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Front Cover: On the Use of Solomon Echoes in 27Al NMR Studies of Complex Aluminium Hydrides (ChemistryOpen 1/2024) 封面:关于在复杂氢化铝的 27Al NMR 研究中使用所罗门回波(ChemistryOpen 1/2024)
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-11 DOI: 10.1002/open.202300294
Dr. Bodo Zibrowius, Dr. Michael Fischer

The Front Cover shows the static solid-state 27Al NMR spectrum of KAlH4 in front of the crystal structure of this material. The spectrum exhibits the typical first-order quadrupole broadening of the satellite transitions that is caused by the interaction of the quadrupole moment of the aluminium nuclei with the electric field gradient. Therefore, the aluminium nuclei act as probe for the charge distribution, and hence for the local geometry. Complementary information can be obtained from density functional theory (DFT) calculations, as highlighted by the DFT electron density map in the lower part of the image. The authors are grateful to Dr. Frank Hoffmann (Hamburg) for preparing the cover image. More information can be found in the Research Article by Bodo Zibrowius et al.

封面显示的是 KAlH4 的静态固态 27Al NMR 光谱和这种材料的晶体结构。光谱显示了卫星跃迁的典型一阶四极扩大,这是由铝核的四极矩与电场梯度的相互作用引起的。因此,铝核是电荷分布的探针,因此也是局部几何形状的探针。从密度泛函理论(DFT)计算中可以获得补充信息,如图像下部的 DFT 电子密度图所示。作者感谢弗兰克-霍夫曼博士(汉堡)制作封面图片。更多信息,请参阅 Bodo Zibrowius 等人的研究文章。
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引用次数: 0
Carbon Nanofibers-Based Anodes for Potassium-Ion Battery 基于碳纳米纤维的钾离子电池阳极。
IF 2.5 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-10 DOI: 10.1002/open.202300286
Dr. Chao Li, Wen-jun Jiang, Dr. Zhen-yu Liu

In recent years, with the global warming getting worse and increasing demand for energy, countries around the world are trying to develop new energy storage technologies to solve this problem. Currently, potassium-ion batteries (PIBs) have attracted tremendous attention from researchers as low-cost and high-performance energy storage devices. However, due to the huge ionic radius of K+, PIBs face significant volume expansion during cycling, which can easily lead to the collapse of electrode structures. In addition, the poor diffusion kinetics of K+ seriously affect the electrochemical performance of the battery. Carbon nanofibers (CNFs)-based materials (including CNFs, metal/CNFs composites, chalcogenide/CNFs composites, and other CNFs-based materials) are widely used as PIBs electrode anode materials due to their three-dimensional conductive network, heteroatom doping and excellent mechanical properties. This review discusses in detail the research progress of CNFs-based materials in PIBs, including material preparation, structural design, and performance optimization. On this basis, this article explores the key issues faced by CNFs-based materials and future development directions, and proposes improvement suggestions for providing new ideas for the development of CNFs-based materials.

近年来,随着全球气候变暖和能源需求的增加,世界各国都在努力开发新的储能技术来解决这一问题。目前,钾离子电池(PIB)作为一种低成本、高性能的储能设备,已经引起了研究人员的极大关注。然而,由于 K+ 的离子半径巨大,PIB 在循环过程中会面临显著的体积膨胀,这很容易导致电极结构的崩溃。此外,K+ 扩散动力学不良也会严重影响电池的电化学性能。碳纳米纤维(CNFs)基材料(包括 CNFs、金属/CNFs 复合材料、卤化物/CNFs 复合材料和其他 CNFs 基材料)因其三维导电网络、杂原子掺杂和优异的机械性能而被广泛用作 PIBs 的电极阳极材料。本综述详细讨论了 CNFs 基材料在 PIB 中的研究进展,包括材料制备、结构设计和性能优化。在此基础上,本文探讨了 CNFs 基材料面临的关键问题和未来的发展方向,并提出了改进建议,为 CNFs 基材料的发展提供了新思路。
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引用次数: 0
Synthesis and properties of RNA constrained by a 2’-O-disulfide bridge 含有 2'-O 二硫桥的 RNA 的合成和特性。
IF 2.5 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-10 DOI: 10.1002/open.202300232
Diallo Traoré, Elisa Biecher, Manon Mallet, Sonia Rouanet, Dr. Jean-Jacques Vasseur, Prof. Michael Smietana, Dr. Christelle Dupouy

