Two new mu-(1,3-azido)-bridged polymers: alternating single and double bridges in a 1D nickel(II) complex and uniform bridge in a 2D copper(II) complex: Syntheses, single-crystal structures and magnetic studies

Two polymeric azido bridged complexes [Ni2L2(N-3)(3)](n)(ClO4). (1) and [Cu(bpdS)(2)(N-3)],(ClO4),(H2O)(2.5n) (2) [L = Schiff base, obtained from the condensation of pyridine-2-aldehyde with N,N,2,2-tetramethyl-1,3-propanediamine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1, C26H42ClN15Ni2O4, crystallizes in a triclinic system, space group P1 with a 8.089(13), b = 9.392(14), c = 12.267(18) angstrom, a = 107.28(l), b 95.95(1), gamma = 96.92(1)degrees and Z = 2; complex 2, C20H21ClCuN7O6.5S4, crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) angstrom and Z = 4. The crystal structure of I consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging mu-(1,3-N-3) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting,of magnetic data was carried out applying the Borris-Almenar formula for such types of alternating one-dimensional S = 1 systems, based on the Hamiltonian H = -J Sigma(S2iS2i-1 + aS(2i)S(2i+1)). The best-fit parameters obtained are J = -106.7 +/- 2 cm(-1); a = 0.82 +/- 0.02; g = 2.21 +/- 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu-II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo-one-dimensional system, with all copper((II)) atoms linked by [mu(1,3-azido) bridging ligands at axial positions (long Cu...N-3 distances) since the coupling through long bpds is almost nil. The best-fit parameters obtained with this model are J = -1.21 +/- 0.2 cm(-1), g 2.14 +/- 0.02. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Cu-II acetate complexes involving N,N,O donor Schiff base ligands: Mono-atomic oxygen bridged dimers and alternating chains of the dimers and Cu-2(OAc)(4)

Two tridentate N,N,O donor Schiff bases, HL1 (4-(2-ethylamino-ethylimino)-pentan-2-one) and HL2 (3-(2-amino-propylimino)-1-phenyl-butan-1-one) on reaction with Cu-II acetate in presence of triethyl amine yielded two basal-apical, mono-atomic acetate oxygen-bridging dimeric copper(II) complexes, [Cu2L21(OAc)(2)] (1), [Cu2L22(OAc)(2)] (2). Whereas two other similar tridentate ligands HL3 (4-(2-amino-propylimino)-pentane-2-one) and HL3 (3-(2-amino-ethylimino)-1-phenyl-butan-1-one) under the same conditions produced a mixture of the corresponding dinners and a one-dimensional alternating chain of the dimer and copper acetate moiety, [Cu4L23(OAc)(6)](n) (3) and [Cu4L24(OAc)(6)](n) (4), formed by a very rare mu(3) bridging mode of the acetate ion. All four complexes (1-4) have been characterized by X-ray crystallography. The isotropic Hamiltonian, H = -JS(1)S(2) has been used to interpret the magnetic data. Magnetic measurements of 1 and 2 in the temperature range 2-300 K reveal a very weak antiferromagnetic coupling for both complexes U = -0.56 and -1.19 cm(-1) for 1 and 2, respectively). (C) 2008 Elsevier Ltd. All rights reserved.

Microblock ionomers: a new concept in high temperature, swelling-resistant membranes for PEM fuel cells

A novel series of polyaromatic ionomers with similar equivalent weights but very different sulphonic acid distributions along the ionomer backbone has been designed and prepared. By synthetically organising the sequence-distribution so that it consists of fully defined ionic segments (containing singlets, doublets or quadruplets of sulphonic acid groups) alternating strictly with equally well-defined nonionic spacer segments, a new class of polymers which may be described as microblock ionomers has been developed. These materials exhibit very different properties and morphologies from analogous randomly substituted systems. Progressively extending the nonionic spacer length in the repeat unit (maintaining a constant equivalent weight by increasing the degree of sulphonation. of the ionic segment) leads to an increasing degree of nanophase separation between hydrophilic and hydrophobic domains in these materials. Membranes cast from ionomers with the more highly phase-separated morphologies show significantly higher onset temperatures for uncontrolled swelling in water. This new type of ionomer design has enabled the fabrication of swelling-resistant hydrocarbon membranes, suitable for fuel cell operation, with very much higher ion exchange capacities (>2 meq g(-1)) than those previously reported in the literature. When tested in a fuel cell at high temperature (120 degrees C) and low relative humidity (35% RH), the best microblock membrane matched the performance of Nafion 112. Moreover, comparative low load cycle testing of membrane -electrode assemblies suggests that the durability of the new membranes under conditions of high temperature and low relative humidity is superior to that of conventional perfluorinated materials.

