| 1. |
- Ahlawat, Paramvir, et al.
(författare)
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A combined molecular dynamics and experimental study of two-step process enabling low-temperature formation of phase-pure alpha-FAPbI3
- 2021
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Ingår i: Science Advances. - : American Association for the Advancement of Science (AAAS). - 2375-2548. ; 7:17
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Tidskriftsartikel (refereegranskat)abstract
- It is well established that the lack of understanding the crystallization process in a two-step sequential deposition has a direct impact on efficiency, stability, and reproducibility of perovskite solar cells. Here, we try to understand the solid-solid phase transition occurring during the two-step sequential deposition of methylammonium lead iodide and formamidinium lead iodide. Using metadynamics, x-ray diffraction, and Raman spectroscopy, we reveal the microscopic details of this process. We find that the formation of perovskite proceeds through intermediate structures and report polymorphs found for methylammonium lead iodide and formamidinium lead iodide. From simulations, we discover a possible crystallization pathway for the highly efficient metastable alpha phase of formamidinium lead iodide. Guided by these simulations, we perform experiments that result in the low-temperature crystallization of phase-pure alpha-formamidinium lead iodide.
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| 2. |
- Bruce, Neil J., et al.
(författare)
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Regulation of adenylyl cyclase 5 in striatal neurons confers the ability to detect coincident neuromodulatory signals
- 2019
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Ingår i: PloS Computational Biology. - : Public Library of Science (PLoS). - 1553-734X .- 1553-7358. ; 15:10
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Tidskriftsartikel (refereegranskat)abstract
- Author summary Adenylyl cyclases (ACs) are enzymes that can translate extracellular signals into the intracellular molecule cAMP, which is thus a 2nd messenger of extracellular events. The brain expresses nine membrane-bound AC variants, and AC5 is the dominant form in the striatum. The striatum is the input stage of the basal ganglia, a brain structure involved in reward learning, i.e. the learning of behaviors that lead to rewarding stimuli (such as food, water, sugar, etc). During reward learning, cAMP production is crucial for strengthening the synapses from cortical neurons onto the striatal principal neurons, and its formation is dependent on several neuromodulatory systems such as dopamine and acetylcholine. It is, however, not understood how AC5 is activated by transient (subsecond) changes in the neuromodulatory signals. Here we combine several computational tools, from molecular dynamics and Brownian dynamics simulations to bioinformatics approaches, to inform and constrain a kinetic model of the AC5-dependent signaling system. We use this model to show how the specific molecular properties of AC5 can detect particular combinations of co-occuring transient changes in the neuromodulatory signals which thus result in a supralinear/synergistic cAMP production. Our results also provide insights into the computational capabilities of the different AC isoforms. Long-term potentiation and depression of synaptic activity in response to stimuli is a key factor in reinforcement learning. Strengthening of the corticostriatal synapses depends on the second messenger cAMP, whose synthesis is catalysed by the enzyme adenylyl cyclase 5 (AC5), which is itself regulated by the stimulatory G alpha(olf) and inhibitory G alpha(i) proteins. AC isoforms have been suggested to act as coincidence detectors, promoting cellular responses only when convergent regulatory signals occur close in time. However, the mechanism for this is currently unclear, and seems to lie in their diverse regulation patterns. Despite attempts to isolate the ternary complex, it is not known if G alpha(olf) and G alpha(i) can bind to AC5 simultaneously, nor what activity the complex would have. Using protein structure-based molecular dynamics simulations, we show that this complex is stable and inactive. These simulations, along with Brownian dynamics simulations to estimate protein association rates constants, constrain a kinetic model that shows that the presence of this ternary inactive complex is crucial for AC5's ability to detect coincident signals, producing a synergistic increase in cAMP. These results reveal some of the prerequisites for corticostriatal synaptic plasticity, and explain recent experimental data on cAMP concentrations following receptor activation. Moreover, they provide insights into the regulatory mechanisms that control signal processing by different AC isoforms.
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| 3. |
- Carrasco Busturia, David, et al.
(författare)
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Multiscale biomolecular simulations in the exascale era
- 2024
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Ingår i: Current opinion in structural biology. - : Elsevier BV. - 0959-440X .- 1879-033X. ; 86
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Tidskriftsartikel (refereegranskat)abstract
- The complexity of biological systems and processes, spanning molecular to macroscopic scales, necessitates the use of multiscale simulations to get a comprehensive understanding. lar dynamics (MD) simulations are crucial for capturing processes beyond the reach of classical MD simulations. The advent of exascale computing offers unprecedented opportunities for scientific exploration, not least within life sciences, where simulations are essential to unravel intricate molecular leveraging the immense computational power of exascale computing requires innovative algorithms and software designs. In this context, we discuss the current status and future prospects of multiscale biomolecular simulations on exascale supercomputers with a focus on QM/MM MD. We highlight our own efforts in developing a versatile and high-performance multiscale simulation framework with the aim of efficient utilization of state-of-the-art supercomputers. We showcase its application in uncovering complex biological mechanisms and its potential for leveraging exascale computing.
