【无机化学学报】doi: 10.11862/CJIC.20250192
碳硼烷作为一类独特的多面体硼簇化合物,因其三维芳香结构和多中心多电子成键,在众多领域展现出广阔的应用前景。然而,碳硼烷的B—H键较为惰性,且存在化学选择性问题,这导致碳硼烷B—H键的官能团化在合成上一直存在挑战。近年来,研究者采用光诱导策略成功实现了碳硼烷的官能团化,不仅合成了一系列碳硼烷基功能分子,也为碳硼烷的官能团化提供了新途径,为碳硼烷化学的进一步发展奠定了基础。
【大学化学】doi: 10.3866/PKU.DXHX202310041
从教学改革的角度出发,通过增加自主设计实验来促进学生的自主学习能力和实验设计思维能力的提升。自主设计实验要求学生自主查阅文献、设计实验方案、分析方案可行性、实验探究后进行综合讨论分析。进一步培养学生独立思考、融会贯通的能力,培养查阅文献、撰写实验方案的能力,为将来的科学研究工作打下坚实基础。
【大学化学】doi: 10.3866/PKU.DXHX202312042
为全面深化信息技术与实验教学的融合,推进化学实验课堂的改革与创新,本文从信息化教学视角出发,借助虚拟仿真技术,开展了以“甘氨酸合铜的制备及其差热分析”为例的双线混融实验教学模式研究,实现了化学实验教学课堂从封闭到开放的转变,构建“过程–结果”二维度,“虚拟与真实、理论与操作、线上与线下”三结合,实施“课前网上预习–课中实验操作–课后总结分析”全过程的多元化实验教学评价方法,培养学生自主学习和实践探索能力,实现从预成性知识到建构性知识的转变。
【大学化学】doi: 10.3866/PKU.DXHX202312056
为培养学生的科研思维及创新能力,加深学生对无机簇合物概念及荧光性能的认识与理解,设计开发了铜碘簇合物的制备及荧光检测亚硝酸盐的综合性实验。利用纳米沉淀的方法合成铜碘簇合物,通过红外光谱、X射线粉末衍射、扫描电子显微镜、紫外光谱、荧光光谱等分析手段对材料进行结构及性能表征,考察材料的荧光及检测亚硝酸盐的性能。结果表明:材料对亚硝酸盐具有高选择、高灵敏检测,检出限为3.73 µmol∙L−1,可作为监测亚硝酸盐的“开-关”荧光探针。通过该实验,学生不仅对簇合物的结构及荧光分析法检测亚硝酸盐等前沿知识加深理解,还可学习紫外分析仪、荧光分光光度计等仪器的基本原理及操作技能,为将来从事相关科研及工作奠定基础。
【无机化学学报】doi: 10.11862/CJIC.20240359
To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects, the new anthraquinone derivatives, 9-pyridylanthrahydrazone (9-PAH) and 9, 10-bispyridylanthrahydrazone (9, 10-PAH) were designed and synthesized. Utilizing 9-PAH and 9, 10-PAH as promising anticancer ligands, their respective copper complexes, namely [Cu(L1)Cl2]Cl (1) and {[Cu4(μ2-Cl)3Cl4(9, 10-PAH)2(DMSO)2]Cl2}n (2), were subsequently synthesized, where the new ligand L1 is formed by coupling two 9-PAH ligands in the coordination reaction. The chemical and crystal structures of 1 and 2 were elucidated by IR, MS, elemental analysis, and single-crystal X-ray diffraction. Complex 1 forms a mononuclear structure. L1 coordinates with Cu through its three N atoms, together with two Cl atoms, to form a five-coordinated square pyramidal geometry. Complex 2 constitutes a polymeric structure, wherein each structural unit centrosymmetrically encompasses two five-coordinated binuclear copper complexes (Cu1, Cu2) of 9, 10-PAH, with similar square pyramidal geometry. A chlorine atom (Cl2), located at the symmetry center, bridges Cu1 and Cu1A to connect the two binuclear copper structures. Meanwhile, the two five-coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom, respectively, thus forming a 1D chain-like polymeric structure. In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin. Specifically, the IC50 values of 2 against HeLa-229 and SK-OV-3 cancer cell lines were determined to be (5.92±0.32) μmol·L-1 and (6.48±0.39) μmol·L-1, respectively. 2 could also block the proliferation of HeLa-229 cells in S phase and significantly induce cell apoptosis. In addition, fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode, offering insights into its underlying anticancer mechanism.
