Crystal Growth & Design最新文献_第10页

MicroED Structures of Fluticasone Furoate and Fluticasone Propionate Provide New Insights into Their Function.

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-12 eCollection Date: 2025-03-05 DOI: 10.1021/acs.cgd.4c01683

Jieye Lin, Johan Unge, Tamir Gonen

{"title":"MicroED Structures of Fluticasone Furoate and Fluticasone Propionate Provide New Insights into Their Function.","authors":"Jieye Lin, Johan Unge, Tamir Gonen","doi":"10.1021/acs.cgd.4c01683","DOIUrl":"10.1021/acs.cgd.4c01683","url":null,"abstract":"The detailed understanding of the conformational pathway of fluticasone, a widely prescribed medicine for allergic rhinitis, asthma, and chronic obstructive pulmonary disease (COPD), from formulation to its protein-bound state, has been limited due to a lack of access to its high-resolution structures. The three-dimensional (3D) structure of fluticasone furoate 1 remains unpublished, and the deposited structure of fluticasone propionate 2 could be further refined due to refinement against new data. We applied microcrystal electron diffraction (MicroED) to determine the 3D structures of 1 and 2 in their solid states. The preferred geometries in solution were predicted by using density functional theory (DFT) calculations. A comparative analysis of the structures of 1 and 2 across three states (in solid state, in solution, and protein-bound conformation) revealed the course of the conformational changes during the entire transition. Potential energy plots were calculated for the most dynamic bonds, uncovering their rotational barriers. This study underscores the combined use of MicroED and DFT calculations to provide a comprehensive understanding of conformational and energy changes during drug administration. The quantitative comparison also highlights the subtle structural differences that may lead to significant changes in the pharmaceutical properties.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1588-1596"},"PeriodicalIF":3.2,"publicationDate":"2025-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11887049/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143583941","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}

引用次数: 0

Correction to “Polymorphism and Phase Stability of Hydrated Magnesium Carbonate Nesquehonite MgCO3·3H2O: Negative Axial Compressibility and Thermal Expansion in a Cementitious Material”

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-12 DOI: 10.1021/acs.cgd.5c0011510.1021/acs.cgd.5c00115

David Santamaría-Pérez*, Raquel Chuliá-Jordán, Javier Gonzalez-Platas, Alberto Otero-dela-Roza, Javier Ruiz-Fuertes, Julio Pellicer-Porres, Robert Oliva and Catalin Popescu,

引用次数: 0

Modulating Elasticity and Plasticity through Halogen Substitution: Insights from Crystal Engineering

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-11 DOI: 10.1021/acs.cgd.4c0155910.1021/acs.cgd.4c01559

Yuanhang Wang, Yang Ye, Yaru Zhang, Ying Sun, Xiaomeng Zhou, Yafei Dong and Chuang Xie*,

{"title":"Modulating Elasticity and Plasticity through Halogen Substitution: Insights from Crystal Engineering","authors":"Yuanhang Wang, Yang Ye, Yaru Zhang, Ying Sun, Xiaomeng Zhou, Yafei Dong and Chuang Xie*, ","doi":"10.1021/acs.cgd.4c0155910.1021/acs.cgd.4c01559","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01559https://doi.org/10.1021/acs.cgd.4c01559","url":null,"abstract":"Modulating the mechanical properties of molecular crystals via crystal engineering is gaining increasing attention in materials research. In this study, three single crystals of pyridine derivatives, 2,3,5-trichloropyridine (Cry-B), 2,5-dichloro-3-bromopyridine (Cry-E), and 2,3-dibromo-5-chloropyridine (Cry-P), were prepared, and their mechanical properties were systematically evaluated. These crystals possess highly similar molecular structures but totally distinct macroscopic mechanical responses. Specifically, Cry-B exhibits brittle behavior, while Cry-E and Cry-P display distinct elastic and plastic deformations, respectively. Single-crystal X-ray diffraction (SC-XRD) and powder X-ray diffraction (P-XRD) analyses revealed differences in molecular packing, which correlate with mechanical performance. Energy framework analysis and micro-Raman spectroscopy were utilized to understand the molecular interactions and structural changes during deformation. It is found that the variations in mechanical behavior correlate with their respective primary structural mechanisms such as the interlocking structure necessary for elastic bending and the slip plane structure for plastic deformation. Furthermore, nanoindentation tests quantified the hardness and elastic moduli, with Cry-B showing the highest stiffness and Cry-P being the most deformable. Hirshfeld surface analysis highlighted the significant role of halogen interactions in controlling crystal flexibility. This study examined the relationship between crystal structure and mechanical properties and highlights the significant potential of crystal engineering to tune mechanical properties via weak intermolecular interactions.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1457–1465 1457–1465"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547472","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}

