Crystal Growth & Design最新文献

{"title":"Brilliantly Red: The Structure of Carmine","authors":"Erik Svensson Grape*,&nbsp;Tom Willhammar and A. Ken Inge,&nbsp;","doi":"10.1021/acs.cgd.5c0018510.1021/acs.cgd.5c00185","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00185https://doi.org/10.1021/acs.cgd.5c00185","url":null,"abstract":"<p >Carmine is a red pigment made from dried cochineal, a scale insect that has been a source of brilliant scarlet reds in clothing and art for more than two millennia, with records dating back to 700 BC. Since the 16th century, it has been intensely traded all over the world and was one of the most important trade goods for the Spanish empire at its economic peak. Despite still being used on an industrial scale, with hundreds of metric tonnes produced annually, the exact molecular and crystal structures of the dyestuff remains undetermined. Notably, both modern-day commercial carmine and pigments prepared following historical recipes show strikingly similar diffraction patterns, indicating a common crystalline structure. Here we show that the crystal structure of carmine can, at last, be determined using three-dimensional electron diffraction measurements, revealing a tetranuclear complex that assembles into a nanoporous supramolecular structure with pore diameters of approximately 1.8 nm, held together by intermolecular hydrogen bonding. Our results establish a definite structure of carmine, unveiling a surprisingly complicated arrangement in a long-used commodity with economic and cultural impact, while also highlighting the serendipitous creation of a man-made supramolecular material that dates back hundreds if not thousands of years.</p><p >The crystal structure of carmine, a long-used pigment made from dried cochineal, is unveiled through three-dimensional electron diffraction measurements. The results establish a definite structure of carmine, which is comprised of a tetranuclear metal complex that assembles into a surprisingly complex hydrogen-bonded nanoporous structure.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4100–4105 4100–4105"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00185","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306050","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":"Polymorph Screening and Investigation of Charge Transport of ditBuC6-BTBT","authors":"Priya Pandey,&nbsp;Federico Modesti,&nbsp;Nemo McIntosh,&nbsp;Christian Ruzié,&nbsp;Nicholas Turetta,&nbsp;Lamiaa Fijahi,&nbsp;Massimiliano Remigio,&nbsp;Guillaume Schweicher,&nbsp;Yves Henri Geerts,&nbsp;Marta Mas-Torrent,&nbsp;Peter Erk,&nbsp;Jérôme Cornil,&nbsp;Paolo Samorì,&nbsp;Enrico Modena* and Lucia Maini*,&nbsp;","doi":"10.1021/acs.cgd.5c0004610.1021/acs.cgd.5c00046","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00046https://doi.org/10.1021/acs.cgd.5c00046","url":null,"abstract":"<p >In this study, we investigate the relationship between the polymorphism and crystallographic parameters and the charge transport properties achieved through the fabrication of organic field-effect transistors (OFETs) based on a novel molecular semiconductor, i.e., 2,7-bis(7,7-dimethyloctyl)benzo[<i>b</i>]benzo[4,5]thieno[2,3-<i>d</i>]thiophene (ditBuC6-BTBT). Four polymorphs of ditBuC6-BTBT were identified: three observed at room temperature (Forms I, Ia, and II), and one appearing above 100 °C (Form III). While cell parameters were measured for all forms, full crystal structures were determined only for Forms Ia and II. Although a direct correlation between molecular packing and charge transport properties could not be established from the present study, the structural analysis of the polymorphs contributes to a broader understanding of the packing motifs in ditBuC6-BTBT. A meticulous examination of the minute discrepancies in the powder patterns substantiated the existence of both the metastable Form I and Form Ia, which became more difficult to isolate due to unintentional seeding of the thermodynamically stable Form II. Nonequilibrium crystallization techniques utilizing thermal gradient and bar-assisted meniscus shearing methods were explored to enhance control over polymorph selection. The intrinsic charge transport properties ruled by the overlap of the frontier orbitals were studied by computing the transfer integrals. Optimized devices fabricated by depositing thin films by solution shearing and vacuum evaporation led to field-effect mobility in the linear regime of ca. 0.05 cm² V^–1 s^–1. The observed device performances were interpreted as a result of the combined effects of crystal packing features, ionization potential values, and polymorphic coexistence, highlighting the challenges in deriving clear structure–property correlations and underscoring the complexities in achieving high-performance organic electronics with this material.</p><p >Polymorph screening and OFET fabrication of a novel BTBT derivative (ditBuC6-BTBT) reveal how molecular design and polymorphic control impact charge transport in organic semiconductors.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4214–4229 4214–4229"},"PeriodicalIF":3.2,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00046","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305743","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":"Optimized Flux Single-Crystal Growth of the Quantum Spin Liquid Candidate NdTa7O19 and Other Rare-Earth Heptatantalates, ErTa7O19 and GdTa7O19","authors":"Lia Šibav,&nbsp;Matic Lozinšek,&nbsp;Zvonko Jagličić,&nbsp;Tina Arh,&nbsp;Panchanana Khuntia,&nbsp;Andrej Zorko and Mirela Dragomir*,&nbsp;","doi":"10.1021/acs.cgd.5c0062410.1021/acs.cgd.5c00624","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00624https://doi.org/10.1021/acs.cgd.5c00624","url":null,"abstract":"<p >Single crystals are essential for characterizing a wide range of magnetic states, including exotic ones such as quantum spin liquids. This study reports a flux method for growing single crystals of NdTa₇O₁₉, the first quantum spin liquid candidate on a triangular spin-lattice with dominant Ising-like spin correlations. Purple NdTa₇O₁₉ single crystals with hexagonal morphology were successfully grown by using a K₂Mo₃O₁₀–B₂O₃ flux. With lateral sizes up to 3.5 mm and a thickness up to 2 mm, these are the largest dimensions reported to date. The chemical composition was confirmed by powder and single-crystal X-ray diffraction along with scanning electron microscopy with energy dispersive X-ray spectroscopy. Aiming for an accurate determination of the magnetic anisotropy and its effect on the magnetic properties, NdTa₇O₁₉ crystals were additionally analyzed by magnetic susceptibility, revealing a substantial anisotropy without long-range magnetic ordering down to 2 K. Single crystals of two novel rare-earth heptatantalates, ErTa₇O₁₉ and GdTa₇O₁₉, were also grown, and their magnetic properties investigated. The magnetic anisotropy of ErTa₇O₁₉ closely resembles that of isostructural NdTa₇O₁₉, indicating the possibility of a similar exotic magnetic ground state. In contrast, GdTa₇O₁₉ shows paramagnetic behavior, consistent with previous results obtained for polycrystalline samples.</p><p >High-quality, large single crystals of NdTa₇O₁₉, an Ising quantum spin liquid candidate on a triangular lattice, were grown using a K₂Mo₃O₁₀–B₂O₃ flux. Magnetic susceptibility measurements down to 2 K reveal strong easy-axis anisotropy without long-range order. The flux method was also extended to grow single crystals of other rare-earth heptatantalates, ErTa₇O₁₉ and GdTa₇O₁₉.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4646–4654 4646–4654"},"PeriodicalIF":3.2,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00624","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306046","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":"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}