IMEP-24 analysis of eight trace elements in toys

The International Measurement Evaluation Program (IMEP) organized the IMEP-24 interlaboratory comparison after reports in the media about high levels of lead in toys. The aim of this comparison was to verify the laboratories’ capacity to evaluate trace-element levels in a possible toy-like material according to the European Standard EN 71-3:1994. As test material, it used a former certified reference material containing levels of antimony, arsenic, barium, cadmium, chromium, mercury, lead and selenium around the limits set in the standard.Four expert laboratories confirmed the reference values (Xref) for all elements but Hg, and established a reference value for Hg. The scatter of the results reported by the participants was large, as expected, but showed a close to normal distribution around the reference values for five of the eight trace elements. The spread of results was mainly attributed to sampling and sample preparation.One major issue observed in this exercise was the lack of legislative rules about how to report the result, or, more specifically, the use of the analytical correction, which was introduced in EN 71-3:1994 to achieve consistent interpretation of results and which is to be applied when values are equal to or above the maximum limits set in the standard. Its application by the participants was very inconsistent and led to problems in their evaluation. There is clearly a need for clarification and for more formal regulations with regard to result reporting in order to minimize the risk of confusion.Participants were also asked to give their opinion with regard to the acceptability of the test material for the market. The majority correctly considered the material as non-compliant. However, almost one-third incorrectly assessed the material as compliant.     

Application of NMR methods to the study of the interaction of natural products with biomolecular receptors

In this review, we present applications of NMR spectroscopy as a potent tool for the study of molecular interactions. It is clear that a variety of NMR methods may be employed to deduce key features of ligand–receptor molecular recognition processes, looking at the process from the perspective of the receptor or the ligand. We have not provided an exhaustive review, but we have tried to focus on describing the different aspects within this research topic. We have therefore selected examples accordingly, depending on the particular problem under study or the application/development of protocols to circumvent the technical problems that may be found when working in this field.     

Synthesis, crystal structures and magnetic properties of M(II)Cu(II) chains (M = Mn and Co) with sterically hindered alkyl-substituted phenyloxamate bridging ligands

A series of neutral oxamato‐bridged heterobimetallic chains of general formula [MCu(L^x)₂(S)₂] ? p S ? q H₂O [p=0–1, q=0–2.5; L¹=N‐2,6‐dimethylphenyloxamate, S=DMF with M=Mn ( 1 a ) and Co ( 1 b ); L²=N‐2,6‐diethylphenyloxamate, S=DMF with M=Mn ( 2 a ) and Co ( 2 b ) or S=DMSO with M=Mn ( 2 c ) and Co ( 2 d ); L³=N‐2,6‐diisopropylphenyloxamate, S=DMF with M=Mn ( 3 a ) and Co ( 3 b ) or S=DMSO with M=Mn ( 3 c ) and Co ( 3 d )] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(L^x)₂]^2? (x=1–3) with M²⁺ cations (M=Mn and Co) in DMF or DMSO as the solvent. The single‐crystal X‐ray structures of 2 a and 3 a reveal the occurrence of well‐isolated, zigzag, oxamato‐bridged manganese(II)–copper(II) chains. The intrachain Cu ??? Mn distances across the oxamato bridge are 5.3761(7) and 5.4002(17) Å for 2 a and 3 a , respectively, whereas the shortest interchain Mn ??? Mn distances are 9.4475(16) and 8.1649(14) Å for 2 a and 3 a , respectively. All of these M^IICu^II chains (M=Mn and Co) exhibit 1D ferrimagnetic behaviour with moderately strong intrachain antiferromagnetic coupling between the square‐planar Cu^II and octahedral high‐spin M^II ions across the oxamato bridge [?J=31.4–35.2 and 33.4–44.8 cm^?1, respectively; H =∑_i?J S _M,i( S _Cu,i+ S _Cu,i?1)]. Only the Co^IICu^II chains show slow magnetic relaxation effects characteristic of single‐chain magnets (SCMs). Analysis of the magnetic relaxation dynamics of 3 d shows a thermally activated mechanism (Arrhenius law dependence) with values of the pre‐exponential factor (τ₀=2.6×10^?9 s) and activation energy (E_a=7.7 cm^?1) that are typical of SCMs. In contrast, two relaxation regimes are observed for 2 d in different temperature regions (τ₀=3.2×10^?10 s and E_a=24.7 cm^?1 for T<4.5 K and τ₀=3.2×10^?14 s and E_a=37.5 cm^?1 for T>4.5 K).     

High proton conduction in a chiral ferromagnetic metal-organic quartz-like framework

A complex-as-ligand strategy to get a multifunctional molecular material led to a metal-organic framework with the formula (NH(4))(4)[MnCr(2)(ox)(6)]·4H(2)O. Single-crystal X-ray diffraction revealed that the anionic bimetallic coordination network adopts a chiral three-dimensional quartz-like architecture. It hosts ammonium cations and water molecules in functionalized channels. In addition to ferromagnetic ordering below T(C) = 3.0 K related to the host network, the material exhibits a very high proton conductivity of 1.1 × 10(-3) S cm(-1) at room temperature due to the guest molecules.     

Balancing binding strength and charge transfer lifetime in supramolecular associates of fullerenes

A macrocyclic exTTF host for fullerenes offers control over the electronic coupling between an electron donor and an acceptor, and stabilizes the charge separated state lifetimes into the range of 500 ps.     

Wraparound hosts for fullerenes: tailored macrocycles and cages

Custom-made macrocyclic receptors for fullerenes are proving a valuable alternative to achieve the affinity and selectivity required to meet challenges such as the selective extraction of higher fullerenes, their chiral resolution, or the self-assembly of functional molecular materials. In this Minireview, we highlight some of the important breakthroughs that this class of fullerene hosts has already produced.     

The effect of selective contact electrodes on the interfacial charge recombination kinetics and device efficiency of organic polymer solar cells

Organic polymer solar cells (OPSCs) have been prepared using TiO(x) metal oxides as selective electrodes for electron collection. The interfacial charge transfer reactions, under working conditions, that limit the energy conversion efficiency of these devices have been measured and compared to the standard OPSC geometry which collects the electrons through a low work function metal contact.     

Electric double layer for spherical particles in salt-free concentrated suspensions including ion size effects

The equilibrium electric double layer (EDL) that surrounds colloidal particles is essential for the response of a suspension under a variety of static or alternating external fields. An ideal salt-free suspension is composed of charged colloidal particles and ionic countercharges released by the charging mechanism. Existing macroscopic theoretical models can be improved by incorporating different ionic effects usually neglected in previous mean-field approaches, which are based on the Poisson-Boltzmann equation (PB). The influence of the finite size of the ions seems to be quite promising because it has been shown to predict phenomena like charge reversal, which has been out of the scope of classical PB approximations. In this work we numerically obtain the surface electric potential and the counterion concentration profiles around a charged particle in a concentrated salt-free suspension corrected by the finite size of the counterions. The results show the high importance of such corrections for moderate to high particle charges at every particle volume fraction, especially when a region of closest approach of the counterions to the particle surface is considered. We conclude that finite ion size considerations are obeyed for the development of new theoretical models to study non-equilibrium properties in concentrated colloidal suspensions, particularly salt-free ones with small and highly charged particles.