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Title:
LIQUID CRYSTAL BLUE PHASE
Document Type and Number:
WIPO Patent Application WO/2013/107014
Kind Code:
A1
Abstract:
Methods of forming a liquid crystal blue phase from composite materials comprising a chiral nematic liquid crystal host and an azobenzene-based bent-shape molecule are described. The composite materials quickly transfer from the liquid crystal blue phase to an isotropic phase under electromagnetic radiation and transfer from the isotropic phase to the liquid crystal blue phase when electromagnetic radiation is removed.

Inventors:
ZHENG ZHIGANG (CN)
Application Number:
PCT/CN2012/070561
Publication Date:
July 25, 2013
Filing Date:
January 19, 2012
Export Citation:
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Assignee:
UNIV EAST CHINA SCIENCE & TECH (CN)
ZHENG ZHIGANG (CN)
International Classes:
C09K19/56; C09K19/42; G02F1/13
Foreign References:
CN102010720A2011-04-13
US20090115957A12009-05-07
JPH02232056A1990-09-14
EP1739151A12007-01-03
Attorney, Agent or Firm:
KING & WOOD MALLESONS (East Tower World Financial Centre,No. 1 Dongsanhuan Zhonglu, Chaoyang District, Beijing 0, CN)
Download PDF:
Claims:
is Claimed is:

A composite material comprising:

a chiral nematic liquid crystal host; and

at least one

compound (I), wherein Ri and R2 are each independently selected from aliphatic hydrocarbons comprising 1 to 10 carbons, wherein exposure of the composite material to electromagnetic radiation induces a transition from a liquid crystal blue phase to an isotropic phase, and wherein removal of electromagnetic radiation from the composite material induces a transition from an isotropic phase to a liquid crystal blue phase.

2. The composite material of claim 1 , wherein the transition from the liquid crystal blue phase to the isotropic phase occurs in about 20 seconds to about 180 seconds.

3. The composite material of claim 1, wherein the transition from the liquid crystal blue phase to the isotropic phase occurs in about 30 seconds.

4. The composite material of claim 1, wherein the transition from the isotropic phase to the liquid crystal blue phase occurs in about 30 minutes to about 180 minutes.

5. The composite material of claim 1, wherein the transition from the isotropic phase to the liquid crystal blue phase occurs in about 30 to about 90 minutes. 6. The composite material of claim 1 , wherein the transition from the liquid crystal blue phase comprises a transition from the liquid crystal blue phase to a chiral nematic phase.

7. The composite material of claim 1, wherein the transition from the isotropic phase comprises a transition from the isotropic phase to a chiral nematic phase.

8. The composite material of claim 1 , wherein Ri and R2 are each independently selected from alkyl chains comprising 1 to 10 carbons.

9. The composite material of claim 1, wherein Ri is C4¾ and R2 is C5Hn.

10. The composite material of claim 1 , wherein compound (I) is present at about 2 weight percent to about 20 weight percent.

11. The composite material of claim 1 , wherein compound (I) is present at about 7 weight percent.

12. The composite material of claim 1, wherein the electromagnetic radiation has at least enough energy to excite compound (I) to an electronically excited state.

13. The composite material of claim 1 , wherein the electromagnetic radiation includes light having a wavelength of about 365 nm.

14. The composite material of claim 1, wherein the chiral nematic liquid crystal host comprises about 50 weight percent to about 75 weight percent eutectic nematic liquid crystals and about 25 weight percent to about 50 weight percent chiral dopant.

15. The composite material of claim 1 , wherein the chiral nematic liquid crystal host comprises about 67 weight percent eutectic nematic crystals and about 33 weight percent chiral dopant. A method of preparing a liquid crystal blue phase, the method comprising: providing a mixture of a chiral nematic liquid crystal host and at least one

compound 0); heating the mixture; and

cooling the heated mixture,

wherein Rj and R2 are each independently selected from aliphatic hydrocarbons comprising 1 to 10 carbons.

