A modern approach for the sensing of aqueous Al(III) ion by Ni(II) Salen‐type Schiff base complexes

In this work, we explore a modern concept of transmetalation (metal exchange) for the effective recognition of aqueous Al(III) ion. Three different Ni(II) salen‐type Schiff base complexes with different spacer diimine groups were prepared for the metal exchange reaction. These probes recognize Al(III) both colorimetically as well as fluorimetrically. The efficiency in sensing is mainly due to the low emission characteristics of the respective Ni(II) complexes which results in enhanced emission on the formation of Al(III) complex. The geometry of the central Ni(II) metal ion in the probe plays a pivotal role in the sensing action with the highest sensitivity being shown by the Ni(II) metal center with distorted square pyramidal geometry. Further DFT calculations and the energetics involved in the sensing mechanism via the formation of Al(III) complexes substantiates the experimental results.     

Enhancing the Aspirin Loading and Release Efficiency of Silver Oxide Nanoparticles Using Oleic Acid-based Bio-Surfactant from Enteromorpha intestinalis

This study is an attempt to improve the loading and release potential of silver oxide nanoparticles (AgO NPs) using Oleic acid based bio-surfactant isolated from Enteromorpha instestinalis. The isolated Oleic acid based bio-surfactant was characterized using GC–MS, NMR, and HPLC. The AgO NPs were then surface-functionalized with the bio-surfactant and analyzed using XRD, HR-TEM/SAED, DLS, UV–Vis, and FTIR spectroscopy to evaluate the loading of aspirin and functional groups responsible for loading. The model drug Aspirin that has depreciated bio-availability due to poor solubility was used to test the drug carrier efficiency of the AgO NPs after the surface-functionalization. The loading of aspirin was increased by up to 80% in bio-surfactants than PEG-coated NPs (72%) at a 1:1 ratio (Aspirin/NP). The drug release profile of aspirin was evaluated by dialysis at different acidic conditions (pH 1.2, 6.8, and 7.4) and the active release of aspirin was observed in pH 6.8 and bio-surfactant produced better release than PEG and commercial tablet in all the pH conditions. To identify the mechanism of release from the carrier, the release kinetics was studied using zero-order, first-order, Higuchi's, and Korsmeyer Peppas equations and found that the release was time-dependent and non-fickian.     

Unique β-Turn Peptoid Structures and Their Application as Asymmetric Catalysts

Peptoids, N-substituted glycine oligomers, represent an important class of peptidomimetics that can fold into three-dimensional structures in solution. Most of the folded peptoid structures, however, resemble helices, and this can limit their applications, specifically in asymmetric catalysis. In this work, for the first time, unique examples of pyrrolidine-based β-turn-like peptoids are described and characterized, both in the solid state, by single-crystal X-ray analysis, and in solution, by circular dichroism spectroscopy. Furthermore, their highly efficient and enantioselective catalytic activity for the production of γ-nitro aldehydes by asymmetric Michael reaction in water was demonstrated. The structural properties and DFT-D3 calculations of the new β-turn-like peptoids, as well as catalytic and spectroscopic studies on designed pyrrolidine-based helical peptoids, suggest that the β-turn structure plays a key role in the stereoselectivity of the catalytic reaction.     

A model for charge transport in semicrystalline polymer thin films

A model for simulating the charge transport properties of semicrystalline polymer (SCrP) using Monte Carlo simulation is reinvented. The model is validated by reproducing the experimentally observed field and temperature dependence of mobility in Poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) thin films. This study also provides a new physical insight to the origin of much debated negative field dependence of mobility (NFDM) observed at low electric field strengths in P3HT thin films. The observed NFDM, which is not explainable with the mechanisms proposed earlier, is attributed to the weak dependence of transit time on the applied electric field strengths. In the semicrystalline films, the charge transport takes place mostly through the crystalline regions, in which the charge transport is weakly dependent on the strength of the applied electric field. In addition, a possible explanation for the origin of Arrhenius temperature dependence of mobility (lnμ ∝ 1/T) commonly observed in SCrP thin films is also proposed. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 137–141     

Wavelet-based numerical techniques for 1D peristatic problems in infinite domain

Peristatics is an important branch of continuum mechanics dealing with nonlocal effects in solid structures. Some 1D peristatic problems with four different micromodulus functions have been studied here. A wavelet-based collocation method has been developed to find multiscale approximate solutions of the peristatic problems that avoid cumbersome evaluation of singular type integrals present in analytical solution available in literature. The obtained results offer important insights into applications and simulations of peristatic models and seem to be useful for investigation in the field of peridynamics in one or higher dimensions.     

One-pot two-step synthesis of fused thiazinofuranone linked geminal bis 1,2,3-triazole hybrids and their in vitro cytotoxic screening

In this study, a series of novel geminal bis 1,2,3-triazoles linked to 2H-furo[2,3-d][1,3]thiazine-2,4,5(1H,6H)-trione ( 3a-3m ) were prepared in one pot starting from 5-Acetyl-4-Hydroxy-1,3-thiazine-2,6-dione ( 1 ) to 6,6-diazido-2H-furo[2,3-d][1,3]thiazine-2,4,5(1H,6H)-trione ( 2 ) followed by Cu(I)-catalyzed azide-alkyne cycloaddition. The synthesized compounds were further explored for in vitro cytotoxic activity against PC3, A549, MCF-7, and HeLa cell lines and results revealed that the five compounds 3c , 3d , 3g , 3l , and 3m have displayed comparable in vitro cytotoxic activity with the standard drug Etoposide.     

Charge-Transfer in Panchromatic Porphyrin-Tetracyanobuta-1,3-Diene-Donor Conjugates: Switching the Role of Porphyrin in the Charge Separation Process

Using a combination of cycloaddition-retroelectrocyclization reaction, free-base and zinc porphyrins (H₂P and ZnP) are decorated at their β-pyrrole positions with strong charge transfer complexes, viz., tetracyanobuta-1,3-diene (TCBD)-phenothiazine ( 3 and 4 ) or TCBD-aniline ( 7 and 8 ), novel class of push-pull systems. The physico-chemical properties of these compounds (MP-Donor and MP-TCBD-Donor) have been investigated using a range of electrochemical, spectroelectrochemical, DFT as well as steady-state and time-resolved spectroscopic techniques. Ground-state charge transfer interactions between the porphyrin and the electron-withdrawing TCBD directly attached to the porphyrin π-system extended the absorption features well into the near-infrared region. To visualize the photo-events, energy level diagrams with the help of free-energy calculations have been established. Switching the role of porphyrin from the initial electron acceptor to electron donor was possible to envision. Occurrence of photoinduced charge separation has been established by complementary transient absorption spectral studies followed by global and target data analyses. Better charge stabilization in H₂P derived over ZnP derived conjugates, and in phenothiazine derived over aniline derived conjugates has been possible to establish. These findings highlight the importance of the nature of porphyrins and second electron donor in governing the ground and excited state charge transfer events in closely positioned donor-acceptor conjugates.