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Multidrug resistance (MDR) is a rising threat to global health because the number of essential antibiotics used for treating MDR infections is increasingly compromised. In this work we report a group of new amphiphilic peptides (AMPs) derived from the well-studied G3 (G(IIKK)3I-NH2) to fight infections from Gram-positive bacteria including susceptible Staphylococcus aureus and methicillin-resistant Staphylococcus aureus (MRSA), focusing on membrane interactions. Time-dependent killing experiments revealed that substitutions of II by WW (GWK), II by FF (GFK) and KK by RR (GIR) resulted in improved bactericidal efficiencies compared to G3 (GIK) on both S. aureus and MRSA, with the order of GWK > GIR > GFK > GIK. Electronic microscopy imaging revealed structural disruptions of AMP binding to bacterial cell walls. Fluorescence assays including AMP binding to anionic lipoteichoic acids (LTA) in cell-free and cell systems indicated concentration and time-dependent membrane destabilization associated with bacterial killing. Furthermore, AMP's binding to anionic plasma membrane via similar fluorescence assays revealed a different extent of membrane depolarization and leakage. These observations were supported by the penetration of AMPs into the LTA barrier and the subsequent structural compromise to the cytoplasmic membrane as revealed from SANS (small angle neutron scattering). Both experiments and molecular dynamics (MD) simulations revealed that GWK and GIR could make the membrane more rigid but less effective in diffusive efficiency than GIK and GFK through forming intramembrane peptide nanoaggregates associated with hydrophobic mismatch and formation of fluidic and rigid patches. The reported peptide-aggregate-induced phase-separation emerged as a crucial factor in accelerated membrane disintegration and fast bacterial killing. This work has demonstrated the importance of membrane interactions to the development of more effective AMPs and the relevance of the approaches as reported in assisting this area of research.
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Antibacterianos , Staphylococcus aureus Resistente à Meticilina , Testes de Sensibilidade Microbiana , Antibacterianos/farmacologia , Antibacterianos/química , Staphylococcus aureus Resistente à Meticilina/efeitos dos fármacos , Staphylococcus aureus/efeitos dos fármacos , Peptídeos Catiônicos Antimicrobianos/química , Peptídeos Catiônicos Antimicrobianos/farmacologia , Cátions/química , Tensoativos/química , Tensoativos/farmacologia , Simulação de Dinâmica MolecularRESUMO
Wide bandgap (WBG) perovskite can construct tandem cells with narrow bandgap solar cells by adjusting the band gap to overcome the Shockley-Queisser limitation of single junction perovskite solar cells (PSCs). However, WBG perovskites still suffer from severe nonradiative carrier recombination and large open-circuit voltage loss. Here, this work uses an in situ photoluminescence (PL) measurement to monitor the intermediate phase evolution and crystallization process via blade coating. This work reports a strategy to fabricate efficient and stable WBG perovskite solar cells through doping a long carbon chain molecule octane-1,8-diamine dihydroiodide (ODADI). It is found that ODADI doping not only suppresses intermediate phases but also promote the crystallization of perovskite and passivate defects in blade coated 1.67 eV WBG FA0.7Cs0.25MA0.05Pb(I0.8Br0.2)3 perovskite films. As a result, the champion single junction inverted PSCs deliver the efficiencies of 22.06% and 19.63% for the active area of 0.07 and 1.02 cm2, respectively, which are the highest power conversion efficiencies (PCEs) in WBG PSCs by blade coating. The unencapsulated device demonstrates excellent stability in air, which maintains its initial efficiency at the maximum power points under constant AM 1.5G illumination in open air for nearly 500 h. The resulting semitransparent WBG device delivers a high PCE of 20.06%, and the 4-terminal all-perovskite tandem device delivers a PCE of 28.35%.
