Miniaturized electronic systems with wireless power and near-field communication capabilities
11118965 · 2021-09-14
Assignee
Inventors
- John A. Rogers (Wilmette, IL)
- Anthony R. Banks (Savoy, IL, US)
- Jeonghyun KIM (Urbana, IL, US)
- Gregory Brown (Champaign, IL, US)
Cpc classification
G06K19/0716
PHYSICS
A61B6/00
HUMAN NECESSITIES
G06K19/07722
PHYSICS
G06K19/0723
PHYSICS
A61B2562/028
HUMAN NECESSITIES
A61B2560/0242
HUMAN NECESSITIES
H02J2310/23
ELECTRICITY
International classification
G06K19/00
PHYSICS
G01T1/00
PHYSICS
A61B5/00
HUMAN NECESSITIES
A61B6/00
HUMAN NECESSITIES
Abstract
The invention provides systems and methods for tissue-mounted electronics and photonics. Devices of some embodiments of the invention implement high performance, and optionally flexible, device components having miniaturized formats in device architectures that minimize adverse physical effects to tissue and/or reduce interfacial stresses when mounted on tissue surfaces. In some embodiments, the invention provides complementary tissue mounting strategies providing for mechanically robust and/or long term integration of the present devices, for example, via mounting on tissue surfaces that are not subject to rapid growth or exfoliation processes such as the fingernail, toenail, tooth or earlobe. Devices of the invention are versatile and support a broad range of applications for sensing, actuating and communication including applications for near field communication, for example, for password authentication, electronic transactions and biometric sensing.
Claims
1. A tissue mounted electronic system, the system comprising: a substrate having an inner surface and an outer surface; and an electronic device comprising one or more inorganic components, organic components or a combination of inorganic and organic components supported by said outer surface of said substrate; wherein said electronic device has a thickness less than or equal to 5 millimeters and has lateral dimensions small enough to provide long-term conformal integration with a tissue without substantial delamination; wherein the electronic device comprises one or more near-field communication coils; and wherein the one or more near-field communication coils are coated in an electrically insulating coating; wherein the electrically insulating coating encapsulates the one or more near-field communication coils such that a gap is formed between the coating of adjacent turns of the one or more coils.
2. The system of claim 1, wherein the electrically insulating coating is a polyimide coating.
3. The system of claim 1, wherein the one or more near-field communication coils are disposed coincident with or proximate to the neutral mechanical surface of the device.
4. The system of claim 1, comprising a first near-field communication coil and a second near-field communication coil, wherein the first and second near-field communication coils are separated by the electrically insulating layer.
5. The system of claim 4 wherein the first near-field communication coil is stacked on top of the second near-field communication coil.
6. The system of claim 1, wherein said inner surface of said substrate conforms to a curvature of a surface of the tissue.
7. The system of claim 1, wherein said substrate is characterized by an average thickness greater than 5 microns.
8. The system of claim 1, wherein said substrate is characterized by a maximum thickness of 50 microns.
9. The system of claim 1, wherein the electronic device is a flexible electronic device or a stretchable electronic device.
10. The system of claim 1, wherein said one or more coils have a geometry selected from the group consisting of an annulus or an elliptical annulus.
11. The system of claim 1, wherein said inner surface of the substrate is bonded to said tissue surface via an adhesive comprising an acrylic, silicone or a combination of these.
12. The system of claim 1, wherein said inorganic or organic components are selected from semiconductor components, metallic conductor components and combinations of inorganic semiconductor components, organic semiconductor components and metallic conductor components.
13. The system of claim 1, wherein each of said inorganic or organic components is independently positioned within 10 millimeters of an edge of the perimeter of said substrate.
14. The system of claim 1, wherein said tissue mounted electronic system has a lateral area footprint less than or equal to 500 mm.sup.2.
15. The system of claim 1, wherein said tissue mounted electronic system has a lateral area footprint selected from the range of 1 mm.sup.2to 500 mm.sup.2.
16. The system of claim 1, wherein said tissue mounted electronic system has an average thickness selected from the range of 5 microns to 5 millimeters.
17. The system of claim 1, wherein said tissue mounted electronic system has an overall maximum thickness less than 0.1 mm and at least one region having a thickness selected from the range of 0.05 mm to 0.09 mm.
18. The system of claim 1, wherein the system has a multilayer geometry comprising a plurality of functional layers, supporting layers, encapsulating layers, planarizing layers or any combination of these.
19. The system of claim 1, wherein said substrate is a flexible substrate or a stretchable substrate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
(31)
(32)
(33)
(34)
(35)
DETAILED DESCRIPTION OF THE INVENTION
(36) In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the invention.
(37) The terms “flexible” and “bendable” are used synonymously in the present description and refer to the ability of a material, structure, device or device component to be deformed into a curved or bent shape without undergoing a transformation that introduces significant strain, such as strain characterizing the failure point of a material, structure, device or device component. In an exemplary embodiment, a flexible material, structure, device or device component may be deformed into a curved shape without introducing strain larger than or equal to 5%, for some applications larger than or equal to 1%, and for yet other applications larger than or equal to 0.5% in strain-sensitive regions. A used herein, some, but not necessarily all, flexible structures are also stretchable. A variety of properties provide flexible structures (e.g., device components) of the invention, including materials properties such as a low modulus, bending stiffness and flexural rigidity; physical dimensions such as small average thickness (e.g., less than 100 microns, optionally less than 10 microns and optionally less than 1 micron) and device geometries such as thin film and mesh geometries.
(38) The term “tissue” is used broadly to describe any types of material of which animals or plants are made, for example, consisting of specialized cells and their products. A used herein tissue may refer to cells corresponding to one or more organs, such as cells that substantially carry out the same or complementary functions. Tissue as referred to herein may correspond to animals, including human and non-human animals (e.g., livestock, veterinary animals, etc.), and plants. Tissue as referred to herein may correspond to living cells or dead cells which may include, but are not limited to, the corpus unguis, (e.g., fingernail, toenail, claw hoof, horn, etc.). Examples of tissues include skin, a fingernail, a toenail, a tooth, a bone, hair or an ear lobe.
