The gas-phase basicity and proton affinity of 1,3,5-cycloheptatriene--energetics,structure and interconversion of dihydrotropylium ions

The hitherto unknown gas-phase basicity and proton affinity of 1,3,5-cycloheptatriene (CHT) have been determined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Several independent techniques were used in order to exclude ambiguities due to proton-induced isomerisation of the conjugate cyclic C(7)H(9)(+) ions, [CHT + H](+). The gas-phase basicity obtained by the thermokinetic method, GB(CHT) = 799 +/- 4 kJ mol(-1), was found to be identical, within the limits of experimental error, with the values measured by the equilibrium method starting with protonated reference bases, and with the values resulting from the measurements of the individual forward and reverse rate constants, when corrections were made for the isomerised fraction of the C(7)H(9)(+) population. The experimentally determined gas-phase basicity leads to the proton affinity of cycloheptatriene, PA(CHT) = 833 +/- 4 kJ mol(-1), and the heat of formation of the cyclo-C(7)H(9)(+) ion, deltaH(f)(0)([CHT + H](+)) = 884 +/- 4 kJ mol(-1). Ab initio calculations are in agreement with these experimental values if the 1,2-dihydrotropylium tautomer, [CHT + H((1))](+), generated by protonation of CHT at C-1, is assumed to be the conjugate acid, resulting in PA(CHT) = 825 +/- 2 kJ mol(-1) and deltaH(f)(0)(300)([CHT + H((1))](+)) = 892 +/- 2 kJ mol(-1). However, the calculations indicate that protonation of cycloheptatriene at C-2 gives rise to transannular C-C bond formation, generating protonated norcaradiene [NCD + H](+), a valence tautomer being 19 kJ mol(-1) more stable than [CHT + H((1))](+). The 1,4-dihydrotropylium ion, [CHT + H((3))](+), generated by protonation of CHT at C-3, is 17 kJ mol(-1) less stable than [CHT + H((1))](+). The bicyclic isomer [NCD + H](+) is separated by relatively high barriers, 70 and 66 kJ mol(-1) from the monocyclic isomers, [CHT + H((1))](+) and [CHT + H((3))](+), respectively. Therefore, the initially formed 1,2-dihydrotropylium ion [CHT + H((1))](+) does not rearrange to the bicyclic isomer [NCD + H](+) under mild protonation conditions.     

Ultraviolet Radiation Effects on a Microscopic Green Alga and the Protective Effects of Natural Dissolved Organic Matter

Abstract— The population and photosynthetic responses of a microscopic green alga ( Selenastrum capricornutum ) to realistic levels of UV radiation (UVA and UVB) were assessed in natural lake waters of different dissolved organic carbon (DOC) concentration. Specific growth rates and photosynthetic competence (as reflected by F_v/F_m [measure of maximal quantum efficiency of photosystem II] and t_1/2 [estimate of electrons transported to the plastoquinone pool] measured by in vivo variable chlorophyll a fluorescence) were compared between two exposure levels of UVR and two concentrations of DOC (2.5 mg C L⁻¹ 7.7 mg C L⁻¹). Exposure periods of 6–9 days (five to nine generations) were used. Exposure to UVA primarily affected the efficiency of photosystem II, as evidenced by significant decreases of F_v/F_m but not growth rates or t_1/2 Exposure to UVB, in the presence of UVA, did not cause significant additional decreases of F_v/F_m but did diminish growth rates. In the low DOC water, t_1/2 was also diminished, suggesting different proximate sites of action from those for UVA. The high DOC water decreased the effective exposure to both UVA and UVB and diminished the negative impact of UV radiation on the cells, but the apparent protection was not explicable solely by the shading action of the DOC. Control values for F_v/F_m, growth rates and t_1/2 were all lower in the high DOC water, suggesting a negative side effect to the apparent protective action of the DOC against UVB.     

Cold storage and cryopreservation of hops (Humulus l.) shoot cultures through application of standard protocols

The USDA-ARS National Clonal Germplasm Repository (NCGR) stores the global diversity of Humulus for the US Plant Germplasm System as trellised plants in a field genebank. In vitro storage and cryopreservation are now considered excellent ways to provide medium and long-term storage for plant collections. Developing a new cryopreservation or cold storage protocol for every accession or genus of large multi-crop collections can be a very time consuming and long-term activity. We propose that standard cold storage and cryopreservation techniques used for other temperate crop genera would be successful for additional crops with few modifications. This study was initiated to determine if a large collection of hops germplasm could be successfully stored with techniques developed for unrelated genera. In this study we characterized the response of diverse Humulus genotypes to in vitro storage under low light at 4 degree C following techniques used for strawberry and mint plants, and cryopreservation in liquid nitrogen by slow cooling with a pear protocol. The average storage time without transfer for the 70 genotypes evaluated was 14 +/- 3.5 months with a range of 6 to 26 months. Mean recovery of cryopreserved shoot tips of accessions with 1-wk cold acclimation was 41 +/- 18 percent and increased to 54 +/- 13 percent with 2-wk cold acclimation. This demonstrates that application of a well-tested standard technique can provide a quick start for storing additional germplasm collections.     

