A novel effective bio-originated methylene blue adsorbent: the porous biosilica from three marine diatom strains of Nanofrustulum spp. (Bacillariophyta).

In the present paper, for the first time the ability of the porous biosilica originated from three marine diatom strains of 'Nanofrustulum spp.' viz. N. wachnickianum (SZCZCH193), N. shiloi (SZCZM1342), N. cf. shiloi (SZCZP1809), to eliminate MB from aqueous solutions was investigated. The highest biomass was achieved under silicate enrichment for N. wachnickianum and N. shiloi (0.98 g L-1 DW and 0.93 g L-1 DW respectively), and under 15 °C for N. cf. shiloi (2.2 g L-1 DW). The siliceous skeletons of the strains were purified with hydrogen peroxide and characterized by SEM, EDS, the N2 adsorption/desorption, XRD, TGA, and ATR-FTIR. The porous biosilica (20 mg DW) obtained from the strains i.e. SZCZCH193, SZCZM1342, SZCZP1809, showed efficiency in 77.6%, 96.8%, and 98.1% of 14 mg L-1 MB removal under pH 7 for 180 min, and the maximum adsorption capacity was calculated as 8.39, 19.02, and 15.17 mg g-1, respectively. Additionally, it was possible to increase the MB removal efficiency in alkaline (pH = 11) conditions up to 99.08% for SZCZP1809 after 120 min. Modelling revealed that the adsorption of MB follows Pseudo-first order, Bangham's pore diffusion and Sips isotherm models.

Removal of the Basic and Diazo Dyes from Aqueous Solution by the Frustules of Halamphora cf. salinicola (Bacillariophyta).

Industrial wastes with hazardous dyes serve as a major source of water pollution, which is considered to have an enormous impact on public health. In this study, an eco-friendly adsorbent, the porous siliceous frustules extracted from the diatom species Halamphora cf. salinicola, grown under laboratory conditions, has been identified. The porous architecture and negative surface charge under a pH of 7, provided by the various functional groups via Si-O, N-H, and O-H on these surfaces, revealed by SEM, the N2 adsorption/desorption isotherm, Zeta-potential measurement, and ATR-FTIR, respectively, made the frustules an efficient mean of removal of the diazo and basic dyes from the aqueous solutions, 74.9%, 94.02%, and 99.81% against Congo Red (CR), Crystal Violet (CV), and Malachite Green (MG), respectively. The maximum adsorption capacities were calculated from isotherms, as follows: 13.04 mg g-1, 41.97 mg g-1, and 33.19 mg g-1 against CR, CV, and MG, respectively. Kinetic and isotherm models showed a higher correlation to Pore diffusion and Sips models for CR, and Pseudo-Second Order and Freundlich models for CV and MG. Therefore, the cleaned frustules of the thermal spring-originated diatom strain Halamphora cf. salinicola could be used as a novel adsorbent of a biological origin against anionic and basic dyes.

Study on Biogenic Spindle-Shaped Iron-Oxide Nanoparticles by Pseudostaurosira trainorii in Field of Laser Desorption/Ionization Applications.

Nanostructures-assisted laser desorption/ionization mass spectrometry (NALDI-MS) is gaining attention for the analysis of a wide range of molecules. In this present investigation, Pseudostaurosira trainorii mediated biosynthesized iron-oxide nanoparticles (IONPs) have been utilized as nanostructures assisting ionization and desorption for laser desorption/ionization mass spectrometry (LDI-MS). The chain forming diatom, P. trainorii showed efficiency in the production of IONPs against 0.01 M Fe+3 (pH 2) aqueous solution at the intracellular and extracellular level. The whole biomass and external media turned dark orange in color after 3 days of reaction with Fe3+ solution. Scanning electron microscopic (SEM) images illustrated that the surface of Fe3+ exposed frustules of P. trainorii were entirely covered by synthesized nanostructures contrasting with the natural surface ornamentation of control cells. The IONPs loaded frustules also exhibited catalytic properties by decolorizing yellow colored nitrophenol after 3 h of reaction. Transmission electron microscopic (TEM) images confirmed that the produced particles are spindle-shaped with ~50-70 nm length and ~10-30 nm width. The biogenic IONPs were utilized as an inorganic matrix in LDI-MS and showed high sensitivity towards small molecules as glucose, alanine and triacylglycerols at nano- and picomolar level per spot, respectively. The presented biocompatible technique offers new perspectives in nanobiotechnology for the production of spindle-shaped IONPs that can be applied in future for the preparation of NALDI plates.

Photonic Nano-/Microstructured Diatom Based Biosilica in Metal Modification and Removal-A Review.

The siliceous exoskeletal shells of diatoms, commonly known as frustules, have drawn attention because of their photoluminescence property and high volume to surface area. Photonic biosilica can also enhance the plasmonic sensitivity of nanoparticles. Because of this, researchers have studied the effectiveness of various metal particles after combining with biosilica. Additionally, naturally occurring diatom-based biosilica has excellent adsorption and absorption capabilities, which have already been exploited for wastewater treatment. Moreover, the nanoporous, ultra-hydrophilic frustules can easily accumulate more molecules on their surfaces. As a consequence, it becomes easier to conjugate noble metals with silica, making them more stable and effective. The main focus of this review is to agglomerate the utility of biocompatible diatom frustules, which is a no-cost natural resource of biosilica, in metal modification and removal.

Diatom Mediated Production of Fluorescent Flower Shaped Silver-Silica Nanohybrid.