【大学化学】doi: 10.12461/PKU.DXHX202504048
顺(反)式二甘氨酸合铜制备实验是几何异构配合物制备的经典化学实验。通过引入量子化学计算和颜色识别技术对该实验进行了创新设计,解决了该实验现象易观测而微观机制难理解,以及反应终点不易控制、产率不高等问题。运用量子化学软件Gaussian 09及其可视化工具GaussView,采用密度泛函理论(DFT)对顺、反式二甘氨酸合铜分子的几何结构、能量、偶极矩以及静电势等参数进行计算,使学生初步掌握运用量子化学计算方法求算几何异构配合物分子的思路和方法,进而从微观层面深入理解顺反异构体之间的差异性。同时,基于C++编程语言与OpenCV库,通过机器视觉技术搭建一个颜色识别系统,利用摄像头捕捉反应区域图像,结合HSV颜色空间模型分析溶液颜色变化,实现对顺式二甘氨酸合铜异构化生成反式二甘氨酸合铜反应过程中溶液颜色变化的实时监控及自动识别与判断,精确监测反应终点。将量子化学计算与颜色识别技术有机结合并融入实验教学内容中,有助于学生更为深入地理解分子结构与性质之间的内在联系,大幅提高实验数据的精准度与可信度。同时能有力增强学生的科学思维能力、跨学科综合运用能力,切实提升学生在数智化领域的应用水平。
Syntheses and photocatalytic CO2 reduction properties of heterometallic Ni/Sn and Co/Sn oxo clusters
【无机化学学报】doi: 10.11862/CJIC.20250353
In this work, by using diphenylphosphonic acid as ligand and butyltin hydroxide oxide as tin source, reacting with nickel acetate and cobalt acetate respectively, two hexanuclear tin oxo clusters formulated as [(n-BuSn)4 Ni2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (1) and [(n-BuSn)4Co2(μ3-O)2(μ3-OH)2(CH3COO)4(Ph2PO2)6] (2) were solvothermally synthesized. Both 1 and 2 were characterized by infrared spectroscopy, elemental analysis, and single-crystal X-ray diffraction. Spectral experiments revealed that the two complexes have absorptions in the visible region. The optical band gaps for complexes 1 and 2 are 1.90 and 1.79 eV, respectively. Complexes 1 and 2 exhibited photocatalytic CO2 reduction activity, and only CO was generated, with rates of 10.01 and 26.89 μmol·g-1·h-1, respectively. CCDC: 2505024, 1; 2505025, 2.
【无机化学学报】doi: 10.11862/CJIC.20250302
以稀土硬脂酸盐为前驱体,乙醇-水-油酸混合试剂为溶剂,采用化学方法合成NaYF4∶Yb,Er上转换荧光微米材料;再以NaYF4∶Yb,Er为基质材料,在其表面依次键合1,4-苯二甲酸(PTA)、Eu3+离子和1,10-菲咯啉(Phen),制备具有双重荧光性质的NaYF4∶Yb,Er-(PTA)Eu(Phen)微米复合材料。经表征发现,复合材料的形貌为表面结合了纳米球的微米棒,在波长为200~310 nm范围内和976 nm处分别产生紫外和近红外吸收,受254和980 nm光源激发分别产生616 nm红色下转换荧光和540 nm绿色上转换荧光。将微米材料、十二烷基硫酸钠与水配制成微米悬浮液,用于潜在手印的悬浮液法显现和双模式荧光增强。经过优化实验,确定手印显现的最优条件如下:NaYF4∶Yb,Er-(PTA)Eu(Phen)的质量分数为1.67%,十二烷基硫酸钠的质量分数为0.50‰,显现时间为30 s。结果表明,手印显现结合荧光增强具有较高的对比度、灵敏度和选择性,荧光增强模式对对比度的影响较大,而对灵敏度和选择性基本没有影响。
【无机化学学报】doi: 10.11862/CJIC.20250347
To address the longstanding challenge in traditional carborane methodology of rapidly and efficiently constructing carboranyl-based polycyclic frameworks, Pd-catalyzed one-pot reactions between pyridyl-substituted nido-carboranes and alkynes directly afford two distinct types of 2D-3D fused carboranyl polycyclic compounds: 3a-3f, 4a-4d. The structures of this series of compounds were characterized by nuclear magnetic resonance spectroscopy, single-crystal X-ray diffraction, and high-resolution mass spectrometry, and a plausible reaction mechanism was proposed. Crystal structures reveal that the multiple rings in such 2D-3D fused carboranyl polycyclic compounds exhibit a certain degree of coplanarity. Furthermore, these compounds exhibited properties distinct from those of conventional 2D polycyclic systems.
