Quantum mechanical calculations of conformationally relevant 1H and 13C NMR chemical shifts of N-, O-, and S-substituted calixarene systems

QM GIAO calculations of (13)C and (1)H chemical shift values of the ArCH(2)Ar group in N-, O-, and S-substituted calixarene systems were performed with a hybrid DFT functional MPW1PW91 and 6-31G(d,p) basis set. A good reproduction of experimental data was obtained for some representative calixarenes and for a series of simplified calixarene models. This allowed the derivation of chemical shift surfaces versus phi and chi dihedral angles. The applicability of chemical shift surfaces in the study of calixarene conformational features is illustrated.     

Encoding Individual Source Sequences for the Wiretap Channel

We consider the problem of encoding a deterministic source sequence (i.e., individual sequence) for the degraded wiretap channel by means of an encoder and decoder that can both be implemented as finite-state machines. Our first main result is a necessary condition for both reliable and secure transmission in terms of the given source sequence, the bandwidth expansion factor, the secrecy capacity, the number of states of the encoder and the number of states of the decoder. Equivalently, this necessary condition can be presented as a converse bound (i.e., a lower bound) on the smallest achievable bandwidth expansion factor. The bound is asymptotically achievable by Lempel–Ziv compression followed by good channel coding for the wiretap channel. Given that the lower bound is saturated, we also derive a lower bound on the minimum necessary rate of purely random bits needed for local randomness at the encoder in order to meet the security constraint. This bound too is achieved by the same achievability scheme. Finally, we extend the main results to the case where the legitimate decoder has access to a side information sequence, which is another individual sequence that may be related to the source sequence, and a noisy version of the side information sequence leaks to the wiretapper.     

Scale factor local search in differential evolution

This paper proposes the scale factor local search differential evolution (SFLSDE). The SFLSDE is a differential evolution (DE) based memetic algorithm which employs, within a self-adaptive scheme, two local search algorithms. These local search algorithms aim at detecting a value of the scale factor corresponding to an offspring with a high performance, while the generation is executed. The local search algorithms thus assist in the global search and generate offspring with high performance which are subsequently supposed to promote the generation of enhanced solutions within the evolutionary framework. Despite its simplicity, the proposed algorithm seems to have very good performance on various test problems. Numerical results are shown in order to justify the use of a double local search instead of a single search. In addition, the SFLSDE has been compared with a standard DE and three other modern DE based metaheuristic for a large and varied set of test problems. Numerical results are given for relatively low and high dimensional cases. A statistical analysis of the optimization results has been included in order to compare the results in terms of final solution detected and convergence speed. The efficiency of the proposed algorithm seems to be very high especially for large scale problems and complex fitness landscapes.     

An intramolecularly self-templated synthesis of macrocycles: self-filling effects on the formation of prismarenes

Ethyl- and propyl-prism[6]arenes are obtained in high yields and in short reaction times, independent of the nature and size of the solvent, in the cyclization of 2,6-dialkoxynaphthalene with paraformaldehyde. PrS[6]Et or PrS[6]nPr adopt, both in solution and in the solid state, a folded cuboid-shaped conformation, in which four inward oriented alkyl chains fill the cavity of the macrocycle. On these bases, we proposed that the cyclization of PrS[6]Et or PrS[6]nPr occurs through an intramolecular thermodynamic self-templating effect. In other words, the self-filling of the internal cavity of PrS[6]Et or PrS[6]nPr stabilizes their cuboid structure, driving the equilibrium toward their formation. Molecular recognition studies, both in solution and in the solid state, show that the introduction of guests into the macrocycle cavity forces the cuboid scaffold to open, through an induced-fit mechanism. An analogous conformational change from a closed to an open state occurs during the endo-cavity complexation process of the pentamer, PrS[5]. These results represent a rare example of a thermodynamically controlled cyclization process driven through an intramolecular self-template effect, which could be exploited in the synthesis of novel macrocycles.

Ethyl- and propyl-prism[6]arenes are obtained by an intramolecular thermodynamic self-template effect: the self-filling of the internal cavity stabilizes their cuboid structure, driving the equilibrium toward their formation.     

Supramolecular polymer networks based on calix[5]arene chained poly(p-phenyleneethynylene) and C60 fulleropyrrolidine

Abstract

A poly(p-phenyleneethynylene) polymer (PCF[5]), bearing two π-rich cone-like calix[5]arene cavities (assembling cores) attached to a rigid p-phenyleneethynylene spacer, was synthesised by a Pd-catalysed cross-coupling reaction. UV–vis absorption and fluorescence spectroscopies combined with dynamic light scattering measurements provide evidence for the self-assembly of PCF[5] (homopolytopic host molecule) with a complementary C₆₀ fulleropyrrolidine (C₆₀-Pyr) guest in solution, in the construction of a supramolecular polymer network. Atomic force microscopy analysis of PCF[5]/C₆₀-Pyr highlights the formation of a bicontinuous network consisting of a uniform distribution of prominent structures, within a polymeric background forming a biphasic structure.     

Two general methods for the isolation of enzyme activities by colony filter screening

We describe two general methodologies, based on filter-sandwich assays, for isolating enzymatic activities from a large repertoire of protein variants expressed in the cytoplasm of E. coli cells. The enzymes are released by the freezing and thawing of bacterial colonies grown on a porous master filter and diffuse to a second "reaction" filter that closely contacts the master filter. Reaction substrates can be immobilized either on the filter or on the enzyme itself (which is then, in turn, captured on the reaction filter). The resulting products are detected with suitable affinity reagents. We used biotin ligase as a model enzyme to assess the performance of the two methodologies. Active enzymes were released by the bacteria, locally biotinylated the immobilized target substrate peptide, and allowed the sensitive and specific detection of individual catalytically active colonies.     

Charm mixing from BABAR

We present recent results from BABAR experiment for D0-D0 mixing measurements. Mixing parameters can be measured in different ways using different D0 decay modes, here we discuss the most sensitive analyses such as DO→K+π- where we had the first evidence of charm mixing, the measurement of the ratio of lifetimes of the decays DO→K+K-and DO→π- relative to D0→K-π+, the time dependent Dalitz plot analysis of D0→K+π-π0.New limits on CP-violating time-integrated asymmetries in D0→K+K- and D0→π+π- are also discussed. The analyses presented are based on 384 fb-1 data collected with the BABAR detector at the PEP-Ⅱ asymmetric B Factory.     

Uncharged Water‐Soluble Metal‐Bis‐Porphyrins Like Molecular Tweezers for Amino Acids

Some new water‐soluble bis‐porphyrins, constituted of two porphyrin units spaced by means of aliphatic bridges of different lengths, were synthesized and characterized by MALDI‐TOF mass spectrometry, ¹H NMR and UV‐vis spectroscopy. The hydrosolubility of these uncharged compounds was guaranteed from the presence of six long PEG chains bound on the peripheral positions of the two porphyrins. Cobalt and zinc derivatives were also prepared. In the case of Co‐bis‐porphyrin, the appearance of induced circular dichroism (ICD) signals in water solution confirmed the formation of stable complexes with some amino acids, in which the bis‐porphyrin behaves like molecular tweezers.