Pro-and eukaryotic algal genera, i.e. Lyngbya majuscula, Spirulina subsalsa (Cyanophyceae) and Rhizoclonium hieroglyphicum (Chlorophyceae), were used for bio-recovery of gold (Au) out of aqueous solution. Au (III) spiked with 198 Au was used for the experiment. Batch laboratory experiments indicated quick metabolic independent binding of Au to the algae followed by active accumulation and subsequent reduction. Gold accumulation by different algal genera was found in order of R. hieroglyphicum > L. majuscula > S. subsalsa (3.28, 1.93 and 1.73 mg g -1 , respectively). It was observed that the algal biomass and the media used for the experiment turned purple in colour indicating reduction of Au (III) to Au (0) at intra-and extracellular level. This was confirmed by TEM studies of L. majuscula biomass exposed in HAuCl 4 solution where <20-nm-sized gold particles were found both inside as well as on the surface of the cell. Up to 90-100% of accumulated gold was recovered from the algal biomass by using nitric acid and acidic thiourea solution.
The cyanobacteria Phormidium valderianum, P. tenue and Microcoleus chthonoplastes and the green algae Rhizoclonium fontinale, Ulva intestinalis, Chara zeylanica and Pithophora oedogoniana were exposed to hydrogen tetrachloroaurate solution and were screened for their suitability for producing nano-gold. All three cyanobacteria genera and two of the green algae (Rhizoclonium fontinale and Ulva intestinalis) produced gold nanoparticles intracellularly, confirmed by purple colouration of the thallus within 72 h of treatment at 20 C. Extracted nanoparticle solutions were examined by UV-vis spectroscopy, transmission electron microscopy (TEM) and X-ray diffractometry (XRD). XRD confirmed the reduction of Au (III) to Au (0). UV-vis spectroscopy and TEM studies indicated the production of nanoparticles having different shapes and sizes. Phormidium valderianum synthesized mostly spherical nanoparticles, along with hexagonal and triangular nanoparticles, at basic and neutral pHs (pH 9 and pH 7, respectively). Medicinally important gold nanorods were synthesized (together with gold nanospheres) only by P. valderianum at acidic pH (pH 5); this was initially determined by two surface plasmon bands in UV-vis spectroscopy and later confirmed by TEM. Spherical to somewhat irregular particles were produced by P. tenue and Ulva intestinalis (TEM studies). The UV-vis spectroscopy of the supernatant of other algal extracts indicated the formation of mostly spherical particles. Production of gold nanoparticles by algae is more ecofriendly than purely chemical synthesis. However, the choice of algae is important: Chara zeylanica and Pithophora oedogoniana were found to be unable to produce nanoparticles.
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