Article
Chemistry, Multidisciplinary
Wanru Gao, Yuping Li, Yunping Zhoujin, Qun Zeng, Liwen Fang, Sean Parkin, Tonglei Li, Shigang Ruan, Sihui Long
Summary: Four 2-hydroxy-N-alkyl-N-phenyl-nicotinamides were synthesized and their crystal structures were analyzed to investigate the effect of substitution on the crystal packing. The molecules were found to be in the keto form and exhibited a peptoid-like structure. Experimental and theoretical calculations provided a reasonable explanation for the formation of the keto tautomer and the hydrates.
Article
Chemistry, Multidisciplinary
Florian Racher, Tom L. Petrick, Doris E. Braun
Summary: The application of computational screening methodologies has led to the discovery of novel cocrystals of dapsone and bipyridine. Experimental screens and virtual screening results were compared to understand the factors governing cocrystal formation. The crystal structures of the cocrystals were fully characterized, and the stability and transformation behaviors were investigated. The study provides valuable insights into the formation and properties of these cocrystals.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Energy & Fuels
Yilin Cao, Zhixiang Zhang, Chao Chen, Linyuan Wen, Yiding Ma, Bozhou Wang, Yingzhe Liu
Summary: A data mining investigation reveals the importance of pi-hole interactions in crystal packing and properties of energetic materials. The statistical analysis shows that pi-hole interactions are present in a majority of energetic materials, and their strength is linearly correlated to the surface electrostatic potential. This study provides insights into the design of low-sensitivity and high-energy materials by considering pi-hole interactions.
Article
Chemistry, Multidisciplinary
B. Haripriya, Avantika Hasija, Aurora J. Cruz-Cabeza, Ipsha Shruti, Deepak Chopra
Summary: A new organic salt and cocrystal of the antidiabetic drug chlorpropamide were synthesized using mechanochemical liquid-assisted grinding, resulting in improved aqueous solubility and dissolution rate compared to the pure drug. Characterization through various methods revealed the formation of polymorphs and cocrystals with different conformers, providing insights for enhanced drug delivery.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Pharmacology & Pharmacy
Ilma Nugrahani, Muhammad Ramadhan Sulaiman, Chiaki Eda, Hidehiro Uekusa, Slamet Ibrahim
Summary: Recently, solid-state engineering has emerged as a promising method to enhance the stability and effectiveness of antibiotics. This study focuses on using antioxidant dihydroxybenzoic acid (DHBA) to react with Levofloxacin (LF) in order to produce a more stable compound and improve potency. Through screening and phase diagrams, two potential DHBA isomers, 2,6-DHBA and 3,5-DHBA, are identified as antioxidants that can react with LF in a (1:1) molar ratio. Multicomponent systems are prepared and their structures are confirmed through various analyses. The resulting salts, LF-26 and LF-35, show improved stability and approximately double the antibiotic potency compared to LF.
Article
Nutrition & Dietetics
Yingjie Ma, You Long, Feng Li, Yan Zhang, Bei Gan, Qiang Yu, Jianhua Xie, Yi Chen
Summary: A kinetic model approach was used to explore the formation and elimination of acrylamide (AA) and 5-hydroxymethylfurfural (5-HMF) in the glucose-asparagine-linoleic acid ternary system. The results showed that the elimination of glucose and asparagine and the formation of various products followed first-order reaction kinetics, with reaction rate constants increasing with temperature.
FRONTIERS IN NUTRITION
(2022)
Article
Chemistry, Multidisciplinary
Lan Fang, Yuntian Xiao, Chengtian Zhang, Zhenguo Gao, Songgu Wu, Junbo Gong, Sohrab Rohani
Summary: This study investigates the preparation of five new multicomponent crystals of 2,4-D and confirms their stability and improved solubility properties through various analyses.
