Lipid-amphotericin B complex structure in solution: A possible first step in the aggregation process in cell membranes

The interactions between the polyene antibiotic amphotericin B with dipalmitoylphosphatidylcholine were investigated in vesicles (using circular dichroism) and in chloroform solution (using circular dichroism and IH, I3C, and 31P nuclear magnetic resonance). The results show that amphotericin B readily aggregates in vesicles and that the extent of aggregation depends on the 1ipid:drug concentration ratio. Introduction of sterol molecules into the membrane hastens the process of aggregation of amphotericin B. In chloroform solutions amphotericin B strongly interacts with phospholipid molecules to form a stoichiometric complex. The results suggest that there are interactions between the conjugated heptene stretch of amphotericin B and the methylene groups of lipid acyl chains, while the sugar moiety interacts with the phosphate head group by the formation of a hydrogen bond. A model is proposed for the lipid-amphotericin B complex, in which amphotericin B interacts equally well with the two lipid acyl chains, forming a 1:l complex.

Turning visual search time on its head

Our everyday visual experience frequently involves searching for objects in clutter. Why are some searches easy and others hard? It is generally believed that the time taken to find a target increases as it becomes similar to its surrounding distractors. Here, I show that while this is qualitatively true, the exact relationship is in fact not linear. In a simple search experiment, when subjects searched for a bar differing in orientation from its distractors, search time was inversely proportional to the angular difference in orientation. Thus, rather than taking search reaction time (RT) to be a measure of target-distractor similarity, we can literally turn search time on its head (i.e. take its reciprocal 1/RT) to obtain a measure of search dissimilarity that varies linearly over a large range of target-distractor differences. I show that this dissimilarity measure has the properties of a distance metric, and report two interesting insights come from this measure: First, for a large number of searches, search asymmetries are relatively rare and when they do occur, differ by a fixed distance. Second, search distances can be used to elucidate object representations that underlie search - for example, these representations are roughly invariant to three-dimensional view. Finally, search distance has a straightforward interpretation in the context of accumulator models of search, where it is proportional to the discriminative signal that is integrated to produce a response. This is consistent with recent studies that have linked this distance to neuronal discriminability in visual cortex. Thus, while search time remains the more direct measure of visual search, its reciprocal also has the potential for interesting and novel insights. (C) 2012 Elsevier Ltd. All rights reserved.

Influence of the Blade Hub Geometry on the Performance of Low-Head Axial Flow Turbines

The influence of geometric parameters, such as blade profile and hub geometry on axial flow turbines for micro hydro application remains poorly characterized. This paper first introduces a holistic theoretical model for studying the hydraulic phenomenon resulting from geometric modification to the blades. It then describes modification carried out on two runner stages, of which one has untwisted blades and the other has twisted blades obtained by modifying the inlet hub. The experimental results showed that the performance of the untwisted blade runner was satisfactory with a maximum efficiency of 68%. However, positive effects of twisted blades were clearly evident with an efficiency rise of more than 2%. This study also looks into the possible limitations of the model and suggests the extension of the experimental work and the use of computational tools to conduct a progressive validation of all experimental findings, especially on the flow physics within the hub region and the slip phenomena. The paper finally underlines the importance of developing a standardization philosophy for axial flow turbines specific for micro hydro requirements. DOI:10.1061/(ASCE)EY.1943-7897.0000060. (C) 2012 American Society of Civil Engineers.

Enantiospecific first total synthesis of (-)-4-thiocyanatoneopupukeanane

The first total synthesis of (-)-4-thiocyanatoneopupukeanane starting from (R)-carvone has been achieved, establishing the relative as well as absolute structure of the natural product.

First donor-acceptor interaction promoted gelation of organic fluids

In recent years there has been considerable interest in developing new types of gelators of organic solvents.1 Despite the recent advances, a priori design of a gelator for gelling a given solvent has remained a challenging task. Various noncovalent interactions like hydrogen-bonding,2 metal coordination3 etc. have been used as the driving force for the gelation process. A special class of cholesterol-based gelators were reported by Weiss,4 and by Shinkai.5 Gels derived from these molecules have been used for chiral recognition/sensing,6 for studying photo- and metal-responsive functions,7 and as templates to make hollow fiber silica.8 Other types of organogels have been used for designing polymerized 9 and reverse aerogels,10 and in molecular imprinting.11 Hanabusa’s group has recently reported organogels with a bile acid derivative.12 This has prompted us to disclose our results on a novel electron donor–acceptor (EDA) interaction mediated two-component13 gelator system based on the bile acid14 backbone.

First principles study of magnetism in divalent Eu perovskites

A comparative first principles study has been carried out for EuLiH3 (ELH) and EuTiO3 (ETO) using the generalized gradient approximation +U approach. While ELH exhibits ferromagnetic ground state for all volumes, the magnetic ground state of ETO has the tendency to switch from G-type antiferromagnetic to a ferromagnetic state with change in volume. The marked difference in magnetic behavior and magnitude of the nearest neighbors exchange interaction of both the compounds are shown to be related to the difference in their respective electronic structure near the Fermi level. The Ti 3d states are shown to play predominant role in weakening the strength of the exchange interaction in ETO.

