Molecular Systems Design & Engineering最新文献

The development of structurally controlled techniques inspired by the structural formation of living systems is of great importance for the fabrication of next-generation functional soft materials using environmentally friendly processes. This study aimed to investigate the formation mechanism of anisotropic structures of the gelatin network in a hydrogel through self-assembly on oriented templates. The effects of the oriented template having a uniaxially oriented surface on the anisotropic structure of the gelatin network were influenced by the structure at different scales: molecular (the secondary structure as the microstructure on the gelatin molecule) and molecular-assembled (the morphology of the gelatin network) scales. The mechanical properties and swelling behavior of the prepared gelatin hydrogels were characterized based on the anisotropic gelatin networks. The formation of an anisotropic gelatin network by self-assembly on the oriented template was presumably achieved by a two-step process due to the following two types of structural control factors: (1) the strength of the interaction between the template and gelatin molecules, and (2) the phase separation between the gelatin and water molecules induced during the hydrogelation process. The first process involves the formation of a thin molecular layer by the interaction between the template and gelatin molecules. The second process involves phase separation between the gelatin and water molecules during the cooling process of hydrogelation. These structurally controlled techniques for the formation of polymer networks inspired by biomineralization have two application prospects, which are the construction of biological tissue-like soft materials with complex hierarchical and anisotropic network structures through self-assembly processes, and expression of biological tissue-like functions.

The story of machine learning in general, and its application to molecular design in particular, has been a tale of evolving representations of data. Understanding the implications of the use of a particular representation – including the existence of so-called ‘activity cliffs’ for cheminformatics models – is the key to their successful use for molecular discovery. In this work we present a physics-inspired methodology which exploits analogies between model response surfaces and energy landscapes to richly describe the relationship between the representation and the model. From these similarities, a metric emerges which is analogous to the commonly used frustration metric from the chemical physics community. This new property shows state-of-the-art prediction of model error, whilst belonging to a novel class of roughness measure that extends beyond the known data allowing the trivial identification of activity cliffs even in the absence of related training or evaluation data.

Photothermal cancer therapy has gained increasing attention as a minimally invasive treatment via the localized heating of photothermal agents to eradicate cancer cells. However, its clinical translation has been limited by insufficient photothermal conversion in the near-infrared (NIR) range and low tumor-targeting efficiency. Here, synthetic melanin-like nanoparticles (∼190 nm in diameter) decorated with a cluster of smaller gold nanoparticles (∼20 nm in diameter) are developed as efficient NIR photothermal agents for in vivo cancer treatment. The melanin-gold hybrid nanoparticles are prepared by the oxidative polymerization of dopamine into colloidal melanin-like nanoparticles, followed by the spontaneous reduction of gold ion precursors into plasmonic nanoparticles on the surface of melanin nanoparticles. The gold nanoparticles significantly increase the NIR light absorption and photothermal conversion of the melanin nanoparticles, making their overall photothermal performance superior to conventional gold nanorods. Chemical conjugation of epidermal growth factor to the hybrid nanoparticles facilitates their cellular internalization into lung adenocarcinoma cells and enables in vivo tumor-targeting in a xenograft mouse model. The nanoparticles also exhibit excellent dispersion stability in serum and maintain high photothermal efficiency even after extensive laser irradiation. Our results suggest that the electronic hybridization of melanin and gold nanostructures provides a new opportunity to fine-tune their optical and chemical properties for tumor-targeted photothermal therapy.

Cooperativity in hydrogen bonds can be crucial for the stabilization of supramolecular systems. In this contribution, we propose a simple covalent modification within a pyrazole-based trimeric rosette that significantly improves its binding strength. Using dispersion-corrected density functional theory, at the BLYP-D3(BJ)/6-311++(d,p) level, we show how an intramolecular hydrogen bond acts as a bridge between an electron-donating group and an electron-withdrawing group by moving the electron density from one group to the other one through the sigma electron system. This effect strongly enhances the inductive ability of the substituents, and further increases the synergy of the cyclic trimer.

Atmospheric corrosion, an electrochemical phenomenon, initiates the degradation of materials, primarily metals, through their interaction with environmental droplets or aerosols. This degradation extends to various aspects such as material performance, longevity, and safety, emphasizing the critical need to comprehend and inhibit corrosion, particularly in industrial and environmental settings. Structural aluminum alloys, prominently used in aerospace, automotive, and marine industries, undergo extensive scrutiny due to their susceptibility to atmospheric corrosion. Nonetheless, the absence of suitable electrochemical techniques capable of accommodating droplet volumes underscores the urgent need for advancements in corrosion research. This paper introduces an innovative and efficient multielectrode cell setup aimed at rapid screening of droplet and thin film electrolyte volumes, presenting a new high-throughput screening method. Utilizing AA6014 as a substrate, this paper demonstrates a proof of concept for this methodology. It explores the influence of a crucial parameter, pH, while considering the effects of evaporation and secondary spreading. Various organic corrosion inhibitors, including some well-known inhibitors, were examined to evaluate the impact of chemically related structures on inhibition efficiency. This investigation predominately focuses on comparing and discussing differences and similarities in inhibition performance between bulk and droplet volumes. Ultimately, this comprehensive investigation aims to enhance the understanding and management of corrosion inhibition in droplet and thin film environments.

