Name: reliable mechanochemistry: protocols for reproducible outcomes of neat and liquid assisted ball-mill grinding experiments
Uploaded: 2018-01-23T14:30:00
Description: Watch this Scientific Journal Video about Reliable Mechanochemistry: Protocols for Reproducible Outcomes of Neat and Liquid Assisted Ball-mill Grinding Experiments at JoVE.com

磁力轴承和 JKMS 感谢 EPSRC 的财政支持。我们感谢在设计和机械安装, 并为软件设计的自动化磨床的重复磨削。我们感谢理查德·南丁格尔, 奥利·诺里斯和西蒙我们从机械车间制造的研磨罐, 和螺线管持有人的 "推一个按钮" 设置和基思 Parmenter 从玻璃车间的化学系为玻璃样品 PXRD 幻灯片的制造。我们感谢贵公司对螺丝瓶盖研磨罐的维护和维修。我们感谢比尔. 琼斯教授使用化学系的 PXRD 设备和克里斯. 亨特教授使用他的实验室设施。我们感谢地球科学部 (吉尔) 的普遍支持。

1. 确认有机溶剂的精确配制
<ol><li>
反向吸管模式下有机溶剂精确移的验证 注: 在反向移模式下, 空气置换管被选择用于一系列滞后溶剂 (丙酮、乙腈 (MeCN)、四氢呋喃 (呋喃)、乙酸乙酯 (EtOAc)、氯仿 (CHCl3) 和胺 (DMF)), 因为它们浸泡非常有效地进入起始材料的粉末 (1-1和2-2)。对这种溶剂范围的反移模式进行了初步校准, 与前向移模式相比, 给出了更精确...

