GB2209751A - Water-soluble photochromic compounds - Google Patents
Water-soluble photochromic compounds Download PDFInfo
- Publication number
- GB2209751A GB2209751A GB8821373A GB8821373A GB2209751A GB 2209751 A GB2209751 A GB 2209751A GB 8821373 A GB8821373 A GB 8821373A GB 8821373 A GB8821373 A GB 8821373A GB 2209751 A GB2209751 A GB 2209751A
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- group
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- alkyl
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/10—Spiro-condensed systems
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
Abstract
Water-soluble photochromic compounds are disclosed which are obtained by introducing a sulphonic acid or chlorosulphonic acid group or acid salt group into the structure. The water-soluble photochromic compounds are useful in flow visualisation methods.
Description
WATER-SObUBLE PHOTOCHROMIC COMPOUNDS
This invention relates to water-soluble photochromic compounds.
Photochromic compounds have been used in flow visualisation methods and more widely in photoelectronics.
Unfortunately, their usefulness in these fields has been limited by the fact that photochromic compounds are generally insoluble in water. Chemical modification of photochromic compounds tends to interfere with or destroy their photochromic properties.
We have now discovered that certain photochromic compounds which are derived from succinic anhydride or are spiropyrans can be rendered water-soluble by introducing a strong acid or acid salt radical substituent.
According to one aspect of the present invention, there is provided a photochromic fulgide or fulgimide having the general formula:
wherein X is oxygen, or > N - R5 and at least one of the groups R1, R2, R3, R4 and R5 includes a water solublising group, and wherein the remaining groups are independently selected from hydrogen, alkyl, aryl, heterocyclic and aralkyl, the water-solubilising group being a strong acid or acid salt radical. Preferably, the group X is oxygen. Generally, at least one of R1 and R2 and of R3 and R4 is of a group other than hydrogen and at least one of these groups is preferably heterocyclic, aryl or aralkyl.
The water-solubilising group is preferably a strong acid or acid salt, e.g. sulphonic acid or a substituted sulphonic acid, such as chlorosulphonic acid or asalt thereof with an inorganic or organic base. Preferably, the base is a strong base e.g. an alkali metal hydroxide such as potassium or sodium hydroxide. However, weaker inorganic bases may be employed or organic bases such as pyridine or an alkylamine, e.g. diethanolamine or trimethylamine. The water-solubilising group is introduced into the fulgide by substitution in an aryl or aralkyl group in one or more of the R1, R2, R3 or R4 positions. In this way the fulgide can be rendered water-soluble without opening the succinic anhydride ring.
Opening the anhydride ring tends to reduce significantly the colouring efficiency and causes a hypsochromic shift, thereby reducing the contrast of any colour change.
A convenient way of preparing a water-soluble fulgide (or fulgimide) in accordance with the invention is to treat a compound having the general formula (1) above, in which at least one of R1, R2, R3, R4 and R5 is an aryl or aralkyl group, with a sulphonating reagent, or chlorosulphonating agent. Suitable sulphonating agents include sulphur trioxide, sulphur trioxide complexes and chlorosulphonic acid. The aryl or aralkyl group may be substituted with halide (e.g. chloro or bromo), hydroxy or alkoxy. The resulting sulphonated or chlorosulphonated fulgide may be converted into its salt form by addition of a base.
Fulgides and fulgimides of the above kind which may be sulphonated to produce water-soluble photochromic compounds are described in U.K. Patents Nos: 1,442,628; 1,464,603 and 1,602,755.
According to one preferred aspect of this invention there is provided a water-soluble photochromic fulgide or fulgimi.de having the general formula:
where X represents oxygen,
R1 is an alkyl, aryl, aralkyl or heterocyclic group, R2 is a 3-furyl, 3-thienyl, 3-benzofuryl or 3benzothienyl group,
R3 and R4 independently represent an alkyl, aryl, aralkyl or heterocyclic group or one represents hydrogen and the other an alkyl, aryl, aralkyl or heterocyclic group, with the proviso that at least one of R1, R3, R4 and R5 is an aryl or aralkyl group which is substituted with a sulphonic acid or chlorosulphonic acid group or an acid salt group.
It is also possible to prepare water-soluble photochromic compounds by sulphonating fulgides of the kind described in U.K. Patent Specification No. 2,002,752.
Thus, the present invention includes a water-soluble photochromic fulgide or fulgimide having the general formula:-
wherein X is oxygen or NR5 and R5 has the same significance as above.
