Liquid-Liquid Interphase (Biphasic) as the Reaction Medium in the Assembly of a Hierarchy of Structures of 4,4 `-Azodibenzoic Acid with Zinc and Cadmium

The compounds Zn(C12H8N2)](2)C12N2H8(COO)(2)](2)center dot(C6H12O)center dot(H2O), I, Zn(C12H8N2)]C12N2H8(COO)(2)], II, Cd(C12H8N2)(H2O)]C12N2H8(COO)(2)]center dot(H2O), III, Zn(C10N2H8)]C12N2H8(COO)(2)]center dot 0.5(C10N2H8), IV, Cd(C12N2H8(COO)(2)center dot H2O], V, and Zn-3(mu(2)-O)(mu(3)-O)(3)]C12N2H8(COO)(2)], VI, have been synthesized by using a biphasic approach (I, III, V, VI) or regular hydrothermal method (II, IV). The compounds exhibit one (I and II), two (In), and three dimensionally (IV, V, VI) extended structures. The flexible azodibenzoate ligand gives rise to a 3-fold interpenetration (IV) when the synthesis was carried out using normal hydrothermal methods. The biphasic approach forms structures without any interpenetrations, especially in the three-dimensional structures of V and VI. Formation of Cd2O2 dimers in V and extended M-O(H)-M two-dimensional layers in VI suggests the subtle structural control achieved by the biphasic method. Transformation studies indicate that it is possible to transform I to II. Lewis acid catalytic studies have been performed to evaluate the role of the coordination environment in such reactions. All the compounds have been characterized by a variety of techniques that includes powder X-ray diffraction, infrared, thermogravitric analysis, UV-vis, photoluminescence studies.

Perturbative growth of cosmological clustering. I: Formalism

Here we rederive the hierarchy of equations for the evolution of distribution functions of various orders using a convenient parameterization. We use this to obtain equations for two- and three-point correlation functions in powers of a small parameter, viz., the initial density contrast. The correspondence of the lowest order solutions of these equations to the results from the linear theory of density perturbations is shown for an OMEGA = 1 universe. These equations are then used to calculate, to the lowest order, the induced three-point correlation function that arises from Gaussian initial conditions in an OMEGA = 1 universe. We obtain an expression which explicitly exhibits the spatial structure of the induced three-point correlation function. It is seen that the spatial structure of this quantity is independent of the value of OMEGA. We also calculate the triplet momentum. We find that the induced three-point correlation function does not have the ''hierarchical'' form often assumed. We discuss possibilities of using the induced three-point correlation to interpret observational data. The formalism developed here can also be used to test a validity of different schemes to close the

Modeling Of Hydrolytic Polymerization In A Semibatch Nylon 6 Reactor

Hydrolytic polymerization of caprolactam to Nylon 6 in a semibatch reactor is carried out by heating a mixture of water and caprolactam. Evaporation of volatiles caused by heating results in a pressure build-up. After the pressure reaches a predetermined value, vapors are vented to keep the pressure constant for some time, and thereafter, to lower the pressure to a value slightly above atmospheric in a preprogrammed manner. The characteristics of the polymer are determined by the chemical reactions and the vaporization of water and caprolactam. The semibatch operation has been simulated and the predictions have been compared with industria data. The observed temperature and pressure histories were predicted with a fair degree of accuracy. It was found that the predictions of the degree of polymerization however are sensitive to the vapor-liquid equilibrium relations. A comparison with an earlier model, which neglected mass transfer resistance, indicates that simulation using the VLE data of Giori and Hayes and accounting for mass transfer resistance is more reliable.

Irreversibility line and the hierarchy of weak links in Bi2Sr2CaCu2O8+?