引用次数: 0

Revealing the Crystal Structure of the Purine Base Xanthine with Three-Dimensional (3D) Electron Diffraction

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-11 DOI: 10.1021/acs.cgd.4c0159410.1021/acs.cgd.4c01594

Helen W. Leung*, Royston C. B. Copley, Giulio I. Lampronti, Sarah J. Day, Lucy K. Saunders, Duncan N. Johnstone and Paul A. Midgley*,

{"title":"Revealing the Crystal Structure of the Purine Base Xanthine with Three-Dimensional (3D) Electron Diffraction","authors":"Helen W. Leung*, Royston C. B. Copley, Giulio I. Lampronti, Sarah J. Day, Lucy K. Saunders, Duncan N. Johnstone and Paul A. Midgley*, ","doi":"10.1021/acs.cgd.4c0159410.1021/acs.cgd.4c01594","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01594https://doi.org/10.1021/acs.cgd.4c01594","url":null,"abstract":"Three-dimensional (3D) electron diffraction (3D-ED) techniques can be used for structure determination, circumventing challenges posed to conventional and bulk X-ray diffraction techniques such as submicrometer-sized crystals, the strong effects of texture, the presence of defects, and polyphasic samples. Such challenges previously prevented the structure solution of xanthine, a purine base chemically similar to guanine that may also be found in organisms. In this work, we use 3D-ED to elucidate the crystal structure of xanthine. The electron diffraction data obtained from a single microcrystal is also of sufficient quality to determine hydrogen positions, confirming the presence of the 7H-tautomer, as expected. This study highlights the potential for the use of 3D-ED on biogenic nanocrystals, for example opening opportunities to understand the links between crystal anisotropy, birefringence, and organism characteristics.3D electron diffraction (3D-ED) is used for structure determination, circumventing challenges posed to conventional X-ray diffraction techniques. We use 3D-ED to elucidate the crystal structure of xanthine, a purine base. The data are of sufficient quality to determine hydrogen positions, confirming the presence of the 7H-tautomer. This study highlights the potential for the use of 3D-ED on biogenic nanocrystals.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1293–1298 1293–1298"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.cgd.4c01594","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547464","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}

引用次数: 0

Revealing the Crystal Structure of the Purine Base Xanthine with Three-Dimensional (3D) Electron Diffraction.

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-11 eCollection Date: 2025-03-05 DOI: 10.1021/acs.cgd.4c01594

Helen W Leung, Royston C B Copley, Giulio I Lampronti, Sarah J Day, Lucy K Saunders, Duncan N Johnstone, Paul A Midgley

引用次数: 0

Cd5As2Br4: A Ternary Arsenide with Nonlinear Optical Property

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-11 DOI: 10.1021/acs.cgd.5c0005910.1021/acs.cgd.5c00059

Qiang Liu, Wenhao Xing, Bohui Xu, Guili Wang, Chunxiao Li, Pifu Gong and Jiyong Yao*,

{"title":"Cd5As2Br4: A Ternary Arsenide with Nonlinear Optical Property","authors":"Qiang Liu, Wenhao Xing, Bohui Xu, Guili Wang, Chunxiao Li, Pifu Gong and Jiyong Yao*, ","doi":"10.1021/acs.cgd.5c0005910.1021/acs.cgd.5c00059","DOIUrl":"https://doi.org/10.1021/acs.cgd.5c00059https://doi.org/10.1021/acs.cgd.5c00059","url":null,"abstract":"In this research, a new ternary arsenide, Cd5As2Br4, with a nonlinear optical (NLO) property has been synthesized. Cd5As2Br4 possesses a noncentrosymmetric structure with a space group belonging to the orthorhombic crystal system, specifically Pna21. The structure of Cd5As2Br4 is formed by the interconnection of three one-dimensional structures, resulting in a three-dimensional structure. The diffuse reflectance spectrum reveals that Cd5As2Br4 has a direct band gap of 1.91 eV. NLO performance tests indicate that at a particle size range of 20–50 μm, the second harmonic generation (SHG) intensity of Cd5As2Br4 is 0.7 times that of AgGaS2 (AGS), and it exhibits nonphase-matching behavior at 2090 nm. Additionally, at a particle size range of 125–150 μm, the laser-induced damage threshold (LIDT) of Cd5As2Br4 is equal to that of AGS. Finally, theoretical calculations elucidate that Cd5As2Br4 possesses a calculated maximum SHG coefficient d15 of −11.66 pm/V.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1675–1681 1675–1681"},"PeriodicalIF":3.2,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547473","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}

