Understanding the Chloride Affinity of Barbiturates for Anion Receptor Design

Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C−H bond is as effective as the N−H bond to coordinate chloride. An analysis of the electron charge density at the C−H⋅⋅⋅Cl⁻ and N−H⋅⋅⋅Cl⁻ bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C−H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C−H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.     

Growth and characterization of ultrathin carbon films on electrodeposited Cu and Ni

Ultrathin carbon films were grown on different types of metallic substrates. Free‐standing foils of Cu and Ni were prepared by electroforming, and a pure Ni film was obtained by galvanic displacement on a Si wafer. Commercial foil of Ni 99.95% was used as a reference substrate. Carbon films were grown on these substrates by chemical vapour deposition in a CH₄‐H₂ atmosphere. Obtained films were characterized by Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy, and ultraviolet photoemission spectroscopy. The XPS at grazing collection angle was used to determine the thickness of carbon films. Depending on the deposition parameters, the films of graphene or graphite were obtained on the different substrates. The uniformity of graphene and its distribution over the sample area were investigated from Raman data, optical images, and XPS chemical maps. The presence of graphene or graphite in the films was determined from the Raman spectra and Auger peak of C KVV. For this purpose, the D parameter, which is a fingerprint of carbon allotropes, was determined from C KVV spectra acquired by using X‐rays and electron beam. A formation of an intermediate layer of metal hydroxide was revealed in the samples with graphene overlayer.     

Synthesis and biological evaluations of mono‐ and bis‐ferrocene uracil derivatives

Mono‐ ( 3a – 3e and 4a – 4e ) and bis‐ferrocene ( 5a – 5e and 6a – 6e ) conjugated 5‐substituted uracil derivatives that are bridged by 1,2,3‐triazole linker were synthesized. The impact of ferrocene unit and spacer between ferrocene and triazole on radical scavenging potency was observed. Bis‐ferrocenyl uracil derivatives exhibited better antiproliferative activities than their mono‐ferrocenyl analogs. Bis‐ferrocenyl methyl‐ ( 5b ) and halogen‐substituted ( 5e , 6c , and 6d ) uracil derivatives showed pronounced and selective cytostatic activities on colon adenocarcinoma (CaCo‐2) and Burkitt lymphoma (Raji) cells, with higher potency and selectivity than the reference drug 5‐fluorouracil. Generation of reactive oxygen species (ROS) in CaCo‐2 and Raji cells when treated with compounds 5b , 5e , and 6d was observed. Bis‐ferrocenyl 5‐chlorouracil 6c induced significant disruption in mitochondrial membrane potential that is accompanied by activation of apoptosis in CaCo‐2, Raji, and acute lymphoblastic leukemia (CCRF‐CEM) cells, while 6d caused mitochondrial dysfunction and apoptosis induction in CaCo‐2 and Raji cells. Potent antiproliferative activity of 6c and 6d could be associated with mitochondrial membrane potential disruption accompanied by apoptosis induction. Our findings highlighted 6c and 6d with potent and selective antiproliferative activity on CaCo‐2, Raji, and CCRF‐CEM cells that may be associated with targeting cancer cell mitochondria, as a molecular target.     

A solution to the Baer splitting problem

Let be a commutative domain. We prove that an -module is projective if and only if for any torsion module . This answers in the affirmative a question raised by Kaplansky in 1962.

     

On a minimal set of generators for the invariants of 3 × 3 matrices

Let K be a field of characteristic p > 0, let L be a restricted Lie algebra and let R be an associative K-algebra. It is shown that the various constructions in the literature of crossed product of R with u(L) are equivalent. We calculate explicit formulae relating the parameters involved and obtain a formula which hints at a noncommutative version of the Bell polynomials.     

Expected reliability of communication protocols

We consider the problem of sending a message from a sender $s$ to a receiver $r$ through an unreliable network by specifying in a protocol what each vertex is supposed to do if it receives the message from one of its neighbors. A protocol for routing a message in such a graph is finite if it never floods $r$ with an infinite number of copies of the message. The expected reliability of a given protocol is the probability that a message sent from $s$ reaches $r$ when the edges of the network fail independently with probability $1?p$.We discuss, for given networks, the properties of finite protocols with maximum expected reliability in the case when $p$ is close to 0 or 1, and we describe networks for which no one protocol is optimal for all values of $p$. In general, finding an optimal protocol for a given network and fixed probability is challenging and many open problems remain.     

On properties of random dissections and triangulations

In this work we study properties of random graphs that are drawn uniformly at random from the class consisting of biconnected outerplanar graphs, or equivalently dissections of large convex polygons. We obtain very sharp concentration results for the number of vertices of any given degree, and for the number of induced copies of a given fixed graph. Our method gives similar results for random graphs from the class of triangulations of convex polygons.     

Switching preconditioners using a hybrid approach for linear systems arising from interior point methods for linear programming

Numerical Algorithms - In general, interior point methods are successful in solving large-scale linear programming problems. Their effectiveness is determined by how fast they calculate each...