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Open Rotaxane Surgery: What Molecular Editing Can Offer to Supramolecular Chemistry?
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-27 DOI: 10.1002/cplu.202500038
Jędrzej P Perdek, Rafał A Grzelczak, Bartosz Szyszko

The skeletal editing approach represents a paradigm shift in organic synthesis by directly targeting the molecular skeleton instead of relying on often long and complicated series of organic transformations. Recent advancements in nitrogen atom deletion reactions have enabled unprecedented late-stage, precise modifications of bioactive compounds and complex natural products, influencing a seemingly distant field such as supramolecular chemistry. In a recent contribution, the Leigh group demonstrated the extrusion of a nitrogen atom from an axle of a [2]rotaxane, extending the applicability of molecular editing to complex, mechanically interlocked architectures. This highlight seeks to examine the significance of the skeletal editing method in supramolecular chemistry, address its challenges, and offer an outlook on future directions in this emerging field.

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引用次数: 0
Computational Insights into the Mechanism of Lewis Acid-Catalyzed Alkene-Aldehyde Coupling.
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-24 DOI: 10.1002/cplu.202400751
Ricardo Meyrelles, Bogdan R Brutiu, Boris Maryasin

The Lewis acid-catalyzed coupling of alkenes and aldehydes presents a modern, versatile synthetic alternative to classical carbonyl addition chemistry, offering exceptional regio- and stereoselectivity. In this work, we present a comprehensive computational investigation into the reaction mechanism of this transformation. Our findings confirm the occurrence of an enantioselective transannular [1,5]-hydride shift step and demonstrate that the enantioselectivity of the reaction arises predominantly from steric clashes between functional groups in the cyclization step. Combining computational and experimental results, we establish that the Lewis acid catalyst facilitates the initial C-O coupling step between the alkene and the activated aldehyde. Investigations into systems with longer alkyl chains reveal that while they follow a similar mechanistic pathway, cyclization becomes kinetically hindered, preventing the reaction from proceeding. These insights illuminate the factors governing reaction outcomes and limitations, paving the way for future developments in this area.

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引用次数: 0
Confined Growth by Self-Combustion of a Cu-Based Nanophase into Mesostructured Acid Supports for DME Production from CO2.
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-23 DOI: 10.1002/cplu.202400760
Fausto Secci, Valentina Mameli, Marco Sanna Angotzi, Luciano Atzori, Lorenza Piroddi, Nicola Pinna, Mauro Mureddu, Carla Cannas

This work deals with the design of nanocomposite hydrogenation-dehydration bifunctional catalysts for the one-pot conversion of CO2 to dimethyl ether (DME), focusing on obtaining a high and homogeneous dispersion of a Cu-based CO2 hydrogenation phase into the pores of mesostructured supports. Particularly, three aluminosilicate mesostructured acid catalysts with catalytic activity towards methanol dehydration and featuring different porous structures (Al-MCM-41, Al-SBA-15, Al-SBA-16) were synthesized and used as supports to host a CuO/ZnO/ZrO2 (CZZ) CO2 hydrogenation catalyst for methanol synthesis. The use of a mesostructured support allows to maximize the exposed surface of the CO2 reduction function by nanostructuring it through its confinement within the mesochannels, thus obtaining nanocomposite bifunctional catalysts with an ultra-small hydrogenation nanophase. The nanocomposites were obtained using an impregnation strategy combined with a self-combustion reaction, allowing to incorporate the CO2 reduction phase inside the mesopores. In all cases, the characterization shows that the hydrogenation phase species are highly and homogeneously dispersed into the supports as either small nanoparticles or as a nanolayer. The as-obtained nanocomposites were tested for their catalytic activity and the results discussed taking into account the structural, textural, and acidic properties of the supports and nanocomposites.

