Pub Date : 2026-01-22DOI: 10.1016/j.molliq.2026.129307
Charu Agarwal , Levente Csóka
The conventional methods for fabrication of nanomaterials have heavily relied on the use of toxic chemicals for their reduction and stabilization as well as organic solvents, which are detrimental to the ecosystem. Thus, developing sustainable synthesis methods in line with the principles of “green” chemistry has always taken foremost precedence and at the same time, been a challenge. Over the past few decades, the synthesis of nanomaterials using environment-friendly agents has captivated the research community around the globe. A variety of plant extracts and microbes have been explored for the biogenic synthesis of different nanomaterials for myriad applications. This review aims to present the synthesis of nanomaterials using various green agents, their mechanism of formation and applications. Focus is also laid on how the morphology or property of the nanomaterials is influenced by different green agents or conditions during synthesis. Finally, the challenges and scope of using green agents for the synthesis of nanomaterials are presented.
{"title":"Developments in green nanotechnology: biogenic synthesis, mechanisms, applications","authors":"Charu Agarwal , Levente Csóka","doi":"10.1016/j.molliq.2026.129307","DOIUrl":"10.1016/j.molliq.2026.129307","url":null,"abstract":"<div><div>The conventional methods for fabrication of nanomaterials have heavily relied on the use of toxic chemicals for their reduction and stabilization as well as organic solvents, which are detrimental to the ecosystem. Thus, developing sustainable synthesis methods in line with the principles of “green” chemistry has always taken foremost precedence and at the same time, been a challenge. Over the past few decades, the synthesis of nanomaterials using environment-friendly agents has captivated the research community around the globe. A variety of plant extracts and microbes have been explored for the biogenic synthesis of different nanomaterials for myriad applications. This review aims to present the synthesis of nanomaterials using various green agents, their mechanism of formation and applications. Focus is also laid on how the morphology or property of the nanomaterials is influenced by different green agents or conditions during synthesis. Finally, the challenges and scope of using green agents for the synthesis of nanomaterials are presented.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129307"},"PeriodicalIF":5.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Proteins in aqueous solutions behave as complex molecular liquids whose conformational and colloidal stability are governed by solvent-mediated interactions and thermodynamic balance between folded and unfolded states. In this study, the effect of two extremolytes, betaine and ectoine, on the structural and colloidal stability of bovine serum albumin were investigated under acidic and thermal stress conditions. Circular dichroism, fluorescence spectroscopy, dynamic light scattering, and high-sensitivity differential scanning calorimetry were employed to probe conformational changes, aggregation behavior, and unfolding thermodynamics. Extremolytes can modify hydration structure and intermolecular forces, thereby altering protein phase behavior under stress conditions. They led to enhanced thermal stability, suppression of aggregation, and shifts in unfolding transitions, indicating solvent-driven stabilization. These effects are interpreted in terms of preferential exclusion, hydration shell modulation, highlighting the role of solvent structure in governing protein behavior in aqueous molecular liquids. The results demonstrate that extremolyte-induced stabilization arises primarily from preferential exclusion and solvent reorganization rather than direct protein–cosolute interactions.
