loading of a biological vesicle , such as a red blood cell ( rbc ), white blood cell ( wbc ), or a liposome with a texaphyrin - lipophilic molecule conjugate has previously not been shown . in the present invention , rbc &# 39 ; s were successfully loaded with gdt2bet - estradiol conjugate ( gte 1 a ). however , attempted loading with gdt2bet alone was not successful , thereby indicating that a lipophilic molecule “ handle ” is an important aspect of the texaphyrin conjugate for loading success . although the examples that follow demonstrate loading of red blood cells , the invention is not limited thereto ; it is contemplated that other cells may be loaded as well , such as stem cells , bone marrow cells , platelets , granulocytes , lymphocytes including t and b cells , monocytes , neutrophils , eosinophils , plasma cells , macrophage , dendritic cells , or a cell of mesenchymal , ectodermal , or endodermal origin . macrophages loaded with a texaphyrin - lipophilic molecule conjugate are expected to have utility in the treatment of atheroma since macrophages complex with cholesterol to form foam cells , a component of early atheroma . loaded vesicles will naturally biolocalize into the blood , liver , spleen , bone marrow or lymphoid organs . due to the size of a vesicle , such as a red blood cell or a liposome , compared to the size of a texaphyrin - lipophilic molecule conjugate , it is expected that the vesicle will dominate in terms of biolocalization , and any localizing effect of a site - directing lipophilic molecule or the inherent biolocalization of texaphyrins will be secondary . for example , a texaphyrin - estradiol conjugate loaded into a vesicle may have some specificity for an estradiol receptor if the estradiol is superficial to the vesicle . similarly , a vesicle loaded with a texaphyrin - cholesterol conjugate may have localization to the liver in addition to the natural localization of the vesicle to the liver . human ldl is a physiologic serum protein metabolized by cells via uptake by high affinity receptors . in particular , neovascularization has been shown to have increased numbers of ldl receptors ; and by increasing the partitioning of the texaphyrin into the lipoprotein phase of the blood , ldl is expected to more efficiently deliver texaphyrin to target tissue . a texaphyrin - ldl conjugate is selective for neovascularization since leakage of the conjugate is expected to occur only in neovasculature due to the large size of the conjugate . ldl can be isolated and purified according to the procedure of hauel et al ., ( j . clin . invest ., 34 : 1345 , 1995 ). in the loading of red blood cells of the present invention , red blood cells are separated from plasma and washed in normal saline . they are then treated with hypertonic saline which leaves them crenated with their internal salt concentration being higher than normal . the crenated cell pellet is resuspended in hypotonic saline containing a texaphyrin - lipophilic molecule conjugate . because of the concentration difference between the cell interior and the hypotonic solution , water and the conjugate are driven into the cells . the cells are then washed several times in normal saline . this procedure results in a red blood cell with extensive labeling with the texaphyrin - lipophilic molecule conjugate . further methods for loading cells are known to those of skill in this art in light of the present disclosure and may be utilized in the preparation of complexes of the present invention , for example , inducing an osmotic difference by use of sucrose solutions , treating with calcium chloride or calcium phosphate , or the like . white cells are obtained from blood by , for example , centrifugation through ficoll hypaque media . this separates the white blood cells from plasma components and red blood cells . other techniques for obtaining specific types of cells are known to one of skill in the art in light of the present disclosure . liposomes may be prepared by any number of techniques that include freeze - thaw , sonication , chelate dialysis , homogenization , solvent infusion , microemulsification , spontaneous formation , solvent vaporization , reverse phase , french pressure cell technique , or controlled detergent dialysis , for example . such preparation methods are known to one of skill in the art in light of the present disclosure . preparation may be carried out in a solution , such as a phosphate buffer solution , containing a texaphyrin - lipophilic molecule conjugate so that the conjugate is incorporated into the liposome membrane . alternatively , the conjugate may be added to already formed liposomes . liposomes employed in the present invention may be of any one of a variety of sizes , preferably less than about 100 nm in outside diameter , more preferably less than about 50 nm . micelles may be prepared by suspension of a texaphyrin - lipophilic molecule and lipid compound ( s ) in an organic solvent , evaporation of the solvent , resuspension in an aqueous medium , sonication and then centrifugation . alternatively , the texaphyrin - lipophilic molecule may be added to preformed micelles , which micelles are made by methods known by one of skill in the art in light of the present disclosure . techniques and lipids for preparing liposomes and micelles are discussed in u . s . pat . no . 5 , 466 , 438 , and references cited therein . the disclosures of each of the foregoing references are incorporated herein by reference . a texaphyrin - lipophilic molecule conjugate as used herein is an aromatic pentadentate expanded porphyrin analog with appended functional groups , at least one of which is a lipophilic molecule . pendant groups may enhance solubility or biolocalization or may provide coupling sites for site - directing molecules . examples of texaphyrin - lipophilic molecule conjugates are those having structure i or structure ii : m is h , or a divalent or trivalent metal cation . a preferred divalent metal cation is ca ( ii ), mn ( ii ), co ( ii ), ni ( ii ), zn ( ii ), cd ( ii ), hg ( ii ), fe ( ii ), sm ( ii ), or uo 2 ( ii ). a preferred trivalent metal cation is mn ( iii ), co ( iii ), ni ( iii ), fe ( iii ), ho ( iii ), ce ( iii ), y ( iii ), in ( iii ), pr ( iii ), nd ( iii ), sm ( iii ), eu ( iii ), gd ( iii ), tb ( iii ), dy ( iii ), er ( iii ), tm ( iii ), yb ( iii ), lu ( iii ), la ( iii ), or u ( iii ). most preferred trivalent metal cations are lu ( iii ) and gd ( iii ). r 1 - r 4 , r 7 and r 8 are independently hydrogen , halide , hydroxyl , alkyl , alkenyl , alkynyl , aryl , haloalkyl , nitro , formyl , acyl , hydroxyalkyl , alkoxy , hydroxyalkoxy , hydroxyalkenyl , hydroxyalkynyl , saccharide , carboxy , carboxyalkyl , carboxyamide , carboxyamidealkyl , amino , aminoalkyl , a lipophilic molecule , or a couple that is coupled to a lipophilic molecule . r 6 and r 9 are independently selected from the groups of r 1 - r 4 , r 7 and r 8 , with the proviso that the halide is other than iodide and the haloalkyl is other than iodoalkyl . r 5 and r 10 - r 12 are independently hydrogen , alkyl , alkenyl , alkynyl , aryl , hydroxyalkyl , alkoxy , hydroxyalkoxy , hydroxyalkenyl , hydroxyalkynyl , carboxyalkyl , carboxyamide , carboxyamidealkyl , amino , aminoalkyl , or a couple that is coupled to a saccharide , or to a lipophilic molecule . the term “ n ” is an integer value less than or equal to 5 . r 13 is alkyl , alkenyl , oxyalkyl , or hydroxyalkyl having up to about 3 carbon atoms and having rotational flexibility around a first - bound carbon atom . rotational flexibility allows the rest of the group to be positioned outside the plane of the texaphyrin . thus , for example , a preferred alkenyl is ch 2 — ch ═ ch 2 . the pyrrole nitrogen substituent is most preferably a methyl group . a texaphyrin having a methyl group attached to a ring nitrogen is described in u . s . pat . no . 