Structural Properties Research Articles

Designing Pathway-Controlled Multicomponent Ultrashort Peptide Hydrogels with Diverse Functionalities at the Nanoscale for Directing Cellular Behavior.

Tuning self-assembling pathways by implementing different external stimuli has been extensively studied, owing to their effective control over structural and mechanical properties. Consequently, multicomponent peptide hydrogels with high structural tunability and stimuli responsiveness are crucial in dictating cellular behavior. Herein, we have implemented both coassembly approach and pathway-dependent self-assembly to design nonequilibrium nanostructures to understand the thermodynamic and kinetic aspects of peptide self-assembly toward controlling cellular response. Our system involved an ultrashort peptide gelator and a hydrophilic surfactant which coassembled through different pathways, i.e., heat-cool and sonication methods with variable energy input. Interestingly, it was possible to access diverse structural and mechanical properties at the nanoscale in a single coassembled system. Further, the hydrophilic surfactant provided additional surface functionalities, thus creating an efficient hydrophilic matrix for cellular interaction. Such diverse functionalities in a single coassembled system could lead to the development of advanced scaffolds, with applications in various biomedical fields.

Electronic Properties of DNA Origami Nanostructures Revealed by In Silico Calculations.

DNA origami is a pioneering approach for producing complex 2- or 3-D shapes for use in molecular electronics due to its inherent self-assembly and programmability properties. The electronic properties of DNA origami structures are not yet fully understood, limiting the potential applications. Here, we conduct a theoretical study with a combination of molecular dynamics, first-principles, and charge transmission calculations. We use four separate single strand DNAs, each having 8 bases (4 × G4C4 and 4 × A4T4), to form two different DNA nanostructures, each having two helices bundled together with one crossover. We also generated double-stranded DNAs to compare electronic properties to decipher the effects of crossovers and bundle formations. We demonstrate that density of states and band gap of DNA origami depend on its sequence and structure. The crossover regions could reduce the conductance due to a lack of available states near the HOMO level. Furthermore, we reveal that, despite having the same sequence, the two helices in the DNA origami structure could exhibit different electronic properties, and electrode position can affect the resulting conductance values. Our study provides better understanding of the electronic properties of DNA origamis and enables us to tune these properties for electronic applications such as nanowires, switches, and logic gates.

Biomaterials-based Technologies in Skeletal Muscle Tissue Engineering.

For many clinically prevalent severe injuries, the inherent regenerative capacity of skeletal muscle remains inadequate. Skeletal muscle tissue engineering (SMTE) seeks to meet this clinical demand. With continuous progress in biomedicine and related technologies including micro/nanotechnology and 3D printing, numerous studies have uncovered various intrinsic mechanisms regulating skeletal muscle regeneration and developed tailored biomaterial systems based on these understandings. Here, we discussed the skeletal muscle structure and regeneration process and explored in detail the diverse biomaterial systems derived from various technologies. Biomaterials serve not merely as local niches for cell growth, but also as scaffolds endowed with structural or physicochemical properties that provide tissue regenerative cues such as topographical, electrical, and mechanical signals. They can also act as delivery systems for stem cells and bioactive molecules that have been shown as key participants in endogenous repair cascades. To achieve bench-to-bedside translation, we have also summarized the typical effect enabled by biomaterial systems and the potential underlying molecular mechanisms. We hope to provide insights into the roles of biomaterials in SMTE from cellular and molecular perspectives. Finally, we provided perspectives on the advancement of SMTE, for which gene therapy, exosomes, and hybrid biomaterials may hold promise to make important contributions. This article is protected by copyright. All rights reserved.

Analysis of structural, electronic and optical properties of Er-doped rock salt AlN using ab-initio calculations.