(39) “Stretchable” refers to the ability of a material, structure, device or device component to be strained without undergoing fracture. In an exemplary embodiment, a stretchable material, structure, device or device component may undergo strain larger than 0.5% without fracturing, for some applications strain larger than 1% without fracturing and for yet other applications strain larger than 3% without fracturing. As used herein, many stretchable structures are also flexible. Some stretchable structures (e.g., device components) are engineered to be able to undergo compression, elongation and/or twisting so as to be able to deform without fracturing. Stretchable structures include thin film structures comprising stretchable materials, such as elastomers; bent structures capable of elongation, compression and/or twisting motion; and structures having an island-bridge geometry. Stretchable device components include structures having stretchable interconnects, such as stretchable electrical interconnects.
(40) “Functional layer” refers to a device-containing layer that imparts some functionality to the device. For example, the functional layer may be a thin film such as a semiconductor layer. Alternatively, the functional layer may comprise multiple layers, such as multiple semiconductor layers separated by support layers. The functional layer may comprise a plurality of patterned elements, such as interconnects running between device-receiving pads or islands. The functional layer may be heterogeneous or may have one or more properties that are inhomogeneous. “Inhomogeneous property” refers to a physical parameter that can spatially vary, thereby effecting the position of the neutral mechanical surface (NMS) within the multilayer device.
(41) “Semiconductor” refers to any material that is an insulator at a low temperature, but which has an appreciable electrical conductivity at temperatures of approximately 300 Kelvin. In the present description, use of the term semiconductor is intended to be consistent with use of this term in the art of microelectronics and electronic devices. Useful semiconductors include those comprising element semiconductors, such as silicon, germanium and diamond, and compound semiconductors, such as group IV compound semiconductors such as SiC and SiGe, group III-V semiconductors such as AlSb, AlAs, Aln, AlP, BN, GaSb, GaAs, GaN, GaP, InSb, InAs, InN, and InP, group III-V ternary semiconductors alloys, such as Al.sub.xGa.sub.1-xAs, group II-VI semiconductors, such as CsSe, CdS, CdTe, ZnO, ZnSe, ZnS, and ZnTe, group I-VII semiconductors, such as CuCl, group IV-VI semiconductors, such as PbS, PbTe and SnS, layer semiconductors, such as PbI.sub.2, MoS.sub.2 and GaSe, and oxide semiconductors, such as CuO and Cu.sub.2O. The term semiconductor includes intrinsic semiconductors and extrinsic semiconductors that are doped with one or more selected materials, including semiconductors having p-type doping materials and n-type doping materials, to provide beneficial electronic properties useful for a given application or device. The term semiconductor includes composite materials comprising a mixture of semiconductors and/or dopants. Specific semiconductor materials useful for some embodiments include, but are not limited to, Si, Ge, SiC, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InP, InAs, GaSb, InP, InAs, InSb, ZnO, ZnSe, ZnTe, CdS, CdSe, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, PbS, PbSe, PbTe, AlGaAs, AlInAs, AlInP, GaAsP, GaInAs, GaInP, AlGaAsSb, AlGaInP, and GaInAsP. Porous silicon semiconductor materials are useful for applications of aspects described herein in the field of sensors and light emitting materials, such as light emitting diodes (LEDs) and solid state lasers. Impurities of semiconductor materials are atoms, elements, ions and/or molecules other than the semiconductor material(s) themselves or any dopants provided to the semiconductor material. Impurities are undesirable materials present in semiconductor materials, which may negatively impact the electronic properties of semiconductor materials, and include but are not limited to oxygen, carbon, and metals including heavy metals. Heavy metal impurities include, but are not limited to, the group of elements between copper and lead on the periodic table, calcium, sodium, and all ions, compounds and/or complexes thereof.
(42) “Coincident” refers to the relative position of two or more objects, planes or surfaces, for example a surface such as a neutral mechanical surface (NMS) or neutral mechanical plane (NMP) that is positioned within or is adjacent to a layer, such as a functional layer, substrate layer, or other layer. In an embodiment, a NMS or NMP is positioned to correspond to the most strain-sensitive layer or material within the layer. “Proximate” refers to the relative position of two or more objects, planes or surfaces, for example a NMS or NMP that closely follows the position of a layer, such as a functional layer, substrate layer, or other layer while still providing desired flexibility or stretchability without an adverse impact on the strain-sensitive material physical properties. In general, a layer having a high strain sensitivity, and consequently being prone to being the first layer to fracture, is located in the functional layer, such as a functional layer containing a relatively brittle semiconductor or other strain-sensitive device element. A NMS or NMP that is proximate to a layer need not be constrained within that layer, but may be positioned proximate or sufficiently near to provide a functional benefit of reducing the strain on the strain-sensitive device element when the device is folded.
(43) In this aspect, “strain-sensitive” refers to a material that fractures or is otherwise impaired in response to a relatively low level of strain. In an aspect, the NMS is coincident or proximate to a functional layer. In an aspect the NMS is coincident to a functional layer, referring to at least a portion of the NMS located within the functional layer that contains a strain-sensitive material for all lateral locations along the NMS. In an aspect, the NMS is proximate to a functional layer, wherein although the NMS may not be coincident with the functional layer, the position of the NMS provides a mechanical benefit to the functional layer, such as substantially lowering the strain that would otherwise be exerted on the functional layer but for the position of the NMS. For example, the position of a proximate NMS is optionally defined as the distance from the strain-sensitive material that provides an at least 10%, 20%, 50% or 75% reduction in strain in the strain-sensitive material for a given folded configuration, such as a device being folded so that the radius of curvature is on the order of the millimeter or centimeter scale. In another aspect, the position of a proximate NMS can be defined in absolute terms such as a distance from the strain-sensitive material, such as less than several mm, less than 2 mm, less than 10 μm, less than 1 μm, or less than 100 nm. In another aspect, the position of a proximate layer is defined relative to the layer that is adjacent to the strain-sensitive material, such as within 50%, 25% or 10% of the layer closest to the strain-sensitive-containing layer. In an aspect, the proximate NMS is contained within a layer that is adjacent to the functional layer.
(44) A “component” is used broadly to refer to an individual part of a device.
(45) “Sensing” refers to detecting the presence, absence, amount, magnitude or intensity of a physical and/or chemical property. Useful device components for sensing include, but are not limited to electrode elements, chemical or biological sensor elements, pH sensors, temperature sensors, strain sensors, mechanical sensors, position sensors, optical sensors and capacitive sensors.
