Bile Acid Derived PET-Based Cation Sensors: Molecular Structure Dependence of their Sensitivity

A number of bile acid derived photoinduced electron transfer (PET) based sensors for metal ions are prepared. A general strategy for designing the sensor with a modular nature allows for making different molecules capable of sensing different metal ions by a change in the fluorophore and receptor unit. Keeping the basic molecular structure the same, different bile acid base fluoroionophores were prepared inorder to achieve the highest sensitivity toward the metal ions. Thesensors showed similar binding constants for the same metal ion, but the degree Of fluorescence enhancement upon addition of the metal salts were different. The sensitivities of the sensors towards a certain metal were determined from the observed fluorescence enhancement upon addition of the metal salt.

Kinetics of Extraction of Iron(II1) by Bis(2-ethylhexyl Phosphate in a Laminar Liquid-Liquid Jet Reactor

The kinetics of iron(II1) extraction by bis(Zethylhexy1) phosphate (HDEHP, HA) in kerosene from sulfuric acid solutions has been studied in a liquid-liquid laminar jet reactor. The contact time of the interface in this reacting device is of the same order of magnitude as the surface renewal time in dispersion mixing and much less than that obtained in the relatively quiescent condition of the Lewis cell. Yet the analysis of the data in this study suggested a rate-controlling step involving surface saturation quite in conformity with that obtained in the Lewis cell and not with that in dispersion mixing as reported in the literature. Further, the mechanism suggested a weaker dependence of the rate on hydrogen ion concentration which was reported by other workers.

Size dependence and dispersion behavior of the first hyperpolarizability of copper nanoparticles

We have probed the size dependency of the first hyperpolarizability (b) of copper nanoparticles by hyper-Rayleigh scattering (HRS). Our results indicate that second harmonic generation (SHG) originates predominantly at the surface of the nanoparticles as long as the size (d) remains small compared to the wavelength (k). However, volume contribution to the SH response due to the retardation effect becomes important when particle size grows beyond the `small particle limit'. There is a significant dispersion in the b values of copper nanoparticles owing tothe presence of the strong surface plasmon resonance (SPR) band.

Doping Dependence of Semiconductor-Metal Transition in InP at High Pressures

The resistivity of selenium-doped n-InP single crystal layers grown by liquid-phase epitaxy with electron concentrations varying from 6.7 x 10$^18$ to 1.8 x 10$^20$ cm$^{-3}$ has been measured as a function of hydrostatic pressure up to 10 GPa. Semiconductor-metal transitions were observed in each case with a change in resistivity by two to three orders of magnitude. The transition pressure p$_c$ decreased monotonically from 7.24 to 5.90 GPa with increasing doping concentration n according to the relation $p_c = p_o [1 - k(n/n_m)^a]$, where n$_m$ is the concentration (per cubic centimetre) of phosphorus donor sites in InP atoms, p$_o$ is the transition pressure at low doping concentrations, k is a constant and $\alpha$ is an exponent found experimentally to be 0.637. The decrease in p$_c$ is considered to be due to increasing internal stress developed at high concentrations of ionized donors. The high-pressure metallic phase had a resistivity (2.02-6.47) x 10$^{-7}$ $\Omega$ cm, with a positive temperature coefficient dependent on doping.

Vibrations of a Beam in Variable Contact With a Flat Surface

We study small vibrations of cantilever beams contacting a rigid surface. We study two cases: the first is a beam that sags onto the ground due to gravity, and the second is a beam that sticks to the ground through reversible adhesion. In both cases, the noncontacting length varies dynamically. We first obtain the governing equations and boundary conditions, including a transversality condition involving an end moment, using Hamilton's principle. Rescaling the variable length to a constant value, we obtain partial differential equations with time varying coefficients, which, upon linearization, give the natural frequencies of vibration. The natural frequencies for the first case (gravity without adhesion) match that of a clamped-clamped beam of the same nominal length; frequencies for the second case, however, show no such match. We develop simple, if atypical, single degree of freedom approximations for the first modes of these two systems, which provide insights into the role of the static deflection profile, as well as the end moment condition, in determining the first natural frequencies of these systems. Finally, we consider small transverse sinusoidal forcing of the first case and find that the governing equation contains both parametric and external forcing terms. For forcing at resonance, w find that either the internal or the external forcing may dominate.