5 , 457 , 183 , incorporated by reference herein . in this texaphyrin - lipophilic molecule conjugate , at least one of r 1 - r 12 is a lipophilic molecule or a couple that is coupled to a lipophilic molecule . in a more preferred embodiment , at least one of r 1 , r 2 , r 3 , r 4 , r 7 and r 8 is a lipophilic molecule , and more preferably is estradiol or cholesterol , or a couple that is coupled to estradiol or cholesterol . in a presently preferred embodiment , the texaphyrin - lipophilic molecule conjugate is the conjugate depicted herein as 1 a or 1 b . texaphyrins of the present conjugates may be metal - free or may be in a complex with a metal . divalent and trivalent metal complexes of texaphyrins are by convention shown with a formal charge of n + , where n = 1 or 2 , respectively . the value “ n ” will typically be an integer less than or equal to 5 ; however , one skilled in the art in light of the present disclosure would realize that the value of n would be altered due to any charges present on substituents r 1 - r 12 . it is understood by those skilled in the art that texaphyrin - metal complexes have one or more additional ligands providing charge neutralization and / or coordinative saturation to the metal ion . such ligands include chloride , nitrate , acetate , cholate , and hydroxide , among others . photosensitive texaphyrins are used for pdt . a photosensitive texaphyrin may be a free - base texaphyrin or may be metallated with a diamagnetic metal . the term “ photosensitive ,” as used herein , means that upon photoirradiation by light associated with the absorption profile of texaphyrin , texaphyrin effects the generation of oxygen products that are cytotoxic . cytotoxic oxygen products may be singlet oxygen , hydroxyl radicals , superoxide , hydroperoxyl radicals , or the like . a photosensitive texaphyrin may be a texaphyrin metal complex , and in this embodiment , the metal m is a diamagnetic metal cation and the diamagnetic metal cation preferably is lu ( iii ), la ( iii ), in ( iii ), y ( iii ), zn ( ii ) or cd ( ii ). a more preferred diamagnetic metal cation is lu ( iii ). representative examples of alkanes useful as alkyl group substituents of the present invention include methane , ethane , straight - chain , branched or cyclic isomers of propane , butane , pentane , hexane , heptane , octane , nonane and decane , with methane , ethane and propane being preferred . alkyl groups having up to about thirty , or up to about fifty carbon atoms are contemplated in the present invention . representative examples of substituted alkyls include alkyls substituted by two or more functional groups as described herein . representative examples of alkenes useful as alkenyl group substituents include ethene , straight - chain , branched or cyclic isomers of propene , butene , pentene , hexene , heptene , octene , nonene and decene , with ethene and propene being preferred . alkenyl groups having up to about thirty or fifty carbon atoms , and up to about five double bonds , or more preferably , up to about three double bonds are contemplated in the present invention . representative examples of alkynes useful as alkynyl group substituents include ethyne , straight - chain , branched or cyclic isomers of propyne , butyne , pentyne , hexyne , heptyne , octyne , nonyne and decyne , with ethyne and propyne being preferred . alkynyl groups having up to about thirty , or up to about fifty carbon atoms , and having up to about five or up to about three triple bonds are contemplated in the present invention . the aryl may be a compound whose molecules have the ring structure characteristic of benzene , naphthalene , phenanthrene , anthracene , and the like , i . e ., either the 6 - carbon ring of benzene or the condensed 6 - carbon rings of the other aromatic derivatives . for example , an aryl group may be phenyl or naphthyl , and the term as used herein includes both unsubstituted aryls and aryls substituted with one or more nitro , carboxy , sulfonic acid , hydroxy , oxyalkyl or halide substituents . in this case , the substituent on the phenyl or naphthyl may be added in a synthetic step after the condensation step which forms the macrocycle . among the halide substituents , chloride , bromide , fluoride and iodide are contemplated in the practice of this invention with the exception of iodide for r 6 and r 9 . r 6 and r 9 may have chloride , bromide or fluoride substituents . representative examples of haloalkyls used in this invention include halides of methane , ethane , propane , butane , pentane , hexane , heptane , octane , nonane and decane , with halides , preferably chlorides or bromides , of methane , ethane and propane being preferred . “ hydroxyalkyl ” means alcohols of alkyl groups . preferred are hydroxyalkyl groups having one to twenty , more preferably one to ten , hydroxyls . “ hydroxyalkyl ” is meant to include glycols and polyglycols ; diols of alkyls , with diols of c 1 - 10 alkyls being preferred , and diols of c 1 - 3 alkyls being more preferred ; and polyethylene glycol , polypropylene glycol and polybutylene glycol as well as polyalkylene glycols containing combinations of ethylene , propylene and butylene . representative examples of oxyalkyls include the alkyl groups as herein described having ether linkages . “ oxyalkyl ” is meant to include polyethers with one or more functional groups . the number of repeating oxyalkyls within a substituent may be up to 200 , preferably is from 1 - 20 , and more preferably , is 1 - 10 , and most preferably is 1 - 5 . a preferred oxyalkyl is o ( ch 2 ch 2 o ) x ch 3 where x = 1 - 100 , preferably 1 - 10 , and more preferably , 1 - 5 . “ oxyhydroxyalkyl ” means alkyl groups having ether or ester linkages , hydroxyl groups , substituted hydroxyl groups , carboxyl groups , substituted carboxyl groups or the like . representative examples of thioalkyls include thiols of ethane , thiols of straight - chain , branched or cyclic isomers of propane , butane , pentane , hexane , heptane , octane , nonane and decane , with thiols of ethane ( ethanethiol , c 2 h 5 sh ) or propane ( propanethiol , c 3 h 7 sh ) being preferred . sulfate - substituted alkyls include alkyls as described above substituted by one or more sulfate groups , a representative example of which is diethyl sulfate (( c 2 h 5 ) 2 so 4 ). representative examples of phosphates include phosphate or polyphosphate groups . representative examples of phosphate - substituted alkyls include alkyls as described above substituted by one or more phosphate or polyphosphate groups . representative examples of phosphate - substituted alkyls include alkyls as described above substituted by one or more phosphonate groups . representative examples of carboxy groups include carboxylic acids of the alkyls described above as well as aryl carboxylic acids such as benzoic acid . representative examples of carboxyamides include primary carboxyamides ( conh 2 ), secondary ( conhr ′) and tertiary ( conr ′ r ″) carboxyamides where each of r ′ and r ″ is a functional group as described herein . representative examples of useful amines include a primary , secondary or tertiary amine of an alkyl as described hereinabove . “ carboxyamidealkyl ” means alkyl groups with secondary or tertiary amide linkages or the like . “ carboxyalkyl ” means alkyl groups having hydroxyl groups , carboxyl or amide substituted ethers , ester linkages , tertiary amide linkages removed from the ether or the like . the term “ saccharide ” includes