To aid in knowledge of macrocyclic complexes and biomedical scientists, we are presenting here a review article with compilation of work done so far along in relation to macrocyclic ligands and their metal complexes. The metal ion chemistry of macrocyclic ligands has now become a major subdivision of coordination chemistry. This overview focuses on developments in design, synthesis, and self-assembly of metal-based architectures and ligands related to macrocyclic chemistry. 1. Introduction and Scope Macrocycles occupy a unique segment of chemical space. In the past decade, their chemical diversity expanded significantly, supported by advances in bioinformatics and synthetic methodology. As a consequence, this structural type has now been successfully tested on most biological target classes. The goal of this paper is to put into perspective the current applications and opportunities associated with macrocycles [1]. Macrocycles are defined herein as molecules containing at least one large ring composed of nine or more atoms. Macrocycles have several features that make them interesting in efforts to tackle “difficult” targets with extended binding sites [2]. Because of their size and complexity, they can engage targets through numerous and spatially distributed binding interactions, thereby increasing both binding affinity and selectivity. Furthermore, cyclization provides a degree of structural preorganization that may reduce the entropy cost of receptor binding compared to linear analogues [3, 4]. A significant number of macrocyclic drugs are currently on the market, predominantly of natural product origin with complex structures [5]. This paper is dedicated to explore the field of macrocycles and to highlight salient features of their versatile chemistry. Cyclization of a linear molecule into a macrocyclic ring constitutes a significant change in molecular shape. This transformation restricts the degrees of conformational freedom of the molecule and imposes structural organization which was absent in the linear precursor [6]. Since the birth of macrocycles as early as 1936 [7], the field only began to blossom in early 1960s with the pioneering work of Thompson and Busch [8]. In such a large subject, this paper can focus only on certain aspects of macrocyclic chemistry. Medicinal chemists have long used macrocyclization as a tool in drug discovery. A classic illustration of this technique was the discovery of potent cyclic peptide somatostatin mimics three decades ago [9, 10]. The method of cyclization since then developed into a general paradigm in
References
[1]
E. Marsault and M. L. Peterson, “Macrocycles are great cycles: applications, opportunities, and challenges of synthetic macrocycles in drug discovery,” Journal of Medicinal Chemistry, vol. 54, pp. 1961–2014, 2011.
[2]
E. M. Driggers, S. P. Hale, J. Lee, and N. K. Terrett, “The exploration of macrocycles for drug discovery—an underexploited structural class,” Nature Reviews Drug Discovery, vol. 7, no. 7, pp. 608–624, 2008.
[3]
J. Mallinson and I. Collins, “Macrocycles in new drug discovery,” Future Medicinal Chemistry, vol. 4, no. 11, pp. 1409–1438, 2012.
[4]
E. De Lorbe, J. H. Clements, B. B. Whiddon, and S. F. Martin, “Thermodynamic and structural effects of macrocyclic constraints in protein-ligand interactions,” ACS Medicinal Chemistry Letters, vol. 1, pp. 448–452, 2012.
[5]
F. Giordanetto and J. Kihlberg, “Macrocyclic drugs and clinical candidates: what can medicinal chemists learn from their properties?” Journal of Medicinal Chemistry, vol. 57, no. 2, pp. 278–295, 2014.
[6]
A. R. Bogdan, N. L. Davies, and K. James, “Comparison of diffusion coefficients for matched pairs of macrocyclic and linear molecules over a drug-like molecular weight range,” Organic and Biomolecular Chemistry, vol. 9, no. 22, pp. 7727–7733, 2011.
[7]
J. V. Alphen and R. T. Chim, “On aliphatic polyamines III,” Pays-Bas, vol. 55, pp. 835–844, 1936.
[8]
M. C. Thompson and D. H. Busch, “Templated organic synthesis,” Chemical and Engineering News, vol. 40, pp. 56–57, 1962.
[9]
D. F. Veber, F. W. Holly, R. F. Nutt et al., “Highly active cyclic and bicyclic somatostatin analogues of reduced ring size,” Nature, vol. 280, no. 5722, pp. 512–514, 1979.
[10]
D. F. Veber, R. M. Freidlinger, D. S. Perlow et al., “A potent cyclic hexapeptide analogue of somatostatin,” Nature, vol. 292, no. 5818, pp. 55–58, 1981.
[11]
S. Poojari, P. Naik, and G. Krishnamurthy, “Synthesis of macrocycles containing 1,3,4-oxadiazole and pyridine moieties,” Tetrahedron Letters, vol. 55, no. 2, pp. 305–309, 2014.
[12]
R. D. Hancock and A. E. Martell, “Ligand design for selective complexation of metal ions in aqueous solution,” Chemical Reviews, vol. 89, no. 8, pp. 1875–1914, 1989.
[13]
R. D. Hancock, S. M. Dobson, and J. C. A. Boeyens, “Metal ion size selectivity of 1-Thia4, 7-diazacyclononane (9-aneN:S), and other tridentate macrocycles. A study by molecular mechanics calculation, structure determination, and formation constant determination of complexes of 9-aneN 2S,” Inorganica Chimica Acta, vol. 133, no. 2, pp. 221–231, 1987.
