Annulation of furan-bridged 10-membered rings on N-heterocycles through [8+2] cycloaddition of dienylazaisobenzofurans and dimethyl acetylenedicarboxylate

One-pot three-component coupling of o-alkynylheteroaryl carbonyl derivatives with α,β-unsaturated Fischer carbene complexes and dimethyl acetylenedicarboxylate leading to the synthesis of heterocyclic analogues of furanophane derivatives has been explored. This involves the generation of conformationally flexible dienylazaisobenzofuran intermediate as transient intermediates, which undergo [8+2] cycloaddition reaction with dienophile. In some cases, this intermediate undergoes twofold Diels-Alder reaction to afford heterolignan derivatives in a single step.     

Unexpected influence of stereochemistry on the cytotoxicity of highly efficient Ti(IV) salan complexes: new mechanistic insights

The effect of stereochemistry on the cytotoxicity of highly active and hydrolytically stable N-methylated Ti(IV) salan complexes is reported. Four bis(isopropoxo) complexes incorporating N-methylated salan ligands with different aromatic substitution patterns have been prepared in racemic and optically active forms for the first time by ligand-to-metal chiral induction from trans-diaminocyclohexyl-based chiral ligands. The configuration of the metal center that derives from that of the ligand has an enormous influence on cytotoxicity, with the racemic mixture mostly being more active than the single enantiomers that are of either similar or different activity. This implies that the active species is a salan-bound heterochiral polynuclear compound, interacting with a chiral target. Four additional complexes of achiral salan and chiral labile sec-butoxo ligands, analyzed as racemic and as homochiral, revealed no influence of stereochemistry, supporting early dissociation of the labile ligands to give the polynuclear products.     

Different ortho and para electronic effects on hydrolysis and cytotoxicity of diamino bis(phenolato) "salan" Ti(IV) complexes

Bis(isopropoxo) Ti(IV) complexes of diamino bis(phenolato) "salan" ligands were prepared, their hydrolysis in 1:9 water/THF solutions was investigated, and their cytotoxicity toward colon HT-29 and ovarian OVCAR-1 cells was measured. In particular, electronic effects at positions ortho and para to the binding phenolato unit were analyzed. We found that para substituents of different electronic features, including Me, Cl, OMe, and NO(2), have very little influence on hydrolysis rate, and all para-substituted ortho-H complexes hydrolyze slowly to give O-bridged clusters with a t(1/2) of 1-2 h for isopropoxo release. Consequently, no clear cytotoxicity pattern is observed as well, where the largest influence of para substituents appears to be of a steric nature. These complexes exhibit IC(50) values of 2-18 μM toward the cells analyzed, with activity which is mostly higher than those of Cp(2)TiCl(2), (bzac)(2)Ti(OiPr)(2) and cisplatin. On the contrary, major electronic effects are observed for substituents at the ortho position, with an influence that exceeds even that of steric hindrance. Ortho-chloro or -bromo substituted compounds possess extremely high hydrolytic stability where no major isopropoxo release as isopropanol occurs for days. In accordance, very high cytotoxicity toward colon and ovarian cells is observed for ortho-Cl and -Br complexes, with IC(50) values of 1-8 μM, where the most cytotoxic complexes are the ortho-Cl-para-Me and ortho-Br-para-Me derivatives. In this series of ortho-substituted complexes, the halogen radius is of lesser influence both on hydrolysis and on cytotoxicity, while OMe substituents do not impose similar effect of hydrolytic stability and cytotoxicity enhancement. Therefore, hydrolytic stability and cytotoxic activity are clearly intertwined, and thus this family of readily available Ti(IV) salan complexes exhibiting both features in an enhanced manner is highly attractive for further exploration.     

Structural and spectroscopic study of the Br2...3-Br-pyridine complex by DFT calculations

The structure and the Raman vibrational spectrum of the complex Br(2)...3-Br-pyridine are determined by DFT calculations using different parametrizations. The calculations are performed taking into account the effects of the dichloromethane as solvent by the CPCM method. A value of 39 kJ mol(-1) for the formation enthalpy and of 1 kJ mol(-1) for the formation free energy at room temperature in presence of the solvent is found. The predicted Raman spectrum is compared with the experimental one and the essential features of the spectrum are well reproduced by the B3LYP parametrization. The intensity changes of the bands when going from the free moieties to the complex are also generally correctly predicted by the theoretical treatment.     