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引用次数: 0
Combining Ionic Groups with Methallyl Dichloride Coupling Delivers New Pathways to Ionic/Non-Ionic Hybrid Detergents.
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-23 DOI: 10.1002/cplu.202400753
Jan-Simon Behnke, Naomi Zink, Carl J M Schoelzel, Inga Beimdick, Leonhard Hagen Urner, Virginia Wycisk

Strategies for combining ionic and non-ionic functional groups are important for altering detergent properties and exploring new chemical spaces within the detergentome. Previous synthesis protocols for ionic/non-ionic hybrid detergents require asymmetric detergent precursors with independently addressable hydroxyl groups that can be decorated with charged groups. However, preparation of ionic/non-ionic headgroups can be tedious in terms of required synthesis steps and resource consumption. To address this challenge, here we explore if we can fuse ionic and non-ionic groups directly with methallyl dichloride in the first step of detergent synthesis. While this delivers a simplified synthesis strategy for ionic/non-ionic headgroups, we find functional groups for which the modification of asymmetric detergent precursors is still the only viable option to obtain related ionic/non-ionic hybrid detergents. Because previously established debenzylation conditions limit overall yields for asymmetric detergent precursors, here we explore optimization strategies, including silyl protecting groups, ozonolysis-hydrolysis, and hydrogenolysis. In summary, we establish a new synthesis route to ionic/non-ionic hybrid detergents, deliver an optimized debenzylation protocol and obtain building blocks for bridged detergent architectures. Our findings facilitate the modular synthesis of hybrid detergents and expand the chemical space of detergents.

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引用次数: 0
The Catalytic Activity of Polyaniline In Hydrogenation Reactions with Molecular Hydrogen. 聚苯胺在分子氢加氢反应中的催化活性。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-17 DOI: 10.1002/cplu.202400674
Igor B Bychko, Yaroslav I Kurys, Olena O Pariiska, Olga Z Didenko, Denys O Mazur, Peter E Strizhak, Vyacheslav G Koshechko, Vitaly D Pohodenko

This study unveils a novel property of polyaniline by establishing its catalytic activity in heterogeneous hydrogenation with molecular hydrogen. Polyaniline was activated by heat-treating at different temperatures in a hydrogen atmosphere. The sample treated at 300 °C exhibited the highest catalytic activity for ethylene hydrogenation in the gas phase at atmospheric pressure and for p-nitrotoluene or α-methylstyrene hydrogenation in the liquid phase. XRD, HRTEM, Raman, XPS, UV-VIS, FTIR, and elemental analysis data as well as electrochemical study indicate that catalytic activity is associated with the conjugated structure of undoped emeraldine base, whereas the polymer cross-linking or an increase in chlorine residues correlates with catalyst deactivation. These results pave the way to use conducting polymers as catalysts for hydrogenation with molecular hydrogen, opening new avenues for their application in catalysis.

本研究通过建立聚苯胺在分子氢非均相加氢反应中的催化活性,揭示了聚苯胺的一种新性质。聚苯胺在氢气气氛中通过不同温度的热处理得到活化。经300℃处理的样品在常压下气相乙烯加氢和液相对硝基甲苯或α-甲基苯乙烯加氢的催化活性最高。XRD、HRTEM、Raman、XPS、UV-VIS、FTIR和元素分析数据以及电化学研究表明,催化活性与未掺杂的祖母绿碱的共轭结构有关,而聚合物交联或氯残基的增加与催化剂失活有关。这些结果为利用导电聚合物作为分子氢加氢催化剂铺平了道路,为其在催化领域的应用开辟了新的途径。
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引用次数: 0
Kinetic Separation of Butane Isomers Using a Formate Metal-Organic Framework. 用甲酸金属-有机骨架动力学分离丁烷异构体。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-16 DOI: 10.1002/cplu.202400756
Yi-Peng Liu, Jing-Hong Li, Zi-Nan Chen, Wei Xue, Hao-Long Zhou, Rui-Biao Lin, Xiao-Ming Chen

