1. A solid-state imaging apparatus having an imaging region in which a plurality of pixels are two-dimensionally arranged,
the plurality of pixels including
a first pixel arranged near a center of the imaging region, and
a second pixel arranged at a position farther away from the center of the imaging region than the first pixel,
the first pixel including a first micro lens having a substantially circular shape as viewed in a plan view, and
the second pixel including a second micro lens having a substantially elliptical shape as viewed in a plan view and having an area larger than an area of the first micro lens,
the imaging region having a rectangular shape and having a first side and a second side that is adjacent to the first side,
the second pixel being arranged at a position closer to the first side than the first pixel in a direction along the second side, and
the second micro lens having a substantially elliptical shape in a direction along with second side,
the plurality of pixels further including a third pixel positioned between the first pixel and the second pixel, and
the third pixel having a third micro lens, the third micro lens having a substantially elliptical shape as viewed in a plan view and having an area larger than the area of the first micro lens and smaller than the area of the second micro lens.
2. The solid-state imaging apparatus according to claim 1, wherein
the second micro lens has a substantially elliptical shape in a direction along the second side.
3. The solid-state imaging apparatus according to claim 2, wherein
a length of a major axis of the third micro lens is larger than a diameter of the first micro lens and smaller than a length of a major axis of the second micro lens.
4. The solid-state imaging apparatus according to claim 1, wherein
the plurality of pixels further include a fourth pixel arranged at a position closer to the second side than the first pixel in a direction along the first side,
the fourth pixel has a fourth micro lens having a substantially elliptical shape as viewed in a plan view and having a fourth micro lens having an area larger than the area of the first micro lens, and
the fourth micro lens has a substantially elliptical shape extending in a direction along the first side.
5. The solid-state imaging apparatus according to claim 4, wherein
a length of a major axis of the fourth micro lens is larger than a diameter of the first micro lens.
6. The solid-state imaging apparatus according to claim 4, wherein
the plurality of pixels further include a fifth pixel positioned between the first pixel and the fourth pixel, and
the fifth pixel has a fifth micro lens having a substantially elliptical shape as viewed in a plan view and having an area larger than the area of the first micro lens and smaller than the area of the fourth micro lens.
7. The solid-state imaging apparatus according to claim 6, wherein
the fifth micro lens has a substantially elliptical shape extending in a direction along the first side.
8. The solid-state imaging apparatus according to claim 7, wherein
a length of a major axis of the fifth micro lens is larger than a diameter of the first micro lens and smaller than a diameter of the fourth micro lens.
9. The solid-state imaging apparatus according to claim 1, wherein
the imaging region further includes a first corner at which the first side and the second side intersect with each other,
the plurality of pixels further include a sixth pixel arranged at a position closer to the first corner than the first pixel, and
the sixth pixel has a sixth micro lens having a substantially circular shape as viewed in a plan view and having an area larger than the area of the first micro lens.
10. The solid-state imaging apparatus according to claim 9, wherein
a diameter of the sixth micro lens is larger than a diameter of the first micro lens.
11. The solid-state imaging apparatus according to claim 9, wherein
the plurality of pixels further include a seventh pixel positioned between the first pixel and the sixth pixel, and
the seventh pixel has a seventh micro lens having a substantially circular shape as viewed in a plan view and having an area larger than the area of the first micro lens and smaller than the area of the sixth micro lens.
12. The solid-state imaging apparatus according to claim 11, wherein
a diameter of the seventh micro lens is larger than a diameter of the first micro lens and smaller than a diameter of the sixth micro lens.
13. A solid-state imaging apparatus having an imaging region in which a plurality of pixels are two-dimensionally arranged,
the plurality of pixels including
a first pixel arranged near a center of the imaging region, and
a second pixel arranged at a position farther away form the center of the imaging region than the first pixel,
the first pixel including a first micro lens having a substantially circular shape as viewed in a plan view, and
the second pixel including a second micro lens, the second micro lens having a substantially elliptical shape as viewed in a plan view and having an area larger than an area of the first micro lens,
the imaging region having a rectangular shape and having a first side and a second side that is adjacent to the first side,
the second pixel being arranged at a position closer to the first side than the first pixel in a direction along the second side, and
the second micro lens having a substantially elliptical shape in a direction along the second side,
among the plurality of pixels, in pixels positioned on a straight line extending in a direction along the second side from the center of the imaging region, lengths of major axes of the micro lenses increasing moving away from the center of the imaging region.
14. The solid-state imaging apparatus according to claim 13, wherein,
among the plurality of pixels, in pixels positioned on a straight line extending in a direction along the second side from the center of the imaging region, areas of the micro lenses increase as moving away from the center of the imaging region.
15. The solid-state imaging apparatus according to claim 13, wherein,
among the plurality of pixels, in pixels positioned on a straight line extending in a direction along the first side from the center of the imaging region, lengths of major axes of the micro lenses increase as moving away from the center of the imaging region.
16. The solid-state imaging apparatus according to claim 15, wherein,
among the plurality of pixels, in pixels positioned on a straight line extending in the direction along the first side from the center of the imaging region, areas of the micro lenses increase as moving away from the center of the imaging region.
