将功能纳米材料发展前沿融入实验教学——隐形荧光墨水的制备

为了让学生了解纳米材料的性质和用途，开发了一个研究型综合性实验——隐形荧光墨水的制备。通过微波反应快速地制备了一种新型的氮掺杂碳量子点，克服了碳量子点制备繁琐的难题，使碳点的制备能够在实验教学中得以实现，利用透射电镜、X射线衍射、红外光谱以及X射线能谱对碳点的结构和形貌进行表征，利用紫外-可见-近红外光谱仪和荧光光谱仪研究碳点的稳定性和光化学性能；并将该碳点制作成隐形荧光墨水，增加了实验的趣味性和实用性。学生实验证明该综合性实验适用于本科生实验教学。     

研究型综合化学实验设计:碳量子点的制备及其在叶酸检测中的应用

以高校创新型人才培养为目标,设计了一个研究型综合化学实验。以柠檬酸和尿素为原料,通过水热法制备了发射强烈蓝色荧光的碳量子点,表征了其紫外-可见吸收光谱和荧光光谱,进一步研究了该碳量子点在叶酸的检测中的应用。本实验涉及纳米材料制备、表征及应用相关知识,适合作为高年级本科生的研究型综合化学实验,有助于激发学生的研究兴趣和培养学生的科研思维。     

碳量子点及其性能研究进展

碳量子点(Carbon Quantum Dots,CQDs)是一种新型的碳纳米材料,因其强的量子限域效应和稳定的荧光性能等一系列优异性能,吸引了化学、物理、材料和生物等各领域科学家的广泛关注。相比传统半导体金属量子点,CQDs还具备优异的低毒性和生物相容性,更拓宽了其在生物领域内的研究前景。本文简要地介绍了CQDs的制备方法,主要包括自上而下和自下而上两个方向。除此之外,本文综述了CQDs突出的物理化学性质和性能,包括CQDs的荧光性能、生物相容性和上转换效应,并对CQDs在其在生物成像上的应用进行了归纳。     

由蚕砂制备的碳量子点在不同激发、pH、金属离子、温度及极性环境下的荧光性质研究

碳量子点作为一种新兴的荧光纳米材料,具有粒径分布均匀、光稳定性好、激发-发射波长可调控、表面可修饰等优良的性质,兼具低毒性、生物相容性好等优点,在分析检测和生物成像等领域展现出广阔的应用前景。而蚕砂是家蚕的干燥粪便,简单易得。利用蚕砂作为碳量子点制备原料,采用微波合成的方法制备得到了一种平均水合粒径为4.86 nm,含氮、硫修饰的碳量子点材料,可作为针对激发波长、pH、金属离子浓度、温度及溶剂极性的变化有着显著响应特性的碳量子点型荧光探针。该探针的荧光最大发射波长随激发波长或pH的增加而红移;荧光强度随温度或pH的降低而增加;随着金属离子,特别是铜离子的加入而逐渐降低,并随着EDTA络离子的加入而逐渐回复。在多种溶剂中该探针均具有较好的溶解度,当换用不同极性的溶剂时,随着溶剂极性的增加荧光发射波长逐渐红移。荧光性质随多重环境参数变化为该碳量子点在未来的生物检测和成像领域提供了广阔的应用前景。     

煤基碳量子点合成研究进展

随着纳米科学技术的出现与发展,各种纳米材料层出不穷,碳量子点以其独特且优异的性质吸引了众多研究者的关注。碳源材料对碳量子点的合成及性质有着重要影响,我国煤炭储量相对丰富,焦炭、煤焦油和煤沥青等煤基衍生物的产量也居于世界前列,煤及煤衍生物富含芳环结构,在微观结构上适宜制备碳量子点。本文主要综述了近年来以煤及煤衍生物为碳源,通过化学试剂氧化、超声和电化学氧化等方法合成碳量子点(统称为煤基碳量子点)的研究进展,阐述了煤及其衍生物作为原料的优势所在,对比分析了不同制备方法的特点,并简要介绍了煤基碳量子点的性质以及其在生物成像、金属离子检测和光催化等领域的应用,最后对煤基碳量子点的可控制备等前景进行了展望。     