引用次数: 0

Mn2+-Induced Robust Radiation Hardness in Bi4Ge3O12 for Next-Generation High-Energy Physical Colliders

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-10 DOI: 10.1021/acs.cgd.4c0157410.1021/acs.cgd.4c01574

Mingxue Deng*, Lei Chen, Xiang Li, Xuejun Qi, Shaohan Wang and Junfeng Chen*,

{"title":"Mn2+-Induced Robust Radiation Hardness in Bi4Ge3O12 for Next-Generation High-Energy Physical Colliders","authors":"Mingxue Deng*, Lei Chen, Xiang Li, Xuejun Qi, Shaohan Wang and Junfeng Chen*, ","doi":"10.1021/acs.cgd.4c0157410.1021/acs.cgd.4c01574","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01574https://doi.org/10.1021/acs.cgd.4c01574","url":null,"abstract":"Future high-performance particle colliders, e.g., the proposed circular electron positron collider (CEPC) or future circular collider (FCC), demand unprecedented levels of accuracy in energy measurement for calorimeters. Although the proposed high-granularity crystal electromagnetic calorimeter has made great progress in recent years, the designing and matching of Bi4Ge3O12 (BGO) scintillators with lower light output and higher radiation resistance, as well as not introducing slow components, lag far behind. Here, a Mn-doped BGO powder exhibits robust radiation resistance with a faster decay time, accelerating by 15%. Doping with Mn3% reduces the intensities of photoluminescence (PL) and radioluminescence (RL) to 55% and 22%, respectively, of those observed in pure BGO powder. Furthermore, Mn-doped BGO exhibits enhanced radiation resistance and can maintain 72% of the initial RL intensity within 2 h of radiation with a high-power UV lamp, while that of pure BGO is severely degraded to 45%. Theoretical calculation mechanism studies show that Mn doping not only maintains the intrinsic luminescence of BGO but also introduces a new intermediate energy level in the energy band to inhibit the formation of color centers. This work provides a new avenue to search for or discover scintillators from existing cost-effective scintillators for future high-energy physics experiments.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1477–1483 1477–1483"},"PeriodicalIF":3.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547459","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}

引用次数: 0

Hybrid Semi-mechanistic and Machine Learning Solubility Regression Modeling for Crystallization Process Development

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-10 DOI: 10.1021/acs.cgd.4c0145110.1021/acs.cgd.4c01451

Gustavo L. Quilló, Satyajeet S. Bhonsale, Alain Collas, Jan F. M. Van Impe* and Christos Xiouras*,

{"title":"Hybrid Semi-mechanistic and Machine Learning Solubility Regression Modeling for Crystallization Process Development","authors":"Gustavo L. Quilló, Satyajeet S. Bhonsale, Alain Collas, Jan F. M. Van Impe* and Christos Xiouras*, ","doi":"10.1021/acs.cgd.4c0145110.1021/acs.cgd.4c01451","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01451https://doi.org/10.1021/acs.cgd.4c01451","url":null,"abstract":"Solubility regression modeling is foundational for several chemical engineering applications, particularly for crystallization process development. Traditionally, these models rely on parametric semimechanistic approaches such as the Van’t Hoff Jouyban-Acree (VH-JA) cosolvency model. Although these models generally provide narrow prediction intervals, they can exhibit increased bias when dealing with significant solute heat capacities or complex mixture effects. This study explores machine learning, including Random Forests, Support Vector Machines, Gaussian Process Regression, and Neural Networks, as potential alternatives. While most machine learning models offered a lower training error, it was observed that their predictive quality quickly deteriorates further from the training data. Hence, a hybrid approach was explored to leverage the low bias of machine learning and the low variance of the VH-JA model through heterogeneous locally weighted bagging ensembles. Key to the methodology is quantifying, tracking, and minimizing the uncertainty using the ensemble. This approach was illustrated through a case study on the solubility of ketoconazole in binary mixtures of 2-propanol and water. The optimal hybrid ensemble, comprising of 58% stepwise VH-JA models and 42% machine learning models, reduced the training root-mean-squared error and maximum absolute percentage error by ≈30% compared to the full VH-JA, while preserving a comparable prediction interval.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 4","pages":"1111–1127 1111–1127"},"PeriodicalIF":3.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435826","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}

引用次数: 0

Carbon-Based Nanoporous Homochiral MOF as a Highly Efficient Platform for Chiral Recognition and Enantioselective Electrooxidation

