Crystal Growth & Design最新文献

{"title":"Optimization of Hot-Melt Extrusion Processing for the Synthesis of Ionic Cocrystals","authors":"Dunja Šilić,&nbsp;Biserka Cetina-Čižmek,&nbsp;Steven A. Ross,&nbsp;Andrew Hurt,&nbsp;Milan Antonijevic and Dennis Douroumis*,&nbsp;","doi":"10.1021/acs.cgd.3c00773","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00773","url":null,"abstract":"<p >Cocrystals are multicomponent crystalline forms that are an appealing alternative to modify undesirable properties of drug substances, such as poor solubility and stability. Hot-melt extrusion (HME), a solvent-free, robust, and scalable technology, has been proven to be a suitable approach for cocrystallization of several drug-coformer pairs. However, HME has been mainly implemented for the synthesis of molecular cocrystals when most of the marketed products are manufactured in the form of ionic cocrystals. In this study, the synthesis of extruded fluoxetine HCl-succinic acid cocrystals was investigated using different screw configurations. Ionic cocrystals manufactured by HME showed complete transformation of the drug-coformer pair with high purity, improved intrinsic dissolution rates, and long-term storage stability when compared to their counterparts produced by solvent evaporation.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7355–7364"},"PeriodicalIF":3.8,"publicationDate":"2023-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41086710","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":"Micropipe-Like Defects in the Expanded Diameter Region of 8 in. SiC Grown by Physical Vapor Transport","authors":"Ying Song,&nbsp;Naiji Yang,&nbsp;Hui Li*,&nbsp;Wenjun Wang and Xiaolong Chen*,&nbsp;","doi":"10.1021/acs.cgd.3c00850","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00850","url":null,"abstract":"<p >This study presents the growth of 8 in. silicon carbide (SiC) single crystals using a multiple-expanding diameter growth process via the physical vapor transport technique, with commercial 6 in. n-type SiC of 4° off-axis toward [11<span>2</span><span>̅</span>0] as the seed. Micropipe-like defects were observed in the expanded diameter region, whereas they are absent in the unexpanded diameter region grown on the SiC seed via step-flow growth mode. Optical microscopy, scanning electron microscopy, micro-Raman spectroscopy, laser scanning confocal microscopy, defect-tracking experiments, and energy-dispersive spectroscopy were employed to investigate the morphology, polytype, and formation mechanism of the defects. The micropipe-like defects, with diameters in the dozens of micrometers scale and an angle ∼50° relative to the [000<span>1</span><span>̅</span>] direction, were found to stem from carbon particles decomposed from SiC powders. No other polytype inclusions were observed in these defects. By applying sintered SiC powders as starting materials, micropipe-like defects were effectively reduced. Our results provide an efficient method for growing large-size SiC single crystals of high-quality and low-defect density via the multiple-expanding diameter growth process.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7440–7447"},"PeriodicalIF":3.8,"publicationDate":"2023-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41086712","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":"UV-Induced Negative Growth of In Nanodroplets and Mounds from Ultrathin In Layers on Sublimated InP(110)","authors":"Songphol Kanjanachuchai*,&nbsp;Thipusa Wongpinij,&nbsp;Pat Photongkam and Chanan Euaruksakul,&nbsp;","doi":"10.1021/acs.cgd.3c00629","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00629","url":null,"abstract":"<p >Ultrathin In layers formed on InP(110) by vacuum sublimation act as reservoirs that, during cooling and simultaneous exposure to ultraviolet (UV) photons, grow into different nanostructures depending on the conductivity type of the underlying semiconductor. In situ observation by synchrotron-based spectroscopic low-energy electron microscopy shows that on <i>n</i>-type InP(110), the ultrathin layers grow into two-dimensional (2D) islands or mounds only. On <i>p</i>-type InP(110), similar 2D mounds also exist, but they are decorated by nanoscale droplets, indicating a Stranski–Krastanow growth mode. The effects that UV exposure has on the ultrathin In layers are optomechanical in nature as induced quantum electronic stress results in partial decoupling of the layers from the semiconductor surface, driving the released atoms to minimize their energies by forming conductivity type-dependent stable configurations. Semiconductor surfaces with different conductivity types have different workfunctions or, equivalently, different chemical potentials for adatoms, which provide the physical origin of the observed different morphologies of In on InP. The results provide an experimental proof that the conductivity type of substrates/supports could influence the final morphologies and thus properties of the overgrown metal structures. Consequently, strategies could be devised to ensure flat, ultrathin metallic or even superconducting films of technological and fundamental interests.