Physical and optical properties of organo-modified silica nanoparticles prepared by sol–gel

A comparative study on the physical and optical properties of silica nanoparticles prepared by sol–gel has been carried out. Post-modification of as-synthesized silica nanoparticles produced organo-functionalized silica nanoparticles slightly increased in size (~20%) and relatively high aggregation. However, in situ method produced sixfold bigger functionalized particles with good dispersion and less aggregation. Higher organic content was observed for in situ modified nanosilica, leading to a higher surface hydrophobicity that improved compatibility and dispersion in preparation of silica-polymer nanocomposite. Furthermore, in situ and post-modified nanosilica demonstrated a distinct optical activity, photoluminescence and UV compared to the unmodified nanoparticles.     

Determination of formal potential of NADH/NAD+ redox couple and catalytic oxidation of NADH using poly(phenosafranin)-modified carbon electrodes

The electrochemical regeneration of NADH/NAD⁺ redox couple has been studied using poly(phenosafranin) (PPS)-modified carbon electrodes to evaluate the formal potential and catalytic rate constant for the oxidation of NADH. The PPS-modified electrodes were prepared by electropolymerization of phenosafranin onto different carbon substrates (glassy carbon (GC) and basal-plane pyrolytic graphite (BPPG)) in different electrolytic solutions. The formal potential was estimated to be ? 0.365 ± 0.002 V vs. SHE at pH 7.0. As for the bare carbon electrodes, the oxidation of NADH at the BPPG electrode was found to be enhanced compared with the GC electrode. For the PPS-modified electrodes, it was found that the electrocatalysis of PPS-modified electrodes for the oxidation of NADH largely depends on the carbon substrate and electrolyte solution employed for their preparation, i.e., the PPS-modified BPPG electrode prepared in 0.2 M NaClO₄/acetonitrile solution exhibits an excellent and persistent electrocatalytic property toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 740 and 670 mV compared with those at the bare GC electrode and the PPS-modified GC electrode prepared in 0.2 M H₂SO₄ solution, respectively. A quantitative analysis of the electrocatalytic reaction based on rotating disk voltammetry gave the electrocatalytic reaction rate constants of the order of 10³–10⁴ M^?1 s^? 1 depending on the preparation conditions of the PPS-modified electrodes.     

Forty years of research on osmolyte-induced protein folding and stability

Most organisms that have adapted to environmental stresses have done so by production and accumulation of certain small organic molecules, known as osmolytes that arose by natural selection and have the ability to stabilize intracellular proteins against the environmental stress. It is well known that osmolytes stabilize proteins and induce folding of aberrant proteins and therefore, it is of therapeutic use for a large number of protein misfolding diseases. Thus, it is very important that the present knowledge of the ability and mechanism of osmolyte-induced protein folding and structural stabilization should reach to researchers working in different avenues. In around 40 years of research, we have gained great advances in various aspects of protein folding and structural stabilization induced by osmolytes. To summarize and discuss the original findings, many short review articles and few long reviews have also been available but almost all have focuses on specific aspects. To get a clear picture of the effect of osmolytes on protein folding and structural stabilization, it is necessary for the benefits of the general readers, to combine and discuss all findings made during its 40 years of life. This review article is therefore, designed to give a collective knowledge on almost all facets of the progresses made on osmolyte-protein interaction to-date.     

Reaction of tri(2-furyl)phosphine with triosmium clusters: C-H and P-C activation to afford furyne and phosphinidene ligands

Addition of tri(2-furyl)phosphine, PFu₃, to [Os₃(CO)₁₀(μ-H)₂] at room temperature gives [HOs₃(CO)₁₀(PFu₃)(μ-H)] (1), while in refluxing toluene the same reactants afford [Os₃(CO)₉{μ₃-PFu₂(C₄H₂O)}(μ-H)] (2) resulting from orthometallatation of a furyl ring. Reaction of PFu₃ with [Os₃(CO)_10−n(NCMe)_n] (n = 0, 1, 2) affords the substituted clusters [Os₃(CO)_12−n(PFu₃)_n] (n = 1-3) (3-5), the phosphine ligands occupying equatorial position in all cases. Heating [Os₃(CO)₁₁(PFu₃)] (3) in refluxing octane gives [Os₃(CO)₉(μ₃-PFu)(μ₃-η²-C₄H₂O)] (6) which results from both carbon-hydrogen and carbon-phosphorus bond activation and contains both μ₃-η²-furyne and furylphosphinidene ligands. All new clusters have been characterized by spectroscopic methods together with single crystal X-ray diffraction for 2, 3 and 6.     

Special susceptive aqueous ammonia chemi-sensor: extended applications of novel UV-curable polyurethane-clay nanohybrid

In this contribution, chemical sensor for the detection of aqueous ammonia has been fabricated using UV-curable polyurethane acrylate (PU) and nanohybrids (NH-1, NH-3 and NH-5). PU has been prepared by reacting polycaprolactone triol (PCLT) and isophorone diisocyanate (IPDI) while the nanohybrids, NH-1, NH-3, and NH-5 have been synthesized by solution blending method using PU with 1, 3, and 5 wt% loading levels of C-20B. PU and their nanohybrids showed higher sensitivity investigated by I-V technique using aqueous ammonia as a target chemical. All the nanohybrids showed higher sensitivity as compared to neat PU. The sensitivity increased with increase in clay content and the nanohybrid containing 5 wt% of clay showed the highest sensitivity (8.5254 μA cm⁻² mM⁻¹) with the limit of detection (LOD) of 0.0175 ± 0.001 μM, being 7.8 times higher than pure PU. The calibration plot for all the sensors was linear over the large range of 0.05 μM to 0.05 M. The response time of the fabricated sensor was <10.0 s. Therefore, one can fabricate efficient aqueous ammonia sensor by utilization of nanohybrid as an efficient electron mediator.     

