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An alternative way of acquiring the data is to observe the signal. These experiments are referred to as reverse- or inverse-detected experiments, in particular the inverse HETCOR experiment is referred to as a heteronuclear multiple quantum coherence (HMQC) spectmm. The ampHtude of the H nuclei is modulated by the coupled frequencies of the C nuclei in the evolution time. The principal difficulty with this experiment is that the C nuclei must be decoupled from the H spectmm. Techniques used to do this are called GARP and WALTZ sequences. The information is the same as that of the standard HETCOR except that the F and F axes have been switched. The obvious advantage to this experiment is the significant increase in sensitivity that occurs by observing H rather than C. [Pg.407]

It is often the case that chemists involved or familiar with ethylene oxide (oxiran) chemistry refer to these cyclic oligomers as EO-4, EO-6 and EO-7 respectively. Such designations are informal if not colloquial but, like any name, are useful if they correctly convey an idea. The difficulty with these informalities, indeed with the crown nomenclature system is that it cannot adequately deal with complicated structures or even isomers of simple ones. [Pg.3]

The type of power and social relationships in a group will also affect the overall performance. Although a formal status hierarchy is specified for each team by the plant management, it is well documented that groups have their own informal status structure which may be different from the formal one. In everyday duties it might be difficult to detect any contradictions between formal and informal status hierarchies. In an emergency situation, however, where different interpretations of the situation may be reached, such status problems may create difficulties with regard to whose opinion is followed. [Pg.145]

Another difficulty with the infrared method is that of determining the band center with sufficient accuracy in the presence of the fine structure or band envelopes due to the overall rotation. Even when high resolution equipment is used so that the separate rotation lines are resolved, it is by no means always a simple problem to identify these lines with certainty so that the band center can be unambiguously determined. The final difficulty is one common to almost all methods and that is the effect of the shape of the potential barrier. The infrared method has the advantage that it is applicable to many molecules for which some of the other methods are not suitable. However, in some of these cases especially, barrier shapes are likely to be more complicated than the simple cosine form usually assumed, and, when this complication occurs, there is a corresponding uncertainty in the height of the potential barrier as determined from the infrared torsional frequencies. In especially favorable cases, it may be possible to observe so-called hot bands i.e., v = 1 to v = 2, 2 to 3, etc. This would add information about the shape of the barrier. [Pg.374]

The Volta potential is defined as the difference between the electrostatic outer potentials of two condensed phases in equilibrium. The measurement of this and related quantities is performed using a system of voltaic cells. This technique, which in some applications is called the surface potential method, is one of the oldest but still frequently used experimental methods for studying phenomena at electrified solid and hquid surfaces and interfaces. The difficulty with the method, which in fact is common to most electrochemical methods, is lack of molecular specificity. However, combined with modem surface-sensitive methods such as spectroscopy, it can provide important physicochemical information. Even without such complementary molecular information, the voltaic cell method is still the source of much basic electrochemical data. [Pg.13]

Recently, Raluca Niesner et al. [14] have published a report in which they developed a noniterative method of fitting multiexponential decays which does not discard information and is nonre-strictive, thereby eliminating the difficulties with excess time being taken by computationally expensive iterative fitting routines. [Pg.461]

Thin-layer chromatography does not provide quantitative information of the highest precision and accuracy. Linear relationships between the mass of a substance and the logarithm or square-root of the spot area can sometimes be established under very closely controlled conditions. The optical absorbance of a spot determined by reflectance measurements can be similarly related to mass, or the substances can be scraped from the plate and dissolved in a suitable solvent for a spectrometric determination. The main difficulties with area and density measurements lie in defining the boundaries of spots and controlling chromogenic reactions in a reproducible manner. Relative precision can be as good as 1-2% but is more usually 5-10%. [Pg.160]

McCarron The difficulty with using agonists to generate InsP3 is the additional second messengers that they produce. It is plausible that the carbachol could suppress ryanodine receptor function by activating protein kinase C. You would block the response to caffeine without gaining any information about the interaction of the two receptors on stores. [Pg.70]

Very recently, rate constants for scavenging of hydroxyl radicals by DMPO, and by the nitrone [18c], have been determined (Marriott et al., 1980) (see Table 5). As might be expected, the figures are close to the diffusion-controlled limit. The report of this work includes a concise and informative discussion of some of the difficulties with, and limitations of, the spin trapping method, especially where these relate to reactions involving hydroxyl radicals. [Pg.53]

