Crystal Growth & Design最新文献

{"title":"Rotaxane-like Complex Consisting of 1D and 2D Cyano-Bridged Coordination Polymers: Fe(4-methylpyrimidine)2[Au(CN)2]2·Fe(4-methylpyrimidine)2(H2O)2[Au(CN)2]·[Au(CN)4]","authors":"Kosuke Kitase*,&nbsp;Daisuke Akahoshi and Takafumi Kitazawa,&nbsp;","doi":"10.1021/acs.cgd.5c0021610.1021/acs.cgd.5c00216","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00216https://doi.org/10.1021/acs.cgd.5c00216","url":null,"abstract":"<p >Coordination polymers showing the spin-crossover (SCO) phenomenon have attracted considerable attention because of their tunable properties and potential applications as sensors or switching materials. Although many of these polymers have been reported, examples with mixed-valence metal ions and N-heteroaromatic ligands other than pyridine-, pyrazine-, and bipyridine-type ligands are scarce. In this study, we synthesized a novel cyano-bridged coordination polymer, Fe(4-methylpyrimidine)₂[Au(CN)₂]₂·Fe(4-methylpyrimidine)₂(H₂O)₂[Au(CN)₂]·[Au(CN)₄] (complex <b>1</b>), with a rotaxane-like structure. This polymer comprised monovalent Au atoms in a two-dimensional Soma–Iwamoto-type {Fe(4-methylpyrimidine)₂[Au(CN)₂]₂}_<i>n</i> layer as well as a one-dimensional {Fe(4-methylpyrimidine)₂(H₂O)₂[Au(CN)₂]}_<i>n</i>^<i>n</i>+ cationic chain and trivalent Au atoms in the zero-dimensional [Au(CN)₄]⁻ anion. Complex <b>1</b> showed a half SCO phenomenon above 300 K. The Fe K-edge X-ray absorption fine structure (XAFS) spectrum of complex <b>1</b> revealed that some of the Fe sites were in a low-spin state at room temperature, while all of the Fe sites were in a high-spin state at 395 K. The Au L₃-edge XAFS spectrum of complex <b>1</b> revealed that monovalent and trivalent Au sites were present at room temperature and 398 K.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4106–4111 4106–4111"},"PeriodicalIF":3.2,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305866","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":"Improved Luminescence Performance for W-LED Applications of the Eu3+-Activated Double Molybdate Red Phosphor NaLu(MoO4)2","authors":"Chonghui Niu,&nbsp;Mingjie Dan,&nbsp;Yi Yu*,&nbsp;Xiurong Zhu,&nbsp;Yixin Fu,&nbsp;Yeqing Wang,&nbsp;Wang Zhao* and Kenneth R. Poeppelmeier*,&nbsp;","doi":"10.1021/acs.cgd.5c0028010.1021/acs.cgd.5c00280","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00280https://doi.org/10.1021/acs.cgd.5c00280","url":null,"abstract":"<p >In this study, a series of novel Eu³⁺-activated NaLu(MoO₄)₂ (NLMO) red phosphors were synthesized for the first time using hydrothermal, sol–gel, and microemulsion methods with varying active agents. The properties of these phosphors, including phase purity, crystal structure, DFT calculations, morphology, luminescence characteristics, thermal stability, and internal quantum efficiency, were comprehensively characterized. The results indicate that the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na)-assisted hydrothermal method is the most suitable approach for the preparation of the phosphor. This method yields phosphors with a regular morphology, outstanding luminescence performance, relatively good thermal stability, and significantly high internal quantum efficiency. The internal quantum efficiency reaches 96.45%, and the phosphor exhibits good thermal stability, with the emission intensity at 423 K remaining about 73% compared to the initial temperature. The CIE chromaticity coordinate of the NLMO/0.13Eu³⁺ sample (0.667, 0.333) is very close to the standard chromaticity coordinate value (0.670, 0.330) from the National Television Standards Committee (NTSC). Remarkably, the color purity of the NLMO:0.13Eu³⁺ phosphor is an impressive 97%. Furthermore, Tb³⁺ was cointroduced in the NLMO:0.13Eu³⁺ phosphor, and its positive effects are discussed. Ultimately, a warm white light-emitting diode (W-LED) was fabricated using the studied NLMO:0.13Eu³⁺ phosphor with a 394 nm near-ultraviolet-emitting LED chip as the excitation source. The W-LED exhibits excellent properties such as high color purity, excellent correlation color temperature, and high color rendering index. Considering all of the results, the NLMO/Eu³⁺ red phosphor obtained by the EDTA-2Na-assisted hydrothermal method is an ideal red component for W-LEDs in various lighting applications.