17. The method of claim 16, wherein R] and R2 are each independently selected from alkyl chains comprising 1 to 10 carbons.

18. The method of claim 16, wherein Rj is C4H9 and R2 is C5H1 ].

19. The method of claim 16, wherein compound (I) is present at about 2 weight percent to about 20 weight percent.

20. The method of claim 16, wherein compound (I) is present at about 7 weight percent.

21. The method of claim 16, wherein the chiral nematic liquid crystal host comprises about 50 weight percent to about 75 weight percent eutectic nematic crystals and about 25 weight percent to about 50 weight percent chiral dopant chiral dopant.

22. The method of claim 16, wherein the chiral nematic liquid crystal host comprises about 67 weight percent eutectic nematic crystals and about 33 weight percent chiral dopant.

23. The method of claim 16, wherein the mixing takes place at about 60°C for about 10 minutes. 24. The method of claim 16, wherein the mixture is heated to a temperature of about 70°C.

25. The method of claim 16, wherein the heated mixture is cooled from about 70°C to about to about 43°C.

26. A display device comprising a composite material, wherein the composite material comprises:

a chiral nematic liquid crystal host; and

at least one compound

wherein Ri and R2 are each independently selected from aliphatic hydrocarbons comprising 1 to 10 carbons, wherein exposure of the composite material to electromagnetic radiation induces a transition from a liquid crystal blue phase to an isotropic phase, and wherein removal of electromagnetic radiation from the composite material induces a transition from an isotropic phase to a liquid crystal blue phase.

27. The display device of claim 26, wherein the transition from the liquid crystal blue phase to the isotropic phase occurs in about 30 seconds to about 180 seconds.

28. The display device of claim 26, wherein the transition from the liquid crystal blue phase to the isotropic phase occurs in about 30 seconds.

29. The display device of claim 26, wherein the transition from the isotropic phase to the liquid crystal blue phase occurs in about 30 minutes to about 180 minutes. 30. The display device of claim 26, wherein the transition from the isotropic phase to the liquid crystal blue phase occurs in about 30 to about 90 minutes.

31. The display device of claim 26, wherein the transition from the liquid crystal blue phase comprises a transition from the liquid crystal blue phase to a chiral nematic phase.

32. The display device of claim 26, wherein the transition from the isotropic phase comprises a transition from the isotropic phase to a chiral nematic phase.

33. The display device of claim 26, wherein R] and R2 are each independently selected from alkyl chains comprising 1 to 10 carbons.

34. The display device of claim 26, wherein R! is C4H9 and R2 is C5Hn.

35. The display device of claim 26, wherein compound (I) is present at about 2 weight percent to about 20 weight percent.

36. The display device of claim 26, wherein compound (I) is present at about 7 weight percent.

37. The display device of claim 26, wherein the electromagnetic radiation has at least enough energy to excite compound (I) to an electronically excited state,

38. The display device of claim 26, wherein the electromagnetic radiation includes light having a wavelength of about 365 ran.

39. The display device of claim 26, wherein the chiral nematic liquid crystal host comprises about 50 weight percent to about 75 weight percent eutectic nematic crystals and about 25 weight percent to about 50 weight percent chiral dopant.

40. The display device of claim 26, wherein the chiral nematic liquid crystal host comprises about 67 weight percent eutectic nematic crystals and about 33 weight percent chiral dopant. 41. An information storage device comprising a composite material, wherein the composite material comprises:

a chiral nematic liquid crystal host; and

at least one

compound (I), wherein Rj and R2 are each independently selected from aliphatic hydrocarbons comprising 1 to 10 carbons, wherein exposure of the composite material to electromagnetic radiation induces a transition from a liquid crystal blue phase to an isotropic phase, and wherein removal of electromagnetic radiation from the composite material induces a transition from an isotropic phase to a liquid crystal blue phase.

42. The infonnation storage device of claim 41, wherein the transition from the liquid crystal blue phase to the isotropic phase occurs in about 30 seconds to about 180 seconds.

