Disorder induced quantum phase transition in random-exchange spin-1/2 chains

We investigate the effect of quenched bond disorder on the anisotropic antiferromagnetic spin-1/2 (XXZ) chain as a model for disorder-induced quantum phase transitions. We find nonuniversal behavior of the average correlation functions for weak disorder, followed by a quantum phase transition into a strongly disordered phase with only short-range xy correlations. We find no evidence for the universal strong-disorder fixed point predicted by the real-space renormalization group, suggesting a qualitatively different view of the relationship between quantum fluctuations and disorder.     

Light Emission Resulting from Hydroxylamine-Induced Singlet Oxygen Formation of Oxidizing LDL Particles

Abstract— Oxidation of low-density lipoprotein (LDL) by low amounts of cupric ions resulted in the formation of singlet oxygen (₁O₂, ₁DL_g) when hydroxylamine (NH2OH) was added. Direct evidence on this excited species came from partial spectral resolution of the emitted light in the red spectral region (634 nm and 703 nm), which can be attributed to the dimol decay of singlet oxygen. Additional evidence for the existence of singlet oxygen came from the enhancing effect of deuterium oxide buffer (D20) on chemiluminescence intensity and the quenching effect of sodium azide. A linear correlation between NH2OH-de-pendent chemiluminescence intensity and the amount of diene conjugates (DC) formed in this reaction was observed. Removal of adventitious transition metals by adequate chelators prevented chemiluminescence in this system; NH2OH was also found to efficiently decrease metabolites of lipid peroxidation (LPO). Our findings are consistent with a sequence of reactions in which NH2OH first converts transition metals to their reduced state, thereby stimulating the formation of alkoxy- and peroxy-radicals. Peroxyradicals decompose in a bimolecular Russel reaction to hydroxyl compounds and singlet oxygen while the majority of alkoxy radicals are eliminated by a secondary reaction with NH2OH. Identical effects were observed when reducing antioxidants such as ascorbic acid or trolox C were used instead of hydroxylamine.     

High resolution rotational Zeeman effect spectroscopy using a Ku-band bridge superheterodyne spectrometer with low frequency Stark effect modulation. The rotational Zeeman effect of malonaldehyde

The construction of a microwave Ku-band bridge superheterodyne spectrometer with 5 kHz Stark effect modulation is described in detail. Typical full widths at half height are 40 to 50 kHz in molecules such as DCCCN, fluorobenzene or fluoropyridine. As an example we present results for a rotational Zeeman effect analysis of malonaldehyde in the two lowest states of the hydrogen bridge tunneling mode.     

Das [C8H8]+-Problem: Der Verlust von Äthylen aus dem Molekülion von Tetralin

Ethylene elimination from the molecular ion of tetralin is shown to be a complex process involving in addition to complete C- and H-scrambling (about 10%) at least two further competing processes.     

The h-SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze

We describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb_0.5W₃O₁₀, in the following denoted as h-Sb_xWO_3+2x with x=0.167, to demonstrate its analogy to classical A_xWO₃ tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C<T<620 °C. It was obtained as a dark-blue polycrystalline powder, and as thin, needle-shaped, blue single crystals. h-Sb_xWO_3+2x crystallizes in the hexagonal space group P6/mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner-sharing WO₆ octahedra. h-Sb_xWO_3+2x has a resistivity of ρ_{300 K}≈1.28 mΩ cm at room temperature, with little if any temperature-dependence on cooling. DFT calculations on a simplified model for this compound find a metallic-like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point.     

Poly[N‐(10‐oxo‐2‐vinylanthracen‐9(10H)‐ylidene)cyanamide] as a novel cathode material for li‐organic batteries

Redox‐active polymers draw significant attention as active material in secondary batteries during the last decade. A new anthraquinone‐based redox‐active monomer was designed, which electrochemical behavior was tailored by mono‐modification of one keto group. The monomer exhibits two one‐electron redox reactions and has a low molar mass, resulting in a high theoretical capacity of 207 mAh/g. The polymerization of the monomer was optimized by variation of solvent and initiator. Moreover, the electrochemical behavior was studied using cyclic voltammetry and the polymer was used as active material in a composite electrode in lithium organic batteries. The polymer reveals a cell potential of 2.3 V and a promising capacity of 137 mAh/g. During the first 100 cycles, the capacity drops to 85% of the initial value. The influence of the charging speed on the charging/discharging properties of the batteries was further investigated. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2517–2523     

ESR- und ENDOR-Untersuchungen an Catecholaminen und deren Metaboliten als paramagnetische Thallium-Komplexe

Zusammenfassung Semichinonradikale, die sich von Catecholaminen und ihren Metaboliten ableiten, können leicht durch Autoxidation mit Hilfe der Spinstabilisierungsmethode dargestellt werden. Die Radikale zeigen charakteristische ESR- und ENDOR-Spektren. Die Vorzeichen der Kopplungskonstanten wurden für einige Schlüsselverbindungen durch TRIPLE-Resonanz-Experimente bestimmt. Mit Hilfe der Vorzeichen konnten eindeutige Zuordnungen der Kopplungsparameter vorgenommen werden. Die ESR-Signale zeigen eine starke Abhängigkeit von der Seitenkette, die Beträge der Kopplungen und ihre Temperaturabhängigkeit weisen bei einigen Verbindungen auf gehinderte Rotation hin. Die untersuchten Semichinone können aufgrund ihrer ESR-Daten zur Charakterisierung und zum Nachweis der ihnen zugrundeliegenden Brenzcatechine herangezogen werden. Wegen der großen Empfindlichkeit der ESR-Methode ist der Substanzbedarf gering. Im allgemeinen reicht 1 ml einer 10^–4 molaren Lösung aus, um gut aufgelöste und damit interpretierbare Spektren zu erhalten. Der ESR-spektroskopische Nachweis von Catecholaminen kann auch dann durchgeführt werden, wenn die Wirkstoffe als Arzneimittelzubereitungen vorliegen, ohne daß vorher Trenn- oder Reinigungsoperationen durchgeführt werden müssen. Brenzcatechinmethylether lassen sich ebenfalls mit der ESR-Methode nachweisen, wenn vorher eine Etherspaltung mit Hilfe von Bortribromid durchgeführt wird.

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ESR and ENDOR investigations of catecholamines and their metabolites as paramagnetic thallium complexes

Summary Semiquinone radicals deriving from catecholamines and related catechols generated smoothly by autoxidation in organic solvents have been studied using the spinstabilization technique. The semiquinones have distinctive ESR and ENDOR spectra. The signs of the coupling constants were determined by TRIPLE resonance experiments for several radicals, and, therefore, an unambiguous assignment of the proton couplings could be done. The spectra are strongly influenced by the side chain, reflecting restricted rotation of the methylene protons in some cases. For this reason a characterization and identification of the investigated catechols by electron-spin resonance is possible. According to the pronounced sensitivity of this method, usually 1 ml of a 10^–4 molar solution was used to obtain well resolved ESR spectra. The semiquinones may likely be detected if the catechols are ingredients of complex mixtures, for example drugs, without any separation or purification operations. Catecholmethylethers may be examined by ESR spectroscopy as well if the ether has been cleaved with borontribromide before the radicals were generated.