We recently reported the properties of RNA hairpins constrained by a dimethylene (DME) disulfide (S−S) linker incorporated between two adjacent nucleosides in the loop and showed that this linker locked the hairpin conformation thus disturbing the duplex/hairpin equilibrium. We have now investigated the influence of the length of the linker and synthesized oligoribonucleotides containing diethylene (DEE) and dipropylene (DPE) S−S bridges. This was achieved via the preparation of building blocks, namely 2′-O-acetylthioethyl (2′-O-AcSE) and 2′-O-acetylthiopropyl (2′-O-AcSP) uridine phosphoramidites, which were successfully incorporated into RNA sequences. Thermal denaturation analysis revealed that the DEE and DPE disulfide bridges destabilize RNA duplexes but do not disrupt the hairpin conformation. Furthermore, our investigation of the duplex/hairpin equilibrium indicated that sequences modified with DME and DEE S−S linkers predominantly lock the hairpin form, whereas the DPE S−S linker provides flexibility. These findings highlight the potential of S−S linkers to study RNA interactions.

我们最近报告了受环路中两个相邻核苷之间的二亚甲基(DME)二硫化物(S-S)连接体约束的 RNA 发夹的特性,结果表明这种连接体锁定了发夹构象,从而扰乱了双链/发夹的平衡。现在,我们研究了连接体长度的影响,并合成了含有二亚乙(DEE)和二丙烯(DPE)S-S 桥的寡核苷酸。这是通过制备构件实现的,即 2'-O-acetylthioethyl (2'-O-AcSE) 和 2'-O-acetylthiopropyl (2'-O-AcSP) 尿苷磷酰胺,并成功地将其整合到 RNA 序列中。热变性分析表明,DEE 和 DPE 二硫桥会破坏 RNA 双链的稳定性,但不会破坏发夹构象。此外,我们对双链/发夹平衡的研究表明,用 DME 和 DEE S-S 连接体修饰的序列主要锁定发夹形式,而 DPE S-S 连接体则提供了灵活性。这些发现凸显了 S-S 连接体在研究 RNA 相互作用方面的潜力。
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引用次数: 0
Interaction of N2, O2 and H2 Molecules with Superalkalis N2、O2 和 H2 分子与超碱液的相互作用。
IF 2.5 4区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2024-01-09 DOI: 10.1002/open.202300253
Harshita Srivastava, Dr. Ambrish Kumar Srivastava, Prof. Dr. Neeraj Misra

Superalkalis (SAs) are exotic clusters having lower ionization energy than alkali atoms, which makes them strong reducing agents. In the quest for the reduction of diatomic molecules (X2) such as N2, O2, and H2 using Møller-Plesset perturbation theory (MP2), we have studied their interaction with typical superalkalis such as FLi2, OLi3, and NLi4 and calculated various parameters of the resulting SA−X2 complexes. We noticed that the SA−O2 complex and its isomers possess strong ionic interaction, which leads to the reduction of O2 to O2 anion. On the contrary, there are both ionic and covalent interactions in SA−N2 complexes such that the lowest energy isomers are covalently bonded with no charge transfer from SA. Further, the interaction between SA and H2 leads to weakly bound complexes, which results in the adsorption of H2 molecules. The nature of interaction is found to be closely related to the electron affinity of diatomic molecules. These findings might be useful in the study of the activation, reduction, and adsorption of small molecules, which can be further explored for their possible applications.