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Metal anodes are emerging as culminating solutions for the development of energy-dense batteries in either aprotic, aqueous, or solid battery configurations. However, unlike traditional intercalation electrodes, the low utilization of "hostless" metal anodes due to the intrinsically disordered plating/stripping impedes their practical applications. Herein, we report ordered planar plating/stripping in a bulk zinc (Zn) anode to achieve an extremely high depth of discharge exceeding 90% with negligible thickness fluctuation and long-term stable cycling. The Zn can be plated/stripped with (0001)Zn preferential orientation throughout the consecutive charge/discharge process, assisted by a self-assembled supramolecular bilayer at the Zn anode-electrolyte interface. Through real-time tracking of the Zn atoms migration, we reveal that the ordered planar plating/stripping is driven by the construction of in-plane ZnâN bindings and the gradient energy landscape at the reaction fronts. The breakthrough results provide alternative insights into the ordered plating/stripping of metal anodes toward rechargeable energy-dense batteries.
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Helicobacter pylori can cause various gastric conditions including stomach cancer in an acidic environment. Although early H. pylori infections can be treated by antibiotics, prolonged antibiotic administrations may lead to the development of antimicrobial resistance, compromising the effectiveness of the treatments. Antimicrobial peptides (AMPs) have been reported to possess unique advantages against antimicrobial-resistant bacteria due to their rapid physical membrane disruptions and anti-inflammation/immunoregulation properties. Herein, we have developed an AMP hydrogel, which can be orally administered for the treatment of H. pylori infection. The hydrogel has potent antimicrobial activity against H. pylori, achieving bacterial eradication within minutes of action. Compared with the AMP solution, the hydrogel formulation significantly reduced the cytotoxicity and enhanced proteolytic stability. In vivo experiments suggested that the hydrogel formed at pH 4 had superior therapeutic effects to those at pH 7 and 10 hydrogels, attributed to its rapid release and bactericidal action within the acidic stomach environment. Compared to conventional antibiotic treatments, the AMP hydrogel had the advantages of fast bacterial killing in the gastric juice and obviated proton pump inhibitors during the treatment. Although both the AMP hydrogel and antibiotics suppressed the expression of pro-inflammatory cytokines, the former uniquely promoted inflammation resolution. These results indicate that the AMP hydrogels with effectiveness and biosafety may be potential candidates for the clinical treatment of H. pylori infections.
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Infecções por Helicobacter , Helicobacter pylori , Humanos , Infecções por Helicobacter/tratamento farmacológico , Infecções por Helicobacter/metabolismo , Infecções por Helicobacter/microbiologia , Peptídeos Antimicrobianos , Hidrogéis/farmacologia , Hidrogéis/uso terapêutico , AntibacterianosRESUMO
The co-assembly of different peptide chains usually leads to the formation of intricate architectures and sophisticated functions in biological systems. Although the co-assembly of stereoisomeric peptides represents a facile and flexible strategy for the synthesis of peptide-based nanomaterials with novel structures and potentially interesting properties, there is a lack of a general knowledge on how different isomers pack during assembly. Through the combined use of simulations and experimental observations, we report that heterochiral pairing is preferred to homochiral pairing at the molecular scale but self-sorting dictates beyond the molecular level for the mixtures of the short stereoisomeric ß-sheet peptides I3K (Ile-Ile-Ile-Lys). Furthermore, we demonstrate that flat ß-sheets and fibril morphology are always preferred to twisted ones during heterochiral pairing and subsequent assembly. However, the heterochiral pairing into flat morphology is not always at an equimolar ratio. Instead, a non-equimolar ratio (1:2) is observed for the mixing of homochiral LI3LK and heterochiral LI3DK, whose strand twisting degrees differ greatly. Such a study provides a paradigm for understanding the co-assembly of stereoisomeric peptides at the molecular scale and harnessing their blending for targeted nanostructures.
