| 1. |
- Raw, Juliana, et al.
(författare)
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Unveiling the Three-Step Model for the Interaction of Imidazolium-Based Ionic Liquids on Albumin
- 2023
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343. ; 8, s. 38101-38110
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Tidskriftsartikel (refereegranskat)abstract
- The effect of the ionic liquids (ILs) 1-methyl-3-tetradecylimidazolium chloride ([C14MIM][Cl]), 1-dodecyl-3-methylimidazolium chloride ([C12MIM][Cl]), and 1-decyl-methylimidazolium chloride ([C10MIM][Cl]) on the structure of bovine serum albumin (BSA) was investigated by fluorescence spectroscopy, ultraviolet-visible (UV-vis) spectroscopy, small-angle X-ray scattering (SAXS), and molecular dynamics (MD) simulations. Concerning the fluorescence measurements, we observed a blue shift and a fluorescence quenching as the IL concentration increased in the solution. Such behavior was observed for all three studied imidazolium-based ILs, being larger as the number of methylene groups in the alkyl chain increased. UV-vis absorbance measurements indicate that even at relatively small IL/protein ratios, like 1:1 or 1:2, ([C14MIM][Cl]) is able to change, at least partially, the sample turbidity. SAXS results agree with the spectroscopic techniques and suggest that the proteins underwent partial unfolding, evidenced by an increase in the radius of gyration (Rg) of the scattering particle. In the absence and presence of ([C14MIM][Cl]) = 3 mM BSA Rg increases from 29.1 to 45.1 Å, respectively. Together, these results indicate that the interaction of BSA with ILs is divided into three stages: the first stage is characterized by the protein in its native form. It takes place for protein/IL ≤ 1:2, and the interaction is predominantly due to the electrostatic forces provided by the negative charges on the surface of BSA and the cationic polar head of the ILs. In the second stage, higher IL concentrations induce the unfolding of the protein, most likely inducing the unfolding of domains I and III, in such a way that the protein’s secondary structure is kept almost unaltered. In the last stage, IL micelles start to form, and therefore, the interaction with protein reaches a saturation point and free micelles may be formed. We believe that this work provides new information about the interaction of ILs with BSA.
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| 2. |
- Medeiros, R., et al.
(författare)
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Understanding Nonlinear Optical Phenomena in N-Pyrimidinyl Stilbazolium Crystals via a Self-Consistent Electrostatic Embedding - DFT Approach
- 2024
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Ingår i: ACS Omega. - : American Chemical Society (ACS). - 2470-1343.
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Tidskriftsartikel (refereegranskat)abstract
- Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) have been used to investigate the nonlinear optical (NLO) properties of phenolic N-pyrimidinyl stilbazolium cationic chromophore in its corresponding noncentrosymmetric crystals. Such a cationic chromophore, the OPR (4-(4-hydroxystyryl)-1-(pyrimidin-2-yl)pyridinium), consists of a strong electron donor, the 4-hydroxyphenyl group, and a strong electron acceptor, the N-pyrimidinylpyridinium group based on two electron-withdrawing groups. The in-crystal NLO properties were determined by applying a supermolecule approach in combination with an iterative electrostatic scheme, in which the surrounding molecules of a unit cell are represented by point charges. With CAM-B3LYP, our absolute estimates for the largest diagonal component of the second-order nonlinear susceptibility tensor of OPR-based crystals range from 64.00 to 80.34 pm/V in the static regime and from 162.09 to 175.52 pm/V at 1907 nm. These values are significant when compared to those of benchmark stilbazolium-based crystals. Furthermore, the third-order susceptibility, which is related to the nonlinear optical process of the intensity-dependent refractive index, is also significant compared to the results for other organic crystals, such as chalcone derivatives. With TD-CAM-B3LYP, the two-state model effectively explains the similarity in the first hyperpolarizability values in the crystalline phase. This similarity arises from the combination of the oscillator strength and the charge transfer of the crucial transition. Therefore, phenolic organic salt crystals show great promise for various nonlinear optical applications.
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| 3. |
- Nicolas, Aude, et al.
