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41.
Jitka Daďová Susanne Kümmel Christian Feldmeier Jana Cibulková Dr. Richard Pažout Dr. Jaroslav Maixner Prof. Dr. Ruth M. Gschwind Prof. Dr. Burkhard König Dr. Radek Cibulka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1066-1075
A series of 10‐arylflavins (10‐phenyl‐, 10‐(2′,6′‐dimethylphenyl)‐, 10‐(2′,6′‐diethylphenyl)‐, 10‐(2′,6′‐diisopropylphenyl)‐, 10‐(2′‐tert‐butylphenyl)‐, and 10‐(2′,6′‐dimethylphenyl)‐3‐methylisoalloxazine ( 2 a – f )) was prepared as potentially nonaggregating flavin photocatalysts. The investigation of their structures in the crystalline phase combined with 1H‐DOSY NMR spectroscopic experiments in CD3CN, CD3CN/D2O (1:1), and D2O confirm the decreased ability of 10‐arylflavins 2 to form aggregates relative to tetra‐O‐acetyl riboflavin ( 1 ). 10‐Arylflavins 2 a – d do not interact by π–π interactions, which are restricted by the 10‐phenyl ring oriented perpendicularly to the isoalloxazine skeleton. On the other hand, N3? H???O hydrogen bonds were detected in their crystal structures. In the structure of 10‐aryl‐3‐methylflavin ( 2 f ) with a substituted N3 position, weak C? H???O bonds and weak π–π interactions were found. 10‐Arylflavins 2 were tested as photoredox catalysts for the aerial oxidation of 4‐methoxybenzyl alcohol to the corresponding aldehyde (model reaction), thus showing higher efficiency relative to 1 . The quantum yields of 4‐methoxybenzyl alcohol oxidation reactions mediated by arylflavins 2 were higher by almost one order of magnitude relative to values in the presence of 1 . 相似文献
42.
Adriaan M. H. van der Veen Hugo Ent Annarita Baldan Valnei S. da Cunha Romeu J. Daroda Brian Lang Michele Schantz Manuela Ulberth-Buchgraber Andrea Held Ruth Hearn Richard J. C. Brown Paul J. Brewer 《Accreditation and quality assurance》2013,18(1):41-50
The main objective of the reference materials for biofuel specifications (BIOREMA) project is the development of two test materials (one bio-ethanol material and one biodiesel material) with well-established reference values. Of a series of three papers, this part describes the material preparation, homogeneity study, stability study, and characterisation of the bio-ethanol material. The test material thus obtained was used in an interlaboratory comparison (ILC) to assess current practices and comparability amongst laboratories providing bio-ethanol testing services. Only 13 participants provided data, resulting in a small dataset for evaluation. Further, it appeared that for a number of laboratories, there was not sufficient material for the determination of all requested parameters. In most cases, as far as the data permit, it can be concluded that the consensus values (based on participant’s results) are in good agreement with the reference or the BIOREMA values (obtained by NMIs participating in the project). For three parameters, namely ethanol content, water content, and density, there is good agreement between the reference and consensus values. For these parameters, the reproducibility standard deviation is close to, or even smaller than, the expanded uncertainty associated with the reference value. A number of parameters show very poor reproducibility, for example, pHe, electrolytic conductivity, and acidity. The same applies to sodium and copper content, which are very low and therefore challenging parameters to measure accurately. The results of the ILC underpin the need for certified reference materials and demonstrate the requirement for more robust quality control to improve the precision and trueness of the results from testing laboratories. 相似文献
43.
Tuija Teerinen Timo Lappalainen Tomi Erho 《Analytical and bioanalytical chemistry》2014,406(24):5955-5965
Morphine was used as a model analyte to examine the possibility of using cellulose, physically modified by papermaking and converting techniques, as a capillary matrix in a lateral flow type of diagnostic assay. This research was directed toward low-cost, disposable, and portable paper-based diagnostics, with the aim of addressing the analytical performance of paper as a substrate in the analysis for drugs of abuse. Antibody Fab fragments were used as sensing molecules, and gold nanoparticle detection was employed. Inkjet printing was used to pattern sensing biomolecules as detection zones on paper. To validate the usefulness of paper as a diagnostic platform, the principle of a direct sandwich assay, based on immunocomplex formation between morphine and the anti-morphine Fab fragment and detection of the formed immunocomplex by another Fab fragment, was implemented. Results were compared with that achieved by using nitrocellulose as a reference material. Possible interfering from the sample matrix on assay quality was investigated with spiked oral fluid samples. Under optimized conditions, a visually assessed limit of detection for the sandwich assay was 1 ng/mL, indicating that the paper-based test devices developed in this work can perform screening for drugs of abuse and can fulfill the requirement for a sensitive assay in diagnostically relevant ranges. Fig
? 相似文献
44.