超级碱(SAs)是一种奇特的团簇,其电离能低于碱原子,因此具有很强的还原性。在利用默勒-普莱塞特扰动理论(MP2)研究 N2、O2 和 H2 等二原子分子(X2)的还原过程中,我们研究了它们与 FLi2、OLi3 和 NLi4 等典型超碱基的相互作用,并计算了所得到的 SA-X2 复合物的各种参数。我们注意到,SA-O2 复合物及其异构体具有很强的离子相互作用,导致 O2 还原成 O2 - 阴离子。相反,SA-N2 复合物既有离子相互作用,也有共价相互作用,能量最低的异构体是共价键,没有来自 SA 的电荷转移。此外,SA 和 H2 之间的相互作用导致形成弱结合复合物,从而吸附 H2 分子。相互作用的性质与二原子分子的电子亲和力密切相关。这些发现可能有助于研究小分子的活化、还原和吸附,从而进一步探索其可能的应用。
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引用次数: 0
Analysis of Photocatalytic Degradation of Phenol by Zinc Oxide Using Response Surface Methodology 利用响应面方法分析氧化锌对苯酚的光催化降解作用
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-09 DOI: 10.1002/open.202300238
Meliha Seloglu, Assoc. Prof. Ramazan Orhan, Assist. Prof. Veyis Selen, Prof. Dr. Gülbeyi Dursun

In this study, the photocatalytic degradation of phenol, which is commonly found in industrial wastewater at high rates, was investigated using a zinc oxide (ZnO) catalyst. It is thought that our findings will contribute to the removal of phenol in industrial wastewater. The experimental study was conducted in a batch-type air-fed cylindrical photocatalytic reactor, and a central composite design (CCD) was chosen and analyzed using response surface methodology (RSM). The study aimed to explore the effects of initial phenol concentration, catalyst concentration, airflow rate, and degradation time on the photocatalytic degradation of phenol and the removal efficiency of total organic carbon (TOC). A quadratic regression model was developed to establish the relationship between phenol degradation, TOC removal effectiveness, and the four factors mentioned. The validity of the model was assessed through an analysis of variance (ANOVA). A good agreement was observed between the model results and the experimental data. As a result of the experiments carried out under optimized conditions, the degradation percentage of phenol was found to be 77.15 %, and the degradation percentage of TOC was 59.87 %. Additionally, pseudo-first-order kinetics were used in the photocatalytic degradation of phenol.

本研究使用氧化锌(ZnO)催化剂对工业废水中常见的苯酚进行了光催化降解。我们认为,我们的研究结果将有助于去除工业废水中的苯酚。实验研究是在一个间歇式进气圆柱形光催化反应器中进行的,选择了一个中心复合设计(CCD),并使用响应面方法(RSM)进行了分析。研究旨在探讨初始苯酚浓度、催化剂浓度、气流速率和降解时间对苯酚光催化降解和总有机碳(TOC)去除效率的影响。建立了一个二次回归模型,以确定苯酚降解、TOC 去除效果和上述四个因素之间的关系。该模型的有效性通过方差分析(ANOVA)进行了评估。结果表明,模型结果与实验数据非常吻合。在优化条件下进行的实验结果表明,苯酚的降解率为 77.15%,TOC 的降解率为 59.87%。此外,苯酚的光催化降解还采用了伪一阶动力学。
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引用次数: 0
Green Synthesis of Copper Nanoparticles Using Sargassum spp. for Electrochemical Reduction of CO2 利用马尾藻属植物绿色合成用于二氧化碳电化学还原的纳米铜颗粒。
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-09 DOI: 10.1002/open.202300190
Dr. Sandra Jazmín Figueroa Ramírez, Dr. Beatriz Escobar Morales, Diego Alonso Pantoja Velueta, Dr. Juan Manuel T. Sierra Grajeda, Dr. Ivonne Liliana Alonso Lemus, Dr. Claudia Alejandra Aguilar Ucán