<ol>
	<li>James, S. L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemistry:+opportunities+for+new+and+cleaner+synthesis.">Mechanochemistry: opportunities for new and cleaner synthesis.</a> Chem Soc Rev. 41 (1), 413-447 (2012).</li><li>Braga, D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvent+effect+in+a+"solvent+free"+reaction.">Solvent effect in a "solvent free" reaction.</a> CrystEngComm. 9 (10), 879-881 (2007).</li><li>Karki, S., Friscic, T., Jones, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Control+and+interconversion+of+cocrystal+stoichiometry+in+grinding:+stepwise+mechanism+for+the+formation+of+a+hydrogen-bonded+cocrystal.">Control and interconversion of cocrystal stoichiometry in grinding: stepwise mechanism for the formation of a hydrogen-bonded cocrystal.</a> CrystEngComm. 11 (3), 470-481 (2009).</li><li>Kaupp, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solid-state+molecular+syntheses:+complete+reactions+without+auxiliaries+based+on+the+new+solid-state+mechanism.">Solid-state molecular syntheses: complete reactions without auxiliaries based on the new solid-state mechanism.</a> CrystEngComm. 5 (23), 117-133 (2003).</li><li>Biswal, B. P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+synthesis+of+chemically+stable+isoreticular+covalent+organic+frameworks.">Mechanochemical synthesis of chemically stable isoreticular covalent organic frameworks.</a> J Am Chem Soc. 135 (14), 5328-5331 (2013).</li><li>Garay, A. L., Pichon, A., James, S. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvent-free+synthesis+of+metal+complexes.">Solvent-free synthesis of metal complexes.</a> Chem Soc Rev. 36 (6), 846-855 (2007).</li><li>Kaupp, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemistry:+the+varied+applications+of+mechanical+bond-breaking.">Mechanochemistry: the varied applications of mechanical bond-breaking.</a> Cryst Eng Comm. 11 (3), 388-403 (2009).</li><li>Morris, R. E., James, S. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solventless+synthesis+of+zeolites.">Solventless synthesis of zeolites.</a> Angew Chem Int Ed Engl. 52 (8), 2163-2165 (2013).</li><li>Stolle, A., Szuppa, T., Leonhardt, S. E., Ondruschka, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ball+milling+in+organic+synthesis:+solutions+and+challenges.">Ball milling in organic synthesis: solutions and challenges.</a> Chem Soc Rev. 40 (5), 2317-2329 (2011).</li><li>Suryanarayana, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanical+alloying+and+milling.">Mechanical alloying and milling.</a> Prog Mater Sci. 46 (1-2), 1-184 (2001).</li><li>Wang, G. W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+organic+synthesis.">Mechanochemical organic synthesis.</a> Chem Soc Rev. 42 (18), 7668-7700 (2013).</li><li>Braga, D., Grepioni, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Reactions+between+or+within+molecular+crystals.">Reactions between or within molecular crystals.</a> Angew Chem Int Ed Engl. 43 (31), 4002-4011 (2004).</li><li>Friscic, T., Childs, S. L., Rizvi, S. A. A., Jones, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+role+of+solvent+in+mechanochemical+and+sonochemical+cocrystal+formation:+a+solubility-based+approach+for+predicting+cocrystallisation+outcome.">The role of solvent in mechanochemical and sonochemical cocrystal formation: a solubility-based approach for predicting cocrystallisation outcome.</a> Cryst Eng Comm. 11 (3), 418-426 (2009).</li><li>Fucke, K., Myz, S. A., Shakhtshneider, T. P., Boldyreva, E. V., Griesser, U. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=How+good+are+the+crystallisation+methods+for+co-crystals?+A+comparative+study+of+piroxicam.">How good are the crystallisation methods for co-crystals? A comparative study of piroxicam.</a> New J Chem. 36 (10), 1969-1977 (2012).</li><li>Bennett, T. D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Facile+mechanosynthesis+of+amorphous+zeolitic+imidazolate+frameworks.">Facile mechanosynthesis of amorphous zeolitic imidazolate frameworks.</a> J Am Chem Soc. 133 (37), 14546-14549 (2011).</li><li>Braga, D., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+preparation+of+molecular+and+supramolecular+organometallic+materials+and+coordination+networks.">Mechanochemical preparation of molecular and supramolecular organometallic materials and coordination networks.</a> Dalton Trans. (10), 1249-1263 (2006).</li><li>Yuan, W., Fri&#353;&#269;i&#263;, T., Apperley, D., James, S. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High+Reactivity+of+Metal-Organic+Frameworks+under+Grinding+Conditions:+Parallels+with+Organic+Molecular+Materials.">High Reactivity of Metal-Organic Frameworks under Grinding Conditions: Parallels with Organic Molecular Materials.</a> Angew Chem Int Ed Engl. 122 (23), 4008-4011 (2010).</li><li>Icli, B., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+of+Molecular+Nanostructures+by+Multicomponent+Condensation+Reactions+in+a+Ball+Mill.">Synthesis of Molecular Nanostructures by Multicomponent Condensation Reactions in a Ball Mill.</a> J Am Chem Soc. 131 (9), 3154-3155 (2009).</li><li>Hsu, C. -. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvent-free+synthesis+of+the+smallest+rotaxane+prepared+to+date.">Solvent-free synthesis of the smallest rotaxane prepared to date.</a> Angew Chem Int Ed Engl. 47 (39), 7475-7478 (2008).</li><li>Boldyreva, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemistry+of+inorganic+and+organic+systems:+what+is+similar,+what+is+different?.">Mechanochemistry of inorganic and organic systems: what is similar, what is different?.</a> Chem Soc Rev. 42 (18), 7719-7738 (2013).</li><li>Gracin, D., &#352;trukil, V., Fri&#353;&#269;i&#263;, T., Halasz, I., U&#382;arevi&#263;, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Laboratory+Real-Time+and+In+Situ+Monitoring+of+Mechanochemical+Milling+Reactions+by+Raman+Spectroscopy.">Laboratory Real-Time and In Situ Monitoring of Mechanochemical Milling Reactions by Raman Spectroscopy.