C-H...O hydrogen bonding in 4-phenyl-benzaldehyde: a comprehensive crystallographic, spectroscopic and computational study

The crystal structure of 4-phenyl-benzaldehyde reveals the presence of a dimer linked by the C=O and C( 9)-H groups of adjacent molecules. In the liquid phase, the presence of C-(HO)-O-... bonded forms is revealed by both vibrational and NMR spectroscopy. A Delta H value of - 8.2 +/- 0.5 kJ mol(-1) for the dimerisation equilibrium is established from the temperature-dependent intensities of the bands assigned to the carbonyl-stretching modes. The NMR data suggest the preferential engagement of the C(2,6)-H and C(10/12)/C(11)-H groups as hydrogen bond donors, instead of the C(9)-H group. While ab initio calculations for the isolated dimers are unable to corroborate these NMR results, the radial distribution functions obtained from molecular dynamics simulations show a preference for C(2,6)-H and C(10/12)/C(11)-(HO)-O-... contacts relative to the C(9)-(HO)-O-... ones.

Synthesis and crystal structure of the thiophene-3-acetonitrile complex fac-[Mo(CO)(3){NCCH2(C4H3S-3)}(3)]

Reaction of fac-[ Mo( CO)(3)( NCMe)(3)] with three equivalents of NCCH2(C4H3S- 3) in acetonitrile gives the tris(thiophene- 3- acetonitrile) complex, fac-[Mo(CO)(3){NCCH2(C4H3S-3)}(3)] (1) in 7% yield. Complex 1 crystallizes out in the orthorhombic space group Pnma with a = 12.714( 17), b = 16.41( 2), c = 11.304(16) Angstrom, Z = 4. The structure has crystallographic m symmetry and the metal is in an almost perfect octahedral environment, with a facial arrangement of carbonyl and thiophene- 3- acetonitrile groups. The thiophene rings are disordered.

Crystallization in poly(L-lactide)-b-poly(epsilon-caprolactone) double crystalline diblock copolymers: a study using X-ray scattering, differential scanning calorimetry, and polarized optical microscopy

The crystallization of well-defined poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers, PLLA-b-PCL, was investigated by time-resolved X-ray techniques, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). Two compositions were studied that contained 44 and 60 wt % poly(L-lactide), PLLA (they are referred to as (L44C5614)-C-11 and (L60C409)-C-12, respectively, with the molecular weight of each block in kg/mol as superscript). The copolymers were found to be initially miscible in the melt according to small-angle X-ray scattering measurements (SAXS). Their thermal behavior was also indicative of samples whose crystallization proceeds from a mixed melt. Sequential isothermal crystallization from the melt at 100 degreesC (for 30 min) and then at 30 degreesC (for 15 min) was measured. At 100 degreesC only the PLLA block is capable of crystallization, and its crystallization kinetics was followed by both WAXS and DSC; comparable results were obtained that indicated an instantaneous nucleation with three-dimensional superstructures (Avrami index of approximately 3). The spherulitic nature of the superstructure was confirmed by POM. When the temperature was decreased to 30 degreesC, the PCL block was able to crystallize within the PLLA negative spherulites (with an Avrami index of 2, as opposed to 3 in homo-PCL), and its crystallization rate was much slower than an equivalent homo-PCL. Time-resolved SAXS experiments in (L60C409)-C-12 revealed an initial melt mixed morphology at 165 degreesC that upon cooling transformed into a transient microphase-separated lamellar structure prior to crystallization at 100 degreesC.

Supramolecular hydrogen-bond structures and magnetic interactions in basal-apical, dinuclear, azide-bridged copper(II) complexes