(46) “Actuating” refers to stimulating, controlling, or otherwise affecting a structure, material or device component. Useful device components for actuating include, but are not limited to, electrode elements, electromagnetic radiation emitting elements, light emitting diodes, lasers, magnetic elements, acoustic elements, piezoelectric elements, chemical elements, biological elements, and heating elements.
(47) The terms “directly and indirectly” describe the actions or physical positions of one component relative to another component. For example, a component that “directly” acts upon or touches another component does so without intervention from an intermediary. Contrarily, a component that “indirectly” acts upon or touches another component does so through an intermediary (e.g., a third component).
(48) “Encapsulate” refers to the orientation of one structure such that it is at least partially, and in some cases completely, surrounded by one or more other structures, such as a substrate, adhesive layer or encapsulating layer. “Partially encapsulated” refers to the orientation of one structure such that it is partially surrounded by one or more other structures, for example, wherein 30%, or optionally 50%, or optionally 90% of the external surface of the structure is surrounded by one or more structures. “Completely encapsulated” refers to the orientation of one structure such that it is completely surrounded by one or more other structures.
(49) “Dielectric” refers to a non-conducting or insulating material.
(50) “Polymer” refers to a macromolecule composed of repeating structural units connected by covalent chemical bonds or the polymerization product of one or more monomers, often characterized by a high molecular weight. The term polymer includes homopolymers, or polymers consisting essentially of a single repeating monomer subunit. The term polymer also includes copolymers, or polymers consisting essentially of two or more monomer subunits, such as random, block, alternating, segmented, grafted, tapered and other copolymers. Useful polymers include organic polymers or inorganic polymers that may be in amorphous, semi-amorphous, crystalline or partially crystalline states. Crosslinked polymers having linked monomer chains are particularly useful for some applications. Polymers useable in the methods, devices and components include, but are not limited to, plastics, elastomers, thermoplastic elastomers, elastoplastics, thermoplastics and acrylates. Exemplary polymers include, but are not limited to, acetal polymers, biodegradable polymers, cellulosic polymers, fluoropolymers, nylons, polyacrylonitrile polymers, polyimide-imide polymers, polyimides, polyarylates, polybenzimidazole, polybutylene, polycarbonate, polyesters, polyetherimide, polyethylene, polyethylene copolymers and modified polyethylenes, polyketones, poly(methyl methacrylate), polymethylpentene, polyphenylene oxides and polyphenylene sulfides, polyphthalamide, polypropylene, polyurethanes, styrenic resins, sulfone-based resins, vinyl-based resins, rubber (including natural rubber, styrene-butadiene, polybutadiene, neoprene, ethylene-propylene, butyl, nitrile, silicones), acrylic, nylon, polycarbonate, polyester, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyolefin or any combinations of these.
(51) “Elastomer” refers to a polymeric material which can be stretched or deformed and returned to its original shape without substantial permanent deformation. Elastomers commonly undergo substantially elastic deformations. Useful elastomers include those comprising polymers, copolymers, composite materials or mixtures of polymers and copolymers. Elastomeric layer refers to a layer comprising at least one elastomer. Elastomeric layers may also include dopants and other non-elastomeric materials. Useful elastomers include, but are not limited to, thermoplastic elastomers, styrenic materials, olefinic materials, polyolefin, polyurethane thermoplastic elastomers, polyamides, synthetic rubbers, PDMS, polybutadiene, polyisobutylene, poly(styrene-butadiene-styrene), polyurethanes, polychloroprene and silicones. Exemplary elastomers include, but are not limited to silicon containing polymers such as polysiloxanes including poly(dimethyl siloxane) (i.e. PDMS and h-PDMS), poly(methyl siloxane), partially alkylated poly(methyl siloxane), poly(alkyl methyl siloxane) and poly(phenyl methyl siloxane), silicon modified elastomers, thermoplastic elastomers, styrenic materials, olefinic materials, polyolefin, polyurethane thermoplastic elastomers, polyamides, synthetic rubbers, polyisobutylene, poly(styrene-butadiene-styrene), polyurethanes, polychloroprene and silicones. In an embodiment, a polymer is an elastomer.
(52) “Conformable” refers to a device, material or substrate which has a bending stiffness that is sufficiently low to allow the device, material or substrate to adopt a contour profile desired for a specific application, for example a contour profile allowing for conformal contact with a surface having a non-planar geometry such as a surface with relief features or a dynamic surface (e.g. changes with respect to time). In certain embodiments, a desired contour profile is that of a finger nail, skin, tooth, toe nail or ear lobe.
(53) “Conformal contact” refers to contact established between a device and a receiving surface. In one aspect, conformal contact involves a macroscopic adaptation of one or more surfaces (e.g., contact surfaces) of a device to the overall shape of a surface. In another aspect, conformal contact involves a microscopic adaptation of one or more surfaces (e.g., contact surfaces) of a device to a surface resulting in an intimate contact substantially free of voids. In an embodiment, conformal contact involves adaptation of a contact surface(s) of the device to a receiving surface(s) such that intimate contact is achieved, for example, wherein less than 20% of the surface area of a contact surface of the device does not physically contact the receiving surface, or optionally less than 10% of a contact surface of the device does not physically contact the receiving surface, or optionally less than 5% of a contact surface of the device does not physically contact the receiving surface.
(54) “Young's modulus” or “modulus” are used interchangeably and refer to a mechanical property of a material, device or layer which refers to the ratio of stress to strain for a given substance. Young's modulus may be provided by the expression:
(55)
where E is Young's modulus, L.sub.0 is the equilibrium length, ΔL is the length change under the applied stress, F is the force applied, and A is the area over which the force is applied. Young's modulus may also be expressed in terms of Lame constants via the equation:
(56)
where A and p are Lame constants. High Young's modulus (or “high modulus”) and low Young's modulus (or “low modulus”) are relative descriptors of the magnitude of Young's modulus in a given material, layer or device. In some embodiments, a high Young's modulus is larger than a low Young's modulus, preferably about 10 times larger for some applications, more preferably about 100 times larger for other applications, and even more preferably about 1000 times larger for yet other applications. In an embodiment, a low modulus layer has a Young's modulus less than 100 MPa, optionally less than 10 MPa, and optionally a Young's modulus selected from the range of 0.1 MPa to 50 MPa. In an embodiment, a high modulus layer has a Young's modulus greater than 100 MPa, optionally greater than 10 GPa, and optionally a Young's modulus selected from the range of 1 GPa to 100 GPa. In an embodiment, a device of the invention has one or more components having a low Young's modulus. In an embodiment, a device of the invention has an overall low Young's modulus.