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4377–4393 4377–4393"},"PeriodicalIF":3.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306139","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":"Controllable Fabrication of Hollow Structure within SAPO-34 Molecular Sieves via a Novel Synthesis Route Using Industrial Waste Catalyst","authors":"Yue Hu,&nbsp;Yuchao Lyu*,&nbsp;Xuejie Sui,&nbsp;Weiwei Zheng,&nbsp;Xuchao Geng,&nbsp;Jianye Fu and Xinmei Liu*,&nbsp;","doi":"10.1021/acs.cgd.5c0004310.1021/acs.cgd.5c00043","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00043https://doi.org/10.1021/acs.cgd.5c00043","url":null,"abstract":"<p >Features of hollow structure within molecular sieves inevitably influence the catalytic performance, while the precise control of hollow structure parameters via a facile method remains challenging. Herein, a novel and facile approach is proposed to regulate the shape and size of the hollow structure within SAPO-34 using industrial waste methanol-to-olefins (MTO) catalyst as raw materials. The hole-like or butterfly-like hollow structure of various sizes was fabricated by pretreating the raw materials with phosphoric acid. The hole-like hollow structure results from the dissolution of the encapsulated nanocrystalline fragments provided by the waste catalyst. However, the phosphoric acid pretreatment decomposes these microcrystalline structures. It causes the synthesis system to be closer to the conventional one, where a butterfly-like hollow structure always forms. In addition, the size of the hollow structure is tuned by varying the extent of decomposition of the microcrystalline structure, which is realized by different leaching times with phosphoric acid. The obtained SAPO-34 with an optimized hollow structure exhibits a lifetime of 560 min in the MTO reaction. It also exhibits the light olefin selectivity as high as 89.4%. Therefore, this study provides a novel strategy to regulate the features of hollow SAPO-34 and lays the foundation for MTO catalyst design characterized by long lifetime.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4230–4238 4230–4238"},"PeriodicalIF":3.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305611","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":"When CuCl42– and CuBr42– Form Anion···Anion Networks Assembled via Cu···Cl/Br Regium Bonds","authors":"Cristina Lo Iacono,&nbsp;Andrea Pizzi,&nbsp;Kamran T. Mahmudov,&nbsp;Rosa M. Gomila,&nbsp;Antonio Frontera and Giuseppe Resnati*,&nbsp;","doi":"10.1021/acs.cgd.5c0023810.1021/acs.cgd.5c00238","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00238https://doi.org/10.1021/acs.cgd.5c00238","url":null,"abstract":"<p >This study presents the design, preparation, and single-crystal X-ray characterization of CuCl₄^2– and CuBr₄^2– salts, wherein dianions self-assemble into supramolecular (4,4) networks via short Cu···Cl/Br contacts (regium bonds). In the described salts, the organic cations play a pivotal role in promoting the ability of Cu atoms to act as electrophiles. The used cations are the protonated forms of primary amines and form a tight network of N⁺H···Cl/Br hydrogen bonds that promote the regium bond donor ability of Cu by dissipating the anion negative charge. Calculations, namely determination of the molecular electrostatic potential, quantum theory of atoms in molecules and natural bond orbital analyses and other approaches, afford a comprehensive understanding of the Cu···Cl/Br short contacts identified via crystallography and confirm the attractive character of the charge transfer from an occupied lone pair on the halogen of one anion to an empty σ* orbital on copper of another anion.</p><p >Single-crystal X-ray analyses identify anion···anion networks assembled via short Cu···Cl/Br regium bonds in CuCl₄²⁻ and CuBr₄²⁻ salts wherein cations promote Cu electrophilicity by dissipating anions’ negative charge via a network of N⁺H···Cl/Br hydrogen bonds. Calculations prove the attractive character of the charge transfer from the halogen of one anion to the copper of another anion.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4338–4347 4338–4347"},"PeriodicalIF":3.