[14]
B. C. Westerby, K. L. Juntunen, G. H. Leggett, et al., “Macrocyclic polyamino polythiaether ligands with NxS4-x and NxS5-x donor sets: protonation constants, stability constants, and kinetics of complex formation with the aquocopper(II) ion,” Inorganic Chemistry, vol. 30, no. 9, pp. 2109–2120, 1991.
[15]
T. L. Walker, W. Malasi, S. Bhide, et al., “Synthesis and characterization of 1,8-dithia-4,11-diazacyclotetradecane,” Tetrahedron Letters, vol. 53, no. 48, pp. 6548–6551, 2012.
[16]
G. Papini, S. Alidori, J. S. Lewis et al., “Synthesis and characterization of the copper(ii) complexes of new N2S2-donor macrocyclic ligands: synthesis and in vivo evaluation of the 64Cu complexes,” Dalton Transactions, vol. 7, pp. 177–184, 2009.
[17]
G. Aquilanti, M. Giorgetti, M. Minicucci et al., “A study on the coordinative versatility of new N,S-donor macrocyclic ligands: XAFS, and Cu2+ complexation thermodynamics in solution,” Dalton Transactions, vol. 40, no. 12, pp. 2764–2777, 2011.
[18]
M. Kodama, T. Koike, N. Hoshiga, R. MacHida, and E. Kimura, “Metal chelates of sulphur-containing polyamine macrocycles and oxygenation of the corresponding cobalt(II) complexes,” Journal of the Chemical Society, Dalton Transactions, no. 4, pp. 673–678, 1984.
[19]
R. Huszánk, G. Lendvay, and O. Horváth, “Air-stable, heme-like water-soluble iron(II) porphyrin: in situ preparation and characterization,” Journal of Biological Inorganic Chemistry, vol. 12, no. 5, pp. 681–690, 2007.
[20]
M. B. Deshmukh, K. N. Alasundkar, D. K. Salunkhe, and S. A. Sankpal, “Synthesis and evaluation of dibenzo- 18—crown -6 ether containing hydrazine derivative as antibacterial drug derivatives,” Journal of Chemical and Pharmaceutical Research, vol. 2, no. 4, pp. 437–441, 2010.
[21]
M. Tyagi, S. Chandra, and S. K. Choudhary, “Tetraaza macrocyclic complexes: synthesis, spectral and antifungal studies,” Journal of Chemical and Pharmaceutical Research, vol. 3, no. 1, pp. 56–63, 2011.
[22]
C. P. Bhasin, K. V. Goswami, and M. Gongiwala, “A novel approach to macrocyclic complexes with mixed ligands: synthesis, characterization, catalytic and antimicrobial studies of some alkylene dithiophosphate derivatives of macrocyclic complexes of Ni(II),” Journal of Indian Council of Chemists, vol. 26, no. 1, pp. 12–22, 2009.
[23]
D. P. Singh and R. M. Chopra, “Divalent metal complexes with ligand derived from ninhydrin and aromatic diamines and comparisons of their reactivities,” Rasayan Journal of Chemistry, vol. 1, no. 1, pp. 93–98, 2008.
[24]
V. Pawar, S. Joshi, and V. Uma, “Synthesis, antioxidant and biocidal features of macrocyclic Schiff bases with oxoanadium (V) complexes,” Journal of Chemical and Pharmaceutical Research, vol. 3, no. 1, pp. 169–175, 2011.
[25]
D. Kumar, S. Sharma, and R. C. Sharma, “Characterization and biological studies of some newly synthesized macrocyclic complexes of bivalent metal ions,” Journal of the Indian Chemical Society, vol. 87, no. 12, pp. 1547–1550, 2010.
[26]
A. Bianchi, L. Calabi, F. Corana et al., “Thermodynamic and structural properties of Gd(III) complexes with polyamino-polycarboxylic ligands: basic compounds for the development of MRI contrast agents,” Coordination Chemistry Reviews, vol. 204, no. 1, pp. 309–393, 2000.
[27]
S. Chandra, D. Jain, and B. Ratnam, “Synthesis and spectroscopic characterization of copper (II) metal complexes of a 16 membered pentaaza (N5) bis (macrocyclic) complexes,” Journal of Chemical and Pharmaceutical Research, vol. 2, no. 1, pp. 533–538, 2010.
[28]
X. Xiao, L. Yan, Z. Mei, D. Zhu, and L. Xua, “Two novel macrocyclic organotin (IV) carboxylates based on amide carboxylic acids,” RSC Advances, vol. 4, no. 201, pp. 3096–3108, 2014.
[29]
M. A. Tetilla, M. C. Aragoni, M. Arca et al., “Colorimetric response to anions by a “robust” copper(II) complex of a [9]aneN3 pendant arm derivative: CN- and I- selective sensing,” Chemical Communications, vol. 47, no. 13, pp. 3805–3830, 2011.
