Electronic and optical properties of Sr3X2 (X=N,P, As,Sb and Bi) compounds: first principles study

ABSTRACT

Direct bandgap semiconductors are very essential to fulfil the demand for the advancement in optoelectronic devices. Therefore it is important to predict new potential candidates having such unique features. In current work, Sr₃X₂ (X=N, P, As, Sb and Bi) compounds have been reported for the first time by well trusted FP-APW+lo method. For the better prediction of the energy band gap, mBJ is used alongwith routine generalised gradient approximation (GGA). The results show small and direct energy band gaps at Γ-Γ symmetry points with magnitude in the range from 0.62?eV (Sr₃P₂) to zero energy band gap (Sr₃Bi₂). In partial density of state Sr-d state and X-p state are contributed in the band structure. The compounds show mostly covalent bonding nature. The frequecy dependent optical properties in the linear optical range are also investigated.     

NMR spectral analysis of strongly second-order 6-, 8-, 9- and 10- spin-systems (1H─19F, 19F─19F,and 13C─19F) in perfluorotoluyl- and tetrafluoro-pyridyl-aromatics using the lineshape method ANATOLIA

A simple to use nuclear magnetic resonance analysis method has been tested on complex ¹H, ¹⁹F, and ¹³C multiplets. This open-source line-shape analysis method analysis of total lineshape (ANATOLIA)¹ provides some significant advantages over traditional assign-iterate methods of NMR spectral analysis by avoiding false minima and progressing optimisation to the global minimum. The target molecules are 1-perfluorotol-4-yl-2-perfluorotol-4-yl-oxymethyl-1H-benzimidazole (molecule-I) and 1-tetrafluoropyrid-4-yl-2-tetrafluoropyrid-4-yl-thio-1H-benzimidazole (molecule-II) which were produced as part of a family of fluorinated drug scaffolds prepared for anticancer and antiparasitic screening. Spectra display significant second-order effects with ¹H Δδ = 3.68 and 4.67 Hz for the aromatic hydrogen “triplets”, with ¹⁹F ⁴J_AA', ⁴J_BB', ⁴J_XX', and ⁴J_YY' coupling constants range from +4.8 to −14.0 Hz and for ¹³C-isotopomers ¹⁹F Δδ of up to 111.56 Hz. A spin-system of six coupling nuclei (H_aH_bH_cH_d F_YF_Y') was analysed in 12 s, a spin-system of nine coupling fluorine nuclei (AA'BB'CCC-YY') was analysed within 2 min, and 10 coupling nuclei (XX'YY'ZZZ-BB'-H_d) was optimised in 6 min using a laptop computer. ANATOLIA was also robust enough to be able to yield accurate spectral values from inaccurate input values. In both compounds, a fluorine–fluorine coupling constant was identified between the two fluoro-aromatic rings (F_BB' and F_YY') of +4.05 and +4.67 Hz and attributed to a through-space interaction. Ab initio structure optimisations and coupling constant calculations provided useful input data for spectral analysis. A modern ¹⁹F nuclear magnetic resonance spectrum of perfluorotoluene (octafluorotoluene) and analysis from 1975 was used as a test data set to assess ANATOLIA.     

Designing spirobifullerene core based three-dimensional cross shape acceptor materials with promising photovoltaic properties for high-efficiency organic solar cells

The development of organic electron acceptor materials is one of the key factors for realizing high-performance organic solar cells (OSCs). Nonfullerene electron acceptors, compared to traditional fullerene acceptor materials, have gained much impetus owing to their better optoelectronic tunabilities and lower cost, as well as higher stability. Therefore, 5 three-dimensional (3D) cross-shaped acceptor materials having a spirobifullerene core flanked with 2,1,3-benzothiadiazole are designed from a recently synthesized highly efficient acceptor molecule SF(BR) ₄ and are investigated in detail with regard to their use as acceptor molecules in OSCs. The density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed for the estimation of frontier molecular orbital (FMO) analysis, density of states analysis, reorganization energies of electron and hole, dipole moment, open-circuit voltage, photo-physical characteristics, and transition density matrix analysis. In addition, the structure-property relationship is studied, and the influence of end-capped acceptor modifications on photovoltaic, photo-physical, and electronic properties of newly selected molecules ( H1-H5 ) is calculated and compared with reference ( R ) acceptor molecule SF(BR) ₄ . The structural tailoring at terminals was found to effectively tune the FMO band gap, energy levels, absorption spectra, open-circuit voltage, reorganization energy, and binding energy value in selected molecules H1 to H5 . The 3D cross-shaped molecules H1 to H5 suppress the intermolecular aggregation in PTB7-Th blend, which leads to high efficiency of acceptor material H1 to H5 in OSCs. Consequently, better optoelectronic properties are achieved from designed molecules H1 to H5 . It is proposed that the conceptualized molecules are superior than highly efficient spirobifullerene core-based SF(BR) ₄ acceptor molecules and, thus, are recommended to experiments for future developments of highly efficient solar cells.     

