SOLID PHASE MICROEXTRACTION DEVICE AND METHOD FOR FORMING

Abstract

A solid phase microextraction device is disclosed, including a substrate having a planar surface and a sorbent layer disposed on the planar surface. The planar surface is defined by a base edge, a spray edge disposed distal across the substrate from the base edge, the spray edge including a tapering tip extending away from the base edge, a first lateral edge extending from the base edge to the tapering tip, and a second lateral edge extending from the base edge to the tapering tip, the second lateral edge being disposed distal across the substrate from the first lateral edge. The sorbent layer extends a sampling length from the spray edge toward the base edge and includes sorbent particles. A method for forming the solid phase microextraction device is disclosed, including applying the sorbent layer on the planar surface utilizing at least one of screen printing, stencil printing, or additive manufacturing.

Claims

1. A solid phase microextraction device, comprising: a substrate having a first planar surface defined by: a base edge; a spray edge disposed distal across the substrate from the base edge, the spray edge including a tapering tip extending away from the base edge; a first lateral edge extending from the base edge to the tapering tip; and a second lateral edge extending from the base edge to the tapering tip, the second lateral edge being disposed distal across the substrate from the first lateral edge; and a first sorbent layer disposed on the first planar surface and extending a sampling length from the spray edge toward the base edge, the first sorbent layer including first sorbent particles, wherein the first sorbent layer is disposed over less than an entire width of the first planar surface from the first lateral edge to the second lateral edge along the sampling length.

2. The solid phase microextraction device of claim 1, further including a second sorbent layer including second sorbent particles disposed on the first planar surface and extending from the spray edge toward the base edge, the second sorbent particles being compositionally distinct from the first sorbent particles.

3. The solid phase microextraction device of claim 2, wherein the first sorbent layer and the second sorbent layer together are disposed over less than the entire width of the first planar surface from the first lateral edge to the second lateral edge along the sampling length.

4. The solid phase microextraction device of claim 1, further including a second sorbent layer including second sorbent particles disposed on a second planar surface and extending from the spray edge toward the base edge.

5. The solid phase microextraction device of claim 4, wherein the second sorbent particles are compositionally distinct from the first sorbent particles.

6. The solid phase microextraction device of claim 4, wherein the second sorbent particles are compositionally identical to the first sorbent particles.

7. The solid phase microextraction device of claim 4, wherein the second sorbent layer is disposed over less than the entire width of the second planar surface from the first lateral edge to the second lateral edge along the sampling length.

8. The solid phase microextraction device of claim 1, wherein the first sorbent layer includes a first portion including first sorbent particles and a second portion including second sorbent particles, the first sorbent particles being compositionally distinct from the second sorbent particles.

9. The solid phase microextraction device of claim 8, wherein the first sorbent layer further includes a third portion including third sorbent particles, the third sorbent particles being compositionally distinct from the first sorbent particles and the second sorbent particles.

10. The solid phase microextraction device of claim 9, wherein the first portion is disposed between the spray edge and each of the second portion and the third portion.

11. The solid phase microextraction device of claim 1, wherein the first sorbent layer has a composition including an organic polymer having a first bulk density of up to 1.5 g/cm.sup.3 and an inorganic material and having a second bulk density of at least 5.0 g/cm.sup.3.

12. The solid phase microextraction device of claim 1, wherein the first sorbent particles include at least one of electrically conductive particles or magnetic particles.

13. The solid phase microextraction device of claim 1, further including a primer layer disposed between the substrate and the first sorbent layer.

14. A method for forming a solid phase microextraction device, comprising: applying a first sorbent layer including first sorbent particles on a first planar surface of a substrate, the first planar surface being defined by: a base edge; a spray edge disposed distal across the substrate from the base edge, the spray edge including a tapering tip extending away from the base edge; a first lateral edge extending from the base edge to the tapering tip; and a second lateral edge extending from the base edge to the tapering tip, the second lateral edge being disposed distal across the substrate from the first lateral edge, wherein: the first sorbent layer extends a sampling length from the spray edge toward the base edge; and the applying of the first sorbent layer on the first planar surface includes at least one of screen printing, stencil printing, or applying by additive manufacturing the first sorbent particles on the first planar surface.

15. The method of claim 14, wherein the applying of the first sorbent layer includes screen printing the first sorbent particles on the first planar surface.