[30]
B. P. Burke and S. J. Archibald, “Macrocyclic coordination chemistry,” Annual Reports on the Progress of Chemistry, Section A: Inorganic Chemistry, vol. 109, pp. 227–232, 2013.
[31]
Z. Guo, H. Yan, Z. Li, and Z. Lu, “Synthesis of mono- and di-[12]aneN3 ligands and study on the catalytic cleavage of RNA model 2-hydroxypropyl-p-nitrophenyl phosphate with their metal complexes,” Organic and Biomolecular Chemistry, vol. 9, pp. 6788–6796, 2011.
[32]
J. D. Silversides, C. C. Allan, and S. J. Archibald, “Copper(II) cyclam-based complexes for radiopharmaceutical applications: synthesis and structural analysis,” Dalton Transactions, no. 9, pp. 971–978, 2007.
[33]
X. Chen, Q. Du, R. Jin et al., “Diverse bonding modes of the pentalene ligand in binuclear cobalt carbonyl complexes,” Inorganica Chimica Acta, vol. 415, pp. 111–124, 2014.
[34]
D. W？hrle, O. Tsaryova, A. Semioshkin, D. Gabel, and O. Suvorova, “Synthesis and photochemical properties of phthalocyanine zinc(II) complexes containing o-carborane units,” Journal of Organometallic Chemistry, vol. 747, pp. 98–105, 2013.
[35]
B. Birsoz, I. Narb, and A. Gul, “Synthesis, characterization and electrochemical investigation of phthalocyanines carrying 96 boron atoms,” Journal of Organometallic Chemistry, vol. 755, pp. 64–71, 2014.
[36]
A. Sarnicka, P. Starynowicz, and J. Lisowski, “Controlling the macrocycle size by the stoichiometry of the applied template ion,” Chemical Communications, vol. 48, no. 16, pp. 2237–2239, 2012.
[37]
E. L. Gavey, Y. Beldjoudi, J. M. Rawson, T. C. Stamatatos, and M. Pilkington, “Slow relaxation in the first penta-aza Dy(iii) macrocyclic complex,” Chemical Communications, vol. 50, no. 28, pp. 3741–3743, 2014.
[38]
M. M. Khan, “Spectroscopic and physico-chemical characterization of Ir(I) and Ru(III) complexes of 32-membered unsymmetrical dinucleating macrocyclic ligand,” Journal of Inclusion Phenomena and Macrocyclic Chemistry, vol. 78, pp. 257–263, 2014.
[39]
H. Naeimi, J. Safari, and A. Heidarnezhad, “Synthesis of Schiff base ligands derived from condensation of salicylaldehyde derivatives and synthetic diamine,” Dyes and Pigments, vol. 73, no. 2, pp. 251–253, 2007.
[40]
K. Ambroziak, R. Pelech, E. Milchert, T. Dziembowska, and Z. Rozwadowski, “New dioxomolybdenum(VI) complexes of tetradentate Schiff base as catalysts for epoxidation of olefins,” Journal of Molecular Catalysis A: Chemical, vol. 211, no. 1-2, pp. 9–16, 2004.
[41]
W. A. Zoubi, F. Kandil, and M. K. Chebani, “Synthesis of macrocyclic schiff bases based on pyridine-2,6-dicarbohydrazide and their use in metal cations extraction,” Organic Chemistry: Current Research, vol. 1, no. 1, pp. 1–7, 2012.
[42]
C. J. Pedersen, “Cyclic polyethers and their complexes with metal salts,” Journal of the American Chemical Society, vol. 89, no. 26, pp. 7017–7036, 1967.
[43]
W. Walkowiak and C. A. Kozlowski, “Macrocycle carriers for separation of metal ions in liquid membrane processes—a review,” Desalination, vol. 240, pp. 186–197, 2009.
[44]
E. R. Kay, D. A. Leigh, and F. Zerbetto, “Synthetische molekulare Motoren und mechanische Maschinen,” Angewandte Chemie International Edition, vol. 119, pp. 72–196, 2007.
[45]
J. F. Stoddart and H. M. Colquhoun, “Big and little Meccano,” Tetrahedron, vol. 64, no. 36, pp. 8231–8263, 2008.
[46]
J. D. Crowley, S. M. Goldup, A.-L. Lee, D. A. Leigh, and R. T. McBurney, “Active metal template synthesis of rotaxanes, catenanes and molecular shuttles,” Chemical Society Reviews, vol. 38, no. 6, pp. 1530–1541, 2009.
[47]
X. Ma and H. Tian, “Bright functional rotaxanes,” Chemical Society Reviews, vol. 39, pp. 70–80, 2010.
[48]
D. Qu and H. Tian, “Novel and efficient templates for assembly of rotaxanes and catenanes,” Chemical Science, vol. 2, no. 6, pp. 1011–1015, 2011.
