A Donor-Acceptor Tetrathiafulvalene Ligand Complexed to Iron(II): Synthesis, Electrochemistry, and Spectroscopy of Fe(phen)(2)(TTF-dppz)(PF6)(2)

The synthesis and photophysical properties of the complex Fe(phen)(2)(TTF-dppz)(2+) (TTF-dppz = 4',5'-bis-(propylthio)tetrathiafulvenylidipyrido3,2-a:2',3'-c-phenazine, phen = 1,10-phenanthroline) are described. In this complex, excitation into the metal ligand charge transfer bands results in the population of a high-spin state of iron(II), with a decay lifetime of approximately 1.5 ns, in dichloromethane, at room temperature. An intraligand charge transfer state can also be obtained and has a lifetime of 38 ps. A mechanism for the different states reached is proposed based on transient absorption spectroscopy.

Iron fluxes to Talos Dome, Antarctica, over the past 200 kyr

Atmospheric fluxes of iron (Fe) over the past 200 kyr are reported for the coastal Antarctic Talos Dome ice core, based on acid leachable Fe concentrations. Fluxes of Fe to Talos Dome were consistently greater than those at Dome C, with the greatest difference observed during interglacial climates. We observe different Fe flux trends at Dome C and Talos Dome during the deglaciation and early Holocene, attributed to a combination of deglacial activation of dust sources local to Talos Dome and the reorganisation of atmospheric transport pathways with the retreat of the Ross Sea ice shelf. This supports similar findings based on dust particle sizes and fluxes and Rare Earth Element fluxes. We show that Ca and Fe should not be used as quantitative proxies for mineral dust, as they all demonstrate different deglacial trends at Talos Dome and Dome C. Considering that a 20 ppmv decrease in atmospheric CO2 at the coldest part of the last glacial maximum occurs contemporaneously with the period of greatest Fe and dust flux to Antarctica, we confirm that the maximum contribution of aeolian dust deposition to Southern Ocean sequestration of atmospheric CO2 is approximately 20 ppmv.�

Haematologic data, iron parameters and molecular findings in two new cases of iron-refractory iron deficiency anaemia

Matriptase-2 (Tmprss6), a type II transmembrane serine protease, has an essential role in iron homoeostasis as a hepcidin regulator. Recently, patients with TMPRSS6 mutations and suffering from iron-refractory iron deficiency anaemia (IRIDA) have been reported. We describe two new cases of IRIDA, one patient of Swiss origin and the second of Italian origin. The first case results from a large deletion of 1054 nucleotides corresponding to an in frame deletion of 30 amino acid residues in the low-density lipoprotein receptor-1/-2 (LDLR-1/-2) domains and from a missense mutation in CUB1 (S304L). In the second case, a homozygous G-->C mutation in the last nucleotide of exon 15 and which modified the consensus sequence of the 5' splice donor site of intron 15 (AGgt-->ACgt) was identified. Both patients had a high hepcidin level and low serum iron and transferrin saturation compared to age-matched controls. Continuous perfusion of i.v. iron 4 h/d x 5 d in the first case resulted in a significant rise in haemoglobin. These new cases of IRIDA illustrate the importance of LDLR-1/-2 and CUB1 domains in matriptase-2 function as well as the role of matriptase-2 in hepcidin regulation. Furthermore a deletional form of TMPRSS6 (in LDLR-1/-2 domains) resulting in IRIDA is described for the first time. These cases reinforce the belief that patients suffering from IRIDA have no specific geographical or ethnic distribution and are sporadic secondary to different mutations of the matriptase-2 gene.

Contrasts, Contacts, and Interconnections — Tel Kinrot as an Early Iron Age Key Site in the Northern Jordan Rift Valley at the Dawn of the 1st Millennium BCE

Ancient Kinneret (Tēl Kinrōt [Hebrew]; Tell el-ʿOrēme [Arabic]) is located on a steep limestone hill on the northwestern shores of the Sea of Galilee (2508.7529 [NIG]). The site, whose settlement history began sometime during the Pottery-Neolithic or the early Chalcolithic period, is emerging as one of the major sites for the study of urban life in the Southern Levant during the Early Iron Age (c. 1130–950 BCE). Its size, accessibility by major trade routes, and strategic location between different spheres of cultural and political influence make Tēl Kinrōt an ideal place for studying the interaction of various cultures on urban sites, as well as to approach questions of ethnicity and regionalism during one of the most debated periods in the history of the ancient Levant. The paper will briefly discuss the settlement history of the site during the Early Iron Age. However, the main focus will lie on the material culture of the late Iron Age IB city that rapidly evolved to a regional center during the transition from the 11th to the 10th century BCE. During this period, ancient Kinneret features a multitude of cultural influences that reach from Egypt via the Central Hill Country until the Northern parts of Syria and the Amuq region. While there are indisputably close ties with the ‘Aramaean’ realm, there are also strong indications that there were – at the same time – vivid socio-economic links with the West, i.e. the Southern and Northern Mediterranean coasts and their hinterland. It will be argued that the resulting ‘cultural blend’ is a typical characteristic of the material culture of the Northern Jordan Rift Valley in the advent of the emerging regional powers of the Iron Age II.

Chiral Templating Activity of Tris(bipyridine)ruthenium(II) Cation in the Design of Three-Dimensional (3D) Optically Active Oxalate-Bridged {[Ru(bpy) 3 ][Cu 2 x Ni 2(1 - x ) (C 2 O 4 ) 3 ]} n (0 ≤ x ≤ 1; bpy = 2,2‘-bipyridine): Structural, Optical, and Magnetic Studies

Three-dimensional oxalate-based {[Ru(bpy)3][Cu2xNi2(1-x)(ox)3]}n (0≤ x ≤ 1, ox = C2O42-, bpy = 2,2‘bipyridine) were synthesized. The structure was determined for x = 1 by X-ray diffraction on single crystal. The compound crystallizes in the cubic space group P4132. It shows a three-dimensional 10-gon 3-connected (10,3) anionic network where copper(II) has an unusual tris(bischelated) environment. X-ray powder diffraction patterns and their Rietveld refinement show that all the compounds along the series are isostructural and single-phased. According to X-ray absorption spectroscopy, copper(II) and nickel(II) have an octahedral environment, respectively elongated and trigonally distorted. As shown by natural circular dichroism, the optically active forms of {[Ru(bpy)3][CuxNi2(1-x)(ox)3]}n are obtained starting from resolved Δ- or Λ-[Ru(bpy)3]2+. The Curie−Weiss temperatures range between −55 (x = 1) and −150 K (x = 0). The antiferromagnetic exchange interaction thus decreases when the copper contents increases in agreement with the crystallographic structure of the compounds and the electronic structure of the metal ions. At low temperature, the compounds exhibit complex long-range ordered magnetic behavior.