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1.
Spectroscopic information pertaining to interstate coupling between the S2 and S1 electronic states of ovalene, whose electronic origins are separated by ≈ 1800 cm?1, has been obtained by the interrogation of the fluorescence action spectrum and of the energy-resolved fluorescence in seeded supersonic beams. 相似文献
2.
Mezer A Friedman R Noivirt O Nachliel E Gutman M 《The journal of physical chemistry. B》2005,109(22):11379-11388
The surface of a protein, or a membrane, is spotted with a multitude of proton-binding sites, some of which are only a few angstroms apart. When a proton is released from one site, it propagates through the water by a random walk under the bias of the local electrostatic potential determined by the distribution of the charges on the protein. Some of the released protons disperse into the bulk, but during the first few nanoseconds, the released protons can be trapped by encounter with nearby acceptor sites. This process resembles a scenario which corresponds with the time-dependent Debye-Smoluchowski equation. In the present study, we investigated the mechanism of proton transfer between sites that are only a few angstroms apart, using as a model the proton exchange between sites on a small molecule, fluorescein, having two, spectrally distinguishable, proton-binding sites. The first site is the oxyanion on the chromophore ring structure. The second site is the carboxylate moiety on the benzene ring of the molecule. Through our experiments, we were able to reconstruct the state of protonation at each site and the velocity of proton transfer between them. The fluorescein was protonated by a few nanosecond long proton pulse under specific conditions that ensured that the dye molecules would be protonated only by a single proton. The dynamics of the protonation of the chromophore were measured under varying initial conditions (temperature, ionic strength, and different solvents (H(2)O or D(2)O)), and the velocity of the proton transfer between the two sites was extracted from the overall global analysis of the signals. The dynamics of the proton transfer between the two proton-binding sites of the fluorescein indicated that the efficiency of the site-to-site proton transfer is very sensitive to the presence of the screening electrolyte and has a very high kinetic isotope effect (KIE = 55). These two parameters clearly distinguish the mechanism from proton diffusion in bulk water. The activation energy of the reaction (E(a) = 11 kcal mol(-1)) is also significantly higher than the activation energy for proton dissociation in bulk water (E(a) approximately 2.5 kcal mol(-1)). These observations are discussed with respect to the effect of the solute on the water molecules located within the solvation layer. 相似文献
3.
Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that
- Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
- Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
- Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
- Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.
4.
Different methods for the interpretation of linear dichroic spectra of molecules incorporated in uniaxial matrices are discussed. A method based on the combination of both polarized absorption and emission measurements is described for the resolution of absorption and emission spectra into their different polarized components, and for the investigation of molecular distributions in the oriented matrix. The distributions of some planar molecules of different shapes incorporated in stretched polyethylene films are presented. 相似文献
5.
Shady Farah Oren Aviv Natalia Laout Stanislav Ratner Nurit Beyth Abraham J. Domb 《先进技术聚合物》2014,25(6):689-692
Silica particles functionalized with quaternary ammonium groups were prepared by interpenetrating polyethylenimine (PEI) into silica particles and crosslinking with diiodopentane, followed by octyliodide alkylation and methyliodide quaternarization (S‐QA‐PEI). The synthesized S‐QA‐PEI particles were identified with a slight particle size increase of 2–3 µm. Different ratios of PEI:silica particles were prepared and analyzed. While silica particles are negatively charged, ?16.7 ± 5.11 mV, the prepared S‐QA‐PEI particles are positively charged, +50–60 mV. These particles were embedded in poly(ethylene vinyl acetate) and poly(ethylene methacrylic acid) coatings which exhibited strong antibacterial activity. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
6.
The Soreq Applied Research Accelerator Facility (SARAF): Overview,research programs and future plans
Israel Mardor Ofer Aviv Marilena Avrigeanu Dan Berkovits Adi Dahan Timo Dickel Ilan Eliyahu Moshe Gai Inbal Gavish-Segev Shlomi Halfon Michael Hass Tsviki Hirsh Boaz Kaiser Daniel Kijel Arik Kreisel Yonatan Mishnayot Ish Mukul Ben Ohayon Michael Paul Amichay Perry Hitesh Rahangdale Jacob Rodnizki Guy Ron Revital Sasson-Zukran Asher Shor Ido Silverman Moshe Tessler Sergey Vaintraub Leo Weissman 《The European Physical Journal A - Hadrons and Nuclei》2018,54(5):91
7.
