ChemPlusChemPub Date : 2025-06-04DOI: 10.1002/cplu.202500113
Roxana Bugoi, Constantin Haitǎ, Cristina Talmaţchi, Ana-Maria Banici
{"title":"Archaeometric Analyses of Medieval Pottery From the Lower Danube Region, Romania.","authors":"Roxana Bugoi, Constantin Haitǎ, Cristina Talmaţchi, Ana-Maria Banici","doi":"10.1002/cplu.202500113","DOIUrl":"https://doi.org/10.1002/cplu.202500113","url":null,"abstract":"<p><p>This paper discusses the pottery manufacturing in the Lower Danube region during the Early Medieval period. Optical Microscopy (OM), Particle Induced X-ray Emission (PIXE) and X-ray Diffraction (XRD) were performed on thirty-two ceramic shards unearthed at Pantelimonu de Sus, Romania, dated to the 8th-10th c. AD. The petrographic observations showed an important variability in terms of mineral composition, homogeneity and porosity, documented by the presence of four types of ceramic paste, indicating the use of alluvial and kaolinitic clays. The mineralogy of selected ceramic fragments was further refined by powder XRD. The Principal Component Analysis (PCA) of the PIXE data separated the fragments made of kaolinitic clays from the rest. The archaeometric investigations showed that during the Early Middle Age, the potters from Pantelimonu de Sus used alluvial and kaolinitic clays, most likely of local or regional origin to manufacture various kind of vessels. Most potteries were fired in an oxidising atmosphere - complete or incomplete - at temperatures ranging from 600 °C to 900 °C. The analytical data were compared to those previously obtained on coeval ceramic finds from some nearby archaeological sites; a certain degree of similarly of the results was evidenced.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500113"},"PeriodicalIF":3.0,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214477","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-06-04DOI: 10.1002/cplu.202400640
Marimuthu Senthilkumaran, Bharathkumar H Javaregowda, Prakash Babu Rajendran, Rajalakshmi Balasubramanian, Thalasseril G Ajithkumar, Sapna Ravindranathan, Kothandam Krishnamoorthy
{"title":"Mechanochemical Large-Scale Rapid Synthesis of Ultrapure Sodium Hexafluorophosphate.","authors":"Marimuthu Senthilkumaran, Bharathkumar H Javaregowda, Prakash Babu Rajendran, Rajalakshmi Balasubramanian, Thalasseril G Ajithkumar, Sapna Ravindranathan, Kothandam Krishnamoorthy","doi":"10.1002/cplu.202400640","DOIUrl":"https://doi.org/10.1002/cplu.202400640","url":null,"abstract":"<p><p>Among the sodium battery electrolytes, sodium hexafluorophosphate (NaPF<sub>6</sub>) exhibits superior conductivity, anodic stability, and stable cathode electrolyte interface compared to other electrolytes. Therefore, the synthesis of pure NaPF<sub>6</sub> through a simple process is very important. Usually, NaPF<sub>6</sub> is synthesized using HF. In our approach, NaPF<sub>6</sub> is synthesized by grinding dry ammonium hexafluorophosphate (NH<sub>4</sub>PF<sub>6</sub>) and sodium metal. Sodium injects an electron into the ammonium ion, which results in the formation of ammonia and hydrogen. The gram scale synthesis is completed in about 30 min. Purification of the product is not needed. The product purity is confirmed by various spectroscopic and electrochemical techniques. Usually, NaPF<sub>6</sub> comprises NaF, HF, and solvents as impurities that affect the performance of SIBs. It has been confirmed that the NaPF<sub>6</sub> synthesized by our mechanochemical approach in the absence of solvent is devoid of impurities despite the absence of product purification step. Furthermore, the synthesis of pure NaPF<sub>6</sub> (250 g) is demonstrated using a grinder used as household item in cooking Indian pancakes, which costs about 300 USD. The duration of the synthesis of 250 g pure NaPF<sub>6</sub> is 1 h. The purity of this sample is comparable to that of NaPF<sub>6</sub> (5 g) synthesized using mortar and pestle.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2400640"},"PeriodicalIF":3.0,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-06-03DOI: 10.1002/cplu.202500243
Nicholas J DeWeerd, Sebastian Balser, Long K San, Rogger Palacios-Rivera, Steven H Strauss, Esther Barrena, Yu-Sheng Chen, Carmen Ocal, Daniel Martin-Jimenez, Olga V Boltalina