{"title":"Exploring the effect of extremolytes on thermal and colloidal stability of bovine serum albumin","authors":"Anasuya Patil , Tanu Rawal , Akhtar Rasool , Atul Singh , Omar Awad Alsaidan , Sami I. Alzarea , Chandan Mukherjee , Juhikaben Vaibhavkumar Patel , Debashis Purohit , Shiv Bahadur , Rajat Garg , Amin Gasmi","doi":"10.1016/j.molliq.2026.129300","DOIUrl":"10.1016/j.molliq.2026.129300","url":null,"abstract":"<div><div>Proteins in aqueous solutions behave as complex molecular liquids whose conformational and colloidal stability are governed by solvent-mediated interactions and thermodynamic balance between folded and unfolded states. In this study, the effect of two extremolytes, betaine and ectoine, on the structural and colloidal stability of bovine serum albumin were investigated under acidic and thermal stress conditions. Circular dichroism, fluorescence spectroscopy, dynamic light scattering, and high-sensitivity differential scanning calorimetry were employed to probe conformational changes, aggregation behavior, and unfolding thermodynamics. Extremolytes can modify hydration structure and intermolecular forces, thereby altering protein phase behavior under stress conditions. They led to enhanced thermal stability, suppression of aggregation, and shifts in unfolding transitions, indicating solvent-driven stabilization. These effects are interpreted in terms of preferential exclusion, hydration shell modulation, highlighting the role of solvent structure in governing protein behavior in aqueous molecular liquids. The results demonstrate that extremolyte-induced stabilization arises primarily from preferential exclusion and solvent reorganization rather than direct protein–cosolute interactions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129300"},"PeriodicalIF":5.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.molliq.2026.129305
Marwa Chaabene , Soumaya Agren , Mohamed Hassen V. Baouab , Rafik Ben Chaâbane
We report the design, sonochemical synthesis, and comprehensive characterization of two Schiff base ligands, (a) and (b), as highly effective colorimetric sensors for transition and alkaline earth metal cations. Experimental UV–Vis titration studies revealed distinct and selective optical responses. Ligand (b) demonstrated exceptional sensitivity, with detection limits (LOD) as low as 1.7 μM for Zn2+, 4.5 μM for Cu2+, and 6.1 μM for Co2+. In contrast, ligand (a) showed higher LODs, such as 42.5 μM for Ni2+, highlighting the critical role of the electron-donating methyl group in enhancing binding affinity. Both ligands produced vivid color changes, dark green for Ni2+/Cu2+ and orange for Co2+, and exhibited clear isosbestic points, confirming well-defined complexation. Theoretical DFT and TD-DFT calculations corroborated the experimental findings, showing that coordination significantly narrows the HOMO-LUMO gap (e.g., from 6.80 eV in free (a) to 4.08 eV in its Ni2+ complex) and induces strong ligand-to-metal charge transfer (LMCT) bands. Furthermore, adsorption energy calculations identified the (a)/Ni2+ complex as the most stable, with an energy of −703 kcal mol−1. Molecular docking further illustrated how the methyl substituent fine-tunes binding interactions, enhancing hydrophobic stabilization within the α-amylase active site. The study conclusively establishes that strategic substituent modulation (methyl substitution) allows precise tuning of selectivity and sensitivity, positioning these Schiff bases as promising, tunable platforms for the “naked-eye” detection of environmentally and biologically relevant metal ions.
{"title":"Decoding the methyl substitution effect: a combined experimental, DFT and docking strategy for optimizing Schiff base structures","authors":"Marwa Chaabene , Soumaya Agren , Mohamed Hassen V. Baouab , Rafik Ben Chaâbane","doi":"10.1016/j.molliq.2026.129305","DOIUrl":"10.1016/j.molliq.2026.129305","url":null,"abstract":"<div><div>We report the design, sonochemical synthesis, and comprehensive characterization of two Schiff base ligands, (a) and (b), as highly effective colorimetric sensors for transition and alkaline earth metal cations. Experimental UV–Vis titration studies revealed distinct and selective optical responses. Ligand (b) demonstrated exceptional sensitivity, with detection limits (LOD) as low as 1.7 μM for Zn<sup>2+</sup>, 4.5 μM for Cu<sup>2+</sup>, and 6.1 μM for Co<sup>2+</sup>. In contrast, ligand (a) showed higher LODs, such as 42.5 μM for Ni<sup>2+</sup>, highlighting the critical role of the electron-donating methyl group in enhancing binding affinity. Both ligands produced vivid color changes, dark green for Ni<sup>2+</sup>/Cu<sup>2+</sup> and orange for Co<sup>2+</sup>, and exhibited clear isosbestic points, confirming well-defined complexation. Theoretical DFT and TD-DFT calculations corroborated the experimental findings, showing that coordination significantly narrows the HOMO-LUMO gap (e.g., from 6.80 eV in free (a) to 4.08 eV in its Ni<sup>2+</sup> complex) and induces strong ligand-to-metal charge transfer (LMCT) bands. Furthermore, adsorption energy calculations identified the (a)/Ni<sup>2+</sup> complex as the most stable, with an energy of −703 kcal mol<sup>−1</sup>. Molecular docking further illustrated how the methyl substituent fine-tunes binding interactions, enhancing hydrophobic stabilization within the α-amylase active site. The study conclusively establishes that strategic substituent modulation (methyl substitution) allows precise tuning of selectivity and sensitivity, positioning these Schiff bases as promising, tunable platforms for the “naked-eye” detection of environmentally and biologically relevant metal ions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129305"},"PeriodicalIF":5.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035957","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.molliq.2026.129308
Kun Zhao , Jianxue Li , Ke Meng , Lei Tan , Zhimin Chen , Jiafu Chen , Shaohua Liu , Jianwei Fu
The presence of Pb2+ in water systems poses potential dangers to the environment and public health, and developing efficient adsorbents is a feasible solution to the predicament. Herein, a cross-linked poly(tricholorotriazine-tannic acid) (TCA) nanosphere has been facilely prepared through one-step precipitation polymerization. The microstructure of TCA was well analyzed by TEM, SEM, FT-IR, XRD, TGA and N2 sorption and its adsorption performance for aqueous Pb2+ was systematically evaluated. Results showed that TCA owned a hard spherical structure with size of about 250 nm and specific surface area of 22.3 m2 g−1. The adsorption capacity of TCA for Pb2+ in 50 mg L−1 lead nitrate solution could be up to 136.3 mg g−1 at pH = 5 and 298 K. The adsorption rate is extremely fast, completing 91% of the equilibrium adsorption capacity within one minute. After five cycles of adsorption-desorption, the TCA nanospheres still maintained a high adsorption capacity of 109 mg g−1 for Pb2+. Adsorption kinetics and isotherm analysis suggested that the removal of Pb2+ by TCA followed the pseudo-second-order dynamics model and the Langmuir isotherm model. Thermodynamic parameters revealed that the Pb2+ removal process was spontaneous and endothermic in nature. The plausible removal mechanism could be attributed to coordination, chemical bonding and ion exchange between TCA and Pb2+.
{"title":"Facile fabrication of poly(tricholorotriazine-tannic acid) nanosphere and its rapid removal feature towards lead ions","authors":"Kun Zhao , Jianxue Li , Ke Meng , Lei Tan , Zhimin Chen , Jiafu Chen , Shaohua Liu , Jianwei Fu","doi":"10.1016/j.molliq.2026.129308","DOIUrl":"10.1016/j.molliq.2026.129308","url":null,"abstract":"<div><div>The presence of Pb<sup>2+</sup> in water systems poses potential dangers to the environment and public health, and developing efficient adsorbents is a feasible solution to the predicament. Herein, a cross-linked poly(tricholorotriazine-tannic acid) (TCA) nanosphere has been facilely prepared through one-step precipitation polymerization. The microstructure of TCA was well analyzed by TEM, SEM, FT-IR, XRD, TGA and N<sub>2</sub> sorption and its adsorption performance for aqueous Pb<sup>2+</sup> was systematically evaluated. Results showed that TCA owned a hard spherical structure with size of about 250 nm and specific surface area of 22.3 m<sup>2</sup> g<sup>−1</sup>. The adsorption capacity of TCA for Pb<sup>2+</sup> in 50 mg L<sup>−1</sup> lead nitrate solution could be up to 136.3 mg g<sup>−1</sup> at pH = 5 and 298 K. The adsorption rate is extremely fast, completing 91% of the equilibrium adsorption capacity within one minute. After five cycles of adsorption-desorption, the TCA nanospheres still maintained a high adsorption capacity of 109 mg g<sup>−1</sup> for Pb<sup>2+</sup>. Adsorption kinetics and isotherm analysis suggested that the removal of Pb<sup>2+</sup> by TCA followed the pseudo-second-order dynamics model and the Langmuir isotherm model. Thermodynamic parameters revealed that the Pb<sup>2+</sup> removal process was spontaneous and endothermic in nature. The plausible removal mechanism could be attributed to coordination, chemical bonding and ion exchange between TCA and Pb<sup>2+</sup>.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129308"},"PeriodicalIF":5.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-22DOI: 10.1016/j.molliq.2026.129268
Kui Wu , Lemei Huang , Xiaofang Li , Bin Ou
Errors were found in the thermodynamic model fitting results of the experimental solubility data of 4-chlorobenzophenone in 11 organic solvents reported by Ouyang and collaborators [Journal of Molecular Liquids 2022, 360, 119438]. The back-calculation values of the Apelblat model parameters showed significant differences from the reported experimental data. Detailed errors of the Apelblat model parameters were pointed out.
