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1.
J Am Chem Soc ; 145(1): 697-705, 2023 01 11.
Article in English | MEDLINE | ID: mdl-36573894

ABSTRACT

Semi-aromatic polyamides (SAPs) synthesized from petrochemical diacids and diamines are high-performance polymers that often derive their desirable properties from a high degree of crystallinity. Attempts to develop partially renewable SAPs by replacing petrochemical diacids with biobased furan-2,5-dicarboxylic acid (FDCA) have resulted in amorphous materials or polymers with low melting temperatures. Herein, we report the development of poly(5-aminomethyl-2-furoic acid) (PAMF), a semicrystalline SAP synthesized by the polycondensation of CO2 and lignocellulose-derived monomer 5-aminomethyl-2-furoic acid (AMF). PAMF has glass-transition and melting temperatures comparable to that of commercial materials and higher than that of any previous furanic SAP. Additionally, PAMF can be copolymerized with conventional nylon 6 and is chemically recyclable. Molecular dynamics (MD) simulations suggest that differences in intramolecular hydrogen bonding explain why PAMF is semicrystalline but many FDCA-based SAPs are not.


Subject(s)
Dicarboxylic Acids , Nylons , Nylons/chemistry , Dicarboxylic Acids/chemistry , Temperature
2.
Bone Joint J ; 102-B(8): 1048-1055, 2020 Aug.
Article in English | MEDLINE | ID: mdl-32731828

ABSTRACT

AIMS: The Fassier Duval (FD) rod is a third-generation telescopic implant for children with osteogenesis imperfecta (OI). Threaded fixation enables proximal insertion without opening the knee or ankle joint. We have reviewed our combined two-centre experience with this implant. METHODS: In total, 34 children with a mean age of five years (1 to 14) with severe OI have undergone rodding of 72 lower limb long bones (27 tibial, 45 femoral) for recurrent fractures with progressive deformity despite optimized bone health and bisphosphonate therapy. Data were collected prospectively, with 1.5 to 11 years follow-up. RESULTS: A total of 24 patients (33%) required exchange of implants (14 femora and ten tibiae) including 11 rods bending with refracture. Four (5%) required reoperation with implant retention. Loss of proximal fixation in the femur and distal fixation in the tibia were common. Four patients developed coxa vara requiring surgical correction. In total, 13 patients experienced further fractures without rod bending; eight required implant revision. There was one deep infection. The five-year survival rate, with rod revision as the endpoint, was 63% (95% confidence interval (CI) 44% to 77%) for femoral rods, with a mean age at implantation of 4.8 years (1.3 to 14.8), and 64% (95% CI 36% to 82%) for tibial rods, with a mean age at implantation of 5.2 years (2.0 to 13.8). CONCLUSION: FD rods are easier to implant but do not improve on the revision rates reported for second generation T-piece rods. Proximal femoral fixation is problematic in younger children with a partially ossified greater trochanter. Distal tibial fixation typically fails after two years. Future generation implants should address proximal femoral and distal tibial fixation to avoid the majority of complications in this series. Cite this article: Bone Joint J 2020;102-B(8):1048-1055.


Subject(s)
Femoral Fractures/surgery , Fracture Fixation, Intramedullary/methods , Fracture Healing/physiology , Osteogenesis Imperfecta/surgery , Reoperation/methods , Tibial Fractures/surgery , Adolescent , Age Factors , Child , Child, Preschool , Databases, Factual , Female , Femoral Fractures/diagnostic imaging , Femoral Fractures/etiology , Follow-Up Studies , Fracture Fixation, Intramedullary/adverse effects , Fracture Fixation, Intramedullary/instrumentation , Humans , Internal Fixators , Male , Osteogenesis Imperfecta/complications , Osteogenesis Imperfecta/diagnostic imaging , Prospective Studies , Recurrence , Reoperation/statistics & numerical data , Risk Assessment , Severity of Illness Index , Sex Factors , Tibial Fractures/diagnostic imaging , Tibial Fractures/etiology , Time Factors
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