Original Research PaperBiomass-derived thermal preparation of calcite, from phyto-capped marine gastropod shell, Turbinella pyrum L
Graphical abstract
Introduction
Marine endowed resources of pharmaceutics are aplenty in conch shells, corals, coral reefs, pearls, pearl oyster shells, cowries (gastropods) and bi-valve molluscs. These biogenic shells comprise of carbonate salts of calcium in combination with strontium, magnesium and barium as trace interstitial elements existing with different polymorphs [1]. Calcite is the most stable crystalline form of CaCO3 and all other forms are interconverted into calcite by thermal treatment [2]. The structural transformation of aragonite to stable calcite, is an endothermic process controlled by kinetics [3]. The high porosity, surface area to volume ratio, non-toxicity and biocompatibility towards bodily fluids naturally facilitate the potential utility of CaCO3 particles in the field of medicine, catalysis, environment, food processing and material reinforcement while enhancing their physical and chemical properties at the same time. Polymorphs of CaCO3 have diverse applications in various fields including pharmaceutics as nano-drug delivery system, and for calcium supplementation and also in material science. Cockle shell-derived aragonite nanoparticle, a metastable form of CaCO3, is used as a nano-drug delivery system in breast cancer treatment [4], and as an antibiotic for the treatment of osteomyelitis [5]. Nanocalcium from oyster shell has been found to be highly bioavailable and studied for preventing osteoporosis in rats [6], while calcined oyster shell has been used in the stabilization of contaminated soil by immobilizing arsenic, copper and lead [7].
Some of the marine products have been used in Indian Systems of Medicine including Siddha and Ayurveda since many centuries. Conches and bivalves have been used by humans since the period of Indus valley civilization [8], [9]. Among numerous types of conches, the ‘sacred chank’ or ‘Shankha’ or ‘Sangu’, which is zoologically known as Turbinella pyrum L finds much usage in India since ancient times [10] especially in terms religious and traditional practices. Calcite, known as ‘Sangu Parpam’ (SP) in the traditional Siddha System of Medicine is widely used in India and is one of the classical formulations used to treat arthritis, gastritis and skin disorders. Its actions are nutritive, carminative, stomachic, anodyne, febrifuge and expectorant. The clinical significance is that it greatly relieves dysmenorrhoea and enhances beauty, charm and renders physical strength and wellness and its anti-ulcer effect on albino rats has already been reported [11].
Biomimetic synthesis and CO2 bubbling methods are the two well-known methods to synthesize CaCO3 micro and nano particles [12]. Biomimetic methods are further classified into precipitation and reverse emulsion methods. Precipitation methods are further divided into spontaneous precipitation process and slow carbonation method. CO2 bubbling methods are the well-known, proven protocols for industrial production. Both the methods find their advantages in controlling the size, shape, polymorphs and morphology of the particles.
Pertaining to the synthesis of Calcite from natural resources, there are numerous methods that include, polymer coated CaCO3 nanoparticle synthesis using natural limestone [13], mechanical activation of egg shell biomaterial using a planetary ball mill to obtain two-phase calcite-aragonite systems [14], surfactant-assisted synthesis of Calcium carbonate nanoparticles [15] from naturally occurring dolomite. Lakshtanov et al. (2015) reported the role of alginate in recrystallization of natural Calcite [16]. Yang et al. (2010) reported the biomimetic mineralization of Calcite on phospholipid monolayers [17].
Plant materials mediated synthesis, including whole plant or specific part of it, is followed to synthesize novel materials of desired morphology. Plant extract mediated synthesis of metal nanoparticles (M-NPs) and metal-oxide nanoparticles (MO-NPs) have also been reported. For example, in the year 2014, the green synthesis of silver nanoparticles using different plant extracts [18] and in 2019, a review on plant extract mediated biogenic synthesis of CdO nanoparticles has been reported [19]. The role of the phyto-constituents in the plant extract mediated synthesis are to act as redox players in the stabilization of the metals and provide further assistance to yield nanoparticles. However, in the phyto-capping process reported here currently, the key starting material is completely triturated with herbal-pasty mass of 2–3 mm thickness, subsequent drying, followed by incineration, have resulted in the synthesis of Calcite particles of nano to micro dimensions.
The herbs namely, Pistia stratiotes L, Pergularia daemia (Forssk) Chiov, Phyllanthus amarus Schumach & Thonn and Ocimum tenuiflorum L, were chosen for the phyto-capping, due to their medicinal uses [20]. As a part of our ongoing research towards the synthesis of biologically active novel molecules [21], literature reviews [12] and inspired by the potential applications of Calcite, herein, we report, the synthesis, process optimization and characterization of Calcite from marine gastropod shell using phyto-capping of herbs followed by bio-mass derived thermal treatment. To the best of our knowledge, there were no scientific reports available for the aforesaid process so far.
Section snippets
Materials
The raw conch shell was collected from Bay of Bengal near Chennai [13.08°N, 80.27°E], India and was duly authenticated as Turbinella pyrum L. by the Marine Biology division, Zoological Survey of India (ZSI), Chennai, India.
The herbs Pistia stratiotes L, Pergularia daemia (Forssk) Chiov, Phyllanthus amarus Schumach & Thonn and Ocimum tenuiflorum L collected from Siddha Medicinal Plants Garden, Mettur (11.79°N, 77.80°E), India, a peripheral unit of Central Council for Research in Siddha, where
Results and discussion
The process involves five stages in which the first stage is the purification of raw conch shell and the second stage is the preparation of wet Pistia stratiotes L herbal paste. The third stage is the capping of purified conch shell with wet Pistia stratiotes L herbal paste with the fourth stage being the subsequent drying of third stage product and the fifth stage being the incineration process [Fig. 1].
PXRD data of raw and purified conch shell (a, b) is found to be an aragonite [JCPDS No.:
Conclusions
The process of preparing Calcite by biomass-derived incineration of phyto-capped, marine gastropod shell, Turbinella pyrum L has been described methodically with significant characterization specifics, expounding its clinical scope. The mechanically hard shell of Turbinella pyrum is found be to basically Aragonite. The phyto-capped and incinerated shell was processed to prepare Calcite powder of nano-micro sizes. The phyto-constituents through the process of phyto-capping resulted in the
Acknowledgements
The authors acknowledge Dr. Rajkumar Rajan, Senior scientist, Zoological Survey of India, Chennai for the authentication of conch shell. The corresponding author thank Central Council for Research in Siddha, Ministry of AYUSH, Chennai for the funding through Intramural research scheme vide sanction no. 279/2016-17 dated 26.09.2016.
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