16. The method of claim 14, wherein the applying of the first sorbent layer includes stencil printing the first sorbent particles on the first planar surface.

17. The method of claim 14, wherein the applying of the first sorbent layer includes applying by additive manufacturing the first sorbent particles on the first planar surface.

18. The method of claim 14, wherein the first sorbent layer is disposed over less than an entire width of the first planar surface from the first lateral edge to the second lateral edge along the sampling length.

19. The method of claim 14, wherein applying the first sorbent layer includes applying a slurry comprising the first sorbent particles, a binder, and a solvent.

20. The method of claim 20, wherein applying the first sorbent layer further includes removing the solvent by drying to form the first sorbent layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] FIG. 1A illustrates a CBS device having a sorbent particle bed applied to a portion of surface of a solid substrate, according to an embodiment of the present disclosure.

[0014] FIG. 1B illustrates a CBS device having a sorbent particle bed applied to a portion of a surface of a solid substrate less than the entire width of the surface, according to an embodiment of the present disclosure.

[0015] FIG. 1C illustrates a CBS device having a primer layer applied to a portion of a solid substrate and a sorbent particle bed applied to the primer layer over a portion of a surface of a solid substrate less than the entire width of the surface, according to an embodiment of the present disclosure.

[0016] FIG. 1D illustrates a CBS device having a primer layer applied to a portion of a solid substrate, a first sorbent particle bed applied to the primer layer over a portion of a first surface of a solid substrate less than the entire width of the first surface, and a second sorbent particle bed applied to the primer layer over a portion of a second surface of a solid substrate less than the entire width of the second surface, according to an embodiment of the present disclosure.

[0017] FIG. 1E illustrates a CBS device having a first sorbent particle bed and a second sorbent particle bed applied to a portion of a surface of a solid substrate, according to an embodiment of the present disclosure.

[0018] FIG. 1F illustrates a CBS device having a primer layer applied to a solid substrate and a sorbent particle bed applied to the primer layer over a portion of a surface of a solid substrate less than the entire width of the first surface, according to an embodiment of the present disclosure.

[0019] FIG. 1G illustrates a CBS device having a primer layer applied to a solid substrate and a sorbent particle bed applied to the primer layer over a portion of a surface of a solid substrate less than the entire width of the surface such that the sorbent particle bed tapes more sharply than a tapered portion of the solid substrate, according to an embodiment of the present disclosure.

[0020] FIG. 2 illustrates a CBS device having a first sorbent particle bed applied to a first portion of a surface of a solid substrate, a second sorbent particle bed applied to a second portion of the surface of the solid substrate less than the entire width of the surface, and a third sorbent particle bed applied to a third portion of the surface of the solid substrate less than the entire width of the surface, according to an embodiment of the present disclosure.

[0021] FIGS. 3A, 3B, and 3C are photographs each of four replicate CBS devices having sorbent particle beds applied to portions of surfaces of solid substrates less than the entire widths of the surfaces, according to embodiments of the present disclosure.

[0022] FIG. 4 illustrates a CBS device having a sorbent particle bed applied to a portion of surface of a solid substrate, the sorbent particle bed including a single type of sorbent particle, according to an embodiment of the present disclosure.

[0023] FIG. 5 illustrates a CBS device having a sorbent particle bed applied to a portion of surface of a solid substrate, the sorbent particle bed including two types of sorbent particles, according to an embodiment of the present disclosure.

[0024] FIG. 6 illustrates a CBS device having a sorbent particle bed applied to a portion of surface of a solid substrate, the sorbent particle bed including three types of sorbent particles, according to an embodiment of the present disclosure.

[0025] Wherever possible, the same reference numbers will be used throughout the drawings to represent the same parts.

DETAILED DESCRIPTION OF THE INVENTION

[0026] Disclosed herein are solid phase microextraction devices including a sorbent layer disposed over less than an entire width of the devices and methods for forming solid phase microextraction devices with stenciling techniques. The devices and methods disclosed herein, in comparison to devices and methods not including one or more of the features disclosed herein, increase spatial resolution of the extractive coating, facilitate intricate coating geometries and sophisticated combinations of coating chemistries on the substrates, decrease waste, increase production capacity, or combinations thereof.