(57) “Low modulus” refers to materials having a Young's modulus less than or equal to 10 MPa, less than or equal to 20 MPa or less than or equal to 1 MPa.
(58) “Bending stiffness” is a mechanical property of a material, device or layer describing the resistance of the material, device or layer to an applied bending movement. Generally, bending stiffness is defined as the product of the modulus and area moment of inertia of the material, device or layer. A material having an inhomogeneous bending stiffness may optionally be described in terms of a “bulk” or “average” bending stiffness for the entire layer of material.
(59) “Lateral dimensions” refer to physical dimensions of a structure such as a tissue mounted electronic system or component thereof. For example, lateral dimensions may refer to one or more physical dimensions oriented orthogonal to axes extending along the thickness of a structure, such as the length, the width, the radius or the diameter of the structure. Lateral dimensions are useful for characterizing the area of an electronic system or component thereof, such as characterizing the lateral area footprint of a system corresponding to a two dimensional area in a plane or a surface positioned orthogonal to axes extending along the thickness of the structure.
(60)
(61) As shown in
(62) As shown in
(63) In the example shown in
Example 1
(64) Abstract
(65) This Example introduces a class of thin, lightweight, flexible near field communication (NFC) devices with ultraminiaturized format, and presents systematic investigations of the mechanics, radio frequency characteristics and materials aspects associated with their optimized construction. These systems allow advantages in mechanical strength, placement versatility, and minimized interfacial stresses compared to other NFC technologies and wearable electronics. Detailed experimental studies and theoretical modeling of the mechanical and electromagnetic properties of these systems establish understanding of the key design considerations. These concepts can apply to many other types of wireless communication systems including bio-sensors and electronic implants.
(66) Introduction
(67) Wearable electronic technologies form the foundation for a rapidly growing consumer device segment. Projections suggest that over $100 billion will be spent in materials alone over the coming decade in the pursuit of new wearable devices.sup.[1]. Advances in materials and device architectures for these systems will create opportunities for increasing the range of capabilities, expanding the modes of use, improving the robustness/reliability, reducing the size/weight and lowering the cost. The cellular phone platform will likely remain a key element in the broader technology landscape, as in currently available wrist band and watch style devices that measure body processes and communicate data to the phone.sup.[2,3]. Recent research demonstrates much different types of integration strategies compared to those of these existing systems, in which the wearable devices take the form of temporary transfer tattoos. The result is greatly improved contact with the body and corresponding increases in the diversity and accuracy of information that can be collected from integrated sensors.sup.[2,4,5]. Here, an overarching goal is to engineer the physical properties, and in particular the elastic modulus and elastic stretchability, to match those of the epidermis, as a way to reduce irritation and discomfort at the skin interface and to improve the robustness of the bonding.sup.[2,4,6]. In this Example, we present a complementary strategy, in which overall size miniaturization serves as an additional, and sometimes primary, means for minimizing physical effects on the skin. This scheme also expands the options in mounting locations, to include areas such as the fingernails and the teeth, where mechanical compliance is not always required and where mounting times can extend to several months, or more. In particular, we introduce thin, lightweight, flexible near field communication (NFC) devices in ultraminiaturized formats, along with systematic studies of the mechanics and materials aspects associated with their optimized construction. The potential applications include password authentication.sup.[7], electronic transactions.sup.[8] and biometric sensing.sup.[9], each performed via wireless power and communication to cellular phones or other NFC enabled platforms. Such devices consume nearly one hundred times less area than conventional wrist-worn NFC devices and they are ˜100 and ˜10,000 times thinner and lighter in weight, respectively. The areas are also nearly ten times smaller than those of recently reported NFC devices with epidermal construction.sup.[2] and are, to our knowledge, the smallest to be explored for integration on the surface of the human body. Rigid, capsule-shaped NFC devices with volumes ˜10 times larger than those of the devices reported here are available for implantation into the human body.sup.[10]. Open architecture designs provide a high tolerance to deformation and physical stresses when mounted on soft surfaces such as the epidermis. Experimental measurements of the mechanical and electromagnetic properties compare favorably to theoretical modeling results. Device operation using standard NFC enabled consumer electronics demonstrate the capabilities in evaluations that are supportive of a range of applications.
(68) Results and Discussion
(69)
(70) The fingernails and toenails provide examples. By comparison to the skin, the nails are hard, physically static and they lack sensory capacity, thereby providing a minimally invasive interface for robust, long-term integration. The growth cycle from the quick to the end of the nail can exceed 6 months, thereby allowing integration for several months.sup.[11]. Such timeframes greatly exceed those associated with mounting on the skin, where the cycle for skin cell differentiation and exfoliation occurs on the timescale of a few weeks. The fingernails of adults have radii of curvature that range from ˜13 mm to ˜5 mm, depending on age, sex, overall body size, and finger.sup.[12]. Properly designed devices can accommodate bending associated with mounting on such surfaces, without significant change in operating characteristics.
(71) The electromagnetic coupling between a primary coil and an mm-NFC device depends strongly on size, as expected from the expression for magnetic flux. Three mm-NFC devices with different radii given in Table 1 are studied, where the number of turns and layers are adjusted to offer the same inductances, i.e., these mm-NFC devices have the same resonant frequency and Q factor as shown in Table 1 and return loss spectra as shown in
(72) TABLE-US-00001 TABLE 1 Three mm-NFC devices with different radii Diameter Turns/ Resonant Inductance Q factor (mm) Layers layer frequency f.sub.0 at f.sub.0 (μH) at f.sub.0 Coil 1 7.76 2 8 13.88 MHz 4.76 13.9 Coil 2 7.04 2 9 13.72 MHz 4.87 13.4 Coil 3 4 4 8 13.93 MHz 4.73 12.3
(73) The nature of fingernail growth affords increased mounting times for mm-NFC devices that adopt elliptical shapes with major axes oriented parallel to the base of the nail.
(74) Flexible mm-NFC devices also offer advantages for mounting on the skin. Here, the small sizes minimize sensory perception and reduce energy release rates for delamination.