oxidized , reduced or substituted saccharide ; hexoses such as d - glucose , d - mannose or d - galactose ; pentoses such as d - ribose or d - arabinose ; ketoses such as d - ribulose or d - fructose ; disaccharides such as sucrose , lactose , or maltose ; derivatives such as acetals , amines , and phosphorylated sugars ; oligosaccharides , as well as open chain forms of various sugars , and the like . examples of amine - derivatized sugars are galactosamine , glucosamine , sialic acid and d - glucamine derivatives such as 1 - amino - 1 - deoxysorbitol . a couple may be described as a linker , i . e ., the covalent product formed by reaction of a reactive group designed to attach covalently another molecule at a distance from the texaphyrin macrocycle . exemplary linkers or couples are amides , amine , disulfide , thioether , ether , polyether , ester , or phosphate covalent bonds . pct publication wo 94 / 29316 is incorporated by reference herein for providing syntheses of texaphyrin - conjugates having these types of linkages or couples . in most preferred embodiments , conjugates and appended groups are covalently bonded to the texaphyrin via a carbon - carbon , carbon - nitrogen , carbon - sulfur , or a carbon - oxygen bond , more preferably a carbon - oxygen or a carbon - nitrogen bond . in the practice of the present invention , preferred functionalizations for texaphyrin i or ii are : when r 6 and r 9 are other than hydrogen , then r 5 and r 10 are hydrogen or methyl ; and when r 5 and r 10 are other than hydrogen , then r 6 and r 9 are hydrogen , hydroxyl , or halide other than iodide . other preferred functionalizations are where r 6 and r 9 are hydrogen , then r 5 , r 10 , r 11 , and r 12 are independently hydrogen , phenyl , lower alkyl or lower hydroxyalkyl . the lower alkyl is preferably methyl or ethyl , more preferably methyl . the lower hydroxyalkyl is preferably of 1 to 6 carbons and 1 to 4 hydroxy groups , more preferably 3 - hydroxypropyl . the phenyl may be substituted or unsubstituted . in a presently preferred texaphyrin i or ii , r 1 is ch 2 ch 3 or ( ch 2 ) 2 ch 2 oh ; r 2 and r 3 are ch 2 ch 3 ; r 4 is ch 3 ; r 5 , r 6 , and r 9 - r 12 are h ; r 8 is a lipophilic molecule or a couple that is coupled to a lipophilic molecule ; and r 7 is h , oh , och 3 or o ( ch 2 ch 2 o ) x ch 3 where x is 1 - 10 and preferably 1 - 5 , more preferably 3 . preferably , r 8 is estradiol or cholesterol , or a couple that is coupled to estradiol or cholesterol . a couple that is coupled to a lipophilic molecule may be further described as o ( ch 2 ch 2 o ) m — where m is 1 - 10 and preferably 1 - 5 , or as o ( ch 2 ) n co — where n is 1 - 10 and preferably 1 - 3 . presently preferred texaphyrin - lipophilic molecule conjugates , t2bet - estradiol conjugates , are provided as 1 a and 1 b . “ t2 ” refers to two hydroxyl groups on the tripyrrane portion of texaphyrin , “ bet ” refers to the ethoxy r groups on the benzene portion of the molecule , and estradiol is the lipophilic molecule of this conjugate . the synthesis of this conjugate is provided in example 1 . in other presently preferred texaphyrin compounds i or ii , r 1 - r 12 are as in tables a and b for texaphyrins a1 - a108 , and m is as defined hereinabove . while the cited texaphyrins are presently preferred for use in the present invention , the invention is not limited thereto . table a representative substituents for texaphyrin macrocycles a1 - a108 of the present invention . substituents for r 1 - r 6 are provided in table a and for r 7 - r 12 in table b . txp r 1 r 2 r 3 r 4 r 5 r 6 a1 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 3 ch 3 h h a2 ″ ″ ″ ″ ″ ″ a3 ″ ″ ″ ″ ″ ″ a4 ″ ″ ″ ″ ″ ″ a5 ″ ″ ″ ″ ″ ″ a6 ″ ″ ″ ″ ″ ″ a7 ″ ″ ″ ″ ″ ″ a8 ″ ″ ″ ″ ″ ″ a9 ″ ″ ″ ″ ″ ″ a10 ″ ″ ″ ″ ″ ″ a11 ″ ″ ″ ″ ″ ″ a12 ″ cooh cooh ″ ″ ″ a13 ch 2 ( ch 2 ) 2 oh cooch 2 ch 3 cooch 2 ch 3 ch 3 h h a14 ch 2 ch 2 con ( ch 2 ch 2 oh ) 2 ch 2 ch 3 ch 2 ch 3 ″ ″ ″ a15 ch 2 ch 2 on ( ch 3 ) ch 2 - ″ ″ ″ ″ ″ ( choh ) 4 ch 2 oh a16 ch 2 ch 3 ″ ″ ″ ″ ″ a17 ch 2 ( ch 2 ) 2 oh ″ ″ ″ ″ ″ a18 ″ ″ ″ ″ ″ ″ a19 ″ ″ ″ ″ ″ ″ a20 ch 2 ch 3 ch 3 ch 2 ch 2 cooh ″ ″ ″ a21 ″ ″ ch 2 ch 2 co - ″ ″ ″ lipophilic molecule a22 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 3 ″ ″ ″ a23 ″ ″ ″ ″ ″ ″ a24 ″ ″ ″ ″ ″ ″ a25 ″ ″ ″ ″ ″ ″ a26 ″ ″ ″ ″ ″ ″ a27 ″ cooh cooh ″ ″ ″ a28 ″ cooch 2 ch 3 cooch 2 ch 3 ″ ″ ″ a29 ch 2 ch 2 co - lipophilic ch 2 ch 3 ch 2 ch 3 ch 3 h h molecule a30 ch 2 ch 2 o - lipophilic molecule ″ ″ ″ ″ ″ a31 ch 2 ( ch 2 ) 2 oh ″ ch 2 ch 2 co - ″ ″ ″ lipophilic molecule a32 ″ ″ ch 2 ch 2 co - ″ ″ ″ lipophilic molecule a33 ch 2 ch 3 ch 3 ch 2 ch 2 cooh ″ ″ ″ a34 ″ ″ ch 2 ch 2 co - ″ ″ ″ lipophilic molecule a35 ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a36 ″ ″ ″ ″ ″ ″ a37 ″ ″ ″ ″ ″ ″ a38 ″ ″ ″ ″ ″ ″ a39 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 3 ch 3 h cooh a40 ″ ″ ″ ″ ″ cooh a41 ″ ″ ″ ″ ″ conhch — ( ch 2 oh ) 2 a42 ″ ″ ″ ″ ″ conhch — ( ch 2 oh ) 2 a43 ″ ″ ″ ″ ″ h a44 ″ ″ ″ ″ ″ och 3 a45 ″ ″ ″ ″ ″ ″ a46 ″ ″ ″ ″ ″ ″ a47 ″ ″ ″ ″ ″ ″ a48 ″ ″ ″ ″ ″ ″ a49 ″ ″ ″ ″ ″ ″ a50 ″ ″ ″ ″ ″ ch 3 a51 ″ ″ ″ ″ ″ ″ a52 ″ ″ ″ ″ ″ ″ a53 ″ ″ ″ ″ ″ ″ a54 ″ ″ ″ ″ ch 3 h a55 ″ ″ ″ ″ ″ ″ a56 ″ ″ ″ ″ ″ ″ a57 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 3 ch 3 ch3 h a58 ″ ″ ″ ″ ″ ″ a59 ″ ″ ″ ″ ″ ″ a60 ″ ″ ″ ″ ″ ″ a61 ″ ″ ″ ″ ″ ″ a62 ″ ″ ″ ″ ″ ″ a63 ″ ″ ″ ″ ″ oh a64 ″ ″ ″ ″ ″ f a65 ″ ″ ″ ″ ch 2 ( ch 2 ) 6 oh h a66 ″ ″ ″ ″ h br a67 ″ ″ ″ ″ ″ no 2 a68 ″ ″ ″ ″ ″ cooh a69 ″ ″ ″ ″ ″ ch 3 a70 ″ ″ ″ ″ c 6 h 5 h a71 ″ cooh cooh ″ ch 2 ch 3 ″ a72 ″ cooch 2 ch 3 cooch 2 ch 3 ″ ch 3 ″ a73 ch 2 ch 2 con ( ch 2 ch 2 oh ) 2 ch 2 ch 3 ch 2 ch 3 ″ ″ ″ a74 ch 2 ch 2 on ( ch 3 ) ch 2 ″ ″ ″ ″ ″ ( choh ) 4 ch 2 oh a75 ch 2 ch3 3 ″ ″ ″ ch 2 ( ch 2 ) 6 oh ″ a76 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 3 ch 3 ch 3 or ch 2 ch 3 h a77 ″ ″ ″ ″ ″ ″ a78 ″ ″ ″ ″ ″ ″ a79 ″ ″ ″ ″ ″ ″ a80 ″ ″ ″ ″ ″ ″ a81 ″ ″ ″ ″ ″ ″ a82 ″ ″ ″ ″ ″ ″ a83 ″ ″ ″ ″ ″ ″ a84 ″ ″ ″ ″ ″ ″ a85 ″ ″ ″ ″ h ″ a86 ″ ″ ″ ″ ″ ″ a87 ″ ″ ″ ″ ch 3 or ch 2 ch 3 a88 ″ ″ ″ ″ ″ ″ a89 ″ ″ ″ ″ h h a90 ″ ″ ″ ″ ″ ″ a91 ″ ″ ″ ″ ″ ″ a92 ″ ″ ″ ″ ″ ″ a93 ″ cooh cooh ″ ″ ″ a94 ″ cooch 2 ch 3 cooch 2 ch 3 ″ ″ ″ a95 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 2 co - ″ ″ ″ lipiphilic molecule a96 ch 2 ch 3 ch 3 ch 2 ch 2 cooh ″ ″ ″ a97 ″ ″ ch 2 ch 2 co - ″ ″ ″ lipiphilic molecule a98 ch 2 ( ch 2 ) 2 oh ch 2 ch 3 ch 2 ch 3 ″ ″ ″ a99 ch 2 ch 3 ″ ″ ″ ″ ″ a100 ″ ″ ″ ″ ″ ″ a101 ″ ″ ″ ″ ″ ″ a102 ″ ″ ″ ″ ″ ″ a103 ″ ″ ″ ″ ″ ″ a104 ″ ″ ″ ″ ″ ″ a105 ch 2 ( ch 2 ) 2 oh ″ ″ ″ ″ ″ a106 ″ ″ ″ ″ ″ ″ a107 ″ ″ ″ ″ ″ ″ a108 ″ ″ ″ ″ ″ ″ [ 0093 ] table b representative substituents for texaphyrin macrocycles a1 - a108 of the present invention . substituents for r 1 - r 6 are provided in table a and for r 7 - r 12 in table b . txp r 7 r 8 r 9 r 10 r 11 r 12 a1 o ( ch 2 ) 3 oh o ( ch 2 ) 3 oh h h h h a2 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ a3 o ( ch 2 ) n con - linker - lipophilic ″ ″ ″ ″ ″ molecule , n = 1 - 10 a4 o ( ch 2 ) n con - linker - lipophilic h ″ ″ ″ ″ molecule , n = 1 - 10 a5 och 2 co - lipophilic molecule ″ ″ ″ ″ ″ a6 o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ ″ a7 och 2 con - linker - lipophilic o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ molecule a8 och 2 co - lipophilic molecule ″ ″ ″ ″ ″ a9 o ( ch 2 ch 2 o ) 100 ch 3 ″ ″ ″ ″ ″ a10 och 2 con ( ch 2 ch 2 oh ) 2 h ″ ″ ″ ″ a11 ch 2 con ( ch 3 ) ch 2 — ″ ″ ″ ″ ″ ( choh ) 4 ch 2 oh a12 ch 2 con ( ch 3 ) ch 2 — ″ ″ ″ ″ ″ ( choh ) 4 ch 2 oh a13 ch 2 con ( ch 3 ) ch 2 — h h h h h ( choh ) 4 ch 2 oh a14 ch 2 con ( ch 3 ) ch 2 — ″ ″ ″ ″ ″ ( choh ) 4 ch 2 oh a15 och 3 och 3 ″ ″ ″ ″ a16 och 2 co 2 - lipophilic molecule h ″ ″ ″ ″ a17 o ( ch 2 ) n cooh , n = 1 - 10 ″ ″ ″ ″ ″ a18 ( ch 2 ) n - con - linker - lipophilic ″ ″ ″ ″ ″ molecule , n = 1 - 10 a19 ycoch 2 - linker - lipophilic ″ ″ ″ ″ ″ molecule , y = nh , o a20 o ( ch 2 ) 2 ch 2 oh o ( ch 2 ) 2 ch 2 oh ″ ″ ″ ″ a21 ″ ″ ″ ″ ″ ″ a22 och 2 cooh o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ a23 o ( ch 2 ) n co - lipophilic h ″ ″ ″ ″ molecule , n = 1 - 10 a24 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) n - lipophilic ″ ″ ″ ″ molecule , n = 1 - 10 , in particular , n = 3 or 5 a25 och 3 och 2 co - lipophilic ″ ″ ″ ″ molecule a26 ″ ch 2 co - lipophilic molecule ″ ″ ″ ″ a27 ″ ″ ″ ″ ″ ″ a28 och 3 ch 2 co - lipophilic molecule h h h h a29 ″ och 3 ″ ″ ″ ″ a30 ″ ″ ″ ″ ″ ″ a31 h o ( ch 2 ) n cooh , n = 1 - 10 ″ ″ ″ ″ a32 ″ ( ch 2 ) n - con - linker - ″ ″ ″ ″ lipophilic molecule , n = 1 - 10 a33 och 3 o ( ch 2 ch 2 o ) 3 — ch 3 ″ ″ ″ ″ a34 ″ ″ ″ ″ ″ ″ a35 h o ( ch 2 ) co - lipophilic ″ ″ ″ ″ molecule , n = 1 - 10 a36 och 3 o ( ch 2 ) co - lipophilic ″ ″ ″ ″ molecule , n = 1 - 10 a37 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ) n co - lipophilic ″ ″ ″ ″ molecule , n = 1 - 10 a38 ″ o ( ch 2 ch 2 o ) n - lipophilic ″ ″ ″ ″ molecule , n = 1 - 10 a39 o ( ch 2 ) 3 oh o ( ch 2 ) 3 oh o ( ch 2 ) 3 oh h h h a40 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 3 ch 3 cooh ″ ″ ″ a41 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 3 ch 3 ( ch 2 ) 3 oh ″ ″ ″ a42 ″ ″ o ( ch 2 ch 2 o ) 3 c ″ ″ ″ h 3 a43 ″ o ( ch 2 ) 3 cooh o ( ch 2 ch 2 o ) 3 c ″ ″ ″ h 3 a44 h och 2 cooh och 3 ″ ″ ″ a45 ″ och 2 cooh ″ ″ ″ ″ a46 ″ o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ a47 o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ ″ a48 ″ och 2 co - lipophilic ″ ″ ″ ″ molecule a49 ″ och 2 cooh ″ ″ ″ ″ a50 ″ o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) hd 3c ″ ″ ″ h 3 a51 ″ och 2 cooh o ( ch 2 ch 2 o ) 3 c ″ ″ ″ h 3 a52 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 100 ch 3 och 3 ″ ″ ″ a53 h och 2 co - lipophilic ″ ″ ″ ″ molecule a54 o ( ch 2 ) 3 oh o ( ch 2 ) 3 oh h ch 3 ″ ″ a55 h o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ a56 o ( ch 2 ch 2 o ) 3 ch 3 ″ ″ ″ ″ ″ a57 h och 2 co - lipophilic h ch 3 ″ ″ molecule a58 ″ och 2 co - lipophilic ″ ″ ″ ″ molecule a59 ″ och 2 con ″ ″ ″ ″ ( ch 2 ch 2 oh ) 2 a60 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 100 ch 3 ″ ″ ″ ″ a61 ″ och 2 co - lipophilic ″ ″ ″ ″ molecule a62 h ch 2 con ( ch 3 ) ch 2 ″ ″ ″ ″ ( choh ) 4 ch 2 oh a63 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 3 ch 3 oh ″ ″ ″ a64 ″ ″ f ″ ″ ″ a65 ″ ″ h ch 2 ( ch 2 ) 6 oh ″ ″ a66 ″ ″ br h ″ ″ a67 ″ ″ no 2 ″ ″ ″ a68 ″ ″ cooh ″ ″ ″ a69 ″ ″ ch 3 ″ ″ ″ a70 ″ ″ h c 6 h 5 ″ ″ a71 ″ ″ ″ ch 2 ch 3 ″ ″ a72 ″ ″ ″ ch 3 ″ ″ a73 ″ ″ ″ ″ ″ ″ a74 och 3 och 3 ″ ″ ″ ″ a75 h och 2 co - lipophilic ″ ch 2 ( ch 2 ) 6 oh ″ ″ molecule a76 o ( ch 2 ) 3 oh o ( ch 2 ) 3 oh h ch 3 or ch 3 or ch 3 or ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a77 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 3 ch 3 ″ ch 3 or ch 3 or ch 3 or ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a78 o ( ch 2 ) 3 oh o ( ch 2 ch 2 o ) 3 ch 3 ″ ch 3 or ch 3 or ch 3 or ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a79 h o ( ch 2 ) n co - lipophilic ″ ch 3 or ch 3 or ch 3 or molecule , n = 1 , 2 , 3 ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a80 h o ( ch 2 ) n c0 - lipophilic ″ ch 3 or ch 3 or ch 3 or molecule , n = 1 , 2 , 3 ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a81 h o ( ch 2 ) 3 oh ″ ch 3 or ch 3 or ch 3 or ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a82 o ( ch 2 ) 3 oh o ( ch 2 ) n co - lipophilic ″ ch 3 or ch 3 or ch 3 or molecule , n = 1 , 2 , 3 , ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a83 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ) n c0 - lipophilic ″ ch 3 or ch 3 or ch 3 or molecule , n = 1 - 10 ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a84 ″ o ( ch 2 ) n co - lipophilic ″ ch 3 or ch 3 or ch 3 or molecule , n = 1 , 2 , 3 ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a85 ″ o ( ch 2 ch 2 o ) 3 ch 3 ″ ch 3 or ch 3 or ch 3 or ch 2 ch 3 ch 2 ch 3 ch 2 ch 3 a86 ″ ″ ″ ch 3 or ch 2 ( ch 2 ) 2 ch 2 ( ch 2 ) 2 ch 2 ch 3 oh oh a87 ″ ″ ″ ch 3 or ch 2 ( ch 2 ) 2 ch 2 ( ch 2 ) 2 ch 2 ch 3 oh oh a88 ″ o ( ch 2 ch 2 o ) 3 ch 3 ″ ch 3 or ch 2 ( ch 2 ) 2 ch 2 ( ch 2 ) 2 ch 2 ch 3 oh oh a89 o ( ch 2 ch 2 o ) 3 ch 2 — ch 2 - o ( ch 2 ch 2 o ) 120 ch 3 h h h h lipophilic molecule a90 h lipophilic molecule ″ ″ ″ ″ a91 och 2 co - lipophilic molecule och 2 co - lipophilic ″ ″ ″ ″ molecule a92 ch 2 co - lipophilic molecule ch 2 co - lipophilic molecule ″ ″ ″ ″ a93 ″ ″ ″ ″ ″ ″ a94 ″ ″ ″ ″ ″ ″ a95 h ycoch 2 - linker - lipophilic ″ ″ ″ ″ molecule y = nh , o a96 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ch 2 o ) 5 - lipophilic ″ ″ ″ ″ molecule a97 ″ ″ ″ ″ ″ ″ a98 h o ( ch 2 ) 3 co - lipophilic ″ ″ ″ ″ molecule a99 ″ o ( ch 2 ) 3 co - lipophilic ″ ″ ″ ″ molecule a100 och 3 o ( ch 2 ) 3 co - lipophilic ″ ″ ″ ″ molecule a101 o ( ch 2 ch 2 o ) 3 ch 3 o ( ch 2 ) 3 co - lipophilic ″ ″ ″ ″ molecule a102 ″ o ( ch 2 ch 2 o ) 5 - estradiol ″ ″ ″ ″ a103 ″ o ( ch 2 ch 2 o ) 5 - estradiol , ″ ″ ″ ″ n = 1 - 10 a104 ″ o ( ch 2 ch 2 o ) n - cholesterol , ″ ″ ″ ″ n = 1 - 10 a105 ″ o ( ch 2 ch 2 o ) n - cholesterol , ″ ″ ″ ″ n = 1 - 10 a106 och 3 o ( ch 2 ch 2 o ) n - estradiol , ″ ″ ″ ″ n = 1 - 10 a107 h o ( ch 2 ch 2 o ) n - estradiol , ″ ″ ″ ″ n = 1 - 10 a108 o ( ch 2 ch 2 o ) x ch 3 , x = 1 - 10 o ( ch 2 ch 2 o ) n - estradiol , ″ ″ ″ ″ n = 1 - 10 one skilled in the art of organic synthesis in light of the present disclosure and the disclosures in the patents , applications and publications incorporated by reference herein could extend and refine the referenced basic synthetic chemistry to produce texaphyrins having various substituents . for example , polyether - linked polyhydroxylated groups , saccharide substitutions in which the saccharide is appended via an acetal - like glycosidic linkage , an oligosaccharide or a polysaccharide may be similarly linked to a texaphyrin . a doubly carboxylated texaphyrin in which the carboxyl groups are linked to the texaphyrin core via aryl ethers or functionalized alkyl substituents could be converted to various esterified products wherein the ester linkages serve to append further hydroxyl - containing substituents . polyhydroxylated texaphyrin derivatives may be synthesized via the use of secondary amide linkages . saccharide moieties may be appended via amide bonds . polyhydroxylated texaphyrin derivatives containing branched polyhydroxyl ( polyol ) subunits may be appended to the texaphyrin core via aryl ethers or ester linkages . treatment of carboxylated texaphyrins with thionyl chloride or p - nitrophenol acetate would generate activated acyl species suitable for attachment to monoclonal antibodies or other biomolecules of interest . standard in situ coupling methods ( e . g ., 1 , 1 ′- carbonyldiimidazole ) could be used to effect the conjugation . substituents at the r 6 and r 9 positions on the b ( benzene ring ) portion of the macrocycle are incorporated into the macrocycle by their attachment to ortho - phenylenediamine in the 3 and 6 positions of the molecule . substituents at the r 5 and r 10 positions on the t ( tripyrrane ) portion of the macrocycle are incorporated by appropriate functionalization of carboxyl groups in the 5 positions of the tripyrrane at a synthetic step prior to condensation with a substituted ortho - phenylenediamine . a lipophilic molecule may be added after the condensation step to form the texaphyrin macrocycle . lipophilic molecules having an amine functionality are modified post - synthetically with an activated carboxylic ester derivative of a texaphyrin . in