[0027] As used herein, “about” indicates a variance of ±50% of the value being modified by “about,” unless otherwise indicated to the contrary.

[0028] As used herein, “solid phase microextraction” includes, but is not limited to, a solid substrate coated with a polymeric sorbent coating, wherein the coating may include metallic particles, silica-based particles, metal-polymeric particles, polymeric particles, or combinations thereof, which are physically or chemically attached to the substrate. In some non-limiting examples, the solid substrate has at least one depression disposed in or protrusion disposed on a surface of the substrate and said substrate includes at least one polymeric sorbent coating disposed in or on the at least one depression or protrusion. The term “solid phase microextraction” further includes a solid substrate with at least one indentation or protrusion that contains at least one magnetic component for the collection of magnetic particles or magnetic molecules onto the solid substrate.

[0029] In contrast to dip-coating, spray coating, sputtering, spin-coating, doctor blading, sol-gel chemistry, and electrospinning, stenciling techniques, such as, but not limited to, screen printing and stencil printing, may be adapted to as to provide thin coating and high spatial resolution distribution of an extractive coating (<100 μm). Additive manufacturing techniques, such as, but not limited to, binder jet three-dimensional printing, stereolithography, fused capillary additive manufacturing, or combinations thereof, may also be used in lieu of stenciling techniques.

[0030] In the case of screen printing, a screen of a woven material (e.g., a stainless steel mesh) is attached to a frame under tension, and the pattern to be printed on the substrate is produced by selectively filling portions of the screen with an emulsion that is impermeable to the coating solution. Screen printing requires a viscous coating solution and low volatility, which in turn yields thicker coatings in comparison to dip coating or spin coating. The wet thickness of the coating is governed by the volume between the threads of the mask and thickness of the screen. Other factors such as the snap-off distance, the force with which the squeegee is pushed into the screen, and the viscosity of the solution are also relevant. Screen printing processes utilize a fixture where the substrates are mounted. Typically, the fixture comprises multiple ducts that, after activating vacuum suction, affix the parts to the fixture. Such fixtures inhibit movement of the parts during the screen printing process, assuring reproducible printing among parts. Unlike dip-coating, screen printing is suitable for creating well defined geometries with a high degree of resolution. The spatial resolution obtainable with screen printing is lower that inkjet printing; however, screen printing is significantly faster than inkjet printing, is scalable for mass-production, and provides sufficient spatial resolution for the uses described herein. In addition, screen printing may be applied to only a single side of a substrate at a time, facilitating the development of tridimensional complexity on the flat areas of the substrate.

[0031] In contrast to screen printing, stencil printing is typically made by either photoetching, laser cutting, or combinations thereof, on a sheet of metal or plastic. In addition, a cement-like slurry with ultra-low volatility (essentially a paste having a viscosity of at least 1,000 cP, alternatively at least 2,000 cP) is required to coat the surface. Furthermore, there is no need for a frame under tension as the squeegee delivers the coating on each of the open apertures and the thickness of the coating is determined by the thickness of the stencil. Similar to screen printing, a fixture where the substrates are mounted is utilized to assure the parts do not move during the printing process; hence, securing reproducible printing among devices. Unlike dip-coating, stencil printing is suitable for creating well defined geometries with a high degree of resolution. The spatial resolution obtainable with stencil printing is lower that inkjet printing; however, stencil printing is significantly faster than inkjet printing, is scalable for mass-production, and provides sufficient spatial resolution for the uses described herein. In addition, stencil printing may be applied to only a single side of a substrate at a time, facilitating the development of tridimensional complexity on the flat areas of the substrate.

[0032] Appropriately coated areas of the solid substrate may be used to collect molecules of interest from a sample and then said coated solid substrates may be interfaced with analytical instrumentation for measurement of said molecules. Slurries comprised of particles, binders, additives, and solvents may be disposed on a solid substrate via stenciling techniques or additive manufacturing to form the requisite coatings for collection of molecules. After applying the slurry to the solid substrate, the substrate slurry may be dried at a constant temperature to evaporate the solvent and adhere the binder to the surface of the solid substrate, thereby adhering the particles to the solid substrate.

