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Coordination polymers containing dimeric Cu2X2 and polymeric (CuI)n clusters linked by unsymmetrical isomeric pyridine-benzimidazole linkers: modulating photophysical properties by mechanical stimuli† 含二聚体Cu2X2和由不对称异构体吡啶-苯并咪唑连接的聚合物(CuI)n簇的配位聚合物:通过机械刺激调节光物理性质
Pub Date : 2024-11-05 DOI: 10.1039/D4MR00071D
Prantik Dutta, Abhijit Garai and Kumar Biradha

Two rigid unsymmetrical linkers, 4-PBI and 3-PBI, have been successfully employed to synthesize three CuX cluster-based coordination polymers (CPs). The complexation reaction of 4-PBI with CuI and CuBr resulted in isostructural crystalline CP1 and CP2, respectively, containing Cu2X2 clusters. On the other hand, the isomeric 3-PBI with CuI resulted in crystalline CP3 containing a one-dimensional polymeric (CuI)n cluster. Furthermore, the mechanochromism of the CPs has been examined using DRS, solid state PL, FT-IR and Raman spectroscopy. CP1 and CP2 exhibited mechanochromism as their colours changed from reddish brown to orangish yellow upon grinding. The pressure induced local distortion around the flexible dimeric cores of CP1 and CP2 was responsible for the resultant mechanochromism. The presence of a polymeric CuI cluster with μ3-bridging I atoms within the 2D layer of CP3 renders it rigid, thereby hampering its ability to display mechanochromism.

4-PBI和3-PBI两种刚性不对称连接剂成功地合成了三种CuX簇基配位聚合物(CPs)。4-PBI与CuI和cur的络合反应分别生成了含有Cu2X2簇的CP1和CP2等结构晶体。另一方面,3-PBI与CuI的同分异构体形成了含有一维聚合物(CuI)n簇的结晶CP3。此外,利用DRS、固态PL、FT-IR和拉曼光谱对CPs的机械显色性进行了研究。CP1和CP2表现出机械致色性,研磨后颜色由红棕色变为橙黄色。压力诱导CP1和CP2柔性二聚体核心周围的局部扭曲是导致机械变色的原因。在CP3的二维层中存在具有μ3桥接I原子的聚合物CuI簇,使其具有刚性,从而阻碍了其显示机械变色的能力。
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引用次数: 0
Shaking up conjugates between chitosan and aldehydes via mechanochemistry† 壳聚糖和醛之间的偶联物的机械化学研究
Pub Date : 2024-11-05 DOI: 10.1039/D4MR00110A
Casper Van Poucke, Sven Mangelinckx and Christian V. Stevens

A solid-state mechanochemical protocol to synthesize Schiff base and N-alkyl chitosan derivatives is described. The transition from a liquid reaction medium to a solid-state reaction allowed for a more efficient conjugation between the added hydrophobic aldehydes and hydrophilic chitosan by circumventing the generally observed solubility mismatch. Furthermore, for the reductive amination, the utilization of NaBH4 was facilitated instead of NaCNBH3. The overall sustainable character of the reaction was compared to other solution-based methods via the calculation of the RME and PMI green metrics.

介绍了一种固态机械化学方法合成希夫碱和n -烷基壳聚糖衍生物。从液体反应介质到固态反应的转变允许添加的疏水醛和亲水壳聚糖之间通过绕过通常观察到的溶解度失配而更有效地结合。此外,对于还原胺化,NaBH4取代NaCNBH3更容易被利用。通过计算RME和PMI绿色指标,将反应的整体可持续性与其他基于解决方案的方法进行了比较。
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引用次数: 0
Efficient racemization of the pharmaceutical compound Levetiracetam using solvent-free mechanochemistry† 用无溶剂机械化学研究药物化合物左乙拉西坦的高效消旋作用
Pub Date : 2024-10-31 DOI: 10.1039/D4MR00103F
Chrystal Lopes, Lucia Casali, Franziska Emmerling, Tom Leyssens, Valérie Dupray, Clement Brandel and Yohann Cartigny

We present the racemization of an active pharmaceutical ingredient Levetiracetam using a novel approach. We demonstrate the design of a 100% solvent-free process that proceeds by high energy milling inside a regular mixer mill. The kinetics of the racemization process is drastically improved compared to the solution-based approach and illustrates the tremendous potential of mechanochemistry. In this study, we highlight the importance of mixing efficiency regarding data reproducibility, and we show, in particular, that water contamination has a negative impact on the reaction rate. Moreover, in situ X-ray diffraction gives us first insights into the mechanisms involved in the solid state during the mechanochemical racemization process.

