A method for 13C‐labeling of metabolic carbohydrates within French bean leaves (Phaseolus vulgaris L.) for decomposition studies in soils

The molecular composition of plant residues is suspected to largely govern the fate of their constitutive carbon (C) in soils. Labile compounds, such as metabolic carbohydrates, are affected differently from recalcitrant and structural compounds by soil‐C stabilisation mechanisms. Producing ¹³C‐enriched plant residues with specifically labeled fractions would help us to investigate the fate in soils of the constitutive C of these compounds. The objective of the present research was to test ¹³C pulse chase labeling as a method for specifically enriching the metabolic carbohydrate components of plant residues, i.e. soluble sugars and starch. Bean plants were exposed to a ¹³CO₂‐enriched atmosphere for 0.5, 1, 2, 3 and 21 h. The major soluble sugars were then determined on water‐soluble extracts, and starch on HCl‐hydrolysable extracts. The results show a quick differential labeling between water‐soluble and water‐insoluble compounds. For both groups, ¹³C‐labeling increased linearly with time. The difference in δ¹³C signature between water‐soluble and insoluble fractions was 7‰ after 0.5 h and 70‰ after 21 h. However, this clear isotopic contrast masked a substantial labeling variability within each fraction. By contrast, metabolic carbohydrates on the one hand (i.e. soluble sugars + starch) and other fractions (essentially cell wall components) on the other hand displayed quite homogeneous signatures within fractions, and a significant difference in labeling between fractions: δ¹³C = 414 ± 3.7‰ and 56 ± 5.5‰, respectively. Thus, the technique generates labeled plant residues displaying contrasting ¹³C‐isotopic signatures between metabolic carbohydrates and other compounds, with homogenous signatures within each group. Metabolic carbohydrates being labile compounds, our findings suggest that the technique is particularly appropriate for investigating the effect of compound lability on the long‐term storage of their constitutive C in soils. Copyright © 2009 John Wiley & Sons, Ltd.     

Copper(II) halide salts and complexes of 4-amino-2-fluoropyridine: synthesis,structure and magnetic properties

Reaction of 4-amino-2-fluoropyridine (2-F-4-AP) with copper halides produced the neutral coordination complexes: (2-F-4-AP)₂CuX₂ (X = Cl(1), Br(2)). 1 crystallizes in the orthorhombic space group Pccn in a distorted square planar geometry. Magnetic susceptibility data were fit to the uniform chain Heisenberg model resulting in C = 0.439(6)emu-K/mole-Oe and J = ?28(1) K. 2 crystallizes in the monoclinic space group C2/m and is closer to distorted tetrahedral. Intermolecular Br?Cu contacts generate a square layer. Magnetic data show very weak ferromagnetic interactions [C = 0.42(1)emu-K/mol-Oe, J = 0.71(2) K]. Similarly, reaction of 2-F-4-AP with copper halides and aqueous HX in alcohol solvents produced the salts (2-F-4-APH)₂CuX₄ (X = Cl(3), Br(4)). 3 crystallizes in the triclinic space group P-1. Crystal packing reveals short Cl?Cl contacts which generate a structural ladder. However, analysis of the magnetic data suggests that only the rails of the ladder produce a viable magnetic superexchange pathway; the uniform Heisenberg chain model provides C = 0.449(1)emu-K/mol-Oe and J = -6.9(1) K. 4 is isostructural and is also best fit by a chain model [J = ?2.7(4) K]. The brominated complex (2-F-3-Br-4-APH)₂CuBr₄·2H₂O, 5, (2-F-3-Br-4-APH = 4-amino-3-bromo-2-fluoropyridinium) was serendipitously produced as a byproduct of the synthesis of 4 and was characterized by single-crystal X-ray diffraction.     

Short and efficient access to imidazo[1,2-a]pyrrolo[3,2-c]pyridine derivatives

Access to N-protected or N-free imidazo[1,2-a]pyrrolo[3,2-c]pyridine derivatives as potential antiviral compounds was achieved in good yields from N-protected 7-amino-8-halo-2-methylimidazo[1,2-a]pyridines by catalytic coupling of terminal acetylenes under mild conditions using [PdCl₂(PPh₃)₂] or [Cu(Phen)(PPh₃)₂]NO₃.     

Presenegenin Glycosides from Securidaca welwitschii

The five new presenegenin glycosides 1 – 5 were isolated from Securidaca welwitschii, together with one known sucrose diester. Compounds 1 – 4 were obtained as pairs of inseparable (E)/(Z)‐isomers of a 3,4‐dimethoxycinnamoyl derivative, i.e., 1 / 2 and 3 / 4 . Their structures were elucidated mainly by 2D‐NMR techniques and mass spectrometry as 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 1 ) and its (Z)‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐galactopyranosyl‐(1→4)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐3‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 3 ) and its (Z)‐isomer 4 , and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐[O‐β‐D ‐galactopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐fucopyranosyl] ester ( 5 ) (presenegenin=(2β,3β,4α)‐2,3,27‐trihydroxyolean‐12‐ene‐23,28‐dioic acid).     

