Structure-property Relationships Research Articles

Modeling and estimation of physiochemical properties of cancer drugs using entropy measures

Hyaluronic acid-paclitaxel conjugate is a nanoparticle-based drug delivery system that combines hyaluronic acid with paclitaxel, enhancing its solubility, stability, and targeting specificity. This conjugate shows promise in treating breast, lung, and ovarian cancers with reduced side effects. Entropy measures are used to predict physical and chemical properties of drugs. In this paper, we compute entropy measures for the hyaluronic acid-paclitaxel conjugate using the edge/connectivity partition approach. We establish a quantitative structure-property relationship using reverse entropy measures to predict physical properties of cancer drugs. Multiple linear, Ridge, Lasso, ElasticNet, and Support Vector regression models are employed using Python software. Our results show that reverse entropy measures exhibit high predictive capability for physical properties, based on the highest coefficient of determination and lowest mean squared error. We conclude that physical properties, including boiling point, enthalpy of vaporization, flash point, molar refractivity, molar volume, polarization, molecular weight, monoisotopic mass, topological polar surface area, and complexity, can be predicted using reverse entropy measures. We propose models for each relationship, including only the most significant models for estimating uncalculated physical properties.

Self-Assembled Monolayers of Triazolylidenes on Gold and Mixed Gold/Dielectric Substrates.

N-Heterocyclic carbenes (NHCs) have emerged as valuable ligands for surface chemistry. They can be used to prepare robust self-assembled monolayers (SAMs) for a variety of applications, including as small-molecule inhibitors (SMIs) for metal surfaces in the fabrication of next-generation integrated circuits with angstrom precision. However, little work has been performed to assess the effect of structural and electronic modifications to the basic NHC structure. Herein, we report the design and deposition of a series of 1,2,3-triazolylidene (Tz)-type carbenes on gold (Au) and Au/SiO2 patterned substrates. Triazolylidenes are an important class of stable carbenes that can be prepared with ease by using click chemistry. In this work, we studied the selective deposition of 1,2,3-triazolium hydrogen carbonate salts. The thermal properties of these precursors were measured and shown to be appropriate for either solution or vapor phase deposition. Tz-SAM stability was studied by time-of-flight secondary-ion mass spectrometry (ToF-SIMS) of Tz SAMs before and after exposure to various conditions, leading to the conclusion that Tz SAMs have thermal stabilities greater than that of NHC SAMs reported to date. Tz SAMs were analyzed by using X-ray and ultraviolet photoelectron spectroscopy (XPS, UPS) and contact angle measurements. High selectivity for deposition on metal regions over dielectric regions on patterned Au/SiO2 substrates enabled the use of Tzs as an entirely new class of SMIs on preventing ZnO deposition, providing considerable potential utility in microelectronics fabrication methods. Structure-property relationships were studied and provided key insight into the effectiveness of the SAM as a blocking agent.

Fan-Shaped Extending Conjugation Strategies for Achieving Narrowband Emissions of Boron-Nitrogen-Based Molecules.

Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials have attracted extensive attention due to their 100% exciton utilization efficiency and narrowband emissions. Numerous tube-shaped MR-TADF emitters with full-color narrowband emissions have been reported, and updated molecular design strategies need to be proposed to find more molecular "recipes" to narrow the emission spectral range. Upon changing the shape of the fluorophore from a tubular to fan-shaped structure, the investigated molecules exhibit narrowband emissions based on the analysis of the geometric and electronic structures, reorganization energies, charge transfer characters upon excitation, and absorption and emission properties. The small reorganization energies and short-range charge transfer properties upon excitation are the key to narrowing the spectral range of the molecules. Such theoretical investigations give an in-depth insight into the structure-property relationship, and the updated molecular design strategies would provide important guidance for the design of multiple-resonance molecules with narrowband emissions.

Stress-Free Two-Way Shape Memory Polymers with Dual-Crystalline Phase Based on Poly(Tetramethylene Ether Glycol) and Poly(ε-Caprolactone).