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. A compound of formula (I):
15
wherein
Ff is F(-K)m(Y-Z)q in which F is a fullerene core; each K, independently, is OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, NHCH2CO2H, CH(CO2H)CH21-100OH, CH(CO2Ra)CH21-100OH, C(CH3)(CO2H)CH21-100OH, C(CH3)(CO2 Ra)CH21-100OH, N(OH)2, NH3, NH2Ra, NHRaRb, or NRaRbRc; each Y is -A-B-, in which A is O, NH, S, COO, OCO, OCOO, OCONH, NHCONH, CONH, or NHCO; and B is RaOSi(CH3)2O1-100 alkyl, C6-40 aryl, C7-2000 alkylaryl, C7-2000 arylalkyl, (C1-30 alkyl ether)1-100, (C6-40 aryl ether)1-100, (C7-2000 alkylaryl ether)1-100, (C7-2000 arylalkyl ether)1-100, (C1-30 alkyl thioether)1-100, (C6-40 aryl thioether)1-100, (C7-2000 alkylaryl thioether)1-100, (C7-2000 arylalkyl thioether)1-100, (C2-50 alkyl ester)1-100, (C7-2000 aryl ester)1-100, (C8-2000 alkylaryl ester)1-100, (C8-2000 arylalkyl ester)1-100, RaCOO(C1-30 alkyl ether)1-100, RaCOO(C6-40 aryl ether)1-100, R_O(C7-2000 alkylaryl ether)1-100, RaCO_O(C7-2000 arylalkyl ether)1-100, (C4-50 alkyl urethane)1-100, (C14-60 aryl urethane)1-100, (C10-2000 alkylaryl urethane)1-100, (C10-2000 arylalkyl urethane)1-100, (C5-50alkyl urea)1-100, (C14-60 aryl urea)1-100, (C10-2000 alkylaryl urea)1-100, (C10-2000 arylalkyl urea)1-100, (C2-50 alkyl amide)1-100, (C7-60 aryl amide)1-100, (C8-2000 alkylaryl amide)1-100, (C8-2000 arylalkyl amide)1-100, (C3-30 alkyl anhydride)1-100, (C8-50 aryl anhydride)1-100, (C9-2000 alkylaryl anhydride)1-100, (C9-2000 arylalkyl anhydride)1-100, (C2-30 alkyl carbonate)1-100, (C7-50 aryl carbonate)1-100, (C8-2000 alkylaryl carbonate)1-100, (C8-2000 arylalkyl carbonate)1-100, RaOCONH(Rb or ArRbAr)NHCOO (C1-30alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaOCONH(Rb or ArRAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100OCONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaNHCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaNHCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRbAr) NHC OO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100OCONH(Rb or ArRbAr)NHCOO, RaOCONH_(Rb or ArRbAr)NHCONH(C2-50 alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, RaNHCONH(Rb or ArRbAr)NHCONH(C2-50 alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, or a bond; each Z, independently, is -G-D, wherein G is Ra, RaAr, ArRa, or Ar; and D is H, OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, CH(NH2)CO2H, NHCH2CO2H, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, -oligosaccharide, CO-glycoside, CO-oligosaccharide, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, COOCH2(CHOH)4CH2OH, C6H3(OH)2, N(CH2CO2H)2, CON(CH2CO2H)2, CONHC(CH2CH2CO2H)3, CONHC(CH2CH2OH)3, CH2CH(CO2Ra)1-100H, NH3, NH2Ra, NHRaRb, or NRaRbRc, each of Ra, Rb, and Rc, independently, being C1-20 alkyl and Ar being aryl; q is 0-30; and m is 0-30; provided that the sum of q and im is 0-30;
each of R1 and R4, independently, is O or C1-20 hydrocarbon; and each of R2 and R5, independently, is C1-20 hydrocarbon; wherein R and R2, or R4 and R5 can join together to form C6-40 aryl which is optionally substituted with halide, OH, NHNH2, NH2OH, NHCH2CO2H, CH2CH2-D, CH2-B-Z, COCH2-D, CO-B-Z, O-B-Z, or NH-B-Z; each of B, D, and Z having been defined above;
each of R3 and R6, independently, is H, CH2-D, -B-Z, -G-E, -G-CO-E, or a side chain of an amino acid; each of B, D, and Z having been defined above, and E being E1, E2, or E3, in which E1 is Y1,Y2-amino, (Y1,Y2-alkyl)-amino, Y1,Y2-ethylenediamino, (dihydroxymethyl)alkylamino, (X1,X3-aryl)amino, or X1,X3-aryloxy; E2 is Y1,Y2-alkoxy, (Y1,Y2-amino)alkoxy, (Y1,Y2,Y3-aryl)oxy, (dihydroxyalkyl)-aryloxy, (Y1,Y2,Y3-alkyl)amino, (Y1,Y2,Y3-aryl)amino, dihydroxyalkylamino, Y1,Y2,Y3-alkoxy, (trihydroxyalkyl)alkoxy, (trihydroxyalkyl)alkylamino, (dicarboxyalkyl)amino, (Y1,Y2,Y3-alkyl)thio, (X1,X3-aryl)thio, (Y1,Y2-alkyl)thio, (dihydroxyalkyl)thio, Y1,Y2-dioxoalkyl, or tri-(Y1,Y2,Y3-methylaminocarboxyethyl)methylamino; and E3 is ((glycosidyl)oxoheteroaryl)amino, ((glycosidyl)oxoaryl)amino, (X1,X2,X3-heteroaryl)amino, (X1-diarylketone)amino, (X,X1-oxoaryl)amino, (X,X1-dioxoaryl)amino, (Y1-alkyl,Y2-alkyldioxoheteroaryl)amino, (Y1-alkyl,Y2-alkyldioxoaryl)amino, (di(Y1,Y2-methyl)dioxoheteroaryl)amino, (di(Y1,Y2-methyl)dioxoaryl)amino, ((glycosidyl)heteroaryl)amino, ((glycosidyl)aryl)amino, ((carboxylacetylalkyl)oxo-heteroaryl)amino, ((carboxylacetylalkyl)oxoaryl)amino, ((isopropylaminohydroxy-alkoxy)aryl)amino, (X1,X2,X3-alkylaryl)amino, (X1,X2,X3-heteroaryl)oxy, (isopropylaminohydroxyalkyl)aryloxy, (X1,X2,X3-oxoheteroaryl)oxy, (X1,X2,X3-oxoaryl)oxy, (X1,Y -oxoheteroaryl)oxy, (X1-diarylketone)oxy, (X,X1-oxoaryl)oxy, (X1,X2-dioxoaryl)oxy, (Y1,Y2,di-aminodihydroxy)alkyl, (X1,X2-heteroaryl)thio, ((tricarboxylalkyl)ethylene-diamino)alkoxy, (X1,X2-oxoaryl)thio, (X1,X2-dioxoaryl)thio, (glycosidylheteroaryl)thio, (glycosidylaryl)thio, Y1-alkyl(thiocarbonyl)thio, Y1,Y2-alkyl(thiocarbonyl)thio, Y1,Y2,Y3-alkyl(thiocarbonyl)thio, (Y1,Y2-aminothiocarbonyl)thio, (pyranosyl)thio, cysteinyl, tyrosinyl, (phenylalainyl)amino, (dicarboxyalkyl)thio, (aminoaryl)1-100amino, (pyranosyl)amino, (Y1-aminoaryl)1-100amino, (amino(sulfoaryl))1-100amino, peptidyl, thymidinyl, uridinyl, guanosinyl, adenosinyl, cholesteryl, or biotinylalkoxy; wherein X is halide; each of X1, X2, and X3, independently is Y1, OY1, SY1, NHY1, COOY1, OCOY1, CONHY1, CONY1Y2, NHCOY1, SO2Y1, CHY1Y2, or NY1Y2; and each ofY1, Y2, and Y3, independently, is -Z or -B-Z;
RN is H; or one of R3 and R6, together with RN is a bond and the other of R3 and R6 is as defined above.
each of x and y, independently, is 0 or 1; and
s is 1-6;
provided that when x is 0, R1 is O; that when y is 0, R4 is O; that when x is 1, R1 and R2 join together to form C6-40 aryl; and that when y is 1, R4 and R5 join together to form C6-40 aryl; and
or a salt thereof.