Ar represents a heterocyclic, aryl or aralkyl group, and
R represents hydrogen, alkyl, aryl or aralkyl, and
wherein at least one of Ar, R and R5 represents an aryl or aralkyl group which is sulphonated (including sulphonated with a substituted sulphonic acid) and optionally converted to the corresponding salt.
Preferably X is oxygen.
In addition to the fulgides mentioned above, a series of photochromic benzo- and naphthopyran compounds can also be rendered water-soluble by sulphonation with sulphonic acid or a substituted sulphonic acid and optionally treated with a base.
These latter compounds which may be rendered watersoluble in accordance with this invention are benzo- and naphthopyran compounds in which a spiro-adamantane group is present in the 2-posi.tion of the pyran ring.
Compounds of this kind are disclosed in U.K. Patent
Specification No. 2,190,379. As described in U.K. Patent
Specification No. 2,190,379, many of these spiropyrans exhibit pronounced heliochromic properties. For example, compounds as described in U.K. Patent Specification No.
2,190,379 commonly exhibit a colour change from colourless to yellow-orange in unfiltered sunlight, while rapidly fading in white light.
The spiropyrans which may be water-solubilised according to the invention are represented in general terms by the following general formulae (I), (II) and (III) in which formula (I) represents the 2H-benzopyran series and formulae (II) and (III) represent the isomeric naphthopyran series
A wide variety of substituents are possible in the benzopyran or naphthopyran rings.For example, the rings can be substituted in the positions represented by R3 to
R8 (or R3 to Rlo) with alkyl, aryl (including substituted phenyl, e.g. alkoxyphenyl and halophenyl), alkoxy, hydroxy, alkyl or dialkylamino (e.g. dimethylami.no), alkylaminophenyl, halogen or heterocyclic groups, with the proviso that hydroxy or alkoxy or alkyl- or dialkylamino may not be a substituent in the R3 or R4 position.
Preferred substituents are lower alkyl (e.g. methyl or ethyl), chlorine, bromine, hydroxy, phenyl, methoxy, or methoxy phenyl groups.
Normally, the water-solubilising group is a sulphonic or chlorosulphonic acid group or salt thereof, so that the groups or elements represented by R3 to R10 should be such that they do not interfere with the suiphonation reaction.
The preferred range of spiropyran compounds used as starting materials in the water-solubilising process are compounds represented by the general formula (II) above.
We have further discovered water-soluble derivatives of a range of heliochromic adamantylidene fulgide compounds as described in U.K. Patent No. 2,146,327B.
These heliochromic adamantylidene compounds can be represented by the following general formula (IV):
represents an adamantylidene or a substituted adamantylidene group,
R1 represents hydrogen, alkyl, aryl, aralkyl or a heterocyclic group,
X represents oxygen or > NR2, in which R2 is hydrogen, aryl, alkyl or aralkyl, and
represents an aromatic group, an unsaturated heterocyclic group or a benzannelated heterocyclic group.
Preferably, the group represented by
is derived from a 2,5-, 2,4- or 3,5-dimethoxyphenyl group or from a 2- or 3- furyl or a 2- or 3- thienyl group.
The starting materials described above can all be sulphonated rapidly by treatment with stabilised sulphur trioxide or a dioxan-sulphur trioxide complex in an inert solvent. The reaction product is extracted with water and may be purified by chromatography.
The following Examples will illustrate the invention:
Example 1
To N-(p-hydroxyphenyl)-isopropylidene-(2, 5-dimethyl- 3-furyl)ethylidene succinimide (lg) in pyx iodine (10cam3) was added chlorosulphonic acid (lcm3) in pyridine (10cm3) and the resultant solution stirred at 00C (6 hrs). The reaction mixture was extracted with water to yield an aqueous solution that coloured to red on exposure to ultra violet light.
Example 2
To p-chlorophenyl(methylidene)-2, 5-dimethyl-3-furyl (ethylidene) succinic anhydride was added a solution of sulphur trioxide/dioxan complex in dichloromethane. The mixture was stirred at room temperature for 6 hours.
Dilute sodium hydroxide was added dropwise to precipitate the sodium salt of the sulphonic acid derivative.
