"I might not fit that doctor image": Ideal worker norms and women medical students.

Despite the increasing numbers of women students in medical schools, focused attention on their perceptions about medical school and the medical profession remain underexamined. These perceptions are important to understand, particularly since women students are likely burdened with a host of gender norms related to work, family, and their future roles as physicians. Early experiences in medical school offer important insights into the larger student experience and are tied to academic outcomes and feelings of belonging. To examine early experiences of women medical students, this qualitative study used sensemaking theory to describe the current context and "story" of ideal worker norms. Critical qualitative interviews of 38 women students were performed during their first 2 months of medical school and explored both how the students perceived and experienced ideal worker norms, and how they made sense of the "story" of ideal worker norms. The participants described ways they encountered gendering and ideal worker norms through displays of nurturing behaviour, expectations to balance a future family, and whether they looked or acted the part of a doctor. This article highlights the challenges women medical students are already aware they will face, the opportunities they look forward to, and the strengths they anticipate leaning on to navigate their profession. Results from this study have implications for women medical students' learning experiences and transitions into medical school and for faculty, staff, and scholars concerned with challenging gendering norms that shape medical education.

[2.2.2]- to [3.2.1]-Bicycle Skeletal Rearrangement Approach to the Gibberellin Family of Natural Products.

Synthetic studies toward the gibberellin family of natural products are reported. An oxidative dearomatization/Diels-Alder cascade assembles the carbon skeleton as a [2.2.2]-bicycle, which is then transformed to the [3.2.1]-bicyclic gibberellin core via a novel Lewis acid catalyzed rearrangement. Strategic synthetic handles allow for late-stage modification of the gibberellin skeleton and provides efficient access to this important family of natural compounds.

Review of synthetic approaches toward maoecrystal V.

Synthetic approaches toward the complex natural product diterpenoid maoecrystal V are reviewed, including successful total syntheses, published synthetic efforts, and efforts compiled from dissertations. The review focuses on general synthetic strategies and chronicles efforts toward the molecule since its isolation in 2004, summarizing key contributions of these efforts to the broader synthetic community.

Double-Diels-Alder Approach to Maoecrystal V. Unexpected C-C Bond-Forming Fragmentations of the [2.2.2]-Bicyclic Core.

Synthetic studies toward maoecrystal V are reported. An oxidative dearomatization/Diels-Alder cascade to assemble the natural product carbocyclic core in one step is proposed. A facile electrocyclization is shown to suppress the intramolecular allene Diels-Alder pathway. This obstacle is alleviated via a stepwise approach with an allene equivalent to access the key cyclopentadiene-fused [2.2.2]-bicyclic core. Upon treatment with Lewis acid, the proposed intramolecular hetero-Diels-Alder reaction is cleanly and unexpectedly diverted either via C-C bond-forming fragmentation to the spiro-indene product (when R = OMe) or via elimination (when R = H).

Beyond C, H, O, and N! Analysis of the elemental composition of U.S. FDA approved drug architectures.

The diversity of elements among U.S. Food and Drug Administration (FDA) approved pharmaceuticals is analyzed and reported, with a focus on atoms other than carbon, hydrogen, oxygen, and nitrogen. Our analysis reveals that sulfur, chlorine, fluorine, and phosphorous represent about 90% of elemental substitutions, with sulfur being the fifth most used element followed closely by chlorine, then fluorine and finally phosphorous in the eighth place. The remaining 10% of substitutions are represented by 16 other elements of which bromine, iodine, and iron occur most frequently. The most detailed parts of our analysis are focused on chlorinated drugs as a function of approval date, disease condition, chlorine attachment, and structure. To better aid our chlorine drug analyses, a new poster showcasing the structures of chlorinated pharmaceuticals was created specifically for this study. Phosphorus, bromine, and iodine containing drugs are analyzed closely as well, followed by a discussion about other elements.