[0033] By the methods disclosed herein, particle beds may be deposited on flat substrates. In particular, the particle bed shape may be different than the underlying substrate and, with respect to the flat plane surface area, the coating area is smaller. The particle bed shape may include regions of pads or channels, or other shapes, which are designed to direct the flow of the elution/ionization solvent along a localized portion of the CBS device, ultimately terminating at the tapered tip in one of the flat faces of the substrate. The regions of the CBS device where there is no particle bed may be simply exposed substrate, or substrate that has been primed, or substrate covered with a second different coating confined to the “negative space” of the blade with respect to the sorbent particle bed.

[0034] In order for complex sorbent particle bed shapes to effectively direct the flow of the elution solvent from one region of the CBS device to another, it is desirable for the elution solvent to be confined to the sorbent particle bed region and not wick onto the adjacent exposed substrate. One novel technique to confine the elution solvent to the sorbent particle bed region is to employ a substrate with a different chemical polarity than the elution solvent and the sorbent bed. This in turn inhibits or prevents the elution solvent from contacting the substrate region while freely moving along the sorbent particle bed region.

[0035] Particle to solvent ratios affect the slurry viscosity. Application techniques employing inherently higher viscosity slurries are less dependent on composition ratios. For instance, stenciling techniques employ high viscosity slurries. Higher viscosity decreases the movement of individual particles when the slurry is in a still state. As such, the higher viscosities used for stenciling techniques facilitate homogeneously suspending particles having different surface properties, densities, sizes, and chemical polarities for extended periods of time, and therefore promote an evenly homogenously distributed particle mixture in the sorbent bed.

[0036] Stenciling techniques also facilitate the formation of complex shaped sorbent particle beds on CBS device substrates, providing a pathway for additional flow-based functionality in CBS devices. More complex bed shapes such as channels, additional reservoir regions, and narrower channels towards the tip regions provide functionality to improve analysis signal, provide additional stages of sample preparation using the CBS device as the reaction vessel, or combinations thereof.

[0037] In cases where the solvent molecules include both polar and nonpolar moieties, additive particles may adjust the bulk polarity of the slurry. Relevant physical properties include the slurry viscosity, the vapor pressure of the slurry, and the bulk polarity of the slurry. The resulting cured bed physical properties may include the bulk polarity, the chemical reactivity, the bonding effectivity of the bed to the substrate, the long-term bed stability, and the sorbent compatibility with a wider range of elution solvents.

[0038] In cases where a primer layer polarity is essentially the same as the solvent employed when depositing the sorbent particle bed layer, the polarity properties of the sorbent particle bed and the underlying primer are very similar.

[0039] In CBS device designs employing more complex-shaped sorbent particle beds, the sorbent particle bed region is typically a portion of the underlying CBS device surface area. As such, there may be exposed substrate available to the elution solvent when the solvent is applied to the sorbent particle bed region. Unless there is a sufficient mechanical or chemical barrier to the elution solvent, the solvent may migrate off the sorbent particle bed region and onto the substrate itself. This migration behavior is often undesirable, particularly if the sorbent particle bed design is configured to direct the solvent flow from one confined region of the sorbent particle bed to another.

[0040] One specific goal when stenciling sorbent particle bed patterns on the CBS device substrate is to localize the liquid to the sorbent particle beds themselves. This provides a means for the liquid to travel along a predetermined route on the CBS device substrate. Localized flow routes may be achieved with channels cut into the CBS device substrate, or physical barriers (e.g., walls) built up onto the CBS device substrate surface and the sorbent particles filled within the resulting channels.

[0041] Localized flow routes may also be achieve by forming inherent liquid barriers between the sorbent particle bed and the substrate of the CBS device based on hydrophilic polarity differences, or in cases where a primer coating is first applied to the substrate, between the sorbent particle bed and the primer layer. Inherent liquid barriers may rely on a difference between the hydrophilic polarity between the sorbent bed and the underlying surface, where the polarity of the elution solvent is similar to the sorbent bed as compared to the underlying substrate. The elution solvent will then interact only with the particle bed and not flow into regions of negative space on the substrate.

[0042] A primer layer, which is chemically adhesive to the substrate and chemically adhesive to the sorbent particles, may enhance the bonding of the sorbent particle bed to the substrate. The primer may be chemically similar to the sorbent particles, thereby reducing any hydrophilic polarity difference.