[49]
T. Ogoshi, D. Yamafuji, T. Aoki, and T.-A. Yamagishi, “Thermally responsive shuttling behavior of a pillar[6]arene-based [2]rotaxane,” Chemical Communications, vol. 48, no. 54, pp. 6842–6844, 2012.
[50]
G. T. Spence, M. B. Pitak, and P. D. Beer, “Anion-induced shuttling of a naphthalimide triazolium rotaxane,” Chemistry European Journal, vol. 18, no. 23, pp. 7100–7108, 2012.
[51]
M. Baroncini, S. Silvi, M. Venturi, and A. Credi, “Photoactivated directionally controlled transit of a non-symmetric molecular axle through a macrocycle,” Angewandte Chemie International Edition, vol. 51, no. 17, pp. 4223–4226, 2012.
[52]
Y. Li, W. Yang, H. Liu, and L. Chi, “Design and assembly of rotaxane-based molecular switches and machines,” Small, vol. 8, no. 4, pp. 504–516, 2012.
[53]
C. Gao, X. Ma, Q. Zhang, Q.-C. Wang, D.-H. Qu, and H. Tian, “A light-powered stretch-contraction supramolecular system based on cobalt coordinated [1]rotaxane,” Organic & Biomolecular Chemistry, vol. 9, pp. 1126–1132, 2011.
[54]
W. Zhou, H. Zhang, H. Li, Y. Zhang, Q. Wang, and D. Qu, “A bis-spiropyran-containing multi-state [2]rotaxane with fluorescence output,” Tetrahedron, vol. 69, pp. 5319–5325, 2014.
[55]
B. Zheng, F. Klautzsch, M. X. F. Huanga, and C. A. Schalley, “Self-sorting of crown ether/secondary ammonium ion hetero-[c2]daisy chain pseudorotaxanes,” Organic Chemistry Frontiers, vol. 1, no. 5, pp. 532–540, 2014.
[56]
S. M. Pluzhnik-Gladyr, V. C. Kravtsov, M. S. Fonari, and G. L. Kamalov, “Halogen impact into new oxonium benzo-crown ether complexes with tetrachloro- and tetrabromoaurates(iii),” Dalton Transactions, vol. 43, no. 19, pp. 7087–7095, 2014.
[57]
Q. Zhou, L. Su, T. Jiang, et al., “Copper/iron-catalyzed Ullmann coupling of diiodo- and dibromoarenes and diphenols for the synthesis of aryl ether macrocycles,” Tetrahedron, vol. 70, no. 6, pp. 1125–1132, 2014.
[58]
N. Sommer and H. A. Staab, “Zur konjugation in makrocyclischen bindungssystemen V cyclische meta-verknüpfte arylen-？ther,” Tetrahedron Letters, vol. 7, no. 25, pp. 2837–2841, 1966.
[59]
A. Nezhadali and M. Akbarpour, “Selective transport of silver(I) ion through polymer membranes containing thioether donor macrocycles as carriers,” E-Journal of Chemistry, vol. 5, no. 2, pp. 271–274, 2008.
[60]
F. B. L. Cougnon and J. K. M. Sanders, “Evolution of dynamic combinatorial chemistry,” Accounts of Chemical Research, vol. 45, no. 12, pp. 2211–2221, 2012.
[61]
M. S. Collins, M. E. Carnes, A. C. Sather et al., “Pnictogen-directed synthesis of discrete disulfide macrocycles,” Chemical Communications, vol. 49, no. 59, pp. 6599–6601, 2013.
[62]
L. S. Rajni, “A review on synthesis and application of macrocyclic ligands and their transition metal complexes,” International Journal of Advanced Engineering Applications, vol. 6, no. 6, pp. 74–78, 2012.
[63]
M. U. Rehman, M. Imran, M. Arif, and M. Farooq, “Synthesis, characterization and metal picrate extraction studies of salicylaldehyde derived macrocyclic schiff bases,” International Research Journal of Pure and Applied Chemistry, vol. 4, no. 2, pp. 243–250, 2014.
[64]
L. F. Lindoy, G. V. Meehan, I. M. Vasilescu, H. J. Kim, J.-E. Lee, and S. S. Lee, “Transition and post-transition metal ion chemistry of dibenzo-substituted, mixed-donor macrocycles incorporating five donor atoms,” Coordination Chemistry Reviews, vol. 254, no. 15-16, pp. 1713–1725, 2010.
[65]
S.-G. Lee, K.-M. Park, Y. Habata, and S. S. Lee, “Endo- and exocyclic supramolecular complexes of mixed-donor macrocycles via [1:1] and [2:2] cyclizations,” Inorganic Chemistry, vol. 52, no. 15, pp. 8416–8426, 2013.
[66]
B. Jiang, S. Cai, F. Feng, and J. Xie, “Spectral analysis and catalytic activity in the hydrolysis of the phosphate ester by aza-crown ether cerium (III) complex,” Journal of Chemical and Pharmaceutical Research, vol. 6, no. 3, pp. 1520–1526, 2014.
[67]
G. Blanita, M. Bucsa, and M. Vlassa, “Convenient method for preparation of Aza-crown ethers,” Synthetic Communications, vol. 36, no. 11, pp. 1561–1569, 2006.
