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  1. A series of low-valent iron complexes that feature a phosphine-substituted α-diimine (DI) ligand have been synthesized. Reduction of (Ph2PPrDI)FeBr2 with an excess of Na/Hg in the presence of carbon monoxide afforded the corresponding dicarbonyl complex, (Ph2PPrDI)Fe(CO)2. Through multinuclear NMR and single crystal X-ray diffraction analysis, this complex was found to possess a 3-coordinate DI ligand. Upon heating for 10 days at 110 °C while applying intermittent vacuum, (Ph2PPrDI)Fe(CO)2 was successfully converted to the corresponding monocarbonyl complex, (Ph2PPrDI)Fe(CO), which was found to feature a tetradentate chelate. Similar reactivity was explored using the analogous bis(tert-butyl)phosphine-substituted ligand, tBu2PPrDI. Addition of this chelate to FeBr2 afforded (tBu2PPrDI)FeBr2, and subsequent reduction yielded (tBu2PPrDI)FeBr, which was found to possess a tridentate DI ligand by single crystal X-ray diffraction. Performing the reduction of (tBu2PPrDI)FeBr2 in the presence of CO afforded the corresponding dicarbonyl complex, (tBu2PPrDI)Fe(CO)2. Like aryl-substituted (Ph2PPrDI)Fe(CO)2, alkyl-substituted (tBu2PPrDI)Fe(CO)2 was found to feature a pendant phosphine arm. However, heating (tBu2PPrDI)Fe(CO)2 under vacuum did not allow for phosphine substitution and conversion to the corresponding monocarbonyl complex, highlighting the importance of phosphine π-acidity for substitution and the stabilization of low-valent iron. 
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    Free, publicly-accessible full text available May 1, 2025
  2. Abstract

    The development of tunable organic photoredox catalysts remains important in the field of photoredox catalysis. A highly modular and tunable family of trianguleniums (azadioxatriangulenium, diazaoxatriangulenium, and triazatriangulenium), and the related [4]helicene quinacridinium have been used as organic photoredox catalysts for photoreductions and photooxidations under visible light irradiation (λ = 518–640 nm). A highlight of this family of photoredox catalysts is their readily tunable redox properties, leading to different reactivities. We report their use as photocatalysts for the aerobic oxidative hydroxylation of arylboronic acids and the aerobic cross-dehydrogenative coupling reaction of N-phenyl-1,2,3,5-tetrahydroisoquinoline with nitromethane through reductive quenching. Furthermore, their potential as photoreduction catalysts has been demonstrated through the catalysis of an intermolecular atom-transfer radical addition via oxidative quenching. These transformations serve as benchmarks to highlight that the easily synthesized trianguleniums, congeners of the acridiniums, are versatile organic photoredox catalysts with applications in both photooxidations and photoreductions.

     
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    Free, publicly-accessible full text available January 29, 2025
  3. We often use cues from our environment when we get stuck searching our memories, but prior research has failed to show benefits of cuing with other, randomly selected list items during memory search. What accounts for this discrepancy? We proposed that cues’ content critically determines their effectiveness and sought to select the right cues by building a computational model of how cues affect memory search. Participants ( N = 195 young adults from the United States) recalled significantly more items when receiving our model’s best (vs. worst) cue. Our model provides an account of why some cues better aid recall: Effective cues activate contexts most similar to the remaining items’ contexts, facilitating recall in an unsearched area of memory. We discuss our contributions in relation to prominent theories about the effect of external cues.

     
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    Free, publicly-accessible full text available January 1, 2025
  4. Free, publicly-accessible full text available December 10, 2024
  5. Abstract

    Sea surface temperature (SST) variability on decadal timescales has been associated with global and regional climate variability and impacts. The mechanisms that drive decadal SST variability, however, remain highly uncertain. Many previous studies have examined the role of atmospheric variability in driving decadal SST variations. Here we assess the strength of oceanic forcing in driving decadal SST variability in observations and state‐of‐the‐art climate models by analyzing the relationship between surface heat flux and SST. We find a largely similar pattern of decadal oceanic forcing across all ocean basins, characterized by oceanic forcing about twice the strength of the atmospheric forcing in the mid‐ and high latitude regions, but comparable or weaker than the atmospheric forcing in the subtropics. The decadal oceanic forcing is hypothesized to be associated with the wind‐driven oceanic circulation, which is common across all ocean basins.

     
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  6. Free, publicly-accessible full text available September 1, 2024
  7. California's network of marine protected areas was created to protect the diversity and abundance of native marine life, but the status of some taxa is very poorly known. Here we describe the sponges (phylum Porifera) from the Carmel Pinnacles State Marine Reserve, as assessed by a SCUBA-based survey in shallow waters. Of the 29 sponge species documented, 12 (41%) of them were previously unknown. Using a combination of underwater photography, DNA sequencing, and morphological taxonomy, we greatly improve our understanding of the status and distribution of previously described species and formally describe the new species as Hymedesmia promina sp. nov., Phorbas nebulosus sp. nov., Clathria unoriginalis sp. nov., Clathria rumsena sp. nov., Megaciella sanctuarium sp. nov., Mycale lobos sp. nov., Xestospongia ursa sp. nov., Haliclona melissae sp. nov., Halichondria loma sp. nov., Hymeniacidon fusiformis sp. nov., Scopalina carmela sp. nov., and Obruta collector gen. nov., sp. nov. An additional species, Lissodendoryx topsenti (de Laubenfels 1930), is moved to Hemimycale, and H. polyboletus comb. nov., nom. nov. is created due to preoccupation by H. topsenti (Burton, 1929). Several of the new species appear to be rare and/or have very restricted distributions, as they were not found at comparative survey sites outside of Carmel Bay. These results illustrate the potential of qualitative presence/absence systematic surveys of understudied taxa to discover and document substantial novel diversity. 

