Magnetic behaviour in metal-organic frameworks-Some recent examples

The article describes the synthesis, structure and magnetic investigations of a series of metal-organic framework compounds formed with Mn+2 and Ni+2 ions. The structures, determined using the single crystal X-ray diffraction, indicated that the structures possess two- and three-dimensional structures with magnetically active dimers, tetramers, chains, two-dimensional layers connected by polycarboxylic acids. These compounds provide good examples for the investigations of magnetic behaviour. Magnetic studies have been carried out using SQUID magnetometer in the range of 2-300 K and the behaviour indicates a predominant anti-ferromagnetic interactions, which appears to differ based on the M-O-C-O-M and/or the M-O-M (M = metal ions) linkages. Thus, compounds with carboxylate (Mn-O-C-O-Mn) connected ones, [C3N2H [Mn(H2O)''C6H3(COO)(3)''], I, [''Mn(H2O (3)''aEuroeC(12)H(8)O(COO)(2)'']center dot H2O, II, [''Mn(H2O)''aEuroeC(12)H(8)O(COO)(2)''], III, show simple anti-ferromagnetic behaviour. The compounds with Mn-O/OH-Mn connected dimer and tetramer units in [NaMn''C6H3(COO)(3)''], IV, [Mn-2(A mu(3)-OH) (H2O)(2)''C6H3(COO)(3)'']center dot 2H(2)O, V, show canted-antiferromagnetic and anti-ferromagnetic behaviour, respectively. The presence of infinite one-dimensional -Ni-OH-Ni- chains in the compound, [Ni-2(H2O)(A mu(3)-OH)(2)(C8H5NO4], VI, gives rise to ferromagnet-like behaviour at low temperatures. The compounds, [Mn-3''C6H3(COO)(3)''(2)], VII and [''Mn(OH)''(2)''C12H8O(COO)(2)''], VIII, have two-dimensional infinite -Mn-O/OH-Mn- layers with triangular magnetic lattices, which resemble the Kagome and brucite-like layer. The magnetic studies indicated canted-antiferromagnetic behaviour in both the cases. Variable temperature EPR and theoretical magnetic modelling studies have been carried out on selected compounds to probe the nature of the magnetic species and their interactions with them.

Apparent shortening of the Csp(3)-Csp(3) bond analysed via a variable-temperature X-ray diffraction study in racemic 1,1 '-binaphthalene-2,2 '-diyl diethyl bis(carbonate)

Crystal structure determination at room temperature [292 (2) K] of racemic 1,1'-binaphthalene-2,2'-diyl diethyl bis(carbonate), C26H22O6, showed that one of the terminal carbon-carbon bond lengths is very short [Csp(3)-Csp(3) = 1.327 (6) angstrom]. The reason for such a short bond length has been analysed by collecting data sets on the same crystal at 393, 150 and 90 K. The values of the corrected bond lengths clearly suggest that the shortening is mainly due to positional disorder at two sites, with minor perturbations arising as a result of thermal vibrations. The positional disorder has been resolved in the analysis of the 90 K data following the changes in the unit-cell parameters for the data sets at 150 and 90 K, which appear to be an artifact of a near centre of symmetry relationship between the two independent molecules in the space group P (1) over bar at these temperatures. Indeed, the unit cell at low temperature (150 and 90 K) is a supercell of the room-temperature unit cell.

Influence of spatial variability of permeability property on steady state seepage flow and slope stability analysis

In recent years, spatial variability modeling of soil parameters using random field theory has gained distinct importance in geotechnical analysis. In the present Study, commercially available finite difference numerical code FLAC 5.0 is used for modeling the permeability parameter as spatially correlated log-normally distributed random variable and its influence on the steady state seepage flow and on the slope stability analysis are studied. Considering the case of a 5.0 m high cohesive-frictional soil slope of 30 degrees, a range of coefficients of variation (CoV%) from 60 to 90% in the permeability Values, and taking different values of correlation distance in the range of 0.5-15 m, parametric studies, using Monte Carlo simulations, are performed to study the following three aspects, i.e., (i) effect ostochastic soil permeability on the statistics of seepage flow in comparison to the analytic (Dupuit's) solution available for the uniformly constant permeability property; (ii) strain and deformation pattern, and (iii) stability of the given slope assessed in terms of factor of safety (FS). The results obtained in this study are useful to understand the role of permeability variations in slope stability analysis under different slope conditions and material properties. (C) 2009 Elsevier B.V. All rights reserved.

