THERMAL MECHANISM TO PREVENT REPROCESSING OR REUSE OF MECHANICAL SURGICAL DEVICES

Abstract

A surgical apparatus comprising: a mechanism that is configured to perform an operational motion of the surgical apparatus; and at least one transformation member having an original shape and a deformed shape, the at least one transformation member connecting the mechanism together, when the at least one transformation member is in the deformed shape so that the mechanism is capable of performing the operational motion; and wherein after the transformation member is subject a transition temperature, the at least one transformation member changes from the deformed shape to the original shape and disengages a portion of the mechanism so that the mechanism is prevented from performing the operational motion.

Claims

1. A surgical apparatus comprising: a mechanism configured to perform an operational motion of the surgical apparatus; at least one transformation member configured to respond to exposure to a transition temperature by deforming to inhibit the mechanism from performing the operational motion; and at least one pre-load component, configured to be removable before a first use of the surgical apparatus, that is arranged to inhibit deformation of the at least one transformation member before removal of the at least one pre-load component.

2. The surgical apparatus of claim 1, wherein the mechanism includes at least one of a gear, a housing, a pin, a universal joint, a link, a sliding member, a stationary member, a transformation member, a pivot pin, a guideway, a crank, a connecting rod, a connection, a bevel gear, a gear, a spur gear, a shaft, a cross-journal, or a combination of any of these.

3. The surgical apparatus of claim 2, wherein the mechanism is the bevel gear having a first gear and a second gear and the transformation member is a pin that aligns the first gear in a perpendicular position relative to the second gear and when the pin is deformed, the first gear is misaligned with the second gear and the bevel gear no longer functions.

4. The surgical apparatus of claim 2, wherein the mechanism is the spur gear having a first gear and a second gear and the transformation member is a pin aligns the first gear in a parallel axial orientation with the second gear such that first gear operatively couples with the second gear and wherein when the pin is deformed, the first gear is misaligned with the second gear and the spur gear no longer functions.

5. The surgical apparatus of claim 2, wherein the mechanism is the housing, wherein when the transformation member is deformed, the housing falls apart.

6. The surgical apparatus of claim 2, wherein the mechanism is the universal joint having a first shaft and a second shaft, wherein a cross-journal couples the first shaft with the second shaft when the transformation aligns the first shaft with the second shaft in a coaxial orientation and wherein when the transformation member is deformed, the universal joint no longer functions.

7. The surgical apparatus of claim 1, wherein at least a portion of the transition member includes a shape-memory material.

8. The surgical apparatus of claim 1, wherein the pre-load component includes at least one of a pin, a wire, or a flat or shaped plate.

9. The surgical apparatus of claim 1, wherein the pre-load component is arranged to support the transformation member during an initial thermal event at or exceeding a transition temperature to inhibit deformation during an initial sterilization at manufacturing or packaging of the surgical apparatus.

10. The surgical apparatus of claim 1, wherein the preload component includes at least one of a metal, a polymer, or a ceramic.

11. A method of forming a surgical apparatus comprising: providing a mechanism having a first element and a second element configured to perform an operational motion of the surgical apparatus; coupling the first element with the second element with at least one transformation member configured to respond to exposure to a transition temperature by deforming to inhibit the mechanism from performing the operational motion; providing at least one pre-load component, configured to be removable before a first use of the surgical apparatus, that is arranged to inhibit deformation of the at least one transformation member before removal of the at least one pre-load component; and subjecting the mechanism and the transformation member to a heating process.

12. The method of claim 11, the method further comprising removing the pre-load component prior to an initial use of the surgical apparatus.

13. The method of claim 11, wherein the pre-load component is one of a pin, a wire, a flat or shaped plate and is formed from a metal, a polymer, or a ceramic.

14. The method of claim 11, wherein the pre-load component is configured to support the transformation member during the initial heating process.

15. The method of claim 11, wherein the heating process is a sterilization.

16. A surgical apparatus comprising: a mechanism configured to perform an operational motion of the surgical apparatus, the mechanism including a first gear operatively coupled to a second gear; at least one transformation member configured to respond to exposure to a transition temperature by deforming to inhibit the mechanism from performing the operational motion, the pin aligning the first gear with the second gear; and at least one pre-load component, configured to be removable before a first use of the surgical apparatus, that is arranged to inhibit deformation of the at least one transformation member before removal of the at least one pre-load component.