This investigation includes the structural and optoelectronic characteristics of both pure and Er-doped rock salt aluminium nitride (AlN). Upon introducing Er doping into the AlN host, the calculations reveal a rise in the atomic parameter. Incorporating Er into the system leads to enhancements in the static dielectric coefficient ɛ1(0), static reflectivity R(0), as well as static refractive index n(0), at zero frequency. After doping, the peaks of imaginary dielectric tensor, extinction coefficient and absorption coefficient shift towards lower energy levels. Various exchange correlation potentials are incorporated to compare the results of electronic and optical characteristics. We employed the full potential linearized augmented plane wave (FP-LAPW) approach with WIEN2k code in conjunction with the density functional theory (DFT). To explore the optoelectronic characteristics of both pure as well as doped systems, three distinct exchange correlation potentials are utilized: the Perdew-Burke-Ernzerhof Generalized Gradient Approximation (PBE-GGA), Modified Becke Johnson Generalized Gradient Approximations (mBJ + GGA) and Hubbard potential (GGA + U).

Structure and dynamics in suspensions of magnetic platelets.

In this research, we employ Brownian dynamics simulations, density functional theory, and mean-field theory to explore the profound influence of shape anisotropy of magnetic nanoplatelets on suspension magnetic response. Each platelet is modelled as an oblate cylinder with a longitudinal point dipole, with an emphasis on strong dipolar interactions conducive to self-assembly. We investigate static structural and magnetic properties, characterising the system through pair distribution function, static structure factor, and cluster-size distribution. The findings demonstrate that shape-specific interactions and clustering lead to significant changes in reorientational relaxation times. Under zero field, distinctive modes in the dynamic magnetic susceptibility identify individual particles and particle clusters. In the presence of an applied field, the characteristic relaxation time of clusters increases, while that of single particles decreases. This research provides insights into the intricate interplay between shape anisotropy, clustering, and magnetic response in platelet suspensions, offering valuable perspectives for recent experimental observations.

Nanoscale Dodecahedral and Fullerene-Type Organoboroxine and Borazine Cages from Planar Building Units.

Boroxine- and borazine-cage analogs to C20, C60, and C70 were calculated and compared in terms of structure, strain indicators, and physical properties relevant to nanoscale applications. The results show C60 and C70 type cages are less strained than the smaller congener, primarily due to minimized bending in the B-arylene-B segments. The smallest cage calculated has a diameter of 2.4 nm, which increases up to 4.9 nm by either variation of the polyhedron (C20 < C60 < C70-type cage) or organic spacer elongation between boron centers. All calculated cages are porous (apertures ranging from 0.6 to 1.9 nm). Molecular electrostatic potential and Hirshfeld population analysis revealed both nucleophilic and electrophilic sites in the interior and exterior cage surfaces. HOMO-LUMO gaps range from 3.98 to 4.89 eV and 5.10-5.18 eV for the boroxine- and borazine-cages, respectively. Our findings provide insights into the design and properties of highly porous boroxine and borazine cages for nanoscience.

Experimental and Theoretical Insights on the Structural, Electronic, and Magnetic Properties of the Quaternary Selenides EuPrCuSe3 and EuNdCuSe3.

Magnetic semiconductors EuPrCuSe3 and EuNdCuSe3 were obtained by using the halide flux method. Their crystal structures and magnetic properties were studied and discussed. Optical properties of the obtained selenides were studied by the means of diffuse reflectance spectroscopy, which revealed the values of 1.92/1.97 and 0.90/0.94 eV for the direct and indirect band gaps of Ln = Nd/Pr, respectively. The structural, electronic, and magnetic properties of the obtained compounds were additionally studied with spin-polarized density functional theory calculations, wherein both systems were found to be two new examples of semiconducting quaternary selenides with disperse conduction bands of Nd/Pr 5d character. The modeling showed that various magnetic orderings in the systems have subtle influences on the alignments/overlaps between the Se/Cu, Eu, and Pr/Nd bands, and that the spin-state energetics are very dependent upon the treatment of electron correlation, but a distinguishing feature in the case of ferromagnetic coupling is that the spin density on the Se atoms is maximized. Overall, the calculations are in good agreement with the experimental characterization of ferromagnetism in the bulk crystals, wherein the ferromagnetic transition occurs at temperatures of about 2.5 K for EuPrCuSe3 and about 3 K for EuNdCuSe3.

