Interesting Properties of P-, D-, and F-Block Elements When
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Old Dominion University ODU Digital Commons Chemistry & Biochemistry Faculty Publications Chemistry & Biochemistry 2015 Interesting Properties of p-, d-, and f-Block Elements When Coordinated With Dipicolinic Acid and Its Derivatives as Ligands: Their seU as Inorganic Pharmaceuticals Michael J. Celestine Old Dominion University, [email protected] Jimmie L. Bullock Old Dominion University Shivani Boodram Varma H. Rambaran Alvin A. Holder Old Dominion University, [email protected] Follow this and additional works at: https://digitalcommons.odu.edu/chemistry_fac_pubs Part of the Inorganic Chemistry Commons, and the Medicinal-Pharmaceutical Chemistry Commons Repository Citation Celestine, Michael J.; Bullock, Jimmie L.; Boodram, Shivani; Rambaran, Varma H.; and Holder, Alvin A., "Interesting Properties of p-, d-, and f-Block Elements When Coordinated With Dipicolinic Acid and Its Derivatives as Ligands: Their sU e as Inorganic Pharmaceuticals" (2015). Chemistry & Biochemistry Faculty Publications. 152. https://digitalcommons.odu.edu/chemistry_fac_pubs/152 Original Publication Citation Celestine, M. J., Bullock, J. L., Boodram, S., Rambaran, V. H., & Holder, A. A. (2015). Interesting properties of p-, d-, and f-block elements when coordinated with dipicolinic acid and its derivatives as ligands: Their use as inorganic pharmaceuticals. Reviews in Inorganic Chemistry, 35(2), 57-67. doi:10.1515/revic-2014-0004 This Article is brought to you for free and open access by the Chemistry & Biochemistry at ODU Digital Commons. It has been accepted for inclusion in Chemistry & Biochemistry Faculty Publications by an authorized administrator of ODU Digital Commons. For more information, please contact [email protected]. Rev Inorg Chem 2015; 35(2): 57–67 Michael J. Celestine, Jimmie L. Bullock, Shivani Boodram, Varma H. Rambaran* and Alvin A. Holder* Interesting properties of p-, d-, and f-block elements when coordinated with dipicolinic acid and its derivatives as ligands: their use as inorganic pharmaceuticals Abstract: This is a review of the literature concerning the et al. 2000, Muller et al. 2001, Hunag et al. 2003, Storm and interesting properties of p-, d-, and f-block elements when Luning 2003, Haino et al. 2005). It is a versatile, strong, coordinated with 2,6-pyridinedicarboxylic acid (dipicolinic nitrogen-oxygen, multimodal donor ligand, which forms acid, H2dipic) and its derivatives as ligands, with a focus on stable complexes with diverse metal ions, sometimes in their use as inorganic pharmaceuticals. Some of the com- unusual oxidation states (Renaud et al. 1997a,b, Jackson plexes reported were used as insulin-like, bioimaging con- et al. 2001, Devereux et al. 2002, Ouali et al. 2002, Kapoor trasting agents, antimicrobial agents, and anticancer agents. et al. 2005, Tse et al. 2006, Kirillova et al. 2007). O O Keywords: bacteria; cancer; complexes; dipicolinic acid; N insulin. OH OH I DOI 10.1515/revic-2014-0004 Received April 30, 2014; accepted July 26, 2014; previously pub- The crystal structure of dipicolinic acid was first solved lished online September 13, 2014 by Takusagawa et al. (1973). Lately, the pharmacological studies on dipicolinic acid have been given pertinent atten- tion because of its low toxicity and amphophilic nature. Dipicolinic acid is also present in natural systems as a Introduction product of oxidative degradation of vitamins, coenzymes, and alkaloids, to name a few (Siddiqi et al. 2010). Further- The review focuses on the interesting properties of p-, d-, more, it is constituent of fulvic acid, and is an intermediate and f-block elements when coordinated with 2,6-pyridine- during l-tryptophan degradation as well as a precursor for dicarboxylic acid (dipicolinic acid, H dipic) and its deriv- 2 the NAD enzyme (Siddiqi et al. 2010). Dipicolinic acid and atives as ligands, with a focus on their use as inorganic its derivatives are now being featured as ligands in coor- pharmaceuticals. 2,6-Pyridinedicarboxylic acid (dipico- dination complexes that have medicinal uses. The readers linic acid, H dipic), I, is a widely used building block in 2 are encouraged to read reviews and articles for informa- coordination and supramolecular chemistry (Froidevaux tion regarding the solution chemistry of dipicolinic acid, its derivatives, and its coordination complexes (Buglyo *Corresponding authors: Varma H. Rambaran, The University of et al. 2005, Smee et al. 2009, Kirillov and Shul’pin 2013). Trinidad and Tobago, O’Meara Campus, Lots 74-98, Please see the following review “Pyrazinecarboxylic acid O’Meara Industrial Park, Arima, Trinidad and Tobago, and analogs: Highly efficient co-catalysts in the metal- e-mail: [email protected]; and Alvin