STERILISATION APPARATUS FOR PRODUCING PLASMA AND HYDROXYL RADICALS

Abstract

Sterilisation systems suitable for clinical use for generating a flow of hydroxyl radicals, comprising: a coaxial transmission line comprising an inner and outer conductor; an end cap mounted on a distal end of the coaxial transmission line, wherein the end cap comprises an outlet aperture; a fluid conduit extending from a fluid inlet to the outlet aperture; and a plasma generating region at a proximal end of the outlet aperture, wherein the plasma generating region contains a first electrode electrically connected to the inner conductor, and a second electrode electrically connected to the outer conductor, wherein the fluid conduit defines a fluid flow path through the device aligned with a feed direction in which fluid is receivable through the fluid inlet, and wherein the first electrode and second electrode oppose each other in a transverse direction across the longitudinal fluid flow path in the plasma generating region.

Claims

1. A sterilisation device for generating a flow of hydroxyl radicals, the sterilisation device comprising: a coaxial transmission line for conveying radiofrequency (RF) or microwave frequency electromagnetic (EM) energy, the coaxial transmission line extending in a longitudinal direction and comprising an inner conductor and an outer conductor located around and spaced away from the inner conductor; an end cap mounted on a distal end of the coaxial transmission line, wherein the end cap comprises a distally facing outlet aperture; a fluid conduit extending in the longitudinal direction from a fluid inlet at a distal end of the coaxial transmission line through the end cap to the outlet aperture; and a plasma generating region at a proximal end of the outlet aperture, wherein the plasma generating region contains a first electrode that is electrically connected to the inner conductor, and a second electrode that is electrically connected to the outer conductor, wherein the fluid conduit defines a longitudinal fluid flow path through the device that is aligned with a feed direction in which fluid is receivable through the fluid inlet, and wherein the first electrode and second electrode oppose each other in a transverse direction across the longitudinal fluid flow path in the plasma generating region.

2. The sterilisation device of claim 1, wherein the fluid conduit includes a passage between the inner conductor and outer conductor of the coaxial transmission line.

3. The sterilisation device of claim 1, wherein the fluid conduit includes a duct that runs parallel to the coaxial transmission line.

4. The sterilisation device of claim 1 further comprising a water conduit arranged to deliver water to the plasma generating region.

5. The sterilisation device of claim 4, wherein the water conduit includes a longitudinal passageway formed within the inner conductor of the coaxial transmission line.

6. The sterilisation device of claim 4, wherein the water conduit includes a longitudinal passageway formed within the first electrode.

7. The sterilisation device of claim 4 further comprising a spray unit at a distal end of the water conduit.

8. The sterilisation device of claim 7, wherein the spray unit comprises an aerosoliser configured to produce a cone-shaped spray of water mist.

9. The sterilisation device of claim 4, wherein the water conduit has a proximal inlet, and wherein the water conduit defines a longitudinal flow path through the device that is aligned with a feed direction in which water is receivable through the proximal inlet.

10. The sterilisation device of claim 1, wherein the first electrode is a rod that protrudes in the longitudinal direction from a distal end of the inner conductor, the rod having a smaller diameter than the inner conductor.

11. The sterilisation device of claim 1, wherein the plasma generating region is located in a proximal region of the outlet aperture.

12. The sterilisation device of claim 11, wherein the second electrode comprises a plurality of radial tabs extending inwards from a side wall of the outlet aperture.

13. The sterilisation device of claim 1 further comprising an insulating tube mounted in the outlet aperture distally from the plasma generating region.

14. The sterilisation device of claim 1 further comprising a transverse coaxial feed connected to introduce the RF or microwave energy to the coaxial transmission line in a proximal region thereof.

15. The sterilisation device of claim 14, wherein the transverse coaxial feed is configured to couple microwave energy into the coaxial transmission line, and wherein the transverse coaxial feed is connected to a point on the coaxial transmission line located at a distance ((2n−1)λ)/4 from a proximal end thereof, where n is a positive integer, and λ is a wavelength of the microwave energy conveyed by the coaxial transmission line.

16. The sterilisation device of claim 14 further comprising a proximal transverse coaxial feed connected to introduce the RF energy directly to the plasma generating region.

17. The sterilisation device of claim 1 further comprising a choke mounted at a proximal end of the coaxial transmission line.

