Layered assemblies of a dialuminum-substituted silicotungstate trimer and the reversible interlayer cation-exchange properties

Two polyoxometalate assemblies, TBA(9)[{γ-H(2)SiW(10)O(36)Al(2)(μ-OH)(2)(μ-OH)}(3)] (1; TBA = tetra-n-butylammonium) and TBA(6)Li(3)[{γ-H(2)SiW(10)O(36)Al(2)(μ-OH)(2)(μ-OH)}(3)]·18H(2)O (2), were synthesized by trimerization of a dialuminum-substituted silicotungstate monomer. Both 1 and 2 possessed a layered structure composed of a basal sheet unit [TBA(3){γ-H(2)SiW(10)O(36)Al(2)(μ-OH)(2)(μ-OH)}(3)](6-) and interlayer cations. The interconversion between 1 and 2 reversibly took place through interlayer cation exchange.     

A probable hydrogen-bonded Meisenheimer complex: an unusually high S(N)Ar reactivity of nitroaniline derivatives with hydroxide ion in aqueous media

Observations show that nitroanilines exhibit an unusually high S(N)Ar reactivity with OH(-) in aqueous media in reactions that produce nitrophenols. S(N)Ar reaction of 4-nitroaniline (2a) in aqueous NaOH for 16 h yields 4-nitrophenol (4a) quantitatively, whereas a similar reaction of 4-nitrochlorobenzene (1a) gave 4a in 2% yield together with recovered 1a in 97%, suggesting that the leaving ability of the NH(2) group far surpasses that of Cl under these conditions. An essential feature of S(N)Ar reactions of nitroanilines is probably that the NH(2) leaving group participates in a hydrogen-bonding interaction with H(2)O. Density functional theory (DFT) calculations for a set of 4-nitroaniline, OH(-), and H(2)O suggest a possible formation of a Meisenheimer complex stabilized by hydrogen-bonding interactions and a six-membered ring structure. The results obtained here contrast with conventional S(N)Ar reactivity profiles in which nitroanilines are nearly unreactive with nucleophiles in organic solvents.     

Immobilization of folic acid on Eu3+-doped nanoporous silica spheres

Folic acid (FA) was immobilized on Eu(3+)-doped nanoporous silica spheres (Eu:NPSs) through mediation of the 3-aminopropyltriethoxysilane adlayer. The ordered nanopores of Eu:NPS were preserved by the immobilization. The FA-immobilized Eu:NPSs showed the characteristic photoluminescence peak due to interactions between the FA molecules and Eu(3+) ions, and highly dispersed stability in phosphate buffered saline.     

The CH/π hydrogen bond in chemistry. Conformation, supramolecules, optical resolution and interactions involving carbohydrates

The CH/π hydrogen bond is an attractive molecular force occurring between a soft acid and a soft base. Contribution from the dispersion energy is important in typical cases where aliphatic or aromatic CH groups are involved. Coulombic energy is of minor importance as compared to the other weak hydrogen bonds. The hydrogen bond nature of this force, however, has been confirmed by AIM analyses. The dual characteristic of the CH/π hydrogen bond is the basis for ubiquitous existence of this force in various fields of chemistry. A salient feature is that the CH/π hydrogen bond works cooperatively. Another significant point is that it works in nonpolar as well as polar, protic solvents such as water. The interaction energy depends on the nature of the molecular fragments, CH as well as π-groups: the stronger the proton donating ability of the CH group, the larger the stabilizing effect. This Perspective focuses on the consequence of this molecular force in the conformation of organic compounds and supramolecular chemistry. Implication of the CH/π hydrogen bond extends to the specificity of molecular recognition or selectivity in organic reactions, polymer science, surface phenomena and interactions involving proteins. Many problems, unsettled to date, will become clearer in the light of the CH/π paradigm.     

Difference equations arising from cluster algebras

Journal of Algebraic Combinatorics - We characterize Y/T-system-type difference equations arising from cluster algebras by triples of matrices, which we call T-data, that have a certain symplectic...     

Structural analysis of the c(4 × 2) reconstruction in Si(0 0 1) and Ge(0 0 1) surfaces by low-energy electron diffraction

The c(4 × 2) structures in (0 0 1) surfaces of Si and Ge have been studied by low-energy electron diffraction (LEED). Using a proper cleaning method for the Si surface, we were able to observe clear c(4 × 2) LEED patterns up to incident energy of ∼400 eV as well as the Ge surface. Extensive experimental intensity-voltage curves allowed us to optimize the asymmetric dimer model up to the eighth layer (including the dimer layer) in depth in the dynamical LEED calculation. Optimized structural parameters are almost the same for the Si and Ge except for the height of the buckled-up atom of the asymmetric dimer. For the Ge surface, the structural parameters are in excellent agreement with those obtained by a previous theoretical calculation. The tilt angle and bond length of the dimer are 18 ± 1 (19 ± 1)° and 2.4 ± 0.1 (2.5 ± 0.1) Å for the Si(0 0 1) (Ge(0 0 1)), respectively.     

James-Stein estimators for time series regression models

The least squares (LS) estimator seems the natural estimator of the coefficients of a Gaussian linear regression model. However, if the dimension of the vector of coefficients is greater than 2 and the residuals are independent and identically distributed, this conventional estimator is not admissible. James and Stein [Estimation with quadratic loss, Proceedings of the Fourth Berkely Symposium vol. 1, 1961, pp. 361-379] proposed a shrinkage estimator (James-Stein estimator) which improves the least squares estimator with respect to the mean squares error loss function. In this paper, we investigate the mean squares error of the James-Stein (JS) estimator for the regression coefficients when the residuals are generated from a Gaussian stationary process. Then, sufficient conditions for the JS to improve the LS are given. It is important to know the influence of the dependence on the JS. Also numerical studies illuminate some interesting features of the improvement. The results have potential applications to economics, engineering, and natural sciences.     

Adsorption behavior of metal ions onto a bovine serum albumin (BSA) membrane monitored by means of an electrode-separated piezoelectric quartz crystal.

The interaction between metal ions and bovine serum albumin (BSA) was studied by using a piezoelectric quartz crystal (PQC) arranged in the electrode-separated configuration. A silanized surface of the PQC was coated with a BSA membrane via a coupling reaction with glutaraldehyde. The frequency shifts obtained from PQC coated with a BSA membrane suggested that various kinds of metal ions could be adsorbed onto the BSA membrane from aqueous solutions containing a low concentration of metal ions (2 or 10 micromol dm(-3)), only when the BSA was denatured with an alkaline solution. Anionic species of Pt(IV) and Au(III) were adsorbed onto the denatured BSA membrane from an acetic acid solution at pH 2.2, and cationic species of Cd(II), Zn(II), Co(II), Ni(II), Cu(II), and Ag(I), and cations, such as Ca2+, Ba2+, and Mg2+, were adsorbed from ammonia buffer at pH 9.5, whereas Al(III), Cr(III), Fe(III), Hg(II), and Pb(II) were hardly adsorbed. The adsorption mechanisms of these metal ions are discussed, based on the electrostatic interaction between the metal ions and the denatured BSA membrane, and complex formation between the metal ions and amino acid residues of the denatured BSA. Further, the PQC coated with a denatured BSA membrane was applied to the determination of Pt and Cd, using large frequency shifts for Pt(IV) and Cd(II).