Adjustable intraocular lens with a modifiable anterior absorption protection layer

Abstract

Examples of a Modulatable Absorbing Light Adjustable Lens (MALAL) include: a light adjustable lens capable of changing its optical properties upon adjustment of illumination, including a light modifiable material; and a pre-modulation absorbing protective layer including a modulatable absorbing compound whose absorption characteristics can be modulated by a modulation stimulus. Other examples include a method of adjusting the optical properties of a modulatable absorbing light adjustable lens, the method including: reducing the absorption of the modulatable absorbing compound of the pre-modulation absorbing protective layer of the MALAL by a modulation stimulus, the MALAL having been previously implanted in an eye; and changing the optical properties of the light adjustable lens of the MALAL by applying adjustment illumination.

Description

Technical Field

[0001] The present invention relates to light - adjustable lenses, and more particularly to light - adjustable lenses having modifiable absorption. Background Art

[0002] Techniques and tools for cataract surgery are undergoing continuous and impressive advancements. Successive generations of phacoemulsification platforms and newly invented surgical lasers are constantly improving the placement accuracy of intraocular lenses (IOLs) and continuously reducing unwanted medical outcomes.

[0003] However, even after carefully planning the selection of the IOL and implanting it into the capsular bag using precision surgical equipment, the post - implantation healing and scar formation of ocular tissues often cause the IOL to shift or tilt from its planned and optimal position in the eye's capsular bag. This settling process can take several weeks. Such shifts and tilts have the potential to deteriorate the optical performance of the IOL and thus the overall medical outcome of cataract surgery.

[0004] Recently, an intraocular light - adjustable lens (LAL) technology has been invented and developed to address this problem. Just like conventional IOLs, LALs can shift and tilt during the several - week settling process after being implanted into the capsular bag. However, the shift and tilt of LALs can be compensated for by adjusting the optical properties of the implanted LAL. This adjustment can be achieved by illuminating the LAL with ultraviolet (UV) light beams having a carefully selected spatial distribution.

[0005] To prevent the UV portion of sunlight from altering the optical properties of the LAL during the weeks between implantation and dimming, patients are required to follow instructions to wear UV - blocking glasses. However, even a limited interruption in compliance, such as a patient forgetting to wear anti - UV sunglasses while walking on a sunny day, can lead to uncontrolled and undesired changes in the optical properties of the LAL. U.S. Patents 8,604,098 and 8,933,143, both entitled “On - demand photoinitiated polymerization” and assigned to Boydston et al., propose introducing “masking compounds” to address this problem. However, as described below, these designs do not address the challenge of unexpected lens modification due to patient non - compliance. Thus, there remains an unmet medical need for improvements in light - adjustable lens technology that reduce and possibly eliminate the need for patients to strictly adhere to wearing UV - blocking glasses. Summary of the Invention

[0006] The above need is addressed by embodiments of a modifiable - absorption light - adjustable lens (MALAL), comprising: a light - adjustable lens capable of changing its optical properties upon conditioning illumination, including a light - modifiable material; and a pre - protective layer of modifiable absorption, including a modifiable - absorption compound whose absorption properties can be modulated by a modulation stimulus.

[0007] Other embodiments include a method of adjusting the optical properties of a tunable absorption light - adjustable lens, the method comprising: reducing the absorption of a tunable absorption compound of a tunable absorption front - protective layer of a MALAL by modulating a stimulus, the MALAL having been previously implanted into an eye; and changing the optical properties of the light - adjustable lens of the MALAL by applying an adjustment irradiation. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 Illustrates a light - adjustable lens 10.

[0009] Figure 2 Illustrates the formation of a region having modified optical properties by excessive UV radiation.

[0010] Figure 3A -F illustrates an embodiment of a tunable absorption light - adjustable lens (MALAL) 100.

[0011] Figure 4 Illustrates the chemical properties of a light - modifiable material 111.

[0012] Figure 5A -F illustrates the light - adjustment steps of the MALAL 100.

[0013] Figure 6 Illustrates the absorption of single - source illumination in the front - protective layer 120 and the LAL 110 during treatment.

[0014] Figure 7A -D illustrates various ways in which a tunable absorption compound 300 can be associated with a polymer host matrix 112.

[0015] Figure 8A -B illustrates the chemical composition and absorption spectrum of azobenzene.

[0016] Figure 9 Illustrates the chemical composition and absorption spectrum of the trans - photoisomer of vinylphenylazo - pyrazole.

[0017] Figure 10A Illustrates the chemical composition and absorption spectrum of 4 - aminoazobenzene.

[0018] Figure 10B Illustrates the chemical composition and absorption spectrum of 4-(4'-hydroxyphenylazo) benzoic acid.

[0019] Figure 11 Illustrates the time evolution of the absorption rate during the trans - cis transition.

[0020] Figure 12A-Figure B illustrates the time evolution of the "absorbance" during the trans-cis transition, magnified to the wavelength region in the visible spectrum.

[0021] Figure 13 The reversibility of the absorption modulation is illustrated.

[0022] Figure 14A -Figure C illustrates small regions that are possible but highly unlikely to form in MALAL 100.

[0023] Figure 15A -Figure B illustrates the steps of a method for adjusting the optical properties of an optically tunable lens with modifiable absorption. Detailed Description of the Invention

[0024] This document describes embodiments of an optically tunable intraocular lens that provides improvements with respect to the above-described medical needs. The description begins with a detailed review of optically tunable lens technology.

[0025] Figure 1 Figure shows an optically tunable lens (LAL) 10 that can be stabilized in the capsular bag during implantation by a haptic 12. As previously mentioned, within weeks after cataract surgery, scar formation and healing of the ocular tissue can displace and tilt the LAL 10 from its planned optimal position within the capsular bag. In addition, healing of the cornea can have a significant impact on the resulting refraction. A key innovation in LAL technology is to determine, after the LAL 10 has settled in the capsular bag, what adjustments to the optical properties of the LAL 10 can compensate for this unplanned displacement and tilt. This determination can involve objective measurements and subjective feedback from the patient. The LAL 10 is then illuminated with ultraviolet (UV) light having a spatial distribution or nomogram that is selected to cause a determined adjustment to the optical properties of the LAL to compensate for the displacement and tilt.

[0026] Given the sensitivity of the optical properties of the LAL 10 to UV light, during the weeks between implantation and adjustment, the patient is instructed to wear UV-blocking glasses to prevent the UV portion of solar radiation from accidentally modifying the optical properties of the LAL 10. However, even a limited lapse in compliance, such as the patient forgetting to put on the UV-blocking glasses when going outside, can result in a significant change in the optical properties of the LAL 10.

[0027] Figure 2 The results of such non-compliance are illustrated in detail via a cross-section of the LAL 10 after its exposure to an accidental large amount of UV illumination. The UV illumination causes the LAL 10 to photopolymerize in a region 20 having a considerable spatial extent, thus adjusting the optical properties of the LAL 10 to a considerable degree in an uncontrolled manner, resulting in a degraded visual outcome.

[0028] Figure 3A-F shows an embodiment of a Modulatable Absorbing Light Adjustable Lens (MALAL) 100, which is suitable for preventing the formation of such an undesired region in case of accidental non-compliance. Figure 3A The MALAL 100 in Figure 3A may include a light adjustable lens LAL110, which is capable of changing its optical properties upon adjustment of irradiation. The LAL 110 includes a light modifiable material 111; and a modulatable pre-absorbing protective layer 120, which includes a modulatable absorbing compound 300, whose absorption properties can be modulated with a modulation stimulus. The optical properties of the LAL110 can be adjusted by adjusting the shape of the LAL 110, the refractive properties of the LAL 110, the refractive index, the absorption properties or the polarization properties of the LAL110, or a combination of these properties of the LAL110, thereby also changing the optical properties of the MALAL 100. The MALAL 100 may also include a haptic member 130, typically extending from the light adjustable lens 110. Embodiments of the haptic member 130 may include 1, 2, 3 or more separate arms extending from the LAL110. In other embodiments, the haptic member may be a flat, flexible extension of the LAL 110, having a rectangular or modified circular rectangular design. In some embodiments, the haptic member 130 may extend from the modulatable pre-absorbing protective layer 120 or from an auxiliary structure.

[0029] To place the description of the MALAL 100 in context, the light adjustable lens LAL 110 itself will first be described in detail in Figure 4 and Figure 5A -F.

[0030] Figure 4 It is shown that in the LAL 110 of the MALAL 100, the light modifiable material 111 may include a polymer host matrix 112. The polymer host matrix 112 may be a silicone-based matrix, an acrylate-based matrix, a collagen polymer (collamer), a hybrid silicone-acrylate-based matrix, or a multi-layer matrix combining at least two of the foregoing matrices.

[0031] In the LAL 110 of the MALAL 100, the light modifiable material 111 may also include a photopolymerizable monomer or macromonomer 113 capable of photopolymerization. These photopolymerizable monomers / macromonomers 113 may also include photopolymerizable end groups 114. In addition, the light modifiable material 111 may include a photoinitiator 115, which may be separate from the photopolymerizable monomer / macromonomer 113, or may be a functional group at the end of the photopolymerizable monomer / macromonomer 113.

[0032] Modulating stimuli, such as the aforementioned UV illumination, can activate the photoinitiator 115, which in turn can induce the photopolymerization of the photopolymerizable monomer / macromonomer 113, typically via their photopolymerizable end groups 114. This photopolymerization process modulates the optical properties of the LAL 110, thereby modulating the optical properties of the MALAL 100, as described below.

[0033] The LAL 110 of the MALAL 100 can also include dispersed ultraviolet (UV) light absorbers 116. Such UV light absorbers 116 can serve different functions. One of them is to ensure that substantially all of the incident UV illumination within the LAL 110 is safely absorbed, thus providing retinal safety for the eye. Additionally, the UV light absorber 116 can also play a role in controlling and shaping the spatially varying depth profile of the MALAL 100.

[0034] So far, embodiments of modulating the MALAL 100 by UV illumination as modulating irradiation have been described. In other embodiments, the modulating irradiation can involve other parts of the electromagnetic spectrum, such as a specific part of the UV spectrum or the infrared part. Additionally, the modulating irradiation can be incoherent or coherent laser-like illumination, which can be applied simultaneously or sequentially in a scanning manner to a large area of the LAL 110.

