Self-assembled molecular complexes and coordination polymers of CdII, hexamine, and monocarboxylates: structural analysis and theoretical studies of supramolecular interactions

Four new cadmium(II) complexes [Cd-2(bz)(4)(H2O)(4)(mu 2-hmt)]center dot Hbz center dot H2O (1), [Cd-3(bz)(6)(H2O)(6)(mu 2-hmt)(2)]center dot 6H(2)O (2), [Cd(pa)(2)(H2O)(mu(2)-hmt)](n) (3), and {[Cd-3(ac)(6)(H2O)(3)(mu(3)-hmt)(2)]center dot 6H(2)O}(n) (4) with hexamine (hmt) and monocarboxylate ions, benzoate (bz), phenylacetate (pa), or acetate (ac) have been synthesized and characterized structurally. Structure determinations reveal that 1 is dinuclear, 2 is trinuclear, 3 is a one-dimensional (1D) infinite chain, and 4 is a two-dimensional (2D) polymer with fused hexagonal rings consisting of Cd-II and hmt. All the Cd-II atoms in the four complexes (except one CdII in 2) possess seven-coordinate pentagonal bipyramidal geometry with the various chelating bidentate carboxylate groups in equatorial sites. One of the CdII ions in 2, a complex that contains two monodentate carboxylates is in a distorted octahedral environment. The bridging mode of hmt is mu 2- in complexes 1-3 but is mu 3- in complex 4. In all complexes, there are significant numbers of H-bonds, C-H/pi, and pi-pi interactions which play crucial roles in forming the supramolecular networks. The importance of the noncovalent interactions in terms of energies and geometries has been analyzed using high level ab initio calculations. The effect of the cadmium coordinated to hmt on the energetic features of the C-H/pi interaction is analyzed. Finally, the interplay between C-H/pi and pi-pi interactions observed in the crystal structure of 3 is also studied.

The Spanish Ambassador and Samuel Daniel's Vision of the Twelve Goddesses: A New Document [with text]

The performance of Samuel Daniel's masque The Vision of the Twelve Goddesses at court on January 8, 1604 took place in the midst of the preliminary negotiations that would lead to the signing of the Anglo-Spanish peace at Somerset House the following August. Philip III sent a special ambassador to England to congratulate James on his accession, and a series of tussles between Juan de Tassis and his French counterpart ensued. As a recently-discovered document in the Archivo General de Simancas reveals, Anna of Denmark intervened personally to insure that de Tassis, and not the Frenchman, attended the masque. This was a clear signal of James and Anna's peace aims, which de Tassis conveyed to the King of Spain; moreover, he enclosed in his dispatch a text of Daniel's masque which he clearly considered both political intelligence and of interest to the theater-loving Hapsburg monarch. The Simancas text of the Daniel masque is a new version, hitherto unknown, which adds to our knowledge of the circumstances in which the first Stuart masque was performed. Here we present a transcription and annotated translation of both de Tassis' letter and the text of the masque he had compiled for Philip III. (B. C.-E. and M. H.)

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(III)/lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin- 3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III),U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UVabsorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO2 2+) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III)complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III)from Ln(III) by quadridentate N-donor ligands.

The influence of ozone precursor emissions from four world regions on tropospheric composition and radiative climate forcing

