Amino Acid Based MOFs: Synthesis, Structure, Single Crystal to Single Crystal Transformation, Magnetic and Related Studies in a Family of Cobalt and Nickel Aminoisophthales

Four new 5-aminoisophthalates of cobalt and nickel have been prepared employing hydro/solvothermal methods: [Co2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (I), [Ni2(C8H5NO4)2(C4H4N2)(H2O)2]·3H2O (II), [Co2(H2O)(μ3-OH)2(C8H5NO4)] (III), and [Ni2(H2O)(μ3-OH)2(C8H5NO4)] (IV). Compounds I and II are isostructural, having anion-deficient CdCl2 related layers bridged by a pyrazine ligand, giving rise to a bilayer arrangement. Compounds III and IV have one-dimensional M−O(H)−M chains connected by the 5-aminoisophthalate units forming a three-dimensional structure. The coordinated as well as the lattice water molecules of I and II could be removed and inserted by simple heating−cooling cycles under the atmospheric conditions. The removal of the coordinated water molecule is accompanied by changes in the coordination environment around the M2+ (M = Co, Ni) and color of the samples (purple to blue, Co; green to dark yellow, Ni). This change has been examined by a variety of techniques that include in situ single crystal to single crystal transformation studies and in situ IR and UV−vis spectroscopic studies. Magnetic studies indicate antiferromagnetic behavior in I and II, a field-induced magnetism in III, and a canted antiferromagnetic behavior in IV.

The complete primary structure of a unique mannose/glucose-specific lectin from field bean (Dolichos lab lab)

The complete amino acid sequence of two non identical subunits of the glucose/mannose-specific lectin from Dolichos lab lab (field bean) has been determined by sequential Edman analyses of the intact subunits and peptides derived by enzymatic and chemical cleavage. Peptides were purified by reverse phase high performance liquid chromatography and ion pair chromatography. The D. lab lab lectin is a glycoprotein having two polypeptide chains of 132 and 105 amino acid residues. The amino acid sequence of the D. Lab lab lectin is compared with the various lectins of the family Leguminosae. The D. lab lab lectin is the only species of the tribe Phaseoleae that contains two nonidentical subunits of almost equal size and that shows a specificity to glucose/ mannose. The lectin shows a greater homology to the glucose/mannose specific lectins, especially concanavalin A. The unique subunit architecture of the D. lab lab lectin indicates the presence of new post translational cleavage sites.

Field Induced Dielectric Properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 Thin Films

DC electric field induced dielectric properties of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT) thin films were studied as a function of frequency at different temperatures. It was observed that the dielectric constant (ε) and dissipation factor (tanδ) were decreased in presence of bias field. The temperature of dielectric maxima was found to increase with increasing bias level. The low temperature (family is believed to be the origin of relaxor behavior, disappearance of relaxor nature in PMN-PT (70/30) films could be attributed to manifestation of long-range order at higher bias voltage. This was observed in the temperature dependence of dielectric constant i.e. the films neither exhibited any frequency dispersion in the temperature of dielectric maximum (Tm) nor showed any diffused phase transition. The relaxor property of PMN-PT thin films was studied in terms of diffused phase transition together with frequency dispersion of the temperature of dielectric maximum (Tm). Vogel-Fulcher relation was used to analyze the frequency dependence of temperature of dielectric maximum.

Diketopyrrolopyrrole-Diketopyrrolopyrrole-Based Conjugated Copolymer for High-Mobility Organic Field-Effect Transistors

In this communication, we report the synthesis of a novel diketopyrrolopyrrole-diketopyrrolopyrrole (DPP-DPP)-based conjugated copolymer and its application in high-mobility organic field-effect transistors. Copolymerization of DPP with DPP yields a copolymer with exceptional properties such as extended absorption characteristics (up to similar to 1100 nm) and field-effect electron mobility values of >1 cm(2) V-1 s(-1). The synthesis of this novel DPP-DPP copolymer in combination with the demonstration of transistors with extremely high electron mobility makes this work an important step toward a new family of DPP-DPP copolymers for application in the general area of organic optoelectronics.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Evolution of multivariant microstructures with anisotropic misfit: A phase field study

We study, in two dimensions, the effect of misfit anisotropy on microstructural evolution during precipitation of an ordered beta phase from a disordered alpha matrix; these phases have, respectively, 2- and 6-fold rotation symmetries. Thus, precipitation produces three orientational variants of beta phase particles, and they have an anisotropic (and crystallographically equivalent) misfit strain with the matrix. The anisotropy in misfit is characterized using a parameter t = epsilon(yy)/epsilon(xx), where epsilon(xx) and epsilon(yy) are the principal components of the misfit strain tensor. Our phase field, simulations show that the morphology of beta phase particles is significantly influenced by 1, the level of misfit anisotropy. Particles are circular in systems with dilatational misfit (t = 1), elongated along the direction of lower principal misfit when 0 < t < 1 and elongated along the invariant direction when - 1 <= t <= 0. In the special case of a pure shear misfit strain (t = - 1), the microstructure exhibits star, wedge and checkerboard patterns; these microstructural features are in agreement with those in Ti-Al-Nb alloys.