18. The sterilisation device of claim 1 configured as a handheld unit.

19. A sterilisation apparatus comprising: the sterilisation device of claim 1; a water supply connected to supply water to the plasma generating region; a gas supply connected to supply gas to the plasma generating region via the fluid conduit; and a generator connected to supply RF or microwave frequency EM energy to the plasma generating region.

20. The sterilisation apparatus of claim 19, wherein the water supply comprises a pump.

21. The sterilisation apparatus of claim 19, wherein the water supply comprises a mist generator.

22. The sterilisation apparatus of claim 21, wherein the mist generator comprises either: an ultrasonic transducer, or a heating element.

23. The sterilisation apparatus of claim 21, wherein the gas supply is connected to supply gas to the handheld sterilisation device via the mist generator.

24. A sterilisation apparatus according to claim 19, wherein the gas supply is a supply of argon gas.

25. A sterilisation apparatus according to claim 19, wherein the generator is powered by a battery.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Features of the invention are now explained in the detailed description of examples of the invention given below with reference to the accompanying drawings, in which:

[0044] FIG. 1 is a schematic diagram of a sterilisation apparatus according to an embodiment of the present invention;

[0045] FIG. 2 is a cross-sectional view of an applicator according to an embodiment of the present invention; and

[0046] FIG. 3 is a cross-sectional view of an applicator according to another embodiment of the present invention.

DETAILED DESCRIPTION; FURTHER OPTIONS AND PREFERENCES

[0047] This invention relates to a device for performing sterilisation using hydroxyl radicals that are generated by creating a plasma in the presence of water mist.

[0048] FIG. 1 is a schematic diagram of a sterilisation apparatus 100 which is an embodiment of the present invention. The apparatus 100 is capable of generating hydroxyl (OH) radicals in order to sterilise a surface or an area. For example, the apparatus 100 may be used to sterilise medical apparatuses or hospital bed spaces.

[0049] The apparatus 100 comprises a generator 102 which is able to controllably deliver radiofrequency (RF) and/or microwave electromagnetic (EM) energy to a sterilisation device, referred to herein as an applicator 104, which is preferably a handheld unit.

[0050] The generator 102 may be of the type disclosed in WO 2012/076844, for example. The generator 102 is connected to the applicator 104 by a coaxial cable 106. The coaxial cable 106 comprises an inner conductor, an outer conductor and a dielectric material separating the inner conductor from the outer conductor. The coaxial cable 106 may couple energy into the applicator 104 through a QMA connector or the like. In some examples, the generator 102 may be arranged to monitor reflected signals (i.e. reflected power) received back from the applicator 104 in order to determine an appropriate signal to be conveyed to the applicator 104. The radiofrequency and/or microwave energy is utilised at the applicator 104 in order to strike and sustain a thermal or non-thermal plasma in order to generate hydroxyl radicals in a manner which is explained in more detail below.

[0051] In some examples, the thermal or non-thermal plasma may be emitted from the applicator and usable directly to sterilise surfaces. In the apparatus shown in FIG. 1, a single generator 102 is arranged to supply RF and/or microwave frequency EM energy. However, in some embodiments of the present invention, the apparatus may comprise an RF EM energy generator and a microwave energy EM generator as individual components, which are each connected to the applicator 104 by a respective coaxial cable.

[0052] The apparatus 100 further comprises a water supply 108, which is arranged to deliver water to the applicator 104. In one example, the water may be supplied as a stream of water which may be arranged to form a spray (e.g. a shower of fine water droplets) to be emitted from the applicator 104. In another example, the water may be supplied as a water mist (e.g. moisture of fog). The water supply 108 may thus comprise a mist generator. A mist generator may generate a mist by means of an ultrasonic transducer, for example. Alternatively, the mist generator may be arranged to heat water to generate steam or mist to be passed to the applicator 104. A mist generator may include a pump or other fluid driving unit to cause generated mist to flow towards the applicator 104. The water is supplied to the applicator 104 in order to generate hydroxyl radicals by a process which will be explained in more detail below. By using water in this way the apparatus 100 can be used to sterilise surfaces or objects without the use of any cleaning chemicals, reducing costs associated with sterilisation and allowing sterilisation to be performed when cleaning chemicals are in short supply. The use of hydroxyl radicals for sterilisation also ensures that there are no harmful by-products.

