Crystal Growth & Design最新文献

{"title":"Guanine Crystal Formation at Physiological pH","authors":"Bidisha Tah Roy,&nbsp;Lukas Jorin Hasselt,&nbsp;Ross Young,&nbsp;Zijiang Yang,&nbsp;Jeanine Williams,&nbsp;Johanna M. Galloway,&nbsp;Alex Heyam,&nbsp;Yi-Yeoun Kim* and Fiona C. Meldrum*,&nbsp;","doi":"10.1021/acs.cgd.5c0020510.1021/acs.cgd.5c00205","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00205https://doi.org/10.1021/acs.cgd.5c00205","url":null,"abstract":"<p >Guanine crystals are the principal component of many biocrystals with optical functions. Typically exhibiting unique morphologies and being metastable β anhydrous guanine (β-AG) rather than the thermodynamically stable α anhydrous polymorph (α-AG), many questions remain regarding the mechanisms by which organisms control their formation. However, efforts to elucidate these using bio-inspired approaches have been limited by the very low solubility of guanine in aqueous solutions at physiological pH. Here, we demonstrate an enzymatic approach based on the purine metabolism process that yields significant quantities of guanine crystals in aqueous solution at neutral pH. Significantly, this mirrors processes believed to generate guanine crystals in vivo. The enzyme purine nucleoside phosphorylase (PNP) is used to continuously convert guanosine to guanine and generate supersaturation, and pure β-AG or α-AG can be produced by changing the reagent concentrations or introducing stirring. We also show that the rate of change of supersaturation is crucial in determining the polymorph, demonstrating that organisms can generate β-AG crystals by simply controlling the crystallization conditions. This work bridges the gap between in vitro and biological crystallization and provides a facile means of studying the crystallization of biological molecules and ultimately generating functional materials using sustainable processes.</p><p >An enzyme-mediated synthesis of guanine crystals at neutral pH is presented that offers control over polymorphs and enables pure β anhydrous or α anhydrous guanine crystals to be reproducibly synthesized. This approach shows that polymorph selection is governed by the rate of change of the solution supersaturation and lays a foundation for exploring biogenic crystallization mechanisms.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4316–4324 4316–4324"},"PeriodicalIF":3.2,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00205","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Diffusion-Controlled Formation and Differentiation of Calcite and Vaterite in a Hydrogel","authors":"Ki Min Jeong,&nbsp;Yu Seob Shin and Sung Ho Yang*,&nbsp;","doi":"10.1021/acs.cgd.5c0027210.1021/acs.cgd.5c00272","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00272https://doi.org/10.1021/acs.cgd.5c00272","url":null,"abstract":"<p >Two crystal phases of calcium carbonate, calcite and vaterite, were synthesized and controlled within a single hydrogel by using an orthogonal diffusion method. By precise regulation of the diffusion of hydrogen carbonate and hydroxide ions in a hydrogel containing calcium ions, the local pH and ion supersaturation levels were adjusted, optimizing conditions for vaterite formation. Unlike conventional solution-based methods, where rapid precipitation occurs, the hydrogel system facilitated slow diffusion, mimicking biological mineralization and allowing the stabilization of less stable intermediates and crystal phases. This controlled microenvironment enabled the simultaneous observation of spatial variations in calcium carbonate crystallization, providing insights into phase transitions and polymorph selection. The findings highlight the potential of hydrogel-based systems for regulating biomineralization, offering valuable implications for crystallization mechanisms in biomaterials and tissue engineering.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4367–4376 4367–4376"},"PeriodicalIF":3.2,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305757","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}

