On the survival of peptide cations after electron capture: Role of internal hydrogen bonding and microsolvation

Electron capture by both bare and microsolvated small peptide dications was investigated by colliding these ions with sodium vapor in an accelerator mass spectrometer to provide insight into processes that occur on the microsecond time frame. Survival of the intact peptide monocation after electron capture depends strongly on molecular size. For dipeptides, no intact reduced species were observed; the predominant ions correspond to loss of hydrogen and ammonia. In contrast, the intact reduced species was observed for larger peptides. Calculated structures indicate that the diprotonated dipeptide ions form largely extended structures with low probability of internal ionic hydrogen bonding (i.e., charge solvation) whereas internal ionic H-bonding occurs extensively for larger peptide dications. Solvation of the peptide ions with between one to seven methanol molecules reduces the total extent of H loss even for dipeptides where intact reduced species can survive more than a microsecond after electron capture. The yield of ions corresponding to cleavage of NCalpha bonds (c+ and z+* ions) does not depend strongly on peptide size but decreases with the extent of microsolvation for the dipeptide dications. H-bonding appears to play an important role for the survival of the intact reduced ions but less so for the formation of c+ and z+* ions. Our results indicate that electron capture predominantly occurs at the ammonium groups (at least 70 to 80%), and provides important new insights into the electron capture dissociation process.     

Ion beam synthesis of metal-quantum dots for photonic applications

Although electronics technologies have made great advances in device speed, optical devices can function in the time domain inaccessible to electronics. In the time domain less than 1 ps, optical devices have no competition. Photonic or optical devices are designed to switch and process light signals without converting them to electronic form. The major advantages that these devices offer are speed and preservation of bandwidth. The switching is accomplished through changes in refractive index of the material that are proportional to the light intensity. The third-order optical susceptibility, χ⁽³⁾, known as the optical Kerr susceptibility which is related to the non-linear part of the total refractive index, is the nonlinearity which provides this particular feature. Future opportunities in photonic switching and information processing will depend critically on the development of improved photonic materials with enhanced Kerr susceptibilities, as these materials are still in a relatively early stage of development. Different glass systems are now under investigation to increase their nonlinearity by introducing a variety of modifiers into the glass-network. Ion implantation is an attractive method for inducing colloid formation at a high local concentration unattainable by the melt-glass fabrication process and for confining the non-linearities to specific patterned regions in a variety of host matrices. Recent works on metal-ion implanted colloid generation in bulk fused silica glasses have shown that these nanocluster-glass composites under favourable circumstances have significant enhancement of χ⁽³⁾ with picosecond to femtosecond temporal responses.     

Automated leukocyte recognition using fuzzy divergence

This paper aims at introducing an automated approach to leukocyte recognition using fuzzy divergence and modified thresholding techniques. The recognition is done through the segmentation of nuclei where Gamma, Gaussian and Cauchy type of fuzzy membership functions are studied for the image pixels. It is in fact found that Cauchy leads better segmentation as compared to others. In addition, image thresholding is modified for better recognition. Results are studied and discussed.     

AC Conduction and Time–Temperature Superposition Scaling in a Reduced Graphene Oxide–Zinc Sulfide Nanocomposite

We report, herein, the results of an in depth study and concomitant analysis of the AC conduction [σ′(ω): f=20 Hz to 2 MHz] mechanism in a reduced graphene oxide–zinc sulfide (RGO–ZnS) composite. The magnitude of the real part of the complex impedance decreases with increase in both frequency and temperature, whereas the imaginary part shows an asymptotic maximum that shifts to higher frequencies with increasing temperature. On the other hand, the conductivity isotherm reveals a frequency‐independent conductivity at lower frequencies subsequent to a dispersive conductivity at higher frequencies, which follows a power law [σ′(ω)∝ω^s] within a temperature range of 297 to 393 K. Temperature‐independent frequency exponent ′s′ indicates the occurrence of phonon‐assisted simple quantum tunnelling of electrons between the defects present in RGO. Finally, this sample follows the “time–temperature superposition principle”, as confirmed from the universal scaling of conductivity isotherms. These outcomes not only pave the way for increasing our elemental understanding of the transport mechanism in the RGO system, but will also motivate the investigation of the transport mechanism in other order–disorder systems.     

Singular Propositions,Negation and the Square of Opposition

This paper contains two traditions of diagrammatic studies namely one, the Euler–Venn–Peirce diagram and the other, following tradition of Aristotle, the square of oppositions. We put together both the traditions to study representations of singular propositions (through a diagram system Venn-i, involving constants), their negations and the inter relationship between the two. Along with classical negation we have incorporated negation of another kind viz. absence (taking a cue from the notion of ‘abhãva’ existing in ancient Indian knowledge system). We have also considered the changes that take place in the context of open universe.     

Viscoelastic flow in a two-dimensional collapsible channel

We compute the flow of three viscoelastic fluids (Oldroyd-B, FENE-P, and Owens blood model) in a two-dimensional channel partly bounded by a tensioned membrane, a benchmark geometry for fluid–structure interactions. The predicted flow patterns are compared to those of a Newtonian liquid. We find that computations fail beyond a limiting Weissenberg number. Flow fields and membrane shape differ significantly because of the different degree of shear thinning and molecular extensibility underlying the three different microstructural models.     

Interaction of BSA with proflavin: A spectroscopic approach

The interaction of bovine serum albumin (BSA) with proflavin was investigated by spectroscopic tools like absorption and fluorescence spectroscopy as well as laser flash photolysis. Absorption spectroscopy proved the formation of ground-state BSA-proflavin complex. Proflavin was found to quench the intrinsic fluorescence of BSA via static quenching. High value of quenching constant suggested that energy transfer occurred from BSA to proflavin. Distance between the fluorophore in the protein and the ligand (proflavin) was evaluated. Binding constant and number of binding site were determined for proflavin-BSA interaction both in phosphate buffer (pH∼6.8) and in sodium dodecylsulphate media. The values of the thermodynamic parameters suggested that the key interacting forces are van der Waal's interaction and hydrogen bonding. Laser flash photolysis study reconfirmed the formation of complex between BSA and proflavin.     

Imaging delocalized electron clouds: photoionization of C(60) in Fourier reciprocal space

The dynamics of the photoionization of the two outermost orbitals of C(60) has been studied in the oscillatory regime from threshold to the carbon K edge. We show that geometrical properties of the fullerene electronic hull, such as its diameter and thickness, are contained in the partial photoionization cross sections by examining ratios of partial cross sections as a function of the photon wave number in the Fourier conjugated space. Evaluated in this unconventional manner photoemission data reveal directly the desired spatial information.     

Unitary group decomposition of hamiltonian operators. II. SU (4) irreducible tensors,norms and their energy variation and symmetry breaking

SU(6) ? SU(4) tensor decomposition of effective interactions in the 2s-1d shell has been carried out to examine the relative importance of the various irreducible tensors in many-particle spaces. For this purpose norms of the irreducible tensors are evaluated in many-particle spaces. Variation of the expectation value of the square of the irreducible tensor parts with excitation energy has also been examined using the polynomial expansion method. A new measure of symmetry breaking that is theoretically more sound is derived which includes in its definition partial width as well as internal width. This is used to study SU(4) symmetry mixing in nuclei.