Electrochemical sensor and method for manufacturing

Information

  • Patent Grant
  • 11150212
  • Patent Number
    11,150,212
  • Date Filed
    Thursday, September 1, 2016
    8 years ago
  • Date Issued
    Tuesday, October 19, 2021
    3 years ago
Abstract
The present disclosure relates to a sensor including an elongated member including at least a portion that is electrically conductive. The elongated member includes a sensing layer adapted to react with a material desired to be sensed. An insulating layer surrounds the elongated member. The insulating layer defines at least one access opening for allowing the material desired to be sensed to enter an interior region defined between the elongated member and the insulating layer. The insulating layer has an inner transverse cross-sectional profile that is different from an outer transverse cross-sectional profile of the elongated member. The difference in transverse cross-sectional profiles between the elongated member and the insulating layer provides channels at the interior region defined between the insulating layer and the elongated member. The channels extend generally along the length of the elongated member and are sized to allow the material desired to be sensed to move along the length of the sensor.
Description
TECHNICAL FIELD

The present disclosure relates to sensors for measuring bioanalytes and to methods for making such sensors.


BACKGROUND

Electrochemical bio-sensors have been developed for detecting analyte concentrations in a given fluid sample. For example, U.S. Pat. Nos. 5,264,105; 5,356,786; 5,262,035; 5,320,725; and 6,464,849, which are hereby incorporated by reference in their entireties, disclose wired enzyme sensors for detecting analytes such as lactate or glucose. Technology adapted for enhancing sensor miniaturization and durability is desirable.


SUMMARY

One aspect of the present disclosure relates to an electrochemical sensor including a sensing layer provided on an at least partially conductive fiber having a non-circular transverse cross-sectional profile.


Another aspect of the present disclosure relates to a sensor including an elongated member including at least a portion that is electrically conductive. The elongated member including a sensing layer adapted to react with a material desired to be sensed. An insulating layer surrounds the elongated member. The insulating layer defines at least one access opening for allowing the material desired to be sensed to enter an interior region defined between the elongated member and the insulating layer. The insulating layer has an inner transverse cross-sectional profile that is different from an outer transverse cross-sectional profile of the elongated member. The difference in transverse cross-sectional profiles between the elongated member and the insulating layer provides channels at the interior region defined between the insulating layer and the elongated member. The channels extend generally along the length of the elongated member and are sized to allow the material desired to be sensed to move along the length of the sensor.


A variety of additional inventive aspects will be set forth in the description that follows. The inventive aspects can relate to individual features and to combinations of features. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the broad inventive concepts upon which the embodiments disclosed herein are based.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a perspective view showing a sensing tip of a first sensor having features that are examples of inventive aspects in accordance with the principles of the present disclosure;



FIG. 2 is an end view showing the sensing tip of the sensor of FIG. 1;



FIG. 3 is a cross-sectional view taken along section-line 3-3 of FIG. 2;



FIG. 4 is a transverse cross-sectional view of a fiber used within the sensor of FIG. 1, the fiber is shown covered with a layer of sensing chemistry;



FIG. 5 is a schematic view of a sensor system incorporating the sensor of FIG. 1;



FIG. 6 is an end view showing the sensing tip of a second sensor having features that are examples of inventive aspects in accordance with the principles of the present disclosure;



FIG. 7 is a cross-sectional view taken along section line 7-7 of FIG. 6;



FIG. 8 is a schematic view of a sensor system incorporating the sensor of FIG. 6;



FIG. 9 is an end view showing the sensing tip of a third sensor having features that are examples of inventive aspects in accordance with the principles of the present disclosure;



FIG. 10 is a cross-sectional view taken along section-line 10-10 of FIG. 9;



FIG. 11 is a cross-sectional view taken along section line 11-11 of FIG. 10;



FIG. 12 is an end view showing the sensing tip of a fourth sensor having features that are examples of inventive aspects in accordance with the principles of the present disclosure;



FIG. 13 is a cross-sectional view taken along section-line 13-13 of FIG. 12;



FIG. 14 is a cross-sectional view taken along section line 14-14 of FIG. 13;



FIG. 15 shows a fifth sensor having features that are examples of inventive aspects in accordance with the principles of the present disclosure, the sensor is shown in cross-section along a section line that bisects a length of the sensor;



FIG. 16 is a cross-sectional view taken along section line 16-16 of FIG. 15;



FIG. 17 is a cross-sectional view taken along section line 17-17 of FIG. 15; and



FIG. 18 shows a sixth sensor having features that are examples of inventive aspects in accordance with the principles of the present disclosure, the sensor is shown in cross-section along a section line that is transverse with respect to the length of the sensor.





DETAILED DESCRIPTION

Reference will now be made in detail to exemplary aspects of the present disclosure which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.


The following definitions are provided for terms used herein:


A “working electrode” is an electrode at which the analyte (or a second compound whose level depends on the level of the analyte) is electrooxidized or electroreduced with or without the agency of an electron transfer agent.


A “reference electrode” is an electrode used in measuring the potential of the working electrode. The reference electrode should have a generally constant electrochemical potential as long as no current flows through it. As used herein, the term “reference electrode” includes pseudo-reference electrodes. In the context of the disclosure, the term “reference electrode” can include reference electrodes which also function as counter electrodes (i.e., a counter/reference electrode).


A “counter electrode” refers to an electrode paired with a working electrode to form an electrochemical cell. In use, electrical current passes through the working and counter electrodes. The electrical current passing through the counter electrode is equal in magnitude and opposite in sign to the current passing through the working electrode. In the context of the disclosure, the term “counter electrode” can include counter electrodes which also function as reference electrodes (i.e., a counter/reference electrode).