Separation of lithium and potassium isotopes has been achieved using the isotopic differences in the radiofrequency spectrum. The isotope separation was studied in a supersonic molecular beam magnetic resonance spectrometer, and enrichment factors up to 30 obtained. 相似文献
8.
A spray‐based technique, originally developed for the production of semiconductor nanocrystals, is utilized for the preparation of high‐quality nanocrystalline thin films, as demonstrated with manganese sulfide. The films are formed by the use of pneumatic‐assisted thermospray or pneumatic nebulizers. Our simple, low‐cost, and low‐temperature process results in a dense and phase‐pure grain structure. The concepts and benefits of this technique are described and discussed. The film characteristics show dependence on the experimental parameters, in particular the rate of solvent vaporization. Three alternative film formation mechanisms are suggested for cases with varied experimental conditions. 相似文献
9.
Alexander B. Fialkov Elias Ikonen Tiina Laaksonen Aviv Amirav 《Journal of mass spectrometry : JMS》2020,55(9)
A new type of photoionization ion source was developed for the ionization of cold molecules in supersonic molecular beams (named Cold PI). The system was based on a GC–MS with supersonic molecular beams and its fly‐through EI of cold molecules ion source (Cold EI) plus quadrupole mass analyzer. A continuously operated deuterium VUV photoionization lamp was added and placed above and between the supersonic nozzle and skimmer whereas the Cold EI ion source served only as a portion of the ion transfer ion optics. The supersonic nozzle and skimmer were voltage biased and the VUV light crossed the supersonic expansion about 10 mm from the nozzle. We obtained over three orders of magnitude enhancement in the relative abundance of the molecular ion of squalane in Cold PI versus in photoionization of this compound as a thermal compound. Accordingly, we also proved that standard photoionization is not as soft ionization method as previously perceived for large compounds. We found that Cold PI is as soft as and possibly softer than field ionization; thus, it could be the softest known ionization method. The ionization yield was about 200–300 times weaker than with Cold EI yet our limit of detection was about 200 femtogram in SIM mode for cholesterol and pyrene which is reasonable. Practically, all hydrocarbons gave only molecular ions with rather uniform response whereas alcohols gave some molecular ions plus major fragment ions particularly with a loss of water (similarly to field ionization). We tested Cold PI in the GC–MS analysis of diesel fuels and analyzed the time averaged data for group type information. We also found that we can analyze the diesel fuels by fast under 20‐s flow injection analysis in which the generated averaged mass spectrum of molecular ions only could serve for the characterization of fuels. 相似文献
10.
Pharmaceuticals require careful and precise determination of their impurities that might harm the user upon consumption. Although today, the most common technique for impurities identification is liquid chromatography‐mass spectrometry (LC‐MS/MS), it has several downsides due to the nature of the ionization method. Also, the analyses in many cases are targeted thus despite being present, some of the compounds will not be revealed. In this paper, we propose and show a new method for untargeted analysis and identification of impurities in active pharmaceutical ingredients (APIs). The instrument used for these analyses is a novel electron ionization (EI) LC‐MS with supersonic molecular beams (SMB). The EI‐LC‐MS‐SMB was implemented for analyses of several drug samples spiked with an impurity. The instrument provides EI mass spectra with enhanced molecular ions, named Cold EI, which increases the identification probabilities when the compound is identified with the aid of an EI library like National Institute of Standards and Technology (NIST). We analyzed ibuprofen and its impurities, and both the API and the expected impurity were identified with names and structures by the NIST library. Moreover, other unexpected impurities were found and identified proving the ability of the EI‐LC‐MS‐SMB system for truly untargeted analysis. The results show a broad dynamic range of four orders of magnitude at the same run with a signal‐to‐noise ratio of over 10 000 for the API and almost uniform response. 相似文献