Hexafluoroantimonic Acid Catalysis: Formal [3+2+2] Cycloaddition of Aziridines with Two Alkynes

A practical method for the synthesis of azepine derivatives, a typical seven‐membered heterocyclic ring system, was developed and involves the use of hexafluoroantimonic acid to catalyze a formal [3+2+2] cycloaddition of aziridines with two alkynes. This method was applicable to two of the same or different terminal alkynes for the [3+2+2] cycloaddition with unactivated aziridines, and furnished the corresponding azepine derivatives in good yields with good levels of chemo‐ and regioselectivity. The mechanism was also discussed according to the results of the in situ HRMS and ¹H NMR analysis.     

Self‐Assembly of Pyridinium‐Functionalized Anthracenes: Molecular‐Skeleton‐Directed Formation of Microsheets and Microtubes

Two amphiphilic regioisomers, 9‐AP (1‐[11‐(9‐anthracenylmethoxy)‐11‐oxoundecyl]pyridinium bromide), and 2‐AP (1‐[11‐(2‐anthracenyl methoxy)‐11‐oxoundecyl]pyridinium bromide), were synthesized and their assembly behaviors were studied. Due to the anisotropic features of the anthracene structure, different substituted positions on the anthracene ring lead 9‐AP and 2‐AP to adapt “shaver” and “spatula”‐like molecular shapes, respectively, which consequently dictate the structure of their final assemblies. While “shaver”‐shaped 9‐AP assembled into microsheets, driven by π–π interactions, “spatula”‐shaped 2‐AP assembled into microtubular structures, promoted primarily by charge‐transfer interactions.     

Sponge Phase Producing Porous CeO2 for Catalytic Oxidation of CO

The aggregation behavior of mixtures of the alkaline amino acid L ‐Arginine (L ‐Arg) and bis(2‐ethylhexyl)phosphoric acid (DEHPA) in water was studied in detail. At a fixed L ‐Arg concentration, a phase sequence of micellar phase (L₁ phase), vesicle phase (L_αv phase), planar lamellar phase (L_αl phase), and sponge phase (L₃ phase) was obtained with increasing DEHPA concentration due to changes in the packing parameter. The phase transition of the lamellar structures was determined by freeze‐fracture TEM and ²H NMR spectroscopy. Rheological measurements reflected the phase transition through significant variations of both the elastic modulus and the viscous modulus. Porous CeO₂ materials were produced by utilizing the L₃ phase as template, and the porous CeO₂ exhibited excellent catalytic oxidation activity toward CO due to its high surface area, which provides more active sites for CO conversion.     

Rhodium(III)‐Catalyzed N‐Nitroso‐Directed CH Addition to Ethyl 2‐Oxoacetate for Cycloaddition/Fragmentation Synthesis of Indazoles

Rh^III‐catalyzed N‐nitroso‐directed C?H addition to ethyl 2‐oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N‐nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C?H functionalization‐based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tricyclic‐fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.     

Magnetically Encoded Luminescent Composite Nanoparticles through Layer‐by‐Layer Self‐Assembly

Sensitive and rapid detection of multiple analytes and the collection of components from complex samples are important in fields ranging from bioassays/chemical assays, clinical diagnosis, to environmental monitoring. A convenient strategy for creating magnetically encoded luminescent CdTe@SiO₂@n Fe₃O₄ composite nanoparticles, by using a layer‐by‐layer self‐assembly approach based on electrostatic interactions, is described. Silica‐coated CdTe quantum dots (CdTe@SiO₂) serve as core templates for the deposition of alternating layers of Fe₃O₄ magnetic nanoparticles and poly(dimethyldiallyl ammonium chloride), to construct CdTe@SiO₂@n Fe₃O₄ (n=1, 2, 3, …?) composite nanoparticles with a defined number (n) of Fe₃O₄ layers. Composite nanoparticles were characterized by zeta‐potential analysis, fluorescence spectroscopy, vibrating sample magnetometry, and transmission electron microscopy, which showed that the CdTe@SiO₂@n Fe₃O₄ composite nanoparticles exhibited excellent luminescence properties coupled with well‐defined magnetic responses. To demonstrate the utility of these magnetically encoded nanoparticles for near‐simultaneous detection and separation of multiple components from complex samples, three different fluorescently labeled IgG proteins, as model targets, were identified and collected from a mixture by using the CdTe@SiO₂@n Fe₃O₄ nanoparticles.     

