Design and Sensing Properties of a Self‐Assembled Supramolecular Oligomer

Supramolecular polymers are a class of macromolecules stabilized by weak non‐covalent interactions. These self‐assembled aggregates typically undergo stimuli‐induced reversible assembly and disassembly. They thus hold great promise as so‐called functional materials. In this work, we present the design, synthesis, and responsive behavior of a short supramolecular oligomeric system based on two hetero‐complementary subunits. These “monomers” consist of a tetrathiafulvalene‐functionalized calix[4]pyrrole (TTF‐C[4]P) and a glycol diester‐linked bis‐2,5,7‐trinitrodicyanomethylenefluorene‐4‐carboxylate (TNDCF), respectively. We show that when mixed in organic solvents, such as CHCl₃, CH₂ClCH₂Cl, and methylcyclohexane, supramolecular aggregation takes place to produce short oligomers stabilized by hydrogen bonding and donor–acceptor charge‐transfer (CT) interactions. The self‐associated materials were characterized by ¹H NMR and UV/Vis/NIR absorption spectroscopy, as well as by concentration‐ and temperature‐dependent absorption spectroscopy and dynamic light scattering (DLS) analyses of both the monomeric and oligomerized species. The self‐associated system produced from TTF‐C[4]P and TNDCF exhibits a concentration‐dependent aggregation behavior typical of supramolecular polymers. Further support for the proposed self‐assembly came from theoretical calculations. The fluorescence emitting properties of TNDCF are quenched under conditions that promote the formation of supramolecular aggregates containing TTF‐C[4]P and TNDCF. This quenching effect has been utilized as a probe for the detection of substrates in the form of anions (i.e., chloride) and nitroaromatic explosives (i.e., 1,3,5‐trinitrobenzene). Specifically, the addition of these substrates to mixtures of TTF‐C[4]P and TNDCF produced a fluorescence “turn‐on” response.     

QCD exotics

I review first some theoretical motivations for violation of Lorentz and/or CPT Invariance. Although the latter symmetries may be violated in a quantum gravity setting, nevertheless there are situations in which these violations are due to a given classical background geometry that may characterised early epochs of our Universe, and in fact be responsible for the observed dominance of matter over antimatter in the Universe. In this way I estimate some of the coefficients of the Standard Model Extension (SME), which is a framework for a field theoretic study of such a breakdown of fundamental symmetries. Then I describe briefly some tests of these symmetries, giving emphasis in low-energy antiproton physics and electric dipole moment measurements, of interest to this conference. I also mention the rôle of entangled states of neutral mesons in providing independent measurements of T(ime reversal) and CP Violation, thus providing independent tests of CPT symmetry, as well as novel (“smoking-gun” type) tests of decoherence-induced CPT violation, which may characterise some models of quantum gravity.     

Polyether-bridged bis(tert-butyl nitroxide) paramagnetic hosts showing receptor ability to calcium(II) and barium(II) ions

The title compounds, Ph2bNO and Ph3bNO, were designed as a biradical paramagnetic host, and their chelation ability was confirmed by inclusion of a size-matched alkaline-earth metal ion. The crystal structures of [Ca(hfac)₂(Ph2bNO)] and [Ba(hfac)₂(Ph3bNO)] were determined, where Hhfac stands for 1,1,1,5,5,5-hexafluoropentane-2,4-dione. The solution electron paramagnetic resonance spectra showed switching behavior. Five lines were found for Ph3bNO and charecterized as the hyperfine splitting due to the two nitrogen atoms. After addition of barium(II) ion, the spectrum turned to be three lines. Removal of the barium ion recovered the five line pattern. The present system can be regarded as a reversible magnetic-coupling switch by means of a supramolecular technique.     

Synthesis of Some Novel bis‐Spiro[indole‐pyrazolinyl‐thiazolidine]‐2,4′‐diones

The reaction of 1H‐indol‐2,3‐diones with 1,6‐dibromohexane has resulted in the formation of new 1H‐indol‐2,3‐diones‐1,1′‐(1,6‐hexanediyl)bis in quantitative yields. These compounds have been used for the synthesis of novel [3′‐(2,3‐dimethyl‐5‐oxo‐1‐phenyl‐3‐pyrazolin‐4‐yl)spiro[3H‐indol‐3,2′‐thiazolidine]‐2,4′‐dione]‐1,1′‐(1,6‐hexanediyl)bis via bis Schiff's bases, [3‐(2,3‐dimethyl‐5‐oxo‐1‐phenyl‐3‐pyrazolin‐4‐yl) imino‐1H‐indol‐2‐one]‐1,1′‐(1,6‐hexanediyl)bis.     

