̇ r, A. Tekgul, C. Ünlü, K. Ocakoğlu, N. Di̇ zge, Synthesis andcharacterization of perovskite type of La1-xBaxMnO3 nanoparticles withinvestigation of biological activity, Advanced Powder Technology. 33 (2022).https://doi.org/10.1016/j.apt.2021.10.038.[83] Avaji, P.G., B.N. Reddy, S.A. Patil, P.S. Badami, Synthesis, spectralcharacterization, biological and fluorescence studies of lanthanum(III) complexeswith 3-substituted-4-amino-5-hydrazino-1,2,4-triazole Schiff bases, Transition MetChem. 31 (2006) 842–848. https://doi.org/10.1007/s11243-006-0066-5.[84] Avaji, P.G., S.A. Patil, P.S. Badami, Synthesis, spectral, thermal, solid state d.c.electrical conductivity and biological studies of lanthanum(III) and thorium(IV)complexes with thiocarbohydrazone, Transition Met Chem. 32 (2007) 379–386.https://doi.org/10.1007/s11243-006-0178-y.[85] El-Gamel, N.E.A. Thermal studies, structural characterization, and antimicrobialevaluation of coordinated metal complexes containing salen moiety, MonatshChem. 144 (2013) 1627–1634. https://doi.org/10.1007/s00706-013-1049-9.[86] Andotra, S., N. Kalgotra, S.K. Pandey, Syntheses, Characterization, Thermal, andAntimicrobial Studies of Lanthanum(III) Tolyl/Benzyldithiocarbonates,Bioinorganic Chemistry and Applications. 2014 (2014) e780631. https://doi.org/10.1155/2014/780631.[87] Köse, M., G. Ceyhan, E. Atci, V. McKee, M. Tümer, Synthesis, structuralcharacterization and photoluminescence properties of a novel La(III) complex,Journal of Molecular Structure. 1088 (2015) 129–137. https://doi.org/10.1016/j.molstruc.2015.02.023.[88] Alghool, S., H.F. Abd El-Halim, M.S. Abd El-sadek, I.S. Yahia, L.A. Wahab,Synthesis, thermal characterization, and antimicrobial activity of lanthanum,cerium, and thorium complexes of amino acid Schiff base ligand, J Therm AnalCalorim. 112 (2013) 671–681. https://doi.org/10.1007/s10973-012-2628-4.[89] Niroomand, S., M. Khorasani-Motlagh, M. Noroozifar, S. Jahani, A. Moodi,Photochemical and DFT studies on DNA-binding ability and antibacterial activityof lanthanum(III)-phenanthroline complex, Journal of Molecular Structure. 1130(2017) 940–950. https://doi.org/10.1016/j.molstruc.2016.10.076.[90] Patil, S.S., B.P. Langi, M.N. Gurav, D.K. Patil, Synthesis, Physical and SpectralInvestigations and Biological Studies of Mixed Ligand Lanthanum Complexes,Annals of the Romanian Society for Cell Biology. (2021) 10559–10569.[91] Köse, M., G. Ceyhan, E. Atci, V. McKee, M. Tümer, Synthesis, structuralcharacterization and photoluminescence properties of a novel La(III) complex,Journal of Molecular Structure. 1088 (2015) 129–137. https://doi.org/10.1016/j.molstruc.2015.02.023.[92] Horrocks Jr., W.D., Schmidt, D.R. Sudnick, C. Kittrell, R.A. Bernheim, Laser induced lanthanide ion luminescence lifetime measurements by direct excitation ofmetal ion levels. A new class of structural probe for calcium-binding proteins andnucleic acids, ACS Publications. (2002). https://doi.org/10.1021/ja00449a079.[93] Horrocks Jr., W.D., Sudnick D.R. Lanthanide ion probes of structure in biology.Laser-induced luminescence decay constants provide a direct measure of thenumber of metal-coordinated water molecules, ACS Publications. (2002).https://doi.org/10.1021/ja00496a010.[94] Bkouche-Waksman, I., J. Guilhem, C. Pascard, B. Alpha, R. Deschenaux, J.-M.Lehn, Crystal Structures of the Lanthanum(III), Europium(III), and Terbium(III)Cryptates of Tris(bipyridine) Macrobicyclic Ligands, Helvetica Chimica Acta. 74(1991) 1163–1170. https://doi.org/10.1002/hlca.19910740603.[95] Zhu, Y.-J., J.-X. Chen, W.-H. Zhang, Z.-G. Ren, Y. Zhang, J.-P. Lang, S.-W. Ng,Syntheses, crystal structures and luminescent properties of two novel lanthanide/4-pya complexes: [Ln(4-pya)3(H2O)2]2 (Ln = Eu, La; 4-pya=trans-4-pyridylacrylate), Journal of Organometallic Chemistry. 690 (2005) 3479–3487.https://doi.org/10.1016/j.jorganchem.2005.04.041.[96] Xiong, D.-B., M.-R. Li, W. Liu, H.-H. Chen, X.-X. Yang, J.-T. Zhao, Synthesis,structure and luminescence property of two lanthanum phosphite hydrates:La2(H2O)x(HPO3)3 (x=1,2), Journal of Solid State Chemistry. 179 (2006) 2571–2577. https://doi.org/10.1016/j.jssc.2006.04.035.[97] Tang, K.-Z., J. Zhang, Y. Tang, W.-S. Liu, M.-Y. Tan, Y.