Iron complexes of the Schiff base ligand bis(2,5-dihydroxyacetophenone) ethylenediamine

Summary Iron complexes of the tetradentate ligand, bis(2,5-dihydroxyacetophenone) ethylenediamine, and a fifth anionic ligand have been prepared and characterized by spectroscopic techniques. E.p.r. studies of the X-band frozen DMF solution reveal the presence of a broad, g ca. 4.0, signal with weak features at lower fields. The complexes exhibit a broad visible band with _max in the 550–605 nm range which is assigned to the phenolate Fe charge transfer transition. The LMCT band energy varies with the anionic ligand, namely, N ₃ ^- > Bz^- > HCOO^- > Cl^- > ClO ₄ ^- (Bz^- = benzimidazole anion), similar to the behaviour of dioxygenases and proteins containing tyrosine coordinated to iron.     

T3P catalyzed one pot three-component synthesis of 2,3-disubstituted 3H-quinazolin-4-ones

An efficient methodology for the synthesis of 2,3-disubstituted 3H-quinazolin-4-ones is described via one-pot three component reaction from anthranilic acid using T3P as catalyst. Mild reaction conditions, short reaction time, broad functional group tolerance, easy isolation of products and good yields are main advantages of this protocol.     

Theoretical and experimental characterization of amino‐PEG‐phosphonate‐terminated Polyphosphorhydrazone dendrimers: Influence of size and PEG capping on cytotoxicity profiles

The synthesis of new series of PPH (poly(phosphorhydrazone)) dendrimers with amino‐PEG phosphonates or the corresponding amino‐PEG phosphonic acids as terminal groups is presented, from generations 1–3. The size of PEG‐terminated dendrimers is experimentally measured by diffusional NMR, and by means of dynamic light scattering. Classical molecular dynamics and well‐tempered metadynamics simulations are used to assess or confirm the formation of aggregates in some cases. The influence of PEG capping on the cytotoxicity profiles of the dendrimers is evaluated on human peripheral blood mononuclear cells by means of LIVE/DEAD assays, and confirms the importance of PEG capping to ensure low cytotoxicity. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 761–774     

Vanadium complexes with thiosemicarbazones: Synthesis,characterization, crystal structures and anti-Mycobacterium tuberculosis activity

The development of more efficient anti-tuberculosis drugs is of interest. Three oxovanadium(IV) and three cis-dioxovanadium(V) complexes with thiosemicarbazone derivatives bearing moieties with different lipophilicity have been prepared and had their inhibitory activity against Mycobacteriumtuberculosis H₃₇Rv ATCC 27294 evaluated. The analytical methods used by the complexes’ characterization included IR, EPR, ¹H, ¹³C and ⁵¹V NMR spectroscopies, elemental analysis, cyclic voltammetry, magnetic susceptibility measurement and single crystal X-ray diffractometry. [VO(acac)(aptsc)], [VO(acac)(apmtsc)] and [VO(acac)(apptsc)] (acac = acetylacetonate; Haptsc = 2-acetylpyridinethiosemicarbazone; Hapmtsc = 2-acetylpyridine-N(4)-methyl-thiosemicarbazone and Happtsc = 2-acetylpyridine-N(4)-phenyl-thiosemicarbazone) are paramagnetic and their EPR spectra are consistent with the monoanionic N,N,S-tridentate coordination of the thiosemicarbazone ligands, resulting in octahedral structures of rhombic symmetry and with the oxidation state +IV for the vanadium atom. As result of oxidation of the vanadium(IV) complexes above, the diamagnetic cis-dioxovanadium(V) complexes [VO₂(aptsc)], [VO₂(apmtsc)] and [VO₂(apptsc)] are formed. Their ¹H, ¹³C and ⁵¹V NMR spectra were acquired and support a distorted square pyramidal geometry for them, in accord with the solid state X-ray structures determined for [VO₂(aptsc)] and [VO₂(apmtsc)]. In general, the vanadium compounds show comparable or larger anti-M. tuberculosis activities than the free thiosemicarbazone ligands, with MIC values within 62.5–1.56 (μg/mL).     