{"title":"Cocrystals of the Highly Potent Sickle Cell Anemia Drug Voxelotor with Trimesic Acid: A Substantial Enhancement in In Vitro Dissolution Performance at Physiological pH","authors":"Akram A. Khan,&nbsp;Tabrez R. Shaikh,&nbsp;Christy P. George and Rajesh G. Gonnade*,&nbsp;","doi":"10.1021/acs.cgd.5c0030010.1021/acs.cgd.5c00300","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00300https://doi.org/10.1021/acs.cgd.5c00300","url":null,"abstract":"<p >Global Blood Therapeutic’s (GBT’s) Voxelotor is an investigational oral therapy for treating sickle cell anemia. It functions by increasing the affinity between hemoglobin and oxygen, thereby preventing the sickling of red blood cells and altering the disease’s pathology. The US FDA has approved Voxelotor for the treatment of sickle cell anemia and granted it an orphan drug status. However, Voxelotor is classified as a BCS class II, indicating poor water solubility. The current study explores the enhancement of Voxelotor’s water solubility by forming cocrystals with trimesic acid (<b>TMA</b>). Novel cocrystals, cocrystal solvates, and hydrates of Voxelotor (<b>Vox</b>) with trimesic acid (<b>TMA</b>) have been developed to improve their solubility. The new solids were characterized using PXRD, DSC, TGA, XPS, HSM, and single-crystal X-ray diffraction studies, and the intermolecular interactions were quantified using Hirshfeld surface analysis. Detailed crystallographic analysis revealed strong O–H···N hydrogen bonding interactions between <b>Vox</b> and <b>TMA</b>, primarily involving the COOH functional group of <b>TMA</b> and the pyridine or pyrazole groups of <b>Vox</b>. Additionally, <b>TMA</b> molecules participate in further hydrogen bonding─either with themselves or with solvates, including hydrates, through mono- or dimeric O–H···O H-bonding synthons. <i>In vitro</i> solubility studies demonstrated a significant increase in the solubility of Voxelotor in the <b>Vox</b>-<b>TMA</b> cocrystals compared to the pristine drug at physicochemical pH 4.5 and 6.8. Stability studies confirmed that the nonsolvated multicomponent crystal retains their structural integrity under nonambient conditions without undergoing polymorphic phase transitions. In contrast, the solvated crystals, including hydrates, undergo phase transitions within the temperature range of 100–130 °C, losing solvents and converting into one of the nonsolvated cocrystal forms. These findings suggest that the novel <b>Vox</b>-<b>TMA</b> cocrystals have the potential to enhance the therapeutic performance and clinical utility of Voxelotor.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4405–4425 4405–4425"},"PeriodicalIF":3.2,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305731","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}

{"title":"Homochiral BINAPO-Based Metal–Organic Frameworks for Luminescence Sensing of Phenylglycinol Enantiomers","authors":"Chenghua Deng,&nbsp;Zitong Wang,&nbsp;Zhihao Zhao and Wenbin Lin*,&nbsp;","doi":"10.1021/acs.cgd.5c0024910.1021/acs.cgd.5c00249","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00249https://doi.org/10.1021/acs.cgd.5c00249","url":null,"abstract":"<p >Chiral metal–organic frameworks (CMOFs) with luminescent properties are promising enantioselective sensors for important chiral molecules. Herein, we report the synthesis and characterization of four CMOFs, Cu-<b>L</b>, Zn-<b>L</b>, Cd-<b>L</b>, and Mn-<b>L</b>, based on the BINAP oxide (BINAPO) ligand <i>R</i>-2,2′-Bis(diphenylphosphoryl)-1,(1′-binaphthyl)-4,4′-bis(4-carboxyphenyl) (H₂<b>L</b>). In the isostructural Cu-<b>L</b> and Zn-<b>L</b> MOFs, the metal cations coordinate with carboxylate groups and solvent molecules to form paddle-wheel shaped secondary building units (SBUs). These SBUs are further connected by the ligands as 4-connected nodes, resulting in square lattice (<b>sql</b>) networks. The metal centers in Cd-<b>L</b> and Mn-<b>L</b> coordinate with phosphine oxides and carboxylates, with each Mn cation additionally coordinating to one aqua molecule. The resulting frameworks adopt 2D and 3D networks of <b>fes</b> and <b>qtz-h</b> topologies, respectively. At a ligand concentration of 28 μM, the fluorescence of an H₂<b>L</b> solution in acetonitrile was quenched by <i>R</i>-phenylglycinol (<i>R</i>-PG) and <i>S</i>-PG, with Stern–Völmer constants (<i>K</i>_sv) of 69.6 ± 1.0 and 34.2 ± 0.5 M^–1, respectively. At the same ligand concentration, a Zn-<b>L</b> suspension in acetonitrile exhibited slightly lower quenching efficiencies, with <i>K</i>_sv values of 16.2 ± 0.3 M^–1 for <i>R</i>-PG and 27.5 ± 0.4 M^–1 for <i>S</i>-PG. In tetrahydrofuran, Zn-<b>L</b> was quenched by R-PG and S-PG with <i>K</i>_sv values of 44.5 ± 0.7 and 21.7 ± 0.4 M^–1, respectively, and H₂<b>L</b> exhibited lower quenching efficiencies. The reversed enantioselectivity observed in Zn-<b>L</b> in acetonitrile, compared to H₂<b>L</b>, suggests the presence of distinct chiral recognition sites, potentially influenced by solvent effects on the coordinated BINAPO ligand within the MOF.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4360–4366 4360–4366"},"PeriodicalIF":3.2,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305756","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}

