1. A photoinitiator composition comprising at least one N-oxyazinium salt photoinitiator, an aryl aldehyde or alkyl aldehyde each having one or more aldehyde moieties and a molecular weight of less than 1000, and at least one organic phosphine as an N-oxyazinium salt efficiency amplifier.
2. The composition of claim 1 wherein the organic phosphine is represented by the following Structure (I) or (II):
(R\u2032)3P \u2003\u2003(I)
(R\u2032)2P-L-P(R\u2032)2 \u2003\u2003(II)
wherein the multiple R\u2032 groups are:
(1) hydrogen,
(2) the same or different substituted or unsubstituted alkyl groups,
(3) the same or different substituted or unsubstituted cycloalkyl groups,
(4) the same or different substituted or unsubstituted aryl groups,
(5) the same or different HO{CH(R)}xy groups wherein the multiple R groups are the same or different and can be hydrogen atoms or substituted or unsubstituted alkyl or cycloalkyl groups, or two R\u2032 groups together can form a cyclic aliphatic ring or fused ring system, x is an integer of at least 2 and up to and including 20, and y is an integer of at least 1 and up to and including 20, or
(6) two adjacent R\u2032 groups are joined together to form a cyclic ring with the phosphorus atom, provided at least one R\u2032 group is not hydrogen, and
L is a connecting group having at least 1 to 12 carbon atoms in the linking chain.
3. The composition of claim 1 comprising one or more of methyl phosphine, dimethyl phosphine, trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tri-n-butyl phosphine, triisobutyl phosphine, triamyl phosphine, trihexyl phosphine, trinonyl phosphine, tri-(ethylene glycol)phosphine, tri-(propylene glycol)phosphine, tri(isopropylene glycol)phosphine, tri(butylene glycol)phosphine, tri(isobutylene glycol)phosphine, tri(pentylene glycol)phosphine, tri(hexylene glycol)phosphine, tri(nonylene glycol)phosphine, tri(diethylene glycol)phosphine, tri(triethylene glycol)phosphine, tri(polyethylene glycol)phosphine, tri(polypropylene glycol)phosphine, di(ethylamino)phenylphosphine, triphenylphosphine, tritoylphosphine, tris(4-methoxyphenyl)phosphine, tri(polybutylene glycol)phosphine, bis(diphenylphosphinoethyl)phenylphosphine, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,5-bis(dicyclohexylphosphino)pentane, 1,4-bis(dicyclohexylphosphino)butane, 1,2-bis(dicyclohexylphosphino)ethane, bis(dicyclohexylphosphino)methane, bis(diphenylphosphino)methane monoxide, and the compound represented by the following structure:
4. The composition of claim 1 wherein the N-oxyazinium salt photoinitiator is represented by either of the following Structures (III) and (IV):
wherein A and B in Structure (III) independently represent a carbon, C\u2014R5, C\u2014R6 or nitrogen, X is O, R1, R2, R3, R4, R5, and R6 are independently hydrogen, or alkyl or aryl groups, any of the A, B, and R groups where chemically feasible can be joined together to form a ring, and Y\u2212 is a charge balancing anion that can be a separate moiety or a charged part of an A, B, or R group,
wherein A in Structure (IV) represents a carbon, C\u2014R5, nitrogen, sulfur or oxygen atom with sufficient bonds and substituents to form a heteroaromatic ring, X is O, R1, R2, R3, R4, and R5 are independently hydrogen, or alkyl or aryl groups, or any two R groups together can form a ring, and Y\u2212 is a charge balancing anion that can be a separate moiety or part of a charged R group.
5. The composition of claim 1 wherein the N-oxyazinium salt photoinitiator has a cation represented by one of the following formulae:
wherein R1 represents a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or an acyl group, wherein R1 can also include a charge balancing anion, the R2 groups independently represent hydrogen, or a substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted heteroaryl group, or nitrile group, X is a divalent linking group, and Z is an aliphatic linking group.
6. The composition of claim 1 wherein the N-oxyazinium salt photoinitiator has a reduction potential less negative than \u22121.4 V and comprises an N-oxy group that is capable of releasing an oxy radical during irradiation of the photocurable composition.
