ROMP-Facilitated Methodologies and Automated Library Development of Thiadiazepin-1,1-dioxide-4-ones

The use of ring-opening metathesis polymerization (ROMP) for polymer-assisted solution phase (PASP) synthesis is described herein. Multiple ROMP-based strategies will be discussed in the scope of this dissertation. These include the development and application of a multifaceted oligomeric phosphate as a facilitated leaving group in both SN2 and SN2´ processes, as well as an in-situ generated sequestration reagent. We also investigate the use of ROMP in an atom-economical approach to generate a diverse collection of cyclic sulfonamides (sultams) whereby a vanishing support protocol imparts a traceless, chromatography-free synthesis of these motifs. Also highlighted within is the ability to use ROMP technology to aid in the development of higher-loading magnetic nanoparticles for the purpose of supported catalysis. These cobalt-based ROMPgel nanoparticles were subsequently doped with Pd and demonstrated for use in several Suzuki-Miyaura coupling reactions. The nanoparticles were conveniently reclaimed via external magnetic field and recycled for later use. Lastly, we present the design, validation, and completion of a 225-member library of thiadiazepin-1,1-dioxide-4-ones using both solution- and polymer-assisted solution phase protocols. The library was validated and conducted on an automated parallel synthesis platform in which a facile, two-step diversity-rendering sequence was performed

Children with Disabilities Attending Montessori Programs in the United States

Early childhood education plays a critical role in establishing positive social-emotional behaviors and promoting the development of skills needed to succeed in elementary school. Although inclusion of children with disabilities (CWD) in early childhood classrooms is increasing throughout the world, numerous social, logistical, and political factors continue to present challenges to full inclusion. The Montessori educational approach, established at the beginning of the 20th century and now applied widely throughout Europe and the United States, may present a highly suitable learning context for CWD, particularly given its historical basis in efforts to meet the needs of underprivileged and cognitively delayed children. On a theoretical level, the inclusion of CWD should be an accepted practice for Montessori programs yet reports of the number and characteristics of CWD attending Montessori programs are scarce. This paper reports upon the findings of a survey of U.S. Montessori early childhood programs’ current enrollment of CWD. The survey indicated that CWD represent 3.75% of the infant and toddler (0–3 years) population and 8.49% of the preschool/early childhood (3–6 years) population at responding institutions. Additionally, although school directors indicate that their teachers generally feel confident and competent including CWD in their classrooms, they expressed a need for ongoing professional development and additional support from special education experts to further empower the inclusion of CWD in all aspects of Montessori education

Children with Disabilities Attending Montessori Programs in the United States

Early childhood education plays a critical role in establishing positive social-emotional behaviors and promoting the development of skills needed to succeed in elementary school. Although inclusion of children with disabilities (CWD) in early childhood classrooms is increasing throughout the world, numerous social, logistical, and political factors continue to present challenges to full inclusion. The Montessori educational approach, established at the beginning of the 20th century and now applied widely throughout Europe and the United States, may present a highly suitable learning context for CWD, particularly given its historical basis in efforts to meet the needs of underprivileged and cognitively delayed children. On a theoretical level, the inclusion of CWD should be an accepted practice for Montessori programs yet reports of the number and characteristics of CWD attending Montessori programs are scarce. This paper reports upon the findings of a survey of U.S. Montessori early childhood programs’ current enrollment of CWD. The survey indicated that CWD represent 3.75% of the infant and toddler (0–3 years) population and 8.49% of the preschool/early childhood (3–6 years) population at responding institutions. Additionally, although school directors indicate that their teachers generally feel confident and competent including CWD in their classrooms, they expressed a need for ongoing professional development and additional support from special education experts to further empower the inclusion of CWD in all aspects of Montessori education

Promoting Professional Development for Physical Therapists in Early Intervention

Early intervention (EI) service providers are expected to form cohesive teams to build the capacity of a family to promote their child’s development. Given the differences in personnel preparation across disciplines of service providers, the Early Childhood Personnel Center (ECPC) is creating integrated and comprehensive professional development models for those who provide services for young children with disabilities and their families. To help guide this process it is important to identify inter-disciplinary competencies as well as the unique knowledge and skills that each discipline contributes to the development and implementation of effective intervention plans. This paper describes personnel preparation of pediatric physical therapists from entry-level to ongoing professional development. Topics include licensure requirements, specialist certification, and EI competencies. This paper explains the unique knowledge and skills that pediatric physical therapists offer to the team as movement specialists. It also highlights particular challenges to professional development faced by novice and experienced physical therapists who work in natural environments. Finally, recommendations for personnel development including structured mentorship, interdisciplinary and team based learning, and strategies for knowledge translation are suggested

