Elemental and Lead Isotopic Data of Copper Finds from the Singen Cemetery, Germany – a Methodological Approach to Investigate Early Bronze Age Trade Networks

We report a trace element - Pb isotope analytical (LIA) database on the "Singen Copper", a peculiar type of copper found in the North Alpine realm, from its type locality, the Early Bronze Age Singen Cemetery (Germany). What distinguishes “Singen Copper” from other coeval copper types? (i) is it a discrete metal lot with a uniform provenance (if so, can its provenance be constrained)? (ii) was it manufactured by a special, unique metallurgical process that can be discriminated from others? Trace element concentrations can give clues on the ore types that were mined, but they can be modified (more or less intentionally) by metallurgical operations. A more robust indicator are the ratios of chemically similar elements (e.g. Co/Ni, Bi/Sb, etc.), since they should remain nearly constant during metallurgical operations, and are expected to behave homogeneously in each mineral of a given mining area, but their partition amongst the different mineral species is known to cause strong inter-element fractionations. We tested the trace element ratio pattern predicted by geochemical arguments on the Brixlegg mining area. Brixlegg itself is not compatible with the Singen Copper objects, and we only report it because it is a rare instance of a mining area for which sufficient trace element analyses are available in the literature. We observe that As/Sb in fahlerz varies by a factor 1.8 above/below median; As/Sb in enargite varies by a factor of 2.5 with a 10 times higher median. Most of the 102 analyzed metal objects from Singen are Sb-Ni-rich, corresponding to “antimony-nickel copper” of the literature. Other trace element concentrations vary by > 100 times, ratios by factors > 50. Pb isotopic compositions are all significantly different from each other. They do not form a single linear array and require > 3 ore batches that certainly do not derive from one single mining area. Our data suggest a heterogeneous provenance of “Singen copper”. Archaeological information limits the scope to Central European sources. LIA requires a diverse supply network from many mining localities, including possibly Brittany. Trace element ratios show more heterogeneity than LIA; this can be explained either by deliberate selection of one particular ore mineral (from very many sources) or by processing of assorted ore minerals from a smaller number of sources, with the unintentional effect that the quality of the copper would not be constant, as the metallurgical properties of alloys would vary with trace element concentrations.

A copper-induced quinone degradation pathway provides protection against combined copper/quinone stress in Lactococcus lactis IL1403.

Quinones are ubiquitous in the environment. They occur naturally but are also in widespread use in human and industrial activities. Quinones alone are relatively benign to bacteria, but in combination with copper, they become toxic by a mechanism that leads to intracellular thiol depletion. Here, it was shown that the yahCD-yaiAB operon of Lactococcus lactis IL1403 provides resistance to combined copper/quinone stress. The operon is under the control of CopR, which also regulates expression of the copRZA copper resistance operon as well as other L. lactis genes. Expression of the yahCD-yaiAB operon is induced by copper but not by quinones. Two of the proteins encoded by the operon appear to play key roles in alleviating quinone/copper stress: YaiB is a flavoprotein that converts p-benzoquinones to less toxic hydroquinones, using reduced nicotinamide adenine dinucleotide phosphate (NADPH) as reductant; YaiA is a hydroquinone dioxygenase that converts hydroquinone putatively to 4-hydroxymuconic semialdehyde in an oxygen-consuming reaction. Hydroquinone and methylhydroquinone are both substrates of YaiA. Deletion of yaiB causes increased sensitivity of L. lactis to quinones and complete growth arrest under combined quinone and copper stress. Copper induction of the yahCD-yaiAB operon offers protection to copper/quinone toxicity and could provide a growth advantage to L. lactis in some environments.

Evaluation of chocolate as a source of dietary copper

Chocolate has frequently been proposed to be a valuable source of dietary copper, but data on the copper content of major contemporary chocolate brands are scarce. The copper content of 22 brands of chocolate, many of which are sold worldwide, is thus presented here. A reliable hot ashing procedure to determine the copper content of chocolate by inductively coupled plasma atomic emission spectroscopy is also described. It was found that the copper contents of the chocolates analyzed here varied in the range of 1.85 ± 0.10 to 16.50 ± 1.29 μg/g. There was a linear correlation of the copper content of chocolate to its cocoa content with a correlation coefficient R2 of 0.89, showing that the copper was largely contributed to the chocolate by the cocoa. The value of chocolate as a source of dietary copper is discussed.