川木香水热法一步合成荧光碳量子点及光学性能研究

以中药材川木香原药为碳源，采用水热法一步合成了荧光碳量子点。通过水热法实验条件优化，获得制备荧光碳量子点的最佳实验参数，通过透射电镜(TEM)对荧光碳量子点进行形貌表征，通过X射线光电子能谱分仪(XPS)对荧光碳量子点进行元素组成分析，通过荧光光谱和紫外-可见吸收光谱对荧光碳量子点进行了光学性能研究。结果表明：川木香用量1.00 g,水热反应温度180℃,水热反应时间2.0 h时，制备得到的荧光碳量子点光学性能最佳。荧光碳量子点平均粒径为5 nm,主要含有C元素和O元素，最大激发波长为360 nm,对应的发射波长为420 nm,特征吸收峰为280 nm,量子产率为12.9%。     

碳点荧光探针的制备及其在食品分析中的应用

碳点作为一种新型荧光碳纳米材料,具有优良的光学性能和小尺寸特性,以及良好的生物相容性、低毒性以及易于实现表面功能化等特点,是潜在的可以代替传统半导体量子点等荧光探针的良好选择.基于其独特的荧光特性和高灵敏度,碳点荧光探针在食品分析领域具有很好的应用潜力.本文对近年来荧光碳点的研究进展进行了综述,简述碳点的性能并对碳点的制备方法进行总结对比,重点介绍了碳点荧光探针在食品分析领域的应用,对目前碳点应用的限制进行了分析,对其发展前景和展望.     

量子点的制备及应用研究进展

综述了量子点的制备方法以及在分析检测、生物、药学、光电器材、指纹显现等领域的应用.指出量子点是一种新型的荧光纳米材料,因其具有独特的光电性质而引起了广泛的关注;并就它的发展方向及应用前景进行了展望.     

发光碳量子点的合成及应用

碳元素是地球上所有已知生命的基础.由于其具有多样的电子轨道特性(sp、sp²、sp³),因此形成许多结构和性质奇特的物质.碳量子点是2004年发现的一种新型碳材料,相对于传统的半导体量子点和有机染料,这位碳家族中的新成员不仅保持了碳材料毒性小、生物相容性好等优点,而且还拥有发光范围可调、双光子吸收截面大、光稳定性好、无光闪烁、易于功能化、价廉、易大规模合成等无可比拟的优势.虽然在某些性能方面,稀土荧光纳米颗粒可以与之媲美,但是稀土元素昂贵的价格极大地限制了其在实际生产中的应用.因此,对碳量子点这一新兴领域的研究必将对材料科学的发展产生重大影响,它也会为碳家族赢得更多的荣耀.本论文的主要工作是建立了一步合成高荧光量子效率碳量子点的合成方法;对碳量子点的表面进行功能化;制备了碳量子点薄膜、块体和流体材料。     

基于纸基的荧光碳量子点传感器的可视化检测研究进展

碳量子点作为一种新型的纳米材料,其独特的荧光性能使其在物质检测领域得到了越来越多的关注。利用碳量子点与物质反应导致荧光强度发生变化的特性,可将其应用于可视化检测,检测方法分为荧光猝灭型和荧光恢复型。基于纸基的荧光传感器与基于液相反应的荧光检测相比,其快速、现场和可视化的特点更加突出,因此有着更为广泛的应用。本文针对碳量子点的荧光特性、可视化荧光检测、纸基传感器的研究现状,并结合本课题组相关研究进展进行论述,以期为今后纸基碳量子点荧光传感器的研究和应用提供参考。     

Novel arylpyridine‐based 1,3,4‐oxadiazoles: Synthesis,antibacterial, and anti‐inflammatory evaluation

In view of developing novel bioactive compounds, a series of 2‐(5‐[2‐methyl‐6‐arylpyridin‐3‐yl]‐1,3,4‐oxadiazol‐2‐ylthio)‐1‐arylethanones (6a–n) were designed and synthesized in good yield. Novel compounds were evaluated for their antibacterial and anti‐inflammatory activities. All synthesized compounds were screened for their antibacterial activity against Staphylococcus aureus, Bascillus subtilis, Eschericia coli, and Pseudomonas aeruginosa strains. Compounds 6a , 6b , 6c , 6h , and 6i displayed the highest antibacterial activity with minimal inhibitory concentration (MIC) values ranging from 6.25–12.5 μg/mL in comparison with the standard Ciprofloxacin. The results of anti‐inflammatory activity of carrageenan‐induced footpad edema assay indicated that tested compounds exhibited remarkable anti‐inflammatory activity with percentage of inhibition of 63.9–70.1% (potency 96.8–106.20% of indomethacin activity) after 3 hr. Particularly, 6c – e and 6j – l were found to be excellent inhibitors of inflammation, with potential higher than that of the standard, Indomethacin.     

