Low-energy (3-24 eV) electron damage to the peptide backbone

We report the mass spectrometric measurement of anions desorbed by 3-24 eV electron impact on thin films of formamide-1-d (DCONH2) and on the self-assembled monolayer (SAM) of two different Lys amide molecules used as a molecular model of the peptide backbone. In the present SAM configuration, the amides are elevated from a gold substrate by hydrocarbon chains to remove the effects of the metal substrate. Electron irradiation produces H- and D- from the formamide-1-d film and H-, CH3-, O-, and OH- from the SAM Lys amides. Below 13 eV, the dependence of the anion yields on the incident electron energy exhibits structures indicative of the dissociative electron attachment process, which is responsible for molecular fragmentation via the initial formation of core-excited anions. Above 13 eV, anion desorption is dominated principally by non-resonant dipolar dissociation. Our results suggest that the sensitivity of the peptide backbone to secondary electrons produced by ionizing radiation depends on the chemical environment (i.e., the amino acids sequence).     

Mutagenic, antimutagenic and antioxidant activities of a new class of beta-glucoside hydroxyhydroquinone from Anagallis monelli growing in Tunisia

A new skeleton of an O-heteroside natural substance named zinolol, the first representative of a new class of aminated hydroxyhydroquinone, has been isolated from the whole plant Anagallis monelli. Its structure has been established by one and two dimensional NMR spectroscopic procedures. Antioxidant, mutagenic, antimutagenic activities were realised and positive results were recorded.     

Neon‐Bearing Ammonium Metal Formates: Formation and Behaviour under Pressure

The incorporation of noble gas atoms, in particular neon, into the pores of network structures is very challenging due to the weak interactions they experience with the network solid. Using high‐pressure single‐crystal X‐ray diffraction, we demonstrate that neon atoms enter into the extended network of ammonium metal formates, thus forming compounds Ne_x[NH₄][M(HCOO)₃]. This phenomenon modifies the compressional and structural behaviours of the ammonium metal formates under pressure. The neon atoms can be clearly localised within the centre of [M(HCOO)₃]₅ cages and the total saturation of this site is achieved after ～1.5 GPa. We find that by using argon as the pressure‐transmitting medium, the inclusion inside [NH₄][M(HCOO)₃] is inhibited due to the larger size of the argon. This study illustrates the size selectivity of [NH₄][M(HCOO)₃] compounds between neon and argon insertion under pressure, and the effect of inclusion on the high‐pressure behaviour of neon‐bearing ammonium metal formates.     

Preliminary 1H NMR study on archaeological waterlogged wood

Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood.     

Benzene-assisted atmospheric-pressure chemical ionization: a new liquid chromatography/mass spectrometry approach to the analysis of selected hydrophobic compounds

Charge-exchange reactions involving benzene have been successfully exploited to increase the sensitivity of atmospheric-pressure chemical ionization mass spectrometry (APCI-MS) towards hydrophobic compounds of significant environmental relevance which are not detectable with the ordinary APCI techniques. Among them, good sensitivity have been found for (a) highly chlorinated biphenyl derivatives such as dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethene (DDE); (b) cyclopentadienes such as Aldrin and its epoxy derivatives Dieldrin and Endrin; and (c) dibenzofurans and dibenzo-para-dioxins such as 2,3,7,8-tetrachlorodibenzofuran (2,3,7,8-TCDF) and 2,3,7,8-tetrachloro-dibenzo-para-dioxin (2,3,7,8-TCDD). The reactant benzene molecules were introduced into the source either through the nebulizer gas or by direct post-column addition of neat liquid, whereas the targeted compounds were analyzed using a high-performance liquid chromatography (HPLC) RP-18 column using methanol/water solutions as mobile phase. By using benzene as post-column reagent, positive ion mode detection was proven to be significantly enhanced as compared with APCI measurements carried out without benzene assistance.     

Determination of organophosphate pesticides at a carbon nanotube/organophosphorus hydrolase electrochemical biosensor

An amperometric biosensor for oganophosphorus (OP) pesticides based on a carbon nanotube (CNT)-modified transducer and an organophosphorus hydrolase (OPH) biocatalyst is described. A bilayer approach with the OPH layer atop of the CNT film was used for preparing the CNT/OPH biosensor. The CNT layer leads to a greatly improved anodic detection of the enzymatically generated p-nitrophenol product, including higher sensitivity and stability. The sensor performance was optimized with respect to the surface modification and operating conditions. Under the optimal conditions the biosensor was used to measure as low as 0.15 μM paraoxon and 0.8 μM methyl parathion with sensitivities of 25 and 6 nA/μM, respectively.     

New Furano-sesquiterpenoids from Mediterranean Sponges

A mixture of sponges of the East Pyrenean Mediterranean is shown to contain the known sponge products longifolin ( 1 ), avarol ((+)- 3 ), and avarone ( 4 ) and the terrestrial-plant product sesquirosefuran ( 2 ), besides to the new furano-sesquiterpenoids tavacfuran (= 3-methyl-2-[(3′Z)-3′-methyl-4″-methyl-2″-furyl-3′-butenyl]furan; ( 5 ) and tavacpallescensin (= 5,10-dihydro-6,9-dimethyl-4H-benzo[5,6]cyclohepta[1,2-b]furan; 6 ) and the new furano-butenolide sesquiterpenoids tavacbutenolide-1 (= (±-4-ethoxy-2-methyl-4-)[(2′E)-2′-methyl-4′-(3″-methyl-2″-furyl)-2′-butenyl]-2-buten-4-olide; (±)- 7 ) and tavacbutenolide-2 (= (±)-4-ethoxy-3-methyl-4-[2′E)-3′-methyl-4′-(4″-methyl-2″-furyl)-2′-butenyl]-2-buten-4-olide; (±)- 8 ). Structural assignments are based on NMR data and on the synthesis of the (E)-isomer of 5 . The sponge Dysidea tupha of the same area is also shown to contain the two sesquiterpenoids ent-furodysinin ((?)- 14 ), which is enantiomeric to a product of a Dysidea sp. of Australian waters, and tuphabutenolide ((+)- 15 ).     