This study presents a green method of producing copper nanoparticles (CuNPs) using aqueous extracts from Sargassum spp. as reducing, stabilizing, and capping agents. The CuNPs created using this algae-based method are not hazardous, they are eco-friendly, and less toxic than their chemically synthesized counterparts. The XRD characterization of the CuNPs revealed the presence of Cu and CuO, with a crystallite size ranging from 13 to 17 nm. Following this, the CuNPs were supported onto a carbon substrate, also derived from Sargassum spp. (biochar CSKPH). The CuNPs in biochar (CuNPs-CSKPH) did not appear in the XRD diffractograms, but the SEM-EDS results showed that they accounted for 36 % of the copper weight. The voltamperometric study of CuNps-CSKPH in acid media validated the presence of Cu and the amount was determined to be 2.58 μg. The catalytic activity of CuNPs-CSKPH was analyzed for the electrochemical reduction of CO2. The use of Sargassum spp. has great potential to tackle two environmental problems simultaneously, by using it as raw material for the synthesis of activated biochar as support, as well as the synthesis of CuNPs, and secondly, by using it as a sustainable material for the electrochemical conversion of CO2.

本研究介绍了一种利用马尾藻水提取物作为还原剂、稳定剂和封盖剂生产纳米铜粒子(CuNPs)的绿色方法。用这种基于藻类的方法制备的 CuNPs 不含有害物质,对生态友好,而且毒性低于化学合成的同类产品。CuNPs 的 XRD 表征显示了铜和氧化铜的存在,晶粒大小在 13 到 17 纳米之间。随后,CuNPs 被支撑在碳基底上,碳基底也来自马尾藻属(生物炭 CSKPH)。生物炭中的 CuNPs(CuNPs-CSKPH)没有出现在 XRD 衍射图中,但 SEM-EDS 结果显示它们占铜重量的 36%。在酸性介质中对 CuNps-CSKPH 进行的伏安计研究验证了铜的存在,并确定其含量为 2.58 微克。分析了 CuNPs-CSKPH 电化学还原 CO2 的催化活性。使用马尾藻属植物有同时解决两个环境问题的巨大潜力:一是将其作为合成活性生物炭的原料,并将其作为支持物,同时合成 CuNPs;二是将其作为二氧化碳电化学转化的可持续材料。
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引用次数: 0
Cinchona-Based Hydrogen-Bond Donor Organocatalyst Metal Complexes: Asymmetric Catalysis and Structure Determination 金鸡纳树基氢键给体有机催化剂金属络合物:不对称催化和结构确定。
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-08 DOI: 10.1002/open.202300180
Dr. Sándor Nagy, Dóra Richter, Gyula Dargó, Balázs Orbán, Gergő Gémes, Dr. Tibor Höltzl, Zsófia Garádi, Zsuzsanna Fehér, Dr. József Kupai

In this study, we describe the synthesis of cinchona (thio)squaramide and a novel cinchona thiourea organocatalyst. These catalysts were employed in pharmaceutically relevant catalytic asymmetric reactions, such as Michael, Friedel–Crafts, and A3 coupling reactions, in combination with Ag(I), Cu(II), and Ni(II) salts. We identified several organocatalyst-metal salt combinations that led to a significant increase in both yield and enantioselectivity. To gain insight into the active catalyst species, we prepared organocatalyst-metal complexes and characterized them using HRMS, NMR spectroscopy, and quantum chemical calculations (B3LYP-D4/def2-TZVP), which allowed us to establish a structure-activity relationship.

