Analysis of samples

Abstract: This invention relates to apparatus for analysis of samples and especially to equipment wherein interior surfaces of such apparatus are in contact with a sample as more particularly occurs in ionization chamber and ion trap apparatus.

Description: This invention relates to apparatus for analysis of samples and especially to equipment wherein interior surfaces of such apparatus are in contact with a sample as more particularly occurs in ionization chamber and ion trap apparatus. In apparatus for chemical analysis of a sample, the sample, in some form is frequently exposed to surfaces such as electrodes for establishing desired electric field, within the interior of a detector. The interaction of sample substance on these surfaces may create an undesired effect. These surfaces, for example, may catalyze some chemical reaction by which the chemical analysis is distorted, or these surfaces may be at an elevated temperature which promotes decomposition of sample molecules in contact therewith. Surface-sample molecular interactions may also distort the subsequent analysis of the sample, for example by distortion of the peak shape in a chromatogram due to surface forces acting on the sample at the electrode surfaces which affect retention time within an ion trap or similar detector. These phenomena are known in the prior art and it was known to reduce the catalytic decomposition effect by applying a specific passivating agent. US-A-5,055,678 describes the use of chromium or oxidized chromium surfaces for ion trap and ionization chambers. The same reference also describes the use of organic silanizing reagents which chemically bond to specific chemical sites of the electrode surface. GB-A-2 262 649 discloses a device for measuring the energy of charged particles. The device has a monolithic structure comprising a collector electrode layer and a rejection electrode layer separated from the collector layer by an insulating layer. Apertures are formed in the rejection and insulating layers to allow charged particles to flow towards the collector layer. A voltage source is provided for biasing the collector and rejecter layer such that charged particles of a given polarity and having a kinetic energy less than the predetermined level are repelled away from the collector layer, which therefore receives only particles having that polarity and a greater kinetic energy. Exposed portions of the surface of the collector layer may be coated with graphite. US-A-5 283 436 discloses a quadrupole detector having electrodes which consist of an insulating substrate having a coating of a semiconductor material facing the interior volume. It is desired to achieve a greater degree of isolation between samples and the instrumental environment for an analytical component. This is achieved with the system set out in claim 1, 2 or 3. An outer surface layer of fused. silica having a thickness of the order of 0.02 to 0.1 micron has been found substantially to improve peak shapes in chromatographic apparatus in comparison with chromium coated stainless steel electrodes of prior art. Fused silica has been shown to have the advantage of not only reducing chemical decomposition at the surface, but also reducing peak tailing due to physical or chemical absorption on the ion trap surfaces. An example of the invention will now be described with reference to the accompanying drawings in which: Figure 1A shows a typical chemical analysis system forming the context of the invention. Figure 1B shows a representative detector. Figures 2A-E inclusive show mass analyzed chromatograms for five respective samples using a standard ion trap having chromium coated electrodes. Figures 3A-E show the chromatograms of the samples of Figure 1A-E, respectively, using the fused silica coating of the present invention. A suitable context for the practice of the invention may be described with the aid of figure 1A and B. The system of figure 1A is a gas chromatographic analysis apparatus incorporating a quadrupole mass spectrometer. A representative example of this apparatus includes a carrier gas source 12 which is mixed with a sample at injector 14 and introduced to a GC column 16. The concentration of effluent from the GC column 16 is detected (and further analyzed) in detector apparatus 18. The nature of the detector apparatus varies. For specificity a quadrupole ion trap for mass analysis is shown schematically in fig. 1B (although various other detectors might utilize the invention). The effluent from GC column 16 is introduced through sample input 20 to the quadrupole ion trap comprising electrodes 22, 24 and 26, electron beam source 28, ion detector 30 and full support electronics package 32. The details of a quadrupole ion trap are well known and need not be further discussed here except for the observation that the operation of this device depends upon fields established by a complex system of electrodes driven at selected frequencies, phases and amplitudes. In the quadrupole ion trap the electrode shapes employed are approximations to specific quadratic geometries which critically control operation of the trap. As a result of an ionization process, static charge density distributions accumulate on the insulatively coated electrodes and might reach values which will cause arcing resulting in a false signal, or such charge distribution may distort the field thereby altering the operation of the trap. It is preferred that the thickness of the insulating coating is sufficiently thin for given dielectric constant, such that the areal charge density be small enough to have negligible distortion in respect to the electric field distribution. This limit obviously depends upon specific applications, electrode geometry and applied potentials. In the present example an inert fused silica coating with a thickness on the order of less than 0.1 micron was employed. Coatings of aluminum oxide, silicon nitride or selected semiconductor materials are alternative embodiments. In order to achieve an effective passivation, the thickness of the coating should preferably be of the order of achievable uniformity variations in order to ensure that there are no uncoated areas or pinholes. Figures 2A-E, inclusive, and Figures 3A-E, inclusive, are respective comparisons of the identical corresponding sample chromatograms in otherwise identical apparatus. For purposes of comparison a comprehensive drug mix test sample was formed from five separate samples of equal masses which, mixed together, were injected into a standard chromographic analyzing apparatus (Saturn model gas chromatograph-mass spectrometer manufactured by Varian Associates, Inc.). Effluent of the column is ionized and is mass analyzed for ions uniquely representative of each of the original sample components and the respective chromatograms are shown for comparison. In the data acquired from Figures 2A-E the standard chromatograph included an ion trap having chromium coated electrodes. The injected sample is analyzed within the ion trap and specific retention time chromatograms for representative ion masses are exhibited in Figures 2A-E. In Figures 3A-E the same analysis was carried out, the only difference being the fused silica coating of the present invention employed for the electrodes of the ion trap. The principal difference is dramatically apparent in the absence of tailing in retention time which contributes an asymmetry toward larger retention times. (The difference in position on the abscissa for respective peaks is not significant and (likely) represents a difference in column head pressure for the respective measurements). The utility of the invention in the context of an ion trap is exemplary and not limiting. Detectors of various types form electric fields in which ions describe-certain classes of trajectories. A fraction of the neutral precursors of these ions may be affected by collision with electrodes as well as insulating surfaces. The invention features coated electrodes which are electrically active. The invention may be used with detectors other than ion traps where the interaction of neutrals with detector surfaces may yield a distortion of data derived from the detector. In the case of an ion trap mass spectrometer the retention time effect from electrode surfaces is observed to distort peak shapes. Insulating members as well as conductors in the interior of the detector may contribute to this particular problem. Other effects may conceivably result in spectral peaks characterizing catalyzed products from collision of sample ions with such surfaces. Detectors of various types in the context of chromatography apparatus can be expected to exhibit similar retention time effects.