(75)
where D is the diameter of the mm-NFC device, L.sub.0 is the length of substrate in the stretching direction, ε.sub.app is the average strain in the substrate, and E.sub.sub and ν.sub.sub are the Young's modulus and Poisson's ratio of the substrate, respectively. As shown in
(76)
This scaling affords advantages in the reduced possibility for delamination of mm-NFC devices from the skin.
(77)
(78) Conclusion
(79) The materials, device designs and integration strategies presented here provide a framework for mm-scale, flexible, body-worn NFC systems, with potential applications in password authentication, electronic transactions and biometric sensing. The ultraminiaturized geometries and mechanically flexible designs, in particular, afford advantages in mechanical strength, placement versatility, and minimized interfacial stresses. Combined theoretical and experimental considerations in materials, electromagnetic characteristics and mechanical properties are essential to proper design. These concepts can apply to many other types of wireless communication systems including various bio-sensors and electronic implants.
(80) Experimental Section
(81) Fabrication of the Coils:
(82) A Cu foil (18 μm thick, Oak Mitsui Micro-thin series) served as the material for the first coil layer. A layer of polyimide (2.4 μm thick, PI2545, HD Microsystems) spin-cast at 2000 rpm for 30 s, baked on a hot plated at 150° C. for 5 min, and in a vacuum oven at 250° C. for 70 min formed an insulating coating. Laminating this PI-coated Cu foil onto a glass slide coated with polydimethylsiloxane (PDMS, Sylgard 184), with the PI side down, allowed patterning of the Cu into a coil geometry by photolithography (AZ 4620 photo-resist, spin-casting at 3000 rpm for 30 s, baking at 110° C. for 3 mins, UV irradiance for 300 mJ/cm.sup.2, development for ˜40 s with developer AZ 400K/deionized water solution of 1:2 volume ratio) and wet etching (CE-100 copper etchant, Transense, etching for ˜10 mins with frequent rinsing by water). A coating of PI spin-cast at 1000 rpm for 30 s covered the first coil layer. Photolithography (AZ 4620) and oxygen plasma etching created via holes through the PI. Oxide remover (Flux, Worthington) eliminated the native copper oxide at the base of via holes. Electron beam evaporation formed a conducting layer (500 nm thick) for electroplating. Next, electroplating (11 wt % cupric sulfate pentahydrate in water, current of 13 mA/cm.sup.2 for 55 mins, distance between positive electrode and negative electrode of 1.7 cm) generated a second coil in a 20 μm thick layer of Cu, also patterned by photolithography (AZ 4620) and wet etching (copper etchant). Spin casting formed another 2.4 μm thick layer of PI over the entire coil structure. Electron beam evaporation of a 50 nm thick layer of SiO.sub.2 created a hard mask in a geometry defined by photolithography (AZ 4620) and RIE etching (50 mTorr, 40 sccm CF.sub.4, 100 W for 10 min). Oxygen plasma removed the exposed PI, leaving PI only in the regions of the coil, for an open architecture design that improves the mechanical deformability.
(83) NFC Die:
(84) The NTAG216 (NXP Semiconductor, ISO/IEC 14443, input capacitance of 50 pF) chip served as the electronics for the smallest device. The M24LR04E (ST Microelectronics, ISO/IEC 15693, input capacitance of 27.5 pF) chip was used for the energy harvesting device. The SL13A (AMS AG, ISO/IEC 15693, input capacitance of 25 pF) chip enabled the temperature sensing device. All chips were thinned (<100 μm thick) and used as bare die without packages.
(85) Transfer and Chips Assembly:
(86) A cellulose-based water-soluble tape (Grainger) allowed retrieval of the fabricated coils from the substrate and integration onto an adhesive substrate. Removal of the water-soluble tape by dissolution in water completed the transfer. Thinned NFC die and LEDs attached to the coil by a modified flip-chip bonding method with an Indium/Ag based solder paste (Ind. 290, Indium Corporation; ˜165° C. for 2 min in a reflow oven). A droplet of silicone elastomer (Q1-4010, Dow corning) encapsulated the chips.
(87) Electromagnetic Characterization:
(88) Electromagnetic characterization used an impedance analyzer (4291A RF impedance/material analyzer, Hewlett Packard) with a commercial primary coil (Samsung Galaxy Note II; resonant frequency ˜47.5 MHz) over a frequency range of 5 to 20 MHz. The Min-phase method defined the resonance frequencies of the NFC devices. Measurements involved placement of the device at the center of the primary coil at a vertical distance of ˜2 mm, as shown
REFERENCES
(89) [1] H. P, H. J, 2015; G. B. Raupp, Ecs Transactions 2011, 37, 229. [2] J. Kim, A. Banks, H. Y. Cheng, Z. Q. Xie, S. Xu, K. I. Jang, J. W. Lee, Z. J. Liu, P. Gutruf, X. Huang, P. H. Wei, F. Liu, K. Li, M. Dalal, R. Ghaffari, X. Feng, Y. G. Huang, S. Gupta, U. Paik, J. A. Rogers, Small 2015, 11, 906. [3] J. Sidén, V. Skerved, J. Gao, S. Forsström, H.-E. Nilsson, T. Kanter, M. Gulliksson, “Home care with nfc sensors and a smart phone”, presented at Proceedings of the 4th International Symposium on Applied Sciences in Biomedical and Communication Technologies, 2011. [4] D. H. Kim, N. S. Lu, R. Ma, Y. S. Kim, R. H. Kim, S. D. Wang, J. Wu, S. M. Won, H. Tao, A. Islam, K. J. Yu, T. I. Kim, R. Chowdhury, M. Ying, L. Z. Xu, M. Li, H. J. Chung, H. Keum, M. McCormick, P. Liu, Y. W. Zhang, F. G. Omenetto, Y. G. Huang, T. Coleman, J. A. Rogers, Science 2011, 333, 838. [5] S. Xu, Y. H. Zhang, L. Jia, K. E. Mathewson, K. I. Jang, J. Kim, H. R. Fu, X. Huang, P. Chava, R. H. Wang, S. Bhole, L. Z. Wang, Y. J. Na, Y. Guan, M. Flavin, Z. S. Han, Y. G. Huang, J. A. Rogers, Science 2014, 344, 70; J. R. Windmiller, A. J. Bandodkar, G. Valdes-Ramirez, S. Parkhomovsky, A. G. Martinez, J. Wang, Chem Commun 2012, 48, 6794. [6] K. I. Jang, H. U. Chung, S. Xu, C. H. Lee, H. Luan, J. Jeong, H. Cheng, G. T. Kim, S. Y. Han, J. W. Lee, J. Kim, M. Cho, F. Miao, Y. Yang, H. N. Jung, M. Flavin, H. Liu, G. W. Kong, K. J. Yu, S. I. Rhee, J. Chung, B. Kim, J. W. Kwak, M. H. Yun, J. Y. Kim, Y. M. Song, U. Paik, Y. Zhang, Y. Huang, J. A. Rogers, Nat Commun 2015, 6, 