The irreversibility line for H?c in a single crystal specimen of Bi2Sr2CaCu2O8+? (Bi2212) has been determined via vanishing of hysteresis in isothermal dc magnetization measurements. The hysteresis loops (H?c) in Bi2212 appear to show signatures of two-component magnetic response in several temperature regions where the temperature dependence of irreversibility field charges sharply. It is proposed that the observed behavior may be a consequence of existence of weak links of varying strength in Bi2212

Triaxial A-value versus swell or collapse for compacted soil - Discussion

A discussion of a technical note with the aforementioned title by Day and Marsh, published in this journal (Volume 121, Number 7, July 1995), is presented. Discussers Robinson and Allam assert that the authors' application of the pore-pressure parameter A to predict and quantify swell or collapse of compacted soils is hard to use because the authors visualize the collapse-swell phenomenon to occur in compacted soils broadly classified as sands and clays. The literature demonstrates that mineralogy has an important role in the volume change behavior of fine-grained soils. Robinson and Allam state that the A-value measurements may not completely predict the type of volume change anticipated in compacted soils on soaking without soil clay mineralogy details. Discussion is followed by closure from the authors.

Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

The Wiener-Hopf solution of a class of mixed boundary value problems arising in surface water wave phenomena

Two mixed boundary value problems associated with two-dimensional Laplace equation, arising in the study of scattering of surface waves in deep water (or interface waves in two superposed fluids) in the linearised set up, by discontinuities in the surface (or interface) boundary conditions, are handled for solution by the aid of the Weiner-Hopf technique applied to a slightly more general differential equation to be solved under general boundary conditions and passing on to the limit in a manner so as to finally give rise to the solutions of the original problems. The first problem involves one discontinuity while the second problem involves two discontinuities. The reflection coefficient is obtained in closed form for the first problem and approximately for the second. The behaviour of the reflection coefficient for both the problems involving deep water against the incident wave number is depicted in a number of figures. It is observed that while the reflection coefficient for the first problem steadily increases with the wave number, that for the second problem exhibits oscillatory behaviour and vanishes at some discrete values of the wave number. Thus, there exist incident wave numbers for which total transmission takes place for the second problem. (C) 1999 Elsevier Science B.V. All rights reserved.

A template-free, combustion-chemical route to macroporous nickel monoliths displaying a hierarchy of pore sizes

Recently, we demonstrated a very general route to monolithic macroporous materials prepared without the use of templates (Rajamathi et al. J. Mater. Chem. 2001, 11, 2489). The route involves finding a precursor containing two metals, A and B, whose oxides are largely immiscible. Firing of the precursor followed by suitable sintering results in a monolith from which one of the oxide phases can be chemically leached out to yield a macroporous mass of the other oxide phase. The metals A and B that we employed in the demonstration were Ni and Zn. From the NiO-ZnO monolith that was obtained by decomposing the precursor, ZnO could be leached out at high pH to yield macroporous NiO. In the present work, we show that combustion-chemical (also called self-propagating) decomposition of a mixture of Ni and Zn nitrates with urea as a fuel yields an intimate mixture of the oxides that can be sintered and leached with alkali to form a macroporous NiO monolith. The new process that we present here thereby avoids the need for a crystalline single-source precursor. A novel and unanticipated aspect of the present work is that the combination of high temperatures and rapid quenching associated with combustion synthesis results in an intimate mixture of wurtzite ZnO and the metastable rock-salt Ni1-xZnxO where x is about 0.3. Leaching this monolith with alkali gives a macroporous mass of rock-salt Ni1-xZnxO, which upon reduction in H-2/Ar forms macroporous Ni and ZnO. There are thus two stages in the process that lead to two modes of pore formation. The first is associated with leaching of ZnO by alkali. The second is associated with the reduction of porous Ni1-xZnxO to give porous Ni and ZnO.