[0053] A gas supply 110 is connected to the applicator 104 to supply gas for forming a plasma which is used to generate hydroxyl radicals in a manner which will be explained below. The gas supply 110 may be a pressurised supply of any suitably inert gas for formation of a non-thermal or thermal plasma, for example argon, helium, nitrogen, carbon dioxide or a combination thereof. The gas supply 110 may be configured to allow adjustment of the flow rate of gas which is delivered to the applicator 104. The gas supply can supply between 1.5 and 15 litres of gas per minute, for example.

[0054] The gas supply 110 and water supply 108 may be connected to the applicator 104 by a common feed line. That is, outputs from the gas supply 110 and water supply 108 may be combined before they reach the applicator 104. This arrangement may be particularly suitable in examples where the water supply 108 comprises a mist generator. The flow of gas from the gas supply 110 may entrain the water mist from the water supply 108 to create a combined mist/gas stream that is supplied to the applicator 104. The combined mist/gas stream may be delivered into the applicator 104 through a single fluid conduit. Alternatively, the gas supply 110 and the water supply 108 may provide separate streams for delivery of water and gas. The separate streams may be provided within a combined conduit. For example, a conduit for conveying gas to the applicator 104 may comprise a T-junction to allow water to be fed into the conduit. Alternatively, as shown in FIG. 1, the gas supply 110 and the water supply 108 are separately connected to the applicator 104.

[0055] In some embodiments of the invention it is envisaged that the generator 102 (or multiple generators where present), the mist generator 108 and the gas supply 110 may each be portable, and the applicator 104 may be a handheld applicator such that the present invention provides an effective sterilisation apparatus which is easily transportable by a user. For example, the generator 102 may be powered by a battery or the like.

[0056] Examples of the applicator 104 are shown in more detail in FIGS. 2 and 3 below. To sterilise a surface, a plasma is created in the applicator 104 by applying energy from the generator 102 to the gas delivered from the gas supply 110. For example, RF energy may be used to strike a plasma and microwave energy may be used to sustain the plasma. For example, plasma may be generated as disclosed in WO 2009/060213 A1. Simultaneous with the generation of plasma, water from the water supply 108 is passed to a hydroxyl radical generating region within the applicator 104 where the plasma ionises the water in order to produce a spray 112 of hydroxyl radicals which pass out of the applicator 104 to be directed at a surface or into an area for sterilisation. Examples of hydroxyl radical generation in this manner are disclosed in WO 2009/060214 A1, for example.

[0057] The applicator 104 may be produced at any suitable scale. For example, the applicator may be sized to be gripped by a human hand. Alternatively, a larger version suitable for mounted on a stand may be manufactured. In use, the stream of plasma and/or OH radicals emitted by the applicator may be directed into a volume to be sterilized, e.g. the inside of a vehicle (e.g. ambulance) or a hospital bed or surgical suite.

[0058] FIG. 2 shows a cross-sectional view of an applicator 200 that is a first embodiment of the invention. Although not shown in FIG. 2, the applicator 200 may be contained within a generally elongate housing which allows a user to easily pass the applicator 200 over a surface or object for sterilisation. In particularly preferred embodiments the applicator 200 may be handheld unit to facilitate manual control.

[0059] The applicator 200 comprises an energy delivery structure in the form of a coaxial transmission line 201 for conveying radiofrequency (RF) and/or microwave frequency electromagnetic (EM) energy. The coaxial transmission line 201 comprises an inner conductor 202 and an outer conductor 204 spaced away from the inner conductor 202 to define an annular region 219 therebetween. For example, in a preferred embodiment the inner conductor 202 may have an outer diameter of 3 mm and the outer conductor 204 may have an inner diameter of 7 mm to provide a suitable spacing. The spacing between the inner conductor 202 and the outer conductor 204 may be maintained by radially extending spacers (not shown) which are positioned in the gap, for example the spacers may be spokes or spoked discs made of PTFE.