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Nanoestruturas , Peptídeos , Estereoisomerismo , Peptídeos/química , Nanoestruturas/química , Conformação Proteica em Folha betaRESUMO
BACKGROUND: Clinical treatments ofgastric infections using antibiotics suffer from the undesired killing of commensal bacteria and emergence of antibiotic resistance. It is desirable to develop pH-responsive antimicrobial peptides (AMPs) that kill pathogenic bacteria such as H. pyloriand resistant E. coli under acidic environment with minimal impact to commensal bacteria whilst not causing antibiotic resistance. EXPERIMENTS: Using a combined approach of cell assays, molecular dynamics (MD) simulations and membrane models facilitating biophysical and biochemical measurements including small angle neutron scattering (SANS), we have characterized the pH-responsive physiochemical properties and antimicrobial performance of two amphiphilic AMPs, GIIKDIIKDIIKDI-NH2 and GIIKKIIDDIIKKI-NH2 (denoted as 3D and 2D, respectively), that were designed by selective substitutions of cationic residues of Lys (K) in the extensively studied AMP G(IIKK)3I-NH2 with anionic residue Asp (D). FINDINGS: Whilst 2D kept non-ordered coils across the entire pH range studied, 3D displayed a range of secondary structures when pH was shifted from basic to acidic, with distinct self-assembly into nanofibers in aqueous environment. Further experimental and modeling studies revealed that the AMPs interacted differently with the inner and outer membranes of Gram-negative bacteria in a pH-responsive manner and that the structural features characterized by membrane leakage and intramembrane nanoaggregates revealed from fluorescence spectroscopy and SANS were well linked to antimicrobial actions. Different antimicrobial efficacies of 2D and 3D were underlined by the interplay between their ability to bind to the outer membrane lipid LPS (lipopolysaccharide), outer membrane permeability change and inner membrane depolarization and leakage. Furthermore, AMP's binding with the inner membrane under acidic condition caused both the dissipation of membrane potential (Δψ) and the continuous dissipation of transmembrane ΔpH, with Δψ and ΔpH being the key components of the proton motive force. Combinations of antibiotic (Minocycline) with the pH-responsive AMP generated the synergistic effects against Gram-negative bacteria only under acidic condition. These features are crucial to target applications to gastric infections, anti-acne and wound healing.
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Antibacterianos , Anti-Infecciosos , Antibacterianos/química , Peptídeos Catiônicos Antimicrobianos/química , Escherichia coli , Bactérias Gram-Negativas , Anti-Infecciosos/farmacologia , Lipopolissacarídeos/química , Bactérias/metabolismo , Concentração de Íons de Hidrogênio , Testes de Sensibilidade MicrobianaRESUMO
Peptide assemblies are promising nanomaterials, with their properties and technological applications being highly hinged on their supramolecular architectures. Here, how changing the chirality of the terminal charged residues of an amphiphilic hexapeptide sequence Ac-I4 K2 -NH2 gives rise to distinct nanostructures and supramolecular handedness is reported. Microscopic imaging and neutron scattering measurements show thin nanofibrils, thick nanofibrils, and wide nanotubes self-assembled from four stereoisomers. Spectroscopic and solid-state nuclear magnetic resonance (NMR) analyses reveal that these isomeric peptides adopt similar anti-parallel ß-sheet secondary structures. Further theoretical calculations demonstrate that the chiral alterations of the two C-terminal lysine residues cause the formation of diverse single ß-strand conformations, and the final self-assembled nanostructures and handedness are determined by the twisting direction and degree of single ß-strands. This work not only lays a useful foundation for the fabrication of diverse peptide nanostructures by manipulating the chirality of specific residues but also provides a framework for predicting the supramolecular structures and handedness of peptide assemblies from single molecule conformations.