2. The compound of claim 1, wherein at least one of x and y is 1.
3. The compound of claim 2, wherein R1 and R2, or R4 and R5 can join together to form a benzene ring.
4. The compound of claim 3, wherein F is C60, C61, C62, C63, C64, C65, C70, C76, C78, C82, C84, or C92, or LaCn, HoCn, GdCn, or ErCn, in which n is 60, 74, or 82.
5. The compound of claim 3, wherein the sum of q and m is 0-20.
6. The compound of claim 3, wherein each K, independently, is SH, NHOH, SO3H, OSO3H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, -glycoside, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CHOH, NHRaRk, or NHRaR KR.
7. The compound of claim 3, wherein D is SH, NHOH, SO3H, OSO3H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, -glycoside, -oligosaccharide, CO-glycoside, CO-oligosaccharide, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CHOH, NHRaRb, or NHRaRbRc.
8. The compound of claim 3, wherein only one of x and y is 1.
9. The compound of claim 8, wherein x is 1, y is 0, and R and R2 join together to form a benzene ring.
10. The compound of claim 9, wherein R3 is H, -B-Z, -G-E, or -G-CO-E.
11. The compound of claim 9, wherein R6 is -G-E, -G-CO-E, or a side chain of an amino acid.
12. The compound of claim 11, wherein R6 is a side chaini of alanine, aspartic acid, cysteine, glutamic acid, phenylalanine, halophenylalanine, hydroxyphenylalanine, glycine, histidine, isoleucine, lysine, leucine, methionine, asparagine, glytamine, arginine, serine, theronine, valine, tryptophan, tyrosine, 2-aminobutyric acid, halophenylalaniine, cyclohexylalanine, citrulline, homocitrulline, homoserine, norleucine, norvaline, or ornithille.
13. The compound of claim 12, wherein R3 is H, -B-Z, -G-E, or -G-CO-E.
14. The compound of claim 13, wherein F is C60, and the sum of q and m is 0-20.
15. The compound of claim 14, said compound is the E-isomer of 1-dimetlhyl-3-hydroxyphenylmethyl-fulleropyrrolidine-1,3-dicarboxylic acid, 1-dimethyl-3-(3,4-dihydroxyphenyl)methyl-fulleropyrrolidine-1,3-dicarboxylic acid, 1-isobutyl-3-(o-hydroxyphenyl)-fulleropyrrolidine-1-carboxylic acid, 1-methyl-3-ethyl-3-(o-hydroxyphenyl)-fulleropyrrolidine-1-carboxylic acid, or 1-metlhyl-3-(2,3,4-trihydroxyphenyl)-fulleropyrrolidine-1-carboxylic acid.
16. The compound of claim 1, wherein both x and y are 0.
17. The compound of claim 16, wherein F is C60, C61, C62, C63, C64, C65, C70, C76, C78, C82, C84, or C92, or LaCn, HoCn, GdCn, or ErCn, in which1 n is 60, 74, or 82.
18. The compound of claim 16, wherein the sum of q and m is 0-20.
19. The compound of claim 16, wherein each K, independently, is SH, NHOH, SO3H, OSO3H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, -glycoside, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CHOH, NHRaRb, or NHRaRbRc.
20. The compound of claim 16, wherein D is SH, NHOH, SO3H, OSO3H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, -glycoside, -oligosaceharide, CO-glycoside, CO-oligosaccharide, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CHOH, NHRaRb, or NHRaRbRc.
21. The compound of claim 16, wherein each of R3 and R6, independently, is -B-Z, -G-E, -G-CO-E, or a side chain of alanine, aspaitic acid, cysteilne, glutamic acid, phenylalanine, halophenylalanine, hydroxyphenylalaninie, glycine, hiistidinie, isoleucine, lysine, leucine, mnethionine, asparagine, glytamine, arginine, serine, theroinine, valine, tryptophan, tyrosine, 2-aminobutyric acid, haloplhenylalaniine, cyclohexylalaninie, citrulline, homocitrulline, homoserine, norleucine, norvaline, or ornithine.
22. The compound of claim 21, wherein F is C60, and the sum of q and m is 0-20.
23. The compound of claim 22, said compound is the E-isomer of 1,3-dimethyl-fulleropyrrolidine-1,3-dicarboxylic acid, fLilleropyrrolidine-1,3-di(3-propanoic acid)-1,3-dicarboxylic acid, 1-methyl-3-thiomethyl-fulleropyrrolidine-1,3-dicar-boxylic acid, or 1-methyl-3-hydroxymethyl-fulleropyirolidine-1,3-dicarboxylic acid.
