A Pt(II) complex with both a phenanthroline and a tetrathiafulvalene-extended dithiolate ligand: Synthesis, crystal structure, electrochemical and spectroscopic properties

The reaction of 4,5-bis(2'-cyanoethylsulfanyl)-4',5'-dipropylthiotetrathiafulvalene with Pt(phen)Cl-2 (phen = 1,10-phenanthroline) with CsOH as base in CH3OH-THE affords the target complex I in 44% yield. This complex crystallizes in the monoclinic space group P2(1)/c, M = 790.01, a = 12.1732(12), b = 15.851(2), c = 14.5371(16) angstrom, beta = 107.693(12)degrees, V = 2672.4(5) angstrom(3) and Z = 4. It undergoes two reversible single-electron oxidation and two irreversible reduction processes. An intense electronic absorption band at 15200 cm(-1) (658 nm) in CH2Cl2 is assigned to the intramolecular mixed metal/ligand-to-ligand charge transfer (LLCT) from a tetrathiafulvalene-extended dithiolate-based HOMO to a phenanthroline-based LUMO. This band shifts hypsochromically with increasing solvent polarity. Systematic changes in the optical spectra upon oxidation allow precise tuning of the oxidation states of 1 and reversible control over its optical properties. Irradiation of 1 at 15625 cm(-1) (640 nm) in glassy solution below 150K results in emission from the (LLCT)-L-3 excited state. GRAPHICS (C) 2013 Elsevier Ltd. All rights reserved.

Microgram-Level Radiocarbon Determination of Carbonaceous Particles in Firn and Ice Samples: Pretreatment and Oc/Ec Separation

Carbonaceous particles that comprise organic carbon (OC) and elemental carbon (EC) are of increasing interest in climate research because of their influence on the radiation balance of the Earth. The radiocarbon determination of particulate OC and EC extracted from ice cores provides a powerful tool to reconstruct the long-term natural and anthropogenic emissions of carbonaceous particles. However, this C-14-based source apportionment method has not been applied for the firn section, which is the uppermost part of Alpine glaciers with a typical thickness of up to 50 m. In contrast to glacier ice, firn samples are more easily contaminated through drilling and handling operations. In this study, an alternative decontamination method for firn samples consisting of chiselling off the outer parts instead of rinsing them was developed and verified. The obtained procedural blank of 2.8 +/- 0.8 mu g C for OC is a factor of 2 higher compared to the rinsing method used for ice, but still relatively low compared to the typical OC concentration in firn samples from Alpine glaciers. The EC blank of 0.3 +/- 0.1 mu g C is similar for both methods. For separation of OC and EC for subsequent C-14 analysis, a thermal-optical method instead of the purely thermal method was applied for the first time to firn and ice samples, resulting in a reduced uncertainty of both the mass and C-14 determination. OC and EC concentrations as well as their corresponding fraction of modern for firn and ice samples from Fiescherhorn and Jungfraujoch agree well with published results, validating the new method.

Three strategically placed hydrogen-bonding residues convert a proton pump into a sensory receptor.

In haloarchaea, light-driven ion transporters have been modified by evolution to produce sensory receptors that relay light signals to transducer proteins controlling motility behavior. The proton pump bacteriorhodopsin and the phototaxis receptor sensory rhodopsin II (SRII) differ by 74% of their residues, with nearly all conserved residues within the photoreactive retinal-binding pocket in the membrane-embedded center of the proteins. Here, we show that three residues in bacteriorhodopsin replaced by the corresponding residues in SRII enable bacteriorhodopsin to efficiently relay the retinal photoisomerization signal to the SRII integral membrane transducer (HtrII) and induce robust phototaxis responses. A single replacement (Ala-215-Thr), bridging the retinal and the membrane-embedded surface, confers weak phototaxis signaling activity, and the additional two (surface substitutions Pro-200-Thr and Val-210-Tyr), expected to align bacteriorhodopsin and HtrII in similar juxtaposition as SRII and HtrII, greatly enhance the signaling. In SRII, the three residues form a chain of hydrogen bonds from the retinal's photoisomerized C(13)=C(14) double bond to residues in the membrane-embedded alpha-helices of HtrII. The results suggest a chemical mechanism for signaling that entails initial storage of energy of photoisomerization in SRII's hydrogen bond between Tyr-174, which is in contact with the retinal, and Thr-204, which borders residues on the SRII surface in contact with HtrII, followed by transfer of this chemical energy to drive structural transitions in the transducer helices. The results demonstrate that evolution accomplished an elegant but simple conversion: The essential differences between transport and signaling proteins in the rhodopsin family are far less than previously imagined.