在本研究中,我们介绍了金鸡纳(硫)方酰胺和一种新型金鸡纳硫脲有机催化剂的合成。我们将这些催化剂与 Ag(I)、Cu(II) 和 Ni(II) 盐结合,用于医药相关的催化不对称反应,如迈克尔、弗里德尔-卡夫斯和 A3 偶联反应。我们发现了几种有机催化剂-金属盐组合,它们能显著提高产率和对映体选择性。为了深入了解活性催化剂种类,我们制备了有机催化剂-金属复合物,并利用 HRMS、NMR 光谱和量子化学计算(B3LYP-D4/def2-TZVP)对其进行了表征,从而建立了结构-活性关系。
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引用次数: 0
Design of Promising Uranyl(VI) Complexes Thin Films with Potential Applications in Molecular Electronics 设计在分子电子学中具有潜在应用前景的铀(VI)配合物薄膜。
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-05 DOI: 10.1002/open.202300219
Dr. César Raúl Monzón González, Prof. Dr. María Elena Sánchez Vergara, Prof. Dr. Milton Carlos Elías-Espinosa, M.Sc. Sergio Arturo Rodríguez-Valencia, Dr. Byron José López-Mayorga, M.Sc. José León Castillo-Arroyave, Dr. Rubén Alfredo Toscano, Prof. Dr. Octavio Lozada Flores, Dr. Cecilio Álvarez Toledano

In this work, it is proposed the development of organic semiconductors (OS) based on uranyl(VI) complexes. The above by means of the synthesis and the characterization of the complexes by Infrared spectroscopy, Nuclear magnetic resonance spectroscopy, mass spectrometry, and X-ray diffraction. Films of these complexes were deposited and subsequently, topographic and structural characterization was carried out by Scanning Electron Microscopy, X-ray diffraction, and Atomic Force Microscopy. Additionally, the nanomechanical evaluation was performed to know the stiffness of uranyl films using their modulus of elasticity. Also, the optical characterization took place in the devices and their bandgap value ranges between 2.40 and 2.93 eV being the minor for the film of the uranyl complex with the N on pyridine in position 4 (2 c). Finally, the electrical behavior of the uranyl(VI) films was evaluated, and important differences were obtained: the uranyl complex with the N on pyridine in position 2 (2 a) film is not influenced by changes in lighting and its current density is in the order of 10−3 A/cm2. The film with uranyl complex with the N on pyridine in position 3 (2 b) and 2 c presents a greater current flow under lighting conditions and two orders of magnitude larger than in film 2 a. In these films 2 b and 2 c, ohmic behavior occurs at low voltages, while at high voltages the charge transport changes to space-charge limited current behavior.

本研究提出了基于铀酰(VI)络合物的有机半导体(OS)的开发方案。通过红外光谱、核磁共振光谱、质谱分析和 X 射线衍射等方法合成和表征了上述络合物。这些复合物的薄膜被沉积下来,随后通过扫描电子显微镜、X 射线衍射和原子力显微镜进行了形貌和结构表征。此外,还进行了纳米力学评估,利用弹性模量了解铀酰薄膜的硬度。此外,还对器件进行了光学表征,其带隙值介于 2.40 和 2.93 eV 之间,其中位于 4(2 c)位的吡啶上有 N 的铀络合物薄膜的带隙值最小。最后,对铀酰(VI)薄膜的电学行为进行了评估,结果发现了重要的差异:吡啶上 N 位于 2 位(2 a)的铀酰络合物薄膜不受光照变化的影响,其电流密度为 10-3 A/cm2 量级。位置 3(2 b)和 2 c 含吡啶上 N 的铀酰络合物薄膜在光照条件下的电流更大,比 2 a 薄膜大两个数量级。在这些薄膜 2 b 和 2 c 中,低电压下出现欧姆行为,而在高电压下,电荷传输变为空间电荷限制电流行为。
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引用次数: 0
Photocatalytic Degradation of Malachite Green by Titanium Dioxide/Covalent Organic Framework Composite: Characterization, Performance and Mechanism 二氧化钛/共价有机框架复合材料对孔雀石绿的光催化降解:特性、性能和机理。
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-05 DOI: 10.1002/open.202300209
Dr. Dongmei Yao, Xiaoting Xie, Xuling Liang, Sufen Lu, Prof. Hongfang Lai

