Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in Ni-II and Cu-II complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]center dot 2H(2)O (1) of mono-condensed tridentate Schiff base ligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the Nil, as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)(2)center dot 4H(2)O furnishing the complex [NiL(NCS)] (2) and with CuCl2 center dot 2H(2)O in the presence of NaN3 or NH4SCN producing [CuL(N-3)](2) (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)(2)center dot 6H(2)O and Cu(NO3)(2)center dot 3H(2)O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)(2)center dot 6H(2)O or Ni(NO3)(2)center dot 6H(2)O to yield [Ni(hap)(2)] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, Ni-II possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around Cu-II in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around Cu-II is square pyramidal. In both 5 and 6, the Cu-II atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine ando-hydroxyacetophenone in NiII and CuII Complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]·2H2O (1) of mono-condensed tridentate Schiff baseligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the NiII as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)2·4H2O furnishing the complex [NiL(NCS)] (2) and with CuCl2·2H2O in the presence of NaN3 or NH4SCN producing [CuL(N3)]2 (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)2·6H2O and Cu(NO3)2·3H2O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)2·6H2O or Ni(NO3)2·6H2O to yield [Ni(hap)2] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, NiII possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around CuII in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around CuII is square pyramidal. In both 5 and 6, the CuII atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks.

Mono-aqua-bridged dinuclear complexes of Cu(II) containing NNO donor Schiff base ligand: Hydrogen-bond-mediated exchange coupling

Two new mono-aqua-bridged dinuclear Cu(II) complexes of tridentate NNO Schiff bases, [Cu-2(mu-H2O)L-2(1)(H2O)(2)](BF4)(2)center dot 2H(2)O (1) and [Cu-2(mu-H2O)L-2(2)(H2O)(2)](BF4)(2)center dot 2H(2)O (2) where HL1 = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol and HL2 =2-[(2-dimethylamino-ethylimino)-methyl]-phenol were synthesized. Both the complexes were characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. For both the complexes each Cu(II) ion is in a square-pyramidal environment being bonded to three atoms from the tridentate NNO Schiff base and a terminal H2O molecule in the equatorial plane; a second H2O ligand acts as a bridge between the two Cu(II) centres through the axial positions. Hydrogen bonds between the terminal H2O ligand and the Schiff base of the adjacent centre complete the intra-dimer linkages. Variable-temperature (4-300 K) magnetic susceptibility measurement shows the presence of significant antiferromagnetic coupling for both the complexes (J = -12.2 and -12.5 cm(-1), respectively, for 1 and 2), mediated mainly through the intra-dimer H-bonds.

Characteristics of Langmuir Turbulence in the Ocean Mixed Layer

This study uses large-eddy simulation (LES) to investigate the characteristics of Langmuir turbulence through the turbulent kinetic energy (TKE) budget. Based on an analysis of the TKE budget a velocity scale for Langmuir turbulence is proposed. The velocity scale depends on both the friction velocity and the surface Stokes drift associated with the wave field. The scaling leads to unique profiles of nondimensional dissipation rate and velocity component variances when the Stokes drift of the wave field is sufficiently large compared to the surface friction velocity. The existence of such a scaling shows that Langmuir turbulence can be considered as a turbulence regime in its own right, rather than a modification of shear-driven turbulence. Comparisons are made between the LES results and observations, but the lack of information concerning the wave field means these are mainly restricted to comparing profile shapes. The shapes of the LES profiles are consistent with observed profiles. The dissipation length scale for Langmuir turbulence is found to be similar to the dissipation length scale in the shear-driven boundary layer. Beyond this it is not possible to test the proposed scaling directly using available data. Entrainment at the base of the mixed layer is shown to be significantly enhanced over that due to normal shear turbulence.

