Unveiling chiral optical constants of α-pinene and propylene oxide through ATR and VCD spectroscopy in the mid-infrared range.

Optical constants functions of analytes are indispensable for the effective design of plasmonic sensors. Such sensors are potentially able to enhance the sensitivity by several order of magnitudes which can greatly facilitate the determination of the generally weak spectral signals caused by vibrational circular dichroism. Accordingly, to demonstrate how to obtain these functions, we have determined the dielectric and chirality admittance functions of α-Pinene and Propylene oxide in the mid-infrared spectral range using attenuated total reflection and vibrational circular dichroism spectroscopy. Our iterative formalism starts with an estimation of the absorption index function, followed by the calculation of the refractive index function using the Kramers-Kronig relation and a modelled spectrum based on Fresnel's equations. By comparing the experimental and modelled spectra, we improve the absorption index function. To determine the chirality admittance function, we use the same iterative formalism, but with a modified 4x4 matrix formalism formulated by Berreman. Our results show that the experimental absorbance difference is independent of the dielectric function of the chiral substance and depends linearly on the cuvette thickness. Additionally, we provide a sum rule that can be used to assess the quality of VCD spectra and determine the position of the baseline. Our findings provide crucial insights into the optical properties of chiral substances in the mid-infrared spectral range, which have important implications for a range of applications in fields such as analytical chemistry and materials science.

Bioaccumulation of selenium in halotolerant microalga Dunaliella salina and its impact on photosynthesis, reactive oxygen species, antioxidative enzymes, and neutral lipids.

Selenium (Se) is an essential element for living systems, however, toxic at higher levels. In the present study, Dunaliella salina cells were exposed to different Se concentrations for their growth (EC50 195 mg L-1) as well as Se accumulation. The cells exposed to 50 mg L-1 Se showed photoautotrophic growth parallel to control and accumulated 65 µg Se g-1 DW. A decrease in photosynthetic quantum yield, chlorophyll content, and the increase in intracellular reactive oxygen species, proline content, and lipid peroxidation accompanied by higher neutral lipid accumulation, were recorded at higher Se level. The enzymes superoxide dismutase and catalase played a pivotal role in antioxidative defense. Heterogeneity in accumulated carotenoids at varying concentrations of selenium was prevalent. The cells exposed to 200 mg L-1 Se resulted in the disorganization of organelles. Thus, the Se enriched biomass obtained at 50 mg L-1 may be explored for bio-fortification of food and feed.

Biochemical and physiological characterization of a halotolerant Dunaliella salina isolated from hypersaline Sambhar Lake, India.

The objective of the present study was to characterize intrinsic physiological and biochemical properties of the wall-less unicellular cholorophyte Dunaliella salina isolated from a hypersaline Sambhar Lake. The strain grew optimally at 0.5 M NaCl and 16:8 h L:D photoperiod along with maintaining low level of intracellular Na+ even at higher salinity, emphasizing special features of its cell membranes. It was observed that the cells experienced stress beyond 2 M NaCl as evidenced by increased intracellular reactive oxygen species and antioxidative enzymes, nevertheless proline and malondialdehyde content declined sharply accompanied by higher neutral lipid accumulation. Salinity exceeding 2 M resulted decrease in photosynthetic quantum yield (Fv/Fm) and enhanced glycerol synthesis accompanied by leakage. Super oxide dismutase seemed to play a pivotal role in antioxidative defense as eight isoforms were expressed differentially while catalase and glutathione peroxidase showing no significant change in their expression at higher salinity. The ability of D. salina to grow in range of salinities by sustaining healthy photosynthetic apparatus along with accumulation of valuable products made this alga an ideal organism that can be exploited as resource for biofuel and commercial products.

Development of ALD Coatings for Harsh Environment Applications.