Toluene steam reforming as tar model molecule produced during biomass gasification with an iron/olivine catalyst

Tar produced during biomass steam reforming is a complex mixture of single to multiple ring aromatic compounds and it is necessary to eliminate them in order to prevent any condensation-polymerisation problem. Tar steam reforming leads to additional hydrogen that improves gas production. Previous works have shown that olivine was active in tar removal during biomass gasification and the iron distribution into the mineral different phases has a real influence on its efficiency. A Fe/olivine catalytic system has been designed to study tar steam reforming. This work presents the Fe/olivine catalyst characterizations (XRD, Mössbauer, TPR) and compares the Fe/olivine and olivine reactivity in toluene steam reforming, a tar model molecule. At 850 °C, an important conversion (95%) was observed for Fe/olivine during 7 h. The strong interaction between iron and olivine, and the equilibrium between Fe⁰/Fe^II/Fe^III seem to be responsible of the catalyst activity and stability in toluene steam reforming.     

Comparative dissociation of peptide polyanions by electron impact and photo-induced electron detachment

We compare product-ion mass spectra produced by electron detachment dissociation (EDD) and electron photodetachment dissociation (EPD) of multi-deprotonated peptides on a Fourier transform and a linear ion trap mass spectrometer, respectively. Both methods, EDD and EPD, involve the electron emission-induced formation of a radical oxidized species from a multi-deprotonated precursor peptide. Product-ion mass spectra display mainly fragment ions resulting from backbone cleavages of C_α-C bond ruptures yielding a and x ions. Fragment ions originating from N-C_α backbone bond cleavages are also observed, in particular by EPD. Although EDD and EPD methods involve the generation of a charge-reduced radical anion intermediate by electron emission, the product ion abundance distributions are drastically different. Both processes seem to be triggered by the location and the recombination of radicals (both neutral and cation radicals). Therefore, EPD product ions are predominantly formed near tryptophan and histidine residues, whereas in EDD the negative charge solvation sites on the backbone seem to be the most favorable for the nearby bond dissociation.     

Synthesis,Spectroscopy, Crystal Structure Determination,and Quantum Chemical Calculations of BODIPY Dyes with Increasing Conformational Restriction and Concomitant Red‐Shifted Visible Absorption and Fluorescence Spectra

Starting from the conformationally unconstrained compound 3,5‐di‐(2‐bromophenoxy)‐4,4‐difluoro‐8‐(4‐methylphenyl)‐4‐bora‐3a,4a‐diaza‐s‐indacene ( 1 ), two BODIPY dyes ( 2 and 3 ) with increasingly rigid conformations were synthesized in outstanding total yields through palladium catalyzed intramolecular benzofuran formation. Restricted bond rotation of the phenoxy fragments leads to dyes 2 and 3 , which absorb and fluoresce more intensely at longer wavelengths relative to the unconstrained dye 1 . Reduction of the conformational flexibility in 2 and 3 leads to significantly higher fluorescence quantum yields compared to those of 1 . X‐ray diffraction analysis shows the progressively more extended planarity of the chromophore in line with the increasing conformational restriction in the series 1 → 2 → 3 , which explains the larger red shifts of the absorption and emission spectra. These conclusions are confirmed by quantum chemical calculations of the lowest electronic excitations in 1 , 1a , 2 , 2a , 3 and dyes of related chemical structures. The effect of the molecular structure on the visible absorption and fluorescence emission properties of 1 , 1a , 2 , 2a , 3 has been examined as a function of solvent by means of the new, generalized treatment of the solvent effect (J. Phys. Chem. B 2009 , 113, 5951–5960). Solvent polarizability is the primary factor responsible for the small solvent‐dependent shifts of the visible absorption and fluorescence emission bands of these dyes.     

Development of novel flexible black silicon

We report a new type of black silicon: flexible black silicon. A silicon-on-insulator (SOI) wafer is irradiated by automatically scanning a femtosecond laser and then split by etching out the SOI silica middle layer. Large-area, uniform micro spikes on the surface of a very thin flexible silicon layer are obtained. The black silicon shows good flexibility and optical properties. The absorption spectrum of the flexible black silicon is as high as 97% in the visible and insensitive to the change of the incident angle of the light, which makes it a potential good candidate as an absorber for the solar-thermo generator.     

Pulse compression and fiber delivery of 45 fs Fourier transform limited pulses at 830 nm

A specific scheme is used for fiber delivery of ultrashort pulses using conventional elements. Starting from a standard femtosecond Ti:Al(2)O(3) oscillator (150 fs @ 830 nm), perfectly compressed ultrashort pulses with a duration of 45 fs are produced at the output of a standard two meter long single-mode fiber. The setup allows compensating independently and simultaneously second and third orders of chromatic dispersion as well as management of self-phase modulation in the fiber. It includes an optimized dispersion compensation line made of the assembly of diffraction gratings and prisms. The unsurpassed performances of the device are experimentally and numerically highlighted. Fiber delivery of sub-30 fs multinanojoule pulses is discussed.     

Accelerated ageing and degradation in poly-l-lactide/hydroxyapatite nanocomposites

Dry, compression molded films of medical grade poly-l-lactide (PLLA) showed a marked reduction in tensile strength and strain after accelerated ageing in aqueous NaOH at 50 °C, accompanied by mass loss, surface erosion, increased hydrophilicity and, in the case of the initially amorphous films, cold crystallization owing to the plasticizing effect of the ageing medium. Addition of well dispersed nanosized hydroxyapatite (nHA) particles resulted in increases in the rate of mass loss during ageing, identified with accelerated degradation at the matrix/particle interfaces. However, the associated decreases in tensile strength and strain to fail with ageing time were far less marked in the presence of the nHA than in the unmodified films. This implied that nHA acts as an effective toughener of the bulk material, consistent with TEM observations of the deformed films, which indicated failure of the particle-matrix interfaces to promote plastic deformation of the PLLA.