Influence of Relative Permeability on the Stability Characteristics of Immiscible Flow in Porous Media

Relative permeability functions for immiscible displacements in porous media show a wide range of profiles. Although, this behavior is well known, its impact on the stability of the displacement process is unexplored. Our analysis clearly demonstrates for the first time that the viscous instability characteristics of two-phase flows are governed not only by their end point values, but are strongly dependent on the actual profile of relative permeability functions. Linear stability analysis predicts the capacity of the flow to develop large scale fingers which can result in substantial bypassing of the resident fluid. It is observed that relative permeability functions attributed to drainage processes yield a more unstable displacement as compared to functions related to imbibition processes. Moreover, instability is observed to increase for those relative permeability functions which result from increased wettability of the wetting fluid. High accuracy numerical simulations show agreement with these predictions and demonstrate how large amplitude viscous fingers result in significant bypassing for certain relative permeability functions. In the nonlinear regime, the finger amplitude grows at a rate ∝ t^1/2 initially, drops to t^1/4 at a later time and finally grows ∝ t. The basic mechanisms of finger interaction, however, are not substantially influenced by relative permeability functions.     

New catalytic effect of thiourea on the oxidative cyanation of N-aryltetrahydroisoquinolines

Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experimental investigations demonstrated that thiourea acts as a radical initiator by abstracting hydroxyl radical (OH) from tert-butyl hydroperoxide (TBHP) directly instead of non-covalent hydrogen bondings (H-bondings) activation. The use of thiourea as a radical initiator offers a new avenue for innovative chemical transformations in organocatalyzed radical chemistry.     

Large-volume stacking in capillary electrophoresis using pH hysteresis of the electroosmotic flow in a bare fused-silica capillary

For large-volume stacking with the electroosmotic flow pump (LVSEP) in capillary electrophoresis of anionic analytes it is required that the electroosmotic mobility (EOM) should be smaller than the magnitudes of the effective mobilities of the analytes. When a fused-silica capillary is treated with an acidic solution, the silanoate group on the silica surface is neutralized to silanol and the EOM is suppressed. Due to the slow deprotonation equilibrium of the silanol group at an intermediate pH, this reduced EOM can be retained during a number of electrophoresis runs. Using a bare fused-silica capillary preconditioned with 0.01 M HCl, successful LVSEP at pH 6.0 was achieved for weakly acidic compounds with two orders of magnitude enhancements in the concentration sensitivity. The repeatability in migration times of ten analytes stacked by LVSEP in a single day was excellent with the relative standard deviation (RSD) less than 1% (n = 6). The day-to-day repeatability was also excellent with RSD less than 3% (n = 3 x 6) when the capillary was preconditioned each day.     

Identification of extracellular nanoparticle subsets by nuclear magnetic resonance

Exosomes are a subset of secreted lipid envelope-encapsulated extracellular vesicles (EVs) of 50–150 nm diameter that can transfer cargo from donor to acceptor cells. In the current purification protocols of exosomes, many smaller and larger nanoparticles such as lipoproteins, exomers and microvesicles are typically co-isolated as well. Particle size distribution is one important characteristics of EV samples, as it reflects the cellular origin of EVs and the purity of the isolation. However, most of the physicochemical analytical methods today cannot illustrate the smallest exosomes and other small particles like the exomers. Here, we demonstrate that diffusion ordered spectroscopy (DOSY) nuclear magnetic resonance (NMR) method enables the determination of a very broad distribution of extracellular nanoparticles, ranging from 1 to 500 nm. The range covers sizes of all particles included in EV samples after isolation. The method is non-invasive, as it does not require any labelling or other chemical modification. We investigated EVs secreted from milk as well as embryonic kidney and renal carcinoma cells. Western blot analysis and immuno-electron microscopy confirmed expression of exosomal markers such as ALIX, TSG101, CD81, CD9, and CD63 in the EV samples. In addition to the larger particles observed by nanoparticle tracking analysis (NTA) in the range of 70–500 nm, the DOSY distributions include a significant number of smaller particles in the range of 10–70 nm, which are visible also in transmission electron microscopy images but invisible in NTA. Furthermore, we demonstrate that hyperpolarized chemical exchange saturation transfer (Hyper-CEST) with ¹²⁹Xe NMR indicates also the existence of smaller and larger nanoparticles in the EV samples, providing also additional support for DOSY results. The method implies also that the Xe exchange is significantly faster in the EV pool than in the lipoprotein/exomer pool.

Diffusion and xenon NMR based methods to determine a very broad range of sizes and sub-sets of extracellular vesicles.     

The aftermath of the interplay between the endoplasmic reticulum stress response and redox signaling

The endoplasmic reticulum (ER) is an essential organelle of eukaryotic cells. Its main functions include protein synthesis, proper protein folding, protein modification, and the transportation of synthesized proteins. Any perturbations in ER function, such as increased demand for protein folding or the accumulation of unfolded or misfolded proteins in the ER lumen, lead to a stress response called the unfolded protein response (UPR). The primary aim of the UPR is to restore cellular homeostasis; however, it triggers apoptotic signaling during prolonged stress. The core mechanisms of the ER stress response, the failure to respond to cellular stress, and the final fate of the cell are not yet clear. Here, we discuss cellular fate during ER stress, cross talk between the ER and mitochondria and its significance, and conditions that can trigger ER stress response failure. We also describe how the redox environment affects the ER stress response, and vice versa, and the aftermath of the ER stress response, integrating a discussion on redox imbalance-induced ER stress response failure progressing to cell death and dynamic pathophysiological changes.Subject terms: Mechanisms of disease, Cell biology     

Decomposition of vegetables for determination of Zn,Cd, Pb and Cu by stripping voltammetry

A simple and accurate digestion method using nitric acid, perchloric acid and hydrogen peroxide has been developed for use in trace analysis for heavy metals in vegetables by differential pulse anodic stripping voltammetry. The recovery of the metals from the samples is lower if the hydrogen peroxide is omitted from the digestion mixture. Standard reference materials have been analysed satisfactorily by this method.