Annular tautomerism: experimental observations and quantum mechanics calculations

The use of MP2 level quantum mechanical (QM) calculations on isolated heteroaromatic ring systems for the prediction of the tautomeric propensities of whole molecules in a crystalline environment was examined. A Polarisable Continuum Model was used in the calculations to account for environment effects on the tautomeric relative stabilities. The calculated relative energies of tautomers were compared to relative abundances within the Cambridge Structural Database (CSD) and the Protein Data Bank (PDB). The work was focussed on 84 annular tautomeric forms of 34 common ring systems. Good agreement was found between the calculations and the experimental data even if the quantity of these data was limited in many cases. The QM results were compared to those produced by much faster semiempirical calculations. In a search for other sources of the useful experimental data, the relative numbers of known compounds in which prototropic positions were often substituted by heavy atoms were also analysed. A scheme which groups all annular tautomeric transformations into 10 classes was developed. The scheme was designed to encompass a comprehensive set of known and theoretically possible tautomeric ring systems generated as part of a previous study. General trends across analogous ring systems were detected as a result. The calculations and statistics collected on crystallographic data as well as the general trends observed should be useful for the better modelling of annular tautomerism in the applications such as computer-aided drug design, small molecule crystal structure prediction, the naming of compounds and the interpretation of protein—small molecule crystal structures.     

A 2:1 sulfamethazine–theophylline cocrystal exhibiting two tautomers of sulfamethazine

In the title cocrystal, 4‐amino‐N‐(4,6‐dimethylpyrimidin‐2‐yl)benzenesulfonamide–4‐amino‐N‐(4,6‐dimethyl‐1,2‐dihydropyrimidin‐2‐ylidene)benzenesulfonamide–1,3‐dimethyl‐7H‐purine‐2,6‐dione (1/1/1), C₇H₈N₄O₂·2C₁₂H₁₄N₄O₂S, two sulfamethazine molecules cocrystallize with a single molecule of theophylline. Each molecule of sulfamethazine forms a hydrogen‐bonded ribbon along the b axis crosslinked by further hydrogen bonding. The two sulfamethazine molecules exhibit a hydrogen‐shift isomerization so that the crystal structure contains both tautomeric forms. Calculation of their relative energies showed that the tautomer protonated at the chain N atom is considerably more stable than the one where an N atom in the aromatic ring is protonated. The latter, here observed for the first time, is stabilized through strong intermolecular interactions with the theophylline molecules.     

Photosynthetic light-harvesting is tuned by the heterogeneous polarizable environment of the protein

In photosynthesis, special antenna proteins that contain multiple light-absorbing molecules (chromophores) are able to capture sunlight and transfer the excitation energy to reaction centers with almost 100% quantum efficiencies. The critical role of the protein scaffold in holding the appropriate arrangement of the chromophores is well established and can be intuitively understood given the need to keep optimal dipole-dipole interactions between the energy-transferring chromophores, as described by Fo?rster theory more than 60 years ago. However, the question whether the protein structure can also play an active role by tuning such dipole-dipole interactions has not been answered so far, its effect being rather crudely described by simple screening factors related to the refractive index properties of the system. Here, we present a combined quantum chemical/molecular mechanical approach to compute electronic couplings that accounts for the heterogeneous dielectric nature of the protein-solvent environment in atomic detail. We apply the method to study the effect of dielectric heterogeneity in the energy migration properties of the PE545 principal light-harvesting antenna of the cryptomonad Rhodomonas CS24. We find that dielectric heterogeneity can profoundly tune by a factor up to ～4 the energy migration rates between chromophore sites compared to the average continuum dielectric view that has historically been assumed. Our results indicate that engineering of the local dielectric environment can potentially be used to optimize artificial light-harvesting antenna systems.     

"Covalent hydration" reactions in model monomeric Ru 2,2'-bipyridine complexes: thermodynamic favorability as a function of metal oxidation and overall spin states

Density functional theory (DFT) has been used to investigate the plausibility of water addition to the simple mononuclear ruthenium complexes, [(NH(3))(3)(bpy)Ru═O](2+/3+) and [(NH(3))(3)(bpy)RuOH](3+), in which the OH fragment adds to the 2,2'-bipyridine (bpy) ligand. Activation of bpy toward water addition has frequently been postulated within the literature, although there exists little definitive experimental evidence for this type of "covalent hydration". In this study, we examine the energetic dependence of the reaction upon metal oxidation state, overall spin state of the complex, as well as selectivity for various positions on the bipyridine ring. The thermodynamic favorability is found to be highly dependent upon all three parameters, with free energies of reaction that span favorable and unfavorable regimes. Aqueous addition to [(NH(3))(3)(bpy)Ru═O](3+) was found to be highly favorable for the S = 1/2 state, while reduction of the formal oxidation state on the metal center makes the reaction highly unfavorable. Examination of both facial and meridional isomers reveals that when bipyridine occupies the position trans to the ruthenyl oxo atom, reactivity toward OH addition decreases and the site preferences are altered. The electronic structure and spectroscopic signatures (EPR parameters and simulated spectra) have been determined to aid in recognition of "covalent hydration" in experimental systems. EPR parameters are found to uniquely characterize the position of the OH addition to the bpy as well as the overall spin state of the system.     