Fractional power dependence of rate on activation energy for reactions with very low internal barriers

The dynamics of reactions with low internal barriers are studied both analytically and numerically for two different models. Exact expressions for the average rate,kI, are obtained by solving the associated first passage time problems. Both the average rate constant, kI, and the numerically calculated long-time rate constant, kL, show a fractional power law dependence on the barrier height for very low barriers. The crossover of the reaction dynamics from low to high barrier is investigated.

Temperature dependence of the surface conductivity of YBa2Cu3O7−δ accompanying the change in the concentration of dimerized oxygen holes

The intensity of inelastically scattered electrons measured by electron energy loss spectroscopy has been employed to monitor the surface conductivity of YBa2Cu3O6.9 as a function of temperature. The study shows a drastic change in surface conductivity precedes the superconducting transition at 90K. The increase in surface conductivity is accompanied by the formation of dimerized holes in the oxygen derived p-band. This phenomenon is not observed in the non-superconducting YBa2Cu3O6.2.

Effects of Isothermal and Adiabatic Thermal Loadings on Size and Strain Rate Dependence of Copper Nanowire

In the present paper, the size and strain rate effects on ultra-thin < 100 >/{100} Cu nanowires at an initial temperature of 10 K have been discussed. Extensive molecular dynamics (MD) simulations have been performed using Embedded atom method (EAM) to investigate the structural behaviours and properties under high strain rate. Velocity-Verlet algorithm has been used to solve the equation of motions. Two different thermal loading cases have been considered: (i) Isothermal loading, in which Nose-Hoover thermostat is used to maintain the constant system temperature, and (ii) Adiabatic loading, i.e., without any thermostat. Five different wire cross-sections were considered ranging from 0.723 x 0.723 nm(2) to 2.169 x 2.169 nm(2) The strain rates used in the present study were 1 x 10(9) s(-1), 1 x 10(8) s(-1), and 1 x 10(7) s(-1). The effect of strain rate on the mechanical properties of copper nanowires was analysed, which shows that elastic properties are independent of thermal loading for a given strain rate and cross-sectional dimension of nanowire. It showed a decreasing yield stress and yield strain with decreasing strain rate for a given cross- section. Also, a decreasing yield stress and increasing yield strain were observed for a given strain rate with increasing cross-sectional area. Elastic modulus was found to be similar to 100 GPa, which was independent of processing temperature, strain rate, and size for a given initial temperature. Reorientation of < 100 >/{100} square cross-sectional copper nanowire into a series of stable ultra-thin Pentagon copper nanobridge structures with dia of similar to 1 nm at 10 K was observed under high strain rate tensile loading. The effect of isothermal and adiabatic loading on the formation of such pentagonal nanobridge structure has been discussed.

Sequence dependence and role of 5'-phosphate in the B to Z transition

Spectroscopic studies on pd(CG)3 and pd(GC)3 have been carried out to elucidate the sequence dependence and effect of free 5'-phosphate on the B to Z transition. Unlike d(CG)3, pd(CG)3 fails to undergo salt-induced B to Z transition at ambient temperature. Model building studies have been carried out to determine the inhibitory role of the 5'-phosphate group, but have been unsuccessful.

Study on the pH dependence of diffraction efficiency of phase holograms in dye sensitized dichromated gelatin

Dichromated gelatin is thought to be a good substitute for photographic emulsions in some uses. The results of a systematic study of the effect of the pH of the developer on the diffraction efficiency of volume holographic gratings recorded in dye sensitized dichromated gelatin are presented.

