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61.
I. M. Perez de Vargas-Sansalvador C. Fay M. D. Fernandez-Ramos D. Diamond F. Benito-Lopez L. F. Capitan-Vallvey 《Analytical and bioanalytical chemistry》2012,404(10):2851-2858
A portable instrument for oxygen determination, based on the quenching of phosphorescent octaethylporphyrin by gaseous O2, has been developed using the fluorimetric paired emitter–detector diode technique (FPEDD). The instrument configuration consists of two light-emitting diodes (LEDs) facing each other, with an interchangeable support containing a phosphorescent membrane in between, in which one of the LEDs is used as the light source (emitter LED) and the other, working in reverse bias mode, as the light detector. The feasibility of using a LED as a luminescence detector is studied. Its small size enables integration of the instrument into a portable measurement system. A systematic study of the system capabilities as a portable instrument was performed to optimize range, sensitivity, short term and long term stability, dynamic behaviour, effect of temperature and humidity, and temporal drift. 相似文献
62.
Gobeaux F Fay N Tarabout C Mériadec C Meneau F Ligeti M Buisson DA Cintrat JC Nguyen KM Perrin L Valéry C Artzner F Paternostre M 《Journal of the American Chemical Society》2012,134(1):723-733
Among noncovalent forces, electrostatic ones are the strongest and possess a rather long-range action. For these reasons, charges and counterions play a prominent role in self-assembly processes in water and therefore in many biological systems. However, the complexity of the biological media often hinders a detailed understanding of all the electrostatic-related events. In this context, we have studied the role of charges and counterions in the self-assembly of lanreotide, a cationic octapeptide. This peptide spontaneously forms monodisperse nanotubes (NTs) above a critical concentration when solubilized in pure water. Free from any screening buffer, we assessed the interactions between the different peptide oligomers and counterions in solutions, above and below the critical assembly concentration. Our results provide explanations for the selection of a dimeric building block instead of a monomeric one. Indeed, the apparent charge of the dimers is lower than that of the monomers because of strong chemisorption. This phenomenon has two consequences: (i) the dimer-dimer interaction is less repulsive than the monomer-monomer one and (ii) the lowered charge of the dimeric building block weakens the electrostatic repulsion from the positively charged NT walls. Moreover, additional counterion condensation (physisorption) occurs on the NT wall. We furthermore show that the counterions interacting with the NTs play a structural role as they tune the NTs diameter. We demonstrate by a simple model that counterions adsorption sites located on the inner face of the NT walls are responsible for this size control. 相似文献
63.
Steinkruger JD Bartlett GJ Hadley EB Fay L Woolfson DN Gellman SH 《Journal of the American Chemical Society》2012,134(5):2626-2633
Elucidating relationships between the amino-acid sequences of proteins and their three-dimensional structures, and uncovering non-covalent interactions that underlie polypeptide folding, are major goals in protein science. One approach toward these goals is to study interactions between selected residues, or among constellations of residues, in small folding motifs. The α-helical coiled coil has served as a platform for such studies because this folding unit is relatively simple in terms of both sequence and structure. Amino acid side chains at the helix-helix interface of a coiled coil participate in so-called "knobs-into-holes" (KIH) packing whereby a side chain (the knob) on one helix inserts into a space (the hole) generated by four side chains on a partner helix. The vast majority of sequence-stability studies on coiled-coil dimers have focused on lateral interactions within these KIH arrangements, for example, between an a position on one helix and an a' position of the partner in a parallel coiled-coil dimer, or between a--d' pairs in an antiparallel dimer. More recently, it has been shown that vertical triads (specifically, a'--a--a' triads) in antiparallel dimers exert a significant impact on pairing preferences. This observation provides impetus for analysis of other complex networks of side-chain interactions at the helix-helix interface. Here, we describe a combination of experimental and bioinformatics studies that show that d'--d--d' triads have much less impact on pairing preference than do a'--a--a' triads in a small, designed antiparallel coiled-coil dimer. However, the influence of the d'--d--d' triad depends on the lateral a'--d interaction. Taken together, these results strengthen the emerging understanding that simple pairwise interactions are not sufficient to describe side-chain interactions and overall stability in antiparallel coiled-coil dimers; higher-order interactions must be considered as well. 相似文献
64.