{"title":"Triel Bonds─Interactions without Borders, Similarly as Hydrogen Bonds","authors":"Sławomir J. Grabowski*,&nbsp;","doi":"10.1021/acs.cgd.5c0046610.1021/acs.cgd.5c00466","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00466https://doi.org/10.1021/acs.cgd.5c00466","url":null,"abstract":"<p >ωB97XD/aug-cc-pVTZ results of calculations on complexes linked by triel bonds are analyzed here. The systems connected by different kinds of triel bonds are considered: those with the one-center electron donor, among which are complexes with halide anions playing the role of Lewis bases. Complexes with π-electron units as electron donors are also considered, i.e., complexes of acetylene, ethylene, and benzene. Finally, species are considered where interactions may be classified as bifurcated triel bonds or as halide and hydride bonds. Apart from ab initio calculations, other theoretical approaches are applied such as the Quantum Theory of Atoms in Molecules (QTAIM) approach and the energy decomposition analysis scheme (EDA). The theoretical analyses are supported by examples of crystal structures where similar interactions occur. The Cambridge Structural Database (CSD) searches were performed to find such structures. The theoretical results and the results of CSD searches show that the triel bond possesses characteristics like those occurring in hydrogen bonded systems. The triel center often changes its trigonal configuration to the tetrahedral configuration in complexes that are linked by strong triel bonds.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4539–4552 4539–4552"},"PeriodicalIF":3.2,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305727","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}

{"title":"Molecular Platform of Isoskeletal {M2IILn4III} Clusters for the Study of the MII (M = Cu, Zn) Effect on the Magnetic Properties","authors":"Konstantinos N. Pantelis,&nbsp;Konstantina H. Baka,&nbsp;Luís Cunha-Silva,&nbsp;Jinkui Tang,&nbsp;Dimitris I. Alexandropoulos* and Theocharis C. Stamatatos*,&nbsp;","doi":"10.1021/acs.cgd.5c0047510.1021/acs.cgd.5c00475","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00475https://doi.org/10.1021/acs.cgd.5c00475","url":null,"abstract":"<p >The Schiff base chelate <i>N</i>-salicylidene-2-amino-5-chlorobenzoic acid (sacbH₂) was used for the first time in studies involving heterometallic 3<i>d</i>/4f-metal clusters, leading to the formation of the isoskeletal complexes [M₂Ln₄(OH)₂(acac)₄(L)₂(sacb)₄(MeOH)₂], where L^– is the 2-amino-5-chlorobenzoate anion, acac^– is the anion of 2,4-pentanedione, and M^II = Cu^II, Zn^II and Ln^III = Dy^III, Gd^III, Ho^III. All complexes share a {M₂Ln₄(μ₃–OH)₂(μ-OR)₂(μ-O₂CR)₄}⁸⁺ “stacked” triangular core, consisting of two M^II ions and four Ln^III ions which adopt distorted square pyramidal and square antiprismatic coordination geometries, respectively. The reported compounds join only a handful of hexanuclear heterometallic complexes with a 2:4 3d/4f-metal stoichiometry. Direct current (<i>dc</i>) magnetic susceptibility measurements revealed the presence of predominant ferromagnetic exchange interactions between the paramagnetic metal centers within <b>2-Cu</b>_<b>2</b><b>Gd</b>_<b>4</b> and <b>5-Zn</b>_<b>2</b><b>Gd</b>_<b>4</b> congeners at low temperatures. Alternating current (<i>ac</i>) magnetic susceptibility measurements showed that compounds <b>1-Cu</b>_<b>2</b><b>Dy</b>_<b>4</b> and <b>4-Zn</b>_<b>2</b><b>Dy</b>_<b>4</b> exhibit tails of out-of-phase <i>ac</i> signals at applied <i>dc</i> fields of 1100 and 500 Oe, respectively, indicating relatively fast magnetization relaxation due to the efficient quantum tunneling mechanism. The reported results demonstrate a new molecular platform of a structurally resistant {M₂Ln₄} topology upon alterations in the chemical, electronic, and sterical properties of the different divalent 3d-metal ion.