Spin-canted antiferromagnetic phase transitions in alternating phenoxo- and carboxylato-bridged Mn(III)-salen complexes

Three new MnIII complexes, {[Mn-2(salen)(2)(OCn)](ClO4)}(n) (1), {[Mn-2(salen)(2)(OPh)](ClO4)}(n) (2) and {[Mn-2(salen)(2)(OBz)](ClO4)}(2) (3) (where salen = N,N'-bis(salicylidene)-1,2-diaminoethane dianion, OCn = cinnamate, OPh = phenylacetate and OBz = benzoate), have been synthesized and characterized structurally and magnetically. The crystal structures reveal that all three structures contain syn-anti carboxylatebridged dimeric [Mn-2(salen)(2)(OOCR)](+) cations (OOCR = bridging carboxylate) that are joined together by weak Mn center dot center dot center dot O(phenoxo) interactions to form infinite alternating chain structures in 1 and 2, but the relatively long Mn center dot center dot center dot O(phenoxo) distance [3.621(2)angstrom] in 3 restricts this structure to tetranuclear units. Magnetic studies showed that 1 and 2 exhibited magnetic long-range order at T-N = 4.0 and 4.6 K (T-N = Neel transition temperature), respectively, to give spin-canted antiferromagnetic structures. Antiferromagnetic coupling was also observed in 3 but no peaks were recorded in the field-cooled magnetization (FCM) or zero-field-cooled magnetization (ZFCM) data, indicating that 3 remained paramagnetic down to 2 K. This dominant antiferromagnetic coupling is attributed to the carboxylate bridges. The ferromagnetic coupling expected due to the Mn-O(phenoxo)center dot center dot center dot Mn bridge plays an auxiliary role in the magnetic chain, but is an essential component of the bulk magnetic properties of the material.

Effect of light and temperature on seed germination in guava (Psidium guajava L. Myrtaceae)

The germination of seeds of Psidium guajava L. (Myrtaceae) is controlled by phytochrome. Guava seeds can germinate with at least one hour per day of irradiation of high red:far-red ratio light preceeded or followed by shade light, indicating that phytochrome B controls germination in these conditions. Under alternating temperatures, in a range of at least 5degreesC, seeds will germinate in darkness, suggesting that in gaps of the canopy, when seeds are covered by a thin layer of soil they will germinate once the alternating temperatures are experienced. Under these conditions phytochrome A is responsible for the control of guava seed germination.

Influence of light and temperature on seed germination of Cereus pernambucensis Lemaire (Cactaceae)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of light and temperature on seed germination in Tibouchina mutabilis (Vell.) Cogn. (Melastomataceae)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Effect of temperature on seed germination of ornamental herbaceous perennials

Antirrhinum majus L. and Senecio douglasii DC. are herbaceous perennial ornamental plants used in landscaping. The multiplication of these plants is by seed; however, there are still doubts about the temperature that can provide higher rates and speed of germination. Thus the aim was to study the effect of temperature on seed germination of A. majus and S. douglasii. The study was conducted separately for each species. The experimental design was entirely randomized with six temperature conditions (temperature controlled constant of 20, 25, 30, 35°C and alternating temperatures of 20-30 and 25-35°C with a photoperiod of 12 hours) with four replications of 100 seeds each. Total germination percentage and germination rate were determined. The means were compared by Tukey test at 5%. For A majus the highest germination percentage was observed at 20°C that did not differ statistically from other temperatures. The highest germination rate was obtained at the temperature of 20 and 25°C. For S. douglasii seeds it was observed that the highest germination percentage and germination rate occurred at 20°C. The lower temperature showed the better percentage and germination rate for these species.

