Foundation garments – For lower torso including thighs – e.g. – corset – girdles – With stiffening strips or stays
Patent
1995-08-28
1998-09-15
Shah, Mukund J.
Foundation garments
For lower torso including thighs, e.g., corset, girdles
With stiffening strips or stays
540 4, 540472, 540145, 536 231, C07D48722
Patent
active
058080597
DESCRIPTION:
BRIEF SUMMARY
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of macrocyclic expanded porphyrins and, more particularly, concerns novel sapphyrin derivatives, conjugates and polymers thereof and polymer-supported expanded porphyrins. Sapphyrin monomer derivatives of the invention include sapphyrin-sugar derivatives and other water soluble sapphyrins; sapphyrin-metal chelating derivatives; and sapphyrin nucleobase conjugates. Also disclosed are oligosapphyrins and polysapphyrins, including sapphyrin nucleobase oligomers and polymers; and silica gel, glass, resin and other polymer-supported expanded porphyrins such as rubyrin- and sapphyrin-containing chromatographic and electroploretic supports.
2. Description of the Related Art
Expanded porphyrins are large pyrrole-containing macrocyclic analogues of the porphyrins (e.g. porphine, structure I, FIG. 1). A number of expanded porphyrin systems are now known. However, only a few fully conjugated examples have been reported that contain more than four pyrrolic subunits, namely the smaragdyrins, sapphyrins, pentaphyrins, hexaphyrins, and superphthalocyanines.sup.1 (Sessler & Burrel, 1991). Sapphyrin, in its generalized substituent-free form, is represented by structure II (FIG. 1). Structure III (FIG. 1) provides a generalized representation of .beta.-substituted sapphyrins.
Sapphyrin, first discovered serendipitously by Woodward.sup.2 is one of the more intriguing products to emerge from initial studies directed towards the synthesis of Vitamin B.sub.12. .sup.2,3 It is a 22 pi-electron pentapyrrolic macrocycle which exhibits an intense Soret-like band at about 450 nm (CHCl.sub.3) along with weaker Q-type transitions in the 620 to 690 nm region. These optical properties, along with the presence of a large central cavity which serves for metal binding, renders sapphyrin useful for certain biomedical applications, including photodynamic therapy (PDT) and magnetic resonance imaging enhancement (MRI).
In addition to the above, certain expanded porphyrins, including especially those of the sapphyrin series, have been found-to act as halide anion chelating agents in both solution and the solid state.sup.4. This finding, along with an appreciation, that the diprotonated form of 3,8,12,13,17,22-hexaethyl-2,7,18,23-tetramethylsapphyrin acts as an efficient carrier for the through-dichloromethane-membrane transport of nucleotide monophosphates, such as e.g. guanosine-5' monophosphate, and related entities at acidic pH.sup.5, led the inventors to consider that the basic sapphyrin structure and related compounds such as the rubyrins, if suitably modified, could be used to bind, recognize, and transport phosphorylated entities at or near neutral pH. The inventors also envisioned that this same approach could be used for the improved chromatographic and electrophoretic separation of anionic species.
Unfortunately, all sapphyrins known at the time of this invention were known both to be essentially insoluble in water and also known to be ineffective as through membrane carriers for phosphate monoesters including those specifically that define the class of compounds known as nucleotides and nucleotide analogues.sup.5. These two deficiencies limited the potential utility of sapphyrins for any applications associated with their use at or near neutral pH and, more generally, any conditions involving partial or complete association with an aqueous environment.
In addition, the sapphyrins known prior to the present invention were all of such simple character in terms of peripheral substituents, such that only hydrogen, alkyl and carboxyl alkyl were known.sup.1,6, that said systems, even if they were to demonstrate binding to nucleotides or nucleotides, would be expected to do so without any degree of specificity with regards the nature of the nucleic acid base ("nucleobase") attached to the phosphate core. Thus, at the time of this invention, it was considered that the development of a sapphyrin derived species capable of binding, recognizing, and
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Furuta Hiroyuki
Iverson Brent L.
Kral Vladimir
Sessler Jonathan L.
Shreder Kevin
Board of Regents University of Texas System
Shah Mukund J.
Sripada Pavanaram K.
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