Evolution of an oxidative dearomatization enabled total synthesis of vinigrol.

The evolution of the synthetic strategy resulting in a total synthesis of vinigrol is presented. Oxidative dearomatization/intramolecular Diels-Alder cycloaddition has served as the successful cornerstone for all of the approaches. Extensive radical cyclization efforts to form the tetracyclic core resulted in interesting and surprising reaction outcomes, none of which could be advanced to vinigrol. These cyclization obstacles were successfully overcome by using Heck instead of radical cyclizations. The total synthesis features a trifluoroethyl ether protecting group being used for the first time in organic synthesis. The logic of its selection and the group's importance beyond protecting the C8a hydroxyl group is presented along with a discussion of strategies for its removal. Because of the compact tetracyclic cage the route is built around many unusual reaction observations and solutions have emerged. For example, a first of its kind Grob fragmentation reaction featuring a trifluoroethyl leaving group has been uncovered, interesting interrupted selenium dioxide allylic oxidations have been observed as well as intriguing catalyst and counterion dependent directed hydrogenations.

Root release and metabolism of organic acids in tea plants in response to phosphorus supply.

Self-rooted, 10-month-old, uniform tea [Camellia sinensis (L.) O. Kuntze cv. Huangguanyin] plants were supplied for 17 weeks with 0, 40, 80, 160, 400, or 1000µM phosphorus (P) to investigate the effects of P supply on root citrate and malate release, the concentrations of malate and citrate and the activities of acid-metabolizing enzymes in leaves and roots. Root malate release and accumulation was induced by both 0 and 40µM P, while root citrate release and accumulation was induced only by 0µM P. Phosphorus-deficiency-induced malate and citrate release coincided with higher concentrations of root malate and citrate. The higher concentrations of malate and citrate were accompanied by increased activities of phosphoenolpyruvate carboxylase (PEPC), phosphoenolpyruvate phosphatase (PEPP), citrate synthase (CS) and NAD-malic enzyme (NAD-ME) and decreased activities of pyruvate kinase (PK), NADP-ME and NADP-isocitrate dehydrogenase (NADP-IDH) in roots. In contrast to roots, malate accumulated in the leaves only in response to 0µM P, and no change was observed in citrate levels. The P-deficiency-induced leaf malate accumulation coincided with increased activities of NADP-ME, NAD-ME and PK. Overall, the P-deficiency-induced changes in organic acid (OA) metabolism differed between roots and leaves. The high tolerance of tea plants to P-deficiency might be involved in two major processes: (a) increasing the availability of P by inducing root release of OA anions; and (b) improving the ability to use P efficiently by inducing bypass enzymes involved in tissue P economy.

Changes in organic acid metabolism differ between roots and leaves of Citrus grandis in response to phosphorus and aluminum interactions.

Seedlings of sour pummelo (Citrus grandis) were irrigated daily for 18 weeks with nutrient solution containing four phosphorus (P) levels (50, 100, 250 and 500 microM KH2PO4) and two aluminum (Al) levels [0 (-Al) and 1.2 mM AlCl3 x 6H2O (+Al)]. Both malate and citrate concentrations in +Al leaves decreased with increasing P supply, but their concentrations in -Al leaves did not change in response to P supply. The concentrations of malate under 50 microM P and of citrate under 50 and 100 microM P were higher in +Al leaves than in -Al ones, but malate concentration was lower in +Al leaves than in -Al ones under 500 microM P. There was no difference in root malate and citrate concentrations among different P and Al combinations except for an increase in malate and citrate under 50 microM P+0 mM Al and a slight decrease in malate under 50 microM P+1.2 mM Al. The activities of acid-metabolizing enzymes (citrate synthase, aconitase, phosphoenolpyruvate carboxylase, NADP-isocitrate dehydrogenase, phosphoenolpyruvate phosphatase, NAD-malate dehydrogenase, NADP-malic enzyme and pyruvate kinase) in most cases were less affected by P and Al interactions in roots compared to the leaves. Our results support the hypothesis that changes in organic acid metabolism differ between roots and leaves of C. grandis in response to P and Al interactions.