[0035] Figure 5A -F illustrates in detail the process of modulating the optical properties of the LAL 110 of the MALAL 100. Figure 5A The first step in illustrating the LAL technology is the conventional implantation of the LAL 110 into the eye of a cataract patient. Figure 5B The illustrated implanted LAL 110 can include photopolymerizable monomer / macromonomer 113 embedded in a polymer host matrix 112. In the weeks following implantation, the LAL 110 often shifts and tilts within the capsular bag. Additionally, as previously mentioned, corneal healing also affects the optical properties of the eye. After a few weeks, once the LAL 110 has settled within the capsular bag, the optical consequences of this shift, tilt, and corneal healing can be optically compensated by applying modulating irradiation 210 to modulate the optical properties of the LAL 110. The modulating irradiation 210 is applied with a spatial distribution, sometimes referred to as a nomogram, which is designed to cause modulation of the optical properties of the LAL 110 to compensate for the shift and tilt of the LAL 110. In some embodiments, the modulating irradiation 210 can be generated by a UV source, such as a mercury lamp or a UV LED. The desired spatial distribution can be achieved by deflecting or modulating the generated modulating irradiation 210 with a digital mirror device or a suitable alternative.

[0036] Figure 5CThe figure illustrates that the conditioning illumination 210 can partially polymerize the spatially varying portion of the photopolymerizable monomer / macromonomer 113 into a photopolymerized macromonomer 113p with a programmed spatial distribution (shown in thick lines).

[0037] Figure 5D The figure shows that the induced spatial variation density of the polymerized macromonomer 113p induces a spatial variation density of the remaining unpolymerized monomer / macromonomer 113. This results in a spatially varying chemical potential that drives the unpolymerized monomer / macromonomer 113 to diffuse into the central region of the LAL 110. This diffusion causes the central region of the LAL 110 to expand, thereby increasing the optical power of the LAL 110 and generating hyperopic accommodation. The embodiments just described adjust the optical properties of the LAL 110 by adjusting the shape of the LAL 110. For certain classes of light-modifiable materials 111, the conditioning illumination 210 can adjust the optical properties of the LAL 110 in other ways, such as by adjusting the refractive index of the light-modifiable material 111. Finally, in some embodiments, the shape and refractive index of the light-modifiable material 111 can be adjusted by the conditioning illumination 210. Additionally, in cases where myopic accommodation is desired, i.e., when reducing the optical power of the LAL 110, the distribution of the conditioning illumination and thus the induced polymerization can be concentrated at the periphery rather than the center of the LAL 110.

[0038] Figure 5E The figure illustrates the fact that there will be remaining photopolymerizable monomer / macromonomer 113 that has not been polymerized by the conditioning illumination 210 and may therefore polymerize later when UV-containing ambient light reaches the LAL 110. This subsequent polymerization will cause uncontrolled and undesirable additional changes in the optical properties of the LAL 110. The LAL technology addresses this challenge by applying a locking illumination 220 to the LAL 110 at some time after the conditioning illumination 210 to polymerize substantially all of the remaining photopolymerizable monomer / macromonomer 113. This locking illumination 220 is typically power-neutral, i.e., it is not meant to further adjust the optical properties of the LAL 110, as Figure 5F shown. In some cases, if Figure 5B the result of the conditioning process does not result in the programmed optical result for some reason, then a non-power-neutral locking illumination 220 can be applied. After substantially all of the macromonomer 113 has been polymerized by the locking radiation 220, subsequent exposure to sunlight or ambient light cannot induce further polymerization of the LAL 110 and further changes in the optical properties. Therefore, Figure 5A the steps described in Figure 5AThis LAL adjustment process described in -F is described in more detail in the co-owned U.S. Patent 6,905,641 to Platt et al., entitled: "Delivery System for post-operate power adjustment of adjustable lens", which is incorporated herein by reference in its entirety.

[0039] As described above, the patient is instructed to wear the UV-blocking glasses through the Figure 5A steps of -E until all the photopolymerizable macromonomers 113 are photopolymerized by the conditioning irradiation 210 and the locking irradiation 220 to prevent accidental changes in the optical properties of the LAL 110. However, over a period of several weeks, such a requirement may inconvenience the patient, and they may ultimately inadvertently break compliance, which may lead to undesired optical changes in the LAL 110. Embodiments of the MALAL 100 provide improved techniques to ensure that the optical properties of the LAL 110 remain under control when included in the MALAL 100, even if the patient slips in terms of compliance, such as forgetting to wear the UV-blocking glasses.

[0040] Return Figure 3A , the MALAL 100 additionally includes a modifiable absorption front protective layer 120 positioned in front of the LAL 110. This layer includes a modifiable absorption compound 300 whose absorption properties can be modulated with a modulation stimulus 310. The modifiable absorption compound 300 can have a high absorption conformation and a low absorption conformation, where the modifiable absorption compound 300 is capable of transitioning from the high absorption conformation to the low absorption conformation when absorbing a high-to-low modulation stimulus 310-htl. Additionally, the modifiable absorption compound 300 is capable of transitioning from the low absorption conformation to the high absorption conformation when absorbing a low-to-high modulation stimulus 310-lth. For simplicity, without causing confusion, the high-to-low modulation stimulus 310-htl and the low-to-high modulation stimulus 310-lth can be collectively referred to as the modulation stimulus 310, even though they may be generated by different sources, because they both modulate the absorption of the modifiable absorption compound 300. Additionally, the modifiable absorption compound 300 in its high absorption conformation will sometimes be referred to as the high absorption isomer 300-h, while the modifiable absorption compound 300 in its low absorption conformation will be referred to as the low absorption isomer 300-l. In still other cases, the modifiable absorption compound 300 will be referred to as a chromophore, its high absorption conformation being the high absorption chromophore 300-h, and its low absorption conformation will be referred to as the low absorption chromophore 300-l.

[0041] When at Figure 5AWhen using this MALAL 100 in the LAL technology of -F, the MALAL 100 can be fabricated with a tunable absorption compound 300 of a highly absorptive conformation in a tunable absorption pre-protective layer 120 and implanted into the eye in this state. By this fabrication method, the tunable absorption pre-protective layer 120 provides strong protection for the photo-modifiable material 111 of the LAL 110 against accidental UV exposure that may occur due to non-compliance within a few weeks between steps Figure 5A and Figure 5B , such as forgetting to wear UV-blocking glasses. Here and subsequently, the photo-regulation process will be described with reference to the steps shown in Figure 5A -F, where the LAL 110 will be the LAL 110 within the MALAL 100 embodiment.

[0042] Some embodiments of the MALAL 100 can provide more than just protection against accidental non-compliance. Some MALAL 100s can be fabricated to provide strong enough protection such that it is not even necessary to wear UV-blocking glasses between the implantation and locking of the MALAL 100. This benefit of the MALAL 100 greatly reduces the burden on patients and doctors as it increases patient comfort and fundamentally eliminates the risk of unintentional non-compliance and undesired outcomes. In these MALAL 100s, a tunable absorption compound 300 with a high enough UV absorption is selected, and a tunable absorption pre-protective layer 120 with a large enough thickness is selected such that the combination of these factors provides sufficient protection for the photo-modifiable material of the LAL 110 against solar UV irradiation during the weeks from the implantation in Figure 5A to the regulation process until Figure 5B and until the locking at Figure 5E , such that the optical properties of the MALAL 100 do not change even when exposed to solar UV irradiation.

[0043] Once the MALAL 100 has settled in the capsular bag, it is necessary to regulate the optical properties of the LAL 110 of the MALAL 100 as outlined previously in Figure 5B . In addition to the conventional LAL technology, this process first applies a high-to-low modulation stimulus 310-htl to transform the tunable absorption compound 300 from the high-absorption isomer 300-h to the low-absorption isomer 300-l. Before this transformation, the regulation irradiation 210 cannot pass through the high-absorption isomer 300-h of the tunable absorption pre-protective layer 120, but after this transformation to the low-absorption isomer 300-l, the regulation irradiation 210 can pass through the tunable absorption pre-protective layer 120 and reach the LAL 110, thereby regulating its optical properties.

[0044] As in Figure 6As shown, in some embodiments, the source of the modulation stimulus 310 can be the same as the source of the conditioning illumination 210, such as a mercury lamp or a UV LED. In such a single shared source embodiment, the MALAL 100 can be illuminated by a UV beam from the shared source that is initially used as the primary high-to-low modulation stimulus 310-htl, but as the illumination converts the modifiable absorption compound 300 in the front protective layer 120 from the high absorption isomer 300-h to the low absorption isomer 300-l, an increasing amount of the UV beam passes through the front protective layer 120 and reaches the LAL 110, and thus increasingly acts as the primary conditioning illumination 210, as shown. In some embodiments, the spatially varying distribution of the illumination from the shared source can vary over time. During an initial time period when the illumination is primarily the modulation stimulus 310, the spatial distribution can be chosen to be flat-top, largely independent of the radius to avoid modulating the optical power of the LAL 110, while at a later time when the illumination is primarily the conditioning illumination 210, the spatially varying distribution can switch to a power-modulated distribution, such as polynomial or Gaussian, truncated at a large radius if necessary. In other embodiments, the spatially varying distribution can be power-modulated over the entire time of the illumination. Finally, in other embodiments, the illumination can be applied with a flat-top distribution when it is primarily the modulation stimulus 310, then stopped, and then restarted with a power-modulated distribution during a time interval when it is primarily the conditioning illumination 210.

[0045] Although embodiments of the MALAL 100 have been described so far as being adjustable by UV illumination as the modulation stimulus 310, in other embodiments, the modulation stimulus 310 can take other forms, including electromagnetic illumination, laser irradiation, infrared irradiation, ultraviolet illumination, magnetic stimulation, electric fields, chemical stimulation, heat transfer, energy transfer, ultrasound-mediated stimulation, mechanical stimulation, thermal stimulation, or thermal relaxation.

[0046] Figure 3A -FIG. illustrates that the front protective layer 120 can be positioned facing the LAL110 in several different ways. In Figure 3A the embodiment, the modifiable absorption compound 300 can be dispersed in the front region 122 of the optically tunable lens LAL 110 to form the modifiable absorption front protective layer 120.