Conservation law with the flux function discontinuous in the space variable- II - Convex-concave type fluxes and generalized entropy solutions

We deal with a single conservation law with discontinuous convex-concave type fluxes which arise while considering sign changing flux coefficients. The main difficulty is that a weak solution may not exist as the Rankine-Hugoniot condition at the interface may not be satisfied for certain choice of the initial data. We develop the concept of generalized entropy solutions for such equations by replacing the Rankine-Hugoniot condition by a generalized Rankine-Hugoniot condition. The uniqueness of solutions is shown by proving that the generalized entropy solutions form a contractive semi-group in L-1. Existence follows by showing that a Godunov type finite difference scheme converges to the generalized entropy solution. The scheme is based on solutions of the associated Riemann problem and is neither consistent nor conservative. The analysis developed here enables to treat the cases of fluxes having at most one extrema in the domain of definition completely. Numerical results reporting the performance of the scheme are presented. (C) 2006 Elsevier B.V. All rights reserved.

Structural Studies on the Second Mycobacterium smegmatis Dps: Invariant and Variable Features of Structure, Assembly and Function

A second DNA binding protein from stationary-phase cells of Mycobacterium smegmatis (MsDps2) has been identified from the bacterial genome. It was cloned, expressed and characterised and its crystal structure was determined. The core dodecameric structure of MsDps2 is the same as that of the Dps from the organism described earlier (MsDps1). However, MsDps2 possesses a long N-terminal tail instead of the C-terminal tail in MsDps1. This tail appears to be involved in DNA binding. It is also intimately involved in stabilizing the dodecamer. Partly on account of this factor, MsDps2 assembles straightway into the dodecamer, while MsDps1 does so on incubation after going through an intermediate trimeric stage. The ferroxidation centre is similar in the two proteins, while the pores leading to it exhibit some difference. The mode of sequestration of DNA in the crystalline array of molecules, as evidenced by the crystal structures, appears to be different in MsDps1 and MsDps2, highlighting the variability in the mode of Dps–DNA complexation. A sequence search led to the identification of 300 Dps molecules in bacteria with known genome sequences. Fifty bacteria contain two or more types of Dps molecules each, while 195 contain only one type. Some bacteria, notably some pathogenic ones, do not contain Dps. A sequence signature for Dps could also be derived from the analysis.

Tendency toward crossover of the effective susceptibility exponent from its doubled Ising value to its doubled mean-field value near a double critical point

The critical behavior of osmotic susceptibility in an aqueous electrolyte mixture 1-propanol (1P)+water (W)+potassium chloride is reported. This mixture exhibits re-entrant phase transitions and has a nearly parabolic critical line with its apex representing a double critical point (DCP). The behavior of the susceptibility exponent is deduced from static light-scattering measurements, on approaching the lower critical solution temperatures (TL’s) along different experimental paths (by varying t) in the one-phase region. The light-scattering data analysis substantiates the existence of a nonmonotonic crossover behavior of the susceptibility exponent in this mixture. For the TL far away from the DCP, the effective susceptibility exponent γeff as a function of t displays a nonmonotonic crossover from its single limit three-dimensional (3D)-Ising value ( ∼ 1.24) toward its mean-field value with increase in t. While for that closest to the DCP, γeff displays a sharp, nonmonotonic crossover from its nearly doubled 3D-Ising value toward its nearly doubled mean-field value with increase in t. The renormalized Ising regime extends over a relatively larger t range for the TL closest to the DCP, and a trend toward shrinkage in the renormalized Ising regime is observed as TL shifts away from the DCP. Nevertheless, the crossover to the mean-field limit extends well beyond t>10−2 for the TL’s studied. The observed crossover behavior is attributed to the presence of strong ion-induced clustering in this mixture, as revealed by various structure probing techniques. As far as the critical behavior in complex or associating mixtures with special critical points (like the DCP) is concerned, our results indicate that the influence of the DCP on the critical behavior must be taken into account not only on the renormalization of the critical exponent but also on the range of the Ising regime, which can shrink with decrease in the influence of the DCP and with the extent of structuring in the system. The utility of the field variable tUL in analyzing re-entrant phase transitions is demonstrated. The effective susceptibility exponent as a function of tUL displays a nonmonotonic crossover from its asymptotic 3D-Ising value toward a value slightly lower than its nonasymptotic mean-field value of 1. This behavior in the nonasymptotic, high tUL region is interpreted in terms of the possibility of a nonmonotonic crossover to the mean-field value from lower values, as foreseen earlier in micellar systems.

