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31.
Vesa Nevalainen 《Tetrahedron: Asymmetry》1993,4(12):2517-2530
Conformers of 4-coordinate adducts of carbonyl compounds and diaza-, oxaza- and dioxaluminolidines were investigated by means of ab initio MO methods (RHF). Formaldehyde was used as a model of carbonyl compounds. Relative stabilities of the conformers indicate formation of syn adducts of carbonyl compounds and aluminolidines (CC=O and aluminolidine ring syn about the Al---OC=O bond) to be favoured over that of the corresponding anti ones (all syn/anti ratios higher than 99:1, 6–31G//6–31G). The energetic preference for the formation of syn adducts of oxazaaluminolidines was about twice as high as that of diaza- or dioxaluminolidines of which the syn/anti selectivities were found to be practically equal. 相似文献
32.
A new sensor for an amplified electrochemical detection of carbohydrates is proposed, where carbohydrates are oxidized by CNT-NiCo-oxide composite in basic solutions. Cyclic voltammograms of the modified electrode show a stable and well defined redox couple in alkaline media due to the synergy of Ni(II)/Ni(III) system with Co(II)/Co(III). The modified electrode shows excellent electrocatalytic activity towards monosaccharides oxidation at reduced overpotential in alkaline solutions. Six monosaccharides were determined amperometrically at the surface of this modified electrode with high sensitivity over a wide range of concentrations, from 0.02 up to 12.12 mM. Low detection limit of 5 μM for glucose could be obtained. 相似文献
33.
Preclassification of Broadband and Sparse Infrared Data by Multiplicative Signal Correction Approach
Hafeez Ur Rehman Valeria Tafintseva Boris Zimmermann Johanne Heitmann Solheim Vesa Virtanen Rubina Shaikh Ervin Nippolainen Isaac Afara Simo Saarakkala Lassi Rieppo Patrick Krebs Polina Fomina Boris Mizaikoff Achim Kohler 《Molecules (Basel, Switzerland)》2022,27(7)
Preclassification of raw infrared spectra has often been neglected in scientific literature. Separating spectra of low spectral quality, due to low signal-to-noise ratio, presence of artifacts, and low analyte presence, is crucial for accurate model development. Furthermore, it is very important for sparse data, where it becomes challenging to visually inspect spectra of different natures. Hence, a preclassification approach to separate infrared spectra for sparse data is needed. In this study, we propose a preclassification approach based on Multiplicative Signal Correction (MSC). The MSC approach was applied on human and the bovine knee cartilage broadband Fourier Transform Infrared (FTIR) spectra and on a sparse data subset comprising of only seven wavelengths. The goal of the preclassification was to separate spectra with analyte-rich signals (i.e., cartilage) from spectra with analyte-poor (and high-matrix) signals (i.e., water). The human datasets 1 and 2 contained 814 and 815 spectra, while the bovine dataset contained 396 spectra. A pure water spectrum was used as a reference spectrum in the MSC approach. A threshold for the root mean square error () was used to separate cartilage from water spectra for broadband and the sparse spectral data. Additionally, standard noise-to-ratio and principle component analysis were applied on broadband spectra. The fully automated MSC preclassification approach, using water as reference spectrum, performed as well as the manual visual inspection. Moreover, it enabled not only separation of cartilage from water spectra in broadband spectral datasets, but also in sparse datasets where manual visual inspection cannot be applied. 相似文献
34.
Electron impact induced fragmentations of the title compounds were studied by exact mass measurement and metastable ion analysis. Sulphur atoms within the ring effectively stabilize the positive charge. In most cases the loss of the larger substituent, and not the other, methyl group, gives rise to the base peak in the spectrum. Examination of competing metastable transitions shows that generally this is also the lowest activation energy primary process. In general primary ring cleavage reactions are not important unless there is a heteroatom in the substituent that can assist this cleavage. 相似文献
35.
High sensitivity in gas analysis with photoacoustic detection 总被引:1,自引:0,他引:1
Introduction of a new type of pressure sensor has been shown to improve orders of magnitude the sensitivity of a photoacoustic measurement system using a black body radiation source. A new pressure sensor was developed to overcome the limitations in the capacitive microphone technology and to obtain ultimate sensitivity in photoacoustic gas detection when using low modulation frequency below 500 Hz. The pressure sensor is a cantilever-type microphone with interferometric measurement of the sensor displacement. By using conventional filter-type photoacoustic setup with the cantilever microphone and a black body radiation source, we obtained a detection limit in the sub-ppb range for methane gas with 100 s measurement time. 相似文献
36.