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| 4. |
- Jeong, Jaeki, et al.
(författare)
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Pseudo-halide anion engineering for α-FAPbI3 perovskite solar cells
- 2021
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Ingår i: Nature. - : Springer Nature. - 0028-0836 .- 1476-4687. ; 592:7854, s. 381-385
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Tidskriftsartikel (refereegranskat)abstract
- Metal halide perovskites of the general formula ABX(3)-where A is a monovalent cation such as caesium, methylammonium or formamidinium; B is divalent lead, tin or germanium; and X is a halide anion-have shown great potential as light harvesters for thin-film photovoltaics(1-5). Among a large number of compositions investigated, the cubic a-phase of formamidinium lead triiodide (FAPbI(3)) hasemerged as the most promising semiconductor for highly efficient and stable perovskite solar cells(6-9), and maximizing the performance of this material in such devices is of vital importance for the perovskite researchcommunity. Here we introduce an anion engineering concept that uses the pseudo-halide anion formate (HCOO-) to suppress anion-vacancy defects that are present at grain boundaries and at the surface of the perovskite films and to augment the crystallinity of the films. Theresulting solar cell devices attain a power conversion efficiency of 25.6 per cent (certified 25.2 per cent), have long-term operational stability (450 hours) and show intense electroluminescence with external quantum efficiencies of more than 10 per cent. Our findings provide a direct route to eliminate the most abundant and deleterious lattice defects present in metal halide perovskites, providing a facile access to solution-processable films with improved optoelectronic performance.
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| 5. |
- Krishna, Anurag, et al.
(författare)
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Mitigating the Heterointerface Driven Instability in Perovskite Photovoltaics
- 2023
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Ingår i: ACS Energy Letters. - : American Chemical Society (ACS). - 2380-8195. ; 8:8, s. 3604-3613
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Tidskriftsartikel (refereegranskat)abstract
- Metal halide perovskites have thepotential to revolutionizethefield of photovoltaics, though limited stability has impeded commercialexploitation. The soft heterointerface between the perovskite andcharge-transporting layer is one of the major bottlenecks that limitsoperational stability. Here, we present rationally designed molecularmodulators that synergistically improve the stability of the & alpha;-FAPbI(3)-based perovskite solar cells while retaining power conversionefficiency (PCE) of 24.0% with a high open-circuit voltage (V (OC)) of & SIM;1.195 V. The interfacially modifiedphotovoltaic cells exhibit high operational stability, whereby thechampion device retains & SIM;88% of initial performance after 2000h of maximum power point tracking at 40 & DEG;C and 1 sun illumination.The molecular origins of such enhanced stability and device performanceare corroborated by multiscale characterization techniques and modeling,providing insights into the origins of performance and stability enhancements.
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| 6. |
- Krishna, Anurag, et al.
(författare)
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Nanoscale interfacial engineering enables highly stable and efficient perovskite photovoltaics
- 2021
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Ingår i: Energy & Environmental Science. - : Royal Society of Chemistry. - 1754-5692 .- 1754-5706. ; 14:10, s. 5552-5562
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Tidskriftsartikel (refereegranskat)abstract
- We present a facile molecular-level interface engineering strategy to augment the long-term operational and thermal stability of perovskite solar cells (PSCs) by tailoring the interface between the perovskite and hole transporting layer (HTL) with a multifunctional ligand 2,5-thiophenedicarboxylic acid. The solar cells exhibited high operational stability (maximum powering point tracking at one sun illumination) with a stabilized T-S80 (the time over which the device efficiency reduces to 80% after initial burn-in) of approximate to 5950 h at 40 degrees C and a stabilized power conversion efficiency (PCE) over 23%. The origin of high device stability and performance is correlated to the nano/sub-nanoscale molecular level interactions between ligand and perovskite layer, which is further corroborated by comprehensive multiscale characterization. These results provide insights into the modulation of the grain boundaries, local density of states, surface bandgap, and interfacial recombination. Chemical analysis of aged devices showed that molecular passivation suppresses interfacial ion diffusion and inhibits the photoinduced I-2 release that irreversibly degrades the perovskite. The interfacial engineering strategies enabled by multifunctional ligands can expedite the path towards stable PSCs.
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| 7. |
- Maurer, Patrick, et al.
