Thiourea Based Dipodal Receptor Development for Electrochemical Detection of Br− Ion in an Aqueous Medium

Thiourea based dipodal receptor ( R1 ) was developed and characterised using ¹H NMR, ¹³C NMR and mass spectroscopy. Using re‐precipitation method, R1 was processed into organic nanoparticles ( N1 ), evaluated its sensor activity in aqueous medium. The prepared N1 were characterized using Transmission Electron Microscopy (TEM) which shows 30 nm size. Dynamic Light Scattering (DLS) was employed for calculating average particle size. To imply N1 as sensor, its interaction with various anions was studied and found reasonable selectively for Br^? ions with detection limit of 3.79 nM. For real life analysis, involving determining Br^? from environmental samples, proposed sensor works successfully with accuracy more than 95 %.     

Analyzing fragment production in mass-asymmetric reactions as a function of density dependent part of symmetry energy

We performed a theoretical investigation of different mass-asymmetric reactions to access the direct impact of the density-dependent part of symmetry energy on multifragmentation. The simulations are performed for a specific set of reactions having same system mass and N/Z content, using isospin-dependent quantum molecular dynamics model to estimate the quantitative dependence of fragment production on themass-asymmetry factor (τ) for various symmetry energy forms. The dynamics associated with different mass-asymmetric reactions is explored and the direct role of symmetry energy is checked. Also a comparison with the experimental data (asymmetric reaction) is presented for a different equation of states (symmetry energy forms).     

Catalytic Hydrosilylation of Imines by Aluminum Hydride Cations

In this work, the catalytic activity of electronically unsaturated three coordinated aluminum hydride cations [ L AlH]⁺[HB(C₆F₅)₃]⁻ ( 1 ) and [ L AlH]⁺[B(C₆F₅)₄]⁻ ( 2 ) in hydrosilylation of imines has been disclosed ( L ={(2,6-ⁱPr₂C₆H₃N)P(Ph₂)}₂N). A variety of organo-silanes such as Et₃SiH, MePhSiH₂, PhSiH₃, TMDSO, and PHMS are screened in this endeavour. The amines as products of catalysis were obtained in good to excellent yields after the hydrolysis of silylamine intermediates. Further, a series of controlled experiments systematically designed to investigate the underlying mechanistic pathway through multinuclear NMR analysis showed Lewis adduct formation between cationic aluminum centre and the imine nitrogen, which subsequently undergoes reaction with silane to afford the product. The hydrosilylation of imine performed with Et₃SiH using catalyst 1 with a loading of 2 mol % at 60 °C occurs smoothly. Whereas 2 led to the product formation with Et₃SiH only when used in stoichiometric quantity. Further, to investigate this unique behaviour of 1 NMR investigations were performed and revealed that the anion in 1 competes for hydride delivery and in-situ generates B(C₆F₅)₃ that cooperatively reinforces the catalytic activity of 1 .     

Nematic Phase of Polar Unsymmetrical Bent-Core Molecules

In liquid crystalline systems, the presence of polar groups at lateral or terminal positions is fundamentally and technologically important. Bent-core nematics composed of polar molecules with short rigid cores usually exhibit highly disordered mesomorphism with some ordered clusters that favourably nucleate within. Herein, we have systematically designed and synthesized two new series of highly polar bent-core compounds comprised of two unsymmetrical wings, highly electronegative −CN and −NO₂ groups at one end, and flexible alkyl chains at the other end. All the compounds showed a wide range of nematic phases composed of cybotactic clusters of smectic-type (N_cyb). The birefringent microscopic textures of the nematic phase were accompanied by dark regions. Further, the cybotactic clustering in the nematic phase was characterized via temperature-dependent XRD studies and dielectric spectroscopy. Besides, the birefringence measurements demonstrated the ordering of the molecules in the cybotactic clusters upon lowering the temperature. DFT calculations illustrated the favourable antiparallel arrangement of these polar bent-core molecules as it minimizes the large net dipole moment of the system.     

