RESUMEN
Three novel TADF (thermally activated delayed fluorescence) emitters based on the well-studied Qx-Ph-DMAC fluorophore are designed and synthesized. The photophysical properties of these materials are studied from a theoretical and experimental point of view, demonstrating the cumulative effects of multiple small modifications that combine to afford significantly improved TADF performance. First, an extra phenyl ring is added to the acceptor part of Qx-Ph-DMAC to increase the conjugation length, resulting in BQx-Ph-DMAC, which acts as an intermediate molecular structure. Next, an electron-deficient coumarin unit is incorporated to fortify the electron accepting ability, affording ChromPy-Ph-DMAC with red-shifted emission. Finally, the conjugated system is further enlarged by 'locking' the molecular structure, generating DBChromQx-DMAC with further red-shifted emission. The addition of the coumarin unit significantly impacts the charge-transfer excited state energy levels with little effect on the locally excited states, resulting in a decrease of the singlet-triplet energy gap. As a result, the two coumarin-based emitters show considerably improved TADF performance in 1 w/w% zeonex films when compared to the initial Qx-Ph-DMAC structure. 'Locking' the molecular structure further lowers the singlet-triplet energy gap, resulting in more efficient reverse intersystem crossing and increasing the contribution of TADF to the total emission.
RESUMEN
Tuberomammillary histamine neurons (TM) in the posterior hypothalamus project to extensive parts of the brain, including the hippocampal formation. The purpose of the present experiments was to investigate whether activation of the TM modulates signal transfer from the perforant pathway (PP) or ventral hippocampal commissure (VHC) to the dentate gyrus (DG) in freely moving rats. Paired pulses of electrical stimulation were delivered to PP or VHC, and evoked field potentials (fEPSPs and pop spikes) were recorded in the DG. Before activating PP or VHC, the TM was triggered by electrical stimulation. Experimentation was performed during four behavioral conditions: exploration, grooming, awake immobility, and slow-wave sleep. Electrical activation of the TM was found to modify dentate fEPSPs evoked by PP or VHC stimulation without generating a field potential by itself. Train stimulation of the TM (100 Hz, 500 ms) preceding paired pulses on the hippocampus by 50 ms decreased dentate fEPSPs in dependence of the ongoing behavior and the pathway stimulated. During exploration but not consummatory behavior, the PP signal was reduced when preceded by TM stimulation; during consummatory behavior but not exploration, the VHC signal was reduced. In contrast to other hippocampal afferents which increase pop spikes but leave fEPSPs unchanged, TM stimulation decreased dentate fEPSPs without affecting pop-spike activity. Thus, the TM-histaminergic system seems to modulate signal processing in the dentate gyrus in a specific way, exerting an inhibitory action on the entorhinal input only during learning-related exploratory behavior.
Asunto(s)
Conducta Animal/fisiología , Hipocampo/fisiología , Tubérculos Mamilares/fisiología , Transducción de Señal/fisiología , Animales , Giro Dentado/fisiología , Estimulación Eléctrica/métodos , Conducta Exploratoria/fisiología , Masculino , Vía Perforante/fisiología , Ratas , Ratas WistarRESUMEN
1. This paper describes two novel population patterns in the dentate gyrus of the awake rat, termed type 1 and type 2 dentate spikes (DS1, DS2). Their cellular generation and spatial distribution were examined by simultaneous recording of field potentials and unit activity using multiple-site silicon probes and wire electrode arrays. 2. Dentate spikes were large amplitude (2-4 mV), short duration (< 30 ms) field potentials that occurred sparsely during behavioral immobility and slow-wave sleep. Current-source density analysis revealed large sinks in the outer (DS1) and middle (DS2) thirds of the dentate molecular layer, respectively. DS1 and DS2 had similar longitudinal, lateral, and interhemispheric synchrony. 3. Dentate spikes invariably were coupled to synchronous population bursts of putative hilar interneurons. CA3 pyramidal cells, on the other hand were suppressed during dentate spikes. 4. After bilateral removal of the entorhinal cortex, dentate spikes disappeared, whereas sharp wave-associated bursts, reflecting synchronous discharge of the CA3-CA1 network, increased several fold. 5. These physiological characteristics of the dentate spikes suggest that they are triggered by a population burst of layer II stellate cells of the lateral (DS1) and medial (DS2) entorhinal cortex. 6. We suggest that dentate spike-associated synchronized bursts of hilar-region interneurons provide a suppressive effect on the excitability of the CA3-CA1 network in the intact brain.