Finite element analysis of moving contact in mechanically fastened joints

The Finite Element Method (FEM) has made a number of otherwise intractable problems solvable. An important aspect for achieving an economical and accurate solution through FEM is matching the formulation and the computational organisation to the problem. This was realised forcefully in the present case of the solution of a class of moving contact boundary value problems of fastener joints. This paper deals with the problem of changing contact at the pin-hole interface of a fastener joint. Due to moving contact, the stresses and displacements are nonlinear with load. This would, in general, need an interactive-incremental approach for solution. However, by posing the problem in an inverse way, a solution is sought for obtaining loads to suit given contact configuration. Numerical results are given for typical isotropic and composite plates with rigid pins. Two cases of loading are considered: (i) load applied only at the edges of the plate and (ii) load applied at the pin and reacted at a part of the edge of the plate. Load-contact relationships, compliance and stress-patterns are investigated. This paper clearly demonstrates the simplification achieved by a suitable formulation of the problem. The results are of significance to the design and analysis of fastener joints.

Finite element analysis of moving contact in mechanically fastened joints

The Finite Element Method (FEM) has made a number of otherwise intractable problems solvable. An important aspect for achieving an economical and accurate solution through FEM is matching the formulation and the computational organisation to the problem. This was realised forcefully in the present case of the solution of a class of moving contact boundary value problems of fastener joints. This paper deals with the problem of changing contact at the pin-hole interface of a fastener joint. Due to moving contact, the stresses and displacements are nonlinear with load. This would, in general, need an interactive-incremental approach for solution. However, by posing the problem in an inverse way, a solution is sought for obtaining loads to suit given contact configuration. Numerical results are given for typical isotropic and composite plates with rigid pins. Two cases of loading are considered: (i) load applied only at the edges of the plate and (ii) load applied at the pin and reacted at a part of the edge of the plate. Load-contact relationships, compliance and stress-patterns are investigated. This paper clearly demonstrates the simplification achieved by a suitable formulation of the problem. The results are of significance to the design and analysis of fastener joints.

Pressure dependence of 35Cl nuclear quadrupole resonance in 2,5-, 2,6- and 3,5-dichlorophenols

Pressure dependence of the 35Cl Nuclear Quadrupole Resonances (N.Q.R.) in 2,5-, 2,6- and 3,5-dichlorophenols (DCP) has been studied up to a pressure of about 6·5 kbar at room temperature. While the pressure dependence of the two resonance lines in 2,6-DCP is essentially similar, the lower frequency line in 2,5-DCP is almost pressure independent and the higher frequency line shows a linear variation with pressure upto about 3·5 kbar but shows a negative pressure coefficient beyond this pressure. The two lines in 3,5-DCP have a non-linear pressure dependence with the curvature changing smoothly with pressure. The pressure coefficient for both lines becomes negative beyond a pressure of 5 kbar. The pressure dependence of the N.Q.R. frequencies is discussed in relation to intra- and inter-molecular contacts. Also, a thermodynamic analysis of the data is carried out to determine the constant volume temperature derivative of the N.Q.R. frequency.

Motional Averaging of Electric Field Gradients. Temperature Dependence of Nqr in Sodium Chlorate and Copper Chlorate

Es wird die Temperaturabhiingigkeit der CI35-Kernquadrupolresonanz in Natriumchlorat und Kupferchlorat im Temperature von 77 bis 300 °K untersucht. Es wird gezeigt, daß die Annahmen, die in der Theorie von Bayer gemacht werden, fur Chlorate gelten. Die Frequenz der Torsionsschwingungen der ClO3-Gruppe wird folglich mit dieser Theorie berechnet. Der berechnete Wert der Torsionsfrequenz stimmt gut mit vorhandenen Werten der Ramanspektroskopie überein.

The real area of contact and compliance of rough cylinders in compression

Bearing area analysis has been used to study the real area of contact and compliance of rough turned steel cylinders in compression. Calculations show that the elastic real area of contact is very small compared to the plastic real area of contact, and that local compliance due to flattening of asperity tips is a small proportion of the total compliance obtained from experiments. The fact that increased load brings more and more new asperities under load rather than enlarging the contact spots leads to a rather simple load-compliance relation for a rough cylinder, viz., W' = Nh · K1δn, where W0 = K1δn defines the load-compliance relation of the individual asperities, and Nh represents the number of asperities bearing the load.