Rolle und Bedeutung der Chemie im Terrorismus

Terrorism is directed by terrorist organizations and terrorist individuals with different ways of carrying out acts of violence against the democratically established order with the aim of political or religious changes. The focus is still the increasing number of attacks with explosives, which is discussed in this article more detailed. Also incendiary bombs are a simple possibility of attack. A major potential risk is seen through the spreading of toxic chemicals (chemical warfare agents, products from industrial production). This is also the case of attacks with radioactive materials by help of explosives. The misuse of chemistry is dicussed also under consideration of potential terrorist attacks by biological and nuclear weapons. Then due to the responsibility of our scientific community we can better engage ourselves in the discussion about terrorism, threats through attacks and possible avoidance strategies.     

Analysis of isotopic signals in the Danube River water at Tulln,Austria, based on daily grab samples in 2012

Results of stable isotope measurements (δ²H, δ¹⁸O) of daily grab samples, taken from the Danube River at Tulln (river km 1963) during 2012, show seasonal and short-term variations depending on the climatic/hydrological conditions and changes in the catchment area (temperature changes, heavy rains and snow melt processes). Isotope ratios in river water clearly reflect the isotopic composition of precipitation water in the catchment area since evaporation influences play a minor role. Average δ²H and δ¹⁸O values in 2012 are?78‰ and?11.0‰, respectively, deuterium excess averages 10‰. The entire variation amounts to 1.8‰ in δ¹⁸O and 15‰ in δ²H. Quick changes of the isotopic composition within a few days emphasise the necessity of daily sampling for the investigation of hydrological events, while monthly grab sampling seems sufficient for the investigation of long-term hydro-climatic trends. ³H results show peaks (half-width 1–2 days, up to about 150 TU) exceeding the regional environmental level of about 9 TU, probably due to releases from nuclear power plants.     

Flying qubits and entangled photons

Efficient generation of polarized single photons or entangled photon pairs is crucial for the implementation of quantum key distribution (QKD) systems. Self organized semiconductor quantum dots (QDs) are capable of emitting on demand one polarized photon or an entangled photon pair upon current injection. Highly efficient single‐photon sources consist of a pin structure inserted into a microcavity where single electrons and holes are funneled into an InAs QD via a submicron AlOx aperture, leading to emission of single polarized photons with record purity of the spectrum and non‐classicality of the photons. A new QD site‐control technique is based on using the surface strain field of an AlO_x current aperture below the QD. GaN/AlN QD based devices are promising to operate at room temperature and reveal a fine‐structure splitting (FSS) depending inversely on the QD size. Large GaN/AlN QDs show disappearance of the FSS. Theory also suggests QDs grown on (111)‐oriented GaAs substrates as source of entangled photon pairs.     

A Continuous-Wave Electron Paramagnetic Resonance Study of Carbon Dioxide Adsorption on the Metal–Organic Frame-Work MIL-53

Continuous-wave electron paramagnetic resonance spectroscopy is applied to explore the adsorption of carbon dioxide (CO₂) over the metal organic framework (MOF) MIL-53. Therefore, paramagnetic Cr³⁺ ions, which replace a small amount of the bulk Al³⁺ ions in MIL-53(Al/Cr), are used as magnetically active probes. CO₂ was adsorbed on samples of MIL-53(Al/Cr) at equilibrium pressures between 0 and 2.5 bar. The transformation from the large pore phase to the narrow pore phase of MIL-53 was observed by electron paramagnetic resonance spectroscopy at small CO₂ pressures between 0.2 and 0.4 bar, which is in accordance with adsorption results reported in literature. By analyzing the electron paramagnetic resonance signal intensities of the corresponding Cr³⁺ probes, the ratio between the amount of the narrow pore phase and the large pore phase before and after this phase transformation was quantified. A small fraction of the large pore phase remains even after this phase transition. CO₂ adsorption at 77  K indicates the occurrence of the transformation of this MOF from a narrow pore phase to a large pore phase triggered by the adsorbed CO₂. Similar observations were already made using powder X-ray diffraction or infrared spectroscopy. But in contrast to these methods electron paramagnetic resonance spectroscopy on Cr³⁺ seems to be very sensitive not only to large differences between crystallographic conformations like large pores and narrow pores but also to different amounts and configurations of CO₂ molecules trapped in the same structural phase of MIL-53, taking advantage of the high sensitivity of the fine structure interaction of Cr³⁺.     

