1,3-Diamido-calix[4]arene conjugates of amino acids: recognition of -COOH side chain present in amino acids, peptides, and proteins by experimental and computational studies

Lower rim 1,3-diamido conjugates of calix[4]arene have been synthesized and characterized, and the structures of some of these have been established by single crystal XRD. The amido-calix conjugates possessing a terminal -COOH moiety have been shown to exhibit recognition toward guest molecules possessing -COOH moiety, viz., Asp, Glu, and reduced and oxidized glutathione (GSH, GSSG), by switch-on fluorescence in aqueous acetonitrile and methanol solutions when compared to the control molecules via forming a 1:1 complex. The complex formed has been shown by mass spectrometry, and the structural features of the complexes were derived on the basis of DFT computations. The association constants observed for the recognition of Asp/Glu by Phe-calix conjugate, viz., 532/676 M(-1), are higher than that reported for the recognition of Val, Leu, Phe, His, and Trp (16-63 M(-1)) by a water-soluble calixarene (Arena, G., et al. Tetrahedron Lett. 1999, 40, 1597). For this recognition, there should be a free -COOH moiety from the guest molecule. AFM, SEM, and DLS data exhibited spherical particles with a hundred-fold reduction in the size of the complexes when compared to the particles of the precursors. These spherical particles have been computationally modeled to possess hexameric species reminiscent of the hexameric micellar structures shown for a Ag(+) complex of a calix[6]arene reported in the literature (Houmadi, S., et al. Langmuir 2007, 23, 4849). Both AFM and TEM studies demonstrated the formation of nanospheres in the case of GSH-capped Ag nanoparticles in interaction with the amido-calix conjugate that possesses terminal -COOH moiety. The AFM studies demonstrated in this paper have been very well applied to albumin proteins to differentiate the aggregational behavior and nanostructural features exhibited by the complexes of proteins from those of the uncomplexed ones. To our knowledge, this is the first report wherein a amido-calix[4]arene conjugate and its amino acid/peptide/protein complexes have been differentiated on the basis of spectroscopy and microscopy studies followed by species modeling by computations.     

A domino approach of Heck coupling for the synthesis of β-trifluoromethylstyrenes

A domino approach of Heck coupling was used to synthesize β-trifluoromethylstyrene derivatives from iodoarenes and 1-iodo-3,3,3-trifluoropropane in moderate to good yields. This method avoids the use of low-boiling, gaseous reagents such as 3,3,3-trifluoropropene, and additives and phosphines in the catalytic system.     

Synthesis of fused polycyclic nitrogen-containing heterocycles via cascade cyclization

A novel strategy for the synthesis of fused polycyclic-nitrogen containing heterocycles via cascade cyclization is described. The methodology involves condensation of 1-(2-aminophenyl)-9H-β-carboline-3-carboxylic acid amide with isothiocyanates followed by in situ treatment of the resulting thioureas with HgCl₂ for 1 h at rt. The one-pot cascade cyclization leads to interesting changes in molecular structure and an increase in molecular complexity. A mechanistic rationale for the cascade cyclization is discussed.     

The Electronic and Magnetic Properties of a Few Transition-Metal Clusters

Using density functional theory we present a systematic study of the electronic and magnetic properties of various nickel clusters and two small bimetallic clusters, Ni _n Co _m and Ni _n Fe _m (n + m ≤ 6). A detail study of binding energy, magnetic moment and stability function of pure nickel clusters of nuclearity (N) 40–60 have been performed. We observe that the magic numbers occur at N = 43, 46, 49, 53, 55, and 58, which correspond to the most stable clusters. We find that, with increase in substitution of Co and Fe atoms in Ni cluster, while Ni _n Co _m becomes more stable, the Ni _n Fe _m clusters become less stable. The significant enhancement of average magnetic moment and suppression of local magnetic moment of nickel atoms are found in both clusters with increase in Co and Fe concentration.     

