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.     

Flexible paper-based borohydride-vanadium fuel cell for powering micro-nanosystems

This work deals about the development of paper-based fuel cells with high open-circuit voltages for application in powering the micro-nanosystems such as bio-sensors. The developed fuel cell employs Whatman paper as the ion conductor placed between the anode and the cathode to replace expensive ion-conducting membranes such as Nafion. A maximum open-circuit voltage of ～2.1 V per single cell and a power output of ～4.5 mW cm^?2 at ～6 mA cm^?2 are obtained when employing 1 M NaBH₄ in 20 wt% NaOH solution and 1 M VO₂ ⁺ in 2.5 M H₂SO₄ solution. Chronoamperometric measurement performed at 1 V indicates that the output power density varies from 6 to 1 mW cm^?2 in about 100 min. The power delivered at the end of even 100 min is comparable to that of the peak power delivered by many of the micro-fuel cell systems reported in the literature.     

Observation and Kinetic Characterization of Transient Schiff Base Intermediates by CEST NMR Spectroscopy

In aqueous solution, many biochemical reaction pathways involve reaction of an aldehyde with an amine, which progresses through generally unstable, hydrated and dehydrated, Schiff base intermediates that often are unobservable by conventional NMR. There are 4 states in the relevant equilibrium: 1) gem‐diol, 2) aldehyde, 3) hemiaminal, and 4) Schiff base. For the reaction between protein amino groups and DOPAL, a highly toxic metabolite of dopamine, the ¹H resonances of both the hemiaminal and the dehydrated Schiff base can be observed by CEST NMR, even when their populations fall below 0.1 %. CEST NMR reveals the quantitative exchange kinetics between reactants and Schiff base intermediates, explaining why the Schiff base NMR signals are rarely observed. The reactivity of DOPAL with N^α‐amino groups is greater than with lysine N^?‐amines and, in the presence of O₂, both types of Schiff base DOPAL–peptide intermediates rapidly react with free DOPAL to irreversibly form dicatechol pyrrole adducts.     

Nature of wave front of light radiations from a tachyon

The nature of wave front of light radiations from a tachyon is studied from the first principles. The elementary approach employed here yields many novel and interesting results. These results, specially the conical envelope of radiation, bear an excellent analogy to the case of Cerenkov radiation. Finally a possible astrophysical method of searching for the existence of tachyonic celestial objects is discussed.     

On the extreme relativistic limit of arbitrary spin wave equations

The extreme relativistic limit (E-representation) of the wave equation in the Schrödinger formi/t =H describing particles and anti-particles of spin s and non-zero rest mass m is presented here. As the wave function has just the minimum number of 2(2s+1) components, the necessity of avoiding redundant components by auxiliary conditions does not arise. Relevant expressions are given for the infinitesimal generators of the Poincaré group and for the operators representing the observables in this representation.     

Relationship between depth of a target in a turbid medium and fluorescence measured by a variable-aperture method

The relationship between the depth of a target in a turbid medium and the fluorescence ratio profile measured by use of illumination and collection apertures with variable diameters and the same optical path is shown. The forward problem was studied by Monte Carlo simulations of the propagation of fluorescent light through a theoretical model of a biologically relevant system for a range of aperture diameters. The curve of the fluorescence ratio as a function of the aperture diameter is characterized by a maximum/minimum point whose position shifts linearly with the depth of the target. Furthermore, the position of the maximum/minimum is observed to be insensitive to variations in the fluorescence efficiency and to the optical properties of the target layer or the entire medium.     

2-hydroxymethyl-4-[5-(4-methoxyphenyl)-3-trifluoromethyl-1H-1-pyrazolyl]-1-benzenesulfonamide (DRF-4367): an orally active COX-2 inhibitor identified through pharmacophoric modulation

Analogs of 1,5-diarylpyrazoles with a novel pharmacophore at N1 were designed, synthesized and evaluated for the in-vitro cyclooxygenase (COX-1/COX-2) inhibitory activity. The variations at/around position-4 of the C-5 phenyl ring in conjunction with a CF3 and CHF2 groups at C-3 exhibited a high degree of potency and selectivity index (SI) for COX-2 inhibition. The in-vivo evaluation of these potent compounds with a few earlier ones indicated the 4-OMe-phenyl analog and the 4-NHMe-phenyl analog with a CF3, and the 4-OEt-phenyl analog with a CHF2 group at C-3 to possess superior potency than celecoxib. In addition to its impressive anti-inflammatory, antipyretic, analgesic and anti-arthritic properties, compound (DRF-4367) was found to possess an excellent pharmacokinetic profile, gastrointestinal (GI) safety in the long-term arthritis study and COX-2 potency in human whole blood assay. Thus, compound was selected as an orally active anti-inflammatory candidate for pre-clinical evaluation.     

Polarization holographic and surface-relief gratings at 257 nm in an amorphous azobenzene polyester

Polarization holographic and surface-relief gratings have been recorded in an amorphous azobenzene polyester by use of a frequency-doubled argon-ion laser beam at 257 nm. Higher excited states of azobenzene in the trans and cis configurations contribute to the formation of a diffraction grating in this experiment. A combination of right and left circularly polarized writing beams has been found to give the highest diffraction efficiency. The contributions to the total phase difference that arise from anisotropy and surface relief have been separated experimentally, and it is shown that the surface-relief grating contributes a larger phase difference than that which is due to anisotropy.     

Assay of p-aminobenzenesulphonamides with chloramine-T

New spectrophotometric and titrimetric methods for the assay of p-aminobenzenesulphonamides with chloramine-T have been developed. They are simple, reproducible and accurate within the limits described (+/-3%) and are useful at high concentration levels. These methods are also applicable to the assay of p-aminobenzenesulphonamides in rat urine.