充满生机和科学机遇的磷化学研究所

简要地综述了第十五届国际磷化学会议的报告内容，介绍了目前磷化学的主要 研究领域，包括不对称合成、配合化学，生物碱化学，药物化学，农业化学等相关 领域的研究动态及新进展。     

Exploring recent developments on 1,2,4-triazole: Synthesis and biological applications

Triazoles are nitrogen-bearing heterocycles. In the last few decades, researchers have focused on fused heterocycles, as they have better pharmacological effect compared to triazoles alone. Among the two isomers of triazole, this article aims to explore the work carried out on 1,2,4-triazole and N-bridged heterocycles derived from 1,2,4-triazole in last 18 years, highlight different synthetic pathways, and present a brief summary of the different biological activities possessed by 1,2,4-triazole derivatives. The information collected in this article is expected to help researchers to discover novel therapeutic agents for better applications in the field of pharmaceutical science.     

Dual zinc catalysts for L‐lactide polymerization and reaction of CO2 with cyclohexene oxide

A series of zinc complexes, [ L ^X ZnEt] ( 1–5 ) and [ L ^X Zn ₂ (OAc) ₃ ] (6–9) , associated with NNO‐tridentate Schiff base ligands (2‐(((2‐((cyclohexyl[methyl]amino)methyl)phenyl)imino)methyl)phenolate (CAP) derivatives), were synthesized, and their activity toward ring‐opening polymerization (ROP) of L‐lactide (LA) and the reaction of CO₂ with cyclohexene oxide were also investigated. All of [ L ^X ZnEt] revealed excellent catalytic activity to ring‐opening polymerization (ROP) of LA in the presence of benzyl alcohol. Among them, [ L ^H ZnEt] (1) showed the highest activity with 82% conversation within 45 s. In contrast, [L ^X Zn ₂ (OAc) ₃ ] (6–9) were inactive in ROP of L‐lactide. In addition, all of these Zn complexes demonstrated moderate activity in the reaction of CO₂ with cyclohexene oxide in the presence of Bu₄NCl.     

化学学科的新视角及其在化学教育中的反映

传统化学以研究变化,关注变化前后的结果而著称。化学与其他学科,特别是生命科学的相互渗透使得化学的动态特征更加突出,化学学科格局也因之发生了变化。因此,化学需要新认识。     

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.     

Cationic Niobium-Sandwich and Piano-Stool Complexes

The syntheses of the homoleptic bis(arene) niobium cations [Nb(arene)₂]⁺ (arene = C₆H₃Me₃, C₆H₅Me) with 16 valence electrons and heteroleptic arene-carbonyl cations [(CO)Nb(arene)₂]⁺ (arene = C₆H₃Me₃, C₆H₅Me) and [(arene)M(CO)₄]⁺ (arene = C₆H₃Me₃, C₆H₆) obeying 18 valence electrons are described. Stabilization of these complexes was achieved by using the weakly coordinating anions [Al(OR^F)₄]⁻ or [F{Al(OR^F)₃}₂]⁻ (R^F = C(CF₃)₃). The limits of two synthesis routes starting from neutral Nb(arene)₂ (arene = C₆H₃Me₃, C₆H₅Me) or [NEt₄][M(CO)₆] (M = Nb, Ta) were investigated. All compounds were analyzed by single crystal X-ray determination, vibrational and NMR spectroscopy. DFT calculations were executed to support the experimental data.     

Synthesis of symmetrically and unsymmetrically substituted S,S-dialkyl phosphonodithioates

Herein, we report the synthesis of a range of S,S-dialkyl phosphonodithioates. Symmetrically substituted analogues were readily prepared from the corresponding phosphonic dichlorides in good to moderate yields, while unsymmetrically substituted variants were obtained by a sequential alkylation-deprotection-alkylation strategy.     

Synthetic and biological polymers--merging the interface

The increasing control that synthetic chemists are able to exert over molecular architecture is allowing the design and preparation of macromolecular and polymeric systems of unprecedented sophistication. In form and function, synthetic polymers are able to mimic many biological polymers, in effect ‘blurring the boundaries’ between the worlds of artificial and natural materials. In this review, some key examples from the merging interface between synthetic and natural polymers are considered, and illustrations of both ‘bio-inspired’ synthetic macromolecular chemistry and new directions in polymer materials are given.     

