30 research outputs found
Hand-Assist Laparoscopic Surgery for the Gynecologic Surgeon
Hand-assisted laparoscopic surgery (HALS) has not been extensively used in gynecologic surgery. This approach may offer a safe, viable alternative for gynecological cases that might otherwise require a large laparotomy incision
Accreditation council for graduate medical education (ACGME) annual anesthesiology residency and fellowship program review: a "report card" model for continuous improvement
<p>Abstract</p> <p>Background</p> <p>The Accreditation Council for Graduate Medical Education (ACGME) requires an annual evaluation of all ACGME-accredited residency and fellowship programs to assess program quality. The results of this evaluation must be used to improve the program. This manuscript describes a metric to be used in conducting ACGME-mandated annual program review of ACGME-accredited anesthesiology residencies and fellowships.</p> <p>Methods</p> <p>A variety of metrics to assess anesthesiology residency and fellowship programs are identified by the authors through literature review and considered for use in constructing a program "report card."</p> <p>Results</p> <p>Metrics used to assess program quality include success in achieving American Board of Anesthesiology (ABA) certification, performance on the annual ABA/American Society of Anesthesiology In-Training Examination, performance on mock oral ABA certification examinations, trainee scholarly activities (publications and presentations), accreditation site visit and internal review results, ACGME and alumni survey results, National Resident Matching Program (NRMP) results, exit interview feedback, diversity data and extensive program/rotation/faculty/curriculum evaluations by trainees and faculty. The results are used to construct a "report card" that provides a high-level review of program performance and can be used in a continuous quality improvement process.</p> <p>Conclusions</p> <p>An annual program review is required to assess all ACGME-accredited residency and fellowship programs to monitor and improve program quality. We describe an annual review process based on metrics that can be used to focus attention on areas for improvement and track program performance year-to-year. A "report card" format is described as a high-level tool to track educational outcomes.</p
In Situ Small-Angle X-ray Scattering Studies During Reversible AdditionâFragmentation Chain Transfer Aqueous Emulsion Polymerization
Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible additionâfragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016, 7, 5078â5090). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization
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Aldehyde-functional thermoresponsive diblock copolymer worm gels exhibit strong mucoadhesion
A series of thermoresponsive diblock copolymer worm gels is prepared via reversible additionâfragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate using a water-soluble methacrylic precursor bearing pendent cis-diol groups. Selective oxidation using an aqueous solution of sodium periodate affords the corresponding aldehyde-functional worm gels. The aldehyde groups are located within the steric stabilizer chains and the aldehyde content can be adjusted by varying the periodate/cis-diol molar ratio. These aldehyde-functional worm gels are evaluated in terms of their mucoadhesion performance with the aid of a fluorescence microscopy-based assay. Using porcine urinary bladder mucosa as a model substrate, we demonstrate that these worm gels offer a comparable degree of mucoadhesion to that afforded by chitosan, which is widely regarded to be a âgold standardâ positive control in this context. The optimum degree of aldehyde functionality is approximately 30%: lower degrees of functionalization lead to weaker mucoadhesion, whereas higher values compromise the desirable thermoresponsive behavior of these worm gels
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Mucoadhesive pickering nanoemulsions via dynamic covalent chemistry
Hypothesis. Submicron oil droplets stabilized using aldehyde-functionalized nanoparticles should adhere to the primary amine groups present at the surface of sheep nasal mucosal tissue via Schiff base chemistry. Experiments. Well-defined sterically-stabilized diblock copolymer nanoparticles of 20 nm diameter were prepared in the form of concentrated aqueous dispersions via reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) using a water-soluble methacrylic precursor bearing cis-diol groups. Some of these hydroxyl-functional nanoparticles were then selectively oxidized using an aqueous solution of sodium periodate to form a second batch of nanoparticles bearing pendent aldehyde groups within the steric stabilizer chains. Subjecting either hydroxyl- or aldehyde-functional nanoparticles to high-shear homogenization with a model oil (squalane) produced oil-in-water Pickering macroemulsions of 20â30 ”m diameter. High-pressure microfluidization of such macroemulsions led to formation of the corresponding Pickering nanoemulsions with a mean droplet diameter of around 200 nm. Quartz crystal microbalance (QCM) experiments were used to examine adsorption of both nanoparticles and oil droplets onto a model planar substrate bearing primary amine groups, while a fluorescence microscopy-based mucoadhesion assay was developed to assess adsorption of the oil droplets onto sheep nasal mucosal tissue. Findings. Squalane droplets coated with aldehyde-functional nanoparticles adhered significantly more strongly to sheep nasal mucosal tissue than those coated with the corresponding hydroxyl-functional nanoparticles. This difference was attributed to the formation of surface imine bonds via Schiff base chemistry and was also observed for the two types of nanoparticles alone in QCM studies. Preliminary biocompatibility studies using planaria indicated only mild toxicity for these new mucoadhesive Pickering nanoemulsions, suggesting potential applications for the localized delivery of hydrophobic drugs