[0047] Figure 7A -FIG. D illustrates that the modifiable absorption compound 300 can be positioned in the polymer host matrix 112 in the front region 122 of the optically tunable lens 110 in various ways. Figure 7A It is shown that the modifiable absorption compound 300 can be positioned in the polymer host matrix 112 by one or more bonds 302 with the crosslinker 117 of the polymer host matrix or the chains 303 of the polymer host matrix, as Figure 7BAs shown. In such embodiments, one or more bonds 302 of the positionable modifiable absorption compound 300 may include bonds coupling carbon or silicon to carbon, silicon, oxygen, nitrogen, hydrogen, sulfur, or halogen atoms.

[0048] Figure 7C Illustrated in some embodiments, the modifiable absorption compound 300 may be movable relative to the polymer host matrix 112, or may be a long-chain polymer that interpenetrates with the photo-modifiable material 111. Finally, Figure 7D Illustrated that the modifiable absorption compound 300 may be bonded to an interpenetrating network 118 that is entangled in the polymer host matrix 112. The greater the mobility of the modifiable absorption compound 300 relative to the polymer host matrix 112, the more likely it is that a barrier layer is needed to prevent the modifiable absorption compound 300 from diffusing into the eye itself or the LAL 110.

[0049] Figure 3B Illustrated in other embodiments of the MALAL 100, the pre-modifiable absorption protective layer 120 may be a layer attached to the front region 122 of the light-adjustable lens LAL 110, or a layer deposited on the front region 122 of the light-adjustable lens LAL 110. In these embodiments, the modifiable absorption compound 300 is less likely to exhibit diffusion into the LAL 110.

[0050] Figure 3C Illustrated in some MALALs 100, the pre-modifiable absorption protective layer 120 may be positioned in front of the light-adjustable lens LAL 110 and at least partially separated therefrom. Such embodiments provide an even clearer separation between the pre-modifiable absorption protective layer 120 and the LAL 110, as well as further design features that can be optimized.

[0051] Figure 3D Illustrated in some MALALs 100, the pre-modifiable absorption protective layer 120 may be mostly or completely separated from the LAL 110 and may be held in place by a carrier structure 140 or simply the carrier 140. The carrier structure 140 may have many different designs, including a rear surface with openings as shown, or no openings in other designs.

[0052] Finally, Figure 3E -F Illustrated in some embodiments, the pre-modifiable absorption protective layer 120 may be an intraocular element that can be independently inserted. It can be inserted into the carrier 140, or in some embodiments, only into a pocket in front of the LAL 110.

[0053] The physical extent of the modifiable pre-absorption protective layer 120 can be characterized by a thickness that is relatively less than 50%, 25%, 5%, or 2% of the thickness of the light adjustable lens LAL 110. Absolutely speaking, the thickness of the modifiable pre-absorption protective layer 120 can be in the range of 1 - 200 microns, in some cases in the range of 1 - 100 microns, and in other cases in the range of 10 - 50 microns.

[0054] Before proceeding, we return to U.S. Patents 8,604,098 and 8,933,143, both titled: “On-demand photoinitiated polymerization,” and both granted to Boydston et al. These patents propose introducing a “masking compound” into the light adjustable lens to reduce the risk of accidental polymerization before light modulation, when photo-isomerization is triggered to allow lens adjustment. However, the solutions provided by these patents do not solve the problem because the masking compound is widely distributed throughout the volume of the light adjustable lens. Since the masking compound is dispersed throughout the lens volume, the front region of the light adjustable lens is not adequately protected and is prone to forming undesired regions, resulting in uncontrolled and undesired changes in its optical properties.

[0055] Embodiments of the MALAL 100 address where prior proposals failed by concentrating the protective modifiable absorption compound 300 in a pre-protective layer 120 formed and positioned relative to the front face of the LAL 110, rather than dispersing the compound 300 throughout the volume of the LAL 110. This is a structural improvement that enables the MALAL 100 to provide comprehensive UV ray protection for the most front-facing region of the LAL 110 because only this front positioning of the protective modifiable absorption compound 300 can prevent the formation of accidental regions and uncontrolled optical changes from implantation to adjustment until locking of the MALAL 100.

[0056] Figure 8A-B continues the description of embodiments of MALAL 100 by identifying and describing specific examples of the modifiable absorption compound 300. For the sake of concreteness, the description starts with a detailed specification of a particular example, followed by a large number of alternative solutions. Azobenzene is one of the compounds known to change its absorption properties upon photo-stimulation. Azobenzene is one of the simplest examples in the family of compounds called azo compounds, which have the general form R-N=N-R', where R and R' can be aryl or alkyl, or groups of these. Azobenzene is known to have two conformations with different bond angles between the N=N double bond and one of the two benzene rings. The "trans" conformation has high absorption in the UV spectrum, with a peak in the wavelength range of 360 - 370 nm, where the absorption involves a π to π* electronic transition. Similar absorption peaks also exist in various functionalized azobenzenes. UV light with a wavelength of approximately 365 nm can be used as a high-to-low modulation stimulus 310-htl to convert azobenzene from its high-absorption isomer 300-h with a trans conformation to its low-absorption isomer 300-l with a cis conformation. As shown, the cis conformation has much lower absorption near a wavelength of 365 nm. Thus, azobenzene is an example of the modifiable absorption compound 300 of the front protective layer 120, which largely blocks incoming UV rays in its trans conformation 300-h but can be converted to the low-absorption cis conformation 300-l to let the conditioning radiation 210 reach the LAL 110. For completeness, it is mentioned that azobenzene-based compounds can have additional conformations.

[0057] As described with respect to Figure 6 what has been described, when illuminating the MALAL 100 with UV light, it first mainly acts as a high-to-low modulation stimulus 310-htl and converts an increasing portion of the azobenzene modifiable absorption compound 300 from its high-absorption trans isomer 300-h to its low-absorption cis isomer 300-l. As the UV illumination continues to modulate the absorption of azobenzene by inducing the trans-to-cis transition, the increasing portion of the UV beam passes through the front protective layer 120 and reaches the LAL 110, where it acts as the conditioning irradiation 210 thereby changing the optical properties of the LAL 110. The UV illumination can be applied in a spatial distribution or a raster pattern, which enables a programmed adjustment of the optical properties of the LAL 110.

[0058] Once the UV beam acting as the conditioning irradiation 210 has been applied, its spatial distribution is what is ultimately required to induce the adjustment of the optical properties of the LAL 110, as Figure 5B shown, the diffusion of the photopolymerizable macromonomer 113 starts, as shown in Figure 5C -D. However, since this diffusion may take a day or more, it is necessary to protect the MALAL 100 again from uncontrolled UV illumination until Figure 5EThe locked irradiation 220. This protection can be achieved by applying a low-to-high modulation stimulus 310-lth to transform the low-absorbing isomer 310-l back to the high-absorbing isomer 300-h. In the case of azobenzene, this translates to transforming the cis conformation back to the trans conformation. This can be done by applying a low-to-high modulation stimulus 310-lth that has a significant spectral weight near the maximum absorption of the low-absorbing cis isomer 300-l.

[0059] Figure 8B The figure shows that the low-absorbing cis isomer 300-l has an absorption peak near 450 nm, which is an absorption peak related to the n to π* electronic transition. Therefore, illumination with strong spectral weight near 450 nm can be used as the low-to-high modulation stimulus 310-lth and can induce the cis-to-trans transformation to re-establish the UV protection for the underlying L AL 110.

[0060] Applying a low-to-high modulation stimulus 310-lth with (1) a dedicated light source may be helpful for some embodiments, but in some other embodiments, this is not necessary. At least the following other reagents can return the cis conformation 300-l to the trans conformation 300-h. (2) Thermodynamic relaxation, since the trans conformation has lower energy than the cis conformation, so thermodynamic relaxation efficiently restores azobenzene to its initial trans conformation. (3) Sunlight or ambient light itself can act as an efficient promoter to drive azobenzene to a driving steady state with a high concentration of trans conformation, as described in detail below.

[0061] Generally speaking, a complete description of photo-isomerization can be considered as a dynamic equilibrium of trans-to-cis and cis-to-trans reactions:

[0062] Reaction R

[0063] VPAP trax +hv→VPAP cis R i (1a)

[0064] VPAP cis +hv→VPAP tranx R c (1b)

[0065] Here the reaction rate can be defined by spectral integration as follows:

[0066]

[0067]

[0068] Here and is the quantum yield of absorption, defined as the photoinduced transitions / absorbed photons and is thus dimensionless. These quantum yields have little wavelength dependence over the relevant wavelength intervals and will be neglected. I s (λ) is the spectral irradiance of the incident radiation, in units of [power / (area * wavelength)), such as [mW / (cm 2 * nm)). The trans-to-cis absorption associated with the π-π* transition is induced by the absorption of photons in the range of λ t1 -λ t2 while the cis-to-trans absorption associated with the n-π* transition is induced by the absorption of photons in the range of λ c1 -λ c2 —these two wavelength intervals will also be referred to as absorption bands and form the boundaries of the integral. ε t (λ) and ε c (λ) are the molar absorptivity values in the trans and cis states, respectively, in units of [volume / (mol * length)), such as [liter / (mol * cm)); and c c and c t are the concentrations of the modifiable absorption compound 300 in its low-absorbing cis and high-absorbing trans conformations, typically in units of [mol / liter). The molar absorptivity can also be considered as the absorption cross-section. Equations (2a)-(2b) yield the reaction rate R t / R c , in units of [(1 / sec) * (reaction / cm 3 )) and is related to the inverse time constant k t / k c via the concentration c t / k c . R therm is the rate of thermal decay of the cis state to the trans state. R therm can be estimated as k therm * c c , where k therm can be defined as the reciprocal of the 1 / e time constant of thermal relaxation. In some typical compounds, k therm -1 is typically in the range of 1 - 20 hours, in some cases up to 1 - 5 days, but can also be 10 - 1,000 seconds. In the presence of a modulation stimulus 310-lth from low to high, even including ambient light, the k therm term is typically 2 or 3 orders of magnitude smaller than the integral term and will be neglected in the current analysis. Additionally, the concentration of the trans conformation is given by c t while the concentration of the cis conformation is given by c c . Naturally, c t + c c = c o, the total concentration of the modifiable absorption compound 300, in this case, is the total concentration of azobenzene that does not change with time. The speed of light is simply denoted by c, and the Planck constant is denoted by h. Using these constants, the term λ / hc = 1 / hv divides the spectral irradiance I s (λ) by its energy hv, thus converting the spectral irradiance from power density to photon number density.