24. A method for preparing a compound of formula (I-A):
16
wherein
Ff is F(-K)m(Y-Z)q in which F is a fullerene core; each K, independently, is OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONRNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, NHCH2CO2H, CH(CO2H)CH21-100OH, CH(CO2Ra)CH21-100OH, C(CH3)(CO2H)CH21-100OH, C(CH3)(CO2 Ra)CH21-100OH, N(OH)2, NH3, NH2Ra, NHRaRb, or NRaRbRc; each Y is -A-B-, in which A is O, NH, S, COO, OCO, OCOO, OCONH, NHCONH, CONH, or NHCO; and B is RaOSi(CH3)2O1-100, C1-2000 alkyl, C6-40 aryl, C7-2000 alkylaryl, C7-2000 arylalkyl, (C1-30 alkyl ether)1-100, (C6-40 aryl ether)1-100, (C7-2000 alkylaryl ether)1-100, (C7-2000 arylalkyl ether)1-100, (C1-30 alkyl thioether)1-100, (C6-40 aryl thioether)1-100, (C7-2000 alkylaryl thioether)1-100, (C7-2000 arylalkyl thioether)1-100, (C2-50 alkyl ester)1-100, (C7-2000 aryl ester)1-100, (C8-2000 alkylaryl ester)1-100, (C8-2000 arylalkyl ester)1-00, RaCOO(C1-30 alkyl ether)1-100, RaCOO(C6-40 aryl ether)1-100, RaCOO(C7-2000 alkylaryl ether)1-100, RaCOO(C7-2000 arylalkyl ether)1-100, (C4-50 alkyl urethane)1-100, (C14-60 aryl urethane)1-100, (C10-2000 alkylaryl urethane)1-100, (C10-2000 arylalkyl urethane)1-100, (C5-50 alkyl urea)1-100, (C14-60 aryl urea)1-100, (C10-2000 alkylaryl urea)1-100, (C10-2000 arylalkyl urea)1-100, (C2-50 alkyl amide)1-100, (C7-60 aryl amide)1-100, (C8-2000 alkylaryl amide)1-100, (C8-2000 arylalkyl amide)1-100, (C3-30 alkyl anhydrlde)1-100, (C8-50 aryl anhydride)1-100, (C9-2000 alkylaryl anhydride)1-100, (C9-2000 arylalkyl anhydride)1-100, (C2-30 alkyl carbonate)1-100, (C7-50 aryl carbonate)1-100, (C8-2000 alkylaryl carbonate)1-100, (C8g2000 arylalkyl carbonate)1-100, RaOCONH(Rb or ArRbAr)NHCO-O(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100RcOCONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaNHCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaNH_CONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100RcOCONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCONH(C2-50 alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, RaNHCONH(Rb or ArRbAr)NHCONH(C2-50 alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, or a bond; each Z, independently, is -G-D, wherein G is Ra, RaAr, ArR, or Ar; and D is H, OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, CH(NH2)CO2H, NHCH2CO2H, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, -oligosaccharide, CO-glycoside, CO-oligosaccharide, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, COOCH2(CHOH)4CH2OH, C6H3(OH)2, N(CH2CO2H)2, CON(CH2CO2H)2, CONHC(CH2CH2CO2H)3, CONHC(CH2CH2OH)3, CH2CH(CO2Ra)1-100H, NH3, NH2Ra, NHRaRb, or NRaRbRc, each of Ra, Rb, and Rc, independently, being C1-20 alkyl and Ar being aryl; q is 0-30; and m is 0-30; provided that the sum of q and m is 0-30;
each of R1 and R4, independently, is O or C1-20 hydrocarbon; and each of R2 and R5, independently, is C1-20 hydrocarbon; wherein R1 and R2, or R4 and R5 can join together to form C6-40 aryl which is optionally substituted with halide, OH, NHNH2, NH2OH, NHCH2CO2H, CH2CH2-D, CH2-B-Z, COCH2-D, CO-B-Z, O-B-Z, or NH-B-Z; each of B, D, and Z having been defined above;
each of R3 and R6, independently, is H, CH2-D, -B-Z, -G-E, -G-CO-E or a side chain of an amino acid; each of B, D, and Z having been defined above, and E being E1, E2, or E3, in which E1 is Y1,Y2-amino, (Y1,Y2-alkyl)-amino, Y1,Y2-ethylenediamino, (dihydroxymethyl)alkylamino, (X1,X3-aryl)amino, or X1,X3-aryloxy; E2 is Y1,Y2-alkoxy, (Y1,Y2-amino)alkoxy, (Y1,Y2,Y3-aryl)oxy, (dihydroxyalkyl)-aryloxy, (Y1,Y2,Y3-alkyl)amino, (Y1,Y2,Y3-aryl)amino, dihydroxyalkylamino, Y1,Y2,Y3-alkoxy, (trihydroxyalkyl)alkoxy, (trihydroxyalkyl)alkylamino, (dicarboxyalkyl)amino, (Y1,Y2,Y3-alkyl)thio, (X1,X3-aryl)thio, (Y1,Y2-alkyl)thio, (dihydroxyalkyl)thio, Y1,Y2-dioxoalkyl, or tri-(Y1,Y2,Y3-methylaminocarboxyethyl)methylamino; and E3 is ((glycosidyl)oxoheteroaryl)amino, ((glycosidyl)oxoaryl)amino, (X1,X2,X3-heteroaryl)amino, (X1-diarylketone)amino, (X,X1-oxoaryl)amino, (X,X1-dioxoaryl)amino, (Y1-alkyl,Y2-alkyldioxoheteroaryl)amino, (Y1-alkyl,Y2-alkyldioxoaryl)amino, (di(Y1,Y2-methyl)dioxoheteroaryl)amino, (di(Y1,Y2-methyl)dioxoaryl)amino, ((glycosidyl)heteroaryl)amino, ((glycosidyl)aryl)amino, ((carboxylacetylalkyl)oxo-heteroaryl)amino, ((carboxylacetylalkyl)oxoaryl)amino, ((isopropylaminohydroxy-alkoxy)aryl)amino, (X1,X2,X3-alkylaryl)amino, (X1,X2,X3-heteroaryl)oxy, (isopropylaminohydroxyalkyl)aryloxy, (X1,X2,X3-oxoheteroaryl)oxy, (X1,X2,X3-oxoaryl)oxy, (X1,Y1-oxoheteroaryl)oxy, (X1-diarylketone)oxy, (X,X1-oxoaryl)oxy, (X1,X2-dioxoaryl)oxy, (Y1,Y2,di-aminodihydroxy)alkyl, (X1,X2-heteroaryl)thio, ((tricarboxylalkyl)ethylene-diamino)alkoxy, (X1,X2-oxoaryl)thio, (X1,X2-dioxoaryl)thio, (glycosidylheteroaryl)thio, (glycosidylaryl)thio, Y1-alkyl(thiocarbonyl)thio, Y1,Y2-alkyl(thiocarbonyl)thio, Y1,Y2,Y3-alkyl(thiocarbonyl)thio, (Y1,Y2-aminothiocarbonyl)thio, (pyranosyl)thio, cysteinyl, tyrosinyl, (phenylalainyl)amino, (dicarboxyalkyl)thio, (aminoaryl)1-100amino, (pyranosyl)amino, (Y1-aminoaryl)1-100amino, (amino(sulfoaryl))1-100amino, peptidyl, thymidinyl, uridinyl, guanosinyl, adenosinyl, cholesteryl, or biotinylalkoxy; wherein X is halide; each of X1, X2, and X3, independently, is Y1, OY1, SY1, NHY1, COOY1, OCOY1, CONHY1, CONY1Y2, NHCOY1, SO2Y1, CHY1Y2, or NY1Y2; and each of Y1, Y2, and Y3, independently, is -Z or -B-Z;
each of x and y, independently, is 0 or 1; and
s is 1-6;
provided that when x is 0, R1 is O; that when y is 0, R4 is O; that when X is 1, R1 and R2 join together to form C6-40 aryl; and that when y is 1, R4 and R join together to form C6-40 aryl; and
or a salt thereof;
the method comprising:
reacting a compound of formula (II)
17
wherein M is a Cu, Mn, Fe, Co, Ni, Ru, Rh, Os, Zn, Cr, Ti, or Zr ion;
with a fullerene compound Ff of the formula F(-K)m,(Y-Z)q wherein the suIml of q and m is 0 to form a compound of formula (III)
18
removing M from the compound of formula (III) to form a compound Of formula (I-A) wherein the sum of q and m is 0; and
optionally treating the compound of formula (I-A) wherein the sum of q and m is 0 with a nitrating or sulfating agent to form a nitrofullerene or cyclosulifatecd fullerene, and contacting the nitrofullerene or cyclosulfated fullerene with a nucleoplilic agent to formi a compound of formula (I-A) wherein the sum of q and m is greater than 0.