</a> Angew Chem Int Ed Engl. 53 (24), 6193-6197 (2014).</li><li>Halasz, I., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=In+situ+and+real-time+monitoring+of+mechanochemical+milling+reactions+using+synchrotron+X-ray+diffraction.">In situ and real-time monitoring of mechanochemical milling reactions using synchrotron X-ray diffraction.</a> Nat. Protocols. 8 (9), 1718-1729 (2013).</li><li>Ma, X., Yuan, W., Bell, S. E. J., James, S. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Better+understanding+of+mechanochemical+reactions:+Raman+monitoring+reveals+surprisingly+simple+'pseudo-fluid'+model+for+a+ball+milling+reaction.">Better understanding of mechanochemical reactions: Raman monitoring reveals surprisingly simple 'pseudo-fluid' model for a ball milling reaction.</a> Chem Commun. 50 (13), 1585-1587 (2014).</li><li>Tumanov, I. A., Michalchuk, A. A. L., Politov, A., Boldyreva, E., Boldyrev, V. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Inadvertent+Liquid+Assisted+Grinding:+A+Key+to+"Dry"+Organic+Mechano-Co-Crystallisation?.">Inadvertent Liquid Assisted Grinding: A Key to "Dry" Organic Mechano-Co-Crystallisation?.</a> CrystEngComm. 19, 2830-2835 (2017).</li><li>Belenguer, A. M., Lampronti, G. I., Cruz-Cabeza, A. J., Hunter, C. A., Sanders, J. K. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solvation+and+surface+effects+on+polymorph+stabilities+at+the+nanoscale.">Solvation and surface effects on polymorph stabilities at the nanoscale.</a> Chem Sci. 7 (11), 6617-6627 (2016).</li><li>Belenguer, A. M., Friscic, T., Day, G. M., Sanders, J. K. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Solid-state+dynamic+combinatorial+chemistry:+reversibility+and+thermodynamic+product+selection+in+covalent+mechanosynthesis.">Solid-state dynamic combinatorial chemistry: reversibility and thermodynamic product selection in covalent mechanosynthesis.</a> Chem Sci. 2 (4), 696-700 (2011).</li><li>Belenguer, A. M., Lampronti, G. I., Wales, D. J., Sanders, J. K. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+Observation+of+Intermediates+in+a+Thermodynamically+Controlled+Solid-State+Dynamic+Covalent+Reaction.">Direct Observation of Intermediates in a Thermodynamically Controlled Solid-State Dynamic Covalent Reaction.</a> J Am Chem Soc. 136 (46), 16156-16166 (2014).</li><li>Evora, A. O. L., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Resolved+structures+of+two+picolinamide+polymorphs.+Investigation+of+the+dimorphic+system+behaviour+under+conditions+relevant+to+co-crystal+synthesis.">Resolved structures of two picolinamide polymorphs. Investigation of the dimorphic system behaviour under conditions relevant to co-crystal synthesis.</a> CrystEngComm. 14 (24), 8649-8657 (2012).</li><li>Trask, A. V., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Selective+polymorph+transformation+via+solvent-drop+grinding.">Selective polymorph transformation via solvent-drop grinding.</a> Chemical Communications. (7), 880 (2005).</li><li>Hasa, D., Miniussi, E., Jones, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanochemical+Synthesis+of+Multicomponent+Crystals:+One+Liquid+for+One+Polymorph?+A+Myth+to+Dispel.">Mechanochemical Synthesis of Multicomponent Crystals: One Liquid for One Polymorph? A Myth to Dispel.</a> Cryst Growth Des. 16 (8), 4582-4588 (2016).</li><li>Hunter, C. A., Anderson, H. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=What+is+cooperativity?.">What is cooperativity?.</a> Angew Chem Int Ed Engl. 48 (41), 7488-7499 (2009).</li><li>McCusker, L. B., Dreele, R. B. V., Cox, D. E., Lou&#235;r, D., Scardi, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rietveld+refinement+guidelines.">Rietveld refinement guidelines.</a> J Appl Crystallogr. 32 (1), 36-50 (1999).</li><li>Allen, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+Cambridge+Structural+Database:+a+quarter+of+a+million+crystal+structures+and+rising.">The Cambridge Structural Database: a quarter of a million crystal structures and rising.</a> Acta Crystallogr Sect B. 58 (3 Part 1), 380-388 (2002).</li><li>Gra&#382;ulis, S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Crystallography+Open+Database-an+open-access+collection+of+crystal+structures.">Crystallography Open Database-an open-access collection of crystal structures.</a> J Appl Crystallogr. 42 (4), 726-729 (2009).</li><li>Cheary, R. W., Coelho, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+fundamental+parameters+approach+to+X-ray+line-profile+fitting.">A fundamental parameters approach to X-ray line-profile fitting.</a> J Appl Crystallogr. 25 (2), 109-121 (1992).</li><li>Tumanov, I. A., Michalchuk, A. A. L., Politov, A., Boldyreva, E., Boldyrev, V. V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Inadvertent+Liquid+Assisted+Grinding:+A+Key+to+"Dry"+Organic+Mechano-Co-Crystallisation?.">Inadvertent Liquid Assisted Grinding: A Key to "Dry" Organic Mechano-Co-Crystallisation?.</a> CrystEngComm. 19, 2830-2835 (2017).</li><li>Batzdorf, L., Fischer, F., Wilke, M., Wenzel, K. J., Emmerling, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Direct+In+Situ+Investigation+of+Milling+Reactions+Using+Combined+X-ray+Diffraction+and+Raman+Spectroscopy.">Direct In Situ Investigation of Milling Reactions Using Combined X-ray Diffraction and Raman Spectroscopy.</a> Angew Chem Int Ed Engl. 54 (6), 1799-1802 (2015).</li><li>Tumanov, N., Ban, V., Poulain, A., Filinchuk, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=3D-printed+jars+for+ball-milling+experiments+monitored+in+situ+by+X-ray+powder+diffraction.">3D-printed jars for ball-milling experiments monitored in situ by X-ray powder diffraction.</a> J Appl Crystallogr. 50 (4), 994-999 (2017).</li></ol>