Search for direct photons from S-Au collisions at 200 GeV/nucleon

The CERES experiment has measured inclusive photon production in S-Au collisions of 200 GeV/nucleon at the CERN SPS. No evidence for direct emission of photons was found. For the kinematic region 2.1<y<2.65 and 0.4 GeV/c<p??<2.0 GeV/c the yield andp??-dependence of the observed photons are well reproduced by hadron decays. Furthermore, their production rate is found to be proportional to the charged particle density. The systematic errors comparing the measured and expected photon yield result in an upper limit of 14% for the emission of direct photons in central S-Au collisions. For a photon source with a yield depending quadratically on the charged particle density the limit can be reduced to 7%.     

Kernels by monochromatic paths in digraphs with covering number 2

We call the digraph D an k-colored digraph if the arcs of D are colored with k colors. A subdigraph H of D is called monochromatic if all of its arcs are colored alike. A set N⊆V(D) is said to be a kernel by monochromatic paths if it satisfies the following two conditions: (i) for every pair of different vertices u,v∈N, there is no monochromatic directed path between them, and (ii) for every vertex x∈(V(D)?N), there is a vertex y∈N such that there is an xy-monochromatic directed path. In this paper, we prove that if D is an k-colored digraph that can be partitioned into two vertex-disjoint transitive tournaments such that every directed cycle of length 3,4 or 5 is monochromatic, then D has a kernel by monochromatic paths. This result gives a positive answer (for this family of digraphs) of the following question, which has motivated many results in monochromatic kernel theory: Is there a natural numberlsuch that if a digraphDisk-colored so that every directed cycle of length at mostlis monochromatic, thenDhas a kernel by monochromatic paths?     

Z charmoniumlike mesons

A brief review of the experimental situation concerning the electrically charged charmoniumlike meson candidates, Z^-, is presented.     

Syntheses of nucleosides with 2′-spirolactam and 2′-spiropyrrolidine moieties as potential inhibitors of hepatitis C virus NS5B polymerase

To discover novel nucleosides as potential antiviral agents, 2′-spirolactam and 2′-spiropyrrolidine-containing nucleoside analogs were envisioned. Efficient synthetic routes were developed with an epoxide opening as the key step to establish the quaternary center at the 2′ position, leading to the design and synthesis of uridine analogs 8 and 21, prodrugs 13–16, and cytidine analog 11.     

Syntheses of 4′-spirocyclic phosphono-nucleosides as potential inhibitors of hepatitis C virus NS5B polymerase

To discover novel nucleosides as potential antiviral agents, 4′-spirocyclic phosphono-nucleosides were designed to mimic the monophosphate of R-1479, a known nucleoside inhibitor of HCV NS5B. Bypassing the first kinase step to nucleoside monophosphate is viewed as advantageous since this phosphorylation is often observed as the rate-limiting transformation to the active NTP for many nucleosides. Efficient synthetic routes were developed with a triphenylphosphine–iodine cyclization reaction as the key step to form the tetrahydrofuran 4′-spirocycle. The desired 4′-spirocyclic phosphono-cytidine analogs 12a, 12b, and 16 were prepared in 11 steps.     

A class of hypo-elastic non-elastic materials and their thermodynamics

Thermodynamics is developed for a class of thermo-hypo-elastic materials. It is shown that materials of this class obey the laws of thermodynamics, but are not elastic.

Table of Symbols

Latin Letters A _ijkl tensor-valued function of t _ij appearing in hypo-elastic constitutive relation - B _ijkl another tensor-valued function. See equation (4.2) - B the square of - d _ij rate of deformation tensor - d _ij deviator of rate of deformation - f, k functions of pressure, p - g, h functions of the invariant - p pressure - q _i heat flux vector - s _ij stress deviator - _ij co-rotational derivative of stress deviator - t time - t ₁ t ₂ specific values of time - t _ij stress tensor - t _ij ⁰ a specific value of stress - T Temperature - T ₀ a specific value of temperature - u _i velocity - V(t) a material volume as a function of time, t - V ₀ a material volume at a reference configuration - W work (W = work done in a deformation—section 5) Sript Letters Specific internal energy - Specific Helmholtz free energy - G Specific Gibbs function Greek Letters an invariant of the stress deviator—see eq. (2.4) - _ij kroneker delta - (W = work done in a deformation—section 5) - specific entropy - hypo-elastic potential - hypo-elastic potential - mass density - ₀ mass density in a reference configuration - specific volume = 1/ - a function of p - _ijkl a constant tensor—see eq. (2.5) - –G/ - _ij rate of rotation tensor This work is dedicated to Jerald L. Ericksen, without whose influence it would not have been possible