{"title":"Donor-Acceptor Interactions of C<sub>60</sub>F<sub>18</sub> with Polycyclic Aromatic Hydrocarbons: Size Effects in Bulk Crystallization and Surface Constraints.","authors":"Nicholas J DeWeerd, Sebastian Balser, Long K San, Rogger Palacios-Rivera, Steven H Strauss, Esther Barrena, Yu-Sheng Chen, Carmen Ocal, Daniel Martin-Jimenez, Olga V Boltalina","doi":"10.1002/cplu.202500243","DOIUrl":"10.1002/cplu.202500243","url":null,"abstract":"<p><p>An in-depth study of donor-acceptor (D/A) interactions between the high-dipole acceptor C<sub>60</sub>F<sub>18</sub> (A) and polycyclic aromatic hydrocarbon (PAH) donors-pyrene, perylene, and coronene-reveals a surprisingly strong PAH size influence on the D/A complex stoichiometry and ordering in co-crystals. The crystallographic study shows the tendency of D/A mixtures to form stacked layered structures for the larger PAHs, perylene and coronene, while the role of aromatic π-π interactions diminishes, in contrast to the smaller pyrene/C<sub>60</sub>F<sub>18</sub> system. The behavior of the layered-D/A assemblies is investigated by utilizing sequential deposition and co-evaporation of C<sub>60</sub>F<sub>18</sub> and coronene on Au(111) surfaces. Scanning tunneling microscopy shows that the flat lying configuration adopted by coronene on the metal, which forms highly ordered close-packed monolayers stabilized by the interaction between their π electrons and the high density of gold surface states, hinders the formation of the ordered assemblies of the corresponding co-crystal. The influence of the substrate plus the critical role played by electronic and steric effects in the co-crystal formation are believed to cause the lack of viability. However, it is remarkable that, on the surface, adsorbed single C<sub>60</sub>F<sub>18</sub> molecules are well centered on top of one coronene molecule, facilitating charge transfer between D and A molecules.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500243"},"PeriodicalIF":3.0,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-06-03DOI: 10.1002/cplu.202500268
Patricia Gonzales, Betty Cristina Galarreta, Sara Isabel Córdova Tuppia, Luis Felipe Villacorta Ostolaza, Ximena Bruna Lema
{"title":"Characterization of the Colorants in Antonio Raimondi's Botanical Watercolors by XRF and Raman Spectroscopies.","authors":"Patricia Gonzales, Betty Cristina Galarreta, Sara Isabel Córdova Tuppia, Luis Felipe Villacorta Ostolaza, Ximena Bruna Lema","doi":"10.1002/cplu.202500268","DOIUrl":"https://doi.org/10.1002/cplu.202500268","url":null,"abstract":"<p><p>X-Ray fluorescence and Raman spectroscopic analysis of a set of 17 of Antonio Raimondi's botanical watercolors was performed. Results from this first non-destructive chemical study allowed us to start to understand the palette of this important Italian naturalist who registered Peruvian botanical history in the 19th century. Carbon-based black, vermillion, Prussian blue, chrome yellow, gamboge, lead white, yellow ochre, red lead, and hematite were the main colorants identified in these watercolors. In addition to this, azurite and lazurite were also detected by Raman but the absence of their corresponding signals in XRF analysis suggests that they may be mixed in small quantities with the main colorants. Finally, the presence of phthalocyanine blue and beta-oxy-naphthoic acid, modern synthetic colorants that were introduced in the 20th century, suggests a later intervention in a few of these illustrations. This information contributes to a better understanding of the materials used by Raimondi specifically, and of the colorants available to artists at that time in Peru.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e202500268"},"PeriodicalIF":3.0,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144207263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Thermally Crosslinked Triphenylamine-Fluorene Conjugated Polymers: A Strategy for Stable and Efficient Electrochromic Materials.","authors":"Dongwen Zou, Xiaopeng Zhang, Hongyang Li, Ying Cui, Qilin Zhang, Yaowu He, Hong Meng","doi":"10.1002/cplu.202500186","DOIUrl":"10.1002/cplu.202500186","url":null,"abstract":"<p><p>A series of thermally crosslinkable triphenylamine-fluorene conjugated polymers (MeVb1, MeVb2, and MeVb3) with varying crosslinking densities are synthesized and systematically studied. Upon thermal crosslinking, these polymers exhibit enhanced solvent resistance and uniform film morphology. All films demonstrate stable electrochromic behavior, with tunable color transitions from transmissive yellow to deeper color. All-solid-state electrochromic devices incorporating these polymers and WO<sub>3</sub> exhibit excellent reversibility. Among them, the MeVb3-X-based device, which has the highest crosslinking density, achieves the best solvent resistance and a high optical contrast (ΔT%) of 61.3% at 900 nm, fast switching speeds (3.3 s for coloration and 1.7 s for bleaching), and high coloration efficiency (up to 296.2 cm<sup>2</sup> C<sup>-1</sup>). Furthermore, it demonstrates good cyclic stability, maintaining 90% of its initial contrast after 1000 cycles. These results highlight the potential of thermally crosslinked conjugated polymers as highly stable and efficient electrochromic materials, making them promising candidates for practical electrochromic applications.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500186"},"PeriodicalIF":3.0,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144214481","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-06-01DOI: 10.1002/cplu.202500144