Analysis of steryl esters in cocoa butter by on-line liquid chromatography-gas chromatography. 总被引:3,自引:0,他引:3
W Kamm F Dionisi L B Fay C Hischenhuber H G Schmarr K H Engel 《Journal of chromatography. A》2001,918(2):341-349
On-line liquid chromatography-gas chromatography (LC-GC) has been applied to the analysis of steryl esters in cocoa butter. Separation of the steryl esters was achieved after on-line transfer to capillary GC. HPLC removes the large amount of triglycerides and pre-separates the components of interest, thus avoiding time-consuming sample preparation prior to GC analysis. The identities of the compounds were confirmed by GC-MS investigation of the collected HPLC fraction and by comparison of the mass spectra (chemical ionization using ammonia as ionization gas) to those of synthesized reference compounds. Using cholesteryl laurate as internal standard, steryl esters were quantified in commercial cocoa butter samples, the detection limit being 3 mg/kg and the quantification limit 10 mg/kg, respectively. Only slight differences in percentage distributions of steryl esters depending on the geographical origin of the material were observed. The patterns were shown to remain unchanged after deodorization. The method described might be a valuable tool for authenticity assessment of cocoa butter. 相似文献
65.
We present spontaneous collapse models of field theories on a 1+1 null lattice, in which the causal structure of the lattice plays a central role. Issues such as “locality,” “nonlocality,” and superluminal signaling are addressed in the context of the models which have the virtue of extreme simplicity. The formalism of the models is related to that of the consistent histories approach to quantum mechanics. 相似文献
66.
R R Fay 《The Journal of the Acoustical Society of America》1989,85(1):500-502
Intensity discrimination thresholds for 500-ms pure-tone bursts were measured as a function of frequency in the goldfish (Carassius auratus) using classical respiratory conditioning. At 55-dB sensation level (SL), thresholds range from 1.44-2.2 dB between 100 and 1600 Hz. There is not important effect of frequency on intensity discrimination. Thresholds at 35-dB SL average 0.7 dB higher than at 55-dB SL. This is a small difference in the context of the threshold variability. In intensity discrimination acuity, the goldfish is quantitatively similar to other vertebrates, including birds and mammals. 相似文献
67.
We review the consistent histories formulations of quantum mechanics developed by Griffiths, Omnès, and Gell-Mann and Hartle, and describe the classification of consistent sets. We illustrate some general features of consistent sets by a few simple lemmas and examples. We consider various interpretations of the formalism, and examine the new problems which arise in reconstructing the past and predicting the future. It is shown that Omnès' characterization of true statements—statements which can be deduced unconditionally in his interpretation—is incorrect. We examine critically Gell-Mann and Hartle's interpretation of the formalism, and in particular their discussions of communication, prediction, and retrodiction, and conclude that their explanation of the apparent persistence of quasiclassicality relies on assumptions about an as-yetunknown theory of experience. Our overall conclusion is that the consistent histories approach illustrates the need to supplement quantum mechanics by some selection principle in order to produce a fundamental theory capable of unconditional predictions. 相似文献
68.
The temporal evolution of masking and frequency selectivity was studied in the goldfish using classical respiratory conditioning and a tracking psychophysical procedure. The temporal position of a brief tonal signal within a longer duration, tonal masker has little or no effect on signal detectability when the frequency of the masker is less than or equal to that of the signal. For masker frequencies above that of the signal, signal detectability improves as the signal onset is delayed relative to that of the masker. These patterns of tone-on-tone masking are quite similar to those observed for humans. These temporal masking patterns are qualitatively similar in shape to the peristimulus-time histogram profiles of the low-frequency saccular fibers thought to be used in this task. Frequency- and time-dependent changes in signal detectability result in specific changes in the sharpness of psychophysical tuning curves (PTC). In general, PTCs determined for signals occurring at masker onset are the most broadly tuned, and PTCs determined in forward masking are the most sharply tuned. The PTCs for signals temporally centered in the masker are intermediate. These results suggest that temporal tone-on-tone masking patterns and the temporal evolution of psychophysical tuning curves result from the response properties of peripheral auditory-nerve fibers. 相似文献
69.
70.