欧阳等报道的4-氯苯乙酮在11种有机溶剂中的溶解度实验数据的热力学模型拟合结果存在误差[Journal of Molecular liquid， 2022, 360,119438]。Apelblat模型参数的反算值与报道的实验数据有显著差异。指出了Apelblat模型参数的详细误差。
{"title":"Comment on “Solubility, dissolution thermodynamics, Hansen solubility parameter and molecular simulation of 4-chlorobenzophenone with different solvents”","authors":"Kui Wu , Lemei Huang , Xiaofang Li , Bin Ou","doi":"10.1016/j.molliq.2026.129268","DOIUrl":"10.1016/j.molliq.2026.129268","url":null,"abstract":"<div><div>Errors were found in the thermodynamic model fitting results of the experimental solubility data of 4-chlorobenzophenone in 11 organic solvents reported by Ouyang and collaborators [Journal of Molecular Liquids 2022, 360, 119438]. The back-calculation values of the Apelblat model parameters showed significant differences from the reported experimental data. Detailed errors of the Apelblat model parameters were pointed out.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129268"},"PeriodicalIF":5.2,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035958","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.molliq.2026.129299
Noémi Péli , Zsófia Molnár , Gergő D. Tóth , Zsolt Lőrincz , Gábor Katona , Beáta G. Vértessy , Diána Balogh-Weiser
Tyrosine hydroxylase (hTH) catalyzes the conversion of l-tyrosine to l-DOPA, the rate-limiting step in dopamine biosynthesis. As impaired hTH function is implicated in dopamine-related neurodegenerative disorders, conventional therapies relying on l-DOPA supplementation often cause adverse side effects. In this study, we investigate the immobilization of recombinant hTH onto silica nanoparticles (SNPs) as a molecularly engineered platform for enzyme replacement therapy (ERT) via intranasal administration. Recombinant GST-tagged hTH was expressed in E. coli with high yield and purity, while SNPs were synthesized with controlled size distribution and surface functionalization to enable efficient ionic binding. Immobilization efficiencies exceeding 70% were achieved. Dynamic light scattering and ζ-potential measurements confirmed enhanced colloidal stability and a reduction in protein aggregation upon immobilization. Enzymatic assays based on dopachrome formation demonstrated that catalytic activity was preserved post-immobilization. Collectively, these findings highlight SNP-based immobilization as a promising liquid-phase nanobiotechnological approach, offering a stable and non-invasive therapeutic platform for dopamine-related pathologies.