25. The method of claim 24, wherein only one of x and y is 0.
26. The method of claim 25, wherein x is I, y is 0, and R1 and ;R2 join together to form a benzene ring.
27. The method of claim 24, wherein both x and y are 0.
28. The method of claim 24, wherein M is a Cu ion.
29. The method of claim 24, wherein the compound of formula (II) is prepared by reacting a compound of fonrula (IV)
19
with a metal salt MX, wherein M has been defined above, and X is an anion.
30. The method of claim 29, wherein X is halide, sulfate, nitrate, or acetate.
31. The method of claim 29, wherein the compound of formula (IV) is prepared by reacting a compound of formula (V)
20
with a compound of formula (VI)
21
32. The method of claim 31, wherein each of R3 and R6, independently, is H, B-Z, -G-E, -G-CO-E, or a side chain of an amino acid, wherein B, E, G, and Z have been defined above.
33. A compound of formula (VII):
22
wherein
Ff is F(-K)m(Y-Z)q in which F is a fullerene core; each K, independently, is OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, NHCH2CO2H, CH(CO2H)CH21-100OH, CH(CO2Ra)CH21-100OH, C(CH3)(CO2H)CH21-100OH, C(CH3)(CO2 Ra)CH21-100OH, N(OH)2, NH3, NH2Ra, NHRaRb, or NRaRbRc; each Y is -A-B-, in which A is O, NH, S, COO, OCO, OCOO, OCONH, NHCONH, CONH, or NHCO; and B is RaSi(CH3)2O1-100, C1-2000 alkyl, C6-40 aryl, C7-2000 alkylaryl, C7-2000 arylalkyl, (C1-30 alkyl ether)1-100, (C6-40 aryl ether)1-100, (C7-2000 alkylaryl ether)1-100, (C7-2000 arylalkyl-ether)1-100, (C1-30 alkyl thioether)1-100, (C6-40 aryl thioether)1-100, (C7-2000 alkylaryl thioether)1-100, (C7-2000 arylalkyl thioether)1-100, (C2-50 alkyl ester)1-100, (C7-2000 aryl ester)1-100, (C8-2000 alkylaryl ester)1-100, (C8-2000 arylalkyl ester)1-100, RCOO(C1-30 alkyl ether)1-100, RaCOO(C6-40 aryl ether)1-100, RaCOO(C7-2000 alkylaryl ether)1-100, RaCOO(C7-2000 arylalkyl ether)1-100, (C4-50 alkyl urethane)1-100, (C14-60 aryl urethane)1-100, (C102000 alkylaryl urethane)1-100, (C10-2000 arylalkyl urethane)1-100, (C5-50 alkyl urea)1-100, (C14-60 aryl urea)1-100, (C10-2000 alkylaryl urea)1-100, (C10-2000 arylalkyl urea)1-100, (C2-50 alkyl amide)1-100, (C7-60 aryl amide)1-100, (C8-2000 alkylaryl amide)1-100, (C8-2000 arylalkyl amide)1-100, (C3-30 alkyl anhydride)1-100, (C8-50 aryl anhydride)1-100, (C9-2000 alkylaryl anhydride)1-100, (C9-2000 arylalkyl anhydride)1-100, (C2-30 alkyl carbonate)1-100, (C7-50 aryl carbonate)1-100, (C8-2000 alkylaryl carbonate)1-100, (C8-2000 arylalkyl carbonate)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaOCONH(Rb or ArRaAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100RaOCONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRaAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaNHCONH(Rb or ArRAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaNHCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100RcOCONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCONH(C2-50 so alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, RaNHCONH(Rb or ArRbAr)NHCONH(C2-50 alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, or a bond; each Z, independently, is -G-D, wherein G is R, RaAr, ArRa, or Ar; and D is H, OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, CH(NH2)CO2H, NHCH2CO2H, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, -oligosaccharide, CO-glycoside, CO-oligosaccharide, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, COOCH2(CHOH)4CH2OH, C6H3(OH)2, N(CH2CO2H)2, CON(CH2CO2H)2, CONHC(CH2CH2CO2H)3, CONHC(CH2CH2OH)3, CH2CH(CO2Ra)1-100H, NH3, NH2Ra, NHRaRb, or NRaRbRc, each of Ra, Rb, and Rc, independently, being C1-20 alkyl and Ar being aryl; q is 0-30; and m is 0-30; provided that the sum of q and m is 0-30;