Two modifications of a five‐coordinate silicon complex

TBPY‐5‐34‐(Butane‐1,4‐diyl)(2‐{[1‐(2‐oxidophenyl)ethylidene‐κO]amino‐κN}ethanolato‐κO)silicon, C₁₄H₁₉NO₂Si, crystallizes in two modifications. The monoclinic form, (IIm), was obtained by crystallization over a period of 2 d at room temperature; the orthorhombic form, (IIo), crystallized overnight at 248 K. The main difference between the two molecular structures involves the angles in the equatorial plane of the trigonal bipyramid around silicon. Form (IIm) has an O—Si—O angle of ca 121° and O—Si—C angles of ca 121 and 116°. In form (IIo), the corresponding angles are ∼123, 124 and 111°. There are also significant differences in the packing: (IIm) shows π stacking, whereas (IIo) does not.     

Dynamics and counterion-dependence of the structures of weakly bound Ag+-P4S3 complexes

In an earlier publication (J. Am. Chem. Soc. 2002 , 124, 7111) we showed that polymeric cationic [Ag(P₄S₃)_n]⁺ complexes (n=1, 2) are accessible if partnered with a suitable weakly coordinating counterion of the type [Al(OR^F)₄]^? (OR^F: poly‐ or perfluorinated alkoxide). The present work addresses the following questions that could not be answered in the initial report: How many P₄S₃ cages can be bound to a Ag⁺ ion? Why are these complexes completely dynamic in solution in the ³¹P NMR experiments? Can these dynamics be frozen out in a low‐temperature ³¹P MAS NMR experiment? What are the principal binding sites of the P₄S₃ cage towards the Ag⁺ ion? What are likely other isomers on the [Ag(P₄S₃)_n]⁺ potential energy surface? Counterion influence: Reactions of P₄S₃ with Ag[Al{OC(CH₃)(CF₃)₂}₄] (Ag[hftb]) and Ag[{(CF₃)₃CO}₃Al‐F‐Al{OC(CF₃)₃)}₃] (Ag[al‐f‐al]) gave [(P₄S₃)Ag[hftb]]_∞ ( 7 ) as a molecular species, whereas [Ag₂(P₄S₃)₆]²⁺[al‐f‐al]^?₂ ( 8 ) is an isolated 2:1 salt. We suggest that a maximum of three P₄S₃ cages may be bound on average to an Ag⁺ ion. Only isolated dimeric dications are formed with the largest cation, but polymeric species are obtained with all other smaller aluminates. Thermodynamic Born–Haber cycles, DFT calculations, as well as solution NMR and ESI mass spectrometry indicate that 8 exhibits an equilibrium between the dication [Ag₂(P₄S₃)₆]²⁺ (in the solid state) and two [Ag(P₄S₃)₃]⁺ monocations (in the gas phase and in solution). Dynamics: ³¹P MAS NMR spectroscopy showed these solid adducts to be highly dynamic, to an extent that the ²J_P,P coupling within the cages could be resolved (J‐res experiment). This is supported by DFT calculations, which show that the extended PES of [Ag(P₄S₃)_n]⁺ (n=1–3) and [Ag₂(P₄S₃)₂]⁺ is very flat. The structures of α‐ and γ‐P₄S₃ were redetermined. Their variable‐temperature ³¹P MAS NMR spectra are discussed jointly with those of all four currently known [Ag(P₄S₃)_n]⁺ adducts with n=1, 2, and 3.     

Synthesis of the Bretonins,Polyolefinic Esterified Glyceryl Ethers of an Unidentified Sponge from the North-Brittany Sea: Absolute Configuration and Novel Structure Assignment

The absolute configurations of acetylated bretonin A (= (+}-( R )-1-[(acetoxy)methyl]-2-{[(4E,6E,8E)-dodeca-4,6,8-trienyl]oxy}ethyl 4-acetoxybenzoate; (?)- 1b ) and isobretonin A (= (+)-(S)-3-{[(4E,6E,8E)-do-deca-4,6,8-trienyl]oxy}-2-hydroxypropyl 4-hydroxybenzoate; (+)-2), previously isolated from an undetermined sponge of the North Brittany sea, were established by comparison with synthetic (+)- lb and (+)- 2 , obtained from the condensation of commerical (?)-(R)-2,2-dimethyl-1,3-dioxolan-4-yl p-toluenesuifonate ((?)-(R)- 15 ) with a mixture of (4E,6E,8E)- ( 14e ) and (4E,6Z,8E)-dodeca-4,6,8-trien-1-ol ( 14z ). This also allowed confirming the structure and configuration of bretonin B (= (S)-2-{[(4E,6Z,8E)-dodeca-4,6,8-trienyl]oxy}-1-(hydroxy-methyl)ethyl 4-hydroxybenzoate; 3 ) which was also isolated from the same sponge, albeit in a too small amount for a complete study. As concerns the glyceryl ethers precursors of the bretonins, co-occurrence of the usual (S)-con-figuration (from 1a ) with the unusual (R)-configuration (from (+)- 2 )) poses intriguing biogenetic problems.