43. The information storage device of claim 41, wherein the transition from the liquid crystal blue phase to the isotropic phase occurs in about 30 seconds.

44. The information storage device of claim 41, wherein the transition from the isotropic phase to the liquid crystal blue phase occurs in about 30 minutes to about 180 minutes.

45. The information storage device of claim 41 , wherein the transition from the isotropic phase to the liquid crystal blue phase occurs in about 30 minutes to 90 minutes.

46. The information storage device of claim 41, wherein R] and R2 are each independently selected from alkyl chains comprising 1 to 10 carbons. 47. The information storage device of claim 41, wherein Ri is C4H9 and R2 is C5Hn.

48. The information storage device of claim 41, wherein compound (I) is present at about 2 weight percent to about 20 weight percent.

49. The information storage device of claim 41, wherein compound (I) is present at about 7 weight percent.

50. The information storage device of claim 41 , wherein the electromagnetic radiation has at least enough energy to excite compound (I) to an electronically excited state.

51. The information storage device of claim 41 , wherein the electromagnetic radiation includes light having a wavelength of about 365 nm.

52. The information storage device of claim 41. wherein the chiral nematic liquid crystal host comprises about 50 weight percent to about 75 weight percent eutectic nematic crystals and about 25 weight percent to about 50 weight percent chiral dopant.

53. The information storage device of claim 41, wherein the chiral nematic liquid crystal host comprises about 67 weight percent eutectic nematic crystals and about 33 weight percent chiral dopant.

Description:
LIQUID CRYSTAL BLUE PHASE

BACKGROUND

[0001] The liquid crystal blue phase is a thermotropic mesophase, usually existing between the isotropic phase and the chiral nematic phase that was first identified in an 1888 report describing the melting behavior of cholesteryl benzoate. The report noted that the substance briefly turned blue as it changed from clear to cloudy upon cooling. The structure of the liquid crystal blue phase is formed by double-twisted cylinders, which are self-assembled and form three dimensional cubic lattices. Such an arrangement endows the liquid crystal blue phase with special properties, such as optical isotropy, tunable reflection of circular polarized light with certain wavelengths, microsecond response, etc. These properties enable many potential applications of liquid crystal blue phase including high efficiency flat panel displays, fast response optical devices and improved laser techniques. Practical applications using the liquid crystal blue phase have been limited by their stability only in a narrow temperature range

(typically about 1 K).

[0002] Photoisomerization materials isomerize with irradiation at a certain wavelength, which when present in a liquid crystal, can lead to rotation of the liquid crystals and cause phase transitions. To date, phase transitions of liquid crystals initiated by photoisomerization materials have needed at least 90 seconds, while the recovery time in a dark environment is at least 8 hours.

SUMMARY

[0003] This disclosure is not limited to the particular systems, devices and methods described, as these may vary. The terminology used in the description is for the purpose of describing the particular versions or embodiments only, and is not intended to limit the scope. While various compositions and methods are described in terms of "comprising" various components or steps (interpreted as meaning "including, but not limited to"), the compositions and methods can also "consist essentially of or "consist of the various components and steps, and such terminology should be interpreted as defining essentially closed-member groups.

[0004] Embodiments describe a composite material which forms a liquid crystal blue phase, methods for preparing the liquid crystal blue phase, and devices comprising the composite material. The liquid crystal blue phase has a stable temperature range of equal to or greater than about 20°C. The composite material transitions from the liquid crystal blue phase to an isotropic phase when subjected to electromagnetic radiation, and from the isotropic phase to the liquid crystal blue phase faster than previously reported materials.

[0005] In an embodiment, a composite material comprises a chiral nematic liquid crystal host and at least one compound (I), wherein exposure of the composite material to

electromagnetic radiation induces a transition from a liquid crystal blue phase to an isotropic phase.