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7207–7216"},"PeriodicalIF":3.8,"publicationDate":"2023-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41086784","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":"Solvent Effect on Molecular Conformational Evolution and Polymorphic Manipulation of Cimetidine","authors":"Beiqian Tian,&nbsp;Hongxun Hao,&nbsp;Xin Huang*,&nbsp;Ting Wang,&nbsp;Jingkang Wang,&nbsp;Jinyue Yang,&nbsp;Xin Li,&nbsp;Wenlei Li,&nbsp;Lina Zhou and Na Wang*,&nbsp;","doi":"10.1021/acs.cgd.3c00661","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00661","url":null,"abstract":"<p >In the field of pharmaceutical crystallization, the success of polymorphic manipulation is vital to the performance of pharmaceutical formulations, and the choice of solvents might affect polymorphic outcomes directly. To better understand the relationship between molecular structure in solution and in the crystal, the solvent effect on molecular conformational evolution and polymorph control of cimetidine (CIM) was investigated. Three polymorphs (A, B, and D) of cimetidine (CIM) were prepared, and it was found that conformers selected in crystals could significantly affect crystal packing and polymorph stability. Two-dimensional nuclear Overhauser effect spectroscopy and quantum chemical calculation results reveal that conformer A is the dominant molecular conformer, although conformational distribution is strongly solvent-dependent. Furthermore, Fourier transform infrared spectroscopy and solvation free energy calculation results show that the interaction strength of CIM with solvents increases in the order isopropanol ≈ acetonitrile &lt; methanol &lt; ethylene glycol, affecting the difficulty of desolvation. The results imply that the interaction strength of CIM with solvents may affect the difficulty of desolvation, conformational rearrangement, and final polymorphic outcome. In the end, the potential mechanism of conformational evolution and polymorphic manipulation of CIM was presented.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7266–7275"},"PeriodicalIF":3.8,"publicationDate":"2023-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41086708","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":"Strong Enhancement of Nucleation Efficiency of Aqueous Ethylenediamine Sulfate Solutions by Nonphotochemical Laser-Induced Nucleation: Investigations on the Role of Solid Impurities in the Mechanism","authors":"Mélody Briard,&nbsp;Clément Brandel* and Valérie Dupray,&nbsp;","doi":"10.1021/acs.cgd.3c00588","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00588","url":null,"abstract":"<p >The nonphotochemical laser-induced nucleation (NPLIN) phenomenon of an inorganic compound, ethylenediamine sulfate, exhibiting crystal chirality has been investigated. Strong enhancement of the nucleation efficiency upon laser irradiation is reported and is shown to rely on the presence of insoluble particles dispersed within the aqueous solutions since filtration drastically reduces the NPLIN effect. Elemental analyses (ICP-OES) show that these particles have a composition close to that of stainless steel. Then, we report a systematic study of the impact of doping the filtered solutions with several types of metallic particles on NPLIN efficiency as a function of irradiation wavelength and show that suitable doping permits to retrieve high nucleation probabilities. The impact of the geometry of light polarization on the distribution of crystal enantiomorphs is also investigated to assess the possibility of stereoselectively triggering the NPLIN effect in the case of ethylenediamine sulfate solutions irradiated with a single nanosecond laser pulse.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7169–7178"},"PeriodicalIF":3.8,"publicationDate":"2023-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41086705","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":"Selective Inclusion of Cyclohexanone from a Mixture with Cyclohexanol Using 1,3-Diaminocalix[4]arene Crystals","authors":"Tomoaki Matsumoto,&nbsp;Kenta Hoshi,&nbsp;Ikumi Koyama,&nbsp;Naoya Morohashi* and Tetsutaro Hattori,&nbsp;","doi":"10.1021/acs.cgd.3c00514","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00514","url":null,"abstract":"<p >1,3-Diaminocalix[4]arene <b>3</b> crystals selectively include cyclohexanone over cyclohexanol, which is one of the hard-to-separate organic molecules, from their decane solution. X-ray structural analysis of <b>3</b>·Cy=O and <b>3</b>·Cy–OH revealed that a guest molecule is included in the cavity of the host molecule to form the same 1:1 (host/guest) inclusion complexes. <b>3</b>·Cy=O is observed to be slightly more stable than <b>3</b>·Cy–OH through thermogravimetric analysis of inclusion crystals. A noncompetitive inclusion experiment from decane solution revealed that the inclusion of cyclohexanone into the crystals of <b>3</b> is kinetically and thermodynamically more favorable than that of cyclohexanol. A comparison of the inclusion behavior of each guest molecule from decane and water revealed that the preferential inclusion of cyclohexanone seems to be amplified by the inhibition of the inclusion of cyclohexanol by the formation of aggregates with intermolecular hydrogen bonds in a non-polar solvent.