7. The composition of claim 1, wherein the organic phosphine is present in a molar amount relative to total aldehyde moieties of at least 1:1 and up to and including 4:1.
8. The composition of claim 1 further comprising a photosensitizer for the N-oxyazinium salt photoinitiator that is selected from the group consisting of ketocoumarins, benzophenones, xanthones, thioxanthones, arylketones, and polycyclic aromatic hydrocarbons.
9. The composition of claim 1 wherein the N-oxyazinium salt photoinitiator is present in an amount of at least 1 weight % and up to and including 50 weight %, based on the total composition solids, and the weight ratio of organic phosphine to N-ozyazinium salt photoinitiator is at least 0.01:1 and up to and including 100:1.
10. The composition of claim 1 wherein the aryl aldehyde or alkyl aldehyde has a molecular weight of less than 500.
11. The composition of claim 1 that is a photocurable composition further comprising at least one photocurable compound.
12. The composition of claim 11 comprising at least one acrylate as a photocurable compound.
13. The composition of claim 11 wherein the organic phosphine is represented by the following Structure (I) or (II):
(R\u2032)3P \u2003\u2003(I)
(R\u2032)2P-L-P(R\u2032)2 \u2003\u2003(II)
wherein the multiple R\u2032 groups are:
(1) hydrogen,
(2) the same or different substituted or unsubstituted alkyl groups,
(3) the same or different substituted or unsubstituted cycloalkyl groups,
(4) the same or different substituted or unsubstituted aryl groups,
(5) the same or different HO{CH(R)}xy groups wherein the multiple R groups are the same or different and can be hydrogen atoms or substituted or unsubstituted alkyl or cycloalkyl groups, or two R\u2032 groups together can form a cyclic aliphatic ring or fused ring system, x is an integer of at least 2 and up to and including 20, and y is an integer of at least 1 and up to and including 20, or
(6) two adjacent R\u2032 groups are joined together to form a cyclic ring with the phosphorus atom, provided at least one R\u2032 group is not hydrogen, and
L is a connecting group having at least 1 to 12 carbon atoms in the linking chain.
14. The composition of claim 11 wherein the N-oxyazinium salt photoinitiator is represented by either of the following Structures (III) and (IV):
wherein A and B in Structure (III) independently represent a carbon, C\u2014R5, C\u2014R6 or nitrogen, X is O, R1, R2, R3, R4, R5, and R6 are independently hydrogen, or alkyl or aryl groups, any of the A, B, and R groups where chemically feasible can be joined to form a ring, and Y is a charge balancing anion that can be a separate moiety or a charged part of an A, B, or R group,
wherein A in Structure (IV) represents a carbon, C\u2014R5, nitrogen, sulfur or oxygen atom with sufficient bonds and substituents to form a heteroaromatic ring, X is O, R1, R2, R3, R4, and R5 are independently hydrogen, or alkyl or aryl groups, or any two R groups can form a ring, and Y is a charge balancing anion that can be a separate moiety or part of a charged R group.
15. The composition of claim 11 wherein the N-oxyazinium salt photoinitiator has a cation represented by one of the following formulae:
wherein R1 represents a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or an acyl group, wherein RI can also include a charge balancing anion, the R2 groups independently represent hydrogen, or a substituted or unsubstituted alkyl, aryl, alkoxy, or heteroaryl group, or a nitrile group, X is a divalent linking group, and Z is an aliphatic linking group.
16. The composition of claim 11 wherein the N-oxyazinium salt photoinitiator has a reduction potential less negative than \u22121.4 V and comprises an N-oxy group that is capable of releasing an oxy radical during irradiation of the photocurable composition.
17. The composition of claim 11 further comprising a photosensitizer for the N-oxyazinium salt photoinitiator that is selected from the group consisting of ketocoumarins, benzophenones, xanthones, thioxanthones, arylketones, and polycyclic aromatic hydrocarbons.
