Uptake, Distribution, and Transformation of Zerovalent Iron Nanoparticles in the Edible Plant Cucumis sativus.

Here, we investigated the fate of nanoscale zerovalent iron (nZVI) on the Cucumis sativus under both hydroponic and soil conditions. Seedlings were exposed to 0, 250, and 1000 mg/L (or mg/kg soil) nZVI during 6-9 weeks of a growth period. Ionic controls were prepared using Fe-EDTA. None of the nZVI treatments affected the plant biomass. On the basis of the total iron contents and the superparamagnetic property of nZVI-exposed roots, there was no evidence of pristine nZVI translocation from the roots to shoots. Electron microscopy revealed that the transformed iron nanoparticles are stored in the root cell membrane and the vacuoles of the leaf parenchymal cells. X-ray absorption spectroscopy identified ferric citrate (41%) and iron (oxyhydr)oxides (59%) as the main transformed products in the roots. The shoot samples indicated a larger proportion of ferric citrate (60%) compared to iron (oxyhydr)oxides (40%). The 1.8-fold higher expression of the CsHA1 gene indicated that the plant-promoted transformation of nZVI was driven by protons released from the root layers. The current data provide a basis for two potential nZVI transformation pathways in Cucumis sativus: (1) interaction with low molecular weight organic acid ligands and (2) dissolution-precipitation of the mineral products.

Tunichrome-Inspired Gold-Enrichment Dispersion Matrix and Its Application in Water Treatment: A Proof-of-Concept Investigation.

Tunicate, a filter-feeder in seawater, is able to accumulate high amount of metals using intracellular polymer matrices. The woven pyrogallol structures of tunichrome, a small peptide contained in tunicate's blood cells, is believed to be responsible for selective metal sequestration in tunicates from seawater. However, the intriguing tunichrome matrix is difficult both to harvest from the tunicate and to synthesize massively due to the extreme oxidation sensitivity of the pyrogallol moiety which limits the study scope. Here, we succeeded to mimic tunichrome by conjugating two cheap and naturally occurring components: pyrogallol-5-carboxylic acid (gallic acid) and chitin nanofiber. A tunicate-mimetic infiltration matrix of surface-tailored chitin nanofibers with pyrogallol moieties (CGa) demonstrated the versatility of this strategy in generation of ingenious filtration material, especially for unprecedented fine and clean gold recovery inside of the tunicate-mimetic infiltration matrix (>99%, 533 mg gold per gram weight), which exceeds that of the presently most popular materials. Complexation between pyrogallol on the nanofiber and gold was similar to that of a tunichrome's metal sequestration. Extended X-ray absorption fine structure (EXAFS) spectroscopy and data-fitting elucidated the decreased coordination numbers for Au-Au nearest neighbors, demonstrating that gold coordinated to pyrogallol units, followed by an intramolecular association of Au0. A catalytic reduction of 4-nitrophenol mediated by the tunicate-mimetic matrix with harvested gold revealed excellent recyclability up to 30 cycles (∼95% reduction), which together with methylene blue reduction and antimicrobial performances indicates the versatile characteristics of sustainable processes by the tunichrome mimetics. This strategy opens the door for fast-developing new biomimetic alternatives for precious metal recovery, which is not restricted to gold and can offer a tool for multifaceted soft/hard nanomaterials.

Adsorption of As(V) by boehmite and alumina of different morphologies prepared under hydrothermal conditions.

Morphology-controlled materials at the micro- and nanoscale levels are of great significance to the design and application of materials. Stable and well-dispersed boehmite and alumina with different morphologies were fabricated under hydrothermal conditions. The nitrate, chloride, and sulfate aluminum salts yielded nanoplate, microspindle, and microsphere morphologies, respectively. Calcination of the prepared boehmite samples yielded alumina samples with retention of the morphologies. In comparisons of samples with identical morphologies, alumina exhibited better uptake of As(V) than boehmite; the As(V) concentration was analyzed by the standard molybdenum blue method. The adsorption capabilities of the morphologically controlled materials are ranked microspindle > microsphere > nanoplate. The impacts of process parameters, such as reaction time; initial As(V) concentration; solution pH; competing ions (Ca2+, Mg2+, NO3-, PO43-), which are common in most aquatic ecosystems; and co-contaminants (Cr(VI), Pb(II)), on removal efficiencies were examined. A well-defined mesostructure, superior surface area, chemical and electrostatic interaction, and surface charge distribution over the aluminol surface sites could be factors in the uptake of As(V). The design and synthesis of functional hierarchical micro- and nanostructured materials with the desired adsorptive properties, which are suitable for water treatment applications, can be achieved through environmentally benign hydrothermal fabrication.

Distinctive green recovery of silver species from modified cellulose: mechanism and spectroscopic studies.

The present study aimed to recover precious silver in order to identify the adsorption coupled reduction pathways that determine this process. A combination technique of adsorption and nanocrystallization was used to investigate the recovery of silver species from taurine-cellulose (T-DAC) samples. The non-synthetic route of nanocrystallization yielded spherical zero-valent silver sized ∼ 18 nm. Rate-controlling steps were modeled by adsorption parameters by the best fit of Langmuir capacity (55 mg/g), pseudo-second order curves, and exothermic chemical reactions. The T-DAC was an excellent sorbing phase for the treatment of silver-polluted waters over a broad range of pH (2.1-10.1) and varying ionic strengths (8.5-850 mM, as NaCl), which are the conditions often encountered in industrial and mining effluents. A good recovery of silver (40-65%) was also obtained in the presence of Cd(II), Co(II), Cr(VI), Ni(II), and As(V) at lower or equivalent concentrations with Ag(I), either from individually added metals or from all metal ions mixed together. Desorption was compared with a series of five eluents including complexing agents. In these experiments acidified thiourea yielded 86% desorption of Ag(I). Aqueous silver reduced to metallic silver on the surface of the T-DAC samples, which was confirmed by X-ray photo electron spectroscopy.

Protocol for development of various plants leaves extract in single-pot synthesis of metal nanoparticles.

This article is aimed to extend a simple protocol for preparation of various plant leaves extract and their application to green synthesis of the metallic nanoparticles. Five plant leaves extract showed mild reduction and stabilization ability for silver and gold nanoparticles (AgNPs and AuNPs) at room temperature. The particle size range varied from 25 to 42 nm and 21 to 47 nm for AgNPs and AuNPs, respectively. Plant leaves extract-mediated nanoparticles were characterized to confirm the shape, size, crystallinity, and content using different spectroscopic investigations. Differences in stability of nanoparticles at different pH were also measured by zeta potential.

Plant-mediated biosynthesis of silver and gold nanoparticles.

Single-pot biosynthesis of silver and gold quasi-spherical nanoparticles (SNPs and GNPs) in the size range of 10-30 nm was attempted using Chenopodium album (an obnoxious weed). This method is rapid, facile, convenient and environmentally safe. Average crystal size was approximately 12 nm and 10 nm for silver and gold nanocrystals respectively. Synthesized NPs were stable in a wide range of pH as there was less variation in zeta potential values. In synthesis of SNPs and GNPs, naturally occurring oxalic acid played significant role in bio-reduction of silver nitrate and auric acid solution into their corresponding silver and gold nano-colloids in single step rapid process.