Synthesis, structure and magnetic properties of cobalt(II) and copper(II) coordination polymers assembled by phthalate and 4-methylimidazole

New coordination polymers [M(Pht)(4-MeIm)2(H2O)]n (M=Co (1), Cu (2); Pht2−=dianion of o-phthalic acid; 4-MeIm=4-methylimidazole) have been synthesized and characterized by IR spectroscopy, X-ray crystallography, thermogravimetric analysis and magnetic measurements. The crystal structures of 1 and 2 are isostructural and consist of [M(4-MeIm)2(H2O)] building units linked in infinite 1D helical chains by 1,6-bridging phthalate ions which also act as chelating ligands through two O atoms from one carboxylate group in the case of 1. In complex 1, each Co(II) atom adopts a distorted octahedral N2O4 geometry being coordinated by two N atoms from two 4-MeIm, three O atoms of two phthalate residues and one O atom of a water molecule, whereas the square-pyramidal N2O3 coordination of the Cu(II) atom in 2 includes two N atoms of N-containing ligands, two O atoms of two carboxylate groups from different Pht, and a water molecule. An additional strong O–H⋯O hydrogen bond between a carboxylate group of the phthalate ligand and a coordinated water molecule join the 1D helical chains to form a 2D network in both compounds. The thermal dependences of the magnetic susceptibilities of the polymeric helical Co(II) chain compound 1 were simulated within the temperature range 20–300 K as a single ion case, whereas for the Cu(II) compound 2, the simulations between 25 and 300 K, were made for a linear chain using the Bonner–Fisher approximation. Modelling the experimental data of compound 1 with MAGPACK resulted in: g=2.6, |D|=62 cm−1. Calculations using the Bonner–Fisher approximation gave the following result for compound 2: g=2.18, J=–0.4 cm−1.

Nickel(II)-, cobalt(II)-, copper(II)-, and zinc(II)-phthalate and 1-methylimidazole coordination compounds: synthesis, crystal structures and magnetic properties

Three new coordination polymers [M(Pht)(1-MeIm)2]n (where M=Cu (1), Zn (2), Co (3); Pht2−=dianion of o-phthalic acid; 1-MeIm=1-methylimidazole) and two compounds [M(1-MeIm)6](HPht)2 · 2H2O (M=Co (4), Ni (5)) have been synthesized and characterized by X-ray crystallography. The structures of 1–3 (2 is isostructural to 3) consist of [M(1-MeIm)2] building units connected by 1,6-bridging phthalate ions to form infinite chains. In complex 1, each copper(II) center adopts a square coordination mode of N2O2 type by two O atoms from different phthalate ions and two N atoms of 1-MeIm, whereas in 3 two independent metal atoms are tetrahedrally (N2O2) coordinated to a pair of Pht ligands and a pair of 1-MeIm molecules. There are only van der Waals interactions between the chains in 1, while the three-dimensional network in 3 is assembled by C–H⋯O contacts. In contrast to polymers 1–3 the structures of 4 and 5 (complexes are also isostructural) are made up of the [M(1-MeIm)6]2+ cation, two hydrogen phthalate anions (HPht−) and two H2O solvate molecules. The coordination around each metal(II) atom is octahedral with six nitrogen atoms of 1-MeIm. Extended hydrogen bonding networks embracing the solvate water molecules and a phthalate residue as well as the weak C–H⋯O interactions stabilize the three-dimensional structures. Magnetic studies clearly show that the magnetic ions do not interact with each other. Furthermore, in compound 4 we have another example of a highly anisotropic Co2+ ion with a rhombic g-tensor and large zero-field-splitting. The complexes were also characterized by IR and 1H NMR spectroscopy, thermogravimetric analysis, and all data are discussed in the terms of known structures.

