Plasma-based post-processing of colloidal nanocrystals for applications in heterogeneous catalysis.

This review summarizes the work on the use of plasmas to post-process nanostructures, in particular colloidal nanocrystals, as promising candidates for applications of heterogeneous catalysis. Using plasma to clean or modify the surface of nanostructures is a more precisely controlled method compared to other conventional methods, which is preferable when strict requirements for nanostructure morphology or chemical composition are necessary. The ability of plasma post-processing to create mesoporous materials with high surface areas and controlled microstructure, surfaces, and interfaces has transformational potential in catalysis and other applications that leverage surface/interface processes.

Patient and caregiver perspectives of fluid discharge protocols following pituitary surgery.

Background: Post-operative fluid restriction after transsphenoidal surgery (TSS) for pituitary tumors may effectively prevent delayed hyponatremia, the most common cause of readmission. However, implementation of individualized fluid restriction interventions after discharge is often complex and poses challenges for provider and patient. The purpose of this study was to understand the factors necessary for successful implementation of fluid restriction and discharge care protocols following TSS. Methods: Semi-structured interviews with fifteen patients and four caregivers on fluid discharge protocols were conducted following TSS. Patients and caregivers who had surgery before and after the implementation of updated discharge protocols were interviewed. Data were analyzed inductively using a procedure informed by rapid and thematic analysis. Results: Most patients and caregivers perceived fluid restriction protocols as acceptable and feasible when indicated. Facilitators to the protocols included clear communication about the purpose of and strategies for fluid restriction, access to the care team, and involvement of patients' caregivers in care discussions. Barriers included patient confusion about differences in the care plan between teams, physical discomfort of fluid restriction, increased burden of tracking fluids during recovery, and lack of clarity surrounding desmopressin prescriptions. Conclusion: Outpatient fluid restriction protocols are a feasible intervention following pituitary surgery but requires frequent patient communication and education. This evaluation highlights the importance of patient engagement and feedback to effectively develop and implement complex clinical interventions.

Fertility issues in hypopituitarism.

Women with hypopituitarism have lower fertility rates and worse pregnancy outcomes than women with normal pituitary function. These disparities exist despite the use of assisted reproductive technologies and hormone replacement. In women with hypogonadotropic hypogonadism, administration of exogenous gonadotropins can be used to successfully induce ovulation. Growth hormone replacement in the setting of growth hormone deficiency has been suggested to potentiate reproductive function, but its routine use in hypopituitary women remains unclear and warrants further study. In this review, we will discuss the clinical approach to fertility in a woman with hypopituitarism.

Use of the Community of Inquiry Framework to Measure Student and Facilitator Perceptions of Online Flipped Classroom Compared with Online Lecture Learning in Undergraduate Medical Education.

Background: The COVID-19 pandemic and a movement away from traditional lecture-based learning have increased the use of online flipped classroom (FC) and active learning models in medical education. The Community of Inquiry (CoI) framework for online learning may be used to evaluate the effectiveness and strengths of the online FC model compared with other learning formats. Methods: An observational survey study was conducted to measure medical student and facilitator perceptions of an online FC endocrinology tutorial compared with online lecture experiences. For the tutorial, students were instructed to watch short, pre-recorded lecture videos on thyroid pathophysiology prior to class. During class, small groups of students were paired with a faculty facilitator in online Zoom rooms for case discussion. Students were surveyed using the CoI framework to assess elements of cognitive, social, and teaching presence between the two online learning modalities. Facilitators were also surveyed. Survey questions were rated on a 5-point Likert scale. Results: Fifty-three out of 92 students (58% response rate) and seven out of eight facilitators (88% response rate) completed surveys. In general, students felt that online FC learning improved cognitive, teaching, and social presence compared with online lecture. Areas of cognitive presence (mean score 3.9 ± 1.0 SD), such as stimulating curiosity and applying concepts, were highly rated. Certain elements of social presence (3.6 ± 0.9) and teaching presence (3.7 ± 0.9), such as expression of emotion and communication of expectations, garnered lower ratings. All surveyed facilitators felt that online FC was more effective and enjoyable to teach than online lectures but did not feel it was superior to in-person instruction. Conclusion: Medical students and facilitators viewed an online FC tutorial in endocrinology positively. Most, but not all, areas of the CoI framework were enhanced with the online FC tutorial compared with online lecture-based learning.

Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts.

