G‐Tetraplex‐Induced FRET within Telomeric Repeat Sequences Using PyA‐PerA as Energy Donor–Acceptor Pair

G‐tetraplex induced fluorescence resonance energy transfer (FRET) within telomeric repeat sequences has been studied using a nucleoside‐tethered FRET pair embedded in the human telomeric G‐quadruplex forming sequence (5′‐A GGG TT ^Py A GGG TT ^Per A GGG TTA GGG‐3′, Py=pyrene, Per=perylene). Conformational change from a single strand to an anti‐parallel G‐quadruplex leads to FRET from energy donor ( ^Py A ) to acceptor ( ^Per A ). The distance between the FRET donor/acceptor partners was controlled by changing the number of G‐quartet spacer units. The FRET efficiency decreases with increase in G‐quartet units. Overall findings indicate that this could be further used for the development of FRET‐based sensing and measurement techniques.     

Redox Non‐Innocence of Nitrosobenzene at Nickel

Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox‐active nitric oxide derivative. Capture of nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [ⁱPr₂NN_F6]Ni results in reduction of the PhNO ligand to a (PhNO)^./? species coordinated to a square planar Ni^II center in [ⁱPr₂NN_F6]Ni(η²‐ONPh). Ligand centered reduction leads to the (PhNO)^2? moiety bound to Ni^II supported by XAS studies. Systematic investigation of structure–reactivity patterns of (PhNO)^./? and (PhNO)^2? ligands reveals parallels with superoxo (O₂)^./? and peroxo (O₂)^2? ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.     

Targeted synthesis of mu-oxo divanadium(V) compounds with asymmetry in coordination environments

Isovalent mu-oxo divanadium(V) compounds [L1VO(mu-O)VO(salen)] (1) and its bromo derivative [L2VO(mu-O)VO(salen)].CH3CN (2) (both H2L1 and H2L2 are tridentate dithiocarbazate-based ONS ligands) with ligands providing donor set and coordination number asymmetry in tandem have been synthesized for the first time; confirmations in favor of these unsymmetrical molecular structures have come from single-crystal X-ray diffraction analysis, as well as from NMR (both 1H and 51V) spectroscopy.     

Spectroscopic studies on methyl torsional behavior in 1-methyl-2(1H)-pyridone, 1-methyl-2(1H)-pyridinimine, and 3-methyl-2(1H)-pyridone. I. Excited state

The laser induced fluorescence excitation and dispersed fluorescence spectra of three nitrogen heterocyclic molecules 1-methyl-2(1H)pyridone (1MPY), 1-methyl-2(1H)pyridinimine (1MPI), and 3-methyl-2(1H)pyridone (3MPY) have been studied under supersonic jet cooled condition. The methyl torsional and some low frequency vibrational transitions in the fluorescence excitation spectrum were assigned for 1MPY. These new assignments modify the potential parameters to the methyl torsion reported earlier. Some striking similarities exist between the torsional and vibrational transitions in the fluorescence excitation spectra of 1MPY and 1MPI. Apart from pure torsional transitions, a progression of vibration-torsion combination bands was observed for both these molecules. The excitation spectrum of 3MPY resembles the spectrum of its parent molecule, 2-pyridone. The barrier height of the methyl torsion in the excited state of 3MPY is highest amongst all these molecules, whereas the barrier in 1MPI is higher than that of 1MPY. To get an insight into the methyl torsional barrier for these molecules, results of the ab initio calculations were compared with the experimental results. It was found that the conformation of the methyl group undergoes a 60 degrees rotation in the excited state in all these molecules with respect to their ground state conformation. This phase shift of the excited state potential is attributed to the pi*-sigma* hyperconjugation between the out-of-plane hydrogen of the methyl group and the molecular frame. It has been inferred that the change in lowest unoccupied molecular orbital energy plays the dominant role in the excited state barrier formation.     

Mass spectral study of substituted allyl aryl and allyl alkyl selenides and some analogous sulfides

The electron impact (EI) mass spectra of allyl aryl selenides showed abundant molecular ions and many fragment ions containing the selenium atom. alpha-Cleavage is the dominant process in the fragmentation of selenides, and cleavage product ions are characteristic of the substituents. In the case of 3-methyl allyl and related aryl selenides, characteristic delta-hydrogen migration to the selenium atom is observed. A McLafferty-type rearrangement is found in benzyl allyl selenides and substituted alkyl allyl selenides. The charge on the rearrangement products preferably remains on the fragments containing the phenyl group. The [M - SeH](+), [M - CH(3)](+) and [M - C(2)H(4)](+) ions are found only in the EI mass spectrum of allyl phenyl selenide, and are attributed to a Claisen rearrangement in the source of the mass spectrometer. All structurally informative fragmentation processes are supported by collision induced dissociation spectra of molecular ions. The fragmentation patterns found in methane chemical ionization (CI) spectra of the selenides were significantly different from those observed in EI. The EI and CI mass spectra of analogous sulfides showed similar behaviour to that observed in the corresponding selenides. Copyright 1999 John Wiley & Sons, Ltd.     