Fabrication and Characterization of Sulphur-doped Graphitic Carbon Nitride Nanosheets as a Highly Selective and Ultrasensitive Electrochemical Sensor for Detection of 2,4-Dinitrophenol in Real Gym Supplements

Herein, an effective template assisted calcination procedure has been adopted to synthesize the Sulphur-doped graphitic carbon nitride (S_XGCN). Furthermore, the S_XGCN/GCE was then utilized for the electrochemical determination of 2,4-Dinitrophenol (2,4-DNP). It has been inferred that among the variously prepared S_XGCN (x=0 %, 20 %, 40 %, 60 %, 80 %, and 100 %), S₈₀GCN afforded the excellent electrochemical response for detection of 2,4-DNP. The synthesized S_XGCN/GCE (x=80 %) demonstrates with a low detection limit of 0.9083 μM with linear range of 1–90 μM. Furthermore, the practical application of this sensor was successfully proved by detecting spiked 2,4-dinitrophenol in a real gym supplements sample.     

Back Cover: Ligand-Free Ultrasmall Recyclable Iridium(0) Nanoparticles for Regioselective Aromatic Hydrogenation of Phosphine Oxide Scaffolds: An Easy Access to New Phosphine Ligands (Angew. Chem. Int. Ed. 39/2023)

Herein, we developed the recyclable ligand-free iridium (Ir)-hydride based Ir⁰ nanoparticles (NPs) for the first regioselective partial hydrogenation of P^V-substituted naphthalenes. Both the isolated and in situ generated NPs are catalytically active. A control nuclear magnetic resonance (NMR) study revealed the presence of metal-surface-bound hydrides, most likely formed from Ir⁰ species. A control NMR study confirmed that hexafluoroisopropanol as a solvent was accountable for substrate activation via hydrogen bonding. High-resolution transmission electron microscopy of the catalyst supports the formation of ultrasmall NPs, and X-ray photoelectron spectroscopy confirmed the dominance of Ir⁰ in the NPs. The catalytic activity of NPs is broad as showcased by highly regioselective aromatic ring reduction in various phosphine oxides or phosphonates. The study also showcased a novel pathway toward preparing bis(diphenylphosphino)-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl (H₈-BINAP) and its derivatives without losing enantioselectivity during catalytic events.     

Supramolecular Polyphenol-DNA Microparticles for In Vivo Adjuvant and Antigen Co-Delivery and Immune Stimulation

DNA-based materials have attracted interest due to the tunable structure and encoded biological functionality of nucleic acids. A simple and general approach to synthesize DNA-based materials with fine control over morphology and bioactivity is important to expand their applications. Here, we report the synthesis of DNA-based particles via the supramolecular assembly of tannic acid (TA) and DNA. Uniform particles with different morphologies are obtained using a variety of DNA building blocks. The particles enable the co-delivery of cytosine-guanine adjuvant sequences and the antigen ovalbumin in model cells. Intramuscular injection of the particles in mice induces antigen-specific antibody production and T cell responses with no apparent toxicity. Protein expression in cells is shown using capsules assembled from TA and plasmid DNA. This work highlights the potential of TA as a universal material for directing the supramolecular assembly of DNA into gene and vaccine delivery platforms.     

Dependence of fluorescence quenching of a poly(p-phenyleneethynylene) polyelectrolyte on the electrostatic and hydrophobic properties of the quencher

This study investigates the fluorescence quenching of a poly(p-phenyleneethynylene) (1) based polyelectrolyte by positively charged and neutral macromolecules. This work shows that the change in the fluorescence yield of 1 depends on a number of factors, including electrostatic, hydrophobic, and energy transfer interactions with the quencher and also changes in the solution conditions such as concentration and ionic strength. The fluorescence quenching is attributed to the formation of aggregates that form upon addition of different quenchers to a solution of 1 and/or the solution conditions. The extent of 1's aggregation is shown to depend on the type of interaction between the polymer and the quencher, the concentration of the polymer, and the ionic strength of the solution.     

