Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Low-temperature property investigation of the lead indium-niobate-lead nickel-niobate solid solution

The complex perovskite solid solution (1−x) Pb(In_1/2Nb_1/2)O₃-(x) Pb(Ni_1/3Nb_2/3)O₃ has been successfully prepared by the Columbite precursor method. The temperature dependencies of the dielectric constant and pyroelectric coefficient were measured between −261 and 200 °C. Relaxor ferroelectric behavior has been noticed in all compositions across the solid solution. The room-temperature electrostrictive coefficient, Q₃₃, was 1.83×10⁻² C²/m⁴ for x=0.10. No room-temperature piezoelectric activity was detected; however, upon cooling to −261 °C the maximum coupling coefficients k_p=29%, k_t=11%, and k₃₃=31% were observed for the composition x=1.00.     

Constructing ‘hair’ for the three charge hole

It has been found that the states of the 2-charge extremal D1–D5 system are given by smooth geometries that have no singularity and no horizon individually, but a ‘horizon’ does arise after ‘coarse-graining’. To see how this concept extends to the 3-charge extremal system, we construct a perturbation on the D1–D5 geometry that carries one unit of momentum charge P. The perturbation is found to be regular everywhere and normalizable, so we conclude that at least this state of the 3-charge system behaves like the 2-charge states. The solution is constructed by matching (to several orders) solutions in the inner and outer regions of the geometry. We conjecture the general form of ‘hair’ expected for the 3-charge system, and the nature of the interior of black holes in general.     

Collective bounce-off phenomenon in139La+Ag(Br) reaction at 1.1 A GeV energy

Out of a total statistics of 896¹³⁹La+Ag(Br) interactions, 128 interactions having multiplicity of target fragments (Z⩾1)⩾8 and projectile fragments (Z⩾2)⩾4 have been selected. They correspond to quasi-peripheral interactions. Azimuthal angle correlation between sources of target fragments (TFs) and projectile fragments (PFs) shows the existence of bounce-off effect. Using data of La+Ag(Br) and⁸⁴Kr+Ag(Br) reactions it is shown that individual helium [Z=2, PFs] and heavier fragment [Z⩾3, PFs] show different emission characteristics. Further, a two prong correlation functionT(Φ _ij ) plotted for heavier fragments and helium fragments separately, indicates the possibility of existence of different physical conditions. This observation is supported by the different momentum widths of helium fragments and heavier fragments. From the momentum width data of Kr+Ag(Br) reactions normalized density comes out to be ≈4.7. Using quasi-elastic kinematics for the bounce-off nuclei, the excitation energy has been computed from the experimental data of flow angles. The strength of bounce-off seems to decrease with the increase of excitation energy or temperature.     

Studies on the Preparation and Properties of Thiol Derivatives of Biscyclopentadienyl Molybdenum (VI) and Bisindenyl Molybdenum (VI) Oxide Dichloride

Biscyclopentadienyl molybdenum (VI) oxide dichloride (I) and bisindenyl molybdenum (VI) oxide dichloride (II) react with various thiols in tetrahydrofuran and from the complexes of the type (C₃H₅)₂MoO (R₂) and (C₉H₇)₂MoO (R₂) wherein R may be S CH₈, S C₂H₅, S C₃H^N₇, S C₃H₇, S C₄Hⁿ₉, or S C₄H₃ or S C₃H₁₁. The preparation, thermal stabilities, physical characteristics and infrared spectra of these complexes have been studied in this paper.     

Synthesis of Novel Nucleic Acid Mimics via the Stereoselective Intermolecular Radical Coupling of 3'-Iodo Nucleosides and Formaldoximes(1)

A highly convergent free radical coupling of alkyl iodides and oximes, mediated by bis(trimethylstannyl) benzopinacolate (8), has been utilized to prepare a series of dimeric nucleosides as mimics of natural nucleic acids. The systematic optimization of the reaction conditions allowed for the single-step conversion of the appropriate iodides and oximes into the 2'-deoxy dimers 9 in moderate to excellent yields. For example, the reaction of 3'-deoxy-3'-iodo-5'-(triphenylmethyl)thymidine (6a) with 3'-O-(tert-butyldiphenylsilyl)-5'-O-(methyleneimino)thymidine (7a) in the presence of 8 in degassed benzene gave an 81% yield of 3'-de(oxyphosphinico)-3'-(methyleneimino)-5'-O-(triphenylmethyl)thymidylyl-(3'-->5')-3'-O-(tert-butyldiphenylsilyl)thymidine (9a). Similarly prepared were dimers containing both pyrimidine (thymine, 5-methylcytosine) and purine (adenine, guanine) bases. The reaction was highly stereoselective, giving only a single dimeric species having the ribo-configuration of the newly introduced C-3'-branched methylene moiety. Also prepared were dimers 16, incorporating 2'-O-methyl ribonucleosides in both halves of the dimer. This required the synthesis of 3'-deoxy-3'-iodo-2'-O-methyl nucleosides 12 as well as 2'-O-methyl-5'-O-methyleneimino nucleosides 15. For example, 5'-O-(tert-butyldiphenylsilyl)-3'-deoxy-3'-iodo-2'-O-methyl-5-methyluridine (12e) was prepared in 80% yield by displacement of the corresponding triflate with Bu(4)NI. Also prepared were the suitably protected 3'-deoxy-3'-iodo adenosine and guanosine derivatives. Compounds 15 were prepared in high yield by a regioselective Mitsunobu reaction to give the corresponding 5'-O-phthalimido nucleosides 13, which were subsequently converted to the requisite oximes 15. In the 2'-O-methyl series, the pinacolate coupling reaction proceeded with efficiency equal to that observed for the 2'-deoxy series 9, but with slightly less stereoselectivity, giving predominantly the C-3'ribo products 16, contaminated with 5-25% of the epimeric material. Mixed base dimers containing both pyrimidine and purine bases at all possible positions, including purine-purine dimers were prepared. The hydroxylamine or methyleneimino (MI) backbone of several representative dimers so prepared was converted via methylation to give the corresponding methylenemethylimino (MMI)-linked compounds, which are novel phosphate surrogates for use in antisense oligonucleotides.     

Nonlinear dynamics of confined polymer melts with attractive walls

A scaling model is presented to analyze the reversible strain-hardening phenomenon in end-tethered polymer clay nanocomposites (Krishnamoorti, R.; Giannelis, E. P. Langmuir 2001, 17, 1448). It is assumed that for attractive clay-polymer interactions a fraction of the polymer chains that span the space between opposite clay plates get adsorbed on them, thereby bridging the plates. Under large amplitude oscillatory shear, such bridges are stretched, and this results in the strain-hardening behavior. The onset of strain hardening is predicted to be dependent only on the average distance separating the two plates and is independent of the frequency of the oscillations and the polymer molecular weight.     

Synthesis of 2'-O-methoxyethylguanosine using a novel silicon-based protecting group

A short and efficient synthesis of 2'-O-methoxyethylguanosine (8) is described. Central to this strategy is the development of a novel silicon-based protecting group (MDPSCl(2), 2) used to protect the 3',5'-hydroxyl groups of the ribose. Silylation of guanosine with 2 proceeded with excellent regioselectivity and in 79% yield. Alkylation of the 2'-hydroxyl group of 6 proceeded with methoxyethyl bromide and NaHMDS and afforded compound 7 in 85% yield, without any noticeable cleavage of the silyl protecting group and without the need to protect the guanine base moiety. Finally, deprotection of 7 was achieved using TBAF and produced 8 in 97% yield.