The perturbative proton form factor reexamined

We recalculate the proton Dirac form factor based on the perturbative QCD factorization theorem, which includes Sudakov suppression. The evolution scale of the proton wave functions and the infrared cutoffs for the Sudakov re-summation are carefully chosen such that the soft divergences from large coupling constants are diminished and perturbative QCD predictions are stabilized. We find that the King–Sachrajda model for the proton wave function leads to results which are in better agreement with experimental data than those from the Chernyak–Zhitnitsky wave function. Received: 27 November 1998 / Published online: 7 April 1999     

New physics effects from B meson decays

In this talk, we point out some of the present and future possible signatures of physics beyond the Standard Model from B-meson decays, taking R-parity conserving and violating supersymmetry as illustrative examples. An expanded version is available on hep-ph archive.     

A numerical experiment in DLCQ: microcausality, continuum limit and all that

Issues related with microcausality violation and continuum limit in the context of (1+1) dimensional scalar field theory in discretized light-cone quantization (DLCQ) are addressed in parallel with discretized equal time quantization (DETQ) and the fact that Lorentz invariance and microcausality are restored if one can take the continuum limit properly is emphasized. In the free case, it is shown with numerical evidence that the continuum results can be reproduced from DLCQ results for the Pauli–Jordan function and the real part of Feynman propagator. The contributions coming from k⁺ near zero region in these cases are found to be very small. In the interacting case, aspects related to the continuum limit of DLCQ results in perturbation theory in momentum space are discussed.     

Esterification of butyric acid with n-butanol: Kinetic study using experimental data and modeling

Present study involves the investigation of the esterification kinetics between butyric acid and n-butanol. This reaction was conducted in a batch reactor, utilizing homogeneous methanesulfonic acid (MSA) catalyst. Response surface methodology (RSM) was conducted prior to the kinetic study using “Design Expert; version-11.0” for finding the causal factors influencing the conversion of butyric acid. Most important factors identified with their limits against conversions (during optimization of the process using RSM) were taken up to critically analyze the effect of them on butyric acid conversion. Concentration and activity-based model of the process were proposed assuming second order reversible reaction scheme using homogeneous MSA catalyst. During the study of non-ideal behavior of the system, UNIFAC model was adapted for assessing the activity coefficients of species present in equilibrated liquid phase. Experimental data were used to evaluate kinetic and thermodynamic parameters such as rate constants, activation energy, enthalpy, and entropy of the system. The endothermic nature of esterification was confirmed by positive value of enthalpy obtained. The effect of various levels of causal variables like temperature (60–90°C), catalyst concentration (0.5–1.5 wt.%), and molar ratio of n-butanol to butyric acid (1–3) on conversion kinetics of butyric acid was investigated during transient and equilibrium phase of the reaction. It has been observed that molar ratio of butanol to butyric acid has the highest influence on the conversion. The rate equation derived offered a kinetic and thermodynamic framework to the generated data. It also exhibits a notable degree of conformity of predicted data to the experimental ones and effectively characterizes the system across different reaction temperatures, reactant molar ratio, and catalyst concentration.     

Controlled Space Radiation concept for mesh-free semi-analytical technique to model wave fields in complex geometries

Numerical modelling of the ultrasonic wave propagation is important for Structural Heath Monitoring and System Prognosis problems. In order to develop intelligent and adaptive structures with embedded damage detector and classifier mechanisms, detailed understanding of scattered wave fields due to anomaly in the structure is inevitably required. A detailed understanding of the problem demands a good modelling of the wave propagation in the problem geometry in virtual form. Therefore, efficient analytical, semi-analytical or numerical modelling techniques are required. In recent years a semi-analytical mesh-free technique called Distributed Point Source Method (DPSM) is being used for modelling various ultrasonic, electrostatic and electromagnetic wave field problems. In the conventional DPSM approach point sources are placed along the transducer faces, problem boundaries and interfaces to model incident and scattered fields. Every point source emits energy in all directions uniformly. Source strengths of these 360° radiation sources are obtained by satisfying interface and boundary conditions of the problem. In conventional DPSM modelling approach it is assumed that the shadow zone does not require any special consideration. 360° Radiation point sources should be capable of properly modelling shadow zones because all boundary and interface conditions are satisfied. In this paper it is investigated how good this assumption is by introducing the ‘shadow zone’ concept at the point source level and comparing the results generated by the conventional DPSM and by this modified approach where the conventional 360° radiation point sources are replaced by the Controlled Space Radiation (CSR) sources.