6566; J. W. Jeong, W. H. Yeo, A. Akhtar, J. J. S. Norton, Y. J. Kwack, S. Li, S. Y. Jung, Y. W. Su, W. Lee, J. Xia, H. Y. Cheng, Y. G. Huang, W. S. Choi, T. Bretl, J. A. Rogers, Adv Mater 2013, 25, 6839. [7] M. Q. Saeed, C. D. Walter, 2012 International Conference for Internet Technology and Secured Transactions 2012, 730. [8] M. Fisher, Google Patents, 2013. [9] D. P. Rose, M. Ratterman, D. K. Griffin, L. Hou, N. Kelley-Loughnane, R. R. Naik, J. A. Hagen, I. Papautsky, J. Heikenfeld, 2014; E. Freudenthal, D. Herrera, F. Kautz, C. Natividad, A. Ogrey, J. Sipla, A. Sosa, C. Betancourt, L. Estevez, 2007. [10] A. Žnidaršič, B. Werber, 2014; D. Things, Vol. 2014, 2014. [11] W. B. Bean, Arch Intern Med 1980, 140, 73. [12] S. Murdan, Int J Cosmetic Sci 2011, 33, 509. [13] T. J. Harpster, B. Stark, K. Najafi, Sensor Actuat a-Phys 2002, 95, 100; X. Huang, Y. H. Liu, H. Y. Cheng, W. J. Shin, J. A. Fan, Z. J. Liu, C. J. Lu, G. W. Kong, K. Chen, D. Patnaik, S. H. Lee, S. Hage-Ali, Y. G. Huang, J. A. Rogers, Adv Funct Mater 2014, 24, 3846. [14] S. D. Wang, M. Li, J. Wu, D. H. Kim, N. S. Lu, Y. W. Su, Z. Kang, Y. G. Huang, J. A. Rogers, J Appl Mech-T Asme 2012, 79. [15] N. S. Lu, J. I. Yoon, Z. G. Suo, Int J Mater Res 2007, 98, 717.
Example 2—Fingernail Mounted NFC Device for Password Authentication
(90) The invention provides, for example, a fingernail mounted near field communication (NFC) device providing a unique solution for password authentication in the electronic hardware industry. The materials, design, and circuit integration enable the art of biocompatible NFC technology. The built-in NFC technology serves as a digital replacement for passwords, pin numbers, security questions, distinct biometrics, and/or text/email verification dealings. The fingernail-mounted device of this embodiment is able to wirelessly communicate with point of access readers that use NFC antennas. The point of access readers include but are not limited to smartphones, laptops, keyboards, computer mice, remote controls, safes, and/or locks. Instead of recalling passwords, fingerprint touch pads, or safe combinations, authorized fingernail-mounted device users are granted instant access to their electronics and/or safe belongings without producing security passcodes.
(91) In some embodiments, for example, the invention has a devoted chip that stores an encrypted identification number that is unique to each individual device. In addition, the chip has action-specific security codes that change after each point of authorization. The encrypted identification numbers grant access to authorized users. For instance, the authorized user goes straight to his or her home screen once the reader detects the invented hardware. If the encrypted identification numbers do not appropriately match, the foreign user is denied access.
(92) For privacy, individual users are not at risk of exposing their personal information, passwords, pins, biometrics, and/or access restrictions to by-standers. Customers do not have to waste time typing passwords or pins to gain access to their personal electronics. Fingernail mounted devices are waterproof and remainoperational for several days or months. The invention is able to work in conjunction with mobile phone or computer applications developed specifically for authentication purposes. If removed from the nail or tissue, the invented device is permanently disabled and all private information is destroyed.
(93)
(94)
(95)
(96)
(97)
(98)
(99)
(100) Beneficial aspects of the present fingernail mounted systems of the invention include: Ultrathin, flexible, open architecture (one-size-fits-all construction) Designs for stable operation under sharp bending Strategies for robust interface adhesion Designs to prevent removal and re-use Materials for operation under extreme conditions Configurations for flexibility in mounting locations Layouts for options in graphics overlays Coils for operation of multiple devices
Example 3—Fingernail Mounted NFC Device for Electronic Payments
(101) The invention provides, for example, fingernail mounted near field communication (NFC) devices providing a unique platform for mobile payment and digital wallet service providers. The materials, design, and circuit integration enable the art of biocompatible NFC technology. In some embodiments, the built-in NFC technology serves as a digital replacement for the magnetic strip found on the back of all debit, credit, and prepaid gift cards. The fingernail-mounted device is able to wirelessly communicate with point of sale readers that use NFC antennas. Instead of exchanging cash, debit or credit cards, users have the ability to make secure in-store purchases with a single touch or point. Additional payment schemes using the fingernail-mounted device include device and pin, a combination of the devices, or a combination of the device and a second method for authorization.
(102) In an embodiment, for example, the invention has a devoted chip that stores encrypted payment information that is unique to each individual device. In addition, the chip has transaction-specific security codes that change after each transaction. The encrypted payment information and varying security codes are used to process each transaction at time of purchase. In some embodiments, the payment information is never shared with merchants or stored on a server. In some embodiments, all financial information is stored locally on the consumers' personal mobile devices and/or computers.
(103) In some embodiments, for privacy, the invented hardware does not save any kind of transaction information. Individual consumers are not at risk of exposing their name, card number, or security code to retailers or by-standers. Customers do not have to carry their phones, credit cards, and/or cash in order to make electronic payments. In some embodiments, devices are waterproof and remain operational for several days or months. The systems of this aspect of the invention are able to work in conjunction with mobile phone applications developed specifically for payment transactions. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled and all payment information is destroyed.