Article
Chemistry, Multidisciplinary
Shenglong An, Mengyuan Qiao, Xin Jin, Xuanying Chen, Jianhua Su, Lifang Guo, Zhiyun Zhang
Summary: Organic cocrystal has attracted increasing attention as an emerging assembly strategy for constructing multiple functional materials. In this study, N,N'-diphenyl-5,10-dihydrophenazine derivatives (DPPs) with flexible scaffold and different methyl substitutions were used to fabricate a series of cocrystals in collaboration with octafluoronaphthalene (OFN), exhibiting controllable molecule stacking structure, tunable emission, and charge transfer properties.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Spectroscopy
Xiaoyu Sun, Wentao Liang, Xiangdong Li, Di Mai, Yang Zhang, Zhilei Sui, Rucheng Dai, Xianxu Zheng, Zhongping Wang, Xiaohui Duan, Zengming Zhang
Summary: In this study, it was found that the heating of cocrystals can lead to lattice collapse, and simultaneously CL-20 undergoes a transition process from the beta phase to the gamma phase. Ultimately, gamma-CL-20 gradually decomposes with increasing temperature. The activation energy of the cocrystal was determined to be 129 +/- 10 kJ/mol. These findings deepen the understanding of cocrystal explosives and promote further applications.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2023)
Article
Plant Sciences
Anna Berim, David R. Gang
Summary: Salicylic acid (SA) is a key plant hormone involved in various physiological processes, with its concentration in plants finely regulated by structural modifications. The lycophyte Selaginella moellendorffii, representing an ancient clade of vascular plants, primarily stores SA and related metabolites as glucosides in its aerial parts. The study highlights the need for further experimental characterization of enzymes in SA metabolism to elucidate physiological functions and mechanisms in ancestral plant species.
Article
Crystallography
Raquel Alvarez-Vidaurre, Alfonso Castineiras, Antonio Frontera, Isabel Garcia-Santos, Diego M. Gil, Josefa M. Gonzalez-Perez, Juan Niclos-Gutierrez, Rocio Torres-Iglesias
Summary: This work focuses on the preparation of pyridine-3-carbohydrazide cocrystals with two alpha-hydroxycarboxylic acids, characterized by single crystal X-ray crystallography to determine their three-dimensional molecular structure and hydrogen bonding interactions. The study highlights the consistent hydrogen bonding patterns involving the carboxylic acid and the variations in hydrogen bonding sites on the pyridine ring N atom of isoniazid backbone based on steric influences of derivative groups. Hirshfeld surface analysis and Density-functional theory calculations were also performed to further characterize and rationalize the non-covalent interactions.
Article
Engineering, Environmental
Xiaonan Hu, Yang Ye, Yanxi Chen, Min Liu, Wenchao Zhang, Mingshan Zhu
Summary: Reaction parameters such as catalyst dosage, oxidant amount, and initial contaminant concentration play crucial roles in heterogeneous persulfate oxidation processes. Adjusting these parameters can establish inherent connections and generate different synergistic interactions. The study revealed that different reaction parameters can form various reaction modes under specific conditions, significantly enhancing the efficiency of wastewater treatment.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Engineering, Environmental
Xu Liu, Mei Yang, Zihao Deng, Anish Dasgupta, Yang Guo
Summary: This study investigates the mechanism and kinetics of catalytic hydrodeoxygenation of palmitic acid under hydrothermal conditions, revealing that 1-hexadecanol acts as a decarboxylation inhibitor with high adsorption equilibrium constants on the catalyst. Decarboxylation is identified as the main deoxygenation pathway despite the presence of in-situ H-2.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Environmental Sciences
Xiaoqing Wu, Qifeng Hou, Jiabin Huang, Jiajue Chai, Feng Zhang
Summary: In this study, the reaction kinetics of styrene + OH were extensively studied using high-level quantum chemical methods combined with RRKM/master equation simulations. The total rate coefficient for styrene + OH was calculated to be 1.7 x 10-11 cm3 molecule-1 s-1 at 300 K, 1 atm. The main products were identified as add beta (88.2%), add5 (6.9%), add alpha (1.9%) and add3 (1.7%), with an estimated atmospheric lifetime of 8.0 hours for styrene.