-X. Sun, Preparation,crystal structure and luminescent properties of the 3-D netlike supramolecularlanthanide picrate complexes with 2,2′-[1,2-phenylenebis(oxy)]bis(N-benzylaceta mide), Inorganica Chimica Acta. 359 (2006) 1207–1214. https://doi.org/10.1016/j.ica.2005.10.004.[98] Dou, W., J.-N. Yao, W.-S. Liu, Y.-W. Wang, J.-R. Zheng, D.-Q. Wang, Crystalstructure and luminescent properties of new rare earth complexes with a flexibleSalen-type ligand, Inorganic Chemistry Communications. 10 (2007) 105–108.https://doi.org/10.1016/j.inoche.2006.09.017.[99] Galyametdinov, Y.G., A.A. Knyazev, V.I. Dzhabarov, T. Cardinaels, K. Driesen,C. Görller-Walrand, K. Binnemans, Polarized Luminescence from AlignedSamples of Nematogenic Lanthanide Complexes, Advanced Materials. 20 (2008)252–257. https://doi.org/10.1002/adma.200701714.[100] Regulacio, M.D., M.H. Pablico, J.A. Vasquez, P.N. Myers, S. Gentry, M. Prushan,S.-W. Tam-Chang, S.L. Stoll, Luminescence of Ln(III) DithiocarbamateComplexes (Ln = La, Pr, Sm, Eu, Gd, Tb, Dy), Inorg. Chem. 47 (2008) 1512–1523.https://doi.org/10.1021/ic701974q.[101] Li, Y., Y. Zhao, Intramolecular Energy Transfer and Co-luminescence Effect inRare Earth Ions (La, Y, Gd and Tb) Doped with Eu3+ β-diketone Complexes, JFluoresc. 19 (2009) 641–647. https://doi.org/10.1007/s10895-008-0456-5.[102] Roof, I.P., T.-C. Jagau, W.G. Zeier, M.D. Smith, H.-C. zur Loye, Crystal Growthof a New Series of Complex Niobates, LnKNaNbO5 (Ln = La, Pr, Nd, Sm, Eu, Gd,and Tb): Structural Properties and Photoluminescence, Chem. Mater. 21 (2009)1955–1961. https://doi.org/10.1021/cm9003245.[103] Granadeiro, C.M., R.A.S. Ferreira, P.C.R. Soares-Santos, L.D. Carlos, H.I.S.Nogueira, Lanthanopolyoxometalates as Building Blocks for MultiwavelengthPhotoluminescent Organic–Inorganic Hybrid Materials, European Journal ofInorganic Chemistry. 2009 (2009) 5088–5095. https://doi.org/10.1002/ejic.200900615.[104] Hu, M., H.-F. Li, J.-Y. Yao, Y. Gao, Z.-L. Liu, H.-Q. Su, Hydrothermal synthesisand characterization of two 2-D lanthanide-2,2′-bipyridine-3,3′-dicarboxylatecoordination polymers based on zigzag chains, Inorganica Chimica Acta. 363(2010) 368–374. https://doi.org/10.1016/j.ica.2009.11.001.[105] Chai, X.-C., Y.-Q. Sun, R. Lei, Y.-P. Chen, S. Zhang, Y.-N. Cao, H.-H. Zhang, ASeries of Lanthanide Frameworks with a Flexible Ligand, N,N′-Diacetic AcidImidazolium, in Different Coordination Modes, Crystal Growth & Design. 10(2010) 658–668. https://doi.org/10.1021/cg901075r.[106] Yao, M., Y. Li, M. Hossu, A.G. Joly, Z. Liu, Z. Liu, W. Chen, Luminescence ofLanthanide–Dimethyl Sulfoxide Compound Solutions, J. Phys. Chem. B. 115(2011) 9352–9359. https://doi.org/10.1021/jp202350p.[107] Wang, W., Y. Huang, T. Li, G.-N. Lu, Y. Yang, N. Tang, H.-B. Song, Dinuclearrare-earth picrate complexes based on a multidentate amide ligand: syntheses,crystal structures, and luminescence properties, Journal of Coordination Chemistry.65 (2012) 4041–4053. https://doi.org/10.1080/00958972.2012.731503.[108] Bennett, S.D., B.A. Core, M.P. Blake, S.J.A. Pope, P. Mountford, B.D. Ward,Chiral lanthanide complexes: coordination chemistry, spectroscopy, and catalysis,Dalton Trans. 43 (2014) 5871–5885. https://doi.org/10.1039/C4DT00114A.[109] Yin, X., J.-N. Tang, G.-H. Pan, W.-M. Tian, W.-J. Xu, Z.-J. Huang, HydrothermalSynthesis, Structure, Properties of a Novel Supramolecular Complex:[LaCd(bpy)4(NO3)5], Molecular Crystals and Liquid Crystals. 606 (2015) 208–215. https://doi.org/10.1080/15421406.2014.905318.[110] Nedilko, S.G., O. Chukova, V. Chornii, V. Degoda, K. Bychkov, K. Terebilenko,M. Slobodyanik, Luminescence properties of the new complex La,BiVO4:Mo,Eucompounds as materials for down-shifting of VUV–UV radiation, RadiationMeasurements. 90 (2016) 282–286. https://doi.org/10.1016/j.radmeas.2016.02.027.[111] Allendorf, M.D., C.A. Bauer, R.K. Bhakta, R.J.T. Houk, Luminescent metal–organic frameworks, Chem. Soc. Rev. 38 (2009) 1330–1352. https://doi.org/10.1039/B802352M.[112] Amoroso, A.J., S.J.A. Pope, Using lanthanide ions in molecular bioimaging, Chem.Soc. Rev. 44 (2015) 4723–4742. https://doi.org/10.1039/C4CS00293H.[113] Wang, W., Y. Huang, T. Li, G.-N. Lu, Y. Yang, N. Tang, H.-B. Song, Dinuclearrare-earth picrate complexes based on a multidentate amide ligand: syntheses,crystal structures, and luminescence properties, Journal of Coordination Chemistry.65 (2012) 4041–4053. https://doi.org/10.1080/00958972.2012.731503.