18. The composition of claim 1 further comprising a non-reactive organic solvent.
19. The composition of claim 11 that is a photocurable ink that further comprises a colorant.
20. A kit comprising:
a) a precursor composition comprising one or more photocurable acrylates, and
b) a photoinitiator composition comprising at least one N-oxyazinium salt photo initiator, a photosensitizer for the N-oxyazinium salt photoinitiator, an aryl aldehyde or an alkyl aldehyde, and an organic phosphine that is an N-oxyazinium salt efficiency amplifier.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
What is claimed is:
1. An apparatus for use with an endoscope, comprising:
a housing removably attachable to a distal terminating end of the endoscope, the housing comprising an outer surface and a cross-sectional area at least as large as a cross-sectional area of the distal terminating end of the endoscope; and
at least one electrode supported by at least a portion of the outer surface of the housing and capable of delivering energy to a tissue region inside a body to ablate the tissue region.
2. The apparatus of claim 1 wherein the housing comprises an insulator.
3. The apparatus of claim 1 wherein the housing comprises at least one of a ceramic material, a glass, and a polymeric material.
4. The apparatus of claim 2 wherein the insulator comprises a thermal insulator.
5. The apparatus of claim 2 wherein the insulator comprises an electrical insulator.
6. The apparatus of claim 1 wherein at least a portion of the housing is transparent.
7. The apparatus of claim 1 wherein the housing comprises at least one groove and the electrode is positioned in the groove.
8. The apparatus of claim 1 wherein the housing is substantially ring-shaped.
9. The apparatus of claim 1 wherein the housing comprises a distal end and a proximal end, the proximal end comprising an elastomeric material and being sized and shaped to slip over the distal end of the endoscope.
10. The apparatus of claim 1 wherein the housing further comprises a stop ring.
11. The apparatus of claim 1 wherein at least one electrode comprises a pattern.
12. The apparatus of claim 11 wherein the pattern comprises a row of linear elements.
13. The apparatus of claim 11 wherein the pattern comprises a helical pattern.
14. The apparatus of claim 1 wherein the housing comprises a plurality of apertures.
15. The apparatus of claim 1 wherein the housing is foraminous.
16. The apparatus of claim 1 further comprising an electrical conduit in electrical communication with at least one electrode.
17. The apparatus of claim 16 wherein the electrical conduit comprises one of wire and coaxial conductor.
18. The apparatus of claim 17 wherein the wire comprises a twisted pair of wires.
19. The apparatus of claim 16 further comprising a connector in electrical communication with a proximal end of the electrical conduit.
20. The apparatus of claim 1 further comprising at least one light source disposed in the housing for emitting light and a light modulator disposed in the housing for modifying light emitted by the light source.
21. The apparatus of claim 1 wherein at least one electrode comprises a monopolar electrode.
22. The apparatus of claim 1 wherein at least one electrode comprises a bipolar electrode.
23. An apparatus for use with an endoscope, comprising:
a sheath comprising a first channel for receiving the endoscope;
a housing attached to a distal end of the sheath, the housing comprising an outer surface and a cross-sectional area at least as large as a cross-sectional area of a distal terminating end of the endoscope; and
at least one electrode supported by at least a portion of the outer surface of the housing and capable of delivering energy to a tissue region inside a body to ablate the tissue region.
24. The apparatus of claim 23 wherein the sheath further comprises a second channel coextensive with the first channel and an electrical conduit disposed in the second channel, wherein the electrical conduit is in electrical communication with at least one electrode.
25. The apparatus of claim 23 wherein the sheath further comprises a second channel coextensive with the first channel for receiving a fluid.
26. The apparatus of claim 23 wherein the sheath comprises polyethylene.
27. The apparatus of claim 23 wherein the sheath has a thickness in the range from about 0.015 inches to about 0.085 inches.
28. The apparatus of claim 23 further comprising an adjustable stop ring for adjusting a position of the housing relative to the endoscope.
29. The apparatus of claim 23 wherein the housing comprises an insulator.
30. The apparatus of claim 23 wherein at least a portion of the housing is substantially transparent.
31. A medical apparatus, comprising:
an endoscope terminating at a distal end;
a housing removably attachable to the distal terminating end of the endoscope, the housing comprising an outer surface and a cross-sectional area at least as large as a cross-sectional area of the distal terminating end of the endoscope; and
at least one electrode supported by at least a portion of the outer surface of the housing and capable of delivering energy to a tissue region inside a body to ablate the tissue region.