Article
Chemistry, Physical
Leiduo Lai, Haodong Ji, Heng Zhang, Rui Liu, Chenying Zhou, Wen Liu, Zhimin Ao, Naiwen Li, Chao Liu, Gang Yao, Bo Lai
Summary: By utilizing V-Fe concentrate ore to activate peroxydisulfate for carbamazepine degradation, this study revealed the essential role of low valent vanadium in the high activity of V-Fe-based catalysts. Through experiments and modeling, the degradation process and mechanism were inferred, demonstrating the catalyst's excellent recyclability and broad applicability.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Multidisciplinary
Deepak Manoharan, S. N. Megha, Mangalampalli S. R. N. Kiran, Franziska Emmerling, Biswajit Bhattacharya, Soumyajit Ghosh
Summary: This study presents the manipulation of mechanical plasticity in a series of 2-benzylidene-1-indanone derivative crystals through the control of intermolecular interactions for the first time. The influence of intermolecular interactions on plastic properties is rationalized through nanoindentation and energy framework calculations.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Multidisciplinary
Kevin Linberg, Franziska Emmerling, Adam A. L. Michalchuk
Summary: Time-resolved in situ X-ray diffraction has revolutionized the study of mechanochemical transformations, but using poly(methyl methacrylate) jars can significantly alter the kinetics of mechanochemical polymorphism, necessitating a better understanding of these effects.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Paolo P. Mazzeo, Giulio Lampronti, Adam A. L. Michalchuk, Ana M. Belenguer, Alessia Bacchi, Franziska Emmerling
Summary: The debate on the mechanisms behind mechanochemical reactions via ball mill grinding is still ongoing. Accurately measuring the microstructural evolution and phase composition of materials under milling conditions is crucial for understanding the kinetics and driving forces of mechanochemical transformations. Investigating standard samples helps determine the instrumental contribution to X-ray powder diffraction peak broadening.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Physical
Kevin Linberg, Bettina Roder, Dominik Al-Sabbagh, Franziska Emmerling, Adam A. L. Michalchuk
Summary: Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. Little is known about controlling solid forms through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system, this study demonstrates that mechanochemistry can induce polymorphism in molecular solids under conditions different from conventional thermal transition points.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Stephanos Karafiludis, Ana Guilherme Buzanich, Christian Heinekamp, Annett Zimathies, Glen J. Smales, Vasile-Dan Hodoroaba, Johan E. ten Elshof, Franziska Emmerling, Tomasz M. Stawski
Summary: We demonstrate a template-free method for engineering mesoporosity in transition metal phosphate materials. By thermally decomposing M-struvite precursors, we obtained amorphous and mesoporous phases with different structures depending on the transition metal involved. The resulting structures exhibit high surface areas and pore volumes, making them suitable for potential applications in (electro)catalysis. This environmentally friendly approach could utilize waste products from industrial and agricultural wastewaters as recycling sources.
Article
Chemistry, Multidisciplinary
Nikita Y. Gugin, Jose A. Villajos, Olivier Dautain, Michael Maiwald, Franziska Emmerling
Summary: We have developed a method for the batch solid synthesis of ZIF-8 using reactive extrusion. By optimizing the process parameters, a highly crystalline ZIF-8 with a large BET surface area was successfully prepared at mild temperature. Additionally, we have developed an approach to evaluate the environmental friendliness and scalability of MOF syntheses for large-scale production.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Irina Akhmetova, Max Rautenberg, Chayanika Das, Biswajit Bhattacharya, Franziska Emmerling
Summary: This study reports the mechanochemical gram-scale synthesis of two isostructural metal hydrogen-bonded organic frameworks (MHOFs) of Co(II) and Ni(II) based on 1-hydroxyethylide-nediphosphonic acid (HEDPH4) with 2,2'-bipyridine (2,2'-bipy). In situ monitoring of the mechanochemical synthesis using different synchrotron-based techniques revealed a one-step mechanism. Both frameworks exhibited proton conduction of 10(-4) S cm(-1) at room temperature under humid conditions.
Article
Chemistry, Physical
Sivaranjani Kottaipalayam Somasundaram, Ana Guilherme Buzanich, Franziska Emmerling, Sangameswaran Krishnan, Kittusamy Senthilkumar, Raphael Justin Joseyphus
Summary: Chemically synthesized iron is in demand for biomedical applications due to its large saturation magnetization compared to iron oxides. The polyol process, suitable for obtaining Co and Ni particles and their alloys, is laborious in synthesizing Fe. This study shows that a vicinal polyol, such as 1,2-propanediol, is suitable for obtaining Fe rather than 1,3-propanediol owing to the formation of a reducible Fe intermediate complex. X-ray absorption spectroscopy analysis reveals the ferric octahedral geometry and tetrahedral geometry in the ferrous state of the reaction intermediates in 1,2-propanediol and 1,3-propanediol, respectively. The final product obtained using a vicinal polyol is Fe with a γ-Fe2O3 shell, while the terminal polyol is favourable for Fe3O4. The distinct Fe-Fe and Fe-O bond lengths suggest the presence of a carboxylate group and a terminal alkoxide ligand in the intermediate of 1,2-propanediol. A large Fe-Fe bond distance suggests diiron complexes with bidentate carboxylate bridges. Prominent high-spin and low-spin states indicate the possibility of transition, which favors the reduction of iron ions in the reaction using 1,2-propanediol.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Stephanos Karafiludis, Tom William Ryll, Ana G. Buzanich, Franziska Emmerling, Tomasz M. Stawski
Summary: Transition metal phosphates (TMPs) have attracted interest for their low-cost, stability, and tunability. An automated synthesis platform was used to explore the parameter space and characterize the phase stability, transitions, and crystal morphology/sizes. The effect of reactant species NH4+, M2+, and PO43- on the formation of different transition metal phosphate phases was investigated. The automated synthesis proved advantageous for phase diagram exploration due to its modularity, traceability, and reproducibility.