Two-way shape memory polymers (2W-SMPs) are a class of smart materials and can undergo spontaneously reversible deformation after specific stimuli. It is crucial to develop 2W-SMPs to achieve precise control of two-way shape memory behavior without external forces and reveal their structure-property relationships. In this study, dual-crystalline phase crosslinked polymer networks based on poly(tetramethylene ether glycol) (PTMEG) and poly(ε-caprolactone) (PCL) are fabricated via thiol-ene click reactions. The networks with two independent melting temperatures are gained by adjusting the ratio of the two segments and the two-way shape memory is enabled using the temperature difference between the two phases. The effects of network composition, pre-tensile strain, and actuation temperature on the two-way shape memory properties are investigated and the two-way shape memory mechanism of dual-crystalline phase polymers is further elucidated. Among the various compositions of networks, PTMEG8-PCL2 exhibits the optimal two-way shape memory properties, with the actuation strain of 24.25% and reversible strain of up to 10.35% at the actuation temperature and pre-stretch strain of 45°C and 15%, respectively, which is potential for soft robotics applications. It is believed that this work guides the design of semicrystalline networks with two-way shape memory properties.

Many-Body Effects at Heterogeneous Interfaces from First-Principles: Progress, Challenges, and Opportunities.

Heterogeneous interfaces are pivotal in numerous nanoscale devices and applications. First-principles approaches based on quantum mechanics and atomistic structures provide critical insights into structure-property relationships, enabling the informed design of materials and devices. Accurate first-principles methods must reliably capture many-body effects, i.e., electron-electron interactions, which significantly influence system properties compared to the predictions from models using free or noninteracting electrons. In this Perspective, we survey a few computational tools in this context and attempt to be forward looking by discussing the current challenges and emerging research opportunities. We examine diverse manifestations of many-body effects across several domains: geometries and reaction barriers (total-energy properties), orbital energy levels and band alignments (one-particle properties), and optical excited states (two-particle properties).

Conjugated polymer‐reinforced cellulosic frameworks: a promising approach for flexible electronics

AbstractFlexible electronics are seamlessly integrated into our lives, from foldable displays to smart wearables, redefining our interaction with technology. The use of metals and semiconductors in these flexible devices is limited due to their poor bendability and stretchability. Consequently, integrating conjugated polymers (CPs) into a cellulosic framework has emerged as a promising approach for advancing flexible electronics. Cellulose, as an abundant and sustainable biopolymer, offers a compelling solution to the escalating global e‐waste crisis by providing a cost‐effective and biodegradable substrate. This synergy has the potential to address environmental concerns and unlock new avenues of flexible, eco‐friendly and sustainable electronic devices. Herein the unique properties and synthesis routes of CPs are briefly introduced including their opportunities and challenges. The review discusses a facile and efficient approach to circumvent the challenges of CPs using cellulose as a substrate. The review explores fabrication approaches of CP–cellulose composites aimed at enhancing mechanical, electrical and optical properties. Through a critical examination of recent studies and advancements, it highlights how CPs reinforce the cellulose framework and investigates their structure–property relationships, which are crucial for tailoring the properties for desired applications. Finally, the review presents an outlook on potential challenges and prospects for advancing CP‐based cellulose composites in flexible electronics. © 2025 Society of Chemical Industry.

Structure–Property Relationships of Elastomeric Vinylogous Urethane Thermosets and Their Application as Closed-Loop Recyclable Strain Sensors

Structure–Property Relationships of Elastomeric Vinylogous Urethane Thermosets and Their Application as Closed-Loop Recyclable Strain Sensors

A New Combined Computational and Experimental Approach to Characterize Photoactive Conjugated 3D Polymers.

A tractable new computational protocol is proposed to elucidate oligomeric-scale detail from experimental spectra, providing insight into the local and longer-range electronic and molecular structures of amorphous materials. The protocol uses an in-house code Ambuild to grow kinetically-controlled representative oligomeric clusters of an amorphous polymeric material. Generating many clusters, the statistical prevalence of different structural motifs is identified, and used to develop a 'subset' of structures that capture a broad range of important morphologies. Subsequent electronic structure calculations allow the prediction of IR, NMR, and UV-vis spectra of the bulk materials, providing significant insight into oligomeric scale topologies and helping develop structure-property relationships by identifying the underlying structural origins of different spectral features observed experimentally. Two known, and two novel, pyrene-based conjugated microporous polymers (CMPs) are synthesized and characterized as a test bed for this newly-proposed protocol. Meaningful IR, NMR, and UV-vis absorption spectral data, and experimentally comparable computationally derived spectra are obtained. Whilst IR and NMR reliably probe the local environment, UV-vis absorption spectroscopy is found to be particularly sensitive to the longer-range structural motifs observed on an oligomeric scale, providing significant structural insight into the synthesized materials with reasonable computational cost.