{"title":"Effect of particle size and surface linkers of SiO2 nanoparticles on the efficiency of human tyrosine hydroxylase","authors":"Noémi Péli , Zsófia Molnár , Gergő D. Tóth , Zsolt Lőrincz , Gábor Katona , Beáta G. Vértessy , Diána Balogh-Weiser","doi":"10.1016/j.molliq.2026.129299","DOIUrl":"10.1016/j.molliq.2026.129299","url":null,"abstract":"<div><div>Tyrosine hydroxylase (hTH) catalyzes the conversion of <span>l</span>-tyrosine to <span>l</span>-DOPA, the rate-limiting step in dopamine biosynthesis. As impaired hTH function is implicated in dopamine-related neurodegenerative disorders, conventional therapies relying on <span>l</span>-DOPA supplementation often cause adverse side effects. In this study, we investigate the immobilization of recombinant hTH onto silica nanoparticles (SNPs) as a molecularly engineered platform for enzyme replacement therapy (ERT) via intranasal administration. Recombinant GST-tagged hTH was expressed in <em>E. coli</em> with high yield and purity, while SNPs were synthesized with controlled size distribution and surface functionalization to enable efficient ionic binding. Immobilization efficiencies exceeding 70% were achieved. Dynamic light scattering and ζ-potential measurements confirmed enhanced colloidal stability and a reduction in protein aggregation upon immobilization. Enzymatic assays based on dopachrome formation demonstrated that catalytic activity was preserved post-immobilization. Collectively, these findings highlight SNP-based immobilization as a promising liquid-phase nanobiotechnological approach, offering a stable and non-invasive therapeutic platform for dopamine-related pathologies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129299"},"PeriodicalIF":5.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.1016/j.molliq.2026.129306
Mateus Quintano , Ayesh Madushanka , Carlos V. Santos Jr , Francielle C. Machado , Elfi Kraka , Ricardo L. Longo , Renaldo T. Moura Jr.
Liquid water exhibits anomalous behavior, with several of its physical and chemical properties deviating from those of ordinary liquids. Some of these anomalies stem from a bimodality observed in macroscopic properties such as density, isothermal compressibility, and specific heat, as well as the radial distribution function and vibrational spectra, which reflect the collective structural dynamics of liquid water. The infrared spectrum is particularly sensitive to hydrogen-bonded arrangements, thus it could be a crucial link between macroscopic properties and microscopic interactions. This study utilizes structural models that align with the experimental infrared spectrum of liquid water, offering a novel proof of concept. It bridges a critical gap by demonstrating how the bimodality of liquid water can be revealed through fully localized chemical bond descriptors. These descriptors are derived from local vibrational mode theory, the chemical bond overlap model and its topological extension, as well as the quantum theory of atoms in molecules. Key findings reveal that the local force constant, intra-overlap Coulomb repulsion, and Cremer and Kraka’s energy density associated with hydrogen bonds exhibit bimodal behavior. Notably, by employing the unsupervised machine learning algorithm K-means for clustering analysis, we identified distinct regimes of hydrogen-bond strength, revealing systematic patterns that differentiate the low-density liquid and high-density liquid networks. Overall, this study reinforces the concept that liquid water consists of two distinct types of local structures, providing new insights into its bimodal nature and advances in this field.
{"title":"Investigating the bimodality of liquid water via chemical bond descriptors and k-means clustering analysis","authors":"Mateus Quintano , Ayesh Madushanka , Carlos V. Santos Jr , Francielle C. Machado , Elfi Kraka , Ricardo L. Longo , Renaldo T. Moura Jr.","doi":"10.1016/j.molliq.2026.129306","DOIUrl":"10.1016/j.molliq.2026.129306","url":null,"abstract":"<div><div>Liquid water exhibits anomalous behavior, with several of its physical and chemical properties deviating from those of ordinary liquids. Some of these anomalies stem from a bimodality observed in macroscopic properties such as density, isothermal compressibility, and specific heat, as well as the radial distribution function and vibrational spectra, which reflect the collective structural dynamics of liquid water. The infrared spectrum is particularly sensitive to hydrogen-bonded arrangements, thus it