化学的文献大多集中在实际结果或反应机理上, 本文论述了球磨机磨削的热力学终点。从这个角度来看, 动力学研究是确定最终平衡高原的必要步骤。通过我们的动力学和最终平衡研究, 我们知道, 这里讨论的球磨机研磨反应是由热力学驱动的, 导致在给定的铣削条件下最稳定的变形成分。这也是我们第一次认识到, 实验准备方法, 如移方法和铣缸设置-为化学实验, 详细介绍和讨论。
<p class="jove_con...

化学使用手动或球磨机研磨设备已成为近年来越来越流行的一种有吸引力的和可持续的替代传统的解决方法的合成材料。1它具有吸引力, 因为它可以有效和定量地实现固体之间的反应。它是一种 "绿色" 的可持续技术, 需要很少或根本没有溶剂。铣削或手动研磨可以进行整齐, 即不加溶剂或溶剂辅助: 在后者, 称为 "液体辅助研磨" (滞后),2,3,4少量添加的液体可以加速甚至使固体之间无法化学的反应。化学方法已用于越来越多的不同的化学反应和合成的无机和有机化合物,5,6,7,8,9 ,11以及为超分子体系结构的形成, 如分子结构,12,13,14金属框架,15,16,17 , 甚至笼子18和 rotaxanes19。似乎许多过程可以在没有溶剂或以最小的 substoichiometric 量存在溶剂的情况下进行。2,3,4化学条件引起的化学合成和超分子反应所涉及的机制和驱动力是争论的主题。1,13,20,21,22,23,24
本文研究的重点是球磨机磨矿过程的最终平衡结果以及在球磨机滞后条件下的平衡溶剂的作用。事实上, 在球磨机研磨反应达到完成后, 我们在系统中所研究的两个系统中都实现了热力学平衡, 具有稳定的相组成。25影响最终平衡的因素多种多样: 球磨罐的大小和形状和材质, 球轴承的尺寸和重量和材质, 铣削频率, 温度, 溶剂的性质和浓度。这是明显的情况下, 当研磨反应的热力学结果发生了戏剧性的变化, 以响应变化的溶剂体积增加, 这可能是一个低的1µL 每200毫克总粉。25仔细和严格的实验程序必须进行测试和跟踪, 以实现从反应物和产品存储到移和混合前铣削操作的实验结果的重现精度和准确性。在铣削罐中控制或甚至监视参数是很困难的。因此, 使用机械搅拌机 (也称为振动磨), 这使得可重复和控制铣削频率和时间, 和密封的铣削罐是必不可少的。确保所有球磨机研磨反应达到平衡, 需要对实验条件进行初步的动力学研究。用于我们这里的曲线的机械搅拌机被修改了。为了防止罐子在长时间的研磨中通过发动机排气的连续流动而升温, 将砂轮机前部的安全盖封住, 并将外部安全屏放在 place.
作为第一个例子, 我们使用的系统是 bis-2-nitrophenyldisulfide (命名为1-1) 和 bis-4-chlorophenyldisulfide (命名为2-2) 之间的二硫交换反应, 存在少量的碱基催化剂 18-环5.4. 0] undec-7-烯 (dbu) 生产后, 球磨机整齐研磨 (NG) 和滞后化合物 4-氯苯基 2-硝基苯基二硫化物 (名为1-2)。26,27后者是由球磨机研磨成两个不同的型,形成一个和形式 B。对于许多不同的滞后溶剂, form是在球磨机 NG 条件下的热力学产品, 或者当没有足够的溶剂用于平衡的研磨反应时, 而form B是在球的热力学产品下获得的。研磨罐中加入足够的溶剂后, 磨机的滞后条件处于平衡状态。实际上, form a可以从form b中获得, 而窗体 b则可以从窗体 a中获得, 在球磨滞后状态下。在其他系统中, 如前所述的这种直接变换在铣削实验中已被报告,28,29 , 并且据报道, 溶剂的性质和浓度决定了在滞后条件下获得的变形。30我们公布的实验结果包括对一系列有机溶剂的铣削平衡曲线的研究。这里的平衡相组成比R = [form b]/(窗体 A+ [窗体 b]) 是针对每个实验增加的滞后溶剂量绘制的。平衡曲线的开始和曲线的清晰度被发现取决于添加到铣削罐中的溶剂的性质和摩尔量。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56824/56824fig1.jpg"> 图 1: 球磨机研磨试验的反应方案和溶剂平衡曲线的关键概念, 使用 R 值。 这些平衡曲线生动地显示出, 当球磨机研磨足够长的时间达到平衡条件时, 在产品的相组成 (y 轴) 上加入几滴溶剂 (x 轴) 的效果。图的底部对form进行了定量化, 为form b的图的顶部在定量形成的同时, 为溶剂的体积范围形成了形式a和形式 b的混合。计算图的 sigmoidal 部分。这一数字已被转载, 从补充信息在化学 Sci, 2016, 7, 6617 (Ref. 25) 的轻微变化。<a href="//cloudflare.jove.com/files/ftp_upload/56824/56824fig1large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
热力学方面是一般的, 必须适用于任何给定的铣削系统。作为一个进一步的例子来显示我们的观测的共性, 一个类似的平衡曲线也产生了第二个系统: 两个型1:1 钴晶体的茶碱 (tp) 与胺 (bzm),表 I和表二, 其中结果取决于研磨混合物中水的体积。25这些相组成与溶剂浓度平衡曲线对于研究球磨机研磨反应中纳米晶表面与溶剂分子之间的相互作用至关重要。我们的结果表明, 一些平衡曲线是非常尖锐的, 显示了 "全部或无" 的行为, 这是具有大量的吸附点的粒子的特点和结合过程的积极协同。31较浅的平衡曲线表示协同的水平较低, 并建议在平衡状态下存在第三阶段, 可能是涉及溶剂本身的非晶相。这样的铣削平衡曲线已经产生了, 没有其他系统, 我们的知识。我们相信这部分是由于固态系统对球磨滞后条件下的微小环境变化的固有敏感性。
只有当实验仔细验证他们的移技能和训练集, 如果他们完全理解 (i) 管和注射器如何工作以及 (ii) 设备选择用于提供准确和精确的溶剂体积是适合执行预期的工作。交付确切的容量溶剂可以是成功的与各种各样的设备, 这是管或注射器, 并且他们的选择可能取决于可及性, 用户偏爱和技能, 蒸汽压力使用的溶剂和意欲的应用为球磨机研磨试验。
管是商业可利用的作为空气位移或正面位移覆盖许多溶剂范围。这两种类型的管都可商用, 如手动操作或电子自动化。自动管通常是首选的, 因为他们是较少依赖于实验技能, 以能够提取或免除溶剂均匀地在给定的速度。实验必须依靠管的能力来提供准确的溶剂量。这只能发生, 如果管是准确的开始, 良好的维护, 服务和定期校准。通常情况下, 外部吸管校准服务将用水作为溶剂将管校准到 ISO 8655 标准。因此, 对于每一个有机溶剂, 实验应该通过精确的称量实验来验证它们的准确度和移的精确度。
最常用的溶剂输送设备是空气置换管, 其中一个尖端需要安装在注射器桶。他们的工作是气垫原理;活塞的向上运动在尖端产生一个部分真空, 导致液体被拉入尖端, 从活塞的一端被气垫隔开。pipetted 溶剂的汽相将开始在气垫内平衡, 蒸发的程度取决于它的蒸气压。在使用变体积管集的最小体积范围时, 预润湿是至关重要的, 因为空气空间与液体的比值和蒸发的可能性相比, 在其体积范围的顶端设置的吸管会显著增加。实验将知道这个平衡是何时实现的, 因为溶剂分将悬挂, 但从活塞的一端分离为从一个弹簧, 在末端的溶剂保持坚挺, 当吸管是保持在垂直位置超过几秒钟: 尖端内的溶剂不应下垂或滴落。空气置换管可用于两种模式;最普遍使用的是前移模式, 所有的吸气溶剂是定量配发的一个完整的运动活塞。另一种模式是反向移模式;在这种模式下, 计算出的过量的溶剂是吸气的吸管, 因此, 在定量配药后, 残留量的溶剂留在吸管尖端, 需要处置废物。反向移模式可以更适合粘性和分配非常小的溶剂量。然而, 对于高蒸气压的溶剂如二氯甲烷 (DCM) 或乙醚, 平衡在空气置换吸管不能轻易实现。在这种情况下, 正位移管或注射器更合适。
提出了在充分设计、执行和控制球磨机滞后条件下, 任何系统都可以得到平衡相组成与溶剂浓度曲线。

