Mechanochemical metathesis synthesis and characterization of nano-structured MnV2O6·xH2O (x=2, 4)

A solid-state metathesis approach for the synthesis of hydrated MnV₂O₆·xH₂O (x=2, 4) materials driven by mechanochemical activation energy has been demonstrated. The metathesis pathway of forming the desired product is confirmed by the presence of high lattice energy by-product such as NaCl. The structural, optical, and chemical properties of the synthesized materials are examined by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermo gravimetric analysis, scanning electron microscopy, transmission electron microscopy, and diffused reflectance measurements in the UV–vis range. The valence state of Mn and V was determined to be +2 and +5, respectively, for the title compounds and the bandgap values determined showed these materials are likely to be semiconductors.     

Thermophysical properties of neat and radiolytically degraded acidic extractants present in room temperature ionic liquid

In the present work, radon concentrations were measured in surface and underground water samples in Faridabad District of Southern Haryana, India using an active radon monitor based on alpha scintillation technique and results have been inter-compared. The average radon concentration in the underground water samples was observed to be 4 times higher than in the surface water samples. The estimated annual effective dose varied from 5.7 to 58.5 μSvy^?1 with an average of 24.2 μSvy^?1 for underground water samples and 1.1 to 12.5 μSvy^?1 with an average of 6.7 μSvy^?1 for surface water samples. The estimated annual effective dose for both type of samples was found to be less than 0.1 mSvy^?1, which is the safe limit as suggested by World Health Organisation and EU Council.

     

Hellmann–Feynman connection for the relative Fisher information

The (i) reciprocity relations for the relative Fisher information (RFI, hereafter) and (ii) a generalized RFI–Euler theorem are self-consistently derived from the Hellmann–Feynman theorem. These new reciprocity relations generalize the RFI–Euler theorem and constitute the basis for building up a mathematical Legendre transform structure (LTS, hereafter), akin to that of thermodynamics, that underlies the RFI scenario. This demonstrates the possibility of translating the entire mathematical structure of thermodynamics into a RFI-based theoretical framework. Virial theorems play a prominent role in this endeavor, as a Schrödinger-like equation can be associated to the RFI. Lagrange multipliers are determined invoking the RFI–LTS link and the quantum mechanical virial theorem. An appropriate ansatz allows for the inference of probability density functions (pdf’s, hereafter) and energy-eigenvalues of the above mentioned Schrödinger-like equation. The energy-eigenvalues obtained here via inference are benchmarked against established theoretical and numerical results. A principled theoretical basis to reconstruct the RFI-framework from the FIM framework is established. Numerical examples for exemplary cases are provided.     

Finite element computations of viscoelastic two-phase flows using local projection stabilization

A three-field local projection stabilized (LPS) finite element method is developed for computations of a three-dimensional axisymmetric buoyancy driven liquid drop rising in a liquid column where one of the liquid is viscoelastic. The two-phase flow is described by the time-dependent incompressible Navier-Stokes equations, whereas the viscoelasticity is modeled by the Giesekus constitutive equation in a time-dependent domain. The arbitrary Lagrangian-Eulerian (ALE) formulation with finite elements is used to solve the governing equations in the time-dependent domain. Interface-resolved moving meshes in ALE allows to incorporate the interfacial tension force and jumps in the material parameters accurately. A one-level LPS based on an enriched approximation space and a discontinuous projection space is used to stabilize the numerical scheme. A comprehensive numerical investigation is performed for a Newtonian drop rising in a viscoelastic fluid column and a viscoelastic drop rising in a Newtonian fluid column. The influence of the viscosity ratio, Newtonian solvent ratio, Giesekus mobility factor, and the Eötvös number on the drop dynamics are analyzed. The numerical study shows that beyond a critical Capillary number, a Newtonian drop rising in a viscoelastic fluid column experiences an extended trailing edge with a cusp-like shape and also exhibits a negative wake phenomena. However, a viscoelastic drop rising in a Newtonian fluid column develops an indentation around the rear stagnation point with a dimpled shape.     

