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2.
J Am Chem Soc ; 138(2): 696-702, 2016 Jan 20.
Article in English | MEDLINE | ID: mdl-26694767

ABSTRACT

Methods for the practical, intermolecular functionalization of aliphatic C-H bonds remain a paramount goal of organic synthesis. Free radical alkane chlorination is an important industrial process for the production of small molecule chloroalkanes from simple hydrocarbons, yet applications to fine chemical synthesis are rare. Herein, we report a site-selective chlorination of aliphatic C-H bonds using readily available N-chloroamides and apply this transformation to a synthesis of chlorolissoclimide, a potently cytotoxic labdane diterpenoid. These reactions deliver alkyl chlorides in useful chemical yields with substrate as the limiting reagent. Notably, this approach tolerates substrate unsaturation that normally poses major challenges in chemoselective, aliphatic C-H functionalization. The sterically and electronically dictated site selectivities of the C-H chlorination are among the most selective alkane functionalizations known, providing a unique tool for chemical synthesis. The short synthesis of chlorolissoclimide features a high yielding, gram-scale radical C-H chlorination of sclareolide and a three-step/two-pot process for the introduction of the ß-hydroxysuccinimide that is salient to all the lissoclimides and haterumaimides. Preliminary assays indicate that chlorolissoclimide and analogues are moderately active against aggressive melanoma and prostate cancer cell lines.


Subject(s)
Chlorine/chemistry , Diterpenes/chemistry , Succinimides/chemistry , Carbon/chemistry , Hydrogen/chemistry
3.
Neurospine ; 20(4): 1112-1123, 2023 Dec.
Article in English | MEDLINE | ID: mdl-38171281

ABSTRACT

Osteoporotic vertebral fractures (OVFs) are a significant health concern linked to increased morbidity, mortality, and diminished quality of life. Traditional OVF risk assessment tools like bone mineral density (BMD) only capture a fraction of the risk profile. Artificial intelligence, specifically computer vision, has revolutionized other fields of medicine through analysis of videos, histopathology slides and radiological scans. In this review, we provide an overview of computer vision algorithms and current computer vision models used in predicting OVF risk. We highlight the clinical applications, future directions and limitations of computer vision in OVF risk prediction.

4.
J Neurosurg Spine ; 38(4): 417-424, 2023 04 01.
Article in English | MEDLINE | ID: mdl-36681945

ABSTRACT

OBJECTIVE: Knowledge of the manufacturer of the previously implanted pedicle screw systems prior to revision spinal surgery may facilitate faster and safer surgery. Often, this information is unavailable because patients are referred by other centers or because of missing information in the patients' records. Recently, machine learning and computer vision have gained wider use in clinical applications. The authors propose a computer vision approach to classify posterior thoracolumbar instrumentation systems. METHODS: Lateral and anteroposterior (AP) radiographs obtained in patients undergoing posterior thoracolumbar pedicle screw implantation for any indication at the authors' institution (2015-2021) were obtained. DICOM images were cropped to include both the pedicle screws and rods. Images were labeled with the manufacturer according to the operative record. Multiple feature detection methods were tested (SURF, MESR, and Minimum Eigenvalues); however, the bag-of-visual-words technique with KAZE feature detection was ultimately used to construct a computer vision support vector machine (SVM) classifier for lateral, AP, and fused lateral and AP images. Accuracy was tested using an 80%/20% training/testing pseudorandom split over 100 iterations. Using a reader study, the authors compared the model performance with the current practice of surgeons and manufacturer representatives identifying spinal hardware by visual inspection. RESULTS: Among the three image types, 355 lateral, 379 AP, and 338 fused radiographs were obtained. The five pedicle screw implants included in this study were the Globus Medical Creo, Medtronic Solera, NuVasive Reline, Stryker Xia, and DePuy Expedium. When the two most common manufacturers used at the authors' institution were binarily classified (Globus Medical and Medtronic), the accuracy rates for lateral, AP, and fused images were 93.15% ± 4.06%, 88.98% ± 4.08%, and 91.08% ± 5.30%, respectively. Classification accuracy decreased by approximately 10% with each additional manufacturer added. The multilevel five-way classification accuracy rates for lateral, AP, and fused images were 64.27% ± 5.13%, 60.95% ± 5.52%, and 65.90% ± 5.14%, respectively. In the reader study, the model performed five-way classification on 100 test images with 79% accuracy in 14 seconds, compared with an average of 44% accuracy in 20 minutes for two surgeons and three manufacturer representatives. CONCLUSIONS: The authors developed a KAZE feature detector with an SVM classifier that successfully identified posterior thoracolumbar hardware at five-level classification. The model performed more accurately and efficiently than the method currently used in clinical practice. The relative computational simplicity of this model, from input to output, may facilitate future prospective studies in the clinical setting.


