We use mechanical unfolding of single DNA hairpins with modified bases to accurately assess intra- and intermolecular forces in nucleic acids. As expected, the modification stabilizes the hybridized hairpin, but we also observe intriguing stacking interactions in the unfolded hairpin. Our study highlights the benefit of using base-modified nucleic acids in force-spectroscopy.The structure formation and the phase behaviour of monolayers of dumbbell-shaped colloids are explored. For this, we conduct Langmuir-Blodgett experiments at the air/water interface and conventional Brownian dynamic simulations without hydrodynamic interactions. Using Voronoi tessellations and the probability density of the corresponding shape factor of the Voronoi cells p(ζ), the influence of the area fraction φ on the structure of the monolayers is investigated. An increase of the area fraction leads to a higher percentage of domains containing particles with six nearest neighbours and a sharper progression of p(ζ). https://www.selleckchem.com/products/bgb-3245-brimarafenib.html Especially in dense systems, these domains can consist of aligned particles with uniform Voronoi cells. Thus, the increase of φ enhances the order of the monolayers. Simulations show that a sufficient enhancement of φ also impacts the pair correlation function which develops a substructure in its first maxima. Furthermore, we find that reducing the barrier speed in the Langmuir-Blodgett experiments enhances the final area fraction for a given target surface pressure which, in turn, also increases the percentage of particles with six nearest neighbours and sharpens the progression of p(ζ). Overall, the experiments and simulations show a remarkable qualitative agreement which indicates a versatile way of characterising colloidal monolayers by Brownian dynamics simulations. This opens up perspectives for application to a broad range of nanoparticle-based thin film coatings and devices.II-VI semiconductor heterojunctions show huge potential for application in nanodevice fabrication due to their type-II alignments owing to the better spatial separation of electrons and holes. However, the hetero-epitaxial growth of high-quality heterostructures is still a challenge, especially for materials with large lattice mismatch. In this work, well-aligned single-crystalline ZnO/ZnS core/shell nanorod arrays were obtained by introducing an Al2O3 buffer layer. It is interesting that the nature of the ZnS layer varies with the thickness of the Al2O3 layer. When Al2O3 is less than 2 nm, the interaction between the substrate and epilayer is strong enough to penetrate through the buffer layer, enabling the growth of ZnS on Al2O3-coated ZnO nanorod arrays. On the basis of detailed characterization, a rational growth mechanism of the core/shell heterostructure is proposed, in which the Al2O3 interlayer can eliminate voids due to the Kirkendall effect around the interface and accommodate a misfit dislocation between the inner ZnO and outer ZnS, resulting in more sufficient strain relaxation in the epitaxy. In addition, cathodoluminescence measurements demonstrate that the optical properties of the ZnO/ZnS heterostructure could be effectively improved by taking advantage of the thin Al2O3. The I-V curves characterized by PeakForce tunneling atomic force microscopy reveal that the heterostructure shows a typical rectifying behavior and good photoresponse to ultraviolet light. These findings may provide a reasonable and effective strategy for the growth of highly lattice-mismatched heterostructure arrays buffered by the Al2O3 layer, broadening the options for fabricating heterojunctions and promoting their applications in optoelectronic devices.Hybrid perovskites are favoured over other numerous optoelectronic materials, thanks to their rapidly enhanced power conversion efficiency (PCE) and facile processing. At present, future developments are seriously hampered by the high toxicity of heavy metals and poor stability. Inorganic lead-free perovskites, CsSn1-xGexI3-yBry, are herein explored for superior optical performance by first-principles calculations based on density functional theory (DFT). It is unveiled that the valence band maximum (VBM) is mainly occupied by the p-orbit of halide ions, while the conduction band minimum (CBM) is composed of the p-orbit of the metal ion. Moreover, Bader charge analysis shows that CsSn0.5Ge0.5I3 corresponds to the most obvious charge transfer compared to the others. The defect formation energy indicates that perovskite compounds CsSn1-xGexI3-yBry, are more easily synthesized than the series CsSn1-xGexI3, and the physically accessible area is also determined in the coordinate