Variations in Ice Rafted Detritus on Beaches in the South Shetland Islands: A Possible Climate Proxy

Raised beach ridges on Livingston Island of the South Shetland Islands display variations in both quantity and source of ice rafted detritus (IRD) received over time. Whereas the modem beach exhibits little IRD, all of which is of local origin, the next highest beach (similar to250 C-14 yr BP) has large amounts, some of which comes from as far away as the Antarctic Peninsula. Significant quantities of IRD also were deposited similar to 1750 C-14 yr BP. Both time periods coincide with generally cooler regional conditions and, at least in the case of the similar to250 yr old beach, local glacial advance. We suggest that the increases in ice rafting may reflect periods of greater glacial activity, altered ocean circulation, and/or greater iceberg preservation during the late Holocene. Limited IRD and lack of far-travelled erratics on the modem beach are both consistent with the ongoing warming trend in the Antarctic Peninsula region.

Antarctic Glacial History Since the Last Glacial Maximum: An Overview of the Record on Land

This overview examines available circum-Antarctic glacial history archives on land, related to developments after the Last Glacial Maximum (LGM). It considers the glacial-stratigraphic and morphologic records and also biostratigraphical information from moss banks, lake sediments and penguin rookeries, with some reference to relevant glacial marine records. It is concluded that Holocene environmental development in Antarctica differed from that in the Northern Hemisphere. The initial deglaciation of the shelf areas surrounding Antarctica took place before 10000 C-14 yrs before present(sp), and was controlled by rising global sea level. This was followed by the deglaciation of some presently ice-free inner shelf and land areas between 10000 and 8000 yr sp. Continued deglaciation occurred gradually between 8000 yr sp and 5000 yr sp. Mid-Holocene glacial readvances are recorded from various sites around Antarctica. There are strong indications of a circum-Antarctic climate warmer than today 4700-2000 yr sp. The best dated records from the Antarctic Peninsula and coastal Victoria Land suggest climatic optimums there from 4000-3000 yr sp and 3600-2600 yr sp, respectively. Thereafter Neoglacial readvances are recorded. Relatively limited glacial expansions in Antarctica during the past few hundred years correlate with the Little Ice Age in the Northern Hemisphere.

The ethanolic fermentation pathway supports respiration and lipid biosynthesis in tobacco pollen

Rapid pollen tube growth requires a high rate of sugar metabolism to meet energetic and biosynthetic demands. Previous work on pollen sugar metabolism showed that tobacco pollen carry out efficient ethanolic fermentation concomitantly with a high rate of respiration (Bucher et al ., 1995). Here we show that the products of fermentation, acetaldehyde and ethanol, are further metabolised in a pathway that bypasses mitochondrial PDH. The enzymes involved in this pathway are pyruvate decarboxylase, aldehyde dehydrogenase and acetyl-CoA synthetase. Radiolabelling experiments show that during tobacco pollen tube growth label of C-14-ethanol is incorporated into CO2 as well as into lipids and other higher molecular weight compounds. A role for the glyoxylate cycle appears unlikely since activity of malate synthase, a key enzyme of the glyoxylate cycle, could not be detected.

Reclassification of Actinobacillus muris as Muribacter muris gen. nov. comb. nov.

To reinvestigate the taxonomy of [Actinobacillus] muris, 474 strains mainly from mice and rats were characterized by phenotype and 130 strains selected for genotypic characterization by 16S rRNA and partial rpoB gene sequencing. The type strain was further investigated by whole genome sequencing. Phylogenetic analysis of the DNA sequences showed one monophyletic group with intra group similarities of 96.7 % and 97.2 % for 16S rRNA and rpoB genes, respectively. The lowest 16S rRNA similarity to the closest related valid named taxon outside the group was 95.9 % to the type strain of [Pasteurella] pneumotropica. The closest related taxon based on rpoB sequence comparison was 'Haemophilus influenzae-murium' with 88.4 %. A new genus, Muribacter is proposed based on a distinct phylogenetic position based on 16S rRNA and rpoB gene sequence comparisons with major divergence to the existing genera of Pasteurellaceae. The new genus includes the characteristics of [Actinobacillus] muris with the emendation that acid formation from (-)-D-mannitol is variable as well the hydrolysis of esculin while the α-glucosidase test is positive. There is no requirement for exogenously supplied nicotinamide adenine dinucleotide (V factor) for the majority of strains investigated, however, one strain was found positive. The major fatty acids of the type strain of Muribacter muris were C 14:0, C 14:0 3OH/C 16:1 ISOI, C 16:1 ω7c and C 16:0 which is in line with most genera of Pasteurellaceae. The type strain of Muribacter muris is CCUG 16938T ( = NCTC 12432T = ATCC 49577T).