[0069] In a steady state, dynamic equilibrium, the trans-to-cis and cis-to-trans rates are equal

[0070] R t = R c (3)

[0071] The relationship determines the ratio of the cis and trans concentrations in this dynamic equilibrium as:

[0072]

[0073] For individual cis and trans concentrations, the following relationship is obtained:

[0074]

[0075] These results are approximate because they capture the situation when the illumination spectral irradiance I s (λ) is incident on the modifiable absorption compound 300, so they remain near the surface or are for a thin pre-protective layer 120 of modifiable absorption. For the pre-protective layer 120 of modifiable absorption that extends in the z or depth direction, the spectral irradiance decays as the z depth increases as it propagates through the pre-protective layer 120. A more complete treatment captures the effect of this decay on absorption according to the spectral irradiance I s (λ, z) related to the z depth and integrates the rate of the absorption process along the z depth. The results of this in-depth analysis are usually well approximated by the above formula. The effect of the depth dependence of the irradiance will be further analyzed below.

[0076] First, the case of high-to-low modulation stimulus 310-htl will be considered. In a typical situation, such a stimulus 310-htl can be applied by a powerful UV light source, such as a mercury lamp or a UV LED. Such a light source usually produces illumination with a rather narrow band. This can be approximated by a Dirac delta centered at the standard wavelength 365 nm of a mercury lamp:

[0077]

[0078] Thereby simplifying the integral to a product and obtaining a simple expression for the concentration ratio a of this light transmission device LDD:

[0079] For azobenzene, and and the ratio of molar absorbances is about 0.1, yielding a LDD ≈ 0.3. This means that applying a UV light source as the source of the high-to-low modulation stimulus 310-htl causes an equilibrium where the concentration c t of the trans conformation is about one third of the concentration c c of the cis conformation, and thus only about 25% of the modifiable absorption compound 300 will remain in the trans conformation compared to an initial concentration of about 100%. For a suitably chosen thickness of the front protective layer 120, a reduction by about a factor of 4 in this trans conformation concentration is sufficient to allow most of the subsequent conditioning illumination 210 to pass through the front protective layer 120 into the LAL 110. One aspect of the above derivation that is worth stating explicitly is that applying a high-to-low modulation stimulus 310-htl does not convert all of the high-absorbing isomers 300-h entirely into low-absorbing isomers 300-l, but rather the result is a partial modulation and transformation.

[0080] Next, the reverse process is described in the particularly simple case where no explicit light source is applied, but rather ambient light is simply allowed to control the concentrations of the two conformations, the low-to-high modulation stimulus 310-lth. For this case, the spectral irradiance l s (λ) is the solar radiation in the case of direct exposure, i.e., the patient looking directly at the sun. When only diffused sunlight reaches the eye, for indirect diffused exposure, the concentration ratio a remains constant because the equation (4) that controls the concentration ratio is controlled only by the ratio of solar irradiances, and the diffused effect cancels out from this ratio.

[0081] The magnitude of the solar irradiance at wavelengths below 300 nm reaching the IOL is negligible because the cornea efficiently absorbs the shorter wavelength UV light, and the molar absorption above 500 nm of the azobenzene and related compounds considered is similarly negligible. Thus, the integral in equation (4) is performed using the solar spectral irradiance in the wavelength range λ = 300 nm - 500 nm, yielding:

[0082]

[0083] Equation (7) yields for some azo compounds and other compounds described below a concentration ratio a of about 3. For some other modifiable absorption compounds 300, a is in the range of 5 - 10. These values translate for a = 3 to a trans conformation concentration c t = 75%, and for a = 5 - 10 to a trans conformation concentration c t = 84 - 91%. A front protective layer 120 with a modifiable absorption compound within its high-absorbing conformation 300-h and a concentration in the range of 75 - 91% can provide robust UV protection for the underlying LAL 110.

[0084] For completeness, several different embodiments of the modulation stimulus 310-lth from low to high can be employed for the various MALAL 100. (1) As discussed herein, a patient exposed only to ambient light can increase the concentration of the highly absorbing isomer 300-h to a level where it can be used as an effective front protective layer 120. For a thickness of 10 - 100 μ, in some cases 20 - 50 μ, and a total molar concentration c 0 For a front protective layer in the range of 10 - 100 millimoles, in some cases in the range of 20 - 30 millimoles, the time increase of this concentration can be in the range of 1 - 10 seconds. After Figure 5B the conditioning step or Figure 5E the locking step, such switching times can be naturally accommodated in an ophthalmologist's office without the risk of forming uncontrolled regions in the LAL 110 within this very short time. (2) In other embodiments, a dedicated light source can be used as the source of the modulation stimulus 310-lth from low to high to induce the switching back to the highly absorbing isomer 300-h even faster. For example, a solar simulator, a white flashlight, or a stronger illumination source, potentially with a UV filter, can be employed to maximize the conversion rate of 300-l to 300-h. (3) Finally, since the energy of the highly absorbing isomer 300-h is lower than that of the low absorbing isomer 300-l, simple thermal relaxation also restores the modifiable absorbing compound to the protective highly absorbing conformation 300-h. As previously mentioned, for azobenzene, this process may be about a hundred times slower, but this still only translates to a few minutes without any rapid low-to-high modulation stimulus 310-lth. Thus, placing the patient under simple office lighting conditions for a few minutes after surgery can also restore the protective effect of the front protective layer 120.

[0085] The above considerations show that the modifiable absorbing compound 300 has a concentration ratio a << 1 for the narrow-bandwidth UV modulation stimulus 310-htl, while having a concentration ratio a >> 1 for solar radiation, or an explicit low-to-high modulation stimulus 310-lth, and is well-suited to provide two beneficial effects: (1) such modifiable absorbing compounds 300 are capable of protecting the MALAL 100 from uncontrolled optical modulation due to involuntary non-compliance of the patient from implantation to locking; (2) at the same time they are capable of applying the conditioning illumination 210 through conformational changes induced by the modulation stimulus 310.

[0086] Now we return to the issue of the attenuation of spectral irradiance as the z-depth increases. It is worth noting that this attenuation only increases the effectiveness of MALAL 100 because it induces a "self-screening effect". In embodiments where ambient solar irradiance serves as information for modulating stimuli 310-lth from low to high, as solar irradiance propagates deeper into the front protective layer 120, the UV portion I s (λ, z) of the solar irradiance is absorbed faster than the visible portion. This is because there is a substantial amount of the trans-high-absorbing isomer 300-h, such as the previously determined c t > 25%, and the absorption rate in the UV range is higher than that in the visible range. Specifically, in a typical modifiable absorption compound 300 containing the trans-high-absorbing isomer 300-h and the cis-low-absorbing isomer 300-l, this translates to ε(λ = 365 nm) > ε(λ = 450 nm). Examination of the concentration ratio α solar in Equation (7) shows that as the spectral irradiance I s (λ, z) decays faster in the UV range, α solar increases faster. In a simplified explanation, deeper in the front protective layer 120, fewer LTV photons are converting the modifiable absorption compound 300 from the trans-high-absorbing isomer 300-h to the cis-low-absorbing isomer 300-l, while relatively more visible photons are driving the reverse process from the cis-low-absorbing isomer 300-l to the trans-high-absorbing isomer 300-h, thus increasing α solar with increasing depth and further increasing the overall UV-blocking function of the front protective layer 120.

[0087] Next, another aspect of the depth dependence of spectral irradiance is elaborated. The overall reduction of the spectral irradiance leaving the front protective layer 120 through its distal surface is controlled by the absorbance, which is given by the product of ε, the molar absorption rate of the modifiable absorption compound 300, c, the molar concentration of the modifiable absorption compound 300, and D, the thickness of the front protective layer 120. In optical design terms, absorbance is sometimes also referred to as optical density. Thus, different embodiments of the front protective layer 120 containing different modifiable absorption compounds 300 with different molar absorption rates, different molar concentrations, and different thicknesses will provide roughly the same protection as long as the product of these three quantities is the same. The final selection of the modifiable absorption compound 300, its concentration, and thickness can be driven by additional considerations, such as the desire to avoid excessive yellowing of the patient's visual experience.

[0088] Before proceeding, it is useful to summarize the potential benefits of MALAL 100 with the above-described front protective layer 120 relative to existing designs, some of which have been mentioned previously.

[0089] (1) The MALAL 100 with the front protective layer 120 greatly reduces the risk of uncontrolled optical changes in the LAL 110 due to accidental patient non - compliance, such as forgetting to wear UV - blocking glasses.

[0090] (2) Additionally, in the MALAL 100, a relatively low concentration of UV - absorbent 116 dispersed in the volume of the LAL 110 can be employed. Such LAL 110 requires a significantly lower dose for the locking irradiation 220. Any reduction in the UV - locking irradiation dose of the MALAL technology further improves the safety of the surgery.

[0091] (3) The MALAL 100 with a more absorbent front protective layer 120 can even provide such effective UV blocking that the patient may not even need to wear UV - blocking glasses from implantation to adjustment until locking. This is highly beneficial as such a MALAL 100 fundamentally eliminates the risk caused by accidental patient non - compliance and greatly improves the patient's comfort from implantation to locking.

[0092] (4) The MALAL 100 with an even more absorbent front protective layer 120 may not even require Figure 5E the locking step. Once the front protective layer 120 reverts to its highly absorbent isomer 300 - h after the adjustment irradiation 210, the UV blocking of the front protective layer 120 can be so efficient and robust that it can completely prevent UV radiation from entering the LAL 110 for a long time, such as years and decades. In such a highly protective MALAL 100, even if their LAL 110 may contain a significant concentration of non - polymerized photo - polymerizable monomers and macromonomers 113 left over from Figure 5B the adjustment step, the robust, long - term UV absorption of the front protective layer 120 can ensure that the un - polymerized monomers and macromonomers 113 will not be photo - polymerized by sunlight for years and decades. Thus, the MALAL 100 will reliably maintain and provide the optical properties formed by the adjustment irradiation 210 during Figure 5B the adjustment step. Such a "lock - free" MALAL can reduce the number of patient visits required to a single adjustment procedure.

