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.

Polymorphism in Opto-Electronic Materials with a Benzothiazole-fluorene Core: A Consequence of High Conformational Flexibility of pi-Conjugated Backbone and Alkyl Side Chains

Fluorene and its derivatives are well-known organic semiconducting materials in the field of opto-electronic devices because of their charge transport properties. Three new organic semiconducting materials, namely, 2,2'-((9,9-butyl-9H-fluorene-2,7-diyl)bis(4,1 phenylene))bisbenzod]thiazole, C4; 2,2'-((octyl-9H-fluorene-2,7-diyl)bis(4,1 phenylene))bisbenzod]thiazole, C8; and 2,2'-((9,9-dodecayl-9H-fluorene-2,7-diyl)bis(4,1 phenylene))bisbenzod]thiazole, C12 with a benzothiazole-fluorene backbone, were synthesized and characterized for their photophysical properties. A phenomenon of concomitant polymorphism has been investigated in the first two derivatives (C4 and C8) and has been analyzed systematically in terms of the packing characteristics involving pi ... pi interactions. The conformational flexibility of the pi-conjugated 2,2'-(fluorene-2,7-diyl)bis(4,1 phenylene)bisbenzod]thiazole backbone coupled with orientational freedom of the terminal alkyl chains were found to be the key factors responsible for these polymorphic modifications. Attempts to grow suitable crystals for single crystal X-ray diffraction of compound C12 were unsuccessful.

Nematogens with more flexible chains than aromatic rings in the core

Mesogens containing four rings in the main core can accommodate one terminal and two nearby lateral chains on each outside aromatic ring. These compounds containing six chains present an enantiotropic nematic range which is influenced by the rigidity of the links. The conformational behaviour of the first methyleneoxy group within the chains was investigated by one and two dimensional C-13 NMR. The sign of the jump in chemical shifts when entering the nematic phase indicates the folding of each lateral branch. Dipolar oscillations during cross-polarization contact provide the values of the bond order parameter. The two First lateral fragments do not behave in the same way, demonstrating the influence of the fragment along which the chain is back: folded.

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.

Vesicle formation from dimeric ion-paired amphiphiles. Control over vesicular thermotropic and ion-transport properties as a function of intra-amphiphilic headgroup separation

A novel series of vesicle-forming ion-paired amphiphiles, bis(hexadecyldimethylammonium)alkane dipalmitate (1a-1h), containing four chains were synthesized with two isolated headgroups. In each of these amphiphiles, the two headgroup charges are separated by a flexible polymethylene spacer chain -[(CH2)(m)]- of varying lengths (m) such that the length and the conformation of the spacer chain determine the intra-"monomer" headgroup separation. Transmission electron microscopy indicated that each of these forms bilayer membranes upon dispersion in aqueous media. The vesicular properties of these aggregates have been examined by differential scanning calorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, their T-m values decreased with the increase in the m value. Thus while the apparent T-m of the lipid with m = 2 (1a) is 74.1 degrees C, the corresponding value observed for the lipid with m = 12 (1h) is 38.9 degrees C. The fluorescence anisotropy values (r) for 1b-1g were quite high (r similar to 0.3) compared to that of 1h (r similar to 0.23) at 20-30 degrees C in their gel states. On the other hand, the r value for vesicular 1b beyond melting was higher (0.1) compared to any of those for 1c-1h (similar to 0.04-0.06). X-ray diffraction of the cast films was performed to understand the nature and the thickness of these membrane organizations. The membrane widths ranged from 30 to 51 A as the m values varied. The entrapment of a small water-soluble solute, riboflavin, by the individual vesicular aggregates, and their sustenance: under an imposed transmembrane pH gradient have also been examined. These results show that all lipid vesicles entrap riboflavin and that generally the resistance to OH- permeation decreases with the increase in m value. Finally,all the above observations were comparatively analyzed, and on the basis of the calculated structures of these lipids, it was possible to conclude that membrane propel-ties can be modulated by spacer chain length variation of the ion-paired amphiphiles.

Synthesis of novel cationic lipids with fully or partially non-scissile linkages between the hydrocarbon chains and pseudoglyceryl backbone

Five novel cationic lipids with fully or partially non-scissile linkage regions between the pseudoglyceryl backbone and the hydrocarbon chains have been synthesized. The membrane-forming properties of these new lipids are briefly presented.