A “counter/reference electrode” is an electrode that functions as both a counter electrode and a reference electrode.


An “electrochemical sensing system” is a system configured to detect the presence and/or measure the level of an analyte in a sample via electrochemical oxidation and reduction reactions on the sensor. These reactions are transduced to an electrical signal that can be correlated to an amount, concentration, or level of an analyte in the sample. Further details about electrochemical sensing systems, working electrodes, counter electrodes and reference electrodes can be found at U.S. Pat. No. 6,560,471, that is hereby incorporated by reference in its entirety.


“Electrolysis” is the electrooxidation or electroreduction of a compound either directly at an electrode or via one or more electron transfer agents.


An “electron transfer agent” is a compound that carries electrons between the analyte and the working electrode, either directly, or in cooperation with other electron transfer agents. One example of an electron transfer agent is a redox mediator.


A “sensing layer” is a component of the sensor which includes constituents that facilitate the electrolysis of the analyte. The sensing layer may include constituents such as an electron transfer agent, a catalyst which catalyzes a reaction of the analyte to produce a response at the electrode, or both. In some embodiments, the sensing layer has a generally dry or non-hydrated state prior to use. In such embodiments, the sensing layer can be hydrated during use by water within the fluid sample being tested.



FIGS. 1-4 illustrate a sensor 20 having features that are examples of inventive aspects in accordance with the principles of the present disclosure. The sensor 20 includes an elongated member 22 having at least a portion that is electrically conductive and that functions as a working electrode. The elongated member 22 can include a sensing layer 24 that covers or is positioned adjacent to the working electrode. An insulating layer 26 surrounds the elongated member 22. The sensor 20 includes a sensing tip 28 at which the insulating layer 26 does not cover/enclose the elongated member 22 (e.g., the tip of the elongated member 22 is exposed). This open tip configuration provides an access opening 30 at the sensing tip 28 for allowing the material desired to be sensed to enter an interior region 32 of the sensor 20. The interior region 32 is defined between the elongated member 22 and the insulating layer 26. The sensor 20 also includes a base end 29 positioned opposite from the sensing tip 28.


Referring to FIG. 2, the insulating layer 26 has an inner transverse cross-sectional profile that is different from an outer transverse cross-sectional profile of the elongated member 22. For example, in the embodiment of FIGS. 1-4, the inner transverse cross-sectional profile of the insulating layer 26 is generally circular, while the outer transverse cross-sectional profile of the elongated member 22 is generally triangular. The difference in transverse cross-sectional profiles between the elongated member 22 and the insulating layer 26 provides channels 34 at the interior region 32 defined between the insulating layer 26 and the elongated member 22. The channels 34 extend generally along the length (i.e., generally along a central longitudinal axis 36 of the sensor 20) of the elongated member 22 and are sized to allow the material desired to be sensed to move through the interior region 32 along the length of the sensor 20. In other embodiments, the shapes could be reversed such that the cross-sectional profile of the insulating layer is generally triangular and the cross-sectional profile of the elongated member is generally circular. In other embodiments, other cross-sectional profile shapes (e.g., other multi-sided shapes such as squares, rectangles, pentagons, octagons, etc.) could be used.



FIG. 5 illustrates an electrochemical sensing system 40 that incorporates the sensor 20 of FIGS. 1-4. The working electrode of the elongated 10 member 22 is electrically connected to a wire 41 by a connector or hub 42 positioned at the base end 29 of the sensor 20. The wire 41 electrically connects the working electrode of the elongated member 22 to a controller 46. The controller 46 can be any type of controller such as a micro-controller, a mechanical controller, a software driven controller, a hardware driven controller, a firmware driven controller, etc. The controller can include a microprocessor that interfaces with memory. The controller 46 is also electrically connected to a counter electrode 48. In one embodiment, the counter electrode is only a counter electrode. In other embodiments, the counter electrode 48 can function as a counter/reference electrode and can include a layer of silver silver-chloride.


In use of the sensing system 40, the sensing tip 28 of the sensor 20 is immersed within a test volume 50 of a liquid sample (e.g., a blood sample) containing an analyte desired to be sensed. The sample may be an ex vivo or in vivo sample. The test volume 50 is the volume from which the analyte desired to be sensed can diffuse into the sensor 20 during the sensing period. With the sensor 20 so positioned, the liquid sample enters the channels 34 through the sensing tip 28 and can move along the lengths of the channels 34 (e.g., by capillary action) in a direction from the sensing tip 28 toward the base end 29. Water within the test volume 50 can diffuse into the sensing layer 24 such that the sensing layer 24 is hydrated. The analyte within the test volume 50 also diffuses into the sensing layer 24. A voltage potential is then applied between the counter electrode 48 and the working electrode. When the potential is applied, an electrical current will flow through the test volume 50 between the counter electrode 48 and the working electrode. The current is a result of the oxidation or reduction of the analyte in the test volume 50. This electrochemical reaction occurs via the electron transfer agent in the sensing layer 24 and the optional electron transfer catalyst/enzyme in the sensing layer 24. By measuring the current flow generated at a given potential, the concentration of a given analyte in the test sample can be determined. Those skilled in the art will recognize that current measurements can be obtained by a variety of techniques including, among other things, coulometric, potentiometric, amperometric, voltammetric, and other electrochemical techniques.