Rotatable Aggregation‐Induced‐Emission/Aggregation‐Caused‐Quenching Ratio Strategy for Real‐Time Tracking Nanoparticle Dynamics

Real‐time tracking of the dynamics change of self‐assembled nanostructures in physiological environments is crucial to improving their delivery efficiency and therapeutic effects. However, such tracking is impeded by the complex biological microenvironment leading to inhomogeneous distribution. A rotatable fluorescent ratio strategy is introduced that integrates aggregation‐induced emission (AIE) and aggregation‐caused quenching (ACQ) into one nanostructured system, termed AIE and ACQ fluorescence ratio (AAR). Following this strategy, an advanced probe, PEG^5k‐TPE₄‐ICGD₄ (PTI), is developed to track the dynamics change. The extremely sharp fluorescent changes (up to 4008‐fold) in AAR allowed for the clear distinguishing and localization of the intact state and diverse dissociated states. The spatiotemporal distribution and structural dynamics of the PTI micelles can be tracked, quantitatively analyzed in living cells and animal tissue by the real‐time ratio map, and be used to monitor other responsive nanoplatforms. With this method, the dynamics of nanoparticle in different organelles are able to be investigated and validated by transmission electron microscopy. This novel strategy is generally applicable to many self‐assembled nanostructures for understanding delivery mechanism in living systems, ultimately to enhance their performance in biomedical applications.     

Calcium Alginate Bead-mediated Enhancement of the Selective Recovery of a Lead Novel Antifungal Bacillomycin Variant

In the pursuit of new antifungal compounds, five coproduced lipopeptide variants (AF₁ to AF₅) from wild-type Bacillus subtilis RLID 12.1 were identified in our previous study. Out of five, AF₄ was identified as a novel lead molecule belonging to the bacillomycin family showing less cytotoxicity at its respective minimum inhibitory concentrations (MIC) evaluated against 81 strains of Candida and Cryptococcus species (including clinical isolates); besides this, AF₄ purified in the present study exhibited encouraging MIC values against 10 clinical mycelial fungi. Aiming for a selective production augmentation of AF₄ lipopeptide variant, a new fermentation media comprising malt extract (1.01%), dextrose (0.55%), peptone (1.79%), MnSO₄ (2 mM), and NaCl (0.5%) was formulated. Maximum production of 954.8?±?10.8 mg/L was achieved with 44% selectivity at 30 °C compared to unoptimized conditions (186.4?±?6.1 mg/L). Use of calcium alginate beads in the formulated media during the onset of lipopeptide production resulted in an augmentation in the selectivity of the most efficacious AF₄ variant to about 72% presumably due to attenuation of other coproduced lipopeptide variants AF₁ and AF₂. Difference in yield of lipopeptides varied with bead size, bead preparation ratios, and sodium alginate concentrations. Use of Ca-alginate beads in the upstream production process of the lead AF₄ variant may be considered as a novel strategy to address the potential challenge that may arise during the scale-up and downstream processing steps. Another significant finding derived from the study is that the proportion of bacillomycin variants of B. subtilis RLID 12.1 could be controlled by temperature and metal ions under static and shaking conditions.     

Direct,high-yielding,one-step synthesis of vic-diols from aryl alkynes

An unprecedented, high yielding, direct, one-step synthesis of vic-diols from alkynes has been developed via metal-free, open-to-air dihydroboration with ammonia borane. The electronics of the alkyne and the reaction stoichiometry are critical for obtaining optimal yields of the 1,2-diol.     

Synthesis of highly functionalized strained bicyclic dilactam derivatives

An efficient and modest protocol has been utilized for the synthesis of bicyclic dilactam derivatives through one-pot multicomponent domino reaction starting from various cyclic ketones under mild condition. The synthesized motif shows four stereogenic centers with two quaternary amine functionalities and such molecular arrangements are very fascinating and rare to obtain. We propose a mechanism for the formation of bicyclic dilactams through aldol condensation/condensation of cyanoacetamides/cyclization of condensed intermediate.