Resolution dependence

For the highest resolution and sensitivity, laser-based spectrometers must be used. These have tire advantage that the resolution depends on the linewidth of the laser, rather than the monocln-omator. Furthennore, at any given moment, all of the power is at the frequency of mterest, rather than being spread out over the whole IR... 

The HOSE code can be determined to various degrees of resolution, depending on how many spheres of neighbor atoms are considered. Figure 10.2-1 shows the first, second, and third spheres of neighbors for the carbon atom being considered, for C NMR spectra a HOSE code for each carbon atom in a molecule has to be determined. 

Since the microchannel plate collector records the arrival times of all ions, the resolution depends on the resolution of the TOP instrument and on the response time of the microchannel plate. A microchannel plate with a pore size of 10 pm or less has a very fast response time of less than 2 nsec. The TOP instrument with microchannel plate detector is capable of unit mass resolution beyond m/z 3000. 

As already mentioned, fhe resolution in XPS is usually limited by fhe line widfh of fhe ionizing radiation. In UPS fhe obfainable resolution depends on such factors as fhe... 

Isoelectric Focusing. Isoelectric focusing is a technique used for protein separation, by driving proteins to a pH where they have no mobiUty. Resolution depends on the slope of a pH gradient that can be achieved in a gel. 

Resolution depends upon differences in mobihties of the species. Background elec trolyte of low ionic strength is advantageous, not only to increase elec trophoretic (solute) mobilities, but also to achieve low elec trical conductivity and thereby to reduce the thermal-convec tion current for any given field [Finn, in Schoen (ed.). New Chemical Engineering Separation Techniques, Interscience, New York, 1962]. 

Depth resolution depends on the (spectrally dependent) optical absorption coefficient of the material. Near-surface analysis (first 50 nm) frequendy can be per-... 

Another means of resolution depends on the difference in rates of reaction of two enantiomers with a chiral reagent. The transition-state energies for reaction of each enantiomer with one enantiomer of a chiral reagent will be different. This is because the transition states and intermediates (f -substrate... f -reactant) and (5-substrate... R-reactant) are diastereomeric. Kinetic resolution is the term used to describe the separation of enantiomers based on different reaction rates with an enantiomerically pure reagent. 

The flow rate in SEC significantly affects the resolution. Depending on the selectivity wanted, linear flow rates have to be adapted to the column dimensions. In general, running the column at a low flow rate results in higher resolution, but diffusion may produce diminishing resolution when the flow rate is too low. The flow rates recommended for a particular column diameter should not be increased. In the case of Superformance columns, the best results can be obtained by applying linear flow rates of about 30-80 cm/hr. Of course, linear flow rates below 30 cm/hr can contribute to further increased resolution. 

To investigate the interface between polymeric materials, i.e. a so-called buried interfaces, several techniques are available schematically shown in Fig. 4 and listed in Table 2. They have quite different characteristics and depth resolution depending... 

A kinetic resolution depends on the fact that the two enantiomers of a racemic substrate react at different rates with the enzyme. The process is outlined in Figure 6.1, assuming that the (S) substrate is the fast-reacting enantiomer (ks > ka) and Kic = 0-In ideal cases, only one enantiomer is consumed and the reaction ceases at 50% conversion. In most cases, both enantiomers are transformed and the enantiomeric composition ofthe product and the remaining starting material varies with the extent... 

The relative resolution of an MRI does not depend particularly on the size of the imaged object and usually is of the order of one part in 102. Thus, the absolute resolution obtainable by MRI depends on the size of the system being imaged. The density resolution depends on many factors, but is usually of the order of a few percent. 

An interesting extension of this reaction is shown in the asymmetric kinetic resolution of cyclic allylic ether 44 under alkene coupling conditions. Use of (R)-12 as the catalyst gives (R)-45 in > 99% ee at 58% conversion. The ethylated product 46 is also formed in the reaction in 94% ee (Eq. 7) [25]. The reaction is effective for six- to eight-membered 3-oxacycloalkenes 47 as well as for a wide variety of alkoxycycloalkenes 48 [27], with some resolution dependency on the ring size of 47 (Fig. 2) [26]. 

