Table of Contents Author Guidelines Submit a Manuscript
Journal of Chemistry
Volume 2013, Article ID 820328, 6 pages
http://dx.doi.org/10.1155/2013/820328
Research Article

Synthesis and Characterization of Metallic Gel Complexes Derived from Carboxymethyl Cellulose

1Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur 440033, India
2Department of Chemistry, Priyadarshini College of Engineering, Nagpur 440019, India

Received 29 June 2012; Revised 11 September 2012; Accepted 25 September 2012

Academic Editor: Ester Chiessi

Copyright © 2013 H. D. Juneja et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract

The oxaloyl carboxymethyl cellulose (OCMC) complexes of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) metal ions have been synthesized and the coordination of OCMC in these complexes has been investigated through IR spectra, reflectance spectra, and thermal analysis. On the basis of spectral and thermal data an octahedral geometry was assigned to Mn(II)OCMC(H2O)2 and Co(II)OCMC(H2O)2 , square planar geometry was assigned to , and tetrahedral geometry was assigned to and Metallic Gel complexes.

1. Introduction

Cellulose is a naturally occurring polysaccharide and is the most abundant renewable resource available. It is a glucose polymer photosynthesized by solar energy in various plants and acts as the structural basis of the plant cell wall [1]. Cellulose is a linear polymer of anhydroglucose units linked at C-1 and C-4 by b-glycosidic bonds. This is confirmed by the presence of three hydroxyl groups with different acidity/reactivity, secondary OH at the C-2, secondary OH at the C-3, and primary OH at the C-6 position and, accordingly, by the formation of strong various intermolecular and intramolecular hydrogen bonds. Despite its simple molecular structure, cellulose shows a large complexity and variability in its supermolecular arrangement in cellulose fibrils [2]. Production of cellulose derivatives was done by reacting the free hydroxyl groups in the anhydroglucose units (AGU) with various chemical substitution groups. The introduction of the substituent disturbs the inter- and intramolecular hydrogen bonds in cellulose, which leads to liberation of the hydrophilic character of the numerous hydroxyl groups and restriction of the chains to closely associate [3]. Cellulose ether is the most widely used cellulose derivative in food and pharmaceutical industries. It is obtained by replacing the hydroxyl groups with either alkyl or hydroxy-alkyl groups. Accordingly, a wide range of cellulose ethers was manufactured to meet specific needs of industrial applications [4]. This is the case with sodium carboxymethylcellulose (Na-CMC), an anionic linear cellulose ether. CMC presents the structure of a polyanion consisting of repeating units of anhydroglucose residues, substituted by sodium carboxymethyl groups. Cellulose derivatives such as carboxymethylcellulose (CMC) and hydroxypropylcellulose are biocompatible [5] and have been applied in drug delivery formulations [69] and as components of therapies for preventing postsurgical adhesions (e.g., Genzyme’s Seprafilm) [1014]. A number of papers have been published on the uses of chelating exchanges for trace element preconcentration from various matrices using cellulose as solids sorbents for the separation of the transition metals in analyses such as GFAAS spectrometry, ICP-MS for reduction and aggregation of silver, copper, and cadmium ions in aqueous solutions of gelatin and CMC, and with dichromate for separation of copper-lead in secondary copper minerals [1518].

The Navy also makes use of polymers in load-bearing polymeric matrix composites, special coatings for signature control, coatings for corrosion reduction in waste-holding tanks, fuel storage tanks and metal pipe linings, and so on, where polymers have been often applied as part of a technology package to meet the needed performance criteria [19].

The present work is a part of systematic investigation undertaken in the laboratory which includes the synthesis of thermally stable Metallic Gel complexes, mechanism of their formation, structural aspects, and applications as coating materials. The metal ions selected for the present work belong to 3d block transition elements namely Mn(II), Co(II), Ni(II), Cu(II), and Zn(II). These metal ions have an ability to form complexes with ligands having one or more lone pair of electrons, which they can easily donate to the transition metal ion and thus complete the vacant orbital of cation through the formation of L→M bond. Since the electropositive nature decreases on moving down in each group of transition metals, the members of first transition series form more stable complexes with ligands containing nitrogen and oxygen. The resulting complexes formed due to interaction between metal ions and ligands were highly thermally stable and have numerous applications in various fields. Although a good amount of work has been reported in literature on solid complexes of first transition series metal ions with organic ligands containing Nitrogen, Oxygen, and Sulphur atoms as donors no much work has been done on solid complexes of these metals with ligands containing carboxymethyl cellulose.