Variable Bonding Modes of Pyrimidine‐2‐thione in PdII/PtII Complexes [M(η2‐N,S‐pymS)(η1‐S‐pymS)(PPh3)] and [M(η1‐S‐pymS)2(L‐L)] (L‐L = dppm,dppe)

Reactions of pyrimidine‐2‐thione (HpymS) with Pd^II/Pt^IV salts in the presence of triphenyl phosphine and bis(diphenylphosphino)alkanes, Ph₂P‐(CH₂)_m‐PPh₂ (m = 1, 2) have yielded two types of complexes, viz. a) [M(η²‐N, S‐ pymS)(η¹‐S‐ pymS)(PPh₃)] (M = Pd, 1 ; Pt, 2 ), and (b) [M(η¹‐S‐pymS)₂(L‐L)] {L‐L, M = dppm (m = 1) Pd, 3 ; Pt, 4 ; dppe (m = 2), Pd, 5 ; Pt, 6 }. Complexes have been characterized by elemental analysis (C, H, N), NMR spectroscopy (¹H, ¹³C, ³¹P), and single crystal X‐ray crystallography ( 1 , 2 , 4 , and 5 ). Complexes 1 and 2 have terminal η¹‐S and chelating η²‐N, S‐modes of pymS⁻, while other Pd/Pt complexes have only terminal η¹‐S modes. The solution state ³¹P NMR spectral data reveal dynamic equilibrium for the complexes 3 , 5 and 6 , whereas the complexes 1 , 2 and 4 are static in solution state.     

Modulation of the ligand-field anisotropy in a series of ferric low-spin cytochrome c mutants derived from Pseudomonas aeruginosa cytochrome c-551 and Nitrosomonas europaea cytochrome c-552: a nuclear magnetic resonance and electron paramagnetic resonance study

Cytochromes of the c type with histidine-methionine (His-Met) heme axial ligation play important roles in electron-transfer reactions and in enzymes. In this work, two series of cytochrome c mutants derived from Pseudomonas aeruginosa (Pa c-551) and from the ammonia-oxidizing bacterium Nitrosomonas europaea (Ne c-552) were engineered and overexpressed. In these proteins, point mutations were induced in a key residue (Asn64) near the Met axial ligand; these mutations have a considerable impact both on heme ligand-field strength and on the Met orientation and dynamics (fluxionality), as judged by low-temperature electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectra. Ne c-552 has a ferric low-spin (S = 1/2) EPR signal characterized by large g anisotropy with g(max) resonance at 3.34; a similar large g(max) value EPR signal is found in the mitochondrial complex III cytochrome c1. In Ne c-552, deletion of Asn64 (NeN64Delta) changes the heme ligand field from more axial to rhombic (small g anisotropy and g(max) at 3.13) and furthermore hinders the Met fluxionality present in the wild-type protein. In Pa c-551 (g(max) at 3.20), replacement of Asn64 with valine (PaN64V) induces a decrease in the axial strain (g(max) at 3.05) and changes the Met configuration. Another set of mutants prepared by insertion (ins) and/or deletion (Delta) of a valine residue adjacent to Asn64, resulting in modifications in the length of the axial Met-donating loop (NeV65Delta, NeG50N/V65Delta, PaN50G/V65ins), did not result in appreciable alterations of the originally weak (Ne c-552) or very weak (Pa c-551) axial field but had an impact on Met orientation, fluxionality, and relaxation dynamics. Comparison of the electronic fingerprints in the overexpressed proteins and their mutants reveals a linear relationship between axial strain and average paramagnetic heme methyl shifts, irrespective of Met orientation or dynamics. Thus, for these His-Met axially coordinated Fe(III), the large g(max) value EPR signal does not represent a special case as is observed for bis-His axially coordinated Fe(III) with the two His planes perpendicular to each other.