Thermoplastic polyurethanes containing 12-hydroxymethylabietanol

Thermoplastic polyurethane elastomers incorporating the resin acid-derived 12-hydroxymethylabietanol (12-HMA) were prepared, and some physical properties are reported. A polyester macroglycol was prepared from 12-HMA, adipic acid, and ethylene glycol. This macroglycol then was combined with either poly(tetramethylene adipate) glycol (PTAd) or poly(ethylene adipate) glycol (PEAd) and 1,4-butanediol to give a glycol blend of 300 average hydroxyl equivalent weight (OHE). The glycol mixture then was combined with diphenylmethane 4,4′-diisocyanate (MDI) (NCO/OH = 1.0) to give urethane polymers soluble in tetrahydrofuran. Polymers were prepared with 0, 5, 10, 15, 20, and 25%, by weight, 12-HMA with PTAd as the other macroglycol and with 0, 10, 15, and 20% 12-HMA with PEAd as the other macroglycol. At 15% 12-HMA, polymers were made from glycol mixtures having 275 and 350 average OHE to demonstrate the effect of changing the hard-segment concentration. The presence of 12-HMA is shown to have its maximum effect on tensile properties at 15–20% in the PTAd series and at 10% in the PEAd series. In general, this effect is an increase in tensile strength and modulus and a decrease in elongation when compared with a similar polymer without the 12-HMA.     

Phosphines: Nucleophilic organic catalysts for the controlled ring‐opening polymerization of lactides

A new metal‐free synthetic approach to the controlled ring‐opening polymerization (ROP) of lactide with nucleophilic phosphines as transesterification catalysts is described. P(Bu)₃, PhPMe₂, Ph₂PMe, PPh₃, and related phosphines are commercially available, inexpensive catalysts that generate narrowly dispersed polylactides with predictable molecular weights. These organic catalysts must be used in combination with an initiator, such as an alcohol, to generate an alcoholate ester α‐end group upon ROP. A likely polymerization pathway is through a monomer‐activated mechanism, with minimal active species, facilitating narrow molecular weight distributions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 844–851, 2002; DOI 10.1002/pola.10168     

Imide-aryl ether ketone block copolymers

Imide-aryl ether ketone block copolymers were prepared and their morphology and thermal and mechanical properties investigated. Two aryl ether ketone blocks were incorporated; the first was an amorphous block derived from bisphenol–A and the second block was a semi-crystalline poly(aryl ether ether ketone) prepared from a soluble and amorphous ketimine precursor. Bis(amino) aryl ether ketone and aryl ether ketimine oligomers were prepared via a nucleophilic aromaic substitution reaction with molecular weights ranging from 6,000 to 12,000 g/mol. The oligomers were co-reacted with 4,4′-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in N-methyl–2-pyrrolidone (NMP) in the presence of N-methylmorpholine. The copolymer compositions, determined by H-NMR, of the resulting amic ester based copolymers ranged from 8 to 50 wt % aryl ether ketone or ketimine content. Prior to imide formation, the ketimine moiety of the aryl ether ketimine block was hydrolyzed (p-toluene sulfonic acid) to the ketone form producing the aryl ether ether ketone block. Compositions of this block were maintained low to retain solubility. Solutions of the copolymers were cast and cured to effect imidization, producing clear films with high moduli (ca. 2200 MPa) and elongations (33–100%). The copolymers displayed good thermal stability with decomposition temperatures in excess of 450°C. Multiphase morphologies were observed irrespective of the co-block type, block length or composition. © 1992 John Wiley & Sons, Inc.     

Total synthesis of ningalin B utilizing a heterocyclic azadiene Diels-Alder reaction and discovery of a new class of potent multidrug resistant (MDR) reversal agents

A concise, efficient approach to the total synthesis of ningalin B (1) based on a heterocyclic azadiene Diels-Alder strategy (1,2,4,5-tetrazine-->1,2,-diazine-->pyrrole) ideally suited for construction of the densely functionalized pyrrole core found in the natural product is detailed. Examination of the natural product and a number of synthetic intermediates revealed that while lacking inherent cytotoxic activity, many reverse the multidrug-resistant (MDR) phenotype, resensitizing a human colon cancer cell line (HCT116/VM46) to vinblastine and doxorubicin at lower doses than the prototypical agent verapamil.     

MRI findings of primary small-cell carcinoma of kidney

We report the MRI findings of primary small-cell carcinoma of the kidney (PSCCK) in a 59-year-old female. This tumor appeared as a 16-cm mass that arose from the right kidney. This lesion had diminished signal on T1-weighted images and heterogeneous mixed signal on T2-weighted images. The tumor primarily involved the renal medulla with persistent thin renal cortex. Despite the tumors' large size, no substantial central necrosis was present. The predominant medullary location and the lack of central necrosis in this large tumor were features unusual for renal cell carcinoma and should raise the suspicion of another malignancy, the differential diagnosis of which should contain extrapulmonary small-cell carcinoma of the kidney.