Cholesterol-induced modulated phase in phospholipid membranes

We report the observation of a cholesterol-induced modulated phase (Pbeta) in dipalmitoyl phosphatidylcholine bilayers. It occurs below the main transition of the lipid at cholesterol concentrations of around 15 to 20 mol % and is distinct from the ripple (Pbeta') phase found in between the main and pretransitions at lower cholesterol concentrations. An electron density map of this phase, constructed from x-ray diffraction data from oriented multilayers, shows that the bilayers in this phase have a one-dimensional periodic height modulation with an amplitude of about 2.5 A. A partial phase diagram of the system deduced from diffraction data is in broad agreement with earlier studies.     

A new theory for including short range order in the cluster Bethe lattice method: Application to the Hubbard model

A new theory for incorporating short range order (SRO) in the cluster Bethe lattice method (CBLM) for disordered binary alloys is proposed. It is applied to determine the condition for the appearance of moments in the disordered phase of a narrow-band metal for general values of concentration and SRO parameter. The final result (i) yields all the known limiting conditions exactly and (ii) displays in a transparant form the SRO dependence, indicating the merit of the present approach.     

Distinguishing between Kerr and rotating JNW space-times via frame dragging and tidal effects

We investigate two physical quantities that might observationally distinguish between Kerr black holes and rotating naked singularities. These are the Lense–Thirring precession frequency as measured by a Copernican observer, and tidal forces. We establish strong enhancement for both these quantities due to a Janis–Newman–Winicour naked singularity background, as compared to the Kerr case. We first show that the precession frequency of a test gyroscope at a given radius can be enhanced by almost an order of magnitude in the background of the naked singularity, as compared to the Kerr black hole. We then show that a critical mass for celestial objects below which these disintegrate due to tidal forces might increase by more than an order of magnitude in the naked singularity background, compared to the black hole. Our results complement the existing ones in the literature regarding differences in observable quantities in such backgrounds, and might be of significance in futuristic experiments.     

Transition-metal-induced fluorescence resonance energy transfer in a cryptand derivatized with two different fluorophores

A laterally nonsymmetric aza cryptand has been derivatized with one 7-nitrobenz-2-oxa-1,3-diazole (fluorophore(1)) and one/two anthracenes (fluorophore(2)) to obtain 1 and 2. Their emission characteristics are probed in the presence of a number of transition metals and proton. In the case of 1, Cu(II), Zn(II), Cd(II), and proton afford a large enhancement of fluorescence, whereas Fe(II) and Ag(I) exhibit one order of magnitude less enhancement. In contrast, 2 gives a large enhancement with Cu(II), Ag(I), and proton. The enhancement is observed in the diazole moiety even when the anthracene fluorophore is excited because of substantial fluorescence resonance energy transfer from anthracene to the diazole moiety. Compounds 1 and 2 can be termed as the second-generation fluorescence signaling systems.     

Controlled coupling of spin-resolved quantum Hall edge states

We introduce and experimentally demonstrate a new method that allows us to controllably couple copropagating spin-resolved edge states of a two-dimensional electron gas (2DEG) in the integer quantum Hall regime. The scheme exploits a spatially periodic in-plane magnetic field that is created by an array of Cobalt nanomagnets placed at the boundary of the 2DEG. A maximum charge or spin transfer of 28±1% is achieved at 250 mK.     

Tuning A-site ionic size in R(0.5)Ca(0.5)MnO3 (R = Pr, Nd and Sm): robust modulation in dc and ac transport behavior

Structural investigations on Pr(0.5)Ca(0.5)MnO(3), Nd(0.5)Ca(0.5)MnO(3) and Sm(0.5)Ca(0.5)MnO(3) display a systematic tuning in orthorhombic distortion which appears due to a change in A-site ionic size. Comprehensive investigations on dc conduction using various models indicate strong correlation with structural changes. Careful analysis of the ac conductivity mechanism as a function of frequency and temperature brings out a pronounced effect of structural modifications on the polaron conduction mechanism. Contrary to typical manifestations, dc conductivity and relaxation of charge carriers reveal non-Arrhenius behavior. This work provides a detailed and systematic addition to the phase diagram of electronic transport in the rare-earth manganite system doped with a divalent alkali atom.     