[0006] In an embodiment, a method of preparing a liquid crystal blue phase comprises: providing a mixture of at least one compound (I) and a chiral nematic liquid crystal host; heating the mixture an isotropic phase; and cooling the heated mixture to provide the liquid crystal blue phase.

[0007] In an embodiment, a display device comprises a composite material, wherein the composite material comprises a chiral nematic liquid crystal host and at least one compound (I). In these embodiments, the display device may be a blue phase mode liquid crystal display with improved fabrication costs relative to traditional liquid crystal displays.

[0008] In an embodiment, an information storage device comprises a composite material, wherein the composite material comprises a chiral nematic liquid crystal host and at least one compound (I). In these embodiments, the information storage device may be an optical disc comprising at least one layer of the composite material embedded in a transparent substrate.

DETAILED DESCRIPTION

[0009] Described herein is a composite material comprising a chiral nematic liquid crystal and an azobenzene-based bent-shaped molecule such as compound (I), which fonns a liquid crystal blue phase. The composite material transitions from the liquid crystal blue phase to an isotropic phase when subjected to electromagnetic radiation and from the isotropic phase to the liquid crystal blue phase faster than previously reported materials. The liquid crystal blue phase has a stable temperature range of equal to or greater than about 20°C. Methods for preparing the liquid crystal blue phase, a display device comprising the composite material, and an information storage device comprising the composite material are further described.

[0010] In embodiments, compound (I) may have the structure:

wherein Ri and R 2 may each be independently selected from aliphatic hydrocarbons comprising 1 to 10 carbons. In some embodiments, Ri and R 2 may each be independently selected from alkyl chains comprising 1 to 10 carbons. In some embodiments, Rj is C4H9 and R 2 is CsHn,

[0011] Azobenzene-based molecules, like compound (I), may photoisomerize when subjected to electromagnetic radiation and may revert to the resting state when the

electromagnetic radiation is removed. In these molecules, photoisomerization may also be termed cis/trans inversion about the N=N double bond. In embodiments, exposing a solution comprising an azobenzene-based bent-shaped molecule such as compound (I) to electromagnetic radiation may cause the absorbance properties of the solution to change. These spectral changes may indicate reversible changes in the conjugation of the azobenzene-based bent-shaped molecule resulting from photoisomerization triggered by the applied electromagnetic radiation, and recovery of the chemical geometry in the dark. In these embodiments, the intensity of an absorbance peak observed in an UV- Visible absorption spectrum may decrease and may be blue- shifted (a decrease in wavelength) with prolonged irradiation. Removing the electromagnetic radiation from the solution may cause a rise in the intensity and a red-shift of the effected absorbance peak. In some embodiments, the UV- Visible may comprise an absorbance peak of about 360nm to about 370nm. In these embodiments, irradiating the solution with

electromagnetic radiation comprising light with a wavelength of about 365nm may cause the absorbance peak of about 360nm to about 370nm to decrease in intensity and to be blue-shifted by about 30 nm (to about 330nm to about 340nm) with continued irradiation.

[0012] In an embodiment, a composite material capable of forming a liquid crystal blue phase may comprise a chiral nematic liquid crystal and an azobenzene-based bent-shaped molecule such as compound (I). In embodiments, the liquid crystal blue phase of the composite material may have a stable temperature range of about 10°C to about 60 °C. In some embodiments, the liquid crystal blue phase of the composite material may have a stable temperature range of about 20°C. Compared to typical ranges of only a few degrees, this improved range of stability for the liquid crystal blue phase may facilitate the use of composite materials in, for example, display and information storage applications.

[0013] In an embodiment, exposing a composite material comprising a chiral nematic liquid crystal host and an azobenzene-based bent-shaped molecule such as compound (I) with electromagnetic radiation may cause a photoinduced phase transition from a liquid crystal blue phase to an isotropic phase. In embodiments, removing electromagnetic radiation from the composite material may cause a phase transition from an isotropic phase to a liquid crystal blue phase. In further embodiments, a pattern comprising liquid crystal blue phase regions and isotropic phase regions may be made in the composite material by exposing the composite material to electromagnetic radiation through a patterned photomask. This ability to pattern the composite material may facilitate applications such as display devices and information storage devices to incorporate the composite material. In some embodiments, the patterned photomask may be configured to create a striped pattern comprising alternating liquid crystal blue phase regions and isotropic phase regions in the composite material.