<table>
	<tbody>
		<tr>
			<td>Bis(2-nitrophenyl) disulfide named 1-1</td>
			<td>Aldrich</td>
			<td>215228-25G</td>
			<td>[1155-00-6] 
			(98%)</td>
		</tr>
		<tr>
			<td>Bis(4-chlorophenyl) disulfide named 2-2</td>
			<td>TCI</td>
			<td>D0360</td>
			<td>[1142-19-4] 
			(98+%)</td>
		</tr>
		<tr>
			<td>1,8-Diazabicyclo [5.4.0]undec-7-ene (dbu)</td>
			<td>Acros Organics</td>
			<td>160610250</td>
			<td>[6674-22-2] 
			(&#62;97.5 % by GC)</td>
		</tr>
		<tr>
			<td>2-nitrophenyl-4-chlorophenyl-disulfide named 1-2</td>
			<td>in house synthesis</td>
			<td></td>
			<td>Synthesised by ball mill grinding: 1:1 of 1-1 + 2-2 + 2%M dbu</td>
		</tr>
		<tr>
			<td>Form A</td>
			<td>in house synthesis</td>
			<td></td>
			<td>Polymorph of 1-2 prepared by ball mill neat grinding</td>
		</tr>
		<tr>
			<td>Form B</td>
			<td>in house synthesis</td>
			<td></td>
			<td>Polymorph of 1-2 prepared by ball mill liquid assisted grinding</td>
		</tr>
		<tr>
			<td>Formic Acid</td>
			<td>Scientific Laboratory Supplies</td>
			<td>56302-50ML</td>
			<td>[64-18-6] 
			Mass spectrometry grade</td>
		</tr>
		<tr>
			<td>Trifluoroacetic acid (TFA)</td>
			<td>ThermoFisher</td>
			<td>85183</td>
			<td>[76-05-1] 
			Reagent-Plus 99%</td>
		</tr>
		<tr>
			<td>Water (H2O)</td>
			<td>Rathburn</td>
			<td>W/0106/PB17</td>
			<td>[7732-18-5] 
			HPLC gradient analysis grade used also for HPLC analysis</td>
		</tr>
		<tr>
			<td>Acetonitrile (MeCN),</td>
			<td>Merck</td>
			<td>160610250</td>
			<td>[75-05-8] 
			Hypergrade for LCMS grade LiChrosolv used also for HPLC analysis</td>
		</tr>
		<tr>
			<td>Acetone</td>
			<td>Fisher Scientific</td>
			<td>A/0606/17</td>
			<td>[67-64-1] 
			HPLC grade</td>
		</tr>
		<tr>
			<td>Methanol (MeOH)</td>
			<td>Fisher Scientific</td>
			<td>M/4062/17</td>
			<td>[67-56-1] 
			LCMS grade</td>
		</tr>
		<tr>
			<td>Ethanol (EtOH)</td>
			<td>Sigma Aldrich</td>
			<td>15727-5L</td>
			<td>[64-17-5] 
			laboratory reagent, absolute,</td>
		</tr>
		<tr>
			<td>isopropanol (IPA)</td>
			<td>Fisher Scientific</td>
			<td>P/7508/17</td>
			<td>[67-63-0] 
			HPLC grade</td>
		</tr>
		<tr>
			<td>Tetrahydrofurane (THF)</td>
			<td>Acros Organics</td>
			<td>268290010</td>
			<td>[109-99-9] 
			For HPLC; 99%8, unstabilised</td>
		</tr>
		<tr>
			<td>Ethyl acetate (EtOAc)</td>
			<td>Fisher Scientific</td>
			<td>E/0906/15</td>
			<td>[141-78-6]</td>
		</tr>
		<tr>
			<td>Chloroform (CHCl3,)</td>
			<td>Fisher Scientific</td>
			<td>C/4966/17</td>
			<td>[67-66-3] 
			HPLC grade, stabilised with amylene</td>
		</tr>
		<tr>
			<td>Dichloromethane (DCM)</td>
			<td>Fisher Scientific</td>
			<td>D/1857/17</td>
			<td>[75-09-2] 
			HPLC grade, unstabilised</td>
		</tr>
		<tr>
			<td>Dimethylformamide (DMF)</td>
			<td>Alfa Aesar</td>
			<td>22915</td>
			<td>[68-12-2] very toxic 
			HPLC grade 99+% pure</td>
		</tr>
		<tr>
			<td>Dimethylsulfoxide (DMSO)</td>
			<td>Alfa Aesar</td>
			<td>36480</td>
			<td>[67-68-5] very toxic 
			ACS, 99.9% min</td>
		</tr>
		<tr>
			<td>Cyclohexane</td>
			<td>Fisher Scientific</td>
			<td>C/8936/15</td>
			<td>[110-82-7] 
			HPLC grade, 99.8+%</td>
		</tr>
		<tr>
			<td>Toluene</td>
			<td>Fisher Scientific Ltd</td>
			<td>T/2306/15</td>
			<td>[108-88-3] 
			HPLC grade</td>
		</tr>
		<tr>
			<td>Benzene</td>
			<td>Sigma Aldrich</td>
			<td>401765</td>
			<td>[71-43-2] 
			puriss pa reagent</td>
		</tr>
		<tr>
			<td>5 -120 mL automatic pipette</td>