Vom Urwald zur Kulturlandschaft des Oberengadins : Vegetationsgeschichte der letzten 6200 Jahre

Aufgrund der Untersuchung von Pollen, pflanzlichen Makrofossilien und organischen Sedimentpartikeln (z. B. Holzkohle) in zwei Oberengadiner Seen wird die Vegetationsentwicklung der letzten 6200 Jahre rekonstruiert und im Licht der Entwicklung menschlicher Einflussnahme betrachtet. Der zeitliche Ablauf der Vegetationsveränderungen beruht auf 38 C-14-Datierungen terrestrischer Makroreste aus zwei Sedimentkernen. Die paläobotanischen Daten aus dem St. Moritzer See (Lej da San Murezzan) zeigen für die Zeit von 4200 bis ca. 3550 v. Chr. eine natürliche Waldvegetation bestehend aus Fichte (Picea), Wald- resp. Bergföhre (Pinus sylvestris/P. mugo), Arve (Pinus cembra) und Lärche (Larix decidua). Palynologische Kulturzeiger belegen erste Spuren neolithischer Veränderungen dieser Vegetation in der Zeit um ca. 3500 v. Chr. Eine tiefgreifende Vegetationsveränderung ist für die frühe Bronzezeit, um 2000 v.Chr. zu belegen. Die menschliche Besiedlung führte zu einer ausgeprägten Auflockerung des Waldes mit massiver Zunahme der Weide- und Kulturzeiger (z. B. Getreide, Rumex acetosella, Plantago lanceolata, Urtica, Cichorioideae) sowie einer starken Ausbreitung der Grünerle (Alnus viridis) und der Lärche (Larix decidua). Die Vegetationsentwicklung und die Verteilung von Holzkohlepartikeln in den Sedimenten weisen auf Waldbrände hin. Das Zurückdrängen des Waldes erfolgte in verschiedenen Phasen, die sich mit Besiedlungs- oder Kulturphasen erklären lassen. Der stärkste Rückgang des Waldes fällt ins Mittelalter (ab ca. 800 n. Chr.). In den letzten 200 Jahren nimmt die Baumvegetation vermutlich als Folge eines Nutzungsrückgangs wieder zu. Die ausgeprägtesten Veränderungen der Vegetation fallen mit Epochengrenzen zusammen, was sich mit technologischen Erneuerungen oder möglicherweise mit Einwanderungsphasen erklären lässt.

Aspectos biológicos y poblacionales de Sipha Maydis (Passerini) y Schizaphis Graminum (Rondani) en cebada

El objetivo del presente estudio fue obtener los parámetros bioetológicos de Sipha maydis (Passerini) y Schizaphis graminum (Rondani) sobre cebada, Hordeum vulgare L. cv. Pampa. Los pulgones se criaron en condiciones de laboratorio a 20±1 °C, 14:10 horas de fotofase y una humedad relativa del 50-70 %. Se obtuvieron cohortes a partir de poblaciones de estos áfidos, sobre las que se realizó el registro diario de los cambios de estado, número de individuos muertos y los nacimientos una vez alcanzado el estado adulto. Se analizaron las curvas de supervivencia por edades (lx) y fecundidad (mx) y los siguientes estadísticos vitales: tasa reproductiva neta (Ro); tasa intrínseca de crecimiento natural (rm); tiempo generacional medio (T) y tiempo de duplicación (D). Para la comparación de las rm se obtuvieron las rm estimadas junto con su error standard mediante el procedimiento <jackknife». Si bien el pulgón verde de los cereales S. graminum posee mayor eficiencia reproductiva, S. maydis presenta valores de supervivencia y fecundidad de importancia, que indicaría que este áfido podría constituirse en una plaga potencial de gramíneas cultivadas.