the presence of a lewis acid such as febr 3 , a bromide - derivatized texaphyrin will react with an hydroxyl group of a lipophilic molecule to form an ether linkage between the texaphyrin linker and the lipophilic molecule . a couple that is coupled to a lipophilic molecule may be further described as o ( ch 2 ch 2 o ) m — where m is 1 - 10 and preferably 1 - 5 , or as o ( ch 2 ) n co — where n is 1 - 10 and preferably 1 - 3 . texaphyrin - lipophilic molecule conjugates may be made by methods as described herein and as known and described in the art , such as in u . s . patents , in pending applications , previously incorporated by reference herein . texaphyrins have a number of properties that lend themselves for use in imaging and photodynamic treatment protocols , for example : texaphyrins have inherent biolocalization , localizing to tumors , atheroma , or the liver ; they have absorption in the physiologically important range of 700 - 900 nm ; they provide stable chelation for an otherwise toxic metallic cation ; and are sufficiently nontoxic for in vivo use . an aspect of the present invention is use of texaphyrin - lipophilic molecules or texaphyrin - lipophilic molecule - vesicle complexes in ocular diagnosis and therapy ; especially diagnostic angiograms , and photodynamic therapy of conditions of the eye characterized by abnormal vasculature . “ abnormal vasculature ”, as used herein , means undesirable vasculature ; neovasculature ; irregular , occluded , weeping , or inflamed ocular vessels or ocular tissues ; inflammatory ocular membranes ; abnormal conditions having to do with channeling of fluids in the ocular area , especially blood vessels ; and includes conditions such as macular degeneration , glaucoma , disc or retinal neovascularization in diabetic retinopathy , pannus which is abnormal superficial vascularization of the cornea or conjunctiva , pterygium which is thickening of the bulbar conjunctiva on the cornea , conditions having retinal or choroidal neovasculature , ocular histoplasmosis syndrome , myopia , ocular inflammatory diseases , central serous retinopathy , subretinal neovascular membrane , or neovasculature induced by neoplasm , such as melanoma or retinal blastoma , for example . “ observing the vasculature ”, as used herein , means carrying out an imaging procedure and collecting information from an angiogram where fluorescent texaphyrins are used , from an x - ray , or from magnetic resonance image , for example , to interpret the condition of the eye . the condition of the eye may be normal , or may include vascular leakage or occlusions , for example . as used herein , “ eye ” or “ ocular ” includes the eye , underlying and adjacent tissue , and related tissues near and around the eye that have an influence on the functioning of the eye . the parameters used for effective angiography and effective treatment in pdt methods of the invention are interrelated . therefore , the dose is adjusted with respect to other parameters , for example , fluence , irradiance , duration of the light used in photodynamic therapy , and the time interval between administration of the dose and the therapeutic irradiation . such parameters should be adjusted to produce significant damage to abnormal vascular tissue without significant damage to the surrounding tissue or , on the other hand , to enable the observation of blood vessels in the eye without significant damage to the surrounding tissue . typically , the dose of texaphyrin of the texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex used is within the range of from about 0 . 1 to about 50 μmol / kg / treatment , and preferably from about 0 . 10 - 20 μmol / kg / treatment . further , as the texaphyrin dose is reduced , the fluence required to treat neovascular tissue may change . after the photosensitizing texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex has been administered , the tissue being treated in the eye is irradiated at the wavelength of maximum absorbance of the texaphyrin , usually either about 400 - 500 nm or about 700 - 800 nm . the light source may be a laser , a light - emitting diode , or filtered light from , for example , a xenon lamp ; the light may have a wavelength range of about 400 - 900 nm , preferably about 400 - 500 nm or 700 - 800 nm , more preferably about 730 - 770 nm ; and the light may be administered topically , endoscopically , or interstitially ( via , e . g ., a fiber optic probe ). preferably , the light is administered using a slit - lamp delivery system . a wavelength in this range is especially preferred since blood and retinal pigment epithelium are relatively transparent at longer wavelengths and , therefore , treatment results in less tissue damage and better light penetration . the fluence and irradiance during the irradiating treatment can vary depending on type of tissue , depth of target tissue , and the amount of overlying fluid or blood . the optimum length of time following texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex administration until light treatment can vary depending on the mode of administration , the form of administration , and the type of target tissue . for example , a time interval of minutes to about 5 h should be appropriate for vascular tissue . the time of light irradiation after administration may be important as one way of maximizing the selectivity of the treatment , thus minimizing damage to structures other than the target tissues . for a human , it is believed that the texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex begins to reach the retinal and choroidal vasculature within seconds following administration , and persists for a period of minutes to hours , depending on the dose given . treatment within the first five minutes following administration should generally be activated with focused light . at later time points , both focused or general illumination may be used . in addition , texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex can be used to observe the condition of blood vessels as a single agent , or in concert with other dyes such as fluorescein or indocyanine green to follow the progress of destruction of abnormal vascular tissue . in such angiographic systems , a sufficient amount of texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex is administered to produce an observable fluorescent emission when excited by light , preferably light having a wavelength in the range of about 430 - 480 nm . images are recorded by illuminating the eye with light in the excitation wavelength range and detecting the amount of fluorescent light emitted at the emission wavelength of about 730 - 760 nm . a preferred device , which both emits and receives light in the 430 - 760 nm range , is the topcon ™ 50vt camera in the ophthalmic imaging system ( ophthalmic imaging system inc ., 221 lathrop way , suite 1 , sacramento calif .). a camera is used to collect the emitted fluorescent light , digitize the data , and store it for later depiction on a video screen , as a hard paper copy , or in connection with some other imaging system . while a film recording device may be used when additional dyes such as fluorescein are being used in combination with the texaphyrin - lipophilic molecule conjugate or texaphyrin - lipophilic molecule - vesicle complex , a ccd camera ( charge - coupled device ) is preferable as being able to capture emissions at higher wavelengths . as a result , one can obtain more sophisticated information regarding the pattern and extent of vascular structures in different ocular tissue layers , giving the ability to detect the “ leakiness ” that is characteristic of new or inflamed blood vessels . further , it is preferable to use a camera that is capable of providing the excitation light , appropriately filtered to deliver only light of the desired excitation wavelength range , and then to capture the emitted , fluorescent light with a receiving device , appropriately filtered to receive only light in the desired emission wavelength range . for the above - described uses , texaphyrin - lipophilic molecule - cell or - liposome complexes are provided as pharmaceutical preparations . a pharmaceutical preparation of such a complex may be administered alone or in combination with pharmaceutically acceptable carriers , in either single or multiple doses . suitable pharmaceutical carriers include inert solid diluents or fillers , sterile aqueous solution and various organic solvents . the pharmaceutical compositions formed by combining a complex of the present invention and the pharmaceutically acceptable carriers are then easily administered in a variety of dosage forms such as injectable solutions . for parenteral administration , suspensions of the liposomal complex in sesame or peanut oil , aqueous propylene glycol , or in sterile aqueous solution may be employed . such aqueous solutions should be suitably buffered if necessary and the liquid diluent first rendered isotonic with sufficient saline or glucose . these particular aqueous solutions are especially suitable for intravenous , intramuscular , subcutaneous and intraperitoneal administration . in this connection , sterile aqueous media which can be employed will be known to those of skill in the art in light of the present disclosure . intravenous administration of loaded red or white blood cell complexes of the present invention is contemplated as the most preferred method of administration . sterile technique is used for removal of cells from a patient , loading with a sterile texaphyrin - lipophilic molecule conjugate and replacement of loaded cells into the same patient . a pharmaceutically acceptable carrier may be used , which carrier can be a solvent or dispersion medium containing , for example , water , ethanol , polyol ( for example , glycerol , propylene glycol , and liquid polyethylene glycol , and the like ), suitable mixtures thereof , and vegetable oils . the proper fluidity can be maintained , for example , by the use of a coating , such as lecithin , and by the use of surfactants . the prevention of the action of microorganisms can be brought about by various antibacterial and antifungal agents , for example , parabens , chlorobutanol , phenol , sorbic acid , thimerosal , and the like . in many cases , it will be preferable to include isotonic agents , for example , sugars such as mannitol or dextrose or sodium chloride . a more preferable isotonic agent is a mannitol solution of about 2 - 8 % concentration , and , most preferably , of about 5 % concentration . sterile conjugate solutions are prepared by incorporating the active compounds in the required amount in the appropriate solvent with various of the other ingredients enumerated above , as required , followed by filtered sterilization . generally , dispersions are prepared by incorporating the various sterilized active ingredients into a sterile vehicle which contains the basic dispersion medium and the required other ingredients from those enumerated above . in the case of sterile powders for the preparation of sterile injectable solutions , the preferred methods of preparation are vacuum - drying and freeze - drying techniques which yield a powder of the active ingredient plus any additional desired ingredient from a previously sterile - filtered solution thereof . as used herein , “ pharmaceutically acceptable carrier ” includes any and all solvents , dispersion media , coatings , antibacterial and antifungal agents , isotonic and absorption delaying agents and the like . the use of such media and agents for pharmaceutically active substances is well known in the art . except insofar as any conventional media or agent is incompatible with the active ingredient , its use in the therapeutic compositions is contemplated . supplementary active ingredients can also be incorporated into the compositions . for fluorescent detection methods of the present invention , a sufficient amount of texaphyrin is administered to produce an observable fluorescent emission when excited by light , preferably light having a wavelength in the range of about 430 - 480 nm . images are recorded by illuminating with light in the excitation wavelength range and detecting the amount of fluorescent light emitted at the emission wavelength of preferably about 730 - 760 nm . such dose can be determined without undue experimentation by methods known in the art or as described herein . the complexes to be used in the photodynamic methods of the present invention are administered in a pharmaceutically effective amount . by “ pharmaceutically effective ” is meant that dose which will , upon exposure to light , cause disruption of the loaded vesticle . the specific dose will vary depending on the particular complex chosen , the dosing regimen to be followed , photoirradiation exposure , and timing of administration . such dose can be determined without undue experimentation by methods known in the art or as described herein . the following examples are included to demonstrate preferred embodiments of the invention . it should be appreciated by those of skill in the art that the techniques disclosed in the examples which follow represent techniques discovered by the inventors to function well in the practice of the invention , and thus can be considered to constitute preferred modes for its practice . however , those of skill in the art should , in light of the present disclosure , appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention . the present example provides the synthesis of a texaphyrin - lipophilic molecule conjugate where the lipophilic molecule is estradiol . the synthetic route is provided by schematic a . penta ( ethyleneglycol ) diiodide ( 2 ). penta ( ethyleneglycol ) ditosylate 1 ( 25 g , aldrich chemical , milwaukee , wis . ), sodium iodide ( 17 . 15 g , 2 . 5 eq . ), and acetone ( ca . 500 ml ) were combined and heated at reflux for 4 hours . upon cooling , solids were removed by filtration and washed with acetone . acetone was removed from the combined filtrate and washed by rotary evaporation . the resulting solid was dissolved in chcl 3 ( 250 ml ), and washed with water ( 250 ml ), a 5 % aqueous solution of na 2 s 2 o 3 ( 2 × 250ml ) and water ( 250 ml ). solvent was removed by rotary evaporation and the resulting solid dried in vacuo to give diiodide 2 ( 19 . 164 g , 91 . 3 %). 3 -( 2 -( ethoxy - 2 -( ethoxy - 2 -( ethoxy -( 2 - iodoethoxy )))) ethoxy ) 17β - hydroxy - 3 - oxy - 1 , 3 , 5 ( 10 )- estratriene ( 4 ). the diiodide 2 ( 12 . 50 g ), β - estradiol 3 ( 2 . 500 g , aldrich chemical , milwaukee , wis . ), potassium carbonate ( 1 . 500 g ) and anhydrous acetonitrile ( 250 ml ) were combined in a flask . the reaction mixture was heated at reflux for 9 hours , whereupon it was allowed to cool in ambient temperature , and solvent removed by rotary evaporation . the residue was dissolved in chcl 3 ( 125 ml ), washed with water , and solvent removed by rotary evaporation . the crude product was purified by silica gel chromatography using 0 . 5 to 1 . 0 % meoh in chcl 3 as eluent . fractions containing only product were combined , solvent was removed by rotary evaporation , and the residue dried in vacuo to give iodide 4 ( 2 . 010 g , 36 . 4 %). dinitrobenzene sodium salt ( 5 ), method one . the dinitrobenzene sodium salt 5 was prepared by reacting 4 , 5 - dinitrocatechol ( 5 g , 0 . 