Solvent- and Substrate-Induced Chiroptical Inversion in Amphiphilic,Biocompatible Glycoconjugate Supramolecules: Shape-Persistent Gelation,Self-Healing,and Antibacterial Activity

We have shown solvent- and substrate-dependent chiral inversion of a few glycoconjugate supramolecules. (Z)-F-Gluco, in which d -glucosamine has been attached chemically to Cbz-protected l -phenylalanine at the C terminus, forms a self-healing hydrogel through intertwining of the nanofibers wherein the gelators undergo lamellar packing in the β-sheet secondary structures with a single chiral handedness. Dihybrid (Z)-F-gluco nanocomposite gel was prepared by in-situ formation of silver nanoparticles AgNPs in the gel; this enhances the mechanical properties of the composite gel through physical crosslinking without altering the packing pattern. In contrast, (Z)-L-gluco bearing an l -leucine moiety does not form a hydrogel but an organogel. Interestingly, the chiral handedness of the aggregates of (Z)-L-gluco can be reversed by choosing suitable solvents. In addition to self-healing behavior, (Z)-L-gluco gel revealed shape persistency. Further, (Z)-F-gluco hydrogel is benign, nontoxic, non-immunogenic, and non-allergenic in animal cells. AgNP-loaded (Z)-F-gluco hydrogel showed antibacterial activity against both Gram-positive and Gram-negative bacteria.     

Experimental investigation for stability and surface properties of TiO2 and Al2O3 water-based nanofluids

Journal of Thermal Analysis and Calorimetry - Nanofluids have gained recent attention because of their potential applications in diverse engineering fields like enhancing thermal transport,...     

Impact of FRET between Molecular Aggregates and Quantum Dots

Energy transfer has been employed in third‐generation solar cells for the conversion of light into electrical energy. Long‐range nonradiative energy transfer from semiconductor quantum dots (QDs) to fluorophores has been demonstrated by using CdS QDs and thiophene?BODIPY (boron dipyrromethene, abbreviated as TG2). TG2 shows a broad photoluminescence (PL) spectrum, which varies with concentration. At very low concentrations, monomeric units are present; then, upon increasing the concentration, these monomers form a mixed (J‐/H‐)aggregated state. Energy transfer between the CdS QDs and TG2 was confirmed by separately investigating the interactions between CdS and the monomer of TG2 and between CdS and the aggregated states of TG2. Size‐dependent PL quenching confirmed that nonradiative Förster resonance energy transfer (FRET) from photoexcited CdS QDs to the J‐aggregate state of TG2 was the major energy‐relaxation channel, which occurred on the timescale of hundreds of fs. These results have broad applications in the field of light harvesting based on the assembly of molecular aggregates.     

Advantage of Quantum Theory over Nonclassical Models of Communication

Quantum correlations provide dramatic advantage over the corresponding classical resources in several communication tasks. However, a broad class of probabilistic theories exists that attributes greater success than quantum theory in many of these tasks by allowing supra-quantum correlations in “space-like” and/or “time-like” paradigms. In this letter, a communication task involving three spatially separated parties is proposed where one party (verifier) aims to verify whether the bit strings possessed by the other two parties (terminals) are equal or not. This task is called authentication with limited communication, the restrictions on communication being: i) the terminals cannot communicate with each other, but (ii) each of them can communicate with the verifier through single use of channels with limited capacity. Manifestly, classical resources are not sufficient for perfect success of this task. Moreover, it is also not possible to perform this task with certainty in several nonclassical theories although they might possess stronger “space-like” and/or “time-like” correlations. Surprisingly, quantum resources can achieve the perfect winning strategy. The proposed task thus stands apart from all previously known communication tasks as it exhibits quantum advantage over other nonclassical strategies.     

Self‐Assembled Discrete Molecules for Sensing Nitroaromatics

Efficient sensing of trace amount nitroaromatic (NAC) explosives has become a major research focus in recent time due to concerns over national security as well as their role as environment pollutants. NO₂‐containing electron‐deficient aromatic compounds, such as picric acid (PA), trinitrotoluene (TNT), and dinitrotoluene (DNT), are the common constituents of many commercially available chemical explosives. In this article, we have summarized our recent developments on the rational design of electron‐rich self‐assembled discrete molecular sensors and their efficacy in sensing nitroaromatics both in solution as well as in vapor phase. Several π‐electron‐rich fluorescent metallacycles (squares, rectangles, and tweezers/pincers) and metallacages (trigonal and tetragonal prisms) have been synthesized by means of metal–ligand coordination‐bonding interactions, with enough internal space to accommodate electron‐deficient nitroaromatics at the molecular level by multiple supramolecular interactions. Such interactions subsequently result in the detectable fluorescence quenching of sensors even in the presence of trace quantities of nitroaromatics. The fascinating sensing characteristics of molecular architectures discussed in this article may enable future development of improved sensors for nitroaromatic explosives.     

Cu (II) and Co (II/III) complexes of N,O‐chelated Schiff base ligands: DNA interaction,protein binding,cytotoxicity, cell death mechanism and reactive oxygen species generation studies

A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH ₂ (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH ₂ = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC₅₀ values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished.     

Mesoscopic Modeling of Capillarity-Induced Two-Phase Transport in a Microfluidic Porous Structure

Mesoscopic modeling at the pore scale offers great promise in exploring the underlying structure transport performance of flow through porous media. The present work studies the fluid flow subjected to capillarity-induced resonance in porous media characterized by different porous structure and wettability. The effects of porosity and wettability on the displacement behavior of the fluid flow through porous media are discussed. The results are presented in the form of temporal evolution of percentage saturation and displacement of the fluid front through porous media. The present study reveals that the vibration in the form of acoustic excitation could be significant in the mobilization of fluid through the porous media. The dependence of displacement of the fluid on physicochemical parameters like wettability of the surface, frequency along with the porosity is analyzed. It was observed that the mean displacement of the fluid is more in the case of invading fluid with wetting phase where the driving force strength is not so dominant.     

Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification

A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH₂ groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m² g^?1. The material also possesses good CO₂ (8 wt %) and H₂ (1.87 wt %) adsorption capabilities.