			<td>Sartorius</td>
			<td>Picus eLine</td>
			<td>systematic error in specification: 
			for 120mL is &#177;0.48 mL, 
			for 60 mL is &#177;0.36 mL, 
			for 12 mL is &#177;0.24 mL</td>
		</tr>
		<tr>
			<td>VIAL screw clear 1.5ml + CAP bakelite solid screw PTFE lined for 10mm vial</td>
			<td>Jaytee Biosciences</td>
			<td>JW41110 + 
			JW43927</td>
			<td>Capped vial used for validating accuracy and precision of dispensed solvent</td>
		</tr>
		<tr>
			<td>Crystal Structural Database</td>
			<td>The Cambridge Crystallogra-phic Data Centre (CCDC)</td>
			<td>Cambridge Structural Database (CSD)</td>
			<td>Containing over 900,000 entries from x-ray and neutron diffraction analyses</td>
		</tr>
		<tr>
			<td>powder X-ray diffractometer</td>
			<td>Panalytical</td>
			<td>X-Pert PRO MPD</td>
			<td>Equipped with an X&#8217;Celerator detector with Cu K&#945; radiation</td>
		</tr>
		<tr>
			<td>powder X-ray diffractometer data Collector software</td>
			<td>Panalytical</td>
			<td>X&#8217;Pert HighScore Plus v3.0</td>
			<td>solftware package used to adquire the PXRD data</td>
		</tr>
		<tr>
			<td>Rietveld refinement software including Scherrer equation</td>
			<td>BRUKER</td>
			<td>Version 6 of TOPAS-Academic</td>
			<td>To prepare phase composition and crystal size from PXRD scans</td>
		</tr>
		<tr>
			<td>HPLC equipment</td>
			<td>Agilent</td>
			<td>HP1200 Series modular HPLC system</td>
			<td>HPLC high pressure binary pump, autosampler, Peltier type column oven with 6 &#181;L heat exchanger and Diode Array Detector with a semi-micro flow cell (1.6uL, 6mm pathlength).</td>
		</tr>
		<tr>
			<td>HPLC column</td>
			<td>Agilent</td>
			<td>1.8mm Zorbax XDB C18,</td>
			<td>(4.6mm ID &#215; 50 mm length)</td>
		</tr>
		<tr>
			<td>Ball mill grinder</td>
			<td>Retsch</td>
			<td>MM400</td>
			<td>modified: replaced safety cover for external safety screen</td>
		</tr>
		<tr>
			<td>14 mL snap closure stainless steel jars</td>
			<td>In house</td>
			<td></td>
			<td>manuctured from 316 stainless steel</td>
		</tr>
		<tr>
			<td>14 mL screw closure stainless steel jars</td>
			<td>In house</td>
			<td></td>
			<td>manuctured from 316 stainless steel - 
			contains a PTFE washer</td>
		</tr>
		<tr>
			<td>Stainless steel ball bearings:</td>
			<td>Dejay Distribution Ltd</td>
			<td>7.0 mm (1.37g)</td>
			<td>Stainless Steel Balls A.I.S.I. 420 Carbon (0.25/0.35%) &#38; Chromium (12/14%)</td>
		</tr>
		<tr>
			<td>&#34;Push a Button&#34; software</td>
			<td>Developed at Department of Chemistry</td>
			<td></td>
			<td>Written in Visual Basic. It activates an electronically controlled switch (relay).</td>
		</tr>
		<tr>
			<td>&#34;Push a Button&#34; Solenoid</td>
			<td>Magnet Schultz</td>
			<td>Type 609RP 
			12 Volt DC</td>
			<td>609RP (RP stands for) 
			R - for spring-return 
			P - for push-rod</td>
		</tr>
		<tr>
			<td>&#34;Push a Button&#34; 
			Solenoid holder</td>
			<td>Department of Chemistry</td>
			<td></td>
			<td>To hold solenoid over START button on the MM400</td>
		</tr>
		<tr>
			<td>&#34;Push a Button&#34; Relay</td>
			<td>KM Tronic</td>
			<td>USB one relay</td>
			<td>USB Relay Controller - One Channel - HyperTerminal ASCII commands. Connection to a PC&#39;s USB port using VCP (Virtual COM port).</td>
		</tr>
		<tr>
			<td>re-usable adhesive putty</td>
			<td>Bostik</td>
			<td>Blu-Tack</td>
			<td>Used to hold the jar fixed on the bench.</td>
		</tr>
	</tbody>
</table>