[0043] Referring to FIG. 1A, in one embodiment, a method for forming a solid phase microextraction device 100 includes applying a first sorbent layer 102 including first sorbent particles 104 on a first planar surface 106 of a substrate 108. The solid phase microextraction device 100 may be a CBS device 110. The first planar 106 surface is defined by a base edge 112, a spray edge 114 disposed distal across the substrate 108 from the base edge 112, the spray edge 114 including a tapering tip 116 extending away from the base edge 112, a first lateral edge 118 extending from the base edge 112 to the tapering tip 116, and a second lateral edge 120 extending from the base edge 112 to the tapering tip 116, the second lateral edge 120 being disposed distal across the substrate 108 from the first lateral edge 118. The tapering tip 116 may terminate at a tip terminus 122. The tip terminus 122 may be an angular point, a rounded point, or combinations thereof. The first sorbent layer 102 extends a sampling length 124 from the spray edge 114 toward the base edge 112. Applying the first sorbent layer 102 on the first planar surface 106 includes at least one of screen printing, stencil printing, or applying by additive manufacturing the first sorbent particles 104 on the first planar surface 106.

[0044] Suitable dimensions for the solid phase microextraction device 100 include, but are not limited to, about 2.5 mm wide by about 42 mm long by about 0.35 mm thick.

[0045] The substrate 108 may be formed of any suitable material, including, but not limited to, stainless steel, wood, polymer, conductive polymer, metals, metal alloys, plastic-metal composites, or combinations thereof.

[0046] Applying the first sorbent layer 102 may include applying a slurry comprising the first sorbent particles 104, a binder, and a solvent. Applying the first sorbent layer 102 may further include removing the solvent by drying to form the first sorbent layer 102. Suitable sorbent particles include, but are not limited to, polymeric particles such as silica modified with C.sub.18 functional groups. Suitable sorbent particles may alternatively include any other sorbent particles known in the liquid chromatography, gas chromatography, or sample preparation arts may be used. Suitable binders include, but are not limited to, polyacrylonitrile, polydimethylsiloxane (“PDMS”), polyvinylidene difluoride (“PVDF”), copolymers of tetrafluoroethylene and 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole, NAFION, or combinations thereof.

[0047] The first sorbent particles 104 may include electrically conductive particles, magnetic particles, or both.

[0048] The first sorbent layer 102 may have any suitable composition, including, but not limited to, a composition including an organic polymer having a first bulk density of up to 1.5 g/cm.sup.3 and an inorganic material and having a second bulk density of at least 4.0 g/cm.sup.3.

[0049] Referring to FIG. 1B, in one embodiment, the first sorbent layer 102 is disposed over less than an entire width 126 of the first planar surface 106 from the first lateral edge 118 to the second lateral edge 120 along the sampling length 124. Alternatively, as seen in FIG. 1A, the first sorbent layer 102 may be disposed over the entire width 126 of the first planar surface 106 from the first lateral edge 118 to the second lateral edge 120 along the sampling length 124. The recession of the first sorbent layer 103 from the first lateral edge 118 and the second lateral edge 120 leaves exposed strips 138 of substrate 108 (or primer 128, if present) along the first sorbent layer 102.

[0050] Referring to FIG. 1C, in one embodiment, a primer layer 128 is disposed between the substrate 108 and the first sorbent layer 102. “Primer layer” may be used interchangeably with “protective layer.” The primer layer 128 may provide an intermediary layer to facilitate bonding of the first sorbent layer 102 to the substrate 108, particularly where the substrate 108 and the first sorbent layer 102 are incompatible or partially incompatible with one another. The primer layer 128 may also provide a protective layer to prevent samples from interacting with the underlying substrate 108 when the solid phase microextraction device 100 is immersed in a sample. In this way, the primer layer 128 may be advantageous in cases where the substrate 108 promotes undesirable adsorption of sample matrix or promotes undesired chemical reaction with elements of the sample. The composition of the primer layer 128 may include, but is not limited to, organic polymers, organic self-assembled monolayers, metal oxides, metals, metalloids, or combinations thereof, such as PAN, PDMS, PVDF, copolymers of tetrafluoroethylene and 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxole, NAFION, or combinations thereof. Application of the primer layer 128 to the substrate 108 may employ any coating techniques known in the art or the stenciling techniques herein described.