Tuning Two-Dimensional Phthalocyanine Dual Site Metal-Organic Framework Catalysts for the Oxygen Reduction Reaction.

Metal-organic frameworks (MOFs) offer an interesting opportunity for catalysis, particularly for metal-nitrogen-carbon (M-N-C) motifs by providing an organized porous structural pattern and well-defined active sites for the oxygen reduction reaction (ORR), a key need for hydrogen fuel cells and related sustainable energy technologies. In this work, we leverage electrochemical testing with computational models to study the electronic and structural properties in the MOF systems and their relationship to ORR activity and stability based on dual transitional metal centers. The MOFs consist of two M1 metals with amine nodes coordinated to a single M2 metal with a phthalocyanine linker, where M1/M2 = Co, Ni, or Cu. Co-based metal centers, in particular Ni-Co, demonstrate the highest overall activity of all nine tested MOFs. Computationally, we identify the dominance of Co sites, relative higher importance of the M2 site, and the role of layer M1 interactions on the ORR activity. Selectivity measurements indicate that M1 sites of MOFs, particularly Co, exhibit the lowest (<4%), and Ni demonstrates the highest (>46%) two-electron selectivity, in good agreement with computational studies. Direct in situ stability characterization, measuring dissolved metal ions, and calculations, using an alkaline stability metric, confirm that Co is the most stable metal in the MOF, while Cu exhibits notable instability at the M1. Overall, this study reveals how atomistic coupling of electronic and structural properties affects the ORR performance of dual site MOF catalysts and opens new avenues for the tunable design and future development of these systems for practical electrochemical applications.

Photocatalytic degradation of antibiotics and antimicrobial and anticancer activities of two-dimensional ZnO nanosheets

Active pharmaceutical ingredients have emerged as an environmentally undesirable element because of their widespread exploitation and consequent pollution, which has deleterious effects on living things. In the pursuit of sustainable environmental remediation, biomedical applications, and energy production, there has been a significant focus on two-dimensional materials (2D materials) owing to their unique electrical, optical, and structural properties. Herein, we have synthesized 2D zinc oxide nanosheets (ZnO NSs) using a facile and practicable hydrothermal method and characterized them thoroughly using spectroscopic and microscopic techniques. The 2D nanosheets are used as an efficient photocatalyst for antibiotic (herein, end-user ciprofloxacin (CIP) was used as a model antibiotic) degradation under sunlight. It is observed that ZnO NSs photodegrade ~ 90% of CIP within two hours of sunlight illumination. The molecular mechanism of CIP degradation is proposed based on ex-situ IR analysis. Moreover, the 2D ZNO NSs are used as an antimicrobial agent and exhibit antibacterial qualities against a range of bacterial species, including Escherichia coli, Staphylococcus aureus, and MIC of the bacteria are found to be 5 μg/l and 10 μg/l, respectively. Despite having the biocompatible nature of ZnO, as-synthesized nanosheets have also shown cytotoxicity against two types of cancer cells, i.e. A549 and A375. Thus, ZnO nanosheets showed a nontoxic nature, which can be exploited as promising alternatives in different biomedical applications.

Tetrazole-functionalized Organoboranes Exhibiting Dynamic Intramolecular N→B-Coordination and Cyanide-selective Anion Binding.

Starting from two different cyano-functionalized organoboranes, we demonstrate that 1,3-dipolar [3+2] azide-nitrile cycloaddition can serve to generate libraries of alkyl-tetrazole-functionalized compounds capable of intramolecular NàB-Lewis adduct formation. Due to the relatively low basicity of tetrazoles, structures can be generated that exhibit weak and labile NàB-coordination. The reaction furnishes 1- and 2-alkylated regio-isomers that exhibit different effective Lewis-acidities at the boron centers, and vary in their optical absorption and fluorescence properties. Indeed, we identified derivatives capable of selectively binding cyanide over fluoride, as confirmed by 11B NMR. This finding demonstrates the potentialities of this synthetic strategy to systematically fine-tune the properties of lead structures that are of interest as chemical sensors.

