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31.
32.
Kuniharu Fujii Satoshi Kera Mika Oiwa Koji K. Okudaira Kazuyuki Sakamoto Nobuo Ueno 《Surface science》2007,601(18):3765-3768
We have investigated the relation between the intramolecular vibrational modes of pentacene and the charge redistribution at the pentacene-graphite interface by using high-resolution electron-energy-loss-spectroscopy. The three main vibrational peaks shift to lower energies as the pentacene film thickness decreases. In order to discuss this energy shift, we have calculated the vibrational energies of a free pentacene molecule by changing its charge state. We have also calculated the vibrational energies of a pentacene molecule adsorbed on a graphite sheet by changing the pentacene-graphite distance. Taking the experimental and calculation results into account, we conclude that the observed energy shifts result from an intramolecular charge redistribution. The present results indicate that the effect of an intramolecular charge redistribution is essential to discuss the origin of an energy shift observed in a vibrational study of an organic molecule/substrate interface. 相似文献
33.
Mika Tiainen Hannu Maaheimo Pasi Soininen Reino Laatikainen 《Magnetic resonance in chemistry : MRC》2010,48(2):117-122
The one‐ and two‐bond 13C isotope shifts, typically ?1.5 to ?2.5 ppb and ?0.7 ppb respectively, in non‐cyclic aliphatic systems and up to ?4.4 ppb and ?1.0 ppb in glucose cause effects that need to be taken into account in the adaptive NMR spectral library‐based quantification of the isotopomer mixtures. In this work, NMR spectral analyses of some 13C‐labelled amino acids, D ‐glucose and other small compounds were performed in order to obtain rules for prediction of the 13C isotope effects on 1H chemical shifts. It is proposed that using the additivity rules, the isotope effects can be predicted with a sufficient accuracy for amino acid isotopomer applications. For glucose the effects were found strongly non‐additive. The complete spectral analysis of fully 13C‐labelled D ‐glucose made it also possible to assign the exocyclic proton signals of the glucose. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
34.
35.
Mikaël Pichot 《Israel Journal of Mathematics》2008,167(1):63-90
Harmonic analysis is applied in a quasi-periodic context to get rigidity results in orbit equivalence theory.
This paper has been written while the author was visiting the University of Tokyo under a JSPS Fellowship for European researchers. 相似文献
36.
The humidity and water tolerance of a sol-gel derived binder prepared using a cheap, multicomponent precursor has been studied.
The sol was prepared by dissolving the precursor in water under acidic conditions using either formic acid or a mixture of
formic acid and citric acid for pH adjustments. It is shown that a post-treatment temperature of 400 °C or higher is needed
in order to achieve full binder stability under excess water conditions, as thermal decomposition of metal carboxylates leads
to a pronounced decrease in water solubility of the gels. The mesoporous gel can be made hydrophobic by post-treatments with
either a silane or an organophosphonate, showing that both silica and metal oxides are exposed on the surface of the binder.
Surface functionalization is especially effective for gels heat-treated at higher temperatures where the metal carboxylates
have decomposed to the corresponding oxides or carbonates. The results are expected to be of great importance for the use
of this cheap binder in large scale industrial applications.
Electronic Supplementary Material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
37.
Anne Vuorema Mika Sillanpää Liza Rassaei Matthew J. Wasbrough Karen J. Edler Wim Thielemans Sara E. C. Dale Simon Bending Daniel Wolverson Frank Marken 《Electroanalysis》2010,22(6):619-624
A novel way to produce ultrathin transparent carbon layers on tin‐doped indium oxide (ITO) substrates is developed. The ITO surface is coated with cellulose nanofibrils (from sisal) via layer‐by‐layer electrostatic binding with poly(diallyldimethylammonium chloride) or PDDAC acting as the binder. The cellulose nanofibril‐PDDAC composite film is then vacuum‐carbonised at 500 °C. The resulting carbon films are characterised by atomic force microscopy (AFM), small angle X‐ray scattering (SAXS), wide‐angle X‐ray scattering (WAXS), and Raman methods. Smooth carbon films with good adhesion to the ITO substrate are formed. The electrochemical characterisation of the carbon films is based on the oxidation of hydroquinone and the reduction of benzoquinone in aqueous phosphate buffer media. A modest effect of the cellulose nanofibril‐PDDAC film on the rate of electron transfer is observed. The effect of the film on the rate of electron transfer after carbonisation is more dramatic. For a 40‐layer cellulose nanofibril‐PDDAC film after carbonisation a two‐order of magnitude change in the rate of electron transfer occurs presumably due to a better interaction of the hydroquinone/benzoquinone system with the electrode surface. 相似文献
38.
Mika Mahosenaho Felice Caprio Laura Micheli Adama M. Sesay Giuseppe Palleschi Vesa Virtanen 《Mikrochimica acta》2010,170(3-4):243-249
A disposable tri-enzymatic biosensor is presented for the determination of α-amylase in human saliva. It is based on the quantity of maltose generated by hydrolysis of maltopentose in the presence of salivary α-amylase. The biosensor is fabricated by co-immobilization of the enzymes α-glucosidase, glucose oxidase, and mutarotase on screen-printed electrodes modified with Prussian Blue. The assay can be performed with a “drop” of sample, this allowing for ease and simplicity. A linear relationship is found for the range from 5 to 250 units per mL, with an LOD of 5 units per mL. The biosensor is stable for at least one month and over this time retains 80% of its original activity. The system was then evaluated for matrix effects of human saliva and compared to a spectrometric method using a commercially available kit. 相似文献
39.
Leo Syrjänen Martti Tolvanen Mika Hilvo Ayodeji Olatubosun Alessio Innocenti Andrea Scozzafava Jenni Leppiniemi Barbara Niederhauser Vesa P Hytönen Thomas A Gorr Seppo Parkkila Claudiu T Supuran 《BMC biochemistry》2010,11(1):1-13
Background
The β-carbonic anhydrase (CA, EC 4.2.1.1) enzymes have been reported in a variety of organisms, but their existence in animals has been unclear. The purpose of the present study was to perform extensive sequence analysis to show that the β-CAs are present in invertebrates and to clone and characterize a member of this enzyme family from a representative model organism of the animal kingdom, e.g., Drosophila melanogaster.Results
The novel β-CA gene, here named DmBCA, was identified from FlyBase, and its orthologs were searched and reconstructed from sequence databases, confirming the presence of β-CA sequences in 55 metazoan species. The corresponding recombinant enzyme was produced in Sf9 insect cells, purified, kinetically characterized, and its inhibition was investigated with a series of simple, inorganic anions. Holoenzyme molecular mass was defined by dynamic light scattering analysis and gel filtration, and the results suggested that the holoenzyme is a dimer. Double immunostaining confirmed predictions based on sequence analysis and localized DmBCA protein to mitochondria. The enzyme showed high CO2 hydratase activity, with a kcat of 9.5 × 105 s-1 and a kcat/KM of 1.1 × 108 M- 1s- 1. DmBCA was appreciably inhibited by the clinically-used sulfonamide acetazolamide, with an inhibition constant of 49 nM. It was moderately inhibited by halides, pseudohalides, hydrogen sulfide, bisulfite and sulfate (KI values of 0.67 - 1.36 mM) and more potently by sulfamide (KI of 0.15 mM). Bicarbonate, nitrate, nitrite and phenylarsonic/boronic acids were much weaker inhibitors (KIs of 26.9 - 43.7 mM).Conclusions
The Drosophila β-CA represents a highly active mitochondrial enzyme that is a potential model enzyme for anti-parasitic drug development. 相似文献40.
Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character. 相似文献