Reactivity and selectivity of homolytic substitution reactions on the peroxyacid group

Peracids in solution may undergo homolytic decomposition leading mostly to mixtures of acid and alcohols, these Latters being formed from either the peracid or the solvent

The peracid behaves as source of radicals and also as substrate thus presenting two radicophile centers

- with a nucleophilic radical (R' from peracid or S' from solvent) the site of attack is the 0-0 bond of the peracid yielding an alcohol (NuOH). The rate of this reaction increases with increasing nucleophilicity of the radical ; this reactivity is interpreted in terms of frontier orbital perturbation theory, taking into account both the orbital energy level difference and the orbital overlap.- when the radical is electrophilic, it abstracts rather the hydrogen of the peroxidic group Leading to decomposition of the peracid into acid.Hydrogen abstraction from the solvent may be also observed in appropriate cases : this process can be used for free radical hydroxylation of hydrocarbons.The relative importance of these three chain reactions in competition : 0-0 bound attack, hydrogen abstraction from the peracid and solvent transfer reaction were studied as a function of structure of the radicals, solvent properties and temperature.     

Pressure broadening mechanisms of the ammonia lines: Rotation,inversion and rotation-inversion spectra of NH3 perturbed by monoatomic gases

The half-widths of rotation, inversion and rotation-inversion spectral lines of NH₃ perturbed by rare gases have been calculated. These calculations take into account the R^-7 dispersion potential energy, which was previously studied by the present authors. A detailed analysis of the contribution of various induced collisional processes has shown that the ΔK = ±3 transitions induced by the dispersion potential are of importance for both the pure rotation spectrum and the inversion and rotation-inversion spectrum.     

Unimolecular reactivity of strong metal-cation complexes in the gas phase: ethylenediamine-Cu(+)

The gas-phase reactions between ethylenediamine (en) and Cu(+) have been investigated by means of mass spectrometry techniques. The MIKE spectrum reveals that the adduct ions [Cu(+)(H(2)NCH(2)CH(2)NH(2))] spontaneously decompose by loosing H(2), NH(3) and HCu, the loss of hydrogen being clearly dominant. The spectra of the fully C-deuterated species show the loss of HD, NH(3) and CuD but no losses of H(2), D(2), NH(2)D, NHD(2), ND(3) or CuH are observed. This clearly excludes hydrogen exchange between the methylene and the amino groups as possible mechanisms for the loss of ammonia. Conversely, methylene hydrogen atoms are clearly involved in the loss of molecular hydrogen. The structures and bonding characteristics of the Cu(+)(en) complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by DFT calculations carried out at B3LYP/6-311+G(2df,2p)//B3LYP/6-311G(d,p) level. Based on the topology of this PES the most plausible mechanisms for the aforementioned unimolecular fragmentations are proposed. Our theoretical estimates indicate that Cu(+) strongly binds to en, by forming a chelated structure in which Cu(+) is bridging between both amino groups. The binding energy is quite high (84 kcal mol(-1)), but also the products of the unimolecular decomposition of Cu(+)(en) complexes are strongly bound Cu(+)-complexes.     

Synthesis of Reactive Intermediates for Natural Cyclopentane Derivatives from (−)-Quinic Acid: Preparation of 11α-hydroxy-13-oxaprostanoic acid

We describe a flexible, stereocontrolled synthesis of enantiomerically pure substituted cyclopentenes and cyclopentanes - including 11α-hydroxy-13-oxaprostanoic acid 20 - (?)-quinic acid via an acyclic precursor 6 by an intramolecular aldolisation-dehydration reaction.     

Ni(+) reactions with aminoacetonitrile, a potential prebiological precursor of glycine

The gas-phase reactions between Ni(+) ((2)D(5/2)) and aminoacetonitrile, a molecule of prebiological interest as possible precursor of glycine, have been investigated by means of mass spectrometry techniques. The mass-analyzed ion kinetic energy (MIKE) spectrum reveals that the adduct ions [NC--CH(2)--NH(2), Ni(+)] spontaneously decompose by loosing HCN, H(2), and H(2)CNH, the loss of hydrogen cyanide being clearly dominant. The structures and bonding characteristics of the aminoacetonitrile-Ni(+) complexes as well as the different stationary points of the corresponding potential energy surface (PES) have been theoretically studied by density functional theory (DFT) calculations carried out at B3LYP/6-311G(d,p) level. A cyclic intermediate, in which Ni(+) is bisligated to the cyano and the amino group, plays an important role in the unimolecular reactivity of these ions, because it is the precursor for the observed losses of HCN and H(2)CNH. In all mechanisms associated with the loss of H(2), the metal acts as hydrogen carrier favoring the formation of the H(2) molecule. The estimated bond dissociation energy of aminoacetonitrile-Ni(+) complexes (291 kJ mol(-1)) is larger than those measured for other nitrogen bases such as pyridine or pyrimidine and only slightly smaller than that of adenine.