17. The surgical apparatus of claim 16, wherein the first and second gears are a bevel gear and the transformation member is a pin that aligns the first gear in a perpendicular orientation.

18. The surgical apparatus of claim 17, wherein when the pin is deformed, the bevel gear no longer functions.

19. The surgical apparatus of claim 16, wherein the first and second gears are a spur gear and the transformation member is a pin that aligns the first gear in a parallel axial orientation with the second gear such that first gear operatively couples with the second gear.

20. The surgical apparatus of claim 19, wherein when the pin is deformed, the spur gear no longer functions.

Description

DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 illustrates a plan view of a surgical device.

[0013] FIG. 2 is a cross-sectional view of FIG. 1 with a transformation member in a deformed shape;

[0014] FIG. 3 is a cross-sectional view of FIG. 1 with a transformation member in an original shape;

[0015] FIG. 4 illustrates a plan view of a surgical device,

[0016] FIG. 5A is a cross-sectional view of FIG. 4 with a transformation member deformed shape and including a pre-load component;

[0017] FIG. 5B is a cross-sectional view of FIG. 4 with a transformation member in a deformed shape;

[0018] FIG. 5C is a cross-sectional view of FIG. 4 with a transformation member in an original shape;

[0019] FIG. 6 is a side view of a connection between a button or handle and a sliding shaft of a surgical device that are connected by a transformation member that is in a deformed shape;

[0020] FIG. 7 is a cross-sectional view of FIG. 6;

[0021] FIG. 8A is a side view of a button or handle and sliding shaft with the transformation member in an original shape so that the button and shaft are not connected:

[0022] FIG. 8B is a cross-sectional view of FIG. 8A;

[0023] FIG. 9A is a cross-sectional view of a sliding member connected to a housing by a transformation member that is in a deformed shape;

[0024] FIG. 9B is a cross-sectional view of the transformation member of FIG. 9A in an original shape so that the sliding member is not constrained by the transformation member;

[0025] FIG. 10A, 10B, 10C, and 10D illustrate 4 bar mechanisms and shapes of 4 bar mechanisms;

[0026] FIG. 11 is a side view of a slider crank;

[0027] FIG. 12 is a perspective view of a bevel gear;

[0028] FIG. 13 is a plan view of a spur gear; and

[0029] FIG. 14 is a perspective view of a universal joint.

DETAILED DESCRIPTION

[0030] The present teachings are an improved surgical device that includes one or more innovative features that prevent successful reprocessing or reuse after reprocessing, particularly after reprocessing with thermal methods. Each relevant component of the device may be described in further detail in the following paragraphs, in the drawings, or in the other patent applications that are incorporated by reference herein for the purposes stated. it should be appreciated that the above referenced aspects and examples are non-limiting, as others exist within the present teachings, as shown and described herein.

[0031] The present teachings provide a mechanical device that may preferably be a surgical device, an electromechanical device, or similar device. In particular, the surgical device is intended as a single use device. Exemplary examples include, surgical scissors, forceps, cutting forceps, debriefs, stone retrieval devices, and similarly known devices. Additional example devices where the use of the present teachings is contemplated may be described and disclosed in U.S. Pat. Nos.: 7,204,835; 9,089,337, 9,198,719; 7,998,159; 6,808,525; and D748,787, all of which are expressly incorporated by reference herein for the teachings of the structure of a surgical device.

[0032] Of particular interest in the present teachings, is providing for a surgical device that includes one or more features that prevent successful functioning of the device after reprocessing. The present teachings relate to anti reuse devices. The present teachings relate to providing such features via components, materials, and/or mechanisms that cause at least a portion of a device's active mechanisms to disengage or fall apart under predetermined conditions, thus preventing successful functioning. The present teachings provide a device that prevents reuse of a mechanical device and thus the teachings herein contemplate an anti-use device for any mechanical device but preferably for a surgical device. The anti-reuse device (recited herein as a transformation member) may function to disable all or a portion of a mechanical device upon the device obtaining a transformation temperature. The mechanical device may include a housing that surrounds or includes one or more and preferably all of the components.

