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1.
Dissociative recombination of the weakly bound NO-dimer cation: cross sections and three-body dynamics 总被引:1,自引:0,他引:1
Petrignani A Andersson PU Pettersson JB Thomas RD Hellberg F Ehlerding A Larsson M van der Zande WJ 《The Journal of chemical physics》2005,123(19):194306
Dissociative recombination (DR) of the dimer ion (NO)(2) (+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69+/-0.02. The second most important channel yields NO+NO fragments with a probability of 0.23+/-0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N((4)S)+O((3)P), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer. 相似文献
2.
Petrignani A van der Zande WJ Cosby PC Hellberg F Thomas RD Larsson M 《The Journal of chemical physics》2005,122(1):14302
We have studied the dissociative recombination of the first three vibrational levels of O(2) (+) in its electronic ground X (2)Pi(g) state. Absolute rate coefficients, cross sections, quantum yields and branching fractions have been determined in a merged-beam experiment in the heavy-ion storage ring, CRYRING, employing fragment imaging for the reaction dynamics. We present the absolute total rate coefficients as function of collision energies up to 0.4 eV for five different vibrational populations of the ion beam, as well as the partial (vibrationally resolved) rate coefficients and the branching fractions near 0 eV collision energy for the vibrational levels v=0, 1, and 2. The vibrational populations used were produced in a modified electron impact ion source, which has been calibrated using Cs-O(2)(+) dissociative charge transfer reactions. The measurements indicate that at low collision energies, the total rate coefficient is weakly dependent on the vibrational excitation. The calculated thermal rate coefficient at 300 K decreases upon vibrational excitation. The partial rate coefficients as well as the partial branching fractions are found to be strongly dependent on the vibrational level. The partial rate coefficient is the fastest for v=0 and goes down by a factor of two or more for v=1 and 2. The O((1)S) quantum yield, linked to the green airglow, increases strongly upon increasing vibrational level. The effects of the dissociative recombination reactions and super elastic collisions on the vibrational populations are discussed. 相似文献
3.
Pondikpa Nadjombé Mamatchi Mélila Hodabalo Kamou Essossimna Magamana Annemieke Verbeken K. Atsu Guelly 《印度化学会志》2022,99(6):100407
In order to contribute to the valorisation of wild fungi whose nutritional potential, although considerable, is not sufficiently known in some countries such as Togo, a study has been carried out on Russula species. The diversity of Russula species from Alédjo Wildlife Reserve has been assessed using a focused inventory in woodlands dominated by Isoberlinia doka Craib & Stapf, Isoberlinia tomentosa (Harms) Craib & Stapf, Monotes kerstingii Gilg, Uapaca togoensis Pax and gallery forests dominated by Berlinia grandiflora (Vahl) Hutch & Dalz and Uapaca guineensis Müll. Ethnomycological surveys have been carried out among Tém and Kabyè, two riparian ethnic groups that are mainly represented. Biochemical analyses have been carried out using the AOAC method. Fifteen (15) taxa of edible Russula species are commonly used by Tém and Kabyè people living along the Alédjo Wildlife Reserve among which thirteen (13) taxa have been identified up to species level. R. oleifera is eaten by all interviewed people in both sociolinguistic groups (Fr = 100%) followed by R. compressa (Fr = 92.31%), R. ochrocephala (Fr = 87.18%) among Tém people and R. ochrocephala (Fr = 91.67%), R. compressa (Fr = 83.33%) among Kabyè people. Five (05) new species of edible Russula have been identified for the first time in Togo. The Russula species analysed have been rich in macronutrients with contents ranging from 2.88 g/100 g of dw for fat to 65.83 g/100 g of dw for total carbohydrates. In addition, these Russula species have shown a relatively high mineral content with contents ranging from 405.70 mg/100 g of dw for Ca to 2784 mg/100 g of dw for K. Furthermore, the results have revealed that Russula species analysed are a source of energy with 309.50 Kcal/100 g of dw. The edible Russula species analysed can thus contribute to food security in Togo. 相似文献
4.
Stevens K Claeys DD Catak S Figaroli S Hocek M Tromp JM Schürch S Van Speybroeck V Madder A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(25):6940-6953
Oligodeoxynucleotides incorporating a reactive functionality can cause irreversible cross-linking to the target sequence and have been widely studied for their potential in inhibition of gene expression or development of diagnostic probes for gene analysis. Reactive oligonucleotides further show potential in a supramolecular context for the construction of nanometer-sized DNA-based objects. Inspired by the cytochrome P450 catalyzed transformation of furan into a reactive enal species, we recently introduced a furan-oxidation-based methodology for cross-linking of nucleic acids. Previous experiments using a simple acyclic building block equipped with a furan moiety for incorporation into oligodeoxynucleotides have shown that cross-linking occurs in a very fast and efficient way and that substantial amounts of stable, site-selectively cross-linked species can be isolated. Given the destabilization of duplexes observed upon introduction of the initially designed furan-modified building block into DNA duplexes, we explore here the potential benefits of two new building blocks featuring an extended aromatic system and a restored cyclic backbone. Thorough experimental analysis of cross-linking reactions in a series of contexts, combined with theoretical calculations, permit structural characterization of the formed species and allow assessment of the origin of the enhanced cross-link selectivity. Our experiments clearly show that the modular nature of the furan-modified building blocks used in the current cross-linking strategy allow for fine tuning of both yield and selectivity of the interstrand cross-linking reaction. 相似文献
5.
