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21.
The biosynthesis of the active site of the [FeFe]-hydrogenases (H-cluster) remains a tantalizing puzzle due to its unprecedented and complex ligand environment. It contains a [2Fe] cluster ([2Fe](H)) bearing cyanide and carbon monoxide ligands attached to low-valence Fe ions and an abiological dithiolate ligand (SCH(2)XCH(2)S)(2-) that bridges the two iron centers. Various experimentally testable hypotheses have already been put forward regarding the precursor molecule and the biosynthetic mechanism that leads to the formation of the dithiolate ligand. In this work, we report a density functional theory-based theoretical evaluation of these hypotheses. We find preference for a mechanistically simple and energetically favorable pathway that includes known radical-SAM (S-adenosylmethionine) catalyzed reactions. We modeled this pathway using a long alkyl chain precursor molecule that leads to the formation of pronanadithiolate (X = CH(2)). However, the same pathway can be readily adopted for the biosynthesis of the dithiomethylamine (X = NH) or the dithiomethylether (X = O) analog, provided that the proper precursor molecule is available. 相似文献
22.
Alexios P. Polychronakos 《Annals of Physics》2002,301(2):174-183
The mapping of topologically nontrivial gauge transformations in noncommutative gauge theory to corresponding commutative ones is investigated via the operator form of the Seiberg-Witten map. The role of the gauge transformation part of the map is analyzed. Chern-Simons actions are examined and the correspondence to their commutative counterparts is clarified. 相似文献
23.
Beveratos A Brouri R Gacoin T Villing A Poizat JP Grangier P 《Physical review letters》2002,89(18):187901
We report the full implementation of a quantum cryptography protocol using a stream of single photon pulses generated by a stable and efficient source operating at room temperature. The single photon pulses are emitted on demand by a single nitrogen-vacancy color center in a diamond nanocrystal. The quantum bit error rate is less that 4.6% and the secure bit rate is 7700 bits/s. The overall performances of our system reaches a domain where single photons have a measurable advantage over an equivalent system based on attenuated light pulses. 相似文献
24.
We analyze the noncommutative two-dimensional Wess–Zumino–Witten model and its properties under Seiberg–Witten transformations in the operator formulation. We prove that the model is invariant under such transformations even for the noncritical (non-chiral) case, in which the coefficients of the kinetic and Wess–Zumino terms are not related. The pure Wess–Zumino term represents a singular case in which this transformation fails to reach a commutative limit. We also discuss potential implications of this result for bosonization. 相似文献
25.
Aurélie Urbain Pierre Corbeiller Nektarios Aligiannis Maria Halabalaki Alexios‐Leandros Skaltsounis 《Journal of separation science》2010,33(9):1198-1203
Using a one‐step preparative hydrostatic countercurrent chromatography method, the fragrant massoia lactones were purified from the crude massoia bark oil, in less than 3 h. The fractionation was performed with the biphasic solvent system c‐hexane–methanol–water (10:9:1, v/v/v), leading to target compounds with purity over 96%, as determined by GC‐MS and ultra high pressure LC‐MS analyses. Together with C‐10, C‐12 and C‐14 massoia lactones, two other aromatic compounds used in perfumes, benzyl benzoate and benzyl salicylate, were also obtained as pure compounds. In parallel, an easy and efficient ultra high pressure LC method was developed for the ultra‐fast analysis of massoia lactones, as an alternative to long GC‐MS methods. 相似文献
26.
Alexios Papadimitratos Aram Amassian Aravind S. Killampalli Jared L. Mack George G. Malliaras James R. Engstrom 《Applied Physics A: Materials Science & Processing》2009,95(1):29-35
Top-contact organic thin-film transistors (OTFTs) of pentacene have been fabricated on bare SiO2 and SiO2 modified with hexamethyldisilazane (HMDS) and octadecyltrichlorosilane (OTS). The pentacene films were deposited from a supersonic
molecular beam source with kinetic energy of incident molecules ranging from 1.5 to 6.7 eV. The field-effect mobility of OTFTs
was found to increase systematically with increasing kinetic energy of the molecular beam. The improvements are more important
on HMDS- and OTS-treated surfaces than on bare SiO2. Tapping mode atomic force microscopy images reveal that pentacene thin films deposited at high kinetic energy form with
significantly larger grains—independent of surface treatment—than films deposited using low-energy beams. 相似文献
27.
Encapsulation of Crabtree's Catalyst in Sulfonated MIL‐101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment
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Dr. Alexios Grigoropoulos Dr. Alasdair I. McKay Dr. Alexandros P. Katsoulidis Dr. Robert P. Davies Dr. Anthony Haynes Prof. Lee Brammer Prof. Jianliang Xiao Prof. Andrew S. Weller Prof. Matthew J. Rosseinsky 《Angewandte Chemie (International ed. in English)》2018,57(17):4532-4537
Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL‐101(Cr) metal–organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non‐functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well‐defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways. 相似文献
28.
