- How to Control the Rate of Heterogeneous Electron Transfer across the Rim of M6L12and M12L24Nanospheres
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Catalysis in confined spaces, such as those provided by supramolecular cages, is quickly gaining momentum. It allows for second coordination sphere strategies to control the selectivity and activity of transition metal catalysts, beyond the classical methods like fine-tuning the steric and electronic properties of the coordinating ligands. Only a few electrocatalytic reactions within cages have been reported, and there is no information regarding the electron transfer kinetics and thermodynamics of redox-active species encapsulated into supramolecular assemblies. This contribution revolves around the preparation of M6L12 and larger M12L24 (M = Pd or Pt) nanospheres functionalized with different numbers of redox-active probes encapsulated within their cavity, either in a covalent fashion via different types of linkers (flexible, rigid and conjugated or rigid and nonconjugated) or by supramolecular hydrogen bonding interactions. The redox probes can be addressed by electrochemical electron transfer across the rim of nanospheres, and the thermodynamics and kinetics of this process are described. Our study identifies that the linker type and the number of redox probes within the cage are useful handles to fine-tune the electron transfer rates, paving the way for the encapsulation of electroactive catalysts and electrocatalytic applications of such supramolecular assemblies.
- Zaffaroni, Riccardo,Bobylev, Eduard O.,Plessius, Raoul,Van Der Vlugt, Jarl Ivar,Reek, Joost N. H.
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- Synthesis of Indole-Fused Polycyclics via Rhodium-Catalyzed Undirected C-H Activation/Alkene Insertion
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A Rh(III)-catalyzed undirected C-H activation/alkene insertion to synthesize diversified indole-fused polycyclics has been developed. Intramolecular electrophilic cyclization generated a 3-indolyl rhodium species that went through an aryl-to-aryl 1,4-rhodium migration to realize the C-H activation. The subsequent [4 + 2] carboannulation or hydroarylation of alkenes could be achieved, respectively, by simply adjusting the additives of the reaction.
- Guo, Songjin,Pan, Rui,Guan, Zhe,Li, Panpan,Cai, Libo,Chen, Siwei,Lin, Aijun,Yao, Hequan
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supporting information
p. 6320 - 6324
(2019/08/26)
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- A structure-guided optimization of pyrido[2,3-d]pyrimidin-7-ones as selective inhibitors of EGFRL858R/T790Mmutant with improved pharmacokinetic properties
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Structural optimization of pyrido[2,3-d]pyrimidin-7-ones was conducted to yield a series of new selective EGFRT790Minhibitors with improved pharmacokinetic properties. One of the most promising compound 9s potently suppressed EGFRL858R/T790Mkinase and inhibited the proliferation of H1975?cells with IC50values of 2.0?nM and 40?nM, respectively. The compound dose-dependently induced reduction of the phosphorylation of EGFR and downstream activation of ERK in NCI[sbnd]H1975?cells. It also exhibited moderate plasma exposure after oral administration and an oral bioavailability value of 16%. Compound 9s may serve as a promising lead compound for further drug discovery overcoming the acquired resistance of non-small cell lung cancer (NSCLC) patients.
- Yu, Lei,Huang, Minhao,Xu, Tianfeng,Tong, Linjiang,Yan, Xiao-e,Zhang, Zhang,Xu, Yong,Yun, Caihong,Xie, Hua,Ding, Ke,Lu, Xiaoyun
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p. 1107 - 1117
(2016/12/30)
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- Synthesis of Phenylene Vinylene Macrocycles through Acyclic Diene Metathesis Macrocyclization and Their Aggregation Behavior
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A series of phenylene vinylene macrocycles (PVMs) bearing substituents with various sizes and electronic properties have been synthesized through a one-step acyclic diene metathesis macrocyclization approach and their aggregation behaviors have been investigated. In great contrast to the aggregation of the analogous phenylene ethynylene macrocycles, which aggregate only when substituted with electron-withdrawing groups, these PVMs undergo exceptionally strong aggregation, regardless of the electron-donating or -withdrawing characters of the substituents. The unusual aggregation behavior of the PVMs is further investigated with thermodynamic and computer modeling studies, which show a good agreement with the recently proposed direct through-space interaction model, rather than the polar/π model. The high aggregation tendency of PVMs suggests the great potential of this novel class of shape-persistent macrocycles in a variety of applications, such as ion channels, host-guest recognition, and catalysis.