[0033] A housing may function to contain some or all components and/or mechanisms of the device. The housing may function as a simple cover for the components/mechanisms, or be an integral part (e.g. function as a pivot, pivot bearing, or guide track). Some devices contemplated herein, do not require a separate housing, for example a simple pair of scissors may not, and the housing is the blade/handle itself. The device may be free of a housing. The housing may include an internal cavity. The housing may be made of metal or plastic. The housing may be connected to one or more parts of the mechanism. The housing may be free of contact with the mechanism, The housing may be connected to a transformation member and when the transformation member transforms (e.g., changes from deformed shape to original shape) at least a portion of the housing may fall apart The housing may surround or cover one or more parts of the housing.

[0034] A mechanism may function to allow movement of different components of the device, particularly movement in response to eternal stimulus (e.g. user squeezing the handle or moving a lever). The mechanism may be a simple pivot, or something more complex such as, but not limited to: multiple pivoting arms, guide tracks, crank, bell crank, slider-crank, bevel gear, spur gear, cams, universal joint, roller chain, piston, rack and pinion, 3 bar link, 4 bar link, or any combination thereof (see https://www.scribd.com/doc/28792501/Different-Kinds-of-Mechanisms, accessed on Sep. 7, 2016 and incorporated by reference), The mechanism upon a stimulus may pivot, rotate, slide, or a combination thereof. The mechanism may include one or more of links, sliding members, stationary members, transformation members (acting as one or more of the parts of the mechanism), pivot pin, guideway, crank, connecting rod, connection, bevel gear, gear, universal joint, shaft, cross journal, or a combination thereof. The present teachings are directed at providing a way to cause the disengagement, at least under certain conditions, Preferably, at least a portion of the mechanism is connected together or allowed to operate due to the transformation member and preferably a transformation member in a deformed shape.

[0035] The transformation member may be a single unitary piece or an assembly of dissimilar components. The transformation member may function to change between an original shape and a deformed shape. The transformation member may function to connection two or more parts of the mechanism together. The transformation member may have a deformed shape arid an original shape. The transition member may be sufficiently rigid and durable so that the device retains is shape and configuration during the duration of use. The transition member may change from a deformed shape to an original shape when subjected to a transition temperature. The transition member may render the device and preferably the surgical device inoperable when the transformation member is in the original shape, Preferably, the transformation member connects two or more parts together when the transformation member is in the deformed shape. The transformation member may be free of holding two or more components together when the transformation member is in the original shape. All or a portion of the transformation member may be comprised of a shape-memory material such as Nitinol, a relatively low melting point material such as Polycaprolactone (PCL) or a similarly low melting polymer, or a wax material. The transformation member may partially or entirely be made of a shape-memory material, a low melting point material, or both. The transformation member may be a portion of a guide way, a sliding member, or both. The transformation member may have a working portion and a pivot pin. The working portion, the pivot pin, or both may be made of a shape-memory material.

[0036] The working portion functions as the portion that disengages or causes disengagement of the mechanism when a transition temperature condition is met, The working portion may extend on one or both sides of a recess in a mechanism. The working portion may be the portion that deforms, melts, changes shape, or a combination thereof. The working portion may be connected to another part of the mechanism, The working portion may be connected to the housing (e.g,, at a connection). The working portion may be a shape-memory material. The working portion may be free of shape-memory material and the pivot pin may be made of a shape-memory material, a low melting polymer, a wax material, or a combination thereof and may deform or change shape upon being subjected to a transition temperature. The working portion may be flat, planar, or both, The working portion may have one or more contours, one or more bends, one or more arcs, or a combination thereof. The working portion when flat in the deformed shape may move to an arcuate shape when the working portion moves to an original shape. The working portion when may be arcuate when in the deformed shape and may move to a flat shape when the working portion moves to an original shape. The working portion may be generally U shaped or C shaped. The working portion may be the only part of the transformation member. The working portion may create a guide way, a channel, or both that allows a sliding member to slide along. The working portion may have a part that moves and a pail that is :static. The working portion may axially move a pivot pin.