Yu. D. Chistyakov Yu. A. Baikov H. G. Schneider V. Ruth 《Crystal Research and Technology》1983,18(6):711-723
A recently published theory on the solidification of a one-component melt has been extended to the more complex case of binary systems. The theory is based on the model of a two-phase transitional zone existing between the crystalline phase and the melt. The concentration of solid state atoms within each mono-atomic layer of the transitional zone are assumed to fluctuate due to thermal fluctuations. A crystal growth law has been derived expressing the crystallization velocity in terms of probability functions describing these concentrations fluctuations. When certain restricting conditions concerning the atomic interaction energies within the transitional zone and the distribution of the atoms among the solid and liquid phases at supercooling are fulfilled the crystal growth law attains a simple form predicting for small supercoolings a growth rate proportional to supercooling (linear growth law), roughly proportional to physical parameter θAA, and with a weak dependence on another parameter Δ. 相似文献
45.
46.
James B Whitney Saied Mirshahidi So-Yon Lim Lauren Goins Chris C Ibegbu Daniel C Anderson Richard B Raybourne Fred R Frankel Judy Lieberman Ruth M Ruprecht 《Journal of immune based therapies and vaccines》2011,9(1):2
Background
We have evaluated an attenuated Listeria monocytogenes (Lm) candidate vaccine vector in nonhuman primates using a delivery regimen relying solely on oral vaccination. We sought to determine the impact of prior Lm vector exposure on the development of new immune responses against HIV antigens. 相似文献47.
Culling JF Hawley ML Litovsky RY 《The Journal of the Acoustical Society of America》2004,116(2):1057-1065
Three experiments investigated the roles of interaural time differences (ITDs) and level differences (ILDs) in spatial unmasking in multi-source environments. In experiment 1, speech reception thresholds (SRTs) were measured in virtual-acoustic simulations of an anechoic environment with three interfering sound sources of either speech or noise. The target source lay directly ahead, while three interfering sources were (1) all at the target's location (0 degrees,0 degrees,0 degrees), (2) at locations distributed across both hemifields (-30 degrees,60 degrees,90 degrees), (3) at locations in the same hemifield (30 degrees,60 degrees,90 degrees), or (4) co-located in one hemifield (90 degrees,90 degrees,90 degrees). Sounds were convolved with head-related impulse responses (HRIRs) that were manipulated to remove individual binaural cues. Three conditions used HRIRs with (1) both ILDs and ITDs, (2) only ILDs, and (3) only ITDs. The ITD-only condition produced the same pattern of results across spatial configurations as the combined cues, but with smaller differences between spatial configurations. The ILD-only condition yielded similar SRTs for the (-30 degrees,60 degrees,90 degrees) and (0 degrees,0 degrees,0 degrees) configurations, as expected for best-ear listening. In experiment 2, pure-tone BMLDs were measured at third-octave frequencies against the ITD-only, speech-shaped noise interferers of experiment 1. These BMLDs were 4-8 dB at low frequencies for all spatial configurations. In experiment 3, SRTs were measured for speech in diotic, speech-shaped noise. Noises were filtered to reduce the spectrum level at each frequency according to the BMLDs measured in experiment 2. SRTs were as low or lower than those of the corresponding ITD-only conditions from experiment 1. Thus, an explanation of speech understanding in complex listening environments based on the combination of best-ear listening and binaural unmasking (without involving sound-localization) cannot be excluded. 相似文献
48.
Julia Leitl Dr. Andrew R. Jupp Dr. Evi R. M. Habraken Verena Streitferdt Dr. Peter Coburger Dr. Daniel J. Scott Prof. Dr. Ruth M. Gschwind Prof. Dr. Christian Müller Dr. J. Chris Slootweg Prof. Dr. Robert Wolf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7788-7800
Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2 . The C≡N triple bonds of nitriles insert into the P−B bond of 2 with concomitant C−B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4-phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus–boron bond in 2 , which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P−B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition. 相似文献
49.
Mihály V. Pilipecz Tamás R. Varga Péter Králl Zoltán Vincze Zoltán Mucsi Ruth Deme 《合成通讯》2020,50(11):1712-1723
AbstractThe novel push–pull alkene, the 2-(nitro-nitrosomethylene)-pyrrolidine with numerous aliphatic or aromatic amines as nucleophiles afforded amidoximes. Various substituted oxadiazaborole and oxadiazole derivatives were prepared starting from these amidoximes, widening the synthetic applicability of the push–pull alkenes. Acylation of the amidoximes was also examined. The mechanism of the amidoxime formation was investigated by computational methods. 相似文献
50.
Álvaro Santana-Mayor Ruth Rodríguez-Ramos Bárbara Socas-Rodríguez Miguel Ángel Rodríguez-Delgado Giovanni D'Orazio 《Electrophoresis》2020,41(20):1768-1775
The separation of 11 phthalic acid ester (PAEs) was carried out by nano-liquid chromatography coupled to ultraviolet and MS detection. Preliminary experiments were achieved in order to select suitable stationary phases and chromatographic conditions. The baseline separation was obtained, for all compounds, with an XBridgeTM C18 column in less than 15 min, working in step gradient mode. The sensitivity of the method was improved by on-column focusing. PAEs were extracted from alcoholic and nonalcoholic beverages using vortex-assisted emulsification dispersive liquid–liquid microextration and natural deep eutectic solvents. The whole method was validated in terms of linearity, sensitivity, precision, recovery, and repeatability. Combination of both off-line sample preparation preconcentration and large injection volume led to obtain LOQs in the range 5–47 ng/mL. The developed nano-LC-UV method was extended to MS detection to confirm the presence of PAEs in some beverages commercialized in different types of packaging. 相似文献