(författare)
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Genome-wide Analyses Identify KIF5A as a Novel ALS Gene
- 2018
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Ingår i: Neuron. - : Cell Press. - 0896-6273 .- 1097-4199. ; 97:6, s. 1268-1283.e6
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Tidskriftsartikel (refereegranskat)abstract
- To identify novel genes associated with ALS, we undertook two lines of investigation. We carried out a genome-wide association study comparing 20,806 ALS cases and 59,804 controls. Independently, we performed a rare variant burden analysis comparing 1,138 index familial ALS cases and 19,494 controls. Through both approaches, we identified kinesin family member 5A (KIF5A) as a novel gene associated with ALS. Interestingly, mutations predominantly in the N-terminal motor domain of KIF5A are causative for two neurodegenerative diseases: hereditary spastic paraplegia (SPG10) and Charcot-Marie-Tooth type 2 (CMT2). In contrast, ALS-associated mutations are primarily located at the C-terminal cargo-binding tail domain and patients harboring loss-of-function mutations displayed an extended survival relative to typical ALS cases. Taken together, these results broaden the phenotype spectrum resulting from mutations in KIF5A and strengthen the role of cytoskeletal defects in the pathogenesis of ALS.
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| 4. |
- Silva, Jose Luis, et al.
(författare)
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X‑ray Photoelectron Fingerprints of High-Valence Ruthenium−Oxo Complexes along the Oxidation Reaction Pathway in an Aqueous Environment
- 2019
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Ingår i: The Journal of Physical Chemistry Letters. - : American Chemical Society (ACS). - 1948-7185. ; 10:24, s. 7636-7643
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Tidskriftsartikel (refereegranskat)abstract
- Recent advances in operando-synchrotron-based X-ray techniques are making it possible to address fundamental questions related to complex proton-coupled electron transfer reactions, for instance, the electrocatalytic water splitting process. However, it is still a grand challenge to assess the ability of the different techniques to characterize the relevant intermediates, with minimal interference on the reaction mechanism. To this end, we have developed a novel methodology employing X-ray photoelectron spectroscopy (XPS) in connection with the liquid-jet approach to probe the electrochemical properties of a model electrocatalyst, [RuII(bpy)2(py)-(OH2)]2+, in an aqueous environment. There is a unique fingerprint of the extremely important higher-valence ruthenium−oxo species in the XPS spectra along the oxidation reaction pathway. Furthermore, a sequential method combining quantum mechanics and molecular mechanics is used to illuminate the underlying physical chemistry of such systems. This study provides the basis for the future development of in-operando XPS techniques for water oxidation reactions.
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| 5. |
- Brandao, Idney, et al.
(författare)
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Density functional theory investigation of the second hyperpolarizability of the phenol blue in solution
- 2022
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Ingår i: Chemical Physics Letters. - : Elsevier. - 0009-2614 .- 1873-4448. ; 796
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Tidskriftsartikel (refereegranskat)abstract
- The second electronic hyperpolarizability (gamma) of the phenol blue (PB) in several solvents in a wide range of dielectric constants is investigated using the Density Functional Theory. The performance of hybrid functionals, with and without long-range correction, is addressed by comparison to Hartree-Fock calculations. Among the employed exchange-correlation functionals, the LC-BLYP functional is suitable for describing the behavior of gamma in solution. LC-BLYP results indicate a clear relationship between the second hyperpolarizability and the bond length alternation (BLA) coordinate for PB in solution, in agreement with experiment.
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| 6. |
- Chen, Qiaonan, 1992, et al.
(författare)
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Effects of Flexible Conjugation-Break Spacers of Non-Conjugated Polymer Acceptors on Photovoltaic and Mechanical Properties of All-Polymer Solar Cells
- 2022
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Ingår i: Nano-Micro Letters. - : Springer Science and Business Media LLC. - 2311-6706 .- 2150-5551. ; 14:1
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Tidskriftsartikel (refereegranskat)abstract
- Highlights: A series of non-conjugated acceptor polymers with flexible conjugation-break spacers (FCBSs) of different lengths were synthesized.The effect of FCBSs length on solubility of the acceptor polymers, and their photovoltaic and mechanical properties in all-polymer solar cells were explored.This work provides useful guidelines for the design of semiconducting polymers by introducing FCBS with proper length, which can giantly improved properties that are not possible to be achieved by the state-of-the-art fully conjugated polymers. Abstract: All-polymer solar cells (all-PSCs) possess attractive merits including superior thermal stability and mechanical flexibility for large-area roll-to-roll processing. Introducing flexible conjugation-break spacers (FCBSs) into backbones of polymer donor (PD) or polymer acceptor (PA) has been demonstrated as an efficient approach to enhance both the photovoltaic (PV) and mechanical properties of the all-PSCs. However, length dependency of FCBS on certain all-PSC related properties has not been systematically explored. In this regard, we report a series of new non-conjugated PAs by incorporating FCBS with various lengths (2, 4, and 8 carbon atoms in thioalkyl segments). Unlike common studies on so-called side-chain engineering, where longer side chains would lead to better solubility of those resulting polymers, in this work, we observe that the solubilities and the resulting photovoltaic/mechanical properties are optimized by a proper FCBS length (i.e., C2) in PA named PYTS-C2. Its all-PSC achieves a high efficiency of 11.37%, and excellent mechanical robustness with a crack onset strain of 12.39%, significantly superior to those of the other PAs. These results firstly demonstrate the effects of FCBS lengths on the PV performance and mechanical properties of the all-PSCs, providing an effective strategy to fine-tune the structures of PAs for highly efficient and mechanically robust PSCs.[Figure not available: see fulltext.]