蒋锡夔研究员及其在物理有机化学和有机氟化学领域的成就

蒋锡夔研究员是我国物理有机化学和有机氟化学的主要奠基人。本文首先介绍蒋锡夔研究员的科学经历,然后介绍他在不同时期取得的代表性科学成就,主要包括有关四氟乙烯的亲电加成反应,氟橡胶研究,亲卤反应,自由基化学及有机分子的簇集与自卷等方面的研究。     

绿色化学与绿色化学教育

本文介绍了绿色化学的定义和内涵,绿色化学的 12条原则,“原子经济”概念,绿色化学的研究动态以及实施绿色化学教育的意义和方法。     

Methods and Applications of Quantum Chemistry. Part I: Physical and Mathematical Basis

After an introduction to the fundamental concepts of quantum mechanics it is shown how to describe a chemical system in the language of theoretical physics. The equations which one obtains can not, in general, be solved in closed form. Approximate numerical methods that furnish sufficiently accurate solutions for many problems of interest are, however, available. The most important of these are presented briefly, and are given physically visualizable interpretations as far as this is possible. Special attention is devoted to more modern methods of quantum chemistry, to the basis assumptions underlying them, their scope, and their limitations. Treatment of the theory of the chemical bond is reserved for Part II.     

The nexus between alternatives assessment and green chemistry: supporting the development and adoption of safer chemicals

ABSTRACT

Alternatives assessment and green chemistry share a common goal of supporting the transition to safer, more sustainable chemicals, materials, and products. Yet the two fields, and their respective scientific communities, are not well integrated. To better understand the nexus between alternatives assessment and green chemistry as complementary approaches to support the development and adoption of safer, more sustainable chemicals for specific functional uses, this article discusses the foundations of the two fields and examines two case examples in which companies have utilized the tools and approaches of both disciplines in developing safer chemical solutions. This research demonstrates the importance and utility of the overlapping skillsets and tools of the two disciplines and the potential benefit of educational opportunities and collaborative spaces in jointly strengthening both fields. Additionally, the literature and case examples identify a number of research and practice needs that would bolster the application of both alternatives assessment and green chemistry in supporting the transition to safer, more sustainable chemistry, including: clearer definitions and criteria of what is ‘safer’; improved approaches to evaluate potential unintended consequences of chemical applications; and more effective tools to evaluate toxicity, consider inherent exposure trade-offs, and combine multiple attributes to make an informed decision.     

The electrochemically tuneable hydrogen bonding interactions between a phenanthrenequinone-functionalized self-assembled monolayer and a phenyl-urea terminated dendrimer

We report the application of electrochemistry to detect and modulate hydrogen bonding interactions between a phenanthrenequinone-functionalized self-assembled monolayer and a phenyl-urea terminated dendrimer.     

Multifunctional "clickates" as versatile extended heteroaromatic building blocks: efficient synthesis via click chemistry, conformational preferences, and metal coordination

Click chemistry has been utilized to access 2,6-bis(1-aryl-1,2,3-triazol-4-yl)pyridines (BTPs) as versatile extended heteroaromatic building blocks for their exploitation in supramolecular chemistry, in particular foldamer and ligand design. In addition to their high-yielding synthesis using Cu(I)-catalyzed Huisgen-type 1,3-dipolar cycloaddition reactions the formed triazole moieties constitute an integral part of the BTP framework and encode both its pronounced conformational preferences as well as its chelating ability. A diverse set of symmetrical and non-symmetrical BTPs carrying electron-donating and -withdrawing substituents at both terminal aryl and the central pyridine moieties has efficiently been synthesized and could furthermore readily be postfunctionalized with amphiphilic side chains and porphyrin chromophores. In both solution and solid state, the BTP scaffold adopts a highly conserved horseshoe-like anti-anti conformation. Upon protonation or metal coordination, the BTP scaffold switches to the chelating syn-syn conformation. Iron and europium complexes have been prepared, successfully characterized by single-crystal X-ray diffraction analysis, and investigated with regard to their spin state and luminescent properties. The extended heteroaromatic BTP scaffold should prove useful for the design of responsive foldamer backbones and the preparation of new magnetic and emissive materials.     