A Convex Optimization Framework for Almost Budget Balanced Allocation of a Divisible Good

We address the problem of allocating a single divisible good to a number of agents. The agents have concave valuation functions parameterized by a scalar type. The agents report only the type. The goal is to find allocatively efficient, strategy proof, nearly budget balanced mechanisms within the Groves class. Near budget balance is attained by returning as much of the received payments as rebates to agents. Two performance criteria are of interest: the maximum ratio of budget surplus to efficient surplus, and the expected budget surplus, within the class of linear rebate functions. The goal is to minimize them. Assuming that the valuation functions are known, we show that both problems reduce to convex optimization problems, where the convex constraint sets are characterized by a continuum of half-plane constraints parameterized by the vector of reported types. We then propose a randomized relaxation of these problems by sampling constraints. The relaxed problem is a linear programming problem (LP). We then identify the number of samples needed for ``near-feasibility'' of the relaxed constraint set. Under some conditions on the valuation function, we show that value of the approximate LP is close to the optimal value. Simulation results show significant improvements of our proposed method over the Vickrey-Clarke-Groves (VCG) mechanism without rebates. In the special case of indivisible goods, the mechanisms in this paper fall back to those proposed by Moulin, by Guo and Conitzer, and by Gujar and Narahari, without any need for randomization. Extension of the proposed mechanisms to situations when the valuation functions are not known to the central planner are also discussed. Note to Practitioners-Our results will be useful in all resource allocation problems that involve gathering of information privately held by strategic users, where the utilities are any concave function of the allocations, and where the resource planner is not interested in maximizing revenue, but in efficient sharing of the resource. Such situations arise quite often in fair sharing of internet resources, fair sharing of funds across departments within the same parent organization, auctioning of public goods, etc. We study methods to achieve near budget balance by first collecting payments according to the celebrated VCG mechanism, and then returning as much of the collected money as rebates. Our focus on linear rebate functions allows for easy implementation. The resulting convex optimization problem is solved via relaxation to a randomized linear programming problem, for which several efficient solvers exist. This relaxation is enabled by constraint sampling. Keeping practitioners in mind, we identify the number of samples that assures a desired level of ``near-feasibility'' with the desired confidence level. Our methodology will occasionally require subsidy from outside the system. We however demonstrate via simulation that, if the mechanism is repeated several times over independent instances, then past surplus can support the subsidy requirements. We also extend our results to situations where the strategic users' utility functions are not known to the allocating entity, a common situation in the context of internet users and other problems.

Determining Top K Nodes in Social Networks using the Shapley Value

In this paper, we consider the problem of selecting, for any given positive integer k, the top-k nodes in a social network, based on a certain measure appropriate for the social network. This problem is relevant in many settings such as analysis of co-authorship networks, diffusion of information, viral marketing, etc. However, in most situations, this problem turns out to be NP-hard. The existing approaches for solving this problem are based on approximation algorithms and assume that the objective function is sub-modular. In this paper, we propose a novel and intuitive algorithm based on the Shapley value, for efficiently computing an approximate solution to this problem. Our proposed algorithm does not use the sub-modularity of the underlying objective function and hence it is a general approach. We demonstrate the efficacy of the algorithm using a co-authorship data set from e-print arXiv (www.arxiv.org), having 8361 authors.

STEM+: A Fair and Efficient Algorithm for Scheduling on the DSCH in UMTS Networks

In Universal Mobile Telecommunication Systems (UMTS), the Downlink Shared Channel (DSCH) can be used for providing streaming services. The traffic model for streaming services is different from the commonly used continuously- backlogged model. Each connection specifies a required service rate over an interval of time, k, called the "control horizon". In this paper, our objective is to determine how k DSCH frames should be shared among a set of I connections. We need a scheduler that is efficient and fair and introduce the notion of discrepancy to balance the conflicting requirements of aggregate throughput and fairness. Our motive is to schedule the mobiles in such a way that the schedule minimizes the discrepancy over the k frames. We propose an optimal and computationally efficient algorithm, called STEM+. The proof of the optimality of STEM+, when applied to the UMTS rate sets is the major contribution of this paper. We also show that STEM+ performs better in terms of both fairness and aggregate throughput compared to other scheduling algorithms. Thus, STEM+ achieves both fairness and efficiency and is therefore an appealing algorithm for scheduling streaming connections.