Example 3
Synthesis of Water-Soluble Naphthospiropyran
To adamantylnaphthospiropyran (Example 6 of Patent
Specification No.2,190,379, structure shown in Figure 1 below) in dichloroethane was added sulphan (stabilised
SO3). The reaction mixture was shaken (30 secs.) yielding a dark solution. Water was added which dissipated the dark colour and yielded a pale yellow aqueous solution that coloured to orange on irradiation of the solution with light from an electronic flash. The photochromic compound was purified by reverse phase chromatography (silica gel C-2 plate/methanol:water (50/50).
Example 4
Synthesis of Water-Soluble Heliochromic Fulgide
To the heliochromic compound described in Example 6 of Patent No. 2,146,327B, (structure shown in Figure 2 below), in dichioroethane was added a suspension of dioxan-S03 complex in dichloroethane. The solution obtained was stirred (30 secs) producing a dark solution which on standing crystallised. Water was added to the mixuture which on shaking gave a pale red aqueous solution which coloured to blue under above conditions. The compound was purified as above.
Example 5
Synthesis of Water-Soluble Fulgide
To isopropylidene-2, 5-dimethylfurylethylidene succinic anhydride was added a suspension of SO-3-dioxan complex in dichoroethane. The solution was stirred and left to stand overnight. Water was added to yield a pale yellow solution that coloured to red on UV irradiation.
The water-soluble photochromic compounds of this invention are advantageously employed in flow visualisation systems in which an aqueous test fluid is used.
According to a further aspect of the invention therefore, there is provided a flow visualisation method which comprises forming an aqueous test fluid having dissolved therein a water-soluble photochromic compound as described above, in its uncoloured form, causing the test fluid to flow through a test section having a window therein and subjecting the test fluid in the region of the test section to a high intensity light beam so as to cause the photochromic compound to be converted to its coloured form.
A suitable apparatus and typical flow visualisation techniques are described in the paper by Smith & Hummel published in Journal of the SMPTE, volume 82, pages 278 to 281, and the paper by I & E.C. Fundamentals, volume 8,
No.l, Feb. 1969, pages 160 to 167.
Claims (19)
1. A method of preparing a water-soluble
photochromic compound in which a sulphonic or chlorosulphonic acid group is introduced into an aryl or aralkyl group in the photochromic compound.
2. A method according to claim 1 in which the photochromic compound is sulphonated by treatment with sulphur trioxide or a dioxan-sulphur trioxide complex in an inert solvent.
3. A method according to claim 1 or claim 2 in which the crude product after sulphonati on or chlorosulphonation is purified and the water-soluble photochromic compound isolated by aqueous extraction and chromatography.
4. A water-soluble photochromic fulide or fulgi mide having the general formula :-
wherein X is oxygen, and at least one of the groups
R1, R2, R3, R4 and R5 includes a water-solubilising group, wherein the remaining groups are independently selected from hydrogen, alkyl, aryl, heterocyclic and aralkyl, at least one of R1 and R2 and of R3 and R4 being a group other than hydrogen and wherein the water-solubilising group is derived from a strong acid or acid salt.
5. A water-soluble photochromic fulgide or fulgimide having the general formula :-
where X represents oxygen or > NR5 and R5 is hydrogen, alkyl, aralkyl or aryl,
R1 is an alkyl, aryl, aralkyl or heterocyclic group,
R2 is a 3-furyl, 3-thienyl, 3-benzofuryl or 3 benzothi enyl group,
R3 and R4 independently represent an alkyl, aryl, aralkyl or heterocyclic group or one represents hydrogen and the other an alkyl, aryl, aralkyl or heterocyclic group, with the proviso that at least one of R1, R3, R4 and R5 is an aryl or aralkyl group which is substituted with a sulphonic acid or chlorosulphonic acid group or a salt thereof.
6. A water-soluble photochromic fulgide or fulgimide having the general formula:
wherein X has the same significance as in claim 5,
Ar represents a heterocyclic, aryl or aralkyl group, and
R represents hydrogen, alkyl, aryl or aralkyl, and
wherein at least one of Ar, R and R5 represents an aryl or aralkyl group which is sulphonated or chlorosulphonated.