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7134–7140"},"PeriodicalIF":3.8,"publicationDate":"2023-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41087140","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":"Decentralized Federated Learning: Fundamentals, State of the Art, Frameworks, Trends, and Challenges","authors":"Enrique Tomás Martínez Beltrán;Mario Quiles Pérez;Pedro Miguel Sánchez Sánchez;Sergio López Bernal;Gérôme Bovet;Manuel Gil Pérez;Gregorio Martínez Pérez;Alberto Huertas Celdrán","doi":"10.1109/COMST.2023.3315746","DOIUrl":"10.1109/COMST.2023.3315746","url":null,"abstract":"In recent years, Federated Learning (FL) has gained relevance in training collaborative models without sharing sensitive data. Since its birth, Centralized FL (CFL) has been the most common approach in the literature, where a central entity creates a global model. However, a centralized approach leads to increased latency due to bottlenecks, heightened vulnerability to system failures, and trustworthiness concerns affecting the entity responsible for the global model creation. Decentralized Federated Learning (DFL) emerged to address these concerns by promoting decentralized model aggregation and minimizing reliance on centralized architectures. However, despite the work done in DFL, the literature has not (i) studied the main aspects differentiating DFL and CFL; (ii) analyzed DFL frameworks to create and evaluate new solutions; and (iii) reviewed application scenarios using DFL. Thus, this article identifies and analyzes the main fundamentals of DFL in terms of federation architectures, topologies, communication mechanisms, security approaches, and key performance indicators. Additionally, the paper at hand explores existing mechanisms to optimize critical DFL fundamentals. Then, the most relevant features of the current DFL frameworks are reviewed and compared. After that, it analyzes the most used DFL application scenarios, identifying solutions based on the fundamentals and frameworks previously defined. Finally, the evolution of existing DFL solutions is studied to provide a list of trends, lessons learned, and open challenges.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 4","pages":"2983-3013"},"PeriodicalIF":35.6,"publicationDate":"2023-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"136297476","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":"A Quinary Metal–Organic Framework Composed of One Metal and One Linker with Ethane-Selective Property","authors":"Ze-Hua Jiang,&nbsp;Han Fang,&nbsp;Hong-Xin Li and Dong-Xu Xue*,&nbsp;","doi":"10.1021/acs.cgd.3c00556","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00556","url":null,"abstract":"<p >Solvothermal reaction between Fe₃O(CH₃COO)₆(H₂O)₃ and terphenyl-3,3′’,5,5′’-tetracarboxylic acid (H₄TPTC) afforded a scarce multinary MOF of Quin-Fe-TPTC (Quin and TPTC are abbreviated from quinary and terphenyl-3,3′’,5,5′’-tetracarboxylate, respectively), which exemplifies the first quinary MOF comprising one metal and one linker in contrast to the documented ones assembled from one metal and four linkers or two metals and three linkers. The variation of linker aspect ratio and the deformation of the trinuclear iron cluster may be responsible for creating such a compound. Quin-Fe-TPTC exhibits bihelical channels interconnected through (hemi) cage cavities replete with methyl groups, resulting in C₂H₆-selective adsorption from a binary C₂H₆ and C₂H₄ mixture and benefiting one-step C₂H₄ purification. This was validated by not only IAST prediction but also by dynamic column breakthrough experiments.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7026–7030"},"PeriodicalIF":3.8,"publicationDate":"2023-09-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41087139","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":"Two Series of Tetranuclear Ln(III)-Based Clusters: Structures, Magnetic Behaviors, and Efficient Cycloaddition of CO2 to Oxazolidinones","authors":"Na Qiao,&nbsp;Xiao-Yan Xin,&nbsp;Chen Yang,&nbsp;Ming Fang,&nbsp;Chen-Xi Zhang,&nbsp;Wen-Min Wang* and Zhi-Lei Wu*,&nbsp;","doi":"10.1021/acs.cgd.3c00561","DOIUrl":"https://doi.org/10.1021/acs.cgd.3c00561","url":null,"abstract":"<p >Four new and interesting Ln₄ clusters formulated as [Ln₄(NO₃)₂(acac)₄(HL1)₂(CH₃OH)₂]·2(CH₃CN)] (Ln = Gd(<b>1</b>), Dy(<b>2</b>); H₄L1 = 2-(hydroxymethyl)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)propane-1,3-diol); acac = acetylacetone) and [Ln₄(NO₃)₂(acac)₄(L2)₂(CH₃CH₂OH)₂] (Ln = Gd(<b>3</b>), Dy(<b>4</b>); H₃L2 = 2-(((2-hydroxynaphthalen-1-yl)methylene)amino)-2-methylpropane-1,3-diol; acac = acetylacetone) were designed and constructed. Single-crystal X-ray studies indicate that all clusters have a defect dicubane topology in which four Ln(III) are on a plane bond with an arrangement of a parallelogram with the μ₃-O bridge. The difference between the two series of clusters lies in the change of the ligand substituent and terminal coordinated solvent molecules. All Ln(III)-based clusters <b>1</b>–<b>4</b> have exhibited excellent solvent stability. The magnetic investigation suggests that clusters <b>1</b> and <b>3</b> possess a different magnetothermal effect (−Δ<i>S</i>_m = 35.24 J kg^–1 K^–1 for <b>1</b>, and −Δ<i>S</i>_m = 36.68 J kg^–1 K^–1 for <b>3</b>). In addition, the diversity in the environment of the metal center leads to the distinct dynamic behavior of <i>U</i>_eff/<i>k</i>_B (21.27 K for <b>2</b> and 1.96 K for <b>4</b>) and τ₀ (1.43 × 10^–7 s for <b>2</b> and 2.43 × 10^–6 s for <b>4</b>). More importantly, clusters <b>1</b>–<b>4</b> as heterogeneous catalysts can efficiently catalyze the reaction of CO₂ with bromopropylene oxide and aromatic amine to synthesize oxazolidinones under mild conditions. By comparison, clusters <b>1</b> and <b>2</b> show higher catalytic activity than <b>3</b> and <b>4</b>, in which the Brønsted acidic −OH groups working together with Lewis acid metal sites improve the catalytic activity of Ln(III)-based clusters <b>1</b> and <b>2</b>. To the best of our knowledge, it is the first example of Ln(III)-based clusters that show good magnetic property and high catalytic activity simultaneously by regulating the coordination environment of Ln(III) ions. Our work provided a promising direction for regulating properties of multifunctional polynuclear Ln(III)-based clusters via changing the coordinated environment of the metal center. It also helps inspire the development of polynuclear Ln(III)-based multifunctional materials.</p>","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"23 10","pages":"7159–7168"},"PeriodicalIF":3.8,"publicationDate":"2023-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"41087135","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":"A Survey of Blockchain and Artificial Intelligence for 6G Wireless Communications","authors":"Yiping Zuo;Jiajia Guo;Ning Gao;Yongxu Zhu;Shi Jin;Xiao Li","doi":"10.1109/COMST.2023.3315374","DOIUrl":"10.1109/COMST.2023.3315374","url":null,"abstract":"The research on the sixth-generation (6G) wireless communications for the development of future mobile communication networks has been officially launched around the world. 6G networks face multifarious challenges, such as resource-constrained mobile devices, difficult wireless resource management, high complexity of heterogeneous network architectures, explosive computing and storage requirements, privacy and security threats. To address these challenges, deploying blockchain and artificial intelligence (AI) in 6G networks may realize new breakthroughs in advancing network performances in terms of security, privacy, efficiency, cost, and more. In this paper, we provide a detailed survey of existing works on the application of blockchain and AI to 6G wireless communications. More specifically, we start with a brief overview of blockchain and AI. Then, we mainly review the recent advances in the fusion of blockchain and AI, and highlight the inevitable trend of deploying both blockchain and AI in wireless communications. Furthermore, we extensively explore integrating blockchain and AI for wireless communication systems, involving secure services and Internet of Things (IoT) smart applications. Particularly, some of the most talked-about key services based on blockchain and AI are introduced, such as spectrum management, computation allocation, content caching, and security and privacy. Moreover, we also focus on some important IoT smart applications supported by blockchain and AI, covering smart healthcare, smart transportation, smart grid, and unmanned aerial vehicles (UAVs). Moreover, we thoroughly discuss operating frequencies, visions, and requirements from the 6G perspective. We also analyze the open issues and research challenges for the joint deployment of blockchain and AI in 6G wireless communications. Lastly, based on lots of existing meaningful works, this paper aims to provide a comprehensive survey of blockchain and AI in 6G networks. We hope this survey can shed new light on the research of this newly emerging area and serve as a roadmap for future studies.","PeriodicalId":34,"journal":{"name":"Crystal Growth & Design","volume":"25 4","pages":"2494-2528"},"PeriodicalIF":35.6,"publicationDate":"2023-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"135784561","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}