A. Holder, Department of Chemistry and Biochemistry, Old Dominion complex-catalysed oxidation of organic compounds” University, 4541 Hampton Boulevard, Norfolk, VA 23529-0126, USA, (Kirillov and Shul’pin 2013). In this report, the reviews and e-mail: [email protected] featured articles have been published on the following Michael J. Celestine and Jimmie L. Bullock: Department of Chemistry topics: antidiabetic effects of a series of vanadium dipico- and Biochemistry, Old Dominion University, 4541 Hampton linate complexes in rats with streptozotocin (STZ)-induced Boulevard, Norfolk, VA 23529-0126, USA Shivani Boodram: The University of Trinidad and Tobago, O’Meara diabetes (Willsky et al. 2011); how environment affects Campus, Lots 74-98, O’Meara Industrial Park, Arima, Trinidad and drug activity: localization, compartmentalization, and Tobago reactions of a vanadium insulin-enhancing compound, Authenticated | [email protected] Download Date | 8/21/15 6:56 AM 58 M.J. Celestine et al.: Complexes of dipicolinic acid and its derivatives as medicine dipicolinatooxidovanadium(V) (Crans et al. 2011); and (diaqua)(4-hydroxy-2,6-pyridinedicarbo xylato) metal speciation in health and medicine represented by oxidovanadium(IV), and (4-amino- 2,6-pyridinedi- iron and vanadium (Crans et al. 2013). carboxylato)dioxidovanadium(V). The complex (4-hydroxy- 2,6-pyridinedicarboxylato)oxido vanadium(V) was investi gated in greater detail with regard to the chemistry, structure, kinetics, and insulin-like properties in rats with Titanium STZ-induced diabetes (Crans et al. 2003a). An oral adminis- tration of [VO (dipic-OH)]- was found to be effective in lower- The chelate stabilization of a titanium(IV) (TiIV)-salan 2 ing both the hyperglycemia and hyperlipidemia of diabetes. alkoxide by ligand exchange with dipicolinic acid was This was the first report concerning the effective lowering reported to form the redox inactive, heptacoordinate of diabetic hyperlipidemia by a vanadium(V) (VV) coordina- complex 1. This was found to be stable in both silica gel tion complex (Crans et al. 2003a). and aqueous media (Immel et al. 2012). The complex was Recently, there was a report of a new insulin-like reported to be highly toxic toward cervix carcinoma, HeLa VV complex, the (4-hydroxypyridine-2,6-dicarboxylato) S3, hepatocarcinoma, and Hep G2 cancer cell lines. It was oxovanadate(V) anion 2 (Crans et al. 2003b). The complex also found to have an enhanced antitumor efficacy in a was designed based on the desire to make a compound mouse cervical cancer model (Immel et al. 2012). with more favorable chemical and insulin-like proper- ties than the analogous (pyridine-2,6-dicarboxylato) O oxovanadate(V) anion 3. The aqueous solution studies O O were carried out on complex 2, where the complex was N Ti N found to be more stable at a neutral pH and had a dif- O ferent lability pattern than complex 3. The effect of N O O complexes 2 and 3 anions on various biological systems including cell culture, yeast, and STZ-induced diabetic rats were investigated. The growth of myoblast cells (L6) 1 was inhibited by both complexes 2 and 3 anions (Crans et al. 2003b). Since the complexes have limited stability The relative efficacy of complex 1 was compared to at a neutral pH, yeast growth (pH range from 3.0 to 7.0) another derivative in an in vivo model of cervical cancer; was employed as an adjunct cell model. The effect of the 18 C3 tumor-bearing mice received the complexes in a low- complex 3 anion on the inhibition of yeast cell growth dose regime over multiple applications and their relative was found to be pH dependent. The authors reported that tumor inhibitory effects were monitored. Impressively, these studies supported the hypothesis that the complex mice that were administered doses of complex 1 exhib- 2 anion would be more active as an insulin-like agent ited a significant reduction in tumor size. These data were because of its greater stability at a neutral pH (Crans well received, although a reduction of tumor growth was et al. 2003b). The studies involving the effect of complex previously reported using a high-dose treatment with TiIV 2 anion on hyperglycemia in rats with STZ-induced dia- halo-salan alkoxides. The dipic2- stabilized complex 1, in betes were also carried out. Complex 2 anion was found contrast to the TiIV halo-salan alkoxides, was well toler- to lower the diabetic hyperglycemia and joined the ranks ated and showed an improved efficacy at lower doses of the few VV complexes that have been shown to have (30 mg kg-1). insulin-like properties in a diabetic animal model system (Crans et al. 2003b). Vanadium For many years, it has been reported that vanadium-con- taining complexes have insulin-like properties both in vivo and in vitro. The synthesis and characterization of new vanadium