Reconstructing reactivity in dynamic host–guest systems at atomistic resolution: amide hydrolysis under confinement in the cavity of a coordination cage

Spatial confinement is widely employed by nature to attain unique efficiency in controlling chemical reactions. Notable examples are enzymes, which selectively bind reactants and exquisitely regulate their conversion into products. In an attempt to mimic natural catalytic systems, supramolecular metal–organic cages capable of encapsulating guests in their cavity and of controlling/accelerating chemical reactions under confinement are attracting increasing interest. However, the complex nature of these systems, where reactants/products continuously exchange in-and-out of the host, makes it often difficult to elucidate the factors controlling the reactivity in dynamic regimes. As a case study, here we focus on a coordination cage that can encapsulate amide guests and enhance their hydrolysis by favoring their mechanical twisting towards reactive molecular configurations under confinement. We designed an advanced multiscale simulation approach that allows us to reconstruct the reactivity in such host–guest systems in dynamic regimes. In this way, we can characterize amide encapsulation/expulsion in/out of the cage cavity (thermodynamics and kinetics), coupling such host–guest dynamic equilibrium with characteristic hydrolysis reaction constants. All computed kinetic/thermodynamic data are then combined, obtaining a statistical estimation of reaction acceleration in the host–guest system that is found in optimal agreement with the available experimental trends. This shows how, to understand the key factors controlling accelerations/variations in the reaction under confinement, it is necessary to take into account all dynamic processes that occur as intimately entangled in such host–guest systems. This also provides us with a flexible computational framework, useful to build structure–dynamics–property relationships for a variety of reactive host–guest systems.

Encapsulation of guests in metal–organic cages allows control over chemical reactivity. Focusing on the hydrolysis of amides, here we show an effective molecular simulation approach to reconstruct reactivity in host–guest systems in dynamic regimes.     

Static Response of Composite Circular Cylindrical Shells Studied by Different Theories

A detailed study, on the static response of cross-ply laminated composite circular cylindrical shell of revolution and shell panel with various support conditions, has been made using Levy type of solution and the classical shell theories of FlSanders, Love and Donnell in an unified form. It has been shown that while developing a Levy type of solution using aforementioned theories, certain difficulty is encountered for determining the particular integral in respect of Fl Sanders and Love theories. This difficulty has been overcome by making use of the membrane solution as a particular integral. A comparative study has been carried out using the above shell theories for different geometrical parameters, lamination schemes and support conditions. It has been shown that Donnell theory predicts inaccurate results for certain lamination schemes, support conditions and geometrical parameters of the shell. It is suggested that, for developing shear deformation shell theories, it would be better to use a more accurate shell theory like Flügge Sommario. La risposta statica di gusci cilindrici circolari di materiale composito laminato, a strati incrociati, e di pannelli con varie condizioni di supporto viene analizzata utilizzando in una forma unificata soluzioni tipo Levy e le classiche teorie dei gusci di Flügge Sanders, Love e Donnell. Si mostra che nello sviluppare una soluzione di tipo Levy si incontra una certa difficoltà nel determinare l'integrale particolare rispetto alle teorie di Flügge, Sanders e Love. Tale difficoltà viene superata usando la soluzione di membrana come integrale particolare. Viene sviluppato uno studio comparativo facendo uso delle suddette teorie dei gusci per differenti parametri geometrici, schemi di laminazione e condizioni di vincolo. Si mostra che la teoria di Donnell fornisce risultati non accurati per certi schemi di laminazione, condizioni di supporto e parametri geometrici del guscio. Si suggerisce che per sviluppare teorie dei gusci che tengano conto delle deformazioni di scorrimento sarebbe più opportuno l'uso di una teoria dei gusci più accurata come ad esempio quella di Flügge.     

Ultracold atoms in a tunable optical kagome lattice

We realize a two-dimensional kagome lattice for ultracold atoms by overlaying two commensurate triangular optical lattices generated by light at the wavelengths of 532 and 1064 nm. Stabilizing and tuning the relative position of the two lattices, we explore different lattice geometries including a kagome, a one-dimensional stripe, and a decorated triangular lattice. We characterize these geometries using Kapitza-Dirac diffraction and by analyzing the Bloch-state composition of a superfluid released suddenly from the lattice. The Bloch-state analysis also allows us to determine the ground-state distribution within the superlattice unit cell. The lattices implemented in this work offer a near-ideal realization of a paradigmatic model of many-body quantum physics, which can serve as a platform for future studies of geometric frustration.