[0014] In embodiments, the composite material may be irradiated with electromagnetic radiation having at least enough energy to excite a compound (I) to an electronically excited state. In these embodiments, compound (I) may undergo photoisomerization from the trans isomer to the cis isomer. In some embodiments, the composite material may be irradiated with

electromagnetic radiation comprising light with a wavelength of about 365 nm. [0015] In embodiments, the trans isomer of the azobenzene-based bent-shaped molecule such as compound (I) is bent and leads to biaxiality. Coupling between the chirality of the chiral dopant and the biaxiality of compound (I) may contribute to formation and stabilization of a double- twisted arrangement leading to a liquid crystal blue phase for the composite material. In some embodiments, exposure of the composite material to electromagnetic radiation may cause the colorful platelets of the liquid crystal blue phase to disappear gradually and a number of bright beads, indicative of a chiral nematic liquid crystal, to appear. Electromagnetic radiation may induce photoisomerization of compound (I) to the almost linear cis isomer. The change in molecular geometry may decrease the biaxiality of compound (I) and its coupling effects with the chiral dopant, and may thereby destabilize the fragile double twisted arrangement of the liquid crystal blue phase causing a transition to the single twisted chiral nematic liquid crystal. Extended exposure to electromagnetic radiation may cause destabilization of the single twisted arrangement due to increasing amounts of the cis isomer, and the chiral nematic liquid crystal may transition to the isotropic phase. In embodiments, removal of electromagnetic radiation from the composite material may allow thermal recovery of compound (I) to the trans isomer, which may lead to a transition from the isotropic phase to the liquid crystal blue phase by reversal of the above described process. In these embodiments, the arrangements of liquid crystals may be rebuilt to the single twisted chiral nematic liquid crystal phase and then to the double- twisted cylinderical liquid crystal blue phase.

[0016] Typically, the liquid crystal blue phase exists between the isotropic phase and the chiral nematic phase; however, the order of the thermotropic mesophases may be disrupted in the composite material. In some embodiments, the transition of the composite material from the liquid ciystal blue phase comprises a transition from the liquid crystal blue phase to a chiral nematic phase and then to the isotropic phase. In some embodiments, the transition of the composite material from the isotropic phase comprises a transition from the isotropic phase to a chiral nematic phase and then to the liquid crystal blue phase.

[0017] In embodiments, the time for the phase transition from the liquid crystal blue phase to the isotropic phase may depend on the thickness of the composite material, the intensity of the electromagnetic radiation, the temperature, or combinations thereof, Each of these may affect the amount of electromagnetic radiation absorbed by the material and the isomerization rate. In some embodiments, the composite material may transition from the liquid crystal blue phase to the isotropic phase in about 20 seconds to about 180 seconds, hi some embodiments, the composite material may transition from the liquid crystal blue phase to the isotropic phase in about 30 seconds. Specific examples of time include about 20 seconds, about 30 seconds, about 60 seconds, about 90 seconds, about 120 seconds, about 150 seconds, about 180 seconds, and ranges between any two of these values. In embodiments, the composite material may transition from the isotropic phase to the liquid crystal blue phase in about 30 minutes to about 180 minutes. In some embodiments, the composite material may transition from the isotropic phase to the liquid crystal blue phase in about 30 to about 90 minutes. Specific examples of time include about 30 minutes, about 60 minutes, about 90 minutes, about 120 minutes, about 150 minutes, about 180 minutes, and ranges between any two of these values.