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Lateralidade Funcional , Nanoestruturas , Peptídeos/química , Nanoestruturas/química , Isomerismo , Estrutura Secundária de ProteínaRESUMO
Wide-bandgap (WBG) perovskite solar cells have attracted considerable interest for their potential applications in tandem solar cells. However, the predominant obstacles impeding their widespread adoption are substantial open-circuit voltage (VOC ) deficit and severe photo-induced halide segregation. To tackle these challenges, a crystal orientation regulation strategy by introducing dodecyl-benzene-sulfonic-acid as an additive in perovskite precursors is proposed. This method significantly promotes the desired crystal orientation, passivates defects, and mitigates photo-induced halide phase segregation in perovskite films, leading to substantially reduced nonradiative recombination, minimized VOC deficits, and enhanced operational stability of the devices. The resulting 1.66 eV bandgap methylamine-free perovskite solar cells achieve a remarkable power conversion efficiency (PCE) of 22.40% (certified at 21.97%), with the smallest VOC deficit recorded at 0.39 V. Furthermore, the fabricated semitransparent WBG devices exhibit a competitive PCE of 20.13%. Consequently, four-terminal tandem cells comprising WBG perovskite top cells and 1.25 eV bandgap perovskite bottom cells showcase an impressive PCE of 28.06% (stabilized 27.92%), demonstrating great potential for efficient multijunction tandem solar cell applications.
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Nonionic surfactants used in agri-spraying processes may cause varying degrees of corneal irritation when they come in direct contact with farmers' eyes, and the exact irritations are thought to be determined by how surfactants interact with corneal cell membranes. However, how nonionic surfactants interact with cell membranes at the molecular and nano levels remains largely unexplored. In this study, the interactions between nonionic surfactants (alkyl ethoxylate, C12Em) and lipid membranes were examined by membrane permeability measurement, quartz crystal microbalance with dissipation, dual polarization interferometry, confocal laser scanning microscopy, and neutron reflection, aiming to reveal complementary structural features at the molecular and nano levels. Apart from the extremely hydrophobic surfactant C12E2, all nonionic surfactants studied could penetrate the model cell membrane composed of a phosphocholine lipid bilayer. Nonionic surfactants with intermediate amphiphilicity (C12E6) rapidly fused into the lipid membrane and stimulated the formation of pores across the lipid bilayer, consistent with the cytoplasm leakage and fast cell necrosis observed from the cytotoxicity study of corneal cells. In comparison, while hydrophobic and hydrophilic surfactants [those with long and short ethoxylates (C12E4,12,23)] could cause mild structural alteration to the outer lipid layer of the membrane, these structural changes were insufficient to elicit large cytoplasmic leakage rapidly and instead cell death occurred over longer periods of time due to changes in the membrane permeability. These results reveal the strong link of surfactant-lipid membrane interactions to surfactant cytotoxicity and the association with amphiphilicity of nonionic surfactants.
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Oftalmopatias , Nanoestruturas , Surfactantes Pulmonares , Humanos , Bicamadas Lipídicas , Tensoativos/farmacologia , Tensoativos/química , Córnea , Nanoestruturas/toxicidadeRESUMO
Self-assemblies of de novo designed short peptides at interface and in bulk solution provide potential platforms for developing applications in many medical and technological areas. However, characterising how bioinspired supramolecular nanostructures evolve with dynamic self-assembling processes and respond to different stimuli remains challenging. Neutron scattering technologies including small angle neutron scattering (SANS) and neutron reflection (NR) can be advantageous and complementary to other state-of-the-art techniques in tracing structural changes under different conditions. With more neutron sources now available, SANS and NR are becoming increasingly popular in studying self-assembling processes of diverse peptide and protein systems, but the difficulty in experimental manipulation and data analysis can deter beginners. This review will introduce the basic theory, general experimental setup and data analysis of SANS and NR, followed by provision of their applications in characterising interfacial and solution self-assemblies of representative peptides and proteins. SANS and NR are remarkably effective in determining the morphological features self-assembled short peptides, especially size and shape transitions as a result of either sequence changes or in response to environmental stimuli, demonstrating the unique capability of NR and SANS in unravelling the interactive processes. These examples highlight the potential of NR and SANS in supporting the development of novel short peptides and proteins as biopharmaceutical candidates in the fight against many diseases and infections that share common features of membrane interactive processes.
