Square-planar imido complexes of cobalt: synthesis, reactivity and computational study.

Treatment of [Co(N2)(tBuPNP)] (tBuPNP = anion of 2,5-bis(di-tert-butylphosphinomethyl)pyrrole) with one equivalent of an aryl azide generates the four-coordinate imido complexes [Co(NAr)(tBuPNP)] (Ar = mesityl, phenyl, or 4-tBu-phenyl). X-ray crystallographic analysis of the compounds shows an unusual square-planar geometry about cobalt with nearly linear imido units. In the presence of the hydrogen atom donor, TEMPOH, [Co(NPh)(tBuPNP)] undergoes addition of the H atom to the imido nitrogen to generate the corresponding amido complex, [Co(NHPh)(tBuPNP)], whose structure and composition were verified by independent synthesis. Despite the observation of H atom transfer reactivity with TEMPOH, the imido complexes do not show catalytic activity for C-H amination or aziridination for several substrates examined. In the case of [Co(NPh)(tBuPNP)], addition of excess azide produced the tetrazido complex, [Co(N4Ph2)(tBuPNP)], whose bond metrics were most consistent with an anionic Ph2N4 ligand. Density Functional Theory (DFT) investigations of the imido and tetrazido species suggest that they adopt a ground state best described as possessing a low-spin cobalt(II) ion ferromagnetically coupled to an iminyl radical.

Virtual 3D planning in Maxillofacial surgery : The journey so far and the way ahead.

The capacity of additive manufacturing and three-dimensional (3D) printing to quickly construct intricate structures and accurate geometries sets them apart from traditional production techniques. The fourth industrial revolution and the digitalization of production were fueled by the emergence of 3D printing, which was made possible by the increasing demand for goods with various designs, functions, and materials. The global influence of 3D printing on healthcare has resulted in the replacement of generic implanted medical devices with patient-customized implants. In the field of oral and maxillofacial surgery, where surgeons use precision medicine daily, this revolution has had a huge influence. Treatments enhanced by 3D technology include orthognathic surgery, complete joint replacement therapy, and trauma. Surgical teams now engage in the 3D design and production of devices at point-of-care treatment facilities with internal infrastructure thanks to the growing and broad adoption of 3D technology in clinical settings. The way doctors approach treatment planning and clinical results are affected greatly by 3D technology. While outlining significant clinical applications, the article presents our viewpoint on the use of 3D-based technology in the field of oral and maxillofacial surgery and the road ahead with the advent of Four-dimensional (4D) printing.

The Neurostimulation Appropriateness Consensus Committee (NACC)®: Recommendations for Spinal Cord Stimulation Long-Term Outcome Optimization and Salvage Therapy.

INTRODUCTION: The International Neuromodulation Society (INS) has recognized a need to establish best practices for optimizing implantable devices and salvage when ideal outcomes are not realized. This group has established the Neurostimulation Appropriateness Consensus Committee (NACC)® to offer guidance on matters needed for both our members and the broader community of those affected by neuromodulation devices. MATERIALS AND METHODS: The executive committee of the INS nominated faculty for this NACC® publication on the basis of expertise, publications, and career work on the issue. In addition, the faculty was chosen in consideration of diversity and inclusion of different career paths and demographic categories. Once chosen, the faculty was asked to grade current evidence and along with expert opinion create consensus recommendations to address the lapses in information on this topic. RESULTS: The NACC® group established informative and authoritative recommendations on the salvage and optimization of care for those with indwelling devices. The recommendations are based on evidence and expert opinion and will be expected to evolve as new data are generated for each topic. CONCLUSIONS: NACC® guidance should be considered for any patient with less-than-optimal outcomes with a stimulation device implanted for treating chronic pain. Consideration should be given to these consensus points to salvage a potentially failed device before explant.

Retromandibular Approach and its Different Variations in the Management of Fracture Condyle: Surgical Experience.

The management of condylar fractures is a controversial topic in maxillofacial surgery. Surgical treatment is the preferred treatment choice nowadays and the article aims to describe different variations of the retromandibular approach with their surgical outcome based on experience. A total of 15 cases were managed with the retromandibular approach and its different variations. We advocate retromandibular approach for the management of condyle fractures, and among which retromandibular retroparotid and retromandibular anteroparotid provide best accessiblity with less bleeding and minimal risk of injury to the facial nerve.