A 600 years warm-season temperature record from varved sediments of Lago Plomo, Northern Patagonia, Chile (47°S)

High-resolution records of calibrated proxy data for the past millennium are fundamental to place current changes into the context of pre-industrial natural forced and unforced variability. Although the need for regional spatially-explicit comprehensive reconstructions is widely recognized, the proxy data sources are still scarce, particularly for the Southern Hemisphere and especially for South America. We present a 600-year long warm season temperature record from varved sediments of Lago Plomo, a proglacial lake of the Northern Patagonian Ice field in Southern Chile (46°59′S, 72°52′W, 203 m a.s.l.). The thickness of the bright summer sediment layer relative to the dark winter layer (measured as total brightness; % reflectance 400–730 nm) is calibrated against warm season SONDJF temperature (1900–2009; r = 0.58, p(aut) = 0.056, RE = 0.52; CE = 0.15, RMSEP = 0.28 °C; five-year triangular filtered data). In Lago Plomo, warm summer temperatures lead to enhanced glacier melt and suspended sediment transport, which results in thicker light summer layers and to brighter sediments. Although Patagonia shows pronounced regional differences in decadal temperature trends and variability, the 600 years temperature reconstruction from Lago Plomo compares favourably with other regional/continental temperature records, but also emphasizes significant regional differences for which no data and information existed so far. These regional differences seem to be real as they are also reflected in modern climate data sets (1900–2010). The reconstruction shows pronounced subdecadal – multidecadal variability with cold phases during parts of the Little Ice Age (16th and 18th centuries) and in the beginning of the 20th century. The most prominent warm phase is the 19th century which is as warm as the second half of the 20th century. The exceptional summer warmth AD 1780–1810 is also found in other archives of Northern Patagonia and Central Chile. Our record shows the delayed 20th century warming in the Southern Hemisphere. The comparison between winter precipitation and summer temperature (inter-seasonal coupling) from Lago Plomo reveals alternating phases with parallel and contrasting decadal trends of winter precipitation and summer temperature (positive and negative running correlations Rwinter PP; summer TT). This observation from the sediment proxy data is also confirmed by two sets of reanalysis data for the 20th century. Reanalysis data show that phases with negative correlations between winter precipitation and summer temperature (e.g., dry winters and warm summers) at Lago Plomo are characteristic for periods when circumpolar Westerly flow is displaced southward and enhanced around 60°S.

High temperature micropillar compression of Al/SiC nanolaminates

The effect of the temperature on the compressive stress–strain behavior of Al/SiC nanoscale multilayers was studied by means of micropillar compression tests at 23 °C and 100 °C. The multilayers (composed of alternating layers of 60 nm in thickness of nanocrystalline Al and amorphous SiC) showed a very large hardening rate at 23 °C, which led to a flow stress of 3.1 ± 0.2 GPa at 8% strain. However, the flow stress (and the hardening rate) was reduced by 50% at 100 °C. Plastic deformation of the Al layers was the dominant deformation mechanism at both temperatures, but the Al layers were extruded out of the micropillar at 100 °C, while Al plastic flow was constrained by the SiC elastic layers at 23 °C. Finite element simulations of the micropillar compression test indicated the role played by different factors (flow stress of Al, interface strength and friction coefficient) on the mechanical behavior and were able to rationalize the differences in the stress–strain curves between 23 °C and 100 °C.

Third-generation synchrotron x-ray diffraction of 6-μm crystal of raite, ≈Na3Mn3Ti0.25Si8O20(OH)2⋅10H2O, opens up new chemistry and physics of low-temperature minerals

The crystal structure of raite was solved and refined from data collected at Beamline Insertion Device 13 at the European Synchrotron Radiation Facility, using a 3 × 3 × 65 μm single crystal. The refined lattice constants of the monoclinic unit cell are a = 15.1(1) Å; b = 17.6(1) Å; c = 5.290(4) Å; β = 100.5(2)°; space group C2/m. The structure, including all reflections, refined to a final R = 0.07. Raite occurs in hyperalkaline rocks from the Kola peninsula, Russia. The structure consists of alternating layers of a hexagonal chicken-wire pattern of 6-membered SiO4 rings. Tetrahedral apices of a chain of Si six-rings, parallel to the c-axis, alternate in pointing up and down. Two six-ring Si layers are connected by edge-sharing octahedral bands of Na+ and Mn3+ also parallel to c. The band consists of the alternation of finite Mn–Mn and Na–Mn–Na chains. As a consequence of the misfit between octahedral and tetrahedral elements, regions of the Si–O layers are arched and form one-dimensional channels bounded by 12 Si tetrahedra and 2 Na octahedra. The channels along the short c-axis in raite are filled by isolated Na(OH,H2O)6 octahedra. The distorted octahedrally coordinated Ti4+ also resides in the channel and provides the weak linkage of these isolated Na octahedra and the mixed octahedral tetrahedral framework. Raite is structurally related to intersilite, palygorskite, sepiolite, and amphibole.