The synthesis, characterisation, X-ray single crystal structures and magnetic properties of three new basal-apical mu(2)-1,1-azide-bridged complexes [(CuLN3)-N-1](2) (1), [(CuLN3)-N-2](2) (2) and [(CuLN3)-N-3](2) (3) with very similar tridentate Schiff-base blocking ligands {HL1 = N-[2-(ethylamino) ethyl] salicylaldimine; HL2 = 7-(ethylamino)-4-methyl-5-azahept-3-en-2-one; HL3 = 7-amino-4-methyl-5-azaoct-3-en-2-one} have been reported [complex 1: monoclinic, P2(1)/c, a = 8.390(2), b = 7.512(2), c = 19.822(6) Angstrom, beta = 91.45(5)degrees; complex 2: monoclinic, P2(1)/c, a = 8.070(9), b = 9.787(12), c = 15.743(17) A, beta = 98.467(10)degrees; complex 3: monoclinic, P2(1)/n, a = 5.884(7), b = 16.147(18), c = 11.901(12) Angstrom, beta = 90.050(10)degrees]. The structures consist of neutral dinuclear entities resulting from the pairing of two mononuclear units through end-on azide bridges connecting an equatorial position of one copper centre to an axial position of the other, The copper ions adopt a (4+1) square-based geometry in all the complexes. In complex 2, there is no inter-dimer hydrogen-bonding. However, complexes 1 and 3 form two different supramolecular structures in which the dinuclear entities are linked by H-bonds giving one-dimensional systems. Variable temperature (300-2 K) magnetic-susceptibility measurements and magnetisation measurements at 2 K reveal that all three complexes have antiferromagnetic coupling. Magneto-structural correlations have been made taking into consideration both the azido bridging ligands and the existence of intermolecular hydrogen bonds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Templated synthesis of the novel layered silver-antimony Sulfides [H3NCH2CH2NH2][Ag2SbS3] and [H3NCH2CH2NH2](2)[Ag5Sb3S8]

Two new silver-antimony sulfides, [C2H9N2][Ag2SbS3] (1) and [C2H9N2](2)[Ag5Sb3S8] (2), have been prepared solvothermally in the presence of ethylenediamine and characterized by single-crystal X-ray diffraction, thermogravimetry, and elemental analysis. Compound 1 crystallizes in the space group Pn (a = 6.1781(1) Angstrom, b =11.9491(3) Angstrom, c = 6.9239(2) Angstrom, =111.164(1)degrees) and 2 in the space group Pm (a = 6.2215(2) Angstrom, b = 15.7707(7) Angstrom, c = 11.6478(5) Angstrom, beta = 92.645(2)degrees). The structure of 1 consists of chains of fused five-membered Ag2SbS2 rings linked to form layers, between which the template molecules reside. Compound 2 contains honeycomb-like sheets of fused silver-antimony-sulfide six-membered rings linked to form double layers. The idealized structure can be considered to be an ordered defect derivative of that of lithium bismuthide, Li3Bi, and represents a new solid-state structure type.

Microglial activation correlates with severity in Huntington disease: a clinical and PET study

Background: Huntington disease ( HD) is characterized by the progressive death of medium spiny dopamine receptor bearing striatal GABAergic neurons. In addition, microglial activation in the areas of neuronal loss has recently been described in postmortem studies. Activated microglia are known to release neurotoxic cytokines, and these may contribute to the pathologic process. Methods: To evaluate in vivo the involvement of microglia activation in HD, the authors studied patients at different stages of the disease using [ C-11]( R)-PK11195 PET, a marker of microglia activation, and [ C-11] raclopride PET, a marker of dopamine D2 receptor binding and hence striatal GABAergic cell function. Results: In HD patients, a significant increase in striatal [ C-11]( R)-PK11195 binding was observed, which significantly correlated with disease severity as reflected by the striatal reduction in [ C-11] raclopride binding, the Unified Huntington's Disease Rating Scale score, and the patients' CAG index. Also detected were significant increases in microglia activation in cortical regions including prefrontal cortex and anterior cingulate. Conclusions: These [ C-11]( R)-PK11195 PET findings show that the level of microglial activation correlates with Huntington disease ( HD) severity. They lend support to the view that microglia contribute to the ongoing neuronal degeneration in HD and indicate that [ C-11]( R)-PK11195 PET provides a valuable marker when monitoring the efficacy of putative neuroprotecting agents in this relentlessly progressive genetic disorder.

DMP XV palaeohydrology and palaeoenvironment: initial results and report of 2010 and 2011 fieldwork

This paper reports the results of fieldwork conducted in the 2010 and 2011 DMP field seasons and of analysis of samples collected during these and previous years. Research has involved 1) studying palaeolake sediment outcrops, 2) using ground penetrating radar (GPR) to determine their extent under the Dahān Ubārī, and 3) coring palaeolakes in order to determine their palaeoenvironmental records. Research on these samples is continuing but some initial findings are discussed in this paper. The most extensive palaeolake sediments are found within the al-Mahruqah Formation and were deposited by a giant lake system that developed in the Fazzān Basin during past humid periods. Stratigraphic analysis of Lake Megafazzān sediments suggests two different sedimentary successions, a lake margin succession distinctive for its lacustrine and palaeosol carbonates, and a clastic-dominated, intensely rootleted, basin-centre succession which has terrestrial intervals (aeolian and palaeosols) as well as in the upper parts lacustrine limestones. Both basin margin and basin centre successions are underlain by fluvial deposits. Magnetostratigraphy suggests that the formation may be as old as the mid-Pliocene. After the Lake Megafazzān phase, smaller palaeolakes developed within the basin during subsequent humid periods. One of the largest is found in the Wādī al-Hayāt in the area between Jarma and Ubārī. Similar deposits further west along the Wādī at progressively higher altitudes are interpreted as small lakes and marshes fed by springs issuing from aquifers at the base of the escarpment, last replenished during the Holocene humid phase. Dating of sediments suggests that this was between c. 11 and c. 8 ka. The Wādī ash-Shāţī palaeolake core also provides a Holocene palaeoclimate record that paints a slightly different picture, indicating lake conditions until around 7 ka, whereupon it started oscillating until around 5.5 ka when sedimentation terminates. The reasons for the differences in these records are discussed.

