On‐Line Electrochemistry/Electrospray Ionization Mass Spectrometry (EC/ESI‐MS) for the Generation and Identification of Nucleotide Oxidation Products

The oxidation behavior of DNA and RNA nucleotides is studied by an on‐line set‐up consisting of an electrochemical thin‐layer cell (EC) directly coupled to electrospray ionization mass spectrometry (ESI‐MS). This set‐up allows the generation of nucleotide oxidation products in the electrochemical cell at increasing potentials. Moreover, the products are determined directly, without isolation or derivatization steps, by electrospray ionization time of flight mass spectrometry (ESI‐ToF/MS). The dependence of the mass spectra on the applied potential is displayed as ‘mass voltammograms’. An advanced set‐up, consisting of the electrochemical cell coupled to electrospray ionization tandem mass spectrometry (EC/ESI‐MS/MS) allows further structure elucidation based on fragmentation experiments. The electrochemical conversion is performed using a boron doped diamond (BDD) working electrode, which is known to generate hydroxyl radicals at high potentials. The capability of the EC‐MS system to generate highly relevant oxidation products which also occur upon oxidative damage in vivo is demonstrated in this study by the formation of well known biomarkers for DNA damage, including 2′‐deoxy‐8‐oxo‐guanosine 5′‐monophosphate.     

The Acidity of the HBr/AlBr3 System: Stabilization of Crystalline Protonated Arenes and Their Acidity in Bromoaluminate Ionic Liquids

Bulk protonated mesitylene, toluene, and benzene bromoaluminate salts were stabilized and characterized in the superacidic system HBr/n AlBr₃ with NMR spectroscopy and X‐ray analysis of [HC₆H₃(CH₃)₃]⁺[AlBr₄]^? ( 1 ), [HC₆H₅(CH₃)]⁺[AlBr₄]^? ( 2 ), and [C₆H₇]⁺[Al₂Br₇]^??C₆H₆ ( 3 ). Protonation attempts in bromoaluminate ILs led to a complete protonation of mesitylene, and a protonation degree of up to 15 % for toluene in the IL BMP⁺[Al₂Br₇]^?. Benzene could only be protonated in the more acidic IL BMP⁺[Al₃Br₁₀]^?, with a degree of 25 %. Protonation attempts on aromatics provide evidence that the bromoaluminate ILs tolerate superacidic environments. On the basis of the absolute Brønsted acidity scale, quantum chemical calculations confirmed the superacidic properties, and rank the acidities in ILs down to a pH_abs value of 164 with an error of less than one pH unit compared with experimental findings. The neat AlBr₃/HBr system even may reach acidities down to pH_abs 163.     

Spectral loudness summation of nonsimultaneous tone pulses

The level of broadband signals is usually lower than that of equally loud narrow-band signals. This effect, referred to as spectral loudness summation, is commonly measured for broadband signals where all frequency components are presented simultaneously. The present study investigated to what extent spectral loudness summation also occurs for nonsimultaneously presented frequency components. Spectral loudness summation was measured in normal-hearing listeners with an adaptive forced-choice procedure for sequences of short tone pulses with varying frequencies, randomly chosen from a set of five frequencies. In addition, spectral loudness summation was measured for the simultaneous presentation of all five frequencies. The comparison stimulus consisted of tone pulses with the same frequency for all tone pulses of the sequence and the same repetition rate and overall duration as the test signal. The pulse duration was 10, 20, 50, or 100 ms and the inter-pulse interval ranged from 0 to 390 ms. In general, a considerable nonsimultaneous spectral loudness summation was found for short pulse durations and inter-pulse intervals, but a residual effect was also observed for the largest inter-pulse interval. The data are discussed in the light of repetition-rate dependent spectral loudness summation and effects of persistence of specific loudness after tone-pulse offset.     

Unusually stable liquid foams

Obtaining stable liquid foams is an important issue in view of their numerous applications. In some of these, the liquid foam in itself is of interest, in others, the liquid foam acts as a precursor for the generation of solid foam. In this short review, we will make a survey of the existing results in the area. This will include foams stabilised by surfactants, proteins and particles. The origin of the stability is related to the slowing down of coarsening, drainage or coalescence, and eventually to their arrest. The three effects are frequently coupled and in many cases, they act simultaneously and enhance one another. Drainage can be arrested if the liquid of the foam either gels or solidifies. Coalescence is slowed down by gelified foam films, and it can be arrested if the films become very thick and/or rigid. These mechanisms are thus qualitatively easy to identify, but they are less easy to model in order to obtain quantitative predictions. The slowing down of coarsening requests either very thick or small films, and its arrest was observed in cases where the surface compression modulus was large. The detail of the mechanisms at play remains unclear.     

Substitutional phosphorus incorporation in nanocrystalline CVD diamond thin films

Nanocrystalline diamond (NCD) thin films were produced by chemical vapor deposition (CVD) and doped by the addition of phosphine to the gas mixture. The characterization of the films focused on probing the incorporation and distribution of the phosphorus (P) dopants. Electron microscopy evaluated the overall film morphology and revealed the interior structure of the nanosized grains. The homogeneous films with distinct diamond grains featured a notably low sp²:sp³‐ratio as confirmed by Raman spectroscopy. High resolution spectroscopy methods demonstrated a homogeneous P‐incorporation, both in‐depth and in‐plane. The P concentration in the films was determined to be in the order of 10¹⁹ cm^–3 with a significant fraction integrated at substitutional donor sites. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

A platinum-catalyzed annulation reaction leading to medium-sized rings

A platinum-catalyzed domino process with intermediate benzopyrylium cations reaches its optimum utility in the formation of 7- and 8-membered rings. With iron(III) chloride, a tetracyclic product is isolated, derived from an oxidative transformation of a metal-carbene intermediate.     

Quadrupolar Cyclopenta[hi]aceanthrylene‐Based Electron Donor‐Acceptor‐Donor Conjugates: Charge Transfer versus Charge Separation

Cyclopenta[hi]aceanthrylenes (CPAs) have been functionalized at two of the peripheral positions with electronically inert trimethylsilylethynyl ( 1 ), as well as with electron‐donating 4‐ethynyl‐N,N‐dimethylaniline ( 2 ), ethynyl Zn^IIphthalocyanine ( 3 ), and ethynyl Zn^IIporphyrin ( 4 ) units. Consistent with X‐ray crystal structures of 2 and 4 , analyses of absorption and fluorescence of 2 – 4 point to strong electronic communication between the CPA and the peripheral units, affording quadrupolar electron donor‐acceptor‐donor charge‐transfer conjugates. By virtue of their quadrupolar/dipolar charge‐transfer characters in the excited state, 2 – 4 exhibit fluoro‐solvatochromism. Transient absorption spectroscopy confirmed delocalized quadrupolar ground states and formation of weakly solvent stabilized quadrupolar singlet excited states. The latter transform into strongly stabilized dipolar excited states before deactivating to the ground state in 2 and give rise to a fully charge separated state in 3 and 4 .