The feasibilities of the chemical reactions of indoline were analyzed with density functional theory (DFT) simulation. A series of azo disperse dyes using indoline as a coupling component were synthesized, namely D1–D6. The synthesized dyes were investigated by UV-visible, FT-IR, ¹H-NMR and MS spectroscopies. DFT simulation was applied to analyze the spectrometric properties of designed dyes. The dyeing of polyethylene terephthalate (PET) and nylon (PA) fabrics were assessed and compared. The synthesized indoline azo disperse dyes exhibited a yellow to red hue on the PET and PA fabrics. Deep shades were achieved with increased dye concentrations for D1 and D2 for the PET and PA fabrics. Excellent rubbing fastness and good sublimation fastness were achieved. Interrelations between dye structures and dyeing performance on the PET and PA fabrics were investigated using DFT calculations.

The design of reactive biodegradable polymers and materials is an extremely important topic of research. This work presents the synthesis of a highly reactive and degradable poly(aminoamide) containing indole functional group in each repeating unit. The presence of indole functional groups allows for easy post-modification of such poly(aminoamide), enabling the synthesis of a library of functional poly(aminoamide)s via triazolinedione (TAD)–indole click reactions. Furthermore, the use of bifunctional TAD molecules facilitates the crosslinking of such poly(aminoamide), where the degree of crosslinking directly influencing the surface area of the resulting materials. The thermoreversible characteristics of such crosslinked material was also investigated. Additionally, such indole decorated poly(aminoamide) was used as an excellent platform for layer-by-layer coatings and surface functionalization. Degradation studies reveals that both the linear and crosslinked poly(aminoamide)s can be degraded in alkaline solution, where the crosslinked materials degrade faster compared to the linear analogues.

In the catalytic hydrodeoxygenation (HDO) upgrading process of biomass pyrolysis, adsorption behavior plays a crucial role in subsequent reaction processes. A comprehensive understanding of the interfacial behavior is essential for advancing novel biomaterials and commercial bio-oil. We initially establish their precise orientation on the Ni(111) surface and identify the preferential binding site by calculating the binding energy of eight model components (n-butanol, acetic acid, methyl acetate, n-hexanal, toluene, catechol, guaiacol, and 3-methyl-1,2-cyclopentanone). Differences in the electrostatic potential of functional groups and their interactions with the surface lead to surface electrostatic potential distributions, with compounds containing aldehyde functionality demonstrating increased reactivity. To account for competitive adsorption behavior among multiple molecules, ReaxFF-MD simulations were conducted to investigate the adsorption of guaiacol molecules. The inclusion of acetic acid enhances the polarization effect and non-uniformity, indicating competitive adsorption between guaiacol and acetic acid molecules. The chair conformation of acetic acid was demonstrated to be more reasonable from a kinetic perspective, leading to a stronger surface charge induction effect compared to guaiacol. Additionally, this non-uniform distribution is closely correlated with the characteristic bond activations of adsorbed active molecules, serving as a driving force to enhance further hydrogenation and deoxygenation activities of the molecules.

Owing to their excellent fluorescence properties, coumarin derivatives have diverse applications in phototherapy and optoelectronics. Coumarin derivatives with a trifluoromethyl group at the 4-position have been extensively investigated; however, studies on the photophysical properties of fluorescent 3-trifluoromethylated coumarins in solution and in the solid state are rare. Hence, in this study, the photochemical properties of a coumarin derivative incorporating a promising electron-withdrawing fluoroalkyl group at the 3-position in solution and in the crystal form were investigated in detail by absorption and fluorescence spectral measurements, density functional theory and time-dependent density functional theory calculations, and single crystal X-ray structure analysis. The aim was to verify the reasons for its excellent fluorescence emission in solution and in the crystal form. These molecular compounds are expected to have potential applications as coumarin fluorophores in fluorescent emission probes and electronic light-emitting devices.

Recent progress in bone tissue engineering (BTE) has introduced alternative treatments for sizable and non-healing bone defects. Electrical stimulation (ES) has recently been shown to influence bone cells and foster processes such as adhesion, migration, proliferation, and differentiation, which can enhance the bone regeneration process. In this study, we synthesized molybdenum disulfide (MoS₂) nanoparticles (NPs) and incorporated them into a polycaprolactone (PCL) polymeric matrix to enhance the electrical conductivity of scaffolds. The PCL/MoS₂ nanocomposites were analysed using scanning electron microscopy (SEM), water contact angle measurement, electrical conductivity, and tensile strength assessments. In vitro studies evaluated the adhesion of mesenchymal stem cells (MSCs) and the biocompatibility of the fabricated scaffolds using the MTT assay. Biomineral crystal deposition was determined via in vitro simulated body fluid (SBF) biomineralization, and alizarin red S assays demonstrated enhanced calcium phosphate deposition on the PCL/MoS₂ composite scaffold. Additionally, qPCR analysis revealed that exposing MSCs cultured on PCL/MoS₂ to ES for two weeks transcriptionally upregulated osteogenic markers (osteocalcin (OC) and alkaline phosphatase (ALP)) in cells. Using either ES or a differentiation medium alone could enhance osteogenesis. However, when both stimuli were applied concurrently, improved levels of osteogenic markers were observed. Our findings suggest that ES plays a significant role in boosting osteogenic differentiation, particularly when combined with MoS₂NPs as an osteogenic enhancer. Therefore, PCL/MoS₂ nanofibrous scaffolds can be proposed as suitable candidates for BTE, and ES holds great potential as an effective tool along with commonly used biomaterial scaffolds.