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Spray ionisation techniques solve many of the problems of how to pass liquid solutions into the gas phase. As these techniques all take samples from the liquid phase, these are the ones most easily coupled to a liquid chromatography system. Unlike desorption techniques described above, these techniques take place at ambient pressure rather than in a vacuum. One of the rst spray ionisation techniques to be reported was thermospray ionisation (TI). This technique is best suited to volatile compounds of <1000 Da, so has no role for biological macromolecule of amphiphilic lipid mass analysis, but the technique is illustrative. TI involves passing a solution containing the analyte molecule of interest through a heated capillary; the rapid expansion and cooling of the liquid results in the ejection, from the end of a capillary, of a superheated mist containing a mixture of tiny droplets together with analyte molecules in the vapour phase. Sprayed droplets have a tendency to become charged, allowing molecular ions to develop for onward mass analysis. Thermospray is a useful ionisation technique for the analysis of small oligopeptides, dinucleotides and dideoxynucleotides, small oligosaccharides and other small organic molecules. ESI is the large molecule upgrade of TI. ESI was developed as an elaboration of the atmospheric pressure chemical ionisation (APCI) technique. In the case of ESI, a solution containing the analyte molecule of interest is passed through a capillary to which is applied a potential difference of 3 16 kV, producing a signi cant electrostatic eld around the tip of the capillary that aids in molecular ion generation (Figure 9.7). As the solution leaves the end of the capillary, the electrostatic eld enables the generation of a spray of droplets.

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Preliminary work has been done in this area by the Grid Application Development Software (GrADS) project [72]. The GrADS approach is based on (1) the GrADS Program Preparation System and (2) the GrADS Program Execution System. The Program Preparation System takes user input, along with reusing components and libraries, to produce a con gurable object program. These objects are annotated with their resource requirements and predicted performance. The execution environment uses this information to select appropriate resources for execution, and also to monitor the application s compliance with a performance contract . This type of approach is a cornerstone for the Dynamic Data-Driven Application Systems (DDDAS) concept [73] being developed by the National Science Foundation. DDDAS promotes the notion of a run-time compiling system that accomplishes dynamic application composition. The ultimate goal of DDDAS, however, is to enable dynamic applications that can discover and ingest new data on the y and automatically form new collaborations with both computational systems and physical systems through a network of sensors and actuators.

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and apply simpler binding models wherever possible. In the case of multiple-site, variable af nity binding models, binding behaviour cannot be reduced to a single equilibrium binding event but is comprised of a series of binding equilibria that each t the general scheme (Scheme 7.3), where the total number of independent binding sites of variable af nity located on receptor R is n and the nal saturating binding equilibrium corresponds with the situation when i equals n. Each binding equilibrium for a given site has independent stoichiometric equilibrium binding constants. By analogy to Equation (7.17), the equation for each stoichiometric association constant, Ka,i , is as follows: K a,i = [RLi ] [RLi 1 ][L] (7.29)

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A ring is considered anonymous if processes in the ring do not. have unique identifiers. Furthermore, every process has an identical state machine with the same initial state. It, is not. difficult. to see that there is no deterministic algorithm for leader election in an anonyiiious ring. The reason is that we have cornplet,e symmetry initially--no process is distingiiisliable from other processes. Because there is a unique leader, we know that the system can never terminate in a symmetric state. Thus the algorithm has not terminated in the initial state. We now show an execution that moves t.he system from one symmetric stat,e t o the other. Assume that any process in the ring takes a step. By symmetry, this step is possible at all processes. Thus in the adversarial execiit,ion all processes take t.he same step. Since the algorit,lim is deterniinist,ic, the system must again reach a symmetric state. Therefore, the syst,ern could not have terniiriat,cd (i.e., t,he leader could not have been elected yet,). We can repeat this procedure forever. Observe that our argument, uses the fact, that the algorithm is deterministic. A randomized algorithm can solve the leader election problcm in expected finite time (see Problem 13.1).

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