Metamagnetic Copper(II) Diphosphonates with Layered Structures

Compounds [NH3(CH2)4NH3]Cu3(hedp)2·2H2O (1) and [NH3(CH2)3NH3]Cu3(hedp)2·3.5H2O (2), where hedp represents 1-hydroxyethylidenediphosphonate, exhibit two-dimensional structures closely related to each other. The anionic layers with composition {Cu3(hedp)2}n2n- contain four- and eight-membered rings assembled from vertex-sharing {CuO4} units and {CPO3} tetrahedra. The protonated diamines and lattice water fill the interlayer spaces. Crystal data for 2:  space group P1̄, a = 8.0315(4), b = 11.3713(6), c = 13.3117(7) Å, α = 97.122(1), β = 103.187(1), γ = 108.668(1)°, V = 1095.5(1) Å3, Z = 2. Magnetic properties of the two compounds have been investigated. Both show typical metamagnetic behaviors at low temperature. The critical field at which the antiferromagnetic ground-state switches to a ferrimagnetic state is ∼48 Oe for 1 and 185 Oe for 2 at about 2 K.

Syntheses, structures and magnetic properties of two copper(Ii) diphosphonates: [NH3(CH2)2NH3]2[Cu2(hedp)2]·H2O and [NH3CH(CH3)CH2NH3]2[Cu2(hedp)2] (hedp = 1-hydroxyethylidenediphosphonate)

This paper describes the syntheses and characterization of two new copper(II) diphosphonates: [NH3(CH2)2NH3]2[Cu2(hedp)2]·H2O (1) and [NH3CH(CH3)CH2NH3]2[Cu2(hedp)2] (2) (hedp = 1-hydroxyethylidenediphosphonate). Both compounds exhibit similar one-dimensional linear chain structures. The symmetrical {Cu2(hedp)2} dimers are connected by edge-shared {CuO5} square pyramids and form infinite chains. The Cu(II) ions are alternately bridged by O–P–O groups and O atoms. The Cu–O–Cu angles are 95.8(1) and 96.1(1)° for 1 and 2, respectively. Their magnetic properties show moderately strong antiferromagnetic interactions in both compounds.

A new 1D bimetallic thiocyanate-bridged copper(II)–cobalt(II) compound

The crystal structure of the first one-dimensional hetero-metallic compound containing thiocyanate as bridging ligands,{[Cu(cyclam)][Co(NCS)4]}n, has been determined, togetherwith a preliminary study of the magnetic properties.

A new bidimensional compound containing (μ-thiocyanate)(bpy)copper(II) molecules: synthesis, crystal structure and magnetic properties of [Cu(bpy)(NCS)2]n (bpy = 2,2'-bipyridyl)

The crystal structure of the first bidimensional copper(II) compound containing only thiocyanate as bridging ligands [Cu(bpy)(NCS) 2 ] n , where bpy=2,2'-bipyridyl, has been determined by X-ray diffraction on single-crystals. Two different environments for both types of copper(II) ions in the unit cell are apparent: a distorted octahedron and a square pyramid. A bidimensional structure with a deformed honeycomb-layer motif is formed, the bipyridyl ligands filling the interlayer space. The magnetic susceptibility data of the compound have been investigated between 280 and 1.8 K. The compound presents a very weak antiferromagnetic interaction that has been fitted by using the Bleaney-Bowers expression for a dimeric unit, whereby a J value of -1.01(1) cm - 1 (H=-JS 1 .S 2 ) and a g value of 2.08(1) have been obtained.

Reaction of Copper(II) Chloroacetate with Pyrazole. Synthesis of a One-Dimensional Coordination Polymer and Unexpected Dehydrochlorination Reaction

The reaction of copper(II) chloroacetate (1d) with pyrazole (Hpz) mainly yielded the mononuclear compound [Cu(μ-ClCH2COO)2(Hpz)2] (2m), which self-assembled generating a one-dimensional coordination polymer. Moreover, the concomitant isolation of the tetranuclear [{Cu2(μ-pz)(μ-OCH2COO)(Hpz)(MeOH)}2(μ-ClCH2COO)2] (3t) and hexanuclear [{Cu3(μ3-OH)(μ-pz)3(Hpz)2}2(μ-ClCH2COO)2](Cl)2 (4h) species evidenced the occurrence of a peculiar, previously unreported, dehydrochlorination reaction and the formation of the trinuclear triangular moiety [Cu3(μ3-OH)(μ-pz)3]. Theoretical calculations based on density functional theory including solvation effects indicate a possible pathway for the formation of 3t. Interestingly, besides the energy minimum corresponding to 3t, a further relative energy minimum is found for a species which can be considered a possible reaction intermediate.