each of R1 and R4, independently, is O or C1-20 hydrocarbon; and each of R2 and R5, independently, is C1-20 hydrocarbon; wherein R1 and R2, or R4 and R5 can join together to form C6-40 aryl which is optionally substituted with halide, OH, NHNH2, NH2OH, NHCH2CO2H, CH2CH2-D, CH2-B-Z, COCH2-D, CO-B-Z, O-B-Z, or NH-B-Z; each of B, D, and Z having been defined above;
each of R3 and R6, independently, is H, CH2-D, -B-Z, -G-E, -G-CO-E or a side chain of an amino acid; each of B, D, and Z having been defined above, and E being E1, E2, or E3, in which E1 is Y1,Y2-amino, (Y1,Y2-alkyl)-amino, Y1,Y2-ethylenediamino, (dihydroxymethyl)alkylamino, (X1,X3-aryl)amino, or X1,X3-aryloxy; E2 is Y1,Y2-alkoxy, (Y1,Y2-amino)alkoxy, (Y1,Y2,Y3-aryl)oxy, (dihydroxyalkyl)-aryloxy, (Y1,Y2,Y3-alkyl)amino, (Y1,Y2,Y3-aryl)amino, dihydroxyalkylamino, Y1,Y2,Y3-alkoxy, (trihydroxyalkyl)alkoxy, (trihydroxyalkyl)alkylamino, (dicarboxyalkyl)amino, (Y1,Y2,Y3-alkyl)thio, (X1,X3-aryl)thio, (Y1,Y2-alkyl)thio, (dihydroxyalkyl)thio, Y1,Y2-dioxoalkyl, or tri-(Y1,Y2,Y3-methylaminocarboxyethyl)methylamino; and E3 is ((glycosidyl)oxoheteroaryl)amino, ((glycosidyl)oxoaryl)amino, (X1,X2,X3-heteroaryl)amino, (X1-diarylketone)amino, (X,X1-oxoaryl)amino, (X,X1-dioxoaryl)amino, (Y1-alkyl,Y2-alkyldioxoheteroaryl)amino, (Y1-alkyl,Y2-alkyldioxoaryl)amino, (di(Y1,Y2-methyl)dioxoheteroaryl)amino, (di(Y1,Y2-methyl)dioxoaryl)amino, ((glycosidyl)heteroaryl)amino, ((glycosidyl)aryl)amino, ((carboxylacetylalkyl)oxo-heteroaryl)amino, ((carboxylacetylalkyl)oxoaryl)amino, ((isopropylaminohydroxy-alkoxy)aryl)amino, (X1,X2,X3-alkylaryl)amino, (X1,X2,X3-heteroaryl)oxy, (isopropylaminohydroxyalkyl)aryloxy, (X1,X2,X3-oxoheteroaryl)oxy, (X1,X2,X3-oxoaryl)oxy, (X1,Y1-oxoheteroaryl)oxy, (X1-diarylketone)oxy, (X,X1-oxoaryl)oxy, (X1,X2-dioxoaryl)oxy, (Y1,Y2,di-aminodihydroxy)alkyl, (X1,X2-heteroaryl)thio, ((tricarboxylalkyl)ethylene-diamino)alkoxy, (X1,X2-oxoaryl)thio, (X1,X2-dioxoaryl)thio, (glycosidylheteroaryl)thio, (glycosidylaryl)thio, Y1-alkyl(thiocarbonyl)thio, Y1,Y2-alkyl(thiocarbonyl)thio, Y1,Y2,Y3-alkyl(thiocarbonyl)thio, (Y1,Y2-aminothiocarbonyl)thio, (pyranosyl)thio, cysteinyl, tyrosinyl, (phenylalainyl)amino, (dicarboxyalkyl)thio, (aminoaryl), iooamino, (pyranosyl)amino, (Y1-aminoaryl)1-100amino, (amino(sulfoaryl))1-100amino, peptidyl, thymidinyl, uridinyl, guanosinyl, adenosinyl, cholesteryl, or biotinylalkoxy; wherein X is halide; each of X1, X2, and X3, independently, is Y1, OY1, SY1, NHY1, COOY1, OCOY1, CONHY1, CONY1Y2, NHCOY1, SO2Y1, CHY1Y2, or NY1Y2; and each of Y1, Y2, and Y3, independently, is -Z or -B-Z; B and Z having been defined above;
R7 is Rd or ORe; wherein Rd is OH, OM, NHNH2, NHOH, NHCH2CO2H, O-B-Z, NH-B-Z, -E, O-G-E, NH-G-E, O-G-CO-E, or NH-G-CO-E; M being Cu, Mn, Fe, Co, Ni, Ru, Rh, Os, Zn, Cr, Ti, or Zr ion; and Re is H, CH2CH2-D, CH2-B-Z, CH2-G-E, CH2-G-CO-E, COCH2-D, CO-B-Z, CO-G-E, or CO-G-CO-E; each of B, D, E, G, and Z having been defined above;
8 is Re;
R9 is O or a bond;
R10 is Rd or Re; each of which having been defined above;
each of x and y, independently, is 0 or 1; and
p is 1-30;
provided that when x is 0, R1 is O, and R7 is -Rd; that when y is 0, R4 is O, and R9 is a bond, and R10 is Rd; that when x is 1, R1 and R2 join together to form C6-40 aryl, and R7 is ORe; and that when y is 1, R4 and R5 join together to form C6-40 aryl, R9 is O, and R10 is Re; and
further provided that when p is greater than 1, x is 0;
or a salt thereof.
34. The compound of claim 33, wherein F is C60, C61, C62, C63, C64, C65, C70, C76, C78, C82, C84, or C92, or LaCn, HoCn, GdCn, or ErCn, in which n is 60, 74, or 82.
35. The compound of claim 33, wherein the sum of q and m is 0-20.
36. The compound of claim 33, wherein p is 2-10.
37. The compound of claim 33, wherein each of R3 and R6, independently, is H. -B-Z, -G-E, -G-CO-E or a side chain of an amino acid.