Chemistry of the Positron and of Positronium

In this progress report, the properties and behavior of the positron (“positive electron”, anti-electron) and of the positronium, a “hydrogen atom” containing a positron instead of a proton, are considered from the chemist's viewpoint. Examples are given to demonstrate the development of positronium chemistry, in aqueous solution and in the gaseous, liquid, and solid phases, with its problems and possibilities.     

Novel [1,2,4]triazolo[3,4-b][1,3,4]thiadiazine derivatives embedded with benzimidazole moiety as potent antioxidants

Fourteen novel [1,2,4]triazolo[3,4-b][1,3,4]thiadiazine derivatives bearing benzimidazole moiety ( 7a-n ) have been synthesized using the one-pot nitro reductive cyclization method. All the synthesized compounds were confirmed by ¹H nuclear magnetic resonance (¹H NMR), ¹³C NMR, fourier-transform infrared (FT-IR), mass spectrum, and elemental analyses. All the title compounds were subjected to in vitro antioxidant activity. The free radical scavenging activity of the compounds was examined using DPPH, nitric oxide, and superoxide radical scavenging methods. The results demonstrated that compound 3-(2-(3,4-dimethoxyphenyl)-1-propyl-1H-benzo[d]imidazol-5-yl)-6-4-tolyl-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazine ( 7c ) was potent in scavenging both DPPH and nitric oxide radical with IC₅₀ values of 13.57 and 18.55 μg/ml when compared to the standard with IC₅₀ values of 23.75 and 23.14 μg/ml, respectively, which was due to the presence of electron-donating groups. The activity was found to decline when electron-donating groups were replaced by electron-withdrawing groups. Moderate scavenging activity was observed for the superoxide radical. Structure activity relationship and physiochemical properties were studied for all the derivatives.     

Biologically inspired 3Fe4S cluster as structural mimics of FeMoco M-cluster

A 3Fe4S cluster related to M-cluster of Mo-nitrogenase is reported. [K(THF)₅][Fe₃(μ-bdt)₂(μ-PPh₂)(CO)₅] ( 1 ) is synthesized from photo-assisted structural rearrangement of [K(THF)₂][(μ,κ²-bdt)Fe₂(μ-PPh₂)(CO)₅] under visible light irradiation. The molecular structure of 1 consists of a Fe₃ core bearing one dithiolate bridge and the second dithiolate group capping onto the metallic plane. The structural motif of 1 is analogous to that of Mo-participated 3Fe4S unit in M-cluster of Mo-nitrogenase, with the similar Fe-Fe and Fe-S bond distances. Upon protonation in 193 K, a Fe-hydride species ( 1H ) is generated and characterized to possess the bridging hydride group (δ = −12.57 ppm) by ¹H-NMR spectroscopy and DFT calculation. In CH₃CN solution, complex 1 exhibits a reversible reduction and oxidation process at $E_{1/2}^{\mathrm{red}}$ = −1.94 V and $E_{1/2}^{\mathrm{ox}}$ = −0.18 V, respectively, at 273 K. The reduction behavior of 1 in CH₂Cl₂ solution at 243 K displays a slight modification in the presence of trifluoroacetic acid, revealing a moderate anodic potential shift (~50 mV). The current amplitude of the reduction wave is linearly increased with the increasement of acid added, indicative of the catalytic event.     

无机化学与物理化学课程的协调教学

根据无机化学和物理化学的内容设置及特点, 结合教学实践, 探讨了2者在教学过程中的有机配合和协调统一。无机化学教学应以知识的衔接和实际应用为主, 而物理化学教学则要侧重知识点的挖掘和提升。2者的协调有助于提高课堂利用率, 促进学生学习能力和科学思维的培养。