Transition metal dichalcogenide materials have recently been shown to exhibit a variety of intriguing optical and electronic phenomena. Focusing on the optical properties of semiconducting WS2 nanotubes, we show here that these nanostructures exhibit strong light-matter interaction and form exciton-polaritons. Namely, these nanotubes act as quasi 1-D polaritonic nano-systems and sustain both excitonic features and cavity modes in the visible-near infrared range. This ability to confine light to subwavelength dimensions under ambient conditions is induced by the high refractive index of tungsten disulfide. Using "finite-difference time-domain" (FDTD) simulations we investigate the interactions between the excitons and the cavity mode and their effect on the extinction spectrum of these nanostructures. The results of FDTD simulations agree well with the experimental findings as well as with a phenomenological coupled oscillator model which suggests a high Rabi splitting of ∼280 meV. These findings open up possibilities for developing new concepts in nanotube-based photonic devices.
A new technique of gold nanoparticle (AuNP) growth on the sidewalls of WS2 inorganic nanotubes (INT-WS2) and the surface of MoS2 fullerene-like nanoparticles (IF-MoS2) is developed to produce metal–semiconductor nanocomposites. The coverage density and mean size of the nanoparticles are dependent on the HAuCl4/MS2 (M = W, Mo) molar ratio. AuNPs formation mechanism seems to involve spatially divided reactions of AuCl4 – reduction and WS2/MoS2 oxidation taking place on the surface defects of the disulfide nanostructures rather than directly at the AuNP-INT/IF interface. A strong epitaxial matching between the lattices of the gold nanoparticles and the INT-WS2 or IF-MoS2 seems to suppress plasmon resonance in the nanocomposites with small (<10 nm mean size) AuNPs.
Iron deficiency is a frequent problem for many crops, particularly in calcareous soils and iron humates are commonly applied in the Mediterranean basin in spite of their lesser efficiency than iron synthetic chelates. Development and application of new fertilizers using nanotechnology are one of the potentially effective options of enhancing the iron humates, according to the sustainable agriculture. Particle size, pH, and kinetics constrain the iron humate efficiency. Thus, it is relevant to understand the iron humate mechanism in the plant–soil system linking their particle size, characterization and iron distribution in plant and soil using 57 Fe as a tracer tool. Three hybrid nanomaterials (F, S, and M) were synthesized as iron-humic nanofertilizers ( 57 Fe-NFs) from leonardite potassium humate and 57 Fe used in the form of 57 Fe(NO 3 ) 3 or 57 Fe 2 (SO 4 ) 3 . They were characterized using Mössbauer spectroscopy, X-ray diffraction (XRD), extended X-ray absorption fine structure spectroscopy (EXAFS), transmission electron microscopy (TEM) and tested for iron availability in a calcareous soil pot experiment carried out under growth chamber conditions. Three doses (35, 75, and 150 μmol pot -1 ) of each iron-humic material were applied to soybean iron deficient plants and their iron nutrition contributions were compared to 57 FeEDDHA and leonardite potassium humate as control treatments. Ferrihydrite was detected as the main structure of all three 57 Fe-NFs and the plants tested with iron-humic compounds exhibited continuous long-term statistically reproducible iron uptake and showed high shoot fresh weight. Moreover, the 57 Fe from the humic nanofertilizers remained available in soil and was detected in soybean pods. The Fe-NFs offers a natural, low cost and environmental option to the traditional iron fertilization in calcareous soils.
Availability of Fe in soil to plants is closely related to the presence of humic substances (HS). Still, the systematic data on applicability of iron-based nanomaterials stabilized with HS as a source for plant nutrition are missing. The goal of our study was to establish a connection between properties of iron-based materials stabilized by HS and their bioavailability to plants. We have prepared two samples of leonardite HS-stabilized iron-based materials with substantially different properties using the reported protocols and studied their physical chemical state in relation to iron uptake and other biological effects. We used Mössbauer spectroscopy, XRD, SAXS, and TEM to conclude on iron speciation, size, and crystallinity. One material (Fe-HA) consisted of polynuclear iron(III) (hydr)oxide complexes, so-called ferric polymers, distributed in HS matrix. These complexes are composed of predominantly amorphous small-size components (<5 nm) with inclusions of larger crystalline particles (the mean size of (11 ± 4) nm). The other material was composed of well-crystalline feroxyhyte (δ'-FeOOH) NPs with mean transverse sizes of (35 ± 20) nm stabilized by small amounts of HS. Bioavailability studies were conducted on wheat plants under conditions of iron deficiency. The uptake studies have shown that small and amorphous ferric polymers were readily translocated into the leaves on the level of Fe-EDTA, whereas relatively large and crystalline feroxyhyte NPs were mostly sorbed on the roots. The obtained data are consistent with the size exclusion limits of cell wall pores (5-20 nm). Both samples demonstrated distinct beneficial effects with respect to photosynthetic activity and lipid biosynthesis. The obtained results might be of use for production of iron-based nanomaterials stabilized by HS with the tailored iron availability to plants. They can be applied as the only source for iron nutrition as well as in combination with the other elements, for example, for industrial production of "nanofortified" macrofertilizers (NPK).
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