Crystal Growth & Design最新文献

{"title":"Enhanced Lithium-Ion Storage with Nitrogen-Enriched Triazine Covalent Organic Frameworks via Mechanical Exfoliation","authors":"Stella Vargheese,&nbsp;Satyanarayana K. Konavarapu,&nbsp;Giyong Kim and Sung Yeol Kim*,&nbsp;","doi":"10.1021/acs.cgd.4c0156210.1021/acs.cgd.4c01562","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01562https://doi.org/10.1021/acs.cgd.4c01562","url":null,"abstract":"<p >Covalent organic frameworks (COFs) often demonstrate limited electrochemical performance due to the stacking tendency of their 2D-extended structures, particularly in triazine COFs (T-COFs), where strong π–π interactions cause an eclipsed arrangement. This stacking effect conceals the active sites inside the 1D channels, hindering efficient ion transport, especially under high-charge/discharge conditions. The slow movement of Li⁺ ions through these channels results in the poor utilization of redox-active sites, thereby diminishing both capacity and rate capabilities. In this work, we introduce a facile method to improve the electrochemical properties of <b>COFs</b> when used as anode materials in lithium-ion batteries. A 2D-<b>COF</b> was synthesized by the nucleophilic substitution of cyanuric chloride with melamine, followed by mechanical exfoliation into 2D few-layer nanosheets using a simple mechanical grinding technique. These bulk and exfoliated <b>COFs</b> were characterized using FTIR, XPS, TGA, FESEM, and DRS. Photophysical studies indicate that both bulk and <b>E-COFs</b> exhibited low band gap values of 3.31 and 4.25 eV, respectively, showing their semiconducting nature. Electrochemical tests reveal that the exfoliated <b>COF</b> delivers a maximum capacity of 847 mAh g^–1, with a Coulombic efficiency of 72% at 0.2 A g^–1. The shortened Li⁺ diffusion pathways in exfoliated <b>COF</b> led to significantly enhanced redox site utilization and faster lithium storage kinetics, in contrast to the diffusion-limited behavior seen in bulk <b>COF</b>.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2430–2438 2430–2438"},"PeriodicalIF":3.2,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143833003","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":"Synergistic Effect of Thermal and Flow Fields on Stress Distribution in AlN Crystal Growth by PVT","authors":"Jiahao Chen,&nbsp;Jiamin Chen,&nbsp;Chuhao Yang,&nbsp;Yuheng Du,&nbsp;Hao Yang,&nbsp;Zeren Wang,&nbsp;Huangshu Zhang,&nbsp;Yuchun Xu,&nbsp;Zheng Li,&nbsp;Hailong Wei,&nbsp;Jiahua Zhang,&nbsp;Lun Dai,&nbsp;Jiejun Wu* and Tongjun Yu*,&nbsp;","doi":"10.1021/acs.cgd.5c0017710.1021/acs.cgd.5c00177","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00177https://doi.org/10.1021/acs.cgd.5c00177","url":null,"abstract":"<p >Excessive thermal stress is a serious issue that causes cracking in AlN single crystals during physical vapor transport (PVT) growth. Herein, with numerical simulations and PVT experiments, the thermal stress distribution was investigated to address the challenges in crystal growth. The free side and inclined surfaces of crystals were identified as favorable factors to reduce thermal stress. We proposed a strategy of synergistic control of the thermal and flow fields and carried out PVT growth under the conditions by combining the thermal adjustment components and the integrated flow field regulation components. A positive correlation was established between the simulated von Mises stress of the crystal and the experimentally measured crack density of the wafer. Effective synergistic control ensures a low and evenly distributed thermal stress in crystal growth, facilitating the production of high-quality, crack-free wafers.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2691–2699 2691–2699"},"PeriodicalIF":3.2,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143833002","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":"Uncovering the Molecular Stacking Patterns and Tuning Fluorescence Properties of Organic Molecular Crystals through Cocrystallization","authors":"Chunyan Zhang,&nbsp;Zichen Ning,&nbsp;Zhuoshan Gong,&nbsp;Limin Zhou,&nbsp;Li Xu,&nbsp;Feiqiang He,&nbsp;Zhi Gao,&nbsp;Jerry Y. Y. Heng,&nbsp;Shichao Du and Jinbo Ouyang*,&nbsp;","doi":"10.1021/acs.cgd.4c0169510.1021/acs.cgd.4c01695","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01695https://doi.org/10.1021/acs.cgd.4c01695","url":null,"abstract":"<p >Organic light-emitting materials have demonstrated their application potential in numerous fields, with their optoelectronic properties being profoundly influenced by molecular stacking patterns and intermolecular interactions. In this study, we utilized a mixed-solvent evaporation method and a solid grinding method to synthesize a series of meloxicam (MXM) cocrystals, whose structures and morphology were identified using single crystal X-ray diffraction and a polarization microscope. These crystals exhibited photoinduced fluorescence changes at a macroscopic level. Fluorescence spectral analysis indicated that, while the cocrystals prepared with different coformers displayed varying fluorescence intensities, they shared similar luminescence colors, which can be attributed to their comparable emission wavelengths. Density functional theory (DFT) calculations further elucidated the significant relationship between the fluorescence properties, molecular packing patterns, and charge transfers in MXM cocrystals. This research not only enhances the fluorescence performance of pure MXM crystals, but also offers novel insights and a robust experimental foundation for the advancement of multifunctional organic cocrystal materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2465–2475 2465–2475"},"PeriodicalIF":3.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832927","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":"Understanding Hydration Transitions of CaBr2","authors":"Michaela C. Eberbach,&nbsp;Aleksandr I. Shkatulov,&nbsp;Paul Tinnemans,&nbsp;Hendrik P. Huinink*,&nbsp;Hartmut R. Fischer and Olaf C. G. Adan,&nbsp;","doi":"10.1021/acs.cgd.4c0152210.1021/acs.cgd.4c01522","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01522https://doi.org/10.1021/acs.cgd.4c01522","url":null,"abstract":"<p >Due to climate change and the energy transition, energy storage applications are being studied and developed. One energy storage application is a heat storage battery, which needs materials that can store and release heat with high energy storage capacity. One such material is a salt hydrate. The hydration pathways of salt hydrates can have different numbers of steps. There are salts with single-hydrate steps like for CuCl₂ (0–2) and LiBr (0–1) and multihydrate steps like for MgCl₂ (0–2–4–6) and SrCl₂ (0–1–2–6). Additionally, there are also salts with complex hydration–dehydration pathways like for CaCl₂ (0–1/3–2–1–0). Little is known about the hydrate steps of CaBr₂. The crystal structures of the CaBr₂ nona-, hexa-, and anhydrate are known, but there are no intermediate steps and conditions for these transitions. The hexahydrate and anhydrate have the same structure as CaCl₂ except for the unit cell size due to the different anions. Additionally, the equilibria were determined for the hexa-, tetra-, and dihydrate transitions. However, the intermediate steps are debated. The hydrates 3, 1.5, 1, and 0.5 were all proposed but are disputed and not verified. Therefore, the hydration and dehydration pathways of CaBr₂ from the anhydrate to the dihydrate and back were examined in this study for both the bulk salt and the confinement of mesoporous silica gels. The kinetic phase transition onsets and equilibrium lines were measured for the bulk salt. Powder X-ray diffractograms were used to ensure that the same structures were formed every time during hydration and dehydration. Single-crystal analysis was used to determine the crystal structures of the hydrates. These experiments showed only a stable monohydrate phase between the anhydrate and dihydrate during hydration and dehydration. Furthermore, the dihydrate has the same crystal structure as the dihydrate of CaCl₂ except for the size, while the monohydrate differs from the CaCl₂ monohydrate. Additionally, the composites’ kinetic onsets and powder diffractograms were measured, which showed that CaBr₂ performs the same hydrate steps in confinement as in bulk form.</p><p >The hydration and dehydration steps of the salt hydrate CaBr₂ were determined with their formation and stable conditions together with the crystal structures of the mono- and dihydrate.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2409–2417 2409–2417"},"PeriodicalIF":3.