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Creators/Authors contains: "Clark, Douglas"

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  1. Alkylidene cyclopropanes (ACPs) are valuable synthetic intermediates because of their constrained structure and opportunities for further diversification. Although routes to ACPs are known, preparations of ACPs with control of both the configuration of the cyclopropyl (R vs S) group and the geometry of the alkene (E vs Z) are unknown. We describe enzymatic cyclopropanation of allenes with ethyl diazoacetate (EDA) catalyzed by an iridium-containing cytochrome (Ir(Me)-CYP119) that controls both stereochemical elements. Two mutants of Ir(Me)-CYP119 identified by 6-codon (6c, VILAFG) saturation mutagenesis catalyze the formation of (E)-ACPs with −93% to >99% ee and >99:1 E/Z ratio with just three rounds of 96 mutants. By four additional rounds of mutagenesis, an enzyme variant was identified that forms (Z)-ACPs with up to 94% ee and a 28:72 E/Z ratio. Computational studies show that the orientation of the carbene unit dictated by the mutated positions accounts for the stereoselectivity. 
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  2. What does it mean for a game to engage players in academically meaningful play? Much has been written about the integration of educational learning within the design of games in terms of intrinsic/endogenous design. While these framings capture the positioning of learning within games, they provide less insight into what might distinguish design choices that are powerful in terms of both learning and gameplay from design choices that might be limiting from one or both of these perspectives. In this article, we therefore propose a framework for thinking about academically meaningful play that builds upon and extends more general ideas about meaningful play (Salen & Zimmerman, 2003). The proposed framework focuses on (a) discernability of choice outcomes, (b) integration of choice outcomes into unfolding game state, (c) meaningful choices grounded in core academic ideas, and (d) thematic and challenge access. We analyze three academic games that focus on geometric transformations as comparative cases to consider the potential affordances of the proposed framework for analyzing the implications of design choices. 
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  3. Research on geometric transformations suggests that early learners possess intuitive understandings grounded in motion metaphors, transitioning to mappings. The processes through which students transition between these two conceptions are not fully understood. We propose that Vygotskian hybridizing (related to Vygotsky’s articulation of everyday and scientific concepts) may provide a lens for thinking about the relationship between these conceptions. Design features of block-based programming environments provide affordances to support hybridizing by providing a co-action space for learning. We conducted a comparative case study of four grade seven and eight students working in a Scratch task (Code the Quilts) and a game (Transformations Quest) to construct understandings of geometric transformations. Our findings suggest: (1) students hybridized their personal experience of motion and mathematical knowledge of mapping to build geometric transformations understandings and (2) the co-action space in which students worked promoted distributed interactions between students, block-based environments, and tasks to support hybridizing. 
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  4. Abstract. There is unambiguous evidence that glaciers have retreated from their 19th century positions, but it is less clear how far glaciers have retreated relative to their long-term Holocene fluctuations. Glaciers in western North America are thought to have advanced from minimum positions in the Early Holocene to maximum positions in the Late Holocene. We assess when four North American glaciers, located between 38–60∘ N, were larger or smaller than their modern (2018–2020 CE) positions during the Holocene. We measured 26 paired cosmogenic in situ 14C and 10Be concentrations in recently exposed proglacial bedrock and applied a Monte Carlo forward model to reconstruct plausible bedrock exposure–burial histories. We find that these glaciers advanced past their modern positions thousands of years apart in the Holocene: a glacier in the Juneau Icefield (BC, Canada) at ∼2 ka, Kokanee Glacier (BC, Canada) at ∼6 ka, and Mammoth Glacier (WY, USA) at ∼1 ka; the fourth glacier, Conness Glacier (CA, USA), was likely larger than its modern position for the duration of the Holocene until present. The disparate Holocene exposure–burial histories are at odds with expectations of similar glacier histories given the presumed shared climate forcings of decreasing Northern Hemisphere summer insolation through the Holocene followed by global greenhouse gas forcing in the industrial era. We hypothesize that the range in histories is the result of unequal amounts of modern retreat relative to each glacier's Holocene maximum position, rather than asynchronous Holocene advance histories. We explore the influence of glacier hypsometry and response time on glacier retreat in the industrial era as a potential cause of the non-uniform burial durations. We also report mean abrasion rates at three of the four glaciers: Juneau Icefield Glacier (0.3±0.3 mm yr−1), Kokanee Glacier (0.04±0.03 mm yr−1), and Mammoth Glacier (0.2±0.2 mm yr−1). 
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  5. Olive, Andrea (Ed.)
    Grizzly bears and polar bears often serve as ecological “flagship species” in conservation efforts, but although consumptively used in some areas and cultures they can also be important cultural keystone species even where not hunted. We extend the application of established criteria for defining cultural keystone species to also encompass species with which cultures have a primarily nonconsumptive relationship but that are nonetheless disproportionately important to well-being and identity. Grizzly bears in coastal British Columbia are closely linked to many Indigenous Peoples (including the Haíɫzaqv (Heiltsuk), Kitasoo/Xai’xais, and Nuxalk First Nations), where they are central to the identity, culture, and livelihoods of individuals, families, Chiefs, and Nations. Polar bears in Churchill, Manitoba, provide another example as a cultural keystone species for a mixed Indigenous and non-Indigenous community in which many of the livelihood benefits from the species are mediated by economic transactions in a globalized tourism market. We discuss context specificity and questions of equity in sharing of benefits from cultural keystone species. Our expanded definition of cultural keystone species gives broader recognition of the beyond-ecological importance of these species to Indigenous Peoples, which highlights the societal and ecological importance of Indigenous sovereignty and could facilitate the increased cross-cultural understanding critical to reconciliation. 
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