Multiple unknown degradants generated from the insect repellent DEET by photoinduced processes on TiO2

This paper deals with the photocatalytic transformation of N,N-diethyl-m-toluamide (DEET), one of the most widespread and efficient mosquito repellents, under simulated solar irradiation using titanium dioxide as the photocatalytic source of oxidizing species. The investigation involved monitoring of the DEET decomposition, the identification of intermediate compounds and the assessment of mineralization. High-resolution mass spectrometry was employed to assess the evolution of the photocatalyzed process over time. Fifty-one main species were identified after DEET transformation. Several isomeric species were formed and were characterized by analyzing MS and MS(n) spectra in full, and by comparison with parent molecule fragmentation pathways. In the DEET molecule, the initial transformation involved mono- and polyhydroxylation followed by oxidation of the alcohol groups, cleavage of the alkyl chains or ring opening. All these intermediates are easily degraded and DEET is completely mineralized after 4 h of irradiation. Microtox bioassay (Vibrio fischeri) was employed to evaluate the ecotoxicity of solutions treated by photocatalysis.     

2-difluoromethylene-4-methylenepentanoic acid, a paradoxical probe able to mimic the signaling role of 2-oxoglutaric acid in cyanobacteria

2-Difluoromethylene-4-methylenepentanoic acid (DFMPA), a seemingly deviated analog of 2-oxoglutaric acid (2-OG), could surprisingly mimic its signaling function in cyanobacteria. Computer modeling revealed the favorable binding of DFMPA toward the 2-OG receptor, NtcA, via mutual conformational changes, suggesting that structural alteration of 2-OG is tolerated for it to exercise its signaling role. This extremely useful finding could be exploited for the design of affinity probes with which to study new 2-OG receptors in related signaling pathways.     

Allylpalladium dimers with metals connected by binucleating dithiooxamidates in two different coordination modes: solution behavior and solid-state structure

A series of allylpalladium dimers having metals connected by binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N](2-) [R = methyl, ethyl, isopropyl, benzyl, isoamyl, (S)-1-(1-phenyl)ethyl, meso-(1-phenyl)ethyl, and rac-(1-phenyl)ethyl] were prepared by reacting the monochelate [(η(3)-allyl)Pd(N(R)SC-CS(R)NH κ-S,S Pd)] with [(η(3)-allyl)PdCl](2) in chloroform. At low temperature (20 °C), the bimetallic complexes [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') (kinetic compounds) are formed in a short reaction time (10 min). At a higher temperature (50 °C) and a longer reaction time (24 h), the corresponding bimetallic isomers [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,S Pd, κ-N',S' Pd') (thermodynamic compounds) are obtained. Both kinetic and thermodynamic compounds can exist as endo or exo isomers, depending on the reciprocal orientation of the allyl cuspids. Both endo and exo isomers are only detectable in solution when the alkyl substituents are chiral alkyl groups. Moreover, diffractometric modeling agrees with the presence of both isomers in the solid state even when the alkyl substituent is an achiral alkyl group. In a chloroform solution, endo and exo isomers undergo isomeric conversion owing to the apparent allyl rotation that follows the Pd-N bond rupture in the (η(3)-allyl)Pd(N^N) frame of kinetic compounds or in the (η(3)-allyl)Pd(N^S) frame of thermodynamic compounds. The dithiooxamidate [N(R)SC-CS(R)N](2-), when engaged in a κ-N,S Pd, κ-N',S' Pd' coordination mode, behaves as a hybrid hemilabile binucleating ligand. At room temperature and in a chloroform solution, the kinetic compounds rearrange into the thermodynamically more stable isomers in about 3 or 4 days. The higher stability of the thermodynamic species was evaluated by means of computational studies in accordance with the maximum hardness principle. Finally, the crystal structures of [(η(3)-allyl)Pd](2)(μ-diethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), [(η(3)-allyl)Pd](2)(μ-meso-(1-phenyl)ethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), and [(η(3)-allyl)Pd](2)(μ-rac-(1-phenyl)ethyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') are reported.     

Manifestation of the bound state \bar NN (1870) in the annihilation process \bar pd \to p_s 5\pi

It is shown that the existence of an N?N bound state with a mass of approximately 1870 MeV and width 10 MeV follows from analysis of the experimental data on the momentum distribution of recoil protons in the annihilation process p?d→p _s5π.     

The LAPEX experiment for observation of the supernova SN 1987A in hard X-rays

Summary The LAPEX payload is described in the configuration that will be launched to observe the supernova SN 1987A. The balloon flight will be performed from Alice Springs (Australia) in April 1989 as a part of a NASA balloon campaign. The experiment will allow simultaneous observations of source and background in order to minimize systematic errors due to background variations. The limiting flux sensitivity of the instrument in the (20÷200) keV energy band is 4·10⁻⁶ ph/(cm²s keV) or ∼2.5 mCrab for a 10⁴ s observation of SN 1987A. The presence of a⁵⁷Co emission line in the SN 1987A photon spectrum could be detected down to an intensity level of ∼8·10⁻⁵ photons/cm²s as at 99.7% confidence level. The high resolution of the event timing (<0.1 ms) will make it possible to detect millisecond pulsations with amplitudes down to ∼4% of the expected average flux from SN 1987A in the (20÷60) keV band. To speed up publication, the proofs were not sent to the authors and were supervised by the Scientific Committee.     

Nonlinear optical and electrostatic force microscopy for ferroelectric polarization imaging

Second-harmonic generation (SHG)-based nonlinear optical microscopy is used for spatially resolved imaging of the polarization switching in lead zirconium titanate ferroelectric thin films. The local SHG hysteresis loops reveal a strong dependence on film composition and structure. The SHG microscopy results are in good agreement with the efficiency of electrostatic force microscopy writing and allow us to predict the microscopic dielectric memory efficiency, both in contact and contact-less ways. Received: 15 January 2001 / Revised version: 27 March 2002 / Published online: 6 June 2002     

Transverse momentum distributions of neutral pions from central and peripheral16O+Au collisions at 200A·GeV

The production of neutral pions by the interaction of 200A·GeV p and¹⁶O projectiles with a Au target has been studied in the pseudorapidity range 1.5≦η≦2.1. Transverse momentum spectra have been measured between 0.4 GeV/c and 3.6 GeV/c and their dependence on the centrality of the collision has been investigated. The peripheral-collision spectra display a marked change of slope with a hard component starting at about 1.8 GeV/c, in contrast to central-collision data. The data are discussed in comparison to p+p and α+α data from the ISR.