我们提出了一种活性药物成分左乙拉西坦的消旋化使用一种新的方法。我们演示了100%无溶剂工艺的设计,该工艺通过在普通混合机内进行高能磨粉。与基于溶液的方法相比,外消旋过程的动力学得到了极大的改善,并说明了机械化学的巨大潜力。在本研究中,我们强调了混合效率对数据再现性的重要性,并且我们特别表明,水污染对反应速率有负面影响。此外,原位x射线衍射使我们首次了解了机械化学外消旋过程中涉及固态的机制。
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引用次数: 0
Eco-friendly anaerobic oxidation of aryl diazo esters with heterocyclic N-oxide under ball milling: synthesis of 1,2-dicarbonyl systems† 杂环n -氧化物在球磨下对芳基重氮酯的生态友好厌氧氧化:1,2-二羰基体系的合成
Pub Date : 2024-10-25 DOI: 10.1039/D4MR00097H
Souvik Guha, Subhabrata Sen and Ludovic Gremaud

Herein we report anaerobic oxidation of metal carbenoids generated from aryl diazo esters under ball milling with heterocyclic N-oxide in the presence of catalytic copper(I) to afford 1,2-dicarbonyls in excellent yield. Efficiently progressing across a diverse spectrum of substrates, the reaction demonstrates exceptional tolerance to a variety of functional groups, under mild reaction conditions, at low catalyst loading and minimum volume of solvent as a Liquid-Assisted Grinding (LAG) auxiliary thereby demonstrating a practical strategy to generate these molecules.

本文报道了在催化铜(I)存在下,由芳基重氮酯和杂环n -氧化物在球磨条件下厌氧氧化产生的金属类羰基,以获得高收率的1,2-二羰基。该反应在不同的底物光谱上有效地进行,在温和的反应条件下,在低催化剂负载和最小体积的溶剂作为液体辅助研磨(LAG)辅助下,对各种官能团表现出优异的耐受性,从而证明了生成这些分子的实用策略。
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引用次数: 0
Homogenization offers access to quinoxalines in minutes: a solvent-free, catalyst-free protocol with a near-zero E-factor† 均质可在几分钟内获得喹诺啉:无溶剂,无催化剂,e因子†接近零的协议
Pub Date : 2024-10-17 DOI: 10.1039/D4MR00100A
Abboy Chatterjee, Didreekshya Mahanta, Shamima Hussain, Amrita Chatterjee and Mainak Banerjee

A reagent-free, catalyst-free, sustainable methodology was developed for fast and effortless synthesis of quinoxalines by mixing and homogenizing the substrates in a mini cell homogenizer. The mechanochemical agitation between several aromatic (and heteromatic) 1,2-diamines and various 1,2-dicarbonyl compounds with stainless steel balls in simple polypropylene vials at 4000 rpm afforded the corresponding quinoxalines and pyrido[2,3-b]pyrazines via cyclocondensation within a few minutes mostly in quantitative yields. The use of an equimolar ratio of substrates and complete conversion ensured quick access to quinoxalines in a sufficiently pure form offering the additional advantages of a work-up free and purification-free approach. As eliminated water molecules in the process do not contribute to waste, the E-factor of the method is practically zero.

通过在微型细胞均质机中混合和均质,开发了一种无试剂、无催化剂、可持续的方法,可以快速、轻松地合成喹诺啉类药物。在简单的聚丙烯小瓶中,以4000转/分的速度,用不锈钢球搅拌几种芳香(和杂杂)1,2-二胺和各种1,2-二羰基化合物,在几分钟内通过环缩合反应得到相应的喹诺啉类和吡啶[2,3-b]吡嗪类化合物。使用等摩尔比例的底物和完全转化确保了以足够纯的形式快速获得喹诺啉,提供了免加工和免纯化方法的额外优势。由于过程中消除的水分子不会造成浪费,因此该方法的e因子几乎为零。
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引用次数: 0
A new planetary ball mill device with adjustable speed ratio for enhanced mechanochemical processes† 一种新型的行星球磨机装置,具有可调的速比,用于增强机械化学过程
Pub Date : 2024-10-15 DOI: 10.1039/D4MR00069B
Frank Yntema, Cameron Webster and Emmanouil Broumidis