[0037] The pivot pin may function to extend into a recess to connect two or more pieces together. The pivot pin may function to move one component with another component, Two or more parts of the mechanism may rotate about the pivot pin. Two or more parts may axially move, laterally move, longitudinally move, or a combination thereof by a connection formed by the pivot pin. The operational movement may be rotational movement, lateral movement, axial movement, lateral movement, or a combination thereof. The pivot pin may allow for movement In two directions and prevent movement in one direction. For example, the pin may allow for movement in the X and Y direction and prevent movement in the 2 movement. The pivot pin may axially move, be axially moved, or both when the transformation member is subjected to the transition temperature, The pivot pin may melt, deform, soften, or a combination thereof when subjected to the transition temperature. The pivot pin may change from a deformed shape to an original shape when subjected to the transition temperature so that the pivot pin no longer constrains one or more parts of the mechanism. The pivot pin upon axially movement may cause at least two relatively pivoting arms of the mechanism to become disengaged from each other. The pivot pin may be a catch pin. The catch pin may align the one or more transformation members with a guide, a wall, a guide track, or a combination thereof of the mechanism that the catch pin moves along. The pin, the guide track, or both may disengage upon being subjected to a transition temperature so that the wall, guide, guide track, pin, or a combination thereof are no longer connected and the mechanism is no longer capable of performing the operational motion The transformation member may be free of a pivot pin. The transformation member may have all or a portion that is made of a shape-memory material.

[0038] Shape-memory materials/components, also known as shape-memory ahoy (SMA, smart metal, memory metal, memory alloy, muscle wire, smart alloy) is an alloy that “remembers” its original shape (predetermined shape) and that when deformed returns to its pre-deformed shape when heated to a transition temperature (e.g. as may typically be seen in thermal reprocessing conditions). The transition temperature may be a temperature experienced by an autoclave. The transition temperature of the composition of the shape-memory material may be varied based upon a heating temperature, type of use, manufacturing process to create the device, or a combination thereof. Preferably, the transition temperature is sufficiently high so that the shape-memory materials/components do not transform during a surgical procedure (e,g., in the surgical room) The transition temperature may be sufficiently high so that the shape-memory materials/components are completely deformed, partially deformed, disable one or more functions of a device, completely disable a device, or a combination thereof. The transition temperature may be varied ±5° C. or more, ±10° C. or more, or even about ±20° C. or more than the transition temperatures taught herein. The transition temperature may be about 25° C. or more, about 30° C. or more about 35° C. or more, about 40° C. or more, about 45° C. or more, about 600 or more, or about 100° C. or less. Preferably, the transition temperature is about 100° C. or more, about 125° C. or more, about 150° C., about 175° C. or more, about 200° C. or more, or about 250° C. or less. The transition temperature may be between about 25° C. and 250° C., preferably between about 30° C. and 150° C., or more preferably between: about 35° C. and about 50° C. One example of a shape-memory alloy that is sometimes used in surgical devices is Nitinol. A material with such memory properties to enable the functional aspect of disengagement of the mechanism, or at least a portion of the mechanism via a transformation member. A transition temperature may be defined as the temperature or time and temperature that is required to make a given shape-memory material/component return to its pre -deformed shape. The transformation member may include a portion that is a polycaprolactene (PCL) or a degradable portion.

[0039] PCL is a biodegradable polyester with a low melting point of around .60 and a glass transition temperature of about -60 ‘C. The most common use of polycaprolactone is in the manufacture of specialty polyurethanes. Polycaprolactones impart good water, oil, solvent and chlorine resistance to the polyurethane produced. A transition temperature may be defined as the temperature or time and temperature set forth harem or that is required to soften the PCL such that the working portion functionally disengages or causes disengagement of the mechanism, typically at about 00 over at least one or more minutes.

[0040] This polymer is often used as an additive for resins to improve their processing characteristics and their end use properties (e.g., impact resistance), Being compatible with a range of other materials, PCL can be mixed with starch to lower its cost and increase biodegradability or it can be added as a polymeric plasticizer to PVC.

[0041] In certain instances, it may be advantageous to include a component or feature that functions to prevent the transformation member from returning to the original shape in the case of a shape-memory component or to move: melt away in the case of a polymer, herein referred to as a preload component. in a preferred embodiment, the pre-load component is removable, and particularly removable prior to the first use of the device. As an example, when a surgical device 2 is first assembled and prior to first use in a patient, the device may be subjected to some kind of thermal event (e,g sterilization or stowage conditions). in such a case, a preload member prevents the transformation member from disengaging the mechanism before the intended time, The preload component may be constructed of any appropriate material, such as metals, polymers, or ceramics. It may be in the form of a pin, wire, fiat or shaped plate, or any similar construction that allows it to functionally support the transformation member during the thermal event. The transformation member may connect two or more parts of a mechanism together.