The role of lateral ocean physics in the upper ocean thermal balance of a coupled ocean-atmosphere GCM

The sensitivity of the upper ocean thermal balance of an ocean-atmosphere coupled GCM to lateral ocean physics is assessed. Three 40-year simulations are performed using horizontal mixing, isopycnal mixing, and isopycnal mixing plus eddy induced advection. The thermal adjustment of the coupled system is quite different between the simulations, confirming the major role of ocean mixing on the heat balance of climate. The initial adjustment phase of the upper ocean (SST) is used to diagnose the physical mechanisms involved in each parametrisation. When the lateral ocean physics is modified, significant changes of SST are seen, mainly in the southern ocean. A heat budget of the annual mixed layer (defined as the “bowl”) shows that these changes are due to a modified heat transfer between the bowl and the ocean interior. This modified heat intake of the ocean interior is directly due to the modified lateral ocean physics. In isopycnal diffusion, this heat exchange, especially marked at mid-latitudes, is both due to an increased effective surface of diffusion and to the sign of the isopycnal gradients of temperature at the base of the bowl. As this gradient is proportional to the isopycnal gradient of salinity, this confirms the strong role of salinity in the thermal balance of the coupled system. The eddy induced advection also leads to increased exchanges between the bowl and the ocean interior. This is both due to the shape of the bowl and again to the existence of a salinity structure. The lateral ocean physics is shown to be a significant contributor to the exchanges between the diabatic and the adiabatic parts of the ocean.

Seasonality of reproduction in sheep

Unlike most domestic livestock species, sheep are widely known as an animal with marked seasonality of breeding activity. The annual cycle of daily photoperiod has been identified as the determinant factor of this phenomenon, while environmental temperature, nutritional status, social interactions, lambing date and lactation period are considered to modulate it. The aim of this paper is to review the current state of knowledge of the reproductive seasonality in sheep. Following general considerations concerning the importance of seasonal breeding as a reproductive strategy for the survival of species, the paper describes the manifestations of seasonality in both the ram and the ewe. Both determinant and modulating factors are developed and special emphasis is given to the neuroendocrine base of photoperiodic regulation of seasonal breeding. Other aspects such as the role of melatonin, the involvement of thyroid hormones and the concept of photorefractoriness are also reviewed. (C) 2003 Elsevier Science B.V. All rights reserved.

Genesis and expansion of metazoan transcription factor gene classes

We know little about the genomic events that led to the advent of a multicellular grade of organization in animals, one of the most dramatic transitions in evolution. Metazoan multicellularity is correlated with the evolution of embryogenesis, which presumably was underpinned by a gene regulatory network reliant on the differential activation of signaling pathways and transcription factors. Many transcription factor genes that play critical roles in bilaterian development largely appear to have evolved before the divergence of cnidarian and bilaterian lineages. In contrast, sponges seem to have a more limited suite of transcription factors, suggesting that the developmental regulatory gene repertoire changed markedly during early metazoan evolution. Using whole- genome information from the sponge Amphimedon queenslandica, a range of eumetazoans, and the choanoflagellate Monosiga brevicollis, we investigate the genesis and expansion of homeobox, Sox, T- box, and Fox transcription factor genes. Comparative analyses reveal that novel transcription factor domains ( such as Paired, POU, and T- box) arose very early in metazoan evolution, prior to the separation of extant metazoan phyla but after the divergence of choanoflagellate and metazoan lineages. Phylogenetic analyses indicate that transcription factor classes then gradually expanded at the base of Metazoa before the bilaterian radiation, with each class following a different evolutionary trajectory. Based on the limited number of transcription factors in the Amphimedon genome, we infer that the genome of the metazoan last common ancestor included fewer gene members in each class than are present in extant eumetazoans. Transcription factor orthologues present in sponge, cnidarian, and bilaterian genomes may represent part of the core metazoan regulatory network underlying the origin of animal development and multicellularity.

The evolution of sensory placodes

The vertebrate cranial sensory placodes are ectodermal embryonic patches that give rise to sensory receptor cells of the peripheral paired sense organs and to neurons in the cranial sensory ganglia. Their differentiation and the genetic pathways that underlay their development are now well understood. Their evolutionary history, however, has remained obscure. Recent molecular work, performed on close relatives of the vertebrates, demonstrated that some sensory placodes (namely the adenohypophysis, the olfactory, and accoustico-lateralis placodes) first evolved at the base of the chordate lineage, while others might be specific to vertebrates. Combined with morphological and cellular fate data, these results also suggest that the sensory placodes of the ancestor of all chordates differentiated into a wide range of structures, most likely to fit the lifestyle and environment of each species.

