Photostability of 4,4′‐Dihydroxythioindigo,a Mimetic of Indigo

The photochemical properties of indigo, a widely used industrial dye, has attracted both experimentalists and theoreticians from the beginning. Especially the high photostability of indigo has been the subject of intensive research. Recently, it was proposed that after photoexcitation an intramolecular proton transfer followed by a nonradiative relaxation to the ground state promote photostability. In indigo the hydrogen bond and the proton transfer occur between the opposing hemiindigo parts. Here, we provide experimental and theoretical evidence that a hydrogen transfer within one hemiindigo or hemithioindigo part is sufficient to attain photostability. This concept can serve as an interesting strategy towards new photostable dyes for the visible part of the spectrum.     

The stereochemical outcome of electrophilic addition reactions on the 5,6-double bond in the spinosyns.

The electrophilic addition of reagents to the 5,6-double bond in spinosyn A and spinosyn D systems occurred with high pi-diastereofacial selectivity. Addition occurred preferentially from the beta face of the molecule with selectivities ranging from 5:1 to better than 30:1. Various NMR properties were investigated in order to distinguish the beta and alpha isomers with the help of theoretical models of the products. These NMR properties include a (13)C gamma effect to C-11 and vicinal coupling between H-4 and H-5. To help rationalize the selectivity, computational studies on the transition states for epoxidation were calculated using density functional theory. The results indicate that beta epoxidation is favored and that the geometries of the transition structures are consistent with torsional steering being the source of the selectivity.     

Random walks with imperfect trapping in the decoupled-ring approximation

We investigate random walks on a lattice with imperfect traps. In one dimension, we perturbatively compute the survival probability by reducing the problem to a particle diffusing on a closed ring containing just one single trap. Numerical simulations reveal this solution, which is exact in the limit of perfect traps, to be remarkably robust with respect to a significant lowering of the trapping probability. We demonstrate that for randomly distributed traps, the long-time asymptotics of our result recovers the known stretched exponential decay. We also study an anisotropic three-dimensional version of our model. We discuss possible applications of some of our findings to the decay of excitons in semiconducting organic polymer materials, and emphasize the crucial influence of the spatial trap distribution on the kinetics. Received 23 July 2001 / Received in final form 14 May 2002 Published online 13 August 2002     

Synthesis and chemistry of N‐arylated pyrano[2,3‐c]pyrazoles

Novel N2‐arylated pyrano[2,3‐c]pyrazol‐6‐ones 2 can be prepared in a selective manner by generating the anion of 1 ( R?H ) with lithium hexamethyldisilazide in DMF and quenching with activated aryl halides. Sterically demanding groups such as phenyl as in 5 reduce reactivity significantly while electronwithdrawing substituents such as trifluoromethyl and phenyl at C4 of the pyranone ring as in 10 and 15 render the pyranone carbonyl particularly susceptible to attack by nucleophiles resulting in ring‐opening to give novel crotonyl derivatives. Proof of structure required a variety of nmr methods involving proton, carbon, and nitrogen nuclei.     

In situ bioconjugation—Novel laser based approach to pure nanoparticle-conjugates

The generation and characterization of nanoparticulate carrier systems is important for drug delivery, biosensing and in vivo or in vitro diagnostics. Conventional nanoparticle generation is based on chemical synthesis methods requiring time intensive reaction and additive design for each material. Successive purification and surface functionalisation is often required after the nanoparticle generation to achieve pure nanoparticle-bioconjugates. We established a novel single step method, which allows the generation of pure nanoparticles and their in situ conjugation with biomolecules bearing electron donating moieties using pulsed laser ablation in liquids. For comparison between unspecific binding and binding through strong dative bonds (here: S-Au), we applied this preparation method to the conjugation of gold nanoparticles with unmodified and thiolated oligonucleotides. In order to determine optimal parameters (laser pulse energy, focus diameter), the influence on productivity of nanoparticle generation and their interaction with oligonucleotides is studied. We report quenching of nanoparticle growth and modification of the surface plasmon resonance as evidence of a successful functionalisation. Their stability in ionic solutions is evidenced with relevance to biological and medical assays. Negligible differences between the two model bioconjugations evidence the universality of the established in situ bioconjugation method.     