In this paper, we introduce a novel planetary ball mill device featuring an interchangeable speed ratio, allowing users to manually adjust this parameter to suit the needs of each reaction. The device's modular design offers unprecedented control over the kinetic energy input, enabling enhanced reaction efficiency, selectivity, and precision.

在本文中,我们介绍了一种新颖的行星球磨机装置,具有可互换的速比,允许用户手动调整该参数以适应每种反应的需要。该设备的模块化设计对动能输入提供了前所未有的控制,从而提高了反应效率、选择性和精度。
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引用次数: 0
Naloxone-initiated mechanochemical synthesis of poly(lactic acid)† 纳洛酮引发聚乳酸的机械化学合成
Pub Date : 2024-10-08 DOI: 10.1039/D4MR00046C
Mohammad A. Ebqa'ai, Sandun Bogahawaththa Kasthuri Dias, Andrew J. Kassick, Saadyah Averick and Toby L. Nelson

A mechanochemical approach was utilized for the synthesis of naloxone covalently linked poly(lactic acid) and nanoparticles. This preparation was achieved using lactide as a monomer in anionic ring opening polymerization, naloxone as a drug initiator, and CHCl3 to perform liquid-assisted grinding. This process resulted in the direct preparation of a naloxone nanoparticle with a drug loading of ∼8.3% w/w and nanoparticles around 600 nm. These findings underscore the promise of mechanochemistry in developing drug delivery systems.

采用机械化学方法合成纳洛酮共价聚乳酸和纳米颗粒。该制备以丙交酯为单体进行阴离子开环聚合,纳洛酮为药物引发剂,CHCl3进行液体辅助研磨。该工艺直接制备了纳洛酮纳米颗粒,其载药量为~ 8.3% w/w,纳米颗粒约为600 nm。这些发现强调了机械化学在开发药物输送系统方面的前景。
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引用次数: 0
A method to predict binary eutectic mixtures for mechanochemical syntheses and cocrystallizations† 机械化学合成和共晶二元共晶混合物的预测方法
Pub Date : 2024-10-08 DOI: 10.1039/D4MR00080C
Michele Prencipe, Paolo P. Mazzeo and Alessia Bacchi

The prediction of the phase behaviour of a mixture of solid components when they come into contact is of high interest in fast growing research fields such as mechanochemistry and deep eutectic solvents (DESs). This paper provides a friendly predictive tool (PoEM, i.e. Predictor of Eutectic Mixtures), along with some guidelines and quantitative references, to quickly estimate the variation in the melting point due to the mixture of reactants for a mechanochemical process. An empirical model that estimates the ideal eutectic point and includes deviation from ideality based on intermolecular interactions is presented here, allowing for the design of synthetic procedures for solvent-less cocrystallization processes. PoEM calculations are validated by comparing the prediction with experimental behaviour of a number of mixtures with a low melting eutectic mixture. Finally, as a working example we consider how to identify coformers for the synthesis of a cocrystal containing thymol such that the cocrystallization would proceed through the formation of a metastable liquid phase.

在机械化学和深共晶溶剂(DESs)等快速发展的研究领域中,预测固体组分混合物接触时的相行为具有很高的兴趣。本文提供了一个友好的预测工具(PoEM,即共晶混合物预测器),以及一些指导方针和定量参考,以快速估计机械化学过程中反应物混合引起的熔点变化。本文提出了一个经验模型,该模型估计理想共晶点,包括基于分子间相互作用的理想偏差,允许设计无溶剂共结晶过程的合成程序。通过将预测结果与低熔点共晶混合物的实验行为进行比较,验证了PoEM计算结果。最后,作为一个工作实例,我们考虑如何鉴定合成含有百里香酚的共晶的共晶构象,使共晶将通过亚稳液相的形成进行。
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引用次数: 0
Cathode properties of a controlled crystallinity nano-Li1.2Cr0.4Mn0.4O2 cathode for lithium ion batteries† 锂离子电池用可控结晶度纳米li1.2 cr0.4 mn0.4 o2阴极性能研究
Pub Date : 2024-10-08 DOI: 10.1039/D4MR00051J
Ayuko Kitajou, Shohei Matsuda, Koji Ohara, Kazutaka Ikeda and Shunsuke Muto