When the voltage potential is applied between the working and counter electrodes, the analyte within the interior region 32 reacts with the sensing layer 24 and is consumed. Thereafter, additional analyte from the test volume 50 diffuses into the interior region 32 through the open sensing tip 28. As the analyte enters the interior region 32, the analyte reacts with the portion of the sensing layer 24 located closest to the sensing tip 28 and is consumed before the analyte can migrate further into the sensor along the channels 34. In this way, the open tip configuration of the insulating layer 26 extends sensor life by limiting the amount of the sensor layer 24 that is exposed to the analyte at a given moment in time. Over time, the portion of the sensing layer 24 that is closest to the sensing tip 28 is depleted. When this occurs, the analyte is able to move further along the channels 32 (i.e., deeper into the sensor) to reach an active portion of the sensor layer 24. This process continues until the analyte depletes the sensing layer 24 along the entire lengths of the channels 34 and the life of the sensor ends. In this progression, the portion of the sensing layer 24 located at the deepest portion of the sensor (i.e., the interior region 32 closest to the base end 29) is the last portion of the sensing layer 24 to be depleted.


To oxidize or reduce the analyte, a potential (versus a reference potential) is applied across the working and counter electrodes. The minimum magnitude of the applied potential is often dependent on the particular electron transfer agent, analyte (if the analyte is directly oxidized or reduced at the electrode), or second compound (if a second compound, such as oxygen or hydrogen peroxide, whose level is dependent on the analyte level, is directly oxidized or reduced at the electrode). The applied potential usually equals or is more oxidizing or reducing, depending on the desired electrochemical reaction, than the redox potential of the electron transfer agent, analyte, or second compound, whichever is directly oxidized or reduced at the electrode. The potential at the working electrode is typically large enough to drive the electrochemical reaction to or near completion. When a potential is applied between the working electrode and the counter electrode, an electrical current will flow. The current is a result of the reduction or oxidation of the analyte or a second compound whose level is affected by the analyte. In one embodiment, the electrochemical reaction occurs via an electron transfer agent and the optional catalyst.


In certain embodiments, the elongated member 22 of the sensor 20 can include an electrically conductive wire or fiber. For example, the elongated member 22 can include a metal wire or a glassy carbon fiber. In a preferred embodiment shown at FIG. 4, the elongated member 22 has a composite structure and includes a fiber having a dielectric core 60 surrounded by a conductive layer 62 which forms the working electrode of the sensor 20. A preferred composite fiber is sold under the name Resistat® by Shakespeare Conductive Fibers LLC. This composite fiber includes a composite nylon monofilament conductive thread material made conductive by the suffusion of about a 1 micron layer of carbonized nylon isomer onto a dielectric nylon core material. The Resistat® material is comprised of isomers of nylon to create the basic 2 layer composite thread. However, many other polymers are available for the constmction such as: polyethylene terephthalate, nylon 6, nylon 6,6, cellulose, polypropylene cellulose acetate, polyacrylonitrile and copolymers of polyacrylonitrile for a first component and polymers such as of polyethylene terephthalate, nylon 6, nylon 6,6, cellulose, polypropylene cellulose acetate, polyacrylonitrile and copolymers of polyacrylonitrile as constituents of a second component. Inherently conductive polymers (ICP) such as doped polyanaline or polypyrolle can be incorporated into the conductive layer along with the carbon to complete the formulation. In certain embodiments, the ICP can be used as the electrode surface alone or in conjunction with carbon. The Resistat® fiber product is currently sold with a circular transverse cross-sectional profile. By post forming or extmding the Resistat® fiber, other transverse cross-sectional profiles (e.g., generally triangular) can be provided. The Resistat® fiber is availability in diameters of 0.0025 to 0.016 inches, which as suitable for sensors in accordance with the principles of the present disclosure. Example patents disclosing composite fibers suitable for use in practicing sensors in accordance with the principles of the present disclosure include U.S. Pat. Nos. 3,823,035; 4,255,487; 4,545,835 and 4,704,311, which are hereby incorporated by reference.


The sensing layer 24 preferably includes a sensing chemistry such as a redox compound or mediator. The term redox compound is used herein to mean a compound that can be oxidized or reduced. Exemplary redox compounds include transition metal complexes with organic ligands. Preferred redox compounds/mediators are osmium transition metal complexes with one or more ligands having a nitrogen containing heterocycle such as 2, 2′-bipyridine. The sensing material can also include a redox enzyme. A redox enzyme is an enzyme that catalyzes an oxidation or reduction of an analyte. For example, a glucose oxidase or glucose dehydrogenase can be used when the analyte is glucose. Also, a lactate oxidase or lactate dehydrogenase fills this role when the analyte is lactate. In systems such as the one being described, these enzymes catalyze the electrolysis of an analyte by transferring electrons between the analyte and the electrode via the redox compound. Further information regarding sensing chemistry can be found at U.S. Pat. Nos. 5,264,105; 5,356,786; 5,262,035; and 5,320,725, which were previously incorporated by reference in their entireties.


The insulating layer 26 of the sensor 20 preferably serves numerous functions to the sensor 20. For example, the insulating layer 26 preferably electrically insulates the elongated member 22. Additionally, the insulating layer 26 preferably provides mechanical strength for protecting the elongated member 22. Also, as described above, the insulating layer 26 preferably forms a barrier about the elongated member 22 that prevents the uncontrolled transport of a substance desired to be sensed (e.g., an analyte such as glucose or lactate) to the sensing layer 24. In one nonlimiting embodiment, the insulating layer 26 is made of a polymeric material such as polyimide, polyurethane or other materials. In certain embodiments, the insulating layer 26 can have a maximum outer dimension (e.g., an outer diameter) less than 0.02 inches. In other embodiments, the channels 34 defined between the elongated member 22 and the insulating layer 26 can each have a transverse cross-sectional area less than or equal to 26,000 square microns. In other embodiments, the ratio of perimeter arc section (defined by the inner diameter of the insulating layer 26) to chord length (defined by a side of the elongated member 22) is about 1.2:1.