Neutral-point balancing of neutral-point-clamped three-level inverter with a front end switched rectifier DC source for the full modulationn range

A switched rectifier DC voltage source three-level neutral-point-clamped (NPC) converter topology is proposed here to alleviate the inverter from capacitor voltage balancing in three-level drive systems. The proposed configuration requires only one DC link with a voltage of half of that needed in a conventional NPC inverter. To obtain a rated DC link voltage, the rectifier DC source is alternately connected in parallel to one of the two series capacitors using two switches and two diodes with device voltage ratings of half the total DC bus voltage. The frequency at which the voltage source is switched is independent of the inverter and will not affect its operation since the switched voltage source in this configuration balances the capacitors automatically. The proposed configuration can also be used as a conventional two-level inverter in the lower modulation index range, thereby increasing the reliability of the drivesystem. A space-vector-based PWM scheme is used to verify this proposed topology on a laboratory system.

Effect of associating anions on phosphorus retention in soil II. Under variable anion concentration

The results of the present investigation reveal that the presence of anions in the reacting medium greatly modify the reactions between soil and solution P. Associating anions reduce considerably the retention of phosphate in soils. Citrate, tartrate, and silicate are found to be superior to arsenate, oxalate, and fluoride in reducing phosphate retention in soil. The performance of associating anions depends on the pH and P concentration of the reacting medium. The nature and properties of soil also play a highly significant role on the effectiveness of associating anions.

Long-range synthon Aufbau modules (LSAM) in crystal structures: systematic changes in C6H6-nFn (0 <= n <= 6) fluorobenzenes

We discuss the assembly of a three-dimensional molecular crystal in terms of short-range supramolecular synthons that spontaneously organize themselves according to Aufbau principles into long-range geometries characteristic of the molecules themselves. For this purpose we have examined the systematic changes in the known crystal structures of a family of fluorobenzenes, C6H6-nFn, where 0 <= n <= 6. Crystal assembly is initiated by forming long-range synthon Aufbau modules (LSAM) that carry the imprint of the synthons. For example, when 1 <= n <= 5 the short-range synthons use H center dot center dot center dot F interactions to form the LSAMs. In the n = 0 and n = 6 compounds, the synthons are H center dot center dot center dot C and F center dot center dot center dot C interactions, respectively. The LSAMs are usually one-dimensional. In this study we show that these 1D LSAMs assemble into 2D quasi-hexagonal close-packed layers. The 3D crystal structure is obtained from the various kinds of close-packing known for these 2D layers. The final stages of this 1D -> 2D -> 3D assembly seem to be more influenced by the packing of LSAMs than by any other factor. In these final stages, there may not be so much influence exerted by the stronger short-range synthons. We discuss the evolution of these fluorobenzene crystal structures in terms of putative LSAMs and the purely geometric relationships between the n and (6 - n) compounds that can thus be expected. Such particle-hole pairs show structural similarities. Our discussion is quantified by the interpretation of intermolecular distances in terms of atomic sizes and with qualitative predictions of magnetic model systems.