reliable mechanochemistry: protocols for reproducible outcomes of neat and liquid assisted ball-mill grinding experiments

球磨机磨矿的平衡结果可以在实验条件下的微小变化, 如少量的添加溶剂的存在, 显著地改变。为了性和准确地捕捉这种灵敏度, 实验需要仔细考虑每一个因素, 可以影响球磨机研磨反应的调查, 从确保研磨罐的清洁和干燥前使用, 以准确地添加起始物料的化学计量, 验证溶剂体积的传递是否准确, 以确保溶剂和粉末之间的相互作用得到充分的理解, 并在必要时添加特定浸泡时间程序。初步动力学研究是必不可少的, 以确定必要的铣削时间, 以达到平衡。只有在球磨机液体辅助磨削 (滞后) 条件下, 才能得到精细的相组成曲线作为溶剂浓度的函数。通过使用类似于这里提出的严格和仔细的程序, 这样的铣削平衡曲线可以获得几乎所有的铣削系统。我们用来证明这些过程的系统是从两个 homodimers 的摩尔混合物开始的二硫交换反应, 以获得平衡定量 heterodimer。后者是由球磨机研磨成两个不同的型,形成 A和表 B。在铣削平衡中, R = [表单 b]/(窗体 A) + [窗体 b] 的比率取决于研磨罐中溶剂的性质和浓度。

