The Reissner-Mindlin plate is the Γ-limit of Cosserat elasticity

The linear Reissner-Mindlin membrane-bending plate model is the rigorous Γ-limit for zero thickness of a linear isotropic Cosserat bulk model with symmetric curvature. For this result we use the natural nonlinear scaling for the displacements u and the linear scaling for the infinitesimal microrotations Ā ∈ so(3) affecting the in-plane drill rotations. No boundary conditions on the microrotations are prescribed. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Chemically controlled self-assembly of protein nanorings

The exploitation of biological macromolecules, such as nucleic acids, for the fabrication of advanced materials is a promising area of research. Although a greater variety of structural and functional uses can be envisioned for protein-based materials, systematic approaches for their construction have yet to emerge. Consistent with theoretical models of polymer macrocyclization, we have demonstrated that, in the presence of dimeric methotrexate (bisMTX), wild-type Escherichia coli dihydrofolate reductase (DHFR) molecules tethered together by a flexible peptide linker (ecDHFR(2)) are capable of spontaneously forming highly stable cyclic structures with diameters ranging from 8 to 20 nm. The nanoring size is dependent on the length and composition of the peptide linker, on the affinity and conformational state of the dimerizer, and on induced protein-protein interactions. Delineation of these and other rules for the control of protein oligomer assembly by chemical induction provides an avenue to the future design of protein-based materials and nanostructures.     

Multiferroic materials based on organic transition-metal molecular nanowires

We report on the density functional theory aided design of a variety of organic ferroelectric and multiferroic materials by functionalizing crystallized transition-metal molecular sandwich nanowires with chemical groups such as -F, -Cl, -CN, -NO(2), ═O, and -OH. Such functionalized polar wires exhibit molecular reorientation in response to an electric field. Ferroelectric polarizations as large as 23.0 μC/cm(2) are predicted in crystals based on fully hydroxylized sandwich nanowires. Furthermore, we find that organic nanowires formed by sandwiching transition-metal atoms in croconic and rhodizonic acids, dihydroxybenzoquinone, dichloro-dihydroxy-p-benzoquinone, or benzene decorated by -COOH groups exhibit ordered magnetic moments, leading to a multiferroic organometallic crystal. When crystallized through hydrogen bonds, the microscopic molecular reorientation translates into a switchable polarization through proton transfer. A giant interface magnetoelectric response that is orders of magnitude greater than previously reported for conventional oxide heterostructure interfaces is predicted.     

A recipe for designing molecules with ever-increasing electron affinities

Halogens possess among the highest electron affinities of elements in the periodic table. Superhalogen molecules with electron affinities higher than those of halogen atoms have been known to form when a metal atom is surrounded with halogen atoms. Recently, it was discovered that a new class of molecules called hyperhalogens with electron affinities higher than those of superhalogens can form when the latter serve as the building block. By use of density functional theory and B3LYP hybrid exchange-correlation functional we show that molecules with electron affinities even higher can be formed by using hyperhalogens as building blocks. We demonstrate this by using Na and Li as metal atoms and F, BF(4), and Na(BF(4))(2) as halogen, superhalogen, and hyperhalogen building blocks. The predicted electron affinities of Na[Na(BF(4))(2)](2) and Li[Li(BF(4))(2)](2) are 9.18 and 9.01 eV, which are, respectively, 0.85 and 0.5 eV higher than those of their hyperhalogen [Na(BF(4))(2) and Li(BF(4))(2)] counterparts.     

Stability and spectroscopic properties of singly and doubly charged anions

Using density functional theory and hybrid B3LYP exchange-correlation energy functional we have studied the structure, stability, and spectroscopic properties of singly and doubly charged anions composed of simple metal atoms (Na, Mg, Al) decorated with halogens such as Cl and pseudohalogens such as CN. Since pseudohalogens mimic the chemistry of halogen atoms, our objective is to see if pseudohalogens can also form superhalogens much as halogens do and if the critical size for a doubly charged anion depends upon the ligand. The electron affinities of MCl(n) (M = Na, Mg, Al) exceed the value of Cl for n ≥ (k + 1), where k is the normal valence of the metal atom. However, for M(CN)(n) complexes this is only true when n = k + 1. In addition, while the electron affinities and vertical detachment energies of MCl(n) complexes are close to each other, they are markedly different when Cl is replaced by pseudohalogen, CN. The origin of these anomalous results is found to be due to the large binding energy of cyanogen, (NCCN) molecule. Because of the tendency of CN molecules to dimerize, the ground state geometries of the neutral and anionic M(CN)(n) complexes are very different when their number exceed the normal valence of the metal atom. While our calculations support the conclusion of Skurski and co-workers that pseudohalogens can form the building blocks of superhalogens, we show that there is a limitation on the number of CN moieties where this is true. Equally important, we find large differences between the ground state geometries of the neutral and anionic M(CN)(n) complexes for n ≥ (k + 2) which could play an important role in interpreting future experimental data on M(CN)(n) complexes. This is because the electron affinity defined as the energy difference between the ground states of the anion and neutral can be very different from the adiabatic detachment energy defined as the energy difference between the ground state of the anion and its structurally similar neutral isomer.     

The Role of Interface on the Properties of Cluster Assemblies

Atomic clusters characterized by finite size, low dimensionality, and reduced coordination number exhibit many novel properties that are very different from their bulk. As these clusters are assembled, their properties can be significantly altered due to the interaction of these clusters with each other as well as with their support. This paper provides a brief review of the cluster properties that are affected when clusters are deposited on metallic or organic substrates, isolated in matrices or in zeolite cages, coated with acetate ligands, or simply allowed to self-assemble without the presence of any reactive species. It is shown that the interface between the clusters and their support can play an important role on the properties of clusters as their unique characteristics do.     

Closo‐alanes (Al4H4, AlnHn+2, 4 ≤ n ≤ 8): A New Chapter in Aluminum Hydride Chemistry.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

Formation of 8-nitroguanine and 8-oxoguanine due to reactions of peroxynitrite with guanine

Reactions of peroxynitrite with guanine were investigated using density functional theory (B3LYP) employing 6-31G** and AUG-cc-pVDZ basis sets. Single point energy calculations were performed at the MP2/AUG-cc-pVDZ level. Genuineness of the calculated transition states (TS) was tested by visually examining the vibrational modes corresponding to the imaginary vibrational frequencies and applying the criterion that the TS properly connected the reactant and product complexes (PC). Genuineness of all the calculated TS was further ensured by intrinsic reaction coordinate (IRC) calculations. Effects of aqueous media were investigated by solvating all the species involved in the reactions using the polarizable continuum model (PCM). The calculations reveal that the most stable nitro-product complex involving the anion of 8-nitroguanine and a water molecule i.e. 8NO(2)G(-) + H(2)O can be formed according to one reaction mechanism while there are two possible reaction mechanisms for the formation of the oxo-product complex involving 8-oxoguanine and anion of the NO(2) group i.e. 8OG + NO(2)(-). The calculated relative stabilities of the PC, barrier energies of the reactions and the corresponding enthalpy changes suggest that formation of the complex 8OG + NO(2)(-) would be somewhat preferred over that of the complex 8NO(2)G(-) + H(2)O. The possible biological implications of this result are discussed.