The direct molybdenum-catalyzed sulfuration of a variety of isonitriles with elemental sulfur or propene sulfide as sulfur donors affords the corresponding isothiocyanates in good yields and under mild reaction conditions. A catalytic cycle is suggested, in which the molybdenum oxo disulfur complex operates as the active sulfur-transferring species. A novel adduct between the isonitrile and the molybdenum complex has been characterized by X-ray analysis and its association constant determined by UV-vis spectroscopy, but this adduct appears not to be involved in the sulfur-transfer process.
The molybdenum oxo complexes 1a and 1b catalyze efficiently the sulfur transfer to a series of alkenes 4 and allenes 6, for which elemental sulfur, phenylthiirane, or methylthiirane have been employed as sulfur sources to afford the corresponding episulfides 5 and 7. The most effective catalytic episulfidation system to date is the combination of the dithiophosphate-ligated oxo complex 1b and phenylthiirane (Ibeta). This metathesis process is efficient enough to convert usually reluctant alkenes (cyclopentene, cycloheptene, Z-cyclooctene, Z-cyclononene, E-cyclodecene, norbornene, and even bicyclopropylidene) to their episulfides in good yields under mild conditions. The direct catalytic sulfuration of allenes (cyclonona-1,2-diene, cyclonona-1,2,5-triene, cyclodeca-1,2-diene, and 2,4-dimethylpenta-2,3-diene) to their labile methylenethiiranes is unprecedented.
A long-term absorbable monofilament suture was developed using poly-4-hydroxybutyrate (P4HB) made from a biosynthetically produced homopolymer of the natural metabolite 4-hydroxybutyrate. The suture, called MonoMax, has prolonged strength retention. At 12 weeks, a size 3-0 MonoMax suture retains approximately 50% of its initial tensile strength in vivo and is substantially degraded in one year with minimal tissue reaction. In contrast, PDS II monofilament suture (Ethicon, Inc., Somerville, NJ) has no residual strength in vivo after 12 weeks. In vivo, the MonoMax suture is hydrolyzed primarily by bulk hydrolysis, and is then degraded via the Krebs cycle. MonoMax is substantially more compliant than other monofilament sutures, and incorporates an element of elasticity. Its tensile modulus of 0.48 GPa is approximately one-third of the value of the PDS II fiber providing an exceptionally flexible and pliable fiber with excellent knot strength and security. These features are further enhanced by the fiber's elasticity, which also improves knot security and may help prevent wound dehiscence. Because of its performance advantages, this suture may find clinical utility in applications where prolonged strength retention, and greater flexibility are required, particularly in procedures like abdominal wall closure where wound dehiscence is still a significant postsurgical complication.
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