7. Water-soluble spiropyrans having the general formula I, II or III set forth below in which R3 to R10 independently represent hydrogen, lower alkyl, (1 to 5 carbon atoms), aryl, alkoxy, hydroxy, alkyl- or dialkylamino, halogen or a heterocyclic group, with the proviso that R3 or R4 is not hydroxy, alkoxy or alkyl- or dialkylamino or in the case of formulae I, II or III the benzene or naphthalene ring is benzannelated or annelated with a heterocyclic ring, and with the proviso that at least one of the positions R3 to R10 contains a watersolubilising substituent, said substituent comprising a sulphonic acid or chlorosulphonic c acid group or salt thereof or an aryl or aralkyl group which contains such an acid or salt group,
8.A photochromic spiropyran according to claim 7, wherein the heterocyclic annelated ring is a five or sixmembered oxygen or sulphur containing ring.
9. A photochromic spiropyran according to claim 7 having the general formula (II) and which is benzannelated in the R5-R6 positions.
10. A photochromic spiropyran according to claim 9, having the general formula (I) wherein a fused thiphene, furan or pyrone ring is present in the R6-R7 or R5-R6 or
R7-R8 positions.
11. A photochromic spiropyran according to any one of claims 2 to 5, wherein R3-R4 are both hydrogen.
12. A photochromic spiropyran according to claim 11, wherein R3 is hydrogen and R4 is methyl, phenyl, paramethoxy-phenyl or halogen.
13. A water-soluble photochromic spiro-naphthopyran having the following general formula:
wherein R5 to R10 represent hydrogen, lower alkyl, chlorine, bromine, aryl, hydroxy, alkoxy, alkoxyaryl, alkyl- or dialkylamino, aminoaryl or alkylamino-aryl, or a 5 or 6-membered heterocyclic group or wherein a fused thiophene, furan or pyrone ring is present in the R6-R7,
R5-R6 or R7-R8 positions and R4 represents hydrogen, alkyl, halogen or an aryl group with the proviso that at least one of the positions R5 to R10 contains a watersolubilising substituent, said substituent comprising a sulphonic acid or chlorosulphonic acid group or salt thereof or an aryl or aralkyl group which contains such an acid or salt group.
14. A heliochromic spiro-naphthopyran according to claim 13, wherein R6 is phenyl, chlorine, paramethoxyphenyl, methoxy, thienyl or furyl.
15. A water-soluble photochromic spiropyran having the following general formula:
wherein R1 and R2 each represent one or more substituents selected from hydrogen, lower alkyl, halogen, aryl (including substituted aryl), hydroxy, alkyl or dialkylamino, alkoxy or a heterocyclic group and < Ad represents an adamantane group, and with the proviso that at least one of R1 and R2 represents a water-solubilising substituent, said substituent comprising a sulphonic acid or chlorosulphonic acid group or salt thereof.
16. A photochromic compound of the following general formula : -
represents an adamantylidene or a substituted adamantylidene group;
R1 represents hydrogen, alkyl, aryl, aralkyl or a heterocyclic group,
X represents oxygen or > NR2, in which R2 is hydrogen, aryl, alkyl or aralkyl and
represents an aromatic group, an unsaturated heterocyclic group or a benzannelated heterocyclic group, and which has been sulphonated or chlorosulphonated to introduce a watersolubil ising group into the structure and optionally treated with a base.
17. A photochromic compound of the following general formula : -
wherein R1, X and in claim 16, and
the same significance as
is derived from a 2,5-, 2,4- or 3,5-dimethoxyphenyl group or from a 2- or 3- furyl or a 2- or 3- thienyl group, which may be benzannelated or substituted and which has been sulphonated or chlorosulphonated to introduce a water-solubilising group into the structure and optionally treated with a base.