该协议始终由实验验证他或她的移技能和检查的质量和性能的管或注射器使用。这是最好的执行训练集对移准确体积的具体溶剂, 打算用于球磨机研磨实验。通过称重检查验证了配发卷的准确性, 并重复此验证, 直到达到所需的精确度和精确度。对于用于球磨机研磨试验的每种溶剂都必须进行验证。图 5显示了用乙腈准确移的验证示例。
<p class="jove_...

Watch this Scientific Journal Video about Reliable Mechanochemistry: Protocols for Reproducible Outcomes of Neat and Liquid Assisted Ball-mill Grinding Experiments at JoVE.com

Reliable Mechanochemistry: Protocols for Reproducible Outcomes of Neat and Liquid Assisted Ball-mill Grinding Experiments

在铣削条件下, 我们给出了在固态系统中, 作为溶剂浓度函数的相组成的实验平衡曲线的详细步骤。

可靠的化学: 整洁和液体辅助球磨机研磨试验的可再生结果协议

The equilibrium outcomes of ball mill grinding can dramatically change as a function of even tiny variations in the experimental conditions such as the ...

Research

JoVE Journal

Chemistry

Microwave-assisted Functionalization of Poly(ethylene glycol) and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation

Microwave-assisted Functionalization of Polyethylene glycol and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation

保利的微波辅助功能化（乙二醇）和On-树脂链聚合反应，并形成水凝胶的肽使用

One of the main benefits to using poly(ethylene glycol) (PEG) macromers in hydrogel formation is synthetic versatility. The ability to draw from a large ...

科研

化学

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

Conducting Miller-Urey Experiments

在进行米勒 - 尤列实验

In 1953, Stanley Miller reported the production of biomolecules from simple gaseous starting materials, using an apparatus constructed to simulate the ...

Isolation and Preparation of Bacterial Cell Walls for Compositional Analysis by Ultra Performance Liquid Chromatography

通过超性能液相色谱对细菌细胞壁进行隔离和制备，进行组成分析

The bacterial cell wall is critical for the determination of cell shape during growth and division, and maintains the mechanical integrity of cells in the ...

Post Column Derivatization Using Reaction Flow High Performance Liquid Chromatography Columns

柱后衍生用反应流高效液相色谱柱

A protocol for the use of reaction flow high performance liquid chromatography columns for methods employing post column derivatization (PCD) is ...

CN-GELFrEE - Clear Native Gel-eluted Liquid Fraction Entrapment Electrophoresis

CN-GELFrEE  - 透明天然凝胶洗脱液体馏分偷天陷阱电泳

Protein complexes perform an array of crucial cellular functions. Elucidating their non-covalent interactions and dynamics is paramount for understanding ...

A Straightforward Method for Glucosinolate Extraction and Analysis with High-pressure Liquid Chromatography (HPLC)

A Straightforward Method for Glucosinolate Extraction and Analysis with High-pressure Liquid Chromatography HPLC

简捷方法对硫甙的提取与分析用高压液相色谱法（HPLC）

Glucosinolates are a well-studied and highly diverse class of natural plant compounds. They play important roles in plant resistance, rapeseed oil ...

Liquid-cell Transmission Electron Microscopy for Tracking Self-assembly of Nanoparticles

用于跟踪纳米粒子自组装的液体细胞透射电子显微镜

Drying a nanoparticle dispersion is a versatile way to create self-assembled structures of nanoparticles, but the mechanism of this process is not fully ...

A Convenient Method for Extraction and Analysis with High-Pressure Liquid Chromatography of Catecholamine Neurotransmitters and Their Metabolites

用高压液相色谱法提取和分析儿茶酚胺神经递质及其代谢物的简便方法

The extraction and analysis of catecholamine neurotransmitters in biological fluids is of great importance in assessing nervous system function and ...