3,2-Hydroxypyridinone (3,2-HOPO) vinyl sulfonamide and acrylamide linkers: aza-Michael addition reactions and the preparation of poly-HOPO chelators

The HOPO vinyl sulfonamide 3 and the corresponding HOPO acrylamide 10 were easily prepared by short synthetic sequences. Investigation of the aza-Michael reactions of these linkers showed that they proceed at a higher rate in solvent systems containing water. The scope and limits of the aza-Michael reactions of 3 and 10 were examined. Reagents 3 and 10 reacted cleanly with piperazine to give the corresponding adducts which were deprotected to give the di-HOPO ligands 7 and 16. Reaction of HOPO acrylamide 10 with 1,4,7-triazacyclononane gave the tris-adduct 17 which was deprotected to give the desired tris-HOPO ligand 18. Overall, the aza-Michael reactions of 3 and 10 appear to be governed not only by the solvent but also by the nature of the amine and the solubility of the reaction intermediates.     

Metal-free synthesis of benzimidazo[2,1-a]ellipticines via tandem inter and intramolecular cyclization

Synthesis of the new benzimidazo[2,1-a]ellipticine derivatives via tandem inter and intramolecular, 5-endo,6-endo cyclization of various 9-ethyl-2-(alkynyl)carbazole-3-carbaldehydes with different 1,2-aryldiamines is reported under metal free condition in good yields.     

Numerical simulation of a methane-oxygen rotating detonation rocket engine

The rotating detonation engine (RDE) is an important realization of pressure gain combustion for rocket applications. The RDE system is characterized by a highly unsteady flow field, with multiple reflected pressure waves following detonation and an entrainment of partially-burnt gases in the post-detonation region. While experimental efforts have provided macroscopic properties of RDE operation, limited accessibility for optical and flow-field diagnostic equipment constrain the understanding of mechanisms that lend to wave stability, controllability, and sustainability. To this end, high-fidelity numerical simulations of a methane-oxygen rotating detonation rocket engine (RDRE) with an impinging discrete injection scheme are performed to provide detailed insight into the detonation and mixing physics and anomalous behavior within the system. Two primary detonation waves reside at a standoff distance from the base of the channel, with peak detonation heat release at approximately 10 mm from the injection plane. The high plenum pressures and micro-nozzle injector geometry contribute to fairly stiff injectors that are minimally affected by the passing detonation wave. There is no large scale circulation observed in the reactant mixing region, and the fuel distribution is asymmetric with a rich mixture attached to the inner wall of the annulus. The detonation waves’ strengths spatially fluctuate, with large variations in local wave speed and flow compression. The flow field is characterized by parasitic combustion of the fresh reactant mixture as well as post-detonation deflagration of residual gases. By the exit plane of the RDRE, approximately 95.7% of the fuel has been consumed. In this work, a detailed statistical analysis of the interaction between mixing and detonation is presented. The results highlight the merit of high-fidelity numerical studies in investigating an RDRE system and the outcomes may be used to improve its performance.     

On minimal complements in groups

The Ramanujan Journal - Let $$W,W'subseteq G$$ be non-empty subsets in an arbitrary group G. The set $$W'$$ is said to be a complement to W if $$Wcdot W'=G$$ and it is minimal if no...     

Influerce of chemical structure of nitroxyl spin labels on their reduction by ascorbic acid

The Influence of structure on the reduction of nitroxyl spin labels by ascorbic acid was examined using both piperidine and pyrrolidine nitroxyls. A five-fold molar excess of ascorbic acid and pH of 7.4 were used. The nitroxyl concentration was measured by electron spin resonance spectrometry. The five-membered (pyrrolidine) nitroxyls were more stable than the six-meabered derivatives. Ring substituents also influenced the reaction. The anionic derivatives were more stable than the unionized compounds which, in turn, were more stable than the amines (cations at pH 7.4).