Low-index mesoscopic surface reconstructions of Au surfaces using Bayesian force fields

Metal surfaces have long been known to reconstruct, significantly influencing their structural and catalytic properties. Many key mechanistic aspects of these subtle transformations remain poorly understood due to limitations of previous simulation approaches. Using active learning of Bayesian machine-learned force fields trained from ab initio calculations, we enable large-scale molecular dynamics simulations to describe the thermodynamics and time evolution of the low-index mesoscopic surface reconstructions of Au (e.g., the Au(111)-‘Herringbone,’ Au(110)-(1 × 2)-‘Missing-Row,’ and Au(100)-‘Quasi-Hexagonal’ reconstructions). This capability yields direct atomistic understanding of the dynamic emergence of these surface states from their initial facets, providing previously inaccessible information such as nucleation kinetics and a complete mechanistic interpretation of reconstruction under the effects of strain and local deviations from the original stoichiometry. We successfully reproduce previous experimental observations of reconstructions on pristine surfaces and provide quantitative predictions of the emergence of spinodal decomposition and localized reconstruction in response to strain at non-ideal stoichiometries. A unified mechanistic explanation is presented of the kinetic and thermodynamic factors driving surface reconstruction. Furthermore, we study surface reconstructions on Au nanoparticles, where characteristic (111) and (100) reconstructions spontaneously appear on a variety of high-symmetry particle morphologies.

Electron Spectroscopy and Microscopy: A Window into the Surface Electronic Properties of Polycrystalline Metal Halide Perovskites.

In the past years, an increasing number of experimental techniques have emerged to address the need to unveil the chemical, structural, and electronic properties of perovskite thin films with high vertical and lateral spatial resolutions. One of these is angle-resolved photoemission electron spectroscopy which can provide direct access to the electronic band structure of perovskites, with the aim of overcoming elusive and controversial information due to the complex data interpretation of purely optical spectroscopic techniques. This perspective looks at the information that can be gleaned from the direct measurement of the electronic band structure of single crystal perovskites and the challenges that remain to beovercame to extend this technique to heterogeneous polycrystalline metal halide perovskites.

Finite element analysis of fibre reinforced timber beams under flexural loading

ABSTRACT Laminated Veneer Lumber (LVL) is a popular product used in the building and construction industry because of its high strength, serviceability, aesthetic characteristics, and cost-effectiveness. However, LVL has traditionally been limited to residential and small light commercial buildings. To expand the use of LVL and reduce the need for steel and reinforced concrete structural members, a comprehensive computational study is conducted to understand the material’s structural performance and find an optimal strengthening ratio. In this paper, a new 3-dimensional Finite Element model was introduced and evaluated to predict the structural behaviour, strength properties, and failure damage modes of LVL timber beams reinforced with a Carbon Fibre Reinforcement Polymer (CFRP) sheet. The model is validated with three experimental tests from the literature, with the reinforced timber model showing a 1.8% error compared to the plain timber model’s 7% error. Additionally, a parametric study is conducted to understand the effects of reinforcement length on the structural behaviour of the reinforced beam, with mathematical equations established to express the relationships. The study found that reinforcing 50% of the beam span generally resulted in the most significant strength improvement. This investigation is made for various strength and serviceability parameters.

A Feasible Dual Modification Strategy of Internal Anion Redox Chemistry and Surface Engineering on P2 Layer-Structured Cathodes in Sodium-Ion Batteries.