[0060] A distal tip 203 is mounted at a distal end of the coaxial transmission line 201. The distal tip 203 comprises a cylindrical cap 213, which is an electrically conductive structure electrically connected to the outer conductor 204 of the coaxial transmission line 201. In this embodiment, the cylindrical cap 213 comprises a proximal region that overlies and contacts an outer surface of the outer conductor 204. The cylindrical cap 213 defines an internal volume 215. The inner conductor 202 of the coaxial transmission line 201 protrudes beyond a distal end of the outer conductor 204 into the internal volume. The cylindrical cap 215 has an outlet aperture 217 in its distal end. The internal volume 215 is in fluid communication with an external environment through the outlet aperture 217. In this example, an insulating tube 214 (e.g. formed from quartz or the like) is mounted in the outlet aperture, such that the internal volume 215 communicates with the external environment through a passageway formed by the insulating tube 214.

[0061] The inner conductor 202 is hollow to form a water conduit 206 for conveying water along the coaxial transmission line 201 from a proximal inlet 207 to the internal volume 215 within the distal tip 203. A stream of water is fed into the proximal inlet 207 via a water input pipe 209, such that the stream of water is parallel with the longitudinal axis of the inner conductor 202. This arrangements allows a high water flow rate due to the lack of curves or bends in the water conduit 206. The water input pipe 209 receives water from a pump or other water supply, as described above with respect to FIG. 1.

[0062] The annular region 219 between the inner conductor 202 and the outer conductor 204 forms a fluid conduit 208 for conveying gas to the internal volume 215. Gas is delivered to the fluid conduit 208 through a gas input pipe 211, which is connected to a gas supply as described above with respect to FIG. 1.

[0063] It is envisaged that the applicator 200 may also be operated by conveying a mixture of gas and a water mist through the fluid conduit 208. In such operation, no water is required to be delivered through the water conduit 206, thought water may be simultaneously supplied through the water conduit 206 if necessary.

[0064] RF and/or microwave energy is supplied to the coaxial transmission line 201 via a transverse coaxial feed 220. The transverse coaxial feed 220 couples the RF and/or microwave energy into the coaxial transmission line 201 at a location positioned towards a proximal end of the coaxial transmission line 201. To enable RF energy to be conveyed by the coaxial transmission line 201, the coaxial transmission line 201 has an open circuit condition at its proximal end (i.e. the inner conductor 202 and outer conductor 204 remain isolated from each other). To ensure efficient coupling of the microwave energy into this coaxial transmission line 201, the transverse coaxial feed is preferably positioned away from the proximal end of the coaxial transmission line by a distance equal to one or more half wavelengths of the microwave energy when propagating on the coaxial transmission line 201.

[0065] The transverse coaxial feed 220 has a connector 210 that is detachably connectable to a coaxial cable that conveys RF and/or microwave energy from a generator, as described above with respect to FIG. 1. For example, the connector 210 may comprise a QMA, a SMA, a N connector or the like.

[0066] In order to prevent microwave energy from flowing past the proximal end of the coaxial transmission line 201, a choke 212 is connected at the proximal end of the coaxial transmission line 201. In this example a double choke arrangement is used. The choke 212 is provided with a longitudinal passage therethrough to admit the water input pipe 209 and to provide fluid communication between the gas input pipe 211 and annular region 219.

[0067] As described above, the cylindrical cap 213 is open at its distal end, with an insulating tube 214 positioned within the outlet aperture 217. A proximal region of the insulating tube 214 defines a plasma generating zone 205. A first electrode 218 that is electrically connected to the inner conductor 202 extends into the plasma generating zone 205. In this example, the first electrode 218 is a hollow conductive rod that protrudes from a distal end of the inner conductor 202. The rod has a smaller outer diameter than the outer diameter of the inner conductor 202. The water conduit 206 may be in fluid communication with a longitudinal passage through the first electrode 218. The longitudinal passage may have a smaller diameter than that water conduit 206 so that the speed of water flow in the longitudinal passage is increased relative to the water conduit 206, i.e. the water accelerates towards the plasma generating region 205.

[0068] A spray nozzle is mounted at a distal end of the longitudinal passage. The spray nozzle may comprise a swirl chamber arranged to impart a vortex motion on the flow of water as it exits the longitudinal passage, so that a cone of water droplets or water mist is introduced to the plasma generating region 205.