(författare)
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Automated parametrization of biomolecular force fields from quantum mechanics/molecular mechanics (QM/MM) simulations through force matching
- 2007
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Ingår i: Journal of Chemical Theory and Computation. - : American Chemical Society (ACS). - 1549-9618 .- 1549-9626. ; 3:2, s. 628-639
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Tidskriftsartikel (refereegranskat)abstract
- We introduce a novel procedure to parametrize biomolecular force fields. We perform finite-temperature quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations, with the fragment or moiety that has to be parametrized being included in the QM region. By applying a force-matching algorithm, we derive a force field designed in order to reproduce the steric, electrostatic, and dynamic properties of the QM subsystem. The force field determined in this manner has an accuracy that is comparable to the one of the reference QM/MM calculation, but at a greatly reduced computational cost. This allows calculating quantities that would be prohibitive within a QM/MM approach, such as thermodynamic averages involving slow motions of a protein. The method is tested on three different systems in aqueous solution: dihydrogenphosphate, glycyl-alanine dipeptide, and a nitrosyl-dicarbonyl complex of technetium(I). Molecular dynamics simulations with the optimized force field show overall excellent performance in reproducing properties such as structures and dipole moments of the solutes as well as their solvation pattern.
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| 8. |
- Tress, Wolfgang, et al.
(författare)
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Extended Intermolecular Interactions Governing Photocurrent-Voltage Relations in Ternary Organic Solar Cells
- 2016
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Ingår i: The Journal of Physical Chemistry Letters. - : AMER CHEMICAL SOC. - 1948-7185. ; 7:19, s. 3936-3944
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Tidskriftsartikel (refereegranskat)abstract
- Efficient organic solar cells are based on (electron) donor-acceptor heterojunctions. An optically generated excited molecular state (exciton) is dissociated at this junction, forming a charge-transfer (CT) state in an intermediate step before the electron and hole are completely separated. The observed highly efficient dissociation of this Coulombically bound state raises the question on the dissociation mechanism. Here, we show that the observed high quantum yields of charge carrier generation and CT state dissociation are due to extended (and consequently weakly bound) CT states visible in absorption and emission spectra and first-principles calculations. Identifying a new geminate-pair loss mechanism via donor excimers, we find that the hole on the small-molecule donor is not localized on a single molecule and charge separation is correlated with the energetic offset between excimer and CT states. Thus, the charges upon interface charge transfer and even in the case of back-transfer and recombination are less localized than commonly assumed.
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| 9. |
- van Keulen, Siri Camee, et al.
(författare)
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Does Proton Conduction in the Voltage-Gated H+ Channel hHv1 Involve Grotthuss-Like Hopping via Acidic Residues?
- 2017
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 15:121, s. 3340-3351
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Tidskriftsartikel (refereegranskat)abstract
- Hv1 are ubiquitous highly selective voltage-gated proton channels involved in male fertility, immunology and the invasiveness of certain forms of breast cancer. The mechanism of proton extrusion in Hv1 is not yet understood while it constitutes the first step towards the design of high-affinity drugs aimed at this important pharmacological target. In this contribution, we explore the details of the mechanism via an integrative approach, using classical and QM/MM molecular dynamics simulations of a monomeric hHv1 model. We propose that protons localize in three binding sites along the channel lumen, formed by three pairs of conserved negatively charged residues lining the pore: D174/E153, D112/D185 and E119/D123. Local rearrangements, involving notably a dihedral transition of F150, a conserved phenylalanine lining the permeation pathway, appear to allow protons to hop from one acidic residue to the next through a bridging water molecule. These results constitute a first attempt at rationalizing hHv1 selectivity for H+ and the role of D112 in this process. They pave the way for further quantitative characterization of H+ transport in hHv1.
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| 10. |
- Zhang, Hong, et al.
(författare)
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A universal co-solvent dilution strategy enables facile and cost-effective fabrication of perovskite photovoltaics
- 2022
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Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- Cost management and toxic waste generation are two key issues that must be addressed before the commercialization of perovskite optoelectronic devices. We report a groundbreaking strategy for eco-friendly and cost-effective fabrication of highly efficient perovskite solar cells. This strategy involves the usage of a high volatility co-solvent, which dilutes perovskite precursors to a lower concentration (<0.5 M) while retaining similar film quality and device performance as a high concentration (>1.4 M) solution. More than 70% of toxic waste and material cost can be reduced. Mechanistic insights reveal ultra-rapid evaporation of the co-solvent together with beneficial alteration of the precursor colloidal chemistry upon dilution with co-solvent, which in-situ studies and theoretical simulations confirm. The co-solvent tuned precursor colloidal properties also contribute to the enhancement of the stability of precursor solution, which extends its processing window thus minimizing the waste. This strategy is universally successful across different perovskite compositions, and scales from small devices to large-scale modules using industrial spin-coating, potentially easing the lab-to-fab translation of perovskite technologies.
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