Elemental sensitivity definition

Given stringent requirements for effective sensitizers and the desire to use wavelengths further to the red for therapeutic appHcations, definition of newer sensitizers has been a principal area of research since about 1987. Expanded theoretical and experimental understanding of photophysics has been a key element in identifying new classes of potential sensitizers (93—98). Research has focused on cationic derivatives of Nile Blue (93), metaHo-phthalocyanines (94), naphthalocyanines (95), chlorin-type compounds (96), expanded ring porphyrinoids (97), as well as porphyrins other than hematoporphyrin and its derivatives (98). This work has also been reviewed (10,91). Instmmentation for photodynamic therapy has been reviewed (99). 

By a fortunate coincidence, the depth into the solid from which information is provided by the techniques described here matches the above definition of a surface almost exactly. These techniques are, therefore, surface-specific, in other words, the information they provide comes only from that very shallow depth of a few atom layers. Other techniques can be surface sensitive, in that they would normally be regarded as techniques for bulk analysis, but have sufficient sensitivity for certain elements that can be analyzed only if they are present on the surface only. 

The isotopic distribution of lead (IDMS) in shed teeth from children has been shown to be useful in studies of the history of exposure to lead, including the definition of the source of the exposure, e.g., mine dust vs. food (Gulson and Wilson 1994), so IDMS certainly has important applicability, if not for routine determinations. ICP/MS, however, is easier, more sensitive, allows for multi-element analysis, and provides isotopic data. 

In the ideal case only the diagonal elements of the sensitivity matrix are different from zero. Then no component disturbs any other and the analytical procedure works selectively (see Sect. 7.3). The K-malrix is defined analogously except that the elements are called kij, their definition is the same as the Sij according to Eq. (7.16). 

A comprehensive approach to a states response to a chemical terrorism includes having a plan not only for the crisis and consequence management phases of the incident, but also for all elements required for complete resolution of the event. This may include the necessity to definitively establish whether chemical agents were used, to provide supporting evidence to confirm other analyses, or to provide the forensic proof required to support a criminal prosecution. The collection and analysis of biomedical samples - blood, urine or other tissue from affected humans or animals - is one of the means for providing such information. Although current capabilities such as urinary thiodyglycol excretion or plasma cholinesterase activity can be performed, there is scope for far more sensitive and specific assessments that overcome the limitations of these approaches. 

This phase is intended as a final check of the model as a whole. Testing of individual model elements should be conducted during earlier phases. Evaluation of the model is carried out according to the evaluation criteria and test plan established in the problem definition phase. Next, carry out sensitivity testing of the model inputs... 

We have spoken frequently in this chapter about sensitivity and detection limit in reference to advantages and disadvantages of the various techniques. Sensitivity and detection limit have specific definitions in atomic absorption. Sensitivity is defined as the concentration of an element that will produce an absorption of 1% (absorptivity percent transmittance of 99%). It is the smallest concentration that can be determined with a reasonable degree of precision. Detection limit is the concentration that gives a readout level that is double the electrical noise level inherent in the baseline. It is a qualitative parameter in the sense that it is the minimum concentration that can be detected, but not precisely determined, like a blip that is barely seen compared to the electrical noise on the baseline. It would tell the analyst that the element is present, but not necessarily at a precisely determinable concentration level. A comparison of detection limits for several elements for the more popular techniques is given in Table 9.2. 

From the above definition it is quite evident that the sensitivity takes no cognizance of the noise-level of the base-line, therefore, it is more or less of no use as a definite guide to the least quantity of an element which may be estimated. However, the sensitivity of a 1% absorption-is a pure theoretical number only that would undergo a change solely depending on the efficiency of the lamp (hollow-cathode-lamp), atomizer, flame-system employed, monochromator (prism, grating used), and finally the photomultiplier used. 

