Ligand-Enabled [3+2] Annulation of Aromatic Acids with Maleimides by C(sp3)−H and C(sp2)−H Bond Activation

A palladium-catalyzed [3+2] annulation of substituted benzoic acids with maleimides leading to tricyclic heterocyclic molecules having a free carboxylic group in a high atom- and step-economical manner is described. The reaction proceeds via a dual C−H bond activation such as C(sp³)−H at the benzylic position and C(sp²)−H bond activation at the meta position of substituted aromatics. An external ligand (MPAA) is crucial for the success of present protocol. Further, the decarboxylation and esterification of the free carboxylic acid group of observed products were carried out.     

Synthesis,crystal structures and spectroscopic properties of two Zn(II) Schiff’s base complexes of pyridoxal

Two mononuclear zinc(II) complexes, [ZnL¹H₂Cl]Cl·2H₂O (1·Cl·2H₂O) and [ZnL²HCl]·H₂O (2·H₂O) (L¹H₂ and L²H₂ are N,N′-bis(pyridoxylidene)ethylenediamine and N,N′-bis(pyridoxylidene)1,3-propanediamine, respectively) have been synthesized and characterized by elemental analysis, FT-IR, fluorescence spectroscopy, TG–DTA and single crystal X-ray diffraction studies. The Zn(II) ion in complex 1 have a square pyramidal geometry with appreciable distortion towards trigonal bipyramid, whereas in 2 it has a geometry which is near the midpoint of square pyramid and trigonal bipyramid. The zinc atom is coordinated by two imine nitrogens, two phenolic oxygens and one chloride ion. The Zn(II) complexes show emission at 462 nm when excited at their lowest energy absorption at 372 nm.     

A simple Schiff base as selective and sensitive fluorescent-colorimetric hydrazine chemosensor

ABSTRACT

A new fluorescent-colorimetric chemosensor L has been synthesised by Schiff base condensation reaction between 1,8-diaminooctane and 4-nitro-benzaldehyde in very good yields. Its photo-luminescent properties and selective detection properties for hydrazine have been examined. The synthesised chemosensor exhibited highly selective fluorescence on-off response for hydrazine amongst a wide range of different metal cations, anions and amines, along with the bare eye colour change from colourless to yellow based on intermolecular hydrogen-bond interaction. The limit of detection of the chemosensor L was estimated as 9.77 × 10^?8 M or 3.12 × 10^?6 g L^?1 for hydrazine which is extremely below the limit set by the World Health Organization (WHO) and the binding stoichiometry was proposed to be 1 : 2 based on ¹H NMR spectroscopic techniques and the Job’s plot analysis. The proposed sensing mechanism is the hydrogen-bonding interaction which has further been established by Density Functional Theory (Functional Density Theory (DFT)) studies. This recognition feature of sensor L makes it an efficient chemosensor for hydrazine detection in different water samples.     

Electron Density of Two Bioactive Oligocyclic Indole and Oxindole Derivatives Obtained from Low‐Order X‐Ray Data and Invariom Application

For two indole and oxindole bioactive molecules, low‐order room‐temperature X‐ray data were used to generate aspherical electron density (ED) distributions by application of the invariom formalism. An analysis of the ED using the quantum theory of atoms in molecules (QTAIM) was carried out, which allowed for quantitatively examining bond orders and charge separations in various parts of the molecules. The inspection of electrostatic potentials (ESPs) and Hirshfeld surfaces provided additional information on the intermolecular interactions. Thus, reactive regions of the molecules could be identified, covalent and electrostatic contributions to interactions could be visualized, and the forces causing the crystal packing scheme could be rationalized. As the used invariom formalism needs no extra experimental effort compared to routine X‐ray analysis, its wide application is recommended because it delivers information far beyond the normally obtained steric properties. In this way, complementary contributions to drug design can be given as is demonstrated for indoles in this study, which are involved in the metabolism of plants and animals as well as in cancer therapy.     

Palladium-Catalyzed 8-Exo Trig Intramolecular Heck Reaction Under Microwave Irradiation in the Presence of Basic Alumina

The Heck cross-coupling reaction has been employed for efficient conversion of quinolines to benzoxocinoquinoline through a microwave-assisted palladium-catalyzed intramolecular cyclization in the presence of basic alumina.     