[0069] A second electrode 221 is provided by one more radially protruding conductive tabs formed on the side surfaces of the outlet aperture 217 at a proximal end of the insulating tube 214. Energy supplied to the coaxial transmission line 201 may thus cause a high voltage condition to exist between the first electrode 218 and second electrode 221 within the plasma generating zone 205, such that a plasma can be struck from gas supplied through the fluid conduit 208. The plasma may be struck by a pulse of RF energy and then sustained by a subsequent microwave EM pulse or pulses. In other embodiments either RF or microwave EM energy alone may be used to strike and/or to sustain the plasma.

[0070] A benefit of forming the second electrode as discrete tabs is that it has less effect on the impedance in the cylindrical cap, and hence assists in efficient coupling of energy through the apparatus.

[0071] The conductive tabs may be arranged evenly around the outlet aperture 217. For example there may be two opposed conductive tabs, or four conductive tabs arranged at 90° intervals around the outlet aperture. The conductive tabs provide locations in which arcing preferentially occurs between conductive elements connected to the inner conductor and outer conductor of the coaxial transmission line. That is, arcing and hence plasma generation, occurs preferentially between the first electrode 218 and the second electrode 221. The relative dimensions of the first electrode 218 and second electrode 221 are selected in conjunction with the power supplied to the plasma generating region in order to achieve an electric field strength to strike and sustain the plasma. Where the gas is argon, the field strength required for breakdown may be 600 Vmm.sup.−1, for example. For example, the first electrode 218 may have an outer diameter of 0.5 mm, and the second electrodes 221 may be radially spaced from the first electrode 218 by a distance equal to or less than 1 mm.

[0072] The insulating tube 214 covers the side surface of the outlet aperture 217 beyond the plasma generating zone 205 to avoid unwanted arcing in locations away from the first and second electrode.

[0073] The plasma may be naturally directed out of a distal end of the insulating tube 214 by the direction of the gas flow from the gas input pipe 211.

[0074] Meanwhile, the hollow inner conductor 202 conveys water or mist via the water conduit 206 to the longitudinal passage in the first electrode 218 and onwards as a spray into the plasma generating zone 205. Here the plasma ionises the water molecules to product hydroxyl radicals, which then flow out of the applicator 200. The insulating tube 214 may have an inner diameter selected to narrow the outlet aperture 217 in a manner increases the speed of gas as it exits the applicator. This may aid dispersal of hydroxyl radicals over a region to be sterilised. For example, the insulating tube 214 may have an outer diameter of 10 mm and an inner diameter of 8 mm.

[0075] As explained above, in one example, the first electrode 218 is itself a hollow tube that forms a distal portion of the water conduit 206. The first electrode may have at its distal tip an aerosoliser, i.e. a spray head configured to generate fine droplets from a stream of water provided through the water conduit 206. For example, the aerosoliser may be configured to generate a conical spray of water mist to be directed into the plasma generating zone 205.

[0076] However, in another embodiment, the applicator 200 may be operated by delivering a mixture of a gas and a water mist through the inlet 211 and through the fluid conduit 208. The inner conductor 202 and first electrode 218 need not be hollow in this arrangement. When operating in this way, a plasma may be generated at the plasma generating zone 205 to ionise water molecules and provide hydroxyl radicals in substantially the same manner as described above.

[0077] FIG. 3 shows an applicator 300 which is another embodiment of the invention. Features of the applicator 300 which correspond with the applicator 200 discussed above with respect to FIG. 2 are given the same reference numerals, and are not described again.

[0078] In the applicator 300, energy is coupled into the applicator 300 using two feeds 302, 304 that are mounted transverse to the longitudinal axis of the coaxial transmission line 201. A first feed 302 is connected towards a proximal end of the coaxial transmission line 201. The first feed 302 is a coaxial feedline configured to couple microwave frequency EM energy into the coaxial transmission line 201. In this example, a proximal end of the coaxial transmission line 201 is in a short circuit condition (i.e. the inner conductor 202 is electrically connected to the outer conductor 204). The first feed 302 is then positioned at one or an odd multiple quarter-wavelength distance (at the microwave frequency) from the proximal end of the coaxial transmission line 201. For example, for a microwave frequency of 5.8 GHz, the first feed 302 may be positioned a distance of around 13 mm from the proximal end of the coaxial transmission line 201.