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| 7. |
- Filate, Tadele Tamenu, 1994, et al.
(författare)
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Aqueous Processed All-Polymer Solar Cells with High Open-Circuit Voltage Based on Low-Cost Thiophene-Quinoxaline Polymers
- 2024
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Ingår i: ACS Applied Materials & Interfaces. - : American Chemical Society (ACS). - 1944-8252 .- 1944-8244. ; 16:10, s. 12886-12896
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Tidskriftsartikel (refereegranskat)abstract
- Eco-friendly solution processing and the low-cost synthesis of photoactive materials are important requirements for the commercialization of organic solar cells (OSCs). Although varieties of aqueous-soluble acceptors have been developed, the availability of aqueous-processable polymer donors remains quite limited. In particular, the generally shallow highest occupied molecular orbital (HOMO) energy levels of existing polymer donors limit further increases in the power conversion efficiency (PCE). Here, we design and synthesize two water/alcohol-processable polymer donors, poly[(thiophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-T)) and poly[(selenophene-2,5-diyl)-alt-(2-((13-(2,5,8,11-tetraoxadodecyl)-2,5,8,11-tetraoxatetradecan-14-yl)oxy)-6,7-difluoroquinoxaline-5,8-diyl)] (P(Qx8O-Se)) with oligo(ethylene glycol) (OEG) side chains, having deep HOMO energy levels (∼−5.4 eV). The synthesis of the polymers is achieved in a few synthetic and purification steps at reduced cost. The theoretical calculations uncover that the dielectric environmental variations are responsible for the observed band gap lowering in OEG-based polymers compared to their alkylated counterparts. Notably, the aqueous-processed all-polymer solar cells (aq-APSCs) based on P(Qx8O-T) and poly[(N,N′-bis(3-(2-(2-(2-methoxyethoxy)-ethoxy)ethoxy)-2-((2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-methyl)propyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl)-alt-(2,5-thiophene)] (P(NDIDEG-T)) active layer exhibit a PCE of 2.27% and high open-circuit voltage (VOC) approaching 0.8 V, which are among the highest values for aq-APSCs reported to date. This study provides important clues for the design of low-cost, aqueous-processable polymer donors and the fabrication of aqueous-processable OSCs with high VOC
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| 8. |
- Franco, Leandro R., et al.
(författare)
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Elucidating the conformational change and electronic absorption spectrum of p-dimethylamino-cinnamaldehyde merocyanine across different solvent polarities
- 2023
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Ingår i: Journal of Chemical Physics. - : American Institute of Physics (AIP). - 0021-9606 .- 1089-7690. ; 159:7
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Tidskriftsartikel (refereegranskat)abstract
- We present a theoretical study on the structural and electronic properties of the p-dimethylamino-cinnamaldehyde (DMACA) merocyanine molecule in solvents of different polarities by combining the free energy gradient and the average solvent electrostatic configuration methods via an iterative procedure based on the sequential quantum mechanics/molecular mechanics hybrid methodology. Studying such a system in solution is a crucial step for understanding the solvent effects on its properties, which can have implications in fields such as optoelectronics and biophysics. We found that the DMACA molecule presents different geometries in nonpolar and polar solvents, changing from a polyene-like structure with a pyramidal dimethylamino group (in gas phase or nonpolar solvents) to a cyanine-like structure with a planar dimethylamino group in water due to the stabilizing effect of hydrogen bonds between DMACA and water. The molecular absorption spectrum showed a significant change, increasing solvent polarity with a large shift of the lower energy band, while the other two low lying bands did not shift significantly. The study accurately described the solvatochromic shift of the lowest-energy band and analyzed the structure of the excited states in terms of the one-electron transition density matrix, which showed that the dominant excited state (associated with the first lower energy band) is characterized by a local excitation on the benzene ring with charge transfer character to the carbon conjugated segment.