It will be appreciated that the sensor 20 can be used for ex vivo or in vivo applications. In certain embodiments, the sensor 20 can be incorporated into a peripheral catheter to provide on-line monitoring of bioanalytes in the same manner described in U.S. Pat. No. 6,464,849, that was previously incorporated by reference herein.



FIGS. 6 and 7 show a second electro-chemical sensor 120 having features that are examples of inventive aspects in accordance with the principles of the present disclosure. The sensor 120 has the same configuration as the sensor of FIGS. 1-4, except a counter electrode 148 has been provided at the outer surface of the insulating layer 26. It will be appreciated that the counter electrode can only function as a counter electrode, or could also function as a counter/reference electrode. The counter electrode 148 is made of an electrically conductive material coated or otherwise provided about the exterior of the insulation layer 26. In the case where the counter electrode functions as a counter reference electrode, the electrode 148 is formed by depositing silver silver-chloride about the exterior of the insulating layer 26.



FIG. 8 shows an electrical sensing system 140 that incorporates the sensor 120 of FIGS. 6 and 7. The working electrode of the sensor 120 is electrically connected to a wire 141 by a hub 142 positioned at a base end of the sensor 120. The wire 141 electrically connects the working electrode of the sensor 120 to a controller 146. The hub 142 also electrically connects the counter electrode 148 to a wire 143 that electrically connects the counter electrode 148 to the controller 146. As shown at Figure 8, the open sensing tip of the sensor 120 is shown within a test sample 50.



FIGS. 9-11 show a third electro-chemical sensor 220 having features that are examples of inventive aspects in accordance with the principles of the present disclosure. The sensor 220 has the same construction as the sensor 20 of FIGS. 1-4, except a stop arrangement 210 has been provided within the interior region 32 to limit the distance the sample fluid can move along the length of the sensor 220. The stop arrangement 210 includes blocking portions 211 that fill the channels 34 at a desired location so that sample fluid flow is prevented from moving past the stop arrangement 210. As shown in FIG. 10, the stop arrangement 210 prevents the test fluid from flowing within the channels 34 for a distance greater than a length L. In one embodiment, the blocking elements 211 are made of a material such as polytetrafluoroethylene that allows air to pass through the stop arrangement but does not allow fluid to pass through the stop arrangement.



FIGS. 12-14 show a fourth sensor 320 having features that are examples of inventive aspects in accordance with the principles of the present disclosure. The sensor 320 has the same construction as the sensor 20 of FIGS. 1-4, except a crimp 310 has been provided around the exterior of the sensor 320 to limit the length L that a fluid desired to be tested can flow into the sensor 320. The crimp 310 causes the insulating layer 26 to be compressed against the elongated member 22 thereby closing the channels 34 at the crimp location 310. Air holes can be formed through the insulating layer 26 adjacent the crimp location 310 to allow air to exit the channels 34 when the channels 34 are being filled with test fluid. It will be appreciated that the holes are preferably small enough to prevent the passage of the sample fluid therethrough.



FIGS. 15-17 show a fifth sensor 420 having features that are examples of inventive aspects in accordance with the principles of the present disclosure. The sensor 420 has the same general configuration as the sensor 120 of FIGS. 6 and 7, except the insulating layer 26 is integrally formed with a connector hub 414. The connector hub 414 has an opening 415 that is coaxially aligned with the inner diameter of the insulating layer 26. One end 417 of the opening 414 is tapered to facilitate inserting the elongated member 22 into the insulating layer 26. The connector hub 414 also includes integral stops 416 that fit within the channels 34 and function to prevent a sample fluid from moving within the sensor 420 a distance greater than L. As shown at FIG. 15, a controller is electrically connected to the counter and working electrodes through the connector hub 414.



FIG. 18 shows a sixth sensor 520 having features that are examples of inventive aspects in accordance with the principles of the present disclosure. The sensor 620 has the same configuration as the sensor 120 of FIGS. 6 and 7, except the working electrode has been split into three separate working electrodes 121a, 121b, 121c each corresponding to a separate channel of the sensor 520. Each of the working electrodes is provided on one side of the elongated member 22 and each working electrode is separately connected to the controller. The controller is also electrically connected to an integral counter electrode 148 provided about the insulating layer 26. The separate working electrodes can be used to detect different types of substances/materials and can be coated with the appropriate sensing layers 124a, 124b, 124c. For example, the working electrodes could be used to detect oxygen levels, lactate levels, glucose levels, catecholine levels or other material levels in a test sample and can be coated with sensing layers suitable for detecting these materials. In still other embodiments, one of the working electrodes could be used as a temperature sensor.


To manufacture sensors in accordance with the principles of the present disclosure, a conductive fiber (e.g., a Resistat(r) conductive fiber) is extruded or post-formed to have a desired cross sectional profile (e.g., triangular). As used herein, the term fiber includes threads, filaments, monofilaments, and other like elongated structures. The surface of the fiber is then cleaned (e.g., with an ultrasonic cleaner or degreaser), rinsed and dried. The surface can then be treated to improve its hydrophilic properties and/or can be activated with a plasma. Thereafter, the shaped fiber is passed through sequential coating stations by means of a reel to reel continuous process. At each station successive layers of sensor chemistry are applied uniformly as thin films and cured prior to entering the next station. The processed fiber is collected on storage reels for use in the succeeding step. Estimated process time is ˜20 feet per minute yielding ˜24,000 sub-component fibers per hour.