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.5c00238","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305698","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":"Cobalt Ferrite as a Novel Catalyst for Synthesizing Co3Fe7@BN Microsphere Composites","authors":"Heng Wang*,&nbsp;Zhecheng Li,&nbsp;Yajie Dai,&nbsp;Shaobai Sang,&nbsp;Yawei Li and Tianbin Zhu*,&nbsp;","doi":"10.1021/acs.cgd.5c0043410.1021/acs.cgd.5c00434","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00434https://doi.org/10.1021/acs.cgd.5c00434","url":null,"abstract":"<p >The cobalt ferrite (CoFe₂O₄) nanocatalyst, with an average diameter of 25 nm, was synthesized via an optimized aqueous coprecipitation method utilizing cobalt nitrate, iron nitrate, and ammonium carbonate as precursors. This catalyst demonstrates effective catalytic activity in facilitating the formation of boron nitride (BN) microspheres with a diameter of 3 μm, assembled from nanosheets. Systematic studies on the phase composition and microstructural evolution of BN products were conducted as functions of the annealing temperature and catalyst content, revealing the vapor–liquid–solid (V–L–S) mechanism as the dominant pathway for microsphere formation. Specifically, the high-temperature reaction between CoFe₂O₄ and B generates Co₃Fe₇/CoB and gaseous B₂O₂; subsequently, B₂O₂ along with nitrogen derived from NH₃ decomposition adsorbs onto the surface of Co–B droplets, initiating heterogeneous nucleation of BN crystals. Under appropriate conditions, including annealing temperature and catalyst content, the anisotropic diffusion rate of B–N species within the BN nuclei preferentially occurs along their (002) crystallographic planes, thereby driving the oriented precipitation of 2D nanosheets that spontaneously assemble into 3D BN microspheres via interfacial energy minimization. This work not only deciphers the fundamental growth mechanism but also establishes a versatile platform for morphology-engineered BN nanostructures.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4514–4520 4514–4520"},"PeriodicalIF":3.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305981","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":"5,6,5-Melting Tricyclic Conjugated System: An Effective Strategy for Balancing Stability and Energy","authors":"Yuan Qi,&nbsp;Linan Zhang,&nbsp;Shuaijie Jiang,&nbsp;Shuliang Liu,&nbsp;Huichao Ma,&nbsp;Guang Wu and Qiuhan Lin*,&nbsp;","doi":"10.1021/acs.cgd.4c0159310.1021/acs.cgd.4c01593","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01593https://doi.org/10.1021/acs.cgd.4c01593","url":null,"abstract":"<p >The field of energetic materials should prioritize the development of energy-rich backbones that possess both high energy and low sensitivity, in addition to exhibiting exceptional density and performance characteristics. For this purpose, three new heat-resistant and low-sensitivity energetic compounds with [5,6,5] fused ring skeletons were developed in this study: 9<i>H</i>-tetrazolo[1,5-<i>b</i>][1,2,3]triazolo[4,5-<i>d</i>]pyrimidin-6-ol (<b>3</b>), 9<i>H</i>-tetrazolo[1,5-<i>b</i>][1,2,3]triazolo[4,5-<i>d</i>]pyrimidin-6-amine (<b>4</b>), and 8-azino-8<i>H</i>-imidazo[4,5-<i>d</i>]tetrazolo[1,5-<i>b</i>]pyridazine-6-amine (<b>5</b>). It was determined through single-crystal X-ray diffraction and theoretical analysis that these three compounds exhibited low sensitivity (IS &gt; 20 J and FS &gt; 240 N). Their molecules are planar with abundant intermolecular hydrogen bonds and strong π–π interactions between the molecular layers, all of which account for their low sensitivity. At the same time, <b>3</b> (<i>D</i> = 7734 m·s^–1, <i>P</i> = 22.4 GPa), <b>4</b> (<i>D</i> = 8075 m·s^–1, <i>P</i> = 23.5 GPa), and <b>5</b> (<i>D</i> = 7889 m·s^–1, <i>P</i> = 22.2 GPa) have higher detonation performance than the conventional explosives HNS (<i>D</i> = 7612 m·s^–1, <i>P</i> = 24.3 GPa) and TNT (<i>D</i> = 6881 m·s^–1, <i>P</i> = 19.5 GPa). <b>4</b> has a maximum thermal decomposition temperature (<i>T</i> = 318 °C) comparable to that of the heat-resistant explosive HNS (<i>T</i> = 318 °C). The research findings suggest that compound <b>4</b> exhibits potential as a heat-resistant and low-sensitivity explosive, while compounds <b>3</b> and <b>5</b> demonstrate the potential to be low-sensitivity explosives.