38. The compound of claim 33, wherein Rd is OH, NHNH2, -E, O-G-E, NH-G-E, O-G-CO-E, or NH-G-CO-E.
39. The compound of claim 33, wherein Re is H, CH2-G-E, CH2-G-CO-E, CO-G-E, or CO-G-CO-E.
40. The compound of claim 33, wherein both x and y are 0.
41. The compound of claim 40, wherein Rd is OH, N Hl2, -E, O-G-E, NH-G-E, O-G-CO-E, or NH-G-CO-E.
42. The compound of claim 41, wherein Re is H, CH2-G-E, CH2-G-CO-E, CO-G-E, or CO-G-CO-E.
43. The compound of claim 42, wherein p is 2-10.
44. The compound of claim 43, said compound is oligo(1,3-dimethyl-fulleropyrrolidine-1,3-dicarboxylic N-amide).
45. A compound of formula (VIII):
23
wherein
Ff is F(-K)m(Y-Z)q in which F is a fullerene core; each K, independently, is OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, NHCH2CO2H, CH(CO2H)CH21-100OH, CH(CO2Ra)CH21-100OH, C(CH3)(CO2H)CH21-100OH, C(CH3)(CO2 Ra)CH21-100OH, N(OH)2, NH3, NH2Ra, NHRaRb, or NRaRbRc; each Y is -A-B-, in which A is O, NH, S, COO, OCO, OCOO, OCONH, NHCONH, CONH, or NHCO; and B is RaSi(CH3)2O1-100, C1-2000 alkyl, C6-40 aryl, C7-2000 alkylaryl, C7-2000 arylalkyl, (C1-30 alkyl ether)1-100, (C6-40 aryl ether)1-100, (C7-2000 alkylaryl ether)1-100, (C7-2000 arylalkyl-ether)1-100, (C1-30 alkyl thioether)1-100, (C6-40 aryl thioether)1-100, (C7-2000 alkylaryl thioether)1-100, (C7-2000 arylalkyl thioether)1-100, (C2-50 alkyl ester)1-100, (C7-2000 aryl ester)1-100, (C8-2000 alkylaryl ester)1-100, (C8-2000 arylalkyl ester)1-100, RCOO(C1-30 alkyl ether)1-100, RaCOO(C6-40 aryl ether)1-100, RaCOO(C7-2000 alkylaryl ether)1-100, RaCOO(C7-2000 arylalkyl ether)1-100, (C4-50 alkyl urethane)1-100, (C14-60 aryl urethane)1-100, (C10-2000 alkylaryl urethane)1-100, (C10-2000 arylalkyl urethane)1-100, (C5-50 alkyl urea)1-100, (C14-60 aryl urea)1-100, (C10-2000 alkylaryl urea)1-100, (C10-2000 arylalkyl urea)1-100, (C2-50 alkyl amide)1-100, (C7-60 aryl amide)1-100, (C8-2000 alkylaryl amide)1-100, (C8-2000 arylalkyl amide)1-100, (C3-30 alkyl anhydride)1-100, (C8-50 aryl anhydride)1-100, (C9-2000 alkylaryl anhydride)1-100, (C9-2000 arylalkyl anhydride)1-100, (C2-30 alkyl carbonate)1-100, (C7-50 aryl carbonate)1-100, (C8-2000 alkylaryl carbonate)1-100, (C8-2000 arylalkyl carbonate)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaOCONH(Rb or ArRaAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaOCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100RaOCONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRaAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100, RaNHCONH(Rb or ArRAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100, RaNHCONH(Rb or ArRbAr)NHCOO(C1-30 alkyl ether, C6-40 aryl ether, C7-2000 alkylaryl ether, or C7-2000 arylalkyl ether)1-100CONH(Rb or ArRbAr)NHCOO, RaNHCONH(Rb or ArRbAr)NHCOO(C2-50 alkyl ester, C7-60 aryl ester, C8-2000 alkylaryl ester, or C8-2000 arylalkyl ester)1-100RcOCONH(Rb or ArRbAr)NHCOO, RaOCONH(Rb or ArRbAr)NHCONH(C2-50 so alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, RaNHCONH(Rb or ArRbAr)NHCONH(C2-50 alkyl amide, C7-60 aryl amide, C8-2000 alkylaryl amide, or C8-2000 arylalkyl amide)1-100, or a bond; each Z, independently, is -G-D, wherein G is R, RaAr, ArRa, or Ar; and D is H, OH, SH, NH2, NHOH, SO3H, OSO3H, CO2H, CONH2, CONHNH2, CH(NH2)CO2H, NHCH2CO2H, P(OH)3, PO(OH)2, OPO(OH)2, OPO(OH)OPO(OH)2, OPO(O)OCH2CH2NH3, OPO(O)OCH2CH2N(CH3)3, -glycoside, -oligosaccharide, CO-glycoside, CO-oligosaccharide, OCH3, OCH2(CHOH)4CH2OH, OCH2(CHOH)2CH2OH, COOCH2(CHOH)4CH2OH, C6H3(OH)2, N(CH2CO2H)2, CON(CH2CO2H)2, CONHC(CH2CH2CO2H)3, CONHC(CH2CH2OH)3, CH2CH(CO2Ra)1-100H, NH3, NH2Ra, NHRaRb, or NRaRbRc, each of Ra, Rb, and Rc, independently, being C1-20 alkyl and Ar being aryl; q is 0-30; and m is 0-30; provided that the sum of q and m is 0-30;
each of R1 and R4, independently, is O or C1-20 hydrocarbon; and each of R2 and R5, independently, is C1-20 hydrocarbon; wherein R1 and R2, or R4 and R5 can join together to form C6-40 aryl which is optionally substituted with halide, OH, NHNH2, NH2OH, NHCH2CO2H, CH2CH2-D, CH2-B-Z, COCH2-D, CO-B-Z, O-B-Z, or NH-B-Z; each of B, D, and Z having been defined above;