- Zhang, Chenxi,Yu, Chao,Long, Hai,Denman, Ryan J.,Jin, Yinghua,Zhang, Wei
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supporting information
p. 16935 - 16940
(2015/11/16)
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- M-Terphenyl-3,3″-dioxo-derived oxacalixaromatics: Synthesis, structure, and solvent encapsulation in the solid state
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The synthesis of oxacalix[2]terphenylene[2]aromatics with enlarged macrocyclic holes by cyclooligomerization reaction of 5′-tert-butyl-(1, 1′:3′,1″-terphenyl)-3,3″-diol 1 with electron-deficient dihalogenated benzene and azaheterocycles is described. The structures of the macrocycles were characterized by NMR, HRMS spectroscopic and X-ray diffraction techniques. Single crystal X-ray analysis revealed that the terphenyl-3, 3″-dioxo unit incorporated in the oxacalix[4]aromatics scaffold can adopt all three possible conformations (I, II, III). The cis-conformational terphenyl-3,3″-dioxo (I and II) derived oxacalix[4]aromatics were found to adopt both chair and boat conformations, resulted in creation of molecular cavities capable of hosting solvent molecules of chloroform. The trans-conformational terphenyl-3,3″-dioxo (III) derived oxacalix[4]aromatics, however, adopt a twisted chair conformation with a narrow void space incapable of hosting any guest molecules.
- Hu, Wen-Jing,Liu, Long-Qing,Ma, Ming-Liang,Zhao, Xiao-Li,Liu, Yahu A.,Mi, Xian-Qiang,Jiang, Biao,Wen, Ke
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p. 3934 - 3941
(2013/06/27)
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- Synthesis, structure and conformation of terphenylene-derived oxacalixaromatics
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Oxacalix[4]aromatics comprised of terphenylene units have been synthesized by cyclooligomerization of 5′-tert-butyl-1,1′:3′,1″- terphenyl-4,4″-diol (1) and electron-deficient meta-dihalogenated benzene and heterocycles. Single-crystal X-ray analysis revealed that oxacalix[2]terphenylene[2]pyrazine 13 adopts a chair conformation, forming a molecular cavity to trap an ethyl acetate guest molecule in the solid state. 1,3-Alternate conformations are adopted by other oxacalix[2]terphenylene[2] aromatics (11, 12 and 15), which form a narrow tweezer-like molecular cavity that is incapable of encapsulating any guest molecules. Oxacalix[4]aromatics comprised of terphenylene units have been synthesized, andtheir structures and conformations have been elucidated. Copyright
- Hu, Wen-Jing,Zhao, Xiao-Li,Ma, Ming-Liang,Guo, Fang,Mi, Xian-Qiang,Jiang, Biao,Wen, Ke
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p. 1448 - 1454
(2012/04/11)
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- (3-HYDROXY-4-AMINO-BUTAN-2-YL) -3- (2-THIAZOL-2-YL-PYRROLIDINE-1-CARBONYL) BENZAMIDE DERIVATIVES AND RELATED COMPOUNDS AS BETA-SECRETASE INHIBITORS FOR TREATING
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The present invention provides novel beta-secretase inhibitors and methods for their use, including methods of treating of Alzheimer's disease. (Formula)
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Page/Page column 113
(2009/05/29)
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- THIAZOLE DERIVATIVES AS CXCR3 RECEPTOR MODULATORS
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The invention encompasses compounds of Formula I (I) or pharmaceutically acceptable salts thereof, which are antagonist of the CXCR3 chemokine receptor useful for the treatment or prevention of pathogenic inflammatory processes, autoimmune diseases or graft rejection processes. Methods of use and pharmaceutical compositions are also encompassed.
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Page/Page column 41
(2008/06/13)
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- Synthesis and optical properties of novel blue fluorescent conjugated polymers
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In the present paper we describe new approaches towards the synthesis of conjugated polymers with defined conjugation length, resulting in a blue or green fluorescence. The new approach reported here is to use 1,3-phenylene (type 1) and 10,10'-bianthrylene (type 2) bridges of conjugated segments such as stilbenes and thiophenes which can easily be varied to further change the optical properties.
- Baumgarten, Martin,Yueksel, Timucin
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p. 1699 - 1706
(2007/10/03)
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- Bis[3-tert-butyl-5-(N-oxy-tert-butylamino)phenyl] Nitroxide in a Quartet Ground State: A Prototype for Persistent High-Spin Poly [(oxyimino)-1,3-phenylenes]
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The title trinitroxide 4 was synthesized via the bis[m-(hydroxyamino)phenyl] nitroxides 9 and 10. The ESR spectra obtained in a toluene glass at 4.2 K was consistent with 4 in a quartet state with the zfs parameter |D|/hν of 0.0087 cm-1. The quartet state was shown to be the ground state by the magnetic measurement of its microcrystalline sample on a Faraday balance. The maximum of the effective moment was 3.53 μB at ca. 140 K. The Weiss constant and the energy gap between the lowest excited doublet and the ground quartet states were estimated to be -19 and +240 K, respectively.
- Ishida, Takayuki,Iwamura, Hiizu
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p. 4238 - 4241
(2007/10/02)
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