Kinetics and Efficiency of Triplet-Triplet Annihilation Photon Upconversion under Pulsed Excitation Conditions

Triplet-triplet annihilation is a promising method to convert low energy photons to high energy ones. Due to the long time-scales and the bimolecular nature of the process, the overall efficiency of triplet-triplet annihilation greatly depends on the excitation type and intensity. Upconversion efficiencies are usually measured using continuous wave conditions. Here we develop an analytical and experimental method to investigate how the excitation modulation affects the triplet-triplet annihilation efficiency. The simulated and experimental results demonstrate high consistency. The triplet-triplet annihilation efficiency drops as expected with increasing excitation frequency at a fixed average power density, which our simulations accurately predicts. The method described here allows to relate efficiencies measured at pulsed conditions with those measured at continuous wave conditions

Electron transfer reactions in sub-porphyrin-naphthyldiimide dyads

A series of donor-acceptor compounds based on a sub-porphyrin (SubP) as an electron donor and naphthyldiimide (NDI) as an acceptor has been designed, synthesized and investigated by time-resolved emission and transient absorption measurements. The donor and acceptor are separated by a single phenyl spacer substituted by methyl groups in order to systematically vary the electronic coupling. The electron transfer reactions in toluene are found to be quite fast; charge separation is quantitative and occurs within 5-10 ps and charge recombination occurs in 1-10 ns, depending on the substitution pattern. As expected, when steric bulk is introduced on the adjoining phenyl group, electron transfer rates slow down because of smaller electronic coupling. Quantum mechanical modelling of the potential energy for twisting the dihedral angles combined with a simplified model of the electronic coupling semi-quantitatively explains the observed variation of the electron transfer rates. Investigating the temperature variation of the charge separation in 2-methyltetrahydrofuran (2-MTHF) and analyzing using the Marcus model allow experimental estimation of the electronic coupling and reorganization energies. At low temperature, relatively strong phosphorescence is observed from the donor-acceptor compounds with onset at 660 nm signaling that charge recombination occurs, at least partially, through the sub-porphyrin localized triplet excited state. Finally, it is noted that charge separation in all SubP-NDI dyads is efficient even at cryogenic temperatures (85 K) in 2-MTHF glass

Technology Over-Consumption: Helping Students Find Balance in a World of Alluring Distractions

The last two decades has seen a fundamental shift in society with the growth in technology and the growth of social media. This shift has been embraced in the classroom as a tool to enhance the learning experience of the student. Students have experienced a fundamental shift in interaction with themselves and the world they inhabit with the exponential growth in technology and social media both inside and outside the classroom. The result is the multitasking student, who must constantly switch between a growing number of interactions. Attention spans have a finite limit, and eventually students experience an over-consumption of technology, characterized by increasing levels of anxiety and stress. To better serve our students, marketing educators must reconsider the technology experience in the classroom. Further, marketing educators should educate students on the detrimental effects of technology over-consumption and solutions to relieve themselves from their over-stressed plugged-in world

Exciton Delocalization Counteracts the Energy Gap: A New Pathway toward NIR-Emissive Dyes

Exciton coupling between the transition dipole moments of ordered dyes in supramolecular assemblies, so-called J/H-aggregates, leads to shifted electronic transitions. This can lower the excited state energy, allowing for emission well into the near-infrared regime. However, as we show here, it is not only the excited state energy modifications that J-aggregates can provide. A bay-alkylated quaterrylene was synthesized, which was found to form J-aggregates in 1,1,2,2-tetrachloroethane. A combination of superradiance and a decreased nonradiative relaxation rate made the J-aggregate four times more emissive than the monomeric counterpart. A reduced nonradiative relaxation rate is a nonintuitive consequence following the 180 nm (3300 cm-1) red-shift of the J-aggregate in comparison to the monomeric absorption. However, the energy gap law, which is commonly invoked to rationalize increased nonradiative relaxation rates with increasing emission wavelength, also contains a reorganization energy term. The reorganization energy is highly suppressed in J-aggregates due to exciton delocalization, and the framework of the energy gap law could therefore reproduce our experimental observations. J-Aggregates can thus circumvent the common belief that lowering the excited state energies results in large nonradiative relaxation rates and are thus a pathway toward highly emissive organic dyes in the NIR regime

Anti-SARS-CoV2 antibody responses in serum and cerebrospinal fluid of COVID-19 patients with neurological symptoms

Antibody responses to SARS-CoV-2 in serum and CSF from 16 COVID-19 patients with neurological symptoms were assessed using two independent methods. IgG specific for the virus spike protein was found in 81% of cases in serum and in 56% in CSF. SARS-CoV-2 IgG in CSF was observed in two cases with negative serology. Levels of IgG in both serum and CSF were associated with disease severity (p<0.05). All patients with elevated markers of CNS damage in CSF also had CSF antibodies (p=0.002), and CSF antibodies had the highest predictive value for neuronal damage markers of all tested clinical variables