Synthesis of phenanthrene/pyrene hybrid microparticles: useful synthetic mimics for polycyclic aromatic hydrocarbon-based cosmic dust
Polycyclic aromatic hydrocarbons (PAHs) are found throughout the interstellar medium and are important markers for the evolution of galaxies and both star and planet formation. They are also widely regarded as a major source of carbon, which has implications in the search for extraterrestrial life. Herein we construct a melting point phase diagram for a series of phenanthrene/pyrene binary mixtures to identify the eutectic composition (75 mol % phenanthrene) and its melting point (83 °C). The molten oil obtained on heating this eutectic composition to 90 °C in aqueous solution is homogenized in the presence of a water-soluble polymeric emulsifier. On cooling to 20 °C, polydisperse spherical phenanthrene/pyrene hybrid microparticles are obtained. Varying the stirring rate and emulsifier type enables the mean microparticle diameter to be adjusted from 11 to 279 ÎŒm. Importantly, the phenanthrene content of individual microparticles remains constant during processing, as expected for the eutectic composition. These new hybrid microparticles form impact craters and undergo partial fragmentation when fired into a metal target at 1 km sâ1 using a light gas gun. When fired into an aerogel target at the same speed, microparticles are located at the ends of characteristic âcarrot tracksâ. Autofluorescence is observed in both types of experiments, which at first sight suggests minimal degradation. However, Raman microscopy analysis of the aerogel-captured microparticles indicates prominent pyrene signals but no trace of the more volatile phenanthrene component. Such differential ablation during aerogel capture is expected to inform the in situ analysis of PAH-rich cosmic dust in future space missions
Rational synthesis of epoxy-functional spheres, worms and vesicles by RAFT aqueous emulsion polymerisation of glycidyl methacrylate
The rational synthesis of epoxy-functional diblock copolymer nano-objects has been achieved via RAFT aqueous emulsion polymerisation of glycidyl methacrylate (GlyMA; aqueous solubility âŒ22 g dm-3 at 50 °C) by utilising relatively mild conditions (pH 7, 50 °C) to preserve the epoxy groups. High monomer conversions were achieved within 1 h when using a poly(glycerol monomethacrylate) chain transfer agent with a mean degree of polymerisation (DP) of 28, with GPC analysis indicating relatively narrow molecular weight distributions (Mw/Mn < 1.40) when targeting PGlyMA DPs up to 80. A phase diagram was constructed to identify the synthesis conditions required to access pure spheres, worms or vesicles. Transmission electron microscopy, dynamic light scattering and small-angle X-ray scattering (SAXS) studies indicated the formation of well-defined worms and vesicles when targeting relatively long PGlyMA blocks. These epoxy-functional nano-objects were derivatised via epoxy-thiol chemistry by reaction with l-cysteine in aqueous solution. Finally, an in situ SAXS study was conducted during the RAFT aqueous emulsion polymerisation of GlyMA at 50 °C to examine the nucleation and size evolution of PGMA48-PGlyMA100 diblock copolymer spheres using a bespoke stirrable reaction cell
Supplementary Information Files for Investigating the adsorption of anisotropic diblock copolymer worms onto planar silica and nanocellulose surfaces using a quartz crystal microbalance
Supplementary Information Files for Investigating the adsorption of anisotropic diblock copolymer worms onto planar silica and nanocellulose surfaces using a quartz crystal microbalanceElectrostatic adsorption of cationic polyelectrolytes onto anionic cellulosic substrates is an attractive
route for facile surface modification of biorenewable materials. Recently, attention has focused on
adsorbing cationic spherical diblock copolymer nanoparticles onto model cellulose and/or nanocellulosic
substrates. Herein, we investigate physical adsorption of highly anisotropic copolymer worms bearing
either anionic or cationic charge onto planar silica, cellulose nanocrystal (CNC) or cellulose nanofibril
(CNF) surfaces using quartz crystal microbalance with dissipation monitoring. Electrostatic interactions
dominate in the case of anionic silica and CNC surfaces because the adsorbed mass of cationic worms
was greater than that of anionic worms. However, either anionic or cationic worms could be adsorbed
onto in situ generated CNF substrates, suggesting that additional interactions were involved: hydrogen
bonding, van der Waals forces, and possibly covalent bond formation. Scanning electron and atomic
force microscopy studies of the dried planar substrates after adsorption experiments confirmed the presence of adsorbed copolymer worms. Finally, composite worm/CNF films exhibited restricted swelling behavior when immersed in water compared to reference CNF films, suggesting that the worms reinforce
CNF films by acting as a physical crosslinker. This study is the first investigation of the physical adsorption
of highly anisotropic diblock copolymer worms onto cellulosic surfaces