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Peptídeos , Proteínas , Peptídeos/química , Proteínas/química , Nêutrons , Espalhamento a Baixo ÂnguloRESUMO
Wide-bandgap (WBG) perovskites have been attracting much attention because of their immense potential as a front light-absorber for tandem solar cells. However, WBG perovskite solar cells (PSCs) generally exhibit undesired large open-circuit voltage (VOC) loss due to light-induced phase segregation and severe non-radiative recombination loss. Herein, antimony potassium tartrate (APTA) is added to perovskite precursor as a multifunctional additive that not only coordinates with unbonded lead but also inhibits the migration of halogen in perovskite, which results in suppressed non-radiative recombination, inhibited phase segregation and better band energy alignment. Therefore, a APTA auxiliary WBG PSC with a champion photoelectric conversion efficiency of 20.35% and less hysteresis is presented. They maintain 80% of their initial efficiencies under 100 mW cm-2 white light illumination in nitrogen after 1,000 h. Furthermore, by combining a semi-transparent WBG perovskite front cell with a narrow-bandgap tin-lead PSC, a perovskite/perovskite four-terminal tandem solar cell with an efficiency over 26% is achieved. Our work provides a feasible approach for the fabrication of efficient tandem solar cells.
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Interfacial adsorption of monoclonal antibodies (mAbs) can cause structural deformation and induce undesired aggregation and precipitation. Nonionic surfactants are often added to reduce interfacial adsorption of mAbs which may occur during manufacturing, storage, and/or administration. As mAbs are commonly manufactured into ready-to-use syringes coated with silicone oil to improve lubrication, it is important to understand how an mAb, nonionic surfactant, and silicone oil interact at the oil/water interface. In this work, we have coated a polydimethylsiloxane (PDMS) nanofilm onto an optically flat silicon substrate to facilitate the measurements of adsorption of a model mAb, COE-3, and a commercial nonionic surfactant, polysorbate 80 (PS-80), at the siliconized PDMS/water interface using spectroscopic ellipsometry and neutron reflection. Compared to the uncoated SiO2 surface (mimicking glass), COE-3 adsorption to the PDMS surface was substantially reduced, and the adsorbed layer was characterized by the dense but thin inner layer of 16 Å and an outer diffuse layer of 20 Å, indicating structural deformation. When PS-80 was exposed to the pre-adsorbed COE-3 surface, it removed 60 wt % of COE-3 and formed a co-adsorbed layer with a similar total thickness of 36 Å. When PS-80 was injected first or as a mixture with COE-3, it completely prevented COE-3 adsorption. These findings reveal the hydrophobic nature of the PDMS surface and confirm the inhibitory role of the nonionic surfactant in preventing COE-3 adsorption at the PDMS/water interface.
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Anticorpos Monoclonais , Tensoativos , Tensoativos/química , Adsorção , Anticorpos Monoclonais/química , Dióxido de Silício , Óleos de Silicone/química , Polissorbatos/química , DimetilpolisiloxanosRESUMO
HYPOTHESIS: It is widely regarded that antimicrobial peptides (AMPs) kill bacteria by physically disrupting microbial membranes and causing cytoplasmic leakage, but it remains unclear how AMPs disrupt the outer membrane (OM) of Gram-negative bacteria (GNB) and then compromise the inner membrane. We hypothesise that different AMPs impose different structural disruptions, with direct implications to their antimicrobial efficacies. EXPERIMENTS: The antimicrobial activities of three typical AMPs, including the designed short AMP, G3, and two natural AMPs, melittin and LL37, against E. coli and their haemolytic activities were studied. Lipopolysaccharide (LPS) and anionic di-palmitoyl phosphatidyl glycerol (DPPG) monolayer models were constructed to mimic the outer membrane and inner membrane leaflets of Gram-negative bacteria. The binding and penetration of AMPs to the model lipid monolayers were systematically studied by neutron reflection via multiple H/D contrast variations. FINDING: G3 has relatively high antimicrobial activity, low cytotoxicity, and high proteolytic stability, whilst melittin has significant haemolysis and LL37 has weaker antimicrobial activity. G3 could rapidly lyse LPS and DPPG monolayers within 10-20 min. In contrast, melittin was highly active against the LPS membrane, but the dynamic process lasted up to 80 min, with excessive stacking in the OM. LL37 caused rather weak destruction to LPS and DPPG monolayers, leading to massive adsorption on the membrane surface without penetrating the lipid tail region. These findings demonstrate that the rationally designed AMP G3 was well optimised to impose most effective destruction to bacterial membranes, consistent with its highest bactericidal activity. These different interfacial structural features associated with AMP binding shed light on the future development of active and biocompatible AMPs for infection and wound treatments.