Patrick Teixeira Campos, Pedro Henrique Cunha do Couto, Álex Canez Lemos Souza, Juliano Alex Roehrs
{"title":"Proposal of Molecular-Level Crystallization Mechanism for Halogenated Benzyl Alcohols: A Study of Isostructural Crystals.","authors":"Patrick Teixeira Campos, Pedro Henrique Cunha do Couto, Álex Canez Lemos Souza, Juliano Alex Roehrs","doi":"10.1002/cplu.202500144","DOIUrl":"10.1002/cplu.202500144","url":null,"abstract":"<p><p>Herein, crystallization mechanisms for halogenated benzyl alcohols, based on theoretical energetic and topological data of intermolecular and supramolecular interactions, are proposed. All interactions are verified and energetically classified by density functional theory and their contribution at each contact point is analyzed using quantum theory of atoms in molecules model. Weak interactions, such as CH···X, CH···C e C···X, perform a key role in stabilizing the crystal packing due to the larger contact area of these fragments and their higher occurrence, compared to strong interactions such as OH···O. The crystallization mechanisms are proposed based on the model developed by the research group. The mechanism starts with the strongest interaction (π···π) present in the first coordination sphere, which forms the first 1D supramolecular chain. From this chain, hypotheses of approximation between these chains are analyzed to determine the most stable arrangement for the formation of the supramolecular layer 2D. The process continues until the formation of a supramolecular structure (3D) with growth in its three directions through interactions X···X via σ-hole. The compounds in the ortho and para positions demonstrated isostructuralism in the equivalent positions, even with the variation of the halogen (chlorine and bromine).</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500144"},"PeriodicalIF":3.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-05-31DOI: 10.1002/cplu.202500068
Joses G Nathanael, Haohan Kang, Uta Wille
{"title":"Exploring Substituted Dihydroxybenzenes as Urease Inhibitors through Structure-Activity Relationship Studies in Soil Incubations.","authors":"Joses G Nathanael, Haohan Kang, Uta Wille","doi":"10.1002/cplu.202500068","DOIUrl":"10.1002/cplu.202500068","url":null,"abstract":"<p><p>Urea fertilization as nitrogen (N) source is essential for increasing crop productivity. However, it results in significant N loss through ammonia volatilization, nitrate leaching, and nitrous oxide emissions, causing environmental harm and economic loss. Urease, an enzyme in soil, rapidly catalyzes urea hydrolysis to ammonia/ammonium. To reduce ammonia volatilization, urease inhibitors delay hydrolysis until urea is dissolved in the soil body. The commercial product N-(n-butyl)thiophosphoric triamide (NBPT) is effective only in certain soils, yet it dominates the current global urease inhibitor market. This study examines the performance of un- and substituted dihydroxybenzenes (DHBs) as alternatives to NBPT in two Australian soils. Among them, 4-fluorocatechol (DHB 6) and 4-bromocatechol (DHB 8) are more effective in delaying urea hydrolysis than NBPT in acidic sandy loam soil. Michaelis-Menten kinetics reveals that NBPT acts as a competitive inhibitor, while DHB 8 acts as a noncompetitive inhibitor. Density functional theory calculations suggest that DHB 8 binds to the cysteine residue in the urease mobile flap, reducing its flexibility and preventing it from assisting urea hydrolysis. This study demonstrates the potential of DHBs as efficient urease inhibitors in certain soils, offering an environmentally viable alternative to NBPT.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500068"},"PeriodicalIF":3.0,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144191306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Unveiling Electron Dynamics in the Electrochemical Reduction of CO<sub>2</sub> to Methane on Copper.","authors":"AbhayRam Balakrishnan, Wei-Sen Chen, Yu-Ho Cheng, Kuan-Hua Wang, Mu-Jeng Cheng","doi":"10.1002/cplu.202500250","DOIUrl":"10.1002/cplu.202500250","url":null,"abstract":"<p><p>Electrochemical reduction of CO<sub>2</sub> (CO<sub>2</sub>ER) into fuels is a crucial strategy for mitigating climate change and meeting sustainable energy demands. Among catalytic materials, copper stands out due to its ability to convert CO<sub>2</sub> into a diverse range of hydrocarbons and oxygenates with significant current density. Quantum mechanical studies have greatly advanced the understanding of CO<sub>2</sub>ER on copper surfaces; however, most have focused on thermodynamics and/or kinetics to