Combustion is often difficult to spatially direct or tune associated kinetics-hence a run-away reaction. Coupling pyrolytic chemical transformation to mass transport and reaction rates (Damköhler number), however, we spatially directed ignition with concomitant switch from combustion to pyrolysis (low oxidant). A 'surface-then-core' order in ignition, with concomitant change in burning rate,is therefore established. Herein, alkysilanes grafted onto cellulose fibers are pyrolyzed into non-flammable SiO2 terminating surface ignition propagation, hence stalling flame propagating. Sustaining high temperatures, however, triggers ignition in the bulk of the fibers but under restricted gas flow (oxidant and/or waste) hence significantly low rate of ignition propagation and pyrolysis compared to open flame (Liñán's equation). This leads to inside-out thermal degradation and, with felicitous choice of conditions, formation of graphitic tubes. Given the temperature dependence, imbibing fibers with an exothermically oxidizing synthon (MnCl2 ) or a heat sink (KCl) abets or inhibits pyrolysis leading to tuneable wall thickness. We apply this approach to create magnetic, paramagnetic, or oxide containing carbon fibers. Given the surface sensitivity, we illustrate fabrication of nm- and µm-diameter tubes from appropriately sized fibers.

Halogen Bonding-Driven Reversible Self-Assembly of Plasmonic Colloidal Molecules.

Colloidal molecules (CMs) assembled from plasmonic nanoparticles are an emerging class of building blocks for creating plasmonic materials and devices, but precise yet reversible assembly of plasmonic CMs remains a challenge. This communication describes the reversible self-assembly of binary plasmonic nanoparticles capped with complementary copolymer ligands into different CMs via halogen bonding interactions at high yield. The coordination number of the CMs is governed by the number ratio of complementary halogen donor and acceptor groups on the interacting nanoparticles. The reversibility of the halogen bonds allows for controlling the repeated formation and disassociation of the plasmonic CMs and hence their optical properties. Furthermore, the CMs can be designed to further self-assemble into complex structures in selective solvents. The precisely engineered reversible nanostructures may find applications in sensing, catalysis, and smart optoelectronic devices.

Fabrication of Centimeter-Scale Plasmonic Nanoparticle Arrays with Ultranarrow Surface Lattice Resonances.

Plasmonic surface lattice resonances (SLRs) supported by metallic nanoparticle (NP) arrays show diverse applications including nanolasers, sensors, photocatalysis, and nonlinear optics. However, to rationally fabricate high-quality plasmonic NP arrays with ultranarrow SLR line widths over large areas remains challenging. This article describes a general approach for the efficient fabrication of centimeter-scale inorganic NP arrays with precisely controlled NP size, composition, position, and lattice geometry. This method combines the processes of solvent-assisted soft lithography and in situ site-specific NP growth to reproducibly create many replicates of NP arrays without utilizing cleanroom and specialized equipment. For demonstration, we show that Au NP arrays exhibit ultranarrow SLRs with a line width of 4 nm and a quality factor of 218 toward the theoretical limit.

Severe Posaconazole-Induced Glucocorticoid Deficiency with Concurrent Pseudohyperaldosteronism: An Unfortunate Two-for-One Special.

A 56-year-old Hispanic man with a history of disseminated coccidioidomycosis was diagnosed with persistent glucocorticoid insufficiency and pseudohyperaldosteronism secondary to posaconazole toxicity. This case was notable for unexpected laboratory findings of both pseudohyperaldosteronism and severe glucocorticoid deficiency due to posaconazole's mechanism of action on the adrenal steroid synthesis pathway. Transitioning to fluconazole and starting hydrocortisone resolved the hypokalemia but not his glucocorticoid deficiency. This case highlights the importance of recognizing iatrogenic glucocorticoid deficiency with azole antifungal agents and potential long term sequalae.

Tunable Hydrophobicity via Dimensionally Confined Polymerization of Organometallic Adducts.

Fabrication of tunable fine textures on solid metal surfaces often demands sophisticated reaction/processing systems. By exploiting in situ polymerization and self-assembly of inorganic adducts derived from liquid metals (the so-called HetMet reaction) with concomitant solidification, solid metal films with tunable texture are readily fabricated. Serving as a natural dimensional confinement, interparticle pores and capillary-adhered thin liquid films in a pre-packed bed of undercooled liquid metal particles lead to the expeditious surface accumulation of organometallic synthons, which readily oligomerize and self-assemble into concentration-dictated morphologies/patterns. Tuning particle size, particle packing (flat or textured), and reactant concentration generates diverse, autonomously organized organometallic structures on a metal particle bed. Concomitant solidification and sintering of the underlying undercooled particle bed led to a multiscale patterned solid metal surface. The process is illustrated by creating tunable features on pre-organized metal particle beds with concomitant tunable wettability as illustrated through the so-called petal and lotus effects.

Heat-Free Biomimetic Metal Molding on Soft Substrates.

Fabrication of bio-templated metallic structures is limited by differences in properties, processing conditions, packing, and material state(s). Herein, by using undercooled metal particles, differences in modulus and processing temperatures can be overcome. Adoption of autonomous processes such as self-filtration, capillary pressure, and evaporative concentration leads to enhanced packing, stabilization (jamming) and point sintering with phase change to create solid metal replicas of complex bio-based features. Differentiation of subtle differences between cultivars of the rose flower with reproduction over large areas shows that this biomimetic metal patterning (BIOMAP) is a versatile method to replicate biological features either as positive or negative reliefs irrespective of the substrate. Using rose petal patterns, we illustrate the versatility of bio-templated mapping with undercooled metal particles at ambient conditions, and with unprecedented efficiency for metal structures.