Remarks concerning the double cascade as a necessary mechanism for the instability of steady equivalent-barotropic flows

n a recent paper, Petroniet al. claim that a necessary condition for the instability of two-dimensional steady flows is a «double cascade» of energy and enstrophy respectively to larger and to smaller scales of motion. It is shown here that the analytical reasoning employed by Petroniet al. is flawed and that their conclusions are incorrect. What is true is that in any scale interaction (whether an instability or not), neither energy nor enstrophy can be transferred in one spectral direction only, but this result is extremely well known.

Vegetation history, human impact and climate change during prehistory: an island perspective of the isles of Tiree, Coll and north-west Mull

Results of extensive site reconnaissance on the Isles of Tiree, Coll and north-west Mull, Inner Hebrides are presented. Pollen-stratigraphic records were compiled from a profile from Glen Aros, north-west Mull and from two profiles on Coll located at Loch an t-Sagairt and Caolas an Eilean. Quantification of microscopic charcoal provided records that were used to facilitate a preliminary evaluation of the causal driving mechanisms of vegetation change. Bayesian modelling of radiocarbon dates was used to construct preliminary chronological frameworks for these records. Basal sedimentary deposits at Glen Aros contain pollen records that correspond with vegetation succession typical of the early Holocene dating to c. 11,370 cal BP. Woodland development is a key feature of the pollen records dating to the early Holocene, while records from Loch an t-Sagairt show that blanket mire communities were widespread in north-west Coll by c. 9800 cal BP. The Corylus-rise is dated to c. 10,710 cal BP at Glen Aros and c. 9905 cal BP at Loch an t-Sagairt, with records indicating extensive cover of hazel woodland with birch. All of the major arboreal taxa were recorded, though Quercus and Ulmus were nowhere widespread. Analysis of wood charcoal remains from a Mesolithic site at Fiskary Bay, Coll indicate that Salix and Populus are likely to be under-represented in the pollen records. Reconstructed isopoll maps appear to underplay the importance of alder in western Scotland during the mid-Holocene. Alder-rise expansions in microscopic charcoal dating to c. 7300 cal BP at Glen Aros and c. 6510 to 5830 cal BP on Coll provide records of significance to the issue of human-induced burning related to the expansion of alder in Britain. Increasing frequencies in microscopic charcoal are correlated with mid-Holocene records of increasing aridity in western Scotland after c. 7490 cal BP at Glen Aros, 6760 cal BP at Loch an t-Sagairt and 6590 cal BP at Caolas an Eilean, while several phases of increasing bog surface wetness were detected in the Loch an t-Sagairt archive during the Holocene. At least five phases of small-scale woodland disturbance during the Mesolithic period were identified in the Glen Aros profile dating to c. 11,650 cal BP, 9300 cal BP, 7840 cal BP, 7040 cal BP and 6100 cal BP. The timing of the third phase is coincident with evidence of Mesolithic settlement at Creit Dhu, north-west Mull. Three phases of small-scale woodland disturbance were detected at Loch an t-Sagairt dating to c. 9270 cal BP, 8770 cal BP and 8270 cal BP, all of which overlap chronologically with evidence of Mesolithic activity at Fiskary Bay, Coll. A number of these episodes are aligned chronologically with phases of Holocene climate variability such as the 8.2 K event.