Par-delà la synthèse : l’auto-organisation

The evolution of the universe from the particle to the thinking organism has taken place through self-organization. Chemistry has a major role to play in understanding these processes leading to the generation of complex matter. Chemistry has developed a highly powerful molecular synthetic chemistry, mastering the combination and recombination of atoms into increasingly complex molecules through selective chemical reactions. Supramolecular chemistry is harnessing intermolecular forces for the generation of informed supramolecular systems and processes through supramolecular synthetic chemistry implementing molecular information carried by electromagnetic interactions. Supramolecular chemistry has been actively exploring systems undergoing self-organization, i.e., systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, under the control of interactional molecular recognition events, thus behaving as programmed chemical systems. Molecular chemistry may similarly take advantage of the selectivity of covalent reactions to assemble complex molecular architectures through self-organization processes implementing functional molecular recognition. Supramolecular/non-covalent and molecular/covalent SELF-ORGANIZATION may thus be considered as the ULTIMATE SYNTHETIC CHEMISTRY, whereby chemical objects at both levels are generated on the basis of recognition processes involving either interactional or reactional features. Illustrations from the supramolecular domain will serve as illustrations. Supramolecular entities as well as molecules containing reversible bonds are able to undergo a continuous change in constitution by reorganization and exchange of building blocks. This capability defines a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels. CDC introduces a paradigm shift with respect to constitutionally static chemistry. It takes advantage of dynamic constitutional diversity to allow variation and selection and thus leads towards the emergence of adaptive and evolutive chemistry.     

Feasibility of Ultrafast High‐Resolution Spectroscopy in the Analysis of Molecular‐Mobility‐Restricted Samples in Deuterium‐Free Environments

The feasibility of ultrafast high‐resolution intermolecular multiple‐quantum coherence (UF‐iMQC) spectroscopy for the direct analysis of molecular‐mobility‐restricted samples that are not suitable for magic‐angle spinning, such as a jelly, hand soap, and marrow, is presented. Most components could be directly detected in their original state within 1 min without the need for tedious sample preparation processes. When we use conventional liquid nuclear magnetic resonance (NMR) method to study these systems, the spectral information could not be retrieved owing to the intrinsic inhomogeneous magnetic fields caused by sample inhomogeneity. In addition, the possibility for UF‐iMQC‐based quantifications is shown. The examples presented in this paper demonstrate the potential of UF iMQC NMR for food safety inspection, for quality testing of daily‐life supplies, or in assisting medical diagnosis.     

校本课程开发:从“化学传奇”到“化学阅读”

校本课程“化学传奇”主要是引导学生阅读化学史文章。校本课程从“化学传奇”升级到“化学阅读”,化学阅读的内容拓展了,阅读形式升级了:由文章阅读升级为视频观看和整本书阅读,阅读的时间由校本课程的课内阅读延伸到课外阅读,阅读时段由校本课程季扩展为高中全学段。学生的阅读活动,也由教师规定阅读内容升级到学生在推荐书目内自主选择性阅读和个性化阅读。     

2‐(1 H‐1,2,3‐Triazol‐4‐yl)‐Pyridine Ligands as Alternatives to 2,2′‐Bipyridines in Ruthenium(II) Complexes

The synthesis of a variety of 2‐(1H‐1,2,3‐triazol‐4‐yl)‐pyridines by click chemistry is demonstrated to provide straightforward access to mono‐functionalized ligands. The ring‐opening polymerization of ε‐caprolactone initiated by such a mono‐functionalized ligand highlights the synthetic potential of this class of bidentate ligands with respect to polymer chemistry or the attachment onto surfaces and nanoparticles. The coordination to Ru^II ions results in homoleptic and heteroleptic complexes with the resultant photophysical and electrochemical properties strongly dependent on the number of these ligands attached to the Ru^II core.     

Studies of two different types of intramolecular C–H···F–C interactions from polyfluorinated diiodometal(II) diimine complexes

The X‐ray crystal structures of the polyfluorinated complexes [5,5′‐bis(HCF₂CF₂CF₂CF₂CH₂OCH₂)‐2,2′‐bpy]MI₂ ( 55‐8F‐PtI ₂ and 55‐8F‐PdI ₂ where M = Pt and Pd, respectively) were obtained. These two structures are found to show not only two different types of intramolecular, six‐membered cyclic C–H···F–C interactions (F₂C–H···F–C and HC–H···F–C) as important structural features but also alternating fluorinated and non‐fluorinated layers. The F₂C–H···F–C interactions, which are close to the metal core, are much better structurally characterized in this type of complexes with fluorous ponytails at the 5,5′ positions than those previously reported at the 4,4′ positions. The molecular planes of (bpy)MI₂ are extended by self‐matching, using two C–H···I hydrogen bonds and one C–H···F–C blue‐shifting hydrogen bond. The F₂C–H···F–C hydrogen bonds interact at the supramolecular level such that one polyfluorinated ponytail of the title compounds is transoid without an intramolecular C–H···F–C interaction, while the other polyfluorinated ponytail is cisoid with an intramolecular C–H···F–C interaction. Why one ponytail is cisoidal while the other is transoidal will be explained. Furthermore, the second type of C–H···F–C interactions involving the methylene H atom has been identified for the first time. In addition, these two metal structures are studied by density functional theory (DFT).     

