Theory of spin-peierls transitions in chains of exchange clusters

A theoretical approach to the analysis of magnetostructural phase transitions of chain polymeric heterospin complexes is suggested. The approach is based on a model of the spin-Peierls transition in chains of exchange clusters. The chain elasticity parameter is found to be a main factor determining the order of phase transition.     

Some new results in multiplicative and additive Ramsey theory

There are several notions of largeness that make sense in any semigroup, and others such as the various kinds of density that make sense in sufficiently well-behaved semigroups including and . It was recently shown that sets in which are multiplicatively large must contain arbitrarily large geoarithmetic progressions, that is, sets of the form , as well as sets of the form . Consequently, given a finite partition of , one cell must contain such configurations. In the partition case we show that we can get substantially stronger conclusions. We establish some combined additive and multiplicative Ramsey theoretic consequences of known algebraic results in the semigroups and , derive some new algebraic results, and derive consequences of them involving geoarithmetic progressions. For example, we show that given any finite partition of there must be, for each , sets of the form together with , the arithmetic progression , and the geometric progression in one cell of the partition. More generally, we show that, if is a commutative semigroup and a partition regular family of finite subsets of , then for any finite partition of and any , there exist and such that is contained in a cell of the partition. Also, we show that for certain partition regular families and of subsets of , given any finite partition of some cell contains structures of the form for some .

     

Delicate crystal structure changes govern the magnetic properties of 1D coordination polymers based on 3d metal carboxylates

Homo- and heterometallic 1D coordination polymers of transition metals (Co II, Mn II, Zn II) have been synthesized by an in-situ ligand generation route. Carboxylato-based complexes [Co(PhCOO)2]n (1 a, 1 b), [Co(p-MePhCOO)2]n (2), [ZnMn(PhCOO)4]n (3), and [CoZn(PhCOO)4]n (4) (PhCOOH=benzoic acid, p-MePhCOOH=p-methylbenzoic acid) have been characterized by chemical analysis, single-crystal X-ray diffraction, and magnetization measurements. The new complexes 2 and 3 crystallize in orthorhombic space groups Pnab and Pcab respectively. Their crystal structures consist of zigzag chains, with alternating M(II) centers in octahedral and tetrahedral positions, which are similar to those of 1 a and 1 b. Compound 4 crystallizes in monoclinic space group P2 1/c and comprises zigzag chains of M II ions in a tetrahedral coordination environment. Magnetic investigations reveal the existence of antiferromagnetic interactions between magnetic centers in the heterometallic complexes 3 and 4, while ferromagnetic interactions operate in homometallic compounds (1 a, 1 b, and 2). Compound 1 b orders ferromagnetically at TC=3.7 K whereas 1 a does not show any magnetic ordering down to 330 mK and displays typical single-chain magnet (SCM) behavior with slowing down of magnetization relaxation below 0.6 K. Single-crystal measurements reveal that the system is easily magnetized in the chain direction for 1 a whereas the chain direction coincides with the hard magnetic axis in 1 b. Despite important similarities, small differences in the molecular and crystal structures of these two compounds lead to this dramatic change in properties.     

Toward accurate thermochemical models for transition metals: G3Large basis sets for atoms Sc-Zn

An augmented valence triple-zeta basis set, referred to as G3Large, is reported for the first-row transition metal elements Sc through Zn. The basis set is constructed in a manner similar to the G3Large basis set developed previously for other elements (H-Ar, K, Ca, Ga-Kr) and used as a key component in Gaussian-3 theory. It is based on a contraction of a set of 15s13p5d Gaussian primitives to 8s7p3d, and also includes sets of f and g polarization functions, diffuse spd functions, and core df polarization functions. The basis set is evaluated with triples-augmented coupled cluster [CCSD(T)] and Brueckner orbital [BD(T)] methods for a small test set involving energies of atoms, atomic ions, and diatomic hydrides. It performs well for the low-lying s-->d excitation energies of atoms, atomic ionization energies, and the dissociation energies of the diatomic hydrides. The Brueckner orbital-based BD(T) method performs substantially better than Hartree-Fock-based CCSD(T) for molecules such as NiH, where the starting unrestricted Hartree-Fock wavefunction suffers from a high degree of spin contamination. Comparison with available data for geometries of transition metal hydrides also shows good agreement. A smaller basis set without core polarization functions, G3MP2Large, is also defined.     

Protein‐Sized Bright Fluorogenic Nanoparticles Based on Cross‐Linked Calixarene Micelles with Cyanine Corona

The key challenge in the field of fluorescent nanoparticles (NPs) for biological applications is to achieve superior brightness for sizes equivalent to single proteins (3–7 nm). We propose a concept of shell‐cross‐linked fluorescent micelles, in which PEGylated cyanine 3 and 5 bis‐azides form a covalently attached corona on micelles of amphiphilic calixarene bearing four alkyne groups. The fluorescence quantum yield of the obtained monodisperse NPs, with a size of 7 nm, is a function of viscosity and reached up to 15 % in glycerol. In the on‐state they are circa 2‐fold brighter than quantum dots (QD‐585), which makes them the smallest PEGylated organic NPs of this high brightness. FRET between cyanine 3 and 5 cross‐linkers at the surface of NPs suggests their integrity in physiological media, organic solvents, and living cells, in which the NPs rapidly internalize, showing excellent imaging contrast. Calixarene micelles with a cyanine corona constitute a new platform for the development of protein‐sized ultrabright fluorescent NPs.     

Lower bounds for numbers of real solutions in problems of Schubert calculus

We give lower bounds for the numbers of real solutions in problems appearing in Schubert calculus in the Grassmannian \({\mathop{\rm Gr}(n,d)}\) related to osculating flags. It is known that such solutions are related to Bethe vectors in the Gaudin model associated to \({\mathop{\rm gl}_n}\). The Gaudin Hamiltonians are self-adjoint with respect to a non-degenerate indefinite Hermitian form. Our bound comes from the computation of the signature of that form.     

Structure of an unprecedented G-quadruplex scaffold in the human c-kit promoter

The c-kit oncogene is an important target in the treatment of gastrointestinal tumors. A potential approach to inhibition of the expression of this gene involves selective stabilization of G-quadruplex structures that may be induced to form in the c-kit promoter region. Here we report on the structure of an unprecedented intramolecular G-quadruplex formed by a G-rich sequence in the c-kit promoter in K+ solution. The structure represents a new folding topology with several unique features. Most strikingly, an isolated guanine is involved in G-tetrad core formation, despite the presence of four three-guanine tracts. There are four loops: two single-residue double-chain-reversal loops, a two-residue loop, and a five-residue stem-loop, which contain base-pairing alignments. This unique structural scaffold provides a highly specific platform for the future design of ligands specifically targeted to the promoter DNA of c-kit.     

The former "C60F16" is actually a double-caged adduct: (C60F16)(C60)

X-ray diffraction study of the substance originally believed to be C(60)F(16) reveals a double-caged structure, (C(60)F(16))(C(60)); MALDI mass spectra, 19F NMR spectral data and reasons for stability are discussed.     

Versatile mesoporous carbonaceous materials for acid catalysis

Starbon mesoporous materials were synthesized after pyrolysis of expanded starch and subsequently functionalised with sulfonated groups, providing highly active and reusable materials in various acid catalysed reactions.