Dating WF16: exploring the chronology of a Pre-Pottery Neolithic A settlement in the Southern Levant

A pre-requisite for understanding the transition to the Neolithic in the Levant is the establishment of a robust chronology, most notably for the late Epi-Palaeolithic and Pre-Pottery Neolithic A (PPNA) periods. In this contribution we undertake a dating analysis of the Pre-Pottery Neolithic site of WF16, southern Jordan, drawing on a sample of 46 AMS 14C dates. We utilise Bayesian methods to quantify an old wood effect to provide an offset that we factor into chronological models for a number of individual structures at WF16 and for the settlement as a whole. In doing so we address the influence of slope variations in the calibration curve and expose the significance of sediment and sample redeposition within sites of this nature. We conclude that for the excavated deposits at WF16 human activity is likely to have started by c. 11.84 ka cal bp and lasted for at least c. 1590 years, ceasing by c. 10.24 ka cal bp. This is marked by a particularly intensive period of activity lasting for c. 350 years centred on 11.25 ka cal bp followed by less intensive activity lasting a further c. 880 years. The study reveals the potential of WF16 as a laboratory to explore methodological issues concerning 14C dating of early Neolithic sites in arid, erosional environments.

Novel supramolecular network in tri- and mono-nuclear oxovanadium(V)-salicyl-hydroximate: Synthesis, structure and catalytic oxidation of hydrocarbons using H2O2 as terminal oxidant

oxovanadium(V) salicylhydroximate complexes, [VO(SHA)(H2O)]center dot 1.58H(2)O (1) and [V3O3(CSHA)(3) (H2O)(3)]center dot 3CH(3)COCH(3) (2) have been synthesized by reaction of VO43- with N-salicyl hydroxamic acid (SHAHS) and N-(5-chlorosalicyl) hydroxamic acid (CSHAH(3)), respectively, in methanol medium. Compound 1 on reaction with pyridine 2,6-dicarboxylic acid (PyDCH2) yields mononuclear complex [VO(SHAH(2))(PyDC)] (3). Treatment of compound 3 with hydrogen peroxide at low pH (2-3) and low temperature (0-5 degrees C) yields a stable oxoperoxovanadium(V) complex H[VO(O-2)(PyDC)(H2O)]center dot 2.5H(2)O (4). All four complexes (1-4) have been characterized by spectroscopic (IR, UV-Vis, V-51 NMR) and single crystal X-ray analyses. Intermolecular hydrogen bonds link complex 1 into hexanuclear clusters consisting of six {VNO5} octahedra surrounded by twelve {VNO5} octahedra to form an annular ring. While the molecular packing in 2 generates a two-dimensional framework hydrogen bonds involving the solvent acetone molecules, the mononuclear complexes 3 and 4 exhibit three-dimensional supramolecular architecture. The compounds 1 and 2 behave as good catalysts for oxygenation of benzylic, aromatic, carbocyclic and aliphatic hydrocarbons to their corresponding hydroxylated and oxygenated products using H2O2 as terminal oxidant; the process affords very good yield and turnover number. The catalysis work shows that cyclohexane is a very easily oxidizable substrate giving the highest turnover number (TON) while n-hexane and n-heptane show limited yield, longer time involvement and lesser TON than other hydrocarbons. (C) 2008 Elsevier Ltd. All rights reserved.

Superacid-catalyzed polycondensation of acenaphthenequinone with aromatic hydrocarbons

A novel series of linear, high molecular weight polymers were synthesized by one-pot, superacid-catalyzed reaction of acenaphthenequinone (1) with aromatic hydrocarbons. The reactions were performed at room temperature in the Bronsted superacid CF3SO3H (trifluoromethanesulfonic acid, TFSA) and in a mixture of TFSA with methanesulfonic acid (MSA) and trifluoroacetic acid (TFA), which was used as both solvent and a medium for generation of electrophilic species from acenaphthenequinone. The polymer-forming reaction was found to be dependent greatly on the acidity of the reaction medium, as judged from the viscosity of the polymers obtained. Polycondensations of acenaphthenequinone with 4,4'-diphenoxybenzophenone (f), 1,3-bis(4-phenoxybenzoyl)benzene (g), 1,4-bis(4-phenoxybenzoyl)benzene (h), 1,10-bis(4-phenoxyphenyl)decane-1,10-dione (i), 2,6-diphenoxybenzonitrile), 2,6-diphenoxybenzoic acid (k), and 2-(4-biphenylyl)-6-phenylbenzoxazole (1) proceeded in a reaction medium of wide range of acidity, including pure TFSA (Hammett acidity function H-0 of pure TFSA is -14.1), whereas condensation of 1 with biphenyl, terphenyl, diphenyl ether, and 1,4-diphenoxybenzene needed a reaction medium of acidity H-0 less than -11.5. A possible reaction mechanism is suggested. The polymers obtained were found to be soluble in the common organic solvents, and flexible transparent films could be cast from the solutions. H-1 and C-13 NMR analyses of the polymers synthesized revealed their linear, highly regular structure. The polymers also possess high thermostability. Char yields for polymers 3a, 3c, 3d, and 3l in nitrogen were close to 80% at 1000 degrees C.