The cured length of fiber is collected on reels then supplied as feed stock to an assembly process where the fiber is first caused to enter a small thermoplastic molded hub (e.g., connector hub 414 of FIG. 15) having a tapered opening on one end capable of guiding the fiber preferably into an integral polyimide tube that is fixed to the opposing face of the fiber entry point and that forms the insulating layer of the sensor. The exterior of the tube 26 may be coated by various means with Ag/AgCl in order to provide an integral reference electrode 148 in concert with the working electrode of the internal fiber. In certain embodiments, the Ag/AgCl can be coated directly, or the part can be coated with Ag and then converted to an Ag/AgCl coating by oxidation of the Ag in a high Cl containing electrolyte. The connector hub can be secured to the fiber by means of sonic or induction weld to the fiber. The connector hub can include electrical connections to the working and counter electrodes and can include contact points on the connector hub that will later provide interconnection to a transmitter or output wires according to the application requirement in concert with contacts from the reference electrode. Finally, the fiber is cut to length in place within the insulator tube 26.


Suitable fixtures and “pick and place” robotics can be used to intermittently feed the fiber into the short (e.g., 10 millimeter) hub and tube component, perform the cutting operation and place the completed sensor into carrier pallets for final assembly and packaging.


The various aspects disclosed herein provide numerous advantages. For example, the use of a chemically coated fiber covered by a separate insulator tube that is not adhered to the fiber allows for both structural enhancement and additional design flexibility. Also, the use of composite fiber as compared to pure glassy carbon fibers improves sensor durability and flexibility. Further, by using channels defined between the elongated member and the insulating layer, rapid hydration is possible thereby reducing the time required to activate the sensor. Further, the use of a fiber with an inert/dielectric core assists in blocking potential signal interference that might otherwise occur at the end of the fiber. Moreover, the cross sectional shape of the fiber/insulator interface profile is preferably not concentric but is of differing geometry, typically having multiple sides separated by angles (e.g., triangular, square, rectangular, pentagonal, hexagonal, etc). This configuration provides distinct multiple ports or channels which allow for providing different working electrodes associated with each port or channel. Using angular shaped fibers also provides limited points of contact around the insulator tube interior that both locate the fiber centrally within the tube—thus defining the port openings, as well as create minimal frictional contact between tube and fiber for ease of making a telescoping assembly of the two components. Limited point contacts also act as to prevent damage to the fragile chemistry coating from sliding surfaces between the fiber and the inner tube wall when mated in this fashion. The limited contact points also protect the sensor chemistry after assembly. For example, when the sensor is bent causing relative axial movement between the insulating layer and the conductive fiber, only the corners are subject to friction between the insulating layer and the fiber.


From the foregoing detailed description, it will be evident that modifications and variations can be made without departing from the spirit or scope of the broad inventive aspects embodied in the embodiments disclosed herein. For example, any of the embodiments disclosed herein can use separate reference and counter electrodes instead of combined counter/reference electrodes.

Claims
  • 1. A sensor comprising: a tubular body comprising a wall circumscribing a hollow interior extending along a length of the tubular body;a member comprising a dielectric core having a non-circular transverse cross-sectional profile and extending along a longitudinal axis inside the hollow interior, the member having a chordal side contacting the wall of the tubular body at rounded contact locations circumferentially spaced from each other along the wall, the dielectric core defining a first planar surface extending along the chordal side, the first planar surface facing outwardly from the longitudinal axis towards the wall of the tubular body, the member cooperating with the tubular body to define a first channel between the first planar surface of the dielectric core and the wall of the tubular body, and a second channel between a second surface of the dielectric core and the wall of the tubular body; anda first electrode and a second electrode, the first electrode comprising a working electrode formed by an electrically conductive layer disposed on the first planar surface, the electrically conductive layer having a uniform thickness and conforming to the first planar surface, the working electrode having a planar exterior side facing the wall of the tubular body, the first channel being sized to allow a material desired to be sensed to move through the first channel by capillary action to access the planar exterior side of the working electrode.
  • 2. The sensor of claim 1, wherein the second electrode is disposed on the second surface and is separate from the first electrode.
  • 3. The sensor of claim 1, wherein the channels extend at least partially along a length of the member.
  • 4. The sensor of claim 1, wherein the tubular body defines an open tip leading to the hollow interior.
  • 5. The sensor of claim 1, wherein the chordal side is a first side, wherein the second surface is defined along a second side of the dielectric core, wherein the dielectric core includes a third side, and wherein a third channel is defined between the third side of the dielectric core and the wall of the tubular body.
  • 6. The sensor of claim 1, wherein the channels are accessible through an open tip of the tubular body.
  • 7. The sensor of claim 1, further comprising a sensing layer disposed on the working electrode, the sensing layer including sensing chemistry.
  • 8. The sensor of claim 7, wherein the sensing chemistry is configured to sense lactate.
  • 9. The sensor of claim 7, wherein the sensing chemistry comprises an enzyme.
  • 10. The sensor of claim 7, wherein the sensing chemistry comprises a mediator.
  • 11. The sensor of claim 1, wherein the dielectric core comprises a plastic material.
  • 12. The sensor of claim 7, wherein the tubular body comprises an insulating layer at least partially enclosing the member and the sensing chemistry.
  • 13. The sensor of claim 7, wherein the sensing chemistry is configured to sense glucose.
  • 14. The sensor of claim 1, wherein the second surface of the dielectric core faces outwardly from the longitudinal axis towards the wall of the tubular body.
  • 15. The sensor of claim 14, wherein the second surface is flat.
  • 16. The sensor of claim 1, wherein the hollow interior has a diameter; and wherein the chordal side has a width extending transverse to the longitudinal axis, the width being a majority of the diameter.
  • 17. The sensor of claim 1, wherein the dielectric core has a triangular shape.
  • 18. The sensor of claim 1, wherein the tubular body provides a counter electrode.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 14/257,727, filed Apr. 21, 2014, now U.S. Pat. No. 9,459,228, issued Oct. 4, 2016, which is a continuation of U.S. patent application Ser. No. 12/674,858, filed Apr. 18, 2011, now U.S. Pat. No. 8,702,932, issued Apr. 22, 2014, which is a 371 of PCT/US2008/074644, filed Aug. 28, 2008, which claims the benefit of U.S. Provisional Patent Application Ser. No. 60/969,034, filed Aug. 30, 2007, which applications are hereby incorporated by reference in their entireties.