Jawalekar AM Op de Beeck M van Delft FL Madder A 《Chemical communications (Cambridge, England)》2011,47(10):2796-2798
2'-O-(3-(Furan-2-yl)propyl)adenosine was synthesized and evaluated for interstrand crosslink (ICL) formation in DNA duplexes. In situ oxidation of the furan moiety with NIS showed rapid crosslink formation to dA and dC, while dT and dG were inactive. 相似文献
6.
De Haes P Garmyn M Verstuyf A De Clercq P Vandewalle M Degreef H Vantieghem K Bouillon R Segaert S 《Journal of photochemistry and photobiology. B, Biology》2005,78(2):141-148
Exposure to UVB irradiation is a major risk factor for the development of skin cancer. Therefore, it is important to identify agents that can offer protection against UVB-caused damage. Photocarcinogenesis is caused largely by mutations at sites of incorrectly repaired DNA photoproducts, of which the most common are the cyclobutane pyrimidine dimers (CPDs). In this study, we demonstrated that 1,25-dihydroxyvitamin D3 [1,25(OH)2D3] protects primary human keratinocytes against the induction of CPDs by UVB. This protection required pharmacologic doses 1,25(OH)2D3 and an incubation period of at least 8 h before irradiation. Furthermore, we provided arguments indicating that the anti-proliferative capacity of 1,25(OH)2D3 underlies its protective effect against UVB-induced DNA damage. Finally, we showed that 19-nor-14-epi-23-yne-1,25(OH)2D3 (TX 522) and 19-nor-14,20-bisepi-23-yne-1,25(OH)2D3 (TX 527), two low-calcemic analogues of 1,25(OH)2D3, were even 100 times more potent than the parent molecule in inhibiting UVB-caused DNA damage. These molecules are therefore promising candidates for the chemoprevention of UVB-induced skin cancer. 相似文献
7.
Ioannis Zalachoras Gwendolynn Grootaers Lisa TCM van Weert Yves Aubert Suzanne R de Kreij Nicole A Datson Willeke MC van Roon-Mom Annemieke Aartsma-Rus Onno C Meijer 《BMC neuroscience》2013,14(1):1-12
Background
Antisense oligonucleotide (AON)-mediated exon skipping is a powerful tool to manipulate gene expression. In the present study we investigated the potential of exon skipping by local injection in the central nucleus of the amygdala (CeA) of the mouse brain. As proof of principle we targeted the splicing of steroid receptor coactivator-1 (SRC-1), a protein involved in nuclear receptor function. This nuclear receptor coregulator exists in two splice variants (SRC-1a and SRC-1e) which display differential distribution and opposing activities in the brain, and whose mRNAs differ in a single SRC-1e specific exon.Methods
For proof of principle of feasibility, we used immunofluorescent stainings to study uptake by different cell types, translocation to the nucleus and potential immunostimulatory effects at different time points after a local injection in the CeA of the mouse brain of a control AON targeting human dystrophin with no targets in the murine brain. To evaluate efficacy we designed an AON targeting the SRC-1e-specific exon and with qPCR analysis we measured the expression ratio of the two splice variants.Results
We found that AONs were taken up by corticotropin releasing hormone expressing neurons and other cells in the CeA, and translocated into the cell nucleus. Immune responses after AON injection were comparable to those after sterile saline injection. A successful shift of the naturally occurring SRC-1a:SRC-1e expression ratio in favor of SRC-1a was observed, without changes in total SRC-1 expression.Conclusions
We provide a proof of concept for local neuropharmacological use of exon skipping by manipulating the expression ratio of the two splice variants of SRC-1, which may be used to study nuclear receptor function in specific brain circuits. We established that exon skipping after local injection in the brain is a versatile and useful tool for the manipulation of splice variants for numerous genes that are relevant for brain function. 相似文献8.
Storage and transport of hydrogen constitutes a key enabling technology for the advent of a hydrogen-based energy transition. Main research trends on hydrogen storage materials, including metal hydrides, porous adsorbents and hydrogen clathrates, are reviewed with a focus on recent developments and an appraisal of the challenges ahead. . 相似文献
9.
The synthesis of nucleosides modified with an extra imidazole, carboxyl and hydroxyl group is described. These nucleosides can be incorporated into an oligonucleotide duplex, thus generating a novel type of serine protease mimic. 相似文献
10.
De Gussem K Vandenabeele P Verbeken A Moens L 《Analytical and bioanalytical chemistry》2007,387(8):2823-2832
Confocal Raman spectroscopy is a non-destructive analytical method which is useful to obtain detailed information about the
molecular composition of biological samples. Its high spatial resolution was used to collect spectra of single basidiospores
of macrofungi of the genera Collybia, Gymnopus, Laccaria, Lactarius, Mycena and Russula. These spectra can be divided into three major taxon-related groups, with general compositional differences, such as the
relative amount of lipids compared to proteins. In this study, collapsing of thin-walled spores during storage was often observed,
a phenomenon which has been given little attention in the literature. The Raman spectra are treated with different chemometric
preprocessing techniques, including Savitsky–Golay, standard normal variate (SNV) preprocessing and extended multiplicative
scatter correction (EMSC). By using linear discriminant analysis, approximately 90% of the spectra can be assigned to the
correct genus, but identification on the species level was not possible. 相似文献