Metal‐Ion‐Coated Graphitic Nanotubes: Controlled Self‐Assembly of a Pyridyl‐Appended Gemini‐Shaped Hexabenzocoronene Amphiphile

The assembly line : Hexabenzocoronene amphiphiles appended with pyridyl‐terminated triethylene glycol side chains, in combination with trans‐[Pt(PhCN)₂Cl₂], lead to the formation of graphitic nanotubes. The structural features and dimensions of the nanotubes depend on the assembly conditions. A platinum(II)‐bridged cyclic dimer having two HBC units self‐assembles into a nanotubular structure.

     

The Evolution Aspect in the Crystallization Process of [5,5′‐(HCF2CF2CH2OCH2)2‐2,2′‐bpy]MX2 (M = Pt,Pd; X = I,Br): Role of the Intramolecular CF2─H…X(─M) Hydrogen Bonds

The general species (2,2′‐bpy)MX₂ (M = Pd, Pt; X = Br, I) in a crystallization process results in an isomorphous convergence in P2₁/c. Yet, with polyfluorinated side chains, the general [5,5′‐(HCF₂CF₂CH₂OCH₂)₂‐2,2′‐bpy]MX₂ species proceeds to crystallize the isomorphous structures of 5 (M = Pt; X = I) and 6 (M = Pd; X = I) in P2₁/c only; structure 7 (M = Pt; X = Br) crystallizes in P2₁/c but is not isomorphous with 5 and 6 , and structure 8 (M = Pd; X = Br) forms differently in P–1. The causes making the system nonlinear are (1) the intramolecular CF₂─H^…X(─M) hydrogen bonds found in 5–7 but not in 8, and (2) in response to the transition from I to Br, bifurcated [C─H^…]₂ F ─C hydrogen bonds that are formed in 5 and 6 and bifurcated C─ H [^…F─C]₂ hydrogen bonds in 7 . Additionally, the intramolecular CF₂─H^…X(─M) hydrogen bonding from compounds 5–7 could be affirmed by the IR studies.     

Tunable Self‐Assembly of Triazole‐Linked Porphyrin–Polymer Conjugates

The convergence of supramolecular chemistry and polymer science offers many powerful approaches for building functional nanostructures with well‐defined dynamic behaviour. Herein we report the efficient “click” synthesis and self‐assembly of AB₂‐ and AB₄‐type multitopic porphyrin–polymer conjugates (PPCs). PPCs were prepared using the copper(I)‐catalysed azide–alkyne cycloaddition (CuAAC) reaction, and consisted of linear polystyrene, poly(butyl acrylate), or poly(tert‐butyl acrylate) arms attached to a zinc(II) porphyrin core via triazole linkages. We exploit the presence of the triazole groups obtained from CuAAC coupling to direct the self‐assembly of the PPCs into short oligomers (2–6 units in length) via intermolecular porphyrinatozinc–triazole coordination. By altering the length and grafting density of the polymer arms, we demonstrate that the association constant of the porphyrinatozinc–triazole complex can be systematically tuned over two orders of magnitude. Self‐assembly of the PPCs also resulted in a 6 K increase in the glass transition temperature of the bulk material compared to a non‐assembling PPC. The modular synthesis and tunable self‐assembly of the triazole‐linked PPCs thus represents a powerful supramolecular platform for building functional nanostructured materials.     

An Allosteric Receptor by Simultaneous “Casting” and “Molding” in a Dynamic Combinatorial Library

Allosteric synthetic receptors are difficult to access by design. Herein we report a dynamic combinatorial strategy towards such systems based on the simultaneous use of two different templates. Through a process of simultaneous casting (the assembly of a library member around a template) and molding (the assembly of a library member inside the binding pocket of a template), a Russian‐doll‐like termolecular complex was obtained with remarkable selectivity. Analysis of the stepwise formation of the complex indicates that binding of the two partners by the central macrocycle exhibits significant positive cooperativity. Such allosteric systems represent hubs that may have considerable potential in systems chemistry.