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Anti-Infecciosos , Lipopolissacarídeos , Lipopolissacarídeos/farmacologia , Lipopolissacarídeos/química , Peptídeos Antimicrobianos , Meliteno/farmacologia , Meliteno/metabolismo , Escherichia coli/metabolismo , Anti-Infecciosos/química , Bactérias Gram-Negativas/metabolismo , Bactérias/metabolismo , Membrana Celular/metabolismo , Antibacterianos/químicaRESUMO
Recent developments in antimicrobial peptides (AMPs) have focused on the rational design of short sequences with less than 20 amino acids due to their relatively low synthesis costs and ease of correlation of the structure-function relationship. However, gaps remain in the understanding of how short cationic AMPs interact with the bacterial outer and inner membranes to affect their antimicrobial efficacy and dynamic killing. The membrane-lytic actions of two designed AMPs, G(IIKK)3 I-NH2 (G3 ) and G(IIKK)4 I-NH2 (G4 ), and previously-studied controls GLLDLLKLLLKAAG-NH2 (LDKA, biomimetic) and GIGAVLKVLTTGLPALISWIKRKR-NH2 (Melittin, natural) are examined. The mechanistic processes of membrane damage and the disruption strength of the four AMPs are characterized by molecular dynamics simulations and experimental measurements including neutron reflection and scattering. The results from the combined studies are characterized with distinctly different intramembrane nanoaggregates formed upon AMP-specific binding, reflecting clear influences of AMP sequence, charge and the chemistry of the inner and outer membranes. G3 and G4 display different nanoaggregation with the outer and inner membranes, and the smaller sizes and further extent of insertion of the intramembrane nanoaggregates into bacterial membranes correlate well with their greater antimicrobial efficacy and faster dynamic killing. This work demonstrates the crucial roles of intramembrane nanoaggregates in optimizing antimicrobial efficacy and dynamic killing.
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Anti-Infecciosos , Peptídeos Antimicrobianos , Peptídeos Catiônicos Antimicrobianos/farmacologia , Peptídeos Catiônicos Antimicrobianos/química , Anti-Infecciosos/farmacologia , Bactérias , Simulação de Dinâmica MolecularRESUMO
HYPOTHESIS: Self-assembly of peptides is influenced by both molecular structure and external conditions, which dictate the delicate balance of different non-covalent interactions that driving the self-assembling process. The shifting of terminal charge residue is expected to influence the non-covalent interactions and their interplay, thereby affecting the morphologies of self-assemblies. Therefore, the morphology transition can be realized by shifting the position of the terminal charge residue. EXPERIMENTS: The structure transition from thin nanofibers to giant nanotubes is realized by simply shifting the C-terminal lysine of ultrashort Ac-I3K-NH2 to its N-terminus. The morphologies and detailed structure information of the self-assemblies formed by these two peptides are investigated systemically by a combination of different experimental techniques. The effect of terminal residue on the morphologies of the self-assemblies is well presented and the underlying mechanism is revealed. FINDINGS: Giant nanotubes with a bilayer shell structure can be self-assembled by the ultrashort peptide Ac-KI3-NH2 with the lysine residue close to the N-terminal. The Ac-KI3-NH2 dimerization through intermolecular C-terminal H-bonding promotes the formation of a bola-form geometry, which is responsible for the wide nanotube assembly formation. The evolution process of Ac-KI3-NH2 nanotubes follows the "growing width" model. Such a morphological transformation with the terminal lysine shift is applicable to other analogues and thus provides a facile approach for the self-assembly of wide peptide nanotubes, which can expand the library of good template structures for the prediction of peptide nanostructures.