Linear Dichroism Microscopy Resolves Competing Structural Models of a Synthetic Light-Harvesting Complex.

The initial stages of photosynthesis in light-harvesting antennae, driven by excitonic energy transport, have inspired the design of artificial light-harvesting complexes. Double-walled nanotubes (DWNTs) formed from the cyanine dye C8S3 provide a robust, self-assembled system that mimics natural chlorosomes in both structure and optical properties. Two competing molecular packing models─bricklayer (BL) and herringbone (HB)─have been proposed to explain the structural and optical characteristics of these DWNTs. This study resolves the debate by combining theoretical analysis with advanced polarization-resolved wide-field photoluminescence microscopy. Quantum-classical simulations reveal reduced linear dichroism (LDr) as a decisive parameter for distinguishing between the models. Experimental measurements of single DWNTs yielded LDr values as high as 0.93, strongly favoring the BL model. The BL model's unique excitonic patterns, dominated by negative couplings among individual chromophores, generate superradiant exciton states with transition dipoles preferentially aligned along the nanotube axis. In contrast, the HB model's mixed positive and negative couplings produce destructive interference, leading to a weaker alignment of transition dipoles. Our approach deepens the understanding of the structure-property relationships in self-assembled systems and demonstrates the potential of slip-stacking engineering to fine-tune excitonic properties for artificial light-harvesting applications.

Precision Molecular Engineering of Compact Near-Infrared Fluorophores.

Organic fluorophores with near-infrared (NIR) emission and reduced molecular size are crucial for advancing bioimaging and biosensing technologies. Traditional methods, such as conjugation expansion and heteroatom engineering, often fail to reduce fluorophore size without sacrificing NIR emission properties. Addressing this challenge, our study utilized quantum chemical calculations and structure-property relationship analysis to establish an iterative design approach and enable precision engineering for compact, single-benzene-based NIR fluorophores. These newly developed fluorophores exhibit emissions up to 759 nm and maintain molecular weights as low as 192 g/mol, approximately 50% of that of Cy7. Additionally, they display unique environmental sensitivity─nonemissive in aqueous solutions but highly emissive in lipid environments. This property significantly enhances their utility in wash-free imaging of live cells. Our findings mark a substantial breakthrough in fluorophore engineering, paving the way for more efficient and adaptable imaging methodologies.

Harary Spectra and Energy of Certain Classes of Graphs.

To investigate the H-eigenvalues and H-energy of various types of graphs, including κ-fold graphs, strong κ-fold graphs, and extended bipartite double graphs and establish relationships between the H-energy of κ-fold and strong κ-fold graphs and the H-energy of the original graph G, we explore the connection between the H-energy of extended bipartite double graphs and their ordinary energy and find the graphs that share equienergetic properties with respect to both the ordinary and Harary matrices. The H-eigenvalues of a graph G are the eigenvalues of its Harary matrix H(G). The H-energy ΕH(G) of a graph, G is the sum of the absolute values of its H-eigenvalues. Two connected graphs are said to be H-equienergetic if they have equal H-energies. They are said to A-equienergetic if they have equal A-energies. Adjacency and Harary matrices have applications in chemistry, such as finding total Π-electron energy, quantitative structure-property relationship (QSPR), etc. Objective: We determined the H-spectra of κ-fold graphs, strong κ-fold graphs and extended bipartite double graphs and established connections between the H-energy of different types of graphs and their original graph G for investigating the relationship between the H-energy of extended bipartite double graphs and their ordinary energy and the graphs that share equienergetic properties with respect to both the adjacency and Harary matrices. Spectral algebraic techniques are used to calculate the H-eigenvalues and H-energy for each type of graph and compare the H-energies of different graphs to identify the equienergetic properties and derive relationships between the H-energy of extended double cover graphs and their ordinary energy. We determined the H-spectra of κ-fold graphs, strong κ-fold graphs and extended bipartite double graphs and established relationships between the H-energy of κ-fold and strong κ-fold graphs and the H-energy of the original graph G. Then, we explored the connection between the H-energy of extended bipartite double graphs and their ordinary energy and presented graphs demonstrating equienergetic properties concerning both adjacency and Harary matrices. The study provides insights into the H-eigenvalues, H-energy and equienergetic properties of various types of graphs. The established relationships and connections contribute to a deeper understanding of graph spectra and energy properties and the findings enhance the theoretical framework for analyzing equienergetic graphs and their spectral properties. Possible extensions of this research could include investigating additional types of graphs and exploring further explicit connections between different graph energies and spectral properties. Harary matrices are distance-based matrices, which can model distances between atoms in molecular structures and could be useful in organic synthesis to predict how molecular structures behave.