ROMP-derived Oligomeric Phosphates for Application in Facile Benzylation

The development of new ROMP-based oligomeric benzyl phosphates (OBPn) is reported for use as soluble, stable benzylating reagents. These oligomeric reagents are readily synthesized from commercially available materials and conveniently polymerized and purified in a one-pot process, affording bench stable, pure white, free-flowing solids on multi-gram scale. Utilization in benzylation reactions with a variety of nucleophiles is reported

Synthesis of epoxybenzo[d]isothiazole 1,1-dioxides via a reductive-Heck, metathesis-sequestration protocol

An atom-economical purification protocol, using solution phase processing via ring-opening metathesis polymerization (ROMP) has been developed for the synthesis of tricyclic sultams. This chromatography-free method allows for convenient isolation of reductive-Heck products and reclamation of excess starting material via sequestration involving metathesis catalysts and a catalyst-armed Si-surface

The long shadow of accumulating adverse childhood experiences on mental health in the United Arab Emirates:implications for policy and practice

Introduction: This study investigates the cumulative effects of adverse childhood experiences (ACEs) on adult depression, anxiety, and stress in Abu Dhabi, controlling for demographic factors, lifestyle, and known health and mental health diagnoses.Methods: Utilizing a cross-sectional design and self-report measures, the research aims to fill a critical gap in understanding the specific impacts of ACEs in the UAE. Based on a multi-site, cross-sectional community sample of 697 residents of Abu Dhabi.Results: The findings reveal significant variances in current screening values for depression, anxiety, and stress attributable to ACEs after controlling for demographic factors, lifestyle risk factors, and adult diagnoses of health and mental health conditions.Discussion: The results underline the lifelong impact of ACEs and reinforce the importance of early identification and intervention. In particular, the implications for policy and practice in understanding and mitigating ACEs long-term effects on mental health are considered.</p

Immobilization on a Nanomagnetic Co/C Surface Using ROM Polymerization: Generation of a Hybrid Material as Support for a Recyclable Palladium Catalyst

A novel hybrid material is reported as support for a recyclable palladium catalyst via surface immobilization of a ligand onto Co-based magnetic nanoparticles (NPs). A standard “click” reaction is utilized to covalently attach a norbornene tag (Nb-tag) to the surface of the carbon coated cobalt NPs. The hybrid magnetic nanoparticles are produced by initiating polymerization of a mixture containing both Nb-tagged ligand (Nb-tagged PPh 3) and Nb-tagged carbon coated cobalt NPs. In turn, the norbornene units are suitably functionalized to serve as ligands for metal catalysts. A composite material is thus obtained which furnishes a loading that is one order of magnitude higher than the value obtained previously for the synthesis of functionalized Co/C-nanopowders. This allows for its application as a hybrid support with high local catalyst concentrations, as demonstrated for the immobilization of a highly active and recyclable palladium complex for Suzuki-Miyaura cross-coupling reactions. Due to the explicit magnetic moment of the cobalt- NPs, the overall magnetization of this organic/inorganic framework is significantly higher than of polymer coated iron oxide nanoparticles with comparable metal content, hence, its rapid separation from the reaction mixture and recycling via an external magnetic field is not hampered by the functionalized polymer shell

Bicarbonate-based Purge Solution As A Bleeding Reduction Strategy in Patients on Impella Support

Study: The Impella Catheters require a heparin-containing purge solution to maintain proper pump function by reducing the risk of biomaterial deposition in the purge gaps. A bicarbonate-based purge solution (BBPS) has been proposed as an alternative to a heparin-based purge solution. We review performance in patients supported to date with a BBPS (heparin-induced thrombocytopenia patients were excluded from this analysis). Methods: This review includes patients (n=26) supported using sodium bicarbonate (25 mEq/1L of D5W) in the purge from September 2020 to February 2021. These patients were supported with BBPS post-operatively where heparin in the purge was not desired or were transitioned to BBPS because of bleeding issues. Case data were collected from an internal database to develop the clinical narrative and cross-referenced against Impella Controller data logs to assess purge trends and pump function. Results: All pumps were switched to BBPS in the purge if not started with BBPS (Figure 1A). The average time to initiating BBPS was 1.6 days (excluding n=3 outliers where time to switching was \u3e15 days). The average duration of support with BBPS was 5 days and a maximum duration of 22 days (Figure 1B). Figure 1C shows clinical indications for use. Purge pressure and purge flow remained stable while on BBPS (Figure 1D). In conclusion, this preliminary experience suggests the feasibility of using BBPS to maintain purge patency, ensure pump motor reliability, reduce bleeding risk, and simplify anticoagulation management. Use of a BBPS may be a safe and effective alternative to heparin in the purge for patients in which heparin is contraindicated or not feasible. More patient experience and analysis are needed to evaluate how bicarbonate compares to heparin in the purge for all patients