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1.
A novel dimer based on the disc-like anthraquinone core-bis[1-(4-nitrobenzyloxy)-2,3,6,7-tetrapentyloxy-9,10-anthraquinon-5-oxy]do and its corresponding monomer 1-hexyloxy5-(4-nitrobenzyloxy)-2,3,6,7-tetrapentyloxy-9,10-anthraquinone, have been synthesized and characterized. X-ray diffraction studies show that this novel dimer exhibits a hexagonal columnar phase (Colh) with correlation among the molecular cores along the column. The Colh phase of the dimer exists over a very wide temperature range, extending from 176°C down to at least 60°C (the lowest temperature reached in DSC), whereas the monomer exhibits a Colh phase at high temperature and a three-dimensionally ordered columnar phase (Colx) at low temperature. 相似文献
2.
Dukeson DR Ungar G Balagurusamy VS Percec V Johansson GA Glodde M 《Journal of the American Chemical Society》2003,125(51):15974-15980
A second generation monodendron with dodecyl end-groups based on the AB(3) monomer 3,4,5-trihydroxy benzoate has previously been shown to form a thermotropic cubic phase with Pmthremacr;n symmetry (Balagurusamy et al., J. Am. Chem. Soc. 1997, 119, 1539). A structure consisting of spherical "micelles" was proposed originally, but an alternative choice of structure factor phases, giving a structure of interlocked squashed columns, could not be ruled out by diffraction data on the original material alone. We have therefore synthesized two selectively fluorinated equivalent compounds, the carboxylic acid and its Rb salt, to be able to apply a variant of the isomorphous replacement crystallographic technique. On the basis of the electron density maps of the new labeled compounds, reconstructed using small-angle X-ray diffraction intensities, the interlocking columns model is unequivocally rejected and the spheres model is upheld. Furthermore, the location of the metal cation in the center of the "micelles" is directly confirmed. Micellar diameter was shown to decrease on fluorination of the dodecyl chain ends, and increase significantly on introduction of Rb. This is interpreted in terms of changes in the number of wedge-shaped dendrons fitting into a spherical micelle due to their changing taper angle. It was found that the Rb-rich regions at the centers of six out of eight "micelles" in the unit cell are elongated in the direction of their closest packing. This adds support to the suggestion of a partial "column-like" character of stacked rows of such micelles, consistent with the position of the Pmthremacr;n phase next to the columnar phase in the phase sequence of most taper-shape compounds. The results illustrate the potential of isomorphous replacement, used a great deal in protein crystallography, in structure investigation of liquid crystals and supramolecular soft matter. 相似文献
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Peterca M Imam MR Ahn CH Balagurusamy VS Wilson DA Rosen BM Percec V 《Journal of the American Chemical Society》2011,133(7):2311-2328
The synthesis, structural, and retrostructural analysis of two libraries containing 16 first and second generation C(3)-symmetric self-assembling dendrimers based on dendrons connected at their apex via trisesters and trisamides of 1,3,5-benzenetricarboxylic acid is reported. A combination of X-ray diffraction and CD/UV analysis methods demonstrated that their C(3)-symmetry modulates different degrees of packing on the periphery of supramolecular structures that are responsible for the formation of chiral helical supramolecular columns and spheres self-organizable in a diversity of three-dimensional (3D) columnar, tetragonal, and cubic lattices. Two of these periodic arrays, a 3D columnar hexagonal superlattice and a 3D columnar simple orthorhombic chiral lattice with P222(1) symmetry, are unprecedented for supramolecular dendrimers. A thermal-reversible inversion of chirality was discovered in helical supramolecular columns. This inversion is induced, on heating, by the change in symmetry from a 3D columnar simple orthorhombic chiral lattice to a 3D columnar hexagonal array and, on cooling, by the change in symmetry from a 2D hexagonal to a 2D centered rectangular lattice, both exhibiting intracolumnar order. A first-order transition from coupled columns with long helical pitch, to weakly or uncorrelated columns with short helical pitch that generates a molecular rotator, was also discovered. The torsion angles of the molecular rotator are proportional to the change in temperature, and this effect is amplified in the case of the C(3)-symmetric trisamide supramolecular dendrimers forming H-bonds along their column. The structural changes reported here can be used to design complex functions based on helical supramolecular dendrimers with different degree of packing on their periphery. 相似文献
5.