Vertex-Edge-Weighted Molecular Graphs: A Study on Topological Indices and Their Relevance to Physicochemical Properties of Drugs Used in Cancer Treatment.

Quantitative structure-property relationship (QSPR) analysis plays a crucial role in predicting physicochemical properties and biological activities of pharmaceutical compounds, aiding in drug design and optimization. This study focuses on leveraging QSPR within the framework of vertex and edge-weighted (VEW) molecular graphs, exploring their significance in drug research. By examining 48 drugs used in the treatment of various cancers and their physicochemical properties, previous studies serve as a foundation for our research. Introducing a novel methodology for computing vertex and edge weights, we highlight the importance of considering atomic properties and interbond dynamics. Statistical analysis, employing linear regression models, reveals enhanced correlations between topological indices and the physicochemical properties of drugs. Comparison with previous studies on unweighted molecular graphs highlights the enhancements achieved with our approach.

Engineering Lattice Strain in Co-Doped NiMoO4 for boosting Methanol Oxidation Reaction.

Nickel-based molybdates have attracted considerable attention owing to their distinctive isomorphous structure. In this study, pristine NiMoO4 and Co-doped Ni1-xCoxMoO4 were synthesized and investigated for their electrocatalytic activity in methanol oxidation and methanol-assisted water splitting reactions. Through a comprehensive exploration of the structure-property relationship, it was found that the optimal coexistence of α and β molybdate phases, induced by Co doping, led to lattice strain and facilitated the presence of essential catalytic descriptors such as higher oxidation states of Ni and surface oxygen vacancies within the lattice. These factors contributed to the enhanced electrocatalytic activity of Ni0.7Co0.3MoO4 in methanol oxidation and hydrogen evolution reaction. Detailed kinetic studies were conducted to further elucidate the mechanisms involved. Overall, these findings highlight the promising potential of Ni0.7Co0.3MoO4 as an effective catalyst for electrochemical methanol upgrading in conjunction with water splitting, with implications for sustainable energy conversion technologies.

Cu Intercalation-Stabilized 1T' MoS2 with Electrical Insulating Behavior.

The intercalated two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted much attention for their designable structures and novel properties. Among this family, host materials with low symmetry such as 1T' phase TMDCs are particularly interesting because of their potentials in inducing unconventional phenomena. However, such systems typically have low quality and poor stability, hindering further study of the structure-property relationship and applications. In this work, we intercalated Cu into 1T' MoS2 with high crystallinity and high thermal stability up to ∼300 °C. We identified the distribution and arrangement of Cu intercalators for the first time, and the results show that Cu intercalators occupy partially the tetrahedral interstices aligned with Mo sites. The obtained Cu-1T' MoS2 exhibits an insulating hopping transport behavior with a large temperature coefficient of resistance reaching -4∼-2%·K-1. This work broadens the artificial intercalated structure library and promotes the structure design and property modulation of layered materials.

Metal-free Amorphous Cross-linked Porous Organic Polymers forPhotocatalytic Hydrogen Evolution and Carbon Dioxide Reduction.