32. A medical apparatus, comprising:
an endoscope terminating at a distal end;
a sheath comprising a channel for receiving the endoscope and a housing attached to a distal terminating end of the sheath, the housing comprising an outer surface and a cross-sectional area at least as large as a cross-sectional area of the distal terminating end of the endoscope; and
at least one electrode supported by at least a portion of the outer surface of the housing and capable of delivering energy to a tissue region inside a body to ablate the tissue region.
33. A method of treating tissue in a body, comprising:
a) attaching a housing to a distal terminating end of an endoscope, the housing removably attachable to the distal terminating end of the endoscope, the housing comprising an outer surface supporting at least one electrode on at least a portion of the outer surface and a cross-sectional area at least as large as a cross-sectional area of the distal terminating end of the endoscope;
b) inserting the endoscope and the housing inside the body near a tissue region to be treated; and
c) applying energy to at least one electrode to treat the tissue region.
34. The method of claim 33 further comprising connecting at least one electrode to a power source through an electrical conduit housed in a channel of the endoscope.
35. The method of claim 33 wherein step a) comprises attaching a housing comprising at least one aperture and further comprising providing a fluid to the tissue region through the aperture.
36. The method of claim 35 wherein the fluid comprises at least one of a cooling fluid, a flushing fluid and a conductive fluid.
37. The method of claim 33 wherein step a) comprises attaching a housing comprising an insulating material.
38. The method of claim 33 wherein step a) comprises attaching a housing comprising a substantially transparent material.
39. The method of claim 33 wherein step a) comprises attaching a housing supporting a bipolar electrode.
40. The method of claim 33 wherein step a) comprises attaching a housing supporting a monopolar electrode.
41. The method of claim 33 wherein step c) comprises applying RF energy.
42. The method of claim 33 wherein step c) comprises applying energy to ablate the tissue region.
43. The method of claim 33 further comprising illuminating the tissue region and detecting an optical property of the tissue region.
44. A method of treating tissue in a body, comprising:
a) providing a sheath comprising a channel for receiving an endoscope and a housing attached to a distal end of the sheath, the housing comprising an outer surface supporting at least one electrode on at least a portion of the outer surface and a cross-sectional area at least as large as a cross-sectional area of a distal terminating end of the endoscope;
b) inserting an endoscope inside the channel of the sheath such that the housing is positioned near the distal terminating end of the endoscope;
c) inserting the sheath and the endoscope inside the body near a tissue region to be treated; and
d) applying energy to at least one electrode to treat the tissue region.
45. The method of claim 44 further comprising connecting at least one electrode to a power source through an electrical conduit housed in a second channel of the sheath.
46. The method of claim 44 wherein step a) comprises providing a housing comprising at least one aperture and further comprising providing a fluid to the tissue region through the aperture.
47. The method of claim 46 wherein the fluid comprises at least one of a cooling fluid, a flushing fluid and a conductive fluid.
48. The method of claim 44 wherein step a) comprises providing a housing comprising an insulating material.
49. The method of claim 44 wherein step a) comprises providing a housing comprising a substantially transparent material.
50. The method of claim 44 wherein step a) comprises providing a housing supporting a bipolar electrode.
51. The method of claim 44 wherein step a) comprises providing a housing supporting a monopolar electrode.
52. The method of claim 44 wherein step d) comprises applying RF energy.
53. The method of claim 44 wherein step d) comprises applying energy to ablate the tissue region.
54. The method of claim 44 further comprising illuminating the tissue region and detecting an optical property of the tissue region.
55. A method of manufacturing an ablation apparatus comprising the steps of:
a) providing a housing;
b) providing a slurry comprising a conductive material and a solution;
c) applying the slurry on at least a portion of a surface of the housing; and
d) removing the solution applied on the surface of the housing to form an electrode comprising the conductive material on the surface of the housing.
56. The method of claim 55 wherein step c) comprises printing the slurry on the surface of the housing.
57. The method of claim 56 wherein step b) comprises providing a slurry comprising a sliver epoxy.
58. The method of claim 55 wherein step c) comprises applying the slurry by at least one of spraying, dipping, and brushing.
59. The method of claim 55 wherein step d) comprises heating the slurry to remove the solution and to melt the conductive material to form the electrode.
60. The method of claim 55 wherein step a) comprises providing a housing comprising at least one groove and step d) comprises removing at least a portion of the conductive material to form the electrode in the at least one groove.