Short New Route to the Chiral Spiro‐Tetrahydrofuran Subunit Common to Some Terpenoids

Synthetic strategy based on a stereoselective iodoetherification reaction of a carvone‐derived hydroxyalkene unit has been developed for the asymmetric synthesis of the key spiro‐tetrahydrofuran subunit common to some naturally occurring terpenoids.     

Benzannulation of Triynes to Generate Functionalized Arenes by Spontaneous Incorporation of Nucleophiles

The thermal reaction of ester‐tethered 1,3,8‐triynes provides novel benzannulation products with concomitant incorporation of a nucleophile. Evidence suggests that this reaction proceeds via an allene‐enyne intermediate generated by an Alder‐ene reaction in the first step. Depending on the substituent of the alkyne moiety on the allene‐enyne intermediate, the subsequent transformation can take one of two different paths, each leading to discrete aromatization products. The benzannulation of a silane‐substituted 1,3,8‐triynes provides arene products with a nucleophile incorporated onto the newly formed benzene core, whereas an aryl substituent leads to nucleophile trapping at the benzylic carbon atom connected to the aryl substituent. The formation of these two different products results from the involvement of two regioisomeric allene‐enyne intermediates.     

High-affinity DNA targeting using readily accessible mimics of N2'-functionalized 2'-amino-α-L-LNA

N2'-Pyrene-functionalized 2'-amino-α-L-LNAs (locked nucleic acids) display extraordinary affinity toward complementary DNA targets due to favorable preorganization of the pyrene moieties for hybridization-induced intercalation. Unfortunately, the synthesis of these monomers is challenging (~20 steps, <3% overall yield), which has precluded full characterization of DNA-targeting applications based on these materials. Access to more readily accessible functional mimics would be highly desirable. Here we describe short synthetic routes to a series of O2'-intercalator-functionalized uridine and N2'-intercalator-functionalized 2'-N-methyl-2'-aminouridine monomers and demonstrate, via thermal denaturation, UV-vis absorption and fluorescence spectroscopy experiments, that several of them mimic the DNA-hybridization properties of N2'-pyrene-functionalized 2'-amino-α-L-LNAs. For example, oligodeoxyribonucleotides (ONs) modified with 2'-O-(coronen-1-yl)methyluridine monomer Z, 2'-O-(pyren-1-yl)methyluridine monomer Y, or 2'-N-(pyren-1-ylmethyl)-2'-N-methylaminouridine monomer Q display prominent increases in thermal affinity toward complementary DNA relative to reference strands (average ΔT(m)/mod up to +12 °C), pronounced DNA-selectivity, and higher target specificity than 2'-amino-α-L-LNA benchmark probes. In contrast, ONs modified with 2'-O-(2-napthyl)uridine monomer W, 2'-O-(pyren-1-yl)uridine monomer X or 2'-N-(pyren-1-ylcarbonyl)-2'-N-methylaminouridine monomer S display very low affinity toward DNA targets. This demonstrates that even conservative alterations in linker chemistry, linker length, and surface area of the appended intercalators have marked impact on DNA-hybridization characteristics. Straightforward access to high-affinity building blocks such as Q, Y, and Z is likely to accelerate their use in DNA-targeting applications within nucleic acid based diagnostics, therapeutics, and material science.     

Magnetic and electrical properties of oxygen stabilized nickel nanofibers prepared by the borohydride reduction method

Fine nickel fibers have been synthesized by chemical reduction of nickel ions in aqueous medium with sodium borohydride. The thermal stability and relevant properties of these fibers, as-prepared as well as air-annealed, have been investigated by structural, magnetic and electrical measurements. As-prepared samples appear to have a novel crystal structure due to the presence of interstitial oxygen. Upon annealing in air, the fcc-Ni phase emerges out initially and develops into a nanocomposite subsequently by retaining its fiber-like structure in nano phase. The as-prepared sample is observed to be weakly magnetic at room temperature, but attains surprisingly high magnetization values at low temperatures. This is attributed to the modified spin structure, presumably due to the presence of interstitial oxygen in the lattice. Development of a weakly ferromagnetic and electrically conducting phase upon annealing in air is attributed to the formation of the fcc-Ni phase. The structural phase transformations corroborate well with magnetic and electrical measurements.