EP Sheretov VS Gurov MV Dubkov OV Korneeva 《Rapid communications in mass spectrometry : RCM》1999,13(16):1699-1702
In this article we compare the classical monopole mass filter of von Zahn and the monopole mass filter with a hyperbolic V-shaped electrode. The experimental results and those of computer simulation for both mass spectrometers are presented. We show that the replacement of a conventional 90 degrees V-shaped electrode by an electrode with a hyperbolic profile substantially improves the peak shape of any given mass, and increases the mass resolution by a factor of 3-4 and the abundance sensitivity by a factor of 100. The potential of high analytical performance combined with electroforming techniques for electrode manufacture indicate future practical uses of such instruments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
6.
The discovery of neutron rich isotopes of the lightest elements on the neutron drip line exhibiting a halo structure has opened
up new vistas in research activities. The novel structural features associated with the halo phenomena have been the subject
for extensive theoretical and experimental investigations in recent times. In this talk, I propose to present a broad overview
of the recent developments in this field, bringing out the striking features which show that a large number oflight nuclei
near the neutron drip line are characterized by a clear separation between a ‘normal’ core nucleus and a loosely bound low
density veil of neutrons. Specifically, the two neutron halos offer a natural premises, from a theoretical standpoint, to
employ three body techniques for studying their detailed structural properties. A considerable part of the talk will be devoted
to report and highlight the results on a number of light halo nuclei such as 11Li, 11Be, 19B and 22C on which we have been carrying out investigations employing a simple but realistic three body model. These three body systems
which have been termed as ‘Borromean’ (i.e while three body systems are bound, the corresponding binary subsystems on the
other hand are unbound) are characterized by large spacial extension and very low separation energy of the neutron. They are,
therefore, ideally suited for exploring the possibility of the existence of Efimov states in two neutron halo nuclei. We have
recently carried out the three body analyses to predict the possibility of the occurrence of such states on which experimental
work at various laboratories is underway. 相似文献
7.
V S K Balagurusamy S Krishna Prasad S Chandrasekhar Sandeep Kumar M Manickam C V Yelamaggad 《Pramana》1999,53(1):3-11
We have studied the electrical conductivity of well aligned samples of hexahexylthiotriphenylene (HHTT) in the pure as well
as doped states. The dopant used was a small concentration (0.62 mole %) of the electron acceptor trinitrofluorenone (TNF).
In the columnar phases, doping causes the AC(1 kHz) conductivity along the columnar axis (σ
‖) to increase by a factor of 107 or more relative to that in undoped samples; σ
‖ attains a value of 10−2S/m, which was the maximum measurable limit of our experimental set up. On the other hand, in the isotropic phase doping makes
hardly any difference to the conductivity. The frequency dependence of the conductivity has been investigated. The DC conductivity
of doped samples exhibits an enormous anisotropy, σ
‖/σ
⊥ ≥ 1010, which is 7 orders higher than that reported for any liquid crystalline system, and, to our knowledge, the largest observed
in an organic conductor.
We also report the first thermoelectric power studies on these ‘molecular wires’. The sign of the thermoelectric power is
in conformity with the expected nature of the charge carriers, namely, holes. 相似文献
8.
Percec V Glodde M Peterca M Rapp A Schnell I Spiess HW Bera TK Miura Y Balagurusamy VS Aqad E Heiney PA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(24):6298-6314
Semifluorinated first-generation self-assembling dendrons attached via a flexible spacer to electron-donor molecules induce pi-stacking of the donors in the center of a supramolecular helical pyramidal column. These helical pyramidal columns self-organize in various columnar liquid crystal phases that mediate self-processing of large single crystal liquid crystal domains of columns and self-repair their intracolumnar structural defects. In addition, all supramolecular columns exhibit a columnar phase at lower temperatures that maintains the helical pyramidal columnar supramolecular structure and displays higher intracolumnar order than that in the liquid crystals phases. The results described here demonstrate the universality of this concept, the power of the fluorous phase or the fluorophobic effect in self-assembly and the unexpected generality of pyramidal liquid crystals. 相似文献
9.
NL Asfandiarov AI Fokin VG Lukin EP Nafikova GS Lomakin VS Fal'ko YV Chizhov 《Rapid communications in mass spectrometry : RCM》1999,13(12):1116-1123
A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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