Evolutionary analysis of novel serine proteases in the venom gland transcriptome of Bitis gabonica rhinoceros

Background: Serine proteases are major components of viper venom and target various stages of the blood coagulation system in victims and prey. A better understanding of the diversity of serine proteases and other enzymes present in snake venom will help to understand how the complexity of snake venom has evolved and will aid the development of novel therapeutics for treating snake bites. Methodology and Principal Findings: Four serine protease-encoding genes from the venom gland transcriptome of Bitis gabonica rhinoceros were amplified and sequenced. Mass spectrometry suggests the four enzymes corresponding to these genes are present in the venom of B. g. rhinoceros. Two of the enzymes, rhinocerases 2 and 3 have substitutions to two of the serine protease catalytic triad residues and are thus unlikely to be catalytically active, though they may have evolved other toxic functions. The other two enzymes, rhinocerases 4 and 5, have classical serine protease catalytic triad residues and thus are likely to be catalytically active, however they have glycine rather than the more typical aspartic acid at the base of the primary specificity pocket (position 189). Based on a detailed analysis of these sequences we suggest that alternative splicing together with individual amino acid mutations may have been involved in their evolution. Changes within amino acid segments which were previously proposed to undergo accelerated change in venom serine proteases have also been observed. Conclusions and Significance: Our study provides further insight into the diversity of serine protease isoforms present within snake venom and discusses their possible functions and how they may have evolved. These multiple serine protease isoforms with different substrate specificities may enhance the envenomation effects and help the snake to adapt to new habitats and diets. Our findings have potential for helping the future development of improved therapeutics for snake bites.

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.

Trinuclear and tetranuclear adduct formation between sodium perchlorate and copper(II) complexes of salicylaldimine type ligands: structural characterization and theoretical investigation

The synthesis of two new sodium perchlorate adducts (1:2 and 1:3) with copper(II) "ligand-complexes'' is reported. One adduct is trinuclear [(CuL(1))(2)NaClO(4)] (1) and the other is tetranuclear [(CuL(2))(3)Na]ClO(4)center dot EtOH (2). The ligands are the tetradentate di-Schiff base of 1,3-propanediamines and salicylaldehyde (H(2)L(1)) or 2-hydroxyacetophenone (H(2)L(2)). Both complexes have been characterized by X-ray single crystal structure analyses. In both structures, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes in addition to a chelated perchlorate anion in 1 and to six oxygen atoms from three Schiff-base complexes in 2. We have carried out a DFT theoretical study (RI-B97-D/def2-SVP level of theory) to compute and compare the formation energies of 1:2 and 1:3 adducts. The DFT study reveals that the latter is more stabilized than the former. The X-ray crystal structure of 1 shows that the packing of the trinuclear unit is controlled by unconventional C-H center dot center dot center dot O H-bonds and Cu(2+)-pi non-covalent interactions. These interactions explain the formation of 1 which is a priori disfavored with respect to 2.

The effects of rotation and ice shelf topography on frazil-laden ice shelf water plumes

A model of the dynamics and thermodynamics of a plume of meltwater at the base of an ice shelf is presented. Such ice shelf water plumes may become supercooled and deposit marine ice if they rise (because of the pressure decrease in the in situ freezing temperature), so the model incorporates both melting and freezing at the ice shelf base and a multiple-size-class model of frazil ice dynamics and deposition. The plume is considered in two horizontal dimensions, so the influence of Coriolis forces is incorporated for the first time. It is found that rotation is extremely influential, with simulated plumes flowing in near-geostrophy because of the low friction at a smooth ice shelf base. As a result, an ice shelf water plume will only rise and become supercooled (and thus deposit marine ice) if it is constrained to flow upslope by topography. This result agrees with the observed distribution of marine ice under Filchner–Ronne Ice Shelf, Antarctica. In addition, it is found that the model only produces reasonable marine ice formation rates when an accurate ice shelf draft is used, implying that the characteristics of real ice shelf water plumes can only be captured using models with both rotation and a realistic topography.