025 mol ) and triethylene glycol monomethyl ether monotosylate ( 11 . 9 g , 0 . 037 mol , 1 . 5 eq .) with k 2 co 3 ( 5 . 18 g , 0 . 037 mol , 1 . 5 eq .) in methanol , with heating to reflux under nitrogen atmosphere overnight . the reaction was allowed to cool to rt , and the solvent was removed under reduced pressure . the residue was then resuspended into 250 ml of 1m naoh , after which chloroform was added . the lower chloroform layer plus precipitate were drained off and the orange solid precipitate was collected by filtration and vacuum dried under high vacuum overnight to give the light orange solid product 5 , in 81 % yield . dinitrobenzene sodium salt ( 5 ), method two . an alternate method of synthesis of the dinitrobenzene sodium salt is as follows . in a dry 250 ml round bottom flash , 4 , 5 - dinitrocatechol ( 10 g , 0 . 050 mol ) and k 2 co 3 ( 10 . 37 g , 0 . 075 mol ) were combined in absolute methanol ( 120 ml ) under nitrogen atmosphere . to the orange mixture , triethylene glycol monomethyl ether tosylate ( 23 . 85 g , 0 . 075 mol ) was added and the resulting suspension was heated to reflux . the reaction was deemed complete by tlc analysis by the disappearance of the starting catechol and appearance of the bright yellow monoalkylated intermediate . therefore , after 16 h the red suspension was cooled to 0 ° c . the resulting suspension was filtered , washed thoroughly with cold isopropyl alcohol ( 50 ml ) and hexanes ( 50 ml ). the monoalkylated potassium salt was then suspended in 10 % aqueous naoh ( 100 ml ), vigorously stirred for 15 - 20 min at room temperature , filtered , and then rinsed thoroughly with cold isopropyl alcohol ( 70 ml ) and hexanes ( 50 ml ). ( this step aids the removal of excess k 2 co 3 and potassium tosylate ). the bright orange salt was dried in vacuo and afforded 15 g (˜ 81 %). 1 h nmr ( d 6 acetone ): selected peaks , δ 3 . 40 ( ome ), 6 . 30 ( arh ), 7 . 42 ( arh ); ei ms ( m + na + ) 369 ; ei hrms ( m + na + ) 369 . 0910 ( calcd . for c 13 h 18 n 2 o 9 na 369 . 0910 ). 3 -( 2 -( ethoxy - 2 -( ethoxy - 2 -( ethoxy -( 2 -( 1 - oxy - 2 -( 2 -( ethoxy - 2 -( ethoxy -( 2 - methoxy ))) ethoxy ) 4 , 5 - dinitrobenzene ) ethoxy )))) ethoxy )- 17βhydroxy - 3 - oxy - 1 , 3 , 5 ( 10 )- esratriene ( 6 ). the iodide 4 ( 500 mg ) and the sodium salt of 1 - hydroxy - 2 -( 2 -( ethoxy - 2 -( ethoxy -( 2 - methoxy ))) ethoxy ) 4 , 5 - dinitrobenzene 5 ( 336 mg , 1 . 1 eq .) and acetonitrile ( 5 ml ) were combined in a flask and the reaction mixture was heated at reflux overnight . potassium carbonate ( 126 mg , 1 . 1 eq .) was added , and heating continued for ca . four hours . the reaction mixture was transferred to a separatory funnel with chcl 3 ( ca 25 ml ), washed with water ( 2 × 15 ml ), solvent removed on a rotary evaporator , and the residue dried overnight in vacuo . the crude product was purified by silica gel chromatography using 2 % meoh in chcl 3 as eluent . fractions containing only product were combined , solvent was removed by rotary evaporation , and the residue dried in vacuo to give 6 as a yellowish solid ( 549 mg , 80 . 5 %). fab : mh + 821 . using known chemistry for the synthesis of texaphyrins ( see the texaphyrin patents previously incorporated by reference herein ) the dinitro compound 6 was reduced to the diamine 7 using an atmospheric pressure hydrogenation with 10 % pd on charcoal and 2 eq . of conc . hcl . the reduction was usually complete in 1 - 2 h . afterwards , the catalyst was filtered off using a pad of celite , the diamine solution was diluted with methanol , 1 equivalent of diformyl tripyrrane 8 was added , and the reaction was heated to reflux under nitrogen . the reaction started immediately after the addition of diformyl tripyrrane and was usually complete in 1 - 3 hr . proton and carbon nmr of the resulting non - aromatic macrocycle 9 was consistent with structure . the non - aromatic macrocycle 9 was oxidatively metallated using 1 . 5 equiv . s of either lutetium acetate or gadolinium acetate and 10 equiv . s of trimethylamine under air atmosphere to give the lutetium estradiol complex 10 ( in 38 % yield with a relative purity of 89 %) or the gadolinium estradiol complex 11 ( in 47 % yield with a relative purity of 91 %), respectively . the synthesis of a texaphyrin - cholesterol conjugate is carried out in a similar manner using cholesterol instead of estradiol . the present example provides for the loading of red blood cells with a texaphyrin - estradiol conjugate . red blood cells ( rbc &# 39 ; s ) were successfully loaded with gadolinium texaphyrin - estradiol conjugate 11 (“ gte ”) following an osmotic challenge to the red blood cells . subsequently , uv / vis spectra revealed that most of the conjugate was contained within the cell wall of the red blood cells . for the studies below , the following general procedure was used : whole blood from rabbit was collected in the presence of heparin and centrifuged . the serum layer was removed , and the rbc &# 39 ; s were resuspended in saline ( 138 mm nacl ), and washed three times . after the third wash , the pelleted rbc &# 39 ; s were resuspended in hypertonic saline ( 268 mm nacl ). the cells were mixed gently , held approximately 3 min at room temperature , and centrifuged . the pelleted rbc &# 39 ; s were resuspended in three volumes of hypotonic saline ( 110 mm nacl ) containing gte to give gd texaphyrin - estradiol - red blood cell complex . i . in a first study , 300 ml of pelleted rbc &# 39 ; s were resuspended in 1 . 0 ml of 110 mm nacl with 0 . 2 or 0 . 4 mmoles of gte . the cells were mixed gently and sonicated . after three washes , the pellet of gte - rbc complex ( 300 ml ) was resuspended with saline to a total volume of 2 . 0 ml . to determine the gte content , 750 ml of this 2 . 0 ml solution were removed , 250 ml of fresh saline was added , and the optical density was read on a spectrophotometer . a control cuvette contained an equivalent mass and volume of rbc &# 39 ; s treated similarly but without gte . the o . d . of the 2 . 0 ml solution was 0 . 9859 , which indicated a yield of 120 mg total gte complex ( t2bet2 , 732 nm , a 15 . 35 mg / ml solution has an o . d . of 0 . 3291 ). ii . in a second study , two different amounts of a stock solution of 2 mm gte in 5 % mannitol were used ; 1 . 6 ml with 4 . 0 ml packed rbc &# 39 ; s , and 6 . 6 ml with 5 . 5 ml packed rbc &# 39 ; s . to prepare the respective complexes , the rbc &# 39 ; s were washed as described previously , the respective volumes of rbc &# 39 ; s were resuspended with hypertonic saline to a total volume of 50 ml and centrifuged . the supernatant was removed and solutions of hypotonic saline with gte were added so as to keep the volume at 40 ml . the suspensions were treated as described above and the final washed rbc &# 39 ; s were suspended in a volume of 15 ml with normal saline and transferred to 100 × 17 mm tubes to be analyzed by mri ( see , example 3 ) ( for the 1 . 6 ml reaction , 11 ml of saline ; for the 6 . 6 ml reaction , 9 . 5 ml of saline ; the control was 5 . 0 ml packed rbc &# 39 ; s and 10 ml of saline ). iii . in a further study , rbc &# 39 ; s were loaded with gte to be used as an injectable into rabbits . packed rbc &# 39 ; s ( 5 . 0 ml , washed as described ) were treated with hypertonic saline and 40 ml total volume of hypotonic saline with 6 . 0 ml gte . after sonication , the cells were washed 3 times and resuspended with 2 . 5 ml of normal saline . the resulting complex was used for injection into rabbits ( see , example 4 ). the present example provides in vitro magnetic resonance imaging ( mri ) results with gte - rbc complex . packed or resuspended red blood cell complexes were imaged using a ge 0 . 