[0093] (5) Even more significantly, in a small subset of patients, the implanted MALAL 100 may not even shift or tilt. These patients may report that their vision remains high and does not deteriorate significantly after implantation. For these patients, the doctor may even conclude that no follow-up visit is even needed to adjust the MALAL 100. For all patients who require a long time for adjustment and / or locking procedures, which may even involve air travel, the possibility of not requiring any form of follow-up may mean a further improvement in their overall experience or "journey" quality.

[0094] (6) Finally, in a small number of cases, due to various other eye degenerations, injuries, or any type of shock, unforeseen changes may occur in the eye a long time after cataract surgery. In such cases, the fact that the lockless MALAL 100 remains adjustable can be very beneficial because such a MALAL 100 can be adjusted in response to unforeseen developments even years after implantation.

[0095] In addition to azobenzene, there are many other embodiments of the modifiable absorption compound 300. The modifiable absorption compound 300 can be an azo-aromatic compound, a diazene, an azo-pyrazole, a diene-ethylene, a bactericide, an azulene, a spiropyran, an ethylene-aromatic compound, a macromonomer of one of these compounds, a polymer of these compounds, a composition containing one of these compounds, a composition containing one of these compounds as a side chain, a composition containing one of these compounds as a main chain with a side chain, a nanoparticle bonded to one of these compounds; and one of these compounds dissolved in an ionic fluid. The modifiable absorption compound 300 can also be a polymer that incorporates any of the just-listed compounds into the polymer main body matrix 112 itself, so it does not have to be incorporated as a side chain. Some such compounds can include polymers that bend in response to light. The description continues by outlining a broad list of embodiments of the modifiable absorption compound 300.

[0096] As previously mentioned, the azo-aromatic compound can be, for example, azobenzene, which exhibits the following conformational changes [1]:

[0097]

[0098] In other embodiments of the modifiable absorption compound 300, the azo-aromatic compound can be 4-methoxyazobenzene [2]:

[0099]

[0100] The modifiable absorption compound 300 can also be indazole, allylated azobenzene with various spacer bonds, or another form of phenylazopyrazole, as shown in [3]-[6]:

[0101]

[0102] Figure 9 In still other embodiments, the azopyrazole can be vinylphenyl azopyrazole ("VPAP") [7], which has the absorption rates shown.

[0103]

[0104] Finally, in some embodiments, the ethylene-aromatic compound can be stilbene [8]:

[0105]

[0106] Figure 10A -Figure B illustrates another aspect of an embodiment of the tunable absorption compound 300. These figures show the dependence of the absorption rate curves on the power density of the high-to-low modulation stimulus 310-htl for 4-aminobenzene in Figure 10A and 4-(4'-hydroxyphenylazo)benzoic acid in Figure 10B . It can be seen that 4-aminobenzene has changed from its high-absorption isomer 300-h to its low-absorption isomer 300-l in response to a small power density or irradiance applied within 60 seconds, such as 10 mW / cm 2 ; while the 4-(4'-hydroxyphenylazo)benzoic acid transition only responds to a relatively high power density of about 100 mW / cm 2 applied by the high-to-low modulation stimulus 310-htl within the same 60 seconds. The selection of the specific tunable absorption compound 300 used in a particular embodiment of the MALAL 100 should be based on characteristics similar to those in Figure 10A -Figure B, as well as the quantities earlier appearing in equations (1)-(7), such as the quantum yield and . For example, some MALAL 100s can be designed such that only power densities far above about 3 mW / cm 2 (integrated over the 250-500 nm range portion of the solar spectrum) of solar power density can induce the transition from the high-absorption isomer 300-h to the low-absorption isomer 300-l. In some cases, these power densities or irradiances can be defined by integrating the spectrum over a narrower wavelength range (such as within the 300-450 nm range).

[0107] Figure 11 and 12A-Figure B illustrates another property of MALAL 100: the time evolution of the absorbance as the highly absorbing trans isomer 300-h of vinylphenylazopyrazole (VPAP) as the modifiable absorption compound 300 transforms or converts into the low-absorbing cis isomer 300-l. In Figure 11 , the absorption curves were acquired at specified times, scanning the duration of the modulation stimulus 310-htl from high to low from 0 seconds to 60 seconds. As previously mentioned, different MALAL design principles can lead to modifiable absorption compounds 300 that preferably have one type of time dependence rather than another.

[0108] Figure 12A The time dependence of the absorbance at approximately 450 nm was magnified and the absorbance curves for the duration of the modulation stimulus 310-htl applied from high to low in the range of 0 - 30 seconds were shown. (Note that the quantity shown in Figure 12 is the absorbance characterizing the absorption of the entire MALAL 100. This absorbance tracks Figure 9-1 the molar absorbance typically measured in solution as shown in 0. The absorbance is also affected by the UV absorber 116 dispersed in the LAL 110, which introduces a large additional absorbance below a wavelength of approximately 400 nm). The UV radiation exposure was kept fixed at 150 mJ / cm 2 . Figure 12B Depicts the time dependence of the absorbance or related absorbance according to the duration of the modulation stimulus 310 at a specific wavelength of 448 nm. These curves show that when exposed to UV radiation of 150 mJ / cm 2 , the modulation stimulus 310-htl from high to low is able to transform most of the modifiable absorption compound VPAP 300 into its low-absorbance isomer 300-l in approximately 20 seconds. 20 seconds is a short enough duration to demonstrate that this absorption modulation MALAL technique is consistent with the expectations of convenient phototherapy.

[0109] For many other embodiments of MALAL 100, modulating the stimulus 310-htl from high to low can include illuminating from high to low using light in a band centered at a wavelength in the range of 300 - 400 nm; and modulating the stimulus 310-lth from low to high can include illuminating from low to high using light in a band centered at a wavelength in the range of 300 - 700 nm (including the solar spectrum). In other words, when referring to illumination and its wavelength, the wavelength generally means illumination in a band having a central peak at the said wavelength, and the band also has a bandwidth around the central wavelength, because in many cases the illumination source is not a coherent laser, so the illumination has a limited bandwidth or spectral spread. For the modulating stimulus 310-htl from high to low, the source can be a narrow-band source, and the width of the band can be in the range of 1 - 50 nm, in other embodiments in the range of 1 - 10 nm, such as a mercury lamp or a UV LED. For the modulating stimulus 310-lth from low to high, the source can have a rather wide frequency band, even including the conventional solar spectrum extending from about 300 nm to over 2,500 nm.

[0110] As previously mentioned, for some modifiable absorption compounds 300, natural thermal relaxation may have been sufficient to play the role of modulating the stimulus 310-lth from low to high by inducing a transition from a low-absorbing chromophore 300-1 to a high-absorbing chromophore 300-h. For MALAL 100 that converts the low-absorbing chromophore 300-l to the high-absorbing chromophore 300-h through thermal relaxation, the description of the light source with a central peak and bandwidth in the band is not a natural characterization.

[0111] In some embodiments of MALAL 100, the terms "low absorption" and "high absorption" can be expressed quantitatively. In some MALAL 100s, at a wavelength in the range of 300 - 400 nm, the ratio of the absorption rate of the high-absorbing conformation 300-h to the absorption rate of the low-absorbing conformation 300-l can be greater than 2. As an example, for the modifiable absorption compound 300 based on 4-aminoazobenzene, if a reference wavelength of 350 nm is selected, then the absorption rate is about 5, as Figure 10A shown. This absorption rate can also be called the contrast ratio. For some purposes, other wavelength values can be selected, such as wavelengths in the range of 360 - 370 nm. In some of these embodiments, the absorption rate just described can be greater than 3, and in some cases greater than 4.

[0112] In many embodiments of MALAL 100, the high-absorbance conformation 300-h of the modifiable absorption compound 300 has lower energy than the low-absorbance conformation 300-l. Thus, under equilibrium and ambient conditions, the ratio of the concentration of the high-absorbance isomer 300-h to the concentration of the low-absorbance isomer 300-l is greater than 2 in at least one of the solid phase, dilute solution, and host matrix-bound state. Under low-light conditions, the energies of these high-absorbance isomers 300-h and low-absorbance isomers 300-l control the density ratio of these isomers under ambient conditions according to the exponential activation factor of statistical mechanics.

[0113] In some MALAL 100s, the modifiable absorption compound 300 can have a chemical composition such that at least 25% or 50% of the high-absorbance conformation 300-h transitions to the low-absorbance conformation 300-l under illumination 310-htl from high to low in the range of 1 mJ / cm 2 -1,000 mJ / cm 2 and integrated radiant exposure in the wavelength range of 300 nm - 400 nm.

[0114] Here, the irradiance of illumination is measured in mW / cm 2 and the radiant exposure is measured in mJ / cm 2 broadly speaking, the relationship between radiant exposure and irradiance is: radiant exposure = irradiance * time. However, in some embodiments of MALAL 100, this relationship may be more complex than a simple product. The amount of absorption modulation for a modulation stimulus 310 with twice the irradiance but half the time in MALAL 100 may be different, although the product of these two factors remains the same. This non-linear relationship is sometimes referred to as reciprocity violation. For example, this violation occurs when the thermal relaxation rate R thermal in Equation (2b) is fast and comparable to other rates.

[0115] A similar characterization can also be applied to the inverse transformation. In some embodiments of MALAL 100, the modifiable absorption compound 300 can have a chemical composition such that at least 50% of the low-absorbance conformation 300-l at 1 mJ / cm 2 -1,000 mJ / cm 2Within the range of, within the wavelength range of 300 nm - 700 nm, the radiation exposure from low to high modulation stimulus 310-lth causes a transition to the high absorption conformation 300-h. In many embodiments, the source of the high to low modulation stimulus 310-htl and the source of the conditioning irradiation 210 can be selected to be the same shared source, such as a UV source. A typical example could be a mercury arc lamp or a UV LED with a spectral peak of approximately 365 nm. In contrast, in most embodiments, the source of the low to high modulation stimulus 310-lth typically operates at longer wavelengths with a broader spectrum and is thus different from the shared source. As previously mentioned, for the relevant class of MALAL 100, the ambient light in a doctor's office itself can be an effective source of the low to high modulation stimulus 310-lth, emitting a spectrum that is mainly concentrated within the visible light range of 400 - 700 nm.