The fragment recoil velocity resolution depends on the divergence of the molecular beam, molecular beam velocity distribution in the direction of the molecular beam axis, and the distance of fragments expanded in the velocity axis of the two-dimensional detector. If the divergence of the molecular beam is small and the fragment recoil velocity is much larger than the velocity difference of parent molecules, the recoil velocity resolution can be simply expressed as AV/V = s/L, where L is the length of expansion of... 

The lifetime resolution is the smallest variation in lifetime that can be detected. If external noise sources are ignored, the lifetime resolution depends essentially on the photon-economy of the system. For instance, if a 2 ns lifetime is measured with a 4 gate TG single-photon counting FLIM (F = 1.3) and 1000 photons, variations of about 80 ps can be resolved. However, for reasons discussed earlier, in biological samples these values could be higher. 

Theoretically, chromatographic resolution depends on the square root of the column length. Separation of small molecules may be improved 40% by doubling column length. Retention time may also... 

The acquisition speed is, as for the FTICR, resolution dependent. With Thermo Fischer Scientific s orbitrap the desired mass resolving power can be selected. With the lowest setting (7500 FWHM) the acquisition time for one ion injection is 0.3 s and with the highest setting (100,000 FWHM) it is 1.9 s. 

Registration of a metastable ion in the spectrum is rather useful, as it confirms realization of a certain fragmentation reaction. The fragmentation schemes are considered to be true if corresponding metastable peaks are detected. On the other hand, metastable peaks deteriorate spectral resolution. Depending on the amount of energy released, the forms of the metastable peaks may be quite different. These peaks are eliminated from the spectra as part of the computer deconvolution process. 

There are two possible approaches for the preparation of optically active products by chemical transformation of optically inactive starting materials kinetic resolution and asymmetric synthesis [44,87], For both types of reactions there is one principle in order to make an optically active compound we need another optically active compound. A kinetic resolution depends on the fact that two enantiomers of a racemate react at different rates with a chiral reagent or catalyst. Accordingly, an asymmetric synthesis involves the creation of an asymmetric center that occurs by chiral discrimination of equivalent groups in an achiral starting material. This can be done either by enan-tioselective (which involves the reaction of a prochiral molecule with a chiral substance) or diastereoselective (which involves the preferential formation of a single diastereomer by the creation of a new asymmetric center in a chiral molecule) synthesis. 

It should come as no surprise that a chapter dealing with asymmetric catalysis should mention resolutions. Resolutions depend primarily on the solubility differences of disastereomers in the ground state. X-Ray analyses of diastereomeric salts (4,3) appear to point to a best-fit structure for the least soluble salt. Success in asymmetric catalysis depends on free-energy differences between disastereomeric transition states. When these energy differences approach 2 kcal/ mol, resulting in an e.e. of 93% at 23°C, the favored complex, although the result of a termolecular reaction, shows the best-fit characteristics typical of a diastereomeric salt. 

Laser devices are the most sophisticated image-acquisition tools. They are particularly useful for gels labeled with fluorescent dyes because the lasers can be matched to the excitation wavelengths of the fluorophores. Detection is generally with photomultiplier tubes. Some instruments incorporate storage phosphor screens for detection of radiolabeled and chemiluminescent compounds (not discussed in this chapter). Resolution depends on the scanning speed of the illumination module and can be as low as 10 pm. 

Long term ex vivo maintenance of human hematopoietic stem cells requires growth promoting cytokines , factors that inhibit proliferation of clonogenic cells (such as MIP-la) stroma-derived growth factors and direct contact with stroma. The need for direct cell-to-stroma contact is still a matter of many scientific debates and its resolution depends on the development of new scientific approaches. 

In practice, recombination of structure factors involves first weighting of the phases of the modified structure factors in a resolution dependent fashion, according to their estimated accuracy or probability. Every phase also has an experimental probability (determined by experimental phasing techniques and/or molecular replacement). The two distributions are combined by multiplication, and the new phase is calculated from this combined probability distribution. The measured associated structure factor amplitude is then scaled by the probability of the phase, and we have our set of recombined structure factors. 

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