Subject(s)
Pedicle Screws , Spinal Fusion , Surgery, Computer-Assisted , Humans , Lumbar Vertebrae/diagnostic imaging , Lumbar Vertebrae/surgery , Prospective Studies , Surgery, Computer-Assisted/methods , Spinal Fusion/methods , Thoracic Vertebrae/diagnostic imaging , Thoracic Vertebrae/surgery
5.
World Neurosurg ; 144: e389-e394, 2020 12.
Article in English | MEDLINE | ID: mdl-32890844

ABSTRACT

BACKGROUND: Sonolucent cranioplasty implants were recently introduced into clinical practice and tested for use with transcranioplasty ultrasound (TCUS). In situations where dural substitutes (DSs) are needed during closure, such as in extracranial-intracranial bypass, it is unclear if the DS influences the imaging quality of TCUS. The aim of this study was to assess the influence of DSs on imaging quality during TCUS assessment with sonolucent cranioplasty. METHODS: A tofu vascular brain model was constructed with a ClearFit implant in between 2 layers of tofu. Injection of saline solution through a 6-F Envoy DA XB endovascular catheter (6-F Envoy DA XB) inserted into the deeper tofu layer mimicked an intracranial vessel. TCUS image quality, including Doppler, with 4 different DSs (DuraGen, Durepair, DuraMatrix-Onlay, DuraMatrix Suturable) placed under the cranioplasty was compared against a control by 2 examiners. A literature search of MEDLINE and EMBASE was conducted to find previous reports of acoustic properties of DSs. RESULTS: TCUS assessment including Doppler was feasible with the model in longitudinal and axial planes, and the pulsatile particle injection was visualized in real time. DuraGen and Durepair showed Doppler quality and picture detail comparable to the control, while the DuraMatrix-Onlay and DuraMatrix Suturable were inferior to the control. The literature search yielded only 1 previous report on acoustic properties of DSs. CONCLUSIONS: DSs interfere differentially with imaging quality during TCUS assessment. However, these results are based on a benchtop model and need to be further assessed in the clinical setting.


Subject(s)
Brain/diagnostic imaging , Dura Mater , Prostheses and Implants , Ultrasonography/methods , Craniotomy , Humans , Models, Anatomic , Skull/surgery
6.
World Neurosurg ; 144: e277-e284, 2020 12.
Article in English | MEDLINE | ID: mdl-32827747

ABSTRACT

OBJECTIVE: We sought to analyze the safety and feasibility of elective sonolucent cranioplasty in the setting of extracranial-to-intracranial (EC-IC) bypass surgery to monitor bypass patency using ultrasound. METHODS: Patients who underwent direct EC-IC bypass surgery agreed to sonolucent cranioplasty at the time of surgery and received a sonolucent polymethyl methacrylate (PMMA) implant. Besides monitoring clinical outcome, all patients received transcranioplasty ultrasound (TCUS) on postoperative day 1 and at last follow-up. In addition, bypass patency was confirmed using catheter angiogram and fit of implant using computed tomography. Patient-rated outcome was assessed through phone questionnaire. RESULTS: EC-IC bypass surgery with PMMA cranioplasty was successful in all 7 patients with patent bypasses on postoperative angiogram. Direct TCUS was feasible in all patients, and bypass patency was monitored. There were no complications such as postoperative hemorrhagic/ischemic complications related to the bypass procedure in this patient population, as well as no complications related to the PMMA implant. Postoperative computed tomography showed favorable cosmetic results of the PMMA implant in both the pterional area for superficial temporal artery-middle cerebral artery bypasses and parietooccipital area for occipital artery-middle cerebral artery bypasses as confirmed by high-rated overall patient satisfaction with favorable cosmetic, pain, and sensory patient-rated outcomes. CONCLUSIONS: In this study we were able to show that this novel technique is safe, allows for patency assessment of the EC-IC bypass using bedside TCUS technique, and is cosmetically satisfying for patients.


Subject(s)
Cerebral Revascularization , Craniotomy/methods , Postoperative Complications/diagnostic imaging , Prostheses and Implants , Ultrasonography/methods , Adult , Cerebral Revascularization/adverse effects , Cerebral Revascularization/methods , Feasibility Studies , Female , Humans , Male , Middle Aged , Patient Reported Outcome Measures , Patient Satisfaction , Polymethyl Methacrylate , Postoperative Complications/etiology
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