Article
Chemistry, Inorganic & Nuclear
Stephanos Karafiludis, Biswajit Bhattacharya, Ana Guilherme Buzanich, Friedrich Fink, Ines Feldmann, Johan E. ten Elshof, Franziska Emmerling, Tomasz M. Stawski
Summary: In this study, proton-conductive transition metal phosphates (TMPs) were successfully synthesized by direct thermal processing of precursor M-struvites (NH4MPO4·6H2O, M=Ni2+, Co2+). The thermal history and bulk proton conductivity of the TMP phases were investigated, and their structural information was obtained using vibrational and synchrotron-based spectroscopic methods. It was found that Ni-struvite transformed into a stable amorphous phase, while Co-struvite led to successive crystalline phases, and a highly functional layered M-dittmarite (NH4MPO4·H2O) obtained at low temperatures exhibited high proton conductivity.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Deepak Manoharan, Shamim Ahmad, Franziska Emmerling, Biswajit Bhattacharya, Soumyajit Ghosh
Summary: Mechanically dual-responsive molecular crystals have attracted considerable attention for their significant applications in various fields. Incorporating different mechanical responses in the same crystalline material is still a challenging issue and is being continuously explored. In this study, long acicular crystals derived from 4-bromobenzhydrazide and 9-anthraldehyde exhibit both stress-induced mechanical bending and blue-light induced photomechanical bending. Furthermore, the crystals also show thermal back isomerization upon gradual heating. The structure-property correlation of these two distinct mechanical responses in the crystalline phase has been studied.
Article
Chemistry, Multidisciplinary
Biswajit Bhattacharya, Adam A. L. Michalchuk, Dorothee Silbernagl, Nobuhiro Yasuda, Torvid Feiler, Heinz Sturm, Franziska Emmerling
Summary: This study presents a detailed mechanistic study on the elasto-plastic flexibility in molecular solid, and proposes an atomistic origin for this mechanical behavior. The findings suggest a close link between elastic and plastic bending, and bridge the gap between contested mechanisms, proposing its applicability as a general mechanism for elastic and plastic bending in organic molecular crystals.
Article
Chemistry, Multidisciplinary
Ines C. B. Martins, Anders S. Larsen, Anders O. Madsen, Olivia Aalling Frederiksen, Alexandra Correia, Kirsten M. O. Jensen, Henrik S. Jeppesen, Thomas Rades
Summary: Polyamorphism is a controversial solid-state phenomenon that is still not fully understood. In this study, three distinct polyamorphic forms of hydrochlorothiazide were discovered and their interconversions were investigated. Molecular dynamics simulations revealed differences in dihedral angle distributions between two of the polyamorphs, which may explain their different physicochemical properties.
Article
Chemistry, Multidisciplinary
Stefan Peters, Benny Kunkel, Cafer Tufan Cakir, Anke Kabelitz, Steffen Witte, Thomas Bernstein, Stephan Bartling, Martin Radtke, Franziska Emmerling, Ali Mohamed Abdel-Mageed, Sebastian Wohlrab, Ana Guilherme Buzanich
Summary: A setup for dispersive X-ray absorption spectroscopy (XAS) with spatial, temporal and energy resolution is introduced in this study. By investigating the reduction gradient along the packed bed of Mo/HZSM-5 catalyst during the dehydroaromatization of methane, we demonstrate the effectiveness of our new method, which represents an important addition to the analytical toolbox for in situ characterizations.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Kerstin Scheurrell, Ines C. B. Martins, Claire Murray, Franziska Emmerling
Summary: Mechanochemistry is an effective method for synthesizing organic compounds. Our study on the catalyst-free Knoevenagel reaction reveals a direct relationship between solvent polarity and reaction kinetics.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