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Nanotubos de Peptídeos , Nanotubos , Estrutura Secundária de Proteína , Lisina , Nanotubos/química , Peptídeos/químicaRESUMO
Formamidinium lead iodide (FAPbI3) perovskites are promising emitters for near-infrared light-emitting diodes. However, their performance is still limited by defect-assisted nonradiative recombination and band offset-induced carrier aggregation at the interface. Herein, we introduce a couple of cadmium salts with acetate or halide anion into the FAPbI3 perovskite precursors to synergistically passivate the material defects and optimize the device band structure. Particularly, the perovskite analogs, containing zero-dimensional formamidinium cadmium iodide, one-dimensional δ-FAPbI3, two-dimensional FA2FAn-1PbnI3n+1, and three-dimensional α-FAPbI3, can be obtained in one pot and play a pivotal and positive role in energy transfer in the formamidinium iodide-rich lead-based perovskite films. As a result, the near-infrared FAPbI3-based devices deliver a maximum external quantum efficiency of 24.1% together with substantially improved operational stability. Combining our findings on defect passivation and energy transfer, we also achieve near-infrared light communication with device twins of light emitting and unprecedented self-driven detection.
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Peptide self-assembly is a hierarchical process during which secondary structures formed in the initial stages play a critical role in determining the subsequent assembling processes and final structural ordering. Unusual secondary structures hold promise as a source to develop novel supramolecular architectures with unique properties. In this work, we report the design of a new peptide self-assembly strategy based on unusual α-sheet secondary structures. In light of the strong propensity of leucine toward forming helical conformations and its high hydrophobicity, we design two short amphiphilic peptides Ac-LDLLDLK-NH2 and Ac-DLLDLLDK-NH2 with alternating l- and d-form amino acids. Microscopic imaging, neutron scattering, and spectroscopic measurements indicate that the two heterochiral peptides form highly ordered wide nanotubes and helical ribbons with monolayer thickness, in sharp contrast to twisted nanofibrils formed by the homochiral peptide Ac-LLLLK-NH2. Molecular dynamics simulations from monomers to trimers reveal that the two heteropeptides fold into α-sheets instead of ß-sheets, which readily pack into tubular architectures in oligomer simulations. Simulated circular dichroism spectra based on α-sheet oligomers validate the proposed α-sheet secondary structures. These results form an important basis for the rational design of higher-order peptide assemblies with novel properties based on unusual α-sheet secondary structures.
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Aminoácidos , Peptídeos , Peptídeos/química , Estrutura Secundária de Proteína , Dicroísmo Circular , Conformação Proteica em Folha betaRESUMO
Wide bandgap (WBG) perovskites through tuning iodine/bromine ratios are capable of merging with narrow bandgap organic bulk heterojunctions to construct tandem solar cells to overcome the Shockley-Queisser limitation. However, WBG perovskites readily suffer from light-induced halide ion migration, leading to detrimental phase segregation and hence severe open-circuit voltage (VOC ) loss. Here, to solve this issue, lead thiocyanate (Pb(SCN)2 ) and 2-thiopheneethylammonium chloride (TEACl) are synergistically employed to passivate and stabilize WBG perovskites with 1.79 eV bandgap. It is demonstrated that the synergetic employment of Pb(SCN)2 and TEACl suppresses light-induced phase segregation, passivates WBG perovskite defects, and reduces non-radiative recombination, hence alleviating VOC loss. As a result, optimized WBG perovskite solar cells (PSCs) are obtained with an impressive VOC of 1.26 V and power conversion efficiency (PCE) over 17.0%. Furthermore, the interconnection layer is optimized to minimize the VOC loss and construct two-terminal perovskite/organic tandem solar cells with a narrow bandgap organic blend bulk heterojunction of PM6:Y6 and achieve a champion PCE of 22.29% with a high VOC of 2.072 V. In addition, these tandem solar cells maintain 81% of their initial efficiency after 1000 h continuous tracking at the maximum power point (MPP) under 100 mW cm-2 white light illumination.