US Referenced Citations (236)
Number Name Date Kind
1454224 Schmidt May 1923 A
2291720 Hukle Aug 1942 A
3170968 Rokunohe et al. Feb 1965 A
3766910 Lake Oct 1973 A
3823035 Sanders Jul 1974 A
4008717 Kowarski Feb 1977 A
4073974 Albarino et al. Feb 1978 A
4224125 Nakamura et al. Sep 1980 A
4255487 Sanders Mar 1981 A
4321057 Buckles Mar 1982 A
4399099 Buckles Aug 1983 A
4439303 Cocchi Mar 1984 A
4545283 Sandberg et al. Oct 1985 A
4545382 Higgins et al. Oct 1985 A
4545835 Gusack et al. Oct 1985 A
4552840 Riffer Nov 1985 A
4573968 Parker Mar 1986 A
4640821 Mody et al. Feb 1987 A
4671288 Gough Jun 1987 A
4704311 Pickering et al. Nov 1987 A
4734184 Burleigh et al. Mar 1988 A
4762603 Morin Aug 1988 A
4805624 Yao et al. Feb 1989 A
4820399 Senda et al. Apr 1989 A
4824206 Klainer et al. Apr 1989 A
4833083 Saxena May 1989 A
4846548 Klainer Jul 1989 A
4880752 Keck et al. Nov 1989 A
4908115 Morita et al. Mar 1990 A
4919649 Timothy et al. Apr 1990 A
4927516 Yamaguchi et al. May 1990 A
4945896 Gade Aug 1990 A
4974929 Curry Dec 1990 A
4981779 Wagner Jan 1991 A
5001054 Wagner Mar 1991 A
5002651 Shaw et al. Mar 1991 A
5004583 Guruswamy et al. Apr 1991 A
RE33677 Vazirani Aug 1991 E
5047044 Smith et al. Sep 1991 A
5112455 Cozzette et al. May 1992 A
5131138 Crouse Jul 1992 A
5164229 Hay et al. Nov 1992 A
5165406 Wong Nov 1992 A
5165407 Wilson et al. Nov 1992 A
5171689 Kawaguri et al. Dec 1992 A
5186808 Yamaguchi et al. Feb 1993 A
5205920 Oyama et al. Apr 1993 A
5217533 Hay et al. Jun 1993 A
5220920 Gharib Jun 1993 A
5243982 Möstl et al. Sep 1993 A
5244636 Walt et al. Sep 1993 A
5250264 Walt et al. Oct 1993 A
5262035 Gregg et al. Nov 1993 A
5264092 Skotheim et al. Nov 1993 A
5264103 Yoshioka et al. Nov 1993 A
5264104 Gregg et al. Nov 1993 A
5264105 Gregg et al. Nov 1993 A
5269891 Colin Dec 1993 A
5271815 Wong Dec 1993 A
5271820 Kinlen et al. Dec 1993 A
5277872 Bankert et al. Jan 1994 A
5286362 Hoenes et al. Feb 1994 A
5298144 Spokane Mar 1994 A
5298741 Walt et al. Mar 1994 A
5320725 Gregg et al. Jun 1994 A
5320814 Walt et al. Jun 1994 A
5330634 Wong et al. Jul 1994 A
5356786 Heller et al. Oct 1994 A
5366527 Amos et al. Nov 1994 A
5372133 Hogen esch Dec 1994 A
D354347 Knute et al. Jan 1995 S
D354559 Knute et al. Jan 1995 S
5384028 Ito Jan 1995 A
5386828 Owens et al. Feb 1995 A
5395504 Saurer et al. Mar 1995 A
5422246 Koopal et al. Jun 1995 A
5431174 Knute Jul 1995 A
5437973 Vadgama et al. Aug 1995 A
5503728 Kaneko et al. Apr 1996 A
5505828 Wong et al. Apr 1996 A
5512159 Yoshioka et al. Apr 1996 A
5515848 Corbett et al. May 1996 A
5543012 Watson et al. Aug 1996 A
5575403 Charlton et al. Nov 1996 A
5591139 Lin et al. Jan 1997 A
5593852 Heller et al. Jan 1997 A
5605152 Slate et al. Feb 1997 A
5609749 Yamauchi et al. Mar 1997 A
5645710 Shieh Jul 1997 A
5656241 Seifert et al. Aug 1997 A
5704354 Preidel et al. Jan 1998 A
5720924 Eikmeier et al. Feb 1998 A
5777060 Van Antwerp Jul 1998 A
5800350 Coppleson et al. Sep 1998 A
5810199 Charlton et al. Sep 1998 A
5814601 Winslow et al. Sep 1998 A
5849415 Shalaby et al. Dec 1998 A
5863800 Eikmeier et al. Jan 1999 A
5900215 Seifert et al. May 1999 A
5951764 Hay et al. Sep 1999 A
5971941 Simons et al. Oct 1999 A
5972199 Heller et al. Oct 1999 A
5982959 Hopenfeld Nov 1999 A
5997501 Gross et al. Dec 1999 A
6004818 Freilich et al. Dec 1999 A
6036924 Simons et al. Mar 2000 A
6044665 Lysson et al. Apr 2000 A
6048352 Douglas et al. Apr 2000 A
D424696 Ray et al. May 2000 S
D426638 Ray et al. Jun 2000 S
6071294 Simons et al. Jun 2000 A
6071391 Gotoh et al. Jun 2000 A
6083710 Heller et al. Jul 2000 A
6099484 Douglas et al. Aug 2000 A
6103033 Say et al. Aug 2000 A
6103199 Bjornson et al. Aug 2000 A
6104940 Watanabe et al. Aug 2000 A
6107083 Collins et al. Aug 2000 A
6120676 Heller et al. Sep 2000 A
6143164 Heller et al. Nov 2000 A
6241863 Montbouquette Jun 2001 B1
6299757 Feldman et al. Oct 2001 B1
6329161 Heller et al. Dec 2001 B1
6338790 Feldman et al. Jan 2002 B1