18. A compound according to claim 17 in which R1 is a lower alkyl or aryl group.
19. A flow visualisation method which comprises forming an aqueous test fluid having dissolved therein a water-soluble photochromic compound as claimed in any one of claims 4 to 18, in its uncoloured form, causing the test fluid to flow through a test section having a window therein and subjecting the test fluid in the region of the test section to a high intensity light beam so as to cause the photochromic compound to be converted to its coloured form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878721530A GB8721530D0 (en) | 1987-09-14 | 1987-09-14 | Water soluble photochromic fungides |
| GB878723989A GB8723989D0 (en) | 1987-10-13 | 1987-10-13 | Water soluble photochromic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8821373D0 GB8821373D0 (en) | 1988-10-12 |
| GB2209751A true GB2209751A (en) | 1989-05-24 |
Family
ID=26292721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8821373A Withdrawn GB2209751A (en) | 1987-09-14 | 1988-09-12 | Water-soluble photochromic compounds |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2209751A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811034A (en) * | 1997-10-23 | 1998-09-22 | Ppg Industries, Inc. | 7-methylidene-5-oxo-furo fused naphthopyrans |
| US5879592A (en) * | 1997-12-10 | 1999-03-09 | Ppg Industries, Inc. | Water soluble photochromic compounds, compositions and optical elements comprising the compounds |
| US5888432A (en) * | 1996-12-23 | 1999-03-30 | Corning Incorporated | 2-Adamantyl benzopyrans the compositions and (co)polymer matrices containing them |
| WO1999031081A1 (en) * | 1997-12-12 | 1999-06-24 | James Robinson Limited | Ph sensitive photochromic dyes |
| US20140252666A1 (en) * | 2013-03-11 | 2014-09-11 | U.S. Government As Represented By The Secretary Of The Army | Method of fabricating a liquid crystal polymer film |
| US9753193B2 (en) | 2014-04-16 | 2017-09-05 | Beam Engineering For Advanced Measurements Co. | Methods and apparatus for human vision correction using diffractive waveplate lenses |
| US9976911B1 (en) | 2015-06-30 | 2018-05-22 | Beam Engineering For Advanced Measurements Co. | Full characterization wavefront sensor |
| US9983479B2 (en) | 2010-04-21 | 2018-05-29 | Beam Engineering For Advanced Measurements Co. | Fabrication of high efficiency, high quality, large area diffractive waveplates and arrays |
| US10031424B2 (en) | 2010-04-21 | 2018-07-24 | Beam Engineering For Advanced Measurements Co. | Fabrication of high efficiency, high quality, large area diffractive waveplates and arrays |
| US10036886B2 (en) | 2010-01-29 | 2018-07-31 | Beam Engineering For Advanced Measurements Co. | Broadband optics for manipulating light beams and images |
| US10107945B2 (en) | 2013-03-01 | 2018-10-23 | Beam Engineering For Advanced Measurements Co. | Vector vortex waveplates |
| US10114239B2 (en) | 2010-04-21 | 2018-10-30 | Beam Engineering For Advanced Measurements Co. | Waveplate lenses and methods for their fabrication |
| US10185182B2 (en) | 2013-03-03 | 2019-01-22 | Beam Engineering For Advanced Measurements Co. | Mechanical rubbing method for fabricating cycloidal diffractive waveplates |
| US10191296B1 (en) | 2015-06-30 | 2019-01-29 | Beam Engineering For Advanced Measurements Co. | Laser pointer with reduced risk of eye injury |
| US10197715B1 (en) | 2013-03-15 | 2019-02-05 | Beam Engineering For Advanced Measurements Co. | Methods of diffractive lens and mirror fabrication |
| US10274805B2 (en) | 2017-06-13 | 2019-04-30 | Beam Engineering For Advanced Measurements Co. | Polarization-independent switchable lens system |
| US10423045B2 (en) | 2016-11-14 | 2019-09-24 | Beam Engineering For Advanced Measurements Co. | Electro-optical diffractive waveplate beam shaping system |
| US10436957B2 (en) | 2015-10-27 | 2019-10-08 | Beam Engineering For Advanced Measurements Co. | Broadband imaging with diffractive waveplate coated mirrors and diffractive waveplate objective lens |
| US11175441B1 (en) | 2018-03-05 | 2021-11-16 | Beam Engineering For Advanced Measurements Co. | Polarization-independent diffractive optical structures |
| US11294240B2 (en) | 2019-08-10 | 2022-04-05 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate devices that operate over a wide temperature range |
| US11366254B2 (en) | 2010-01-29 | 2022-06-21 | Beam Engineering For Advanced Measurements Co. | High-efficiency wide-angle beam steering system |
-
1988
- 1988-09-12 GB GB8821373A patent/GB2209751A/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| Kirk-Othmer Encyclopedia of Chemical * |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5888432A (en) * | 1996-12-23 | 1999-03-30 | Corning Incorporated | 2-Adamantyl benzopyrans the compositions and (co)polymer matrices containing them |