Ozone (O3) precursor emissions influence regional and global climate and air quality through changes in tropospheric O3 and oxidants, which also influence methane (CH4) and sulfate aerosols (SO42−). We examine changes in the tropospheric composition of O3, CH4, SO42− and global net radiative forcing (RF) for 20% reductions in global CH4 burden and in anthropogenic O3 precursor emissions (NOx, NMVOC, and CO) from four regions (East Asia, Europe and Northern Africa, North America, and South Asia) using the Task Force on Hemispheric Transport of Air Pollution Source-Receptor global chemical transport model (CTM) simulations, assessing uncertainty (mean ± 1 standard deviation) across multiple CTMs. We evaluate steady state O3 responses, including long-term feedbacks via CH4. With a radiative transfer model that includes greenhouse gases and the aerosol direct effect, we find that regional NOx reductions produce global, annually averaged positive net RFs (0.2 ± 0.6 to 1.7 ± 2 mWm−2/Tg N yr−1), with some variation among models. Negative net RFs result from reductions in global CH4 (−162.6 ± 2 mWm−2 for a change from 1760 to 1408 ppbv CH4) and regional NMVOC (−0.4 ± 0.2 to −0.7 ± 0.2 mWm−2/Tg C yr−1) and CO emissions (−0.13 ± 0.02 to −0.15 ± 0.02 mWm−2/Tg CO yr−1). Including the effect of O3 on CO2 uptake by vegetation likely makes these net RFs more negative by −1.9 to −5.2 mWm−2/Tg N yr−1, −0.2 to −0.7 mWm−2/Tg C yr−1, and −0.02 to −0.05 mWm−2/Tg CO yr−1. Net RF impacts reflect the distribution of concentration changes, where RF is affected locally by changes in SO42−, regionally to hemispherically by O3, and globally by CH4. Global annual average SO42− responses to oxidant changes range from 0.4 ± 2.6 to −1.9 ± 1.3 Gg for NOx reductions, 0.1 ± 1.2 to −0.9 ± 0.8 Gg for NMVOC reductions, and −0.09 ± 0.5 to −0.9 ± 0.8 Gg for CO reductions, suggesting additional research is needed. The 100-year global warming potentials (GWP100) are calculated for the global CH4 reduction (20.9 ± 3.7 without stratospheric O3 or water vapor, 24.2 ± 4.2 including those components), and for the regional NOx, NMVOC, and CO reductions (−18.7 ± 25.9 to −1.9 ± 8.7 for NOx, 4.8 ± 1.7 to 8.3 ± 1.9 for NMVOC, and 1.5 ± 0.4 to 1.7 ± 0.5 for CO). Variation in GWP100 for NOx, NMVOC, and CO suggests that regionally specific GWPs may be necessary and could support the inclusion of O3 precursors in future policies that address air quality and climate change simultaneously. Both global net RF and GWP100 are more sensitive to NOx and NMVOC reductions from South Asia than the other three regions.

SANS/WANS time-resolving neutron scattering studies of polymer phase transitions using NIMROD

We use new neutron scattering instrumentation to follow in a single quantitative time-resolving experiment, the three key scales of structural development which accompany the crystallisation of synthetic polymers. These length scales span 3 orders of magnitude of the scattering vector. The study of polymer crystallisation dates back to the pioneering experiments of Keller and others who discovered the chain-folded nature of the thin lamellae crystals which are normally found in synthetic polymers. The inherent connectivity of polymers makes their crystallisation a multiscale transformation. Much understanding has developed over the intervening fifty years but the process has remained something of a mystery. There are three key length scales. The chain folded lamellar thickness is ~ 10nm, the crystal unit cell is ~ 1nm and the detail of the chain conformation is ~ 0.1nm. In previous work these length scales have been addressed using different instrumention or were coupled using compromised geometries. More recently researchers have attempted to exploit coupled time-resolved small-angle and wide-angle x-ray experiments. These turned out to be challenging experiments much related to the challenge of placing the scattering intensity on an absolute scale. However, they did stimulate the possibility of new phenomena in the very early stages of crystallisation. Although there is now considerable doubt on such experiments, they drew attention to the basic question as to the process of crystallisation in long chain molecules. We have used NIMROD on the second target station at ISIS to follow all three length scales in a time-resolving manner for poly(e-caprolactone). The technique can provide a single set of data from 0.01 to 100Å-1 on the same vertical scale. We present the results using a multiple scale model of the crystallisation process in polymers to analyse the results.

The effects of flavonoid and other polyphenol consumption on cognitive performance: A systematic research review of human experimental and epidemiological studies

Literature reviews suggest flavonoids, a sub-class of polyphenols, are beneficial for cognition. This is the first review examining the effect of consumption of all polyphenol groups on cognitive function. Inclusion criteria were polyphenol vs. control interventions and epidemiological studies with an objective measure of cognitive function. Participants were healthy or mildly cognitively impaired adults. Studies were excluded if clinical assessment or diagnosis of Alzheimer’s disease, dementia, or cognitive impairment was the sole measure of cognitive function, or if the polyphenol was present with potentially confounding compounds such as caffeine (e.g. tea studies) or Ginkgo Biloba. 28 studies were identified; 4 berry juice studies, 4 cocoa studies, 13 isoflavone supplement studies, 3 other supplement studies, and 4 epidemiological surveys. Overall, 16 studies reported cognitive benefits following polyphenol consumption. Evidence suggests that consuming additional polyphenols in the diet can lead to cognitive benefits, however, the observed effects were small. Declarative memory and particularly spatial memory appear most sensitive to polyphenol consumption and effects may differ depending on polyphenol source. Polyphenol berry fruit juice consumption was most beneficial for immediate verbal memory, whereas isoflavone based interventions were associated with significant improvements for delayed spatial memory and executive function. Comparison between studies was hampered by methodological inconsistencies. Hence, there was no clear evidence for an association between cognitive outcomes and polyphenol dose response, duration of intervention, or population studied. In conclusion, however, the findings do imply that polyphenol consumption has potential to benefit cognition both acutely and chronically.