[68]
A. S. Fernandes, M. F. Cabral, J. Costa, et al., “Two macrocyclic pentaaza compounds containing pyridine evaluated as novel chelating agents in copper(II) and nickel(II) overload,” Journal of Inorganic Biochemistry, vol. 105, pp. 292–301, 2011.
[69]
A. Shockravi, M. Sadeghpour, M. Zakeri, E. Abouzari-Lotf, and A. Olyaei, “Synthesis of new multibenzo oxygen-sulfur donor macrocycles containing lactams at room temperature,” Phosphorus, Sulfur and Silicon and the Related Elements, vol. 185, no. 4, pp. 808–815, 2010.
[70]
O. S. M. Nasman, “N2S2-donor macrocycles with some transition metal ions: synthesis and characterization,” Phosphorus, Sulfur and Silicon and the Related Elements, vol. 183, no. 7, pp. 1541–1551, 2008.
[71]
L. F. Lindoy, K. Park, and S. S. Lee, “Metals, macrocycles and molecular assemblies—macrocyclic complexes in metallo-supramolecular chemistry,” Chemical Society Reviews, vol. 42, no. 4, pp. 1713–1727, 2013.
[72]
E. Lee, S. Y. Lee, L. F. Lindoy, and S. S. Lee, “Metallacycles derived from metal complexes of exo-coordinated macrocyclic ligands,” Coordination Chemistry Reviews, vol. 257, no. 21-22, pp. 3125–3138, 2013.
[73]
S. Park, H. J. Jang, and S. S. Lee, “Synthesis and crystal structures of mercury(II) and copper(II) complexes of azathia-macrocycle with pyridylmethyl arm,” Bulletin of the Korean Chemical Society, vol. 33, no. 1, pp. 301–304, 2012.
[74]
S. J. Dorazio, P. B. Tsitovich, K. E. Siters, J. A. Spernyak, and J. R. Morrow, “Iron(II) PARACEST MRI contrast agents,” Journal of the American Chemical Society, vol. 133, no. 36, pp. 14154–14156, 2011.
[75]
I. Prat, A. Company, T. Corona, T. Parella, X. Ribas, and M. Costas, “Assessing the impact of electronic and steric tuning of the ligand in the spin state and catalytic oxidation ability of the FeII(Pytacn) family of complexes,” Inorganic Chemistry, vol. 52, no. 16, pp. 9229–9244, 2013.
[76]
D. H. Busch, “Structural definition of chemical templates and the prediction of new and unusual materials,” Journal of Inclusion Phenomena and Molecular Recognition in Chemistry, vol. 12, pp. 389–395, 1992.
[77]
D. H. Busch and N. A. Stephonson, “Molecular organization, portal to supramolecular chemistry: structural analysis of the factors associated with molecular organization in coordination and inclusion chemistry, including the coordination template effect,” Coordination Chemistry Reviews, vol. 100, pp. 119–154, 1990.
[78]
D. Sandhanamalar, S. Vedanayaki, and R. Rajavel, “Synthesis, characterization, electrochemical and antimicrobial activity of macrocyclic binuclear Cu(II), Ni(II) and VO(II) Schiff base complexes,” Chemical Science Transactions, vol. 2, no. 2, pp. 529–537, 2013.
[79]
S. K. Kim, D. H. Lee, J. I. Hong, and J. Yoon, “Chemosensors for pyrophosphate,” Accounts of Chemical Research, vol. 42, no. 1, pp. 23–31, 2009.
[80]
J. Yoon, S. K. Kim, N. J. Singh, and K. S. Kim, “Imidazolium receptors for the recognition of anions,” Chemical Society Reviews, vol. 35, no. 4, pp. 355–360, 2006.
[81]
E. J. Neil and B. D. Smith, “Anion recognition using dimetallic coordination complexes,” Coordination Chemistry Reviews, vol. 250, pp. 3068–3080, 2006.
[82]
P. A. Gale, “Structural and molecular recognition studies with acyclic anion receptors,” Accounts of Chemical Research, vol. 39, no. 7, pp. 465–475, 2006.
[83]
X. Huang, Y. Lu, Y. He, and Z. Chen, “A metal-macrocycle complex as a fluorescent sensor for biological phosphate ions in aqueous solution,” European Journal of Organic Chemistry, vol. 2010, no. 10, pp. 1921–1927, 2010.
[84]
F. H. Westheimer, “Why nature chose phosphates,” Science, vol. 235, no. 4793, pp. 1173–1178, 1987.
[85]
S. C. L. Kamerlin, P. K. Sharma, R. B. Prasad, and A. Warshel, “Why nature really chose phosphate,” Quarterly Reviews of Biophysics, vol. 46, no. 1, pp. 1–132, 2013.
[86]
S. Sharma, A. Rauk, and A. H. Juffer, “A DFT study on the formation of a phosphohistidine intermediate in prostatic acid phosphatase,” Journal of the American Chemical Society, vol. 130, no. 30, pp. 9708–9716, 2008.