Least-squares linear estimation of signals from observations with Markovian delays

The least-squares linear estimation of signals from randomly delayed measurements is addressed when the delay is modeled by a homogeneous Markov chain. To estimate the signal, recursive filtering and fixed-point smoothing algorithms are derived, using an innovation approach, assuming that the covariance functions of the processes involved in the observation equation are known. Recursive formulas for filtering and fixed-point smoothing error covariance matrices are obtained to measure the goodness of the proposed estimators.     

Best Proximity Pair Results for Relatively Nonexpansive Mappings in Geodesic Spaces

Given A and B two nonempty subsets in a metric space, a mapping T: A ∪ B → A ∪ B is relatively nonexpansive if d(Tx, Ty) ≤ d(x, y) for every x ∈ A, y ∈ B. A best proximity point for such a mapping is a point x ∈ A ∪ B such that d(x, Tx) = dist(A, B). In this work, we extend the results given in Eldred et al. (2005) [A.A. Eldred, W.A. Kirk, P. Veeramani, Proximal normal structure and relatively nonexpansive mappings, Studia Math. 171, 283–293] for relatively nonexpansive mappings in Banach spaces to more general metric spaces. Namely, we give existence results of best proximity points for cyclic and noncyclic relatively nonexpansive mappings in the context of Busemann convex reflexive metric spaces. Moreover, particular results are proved in the setting of CAT(0) and uniformly convex geodesic spaces. Finally, we show that proximal normal structure is a sufficient but not necessary condition for the existence in A × B of a pair of best proximity points.     

Structural and H2 sorption properties of MgH2�C10?wt%ZrCrM (M?=?Cu, Ni) nano-composites

Magnesium and its hydride MgH₂ are widely regarded as promising candidates for hydrogen storage materials due to its benefits of high gravimetric and volumetric capacity, excellent reversibility, abundance in the earth and a low cost. Much attention has been paid to improve its absorption/desorption kinetics, trying to make it useful for practical applications. To make composite of MgH₂ with other hydrogen storage compounds is an effective method to improve the hydrogen storage properties. In this study nano-composite of MgH₂ with ZrCrCu alloy was prepared using high energy ball-milling for 5 h under Ar atmosphere. Microstructure and morphology of the composites were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM). XRD patterns show that no alloy formation between MgH₂ and elements of the alloys takes place during milling. Different morphology of the powders as-milled and after cycling was observed by SEM. Pressure?Ccomposition isotherms of these composites have been obtained in the pressure range 0.1?C10 bar at 275 and 300 °C. The absorption/desorption kinetics data have been analyzed using pressure 0.1?C5.0 bar at 275 and 300 °C to understand the mechanism of the hydriding/dehydriding reaction processes. A comparison of these results has been attempted with our previous published results of MgH₂?C10 wt%ZrCrNi in order to find the better composite for storage applications. It is observed by DSC curves that the onset temperature of hydrogen desorption is decreased for MgH₂?C10%ZrCrNi in comparison to MgH₂ which further decreased for MgH₂?C10%ZrCrCu. However, little loss in hydrogen absorption/desorption capacity is also observed for ZrCrCu composite in comparison to that of ZrCrNi composite.     

Poly(γ‐glutamic acid) esters with reactive functional groups suitable for orthogonal conjugation strategies

We report on a series of novel poly(γ‐glutamic acid) (PGGA) esters, in which the chemical structure and composition, and the molecular weight are systematically changed. Modification of PGGA of microbial origin, used either as the sodium salt or in the free acid form, by means of alkylation with highly reactive bromides under S_N2 conditions, affords copolymers with an essentially random microstructure. These reaction conditions are applied iteratively to achieve full esterification, obtaining allyl or propargyl ester functionalities within the polymer backbone, diluted with inert functional groups, such as benzyl, ethyl, or hexyl ester functionalities. The copolymers have been characterized regarding their chemical structure and thermal and bulk properties using nuclear magnetic resonance, thermogravimetry, differential scanning calorimetry, and X‐ray diffraction techniques. We demonstrate that allyl and propargyl ester groups can be efficiently transformed using click chemistries, such as thiol‐ene or copper(I)‐catalyzed azide–alkyne cycloaddition reactions; such efficient conjugation strategies will be required to transform the native bacterial biopolymer into a material with tailored properties for bulk scale or biomedical applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Fused hexacyclic tin compounds derived from 3-(3,5-di-t-butyl-2-hydroxy-phenylimino)-3H-phenoxazin-2-ol

The template synthesis of two tin compounds [N→Sn] 3-(2-oxo-phenylimino)-3H-phenoxazin-2-oxo-dimethyltin (1) and [N→Sn] 3-(2-oxo-phenylimino)-3H-phenoxazin-2-oxo-diphenyltin (2) is reported. The compounds are fused delocalized planar hexacyclic systems bearing a pentacoordinated diorganyl tin. They were identified by NMR, IR, TOF mass spectra and, for compound 1, by X-ray diffraction analysis.