Boron deficiency decreases growth and photosynthesis, and increases starch and hexoses in leaves of citrus seedlings.

Seedlings of sweet orange (Citrus sinensis) were fertilized for 14 weeks with boron (B)-free or B-sufficient (2.5 or 10 microM H(3)BO(3)) nutrient solution every other day. Boron deficiency resulted in an overall inhibition of plant growth, with a reduction in root, stem and leaf dry weight (DW). Boron-starved leaves showed decreased CO(2) assimilation and stomatal conductance, but increased intercellular CO(2) concentrations. Activities of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco), NADP-glyceraldehyde-3-phosphate dehydrogenase (NADP-GAPDH) and stromal fructose-1,6-bisphosphatase (FBPase) were lower in B-deficient leaves than in controls. Contents of glucose, fructose and starch were increased in B-deficient leaves while sucrose was decreased. Boron-deficient leaves displayed higher or similar superoxide dismutase (SOD), ascorbate peroxidase (APX), monodehydroascorbate reductase (MDAR) and glutathione reductase (GR) activities, while dehydroascorbate reductase (DHAR) and catalase (CAT) activities were lower. Expressed on a leaf area or protein basis, B-deficient leaves showed a higher ascorbate (AsA) concentration, but a similar AsA concentration on a DW basis. For reduced glutathione (GSH), we found a similar GSH concentration on a leaf area or protein basis and an even lower content on a DW basis. Superoxide anion (O(2)(-)) generation, malondialdehyde (MDA) concentration and electrolyte leakage were higher in B-deficient than in control leaves. In conclusion, CO(2) assimilation may be feedback-regulated by the excessive accumulation of starch and hexoses in B-deficient leaves via direct interference with chloroplast function and/or indirect repression of photosynthetic enzymes. Although B-deficient leaves remain high in activity of antioxidant enzymes, their antioxidant system as a whole does not provide sufficient protection from oxidative damage.

Aluminum-induced effects on Photosystem II photochemistry in citrus leaves assessed by the chlorophyll a fluorescence transient.

Seedlings of Citrus grandis (L.) Osbeck cv. Tuyou were irrigated daily for 5 months with nutrient solution containing 0 (control), 0.2, 0.6 or 1.6 mM aluminum (Al) from AlCl(3).6H(2)O. Shoot growth was more sensitive to Al toxicity than root growth, gas exchange, chlorophyll (Chl) concentration, polyphasic Chl a fluorescence (OJIP) induction and related parameters. Leaves of Al-treated plants showed decreased CO(2) assimilation and Chl concentration, yet intercellular CO(2) concentration increased and ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) activity was unchanged. Chlorophyll a fluorescence induction analysis of Al-stressed leaves showed a large rise at the O-step and a large depression at the P-step, accompanied by two new bands at 300 micros (K-band) and at about 150 micros (L-band). Maximum fluorescence, maximum quantum yield of primary photochemistry, oxygen-evolving complex (OEC), quantum yield of electron transport, quantum yield of electron transport from Q(A) (-) to the Photosystem I end electron acceptors, IP phase and total performance index were decreased in leaves of Al-treated plants, whereas minimum fluorescence, relative variable fluorescence at the J-step and I-step, and dissipated energy were increased. We propose that impaired electron transport capacity accompanied by lack of reducing equivalents were the main factors contributing to decreased CO(2) assimilation in Al-treated plants. Aluminum-induced photoinhibition occurring at both the donor (i.e., the OEC) and the acceptor sides of Photosystem II may be associated with growth inhibition. Besides decreased light absorption due to reduced Chl concentration, enhanced energy dissipation protected the leaves of Al-treated plants from photo-oxidative damage in high light.