system defined by the chemical potential change of the host atoms, ΔμSn and ΔμI. Additionally, the absorption spectra show that among the doped compounds of the form CsSn0.5Ge0.5I3-yBry, perovskite CsSn0.5Ge0.5I2Br is superior in terms of optical response in the visible-light range. The results shed a new light on the study of highly efficient and stable lead-free perovskite-based solar cells (PSCs).The mechanisms of glass transitions and the behavior of small solute molecules in a glassy matrix are some of the most important topics of modern thermodynamics. Water plays an important role in the physical and chemical stability of lyophilized biologics formulations, in which glassy carbohydrates act as cryoprotectants and stabilizers. In this study, sorption calorimetry was used for simultaneous measurements of water activity and the enthalpy of water sorption by amorphous sucrose, trehalose and maltodextrins. Moreover, the heat capacity of these carbohydrates in mixtures with water was measured by DSC in a broad range of water contents. The hydration enthalpies of glassy sucrose, trehalose and maltodextrins are exothermic, and the enthalpy change of water-induced isothermal glass transitions is higher for small molecules. The partial molar enthalpy of mixing of water in slow experiments is about -18 kJ mol-1, but less exothermic in the case of small molecules at fast hydration scan rates. By measuring the heat capacities of disaccharides and maltodextrins as a function of water content, we separated the contributions of carbohydrates and water to the total heat capacities of the mixtures. The combination of these data allowed testing of thermodynamic models describing the hydration-induced glass transitions. The heat capacity changes calculated by the fitting of the hydration enthalpy data for disaccharides are in good agreement with the heat capacity data obtained by DSC, while for maltodextrins, the effect of sub-Tg transitions should be taken into account. Combining the data obtained by different techniques, we found a distinct difference in the behavior of water in glassy polymers compared to that in glassy disaccharides. By understanding the behavior of water in glassy carbohydrates, these results can be used to improve the design of freeze-dried formulations of proteins and probiotics.
We use mechanical unfolding of single DNA hairpins with modified bases to accurately assess intra- and intermolecular forces in nucleic acids. As expected, the modification stabilizes the hybridized hairpin, but we also observe intriguing stacking interactions in the unfolded hairpin. Our study highlights the benefit of using base-modified nucleic acids in force-spectroscopy.The structure formation and the phase behaviour of monolayers of dumbbell-shaped colloids are explored. For this, we conduct Langmuir-Blodgett experiments at the air/water interface and conventional Brownian dynamic simulations without hydrodynamic interactions. Using Voronoi tessellations and the probability density of the corresponding shape factor of the Voronoi cells p(ζ), the influence of the area fraction φ on the structure of the monolayers is investigated. An increase of the area fraction leads to a higher percentage of domains containing particles with six nearest neighbours and a sharper progression of p(ζ). https://www.selleckchem.com/products/bgb-3245-brimarafenib.html Especially in dense systems, these domains can consist of aligned particles with uniform Voronoi cells. Thus, the increase of φ enhances the order of the monolayers. Simulations show that a sufficient enhancement of φ also impacts the pair correlation function which develops a substructure in its first maxima. Furthermore, we find that reducing the barrier speed in the Langmuir-Blodgett experiments enhances the final area fraction for a given target surface pressure which, in turn, also increases the percentage of particles with six nearest neighbours and sharpens the progression of p(ζ). Overall, the experiments and simulations show a remarkable qualitative agreement which indicates a versatile way of characterising colloidal monolayers by Brownian dynamics simulations. This opens up perspectives for application to a broad range of nanoparticle-based thin film coatings and devices.II-VI semiconductor heterojunctions show huge potential for application in nanodevice fabrication due to their type-II alignments owing to the better spatial separation of electrons and holes. However, the hetero-epitaxial growth of high-quality heterostructures is still a challenge, especially for materials with large lattice mismatch. In this work, well-aligned single-crystalline ZnO/ZnS core/shell nanorod arrays were