Biologically sustainable rubber resin and rubber‐filler promoter: a precursor study

Enthused by the ever growing demand for sustainable and green based materials in responding to applications based on macromolecules, an attempt was made in seeking a bio‐resin (Terpene). Herein, we report the functionalization of bio‐resin with natural rubber (NR) to produce new sustainable and greener functional polymer. Bio‐resin functionalized NR was prepared by melt mixing using di(2‐tert butyl peroxy isopropyl) benzene initiator. Structure elucidation of the bio‐resin functionalized NR was established by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy, respectively. Bio‐resin functionalized NR facilitates the augmented interaction with highly dispersible silica. Amended state of highly dispersible silica dispersion has been achieved in the absence of toxic process oil, expensive silane coupling agent and conventionally used zinc oxide. Remarkable improvement in overall properties corroborated with various meticulous characterization including nanoindentation, rheological, physico‐mechanical and small angle X‐ray scattering using Becauge model, etc. The dynamic mechanical properties of the greener polymer demonstrated low rolling resistance coupled with high traction. More decisively, the macromolecule system toned up sparingly in the presence of the bio‐resin. Our contribution facilitates a novel avenue to develop sustainable high‐performance elastomeric macromolecule. Copyright © 2017 John Wiley & Sons, Ltd.     

Protein adsorption capability of zinc ferrite nanoparticles formed by a low-temperature solution-based process

We report successful synthesis of zinc ferrite nanoparticles (ZFs) by a facile low-temperature (90 °C) solution-based process from ferric nitrate nonahydrate and zinc nitrate hexahydrate precursors in presence of hydrazine hydrate. X-ray diffraction analysis and transmission electron microscopy confirmed the presence of ZFs, which were further characterized by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric measurements for identification of characteristic chemical bond vibrations and thermal weight loss behavior, respectively. Measurements of magnetic properties at room temperature revealed that the sample showed quite high saturation magnetization (22.0 emu/g at ~19,200 G), implying the presence of less impurities/surface defects in the ZFs. The material also showed zero coercivity as a soft-magnetic material. The protein adsorption performance of the ZFs was checked using bovine serum albumin (BSA) as model protein. Excellent protein adsorption capacity of 210 mg/g (close to the value of 218.81 mg/g calculated using the Langmuir model) for BSA concentration of 0.3 mg/mL was obtained at optimized solution pH of 5. This simple process could be adopted for synthesis of different magnetic nanomaterials for use in biomedical applications.     

Syntheses, crystal structures and magnetic properties of two dicopper(II) complexes and a zigzag 1-D Cu(II) complex of a bidentate pyridyl-pyrazole ligand

Two new dinuclear copper compounds, [Cu₂(pypz)₂(N₃)₂(NO₃)₂] (1) and [Cu₂(pypz)₂(OH)₂(NO₃)₂] (2), and one 1-D polymeric Cu(II) complex, [Cu(pypz)(dca)₃]_n (3) [‘pypz’ = (3,5dimethyl-1-(2′-pyridyl)pyrazole) and dca = (dicyanamide)], have been synthesized and characterized crystallographically and spectroscopically. Complex 1 is pseudo-octahedral, adjacent Cu atoms are connected by a pair of μ(1,1) azido groups and the structure is stabilized by π-π interactions between two pyridyl moieties from two different neighboring complex molecules. Complexes 2 and 3 are square pyramidal. The hydroxo bridged complex 2 is further stabilized through H-bonding. The 1-D polymeric chain of 3 is bridged by an end-to-end dicyanamide bridge and it propagates along the crystallographic b axis, whilst the polymer chains are stacked one upon another along the crystallographic c axis. Low temperature magnetic measurement shows that complexes 1 and 2 are ferromagnetic (J values are 30.81 and 14.79 cm⁻¹, respectively), whereas due to larger Cu-Cu distances, complex 3 shows weak ferromagnetism.     

Synthesis of mesoporous Stöber silica nanoparticles: the effect of secondary and tertiary alkanolamines

The effect of secondary (diethanolamine) and tertiary (triethanolamine) alkanolamines as catalysts on the formation of mesoporous Stöber silica nanoparticles by sol–gel method was studied. The particles were characterized by thermogravimetry and differential thermal analysis, Fourier transform infrared spectroscopy, N₂ physisorption measurements, and field emission scanning electron microscopy. By using ammonia and different alkanolamines as catalysts, the Brunauer–Emmet–Teller (BET) surface area and pore volume increased in the order of ammonia < diethanolamine < triethanolamine. A maximum BET surface area of 140.1 m² g^?1 and pore volume of 0.66 cm³ g^?1 were obtained from triethanolamine catalyzed silica particles. The average particle size of silica prepared by ammonia and different alkanolamines as catalysts decreased in the order of ammonia > diethanolamine > triethanolamine. The role of different alkanolamines on the textural properties and particle size of silica is explained in terms of their relative steric hindrance and basicity.