Effects of alternating current voltage amplitude and oxide capacitance on mid-gap interface state defect density extractions in In0.53Ga 0.47As capacitors

This work looks at the effect on mid-gap interface state defect density estimates for In0.53Ga0.47As semiconductor capacitors when different AC voltage amplitudes are selected for a fixed voltage bias step size (100 mV) during room temperature only electrical characterization. Results are presented for Au/Ni/Al2O3/In0.53Ga0.47As/InP metal–oxide–semiconductor capacitors with (1) n-type and p-type semiconductors, (2) different Al2O3 thicknesses, (3) different In0.53Ga0.47As surface passivation concentrations of ammonium sulphide, and (4) different transfer times to the atomic layer deposition chamber after passivation treatment on the semiconductor surface—thereby demonstrating a cross-section of device characteristics. The authors set out to determine the importance of the AC voltage amplitude selection on the interface state defect density extractions and whether this selection has a combined effect with the oxide capacitance. These capacitors are prototypical of the type of gate oxide material stacks that could form equivalent metal–oxide–semiconductor field-effect transistors beyond the 32 nm technology node. The authors do not attempt to achieve the best scaled equivalent oxide thickness in this work, as our focus is on accurately extracting device properties that will allow the investigation and reduction of interface state defect densities at the high-k/III–V semiconductor interface. The operating voltage for future devices will be reduced, potentially leading to an associated reduction in the AC voltage amplitude, which will force a decrease in the signal-to-noise ratio of electrical responses and could therefore result in less accurate impedance measurements. A concern thus arises regarding the accuracy of the electrical property extractions using such impedance measurements for future devices, particularly in relation to the mid-gap interface state defect density estimated from the conductance method and from the combined high–low frequency capacitance–voltage method. The authors apply a fixed voltage step of 100 mV for all voltage sweep measurements at each AC frequency. Each of these measurements is repeated 15 times for the equidistant AC voltage amplitudes between 10 mV and 150 mV. This provides the desired AC voltage amplitude to step size ratios from 1:10 to 3:2. Our results indicate that, although the selection of the oxide capacitance is important both to the success and accuracy of the extraction method, the mid-gap interface state defect density extractions are not overly sensitive to the AC voltage amplitude employed regardless of what oxide capacitance is used in the extractions, particularly in the range from 50% below the voltage sweep step size to 50% above it. Therefore, the use of larger AC voltage amplitudes in this range to achieve a better signal-to-noise ratio during impedance measurements for future low operating voltage devices will not distort the extracted interface state defect density.

Sea surface temperature and primary productivity reconstruction of sediment core SO130-275KL from the northeastern Arabian Sea during the late Holocene

Variability in the oceanic environment of the Arabian Sea region is strongly influenced by the seasonal monsoon cycle of alternating wind directions. Prominent and well studied is the summer monsoon, but much less is known about late Holocene changes in winter monsoon strength with winds from the northeast that drive convective mixing and high surface ocean productivity in the northeastern Arabian Sea. To establish a high-resolution record of winter monsoon variability for the late Holocene, we analyzed alkenone-derived sea surface temperature (SST) variations and proxies of primary productivity (organic carbon and d15N) in a well-laminated sediment core from the Pakistan continental margin. Weak winter monsoon intensities off Pakistan are indicated from 400 B.C. to 250 A.D. by reduced productivity and relatively high SST. At about 250 A.D., the intensity of the winter monsoon increased off Pakistan as indicated by a trend to lower SST. We infer that monsoon conditions were relatively unstable from ~500 to 1300 A.D., because primary production and SST were highly variable. Declining SST and elevated biological production from 1400 to 1900 A.D. suggest invigorated convective winter mixing by strengthening winter monsoon circulation, most likely a regional expression of colder climate conditions during the Little Ice Age on the Northern Hemisphere. The comparison of winter monsoon intensity with records of summer monsoon intensity suggests that an inverse relationship between summer and winter monsoon strength exists in the Asian monsoon system during the late Holocene, effected by shifts in the Intertropical Convergence Zone.