Locally similar solutions for hydromagnetic and thermal slip flow boundary layers over a flat plate with variable fluid properties and convective surface boundary condition

This paper presents heat transfer process in a two-dimensional steady hydromagnetic convective flow of an electrically conducting fluid over a flat plate with partial slip at the surface of the boundary subjected to the convective surface heat flux at the boundary. The analysis accounts for both temperature-dependent viscosity and temperature dependent thermal conductivity. The local similarity equations are derived and solved numerically using the Nachtsheim-Swigert iteration procedure. Results for the dimensionless velocity, temperature and ambient Prandtl number within the boundary layer are displayed graphically delineating the effect of various parameters characterizing the flow. The results show that momentum boundary layer thickness significantly depends on the surface convection parameter, Hartmann number and on the sign of the variable viscosity parameter. The results also show that plate surface temperature is higher when there is no slip at the plate compared to its presence. For both slip and no-slip cases surface temperature of the plate can be controlled by controlling the strength of the applied magnetic field. In modelling the thermal boundary layer flow with variable viscosity and variable thermal conductivity, the Prandtl number must be treated as a variable irrespective of flow conditions whether there is slip or no-slip at the boundary to obtain realistic results.     

Transient conjugate heat transfer from a hemispherical plate during free liquid jet impingement on the convex surface

This paper considers the analysis of transient heating of a hemispherical solid plate of finite thickness during impingement of a free liquid jet. A constant heat flux was imposed at the inner surface of the hemispherical plate at t = 0 and heat transfer was monitored for the entire duration of the transient until a steady state condition was reached. Calculations were done for Reynolds number (Re) ranging from 500 to 1,500 and dimensionless plate thicknesses to nozzle diameter ratio (b/d _n) from 0.083 to 1.5. Results are presented for local and average Nusselt number using water as the coolant and various solid materials such as silicon, constantan, and copper. It was detected that increasing the Reynolds number decreases the time for the plate to achieve the steady-state condition. Also, a higher Reynolds number increases the Nusselt number. Hemispherical plate materials with higher thermal conductivity maintain lower temperature non-uniformity at the solid–fluid interface. Increasing the plate thickness decreases the maximum temperature in the solid and increases the time to reach the steady-state condition.     

Thermal characteristics of gelatin extracted from shaari fish skin

Gelatin extraction yield increased with the increase of acetic acid concentration and temperature. Gelatin extracted from shaari skin using 0.1 N acid solutions and temperatures of 323 and 353 K gave highest protein content comparable to that of commercial bovine and porcine gelatins. In general, gelatin extracted from shaari gelatin showed lower onset of glass transition temperature than mammalian gelatins. For shaari skin gelatin, the onset of glass transition temperature decreased with the increase of extraction temperature up to 323 K and then remained nearly constant. The decrease in glass transition was more pronounced for gelatin extracted at 0.01 N compared to the 0.1 and 1.0 N samples. Unfolding temperature decreased exponentially with the increase of extraction temperature. The unfolding temperature shifted to lower temperature, and the decrease was more pronounced in the case of higher (1.0 N) concentrated samples. The extraction concentration and temperature did not show significant effect on the onset solids-melting temperature.     

Novel Small-Molecule Scaffolds as Candidates against the SARS Coronavirus 2 Main Protease: A Fragment-Guided in Silico Approach

The ongoing pandemic caused by the novel coronavirus has been the greatest global health crisis since the Spanish flu pandemic of 1918. Thus far, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has resulted in over 1 million deaths, and there is no cure or vaccine to date. The recently solved crystal structure of the SARS-CoV-2 main protease has been a major focus for drug-discovery efforts. Here, we present a fragment-guided approach using ZINCPharmer, where 17 active fragments known to bind to the catalytic centre of the SARS-CoV-2 main protease (SARS-CoV-2 M^pro) were used as pharmacophore queries to search the ZINC databases of natural compounds and natural derivatives. This search yielded 134 hits that were then subjected to multiple rounds of in silico analyses, including blind and focused docking against the 3D structure of the main protease. We scrutinised the poses, scores, and protein–ligand interactions of 15 hits and selected 7. The scaffolds of the seven hits were structurally distinct from known inhibitor scaffolds, thus indicating scaffold novelty. Our work presents several novel scaffolds as potential candidates for experimental validation against SARS-CoV-2 M^pro.     

Aromaticity and Chemical Bonding of Chalcogen-Bonded Capsules Featuring Enhanced Magnetic Anisotropy

We present a theoretical study of chalcogen bonded container capsules ( A_X+A_X ) where X=O, S, Se, and Te, and their encapsulation complexes with n-C₉H₂₀ (n-C₉H₂₀@ A_X+A_X ). Both Se and Te encapsulation complexes have significant experimental and computed binding energies, analogous to the hydrogen bonded counterparts, while the S and O capsules and their encapsulation complexes show only weak binding energies, which are attributed to different types of bonding: chalcogen S⋅⋅⋅N bonds for S-capsules and π–π stacking and weak hydrogen bonds for the O case. All A_X+A_X and C₉H₂₀@ A_X+A_X present unusually high magnetic anisotropies in their interiors. The ¹H NMR spectra of the encapsulation complexes display the proton signals of the encapsulated n-nonane highly upfield shifted, in agreement with the available experimental data for the Se capsule. We found that different factors contribute to the observed magnetic anisotropy of the capsule's interior: for the Te capsule the most important factor is Te's large polarizability; for the O analogue the inductive effects produced by the electronegative nature of the O and N heteroatoms; and for the S and Se capsules, the polarizability of the heteroatoms combines with electric field effects.