Unsteady-Flow Of A Viscous-Fluid Between 2 Parallel Disks With A Time-Varying Gap Width And A Magnetic-Field

The unsteady incompressible viscous fluid flow between two parallel infinite disks which are located at a distance h(t*) at time t* has been studied. The upper disk moves towards the lower disk with velocity h'(t*). The lower disk is porous and rotates with angular velocity Omega(t*). A magnetic field B(t*) is applied perpendicular to the two disks. It has been found that the governing Navier-Stokes equations reduce to a set of ordinary differential equations if h(t*), a(t*) and B(t*) vary with time t* in a particular manner, i.e. h(t*) = H(1 - alpha t*)(1/2), Omega(t*) = Omega(0)(1 - alpha t*)(-1), B(t*) = B-0(1 - alpha t*)(-1/2). These ordinary differential equations have been solved numerically using a shooting method. For small Reynolds numbers, analytical solutions have been obtained using a regular perturbation technique. The effects of squeeze Reynolds numbers, Hartmann number and rotation of the disk on the flow pattern, normal force or load and torque have been studied in detail

Unsteady flow over a stretching surface with a magnetic field in a rotating fluid

The effect of the magnetic field on the unsteady flow over a stretching surface in a rotating fluid has been studied. The unsteadiness in the flow field is due to the time-dependent variation of the velocity of the stretching surface and the angular velocity of the rotating fluid. The Navier-Stokes equations and the energy equation governing the flow and the heat transfer admit a self-similar solution if the velocity of the stretching surface and the angular velocity of the rotating fluid vary inversely as a linear function of time. The resulting system of ordinary differential equations is solved numerically using a shooting method. The rotation parameter causes flow reversal in the component of the velocity parallel to the strerching surface and the magnetic field tends to prevent or delay the flow reversal. The surface shear stresses dong the stretching surface and in the rotating direction increase with the rotation parameter, but the surface heat transfer decreases. On the other hand, the magnetic field increases the surface shear stress along the stretching surface, but reduces the surface shear stress in the rotating direction and the surface heat transfer. The effect of the unsteady parameter is more pronounced on the velocity profiles in the rotating direction and temperature profiles.

Crossover from Ising to mean-field critical behavior in an aqueous electrolyte solution

The near-critical behavior of the susceptibility deduced from light-scattering measurements in a ternary liquid mixture of 3-methylpyridine, water, and sodium bromide has been determined. The measurements have been performed in the one-phase region near the lower consolute points of samples with different concentrations of sodium bromide. A crossover from Ising asymptotic behavior to mean-field behavior has been observed. As the concentration of sodium bromide increases, the crossover becomes more pronounced, and the crossover temperature shifts closer to the critical temperature. The data are well described by a model that contains two independent crossover parameters. The crossover of the susceptibility critical exponent γ from its Ising value γ=1.24 to the mean-field value γ=1 is sharp and nonmonotonic. We conclude that there exists an additional length scale in the system due to the presence of the electrolyte which competes with the correlation length of the concentration fluctuations. An analogy with crossover phenomena in polymer solutions and a possible connection with multicritical phenomena is discussed.

Field and potential around local scatterers in thin metal films studied by scanning tunneling potentiometry

We report the direct observation of electrochemical potential and local transport field variations near scatterers like grain boundaries, triple points, and voids in thin platinum films studied by scanning tunneling potentiometry. The field is highest at a void, followed by a triple point and a grain boundary. The local transport field near a void can even be four orders of magnitude higher than the macroscopic field, indicating that the void is the most likely place for an electromigration induced failure. The field build up for a particular type of scatterer depends on the grain connectivity. We estimate an average grain boundary reflection coefficient for the film from the temperature dependence of its resistivity.

Field imperfection induced axial secular frequency shifts in nonlinear ion traps

This article develops a simple analytical expression that relates ion axial secular frequency to field aberration in ion trap mass spectrometers. Hexapole and octopole aberrations have been considered in the present computations. The equation of motion of the ions in a pseudopotential well with these superpositions has the form of a Duffing-like equation and a perturbation method has been used to obtain the expression for ion secular frequency as a function of field imperfections. The expression indicates that the frequency shift is sensitive to the sign of the octopole superposition and insensitive to the sign of the hexapole superposition. Further, for weak multipole superposition of the same magnitude, octopole superposition causes a larger frequency shift in comparison to hexapole superposition.