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4151–4158 4151–4158"},"PeriodicalIF":3.2,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144306140","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":"Semi-Supervised Vision Transformer Framework for AI-Based RHEED Image Classification of Ferroelectric Nitride MBE Growth","authors":"Yuyang Chen,&nbsp;Danhao Wang*,&nbsp;Dalei Jiang and Zetian Mi*,&nbsp;","doi":"10.1021/acs.cgd.5c0017910.1021/acs.cgd.5c00179","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00179https://doi.org/10.1021/acs.cgd.5c00179","url":null,"abstract":"<p >We report a semi-supervised Vision Transformer (ViT) framework for automated reflection high energy electron diffraction (RHEED) image classification of ferroelectric nitride (ScAlN) materials grown by molecular beam epitaxy (MBE). By incorporating pseudo-labeling, the new framework reduces the need for extensive manual annotations while maintaining robust performance across multiple substrate angles. The effects of three key hyperparameters: labeled-data proportion, the number of Transformer heads, and model depth on classification outcomes are explored. Our findings show that, although parameter tuning can yield incremental accuracy gains, simpler configurations (e.g., two heads and two layers) provide an optimal balance between accuracy and computational overhead. Adjusting embedding dimensions further refines the model without incurring excessive computational costs. Compared with fully supervised approaches, the proposed framework delivers equal or better accuracy using far fewer labeled samples and effortlessly adapts to diverse RHEED angles. These findings underscore the potential of semi-supervised ViT-based solutions to facilitate AI-driven standardization and optimization in semiconductor manufacturing.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4295–4303 4295–4303"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305969","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":"Aerosol Deposited GaN: A Self-Improving Catalyst for Electrolytic Hydrogen Evolution Reaction","authors":"Gutema Teshome Gudena,&nbsp;Dahoon Kim,&nbsp;Daba Deme Megersa,&nbsp;Jae-Young Choi*,&nbsp;Jae-Hyuk Park* and Hak Ki Yu*,&nbsp;","doi":"10.1021/acs.cgd.5c0045810.1021/acs.cgd.5c00458","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00458https://doi.org/10.1021/acs.cgd.5c00458","url":null,"abstract":"<p >In this study, gallium nitride (GaN), a stable and conductive III–V semiconductor, was explored as an alternate electrocatalyst for the hydrogen evolution reaction (HER). Using the aerosol deposition (AD) method, GaN nanoparticles were uniformly deposited onto carbon paper, providing an efficient and scalable approach to electrode fabrication. X-ray photoelectron spectroscopy (XPS) analysis revealed the formation of a thin gallium oxynitride layer resulting from partial oxygen substitution at nitrogen sites. This oxynitride layer alters the material’s electronic structure, enhancing conductivity, creating synergistic active sites, and reducing reaction barriers, which promote efficient electron transfer during water splitting. Our findings demonstrate the potential of GaN as a cost-effective, high-performance electrocatalyst for hydrogen production, with excellent stability and catalytic activity under acidic conditions.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4531–4538 4531–4538"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305583","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":"Development of Cocrystal and Coamorphous Salts of Moxifloxacin with Artificial Sweeteners to Suppress Bitterness","authors":"Peiwen Mo,&nbsp;Yuta Hatanaka,&nbsp;Saki Ohta,&nbsp;Yuzuki Nakayama,&nbsp;Yasuteru Mawatari,&nbsp;Shinya Yamanaka,&nbsp;Katsuhiko Minoura,&nbsp;Mitsunobu Doi,&nbsp;Hiromasa Uchiyama,&nbsp;Kazunori Kadota* and Yuichi Tozuka*,&nbsp;","doi":"10.1021/acs.cgd.5c0017010.1021/acs.cgd.5c00170","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00170https://doi.org/10.1021/acs.cgd.5c00170","url":null,"abstract":"<p >This study explores the formation of a molecular complex between moxifloxacin (MFX) and the artificial sweetener saccharin (SAC) as a strategy to mask the drug’s undesirable taste. MFX particles were combined with SAC in a 1:1 ratio using ball milling, a process that facilitated the