Equivariant cobordism of Grassmann and flag manifolds

We consider certain natural (ℤ₂)ⁿ actions on real Grassmann and flag manifolds andS ¹ actions on complex Grassmann manifolds with finite stationary point sets and determine completely which of them bound equivariantly.     

Design of Organic Transformations at Ambient Conditions: Our Sincere Efforts to the Cause of Green Chemistry Practice

This account summarizes our recent efforts in designing a good number of important organic transformations leading to the synthesis of biologically relevant compounds at room temperature and pressure. Currently, the concept of green chemistry is globally acclaimed and has already advanced quite significantly to emerge as a distinct branch of chemical sciences. Among the principles of green chemistry, one principle is dedicated to the “design of energy efficiency” – that is, to develop synthetic strategies that require less or the minimum amount of energy to carry out a specific reaction with optimum productivity – and the most effective way to save energy is to develop strategies/protocols that are capable enough to carry out the transformations at ambient temperature! As part of on‐going developments in green synthetic strategies, the design of reactions under ambient conditions coupled with other green aspects is, thus, an area of current interest. The concept of developing reaction strategies at room temperature and pressure is now an emerging field of research in organic chemistry and is progressing steadily. This account is aimed to offer an overview of our recent research works directly related to this particular field of interest, and highlights the green chemistry practice leading to carbon–carbon and carbon–heteroatom bond‐forming reactions of topical significance. Green synthetic routes to a variety of biologically relevant organic molecules (heterocyclic, heteroaromatic, alicyclic, acyclic, etc.) at room temperature and pressure are discussed.

     

Formation of Au-Pt bimetallic nanoparticles in a two-layer SiO2 films doped with Au and Pt, respectively, through interlayer diffusion

Bimetallic Au-Pt nanoparticles have been generated inside a relatively porous SiO2 film matrix by a two-layer (2L) coating methodology. Two overlapping coating layers were deposited on glass substrates from Au- and Pt-doped inorganic-organic hybrid silica sols and air dried at 60 degrees C. The 2L coating assembly was then UV- and followed by heat-treated at 450 and 550 degrees C in air. UV-treatment decomposes AuCl(4)(-) and PtCl(6)(2-) ions in the respective layers and the subsequent heat treatment in air influences the diffusion of Au and Pt nanometals to each other to form bimetallic Au-Pt nanoparticles inside the silica matrix. A UV-visible study showed damping of Au-plasmon after heat treatments. GIXRD and TEM analyses reveal the formation of a partial Au/Pt solid solution with a small fraction of Pt ( approximately 16%), while the major fraction of Pt remains fused with the Au(Pt) solid solution.     

Fluorescent gel from a self-assembling new chromophoric moiety containing azobenzene based tetraamide

A new chromophoric low molecular weight (LMW) organic molecule, 1, was synthesized, and it forms gels in various organic solvents including toluene, o-xylene, m-xylene and p-xylene. The resultant gel phase materials exhibit enhanced and red-shifted fluorescence emission in the respective gelling solvents. This gelator molecule is self-assembled using various noncovalent interactions including hydrogen bonding, pi-pi staking and van der Waals interactions to get the gel phase materials. The molecule 1 is very weakly fluorescent in solution, but its intensity is increased by almost 40 times in their respective gelled state depending on the nature of the gelling solvents. Self-assembly of this molecule in the above-mentioned organic solvents gives an elongated nanofibrillar network that can be visualized through Field Emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM).     

Anticooperative Supramolecular Oligomerization Mediated by V-Shaped Monomer Design and Unconventional Hydrogen Bonds

After more than three decades of extensive investigations on supramolecular polymers, strategies for self-limiting growth still remain challenging. Herein, we exploit a new V-shaped monomer design to achieve anticooperatively formed oligomers with superior robustness and high luminescence. In toluene, the monomer-oligomer equilibrium is shifted to the monomer side, enabling the elucidation of the molecular packing modes and the resulting (weak) anticooperativity. Steric effects associated with an antiparallel staircase organization of the dyes are proposed to outcompete aromatic and unconventional B−F⋅⋅⋅H−N/C interactions, restricting the growth at the stage of oligomers. In methylcyclohexane (MCH), the packing modes and the anticooperativity are preserved; however, pronounced solvophobic and chain-enwrapping effects lead to thermally ultrastable oligomers. Our results shed light on understanding anticooperative effects and restricted growth in self-assembly.     