[87]
M. de Vivo, M. dal Peraro, and M. L. Klein, “Phosphodiester cleavage in ribonuclease H occurs via an associative two-metal-aided catalytic mechanism,” Journal of the American Chemical Society, vol. 130, no. 33, pp. 10955–10962, 2008.
[88]
B. Elsasser, M. Valiev, and J. H. Weare, “A dianionic phosphorane intermediate and transition states in an associative mechanism for the ribonucleaseA hydrolysis reaction,” Journal of the American Chemical Society, vol. 131, pp. 3869–3871, 2009.
[89]
V. López-Canut, M. Roca, J. Bertrán, V. Moliner, and I. Tu？ón, “Theoretical study of phosphodiester hydrolysis in nucleotide pyrophosphatase/phosphodiesterase. Environmental effects on the reaction mechanism,” Journal of the American Chemical Society, vol. 132, no. 20, pp. 6955–6963, 2010.
[90]
W. N. Lipscomb and N. Strater, “Recent advances in zinc enzymology,” Chemical Reviews, vol. 96, pp. 2375–2434, 1996.
[91]
D. E. Wilcox, “Binuclear metallohydrolases,” Chemical Reviews, vol. 96, no. 7, pp. 2435–2458, 1996.
[92]
J. Weston, “Mode of action of Bi- and trinuclear zinc hydrolases and their synthetic analogues,” Chemical Reviews, vol. 105, no. 6, pp. 2151–2174, 2005.
[93]
W. W. Cleland and A. C. Hengge, “Enzymatic mechanisms of phosphate and sulfate transfer,” Chemical Reviews, vol. 106, no. 8, pp. 3252–3278, 2006.
[94]
T. Niittym？ki and H. L？nnberg, “Artificial ribonucleases,” Organic and Biomolecular Chemistry, vol. 4, no. 1, pp. 15–25, 2006.
[95]
F. Mancin and P. Tecilla, “Zinc(II) complexes as hydrolytic catalysts of phosphate diester cleavage: from model substrates to nucleic acids,” New Journal of Chemistry, vol. 31, no. 6, pp. 800–817, 2007.
[96]
H. L？nnberg, “Cleavage of RNA phosphodiester bonds by small molecular entities: a mechanistic insight,” Organic & Biomolecular Chemistry, vol. 9, no. 6, pp. 1687–1703, 2011.
[97]
M. Zhao, H.-B. Wang, L.-N. Ji, and Z.-W. Mao, “Insights into metalloenzyme microenvironments: biomimetic metal complexes with a functional second coordination sphere,” Chemical Society Reviews, vol. 42, no. 21, pp. 8360–8375, 2013.
[98]
C. I. Maxwell, N. J. Mosey, and R. Stan Brown, “DFT computational study of the methanolytic cleavage of DNA and RNA phosphodiester models promoted by the dinuclear Zn(II) complex of 1,3-bis(1,5,9-triazacyclododec-1-yl)propane,” Journal of the American Chemical Society, vol. 135, no. 45, pp. 17209–17222, 2013.
[99]
X. Zhang, Y. Zhu, X. Zheng, D. L. Phillips, and C. Zhao, “Mechanismic investigation on the cleavage of phosphate monoester catalyzed by unsymmetrical macrocyclic dinuclear complexes: the selection of metal centers and the intrinsic flexibility of the ligand,” Inorganic Chemistry, vol. 53, no. 7, pp. 3354–3361, 2014.
[100]
S. Anbu, M. Kandaswamy, and B. Varghese, “Structural, electrochemical, phosphate-hydrolysis, DNA binding and cleavage studies of new macrocyclic binuclear nickel(ii) complexes,” Dalton Transactions, vol. 39, no. 16, pp. 3823–3832, 2010.
[101]
P. V. Bernhardt, J. M. Harrowfield, Y. Kim, G. A. Koutsantonis, Y. H. Lee, and P. Thuery, “Functionalized macrocycles from functionalized tetra-amines: pendent-arm macrocycles derived from dichloropivalic acid,” Inorganic Chemistry, vol. 43, pp. 1681–1689, 2004.
[102]
Y. K. Ryu, C. W. Kim, T. H. Noh, K. H. Yoo, and O. S. Jung, “Anion-recognition of an ionic cyclodimeric Pd(II) complex,” Journal of Coordination Chemistry, vol. 63, no. 22, pp. 3888–3894, 2010.
[103]
S. Chandra and D. R. Singh, “Zinc(II) selective poly(vinyl chloride) membrane ISE using a macrocyclic compound 1,12,14-triaza-5,8-dioxo-3(4),9(10)-dibenzoylcyclopentadeca-1,12,14-triene as neutral carrier,” Journal of Saudi Chemical Society, vol. 14, no. 1, pp. 55–60, 2010.
[104]
M. W. Glenny, M. Lacombe, J. B. Love et al., “Design and synthesis of heteroditopic aza-thioether macrocycles for metal extraction,” New Journal of Chemistry, vol. 30, no. 12, pp. 1755–1767, 2006.