[0018] In an embodiment, a composite material may comprise a chiral nematic liquid ciystal host and an azobenzene-based bent-shaped molecule such as compound (I). In some embodiments, the chiral nematic liquid crystal host may comprise about 50 weight percent to about 75 weight percent eutectic nematic crystals and about 25 weight percent to about 50 weight percent chiral dopant. In other embodiments, the chiral nematic liquid crystal host may comprise about 67 weight percent eutectic nematic liquid crystals and about 33 weight percent chiral dopant. In embodiments, the composite material may comprise about 2 weight percent to about 20 weight percent of the azobenzene bent-shaped molecule. In some embodiments, the composite material may comprise about 7 weight percent of the azobenzene bent-shaped molecule.

[0019] An exemplary eutectic nematic liquid crystal includes compound SLC-9023 commercially available from Slichem Co. Ltd. An exemplary chiral dopant includes compound R811 commercially available from Merck Co. Ltd. Alternate and/or additional eutectic nematic liquid crystals and chiral dopants may be used within the scope of this disclosure.

[0020] In an embodiment, a liquid crystal blue phase may be prepared by heating a mixture of least one compound (I) and a chiral nematic liquid crystal host and cooling the heated mixture. In embodiments, compound (I) may be present at about 2 weight percent to about 20 weight percent. In some embodiments, compound (I) may be present at about 7 weight percent. In embodiments, the chiral nematic liquid crystal host may comprise about 50 weight percent to about 75 weight percent eutectic nematic crystals and about 25 weight percent to about 50 weight percent chiral dopant. Γη some embodiments, the chiral nematic liquid crystal host may comprise about 67 weight percent eutectic nematic crystals and about 33 weight percent chiral dopant. In embodiments, the mixture may be formed at a temperature sufficient to disperse the components of the mixture. In some embodiments, the mixture may be formed at about 60°C and held at 60°C for about 10 minutes. In embodiments, the mixture may be heated to a temperature where it is in the isotropic phase. In some embodiments, the mixture may be heated to a temperature of about 70°C. Specific examples of heating temperature include about 30°C, about 60°C, about 90°C, about 120°C, about 150°C, about 180°C, and ranges between any two of these temperatures. In embodiments, the heated mixture may be cooled from the isotropic phase to the liquid crystal blue phase. Specific examples of cooling temperatures include about 0°C, about 20°C, about 40°C, about 60°C, about 90°C, about 120°C, and ranges between any two of these temperatures. In some embodiments, the heated mixture may be cooled from about 70°C to about to about 43°C. In embodiments, the liquid crystal blue phase may have a temperature range of greater than or equal to about 20°C, and the heated mixture may be cooled to any temperature within the liquid crystal blue phase range.

[0021] The composite materials described herein may be used to improve the fabrication costs and performance of display devices. In an embodiment, a display device may comprise the composite material described in the embodiments above. In embodiments, the composite material may comprise the liquid crystal layer in a liquid crystal display. In some embodiments, the liquid crystal display may be a blue phase mode liquid crystal display. In embodiments, anisotropic alignment layers may not be required and the refresh rate may be faster than about 100 Hz.

[0022] A further application for the composite materials described herein may include information storage devices. In an embodiment, an information storage device may comprise the composite material described in the embodiments above. In some embodiments, the information storage device may be an optical disc and may comprise a layer of the composite material embedded in a transparent substrate. In embodiments, regions of the composite material may be in the liquid crystal blue phase or in the isotropic phase and a specific region of the composite material may be read as on or off, or the reverse, by an optical reader.

EXAMPLES Example 1 : Preparation of a liquid crystal blue phase.

[0023] To a mixture containing 67 weight percent eutectic nematic liquid crystals (SLC-

9023 from Slichem Co. Ltd) and 33 weight percent chiral dopant (R811 from Merck Co. Ltd), 7 weight percent of compound (II) was added. The mixture was stirred at 60°C for about 10 minutes, and injected into cells with thicknesses of 5.2 urn, 9.5 μιη, and 15 m, which were labeled sample 1, sample 2, and sample 3, respectively.