n-butane (n-C4H10) and isobutane (i-C4H10) are important raw materials in chemical industry. The separation of the two hydrocarbon isomers via distillation is challenging and energy-consuming. Herein we report the adsorption behavior of a microporous cobalt formate framework [Co3(HCOO)6] for potential kinetic separation of butane isomers. Under ambient condition, [Co3(HCOO)6] shows near adsorption capacity for n-C4H10 (1.77 mmol g-1) and i-C4H10 (1.36 mmol g-1) with different adsorption kinetics. Study on the adsorption kinetics for butane indicates that the smaller isomer is adsorbed at a higher diffusion rate, resulting in a high kinetic selectivity of 193 for n-C4H10/i-C4H10 separation. Analyses of adsorption kinetics and breakthrough experiment have validated the separation potential of [Co3(HCOO)6] for butane purification.

正丁烷(n-C4H10)和异丁烷(i-C4H10)是重要的化工原料。通过蒸馏分离这两种烃类异构体是具有挑战性和耗能的。本文报道了微孔甲酸钴骨架[Co3(HCOO)6]对丁烷异构体潜在动力学分离的吸附行为。常温条件下,[Co3(HCOO)6]对n-C4H10 (1.77 mmol g-1)和i-C4H10 (1.36 mmol g-1)的吸附量相近,但吸附动力学不同。对丁烷的吸附动力学研究表明,较小的同分异构体以较高的扩散速率吸附,对n-C4H10/i-C4H10的分离具有较高的动力学选择性(193)。吸附动力学分析和突破性实验验证了[Co3(HCOO)6]纯化丁烷的分离潜力。
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引用次数: 0
A Review on Sustainable Slow-Release N, P, K Fertilizer Hydrogels for Smart Agriculture. 智能农业用可持续缓释氮、磷、钾肥料水凝胶研究进展
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-16 DOI: 10.1002/cplu.202400643
Manas Mandal, Roop Singh Lodhi, Shivangi Chourasia, Subhasis Das, Paramita Das

The agricultural sector of any country plays a pivotal role in its economy. Irrigation and the provision of appropriate nutrient levels in soil are essential for optimizing plant growth and enhancing crop productivity. To support the increasing need for food due to the growing population worldwide, synthetic fertilizers have been widely used in the agricultural sector. These fertilizers could readily dissolve in the irrigation water or soil moisture, causing excessive release of the nutrients that plants cannot uptake from the root zone. The excess nutrients in the soil further harm the environment via surface run-off, leaching, and volatilization. Thus, materials with high water absorption and retention capacity, and precise control over the prolonged fertilizer release offer a potential solution to address these issues. To meet these requirements, the development of slow-release fertilizer hydrogels (SRFHs) represents a promising approach. SRFHs serve as natural agrochemicals to enhance crop growth and yield through controlled and self-sustained delivery of water and nutrients. This review provides a comprehensive study on the recent advancements in SRFHs, including their preparation methods, properties, slow-release behavior, and applications in smart agriculture. The response of soil microbial diversity to slow-release fertilizers is briefly discussed, and the future potential of SRFHs is highlighted herein.

任何国家的农业部门在其经济中都起着举足轻重的作用。灌溉和在土壤中提供适当的营养水平对于优化植物生长和提高作物生产力至关重要。由于全球人口不断增长,为了满足日益增长的粮食需求,合成肥料已广泛用于农业部门。这些肥料很容易溶解在灌溉水或土壤水分中,导致植物无法从根区吸收的养分过量释放。土壤中过量的养分通过地表径流、淋失和挥发进一步危害环境。因此,具有高吸水性和保持能力的材料,以及对肥料长期释放的精确控制,为解决这些问题提供了一个潜在的解决方案。为了满足这些要求,开发缓释肥料水凝胶(SRFHs)是一种很有前途的方法。SRFHs作为天然农用化学品,通过控制和自我维持的水和养分输送来促进作物生长和产量。本文就SRFHs的制备方法、性质、缓释行为及其在智能农业中的应用等方面的研究进展进行了综述。本文简要讨论了土壤微生物多样性对缓释肥料的响应,并强调了缓释肥料的发展潜力。
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引用次数: 0
Impact of Fluorination on Membrane-Protein Stabilization and Extraction by Lactobionamide Detergents. 氟化对膜蛋白稳定及乳生物酰胺洗涤剂提取的影响。
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/cplu.202400740
Damien Cornut, Marine Soulié, Pierre Guillet, Kenechi Kanayo Onyia, Florian Mahler, Sandro Keller, Alexis Moreno, Grégory Durand