In many cases a Cusum plot will not show the expected horizontal line but rather a line with a small but constant slope owing to the value attributed to the mean of means being incorrect. The plot is still acceptable and in such cases a change in the slope will indicate a change from the expected value and the possibility of error. Some of the difficulties with the Cusum plot is that variations are most obvious retrospectively, little information can be gained from a single point and errors are only apparent from several consecutive points. Thus it is debatable whether this type of plot can be classed as true quality control. [Pg.22]

It is also advisable to tell the study subject that the GP will be informed about the clinical trial. Difficulties occur when the clinical trial is for an indication of a socially unacceptable condition such as a venereal disease. Rightly or wrongly, the subjects have fear that knowledge of the illness may not be safe with the famHY doctor. In these exceptional circumstances, the lEC should decide whether the GP should be informed only with the agreement of the study subject. [Pg.205]

The percentage of patients who are alive with an intact bladder at 5 yr is only 38% with this bladder-sparing approach. This is not surprising, given what we know about the difficulties with clinical staging and the recognition of transitional cell carcinoma (TCC) of the urothelium as a field defect. People who are offered this approach as an equivalent option to cystectomy should be informed of these results. [Pg.298]

The purpose of the MS techniques is to detect charged molecular ions and fragments separated according to their molecular masses. Most flavonoid glycosides are polar, nonvolatile, and often thermally labile. Conventional MS ionization methods like electron impact (El) and chemical ionization (Cl) have not been suitable for MS analyses of these compounds because they require the flavonoid to be in the gas phase for ionization. To increase volatility, derivatization of the flavonoids may be performed. However, derivatization often leads to difficulties with respect to interpretation of the fragmentation patterns. Analysis of flavonoid glycosides without derivatization became possible with the introduction of desorption ionization techniques. Field desorption, which was the first technique employed for the direct analysis of polar flavonoid glycosides, has provided molecular mass data and little structural information. The technique has, however, been described as notorious for the transient... [Pg.68]

Insurance companies have developed several strategies to cope with the information difficulties that lead to moral hazard and adverse selection. They use deductibles and copayments to reduce moral hazard. If cusfomers musf pay some of fhe damage cosfs themselves when accidents occur, they are less likely to engage in unanticipated risky behavior. Some firms also use experience rafing (i.e., raising rates if a claim is made) to reduce moral hazard. Experience rating penalizes cautious clients who still suffer accidents, but insurance firms cannot economically differentiate those careful policyholders from morally hazardous ones. [Pg.60]

This book is rooted in an informal discussion with three researchers. Dr Alatzne Carlosena, Dr Monica Felipe and Dr Maria Jesus Cal, after they had some problems measuring antimony in soils and sediments by electrothermal atomic absorption spectrometry. While we reviewed the results and debated possible problems, much like in a brainstorming session, I realized that some of their difficulties were highly similar to those found in molecular spectrometry (mid-IR spectroscopy, where I had some experience), namely a lack of peak reproducibility, noise, uncontrollable amounts of concomitants, possible matrix interferences, etc. [Pg.324]

Prof. Fleming, the expressions you are using for the nonlinear response function may be derived using the second-order cumulant expansion and do not require the use of the instantaneous normal-mode model. The relevant information (the spectral density) is related to the two-time correlation function of the electronic gap (for resonant spectroscopy) and of the electronic polarizability (for off-resonant spectroscopy). You may choose to interpret the Fourier components of the spectral density as instantaneous oscillators, but this is not necessary. The instantaneous normal mode provides a physical picture whose validity needs to be verified. Does it give new predictions beyond the second-order cumulant approach The main difficulty with this model is that the modes only exist for a time scale comparable to their frequencies. In glasses, they live much longer and the picture may be more justified than in liquids. [Pg.182]

The great difficulty with, and challenge of, psi phenomena is that in so many ways they do not make sense. Indeed, at this stage of our knowledge, they are defined as unexplainable in terms of our generally accepted physical world model. Information is received about a distant event, and desires affect a distant event with no plausible way for the information or energy to get from the event to the percipient or vice versa. [Pg.37]


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See also in sourсe #XX -- [ Pg.179 , Pg.181 , Pg.183 ]

See also in sourсe #XX -- [ Pg.179 , Pg.181 , Pg.183 ]




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