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Herein, a facile strategy is illustrated to develop pyrolysis-free out-of-plane coordinated single atomic sites-based M-POP via a one-pot Friedel Craft acylation route followed by a post-synthetic metalation. The optimized geometry of the Co@BiPy-POP clearly reveals the presence of out-of-plane Co-single atomic sites in the porous backbone. This novel photopolymer Co@BiPy-POP shows extensive π-conjugations followed by impressive light harvesting ability and is utilized for photochemical CO2 fixation to value-added chemicals. A remarkable conversion of styrene epoxide (STE) to styrene carbonate (STC) (≈98%) is obtained under optimized photocatalytic conditions in the existence of promoter tert-butyl ammonium bromide (TBAB). Synchrotron-based X-ray adsorption spectroscopy (XAS) analysis reveals the single atom coordination sites along with the metal (Co) oxidation number of +2.16 in the porous network. Moreover, in situ diffuse reflectance spectroscopy (DRIFTS) and electron paramagnetic resonance (EPR) investigations provide valuable information on the evolution of key reaction intermediates. Comprehensivecomputational analysis also helps to understand the overall mechanistic pathway along with the interaction between the photocatalyst and reactants. Overall, this study presents a new concept of fabricating porous photopolymers based on a pyrolysis-free out-of-plane-coordination strategy and further explores the role of single atomic sites in carrying out feasible CO2 fixation reactions.
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A concise approach for the synthesis of substituted 1,2-dihydroisoquinolines via double nucleophilic addition of primary arylamines to ortho-alkynyl donor-acceptor cyclopropanes (o-ADACs) in the presence of a catalytic Ni(ClO4)2·6H2O and CuI/AgOTf system has been developed. Further applying this protocol, some of the derived malonates were converted into the corresponding monoesters under Krapcho decarboxylation reaction conditions. Thereafter, these esters were transformed into the respective acids and alcohols. In addition, multifunctionalized 4-(2,2,2-trifluoroacetyl) 1,2-dihydroisoquinolines were also obtained with excess TFAA.
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BACKGROUND: Traditional anteromedial incision for pilon fractures would further increase the damage to the subcutaneous tissues anterior and medial to tibia. In this study, we retrospectively evaluated the method and the outcomes of lateral approach for surgical treatment of Gustilo type-I and type-II open pilon fractures with medial soft tissue injuries. METHODS: From May 2014 to September 2017, 35 patients with Gustilo type-I and type-II open pilon fractures were treated with standard protocol using a lateral approach. The initial wound debridement and application of a spanning external fixator or traction of calcaneal tubercle were performed within 24 h and a definitive fixation was performed when the wound was healed. The mean time from primary surgery to definite surgery was 11.8 (range: 8-16) days. Postoperative radiographs, complications, bone union, and American Orthopedic Foot and Ankle Society (AOFAS) ankle/hind foot score were recorded. RESULTS: The mean follow-up period was 17 months (range: 13-23). The average time to bone union was 22 weeks (range: 18-25). In 35 patients, 2 patients had a superficial wound infection and another 1 patient showed limitation of ankle joint motion. No cases of deep infection, skin necrosis, and symptomatic implant reported. The mean AOFAS score was 89.8 (range: 84-95). On final outcome, 25 patients come under excellent and 10 patients had good result. CONCLUSION: From the results of this study, we can conclude that the lateral approach to treat Gustilo type-I and type-II open pilon fractures was a safe option with a low complication rate. On the other hand, it provides sufficient exposure to restore anatomic articulation, which is worthy of clinical recommendation.
Asunto(s)
Fijadores Externos , Fracturas Abiertas/cirugía , Reducción Abierta/métodos , Fracturas de la Tibia/cirugía , Adulto , Femenino , Estudios de Seguimiento , Fijación Interna de Fracturas/métodos , Fracturas Abiertas/diagnóstico , Humanos , Masculino , Persona de Mediana Edad , Radiografía , Estudios Retrospectivos , Fracturas de la Tibia/diagnóstico , Factores de Tiempo , Resultado del TratamientoRESUMEN
PURPOSE: Greater tuberosity fractures (GTFs) account for 17 to 21% of proximal humerus fractures, most of these fractures are treated conservatively, but treatment for displaced fractures is still controversial. The aim of this study is to compare intra-operative clinical conditions and post-operative outcomes when displaced GTFs are treated with either proximal humeral internal locking system (PHILOS) or mini locking plate with trans-osseous sutures. METHODS: This is a retrospective study conducted in Shanghai Tenth People's Hospital. A total of 60 patients (22 males and 38 females) with displaced humeral GTF between May 2013 and March 2017 were included, of whom 43 underwent PHILOS implant treatment and 17 underwent titanium mini plate implant with trans-osseous suture treatment. Intra-operative (incision size, intra-operative blood loss, operative duration) and postoperative (Constant-Murley score (CMS) and implant cost) variables were recorded for the comparison. RESULTS: Mini locking plate with trans-osseous sutures shows better results. Operative duration (PHILOS mean 77.0 minutes vs mean 63.7 minutes, p value < 0.05), blood loss during surgery (PHILOS mean 111.5 vs 66.5 ml, p value < 0.05), incision size (PHILOS mean 7.2 vs 4.6 cm, p value < 0.05), CMS (PHILOS mean 81.0 vs 87.3, p value < 0.05), and implant costs (PHILOS mean 26,192.6 renminbi (RMB) vs mean 21,358.8 RMB, p value < 0.05). On the other hand, 9.30% of impingement in the PHILOS group was observed to have no complications compared to the mini locking plate group. CONCLUSIONS: Mini locking plate with trans-osseous sutures shows better efficacy in reducing the incision size, operative duration, intraoperative blood loss, and implant cost and in improving CMS. No complication was found with its use. Our data can provide rationale and inform sample- size calculations for such studies. Larger, control studies are needed for better understanding.