[0079] A second feed 304 is provided at a distal end of the applicator 300, through a side wall of the cylindrical cap 213 into the plasma generating zone 205. The second feed 304 is a coaxial feedline configured to couple RF EM energy into the plasma generating zone 205. To avoid the second feed 304 coupling out microwave energy, it is desirably placed at one or more half wavelengths from the short circuit condition at the proximal end of the coaxial transmission line 201.

[0080] The second feed 304 may be configured as an igniter for delivering a RF pulse having a voltage capable of striking a thermal or non-thermal plasma in the plasma generating zone 205. The second feed 304 comprises a strike electrode 314 which protrudes into the plasma generating zone 205 to ensure that plasma is struck at the correct place.

[0081] The first feed 302 and the second feed 304 may receive microwave and RF energy respectively from different sources, or via separate feeds from a generator configured to produce both RF and microwave signals.

[0082] In this example, the applicator 300 comprises a gas duct 306 which is parallel to the coaxial transmission line 201. Gas, such as argon, is fed into the gas duct from a gas supply as described above with reference to FIG. 1. At a distal end, the gas duct 306 directs gas into a chamber 308 which encircles the coaxial transmission line 201 at a proximal end of the cylindrical cap 203. Gas flows from the chamber 308 into the internal volume 215 of the cylindrical cap 203 through a number of openings 310a, 310b formed in a proximal end surface of the cylindrical cap 203. The openings 310a, 310b are radially spaced around the coaxial transmission line 201 to ensure even distribution of gas in the internal volume 215.

[0083] As in the arrangement shown in FIG. 2, the inner conductor 202 of the coaxial transmission line 201 is hollow to provide a water conduit 206. The inner conductor 202 protrudes beyond a distal end of the outer conductor 204 into the internal volume 215. A distal portion of the inner conductor 202 and a surrounding annular conductive provided by the cylindrical cap 213 provide a first electrode and second electrode respectively for coupling microwave energy from the coaxial transmission line 201 into plasma formed in the plasma generating zone 205. Plasma may thus be struck using an RF pulse from the second feed 304 and sustained by microwave energy from the first feed 302.

[0084] An aerosoliser 312 is disposed within a distal end of the inner conductor 202. The aerosoliser 312 is configured to produce a conical spray of water mist in the plasma generating zone 205. To produce hydroxyl radicals for sterilisation, water is passed through the water conduit 206 to generate a water mist directed outwards from the aerosoliser 312. At the same time, gas is passed into the fluid conduit 208 from the gas duct 306 to ensure a stream of gas also passes through the plasma generating zone 205. An RF pulse is delivered through the second feed 304 in order to strike a thermal or non-thermal plasma from the gas. The plasma is sustained using a pulse or pulses of microwave EM energy supplied to the coaxial transmission line 201 from the first feed 302. The plasma which is generated in this way ionises water molecules in the water mist, to produce a spray of hydroxyl radicals directed out of the plasma generating zone 205 and through the outlet 216 towards a region to be sterilised.

[0085] The features disclosed in the foregoing description, or in the following claims, or in the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for obtaining the disclosed results, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof.

[0086] While the invention has been described in conjunction with the exemplary embodiments described above, many equivalent modifications and variations will be apparent to those skilled in the art when given this disclosure. Accordingly, the exemplary embodiments of the invention set forth above are considered to be illustrative and not limiting. Various changes to the described embodiments may be made without departing from the spirit and scope of the invention.

[0087] For the avoidance of any doubt, any theoretical explanations provided herein are provided for the purposes of improving the understanding of a reader. The inventors do not wish to be bound by any of these theoretical explanations.

[0088] Throughout this specification, including the claims which follow, unless the context requires otherwise, the words “have”, “comprise”, and “include”, and variations such as “having”, “comprises”, “comprising”, and “including” will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

[0089] It must be noted that, as used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by the use of the antecedent “about,” it will be understood that the particular value forms another embodiment. The term “about” in relation to a numerical value is optional and means, for example, +/−10%.

[0090] The words “preferred” and “preferably” are used herein refer to embodiments of the invention that may provide certain benefits under some circumstances. It is to be appreciated, however, that other embodiments may also be preferred under the same or different circumstances. The recitation of one or more preferred embodiments therefore does not mean or imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the disclosure, or from the scope of the claims.