Description of sampling sites in Northern Russia

The youngest ice marginal zone between the White Sea and the Ural mountains is the W-E trending belt of moraines called the Varsh-Indiga-Markhida-Harbei-Halmer-Sopkay, here called the Markhida line. Glacial elements show that it was deposited by the Kara Ice Sheet, and in the west, by the Barents Ice Sheet. The Markhida moraine overlies Eemian marine sediments, and is therefore of Weichselian age. Distal to the moraine are Eemian marine sediments and three Palaeolithic sites with many C-14 dates in the range 16-37 ka not covered by till, proving that it represents the maximum ice sheet extension during the Weichselian. The Late Weichselian ice limit of M. G. Grosswald is about 400 km (near the Urals more than 700 km) too far south. Shorelines of ice dammed Lake Komi, probably dammed by the ice sheet ending at the Markhida line, predate 37 ka. We conclude that the Markhida line is of Middle/Early Weichselian age, implying that no ice sheet reached this part of Northern Russia during the Late Weichselian. This age is supported by a series of C-14 and OSL dates inside the Markhida line all of >45 ka. Two moraine loops protrude south of the Markhida line; the Laya-Adzva and Rogavaya moraines. These moraines are covered by Lake Komi sediments, and many C-14 dates on mammoth bones inside the moraines are 26-37 ka. The morphology indicates that the moraines are of Weichselian age, but a Saalian age cannot be excluded. No post-glacial emerged marine shorelines are found along the Barents Sea coast north of the Markhida line.

Distribution of benthic and planktic foraminifera in surface sediments of the Indian and Pakistan continental margin, Arabian Sea

During the Indian Ocean Expedition of the German research vessel "Meteor" and the following cruise with the Pakistani fishing vessel "Machhera" in February and March 1965, sediments were sampled from the shelf, continental slope and the Arabian Basin off Pakistan and India. The biostratigraphic studies are based on sedimentary material from 24 sediment cores up to 480 cm long and 100 grab samples. The faunal residues of the > 160 µ fraction (chiefly foraminifera and pteropods) were determined and counted in order to get an idea of the climatic conditions during the Late Quaternary of this region. Biostratigraphic correlations of these Late Quaternary deposits are only possible if the thanatocoenosis of the surface sediments are well known. The analysis of the benthonic foraminiferal populations resulted in the definition of several foraminiferal facies. The following sequence of forarniniferal facies, named after their most characteristic members, can be distinguished from the shelf to the deep-sea: 1. Ammonia-Florilus facies ; 2. Ammonia-Cancris facies; 3. Cassidulina-Cibicides facies; 4. Uvigerina-Cassidulina facies ; 5. Buliminacea facies ; 6. deepwater facies, partly with Bulimina aculeata or with Nonionidae. On the upper continental slope there is a zone extremely poor in benthonic foraminifera. In this water depth the oxygen minimum layer (0.05-0.02 ml/l) of the water column reaches the slope. Almost no connection can be observed between the living and the dead foraminiferal population of the same sample. The regional distribution of the planktonic foraminifera from plankton tows as well as from the surface sediments shows marked differences in the species composition of faunas from different regions within the area of investigation. That depends on oceanographic conditions such as upwelling, dissolution of carbonate at great depths etc. Based on the results of faunal analysis of samples from the recent sea-floor, a biostratigraphic subdivision of the sediments in the cores was established. The following biostratigraphically defined sections could be distinguished from the top of the sediment cores downwards : 1. Relatively cool climatic conditions are reflected by the foraminifera of the uppermost core sections. 2. The next section is characterized by much warmer conditions (Holocene climatic optimum). The C-14 ages of this interval range from 4000 to 10 000 years B.P. according to different authors. C-14 dates on the material investigated do not give reliable clues. 3. Foraminiferal populations adapted to much colder conditions can be observed in the underlying core section. The boundary between the warm climate reflected by the foraminifera of section 2 and the cold climate (section 3) is relatively sharp. It can be correlated from core to core over the whole area investigated. The cold climate sediments of section 3 are underlain by different cool-, warm- and cold-climate sediments which can only be correlated over very short distances. Since it appears certain that the last really cold conditions ended earlier in the Arabian Sea and its vicinity than in Europe it is recommended not to use the European stratigraphic terms for the Quaternary. Because of the lack of reliable absolute sediment ages for the cores no exact sedimentation rates can be given. According to rough estimates, however, the rates are 1-2 cm/1000 years in the deep basin and up to 40 cm/1000 years on the upper continental slope. Sedimentation rates are always larger near the mouth of the Indus-River than off South India at stations of about the same water depth. Planktonic gastropods (mainly pteropods) cannot be used for biostratigraphic purposes in the region under consideration. All of them seem to be displaced from the shelf. Their distribution there is given in.

