ABSTRACT
We investigated if infants with a Barlow positive hip(s) have natural hip stabilization and can thus avoid Pavlik Harness (PH) treatment. We conducted a chart review for infants who presented within two weeks of life, had a Barlow positive hip, and were deferred treatment. Of the thirty infants, eighteen were treated with PH at 4-6 weeks or 12 weeks due to persistent dysplasia. Twelve infants avoided PH entirely. There were zero cases of PH failure. Parents can be counseled that deferring treatment until at least 4-6 weeks of age might avoid treatment altogether without an increased risk of harness failure.
ABSTRACT
CASE: We describe a patient who was diagnosed with developmental hip dislocation at 21 months of age despite having had normal ultrasonography findings at 5 weeks of age. CONCLUSION: This case report provides evidence that late developmental hip dislocation can occur despite normal clinical and sonographic findings early in life, and that it is difficult to know the cause of developmental hip dislocation when it presents late.
Subject(s)
Hip Dislocation, Congenital/diagnostic imaging , Age of Onset , Female , Hip Dislocation, Congenital/surgery , Humans , Infant , UltrasonographyABSTRACT
This contribution presents a full account of experimental and theoretical/computational investigations into the mechanisms of chain initiation, propagation, and termination of the recently discovered N-heterocyclic carbene (NHC)-mediated organocatalytic conjugate-addition polymerization of acrylic monomers. The current study specifically focuses on three commonly used NHCs of vastly different nucleophilicity, 1,3-di-tert-butylimidazolin-2-ylidene (I(t)Bu), 1,3-dimesitylimidazolin-2-ylidene (IMes), and 1,3,4-triphenyl-4,5-dihydro-1H-1,2,4-triazol-5-ylidene (TPT), and two representative acrylic monomers, the linear methyl methacrylate (MMA) and its cyclic analog, biomass-derived renewable γ-methyl-α-methylene-γ-butyrolactone (MMBL). For MMA, there exhibits an exquisite selectivity of the NHC structure for the three types of reactions it promotes: enamine formation (single-monomer addition) by IMes, dimerization (tail-to-tail) by TPT, and polymerization by I(t)Bu. For MMBL, all three NHCs promote no dimerization but polymerization, with the polymerization activity being highly sensitive to the NHC structure and the solvent polarity. Thus, I(t)Bu is the most active catalyst of the series and converts quantitatively 1000-3000 equiv of MMBL in 1 min or 10,000 equiv in 5 min at room temperature to MMBL-based bioplastics with a narrow range of molecular weights of M(n) = 70-85 kg/mol, regardless of the [MMBL]/[I(t)Bu] ratio employed. The I(t)Bu-catalyzed MMBL polymerization reaches an exceptionally high turnover frequency up to 122 s(-1) and a high initiator efficiency value up to 1600%. Unique chain-termination mechanisms have been revealed, accounting for the production of relative high-molecular-weight linear polymers and the catalytic nature of this NHC-mediated conjugate-addition polymerization. Computational studies have provided mechanistic insights into reactivity and selectivity between two competing pathways for each NHC-monomer zwitterionic adduct, namely enamine formation/dimerization through proton transfer vs polymerization through conjugate addition, and mapped out extensive energy profiles for chain initiation, propagation, and termination steps, thereby satisfactorily explaining the experimental observations.
ABSTRACT
Using palladium-catalyzed decarboxylation, several cascade reactions of allyl and prenyl nitroalkanoates that lead to nitro-containing chemical building blocks are described. A nitronate Michael addition/Tsuji-Trost allylation cascade was developed, leading to functionally dense chemical building blocks. Likewise, a Tsuji-Trost/decarboxylative protonation sequence was developed for the synthesis of orthogonally functionalized 2° nitroalkanes. The latter method provides rapid access to the indolizidine core.