elucidate reaction mechanisms or explain experimental trends, leaving orbital-level insights largely unexplored. In this study, density functional theory calculations combined with intrinsic bond orbital analysis to track orbital evolution across 13 protonation steps involved in CO<sub>2</sub>ER to methane are employed. Based on these results, an arrow-pushing diagram is constructed to illustrate the electron flow for each step. This methodology allows to identify the key orbital used by each CO<sub>2</sub>ER intermediate to accommodate the transferred proton. Furthermore, this approach also reveals that the copper electrode actively participates in six protonation steps by exchanging pairs of electrons with CO<sub>2</sub>ER intermediates that are either selectivity-determining or rate-determining steps. These insights deepen the understanding of CO<sub>2</sub>ER mechanisms and provide a foundation for developing strategies to enhance its efficiency and selectivity.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500250"},"PeriodicalIF":3.0,"publicationDate":"2025-05-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144191307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-05-29DOI: 10.1002/cplu.202500049
Raj Kumar Khan
{"title":"4D Printing with Liquid Crystal Elastomers: Materials, Methods, and Emerging Applications.","authors":"Raj Kumar Khan","doi":"10.1002/cplu.202500049","DOIUrl":"10.1002/cplu.202500049","url":null,"abstract":"<p><p>4D printing represents a transformative leap in material science, enabling the fabrication of smart materials that change shape, properties, or functions over time in response to stimuli like heat, light, or magnetic fields. Among these, liquid crystal elastomers (LCEs) stand out due to their unique combination of liquid crystalline order and polymer elasticity. This fusion enables LCEs to undergo large, reversible shape changes, making them ideal for applications in soft robotics, biomedical devices, sensors, and adaptive optics. This review explores the latest advancements in the 4D printing of LCEs, focusing on cutting-edge fabrication techniques such as direct ink writing, VAT photopolymerization, and hybrid approaches. These methods provide precise control over molecular alignment, enabling the creation of programmable structures capable of complex movements. Integrating LCEs with nanoparticles, liquid metals, and shape-memory polymers has further enhanced their mechanical strength, thermal stability, and multifunctionality. Despite these breakthroughs, challenges remain in achieving scalability, long-term stability, and cost-effective production. This review highlights these hurdles and discusses potential solutions while emphasizing the future potential of LCEs in revolutionizing industries such as healthcare, robotics, and environmental monitoring. This article aims to inspire further innovation in 4D-printed LCE technologies by offering a comprehensive overview.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500049"},"PeriodicalIF":3.0,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
ChemPlusChemPub Date : 2025-05-28DOI: 10.1002/cplu.202500190
Lyudmila B Belykh, Nikita I Skripov, Elena A Milenkaya, Tatyana A Kornaukhova, Fedor K Schmidt
{"title":"Modification of Palladium Catalyst Properties by p-Elements (Sulfur and Phosphorus) in the Direct Synthesis of Hydrogen Peroxide: A Comparative Study.","authors":"Lyudmila B Belykh, Nikita I Skripov, Elena A Milenkaya, Tatyana A Kornaukhova, Fedor K Schmidt","doi":"10.1002/cplu.202500190","DOIUrl":"10.1002/cplu.202500190","url":null,"abstract":"<p><p>A combination of physical methods is employed to characterize Pd-S and Pd-P catalysts (Pd-nS/NaZSM-5, Pd-nP/NaZSM-5, Pd-nP/HZSM-5) prepared with varying [modifier]:[Pd] ratios using elemental sulfur or phosphorus as modifiers. These catalysts form solid solutions of sulfur or phosphorus in palladium and exhibit similar dispersity. A comparative study is conducted to evaluate the modifying effects of sulfur and phosphorus on the properties of palladium catalysts in the direct synthesis of hydrogen peroxide under mild conditions. The results demonstrate that sulfur incorporation significantly reduces hydrogen conversion while enhancing H<sub>2</sub>O<sub>2</sub> selectivity. In contrast, Pd-P catalysts achieve a more balanced activity-selectivity profile and exhibit productivity levels an order of magnitude higher than those of the Pd-0.25S/NaZSM-5 catalyst. These findings provide critical insights for selecting p-elements as modifiers to optimize catalyst performance in hydrogen peroxide synthesis.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":" ","pages":"e2500190"},"PeriodicalIF":3.0,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144155417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}