5t signa magnetic resonance imager ( ge medical systems , milwaukee , wis .) and the following parameters : pulse sequences , spin echo 350 / 15 ; acquisition parameters , 20fov , 256 × 256 ; slice thickness / space , 5 mm / 2 . 5 mm ; and nex , 2 . table 2 provides mri values using gte - rbc complex ( from example 2 , ii ). cuso 4 is an imaging standard that allows the intensity ( whiteness ) of the signal to be gauged . the present example demonstrates magnetic resonance imaging of an animal using gte - rbc complexes . mri scans revealed contrast enhancement of tissues and enhanced angiograms for up to 30 min after injection . a new zealand white rabbit ( 2 . 72 kg ) having a v2 carcinoma tumor implanted in each thigh was injected with 7 ml of gte - rbc complex and a normal new zealand white rabbit ( 3 kg ) was also injected with the same amount of the complex as a control . the rabbit having the tumors died after 2 . 5 ml of the complex was injected . the rabbit appeared to be already very sick from the cancer . the normal rabbit was scanned pre - contrast , immediately post - injection , and 30 min after injection . the rabbit was positioned supine inside a knee coil and entered the magnetic field feet first . the rabbit was anesthetized and maintained with ketamine / rompun cocktail during mri . the scan parameters were as in example 3 with the acquisition parameter being 256 × 160 for this animal study and the mr angiogram scanning technique was 2d tof for the aorta . the normal rabbit had good liver and angiogram enhancement for at least 30 min after injection of the gte - rbc complex . the present example provides for the light - dependent lysis of loaded vesicles , such as red blood cells or liposomes , and the consequent deposition of the contents at the irradiated site . when irradiated with light of an appropriate wavelength , vesicles loaded with a photosensitive texaphyrin will lyse . the effect of pdt with photosensitive texaphyrin - loaded vesicles is multifaceted in that specificity is provided by the biolocalization of the vesicle , a pdt effect is seen in the vicinity of the deposited texaphyrin due to singlet oxygen product toxicity , and if a therapeutic agent is incorporated into the vesicle in addition to the texaphyrin , the therapeutic agent is deposited at a target site . a chemotherapeutic drug may be delivered to a target site in this manner , for example . a preferred photosensitive texaphyrin is a lutetium texaphyrin , for example , compound 1 b as described herein . in the present light - dependent lysis , the light may have a wavelength range of about 650 - 900 nm , preferably 700 - 800 nm , and most preferably 730 - 770 nm . the present example provides for the incorporation of a texaphyrin - lipophilic molecule conjugate into liposomes and liposomal - like particles . a texaphyrin - lipophilic molecule conjugate may be incorporated into small unilamellar liposomes as follows , for example . egg phosphatidylcholine conjugated with ethylene glycol and cholesterol ( 8 : 2 molar ratio ) are suspended in chloroform and a 33 % molar concentration of texaphyrin - lipophilic molecule conjugate is added to the solution . the chloroform is evaporated under vacuum and the dried material is resuspended in phosphate buffered saline ( pbs ). the mixture is transferred to a cryovial , quick frozen in liquid nitrogen , and thawed five times . the material is then extruded through an extruder device ( lipex biomembranes , vancouver , b . c ., canada ) 10 times using a 400 nm diameter pore size polycarbonate filter to produce 400 nm liposomes . a portion of the 400 nm liposomes is extruded through 100 nm diameter filters 10 times to produce 100 nm liposomes . a portion of the 100 nm liposomes is then extruded 10 times through 15 nm filters , producing liposomes of 30 nm size . liposomes prepared as described above may also be subjected to a microfluidizer ( microfluidics , newton , mass .). specifically , liposomes may be passed 10 times through the microfluidizer at a pressure of 16 , 000 psi and a flow rate of 450 ml / min . the resulting liposomes are expected to have a mean average size of 30 - 40 nm , which may be verified by quasi elastic light scattering . a texaphyrin - lipophilic molecule conjugate incorporated in this way into liposomes may be physically inside the liposome , incorporated into the lipid bilayer of the liposome , or incorporated in such a way that part of the conjugate is outside of the liposome . a liposome incorporating a texaphyrin - lipophilic molecule can be stabilized using ethylene glycol to slow its uptake by phagocytic white blood cells . induction of antibody formation using texaphyrin - lipophilic molecule - loaded - red blood cells or - liposomes in addition to conventional methods known to those of skill in the art of immunology for making antibodies having a particular binding specificity , antibodies having binding specificity for a texaphyrin molecule may be induced in a host that has been administered a texaphyrin - lipophilic molecule loaded - red blood cell or - liposome . further , if the loaded cell also contains an immunogen , antibodies may be generated having binding specificity for that immunogen . using a photosensitive texaphyrin , light will lyse such a loaded red blood cell or liposome causing release of its contents within a host . consequent exposure of the host to an immunogen contained therein would induce antibody formation to the immunogen . candidate immunogens may include , but are not limited to , surface hiv proteins , such as gp 120 , for example . this method would be particularly effective using a loaded cell from an animal different than the animal injected , for example , using loaded goat red blood cells for injection into a rabbit . the goat cells may act as adjuvant in this case . all of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure . while the compositions and methods of this invention have been described in terms of preferred embodiments , it will be apparent to those of skill in the art that variations may be applied to the composition , methods and in the steps or in the sequence of steps of the method described herein without departing from the concept , spirit and scope of the invention . more specifically , it will be apparent that certain agents which are both chemically and physiologically related may be substituted for the agents described herein while the same or similar results would be achieved . all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit , scope and concept of the invention as defined by the appended claims .
compositions having a texaphyrin - lipophilic molecule conjugate loaded into a biological vesicle and methods for imaging , diagnosis and treatment using the loaded vesicle are provided . for example , liposomes or red blood cells loaded with a paramagnetic texaphyrin - lipophilic molecule conjugate have utility as a blood pool contrast agent , facilitating the enhancement of normal tissues , magnetic resonance angiography , and marking areas of damaged endothelium by their egress through fenestrations or damaged portions of the blood vascular system . liposomes or cells loaded with a photosensitive texaphyrin - lipophilic molecule conjugate can be photolysed , allowing for a photodynamic therapy effect at the site of lysis . availability of red blood cells loaded with a photosensitive texaphyrin - lipophilic molecule conjugate provides a method for delivering a photodynamic therapeutic agent to a desired site with a high concentration of oxygen . by presenting the agent in this way , it is expected that a patient will experience less toxicity .