[0116] Another way to characterize the effect of the modulation stimulus 310 is the quantum yield for the trans to cis and cis to trans transitions and In this case, the modifiable absorption compound 300 can have a chemical composition such that the quantum yield for the conversion from the high absorption conformation 310-h to the low absorption conformation 310-l is greater than 1%. For some MALAL 100s, this quantum yield can be higher than 5%, and some higher than 10%. The higher the quantum yield, the lower the radiation exposure sufficient to convert the high absorption conformation 310-h to the low absorption conformation 310-l. Here, the quantum yield is defined in the conventional way as quantum yield = number of induced transitions / number of absorbed photons.

[0117] The concept of quantum yield can be used to further characterize the modifiable absorption compound 300 as follows. The modifiable absorption compound 300 can have a chemical composition such that the quantum yield for the conversion from the high absorption isomer 300-h to the low absorption isomer 300-l in response to the high to low modulation stimulus 310-htl can be in the range of 1 - 20%, while the quantum yield for the reverse transition from the low absorption isomer 300-l to the high absorption isomer 300-h in response to the low to high modulation stimulus 310-lth can be in the range of 10 - 70%. In other embodiments, these two quantum yields can be respectively in the and range.

[0118] Figure 13 Illustrates that after a few days of the conditioning program ending in Figure 5D the increased light power of the MALAL 100 needs to be locked by the locking irradiation 220, as Figure 5EAs shown. However, the unpolymerized photopolymerizable macromonomer 113 needs to be protected from accidental UV radiation during the time between the conditioning program and the locking program. To provide this protection, the modifiable absorption compound 300 of the front protective layer 120 can switch back to the high-absorption isomer 300-h at the end of the conditioning irradiation 210 of Figure 5B and then change back from the high-absorption conformation 300-h to the low-absorption conformation 300-l again just at the start of the locking irradiation 220 of Figure 5E . Obviously, the modifiable absorption compound 300 needs to repeatedly undergo transitions or switches when the absorption is modulated from high to low by the modulation stimulus 310-htl and from low to high by the modulation stimulus 310-lth. Figure 13 The figure shows the absorbance of the modifiable absorption compound 300 after repeated back-and-forth modulation when the modifiable absorption compound 300 is vinylphenyl azopyrazole. The figure is enlarged to the cis-to-trans absorption peak near 450 nm. Figure 13 It shows that even after six back-and-forth switches, the absorption spectrum remains substantially unchanged, thus indicating that at least some embodiments of the modifiable absorption compound 300 are suitable for repeated modulation between the high-absorption conformation and the low-absorption conformation. Some modifiable absorption compounds 300 have been shown to be repeatedly switchable 1,000 - 1,000,000 times with minimal or immeasurable degradation.

[0119] In some embodiments, the modifiable absorption compound 300 includes a photo-isomerizable moiety linked to one or more polymerizable moieties. In some embodiments, the modifiable absorption compound 300 is described by formula [9]:

[0120] (Z 1 ) n1 -Y-(Z 2 ) n2 [9]

[0121] where Y is a photo-isomerizable moiety (e.g., as described above); n1 and n2 are each independently 0, 1, 2, or 3; and Z 1 and Z 2 are each independently a polymerizable moiety or a crosslinking moiety connected to Y via an optional linker.

[0122] In some embodiments, in formula [9], n1 and n2 are each 1, and Z 1 and Z 2 are each independently connected to Y via a linker having a length of 1 to 20 atoms (e.g., a length of 1 to 6 atoms). In some embodiments, n1 is 2 or 3, and each Z 1 is attached to Y via a branched linker (e.g., an amino or ammonium-containing linker). In some embodiments, when n1 and / or n2 is 2 or 3, then Z 1 and / or Z2 Each is independently connected to Y via an unbranched linear linker. In some embodiments, Y is an azoarylene, a diarylethene, or a dithienylethene. In some embodiments, Z 1 and Z 2 are each independently selected from vinyl, vinylene, diene, olefin, allyl, acrylate, acrylamide, and acrylic acid.

[0123] In some embodiments, in Formula [9], the modifiable absorption compound 300 has the structure Ar 1 -N=N-Ar 2 or Ar 1 -C=C-Ar 2 , where Ar 1 and Ar 2 are independently selected from aromatic 6-membered rings that may be substituted or unsubstituted and may include one or more heteroatoms. In some embodiments, the modifiable absorption compound 300 includes an azobenzene moiety (e.g., where Ar 1 and Ar 2 are phenyl). In some embodiments, the modifiable absorption compound 300 is capable of photoisomerizing from a trans isomer to a cis isomer, e.g., as exemplified by the Ar 1 -N=N-Ar 2 compound shown below. In some embodiments, the cis isomer of the modifiable absorption compound 300 spontaneously isomerizes back to the trans isomer.

[0124]

[0125] In some embodiments, the azobenzene moiety is a photoisomerizable chromophore having an absorption maximum close to that of a photoinitiator (such as any photoinitiator used and described herein). In some embodiments, the absorption maximum of the azobenzene moiety is about 50 nm or less (e.g., about 40 nm or less, about 30 nm or less, about 20 nm or less, or about 10 nm or less) of the absorption maximum of the photoinitiator.

[0126] In some embodiments, the thermodynamically more stable trans-azobenzene (t-AB) moiety tends to absorb at a lower wavelength than the corresponding cis-azobenzene (c-AB) isomer. Upon irradiation, the photoisomerization may be mild and quantitative. In some embodiments, the thermal relaxation from the c-AB moiety to the t-AB isomer occurs within a few hours at ambient temperature (e.g., within 12 hours or less, such as within 6, 5, 4, 3, 2, or 1 hour or less). Irradiating the t-AB moiety near its absorption maximum results in isomerization to the cis isomer and a change in the absorption spectrum (e.g., a shift in the absorption maximum).

[0127] In some embodiments, the modifiable absorption compound 300 further includes a polymerizable moiety, i.e., a functional group capable of polymerizing in a prepolymer composition upon application of a suitable stimulus (e.g., activation of a photoinitiator). The polymerizable moiety may include functional groups such as alkenyl, vinyl, vinylene, diene, olefin, allyl, acrylate or (meth)acrylic acid functional groups. In some embodiments, the polymerizable moiety is allyl or vinyl.

[0128] In some embodiments where the modifiable absorption compound 300 includes a polymerizable moiety, the modifiable absorption compound 300 may be chemically bound to another component of the composition of interest. For example, the modifiable absorption compound 300 may be incorporated into the backbone of a polymer present as a matrix material (see below). Additionally, for example, the modifiable absorption compound 300 may be incorporated into the backbone or as a side group of a prepolymer (see below). In this way, small molecule modifiable absorption compounds 300s can be chemically bound to the polymer components of the composition of interest. In some embodiments and for some applications, binding the modifiable absorption compounds 300s in this manner renders the masking component less likely to diffuse out of the composition of interest.

[0129] In some embodiments, the modifiable absorption compound 300 is described by the structure of formula

[10] :

[0130]

[0131] where: n 3 and n 4 are each independently 0, 1, 2, or 3;

[0132] (Z 3 ) n3 -L 3 - and -L 4 -(Z 4 ) n4 may each independently be absent or present;

[0133] Z 3 and Z 4 are each independently a polymerizable moiety or a crosslinking moiety;

[0134] L 3 and L 4 are linkers;

[0135] n 5 and n 6 are each independently 0, 1, 2, 3, 4, or 5, provided that when (Z 3 ) n3 -L 3 - is present, n 3 is not 5, and when -L 4 -(Z4 ) n4 when n 6 is not 5; and

[0136] each R is independently selected from the group consisting of hydrogen, a hydrocarbon group (e.g., an alkyl group, an alkenyl group, an aryl group, etc.), a heterocycle, a halogen, a haloalkyl group or a perhaloalkyl group (e.g., a trifluoromethyl group), an amino group, a hydroxyl group, an ether, a nitro group, a cyano group, a carboxyl group, an acyl group, an amide group, an ester, a thiol, a thioether, a sulfonyl group, and a sulfonamide group.

[0137] In some embodiments, in Formula

[10] , Z 3 and Z 4 are each independently selected from vinyl, vinylene, diene, olefin, allyl, acrylate, acrylamide, and acrylic acid.

[0138] In some embodiments, in Formula

[10] , L 3 and L 4 are each independently a linker having a length of 1 to 20 atoms, such as a linker having a length of 1 to 6 atoms. In some embodiments, the linker L 3 and / or L 4 , when present, may include an amino group attached to a polymerizable moiety or a crosslinkable moiety. In some embodiments, the linker is present and includes a branched amino group (e.g., a trivalent amino group or a tetravalent ammonium group) for connecting two or three polymerizable moieties and / or crosslinkable moieties to azobenzene. In some embodiments, L 3 and / or L 4 is a branched amino (-N=) group. In some embodiments, L 3 and / or L 4 is a branched ammonium (-N(+)=) group. In some embodiments, L 3 includes a branched amino group or an ammonium group, n 3 is 2 or 3, and Z 3 is allyl or vinyl.

[0139] In some embodiments, in Formula

[10] , L 3 and L 4 , when present, may be attached to the azobenzene ring at any convenient position. For example, L 3 may be attached to the first benzene ring at the 2, 3, or 4 position relative to the azo substituent. For example, L 4 may be attached to the second benzene ring at the 2', 3', or 4' position relative to the azo substituent. All combinations of L 3 and / or L4 located around the first and second benzene rings, respectively, are envisioned. For example, L 3 and L 4 may be attached at the 2 and 2' positions, respectively. For example, L 3 and L4 can be attached separately at the 3 and 3' positions. For example, L 3 and L 4 can be attached separately at the 4 and 4' positions (i.e., in register). Alternatively, L 3 can be attached at the 4-position of the first benzene ring, and L 4 can be attached at the 2'-position of the second benzene ring. Exemplary arrangements of L 3 and L 4 are shown in the following compounds.

[0140] In some embodiments, the tunable absorption compound 300 is described by the structure of formula

[11] :

[0141]

[0142] where L 3 and L 4 are linkers;

[0143] n 5 and n 6 are each independently 0, 1, 2, 3, or 4; and

[0144] each R is independently selected from the group consisting of hydrogen, a hydrocarbon group (e.g., an alkyl, alkenyl, aryl, etc.), a heterocycle, a halogen, a haloalkyl or a perhaloalkyl (e.g., trifluoromethyl), an amino group, a hydroxyl group, an ether, a nitro group, a cyano group, a carboxyl group, an acyl group, an amido group, an ester, a thiol, a thioether, a sulfonyl group, and a sulfonamide.