The milled-Li1.2Cr0.4Mn0.4O2 (milled-LCMO) cathode, a promising material for next-generation Li ion batteries, is prepared by dry ball-milling of layered rocksalt-type Li1.2Cr0.4Mn0.4O2 (layered-LCMO) obtained by solid-state synthesis. Despite undergoing ball-milling treatment, resulting in separation into Cr-rich and Mn-rich phases along with Li2O, milled-LCMO still exhibited a reversible capacity of 277 mA h g−1 at a rate of 16 mA g−1. However, it was also revealed that its cyclability was poor due to the contribution of oxygen redox in the charging process. On the other hand, layered-LCMO exhibited better cyclability because charge and discharge reactions proceeded only through the Cr redox. The thermally treated Li1.2Cr0.4Mn0.4O2 was prepared as a cathode material that combines the favorable properties of these two materials. In fact, each thermally treated sample showed a larger reversible capacity than the layered-LCMO obtained by the solid-phase method, and the cyclability recovered as the heat treatment temperature increased.

将固态合成的层状岩盐型Li1.2Cr0.4Mn0.4O2(层状lcmo)用干球磨法制备了具有广阔前景的下一代锂离子电池正极材料——磨态Li1.2Cr0.4Mn0.4O2 (miled - lcmo)。尽管经过球磨处理,使其与Li2O分离为富cr相和富mn相,但磨后的lcmo仍具有277 mA h g−1的可逆容量,速率为16 mA g−1。然而,由于充电过程中氧氧化还原的影响,其可循环性较差。另一方面,层状lcmo表现出更好的循环性,因为充放电反应仅通过Cr氧化还原进行。将热处理后的Li1.2Cr0.4Mn0.4O2作为正极材料,结合了这两种材料的优良性能。事实上,每个热处理样品都比固相法得到的分层lcmo表现出更大的可逆容量,并且随着热处理温度的升高,循环性恢复。
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引用次数: 0
Vortex mediated fabrication of 2D antimonene sheets from antimony powder† 涡流介导的锑粉二维锑片†制备工艺
Pub Date : 2024-09-26 DOI: 10.1039/D4MR00058G
Fayed Abdullah Alrashaidi, Soraya Rahpeima, Xuan Luo, Kasturi Vimalanathan, Abdulrahman S. Alotabi, Thaar Alharbi, Xianjue Chen, Dechao Chen, Youhong Tang, Christopher Gibson, Nadim Darwish, Qin Li and Colin L. Raston

Antimony powder is transformed into 2D antimonene in a vortex fluidic device (VFD) at ambient conditions, depending on the choice of solvent (optimised as a 1 : 1 mixture of isopropyl alcohol and dimethylformamide) and the operating parameters of the microfluidic platform which houses a rapidly rotating quartz tube inclined at +45°. It is hypothesised that the Coriolis force from the hemispherical base of the tube, as typhoon like high-shear topological fluid flow down to submicron dimensions, generates localised heating at the quartz interface. This melts the antimony powder (m.p. 630.6 °C) in situ which crystallizes in the β-phase, with semi-conducting antimonene a few layers thick, and demonstrating novel photoluminescence.

在涡流流体设备(VFD)中,锑粉在环境条件下转化为二维锑烯,这取决于溶剂的选择(优化为异丙醇和二甲基甲酰胺 1 : 1 的混合物)和微流体平台的操作参数,微流体平台包含一个快速旋转的倾斜度为 +45° 的石英管。据推测,来自石英管半球形底部的科里奥利力,作为台风般的高剪切拓扑流体流向亚微米尺寸,在石英界面产生局部加热。锑粉末(熔点 630.6 °C)因此在原位熔化,并结晶成 β 相,形成几层厚的半导电锑,并发出新颖的光致发光。
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引用次数: 0
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RSC Mechanochemistry
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