[0051] Referring to FIG. 1D, in one embodiment, the solid phase microextraction device 100 further includes a second sorbent layer 130 including second sorbent particles 132 disposed on a second planar surface 134 of the substrate 108 and extending from the spray edge 114 toward the base edge 112. The second sorbent particles 132 may be compositionally distinct from or identical to the first sorbent particles 104. As used herein, “compositionally distinct” includes the material composition of the sorbent particles themselves, the binder composition adhering the sorbent particles, the sorbent particle concentration per unit area of the sorbent layer, the mixture ratios of the different sorbent particles within a sorbent layer, or combinations thereof. The second sorbent layer 130 may be disposed over less than the entire width 136 of the second planar surface 134 from the first lateral edge 118 to the second lateral edge 118 along the sampling length 124 (shown) or over the entire width 136 of the second planar surface 134 from the first lateral edge 118 to the second lateral edge 118 along the sampling length 124 (not shown). Incorporation of different sorbent layers may provide selective chemical extraction of different analytes from a sample at the same time or provide application of different elution or ionization processes. Elution and analysis of the molecules captures in a first sorbent layer 102 and a second sorbent layer 130 may utilize a single elution solvent which is compatible with both, thereby contributing to a single analysis, or may utilize distinct elution solvents for each layer such that the elution solvents may be delivered in series or in parallel analysis methods.

[0052] Referring to FIG. 1E, in one embodiment, the solid phase microextraction device 100 further includes a second sorbent layer 130 including second sorbent particles 132 disposed on the first planar surface 106 and extending from the spray edge 114 toward the base edge 112, wherein the second sorbent particles 132 are compositionally distinct from the first sorbent particles 104. The first sorbent layer 102 and the second sorbent layer 130 together may be disposed over less than the entire width 126 (not shown) or over the entire width 126 (shown) of the first planar surface 106 from the first lateral edge 118 to the second lateral edge 120 along the sampling length 124. The two discreet sorbent layers may provide chemically selectively extraction of different analytes from the same sample at the same time. Subsequent elution and analysis may employ a single elution solvent that is compatible with both sorbent layers, where both layers concurrently contribute to a single analysis, or a first elution solvent compatible with the first sorbent layer 102 and a second elution solvent compatible with the second sorbent layer 130 with the elution solvents delivered either in series or in a parallel analysis methods.

[0053] Referring to FIG. 1F, in one embodiment, the solid phase microextraction device 100 has a first sorbent layer 102 including two finger regions 140 extending from the tapering tip 116. These finger regions 140 may serve as receptacles of the elution solvent which, after application, wicks to the tapering tip 116 and ultimately are sprayed into the mass spectrometer. These finger regions 140 may also provide for application of other liquids such as elution solvents containing internal standards, elution solvents containing reagents to increase target analyte(s) signal, or elution solvents with different physicochemical properties that facilitate elution of other analytes from the first sorbent layer 102.

[0054] Referring to FIG. 1G, in one embodiment, the first sorbent layer 102 includes an acute taper 142 relative to the tapering tip 116. In this manner, the acute taper 142 controls the focusing flow of the elution solvent to the tip terminus 122. The electric field required for generating the electrospray cone may be determined by the shape of the tapering tip 116 of the substrate 108.

[0055] Referring to FIG. 2, in one embodiment, the first sorbent layer 102 includes a first portion 200 including first sorbent particles 104 and a second portion 202 including second sorbent particles 132, the first sorbent particles 104 being compositionally distinct from the second sorbent particles 132. The first sorbent layer 102 may further include a third portion 204 including third sorbent particles 206, the third sorbent particles 206 being compositionally distinct from the first sorbent particles 104 and the second sorbent particles 132. The first portion 200 may be disposed between the spray edge 114 and each of the second portion 202 and the third portion 204. Each of the different portions of the first sorbent layer 102 may have different thicknesses or uniform thickness.

[0056] FIGS. 3A, 3B, and 3C depict photographs of three complex sorbent bed designs applied to solid phase microextraction devices 100. The sorbent compositions are mixtures of PAN and hydrophilic-lipophilic-balanced (“HLB”) particles (in FIG. 3A silver-coated hollow glass microspheres and in FIGS. 3B and 3C are hollow glass microspheres). Each photograph shows four replicate solid phase microextraction devices 100. FIG. 3A depicts a complex solid phase microextraction device 100 with two finger regions 140 similar to those described in FIGS. 1F and 2. The application of first portion 200 and second portion 202 were performed separately, using separate stencils with the final shape being the combination of the two layers. FIGS. 3B and 3C describe designs to control the flow of elution solvent along the first sorbent layer 102 as the solvent migrates to the tip terminus 122. In all three cases, the shape of the first sorbent layer 102 is defined by the first sorbent layer 102 itself and not the substrate 108.

