Cryptocapsinepoxide-type Carotenoids from Red Mamey, Pouteria sapota

Three new carotenoids, cryptocapsin-5,6-epoxide, 3ʹ-deoxycapsanthin-5,6-epoxide, and cryptocapsin-5,8-epoxides, have been isolated from the ripe fruits of red mamey (Pouteria sapota). Cryptocapsin-5,6-epoxide was prepared by partial synthesis via epoxidation of cryptocapsin and the (5R,6S)- and (5S,6R)-stereoisomers were identified by HPLC-ECD analysis. Spectroscopic data of the natural (anti) and semisynthetic (syn) derivatives obtained by acid-catalyzed rearrangement of cryptocapsin-5,8-epoxide stereoisomers were compared for structural elucidation. Chiral HPLC separation of natural and semisynthetic samples of cryptocapsin-5,8-epoxides was performed and HPLC-ECD analysis allowed configurational assignment of the separated stereoisomers

3-D Tracking and Visualization of Hundreds of Pt-Co Fuel Cell Nanocatalysts During Electrochemical Aging

We present an electron tomography method that allows for the identification of hundreds of electrocatalyst nanoparticles with one-to-one correspondence before and after electrochemical aging. This method allows us to track, in three-dimensions (3-D), the trajectories and morphologies of each Pt-Co nanocatalyst on a fuel cell carbon support. The use of atomic-scale electron energy loss spectroscopic imaging enables the correlation of performance degradation of the catalyst with changes in particle/inter-particle morphologies, particle-support interactions and the near-surface chemical composition. We found that, aging of the catalysts under normal fuel cell operating conditions (potential scans from +0.6 V to +1.0 V for 30,000 cycles) gives rise to coarsening of the nanoparticles, mainly through coalescence, which in turn leads to the loss of performance. The observed coalescence events were found to be the result of nanoparticle migration on the carbon support during potential cycling. This method provides detailed insights into how nanocatalyst degradation occurs in proton exchange membrane fuel cells (PEMFCs), and suggests that minimization of particle movement can potentially slow down the coarsening of the particles, and the corresponding performance degradation.Comment: Nano Letters, accepte

Impact of the SPOP Mutant Subtype on the Interpretation of Clinical Parameters in Prostate Cancer.

Purpose: Molecular characterization of prostate cancer, including The Cancer Genome Atlas, has revealed distinct subtypes with underlying genomic alterations. One of these core subtypes, SPOP (speckle-type POZ protein) mutant prostate cancer, has previously only been identifiable via DNA sequencing, which has made the impact on prognosis and routinely used risk stratification parameters unclear. Methods: We have developed a novel gene expression signature, classifier (Subclass Predictor Based on Transcriptional Data), and decision tree to predict the SPOP mutant subclass from RNA gene expression data and classify common prostate cancer molecular subtypes. We then validated and further interrogated the association of prostate cancer molecular subtypes with pathologic and clinical outcomes in retrospective and prospective cohorts of 8,158 patients. Results: The subclass predictor based on transcriptional data model showed high sensitivity and specificity in multiple cohorts across both RNA sequencing and microarray gene expression platforms. We predicted approximately 8% to 9% of cases to be SPOP mutant from both retrospective and prospective cohorts. We found that the SPOP mutant subclass was associated with lower frequency of positive margins, extraprostatic extension, and seminal vesicle invasion at prostatectomy; however, SPOP mutant cancers were associated with higher pretreatment serum prostate-specific antigen (PSA). The association between SPOP mutant status and higher PSA level was validated in three independent cohorts. Despite high pretreatment PSA, the SPOP mutant subtype was associated with a favorable prognosis with improved metastasis-free survival, particularly in patients with high-risk preoperative PSA levels. Conclusion: Using a novel gene expression model and a decision tree algorithm to define prostate cancer molecular subclasses, we found that the SPOP mutant subclass is associated with higher preoperative PSA, less adverse pathologic features, and favorable prognosis. These findings suggest a paradigm in which the interpretation of common risk stratification parameters, particularly PSA, may be influenced by the underlying molecular subtype of prostate cancer

Microbial rhodopsins are major contributors to the solar energy captured in the sea

All known phototrophic metabolisms on Earth rely on one of three categories of energy-converting pigments: chlorophyll-a (rarely -d), bacteriochlorophyll-a (rarely -b), and retinal, which is the chromophore in rhodopsins. While the significance of chlorophylls in solar energy capture has been studied for decades, the contribution of retinal-based phototrophy to this process remains largely unexplored. We report the first vertical distributions of the three energy-converting pigments measured along a contrasting nutrient gradient through the Mediterranean Sea and the Atlantic Ocean. The highest rhodopsin concentrations were observed above the deep chlorophyll-a maxima, and their geographical distribution tended to be inversely related to that of chlorophyll-a. We further show that proton-pumping proteorhodopsins potentially absorb as much light energy as chlorophyll-a–based phototrophy and that this energy is sufficient to sustain bacterial basal metabolism. This suggests that proteorhodopsins are a major energy-transducing mechanism to harvest solar energy in the surface ocean

French responses to the Prague Spring: connections, (mis)perception and appropriation

Looking at the vast literature on the events of 1968 in various European countries, it is striking that the histories of '1968' of the Western and Eastern halves of the continent are largely still written separately.1 Nevertheless, despite the very different political and socio-economic contexts, the protest movements on both sides of the Iron Curtain shared a number of characteristics. The 1968 events in Czechoslovakia and Western Europe were, reduced to the basics, investigations into the possibility of marrying social justice with liberty, and thus reflected a tension within European Marxism. This essay provides an analysis specifically of the responses by the French left—the Communist Party, the student movements and the gauchistes—to the Prague Spring, characterised by misunderstandings and strategic appropriation. The Prague Spring was seen by both the reformist and the radical left in France as a moderate movement. This limited interpretation of the Prague Spring as a liberal democratic project continues to inform our memory of it

Optimal Nitrogen Fertilization to Reach the Maximum Grain and Stover Yields of Maize (Zea mays L.): Tendency Modeling

Utilization of maize stover to the production of meat and milk and saving the grains for human consumption would be one strategy for the optimal usage of resources. Variance and tendency analyses were applied to find the optimal nitrogen (N) fertilization dose (0, 100, 145, 190, 240, and 290 kg/ha) for forage (F), stover (S), cob (C), and grain (G) yields, as well as the optimal grain-to-forage, cob-to-forage, and cob-to-stover ratios (G:F, C:F, and C:S, respectively). The study was performed in central Mexico (20.691389° N and −101.259722° W, 1740 m a.m.s.l.; Cwa (Köppen), 699 mm annual precipitation; alluvial soils). N-190 and N-240 improved the individual yields and ratios the most. Linear and quadratic models for CDM, GDM, and G:F ratio had coefficients of determination (R2) of 0.20–0.46 (p < 0.03). Cubic showed R2 = 0.30–0.72 (p < 0.02), and the best models were for CDM, GDM, and the G:F, C:F, and C:S DM ratios (R2 = 0.60–0.72; p < 0.0002). Neither SHB nor SDM negatively correlated with CDM or GDM (r = 0.23–0.48; p < 0.0001). Excess of N had negative effects on forage, stover, cobs, and grains yields, but optimal N fertilization increased the proportion of the G:F, C:F, and C:S ratios, as well as the SHB and SDM yields, without negative effects on grain production