Flow and heat transfer in a stagnation-point flow over a stretching sheet with a magnetic field

The flow and heat transfer problem in the boundary layer induced by a continuous moving surface is important in many manufacturing processes in industry such as the boundary layer along material handling conveyers, the aerodynamic extrusion of plastic sheet, the cooling of an infinite metalic plate in a cooling bath (which may also be electrolyte). Glass blowing, continuous casting and spinning of fibres also involve the flow due to a stretching surface. Sakiadis [1] was the first to study the flow induced by a semi-infinite moving wall in an ambient fluid. On the other hand, Crane [2] first studied the flow over a linearly stretching sheet in an ambient fluid. Subsequently, Crane [3] also investigated the corresponding heat transfer problem. Since then several authors [4-8] have studied various aspects of this problem such as the effects of mass transfer, variable wall temperature, constant heat flux, magnetic field etc. Recently, Andersson [9] has obtained an exact solution of the Navier-Stokes equations for the MHD flow over a linearly stretching sheet in an ambient fluid. Also Chiam [10] has studied the heat transfer with variable thermal conductivity on a stretching sheet when the velocities of the sheet and the free stream are equal.

Precipitation In Small Systems--II. Mean Field Equations More Effective Than Population Balance

Part I (Manjunath et al., 1994, Chem. Engng Sci. 49, 1451-1463) of this paper showed that the random particle numbers and size distributions in precipitation processes in very small drops obtained by stochastic simulation techniques deviate substantially from the predictions of conventional population balance. The foregoing problem is considered in this paper in terms of a mean field approximation obtained by applying a first-order closure to an unclosed set of mean field equations presented in Part I. The mean field approximation consists of two mutually coupled partial differential equations featuring (i) the probability distribution for residual supersaturation and (ii) the mean number density of particles for each size and supersaturation from which all average properties and fluctuations can be calculated. The mean field equations have been solved by finite difference methods for (i) crystallization and (ii) precipitation of a metal hydroxide both occurring in a single drop of specified initial supersaturation. The results for the average number of particles, average residual supersaturation, the average size distribution, and fluctuations about the average values have been compared with those obtained by stochastic simulation techniques and by population balance. This comparison shows that the mean field predictions are substantially superior to those of population balance as judged by the close proximity of results from the former to those from stochastic simulations. The agreement is excellent for broad initial supersaturations at short times but deteriorates progressively at larger times. For steep initial supersaturation distributions, predictions of the mean field theory are not satisfactory thus calling for higher-order approximations. The merit of the mean field approximation over stochastic simulation lies in its potential to reduce expensive computation times involved in simulation. More effective computational techniques could not only enhance this advantage of the mean field approximation but also make it possible to use higher-order approximations eliminating the constraints under which the stochastic dynamics of the process can be predicted accurately.

Particle field imaging using digital in-line holography

Digital holography is the direct recording of holograms using a CCD camera and is an alternative to the use of a film or a plate. In this communication in-line digital holographic microscopy has been explored for its application in particle imaging in 3D. Holograms of particles of about 10 mu m size have been digitally reconstructed. Digital focusing was done to image the particles in different planes along the depth of focus. Digital holographic particle imaging results were compared with conventional optical microscope imaging. A methodology for dynamic analysis of microparticles in 3D using in-line digital holography has been proposed.

Vertical structure and horizontal gradients of aerosol extinction coefficients over coastal India inferred from airborne lidar measurements during the Integrated Campaign for Aerosol, Gases and Radiation Budget (ICARB) field campaign

Quantitative estimates of the vertical structure and the spatial gradients of aerosol extinction coefficients have been made from airborne lidar measurements across the coastline into offshore oceanic regions along the east and west coasts of India. The vertical structure revealed the presence of strong, elevated aerosol layers in the altitude region of similar to 2-4 km, well above the atmospheric boundary layer (ABL). Horizontal gradients also showed a vertical structure, being sharp with the e(-1) scaling distance (D-0H) as small as similar to 150 km in the well-mixed regions mostly under the influence of local source effects. Above the ABL, where local effects are subdued, the gradients were much shallower (similar to 600-800 km); nevertheless, they were steep compared to the value of similar to 1500-2500 km reported for columnar AOD during winter. The gradients of these elevated layers were steeper over the east coast of India than over the west coast. Near-simultaneous radio sonde (Vaisala, Inc., Finland) ascents made over the northern Bay of Bengal showed the presence of convectively unstable regions, first from surface to similar to 750-1000 m and the other extending from 1750 to 3000 m separated by a stable region in between. These can act as a conduit for the advection of aerosols and favor the transport of continental aerosols in the higher levels (> 2 km) into the oceans without entering the marine boundary layer below. Large spatial gradient in aerosol optical and hence radiative impacts between the coastal landmass and the adjacent oceans within a short distance of < 300 km (even at an altitude of 3 km) during summer and the premonsoon is of significance to the regional climate.