Example 4—Fingernail Mounted NFC for Personal Identification/Authorization
(104) The invention provides, for example, fingernail mounted near field communication (NFC) devices providing a unique solution for personal identification in the alcohol distribution, restaurant, bar, education, and/or health-care industries. The materials, design, and circuit integration enable the art of biocompatible NFC technology. In some embodiments, for example, the built-in NFC technology serves as a digital replacement for drivers' licenses and school identification cards. The fingernail-mounted devices of this aspect, for example, are able to wirelessly communicate with point of access readers that use NFC antennas. Instead of carrying personal identification cards, fingernail-mounted devices are able to serve as proof of an individual's identification and/or store pertinent private information.
(105) In an embodiment, for example, the invention has a devoted chip that stores an encrypted identification number that is unique to each individual device. In addition, the chip has action-specific security codes that change after each point of entry. The encrypted identification numbers can serve as a valid form of identification. For instance, “John Smith” (Adult Male Age: 45) uses his fingernail-mounted device as proof that is he over the age of 21 to purchase alcohol.
(106) In some embodiments, for privacy, individual users are not at risk of exposing their name, age, and/or address. In some embodiments, the devices are waterproof and remain operational for several days or months. The systems of this aspect of the invention are able to work in conjunction with mobile phone applications developed specifically for authentication purposes. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled and all private information is destroyed.
Example 5—Fingernail Mounted NFC for Key Access/Authentication
(107) The invention provides, for example, fingernail mounted near field communication (NFC) devices providing a unique solution for key access to places of residence, offices, hotels, and/or safe industries. The materials, design, and circuit integration enable the art of biocompatible NFC technology. In some embodiments, for example, the built-in NFC technology serves as a digital replacement for all physical keys. The fingernail-mounted devices of this aspect, for example, are able to wirelessly communicate with point of access readers that use NFC antennas. The point of access readers include but are not limited to door handles, windows, counter-tops, lockers, safes, and/or automobiles. Instead of carrying around keys, key cards, and/or wallets, authorized fingernail mounted device users are granted access to specific areas, buildings, rooms, and/or automobiles.
(108) In an embodiment, for example, the invention has a devoted chip that stores an encrypted identification number that is unique to each individual device. In addition, the chip has action-specific security codes that change after each point of entry. Based off volunteered personal information, the encrypted identification numbers have access to designated areas. For instance, the invented device is able to unlock hotel room doors.
(109) In some embodiments, for privacy, individual users are not at risk of exposing their name, room number, and/or access restrictions to third-party retailers or by-standers. Customers are not required to carry their cell phones, keys, and/or identification cards to gain access authorization. In some embodiments, the devices are waterproof and remain operational for several days or months. The systems of this aspect of the invention are able to work in conjunction with mobile phone applications developed specifically for authentication purposes. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled and all private information is destroyed.
Example 6—Finger and Toenail Mounted NFC Device for Hospital Monitoring/Tracking
(110) The invention provides, for example, tissue mounted near field communication (NFC) devices providing a unique service platform for monitoring and tracking hospital patients. The materials, design, and circuit integration enable the art of biocompatible NFC technology. In some embodiments, the built-in NFC technology serves as a digital replacement for the hospital identification wristbands and bio-sensing electrodes using copper wire leads. The fingernail-mounted devices of this aspect are able to wirelessly communicate with point of access readers that use NFC antennas. The point of access readers include but are not limited to smartphones, door handles, windows, and/or counter-tops. The invented device gives health-care professionals a way to electronically track and monitor admitted hospital patients. The fingernail-mounted or tissue-mounted devices optionally provide additional bio-sensing modalities that measure temperature, pH levels, glucose, pulse-oximetry, heart rate, respiratory rate, blood pressure, ECG (electrocardiography), EOG (electrooxulography), EEG (electroencephalography), EMG (electromyography), PPG (photoplethysmogram), peripheral capillary oxygen saturation (SpO2), bilirubin level and/or bili light intensity and dose.
(111) In some embodiments, for privacy, the invention has a devoted chip that stores an encrypted identification number that is unique to each individual device. In addition, the chip has action-specific security codes that change constantly. The encrypted device number helps keep patient health-care information private. Clinicians, hospital management, and insurance providers are the only users with access to the information. In case of emergency, hospital personnel can quickly locate missing patients and/or observe patient vital signs.
(112) Individual users are no longer at risk of exposing their name and/or health-care information to by-standers. In some embodiments, the devices are waterproof and remain operational for several days or months. The systems of this aspect of the invention are able to work in conjunction with mobile phone applications developed specifically for authentication purposes. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled and all private information is destroyed.
Example 7—Finger and Toenail Mounted NFC Device for Safe Handling of Hazardous Equipment
(113) The invention provides, for example, tissue mounted near field communication (NFC) devices providing a unique solution for gun safety and safe handling of potentially hazardous machinery where safety is required. The present invention's materials, design, and circuit integration enable the art of biocompatible NFC technology. In an embodiment, the built-in NFC technology serves as an additional layer of safety and security in operating potentially life-threatening equipment. Life threatening equipment includes but is not limited to guns, saws, and/or cutting machinery. The fingernail-mounted devices of this aspect are able to wirelessly communicate with readers that use NFC antennas. The body designed, wearable NFC technology reduces the misuse of hazardous equipment through the use of radio frequency identification systems. Gun triggers are only able to discharge with the detection of an authorized fingernail-mounted device. The invented devices of certain embodiments can activate kill switches in industrial or trade cutting machinery when the user gets too close to a sharp object.
(114) In an embodiment, the invention has a devoted chip that stores encrypted identification information that is unique to each individual device. In addition, the chip has action-specific security codes that change after time of authorization. The encrypted identification information and varying security codes are used to grant or deny operational access to hazardous equipment.
(115) The systems of this aspect of the invention are able to work in conjunction with mobile applications developed specifically for smart guns and/or hazardous machinery. In some embodiments, the devices are waterproof and remain operational for several days or months. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled.
Example 8—Finger and Toenail Mounted NFC Device for Medication Bottle Compliance and Safety
(116) The invention provides, for example, tissue mounted near field communication (NFC) devices providing a unique solution for medication bottles and access to medication where compliance and/or safety is required. The presented invention's materials, design, and circuit integration enable the art of biocompatible NFC technology. In an embodiment, the built-in NFC technology serves as an additional layer of security and/or compliance monitor for medication bottles. The fingernail-mounted devices of this aspect are able to wirelessly communicate with readers that use NFC antennas. The body designed, wearable NFC technology is able to keep track of the amount of times a certain drug bottle is opened and prevents unauthorized individuals access to the medication through the use of radio frequency identification systems. Pill containers are only able to open with the detection of an authorized fingernail-mounted device.