[0145] In some embodiments, the tunable absorption compound 300 is as described in

[11] , except that one or both of the terminal allyl groups can be independently replaced by any convenient polymerizable or crosslinkable moiety as described herein.

[0146] In some embodiments, in formula

[11] , L 3 and L 4 one or both are connected to the azobenzene via an electron-withdrawing substituent such as a carbonyl, an ester, an amido, a sulfonyl, or a sulfonamide. In some embodiments, L 3 and L 4 are independently -(CH 2 ) m1 -Z 4 -(CH 2 ) m2 -, where m 1 and m 2 are each independently 0 or an integer from 1 to 6, and Z 4Selected from carbonyl (-C(=O)-), ester (-C(=O)O-), acylamino (e.g., -C(=O)NH-), carbamate (e.g., -OC(=O)NH-), sulfonyl (-SO 2 -), sulfonamide (e.g., -SO 2 NH-), ether (-O-), thioether (-S-), or ureido (e.g., -NHC(=NH)NH-). In some embodiments, m 1 is 2 and m 2 is 0. In some embodiments, Z 4 is -O-.

[0147] In some embodiments, the tunable absorption compound 300 is described by one of the following formulas

[12] -

[14] :

[0148]

[0149] wherein L 3 、L 4 、(R) a5 and (R) n6 are as defined in formula

[11] above. In certain embodiments, L 3 and L 4 are independently selected from -O- and -O(CH2)m-, where m is an integer from 1 to 6 (e.g., m is 2). In some embodiments, each R is hydrogen.

[0150] In some embodiments, the tunable absorption compound 300 is described by the structure of formula

[15] or

[16] :

[0151]

[0152] wherein R 1 -R 8 are each independently selected from the group consisting of hydrogen, hydrocarbon group (e.g., alkyl, alkenyl, aryl, etc.), heterocycle, halogen, haloalkyl or perhaloalkyl (e.g., trifluoromethyl), amino, hydroxy, ether, nitro, cyano, carboxyl, acyl, amido, ester, thiol, thioether, sulfonyl, and sulfonamide.

[0153] In some embodiments, in formula

[15] or

[16] , one or more of R 1 -R 8 are -L 5 -O-CH 2 CH=CH 2 ,where L 5 is an optional linker group. In some embodiments, in formula

[15] or

[16] , each L 5 is C 1 -C 6Alkyl chain (e.g., C 2 alkyl). In some embodiments, in Formula

[15] or

[16] , each L 5 is absent. In some embodiments, in Formula

[15] or

[16] , R 1 -R 8 are each hydrogen.

[0154] In some embodiments, the modifiable absorption compound 300 is described by the structure of Formula [17):

[0155]

[0156] wherein A is a heterocycle;

[0157] n 7 is 0 or an integer from 1 to 5;

[0158] each R is independently selected from the group consisting of hydrogen, -L 5 -(Z 5 ) m where m is 1, 2 or 3, hydrocarbon group (e.g., alkyl, alkenyl, aryl, etc.), heterocycle, halogen, haloalkyl or perhaloalkyl (e.g., trifluoromethyl), amino, hydroxy, ether, nitro, cyano, carboxyl, acyl, amido, ester, thiol, thioether, sulfonyl and sulfonamide;

[0159] R 11 -R 15 are each independently selected from the group consisting of hydrogen, hydrocarbon group (e.g., alkyl, alkenyl, aryl, etc.), heterocycle, halogen, haloalkyl or perhaloalkyl (e.g., trifluoromethyl), amino, hydroxy, ether, nitro, cyano, carboxyl, acyl, amido, ester, thiol, thioether, sulfonyl and sulfonamide group hydrocarbon group (e.g., alkyl, alkenyl, aryl, etc.), heterocycle, halogen, haloalkyl or perhaloalkyl (e.g., trifluoromethyl), amino, hydroxy, ether, nitro, cyano, carboxyl, acyl, amido, ester, thiol, thioether, sulfonyl and sulfonamide, and -L 5 -Z 5 ; and

[0160] L 5 is a linker and each Z 5 is independently a polymerizable group or a crosslinking group.

[0161] In some embodiments, in Formula

[17] , A is an N-linked heterocycle, such as but not limited to morpholino, thiomorpholino piperidinyl, piperazinyl, homopiperazine, azepane or pyrrolidinyl. In some embodiments, in Formula

[17] , A is an N-linked heterocycle (e.g., N-morpholino or N-piperidinyl).

[0162] In some embodiments, the modifiable absorption compound 300 is described by the structure of formula

[18] :

[0163]

[0164] where Y is O or N-R 21 , where R 21 is hydrogen, alkyl, aryl, acyl, heterocycle, or -L 3 -Z 3 :

[0165] R 16 -R 20 are each independently selected from the group consisting of hydrogen, hydrocarbon group (e.g., alkyl, alkenyl, aryl, etc.), heterocycle, halogen, haloalkyl or perhaloalkyl (e.g., trifluoromethyl), amino, hydroxy, ether, nitro, cyano, carboxyl, acyl, amido, ester, thiol, thioether, sulfonyl, and sulfonamide, and -L 5 -Z 5 ; and

[0166] L 5 is a linker, and Z 5 is a polymerizable group or a crosslinking group.

[0167] In some embodiments, in formula

[18] , each L 5 is independently a C 1 -C 6 alkyl chain (e.g., C 2 alkyl).

[0168] In some embodiments, in formula

[18] , at least one (e.g., two) of R 16 -R 20 and R 21 includes a polymerizable moiety (e.g., allyl) or a crosslinking moiety. In some embodiments, in formula

[18] , at least one of R 16 -R 20 and R 21 includes allyl or vinyl. In some embodiments, in formula

[18] , R 18 is -(CH 2 ) m2 -L 6 -(CH 2 ) m2 -Z 6 , where m 1 and m 2 are each independently 0 or an integer from 1 to 6, and L 6Selected from carbonyl (-C(=O)-), ester (-C(=O)O-), amide group (e.g., -C(=O)NH-), carbamate (e.g., -OC(=O)NH-), sulfonyl (-SO 2 -), sulfonamide (e.g., -SO 2 NH-), ether (-O-), thioether (-S-) or urea group (e.g., -NHC(=NH)NH-). In some embodiments, m 1 is 2 and m 2 is 0. In some embodiments, L 6 is -O-.

[0169] In some embodiments, at least one of R 16 -R 20 and R 21 (e.g., R 18 , R 19 or R 20 ) is -L 7 -O-CH 2 CH=CH 2 , where L 7 is an optional linker group, which may be a C 1 -C 6 alkyl chain (e.g., C 2 alkyl).

[0170] In some embodiments, in formula

[18] , Y is O. In some embodiments, in formula

[18] , one or more of R 16 -R 20 are nitro groups. In some embodiments, in formula

[18] , R 18 is nitro, and R 16 , R 17 , R 19 and R 20 are hydrogen.

[0171] In some embodiments, the modifiable absorption compound 300 is selected from one of the following formulas

[19] -

[25] :

[0172]

[0173] To avoid unwanted photoinitiated polymerization or crosslinking caused by ambient sunlight during healing, a tunable absorption compound 300 is included in the front protective layer 120 to prevent such photoinitiation by absorbing the UV component of the incident light. The photoinitiator 115 and the tunable absorption compound 300 are optionally selected to have overlapping absorption spectra such that the tunable absorption compound 300 can absorb sufficient ambient UV to prevent activation of the photoinitiator 115. Upon application of a modulation stimulus 310-htl from high to low, photoisomerization of the tunable absorption compound in its high absorption isomer 300-h causes the absorption maximum of the tunable absorption compound 300 to deviate from the absorption maximum of the photoinitiator 115, such that the absorption spectra of the photoisomerized tunable absorption compound 300 and the photoinitiator 115 overlap significantly less at wavelengths suitable for activating the photoinitiator 115.

[0174] In some embodiments, photoisomerization of the tunable absorption compound 300 occurs via cis-trans isomerization, a cyclization reaction, or a ring-opening reaction. Conveniently photoisomerizable compounds include compounds that can block absorption by the photoinitiator 115 and whose absorption maximum undergoes a significant change upon application of a suitable modification stimulus 310. In some embodiments, the tunable absorption compound 300 undergoes a cyclization or ring-opening photoisomerization upon absorption of the modification stimulus 310.

[0175] In some embodiments, the tunable absorption compound 300 includes a photo-isomerizable moiety that is a stilbene (e.g., azastilbene), an azobenzene moiety, an azoarylene, fulgide, spiropyran, naphthopyran, quinone, spirooxazine, nitrone, triarylmethane (e.g., triphenylmethane), thioindigo, diarylethene, dithienylethene, or a highly congested olefin. In some embodiments, the tunable absorption compound 300 includes an alkenyl (C═C) or azo moiety (—N═N—) moiety that undergoes photoisomerization via a cis-trans transition. In some embodiments, the tunable absorption compound 300 includes a diarylethene that undergoes photoisomerization via an electrocyclic ring closure reaction. In some embodiments, the tunable absorption compound 300 includes a spiropyran that undergoes photoisomerization via a ring-opening transition.

[0176] In some embodiments, the photo-isomerizable moiety is selected from azoarylene, diarylethene, and dithienylethene.

[0177] In some embodiments, photoisomerization of the tunable absorption compound 300 results in a thermally unstable second isomer, e.g., when the light source is removed, the second isomer will revert to the first isomer. In this case, the photoisomerization is reversible.

[0178] In some MALAL 100s, the modifiable pre-absorption protective layer 120 may further include additional non-modifiable ultraviolet absorbing compounds, the chemical composition, absorption rate, and thickness of which are sufficient to prevent, when exposed to irradiance not exceeding 3 mW / cm 2 and a radiant exposure of up to 10,000 mJ / cm 2 integrated over a wavelength range of 300 nm - 400 nm, from modulating the optical properties of the light adjustable lens. In some embodiments, the radiant exposure may be up to 50,000 mJ / cm 2 .