[0057] FIG. 4 shows a solid phase microextraction device 100 having a primer layer 128 and a first sorbent layer 102. Magnified view 400 of the first sorbent layer 102 shows one sorbent particle type 402 immobilized into place with binder 404.

[0058] FIG. 5 shows a solid phase microextraction device 100 with two sorbent particle types immobilized in the first sorbent layer 102. Magnified view 400 of the first sorbent layer 102 shows one sorbent particle type 402 and a second particle type 500, both immobilized into place with binder 404.

[0059] FIG. 6 shows a solid phase microextraction device 100 with three sorbent particle types immobilized in the first sorbent layer 102. Magnified view 400 of the first sorbent layer 102 shows one sorbent particle type 402, a second particle type 500, and a third particle type 600 all immobilized into place with binder 404. FIG. 6 illustrates particles having grossly different sizes uniformly distributed throughout the first sorbent layer 102. The high viscosity, paste-like slurries employed with stenciling techniques may provide for homogeneous layers of grossly dissimilar particle sizes, concentration, and densities.

Examples

[0060] Comparative exemplary CBS devices 110 were prepared using a dip-coat technique.

[0061] Inventive CBS devices 110 of Examples 1-5 were stencil printed. For each such CBS device 110, the first planar surface 106 of a substrate 108 was roughened either by chemically etching the first planar surface 106 with HCl or by sand blasting the first planar surface 106 with silicon carbine grit. Surface profilometry measurements indicate both roughening techniques resulted in similar levels of roughness. The roughened substrates 108 were dip primed with the PAM/DMF stock solvent and heated to 150° C. for 2 minutes. The particle slurries were formulated with sorbent particles as described in Table 1.

[0062] Materials for Use in Manufacturing CBS Devices

TABLE-US-00001 Particle Size Particle Ranges Density Source 1 HLB Sorbent 5 μm Waters Particles 2 Hollow Glass 5-30 μm 0.1-0.7 g/cm.sup.3 Cospheric Micro-Spheres LLC (Santa Barbara, CA) 3 Hollow Glass 5-30 μm 0.72 g/cm.sup.3 Cospheric Micro-Spheres, LLC (Santa Silver Coated Silver Barbara, CA) Thickness: 50 Nm 4 Stainless Steel 1-22 μm 7.7-7.9 g/cm.sup.3 Cospheric Micro Spheres LLC (Santa Barbara, CA) 5 Superficially Porous Silica Particles

[0063] Stenciled particle bed shapes illustrated in FIGS. 3A 3B, and 3C were prepared using an HDI stencil system and heated to 150° C. for 2 minutes. The final bed thickness was approximately 30 μm. Visual inspection using a 10× magnification microscope showed uniform particle distribution for all particle types across the sorbent bed regions.

[0064] Equipment used includes a Model MSP-053 from Hary Manufacturing Inc. (Lebanon, N.J.) screen printer and 50 μm thick stainless steel 8″×10″ aluminum frame stencils from Hary Manufacturing Inc. (Lebanon, N.J.).

TABLE-US-00002 TABLE 1 CBS Devices Described in FIGS. 3A, 3B, and 3C and Manufactured Using Stenciling Techniques Herein Described Comparative Example Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 HLB particles 0.65 g 0.31 g 0.31 g 0.31 g 0.31 g 0.31 g Hollow Glass — —  0.5 g — — 0.15 g Micro-spheres Hollow Glass — — —  0.5 g — — Micro-Spheres, Silver Coated Stainless Steel — — — —  0.5 g 0.15 g Micro Spheres Figure — — 3C 3A 3B — Spray results Successful Successful Successful Successful Successful Successful Taylor cone Taylor cone Taylor cone Taylor cone Taylor cone Taylor cone emission to emission to emission to emission to emission to emission to MS inlet MS inlet MS inlet MS inlet MS inlet MS inlet

[0065] While the foregoing specification illustrates and describes exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.