Alexios Matamis Sara Lonn Ludovica Luise Bianca Maria Vaglieco Martin Tuner Oivind Andersson Marcus Alden Mattias Richter 《Proceedings of the Combustion Institute》2021,38(4):5509-5517
In the search for renewable fuels, there are very few candidates as compelling as methanol. It can be derived from refuse material and industrial waste, while the infrastructure exists worldwide to support broad and fast adoption, potentially even as a “drop-in” fuel for existing vehicles with only minor modifications. The most efficient engines currently available are compression-ignition engines, however they often come with high emissions or compromises like the soot-NOx trade-off. Methanol however, is a low sooting fuel that can potentially be used in such engines despite its high resistance to auto-ignition and reduce emissions while maintaining high engine efficiency. Due to the auto-ignition resistance, few studies of methanol compression-ignition exist and even fewer are conducted in an optically accessible engine. Here, two cases of premixed combustion and two of spray-driven combustion of methanol are studied in a Heavy-Duty optically accessible engine. Ignition and combustion propagation are characterized with a combination of time-resolved natural flame luminosity measurements and single-shot, acetone fuel-tracer, laser induced fluorescence. Additionally, Mie-scattering is used to identify the interaction between liquid spray and ignition sites in spray-driven methanol combustion. Results show that methanol combusts drastically different compared to conventional fuels, especially in spray-driven combustion. The evaporative cooling effect of methanol appears to play a major role in the auto-ignition characteristics of the delivered fuel. Ignition sites appear right at the end of injection when the evaporative cooling effect is withdrawn or at liquid length oscillations where, again the effect is momentarily retracted. To the authors’ knowledge, this has not been documented before. 相似文献
29.
Aneta Grabarska Paula Wrblewska-uczka Wirginia Kukula-Koch Jarogniew J. uszczki Eleftherios Kalpoutzakis Grzegorz Adamczuk Alexios Leandros Skaltsounis Andrzej Stepulak 《Molecules (Basel, Switzerland)》2021,26(20)
Palmatine (PLT) is a natural isoquinoline alkaloid that belongs to the class of protoberberines and exhibits a wide spectrum of pharmacological and biological properties, including anti-cancer activity. The aim of our study was to isolate PLT from the roots of Berberis cretica and investigate its cytotoxic and anti-proliferative effects in vitro alone and in combination with doxorubicine (DOX) using human ER+/HER2− breast cancer cell lines. The alkaloid was purified by column chromatography filled with silica gel NP and Sephadex LH-20 resin developed in the mixture of methanol: water (50:50 v/v) that provided high-purity alkaloid for bioactivity studies. The purity of the alkaloid was confirmed by high resolution mass measurement and MS/MS fragmentation analysis in the HPLC-ESI-QTOF-MS/MS-based analysis. It was found that PLT treatment inhibited the viability and proliferation of breast cancer cells in a dose-dependent manner as demonstrated by MTT and BrdU assays. PLT showed a quite similar growth inhibition on breast cancer cells with IC50 values ranging from 5.126 to 5.805 µg/mL. In contrast, growth of normal human breast epithelial cells was not affected by PLT. The growth inhibitory activity of PLT was related to the induction of apoptosis, as determined by Annexin V/PI staining. Moreover, PLT sensitized breast cancer cells to DOX. Isobolographic analysis revealed synergistic and additive interactions between studied agents. Our studies suggest that PLT can be a potential candidate agent for preventing and treating breast cancer. 相似文献
30.
Georgios Floros Fotini Agrafioti Alexios Grigoropoulos Patrina Paraskevopoulou Konstantinos Mertis Maria Tseklima Maria Veli Marinos Pitsikalis 《Journal of polymer science. Part A, Polymer chemistry》2013,51(22):4835-4844
Statistical copolymers of norbornene (NBE) with 5‐vinyl‐2‐norbornene (VNBE) were prepared by ring‐opening metathesis polymerization, employing the triply bonded ditungsten complex Na[W2(μ‐Cl)3Cl4(THF)2].(THF)3. NMR measurements revealed that the side vinyl groups of the VNBE monomer remain intact during the copolymerization reaction. The reactivity ratios were estimated using the Finemann–Ross (FR), the inverted FR, and the Kelen–Tüdos graphical methods. Structural parameters of the copolymers were obtained by calculating the dyad sequence fractions, which were derived using the monomer reactivity ratios. The glass transition temperatures, Tg, of the copolymers were measured by differential scanning calorimetry measurements and were examined in the frame of several theoretical equations allowing the prediction of these Tg values. The best fit was obtained using methods that take into account the monomer sequence distribution of the copolymers. Finally, the kinetics of the thermal decomposition of the copolymers was studied by thermogravimetric analysis in the frame of the Ozawa–Flynn–Wall and Kissinger methods. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4835–4844 相似文献