(117) In an embodiment, the invention has a devoted chip that stores encrypted identification information that is unique to each individual device. In addition, the chip has action-specific security codes that change after time of authorization. The encrypted identification information and varying security codes are used to grant or deny access to prescribed medication.
(118) The systems of this aspect of the invention are able to work in conjunction with mobile applications. In some embodiments, the devices are waterproof and remain operational for several days or months. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled.
Example 9—Fingernail Mounted NFC Device for Hospital Hand Washing
(119) The invention provides, for example, tissue mounted near field communication (NFC) devices, as a unique solution for hospital personnel in monitoring whether or not health-care professionals wash their hands before engaging with patients. The present invention's materials, design, and circuit integration enable the art of biocompatible NFC technology. In an embodiment, the built-in NFC technology serves as an additional health monitor and safety precaution. The fingernail-mounted devices of this aspect are able to wirelessly communicate with readers that use NFC antennas. The body designed, wearable NFC technology reduces the risk of health-care associated infections through the use of radio frequency identification systems. The invented device activates in close proximity to a reader installed at a sink, hand sanitizer station, and/or room access point. The reader records information from the activated device such as who washed their hands, at what time, for how long, and at what temperature. The point of access reader records who was present in specific locations. Data sets from both readers are correlated and used to determine failure to adhere to hand washing protocols and contaminated areas. The invented device holds the employee accountable and ensures a more sanitary environment.
(120) In an embodiment, the invention has a devoted chip that stores encrypted information that is unique to each individual device. In addition, the chip has action-specific security codes that change after time of authorization. The encrypted information and varying security codes are used to accurately identify individuals. In some embodiments, the devices are waterproof and remain operational for several days or months. In some embodiments, if removed from the nail or tissue, the invented device is permanently disabled.
Example 10—Fingernail Mounted NFC Device for Gaming, Music-Sharing, Social and Digital Media Platforms
(121) The invention provides, for example, fingernail mounted near field communication (NFC) devices providing a unique platform for gaming, music-sharing, social and digital media service providers. The materials, design, and circuit integration enable the art of biocompatible NFC technology. The fingernail-mounted devices of this aspect are able to wirelessly communicate with smartphones that have NFC capability. Instead of exchanging phone numbers, email addresses, and/or home addresses, users have the ability to privately share digital content and/or personal information.
(122) In some embodiments, the invention has a devoted chip that stores encrypted personal identification numbers that are unique to each individual device. The encrypted information is a way to privately disclose digital content and information. In some embodiments, personal information is never shared with merchants or stored on a server without user consent. In some embodiments, all digital information is stored and shared locally on the consumers' personal mobile devices, computers, web pages, and/or gaming systems.
(123) In some embodiments, for privacy, individual consumers are not at risk of exposing personal information or digital content with unauthorized parties. Customers do not have to carry their phones and/or business cards to disclose private information. In some embodiments, devices are waterproof and remain operational for several days or months. The systems of this aspect of the invention are able to work in conjunction with mobile phone applications developed specifically for media sharing purposes. In some embodiments, if removed from the nail, the invented device is permanently disabled and all digital content is destroyed.
Example 11—Actuating Tissue Mounted Devices
(124) The invention provides, for example, fingernail-mounted near field communication (NFC) devices providing a unique platform for consumer, defense, and or intelligence agencies. The materials, design, and circuit integration enable the art of biocompatible NFC technology. The fingernail-mounted devices of this aspect are able to wirelessly communicate with smartphones and other devices that have NFC capability. Users have the ability to trigger a response that permanently disables device functionality and erases all digital content in the event of termination of use and or unauthorized possession.
Example 12—Tissue Mounted Devices
(125) The systems and methods of the invention are highly versatile and support a broad range of applications. This example illustrates a range of different device embodiments supporting many different applications. The following description provides examples showing the broad capabilities of the present systems. The common components of the exemplified systems include a substrate that has an antenna and inorganic and/or organic electronic components within the system's dimensions, most of which include but are not limited to a RFID IC that can take on various ISO and non ISO compliant forms. The components are configured to be used in either an active or passive state depending on the application. The devices exemplified have dimensions and geometries allowing for electromagnetic and mechanical form factors which optimally match the desired application.
Example 13—Tissue Mounted Devices
(126) The systems and methods of the invention are highly versatile and support a broad range of applications. This example illustrates a range of different device embodiments supporting many different applications. The following description provides examples showing the broad capabilities of the present systems. The common components of the exemplified systems include a substrate that has an antenna and inorganic and/or organic electronic components within the system's dimensions, most of which include but are not limited to a RFID IC that can take on various ISO and non ISO compliant forms. The components are configured to be used in either an active or passive state depending on the application. The devices exemplified have dimensions and geometries allowing for electromagnetic and mechanical form factors which optimally match the desired application.
(127)
(128)
(129)
(130)
(131)
(132)
(133)
(134)
STATEMENTS REGARDING INCORPORATION BY REFERENCE AND VARIATIONS
(135) All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).
(136) The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, and method steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.
(137) When a group of substituents is disclosed herein, it is understood that all individual members of that group and all subgroups, including any isomers, enantiomers, and diastereomers of the group members, are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer, enantiomer or diastereomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individually or in any combination. Additionally, unless otherwise specified, all isotopic variants of compounds disclosed herein are intended to be encompassed by the disclosure. For example, it will be understood that any one or more hydrogens in a molecule disclosed can be replaced with deuterium or tritium. Isotopic variants of a molecule are generally useful as standards in assays for the molecule and in chemical and biological research related to the molecule or its use. Methods for making such isotopic variants are known in the art. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently.
(138) Many of the molecules disclosed herein contain one or more ionizable groups [groups from which a proton can be removed (e.g., —COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.
(139) Every formulation or combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated.
(140) Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.
(141) All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art. For example, when compositions of matter are claimed, it should be understood that compounds known and available in the art prior to Applicant's invention, including compounds for which an enabling disclosure is provided in the references cited herein, are not intended to be included in the composition of matter claims herein.
(142) As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms “comprising”, “consisting essentially of” and “consisting of” may be replaced with either of the other two terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
(143) One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.