[105]
H. Alp, Z. B？y？kl？o？lu, M. Ocak, ü. Ocak, H. Kantekin, and G. Dilber, “New heavy metal ion-selective macrocyclic ligands with nitrogen and sulfur donor atoms and their extractant properties,” Separation Science and Technology, vol. 42, no. 4, pp. 835–845, 2007.
[106]
O. R. Luca and R. H. Crabtree, “Redox-active ligands in catalysis,” Chemical Society Reviews, vol. 42, no. 4, pp. 1440–1459, 2013.
[107]
V. Lyaskovskyy and B. de Bruin, “Redox non-innocent ligands: versatile new tools to control catalytic reactions,” ACS Catalysis, vol. 2, no. 2, pp. 270–279, 2012.
[108]
J. I. van de Vlugt, “Cooperative catalysis with first-row late transition metals,” European Journal of Inorganic Chemistry, vol. 2012, no. 3, pp. 363–375, 2012.
[109]
S. Kuwata and T. Ikariya, “β-protic pyrazole and N-heterocyclic carbene complexes: synthesis, properties, and metal-ligand cooperative bifunctional catalysis,” Chemistry—A European Journal, vol. 17, no. 13, pp. 3542–3556, 2011.
[110]
F. Hartl, P. Rosa, L. Ricard, P. Le Floch, and S. Zalis, “Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]？ (L2 = chelating redox-active -donor ligand),” Coordination Chemistry Reviews, vol. 251, pp. 557–576, 2007.
[111]
A. Biffis, M. Cipani, E. Bressan, C. Tubaro, C. Graiff, and A. Venzo, “Group 10 metal complexes with chelating macrocyclic dicarbene ligands bearing a 2,6-lutidinyl bridge: synthesis, reactivity, and catalytic activity,” Organometallics, vol. 33, no. 9, pp. 2182–2188, 2014.
[112]
Z. K. Khoramdareh, S. A. Hosseini-Yazdi, B. Spingler, and A. A. Khandar, “Copper(II) and zinc(II) complexes of mono- and tri-linked azacrown macrocycles: synthesis, characterization, X-ray structure, phosphodiester hydrolysis and DNA cleavage,” Inorganica Chimica Acta, vol. 415, pp. 7–13, 2014.
[113]
Y. Wang and X. Peng, “RuRh bimetallic nanoparticles stabilized by 15-membered macrocycles-terminated poly(propylene imine) dendrimer: preparation and catalytic hydrogenation of nitrile-butadiene rubber,” Nano-Micro Letters, vol. 6, no. 1, pp. 55–62, 2014.
[114]
M. Woods, D. E. Woessner, and A. D. Sherry, “Paramagnetic lanthanide complexes as PARACEST agents for medical imaging,” Chemical Society Reviews, vol. 35, no. 6, pp. 500–511, 2006.
[115]
S. Viswanathan, Z. Kovacs, K. N. Green, S. J. Ratnakar, and A. D. Sherry, “Alternatives to gadolinium-based metal chelates for magnetic resonance imaging,” Chemical Reviews, vol. 110, no. 5, pp. 2960–3018, 2010.
[116]
S. Aime, D. D. Castelli, S. G. Crich, E. Gianolio, and E. Terreno, “Pushing the sensitivity envelope of lanthanide-based magnetic resonance imaging (MRI) contrast agents for molecular imaging applications,” Accounts of Chemical Research, vol. 42, no. 7, pp. 822–831, 2009.
[117]
A. X. Li, M. Suchy, C. Li et al., “In vivo detection of MRI-PARACEST agents in mouse brain tumors at 9.4 T,” Magnetic Resonance in Medicine, vol. 66, no. 1, pp. 67–72, 2011.
[118]
P. B. Tsitovich and J. R. Morrow, “Macrocyclic ligands for Fe(II) paraCEST and chemical shift MRI contrast agents,” Inorganica Chimica Acta, vol. 393, pp. 3–11, 2012.
[119]
M. Kueny-Stotz, A. Garofalo, and D. Felder-Flesch, “Manganese-enhanced MRI contrast agents: from small chelates to nanosized hybrids,” European Journal of Inorganic Chemistry, no. 12, pp. 1987–2005, 2012.
[120]
E. Molnár, N. Camus, V. Patinec et al., “Picolinate-containing macrocyclic Mn2+ complexes as potential MRI contrast agents,” Inorganic Chemistry, vol. 53, no. 10, pp. 5136–5149, 2014.
[121]
T. W. Hambley, “Developing new metal-based therapeutics: challenges and opportunities,” Dalton Transactions, no. 43, pp. 4929–4937, 2007.
[122]
S. Ramakrishnan, V. Rajendiran, M. Palaniandavar et al., “Induction of cell death by ternary copper(II) complexes of l-tyrosine and diimines: role of coligands on DNA binding and cleavage and anticancer activity,” Inorganic Chemistry, vol. 48, no. 4, pp. 1309–1322, 2009.