[0024] The samples were heated to an isotropic state at 70°C, and then cooled to 43°C with the rate of 1°C per minute, to obtain the typical liquid crystal blue phase texture.

Example 2: Transition from the liquid crystal blue phase to the isotropic phase and reversal.

[0025] The samples from Example 1 were maintained at 43°C for at least 5 minutes to reach a thermal equilibrium, and then exposed at this temperature to a 365-mn UV source with the intensity of 1 mW per cm 2 for 200 seconds to induce the photoisomerization of compound (II) and transition from the liquid crystal blue phase to the isotropic phase. After the exposure, the samples were conserved in a dark environment at the same temperature of 43°C, and the cis-trans recovery took place. The table below shows the time required for each sample to transition from the liquid crystal blue phase to the chiral nematic liquid crystal phase (BP - N*), from the chiral nematic liquid crystal phase to the isotropic phase (N* -> Iso), from the isotropic phase to the chiral nematic liquid crystal phase (Iso N*), and from the chiral nematic liquid crystal phase to the liquid crystal blue phase (N* BP). The required exposure time for phase transition is extended with increased material-thickness. Such phenomenon is mainly caused by the difference of light absorption in the three samples. There was almost no difference among the three samples for the recovery time, because it is only dependent on the chemical structure of com ound (II).

Example 3: Transition from the liquid crystal blue phase to the isotropic phase under high flux.

[0026] The samples from Example 1 were maintained at 43°C for at least 5 minutes to reach a thermal equilibrium, and then exposed at this temperature to a 365-mn UV source with the intensity of 8 mW per cm 2 . The samples transitioned from the liquid crystal blue phase to the isotropic phase within 30 seconds.

Example 4: Fabrication of a micropattern.

[0027] The samples from Example 1 were maintained at 43°C for at least 5 minutes to reach a thermal equilibrium, and then exposed at this temperature to a 365-mn UV source with the intensity of 8 mW per cm 2 through a photomask with alternating transparent and opaque lines. The samples transitioned from liquid crystal blue phase to chiral nematic liquid crystal, and then to isotropic only in the transparent regions; however, no phase transition occurred in the opaque regions.

[0028] In the present disclosure, reference is made to the accompanying figures, which form a part hereof. The illustrative embodiments described in the detailed description, figure, and claims are not meant to be limiting. Other embodiments may be used, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. It will be readily understood that the aspects of the present disclosure, as generally described herein, and illustrated in the figure, may be arranged, substituted, combined, separated, and designed in a wide variety of different configurations, all of which are explicitly contemplated herein.

[0029] The present disclosure is not to be limited in terms of the particular embodiments described in this application, which are intended as illustrations of various aspects. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and apparatuses within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds, compositions or biological systems, which can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. [0030] With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.

[0031] It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," the term "includes" should be interpreted as "includes but is not limited to," etc.). It will be further understood by those within the art that if a specific number of an mtroduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles "a" or "an" limits any particular claim containing such introduced claim recitation to embodiments containing only one such recitation, even when the same claim includes the introductory phrases "one or more" or "at least one" and indefinite articles such as "a" or "an" (e.g., "a" and/or "an" should be interpreted to mean "at least one" or "one or more"); the same holds true for the use of definite articles used to introduce claim recitations. In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should be interpreted to mean at least the recited number (e.g., the bare recitation of "two recitations," without other modifiers, means at least two recitations, or two or more recitations). Furthermore, in those instances where a convention analogous to "at least one of A, B, and C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., " a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). It will be further understood by those within the art that virtually any disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or figure, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B." [0032] In addition, where features or aspects of the disclosure are described in terms of

Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0033] As will be understood by one skilled in the art, for any and all purposes, such as in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," and the like include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member. Thus, for example, a group having 1-3 substituents refers to groups having 1, 2, or 3 substituents. Similarly, a group having 1-5 substituents refers to groups having 1, 2, 3, 4, or 5 substituents, and so forth.