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| 9. |
- Franco, Leandro R., et al.
(författare)
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Simulations reveal that antimicrobial BP100 induces local membrane thinning, slows lipid dynamics and favors water penetration
- 2022
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Ingår i: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 12:8, s. 4573-4588
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Tidskriftsartikel (refereegranskat)abstract
- BP100, a short antimicrobial peptide, produces membrane perturbations that depend on lipid structure and charge, salts presence, and peptide/lipid molar ratios. As membrane perturbation mechanisms are not fully understood, the atomic scale nature of peptide/membrane interactions requires a close-up view analysis. Molecular Dynamics (MD) simulations are valuable tools for describing molecular interactions at the atomic level. Here, we use MD simulations to investigate alterations in membrane properties consequent to BP100 binding to zwitterionic and anionic model membranes. We focused on membrane property changes upon peptide binding, namely membrane thickness, order parameters, surface curvature, lipid lateral diffusion and membrane hydration. In agreement with experimental results, our simulations showed that, when buried into the membrane, BP100 causes a decrease in lipid lateral diffusion and lipid acyl-chain order parameters and sharp local membrane thinning. These effects were most pronounced on the closest lipids in direct contact with the membrane-bound peptide. In DPPG and anionic-aggregate-containing DPPC/DPPG membranes, peptide flip (rotation of its non-polar facet towards the membrane interior) induced marked negative membrane curvature and enhanced the water residence half-life time in the lipid hydrophobic core and transmembrane water transport in the direction of the peptide. These results further elucidate the consequences of the initial interaction of cationic alpha-helical antimicrobial peptides with membranes.
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| 10. |
- Franco, Leandro R., et al.
(författare)
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Theoretical investigation of solvent and oxidation/deprotonation effects on the electronic structure of a mononuclear Ru-aqua-polypyridine complex in aqueous solution
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry. - 1463-9076 .- 1463-9084. ; 25:36, s. 24475-24494
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Tidskriftsartikel (refereegranskat)abstract
- Mononuclear polypyridine ruthenium (Ru) complexes can catalyze various reactions, including water splitting, and can also serve as photosensitizers in solar cells. Despite recent progress in their synthesis, accurately modeling their physicochemical properties, particularly in solution, remains challenging. Herein, we conduct a theoretical investigation of the structural and electronic properties of a mononuclear Ru-aqua polypyridine complex in aqueous solution, considering five of its possible oxidation/protonation states species: [RuII(H2O)(py)(bpy)2]2+, [RuII(OH)(py)(bpy)2]+, [RuIII(H2O)(py)(bpy)2]3+, [RuIII(OH)(py)(bpy)2]2+ and [RuIV(O)(py)(bpy)2]2+, where py = pyridine and bpy = 2,2 & PRIME;-bipyridine. At first, we investigate the impact of proton-coupled and non-coupled electron transfer reactions on the geometry and electronic structure of the complexes in vacuum and in solution, using an implicit solvent model. Then, using a sequential multiscale approach that combines quantum mechanics and molecular mechanics (S-QM/MM), we examine the explicit solvent effects on the electronic excitations of the complexes, and compare them with the experimental results. The complexes were synthesized, and their absorption spectra measured in aqueous solution. To accurately describe the QM interactions between the metal center and the aqueous ligand in the MM simulations, we developed new force field parameters for the Ru atom. We analyze the solvent structure around the complexes and account for its explicit influence on the polarization and electronic excitations of the complexes. Notably, accounting for the explicit solvent polarization effects of the first solvation shells is essential to correctly describe the energy of the electronic transitions, and the explicit treatment of the hydrogen bonds at the QM level in the excitation calculations improves the accuracy of the description of the metal-to-ligand charge-transfer bands. Transition density matrix analysis is used to characterize all electronic transitions in the visible and ultraviolet ranges according to their charge-transfer (CT) character. This study elucidates the electronic structure of those ruthenium polypyridyl complexes in aqueous solution and underscores the importance of precisely describing solvent effects, which can be achieved employing the S-QM/MM method. Ru-aqua complex in water, showcasing Ru atom, coordinated water, and hydrogen bonds on left; UV-Vis spectrum and comparison to experiment on right. QM/MM approach emphasized.
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