could be a crucial link between macroscopic properties and microscopic interactions. This study utilizes structural models that align with the experimental infrared spectrum of liquid water, offering a novel proof of concept. It bridges a critical gap by demonstrating how the bimodality of liquid water can be revealed through fully localized chemical bond descriptors. These descriptors are derived from local vibrational mode theory, the chemical bond overlap model and its topological extension, as well as the quantum theory of atoms in molecules. Key findings reveal that the local force constant, intra-overlap Coulomb repulsion, and Cremer and Kraka’s energy density associated with hydrogen bonds exhibit bimodal behavior. Notably, by employing the unsupervised machine learning algorithm K-means for clustering analysis, we identified distinct regimes of hydrogen-bond strength, revealing systematic patterns that differentiate the low-density liquid and high-density liquid networks. Overall, this study reinforces the concept that liquid water consists of two distinct types of local structures, providing new insights into its bimodal nature and advances in this field.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129306"},"PeriodicalIF":5.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.molliq.2026.129301
Yuhang Li , Pengyu Cai , Hongxu Shi , Jiajun Feng , Zhongyi He , Yonggang Wang , Xiangqiong Zeng
Copper and its alloys are widely used in electronics, new energy and aerospace applications due to their superior electrical and thermal conductivity and mechanical properties. However, their susceptibility to corrosion in aggressive environments limits the application reliability. Although chromate-based passivation is highly effective, it is harmful to both the environment and human health. This review systematically evaluates recent advances in green copper corrosion inhibitors from experimental and theoretical perspectives. The copper corrosion inhibitors are categorized into inorganic (e.g. molybdates, phosphates, tungstates, rare earth, carbon quantum dots), organic (e.g. nitrogen-containing heterocyclic, sulfur-containing and novel structure compounds, natural plant extracts, expired pharmaceuticals) and organic-inorganic composite (e.g. graphene, SiO2 composites, nanocontainers) systems. Based on the analysis of experimental research results, it is found that they demonstrate enhanced protection through optimized molecular structures, synergistic formulations, multilayer films, and nanocontainer-enabled controlled release. Surface hydrophobic modification further improves performance under harsh conditions. Theoretically, density functional theory, molecular dynamics and adsorption isotherm model analysis reveal that high-efficiency inhibitors typically exhibit energy gaps of 4.00-6.00 eV, dipole moments of 2.00-6.00 Debye, and adsorb parallel to the Cu surface via heteroatoms (N, O, S etc.) with adsorption energies of -800 to -100 kJ/mol. Adsorption generally follows the Langmuir model, combining physical and chemical mechanisms with a dominance of chemisorption. These insights establish structure-performance relationships and guide the rational design of green, high-efficiency inhibitors. Future efforts should focus on scalable synthesis, long-term stability, AI-assisted material discovery, and sustainable engineering solutions.
{"title":"Green Corrosion Inhibitors for Copper Protection: Advances in Experimental and Theoretical Research","authors":"Yuhang Li , Pengyu Cai , Hongxu Shi , Jiajun Feng , Zhongyi He , Yonggang Wang , Xiangqiong Zeng","doi":"10.1016/j.molliq.2026.129301","DOIUrl":"10.1016/j.molliq.2026.129301","url":null,"abstract":"<div><div>Copper and its alloys are widely used in electronics, new energy and aerospace applications due to their superior electrical and thermal conductivity and mechanical properties. However, their susceptibility to corrosion in aggressive environments limits the application reliability. Although chromate-based passivation is highly effective, it is harmful to both the environment and human health. This review systematically evaluates recent advances in green copper corrosion inhibitors from experimental and theoretical perspectives. The copper corrosion inhibitors are categorized into inorganic (e.g. molybdates, phosphates, tungstates, rare earth, carbon quantum dots), organic (e.g. nitrogen-containing heterocyclic, sulfur-containing and novel structure compounds, natural plant extracts, expired