Formation, reactivity, and photorelease of metal bound nitrosyl in [Ru(trpy)(L)(NO)](n+) (trpy = 2,2':6',2'-terpyridine, L = 2-phenylimidazo[4,5-f]1,10-phenanthroline)

Nitrosyl complexes with {Ru-NO} (6) and {Ru-NO} (7) configurations have been isolated in the framework of [Ru(trpy)(L)(NO)] ( n+ ) [trpy = 2,2':6',2'-terpyridine, L = 2-phenylimidazo[4,5- f]1,10-phenanthroline] as the perchlorate salts [ 4](ClO 4) 3 and [ 4](ClO 4) 2, respectively. Single crystals of protonated material [ 4-H (+)](ClO 4) 4.2H 2O reveal a Ru-N-O bond angle of 176.1(7) degrees and triply bonded N-O with a 1.127(9) A bond length. Structures were also determined for precursor compounds of [ 4] (3+) in the form of [Ru(trpy)(L)(Cl)](ClO 4).4.5H 2O and [Ru(trpy)(L-H)(CH 3CN)](ClO 4) 3.H 2O. In agreement with largely NO centered reduction, a sizable shift in nu(NO) frequency was observed on moving from [ 4] (3+) (1953 cm (-1)) to [ 4] (2+) (1654 cm (-1)). The Ru (II)-NO* in isolated or electrogenerated [ 4] (2+) exhibits an EPR spectrum with g 1 = 2.020, g 2 = 1.995, and g 3 = 1.884 in CH 3CN at 110 K, reflecting partial metal contribution to the singly occupied molecular orbital (SOMO); (14)N (NO) hyperfine splitting ( A 2 = 30 G) was also observed. The plot of nu(NO) versus E degrees ({RuNO} (6) --> {RuNO} (7)) for 12 analogous complexes [Ru(trpy)(L')(NO)] ( n+ ) exhibits a linear trend. The electrophilic Ru-NO (+) species [ 4] (3+) is transformed to the corresponding Ru-NO 2 (-) system in the presence of OH (-) with k = 2.02 x 10 (-4) s (-1) at 303 K. In the presence of a steady flow of dioxygen gas, the Ru (II)-NO* state in [ 4] (2+) oxidizes to [ 4] (3+) through an associatively activated pathway (Delta S++ = -190.4 J K (-1) M (-1)) with a rate constant ( k [s (-1)]) of 5.33 x 10 (-3). On irradiation with light (Xe lamp), the acetonitrile solution of paramagnetic [Ru(trpy)(L)(NO)] (2+) ([ 4] (2+)) undergoes facile photorelease of NO ( k NO = 2.0 x 10 (-1) min (-1) and t 1/2 approximately 3.5 min) with the concomitant formation of the solvate [Ru (II)(trpy)(L)(CH 3CN)] (2+) [ 2'] (2+). The photoreleased NO can be trapped as an Mb-NO adduct.     

Synthesis,characterization, and crystal structure of 5,5″-Difluoro-1<Emphasis Type="Italic">H</Emphasis>,1″<Emphasis Type="Italic">H</Emphasis>-[3,3′:3′,3″-terindol]-2′(1′<Emphasis Type="Italic">H</Emphasis>)-one

The new indole derivative, 5,5′′-Difluoro-1H,1′′H-[3,3′:3′,3′′-terindol]-2′(1′H)-one C₂₄H₁₅F₂N₃O, is synthesized in 87% yield, and its crystal structure is determined by X-ray structure analysis. The crystals are monoclinic, sp. gr. P2₁/n, a = 15.4563(7), b = 10.8340(6), c = 16.4718(6) Å, β = 102.403(4)°, Z = 4. Bicyclic indole moieties form dihedral angle of 61.92(5)° with each other; the oxindole ring is twisted with respect to them at angles of 85.70(5)° and 75.62(5)°. The crystal structure is stabilized by N–H···O and C–H···O hydrogen bonds involving both the DMSO solvent molecules. In addition, one C–H···π interaction is observed.     

Anthracene-based ureidopyridyl fluororeceptor for dicarboxylates

Anthracene-labelled ureidopyridyl sensor 1 was designed and synthesized. The emission of the sensor increased in presence of dicarboxylates. The binding properties were studied using ¹H NMR, fluorescence and UV-vis spectroscopic methods. The sensor 1 shows modest selectivity for 1,4-phenylenediacetate.     

An anthracene based bispyridinium amide receptor for selective sensing of anions

A new receptor has been designed and synthesized for selective recognition of anions through hydrogen bonding and electrostatic interactions. The recognition ability has been studied by fluorescence, UV-vis and ¹H NMR spectroscopic methods. The results demonstrate that the receptor exhibits good recognition ability towards anions and shows strong binding to AcO⁻, and F⁻.