</p><p >A series of isoskeletal, heterometallic [M₂Ln₄(OH)₂(acac)₄(L)₂(sacb)₄(MeOH)₂] (M^II = Cu^II, Zn^II; Ln^III = Dy^III, Gd^III, Ho^III) clusters bearing the “ligand blend” of acetylacetone and <i>N</i>-salicylidene-2-amino-5-chlorobenzoic acid (sacbH₂) were prepared and magnetically studied; all complexes possess a {M₂Ln₄(μ₃−OH)₂(μ-OR)₂(μ-O₂CR)₄}⁸⁺ “stacked” triangular core.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4553–4564 4553–4564"},"PeriodicalIF":3.2,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00475","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Do Inhibition Studies of Ice Crystallization Indicate Cryoprotectant Efficacy?","authors":"P. U. Ashvin Iresh Fernando,&nbsp;Daniel W. Tague,&nbsp;Max Friedman,&nbsp;Matthew A. Fort,&nbsp;Brianna M. Fernando,&nbsp;Abigail M. Carson,&nbsp;Mamie E. Mulder,&nbsp;Amara J. Taddeo and Emily Asenath-Smith*,&nbsp;","doi":"10.1021/acs.cgd.5c0022110.1021/acs.cgd.5c00221","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00221https://doi.org/10.1021/acs.cgd.5c00221","url":null,"abstract":"<p >Common cryoprotectants (CPs) (dimethyl sulfoxide, glycerol, trehalose) require high concentrations (&gt;10 wt %) and can cause adverse effects to cells and DNA. Alternative CPs are actively being investigated, and ice recrystallization inhibition (IRI), dynamic ice-shaping (DIS), and nucleation temperature (<i>T</i>_n) assays are being utilized in the discovery and down selection of new CP materials. We performed a three-pronged study with IRI, DIS, and <i>T</i>_n as metrics applied to three classes of molecules saccharides (mono- and di-), small molecules, and polymers (synthetic and biological). The results presented indicate that these metrics do not correlate to the efficacy of known CPs. Select polymeric materials, including antifreeze protein (AFP) and polyvinyl alcohol (PVA), showed positive results across all three metrics even at low concentrations (≤10 μM). At 1 mM, most saccharides and small molecules we studied yielded no positive IRI or DIS activity and did not change <i>T</i>_n significantly. Surprisingly, out of all the molecules studied, cysteamine induced nucleation of ice by elevating <i>T</i>_n by &gt;50% over pure (supercooled) water. These results raise the question of whether the assays provide data that allows for discovery and down selection of new CP materials, or if other metrics should be formulated.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4325–4337 4325–4337"},"PeriodicalIF":3.2,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305608","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}

{"title":"Ammonium Organosulfonates as Machine Learning-Driven “Crystallization Cocktails” for the Structure Determination of Liquid Molecules","authors":"Anastasia Danshina,&nbsp;Ivan Zlobin,&nbsp;Svetlana Solov’eva,&nbsp;Nikolai Rekut and Yulia V. Nelyubina*,&nbsp;","doi":"10.1021/acs.cgd.5c0049810.1021/acs.cgd.5c00498","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00498https://doi.org/10.1021/acs.cgd.5c00498","url":null,"abstract":"<p >A concept of “crystallization cocktails” for crystal structure determination of small (liquid) molecules is introduced, offering a simple one-step procedure of one-pot mixing commercial sulfonic acids (such as <i>p</i>-toluenesulfonic and 1,5-naphtalenedisulfonic) and geometrically diverse amines (such as <i>p</i>-phenylenediamine, 4,4′-oxidianiline, and 4,4′-diamino-3,3′-dichlorodiphenylmethane) in different combinations to cocrystallize with a chosen liquid compound by simple solvent evaporation. These “crystallization cocktails” may adapt to different guests owing to “labile” intermolecular interactions between sulfonate and ammonium ions of diverse geometries and flexibility, as demonstrated by a successful cocrystallization of three model phenol derivatives (2,4-dimethyl-, 2-isopropyl-, and 2-ethylphenol); one of them being characterized by X-ray diffraction for the first time. The guest-to-host ratio in the obtained cocrystals, three of which featured the same ammonium organosulfonate but different phenol guests, was found to depend on the size of the individual components of the “crystallization cocktails”. To get insight into the preferable formation of a cocrystal by some of these “cocktails”─as common (descriptive) crystallographic tools failed to provide a definitive answer─a machine learning (ML) algorithm was developed, which allowed limiting the list of their components to a few most suitable ones for a successful cocrystallization with liquid phenols. “Crystallization cocktails” that can be “mixed to order”─and boosted by the ML─pave the way toward routine structure determination of liquids or other poorly crystallizing substances by X-ray diffraction, streamlining the search for new chemical compounds and identification of “old” ones in natural products, waste and natural waters, and living organisms.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4601–4620 4601–4620"},"PeriodicalIF":3.2,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305728","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}