The use of solar energy for producing valuable chemicals has gained significant attention in recent years. In this area, photocatalytic hydrogen evolution and carbon dioxide reduction have become key focal points. Recently, amorphous cross-linked porous organic polymers (CPOPs) have emerged as promising photocatalysts due to their tunable band gaps, broad light absorption range, and high porosity. In this article, we highlight recent advancements in cutting-edge metal-free amorphous CPOPs for photocatalytic hydrogen evolution and carbon dioxide reduction. We examine the design principles, synthetic strategies, and structure-property relationships of various cross-linked porous polymers to achieve high photocatalytic performance. Additionally, we propose future research directions and offer insights to further advance CPOP-based photocatalysts for efficient solar-driven hydrogen evolution and carbon dioxide reduction.

Controlled bottom-up synthesis and characterization of crystalline and amorphous lead(II) coordination polymers: Sonochemical methods, structure–property relationship, and photocatalytic applications

Controlled bottom-up synthesis and characterization of crystalline and amorphous lead(II) coordination polymers: Sonochemical methods, structure–property relationship, and photocatalytic applications

Structural-property relationship in Pt(N^{NO})Cl: The effect of hydrogenating the Schiff base ligand on spectral, biomolecule-binding and anticancer properties

Structural-property relationship in Pt(N^{NO})Cl: The effect of hydrogenating the Schiff base ligand on spectral, biomolecule-binding and anticancer properties

Accelerating the identification of stable configurations in mixed-anion perovskite materials

Mixed-anion perovskite materials exhibit tunable properties, such as band gaps, stability, and charge transport, by modulating the composition and arrangement of the anions. This tunability enables a wide range of applications in fields such as optoelectronics, catalysis, and energy storage. The structural diversity enriches the material properties and enhances performance; however, it also poses a significant challenge in determining stable structures. The stability of such alloy materials depends not only on the elemental composition but also on the arrangement of X/Y elements within the lattice. To improve the understanding of the structure–property relationship in these alloy systems, a thorough exploration of the vast compositional and configurational space is essential. Herein, we integrate the cluster expansion (CE) method with the atom classification model (ACM) to efficiently pre-screen candidate structures and identify stable configurations. By considering the arrangement of anions, which exhibit short-range ordering within octahedra and randomness between octahedra, we have designed correlation functions for the ACM to reasonably reflect these characteristics. This approach enabled us to identify configurations of BaTa(O1−xNx)3, RbPb(F1−xOx)3 and CsPb(Br1−xClx)3 with higher stabilities without significantly increasing computational costs.

Systematic evaluation of sampling rate influences and variability in POCIS using meta-analysis and quantitative structure property relationship (QSPR).

Despite the significant benefits of aquatic passive sampling (low detection limits and time-weighted average concentrations), the use of passive samplers is impeded by uncertainties, particularly concerning the accuracy of sampling rates. This study employed a systematic evaluation approach based on the combination of meta-analysis and quantitative structure-property relationships (QSPR) models to address these issues. A comprehensive meta-analysis based on extensive data from 298 studies on the Polar Organic Chemical Integrative Sampler (POCIS) identified essential configuration parameters, including the receiving phase (type, mass) and the diffusion-limiting membrane (type, thickness, pore size), as key factors influencing uptake kinetic parameters. The incomplete availability of these details across studies potentially impacts data reproducibility and comparability. The subsequent meta-regression and subgroup analysis were performed to reveal the most significant factors contributing to sampling rate variability and inter-study heterogeneity. The flow rate and octanol-water partitioning (Kow or pH-dependent Dow) were identified from all environmental factors and chemical properties. Furthermore, the impact of chemical properties on the sampling rates of POCIS was predicted by Quantitative Structure-Property Relationship (QSPR) models using 2D descriptors and random forest regression. The analysis highlighted that the electrotopological state and molecular mass are the most important chemical properties influencing the sampling rate. This study systematically unraveled the most important impact factors on reliable estimates of passive sampling rates, and these causes of uncertainty should be further considered in aquatic monitoring and assessment with passive samplers.

Chemical structure–property relationships of photocurable monomers/macromers: Potential binder candidates for ceramic/metal vat photopolymerization

Chemical structure–property relationships of photocurable monomers/macromers: Potential binder candidates for ceramic/metal vat photopolymerization