2. Experimental Procedures

2.1. Materials Used

All the chemicals used as starting materials in the synthesis of ligand and its Metallic Gel complexes were of extra pure quality: Sodium carboxymethyl cellulose (E. Merck, Germany); Oxalic acid (E. Merck, Germany); Manganous acetate, Cobaltous acetate, Nickel acetate (E. Merck, Germany); Cuprous acetate and Zinc acetate (S. D. Fine Chem., India).

2.2. Instruments

Microanalysis of C, H, and N was carried out on Eassuperuser Elemental Analyser System GmbH, Access: VarioEL Superuser, NEERI. Infrared spectra in the region 4000–400 cm−1 were recorded in the solid state (KBr Pallets) in Pharmacy Department, RTMNU, Nagpur, using FTIR-101A SHIMADZU. The kinetics of thermal decomposition were investigated by using nonisothermal manual thermal analyzer at Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur. The heating rate employed was 10°C/min and the mass loss was recorded continuously. Magnetic susceptibility of Metallic Gel complexes was determined by Gouy’s method at room temperature using mercury tetrathiocyanatocobaltate(II) as standard.

2.3. Synthesis of Oxaloyl Carboxymethyl Cellulose (OCMC) Ligand

The ligand was synthesized by triturating the mixture of 10 g of finely powdered Na salt of CMC (low viscosity) and 30 mL of glycerol with mortar and pestle. The triturated mixture is added in small amounts into the vertex of 0.2 M aqueous Oxalic acid solution and stirred electrically until a clear gel was obtained. The synthesized ligand was stored in an airtight wide mouth bottle. The chemical reaction for synthesis of Oxaloyl Carboxymethyl Cellulose ligand is shown in Figure 1.

820328.fig.001
Figure 1: Synthesis of oxaloyl CMC Ligand. for Oxalic acid.

2.4. Synthesis of Metallic Gel Complexes

The Metallic Gel complexes in the present work have been synthesized by refluxing 10 g of OCMC ligand and 100 mL of 0.2 M aqueous metal acetate at 100°C in an oil bath for 2 hrs. The Metallic Gel complexes obtained were then cooled, filtered and washed with hot water to remove any unreacted metal acetate and ligand.

3. Results and Discussions

3.1. Composition of the Metallic Gel Complexes

The composition of the Metallic Gel Complexes was assigned on the basis of elemental analysis. The presence of water of crystallization as well as water of coordination was ascertained on the basis of thermal studies. The composition of Metallic Gel complexes was found to be [M(II)L]n and [M′(II)L·2H2O]n, where M = Ni(II), Cu(II) and Zn(II) and M′ = Mn(II), and Co(II) and L = OCMC ligand. The elemental analysis of OCMC has been reported in Table 1.

tab1
Table 1: Elemental analysis of oxaloyl carboxymethyl cellulose (OCMC) and its Metallic Gel complexes.
3.2. Infrared Spectral Studies

The IR spectral data for OCMC and its Metallic Gel complexes with Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) has been tabulated in Table 2. Characteristic peak of functional groups was observed in the IR spectra of OCMC: –OH group at 3450 cm−1, –CH group at 2920 cm−1, C=O group of nonconjugated ketones, carbonyls and in ester groups at 1718 cm−1 [20, 21], and –COOH group at 1650 cm−1.

tab2
Table 2: IR spectral assignments of OCMC ligand and its Metallic Gel complexes.

The IR spectra of complexes show few new weak absorption bands in the range of 600 to 660 cm−1 which may be assigned to the M–O (Metal-Oxygen) bonds [22]. The weak band observed around 780 cm−1 may be assigned to coordinated water molecule. The infrared spectral assignments of ligand and Metallic Gel complexes have been tabulated in Table 2.

3.3. Magnetic Moment and Electronic Spectral Studies of OCMC Metallic Gel Complexes

The magnetic moment values of OCMC Metallic Gel complexes have been given in Table 3. These magnetic moment values supported the octahedral geometry for Mn(II) and Co(II) Metallic Gel complexes, the tetrahedral geometry for Ni(II), and square planar geometry for Cu(II) gel complexes.

tab3
Table 3: Magnetic moment data of OCMC Metallic Gel complexes.