each of R3 and R6, independently, is H, CH2-D, -B-Z, -G-E, -G-CO-E or a side chain of an amino acid; each of B, D, and Z having been defined above, and E being E1, E2, or E3, in which E1 is Y1,Y2-amino, (Y1,Y2-alkyl)-amino, Y1,Y2-ethylenediamino, (dihydroxymethyl)alkylamino, (X1,X3-aryl)amino, or X1,X3-aryloxy; E2 is Y1,Y2-alkoxy, (Y1,Y2-amino)alkoxy, (Y1,Y2,Y3-aryl)oxy, (dhydroxyalkyl)-aryloxy, (Y1,Y2,Y3-alkyl)amino, (Y1,Y2,Y3-aryl)amino, dihydroxyalkylamino, Y1,Y2,Y3-alkoxy, (trihydroxyalkyl)alkoxy, (trihydroxyalkyl)alkylamino, (dicarboxyalkyl)amino, (Y1,Y2,Y3-alkyl)thio, (X1,X3-aryl)thio, (Y1,Y2-alkyl)thio, (dihydroxyalkyl)thio, Y1,Y2-dioxoalkyl, or tri-(Y1,Y2,Y3-methylaminocarboxyethyl)methylamino; and E3 is ((glycosidyl)oxoheteroaryl)amino, ((glycosidyl)oxoaryl)amino, (X1,X2,X3-heteroaryl)amino, (X1-diarylketone)amino, (X,X1-oxoaryl)amino, (X,X1-dioxoaryl)amino, (Y1-alkyl,Y2-alkyldioxoheteroaryl)amino, (Y1-alkyl,Y2-alkyldioxoaryl)amino, (di(Y1,Y2-methyl)dioxoheteroaryl)amino, (di(Yly2-methyl)dioxoaryl)amino, ((glycosidyl)heteroaryl)amino, ((glycosidyl)aryl)amino, ((carboxylacetylalkyl)oxo-heteroaryl)amino, ((carboxylacetylalkyl)oxoaryl)amino, ((isopropylaminohydroxy-alkoxy)aryl)amino, (X1,X2,X3-alkylaryl)amino, (X1,X2,X3-heteroaryl)oxy, (isopropylaminohydroxyalkyl)aryloxy, (X1,X2,X3-oxoheteroaryl)oxy, (X1,X2,X3-oxoaryl)oxy, (X1,Y1-oxoheteroaryl)oxy, (X1-diarylketone)oxy, (X,X1-oxoaryl)oxy, (X1,X2-dioxoaryl)oxy, (Y1,Y2,di-aminodihydroxy)alkyl, (X1,X2-heteroaryl)thio, ((tricarboxylalkyl)ethylene-diamino)alkoxy, (X1,X2-oxoaryl)thio, (X1,X2-dioxoaryl)thio, (glycosidylheteroaryl)thio, (glycosidylaryl)thio, Y1alkyl(thiocarbonyl)thio, Y1,Y2-alkyl(thiocarbonyl)thio, Y1,Y2,Y3-alkyl(thiocarbonyl)thio, (Y1,Y2-aminothiocarbonyl)thio, (pyranosyl)thio, cysteinyl, tyrosinyl, (phenylalainyl)amino, (dicarboxyalkyl)thio, (aminoaryl)1-100amino, (pyranosyl)amino, (Y1-aminoaryl)1-100amino, (amino(sulfoaryl))1-100amino, peptidyl, thymidinyl, uridinyl, guanosinyl, adenosinyl, cholesteryl, or biotinylalkoxy; wherein X is halide; each of X1, X2, and X3, independently, is Y1, OY1, SY1, NHY1, COOY1, OCOY1, CONHY1, CONY1Y2, NHCOY1, SO2Y1, CHY1Y2, or NY1Y2; and each of Y1, Y2, and Y3, independently, is -Z or -B-Z; B and Z having been defined above;
R7 is Rd or ORe; wherein Rd is OH, OM, NHNH2, NHOH, NHCH2CO2H, O-B-Z, NH-B-Z, -E, O-G-E, NH-G-E, O-G-CO-E, or NH-G-CO-E; M being Cu, Mn, Fe, Co, Ni, Ru, Rh, Os, Zn, Cr, Ti, or Zr ion; and Re is H, CH2CH2-D, CH2-B-Z, CH2-G-E, CH2-G-CO-E, COCH2-D, CO-B-Z, CO-G-E, or CO-G-CO-E; each of B, D, E, G, and Z having been defined above;
R8 is Re, which has the same meaning as set forth above;
R9 is ORf or Rg; wherein Rf is CO-B-G-O, CO-B-G-NH, CO-B-G-COO, or CO-B-G-CONH; and R1 is NH, O, O-B-G-O, NH-B-G-O, NH-B-G-NH, OCO-B-G-COO, or NHCO-B-G-CONH; B and G having been defined above;
R10 is H;
each of x and y, independently, is 0 or 1; and
r is 1-100;
provided that when x is 0, R1 is O, and R7 is Rd; that when y is 0, R4 is O, and R9 is Rg, and R10 is H; that when x is 1, R1 and R2 join together to form C6-40 aryl, and R7 is ORe; and that when y is 1, R4 and R5 join together to form C6-40 aryl, R9 is ORf, and R10 is H; and
further provided that when r is greater than 1, x is 0;
or a salt thereof.
46. The compound of claim 45, wherein F is C60, C61, C62, C63, C64, C65, C70, C76, C78, C82, C84, or C92, or LaCn, HoCn, GdCn, or ErCn, in which n is 60, 74, or 82.
47. The compound of claim 45, wherein the sum of q and m is 0-20.
48. The compound of claim 45, wherein r is 2-30.
49. The compound of claim 45, wherein each of R3 and R6, independently, is H, -B-Z, -G-E, -G-CO-E, or a side chain of an amino acid.
50. The compound of claim 45, wherein Rd is OH, NHNH2, -E, O-G-E, NH-G-E, O-G-CO-E, or NH-G-CO-E.
51. The compound of claim 45, wherein Re is H, CH2-G-E, CH2-G-CO-E, CO-G-E, or CO-G-CO-E.
52. The compound of claim 45, wherein Rf is CO-B-G-NH or CO-B-G-CONH.
53. The compound of claim 45, wherein Rg is O-B-G-O, NH-B-G-O, NH-B-G-NH, OCO-B-G-COO, or NHCO-B-G-CONH.
54. The compound of claim 45, wherein both x and y are 0.
55. The compound of claim 54, wherein each of R3 and R6; independently, is H, -B-Z, -G-E, -G-CO-E, or a side chain of an amino acid.
56. The compound of claim 55, wherein Rd is OH, NHNH2, -E, O-G-E, NH-G-E, O-G-CO-E, or NH-G-CO-E.
57. The compound of claim 56, wherein Re is H, CH2-G-E, CH2-G-CO-E, CO-G-E, or CO-G-CO-E.
58. The compound of claim 57, wherein Rf is CO-B-G-NH or CO-B-G-CONH.
59. The compound of claim 58, wherein R is O-B-G-O, NH-B-G-O, NH-B-G-NH, OCO-B-G-COO, or NHCO-B-G-CONH.
60. The compound of claim 59, wherein r is 2-30.