Synthesis of phospholipids with fatty acid chains containing aromatic units at various depths

A series of diacyl phosphatidylcholine lipid derivatives, which contain aromatic units at various depths of their fatty acid chains, have been synthesized. These lipids produced stable aqueous suspensions. Electron microscopy revealed the presence of vesicular aggregates in the suspensions of these newly synthesized lipids. These membranes were oxidatively stable and maintained fluid character at ambient temperature making them ideal candidates for membrane protein reconstitution studies.

Calcium-Decorated Carbyne Networks as Hydrogen Storage Media

Among the carbon allotropes, carbyne chains appear outstandingly accessible for sorption and very light. Hydrogen adsorption on calcium-decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H(2) molecules per Ca atom with a binding energy of similar to 0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed similar to 8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H(2) molecules on the Ca atom was also investigated using equilibrium grand partition function.

Two-channel Kondo physics in odd impurity chains

We study odd-membered chains of spin-1/2 impurities, with each end connected to its own metallic lead. For antiferromagnetic exchange coupling, universal two-channel Kondo (2CK) physics is shown to arise at low energies. Two overscreening mechanisms are found to occur depending on coupling strength, with distinct signatures in physical properties. For strong interimpurity coupling, a residual chain spin-1/2 moment experiences a renormalized effective coupling to the leads, while in the weak-coupling regime, Kondo coupling is mediated via incipient single-channel Kondo singlet formation. We also investigate models in which the leads are tunnel-coupled to the impurity chain, permitting variable dot filling under applied gate voltages. Effective low-energy models for each regime of filling are derived, and for even fillings where the chain ground state is a spin singlet, an orbital 2CK effect is found to be operative. Provided mirror symmetry is preserved, 2CK physics is shown to be wholly robust to variable dot filling; in particular, the single-particle spectrum at the Fermi level, and hence the low-temperature zero-bias conductance, is always pinned to half-unitarity. We derive a Friedel-Luttinger sum rule and from it show that, in contrast to a Fermi liquid, the Luttinger integral is nonzero and determined solely by the ``excess'' dot charge as controlled by gate voltage. The relevance of the work to real quantum dot devices, where interlead charge-transfer processes fatal to 2CK physics are present, is also discussed. Physical arguments and numerical renormalization-group techniques are used to obtain a detailed understanding of these problems.

Intercalative pyrimido[4',5':4,5]thieno(2,3-b)quinolines induce apoptosis in leukemic cells: a comparative study of methoxy and morpholino substitution

DNA intercalating molecules are promising anticancer agents. Polycyclic aromatic molecules such as ellipticine intercalate into double-stranded DNA and affect major physiological functions. In the present study, we have characterized two molecules with the same chemical backbone but different side chains, namely 8-methoxy pyrimido[4',5':4,5]thieno (2,3-b)quinoline-4(3H)-one (MPTQ) and 4-morpholino pyrimido[4',5':4,5]thieno(2,3-b)quinoline (morpho-PTQ) at the 8th and 4th position, respectively. Although both MPTQ and morpho-PTQ show similar biophysical properties with high DNA affinity, here we show that they differ in their biological activities. We find that MPTQ is many fold more potent than morpho-PTQ and is cytotoxic against different leukemic cell lines. IC(50) value of methoxy PTQ was estimated between 2-15 A mu M among the leukemic cells studied, while it was more than 200 A mu M when morpho-PTQ was used. Cell cycle analysis shows an increase in sub-G1 phase, without any particular cell cycle arrest. Annexin V staining in conjunction with comet assay and DNA fragmentation suggest that MPTQ induces cytotoxicity by activating apoptosis. Thus the observed low IC(50) value of MPTQ makes it a promising cancer chemotherapeutic agent.

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.

A Shapley Value Analysis to Coordinate the Formation of Procurement Networks

In this paper we address the problem of forming procurement networks for items with value adding stages that are linearly arranged. Formation of such procurement networks involves a bottom-up assembly of complex production, assembly, and exchange relationships through supplier selection and contracting decisions. Research in supply chain management has emphasized that such decisions need to take into account the fact that suppliers and buyers are intelligent and rational agents who act strategically. In this paper, we view the problem of procurement network formation (PNF) for multiple units of a single item as a cooperative game where agents cooperate to form a surplus maximizing procurement network and then share the surplus in a fair manner. We study the implications of using the Shapley value as a solution concept for forming such procurement networks. We also present a protocol, based on the extensive form game realization of the Shapley value, for forming these networks.