obtained by introducing an Al2O3 buffer layer. It is interesting that the nature of the ZnS layer varies with the thickness of the Al2O3 layer. When Al2O3 is less than 2 nm, the interaction between the substrate and epilayer is strong enough to penetrate through the buffer layer, enabling the growth of ZnS on Al2O3-coated ZnO nanorod arrays. On the basis of detailed characterization, a rational growth mechanism of the core/shell heterostructure is proposed, in which the Al2O3 interlayer can eliminate voids due to the Kirkendall effect around the interface and accommodate a misfit dislocation between the inner ZnO and outer ZnS, resulting in more sufficient strain relaxation in the epitaxy. In addition, cathodoluminescence measurements demonstrate that the optical properties of the ZnO/ZnS heterostructure could be effectively improved by taking advantage of the thin Al2O3. The I-V curves characterized by PeakForce tunneling atomic force microscopy reveal that the heterostructure shows a typical rectifying behavior and good photoresponse to ultraviolet light. These findings may provide a reasonable and effective strategy for the growth of highly lattice-mismatched heterostructure arrays buffered by the Al2O3 layer, broadening the options for fabricating heterojunctions and promoting their applications in optoelectronic devices.Hybrid perovskites are favoured over other numerous optoelectronic materials, thanks to their rapidly enhanced power conversion efficiency (PCE) and facile processing. At present, future developments are seriously hampered by the high toxicity of heavy metals and poor stability. Inorganic lead-free perovskites, CsSn1-xGexI3-yBry, are herein explored for superior optical performance by first-principles calculations based on density functional theory (DFT). It is unveiled that the valence band maximum (VBM) is mainly occupied by the p-orbit of halide ions, while the conduction band minimum (CBM) is composed of the p-orbit of the metal ion. Moreover, Bader charge analysis shows that CsSn0.5Ge0.5I3 corresponds to the most obvious charge transfer compared to the others. The defect formation energy indicates that perovskite compounds CsSn1-xGexI3-yBry, are more easily synthesized than the series CsSn1-xGexI3, and the physically accessible area is also determined in the coordinate system defined by the chemical potential change of the host atoms, ΔμSn and ΔμI. Additionally, the absorption spectra show that among the doped compounds of the form CsSn0.5Ge0.5I3-yBry, perovskite CsSn0.5Ge0.5I2Br is superior in terms of optical response in the visible-light range. The results shed a new light on the study of highly efficient and stable lead-free perovskite-based solar cells (PSCs).The mechanisms of glass transitions and the behavior of small solute molecules in a glassy matrix are some of the most important topics of modern thermodynamics. Water plays an important role in the physical and chemical stability of lyophilized biologics formulations, in which glassy carbohydrates act as cryoprotectants and stabilizers. In this study, sorption calorimetry was used for simultaneous measurements of water activity and the enthalpy of water sorption by amorphous sucrose, trehalose and maltodextrins. Moreover, the heat capacity of these carbohydrates in mixtures with water was measured by DSC in a broad range of water contents. The hydration enthalpies of glassy sucrose, trehalose and maltodextrins are exothermic, and the enthalpy change of water-induced isothermal glass transitions is higher for small molecules. The partial molar enthalpy of mixing of water in slow experiments is about -18 kJ mol-1, but less exothermic in the case of small molecules at fast hydration scan rates. By measuring the heat capacities of disaccharides and maltodextrins as a function of water content, we separated the contributions of carbohydrates and water to the total heat capacities of the mixtures. The combination of these data allowed testing of thermodynamic models describing the hydration-induced glass transitions. The heat capacity changes calculated by the fitting of the hydration enthalpy data for disaccharides are in good agreement with the heat capacity data obtained by DSC, while for maltodextrins, the effect of sub-Tg transitions should be taken into account. Combining the data obtained by different techniques, we found a distinct difference in the behavior of water in glassy polymers compared to that in glassy disaccharides. By understanding the behavior of water in glassy carbohydrates, these results can be used to improve the design of freeze-dried formulations of proteins and probiotics.
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