6349229 Watanabe et al. Feb 2002 B1
6375627 Mauze et al. Apr 2002 B1
6379317 Kintzig et al. Apr 2002 B1
6461496 Feldman et al. Oct 2002 B1
6464849 Say et al. Oct 2002 B1
6484045 Holker et al. Nov 2002 B1
6500144 Russell et al. Dec 2002 B1
6503381 Gotoh et al. Jan 2003 B1
6560471 Heller et al. May 2003 B1
6561989 Whitson May 2003 B2
6576101 Heller et al. Jun 2003 B1
6576102 Rappin et al. Jun 2003 B1
6591125 Buse et al. Jul 2003 B1
6592745 Feldman et al. Jul 2003 B1
6607658 Heller et al. Aug 2003 B1
6610978 Yin et al. Aug 2003 B2
6616819 Liamos et al. Sep 2003 B1
6618934 Feldman et al. Sep 2003 B1
6620112 Klitmose Sep 2003 B2
6676816 Mao et al. Jan 2004 B2
6706159 Moerman et al. Mar 2004 B2
6707554 Miltner et al. Mar 2004 B1
6740214 Dobson et al. May 2004 B1
6749740 Liamos et al. Jun 2004 B2
6783502 Orloff et al. Aug 2004 B2
6840912 Kloepfer et al. Jan 2005 B2
6881551 Heller et al. Apr 2005 B2
6892085 McIvor et al. May 2005 B2
6893545 Gotoh et al. May 2005 B2
6965791 Hitchcock et al. Nov 2005 B1
7008799 Zimmer et al. Mar 2006 B1
7058437 Buse et al. Jun 2006 B2
7211437 Schabbach et al. May 2007 B2
7264139 Brickwood et al. Sep 2007 B2
7282705 Brennen Oct 2007 B2
7299081 Mace et al. Nov 2007 B2
7322942 Roe Jan 2008 B2
7335294 Heller et al. Feb 2008 B2
7344499 Prausnitz et al. Mar 2008 B1
7378007 Moerman et al. May 2008 B2
7396334 Kuhr et al. Jul 2008 B2
7585278 Aceti et al. Sep 2009 B2
7723099 Miller et al. May 2010 B2
7740581 Buse et al. Jun 2010 B2
7828749 Douglas et al. Nov 2010 B2
7829023 Burke et al. Nov 2010 B2
7860544 Say et al. Dec 2010 B2
8702932 Say Apr 2014 B2
8828200 Marquant et al. Sep 2014 B2
9044178 Say Jun 2015 B2
9459228 Say Oct 2016 B2
9746440 Say Aug 2017 B2
20020040208 Flaherty et al. Apr 2002 A1
20020061589 King et al. May 2002 A1
20020098124 Bentsen et al. Jul 2002 A1
20030083686 Freeman et al. May 2003 A1
20030211619 Olson et al. Nov 2003 A1
20040087033 Schembri May 2004 A1
20040102717 Qi May 2004 A1
20040236251 Roe et al. Nov 2004 A1
20050004438 Ward et al. Jan 2005 A1
20050023137 Bhullar et al. Feb 2005 A1
20050067737 Rappin et al. Mar 2005 A1
20050089944 Shieh et al. Apr 2005 A1
20050143635 Kamath et al. Jun 2005 A1
20050196747 Stiene Sep 2005 A1
20050197548 Dietiker Sep 2005 A1
20050238537 Say et al. Oct 2005 A1
20060241517 Fowler et al. Oct 2006 A1
20070027384 Brister Feb 2007 A1
20070027385 Brister et al. Feb 2007 A1
20070093704 Brister et al. Apr 2007 A1
20070123803 Fujiwara et al. May 2007 A1
20070149897 Ghesquiere et al. Jun 2007 A1
20070197889 Brister et al. Aug 2007 A1
20070199818 Petyt et al. Aug 2007 A1
20070218281 Demir et al. Sep 2007 A1
20070261958 Jiang et al. Nov 2007 A1
20080017645 Garagiola Jan 2008 A1
20080097546 Powers et al. Apr 2008 A1
20080167578 Bryer et al. Jul 2008 A1
20080319314 Hill et al. Dec 2008 A1
20090021901 Stothers Jan 2009 A1
20090032760 Muscatell Feb 2009 A1
20090062767 Van Antwerp et al. Mar 2009 A1
20090069654 Yasuzawa Mar 2009 A1
20090178923 Marquant et al. Jul 2009 A1
20090257917 Nakamura et al. Oct 2009 A1
20100018869 Feldman et al. Jan 2010 A1
20100018871 Feldman et al. Jan 2010 A1
20100051479 Heller et al. Mar 2010 A1
20100059372 Heller et al. Mar 2010 A1
20100059373 Heller et al. Mar 2010 A1
20100072063 Heller et al. Mar 2010 A1
20100072064 Heller et al. Mar 2010 A1
20100326842 Mazza et al. Dec 2010 A1
20110028815 Simpson et al. Feb 2011 A1
20110086373 Wallace-Davis et al. Apr 2011 A1
20110172559 Fei et al. Jul 2011 A1
20110180405 Chinnayelka et al. Jul 2011 A1
20110189762 Say Aug 2011 A1
20110203941 Say Aug 2011 A1
20110265944 Say Nov 2011 A1
20110266149 Say Nov 2011 A1
20110270061 Say Nov 2011 A1
20120046533 Voskanyan et al. Feb 2012 A1
20120291254 Say Nov 2012 A1
20130225957 Kawamoto Aug 2013 A1
20140318988 Say Oct 2014 A1
20150251174 Ma Sep 2015 A1
20150313521 Say Nov 2015 A1
20180106750 Say Apr 2018 A1
Foreign Referenced Citations (45)
Number Date Country
2050677 Mar 1992 CA
4105222 Aug 1992 DE