{"title":"Crystal Engineering Optimization through CF3 Functionalization: An Emerging Strategy for High-Density Energetic Materials","authors":"Xiaoxiao Zheng,&nbsp;Huiliang Hua,&nbsp;Xuhui Xu,&nbsp;Guangbin Cheng,&nbsp;Hongwei Yang,&nbsp;Guoping Wang* and Jinhao Zhao*,&nbsp;","doi":"10.1021/acs.cgd.5c0002710.1021/acs.cgd.5c00027","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00027https://doi.org/10.1021/acs.cgd.5c00027","url":null,"abstract":"<p >In light of the distinctive advantages of −CF₃ groups in density and mechanical sensitivity of energetic materials (EMs), the bifused heterocyclic perchlorate featuring a −CF₃ group (<b>Z-2</b>) was synthesized, exhibiting a remarkable crystal density of 2.008 g cm^–3 at 223 K, which ranks among the top performers of known CF₃-containing energetic materials to date. In comparison with its previously reported analogue 3,7-diamino-6-methyl-7H-[1,2,4]triazolo[4,3-<i>b</i>][1,2,4]triazol-2-ium perchlorate (<b>N-1</b>), compound <b>Z-2</b> exhibits higher detonation performances (<i>D</i>_v = 8649 m s^–1, <i>P</i> = 37.7 GPa for <b>Z-2</b> vs <i>D</i>_v = 7784 m s^–1, <i>P</i> = 24.1 GPa for <b>N-1</b>), featuring a significant density enhancement of 0.27 g cm^–3 (ρ = 1.72 g cm^–3 for <b>N-1</b>) and improved mechanical sensitivities (<i>IS</i> = 20 J, <i>FS</i> = 252 N for <b>Z-2</b> vs <i>IS</i> = 12 J, <i>FS</i> = 144 N for <b>N-1</b>) while maintaining favorable thermal decomposition temperature (<i>T</i>_d = 225 °C). Six new compounds were characterized by single-crystal X-ray diffraction analysis. Notably, the strong electron-withdrawing −CF₃ groups facilitate compact and ordered crystal packing, highlighting the advantages of −CF₃ groups in crystal engineering. Taken together, these findings demonstrate promising prospects for CF₃-containing fused heterocycles, which provides a novel approach for developing high-performance CHNOF-based EMs.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4204–4213 4204–4213"},"PeriodicalIF":3.2,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306120","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}

{"title":"3D Hyperbranched Rod–Tube ZnO Microarchitectonics in Oxygen-Concentration-Dominantly-Driven Photothermic Flames","authors":"Jian-Min Li*,&nbsp; and ,&nbsp;Xian-Lin Zeng,&nbsp;","doi":"10.1021/acs.cgd.5c0034910.1021/acs.cgd.5c00349","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00349https://doi.org/10.1021/acs.cgd.5c00349","url":null,"abstract":"<p >We report the fabrication of all-combinatorial rod–tube monoclinic zinc oxide (ZnO) microarchitectonics (μAs) with an oxygen-concentration-dominantly-driven photothermic flaming (PTF) process. The peculiar single-crystal (SC) ZnO μAs represent an unprecedented level of three-dimensional (3D) structural complexity in SC microwhiskers (μWs), including Rod-on-Rod, Rod-on-Tube, Tube-on-Rod, and Tube-on-Tube. It was found that anisotropic high-temperature oxygen-rich (O₂-rich) etching assisted in the perfect formation of hexagonal microtubes, while oxygen-deficient (O₂-deficient) concentrations favored the growth of solid μWs. A repeated hierarchically epitaxial nucleation-and-growth vapor–solid mechanism was proposed for the high-order hyperbranched 3D ZnO μAs. The 3D rod–tube ZnO μAs hold great promise as potential efficient microscale photocatalysts and photoanodes for dye-sensitized solar cells. The PTF strategy described here offers a streamlined O₂-concentration-dominantly-driven PTF or VS route for the widespread synthesis of other metal-oxide SC semiconductor μWs with controllable structures, such as Co_<i>x</i>(ZnO)_1–<i>x</i>, SnO₂, WO₃.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4450–4457 4450–4457"},"PeriodicalIF":3.2,"publicationDate":"2025-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306156","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}