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HYPOTHESIS: Nonionic surfactants are widely used as co-formulants in agrochemical sprays. During spraying, they may come into direct contact with humans and animals, causing irritation in different tissues. However, how the molecular structures of these surfactants affect their toxicity towards human eye and skin at the cellular level has not been well characterised. EXPERIMENT: In this study, the cytotoxicities of two sets of nonionic surfactants (alkyl ethoxylate, CnEm) against human corneal and skin cell lines were examined, with one set composed of varied surfactant head length but fixed tail length (C12E4-23) and the other set oppositely composed (C10-16E6). The cell viability and morphology against different nonionic surfactants for varied exposure times were studied, followed by characterisation of their membrane-lytic ability. FINDING: Nonionic surfactants with intermediate amphiphilicity killed cells rapidly due to their strong membrane-lytic power. Those with weak or strong hydrophobicity exhibited low cytotoxicity but had different modes of action depending on their hydrophobicity. Hydrophobic surfactants were found to adsorb on to cell membranes with no observed structural damage for 2 hr. Hydrophilic surfactants were also found to adsorb on to cell membranes but did cause mild structural changes. While the changes were not sufficient to elicit large cytoplasmic leakage over short periods of time, membrane associations did cause cell shrinkage which eventually resulted in cell death over longer exposure periods. These results revealed that the specific amphiphilic nature of nonionic surfactants played a crucial role in determining their cytotoxicity. This work provided a useful basis for the assessment of amphiphilicity of the nonionic surfactants used in agrochemical sprays by balancing their efficiency, toxicity and environmental impact.
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Córnea , Tensoativos , Animais , Humanos , Tensoativos/toxicidade , Tensoativos/química , Pele , Interações Hidrofóbicas e Hidrofílicas , AgroquímicosRESUMO
HYPOTHESIS: Acyl-l-carnitines (CnLCs) are potentially important as biosurfactants in drug delivery and tissue engineering due to their good biocompatibility. However, little is currently known about the basic interfacial behavior underlying their technological applications. Following our previous characterization of their solution aggregation and adsorption at the air/water interface, this work examines how they adsorb at the hydrophilic solid/liquid interface. EXPERIMENTS: As the SiO2/water interface has served as the model substrate for many interfacial adsorption studies, so it has been used in this work as the solid substrate to facilitate dynamic adsorption by spectroscopic ellipsometry (SE) and structural determination of the adsorbed layers by neutron reflection (NR) under different conditions at the SiO2/water interface from a group of CnLC (n = 12, 14, and 16). FINDINGS: CnLC surfactants are zwitterionic at neutral pH. They reached saturated adsorption above their critical micellar concentrations (CMCs) and formed a sandwich bilayer with a head-tail-head structure at the hydrophilic SiO2/water interface. The total thicknesses of the adsorbed layers at CMC were found to be 33 ± 2, 35 ± 2, and 37 ± 2 Å for C12LC, C14LC, and C16LC, respectively, with their inner and outer head layers remaining similar but the thickness of the interdigitated middle layer increasing with acyl chain length. As the solution becomes acidic, the carboxyl groups become protonated and the l-carnitine heads are net positively charged, resulting in increased repulsion between the head groups. In this situation, the CnLC surfactants are adsorbed as distinct aggregates to reduce repulsive interaction, resulting in reduced surfactant volume fraction and layer thickness. However, a high ionic strength can screen the repulsive interaction and enhance the adsorbed amount, effectively diminishing the impact of pH. This information provides a useful basis for exploring the technological applications of CnLCs involving a solid substrate.