20009392 Nov 2000 DE
101 12 384 Sep 2002 DE
10 2004 060 742 Jul 2006 DE
0 256 415 Feb 1988 EP
0 327 658 Aug 1989 EP
0 409 033 Jan 1991 EP
0 420 296 Apr 1991 EP
0 567 725 Nov 1993 EP
0 592 805 Apr 1994 EP
0 710 835 May 1996 EP
0 792 620 Sep 1997 EP
0 965 301 Dec 1999 EP
1 462 775 Dec 2007 EP
64-3552 Jan 1989 JP
1-153952 Jun 1989 JP
1-263537 Oct 1989 JP
4-279854 Oct 1992 JP
6-174946 Jun 1994 JP
8-107890 Apr 1996 JP
2007-202632 Aug 2007 JP
WO 8907139 Aug 1989 WO
9010861 Sep 1990 WO
WO 9115993 Oct 1991 WO
WO 9410553 May 1994 WO
WO 9606947 Mar 1996 WO
WO 9622730 Aug 1996 WO
WO 9639616 Dec 1996 WO
WO 9715827 May 1997 WO
WO 0035340 Jun 2000 WO
WO 2005051183 Jun 2005 WO
2007037970 Apr 2007 WO
WO 2007091633 Aug 2007 WO
WO 2008017645 Feb 2008 WO
2008118919 Oct 2008 WO
WO 2009032760 Mar 2009 WO
WO 2009051901 Apr 2009 WO
WO 2010056869 May 2010 WO
WO 2010056876 May 2010 WO
WO 2010056878 May 2010 WO
2011003039 Jan 2011 WO
20121043051 Apr 2012 WO
2012106060 Aug 2012 WO
2014025430 Feb 2014 WO
Non-Patent Literature Citations (19)
Entry
European Search Report for 09826755.2 dated Oct. 5, 2012.
Gough et al., “Short-term In Vivo operation of a glucose sensor,” A.S.A.I.O. Transactions (1986) 32 (1): 148-150.
International Search Report and Written Opinion for PCT/US2008/074649 dated Apr. 20, 2009.
International Search Report and Written Opinion for PCT/US2008/074644 dated May 14, 2009.
International Search Report and Written Opinion for PCT/US2009/064216 dated May 3, 2010.
International Search Report and Written Opinion for PCT/US2009/064225 dated May 4, 2010.
International Search Report and Written Opinion for PCT/US2009/064228 dated Jul. 1, 2010.
Jaraba et al., “NADH amperometric sensor based on poly(3-methylthiophene)-coated cylindrical carbon fiber microelectrodes: application to the enzymatic determination of L-lactate,” Electrochimica Acta. (1998) 43 (23): 3555-3565.
Netchiporouk et al., “Properties of carbon fibre microelectrodes as a basis for enzyme biosensors,” Analytica Chimica Acta (1995) 303: 275-283.
Sakslund et al, “Analysis of the factors determining the sensitivity of a miniaturized glucose biosensor made by codeposition of palladium and glucose oxidase onto an 8 μm carbon filter,” Journal of Electroanalytical Chemistry (1996) 402: 149-160.
Sakslund et al., “Development and evaluation of glucose microsensors based on electrochemical codeposition of ruthenium and glucose oxidase onto carbon fiber microelectrodes,” Journal of Electroanalytical Chemistry (1995). 397: 149-155.
Chinese Office Action and English translation thereof, Application No. 201380069383.1, dated Aug. 15, 2017, 18 pages.
European Search Report for corresponding European Patent Application No. 13860026.7, dated Dec. 23, 2016.
Extended European Search Report for Application No. 15802478.6, dated Feb. 22, 2018.
Hoey et al., “A Review on Aerosol-Based Direct-Write and Its Applications for Microelectronics,” Journal of Nanotechnology, vol. 2012, Article ID 324380, 22 pages (2012).
International Search Report and Written Opinion for PCT/US2013/072846 dated Mar. 26, 2014.
Marinov et al., “Direct-Write Vapor Sensors on FR4 Plastic Substrates,” IEEE Sensors Journal, vol. 7, No. 6, pp. 937-944 (Jun. 2007).
Young et al., “Future Opportunities for Advancing Glucose Test Device Electronics,” Journal of Diabetes Science and Technology, vol. 5, Issue 5, pp. 1077-1086 (Sep. 2011).
Zhang, “Printed Electronics: Manufacturing Technologies and Applications Presentation Outline Introduction to Georgia Tech Manufacturing Institute Overview of printed electronics technology and applications Aerosol Jet Printing (AJP) process Application case studies,” 54 pages (May 12, 2014).
Related Publications (1)
Number Date Country
20170067845 A1 Mar 2017 US
Provisional Applications (1)
Number Date Country
60969034 Aug 2007 US
Continuations (2)
Number Date Country
Parent 14257727 Apr 2014 US
Child 15254423 US
Parent 12674858 US
Child 14257727 US