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01522","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832998","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":"Molecular Insights into the Crystallization of 4’-Hydroxyacetophenone from Water: Solute Aggregation, Liquid–Liquid Phase Separation, and Polymorph Selection","authors":"Carlos E. S. Bernardes*,&nbsp;Ricardo G. Simões,&nbsp;M. Soledade C. S. Santos*,&nbsp;Pedro L. T. Melo,&nbsp;Ângela F.S. Santos,&nbsp;Stéphane Veesler and Manuel E. Minas da Piedade*,&nbsp;","doi":"10.1021/acs.cgd.5c0011710.1021/acs.cgd.5c00117","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00117https://doi.org/10.1021/acs.cgd.5c00117","url":null,"abstract":"<p >In this work, insights into the structural rearrangements occurring in aqueous solution, prior to the nucleation of different 4’-hydroxyacetophenone (HAP) forms from water, were obtained, through a combination of thermomicroscopy, microdifferential scanning calorimetry, density and speed of sound measurements, and molecular dynamics simulations. The results confirmed our previous observation that cooling crystallization of HAP is intermediated by liquid–liquid phase separation (LLPS) and, depending on the initially selected concentration range, selectively leads to the formation of different crystal forms. Analysis of the solution properties before the onset of LLPS revealed that, in the HAP mole fraction range <i>x</i>_HAP &lt; 0.004 (Zone I), where hydrate H2 ultimately crystallizes, small, solvated clusters are initially present in solution, which remain approximately invariant in size, shape, and HAP/H₂O proportion as the temperature decreases. For the <i>x</i>_HAP &gt; 0.005 range (Zone III), where anhydrous form I crystallizes, large HAP/water aggregates (that can even percolate the whole system as <i>x</i>_HAP approaches the 0.005 limit) are already initially present in solution. As cooling progresses, they become more compact, a process accompanied by a reduction in water content, which is more significant as the solution concentration increases. The 0.004 &lt; <i>x</i>_HAP &lt; 0.005 (Zone II) range corresponds to a transition region where, as <i>x</i>_HAP increases, the physical properties of the solution initially evolve from those typical of Zone I and, at a certain point, abruptly change and start converging to those typical of Zone III. In all zones, the colloidal particles formed upon LLPS (from which crystallization results) can also reduce their water content on cooling, but the extent of this process increases as <i>x</i>_HAP moves from Zones I and II, where hydrates are formed, to Zone III, where anhydrous form I is produced.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2617–2630 2617–2630"},"PeriodicalIF":3.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832931","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":"Synthesis of Mixed Anion Rare Earth Sulfate Fluorides LnSO4F·H2O (Ln = Nd, Tb, Dy, and Ho) and LnSO4F (Ln = Tb, Dy, and Ho)","authors":"Lakshani W. Masachchi,&nbsp;Gregory Morrison and Hans-Conrad zur Loye*,&nbsp;","doi":"10.1021/acs.cgd.5c0007610.1021/acs.cgd.5c00076","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00076https://doi.org/10.1021/acs.cgd.5c00076","url":null,"abstract":"<p >Single crystals of the mixed anion rare earth sulfate fluorides <i>Ln</i>SO₄F·H₂O (<i>Ln</i> = Nd, Tb, Dy, and Ho), monoclinic space group <i>P</i>2₁/<i>n</i>, were prepared via an HF-free mild hydrothermal synthesis. Furthermore, the <i>Ln</i>SO₄F (<i>Ln</i> = Tb, Dy, and Ho) phases, orthorhombic space group <i>Pnma</i>, were obtained via the thermal decomposition of <i>Ln</i>SO₄F·H₂O (<i>Ln</i> = Tb, Dy, and Ho). While the <i>Ln</i>SO₄F·H₂O (<i>Ln</i> = Nd, Tb, Dy, and Ho) phases are isostructural, two different structures are observed for the <i>Ln</i>SO₄F (<i>Ln</i> = Tb, Dy, and Ho) series, one for Tb and one for Dy and Ho, differing in the rare earth coordination environments. Green photoluminescence is observed for Tb(SO₄)F·H₂O and Tb(SO₄)F. Magnetic measurements indicate the absence of magnetic order down to 2 K in the <i>Ln</i>(SO₄)F·H₂O and <i>Ln</i>(SO₄)F phases.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2572–2579 2572–2579"},"PeriodicalIF":3.