Ca[Ag2(SCN)4]·2H2O

Calcium tetra­thio­cyanato­diargentate(I) dihydrate, Ca[Ag₂(SCN)₄]·2H₂O, contains eight‐membered Ag₄S₄ rings bonded together through shared atoms to form layers parallel to (100). The thio­cyanate groups link the layers to Ca–O chains running parallel to the c axis. The Ca atom is located on a twofold rotation axis parallel to b and is surrounded by four water molecules of crystallization and four thio­cyanate N atoms in a distorted square antiprism.     

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

ERKALE is a novel software program for computing X‐ray properties, such as ground‐state electron momentum densities, Compton profiles, and core and valence electron excitation spectra of atoms and molecules. The program operates at Hartree–Fock or density‐functional level of theory and supports Gaussian basis sets of arbitrary angular momentum and a wide variety of exchange‐correlation functionals. ERKALE includes modern convergence accelerators such as Broyden and ADIIS and it is suitable for general use, as calculations with thousands of basis functions can routinely be performed on desktop computers. Furthermore, ERKALE is written in an object oriented manner, making the code easy to understand and to extend to new properties while being ideal also for teaching purposes. © 2012 Wiley Periodicals, Inc.     

Surface Plasmon Resonance Spectroscopy as a Tool to Study Polyplex‐Glycoaminoglycan Interactions

Summary: This article reports the application of surface plasmon resonance (SPR) to monitor the interaction between polymer‐DNA complexes and glycoaminoglycans (GAG). The GAG selected was hyaluronic acid (HA). First a HA derivative containing a disulfide linkage was synthesized, enabling chemisorption onto a gold surface. Next, the interaction between different complexes (prepared using PEI or PDMAEMA) and HA was studied using SPR. This study clearly indicates that GAG‐polyplex interactions depend on the type of polymer selected and on the charge ratio of the polyplexes prepared.

The derivative developed opens up new perspectives in the field of nonviral gene delivery.     

A computational and experimental study of the structures and Raman and 77Se NMR spectra of SeX3+ and SeX2 (X = Cl, Br, I): FT-Raman spectrum of (SeI3)[AsF6

The ability of MP2, B3PW91 and PBE0 methods to produce reliable predictions in structural and spectroscopic properties of small selenium-halogen molecules and cations has been demonstrated by using 6-311G(d) and cc-pVTZ basis sets. Optimized structures and vibrational frequencies agree closely with the experimental information, where available. Raman intensities are also well reproduced at all levels of theory. Calculated GIAO isotropic shielding tensors yield a reasonable linear correlation with the experimental chemical shift data at each level of theory. The largest deviations between calculated and experimental chemical shifts are found for selenium-iodine species. The agreement between observed and calculated chemical shifts for selenium-iodine species can be improved by inclusion of relativistic effects using the ZORA method. The best results are achieved by adding spin-orbit correction terms from ZORA calculations to nonrelativistic GIAO isotropic shielding tensors. The calculated isotropic shielding tensors can be utilized in the spectroscopic assignment of the 77Se chemical shifts of novel selenium-halogen molecules and cations. The experimental FT-Raman spectra of (SeI3)[AsF6] in the solid state and in SO2(l) solution are also reported.     

Enhanced ligand affinity for receptors in which components of the binding site are independently mobile

Using calmodulin antagonism as a model, it is demonstrated that, under circumstances in which binding sites are motionally independent, it is possible to create bifunctional ligands that bind with significant affinity enhancement over their monofunctional counterparts. Suitable head groups were identified by using a semiquantitative screen of monofunctional tryptophan analogs. Two bifunctional ligands, which contained two copies of the highest-affinity head group tethered by rigid linkers, were synthesized. The bifunctional ligands bound to calmodulin with a stoichiometry of 1:1 and with an affinity enhancement over their monofunctional counterparts; the latter bound with a stoichiometry of 2:1 ligand:protein. A lower limit to the effective concentrations of the domains of calmodulin relative to each other (0.2-2 mM) was determined. A comparable effective concentration was achieved for bifunctional ligands based on higher-affinity naphthalene sulphonamide derivatives.     

Polymorphism in Cs[AgZn(NCS)4]

The title compound, caesium silver zinc tetrathiocyanate, crystallizes in two polymorphic forms, in space groups P2₁/n and C2/c. Both structures form a continuous three‐dimensional network. The structure in C2/c contains a delocalized Ag atom in a binuclear‐like anion, where two [Ag(NCS)₄] units (delocalized Ag as an average) share two common NCS^? ligands.     

Experimental and theoretical investigations of structural trends for selenium(IV) imides and oxides: X-ray structure of Se3(NAd)2

The thermal decomposition of Se(NAd)(2) (Ad = 1-adamantyl) in THF was monitored by (77)Se NMR and shown to give the novel cyclic selenium imide Se(3)(NAd)(2) as one of the products. An X-ray structural determination showed that Se(3)(NAd)(2) is a puckered five-membered ring with d(Se-Se) = 2.404(1) A and |d(Se-N)| = 1.873(4) A. On the basis of (77)Se NMR data, other decomposition products include the six-membered ring Se(3)(NAd)(3), and the four-membered rings AdNSe(micro-NAd)(2)SeO and OSe(micro-NAd)(2)SeO. The energies for the cyclodimerization of E(NR)(2) and RNEO (E = S, Se; R = H, Me, (t)Bu, SiMe(3)), and the cycloaddition reactions of RNSeO with E(NR)(2), RNSO(2) with Se(NR)(2), and S(NR)(2) with Se(NR)(2) have been calculated at MP2, CCSD, and CCSD(T) levels of theory using the cc-pVDZ basis sets and B3PW91/6-31G* optimized geometries. Sulfur(IV) and selenium(IV) diimide monomers are predicted to be stable, the sole exception being Se(NSiMe(3))(2) that shows a tendency toward cyclodimerization. The cyclodimerization energy for RNSeO and the cycloaddition reaction energies of RNSeO with Se(NR)(2) as well as that of RNSO(2) with Se(NR)(2) are negative, consistent with the observed formation of OSe(micro-N(t)Bu)(2)SeO, OSe(micro-N(t)Bu)(2)SeN(t)Bu, and O(2)S(micro-N(t)Bu)(2)SeN(t)Bu, respectively. Cycloaddition is unlikely when one of the reactants is a sulfur(IV) diimide.