Sensitization competitive processes

In a competitive process, the excess energy can be dissipated by emission of a second or Auger electron from an outer shell of the atom, leaving it in a doubly ionised excited state. The relative importance of AES and XRF depends upon the atomic number (Z) of the element involved. High Z values favour fluorescence, whereas low Z favours AES. This fact, taken together with X-ray absorbance in air, makes XRF into a method which is not very sensitive for elements with atomic numbers below Z 10. Measurements of solid samples are normally made under vacuum, as the absorption of air renders analysis of elements lighter than Ti impossible. 

The quantum yield of the primary act of spectral sensitization is limited by competitive processes fluorescence (fl), thermal deactivation of the excited dye molecule by internal conversion (ic), and intersystem crossing to the triplet manifold (isc). The sum of the quantum yields of sensitization and all competitive processes is one ... 

As essential competitive processes, we have only to consider deactivation processes of S-M. ( L ) and back electron transfer (k ). Thus, the efficiency1"1. "ri primarily depends on the befiavior of the S-ML unit, bBf it is independent of the solvent properties, provideR they do not affect the thermodynamic stability of the sensitizer/complex unit ... 

The fabrication of microelectronic and photonic components involves long sequences of batch chemical processes. The manufacture of advanced microstructures can involve more than 200 process steps and take from 2 to 6 weeks for completion. The ultimate measure of success is the performance of the final circuits. The devices are highly sensitive to process variations and are difficult, if not impossible, to repair if a particular chemical process step should fail. Furthermore, because of intense competition and rapidly evolving technology, the development time from layout to final product must be short. Therefore, process control of electronic materials processing holds considerable interest [30, 31]. The process control issues involve three levels ... 

The adsorption of plasma proteins to polymers precedes the interaction of blood cells with the surfaces, and therefore, is likely to be an important initial event in the response of blood to polymers (25, 29). At present, however, little is known about the adsorbed protein layer, even though it has been studied in some detail in recent years (30-36). Because protein adsorption from blood plasma is a competitive process, differences in the adsorbed layer on different polymer substrates could be a primary cause of differences in thrombogenicity. Previous studies of the composition of the adsorbed protein layer have employed 12oI-labeled protein added to plasma (37-39), antibody binding (34) to detect individual proteins, or electrophoretic analysis of detergent-elutable proteins (17, 33, 35). The procedure used in this study does not require the large surface areas used in previous work (35), nor does it rely on incorporation of radiolabels (36) into adsorbed protein. Instead, a staining method at least 100-fold more sensitive than these other techniques has been used. 

The suitability of MS detectors for quantitative analyses is debated. For example, ESI is a competitive process and, occasionally, matrix (background) material interferes with the ionization of the analyte [40]. These effects of ion suppression are especially aggravated when several species coelute, such as in the case of biological extracts or with direct infusion (without previous separation). Generally, hydrophilic species are more sensitive to ion suppression than hydrophobic ones, which tend to concentrate on the droplet surface during ESI [41]. In MALDI, the sample dispersion is often inhomogeneous or the matrix crystals unevenly distributed on the surface. A truthful representation of the sample composition is obtained exclusively upon thorough laser desorption of the entire spot. In addition, with some instruments the transmission of ions in the mass... 

The enhancement of the curing rate by additions of thioxanthone was studied with time-resolved laser spectroscopy and H-NMR CIDNP. It led to the conclusion that two competitive processes occur from the excited triplet-state sensitizers. One is electron transfer and the other is enei transfer. Whether it is the former or the latter depends upon the structure of the initiator used. ... 

Once the excited state of the reactant has been formed, either by direct or sensitized energy transfer, the stage is set for a photochemical reaction. There are still, however, competitive processes that can occur and result in the return of... 

Later,triplet alkylititrenes 12a-c were generated by intramolecular sensitization in solution. The photochemistry of three a-benzoyl-ft)-azidoalkanes (PhCO(CH2)oN3 (13a-c, n = 3-5) was studied and two competitive processes were found to proceed from the triplet ketone (Scheme 11.8) energy transfer to azide to yield triplet alkyl nitrene and 7-hydrogen abstraction to yield Norrish type II products. Photolysis of azides with a longer methylene chain (13b,c) yields mainly acetophenone, a product of Norrish type II reaction. The major products of the azide 13a photolysis were substituted pyrrole and pyr-roline derived from triplet nitrene 12a. ... 

Ilvespaa (98) has demonstrated that, using some amines, the 2-chloro-5-nitrothiazole undergoes an opening reaction in a competitive reaction parallel to the normal substitution process. This confirms the sensitivity of position 4 to nucleophilic attack when a nitro group is present in position 5 (Scheme 16). 

The electrospray process is susceptible to competition/suppression effects. All polar/ionic species in the solution being sprayed, whether derived from the analyte or not, e.g. buffer, additives, etc., are potentially capable of being ionized. The best analytical sensitivity will therefore be obtained from a solution containing a single analyte, when competition is not possible, at the lowest flow rate (see Section 4.7.1 above) and with the narrowest diameter electrospray capillary. 

This is the first example of a reaction for which the presence of a chelating ligand was observed to facilitate rather than retard metal-catalysed epoxidation (Gao et al., 1987). It was found that the use of molecular sieves greatly improves this process by removing minute amounts of water present in the reaction medium. Water was found to deactivate the catalyst. All these developments led to an improved catalytic version that allows a five-fold increased substrate concentration relative to the stoichiometric method. Sensitive water-soluble, optically active glycidols can be prepared in an efficient manner by an in situ derivatisation. This epoxidation method appears to be competitive with enzyme-catalysed processes and was applied in 1981 for the commercial production of the gypsy moth pheromone, (-1-) disparlure, used for insect control (Eqn. (25)). 

FIG. 11 General mechanism for the heterogeneous photoreduction of a species Q located in the organic phase by the water-soluble sensitizer S. The electron-transfer step is in competition with the decay of the excited state, while a second competition involved the separation of the geminate ion-pair and back electron transfer. The latter process can be further affected by the presence of a redox couple able to regenerate the initial ground of the dye. This process is commonly referred to as supersensitization. (Reprinted with permission from Ref. 166. Copyright 1999 American Chemical Society.)... 

For the El ion source, the generated total ion stream is directly proportional to the gas pressure in the impact field, which provides a basic condition for quantitative analysis. Compounds can only safely be quantified if influences on the sensitivity of detection, such as ion-molecule reactions and competition in the ionisation process, can be excluded by experimental evidence. 

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