Validity of the ice shelf water plume concept beneath Filchner-Ronne Ice Shelf

In winter, brine rejection from sea ice formation and export in the Weddell Sea, offshore of Filchner-Ronne Ice Shelf (FRIS), leads to the formation of High Salinity Shelf Water (HSSW). This dense water mass enters the cavity beneath FRIS by sinking southward down the sloping continental shelf towards the grounding line. Melting occurs when the HSSW encounters the ice shelf, and the meltwater released cools and freshens the HSSW to form a water mass known as Ice Shelf Water (ISW). If this ISW rises, the ‘ice pump’ is initiated (Lewis and Perkin, 1986), whereby the ascending ISW becomes supercooled and deposits marine ice at shallower locations due to the pressure increase in the in-situ freezing temperature. Sandh¨ager et al. (2004) were able to infer the thickness patterns of marine ice deposits at the base of FRIS (figure 1), so the primary aim of this work is to try to understand the ocean flows that determine these patterns. The plume model we use to investigate ISW flow is described fully by Holland and Feltham (accepted) so only a relatively brief outline is presented here. The plume is simulated by combining a parameterisation of ice shelf basal interaction and a multiplesize- class frazil dynamics model with an unsteady, depth-averaged reduced-gravity plume model. In the model an active region of ISW evolves above and within an expanse of stagnant ambient fluid, which is considered to be ice-free and has fixed profiles of temperature and salinity. The two main assumptions of the model are that there is a well-mixed layer underneath the ice shelf and that the ambient fluid outside the plume is stagnant with fixed properties. The topography of the ice shelf that the plume flows beneath is set to the FRIS ice shelf draft calculated by Sandh¨ager et al. (2004) masked with the grounding line from the Antarctic Digital Database (ADD Consortium, 2002). To initiate the plumes, we assume that the intrusion of dense HSSW initially causes melting at the points on the grounding line where the glaciological tributaries feeding FRIS go afloat.

Optimal planning of cocoa clonal selection programmes

Data from three cocoa (Theobroma cacao) clonal selection trials are used to investigate the genetic and environmental components of variation in yield and the percentage of total pods affected by black pod disease (Phytophtora pod rot). Simulations based on these estimated components of variation are then used to discuss the best choice in future of numbers of clones, replicates and years of harvest to maximise selection advances in the traits measured. The three main conclusions are the need to increase the number of clones at the expense of the number of replicates of each clone, the diminishing returns from additional years of harvesting and the importance of widening the genetic base of the clones chosen to be tested.

Evaluation of modelled regional water balance using lake status data: a comparison of 6ka simulations with the NCAR CCM

Variations in lake area and depth reflect climatically induced changes in the water balance of overflowing as well as closed lakes. A new global data base of lake status has been assembled, and is used to compare two simulations for 6 ka (6000 yr ago) made with successive R15 versions of the NCAR Community Climate Model (CCM). Simulated water balance was expressed as anomalies of annual precipitation minus evaporation (P-E); observed water balance as anomalies of lake status. Comparisons were made visually, by comparing regional averages, and by a statistic that compares the signs of simulated P-E anomalies (smoothly interpolated to the lake sites) with the status anomalies. Both CCM0 and CCM1 showed enhanced Northern-Hemisphere monsoons at 6 ka. Both underestimated the effect, but CCM1 fitted the spatial patterns better. In the northern mid- and high-latitudes the two versions differed more, and fitted the data less satisfactorily. CCM1 performed better than CCM0 in North America and central Eurasia, but not in Europe. Both models (especially CCM0) simulated excessive aridity in interior Eurasia. The models were systematically wrong in the southern mid-latitudes. Problems may have been caused by inadequate treatment of changes in sea-surface conditions in both models. Palaeolake status data will continue to provide a benchmark for the evaluation of modelling improvements.