     
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  8. Abstract Background

    Undergraduate STEM instructors want to help students learn and retain knowledge for their future courses and careers. One promising evidence-based technique that is thought to increase long-term memory is spaced retrieval practice, or repeated testing over time. The beneficial effect of spacing has repeatedly been demonstrated in the laboratory as well as in undergraduate mathematics courses, but its generalizability across diverse STEM courses is unknown. We investigated the effect of spaced retrieval practice in nine introductory STEM courses. Retrieval practice opportunities were embedded in bi-weekly quizzes, either massed on a single quiz or spaced over multiple quizzes. Student performance on practice opportunities and a criterial test at the end of each course were examined as a function of massed or spaced practice. We also conducted a single-paper meta-analysis on criterial test scores to assess the generalizability of the effectiveness of spaced retrieval practice across introductory STEM courses.

    Results

    Significant positive effects of spacing on the criterial test were found in only two courses (Calculus I for Engineers and Chemistry for Health Professionals), although small positive effect sizes were observed in two other courses (General Chemistry and Diversity of Life). Meta-analyses revealed a significant spacing effect when all courses were included, but not when calculus was excluded. The generalizability of the spacing effect across STEM courses therefore remains unclear.

    Conclusions

    Although we could not clearly determine the generalizability of the benefits of spacing in STEM courses, our findings indicate that spaced retrieval practice could be a low-cost method of improving student performance in at least some STEM courses. More work is needed to determine when, how, and for whom spaced retrieval practice is most beneficial. The effect of spacing in classroom settings may depend on some design features such as the nature of retrieval practice activities (multiple-choice versus short answer) and/or feedback settings, as well as student actions (e.g., whether they look at feedback or study outside of practice opportunities). The evidence is promising, and further pragmatic research is encouraged.

     
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  9. Abstract

    Insight into the molecular mechanisms governing the development and maintenance of pluripotency is important for understanding early development and the use of stem cells in regenerative medicine. We demonstrate the selective inhibition of mTORC1 signaling is important for developing the inner cell mass (ICM) and the self-renewal of human embryonic stem cells. S6K suppressed the expression and function of pluripotency-related transcription factors (PTFs) OCT4, SOX2, and KLF4 through phosphorylation and ubiquitin proteasome-mediated protein degradation, indicating that S6K inhibition is required for pluripotency. PTFs inhibited mTOR signaling. The phosphorylation of S6 was decreased in PTF-positive cells of the ICM in embryos. Activation of mTORC1 signaling blocked ICM formation and the selective inhibition of S6K by rapamycin increased the ICM size in mouse blastocysts. Thus, selective inhibition of mTORC1 signaling supports the development and maintenance of pluripotency.

     
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  10. Importance

    Neurodevelopmental outcomes for children with congenital heart defects (CHD) have improved minimally over the past 20 years.

    Objectives

    To assess the feasibility and tolerability of maternal progesterone therapy as well as the magnitude of the effect on neurodevelopment for fetuses with CHD.

    Design, Setting, and Participants

    This double-blinded individually randomized parallel-group clinical trial of vaginal natural progesterone therapy vs placebo in participants carrying fetuses with CHD was conducted between July 2014 and November 2021 at a quaternary care children’s hospital. Participants included maternal-fetal dyads where the fetus had CHD identified before 28 weeks’ gestational age and was likely to need surgery with cardiopulmonary bypass in the neonatal period. Exclusion criteria included a major genetic or extracardiac anomaly other than 22q11 deletion syndrome and known contraindication to progesterone. Statistical analysis was performed June 2022 to April 2024.

    Intervention

    Participants were 1:1 block-randomized to vaginal progesterone or placebo by diagnosis: hypoplastic left heart syndrome (HLHS), transposition of the great arteries (TGA), and other CHD diagnoses. Treatment was administered twice daily between 28 and up to 39 weeks’ gestational age.

    Main Outcomes and Measures

    The primary outcome was the motor score of the Bayley Scales of Infant and Toddler Development-III; secondary outcomes included language and cognitive scales. Exploratory prespecified subgroups included cardiac diagnosis, fetal sex, genetic profile, and maternal fetal environment.

    Results

    The 102 enrolled fetuses primarily had HLHS (n = 52 [50.9%]) and TGA (n = 38 [37.3%]), were more frequently male (n = 67 [65.7%]), and without genetic anomalies (n = 61 [59.8%]). The mean motor score differed by 2.5 units (90% CI, −1.9 to 6.9 units;P = .34) for progesterone compared with placebo, a value not statistically different from 0. Exploratory subgroup analyses suggested treatment heterogeneity for the motor score for cardiac diagnosis (Pfor interaction = .03) and fetal sex (Pfor interaction = .04), but not genetic profile (Pfor interaction = .16) or maternal-fetal environment (Pfor interaction = .70).

    Conclusions and Relevance

    In this randomized clinical trial of maternal progesterone therapy, the overall effect was not statistically different from 0. Subgroup analyses suggest heterogeneity of the response to progesterone among CHD diagnosis and fetal sex.

    Trial Registration

    ClinicalTrials.gov Identifier:NCT02133573

     
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    Free, publicly-accessible full text available May 1, 2025