[0042] The parts of the mechanism connected together may be two arms; a handle or button and sliding member; two gears; a cross journal and a shaft; a crank and a connecting rod, two links; a crank and a stationary member, a connecting rod and a sliding member; or a combination Thereof. Each of the parts of the mechanism may include a recess. The recess may be a through hole. The recess may be a depression in a part. The recess may extend partially into a part of the mechanism so that the mechanism may be pushed or pulled by the transformation member.

[0043] FIGS. 1, 2, and 3 show an example of a device 2 that is a surgical scissor. The device 2 includes a housing 10 (in this case, the two arms, 10A and 100), and a transformation member 30. The member 30 is an assembly of a working portion 32 and a pivot pin 34.

[0044] FIG. 2 is a cross-sectional view of the device 2 of FIG. 1 with the member $0 shown in a deformed shape 30A, and FIG. 3 is a cross-sectional view of the device 2 of FIG. 1 shown in en original shape 300 (predetermined shape). The transformation member 30 includes a working portion 32 and a pivot pin 34 that extends into holes in the housing IDA, 100. The holes in the housing 10A, 108 being a bearing surface /interface for the pivot pin 34,

[0045] In FIG. 3, the working portion 32 has returned to (or nearly to) its original shape after being subjected to a transition temperature and the transformation member 30 has disengaged the mechanism 20 at the 100 interface so that the pivot pin 34 is removed from one or both holes in the arms of the housing 10A, 100 such that the arms of the housing 10A, 108 are not connected.

[0046] FIGS. 4 through SC illustrate a transformation member 30 that changes to an original flattened shape (versus FIGS. 2 and 3 that change to an original contoured shape). The surgical device 2 of FIG. 4 is a cutting forceps (for example HALO (Hand Activation for Laparoscopy & Open) PKC Cutting Forceps as commercially available from Olympus). The device 2 includes a housing 10, a handle 12, and a mechanism 20 (handle 12 pivoting about bin (not shown)).

[0047] FIG. 5A is a cross-sectional view of the device 2 of FIG. 4 with a pre-load component 40. The pre-load component 40 is situated between the housing 10 and the transformation member 30 hi this configuration, the preload component 40 acts to maintain the transformation member 30 in its deformed shape 30A and prevent the member 30 from returning to its original shape (not shown) if any transition temperature is experienced. The preload component 40 is removed prior to a first use of the device 2. The component 40 is in the form of a pin and is removable. The transformation member 30 is connected to the housing 10 at a connection 48 that maintains the relationship between the housing 10 and the transformation member 30.

[0048] In FIG. 5B, the device 2 is shown as in FIG. 5A with the preload component 40 removed.

[0049] In FIG. 5C, the mechanism 20 (a portion thereof) has been disengaged form the device 2 after the transformation member 30 has been subject a transition temperature, and the transformation member 30 has disengaged a portion of the mechanism (pivot phi 34 from handle 12) and thus prevent the mechanism 20 from performing an operational motion.

[0050] FIGS. 6, 7, and 8A, 8B show a device 2 with a housing 10 and a sliding handle 12 or button 14 that acts as an input portion of the mechanism 20 that moves a linearly sliding shaft 22 when a transformation member 30 connects the mechanism 20 to the linearly sliding shaft 22.

[0051] FIG. 6 illustrates a side vies of a surgical device 2. The surgical device 2 includes a handle 12 or button 14 that is connected to a linearly sliding shaft 22 by a transformation member 30 that is in a deformed shape 30A. The linearly sliding shaft 22 is movable within a housing 10 with arrows showing the relative motion.

[0052] FIG. 7 illustrates a cross-sectional view of the surgical device 2 of FIG. 6 along line VII-VII. The handle 12 or button 14 is connected to the linearly sliding shaft 22 by the transformation member 30 extending into a recess 38 so that movement of the handle 12 or button 14 moves the linearly sliding shaft 22.

[0053] FIG. 8A is a side view of the surgical device 2 including a mechanism 20 with the handle 12 or button 14 disconnected from the linearly sliding shaft 22 by the transformation member 30 being subjected to a transition temperature so that the transformation member 30 reverts to an original shape 30B. The arrows show the motion of the handle 12 or button 14 relative to the linearly sliding shaft 22.