Divalent manganese forms octahedral, tetrahedral, square planar or low symmetry compounds, but generally manganese gel complexes are either octahedral or tetrahedral. Bivalent manganese is known to form both high spin and low spin complexes. Octahedral as well as tetrahedral Mn(II) complexes show magnetic moment close to the spin only value, that is, 5.92 B.M., which is independent of temperature. However Venkateshwar Rao and Venkata Narasaiah, prepared Mn(II) complexes having magnetic moment 5.52 B.M., which is low as compared to spin only value for high spin Mn(II) complexes. This can be attributed to the spin exchange in the solid state [23].

The theory of paramagnetic susceptibility of Co(II) was originally given by Schlapp and Penny [24]. The magnetic properties of high spin octahedral Co(II) complexes are governed by the orbitally degenerate ground term . This provides an orbital contribution to the magnetic moment so that at room temperature magnetic moment values are found to be in the range of 4.7–5.9 B.M.

In a tetrahedral ligand field, Ni(II), has an orbitally degenerate term which will give rise to a relatively large orbital contribution to the magnetic moment, which is temperature dependent. In a regular tetrahedral stereochemistry magnetic moment is around 3.5–4.5 B.M.

Since [Zn(II)(OCMC)]n is a system and hence was diamagnetic in nature, though, on the basis of elemental analysis, infrared spectra, and thermal decomposition data, its most probable geometry was suggested to be tetrahedral.

Electronic spectral properties include the electronic transitions which take place between the ground levels of coordination clusters and the excited levels. The spectra of the coordination compounds may be classified into ligand field bands and charge transfer bands. The ligand field bands are essentially concerned with the transition between different d-orbitals which results from the application of the ligand field. On the basis of spectral assignments made by the workers as described in the literature and especially calculations made by Tanabe and Sugano [25] the electronic spectra of the Metallic Gel complexes can be suitably discussed [26]. Electronic spectral assignments of OCMC Metallic Gel complexes have been reported in Table 4. The electronic spectra of OCMC metallic gel complexes are shown in Figure 2.

tab4
Table 4: Electronic spectral assignments of OCMC Metallic Gel complexes.
820328.fig.002
Figure 2: Electronic spectra of OCMC Metallic Gel complexes.
3.4. Thermogravimetric Analysis of OCMC Metallic Gel Complexes

In the present study, thermogravimetric analysis of the Metallic Gel complexes of OCMC has been reported. No sharp weight loss was observed in any thermogram of these Metallic Gel complexes, which indicates their polymeric complex nature. The thermogram for OCMC gel complexes has been shown in Figure 3.

820328.fig.003
Figure 3: Thermogram of OCMC-M Metallic Gel complexes.

TG curve of Mn(II)(OCMC) gel complex shows no mass loss up to 140°C due to the absence of water of crystallization. It shows mass loss of 9.5% between 140°C and 200°C due to the loss of two coordinated water molecules. After 240°C it shows a gradual decrease in mass up to 700°C, which may be due to the decomposition of the ligand attached to the metal ion; hereafter no further mass loss was observed, indicating the formation of stable metal oxide. The decomposition temperature was found to be 400°C.

The Co(II)(OCMC) gel complex also shows absence of water of crystallization since no mass loss was observed up to 140°C. It shows mass loss of 9.3% between 160°C and 230°C due to the removal of two coordinated water molecules and then after 260°C gradual loss in mass was observed up to 600°C which may be due to the decomposition of the organic species attached to the metal ion; hereafter no further mass loss was observed due to the formation of stable metal oxide. The decomposition temperature was found to be 380°C.

In TG curve of Ni(II)(OCMC) gel complex, no mass loss was observed up to 200°C. It then shows a gradual loss of mass up to 660°C, which may be due to decomposition of the ligand attached to the metal ion; hereafter no further mass loss was observed, due to the formation of stable metal oxide.

The Cu(II)(OCMC) gel complex was stable up to 230°C, since no weight loss was observed in thermogram up to 230°C. After 230°C, loss in weight was observed up to 640°C, which may be due to loss of organic species attached to the metal ion. After 640°C no mass loss was observed, which may be due to the formation of stable metal oxide. The decomposition temperature was found to be 410°C.

The Zn(II)(OCMC) gel complex was stable up to 220°C, due to absence of lattice and/or coordinated water. After 220°C gradual loss in mass was observed up to 640°C which may be due to the decomposition of the ligand attached to the metal ion. After 640°C, no further mass loss was observed, indicating the formation of stable species. The decomposition temperature was found to be 380°C.

The thermoanalytical data of these Metallic Gel complexes have been reported in Table 5.

tab5
Table 5: Thermoanalytical data of OCMC Metallic Gel complexes.

4. Conclusions

On the basis of elemental analysis, infrared spectra, reflectance spectra, magnetic moment data, and thermal studies, the [Ni(II)(OCMC)]n and [Zn(II)(OCMC)]n metallic gel complexes have tetrahedral geometry, whereas [Mn(II)(OCMC)(H2O)2]n and [Co(II)(OCMC)(H2O)2]n metallic gel complexes were octahedral in nature; however, [Cu(II)(OCMC)]n metallic gel complex has square planar geometry. On the basis of thermal degradation studies, [Cu(II)(OCMC)]n has been found to be highly thermally stable than the rest of the complexes reported in this paper.

All these metallic gel complexes have high thermal stability more than 360°C and get decompose without melt. Hence, they may be used as temperature-resistant coating materials especially for plastic materials, electric wires, and so forth.

Acknowledgment

The authors are thankful to the Head, Department of Chemistry, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, India, for providing necessary facilities to carry out the work.

References

  1. S. Richardson and L. Gorton, “Characterisation of the substituent distribution in starch and cellulose derivatives,” Analytica Chimica Acta, vol. 497, no. 1-2, pp. 27–65, 2003. View at Publisher · View at Google Scholar · View at Scopus
  2. A. Bono, P. H. Ying, F. Y. Yan, C. L. Muei, R. Sarbatly, and D. Krishnaiah, “Synthesis and characterization of carboxymethyl cellulose from palm kernel cake,” Advances in Natural and Applied Sciences, vol. 3, no. 1, pp. 5–11, 2009. View at Google Scholar · View at Scopus
  3. H. Togrul and N. Arslan, Carbohydrate Polymers, vol. 54, pp. 73–82, 2003.
  4. A. P. Franco and A. L. R. Mercê, “Complexes of carboxymethylcellulose in water. 1: Cu2+, VO2+ and Mo6+,” Reactive and Functional Polymers, vol. 66, no. 6, pp. 667–681, 2006. View at Publisher · View at Google Scholar · View at Scopus
  5. T. Miyamoto, S. Takahashi, H. Ito, H. Inagaki, and Y. Noishiki, “Tissue biocompatibility of cellulose and its derivatives,” Journal of Biomedical Materials Research, vol. 23, no. 1, pp. 125–133, 1989. View at Google Scholar · View at Scopus
  6. R. Barbucci, G. Leone, and A. Vecchiullo, “Novel carboxymethylcellulose-based microporous hydrogels suitable for drug delivery,” Journal of Biomaterials Science, vol. 15, no. 5, pp. 607–619, 2004. View at Publisher · View at Google Scholar · View at Scopus
  7. K. Pal, A. K. Banthia, and D. K. Majumdar, “Development of carboxymethyl cellulose acrylate for various biomedical applications,” Biomedical Materials, vol. 1, no. 2, pp. 85–91, 2006. View at Publisher · View at Google Scholar · View at Scopus
  8. R. Rodríguez, C. Alvarez-Lorenzo, and A. Concheiro, “Cationic cellulose hydrogels: kinetics of the cross-linking process and characterization as pH-/ion-sensitive drug delivery systems,” Journal of Controlled Release, vol. 86, no. 2-3, pp. 253–265, 2003. View at Publisher · View at Google Scholar · View at Scopus
  9. C. Tas, Y. Özkan, A. Savaser, and T. Baykara, “In vitro release studies of chlorpheniramine maleate from gels prepared by different cellulose derivatives,” Farmaco, vol. 58, no. 8, pp. 605–611, 2003. View at Publisher · View at Google Scholar · View at Scopus
  10. T. Ito, Y. Yeo, C. B. Highley, E. Bellas, C. A. Benitez, and D. S. Kohane, “The prevention of peritoneal adhesions by in situ cross-linking hydrogels of hyaluronic acid and cellulose derivatives,” Biomaterials, vol. 28, no. 6, pp. 975–983, 2007. View at Publisher · View at Google Scholar · View at Scopus
  11. R. E. Leach, J. W. Burns, E. J. Dawe, M. D. Smithbarbour, and M. P. Diamond, “Reduction of postsurgical adhesion formation in the rabbit uterine horn model with use of hyaluronate/carboxymethylcellulose gel,” Fertility and Sterility, vol. 69, no. 3, pp. 415–418, 1998. View at Google Scholar · View at Scopus