Boosting the anion redox reaction opens up a possibility of further capacity enhancement on transition-metal-ion redox-only layer-structured cathodes for sodium-ion batteries. To mitigate the deteriorating impact on the internal and surface structure of the cathode caused by the inevitable increase in the operation voltage, probing a solution to promote the bulk-phase crystal structure stability and surface chemistry environment to further facilitate the electrochemical performance enhancement is a key issue. A dual modification strategy of establishing an anion redox hybrid activation trigger agent inside the crystal structure in combination with surface oxide coating is successfully developed. P2-type layer structure cathode materials with Zn/Li (Na-O-Zn@Na-O-Li) anion redox hybrid triggers and a ZnO coating layer possess superior capacity and cycle performance, along with outstanding structural stability, decreased Mn-ion dissolution effect, and less crystal particle cracking during the cycling process. This study represents a facile modification solution to perform structure optimization and property enhancement toward high-performance layered structure cathode materials with anion redox features in sodium-ion batteries.

Histological Structure and Immunohistochemical Properties of the Ligamentum Teres in Patients With Developmental Dysplasia of the Hip

Histological Structure and Immunohistochemical Properties of the Ligamentum Teres in Patients With Developmental Dysplasia of the Hip

Redox- and Charge-State Dependent Trends in 5, 6, and 7-Membered Boron Heterocycles: A Neutral Ligand Coordination Chemistry Approach to Boracyclic Cations, Anions, and Radicals.

ConspectusBoron heterocycles represent an important subset of heteroatom-incorporated rings, attracting attention from organic, inorganic, and materials chemists. The empty pz orbital at the boron center makes them stand out as quintessential Lewis acidic molecules, also serving as a means to modulate electronic structure and photophysical properties in a facile manner. As boracycles are ripe for extensive functionalization, they are used in catalysis, chemical biology, materials science, and continue to be explored as chemical synthons for conjugated materials and reagents. Neutral boron(III)-incorporated polycyclic molecules are some of the most studied types of boracycles, and understanding their redox transformations is important for applications relying on electron transfer and charge transport. While relevant redox species can often be electrochemically observed, it remains challenging to isolate and characterize boracycles where the boron center and/or polycyclic skeleton have been chemically reduced.We describe our recent work isolating 5-, 6-, and 7-membered boracyclic radicals, anions, and cations, focusing on stabilization strategies, ligand-mediated bonding situations, and reactivity. We present a versatile neutral ligand coordination chemistry approach that permits the transformation of boracycles from potent electrophiles to powerful nucleophilic heterocycles that facilitate diverse electron transfer and bond activation chemistry. Although there are a wide range of suitable stabilizing ligands, we have employed both diamino-N-heterocyclic carbenes (NHCs) and cyclic(alkyl)(amino) carbenes (CAACs), which led to boracycles with tunable electronic structures and aromaticity trends. We highlight successful isolation of borafluorene radicals and demonstrate their reversible redox behavior, undergoing oxidation to the cation or reduction to the anion. The borafluorene anion is a chemical synthon that has been used to prepare boryl main-group and transition-metal bonds, luminescent oxabora-spirocycles, borafluorenate-crown ethers, and CO-releasing molecules via carbon dioxide activation. We expanded to 6-membered boracycles and characterized neutral bis(NHC-supported 9-boraphenanthrene)s and the corresponding bis(CAAC-stabilized 9-boraphenanthrene) biradical. We detail the interconvertible multiredox states of boraphenalene, where the boraphenalenyl radical, anion, and cation mimic the charge-states of the all-hydrocarbon analogue. Reactivity studies of the boraphenalenyl anion displayed unusual nucleophilic reactivity at multiple sites on the periphery of the boraphenalenyl tricyclic scaffold. Reduced borepins, 7-membered boron containing heterocycles, have also been isolated. We used a stepwise one-pot synthesis combining the halo-borepin precursor, CAAC, and KC8 to afford the monomeric borepin radicals and anions. The π-system was extended to contain two borepin rings fused in a pentacyclic scaffold, which permitted isolation of diborepin biradicals and a diborepin containing a dibora-quinone core.Our goal is to provide a guide explaining the current structure-function trends and isolation strategies for redox-active boron-incorporated polycyclic molecules to initiate the rational design and use of these types of compounds across a vast chemical space.

