Crystal structure and ab initio calculations of a cyano-carbamimidic acid ethyl ester

The structure of one tautomer (amine form) of cyano-carbamimidic acid ethyl ester or (amino-ethoxy-methylidene)aminoformonitrile (CAS: 13947-84-7) was determined by single crystal X-ray diffraction. Ab initio quantum chemical calculations at the B3LYP, MP2 and G3 levels were performed to investigate the stability and the formation of the different tautomers and conformers. The calculations indicate that the amine form is the more stable tautomer, showing a high degree of electron conjugation. The most stable amine conformer located by the calculations corresponds to the crystallized structure. On the contrary, in the less stable imine form, the conjugation is separated by a N2–C2 single bond.     

Local resilience of graphs

In this article, we initiate a systematic study of graph resilience. The (local) resilience of a graph G with respect to a property measures how much one has to change G (locally) to destroy . Estimating the resilience leads to many new and challenging problems. Here we focus on random and pseudorandom graphs and prove several sharp results. © 2008 Wiley Periodicals, Inc. Random Struct. Alg., 2008     

Use of Different Salt Solutions in Salting-Out TLC of Co(III) Complexes on Silica Gel

Saturated aqueous solutions of 28 different salts have been studied as a potential mobile phases for salting-out thin-layer chromatography, on silica gel, of a series of four mixed bis-aminocarboxylato cobalt(III) complexes. In addition, by linear regression analysis of chromatographic data obtained for fifteen mixed aminocarboxylato Co(III) complexes (four series) with solutions of ammonium chloride, three alkali metal chlorides, and four alkaline earth metal chlorides, four linear dependences previously established on different adsorbents with (NH₄)₂SO₄ solutions were confirmed. The qualities of the separations achieved with the salts were compared and Li⁺, Mg²⁺, and Ca²⁺ chlorides are proposed as the most suitable.     

Total Synthesis of Isodaphlongamine H: A Possible Biogenetic Conundrum

Herein we describe the first synthetic efforts toward the total synthesis of isodaphlongamine H, a calyciphylline B‐type alkaloid. The strategy employs a chemoenzymatic process for the preparation of a functionalized cyclopentanol with a quaternary center. This molecule is elaborated to form an enantiopure 1‐aza‐perhydrocyclopentalene core, representing rings A and E of all calyciphylline B‐type alkaloids. Further transformations involve the formation of a cyclic enaminone, 1,4‐conjugate addition with a cyclopentenyl subunit, and intramolecular aldol cyclization to achieve a pentacyclic intermediate, ultimately forming isodaphlongamine H in a total of 24 steps from the commercially available compound 2‐carbethoxycyclopentanone. Isodaphlongamine H exhibits promising inhibitory activity against a panel of human cancer cell lines.     

Decay mild solutions for two-term time fractional differential equations in Banach spaces

In this paper, we deal with the nonlocal Cauchy problem for a class of two-term time fractional differential equations in Banach spaces. By constructing a suitable measure of noncompactness on the space of solutions, we prove the existence of a compact set containing decay mild solutions to the mentioned problem.     

Thermal stability of <Emphasis Type="Italic">meso</Emphasis>-substituted metal corroles in inert and oxidative media

The thermal stability of 5,10,15-triphenylcorrole as the simplest representative of meso-substituted corroles and its complexes with d-metals (Cu³⁺, Mn³⁺, Mn⁴⁺, Co³⁺, Co⁴⁺, and Zn²⁺) is studied for the first time via thermogravimetry in oxidizing and inert atmospheres. It is shown that corroles, both as free ligands and in the form of metal complexes, are less thermally stable than porphyrins with a similar structure. It is found that if the free ligands of porphyrins are thermally more stable with respect to thermal oxidation than d-metal complexes, the thermal stability of metal corroles can be both lower and higher than those of free ligands. It is concluded that the order of thermal stability of compounds MnCor < CoCor < H₃Cor < ZnCorH < CuCor is reversed upon moving from an oxidizing to an inert medium. It is shown that corroles complexes with many d-metals (Co, Mn, and others) readily participate in extracoordination reactions with electron-donating solvents, e.g., DMF, as is indicated by spectrophotometry and thermogravimetry.     

Random walks with different directions

As an extension of Polya’s classical result on random walks on the square grids (\({\mathbf {Z}}^d\)), we consider a random walk where the steps, while still have unit length, point to different directions. We show that in dimensions at least 4, the returning probability after n steps is at most \(n^{-d/2 - d/(d-2) +o(1) }\), which is sharp. The real surprise is in dimensions 2 and 3. In dimension 2, where the traditional grid walk is recurrent, our upper bound is \(n^{-\omega (1) }\), which is much worse than in higher dimensions. In dimension 3, we prove an upper bound of order \(n^{-4 +o(1) }\). We find a new conjecture concerning incidences between spheres and points in \({\mathbf {R}}^3\), which, if holds, would improve the bound to \(n^{-9/2 +o(1) }\), which is consistent to the \(d \ge 4\) case. This conjecture resembles Szemerédi-Trotter type results and is of independent interest.     

Random inscribing polytopes

For convex bodies K with boundary in , we explore random polytopes with vertices chosen along the boundary of K. In particular, we determine asymptotic properties of the volume of these random polytopes. We provide results concerning the variance and higher moments of this functional, as well as an analogous central limit theorem.     

Synthesis and Properties of TRANSDIP,a Rigid Chelator Built upon a Cyclodextrin Cavity: Is TRANSDIP an Authentic trans‐Spanning Ligand?

The C2-symmetrical diphosphane TRANSDIP was obtained in high yield by treating 6A,6B,6D,6E-tetramesylated, permethylated alpha-cyclodextrin with PPhLi2 in excess. The double cascade cyclisation thus produced is regioselective as phosphinidene capping involves only adjacent glucose units. It is also stereospecific, as both lone pairs on the phosphorus atoms are orientated towards the cyclodextrin axis. The restricted flexibility of the phosphorus atoms, which are part of nine-membered heterocyclic rings, is responsible for JP,C spin-spin couplings with the eight-bond distant CH2OMe carbon atoms of glucose units C and F. The treatment of TRANSDIP with Group 10 metal dihalides quantitatively gave square-planar chelate complexes, in which a M--X bond points towards the centre of the cavitand. The favourable P...P separation and the directional control of the lone pairs on the phosphorus atoms rule out the possibility of forming binuclear complexes or higher oligomers. Further, in all the complexes, the phosphorus atoms are in a trans arrangement. TRANSDIP may therefore be regarded as an authentic trans-spanning diphosphane. In the complex [NiBr2TRANSDIP], the cavity provides effective protection of the encapsulated M--X bond towards nucleophilic attack by MeLi. The same complex, upon activation with methylaluminoxane, efficiently dimerises ethene and propene.     

Investigation for Differentiation of Bounding Strength Of Metals in Sediments

Only part of the metal present in sediments are involved in short-term geochemical processes and/or are bioavailable. Hydrous Fe- and Mn-oxides as well as organic matter partly as coatings on films on detail grains, are important substances for the interaction with dissolved metal species in aquatic systems.