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832925","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":"Self-Oriented Polycrystalline InP Nanowires Guided by Nanogrooves and Their Near-Infrared Photoresponse","authors":"Pinyun Ren*,&nbsp;Zheyu Wang,&nbsp;Xiangtao Chen,&nbsp;Yujie Wang,&nbsp;Jing Wu,&nbsp;Wenhan Du,&nbsp;Qianying Zheng,&nbsp;Xianpei Ren and Jinyou Xu*,&nbsp;","doi":"10.1021/acs.cgd.4c0168610.1021/acs.cgd.4c01686","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01686https://doi.org/10.1021/acs.cgd.4c01686","url":null,"abstract":"<p >This study demonstrates the self-oriented growth of polycrystalline indium phosphide (InP) nanowires aligned along nanogrooves on annealed M-sapphire substrates via a catalyst-free chemical vapor deposition process. Morphological characterizations reveal that the nanowires have a highly oriented arrangement, along with a rough surface texture. Structural analyses confirm their polycrystalline nature, which is characterized by distinct grain boundaries and variable crystallite orientations. Angle-resolved polarized Raman spectroscopy uncovers an intermediate anisotropic ratio (1.85) between bulk InP (1.27) and single-crystalline nanowires (2.32), reflecting the interplay of one-dimensional geometry and polycrystallinity. Two-terminal devices fabricated by directly depositing electrodes on the nanowires exhibit significant photoresponses in the near-infrared range, although the photocurrent diminishes over several seconds. This extended response time is attributed to the polycrystalline nature of these nanowires, which results in a decreased electron mobility. The long-lasting photocurrent dynamics align with synaptic plasticity time scales, highlighting the potential of these nanowires for neuromorphic optoelectronics, particularly in artificial synaptic devices. This work advances the synthesis of oriented polycrystalline nanostructures and provides insights into tailoring optoelectronic properties through crystallinity engineering.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2456–2464 2456–2464"},"PeriodicalIF":3.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832926","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":"Replacing C-Nitro with C-Tetrazole: A Promising Strategy to Enhance the Detonation Performance and Stability of Explosives","authors":"Yongbin Zou,&nbsp;Huaqi Zhang,&nbsp;Xue Hao,&nbsp;Guofeng Zhang,&nbsp;Zhen Dong* and Zhiwen Ye*,&nbsp;","doi":"10.1021/acs.cgd.4c0165510.1021/acs.cgd.4c01655","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01655https://doi.org/10.1021/acs.cgd.4c01655","url":null,"abstract":"<p >The fully nitrated azole-based energetic materials are high in energy but unstable, which limits their practical applications. Tetrazole, with its high formation enthalpy and intrinsic acidic hydrogen, can react with nitrogen-rich bases, further enhancing both the formation enthalpy and stability. Consequently, we replaced the C-nitro group in fully nitrated 1,2,4-triazole with C-tetrazole, resulting in the synthesis of 1-(trinitromethyl)-5-nitroimino-3-tetrazole-1,2,4-triazole (TNTT, <b>4</b>). The salts of 1-(dinitromethyl)-5-nitroimino-3-tetrazole-1,2,4-triazole (DNTT) were synthesized via a metathesis reaction with bases derived from silver salts. All of the newly prepared energetic structures (<b>4</b> and <b>7</b>–<b>10</b>) were characterized by using single-crystal X-ray diffraction. Among these compounds, salt <b>9</b> exhibited the best overall performance, with an elevated decomposition temperature (<i>T</i>_d = 181 °C), and its mechanical stability (IS = 17.5 J, FS = 216 N) and detonation velocity (<i>D</i> = 9337 m s^–1) surpassed those of HMX, making it a promising candidate for secondary explosives. Additionally, N₂H₅⁺ salt <b>8</b> and K⁺ salt <b>10</b> demonstrated low mechanical sensitivity (IS ≥ 27.5 J, FS &gt; 360 N) due to the formation of hydrogen-bonded organic frameworks and metal–organic frameworks.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2439–2445 2439–2445"},"PeriodicalIF":3.