[0179] Figure 14A -C illustrates a more attractive aspect of the MALAL 100 embodiments described herein. Due to the presence of the modifiable pre-absorption protective layer 120, even in the highly unlikely event of exposure to excessive UV irradiation, only a small fraction of the incident UV irradiation can pass through the pre-protective layer 120. Thus, even in such an unlikely case where region 20 is formed, its size is significantly smaller than the region formed in an LAL without such a pre-protective layer 120, such as Figure 2 shown in A-B. Figure 14A An abnormally small region 20 formed within the cross-section of the MALAL 100 is shown, and Figure 14B -C shows the formation of the small region 20 as detected by the rapidly varying interference pattern 40 as occurs via standard interferometry.

[0180] If the size of the accidental region 20 is so small, then additional measurements may be performed prior to the Figure 5B adjustment step, and the spatial distribution of the adjustment irradiation 210 may be modified such that the combined effect of the accidental region 20 and the modified adjustment irradiation 210 together cause a planned adjustment of the optical properties of the LAL 110. In other embodiments, the adjustment irradiation 210 may be applied with a spatial distribution that simply approximately compensates for the optical effect of the small region 20. If the accidental region 20 is formed after the Figure 5B adjustment step but before the Figure 5E locking step, then the same can be achieved, in which case the distribution of the locking irradiation 220 will be adjusted to compensate for the presence of the accidental region 20.

[0181] The protective ability of the pre-protective layer 120 can be captured in another way: in some embodiments of the MALAL 100, the absorption modulation time T am of the pre-protective layer 120 may be shorter than the region formation time T zf of the light adjustable lens 110: am T zf。In some representative cases, the absorption modulation time (the time it takes for the modifiable absorption compound 300 to convert from the low absorption isomer 300-l to the high absorption isomer 300-h) can be in the range of 0.1 second to 10 seconds, in some other cases in the range of 0.1 second to 1 second, while the region formation time of the LAL 110 can be in the range of 5 seconds to 100 seconds, and in some other cases in the range of 10 seconds to 50 seconds. Even in the highly unlikely case where the modifiable absorption compound 300 accidentally converts from its high absorption isomer 300-h to its low absorption isomer 300-l, this front protective layer 120 can efficiently prevent region formation: the front protective layer 120 can self-repair before region formation.

[0182] Finally, Figure 15A - Figure -B illustrates a method 400 for adjusting the optical characteristics of a modifiable absorption light adjustable lens MALAL 100, the method comprising the following steps:

[0183] - Reducing 410 the absorption of the modifiable absorption compound 300 of the modifiable absorption front protective layer 120 of the MALAL 100 by modulating the stimulus 310. The MALAL 100 has been pre-implanted into the eye; and

[0184] - Changing 420 the optical characteristics of the light adjustable lens of the MALAL 100 by applying the adjustment irradiation 210.

[0185] In some embodiments of the method 400, reducing 410 the absorption includes applying 415 a modulation stimulus 310-htl from high to low as the modulation stimulus for converting the modifiable absorption compound 300 from the high absorption conformation 300-h to the low absorption conformation 300-l; and

[0186] The change 420 in the optical characteristics is followed by converting 425 the modifiable absorption compound 300 from the low absorption conformation 300-l to the high absorption conformation 300-h by applying a modulation stimulus 310-lth from low to high as the modulation stimulus 310. In some cases, the modulation stimulus 310-htl from high to low includes illuminating from high to low with light having a narrow band centered at a wavelength in the range of 300 - 400 nm; and the modulation stimulus 310-lth from low to high includes illuminating from low to high with light having a broadband centered at a wavelength in the range of 300 - 700 nm, one of ambient illumination and thermal relaxation.

[0187] Although this document contains many details, particulars, and numerical ranges, these should not be construed as limitations on the scope of the invention and the claims, but rather as descriptions of features specific to particular embodiments of the invention. Certain features described in the context of separate embodiments in this document may also be implemented in combination in a single embodiment. Conversely, the various features described in the context of a single embodiment may also be implemented separately or in any suitable sub-combination in multiple embodiments. Additionally, although features may be described as acting in certain combinations and even initially claimed as such, in some cases one or more features of a claimed combination may be removed from the combination, and the claimed combination may be directed to another sub-combination or variant of a sub-combination.

Claims

1. A Modulatable Absorbing Light Adjustable Lens (MALAL) for implantation in an eye, comprising: a light adjustable lens capable of changing its optical properties upon modulated illumination, comprising a light modifiable material, said light modifiable material comprising a polymer host matrix; at least one of a monomer and a macromonomer capable of photopolymerization; a photoinitiator; and dispersed ultraviolet light absorber; a modulatable absorbing front protective layer, comprising a modulatable absorbing compound dispersed in the front region of said light adjustable lens and positioned in said polymer host matrix in the front region of said light adjustable lens by one or more bonds with a crosslinking agent of said polymer host matrix, wherein said modulatable absorbing compound is capable of changing from a high absorption conformation to a low absorption conformation upon absorption of a modulation stimulus from high to low, and changing from a low absorption conformation to a high absorption conformation upon absorption of a modulation stimulus from low to high; and a haptic member extending from said light adjustable lens.

2. The modulatable absorbing light adjustable lens according to claim 1, wherein: said polymer host matrix is selected from the group consisting of: a silicone-based matrix, an acrylate-based matrix, a collagen polymer, a silicone-acrylate-based hybrid matrix, and a multi-layer matrix combining at least two of the foregoing matrices.

3. The modulatable absorbing light adjustable lens according to claim 1, wherein: each of said modulation stimulus from high to low and said modulation stimulus from low to high is selected from the group consisting of: electromagnetic illumination, ambient light illumination, laser irradiation, infrared irradiation, ultraviolet illumination, magnetic stimulation, electric field, chemical or thermal stimulation, heat transfer, energy transfer, ultrasound-mediated stimulation, mechanical stimulation, thermal stimulation, and thermal relaxation.

4. The modulatable absorbing light adjustable lens according to claim 1, wherein: said one or more bonds positioning said modulatable absorbing compound include a bond coupling one of carbon and silicon with one selected from the group consisting of carbon, silicon, oxygen, nitrogen, hydrogen, sulfur, and halogen atoms.

5. The modulatable absorbing light adjustable lens according to claim 1, wherein: said modulatable absorbing front protective layer comprises one of the following: a layer in the front region of said light adjustable lens; a layer attached to the front region of said light adjustable lens; and a layer deposited on the front region of said light adjustable lens.

6. The modulatable absorbing light adjustable lens according to claim 1, wherein: the thickness of said modulatable absorbing front protective layer is less than 50% of the thickness of said light adjustable lens.

7. The modulatable absorbing light adjustable lens according to claim 1, wherein: said modulatable absorbing compound is selected from the group consisting of: azo-aromatic compounds, diazenes, azo-pyrazoles, dienylethenes, bactericides, azulenes, spiropyrans, ethene-aromatic compounds, macromonomers of one of these compounds, polymers of these compounds, compositions containing one of these compounds, compositions containing one of these compounds as a side chain, compositions containing one of these compounds as a main chain with side chains, and nanoparticles bonded to one of these compounds.

8. The modulatable absorbing light adjustable lens according to claim 7, wherein: The azo-aromatic compound is one of azobenzene and 4-methoxyazobenzene, the azo-pyrazole is vinylphenyl azo-pyrazole, and the ethene-aromatic compound is stilbene.

9. The tunable absorption light tunable lens according to claim 1, wherein: The tunable absorption compound is selected from the group consisting of: photo-switchable compounds, photo-activatable compounds, photoisomerizable compounds, photochromic compounds, photo-convertible compounds, and switching chromophores.

10. The tunable absorption light tunable lens according to claim 1, wherein: The high-to-low modulation stimulus includes high-to-low illumination with light having a band centered at a wavelength in the range of 300 - 400 nm; and The low-to-high modulation stimulus includes one of the following: low-to-high illumination with light having a band centered at a wavelength in the range of 400 - 700 nm, ambient illumination, and thermal relaxation.

11. The tunable absorption light tunable lens according to claim 10, wherein: At a wavelength in the range of 300 - 400 nm, the ratio of the absorption rate of the high-absorption conformation to the absorption rate of the low-absorption conformation is greater than 2.

12. The tunable absorption light tunable lens according to claim 10, wherein: The high-absorption conformation of the tunable absorption compound has lower energy than the low-absorption conformation, such that In the equilibrium under ambient conditions, the ratio of the concentration of the tunable absorption compound in the high-absorption conformation to the concentration of the tunable absorption compound in the low-absorption conformation is greater than 2 in at least one of the solid phase, dilute solution, and host matrix bonding state.

13. The tunable absorption light tunable lens according to claim 10, wherein: The modifiable absorption compound has a chemical composition such that at least 25% of the high absorption conformation is converted to the low absorption conformation upon illumination from high to low with radiation exposure in the range of 1 mJ / cm 2 - 1,000 mJ / cm 2 in the wavelength range of 300 nm - 400 nm.

14. The tunable absorption light tunable lens according to claim 13, wherein: The tunable absorption compound has a chemical composition such that the quantum yield for the conversion from the high-absorption conformation to the low-absorption conformation is greater than 0.

01.

15. The tunable absorption light tunable lens according to claim 10, wherein: The modifiable absorption compound has a chemical composition such that at least 50% of the low absorption conformation is converted to the high absorption conformation under radiation exposure in the range of 1 mJ / cm 2 - 1,000 mJ / cm 2 in the wavelength range of 400 nm - 600 nm under modulation stimulation from low to high.

16. The tunable absorption light tunable lens according to claim 1, wherein: The tunable absorption compound is capable of repeatedly transitioning from a high-absorption conformation to a low-absorption conformation and back to the high-absorption conformation when absorbing high-to-low and low-to-high modulation stimuli, respectively.

17. The tunable absorption light tunable lens according to claim 1, wherein: The modifiable front protective layer further comprises an additional non-modifiable ultraviolet light absorbing compound, the chemical composition, absorption rate and thickness of the additional non-modifiable ultraviolet light absorbing compound being sufficient to prevent modulation of the optical properties of the light adjustable lens upon exposure to radiation having an intensity of not more than 3 mW / cm 2 and integrated over a wavelength range of 300 nm to 400 nm up to an exposure of 10,000 mJ / cm 2 .

Images