The bioluminescent reaction of the "sea firefly" Cypridina hilgendorfii is a prototypical system for marine bioluminescence, as its substrate possesses an imidazopyrazinone core that is a common link among organisms of eight phyla. The elucidation of the mechanism behind Cypridina bioluminescence is essential for future applications in bioimaging, biomedicine, and bioanalysis. In this study we have investigated the key step of chemiexcitation with a combined experimental and theoretical approach. The obtained results indicate that neutral dioxetanone is responsible for efficient chemiexcitation, as the thermolysis of this species gives access to a long region of the potential energy surface (PES), where the ground and excited singlet states are degenerated. Contrary to expected, neither chemically induced electron-exchange luminescence (CIEEL) nor charge transfer-initiated luminescence (CTIL) can be used to explain imidazopyrazinone-based bioluminescence, as there is no clear relationship between electron (ET)/charge (CT) transfer (occurring between the electron-rich moiety and dioxetanone) and chemiexcitation. Attractive electrostatic interactions between the CO and oxyluciferin moieties allow neutral dioxetanone to spend time in the PES region of degeneracy, while repulsive interactions for anionic dioxetanone lead to a quicker CO detachment.

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Group work is an essential activity during both graduate and undergraduate formation. Students develop a set of skills, and employ criticism which helps them to better handle future interpersonal situations. There is a vast theoretical literature and numerous case studies about group work, but we haven't yet seen much development concerning the assessment of individual group participants. It is not always easy to have the perception of each student contribution to the whole work. Nevertheless, more than frequently, the assessment of the group is transposed to each group participant, which in turn results in each student having the same final mark. We propose and describe a tool to manage and assess individual group work taking into account the amount of work, interaction, quality, and the temporal evolution of each group participant. The module features the possibility to create two types of activities: collaborative or cooperative group work. We describe the conceptual design of our tool and present the two operating modes of the module, which is based on events, alerts and conditions. We then describe the methodology for the assessment in the two operating modes and how these two major approaches can be deployed through our module into pedagogical situations.

Chemi-/bioluminescence are phenomena in which chemical energy is converted into electronically excited singlet states, which decay with light emission. Given this feature, along with high quantum yields and other beneficial characteristics, these systems have gained numerous applications in bioanalysis, in biomedicine, and in the pharmaceutical field. Singlet chemiexcitation is made possible by the formation of cyclic peroxides (as dioxetanones) as thermolysis provides a route for a ground state reaction to produce singlet excited states. However, such thermolysis can also lead to the formation of triplet states. While triplet states are not desired in the typical applications of chemi-/bioluminescence, the efficient production of such states can open the door for the use of these systems as sensitizers in photocatalysis and triplet-triplet annihilation, among other fields. Thus, the goal of this study is to assess the effect of heavy atom addition on the thermolysis and triplet chemiexcitation of a model dioxetanone. Monobromination does not affect the thermolysis reaction but can improve the efficiency of intersystem crossing, depending on the position of monobromination. Addition of bromine atoms to the triplet state reaction product has little effect on its properties, except on its electron affinity, in which monobromination can increase between 3.1 and 8.8 kcal mol−1.