formation of both cocrystal and coamorphous salts through ionic interactions. Structural analysis of the MFX-SAC complex revealed intermolecular ionic bonds between the amino group of MFX and the sulfonamide group of SAC. Solid-state nuclear magnetic resonance spectroscopy further confirmed that MFX interacts with SAC via ionic bonding. Electronic taste evaluations demonstrated that the MFX-SAC complex not only significantly reduced the bitterness of MFX but also suppressed the overall taste intensity to levels below the quinine reference standard. These findings highlight the potential of molecular complex formation between artificial sweeteners and bitter-tasting drugs as an effective approach for taste modification and masking, offering promising implications for pharmaceutical formulation development.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4283–4294 4283–4294"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305670","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":"Dimyristoylphosphoethanolamine Addition During Chocolate Manufacture Promotes Proper Tempering under Simple Cooling Conditions without Shear","authors":"Jarvis A. Stobbs,&nbsp;Saeed M. Ghazani,&nbsp;Kaiyang Tu,&nbsp;Erica Pensini,&nbsp;Anne-Laure Fameau and Alejandro G. Marangoni*,&nbsp;","doi":"10.1021/acs.cgd.5c0057510.1021/acs.cgd.5c00575","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00575https://doi.org/10.1021/acs.cgd.5c00575","url":null,"abstract":"<p >We report a practical application of using 1,2-dimyristoyl-<i>sn</i>-glycero-3-phosphoethanolamine (DMPE) to temper dark chocolate. Building upon prior research where 1,2-dimyristoyl-<i>sn</i>-glycero-3-phosphocholine (DMPC) was used to direct CB crystallization into the desired Form V polymorph, we investigated whether DMPE could achieve superior results without the structural defects observed with DMPC-tempered chocolate. Chocolate samples containing 0.1 wt % DMPE were prepared and compared to chocolates tempered with DMPC, as well as commercially tempered and statically cooled controls. Small-angle X-ray scattering (SAXS) revealed that the DMPE addition induced the formation of the Form V polymorph, with no detectable amounts of Form IV polymorph, which is often associated with reduced shelf life and fat bloom in chocolate products. Unlike the DMPC-tempered samples, the DMPE chocolate exhibited no blooming or structural defects such as cracks upon prolonged storage. Small-angle neutron scattering (SANS) experiments showed no evidence of micelle formation by DMPE, suggesting a mechanism distinct from that of DMPC. Fourier transform infrared (FTIR) spectroscopy and attenuated total reflectance imaging indicated no significant chemical interactions between DMPE and the main triacylglycerol (TAG) in CB, 1-palmitoyl-2-oleoyl-3-stearoyl-<i>sn</i>-glycerol (POS). We propose that DMPE acts as a unique tempering particle, which facilitates the formation of the stable Form V polymorph and the correct chocolate microstructure through physical interactions with the crystallizing TAGs on its surface. Moreover, DMPE addition also prevents localized material contraction and bloom development due to the absence of induced lattice strain. Crystallization kinetics of the cocoa butter component of chocolate shows an acceleration of crystallization induced by DMPE at 28 °C, relative to both the native refined cocoa butter and the refined cocoa butter containing DMPC. Polarized light micrographs supported this observation. Isolated seed crystals from cocoa butter showed an enrichment in POS and POP in DMPE chocolate, and a characteristic Form V polymorphism for these seeds, in contrast to both native refined cocoa butter and refined cocoa butter with DMPC, where Form IV was identified at the onset of crystallization. The addition of DMPE to chocolate simplifies the tempering process, potentially reducing production costs and energy consumption, and enhancing the quality and stability of the final product, benefiting both artisanal chocolatiers and large-scale manufacturers.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 12","pages":"4621–4635 4621–4635"},"PeriodicalIF":3.2,"publicationDate":"2025-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305669","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}