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832884","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":"Cooperative Spin-Crossover in a Neutral Dinuclear Complex Based on a Functionalized Triazole Ligand","authors":"Thirunavukkarasu Thangavel,&nbsp;Nour-el-Islam Belmouri,&nbsp;Catherine Charles,&nbsp;Ahmad Hobballah,&nbsp;Longhe Li,&nbsp;Carlos J. Gómez-García,&nbsp;Sébastien Pillet,&nbsp;Kamel Boukheddaden* and Smail Triki*,&nbsp;","doi":"10.1021/acs.cgd.5c0015810.1021/acs.cgd.5c00158","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00158https://doi.org/10.1021/acs.cgd.5c00158","url":null,"abstract":"<p >A novel spin-crossover (SCO) dinuclear complex, [Fe₂(μ₂-cp-trz)₃(cp-trz)₂(tcm)₄] (cp-trz = 4-cyclo-pentyl-1,2,4-triazole, tcm- = tricyanomethanide anion), was synthesized and thoroughly characterized. Crystallographic analyses at 250 and 180 K revealed a centrosymmetric dinuclear structure with Fe(II) centers bridged by triazole ligands. The complex exhibits a cooperative hysteretic thermally induced abrupt one-step spin transition between high-spin (HS) and low-spin (LS) states. Magnetic measurements (Magn), X-rays diffraction (XRD), and optical microscopy (OM) show the following switching temperatures: <i>T</i>_1/2↓^Magn = 202 K and <i>T</i>_1/2↑^Magn = 212 K, and <i>T</i>_1/2↓^OM ≃ <i>T</i>_1/2↓^XRD = 203 K and <i>T</i>_1/2↑^OM ≃ <i>T</i>_1/2↑^XRD = 207 K. Moreover, structural and OM studies reveal significant anisotropic lattice changes, driven by strong hydrogen bonding along the <i>c</i> axis, which underpins the cooperative behavior of the SCO transition, and propagation of the HS/LS interface along the spin transition.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2674–2682 2674–2682"},"PeriodicalIF":3.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832900","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":"Role of Specific and Nonspecific Interactions in the Crystallization Behavior of BSA and HSA Protein Solutions","authors":"Maximilian D. Senft*,&nbsp;Georg Zocher*,&nbsp;Sebastian Retzbach,&nbsp;Ralph Maier,&nbsp;Anusha Hiremath,&nbsp;Fajun Zhang*,&nbsp;Thilo Stehle and Frank Schreiber,&nbsp;","doi":"10.1021/acs.cgd.4c0153510.1021/acs.cgd.4c01535","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01535https://doi.org/10.1021/acs.cgd.4c01535","url":null,"abstract":"<p >The crystallization conditions of proteins are sensitive to the prevailing interactions. Even the two similar proteins, bovine and human serum albumin (BSA and HSA), exhibit different crystallization conditions despite their comparable function, biophysical properties, shape, and size (≈60 kDa and a 75.8% sequence identity). In this work, we provide a comparison of specific and nonspecific interactions regarding the crystallization behavior of BSA and HSA. The results of the analysis of crystal packing interfaces indicate that HSA uses a relatively larger part of its surface area to establish crystal contacts compared to its bovine counterpart. Likewise, HSA utilizes more of its residues for crystal contact formation, offering a broader range of options to establish attractive interactions. Phase diagrams of the BSA–PEG and HSA–PEG systems were established in order to gain more precise insights into the nonspecific depletion interactions. It turns out that BSA crystallizes predominantly via depletion interactions, whereas HSA does not. Subsequent systematic small-angle scattering (SAXS) measurements of the two systems in combination with quantitative modeling provide insights into the induced effective interactions, allowing for a better understanding of the two protein–PEG systems. The results obtained were compared to the previously established reentrant condensation (RC) phase behavior of BSA and HSA. The RC phase behavior is caused by the specific interaction of proteins with added multivalent cations. In this case, HSA crystallizes, but BSA does not. This comparison emphasizes the different roles of specific and nonspecific interactions for the crystallization behavior of BSA and HSA.</p><p >This study investigates the different crystallization behavior of the two similar proteins BSA and HSA. While trivalent salts induce specific interactions and promote HSA crystallization involving large areas of its crystal surface, BSA crystallization is promoted by nonspecific interactions via the addition of nonadsorption polymers. Phase diagrams, SAXS measurements, and crystal analyses provide a comprehensive description.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 8","pages":"2418–2429 2418–2429"},"PeriodicalIF":3.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01535","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832898","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}