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-10 DOI: 10.1021/acs.cgd.4c0067410.1021/acs.cgd.4c00674

Salma Mirza*, Muhammad Ateeq, Perveen Fazil, Amir Zada and Malik Shoaib Ahmad*,

{"title":"Carbon-Based Nanoporous Homochiral MOF as a Highly Efficient Platform for Chiral Recognition and Enantioselective Electrooxidation","authors":"Salma Mirza*, Muhammad Ateeq, Perveen Fazil, Amir Zada and Malik Shoaib Ahmad*, ","doi":"10.1021/acs.cgd.4c0067410.1021/acs.cgd.4c00674","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c00674https://doi.org/10.1021/acs.cgd.4c00674","url":null,"abstract":"Even though great progress has been made in the development of electrocatalysts, still a great challenge persists in the design of chiral-based enantiospecific catalysts. Herein, we prepared an enantioselective carbon-based nanoporous homochiral MOF from camphoric acid (D- or LCAM) [Cu2(DCAM)2(DABCO)] templated on a nickel foam substrate and subsequently loaded Pt on the prepared sample by the postsynthetic method. The obtained chiral thin-film template was found to be highly ordered [001] due to the self-assembly of the MOF by the automatic LPE method. DMOF/Pt-600@NF was used as a precursor for the calcination of a chiral nanoporous material. The DMOF/Pt-600 grown on Ni foam with 40 cycles and calcined at 600 °C for 3 h exhibited superior electrooxidation performance with excellent enantiorecognition capability and enantioselective oxidation of R/S-2-butanol with remarkable stability compared to commercial Pt/C. Circular dichroism (CD) spectroscopy, cyclic voltammetry (CV), and chronoamperometry experiments were conducted to determine the existence of chiral motifs in the synthesized nanoporous thin film. This work gives new insight into understanding the effect of highly ordered chiral structures, which is useful in enantioselective chemistry. These results could be the gateway to facilitate the development of advanced chiral material-based analytical tools that will be used in a variety of applications in bio/pharmaceutical quality control, environmental monitoring, food and beverage industries that address the poor selectivity issues in chiral detection, and butanol fuel cell industries.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 4","pages":"903–911 903–911"},"PeriodicalIF":3.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143436083","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}

引用次数: 0

Series of Fluorescent Coordination Polymers Exhibiting Structural Evolution and Optimized Selective Ion Detection

IF 3.2 2区化学

Crystal Growth & Design Pub Date : 2025-02-10 DOI: 10.1021/acs.cgd.4c0160910.1021/acs.cgd.4c01609

Ding Chen, Xing Li*, Yu-Xuan Wang and Jin-Peng Xue*,

{"title":"Series of Fluorescent Coordination Polymers Exhibiting Structural Evolution and Optimized Selective Ion Detection","authors":"Ding Chen, Xing Li*, Yu-Xuan Wang and Jin-Peng Xue*, ","doi":"10.1021/acs.cgd.4c0160910.1021/acs.cgd.4c01609","DOIUrl":"https://doi.org/10.1021/acs.cgd.4c01609https://doi.org/10.1021/acs.cgd.4c01609","url":null,"abstract":"A series of Zn(II)-H2L (H2L = 3,3′-(9,9-diethyl-9H-fluorene-2,7-diyl)dibenzoic acid) fluorescent coordination polymers were synthesized using a mixed-ligand approach through solvothermal methods, demonstrating a structural transition from three-dimensional (3D) to two-dimensional (2D) frameworks. The structural evolution is driven by the gradational size variation of the pyridine-based ligands, L1 (9,10-di(4-pyridyl)anthracene), L2 (1,4-bis(pyridyl)benzene), and L3 (4,4′-bipyridine), resulting in distinct spatial packing and coordination modes. The polymers, designated as {[Zn2(L)2(L1)]}n (1), {[Zn2(L)2(L2)]}n (2), and {[Zn2(L)2(L3)]}n (3), feature a structural evolution from 3D interpenetrated to 2D alternating structures, significantly influencing their fluorescent properties for ion detection. Notably, compound 3 exhibits marked selectivity and sensitivity toward trivalent metal ions (Cr3+, Al3+, and Fe3+) with detection limits of 0.19 μM for Cr3+, 0.30 μM for Al3+, and 0.37 μM for Fe3+. This research provides valuable insights into the designability of metal–organic frameworks and advances the development of MOF-based fluorescent probes for selective ion detection, highlighting the impact of systematic structural adjustments on ion selectivity and sensing performance.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 5","pages":"1497–1505 1497–1505"},"PeriodicalIF":3.2,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547460","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}

引用次数: 0