Fabrication of flower-like nanostructures are gaining attention because of their high surface/volume ratio and extensive adsorption capacity. In the present investigation, flower-shaped, autofluorescent silver-silica (Ag-SiO2) hybrid nanoparticles have been fabricated exploiting diatoms as a source of nanosilica. Two different species of Gedaniella including G. flavovirens and G. mutabilis showed their efficacy in synthesizing fluorescent Ag-SiO2 nanoflowers (NFs) and nanospheres (NSs) against 9 mM silver nitrate solution, respectively. The biogenic nanoconjugate (Ag-SiO2) was characterized by Uv-vis spectroscopy, energy dispersive X-ray spectroscopy (EDS), scanning (SEM) and transmission (TEM) electron microscopy. Production of Ag-SiO2 hybrid nanoparticle was confirmed by observing both Ag and Si signals from a single nanoparticle in an EDS study. The broad and single absorption band at ~420 nm in Uv-vis spectroscopy confirmed proper miscibility and production of hybrid nanoparticles. The Ag-SiO2 nanohybrids revealed autofluorescent property under the blue light region (excitation ~450-490 nm). SEM images of particles synthesized by G. flavovirens revealed the production of microscopic flower shaped Ag-SiO2 particles with several layers of petals. A TEM study confirmed that the synthesized Ag-SiO2 NFs are variable in size with 100-500 nm in diameter. Decolorization of methylene blue after exposure to Ag-SiO2 particles confirmed catalytic activity of synthesized nanostructures. This eco-friendly method provides a new dimension in nanobiotechnology for biogenesis of such hierarchical nanostructure in a cost-effective way.

Reducing Efficiency of Fucoxanthin in Diatom Mediated Biofabrication of Gold Nanoparticles.

In the present investigation, fucoxanthin-one of the major pigments in diatoms-has been extracted from Nanofrustulum shiloi SZCZM1342, and its reducing efficiency in the biogenesis of gold nanoparticles (GNPs) was checked. Fucoxanthin extracted from golden-brown cells of N. shiloi was compared to the healthy, growing biomass of N. shiloi and standard fucoxanthin after separate exposure to 25 mg L-1 aqueous hydrogen tetrachloroaurate solutions at room temperature. Isolated and standard fucoxanthin were found to be able to reduce gold ions within 12 h whereas, the whole biomass turned pink in color after 72 h of reaction. The synthesized particles were characterized by UV-vis spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). UV-vis spectroscopy of purple-colored suspensions showed the absorption band at approximately 520-545 nm, indicating a strong positive signal for GNP synthesis. The SEM study revealed the deposition of GNPs on siliceous frustules of metal-treated diatom cells. The TEM analysis confirmed the GNPs synthesized by whole biomass are triangular, spherical and hexagonal in nature, whereas the particles produced by extracted and standard fucoxanthin are all spherical in nature. This study demonstrates the involvement of fucoxanthin in the reduction of gold ions and subsequent production of gold nanospheres.

In-situ green synthesis of fluorescent silica-silver conjugate nanodendrites using nanoporous frustules of diatoms: an unprecedented approach.

Generally, nanodendrite synthesis is chemical mediated and expensive. The biogenesis of such hierarchical structures is still in its nascent stage. The present study aimed at exploiting the nanoporous frustules of Halamphora subturgida, as a source of biosilica for the biosynthesis and stabilization of conjugate nanodendrites of silica and silver. These minute diatom frustules when exposed to 9 mM of silver nitrate solution, a highly crystalline nanohybride dendrites were synthesized. The nanohybrid dendrite synthesis was initially confirmed by the formation of greyish-brown frustules after 72 h of exposure. The composite dendrites were thoroughly characterized by standard techniques. Electron microscopic images illustrated that the process began with the formation of isotropic hybrid nanospheres with an internal diameter of 20 nm and continued to develop anisotropic nanocrystals with time. The nanodendrites externally formed on the siliceous frustules, acting as a template for the former. They were characterized by distinct 100 nm wide and 1-2 µm long trunks and 70-100 nm wide and 220-220 nm long branches on either side of the trunk. The optical measurement revealed the fluorescence property of the nanostructures owing to the photoluminescent efficiency of the frustules. Both the externally derived hybrid nanodendrites and internally synthesized nanospheres possessed superior stability in the suspension with a zeta potential value of - 35.7 mV and - 24.8 mV, respectively. Thus, this method is eco-friendly and provides a new dimension for nanodendrite synthesis with minimal cost and maximal yield compared to its non-biologically synthesized counterparts that involve several other drawbacks like chemical hazards and high energy consumption.

Nitric oxide sensing by chlorophyll a.

Nitric oxide (NO) acts as a signalling molecule that has direct and indirect regulatory roles in various functional processes in biology, though in plant kingdom its role is relatively unexplored. One reason for this is the fact that sensing of NO is always challenging. There are very few probes that can classify the different NO species. The present paper proposes a simple but straightforward way for sensing different NO species using chlorophyll, the source of inspiration being hemoglobin that serves as NO sink in mammalian systems. The proposed method is able to classify NO from DETA-NONOate or (Z)-1-[N-(2-aminoethyl)-N-(2-ammonioethyl) amino] diazen-1-ium-1,2-diolate, nitrite, nitrate and S-nitrosothiol or SNO. This discrimination is carried out by chlorophyll a (chl a) at nano molar (nM) order of sensitivity and at 293 K-310 K. Molecular docking reveals the differential binding effects of NO and SNO with chlorophyll, the predicted binding affinity matching with the experimental observation. Additional experiments with a diverse range of cyanobacteria reveal that apart from the spectroscopic approach the proposed sensing module can be used in microscopic inspection of NO species. Binding of NO is sensitive to temperature and static magnetic field. This provides additional support for the involvement of the porphyrin ring structures to the NO sensing process. This also, broadens the scope of the sensing methods as hinted in the text.