A Retrospective Study Examining Phentermine on Preconception Weight Loss and Pregnancy Outcomes.

OBJECTIVE: Obesity is a well-known risk factor for infertility. However, the use of weight loss medications prior to conception is underutilized. The objectives of our study are to describe weight loss, pregnancy rates, and live birth rates after short-term phentermine use in women with obesity and infertility. METHODS: This was a retrospective analysis of 55 women (18 to 45 years old) who were overweight or obese, diagnosed with infertility, and prescribed phentermine for weight loss in an ambulatory endocrinology clinic at a single, tertiary level academic medical center. Main outcome measures were mean percent weight change at 3 months after starting phentermine, and pregnancy, and live birth rates from start of phentermine to June 30, 2017. RESULTS: Median duration of phentermine use was 70 days (Q1, Q3 [33, 129]). Mean ± SD percent weight change at 3 months after starting phentermine was -5.3 ± 4.1% (P<.001). The pregnancy rate was 60% and the live birth rate was 49%. There was no significant difference in pregnancy rates (52% versus 68%; P = .23) or live birth rates (44% versus 54%; P = .50) in women who lost ≥5% versus <5% of their baseline weight. The number of metabolic comorbidities was negatively associated with the pregnancy rate. Phentermine was generally well-tolerated with no serious adverse events. CONCLUSION: Phentermine can produce clinically significant weight loss in women with obesity during the preconception period. Higher pregnancy or live birth rates were not observed with a greater degree of weight loss with phentermine.

LIMITED CARBOHYDRATE REFEEDING INSTRUCTION FOR LONG-TERM WEIGHT MAINTENANCE FOLLOWING A KETOGENIC, VERY-LOW-CALORIE MEAL PLAN.

OBJECTIVE: Weight-loss maintenance following very-low-calorie meal plans is poorly studied. This report describes weight-loss efficacy and predictors of weight-loss maintenance of a ketogenic, very-low-calorie meal plan (protein-sparing modified fast, PSMF) in people with obesity. METHODS: A total of 127 consecutive adults in the PSMF meal plan (27.2 ± 19.5 weeks) and 48 adults on a conventional, hypocaloric meal plan (23.6 ± 20.8 weeks) were retrospectively studied for percent weight change from baseline to end of intervention and at 6, 12, and 24 months postintervention. Baseline factors were analyzed for correlations with weight-loss maintenance. RESULTS: At end of intervention, weight loss from baseline was greater for the PSMF group compared to the conventional intervention group (-12.4% vs. -2.6%; P<.001) but was similar between groups by 12 months postintervention. PSMF subjects who attended follow-up visits to receive instruction on gradual and limited carbohydrate refeeding after ketosis saw significant weight loss at the end of PSMF compared to those who did not follow-up to receive instruction (-17.5% vs. -8.0%; P<.001) and maintained greater weight loss through 12 months post-PSMF (-9.8% vs. -1.5%; P<.001). Higher baseline body mass index correlated with less weight loss at 12 months post-PSMF (P = .035). CONCLUSION: PSMF results in effective short-term weight loss of more than 5% from baseline weight. Follow-up for limited carbohydrate refeeding instruction is important for weight-loss maintenance up to 2 years after initial weight loss. ABBREVIATIONS: BMI = body mass index; PSMF = protein-sparing modified fast.

A Student-Led Introduction to Lesbian, Gay, Bisexual, and Transgender Health for First-Year Medical Students.

BACKGROUND AND OBJECTIVES: Lesbian, gay, bisexual, and transgender (LGBT) individuals face significant health disparities. This is in part because many physicians are not sensitive to, and/or are underprepared to address, LGBT-specific concerns. To help meet this need, we, a group of second- and fourth-year medical students with faculty oversight, organized a session on LGBT health for first-year medical students. METHODS: The three second-year and one fourth-year student authors designed a mandatory session for the 167 first-years at Case Western Reserve University School of Medicine in Cleveland, OH. The 2-hour session consisted of a student-delivered presentation, a patient panel, and a small-group session. Students' LGBT health knowledge and confidence in providing care were assessed anonymously before and after the session, and individuals' pre- and post-session assessments were paired using student-generated identifiers. RESULTS: A total of 73 complete, matched pre-/post-session assessments were received. Students' familiarity with LGBT terminology and demographics increased significantly after the session. Students' perceived preparedness and comfort in providing LGBT-specific care significantly improved in most areas as well. Students strongly praised the session, in particular the patient panel. CONCLUSION: A student-led educational session on LGBT health can effectively improve first-year medical students' LGBT knowledge and confidence to provide care.