Claims: A system for analysis of a sample having constituents, said system comprising a detector (18) having electrodes (22, 24, 26) for defining an interior volume therein and for establishing desired electric fields within said detector interior volume, said electrodes (22, 24, 26) comprising a surface layer exposed to said sample constituents in the interior volume, characterised in that the surface layer of at least one of said electrodes (22, 24, 26) is of fused silica. A system for analysis of a sample having constituents, said system comprising a detector (18) having electrodes (22, 24, 26) for defining an interior volume therein and for establishing desired electric fields within said detector interior volume, said electrodes (22, 24, 26) comprising a surface layer exposed to said sample constituents in the interior volume, characterised in that the surface layer of at least one of said electrodes (22, 24, 26) is of alumina. A system for analysis of a sample having constituents, said system comprising a detector (18) having electrodes (22, 24, 26) for defining an interior volume therein and for establishing desired electric fields within said detector interior volume, said electrodes (22, 24, 26) comprising a surface layer exposed to said sample constituents in the interior volume, characterised in that the surface layer of at least one of said electrodes (22, 24, 26) is of silicon nitride. A system as claimed in any one of the preceding claims, wherein the system is a chemical analysis system. A system as claimed in claim 4 for chemical analysis of the sample constituents, said detector (18) being arranged to respond to ions comprising said constituents, said detector electrodes (22, 24, 26) supporting selected electric fields and said electrodes exposed to said ions, said surface layer having a thickness which is less than an upper limit thickness selected to support a given areal charge density and which thickness is sufficient to achieve complete passivation of the underlying surface thereof. A system as claimed in claim 5 wherein said detector (18) further comprises an ion source (28) for creating said ions from said sample. A system as claimed in claims 5 or 6 wherein the areal charge density corresponding to said upper limit thickness has only negligible distorting effect upon said selected electric fields.

Inventors: BRITTAIN ROBERT D, WANG MINGDA, BRITTAIN, ROBERT D., WANG, MINGDA
Applicants: VARIAN INC, VARIAN, INC.
Application year: 1996
Main classification: H01J49
IPC codes: H01J49, G01N30, G01N27