In this paper, a titanium dioxide/covalent organic framework (TiO2/COF) composite was prepared and its photocatalytic removal of dye was investigated. Using tetrabutyl titanate as a titanium source, TiO2 nanomaterial was prepared by sol-gel method. In the presence of TiO2, TiO2/COF core-shell composite was prepared by solvothermal synthesis using melamine and 1,4-phthalaldehyde as ligands. The prepared materials are characterized by SEM, TEM, XPS, XRD, TG, FTIR, BET, EPR, PL, and UV-Vis-DRS techniques. Using malachite green as a model of dye wastewater, the photocatalytic degradation performance of TiO2/COF composites was investigated under the irradiation of ultraviolet light. The results show that the modification of COF significantly improves the photocatalytic efficiency of TiO2, the degradation rate increases from 69.77 % to 93.64 %, and the reaction rate constant of the first-order kinetic equation is increased from 0.0078 min−1 to 0.0192 min−1. Based on the free radical capture experiment, the photocatalytic degradation mechanism of TiO2/COF was discussed, and the feasibility of its photocatalytic degradation of malachite green was theoretically clarified. Accordingly, a simple and practical method for photocatalytic degradation of malachite green was constructed, which has potential application value in the degradation of dye wastewater.

本文制备了一种二氧化钛/共价有机框架(TiO2 /COF)复合材料,并研究了它对染料的光催化去除作用。以钛酸四丁酯为钛源,采用溶胶-凝胶法制备了二氧化钛纳米材料。在 TiO2 的存在下,以三聚氰胺和 1,4-酞醛为配体,通过溶胶热合成法制备了 TiO2 /COF 核壳复合材料。制备的材料通过 SEM、TEM、XPS、XRD、TG、FTIR、BET、EPR、PL 和 UV-Vis-DRS 技术进行表征。以孔雀石绿为染料废水模型,研究了 TiO2 /COF 复合材料在紫外光照射下的光催化降解性能。结果表明,COF 的改性显著提高了 TiO2 的光催化效率,降解率从 69.77% 提高到 93.64%,一阶动力学方程的反应速率常数从 0.0078 min-1 提高到 0.0192 min-1。在自由基捕获实验的基础上,探讨了 TiO2 /COF 的光催化降解机理,从理论上阐明了其光催化降解孔雀石绿的可行性。据此,构建了一种简单实用的光催化降解孔雀石绿的方法,在染料废水降解方面具有潜在的应用价值。
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引用次数: 0
CYTOP® 366: A Tertiary Phosphine Inaccessible by Most Traditional Hydrophosphination Methods CYTOP® 366:大多数传统氢化膦方法无法获得的叔膦。
IF 2.3 4区 化学 Q2 Chemistry Pub Date : 2024-01-03 DOI: 10.1002/open.202300264
Dr. Dino Amoroso, Jeff Dyck, Dr. Andrew Jackson, Michael Humeniuk, Eleanor Kendrick, Angelo Melaragni, Dr. Michael Moser, Dr. Izabela Wiater-Protas, Dr. Serguei Zavorine, Dr. Jade Markham

Homogenous catalysis is an essential tool within the commercial manufacture of bulk and fine chemicals. Within this, phosphine ligands, such as tricyclohexylphosphine, otherwise known as CYTOP® 366, are a crucial component. When designing a pathway to your ligand of choice, some key considerations include safety, yield and quality, but at commercial volumes we must also balance cost and consider the technologies readily available. Herein, we report the synthetic route that was chosen to manufacture tricyclohexylphosphine at commercial scale. We also consider, with the use of computational calculations, why traditional hydrophosphination methods failed, where the selected pathway succeeded.

均相催化是大宗化学品和精细化学品商业化生产的重要工具。其中,膦配体(如三环己基膦,又称 CYTOP® 366)是重要的组成部分。在设计配体的途径时,一些关键的考虑因素包括安全性、产量和质量,但在商业化量产时,我们还必须平衡成本并考虑现有的技术。在此,我们报告了选择用于商业规模生产三环己基膦的合成路线。通过计算,我们还考虑了为什么传统的氢化膦方法失败了,而所选的途径却成功了。
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引用次数: 0
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