pharmaceuticals) and organic-inorganic composite (e.g. graphene, SiO<sub>2</sub> composites, nanocontainers) systems. Based on the analysis of experimental research results, it is found that they demonstrate enhanced protection through optimized molecular structures, synergistic formulations, multilayer films, and nanocontainer-enabled controlled release. Surface hydrophobic modification further improves performance under harsh conditions. Theoretically, density functional theory, molecular dynamics and adsorption isotherm model analysis reveal that high-efficiency inhibitors typically exhibit energy gaps of 4.00-6.00 <em>eV</em>, dipole moments of 2.00-6.00 <em>Debye</em>, and adsorb parallel to the Cu surface via heteroatoms (N, O, S etc.) with adsorption energies of -800 to -100 <em>kJ/mol</em>. Adsorption generally follows the Langmuir model, combining physical and chemical mechanisms with a dominance of chemisorption. These insights establish structure-performance relationships and guide the rational design of green, high-efficiency inhibitors. Future efforts should focus on scalable synthesis, long-term stability, AI-assisted material discovery, and sustainable engineering solutions.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129301"},"PeriodicalIF":5.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.molliq.2026.129303
Ana R.F. Filipe , Letícia S. Contieri , Márcia Braz , Bárbara M.C. Vaz , Ana S. Fernandes , Ana Júlio , Maurício A. Rostagno , Adelaide Almeida , Leonardo M. de Souza Mesquita , Vitor Sencadas , Sónia P.M. Ventura
Propolis, naturally produced by honeybees for the construction and protection of beehives, exhibits numerous health benefits, particularly antimicrobial activity derived from phenolic compounds abundant in Brazilian Green propolis. However, conventional extraction methods and solvents can be environmentally hazardous and potentially harmful to skin, evidencing the need to develop safe solutions without compromising antimicrobial effects, such as the use of eutectic solvent (ES).Although the use of ES for the extraction of phenolic compounds and the antimicrobial activity of propolis are well established, this work is the first to investigate propolis as an active ingredient in the formulation of aqueous-based antiseptic aerosols. A propolis-based extract was developed using ultrasound-assisted extraction (UAE) and a novel ES composed of betaine and 1,4-butanediol in a 1:1 M ratio, and a solid-liquid ratio of 0.02 gpropolis.mLsolvent−1. This methodology yielded an extract with a total phenolic content of 139 ± 15 mgGAE.gpropolis−1, effectively inactivating methicillin-resistant Staphylococcus aureus (MRSA) and Pseudomonas aeruginosa with minimum inhibitory concentration (MIC) values of 0.174 mgGAE.mLsolvent−1 and 0.696 mgGAE.mLsolvent−1, respectively. Furthermore, an aerosol prototype for skin application was successfully developed using this extract. Ex vivo assays on porcine skin confirmed its efficacy, showing a 2-log inactivation of MRSA after 24 h. Cell viability assays in human keratinocytes indicated the biocompatibility of the formulation with the skin. These findings serve as a proof of concept, showing the effectiveness of propolis formulation against bacteria and its potential application as an aqueous aerosol for treating skin infections.
{"title":"Antimicrobial aqueous aerosol formulation using a propolis extract from eutectic solvent extraction","authors":"Ana R.F. Filipe , Letícia S. Contieri , Márcia Braz , Bárbara M.C. Vaz , Ana S. Fernandes , Ana Júlio , Maurício A. Rostagno , Adelaide Almeida , Leonardo M. de Souza Mesquita , Vitor Sencadas , Sónia P.M. Ventura","doi":"10.1016/j.molliq.2026.129303","DOIUrl":"10.1016/j.molliq.2026.129303","url":null,"abstract":"<div><div>Propolis, naturally produced by honeybees for the construction and protection of beehives, exhibits numerous health benefits, particularly antimicrobial activity derived from phenolic compounds abundant in Brazilian Green propolis. However, conventional extraction methods and solvents can be environmentally hazardous and potentially harmful to skin, evidencing the need to develop safe solutions without compromising antimicrobial effects, such as the use of eutectic solvent (ES).Although the use of ES for the extraction of phenolic compounds and the antimicrobial activity of propolis are well established, this work is the first to investigate propolis as an active ingredient in the formulation of aqueous-based antiseptic