  12. J. H. Lee, Y. C. Nho, Y. M. Lim, and T. I. Son, “Prevention of surgical adhesions with barriers of carboxymethylcellulose and poly(ethylene glycol) hydrogels synthesized by irradiation,” Journal of Applied Polymer Science, vol. 96, no. 4, pp. 1138–1145, 2005. View at Publisher · View at Google Scholar · View at Scopus
  13. L. S. Liu and R. A. Berg, “Adhesion barriers of carboxymethylcellulose and polyethylene oxide composite gels,” Journal of Biomedical Materials Research, vol. 63, pp. 326–332, 2002. View at Google Scholar
  14. M. C. Tate, D. A. Shear, S. W. Hoffman, D. G. Stein, and M. C. LaPlaca, “Biocompatibility of methylcellulose-based constructs designed for intracerebral gelation following experimental traumatic brain injury,” Biomaterials, vol. 22, no. 10, pp. 1113–1123, 2001. View at Publisher · View at Google Scholar · View at Scopus
  15. C. Y. Lii, P. Tomasik, H. Zaleska, S. C. Liaw, and V. M. F. Lai, “Carboxymethyl cellulose-gelatin complexes,” Carbohydrate Polymers, vol. 50, no. 1, pp. 19–26, 2002. View at Publisher · View at Google Scholar · View at Scopus
  16. S. Bulatovic, D. M. Wysouzil, and F. C. Bermejo, “Development and introduction of a new copper/lead separation method in the Raura plant (Peru),” Minerals Engineering, vol. 14, no. 11, pp. 1483–1491, 2001. View at Publisher · View at Google Scholar · View at Scopus
  17. K. Zih-Perényi, A. Lásztity, Z. Horváth, and A. Lévai, “Use of a new type of 8-hydroxyquinoline-5-sulphonic acid cellulose (sulphoxine cellulose) for the preconcentration of trace metals from highly mineralised water prior their GFAAS determination,” Talanta, vol. 47, no. 3, pp. 673–679, 1998. View at Google Scholar
  18. S. Kapoor and C. Gopinathan, “Reduction and aggregation of silver, copper and cadmium ions in aqueous solutions of gelatin and CMC,” Radiation Physics and Chemistry, vol. 53, pp. 165–170, 1998. View at Google Scholar
  19. Polymers, Commission on Physical Sciences, Mathematics, and Applications (CPSMA), 15, 1995.
  20. G. Chaudhary Ratiram, D. Juneja Harjeet, and P. Gharpure Mangesh, “Preparation, Conductivity and Morphology Behavior of Bis (Bidentate) Ligand and Its Chelate Polymers,” Journal of Atoms and Molecules, vol. 2, no. 3, pp. 262–272, 2012. View at Google Scholar
  21. H. L. Hergert, “Infrared spectra,” in Lignins: Occurrence, Formation, Structure and Reactions, K. V. Sarkanen and C. H. Ludwig, Eds., pp. 267–297, Wiley Interscience, New York, NY, USA, 1971. View at Google Scholar
  22. A. L. el-Ansary, H. M. Abdel-Fattah, and N. S. Abdel-Kader, “Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases,” Spectrochimica Acta Part A, vol. 79, no. 3, pp. 522–528, 2011. View at Google Scholar
  23. P. Venkateswar Rao and A. Venkata Narasaiah, “Synthesis, characterization and biological studies of oxovanadium(IV), manganese(II), iron(II), cobalt(II), nickle(II) and copper(II) complexes derived from a quadridentate ligand,” Indian Journal of Chemistry Section A, vol. 42, no. 8, pp. 1896–1899, 2003. View at Google Scholar · View at Scopus
  24. R. Schlapp and W. G. Penney, “Influence of crystalline fields on the susceptibilities of salts of paramagnetic ions—II. the iron group, especially Ni, Cr and Co,” Physical Review, vol. 42, no. 5, pp. 666–686, 1932. View at Publisher · View at Google Scholar · View at Scopus
  25. Y. Tanabe and S. Sugano, “On the absorption spectra of complex ions—I,” Journal of the Physical Society of Japan, vol. 9, no. 5, pp. 753–766, 1954. View at Google Scholar · View at Scopus
  26. M. Joshi, H. D. Juneja, and J. P. Kanfade, “Synthesis, spectral characterization and thermogravimetric studies of some inorganic complexes,” International Journal of Knowledge Engineering, vol. 3, no. 1, pp. 69–71, 2012. View at Google Scholar