Design of Enzymatically Cleavable Prodrugs of a Potent Platinum‐Containing Anticancer Agent

Using a versatile synthetic approach, a new class of potential ester prodrugs of highly potent, but systemically too toxic, platinum–acridine anticancer agents was generated. The new hybrids contain a hydroxyl group, which has been masked with a cleavable lipophilic acyl moiety. Both butanoic (butyric) and bulkier 2‐propanepentanoic (valproic) esters were introduced. The goals of this design were to improve the drug‐like properties (e.g., logD) and to reduce the systemic toxicity of the pharmacophore. Two distinct pathways by which the target compounds undergo effective ester hydrolysis, the proposed activating step, have been confirmed: platinum‐assisted, self‐immolative ester cleavage in a low‐chloride environment (LC‐ESMS, NMR spectroscopy) and enzymatic cleavage by human carboxylesterase‐2 (hCES‐2) (LC‐ESMS). The valproic acid ester derivatives are the first example of a metal‐containing agent cleavable by the prodrug‐converting enzyme. They show excellent chemical stability and reduced systemic toxicity. Preliminary results from screening in lung adenocarcinoma cell lines (A549, NCI‐H1435) suggest that the mechanism of the valproic esters may involve intracellular deesterification.     

Study on the interaction between urea and cellulose by combining solid-state 13C CP/MAS NMR and extended Hückel charges

In this article, solid-state ¹³C CP/MAS NMR combined with extended Hückel charges was applied to investigate the interaction between urea and cellulose in the NaOH/urea aqueous solvent system. Direct experimental evidence was provided to support the interaction between urea and cellulose. The solid-state ¹³C CP/MAS NMR results revealed that complicated complexes are formed by urea, NaOH and cellulose in the solution. Excess urea exists in a free state, which explains why 7 wt% NaOH/12 wt% urea/81 wt% H₂O is the optimal ratio selection to dissolve cellulose. Based on the correlation in which the computed extended Hückel charge on carbon of urea is approximately inversely proportional to its ¹³C chemical shift, a possible interaction model of cellulose, NaOH and urea was proposed. Interactions exist between any two of urea, NaOH and cellulose, which results in the cellulose chain being surrounded by NaOH and urea molecules. NaOH and urea may be in the same surface layer of cellulose chains.     

In-situ synthesis,characterization and antimicrobial activity of viscose fiber loaded with silver nanoparticles

In order to broaden applications of viscose fiber, graft copolymerization of acrylic acid was conducted on its surface followed by in situ loading of Ag nanoparticles (Ag-NPs). The loading amount of Ag-NPs was affected by the concentrations of Ag⁺ and trisodium citrate, and their optimum concentrations were found to be 0.014 and 0.030 g/ml. The Ag-NP-loaded fibers presented a prolonged Ag release behavior in aqueous solution, of which the cumulative release was less than 5 % within 48 h. In addition, the viscose fibers showed good antimicrobial activity against S. aureus, and their consecutive antimicrobial activity was kept at more than 90 % after several washing cycles. Modified viscose fibers, therefore, offer a great opportunity for use as antimicrobial fabrics.     

ATRP法制备侧链型聚醚醚酮阴离子交换膜

以二氟二苯甲酮、双酚A和邻甲基氢醌单体缩聚合成聚醚醚酮(PEEK)作为基膜材料.PEEK经修饰改性合成带有异丙基溴端基PEEK,以此为原子转移自由基聚合(ATRP)大分子引发剂,通过ATRP法在PEEK主链上接枝引入聚甲基丙烯酸二甲基胺基乙酯(DMAEMA)侧链,得到梳状PEEK接枝聚合物(PEEK-gDMAEMA).用傅里叶变换红外(FTIR)光谱、核磁共振氢谱(1H-NMR)、热重分析(TG)和扫描电子显微镜(SEM)等方法对PEEK-g-DMAEMA的结构进行表征.实验结果表明,甲基丙烯酸二甲基胺基乙酯被成功地接枝在聚醚醚酮主链上,PEEK-g-DMAEMA膜具有明显的亲水疏水微相分离形貌,叔胺基团相互聚集成形成离子通道.接枝聚合反应10 h,PEEK-g-DMAEMA膜的离子交换容量为2.07 mmol·g-1,以此膜为电解槽隔膜,2 h的OH-离子透过率达0.15 mol·L-1,说明PEEK-g-DMAEMA膜具有良好的离子交换能力.     

四臂聚乙二醇-聚丙交酯立体复合胶束及其药物传输性能

以异辛酸亚锡为催化剂,通过四臂聚乙二醇(4-armed PEG)引发右旋丙交酯(DLA)或左旋丙交酯(LLA)开环聚合合成四臂PEG-PLA对映体共聚物.通过纳米沉淀的方法制备了四臂PEG-b-PDLA胶束(PDM)、四臂PEG-b-PLLA胶束(PLM)和四臂PEG-b-PDLA/四臂PEG-b-PLLA立体复合胶束(SCM),并对其形貌、粒径、稳定性和立体复合机理等进行系统表征.以阿霉素(DOX)为模型抗肿瘤药物载入胶束中,与PDM和PLM相比,SCM具有更优异的药物负载能力.与DOX相比,载药四臂PEG-PLA胶束,尤其是负载DOX的SCM,表现出更优异的肿瘤细胞增殖抑制效果,作用更持久,并且对正常细胞的毒性较小,从而揭示了其作为潜在抗肿瘤药物载体的良好前景.