aerosols. A propolis-based extract was developed using ultrasound-assisted extraction (UAE) and a novel ES composed of betaine and 1,4-butanediol in a 1:1 M ratio, and a solid-liquid ratio of 0.02 g<sub>propolis</sub>.mL<sub>solvent</sub><sup>−1</sup>. This methodology yielded an extract with a total phenolic content of 139 ± 15 mg<sub>GAE</sub>.g<sub>propolis</sub><sup>−1</sup>, effectively inactivating methicillin-resistant <em>Staphylococcus aureus</em> (MRSA) and <em>Pseudomonas aeruginosa</em> with minimum inhibitory concentration (MIC) values of 0.174 mg<sub>GAE</sub>.mL<sub>solvent</sub><sup>−1</sup> and 0.696 mg<sub>GAE</sub>.mL<sub>solvent</sub><sup>−1</sup>, respectively. Furthermore, an aerosol prototype for skin application was successfully developed using this extract. <em>Ex vivo</em> assays on porcine skin confirmed its efficacy, showing a 2-log inactivation of MRSA after 24 h. Cell viability assays in human keratinocytes indicated the biocompatibility of the formulation with the skin. These findings serve as a proof of concept, showing the effectiveness of propolis formulation against bacteria and its potential application as an aqueous aerosol for treating skin infections.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129303"},"PeriodicalIF":5.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-20DOI: 10.1016/j.molliq.2026.129280
Ashish Tiwari , Sanjay Janrao Dhoble
The photophysical behavior of luminescent ionic liquids (ILs) is governed by a complex interplay between IL chemical structure and specific solute–solvent interactions. This review uniquely dissects how the structural diversity of ILs—ranging from cation/anion selection to the incorporation of functional groups such as protic imidazolium or hydrogen-bonding anions—directly modulates excited-state dynamics, radiative and non-radiative decay rates, and quenching mechanisms. We highlight how IL-induced microenvironmental changes, including microviscosity and microheterogeneity, as well as direct electrostatic and coordination interactions, can be leveraged to fine-tune luminescence. Special emphasis is placed on structure–activity relationships, synthetic strategies for luminescent ILs, and the resulting advances in photophysical mechanisms such as Förster Resonance Energy Transfer (FRET), Aggregation-Induced Emission (AIE), Triplet-Triplet Annihilation Upconversion (TTA-UC), and non-radiative decay suppression. The review also presents a forward-looking perspective on the rational design of ILs—covering functionalized, chiral, nanostructured, and polymerizable ILs (PILs)—for next-generation photonic, sensing, and optoelectronic technologies.
{"title":"Ionic liquids beyond the solvent: structure–activity design for tunable luminescence and next-generation photonic applications","authors":"Ashish Tiwari , Sanjay Janrao Dhoble","doi":"10.1016/j.molliq.2026.129280","DOIUrl":"10.1016/j.molliq.2026.129280","url":null,"abstract":"<div><div>The photophysical behavior of luminescent ionic liquids (ILs) is governed by a complex interplay between IL chemical structure and specific solute–solvent interactions. This review uniquely dissects how the structural diversity of ILs—ranging from cation/anion selection to the incorporation of functional groups such as protic imidazolium or hydrogen-bonding anions—directly modulates excited-state dynamics, radiative and non-radiative decay rates, and quenching mechanisms. We highlight how IL-induced microenvironmental changes, including microviscosity and microheterogeneity, as well as direct electrostatic and coordination interactions, can be leveraged to fine-tune luminescence. Special emphasis is placed on structure–activity relationships, synthetic strategies for luminescent ILs, and the resulting advances in photophysical mechanisms such as Förster Resonance Energy Transfer (FRET), Aggregation-Induced Emission (AIE), Triplet-Triplet Annihilation Upconversion (TTA-UC), and non-radiative decay suppression. The review also presents a forward-looking perspective on the rational design of ILs—covering functionalized, chiral, nanostructured, and polymerizable ILs (PILs)—for next-generation photonic, sensing, and optoelectronic technologies.</div></div>","PeriodicalId":371,"journal":{"name":"Journal of Molecular Liquids","volume":"446 ","pages":"Article 129280"},"PeriodicalIF":5.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146035906","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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