[0054] FIG. 8B illustrates a cross-sectional view of the surgical device 2 of FIG. 8A on line VIIIB-VIIIB. As shown, the transformation member 30 moves to the original shape 30B when subjected to a transformation temperature so that the transformation member 30 moves out of the recess 38 of the mechanism 20. The transformation member 30 no longer connects the handle 12 or button 14 to the linearly sliding shaft 22 when the transformation member 30 moves out of the recess 38.

[0055] FIGS. 9A and 9B show a device 2 that has a mechanism 20 that has a sliding member 16 that operationally moves fore and aft within a guideway 36. The guideway 36 comprising the transformational member 30. FIG. 9A showing the member in its deformed shape 30A and functionally acting as a guideway or track 36 for the sliding member 16 to move along, FIG. 9B shows the guideway 30 in its original shape 30B after being subject to a transition temperature and no longer acting as a guideway or track, thus allowing disengagement of the mechanism 20.

[0056] FIGS. 10A-10D illustrate various 4 bar mechanisms 50 with different shapes. Each 4 bar mechanism 50 includes a mechanism 20 having links 24 that are connected together by transformation members 30 that allow the links 24 to move relative to each other.

[0057] FIG. 11 illustrates a slider crank 4 that is a mechanism 20. The slider crank includes one end that is a stationary member 28 connected to a housing 10 and a second end that is a sliding member 20 that moves along the housing 10. The stationary end 28 is connected to a crank 42 via a pivot pin 34 that may be a transformation member 30. The crank 42 is connected to a connecting rod 44 by a pivot pin 34 that may be a transformation member 30. The connecting rod 44 is connected to a sliding member 26 by a pivot pin 34 that may be a transformation member 34. When the transformation member 30 is in a deformed state the sliding member 26 is moved along the housing and when one or more of the transformation member 30 are subjected to a transformation temperature the pivot pins prevent movement of the sliding member 26.

[0058] FIG. 12 illustrates a bevel gear 60, which is a mechanism 20, including two gears 62 that each pivot about a pivot pin 34. One or both of the pivot pins 34 may be a transformation member 30 that when subjected to a transformation temperature reverts back to an original shape so that the bevel gear 60 no longer functions.

[0059] FIG. 13 illustrates a spur gear 70, which is a mechanism 20, including two gears 62 that each pivot about a pivot pin 34. One or both of the pivot pins 34 may be a transformation member 30 that when subjected to a transformation temperature reverts back to an original shape so that the sour gear 70 no longer functions.

[0060] FIG. 14 illustrates a universal joint 80, which is a mechanism 20, including two shafts 82 that are connected together via a cross-journal 84 and pivot pins 34. One or both of the pivot pins 34 may be a transformation member 30 that when subjected to a transformation temperature reverts back to an original shape so that the universal joint 80 no longer functions.

[0061] It is contemplated and expressly stated herein that the embodiments or examples described above may not be mutually exclusive and may be used in combination with each other.

[0062] Unless stated otherwise, dimensions and geometries of the various structures depicted herein are not intended to be restrictive of the teachings, and other dimensions or geometries are possible. Plural structural components can be provided by a single integrated structure, Alternatively, a single integrated structure might be divided into separate plural components. In addition, while a feature of the present teachings may have been described the context of only one of the illustrated embodiments, such feature may be combined with one or more other features of other embodiments, for any given application. It will also be appreciated from the above that the fabrication of the unique structures herein and the operation thereof also constitute methods in accordance with the present teachings.

[0063] The preferred embodiment of the present teachings has been disclosed. A person of ordinary skill in the art would realize however, that certain modifications would come within the teachings of this teachings. Therefore, the following claims should be studied to determine the true scope and content of the teachings.

[0064] Any numerical values recited in the above application include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower, value and any higher value, As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to he expressly stated in this application in a similar manner.

[0065] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of “about ” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30”, inclusive of at least the specified endpoints.

[0066] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes.

[0067] The term “consisting essentially of” to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination.

[0068] The use of the terms “comprising” or “including” describing combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist essentially of the elements, ingredients, components or steps.

[0069] Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of “a” or “one” to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps. All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, inc. 1989. Any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups.