Spray desolvation

Spray desolvation involves spraying a polymer solution onto a desolvating liquid. For example, microparticles can be made by spraying a PVA solution onto an acetone bath. Here, the polymer solvent (water) is extracted into acetone, and PVA precipitates to form solid micro-particles.f In another example, bovine serum albumin (BSA) was encapsulated in poly(lactic-co-glycolic acid) (PLGA) by this method. The micronized drug was suspended in a PLGA-acetone solution and atomized ultrasonically into ethanol bath. ° ... 

Ting, T. Gonda, I. Gripps, E.M. Microparticles of PVA for nasal delivery. I. Generation by spray-drying and spray-desolvation. Pharm. Res. 1992, 9 (10), 1330-1335. 

Sam, A.P. Haan, F.D. Dirix, C. A Novel Process for Manufacturing PLG Microparticles by Spray Desolvation Avoiding the use of Toxic Solvents. International Symposium on Controlled Release of Bioactive Materials. Nice, France, 1994 198-199. 

For the chromatographic column, flow of solution from the narrow inlet tube into the ionization/desolvation region is measured in terms of only a few microliters per minute. Under these circumstances, spraying becomes very easy by application of a high electrical potential of about 3-4 kV to the end of the nanotube. Similarly, spraying from any narrow capillary is also possible. The ions formed as part of the spraying process follow Z-shaped trajectories, as discussed below. 

The nebulization concept has been known for many years and is commonly used in hair and paint spays and similar devices. Greater control is needed to introduce a sample to an ICP instrument. For example, if the highest sensitivities of detection are to be maintained, most of the sample solution should enter the flame and not be lost beforehand. The range of droplet sizes should be as small as possible, preferably on the order of a few micrometers in diameter. Large droplets contain a lot of solvent that, if evaporated inside the plasma itself, leads to instability in the flame, with concomitant variations in instrument sensitivity. Sometimes the flame can even be snuffed out by the amount of solvent present because of interference with the basic mechanism of flame propagation. For these reasons, nebulizers for use in ICP mass spectrometry usually combine a means of desolvating the initial spray of droplets so that they shrink to a smaller, more uniform size or sometimes even into small particles of solid matter (particulates). 

The simplest desolvation chambers consist simply of a tube heated to about 150°C through which the spray of droplets passes. During passage through this heated region, solvent evaporates rapidly from the droplets and forms vapor. The mixed vapor and residual small droplets or particulates of sample matter are swept by argon through a second cooled tube, which allows vapor to... 

Solutions can be examined by ICP/MS by (a) removing the solvent (direct and electrothermal methods) and then vaporizing residual sample solute or (b) nebulizing the sample solution into a spray of droplets that is swept into the plasma flame after passing through a desolvation chamber, where excess solvent is removed. The direct and electrothermal methods are not as convenient as the nebulization inlets for multiple samples, but the former are generally much more efficient in transferring samples into the flame for analysis. 

Many designs of nebulizer are commonly used in ICP/MS, but their construction and mode of operation can be collated into a small number of groups pneumatic, ultrasonic, thermospray, APCI, and electrospray. These different types are discussed in the following sections, which are followed by further sections on spray and desolvation chambers. 

In a concentric-tube nebulizer, the sample solution is drawn through the inner capillary by the vacuum created when the argon gas stream flows over the end (nozzle) at high linear velocity. As the solution is drawn out, the edges of the liquid forming a film over the end of the inner capillary are blown away as a spray of droplets and solvent vapor. This aerosol may pass through spray and desolvation chambers before reaching the plasma flame. 

The thermospray device produces a wide dispersion of droplet sizes and transfers much of sample solution in unit time to the plasma flame. Therefore, it is essential to remove as great a proportion of the bigger droplets and solvent as possible to avoid compromising the flame performance. Consequently, the thermospray device usually requires both spray and desolvation chambers, especially for analyte solutions in organic solvents. 

Thermospray nebulizers are somewhat expensive but can be used on-line to a liquid chromatographic column. About 10% of sample solution is transferred to the plasma flame. The overall performance of the thermospray device compares well with pneumatic and ultrasonic sprays. When used with microbore liquid chromatographic columns, which produce only about 100 pl/min of eluant, the need for spray and desolvation chambers is reduced, and detection sensitivities similar to those of the ultrasonic devices can be attained both are some 20 times better than the sensitivities routinely found in pneumatic nebulizers. 

Introduction of sample solution via a nebulizer may need both spray and a desolvation chamber, but a well-designed, efficient nebulizer needs neither. 

To assist in the deposition of these larger droplets, nebulizer inlet systems frequently incorporate a spray chamber sited immediately after the nebulizer and before the desolvation chamber. Any liquid deposited in the spray chamber is wasted analyte solution, which can be run off to waste or recycled. A nebulizer inlet may consist of (a) only a nebulizer, (b) a nebulizer and a spray chamber, or (c) a nebulizer, a spray chamber, and a desolvation chamber. Whichever arrangement is used, the object is to transfer analyte to the plasma flame in as fine a particulate consistency as possible, with as high an efficiency as possible. 

Spray Drying. Spray-dry encapsulation processes (Fig. 7) consist of spraying an intimate mixture of core and shell material into a heated chamber where rapid desolvation occurs to thereby produce microcapsules (24,25). The first step in such processes is to form a concentrated solution of the carrier or shell material in the solvent from which spray drying is to be done. Any water- or solvent-soluble film-forming shell material can, in principle, be used. Water-soluble polymers such as gum arable, modified starch, and hydrolyzed gelatin are used most often. Solutions of these shell materials at 50 wt % soHds have sufficiently low viscosities that they stiU can be atomized without difficulty. It is not unusual to blend gum arable and modified starch with maltodextrins, sucrose, or sorbitol. 

The second step is to disperse the core material being encapsulated in the solution of shell material. The core material usually is a hydrophobic or water-knmiscible oil, although soHd powders have been encapsulated. A suitable emulsifier is used to aid formation of the dispersion or emulsion. In the case of oil core materials, the oil phase is typically reduced to a drop size of 1—3 p.m. Once a suitable dispersion or emulsion has been prepared, it is sprayed into a heated chamber. The small droplets produced have a high surface area and are rapidly converted by desolvation in the chamber to a fine powder. Residence time in the spray-drying chamber is 30 s or less. Inlet and outlet air temperatures are important process parameters as is relative humidity of the inlet air stream. 

C, is one of the most critical parameters in TSP operation, and should be optimised for different samples, wherever possible. This is considered to be a considerable drawback in routine operation of unknown polymer/additive extracts. Too low a vaporiser temperature results in the solute and solvent spraying into the ionisation source in their liquid form, without formation of gas-phase ions. Too high a vaporiser temperature causes premature evaporation of the solute and solvent before the outlet of the capillary is reached. This causes an unstable, pulsing ion beam. As ion formation in TSP operation depends very critically on the extent of desolvation and the energy of the nebulised droplets, it is clear that an inappropriate vaporiser temperature will cause loss of sensitivity. 

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