Perovskite solar cells using polymer electrolytes

This study deals with the characterization of methylammonium lead iodide (MAPbI3) material and the fabrication of perovskite solar cells using gel polymer electrolyte as the charge transport medium. The crystalline lead–based perovskite has been verified by x-ray diffraction (XRD). The [100], [200], [210], [211], [220], [300] and [222] reflection planes can be observed at 2θ angles of 14.10°, 28.35°, 31.90°, 34.95°, 40.40°, 43.15° and 50.20°, indicating a cubic crystal symmetry for CH3NH3PbI3. EDX spectrum showed a Pb:I ratio of approximately 1:3 as in CH3NH3PbI3. The band gap for lead-based perovskite is 1.45 eV estimated from UV-Vis absorption spectroscopy. The nanocrystalline MAPbI3 have been observed using field emission scanning electron microscopy (FESEM), where the average cuboid size of perovskite nanocrystals is 380 nm. The cell have been fabricated using gel polymer electrolyte with composition 17.02 wt.% PVA–13.93 wt.% TBAI–0.96 wt.% I2– 68.09 wt.% DMF. The cell exhibits a power conversion efficiency (PCE) of 1.28% with open circuit voltage (Voc) 0.58 mV, short circuit current density (Jsc) 3.74 mA cm−2 and fill factor (FF) 59.18%

Polyacrylonitrile gel polymer electrolyte based dye sensitized solar cells for a prototype solar panel

Polyacrylonitrile (PAN) based gel polymer electrolytes (GPE) were prepared using lithium iodide (LiI), 1-butyl-3-methylimidazolium iodide (BMII) and tetrapropyl ammonium iodide (TPAI). The LiI mass fraction in the electrolyte was varied while keeping the masses of other components constant in order to enhance the solar cell performance. The addition of 4.61 wt.% LiI in the GPE increased the electrolyte room temperature ionic conductivity from (2.32 ± 0.02) to (3.91 ± 0.04) mS cm−1. The increase in conductivity with the addition of LiI salts was attributed to the increase in diffusion coefficient, mobility and number density of charge carriers as determined from Nyquist plot fitting. The incorporation of LiI salts in PAN-based GPE has enhanced the efficiency of the DSSC as expected. The best cell performance was obtained with an electrolyte containing 4.61 wt.% LiI sandwiched between a single mesoporous layer of TiO2 soaked in N3 dye sensitizer and a platinum counter electrode, which showed a power conversion efficiency (PCE) of (5.4 ± 0.1) % with a short circuit current density (Jsc) of (21.0 ± 1.1) mA cm−2, an open circuit voltage (Voc) of (0.48 ± 0.02) V and a fill factor (FF) of (53.4 ± 0.9) %. The DSSCs with 4.61 wt.% of LiI have been used to fabricate prototype solar panels for operating small devices. The panels were assembled using a number of cells, each having an area of 2 cm × 2 cm, connected in series and parallel. The panel, consisting of a set of eight cells in series which was connected in parallel with another set of eight cells in series, produces an average power conversion efficiency of (3.7 ± 0.2)% with a maximum output power of (17.1 ± 0.9) mW

Molecular dynamics simulations reveal that AEDANS is an inert fluorescent probe for the study of membrane proteins

Computer simulations were carried out of a number of AEDANS-labeled single cysteine mutants of a small reference membrane protein, M13 major coat protein, covering 60% of its primary sequence. M13 major coat protein is a single membrane-spanning, α-helical membrane protein with a relatively large water-exposed region in the N-terminus. In 10-ns molecular dynamics simulations, we analyze the behavior of the AEDANS label and the native tryptophan, which were used as acceptor and donor in previous FRET experiments. The results indicate that AEDANS is a relatively inert environmental probe that can move unhindered through the lipid membrane when attached to a membrane protein

Why can pulmonary vein stenoses created by radiofrequency catheter ablation worsen during and after follow-up ? A potential explanation

<p>Abstract</p> <p>Background</p> <p>Radiofrequency catheter ablation of excitation foci inside pulmonary veins (PV) generates stenoses that can become quite severe during or after the follow-up period. Since severe PV stenoses have most often disastrous consequences, it would be important to know the underlying mechanism of this temporal evolution. The present study proposes a potential explanation based on mechanical considerations.</p> <p>Methods</p> <p>we have used a mathematical-physical model to examine the cyclic increase in axial wall stress induced in the proximal (= upstream), non-stenosed segment of a stenosed pulmonary vein during the forward flow phases. In a representative example, the value of this increase at peak flow was calculated for diameter stenoses (DS) ranging from 1 to 99%.</p> <p>Results</p> <p>The increase becomes appreciable at a DS of roughly 30% and rise then strongly with further increasing DS value. At high DS values (e.g. > 90%) the increase is approximately twice the value of the axial stress present in the PV during the zero-flow phase.</p> <p>Conclusion</p> <p>Since abnormal wall stresses are known to induce damages and abnormal biological processes (e.g., endothelium tears, elastic membrane fragmentations, matrix secretion, myofibroblast generation, etc) in the vessel wall, it seems plausible that the supplementary axial stress experienced cyclically by the stenotic and the proximal segments of the PV is responsible for the often observed progressive reduction of the vessel lumen after healing of the ablation injury. In the light of this model, the only potentially effective therapy in these cases would be to reduce the DS as strongly as possible. This implies most probably stenting or surgery.</p