Asymmetric diarylmethanes, hydrogenolytic behaviors, 29 229-270, 247-252 catalytic hydrogenolysis, 29 243-258 kinetics and scheme, 29 252-258 M0O3-AI2O3 catalyst, 29 259-269 relative reactivity, 29 255-257 schematic model, 29 254 Asymmetric hydrogenations, 42 490-491 Asymmetric synthesis, 25 82, 83 examples of, 25 82 Asymmetry factor, 42 123-124 Atom-by-species matrix, 32 302-303, 318-319 Atomic absorption, 27 317 Atomic catalytic activities of sites, 34 183 Atomic displacements, induced by adsorption, 21 212, 213 Atomic rate or reaction definition, 36 72-73 structure sensitivity and, 36 86-87 Atomic species, see also specific elements adsorbed... 

Owing to lanthanide contraction, niobium and tantalum have virtually identical atomic rad (1.47 A) and close ionization energies (Nb6.67, Ta7.3eV), and usually display very similt chemical behavior. Some definite differences can however be noted these can usually be trace to the lower sensitivity of tantalum to reduction and to its higher affinity for dioxygen. lb tantalum-element multiple bonds are usually stabler, while MfiXg arrangements are so ft known only for niobium. 

Performance is defined by the sensitivity threshold, or the minimum concentration of element in solution that will yield an analytical signal with amplitude equal to twice that of the average background signal. This classical definition leads to optimistic values that can vary from element to element. The limit of detection represents the concentration of an element that can be detected with a 95% confidence limit (cf. chapter 21). In general, measurements are made in a concentration domain that corresponds to 50 times the limit of detection. 

The most common detectors for GC are the non-selective flame ionisation detector and thermal conductivity detector. For element speciation, selectivity is definitely advantageous, allowing less sample preparation and less demanding separation. Of the conventional GC detectors, the electron capture detector is very sensitive for electrophilic compounds and therefore has some selectivity for polar compounds containing halogens and metal ions. It has been used widely... 

Electrochemical methods have been used for determinations of species of elements in natural waters. Of the many electrochemical techniques, only a few have proved to be useful for studies of speciation in complex samples, and to possess the sensitivity required for environmental applications. The greatest concern is the measurement of the toxic fraction of a metal in an aqueous sample. The definition of a toxic fraction of a metal is that fraction of the total dissolved metal concentration that is recognised as toxic by an aquatic organism. Toxicity is measured by means of bioassays. Elowever, a universally applicable bioassay procedure cannot be adopted because the responses of different aquatic species to metal species vary. Nevertheless, bioassays should be used as means of evaluation and validation of speciation methods. A condition is that the test species (of the bioassay) should be very sensitive to the metals being studied so as to simulate a worst case situation (Florence, 1992). 

The method of defining RSFs described is traditional in analytical chemistry, generates RSFs without units, results in larger numbers for elements for which the SIMS instrument is more sensitive, and is essentially the same as Wittmaack s proposed use of scaled sensitivity ratios [100]. However, an alternative definition of sensitivity factors that has gained much popularity with semiconductor specialists is that of Wilson [69,101] ... 

With this definition, RSF has units of atoms per cubic centimeter, and an element that is detected with more sensitivity in the SIMS instrument has a smaller RSF. 

Here RA is the response of the analyte at unit concentration, c E is a matrix of expected, or estimated, errors and F is the Froebus norm, or root sum of the squared elements, of a matrix. It should be noted that while the NAS is a matrix quantity, selectivity (SEL), sensitivity (SEN), and signal-to-noise (S/N) are all vector quantities. The limit of detection and the limit of quantitation can also be determined via any accepted univariate definition by substituting NAS P for the analyte signal and E P for the error value. 

When spectroscopy with polarized light or other optical polarization measurements are performed the studied sample becomes one element of the optical train which transmits the beam from the radiation source to the detector. Four optical phenomena might take place in a sample sensitive to polarized radiation. We list them below together with their physical definition ... 

It should, however, be borne in mind that the depth sensitivity varies with the element. Moreover, in the case of a heterogeneous sample, the response to the elements present varies dramatically depending on their depth an clement solely present in the first atomic layer will be seen more than the same element present in greater proportion at a depth of several times the mean free path. This highlights an ambiguity in the definition of the notion of surface which poses significant problems when interpreting quantitative results. 

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