6619-10-9Relevant articles and documents
Synthesis, photophysical properties, and photodynamic activity of positional isomers of TFPP-glucose conjugates
Fadlan, Arif,Tanimoto, Hiroki,Ito, Tatsuya,Aritomi, Yusuke,Ueno, Maho,Tokuda, Masaya,Hirohara, Shiho,Obata, Makoto,Morimoto, Tsumoru,Kakiuchi, Kiyomi
supporting information, p. 1848 - 1858 (2018/03/06)
The synthesis and characterization of a ‘complete set’ of positional isomers of tetrakis(perfluorophenyl)porphyrins (TFPP)-glucose conjugates (1OH, 2OH, 3OH, 4OH, and 6OH) are reported herein. The cellular uptake and photocytotoxicity of these conjugates were examined in order to investigate the influence of location of the TFPP moiety on the D-glucose molecule on the biological activity of the conjugates. An In vitro biological evaluation revealed that the certain of these isomers have a greater effect on cellular uptake and cytotoxicity than others. The TFPP-glucose conjugates 1OH, 3OH, and 4OH were found to exert exceptional photocytotoxicity in several types of cancer cells compared to 2OH and 6OH substituted isomers.
18F-Glyco-RGD peptides for PET imaging of integrin expression: Efficient radiosynthesis by click chemistry and modulation of biodistribution by glycosylation
Maschauer, Simone,Haubner, Roland,Kuwert, Torsten,Prante, Olaf
, p. 505 - 515 (2014/03/21)
Glycosylation frequently improves the biokinetics and clearance properties of macromolecules in vivo and could therefore be used for the design of radiopharmaceuticals for positron emission tomography (PET). Recently, we have developed a click chemistry method for 18F-fluoroglycosylation of alkyne-bearing RGD-peptides targeting the integrin receptor. To investigate whether this strategy could yield an 18F-labeled RGD glycopeptide with favorable biokinetics, we generated a series of new RGD glycopeptides, varying the 6-fluoroglycosyl residue from monosaccharide to disaccharide units, which provided the glucosyl ([19F]6Glc-RGD, 4b), galactosyl ([ 19F]Gal-RGD, 4c), maltosyl ([19F]Mlt-RGD, 4e), and cellobiosyl ([19F]Cel-RGD, 4f) conjugated peptides in high yields and purities of >97%. All of these RGD glycopeptides showed high affinity to αvβ3 (11-55 nM), αvβ 5 (6-14 nM), and to αvβ3-positive U87MG cells (90-395 nM). 18F-labeling of the various carbohydrate precursors (1a-f) using cryptate-assisted reaction conditions (CH3CN, 85 C, 10 min) gave 18F-labeled glycosyl azides in radiochemical yields (RCYs) of up to 84% ([18F]2b). The deacetylation and subsequent click reaction with the alkyne-bearing cyclic RGD peptide proceeded in one-pot reactions with RCYs as high as 81% in 15-20 min at 60 C, using a minimal amount of peptide precursor (100 nmol). Optimization of the radiosynthesis strategy gave a decay-uncorrected RCY of 16-24% after 70-75 min (based on [18F]fluoride). Due to their high-yield radiosyntheses, the glycopeptides [18F]6Glc-RGD and [18F]Mlt-RGD were chosen for comparative biodistribution studies and dynamic small-animal PET imaging using U87MG tumor-bearing nude mice. [18F]6Glc-RGD and [ 18F]Mlt-RGD showed significantly decreased liver and kidney uptake by PET relative to the 2-[18F]fluoroglucosyl analog [ 18F]2Glc-RGD, and showed specific tumor uptake in vivo. Notably, [18F]Mlt-RGD revealed uptake and retention in the U87MG tumor comparable to that of [18F]Galacto-RGD. Both [18F]6Glc-RGD and [18F]Mlt-RGD were obtained by a reliable and easy click chemistry-based procedure, much more rapidly than was [18F]Galacto- RGD. Due to its favorable biodistribution and tissue clearance in vivo, [ 18F]Mlt-RGD represents a viable alternative radiotracer for imaging integrin expression in solid tumors by PET.
1,6-Anhydro-1-thio-β-D-glucopyranose (thiolevoglucosan) and the corresponding sulfoxides and sulfone
Budesinsky, Milos,Polakova, Jana,Hamernikova, Michaela,Cisarova, Ivana,Trnka, Tomas,Cerny, Miloslav
, p. 311 - 336 (2007/10/03)
Starting 1,2,3,4-tetra-O-acetyl-6-O-tosyl-β-D-glucopyranose (3) was converted into 2,3,4-tri-O-acetyl-1-thio-6-O-tosyl-β-D-glucopyranose (6) via intermediate glycosyl bromide 4 and S-thiouronium salt 5. Treatment of compound 6 with sodium methoxide gave 1,6-anhydro-1-thio-β-D-glucopyranose (thiolevoglucosan 2a). The isomeric sulfoxides 7 and 8 were prepared by selective oxidation of thiolevoglucosan 2a with hydrogen peroxide or 3-chloroperoxybenzoic acid. The structure of new compounds was confirmed by 1H and 13C NMR spectroscopy or by X-ray analysis; magnetic anisotropy of the sulfinyl and sulfonyl group has been discussed.
Synthesis of sulfur-linked analogues of nigerose, laminarabiose, laminaratriose, gentiobiose, gentiotriose, and laminaran trisaccharide Y
Contour-Galcera, Marie-Odile,Guillot, Jean-Michel,Ortiz-Mellet, Carmen,Pflieger-Carrara, Francoise,Defaye, Jacques,Gelas, Jacques
, p. 99 - 118 (2007/10/03)
Sulfur-linked analogues of 3-O-α-D-glucopyranosyl-D-glucose (nigerose), 3-O-β-D-glucopyranosyl-D-glucose (laminarabiose), 6-O-β-D-glucopyranosyl-D-glucose (gentiobiose), O-β-D-glucopyranosyl-(1 → 3)-O-β-D-glucopyranosyl-(1 → 3)-D-glucose (laminaratriose), O-β-D-glucopyranosyl-(1 → 6)-O-β-D-glucopyranosyl-(1 → 6)-D-glucose (gentiotriose) and 3,6-di-O-β-D-glucopyranosyl-D-glucose (laminaran trisaccharide Y), namely, respectively, 3-thionigerose (6), 3-thiolaminarabiose (II), 6-thiogentiobiose (21), 3(I),3(II)-dithiolaminaratriose (16), 6(I),6(ii)-dithiogentiotriose (29) and 3(I),6(I)-dithiolaminaran trisaccharide Y (37) have been conveniently prepared by S(N)2 reactions of the corresponding anomer of D-glucopyranose 1-thiolate with suitably activated monosaccharide derivatives in N,N-dimethylformamide (for 6 and 21) or in tetrahydrofuran in the presence of a crown ether (for 11). A sequence involving the reaction of non-anomeric thiolates with 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide was alternatively used for the preparation of 11 and 21 but proved less satisfactory. The preparation of thiotrisaccharides 16, 29, and 37 involved a mixed approach.