Identification of the hydrolysis products of AlCl3.6H2O by electrospray ionization mass spectrometry
Sarpola A Hietapelto V Jalonen J Jokela J Laitinen RS 《Journal of mass spectrometry : JMS》2004,39(4):423-430
The hydrolysis reactions of AlCl3 in 0.1 M aqueous solutions at pH 3.27-4.20 were monitored by electrospray ionization time-of-flight mass spectrometry (ESI-ToF MS) as a function of time. The cationic and anionic ESI mass spectra of aluminum(III) solutions gave strong evidence of the presence of a variety of monomeric and polymeric complexes. Competition between the OH- and Cl- ligands within the same aluminum core was observed. The influence of the sample cone voltage on the product distribution was also explored. The optimum sample cone voltage for the cationic spectra was 70 V. For the anionic spectra no optimum sample cone voltage was found and the appearance of the anionic spectra was strongly dependent on the sample cone voltage within the whole range explored. 相似文献
37.
Background noise in ion chromatography with suppressed conductivity detection was significantly reduced for the period of time when the electric current to an anion self regenerating suppressor (ASRS) running in the recycle mode was turned-off. With high capacity AS11-HC columns, it was possible to maintain current free conditions from the beginning of the run past the chloride peak, which enables routine high sensitivity analysis of early to mid eluting peaks. This suppressor current switching was utilized for the analysis of bromate in drinking water with large volume injection using on-line removal of chloride by an On-Guard Ag+-cartridge. The method detection limit (MDL) was 0.21 microg/l in fortified reagent water. Coelution of bromate with an unknown compound was observed, but it was solved by the optimization of gradient program. 相似文献
38.
V. I. Palubinskas N. B. Yankevich K. K. Yanulaitene V. S. Vesa V. G. Bendikene A. V. Maksimenko V. P. Torchilin E. V. Ilyina V. N. Smirnov I. N. Krestyanova Yu. E. Bartoshevich R. Ch. Zabirova 《Applied biochemistry and biotechnology》1984,9(3):231-241
Electrophoretically homogenous proteolytic enzyme with molecular weight 31,500 and pI 3.75 was obtained from a culture medium
ofStreptomyces 771 by chromatography onN-benzyl chitin adsorbent, subsequent chromatography on CM-cellulose, and preparative isofocusing and chromatography on Sephadex
G-75. The enzyme hydrolyzesN- benzoyl-DL-arginine-p-nitroanilideN-benzoyl-DL-lysine-p-nitro-anilideN-benzoyl-DL-arginine ethyl ester, and Na-caseinate. It also exhibits pronounced thrombolytic activity. The activity of the enzyme was
suppressed by soya bean inhibitor, but remained unaffected by chelating agents and phenylmethylsulfonyl fluoride. The enzyme
was immobilized on aldehyde dextran, and some kinetic parameters of the immobilized enzyme were determined. The thrombolytic
activity of native and immobilized enzyme was studied as well. 相似文献
39.
Anesthetized children have dominant blood-oxygen-level-dependent (BOLD) signal sources presenting high-power fluctuations at very low frequencies (VLF <0.05 Hz). Aliasing of frequencies higher than critically sampled has been regarded as one probable origin of the VLF fluctuations. Aliased signal frequencies change when the sampling rate of the data is altered. In this study, the aliasing of VLF BOLD signal fluctuation was analysed by switching the repetition time (TR) of magnetic resonance (MR) images. Eleven anesthetized children were imaged at 1.5 T using TRs of 500 and 1200 ms. The BOLD signal sources were separated with independent component analysis (ICA). Occipital cortex signal sources had nonaliased VLF fluctuation ( approximately 0.03 Hz) in 9 of 11 subjects. Arterial signal sources failed to present stable power peaks at frequencies lower than 0.42 Hz presumably due to aliasing. Cerebrospinal fluid (CSF)-related signal sources showed nonaliased VLF in four subjects. In conclusion, the VLF BOLD signal fluctuation in the occipital cortex is a true physiological fluctuation, not a result of signal aliasing. 相似文献
40.