[123]
S. Fulda and S. Pervaiz, “Apoptosis signaling in cancer stem cells,” International Journal of Biochemistry and Cell Biology, vol. 42, no. 1, pp. 31–38, 2010.
[124]
L. Zheng, X. Lin, N. Wu et al., “Targeting cellular apoptotic pathway with peptides from marine organisms,” Biochimica et Biophysica Acta—Reviews on Cancer, vol. 1836, no. 1, pp. 42–48, 2013.
[125]
S. Anbu, S. Kamalraj, B. Varghese, J. Muthumary, and M. Kandaswamy, “A series of oxyimine-based macrocyclic dinuclear zinc(II) complexes enhances phosphate ester hydrolysis, DNA binding, DNA hydrolysis, and lactate dehydrogenase inhibition and induces apoptosis,” Inorganic Chemistry, vol. 51, no. 10, pp. 5580–5592, 2012.
[126]
T. Hawkins, “Understanding and managing the adverse effects of antiretroviral therapy,” Antiviral Research, vol. 85, no. 1, pp. 201–209, 2010.
[127]
R. Kim and J. D. Baxter, “Protease inhibitor resistance update: where are we now?” AIDS Patient Care and STDs, vol. 22, no. 4, pp. 267–277, 2008.
[128]
A. Joshi, J.-B. Véron, J. Unge, et al., “Design and synthesis of P1-P3 macrocyclic tertiary-alcohol-comprising HIV-1 protease inhibitors,” Journal of Medicinal Chemistry, vol. 56, no. 22, pp. 8999–9007, 2013.
[129]
Y. S. Tsantrizos, G. Bolger, P. Bonneau et al., “Macrocyclic inhibitors of the NS3 protease as potential therapeutic agents of hepatitis C virus infection,” Angewandte Chemie International Edition, vol. 42, no. 12, pp. 1356–1360, 2003.
[130]
A. Hussain and A. R. Chakravarty, “Photocytotoxic lanthanide complexes,” Journal of Chemical Sciences, vol. 124, no. 6, pp. 1327–1342, 2012.
[131]
E. J. New, A. Congreve, and D. Parker, “Definition of the uptake mechanism and sub-cellular localisation profile of emissive lanthanide complexes as cellular optical probes,” Chemical Science, vol. 1, no. 1, pp. 111–118, 2011.
[132]
C. P. Montgomery, B. S. Murrey, E. J. New, R. Pal, and D. Parker, “Cell-penetrating metal complex optical probes: targeted and responsive systems based on lanthanide luminescence,” Accounts of Chemical Research, vol. 42, no. 7, pp. 925–937, 2009.
[133]
E. J. New and D. Parker, “The mechanism of cell uptake for luminescent lanthanide optical probes: the role of macropinocytosis and the effect of enhanced membrane permeability on compartmentalisation,” Organic and Biomolecular Chemistry, vol. 7, no. 5, pp. 851–855, 2009.
[134]
B. S. Murrey, E. J. New, R. Pal, and D. Parker, “Critical evaluation of five emissive europium(III) complexes as optical probes: correlation of cytotoxicity, anion and protein affinity with complex structure, stability and intracellular localisation profile,” Organic & Biomolecular Chemistry, vol. 6, no. 12, pp. 2085–2094, 2008.
[135]
J. Yu, D. Parker, R. Pal, R. A. Poole, and M. J. Cann, “A europium complex that selectively stains nucleoli of cells,” Journal of the American Chemical Society, vol. 128, no. 7, pp. 2294–2299, 2006.
[136]
K. Sharma, S. Agarwal, and S. Gupta, “Antifungal, antibacterial and antifertility activities of biologically active macrocyclic complexes of Tin(II),” International Journal of ChemTech Research, vol. 5, no. 1, pp. 456–463, 2013.
[137]
N. C. Walsh and E. M. Gravallese, “Bone remodeling in rheumatic disease: a question of balance,” Immunological Reviews, vol. 233, no. 1, pp. 301–312, 2010.
[138]
A. D. William, A. C.-H. Lee, A. Poulsen et al., “Discovery of the macrocycle (9 E)-15-(2-(Pyrrolidin-1-yl)ethoxy)-7,12,25- trioxa-19,21,24-triaza-tetracyclo[18.3.1.1(2,5).1(14,18)]hexacosa-1(24),2,4,9, 14(26),15,17,20,22-nonaene (SB1578), a potent inhibitor of Janus kinase 2/Fms-liketyrosine kinase-3 (JAK2/FLT3) for the treatment of rheumatoid arthritis,” Journal of Medicinal Chemistry, vol. 55, no. 6, pp. 2623–2640, 2012.
[139]
S. Chandra, M. Tyagi, and S. Agrawal, “Spectral and antimicrobial studies on tetraaza macrocyclic complexes of PdII, PtII, RhIII and IrIII metal ions,” Journal of Saudi Chemical Society, vol. 15, no. 1, pp. 49–54, 2010.