Long-range synthon Aufbau modules (LSAM) in crystal structures: systematic changes in C6H6-nFn (0 <= n <= 6) fluorobenzenes

We discuss the assembly of a three-dimensional molecular crystal in terms of short-range supramolecular synthons that spontaneously organize themselves according to Aufbau principles into long-range geometries characteristic of the molecules themselves. For this purpose we have examined the systematic changes in the known crystal structures of a family of fluorobenzenes, C6H6-nFn, where 0 <= n <= 6. Crystal assembly is initiated by forming long-range synthon Aufbau modules (LSAM) that carry the imprint of the synthons. For example, when 1 <= n <= 5 the short-range synthons use H center dot center dot center dot F interactions to form the LSAMs. In the n = 0 and n = 6 compounds, the synthons are H center dot center dot center dot C and F center dot center dot center dot C interactions, respectively. The LSAMs are usually one-dimensional. In this study we show that these 1D LSAMs assemble into 2D quasi-hexagonal close-packed layers. The 3D crystal structure is obtained from the various kinds of close-packing known for these 2D layers. The final stages of this 1D -> 2D -> 3D assembly seem to be more influenced by the packing of LSAMs than by any other factor. In these final stages, there may not be so much influence exerted by the stronger short-range synthons. We discuss the evolution of these fluorobenzene crystal structures in terms of putative LSAMs and the purely geometric relationships between the n and (6 - n) compounds that can thus be expected. Such particle-hole pairs show structural similarities. Our discussion is quantified by the interpretation of intermolecular distances in terms of atomic sizes and with qualitative predictions of magnetic model systems.

Intrinsic Electron localization in manganites

We mention here an unusual disorder effect in manganites, namely the ubiquitous hopping behavior for electron transport observed in them over a wide range of doping. We argue that the implied Anderson localization is intrinsic to manganites, because of the existence of polarons in them which are spatially localized, generally at random sites (unless there is polaron ordering). We have developed a microscopic two fluid lb model for manganites, where l denotes lattice site localized l polarons, and b denotes band electrons. Using this, and the self-consistent theory of localization, we show that the occupied b states are Anderson localized in a large range of doping due to the scattering of b electrons from l polarons. Numerical simulations which further include the effect of long range Coulomb interactions support this, as well the existence of a novel polaronic Coulomb glass. A consequence is the inevitable hopping behaviour for electron transport observed in doped insulating manganites.

Tunnel transport in polypyrrole at low temperature

The anomalous behaviour of conductivity below 4 K in polypyrrole can be attributed to the possibility of tunnel transport in disordered polaronic systems. The deviation from T-1/3 and T-1/4, depending on disorder, can be due to the onset of tunnel transport between localised states, apart from the hopping contribution to the conductivity. In intermediately and lightly doped polypyrrole films, the tunnel contribution to conductivity increases with decreasing temperature in a narrow temperature range, which is a feature of the presence of polarons taking part in the conduction mechanisms of disordered systems with strong electron-phonon coupling. The transition from hopping to tunneling dominated process can be observed either by the increase in conductivity in some cases or by the saturation of conductivity, depending crucially on the extent of disorder in the sample. In both cases the transition temperature is seen to increase with the reduction in the number of localised states.

Popular Matchings with Variable Job Capacities

We consider the problem of matching people to jobs, where each person ranks a subset of jobs in an order of preference, possibly involving ties. There are several notions of optimality about how to best match each person to a job; in particular, popularity is a natural and appealing notion of optimality. However, popular matchings do not always provide an answer to the problem of determining an optimal matching since there are simple instances that do not adroit popular matchings. This motivates the following extension of the popular rnatchings problem:Given a graph G; = (A boolean OR J, E) where A is the set of people and J is the set of jobs, and a list < c(1), c(vertical bar J vertical bar)) denoting upper bounds on the capacities of each job, does there exist (x(1), ... , x(vertical bar J vertical bar)) such that setting the capacity of i-th, job to x(i) where 1 <= x(i) <= c(i), for each i, enables the resulting graph to admit a popular matching. In this paper we show that the above problem is NP-hard. We show that the problem is NP-hard even when each c is 1 or 2.