Investigating the Structural and Antimicrobial Properties of Wheat Gluten Nanocomposite Film Containing Zinc Oxide Nanoparticles and Quercetin Nanoliposomes

Investigating the Structural and Antimicrobial Properties of Wheat Gluten Nanocomposite Film Containing Zinc Oxide Nanoparticles and Quercetin Nanoliposomes

Theoretical Insight into the Band Alignment at High-κ Oxide XO2/Diamond (X = Hf and Zr) Interfaces with a SiO2 Interlayer for MOS Devices.

Diamond has become a promising candidate for high-power devices based on its ultrawide bandgap and excellent thermoelectric properties, where an appropriate gate dielectric has been a bottleneck hindering the development of diamond devices. Herein, we have systematically investigated the structural arrangement and electronic properties of diamond/high-κ oxide (HfO2, ZrO2) heterojunctions by first-principles calculations with a SiO2 interlayer. Charge analysis reveals that the C-Si bonding interface attracts a large amount of charge concentrated at the diamond interface, indicating the potential for the formation of a 2D hole gas (2DHG). The diamond/HfO2 and diamond/ZrO2 heterostructures exhibit similar "Type II" band alignments with VBOs of 2.47 and 2.21 eV, respectively, which is consistent with experimental predictions. The introduction of a SiO2 dielectric layer into the diamond/SiO2/high-κ stacks exhibits the typical "Type I″ straddling band offsets (BOs). In addition, the wide bandgap SiO2 interlayer keeps the valence band maximum (VBM) and conduction band minimum (CBM) in the stacks away from those of diamond, effectively confining the electrons and holes in MOS devices. This work exhibits the potential of SiO2/high-κ oxide gate dielectrics for diamond devices and provides theoretical insights into the rational design of high-quality gate dielectrics for diamond-based MOS device applications.

On the Validation of Protein Force Fields Based on Structural Criteria.

Molecular dynamics simulations depend critically on the quality of the force field used to describe the interatomic interactions and the extent to which it has been validated for use in a specific application. Using a curated test set of 52 high-resolution structures, 39 derived from X-ray diffraction and 13 solved using NMR, we consider the extent to which different parameter sets of the GROMOS protein force field can be distinguished based on comparing a range of structural criteria, including the number of backbone hydrogen bonds, the number of native hydrogen bonds, polar and nonpolar solvent-accessible surface area, radius of gyration, the prevalence of secondary structure elements, J-coupling constants, nuclear Overhauser effect (NOE) intensities, positional root-mean-square deviations (RMSD), and the distribution of backbone ϕ and ψ dihedral angles. It is shown that while statistically significant differences between the average values of individual metrics could be detected, these were in general small. Furthermore, improvements in agreement in one metric were often offset by loss of agreement in another. The work establishes a framework and test set against which protein force fields can be validated. It also highlights the danger of inferring the relative quality of a given force field based on a small range of structural properties or small number of proteins.

Long-Chain Lipids Facilitate Insertion of Large Nanoparticles into Membranes of Small Unilamellar Vesicles.

Insertion of hydrophobic nanoparticles into phospholipid bilayers is limited to small particles that can incorporate into a hydrophobic membrane core between two lipid leaflets. Incorporation of nanoparticles above this size limit requires the development of challenging surface engineering methodologies. In principle, increasing the long-chain lipid component in the lipid mixture should facilitate incorporation of larger nanoparticles. Here, we explore the effect of incorporating very long phospholipids (C24:1) into small unilamellar vesicles on the membrane insertion efficiency of hydrophobic nanoparticles that are 5-11 nm in diameter. To this end, we improve an existing vesicle preparation protocol and utilized cryogenic electron microscopy imaging to examine the mode of interaction and evaluate the insertion efficiency of membrane-inserted nanoparticles. We also perform classical coarse-grained molecular dynamics simulations to identify changes in lipid membrane structural properties that may increase insertion efficiency. Our results indicate that long-chain lipids increase the insertion efficiency by preferentially accumulating near membrane-inserted nanoparticles to reduce the thermodynamically unfavorable disruption of the membrane.