The nitrogen costs of photosynthesis in a diatom under current and future pCO2

With each cellular generation, oxygenic photoautotrophs must accumulate abundant protein complexes that mediate light capture, photosynthetic electron transport and carbon fixation. In addition to this net synthesis, oxygenic photoautotrophs must counter the light-dependent photoinactivation of Photosystem II (PSII), using metabolically expensive proteolysis, disassembly, resynthesis and re-assembly of protein subunits. We used growth rates, elemental analyses and protein quantitations to estimate the nitrogen (N) metabolism costs to both accumulate the photosynthetic system and to maintain PSII function in the diatom Thalassiosira pseudonana, growing at two pCO2 levels across a range of light levels. The photosynthetic system contains c. 15-25% of total cellular N. Under low growth light, N (re)cycling through PSII repair is only c. 1% of the cellular N assimilation rate. As growth light increases to inhibitory levels, N metabolite cycling through PSII repair increases to c. 14% of the cellular N assimilation rate. Cells growing under the assumed future 750 ppmv pCO2 show higher growth rates under optimal light, coinciding with a lowered N metabolic cost to maintain photosynthesis, but then suffer greater photoinhibition of growth under excess light, coincident with rising costs to maintain photosynthesis. We predict this quantitative trait response to light will vary across taxa.

Radiocarbon ages, d13C values and rare earth element content of sediment cores BP00-23/07 and BP00-07/06

Two bottom sediment cores (BP00-23/7 and BP00-7/6) recovered from the Yenisei transect in the southern Kara Sea are described. Data on their grain size composition, clay and heavy mineral assemblages, and distribution of a large group of chemical elements are presented. Radiocarbon dates based on AMS C-14 method suggest the Holocene age of sediments in the cores. Literature data on physical properties and foraminifers have also been analyzed. The facies affiliation of the lithostratigraphic subdivisions has been unraveled. History of the Yenisei River runoff in the Holocene has been reconstructed on the basis of different indicators.

Barents and Kara Seas oceanographic data base (BarKode)

Oceanographic data collected by ocean research organisations in Russia, the USA, the United Kingdom, Germany, Norway, and Poland for the Barents, Kara and White Seas region are presented in this atlas. Recently declassified naval data from Norway, the USA, and the UK are also included. More than 1,000,000 oceanographic stations containing temperature and/or sea-water salinity data were originally selected. After correcting errors and eliminating duplicates, data from 206,300 checked stations were placed on CD-ROM, together with many figures describing the characteristics of both the single-input and combined data set. In addition, temperature and salinity measurements were interpolated to the following standard horizons: 0, 25, 50, 100, 150, 200, 250, 300 m, and bottom. This atlas covers the 100-year period 1898 to 1998 and is, to date, the most complete oceanographic data collection for these Arctic shelf seas. This data set is complemented by more than 9,000 measurements of sea surface temperature, which were recently digitized from ships' logbooks. They cover the same geographical area within the time period 1867-1912.

Radiocarbon ages and clay minerals in sediment cores obtained during a 2009 Jan Mayen cruise to the Norwegian Sea

The origin of two acoustic sediment units has been studied based on lithological facies, chronology and benthic stable isotope values as well as on foraminifera and clay mineral assemblages in six marine sediment cores from Kveithola, a small trough west of Spitsbergenbanken on the western Barents Sea margin. We have identified four time slices with characteristic sedimentary environments. Before c. 14.2 cal. ka, rhythmically laminated muds indicate extensive sea ice cover in the area. From c. 13.9 to 14.2 cal. ka, muds rich in ice-rafted debris were deposited during the disintegration of grounded ice on Spitsbergenbanken. From c. 10.3 to 13.1 cal. ka, sediments with heterogeneous lithologies suggest a shifting influence of suspension settling and iceberg rafting, probably derived from a decaying Barents Sea Ice Sheet in the inner-fjord and land areas to the north of Kveithola. Holocene deposition was episodic and characterized by the deposition of calcareous sands and shell debris, indicative of strong bottom currents. We speculate that a marked erosional boundary at c. 8.2 cal. ka may have been caused by the Storegga tsunami. Whilst deposition was sparse during the Holocene, Kveithola acted as a sediment trap during the preceding deglaciation. Investigation of the deglacial sediments provides unprecedented details on the dynamics and timing of glacial retreat from Spitsbergenbanken.