We report the synthesis of a series of detergents with a lactobionamide polar head group and a tail containing four to seven perfluorinated carbon atoms. Critical micellar concentrations (CMCs) were determined using isothermal titration calorimetry (ITC) and surface tension (SFT) measurements, showing a progressive decrease from 27 mM to about 0.2 mM across the series. While the detergent with the longest fluorinated chain exhibited poor water solubility, the other three derivatives were freely soluble. Dynamic light scattering (DLS) measurements indicated an increase in hydrodynamic diameter with chain length, from 5 nm to 17 nm for the soluble derivatives. We evaluated these detergents for extraction and stabilization of two model membrane proteins, the human adenosine A2A receptor (A2AR) and the Bacillus subtilis multidrug resistance ABC transporter BmrA. The perfluorohexyl derivative demonstrated strong solubilization capacity, while the perfluoro-pentyl derivative was more effective for stabilization. The lack of a clear correlation between fluoroalkyl chain length and solubilizing or stabilizing efficacy highlights the importance of screening diverse detergents for membrane-protein studies.

我们报道了一系列具有乳生物酰胺极性头基团和尾部含有4至7个全氟碳原子的洗涤剂的合成。临界胶束浓度(cmc)采用等温滴定量热法(ITC)和表面张力(SFT)测量,显示出从27 mM到0.2 mM在整个系列中逐渐下降。氟化链最长的洗涤剂水溶性较差,而其他三种衍生物均可自由溶解。动态光散射(DLS)测量表明,水溶性衍生物的水动力直径随着链长的增加,从5 nm增加到17 nm。我们评估了这些洗涤剂提取和稳定两种模型膜蛋白,人腺苷A2A受体(A2AR)和枯草芽孢杆菌多药耐药ABC转运体BmrA的效果。全氟己基衍生物具有较强的增溶能力,而全氟戊基衍生物具有较好的稳定作用。氟烷基链长度与增溶或稳定功效之间缺乏明确的相关性,这突出了筛选不同洗涤剂用于膜蛋白研究的重要性。
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引用次数: 0
Front Cover: A New Biphenol-bis(polyazacyclophane) Receptor with Unusual Photophysical Properties Towards Zn2+ (ChemPlusChem 1/2025)
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/cplu.202580101
Dr. Luca Mancini, Dr. Mario Inclán, Dr. Daniele Paderni, Prof. Luca Giorgi, Prof. Mauro Formica, Prof. Enrique García-España, Prof. Vieri Fusi.

The front cover image depicts a new ditopic fluorescent receptor with an unusual luminescent behaviour: the emission is turned ON in the free ligand and, when interacting with zinc cations, the fluorescence is turned OFF. More details can be found in the Research Article by Mario Inclán, Enrique García-España, Vieri Fusi, and co-workers (DOI: 10.1002/cplu.202400342).

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引用次数: 0
The Dual-Role of Benzothiadiazole Fluorophores for Enabling Electrofluorochromic and Electrochromic Devices
IF 3 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2025-01-15 DOI: 10.1002/cplu.202580102
Mohan Raj Anthony Raj, Chengzhang Yao, Gokul Balakrishnan Muthuperumal, Lei Hu, Alexandre Malinge, Mathieu Frémont, Coralie Cambe, Orlando Ortiz, Sacha Porlier, W. G. Skene

The cover feature shows the photoemission of a fluorophore as a thin film. Its fluorescence is quenched upon electrochemically forming its blue colored radical cation, illustrating its role for enabling a combined electrochromic and electrofluorochromic device. More details can be found in the Research Article by William G. Skene and co-workers (DOI: 10.1002/cplu.202400667).

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引用次数: 0
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