The first observation of a Na2TiS2 related structure in a 2-D anionic manganese trimesate intercalated by cationic imidazole

A hydrothermal reaction of Mn(OAc)2·4H2O, trimesic acid, imidazole, KOH and water at 75 °C for 24 h gave rise to a 2-D compound, [HImd][Mn(BTC)(H2O)] (Imd = imidazole; BTC = trimesate), with protonated imidazole molecules occupying the inter-lamellar space, and the structure resembles the classic inorganic compound, the sodium intercalated TiS2 (Na2TiS2).

x-ray studies on crystalline complexes involving amino-acids and peptides .10. head-to-tail sequences in the crystal-structure of l-lysine acetate

l-Lysine acetate crystallises in the monoclinic space group P21 with a = 5.411 (1), b = 7.562(1), c= l2.635(2) Å and β = 91.7(1). The crystal structure was solved by direct methods and refined to an R value of 0.049 using the full matrix least squares method. The conformation and the aggregation of lysine molecules in the structure are similar to those found in the crystal structure of l-lysine l-aspartate. A conspicuous similarity between the crystal structures of l-arginine acetate and l-lysine acetate is that in both cases the strongly basic side chain, although having the largest pK value, interacts with the weakly acidic acetate group leaving the α-amino and the α-carboxylate groups to take part in head-to-tail sequences. These structures thus indicate that electrostatic effects are strongly modulated by other factors so as to give rise to head-to-tail sequences which have earlier been shown to be an almost universal feature of amino acid aggregation in the solid state.

Quantum first-passage problem

Formulation of quantum first passage problem is attempted in terms of a restricted Feynman path integral that simulates an absorbing barrier as in the corresponding classical case. The positivity of the resulting probability density, however, remains to be demonstrated.

Optimal hydrothermal load flow: Formulation and a successive approximation solution for fixed head systems

This paper deals with the optimal load flow problem in a fixed-head hydrothermal electric power system. Equality constraints on the volume of water available for active power generation at the hydro plants as well as inequality constraints on the reactive power generation at the voltage controlled buses are imposed. Conditions for optimal load flow are derived and a successive approximation algorithm for solving the optimal generation schedule is developed. Computer implementation of the algorithm is discussed, and the results obtained from the computer solution of test systems are presented.

First hyperpolarizability of bacteriorhodopsin, retinal and related molecules revisited

The previously reported beta values of BR and retinal based chromophores were very high but subsequent measurements found them to be much less. We have found that the beta values of these compounds do not vary so much with experimental conditions as with the method of analysis. Hyper-Rayleigh scattering measurements at 1543 and 1907 nm produce more realistic beta values close to the intrinsic (static) hyperpolarizability, beta(0) which for BR is still very high (275 x 10 (30) esu). The optical nonlinearity of BR arises entirely due to the protonated retinal Schiff Base (PRSB) which in its isolated form has the same intrinsic hyperpolarizability as that of the rotein.

X-ray absorption spectra of niobium dichalcogenides and their first-row transition-metal intercalates

X-ra!. K-absorption spectra of niobium in niobium dichalcogenides. namely NbS, and NbSe, and their first-row transition-metal intercalates Mi P 3N bSz (M = Cr. Mn. Fe. Co. Ni) and Ml#,NbSe2 (M = Fe. CO). have been measured together with those in niobium metal. The spectra of these materials are \er? similar to one another. They reflect the transitions to the partially filled niobium d band with some p character. A bariety of x-ray absorption nearedge structures (XASES) associated with the K edges of intercalated atoms are also presented and discussed.

Testing approximate theories of first-order phase transitions on the two-dimensional Potts model

The two-dimensional,q-state (q>4) Potts model is used as a testing ground for approximate theories of first-order phase transitions. In particular, the predictions of a theory analogous to the Ramakrishnan-Yussouff theory of freezing are compared with those of ordinary mean-field (Curie-Wiess) theory. It is found that the Curie-Weiss theory is a better approximation than the Ramakrishnan-Yussouff theory, even though the former neglects all fluctuations. It is shown that the Ramakrishnan-Yussouff theory overestimates the effects of fluctuations in this system. The reasons behind the failure of the Ramakrishnan-Yussouff approximation and the suitability of using the two-dimensional Potts model as a testing ground for these theories are discussed.

X-ray studies on crystalline complexes involving amino acids and peptides. Part XIV: Closed conformation and head-to-tail arrangement in a new crystal form of L-histidine L-aspartate monohydrate

A new form of L-histidine L-aspartate monohydrate crystallizes in space group P22 witha = 5.131(1),b = 6.881(1),c= 18.277(2) Å,β= 97.26(1)° and Z = 2. The structure has been solved by the direct methods and refined to anR value of 0.044 for 1377 observed reflections. Both the amino acid molecules in the complex assume the energetically least favourable allowed conformation with the side chains staggered between the α-amino and α-scarboxylate groups. This results in characteristic distortions in some bond angles. The unlike molecules aggregate into alternating double layers with water molecules sandwiched between the two layers in the aspartate double layer. The molecules in each layer are arranged in a head-to-tail fashion. The aggregation pattern in the complex is fundamentally similar to that in other binary complexes involving commonly occurring L amino acids, although the molecules aggregate into single layers in them. The distribution of crystallographic (and local) symmetry elements in the old form of the complex is very different from that in the new form. So is the conformation of half the histidine molecules. Yet, the basic features of molecular aggregation, particularly the nature and the orientation of head-to-tail sequences, remain the same in both the forms. This supports the thesis that the characteristic aggregation patterns observed in crystal structures represent an intrinsic property of amino acid aggregation.