Ab initio study of lithiated N-methylpyridones

Ab initio calculations were performed on the N-methylpyridones lithiated on the aromatic ring using a 6-31G* basis set. Whenever the lithium atom is on a carbon adjacent to the carbonylic group, a bridged structure is obtained where lithium is coordinated to both carbon and oxygen; these structures are the most stable isomers. © 1996 John Wiley & Sons, Inc.     

On the solutions of a singular elliptic equation concentrating on two orthogonal spheres

Let \({A=\{x\in \mathbb{R}^{2m}: 0 < a < |x| < b\}}\) be an annulus. We consider the following singularly perturbed elliptic problem on A $$\left\{\begin{array}{lll}-\varepsilon ^2{\Delta u} + |x|^{\eta}u =|x|^{\eta}u^p, \quad {\rm in} A,\\ u > 0, \quad \quad \quad \quad \quad \quad \quad {\rm in} A, \\ u=0, \quad \quad \quad \quad \quad \quad \quad {\rm on}\partial A,\end{array}\right. $$ where \({1 < p < \frac{m+3}{m-1}}\) . We shall prove the existence of a positive solution \({u_\epsilon }\) which concentrates on two different orthogonal spheres of dimension (m?1) as \({\varepsilon \to 0}\) . We achieve this by studying a reduced problem on an annular domain in \({\mathbb{R}^{m+1}}\) and analysing the profile of a two point concentrating solution in this domain.     

The reductive perturbation method and the Korteweg-de Vries hierarchy

By using the reductive perturbation method of Taniuti with the introduction of an infinite sequence of slow time variables ₁, ₃, ₅, ..., we study the propagation of long surface-waves in a shallow inviscid fluid. The Korteweg-de Vries (KdV) equation appears as the lowest order amplitude equation in slow variables. In this context, we show that, if the lowest order wave amplitude ₀ satisfies the KdV equation in the time ₃, it must satisfy the (2n+1)th order equation of the KdV hierarchy in the time _n+1, withn=2,3,4, ... As a consequence of this fact, we show with an explicit example that the secularities of the evolution equations for the higher-order terms ( ₁, ₂, ...) of the amplitude can be eliminated when ₀ is a solitonic solution to the KdV equation. By reversing this argument, we can say that the requirement of a secular-free perturbation theory implies that the amplitude ₀ satisfies the (2n+ 1)th order equation of the KdV hierarchy in the time _2n+1. This essentially means that the equations of the KdV hierarchy do play a role in perturbation theory. Thereafter, by considering a solitary-wave solution, we show, again with an explicit, example that the elimination of secularities through the use of the higher order KdV hierarchy equations corresponds, in the laboratory coordinates, to a renormalization of the solitary-wave velocity. Then, we conclude that this procedure of eliminating secularities is closely related to the renormalization technique developed by Kodama and Taniuti.     

Self‐Assembly of Amphiphilic Nanocrystals

Amphiphilic hybrid materials are formed from polymer‐coated semiconductor nanoparticles that simulate a surfactant‐like response (see picture). The strength and density of the surface coating are the key assembling forces driving a transition from single particles to cylindrical or vesicular superstructures.

     

Infusion of Variable Chemical Structure to Tune Stacking among Metal-Organic Layers in 2D Nano MOF

Thickness of two-dimensional (2D) metal-organic frameworks (MOFs) govern their intriguing functionalities. Primarily this thickness is controlled by the stacking between the metal-organic layers (MOL). It is observed that until now such modulating factors for stacking efficiency of MOL are not well studied. Here, we report a fundamental hypothesis to comprehend regulation of stacking efficiency among MOLs as a function of chemical structure of organic ligands (dicarboxylic acids and pillar linkers). This basically involves a series of isostructural three-dimensional (3D) MOFs which contain linkers of variable chemical nature that could be depillared to generate 2D stacked MOFs of different thickness. Depending on the linkers, we encountered the formation of single MOL to stacked multiple MOLs as evidenced from atomic force microscopic and other experimental analysis. The present study gives a concrete correlation between the stacking within 2D MOFs (from monolayer to multilayers), and their 3D counter parts, which may provide a thickness tuning pathway for 2D MOFs.     

Large Deviations for Stochastic Nematic Liquid Crystals Driven by Multiplicative Gaussian Noise

Potential Analysis - We study a stochastic two-dimensional nematic liquid crystal model with multiplicative Gaussian noise. We prove the Wentzell-Freidlin type large deviations principle for the...