Capillary-restricted modification

Smirnova et al. demonstrated the determination of the insecticide, carbaryl, using a two-chip system. The first chip (for the hydrolysis of carbaryl) had a simple Y-shaped channel while the second chip (for the diazo couphng reaction between hydrolyzed products and 2,4,6-trimethylaniline)—the extraction required special channel shapes with a partial surface— modification obtained by using capillary-restricted modification (CARM) (Figure 35.11). " Determination of carbaryl pesticide in water with sufficient sensitivity was carried out with an analysis time of 8 min. In a similar manner, Honda et al. developed a combination of a tube-type enzyme-immobilized microreactor and a microextractor with partial surface modification to produce optically pure amino acids. 

Kitamori s group has proposed selective chemical surface modification utilizing capillarity (called the capillarity restricted modification or CARM method) (Hibara et al., 2005). In the CARM method, a microchannel structure combining shallow and deep microchannels and the principle of capillarity are utilized. The procedures are shown in Figure 19. A portion of an ODS/toluene solution (lwt%) is dropped onto the inlet hole of the shallow channel, and the solution is spontaneously drawn into this channel by capillary action. The solution is stopped at the boundary between the shallow and deep channels by the balance between the solid-liquid and gas-liquid interfacial energies. Therefore, the solution does not enter the deep channel. It remains at the boundary for several minutes and is then pushed from the deep channel side by air pressure. 

The former observation is concerned with the effective electrode area. In the early part of drop life, its size is similar to that of the capillary orifice. A significant part of the drop is thus not in contact with the solution, a fact which qualitatively explains the lower observed currents. Also, close to the capillary surface, the diffusion process will be restricted, the so-called shielding effect. This is particularly pertinent with modern polarographic equipment where mechanical drop timers are often used in conjunction with short drop times. These problems have been discussed recently [59]. The following modification was proposed... 

Capillary electrophoresis (CE) coupled to MS has the advantage of high resolution and soft ionization for biomolecules, which may be used to differentiate post-translational modifications and variants of intact proteins and oligonucleotides. Different modes of CE (capillary zone electrophoresis, capillary isoelectric focusing, capillary electrochromatography, micellar electrokinetic chromatography, nonaqueous capillary electrophoresis) to MS as well as online preconcentration techniques (transient capillary isotachophoresis, solid-phase extraction, membrane preconcentration) are used to compensate for the restricted detection sensitivity of the CE methodology [77, 78]. 

The second commercial LC-MS interface, available in 1980, was based on a modification of restricted capillary inlet interfaces [29-31]. Melera [32] demonstrated that by using a diaphragm pinhole a stable and reliable system for DLI could be achieved. The design and performance of the resulting DLI interface was extensively studied and characterized by Arpino and coworkers [73-77]. The system is capable of introducing up to 50 pl/min of mobile phase. Analyte ionization is achieved in solvent-mediated CL The DLI interface is discussed in Ch. 4.5. 

Nebulization of colunrn effluents as large as 1 ml/min into an atmospheric-pressure chamber coimected by means of a restrictive pinhole or capillary to the MS vacuum system requires modification of the MS vacuum system. Aspects related to MS vacuum system for on-line LC-MS are treated in Ch. 5.2. 

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