Oxidation of low-index FeAl surfaces

The oxidation of the (100), (110) and (111) surfaces of the intermetallic compound FeAl has been investigated using LEED and XPS. On all three surfaces, oxidation at room temperature leads to the formation of an amorphous oxide film on top of an Al-depleted interlayer. The film growth can be divided into two regions of differing kinetics, i.e. the initial formation of a closed oxide film and a subsequent thickening. In the first region, the oxygen-uptake rate varies significantly with surface orientation, while in the thickening regime the uptake is the same for all surfaces. The maximum thickness as well as the composition of the oxide films were found to depend on the initial oxidation rate. At higher oxidation temperatures, ordered oxide films of around 5–8 Å in thickness are formed, very similar to those observed on NiAl. Photoemission spectra from these ordered phases showed evidence for Al atoms in two different chemical environments, i.e. the well-known oxide species in the interior of the film and an additional species present at the oxide/alloy interface.     

Metastable anions of dinitrobenzene: resonances for electron attachment and kinetic energy release

Attachment of free, low-energy electrons to dinitrobenzene (DNB) in the gas phase leads to DNB(-) as well as several fragment anions. DNB(-), (DNB-H)(-), (DNB-NO)(-), (DNB-2NO)(-), and (DNB-NO(2))(-) are found to undergo metastable (unimolecular) dissociation. A rich pattern of resonances in the yield of these metastable reactions versus electron energy is observed; some resonances are highly isomer-specific. Most metastable reactions are accompanied by large average kinetic energy releases (KER) that range from 0.5 to 1.32 eV, typical of complex rearrangement reactions, but (1,3-DNB-H)(-) features a resonance with a KER of only 0.06 eV for loss of NO. (1,3-DNB-NO)(-) offers a rare example of a sequential metastable reaction, namely, loss of NO followed by loss of CO to yield C(5)H(4)O(-) with a large KER of 1.32 eV. The G4(MP2) method is applied to compute adiabatic electron affinities and reaction energies for several of the observed metastable channels.     

Determination of phosphine and other fumigants in air samples by thermal desorption and 2D heart-cutting gas chromatography with synchronous SIM/Scan mass spectrometry and flame photometric detection

Fumigants and volatile industrial chemicals are particularly hazardous to health when a freight container is fumigated or the contaminated material is introduced into its enclosed environment. Phosphine is now increasingly used as a fumigant, after bromomethane--the former fumigant of choice--has been banned by the Montreal Protocol. We have enhanced our previously established thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) method by integrating a second gas chromatographic dimension and a flame photometric detector to allow the simultaneous detection of phosphine and volatile organic compounds (VOCs), providing a novel application. A thermal desorption system is coupled to a two dimensional gas chromatograph using both mass spectrometric and flame photometric detection (TD-2D-GC-MS/FPD). Additionally, the collection of mass spectrometric SIM and Scan data has been synchronised, so only a single analysis is now sufficient for qualitative scanning of the whole sample and for sensitive quantification. Though detection limits for the herewith described method are slightly higher than in the previous method, they are in the low μL m(-3) range, which is not only below the respective occupational exposure and intervention limits but also allows the detection of residual contamination after ventilation. The method was developed for the separation and identification of 44 volatile substances. For 12 of these compounds (bromomethane, iodomethane, dichloromethane, 1,2-dichlorethane, benzene, tetrachloromethane, 1,2-dichloropropane, toluene, trichloronitromethane, ethyl benzene, phosphine, carbon disulfide) the method was validated as we chose the target compounds due to their relevance in freight container handling.     

Die Insertion von Sauerstoffatomen in Ga–Ga- und In–In-Bindungen – Bildung von monomeren Verbindungen R2E–O–ER2 [R = CH(SiMe3)2] mit stark aufgeweiteten E–O–E-Winkeln

The Insertion of Oxygen Atoms into Ga–Ga and In–In Bonds – Formation of the Monomeric Compounds R₂E–O–ER₂ [R = CH(SiMe₃)₂] with Strongly Enlarged Angles E–O–E The tetraalkyldielement compounds R₂Ga–GaR₂ ( 1 ) und R₂In–InR₂ ( 2 ) [R = CH(SiMe₃)₂] reacted with trimethylamine N-oxide by the insertion of oxygen atoms in their element-element single bonds. The products R₂E–O–ER₂ are monomeric in the solid state due to the high steric shielding by the voluminous bis(trimethylsilyl)methyl groups. As shown by crystal structure determinations, the E–O–E bridges have large angles of 142.7 (E = Ga, 3 ) and 138.6° (E = In, 4 ) and short separations between the oxygen and the coordinatively unsaturated Ga and In atoms. Both products are extremely hygroscopic.