Atomic layer deposition (ALD) is a well-known technique for the fabrication of ultrathin and highly conformal barrier coatings which have extensively been used for the protection of electronic devices in open atmospheric conditions. Here, we extend the scope for the application of low-temperature-deposited plasma-enhanced ALD barrier coatings for the protection of devices in a variety of chemical environments. The chemical stability tests were conducted in 3.5% NaCl, sea water, HCl (pH 4), and H2SO4 (pH 4) solutions for ALD Al2O3, HfO2, TiO2, and ZrO2, deposited at 100 °C on TiO2-coated Au and ALD ZnO (photoactive)-coated Si substrates. Using electrochemical impedance spectroscopy (EIS) and photoluminescence (PL) study, various aspects of the barrier properties and performance of ALD films in harsh chemical environments were explored. We demonstrate that the combined approach involving EIS and PL provides unique insights into the suitability of ALD films as barriers in harsh environments involving ionic solutions. The observations from EIS and PL tests are supported by the X-ray photoelectron spectroscopy analysis of ALD materials. Of the materials tested, ALD TiO2 and ZrO2 were found to be the most stable, chemically, in all four solutions, whereas TiO2 was a better permeation barrier.

Polarization-Tailored Fano Interference in Plasmonic Crystals: A Mueller Matrix Model of Anisotropic Fano Resonance.

Fano resonance is observed in a wide range of micro- and nano-optical systems and has been a subject of intensive investigations due to its numerous potential applications. Methods that can control or modulate Fano resonance by tuning some experimentally accessible parameters are highly desirable for realistic applications. Here we present a simple yet elegant approach using the Mueller matrix formalism for controlling the Fano interference effect and engineering the resulting asymmetric spectral line shape in an anisotropic optical system. The approach is founded on a generalized model of anisotropic Fano resonance, which relates the spectral asymmetry to physically meaningful and experimentally accessible parameters of interference, namely, the Fano phase shift and the relative amplitudes of the interfering modes. The differences in these parameters between orthogonal linear polarizations in an anisotropic system are exploited to desirably tune the Fano spectral asymmetry using pre- and postselection of optimized polarization states. The concept is demonstrated on waveguided plasmonic crystals using Mueller matrix-based polarization analysis. The approach enabled tailoring of several exotic regimes of Fano resonance in a single device, including the complete reversal of the spectral asymmetry, and shows potential for applications involving control and manipulation of electromagnetic waves at the nanoscale.

Transverse spin and transverse momentum in scattering of plane waves.

We study the near field to the far field evolution of spin angular momentum (SAM) density and the Poynting vector of the scattered waves from spherical scatterers. The results show that at the near field, the SAM density and the Poynting vector are dominated by their transverse components. While the former (transverse SAM) is independent of the helicity of the incident circular polarization state, the latter (transverse Poynting vector) depends upon the polarization state. It is further demonstrated that the interference of the transverse electric and transverse magnetic scattering modes enhances both the magnitudes and the spatial extent of the transverse SAM and the transverse momentum components.

Environmentally Assisted Cracking in Silicon Nitride Barrier Films on Poly(ethylene terephthalate) Substrates.

A singular critical onset strain value has been used to characterize the strain limits of barrier films used in flexible electronics. However, such metrics do not account for time-dependent or environmentally assisted cracking, which can be critical in determining the overall reliability of these thin-film coatings. In this work, the time-dependent channel crack growth behavior of silicon nitride barrier films on poly(ethylene terephthalate) (PET) substrates is investigated in dry and humid environments by tensile tests with in situ optical microscopy and numerical models. The results reveal the occurrence of environmentally assisted crack growth at strains well below the critical onset crack strain and in the absence of polymer-relaxation-assisted, time-dependent crack growth. The crack growth rates in laboratory air are about 1 order of magnitude larger than those tested in dry environments (dry air or dry nitrogen). In laboratory air, crack growth rates increase from ∼200 nm/s to 60 µm/s for applied stress intensity factors, K, ranging from 1.0 to 1.4 MPa·m1/2, below the measured fracture toughness Kc of 1.8 MPa·m1/2. The crack growth rates in dry environments were also strongly dependent on the prior storage of the specimens, with larger rates for specimens exposed to laboratory air (and therefore moisture) prior to testing compared to specimens stored in a dry environment. This behavior is attributed to moisture-assisted cracking, with a measured power law exponent of ∼22 in laboratory air. This study also reveals that much larger densities of channel cracks develop in the humid environment, suggesting an easier initiation of channel cracks in the presence of water vapor. The results obtained in this work are critical to address the time-dependent and environmental reliability issues of thin brittle barriers on PET substrates for flexible electronics applications.