| US5811034A (en) * | 1997-10-23 | 1998-09-22 | Ppg Industries, Inc. | 7-methylidene-5-oxo-furo fused naphthopyrans |
| US5879592A (en) * | 1997-12-10 | 1999-03-09 | Ppg Industries, Inc. | Water soluble photochromic compounds, compositions and optical elements comprising the compounds |
| WO1999031081A1 (en) * | 1997-12-12 | 1999-06-24 | James Robinson Limited | Ph sensitive photochromic dyes |
| US10036886B2 (en) | 2010-01-29 | 2018-07-31 | Beam Engineering For Advanced Measurements Co. | Broadband optics for manipulating light beams and images |
| US11366253B2 (en) | 2010-01-29 | 2022-06-21 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate lenses and applications |
| US10274650B2 (en) | 2010-01-29 | 2019-04-30 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate lenses and applications |
| US10557977B1 (en) | 2010-01-29 | 2020-02-11 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate lenses and applications |
| US11366254B2 (en) | 2010-01-29 | 2022-06-21 | Beam Engineering For Advanced Measurements Co. | High-efficiency wide-angle beam steering system |
| US10120112B2 (en) | 2010-01-29 | 2018-11-06 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate lenses for correcting aberrations and polarization-independent functionality |
| US10802302B2 (en) | 2010-04-21 | 2020-10-13 | Beam Engineering For Advanced Measurements Co. | Waveplate lenses and methods for their fabrication |
| US10031424B2 (en) | 2010-04-21 | 2018-07-24 | Beam Engineering For Advanced Measurements Co. | Fabrication of high efficiency, high quality, large area diffractive waveplates and arrays |
| US10114239B2 (en) | 2010-04-21 | 2018-10-30 | Beam Engineering For Advanced Measurements Co. | Waveplate lenses and methods for their fabrication |
| US9983479B2 (en) | 2010-04-21 | 2018-05-29 | Beam Engineering For Advanced Measurements Co. | Fabrication of high efficiency, high quality, large area diffractive waveplates and arrays |
| US11119257B2 (en) | 2010-04-21 | 2021-09-14 | Beam Engineering For Advanced Measurements Co | Methods of diffractive lens and mirror fabrication |
| US10107945B2 (en) | 2013-03-01 | 2018-10-23 | Beam Engineering For Advanced Measurements Co. | Vector vortex waveplates |
| US10185182B2 (en) | 2013-03-03 | 2019-01-22 | Beam Engineering For Advanced Measurements Co. | Mechanical rubbing method for fabricating cycloidal diffractive waveplates |
| US9617205B2 (en) * | 2013-03-11 | 2017-04-11 | Beam Engineering For Advanced Measurements Co. | Method of fabricating a liquid crystal polymer film |
| US20160023993A1 (en) * | 2013-03-11 | 2016-01-28 | U.S. Government As Represented By The Secretary Of Army | Method of fabricating a liquid crystal polymer film |
| US20140252666A1 (en) * | 2013-03-11 | 2014-09-11 | U.S. Government As Represented By The Secretary Of The Army | Method of fabricating a liquid crystal polymer film |
| US10197715B1 (en) | 2013-03-15 | 2019-02-05 | Beam Engineering For Advanced Measurements Co. | Methods of diffractive lens and mirror fabrication |
| US9753193B2 (en) | 2014-04-16 | 2017-09-05 | Beam Engineering For Advanced Measurements Co. | Methods and apparatus for human vision correction using diffractive waveplate lenses |
| US10191191B2 (en) | 2014-04-16 | 2019-01-29 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate lenses and applications |
| US10191296B1 (en) | 2015-06-30 | 2019-01-29 | Beam Engineering For Advanced Measurements Co. | Laser pointer with reduced risk of eye injury |
| US9976911B1 (en) | 2015-06-30 | 2018-05-22 | Beam Engineering For Advanced Measurements Co. | Full characterization wavefront sensor |
| US10436957B2 (en) | 2015-10-27 | 2019-10-08 | Beam Engineering For Advanced Measurements Co. | Broadband imaging with diffractive waveplate coated mirrors and diffractive waveplate objective lens |
| US10423045B2 (en) | 2016-11-14 | 2019-09-24 | Beam Engineering For Advanced Measurements Co. | Electro-optical diffractive waveplate beam shaping system |
| US10274805B2 (en) | 2017-06-13 | 2019-04-30 | Beam Engineering For Advanced Measurements Co. | Polarization-independent switchable lens system |
| US11175441B1 (en) | 2018-03-05 | 2021-11-16 | Beam Engineering For Advanced Measurements Co. | Polarization-independent diffractive optical structures |
| US11294240B2 (en) | 2019-08-10 | 2022-04-05 | Beam Engineering For Advanced Measurements Co. | Diffractive waveplate devices that operate over a wide temperature range |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8821373D0 (en) | 1988-10-12 |
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