Inverted organic solar cells comprising low-temperature-processed ZnO films

Inverted organic solar cells are fabricated using low-temperature-annealed ZnO film as an electron transport layer. Uniform ZnO films were prepared by spin coating a diethylzinc (DEZ) precursor solution in air, followed by annealing at 100 °C. Organic solar cells prepared on these ZnO films with a 1:1 P3HT:PCBM blend as the active layer show a high power conversion efficiency of 4.03 %, which is more than 10 % higher than the PCE of solar cells comprising ZnO prepared via a high-temperature sol–gel route.     

Merging organocatalysis and gold catalysis-a critical evaluation of the underlying concepts

While both organocatalysis and gold catalysis have their roots deeply entrenched in the landscape of modern organic chemistry, an exciting trend in the complementary merging of organocatalysis and especially Au(I) catalysis has emerged in the last four years. This niche area has been developing rapidly and this minireview serves to pin-point the fundamental concepts guiding reaction design in these binary catalytic systems. Moreover, the proven synthetic utility of organo/Au(I) multicatalytic systems in accessing molecular frameworks, previously a challenge to single catalytic systems, has resulted in this new concept permeating numerous areas of organocatalysis, such as primary/secondary amine, Br?nsted acid, hydrogen-bonding as well as N-heterocyclic carbene (NHC) catalysis. The first detailed account of these recent developments is systematically presented.     

Organocatalytic, asymmetric synthesis of 3-sulfenylated N-boc-protected oxindoles

Sulfenylated oxindoles: The first asymmetric sulfenylation of N-Boc-protected oxindoles has been developed to provide products containing a tetrasubstituted stereogenic center in high to excellent yields (86-98?%) and, in most cases, excellent enantioselectivities (up to 96?%?ee; see scheme).     

A fluorescently labeled dendronized polymer-enzyme conjugate carrying multiple copies of two different types of active enzymes

A hybrid structure of a synthetic dendronized polymer, two different types of enzymes (superoxide dismutase and horseradish peroxidase), and a fluorescent dye (fluorescein) was synthesized. Thereby, a single polymer chain carried multiple copies of the two enzymes and the fluorescein. The entire attachment chemistry is based on UV/vis-quantifiable bis-aryl hydrazone bond formation that allows direct quantification of bound molecules: 60 superoxide dismutase, 120 horseradish peroxidase, and 20 fluorescein molecules on an average polymer chain of 2000 repeating units. To obtain other enzyme ratios the experimental conditions were altered accordingly. Moreover, it could be shown that both enzymes remained fully active and catalyzed a two-step cascade reaction.     

Solid-state photopolymerization of a shape-persistent macrocycle with two 1,8-diazaanthracene units in a single crystal

A macrocyclic monomer with two opposing 1,8-diazaanthracene units is polymerized in a single crystal by a photochemically induced [4 + 4] cycloaddition reaction between neighboring monomers in which the anthracene units are stacked face-to-face at the critical Schmidt distance. The severe structural changes associated with this are minimized by the monomer design, wherein the linkers between the two opposing photoreactive 1,8-diazaanthracene units are connected to the 4 and 5 positions of the latter, whose spatial positioning is changed the least during dimerization. This helps to keep the monomer's overall shape basically unchanged during the polymerization. The resulting new rigid-rod polymer is soluble in its protonated form, and after counterion exchange with a surfactant, it can be depolymerized back into monomer upon relatively mild thermal treatment (120 °C) in an organic solvent.