4464-18-0Relevant articles and documents
Readily useable bulk phenoxazine-based covalent organic framework cathode materials with superior kinetics and high redox potentials
Meng, Zhiying,Zhang, Ying,Dong, Mengqing,Zhang, Yue,Cui, Fengmin,Loh, Teck-Peng,Jin, Yinghua,Zhang, Wei,Yang, Haishen,Du, Ya
supporting information, p. 10661 - 10665 (2021/05/14)
Redox-active covalent organic frameworks (COFs) with dense redox sites are promising electrical energy storage materials with robust architectures, high surface areas, insolubility in electrolytes, and open pores for electrolyte transportation. However, low redox potentials and poor electrical conductivity of pristine COFs often result in low accessibilities of redox-active sites and slow redox kinetics, greatly limiting their practical applications. Herein, we report the design and synthesis of two novel p-type phenoxazine-based COFs (DAPO-COFs) with high redox potentials (～3.6 V vs. Li/Li+) and excellent electrical conductivities. Simply blended with conductive additives (CAs) and binders, pristine bulk DAPO-COFs without pre-composition with CAs or extra exfoliation are readily useable as cathode materials for lithium-ion batteries. Both as-synthesized DAPO-COF powders displayed superior active-site accessibility, ultrafast redox kinetics, and remarkable cycling stability. This work provides new perspectives on the development of readily useable COF-based cathode materials, and contributes to the advancement of eco-friendly and sustainable organic-based energy storage devices. This journal is
A porous fluorinated organic [4+4] imine cage showing CO2and H2adsorption
Kunde, Tom,Nieland, Esther,Schr?der, Hendrik V.,Schalley, Christoph A.,Schmidt, Bernd M.
supporting information, p. 4761 - 4764 (2020/05/13)
We present the synthesis of a porous, organic [4+4] imine cage containing perfluorinated aromatic panels. Gas adsorption experiments show an uptake of 19.0 wt% CO2(4.2 mmol g-1, 273 K and at 1 bar) and 1.5 wt% H2(7.5 mmol g-1, 77 K and at 1 bar) for the specific surface area of 536 m2g-1of the crystalline material obtained directly from the reaction mixture, combined with an outstanding thermal stability, making it a very interesting porous material suitable for gas adsorption.
Aromatic Linkers Unleash the Antiproliferative Potential of 3-Chloropiperidines Against Pancreatic Cancer Cells
Helbing, Tim,Carraro, Caterina,Francke, Alexander,Sosic, Alice,De Franco, Michele,Gandin, Valentina,G?ttlich, Richard,Gatto, Barbara
supporting information, p. 2040 - 2051 (2020/09/21)
In this study, we describe the synthesis and biological evaluation of a set of bis-3-chloropiperidines (B?CePs) containing rigid aromatic linker structures. A modification of the synthetic strategy also enabled the synthesis of a pilot tris-3-chloropiperidine (Tri-CeP) bearing three reactive meta-chloropiperidine moieties on the aromatic scaffold. A structure–reactivity relationship analysis of B?CePs suggests that the arrangement of the reactive units affects the DNA alkylating activity, while also revealing correlations between the electron density of the aromatic system and the reactivity with biologically relevant nucleophiles, both on isolated DNA and in cancer cells. Interestingly, all aromatic 3-chloropiperidines exhibited a marked cytotoxicity and tropism for 2D and 3D cultures of pancreatic cancer cells. Therefore, the new aromatic 3-chloropiperidines appear to be promising contenders for further development of mustard-based anticancer agents aimed at pancreatic cancers.
Design, synthesis, and biological characterization of a new class of symmetrical polyamine-based small molecule CXCR4 antagonists
An, Jing,Fang, Xiong,Huang, Lina S.,Huang, Ziwei,Liang, Boqiang,Meng, Qian,Schooley, Robert T.,Wang, Juan,Xu, Yan,Zhang, Chaozai,Zhang, Huijun,Zhang, Xingquan,Zhu, Siyu
supporting information, (2020/06/03)
CXCR4, a well-studied coreceptor of human immunodeficiency virus type 1 (HIV-1) entry, recognizes its cognate ligand SDF-1α (also named CXCL12) which plays many important roles, including regulating immune cells, controlling hematopoietic stem cells, and directing cancer cells migration. These pleiotropic roles make CXCR4 an attractive target to mitigate human disorders. Here a new class of symmetrical polyamines was designed and synthesized as potential small molecule CXCR4 antagonists. Among them, a representative compound 21 (namely HF50731) showed strong CXCR4 binding affinity (mean IC50 = 19.8 nM) in the CXCR4 competitive binding assay. Furthermore, compound 21 significantly inhibited SDF-1α-induced calcium mobilization and cell migration, and blocked HIV-1 infection via antagonizing CXCR4 coreceptor function. The structure-activity relationship analysis, site-directed mutagenesis, and molecular docking were conducted to further elucidate the binding mode of compound 21, suggesting that compound 21 could primarily occupy the minor subpocket of CXCR4 and partially bind in the major subpocket by interacting with residues W94, D97, D171, and E288. Our studies provide not only new insights for the fragment-based design of small molecule CXCR4 antagonists for clinical applications, but also a new and effective molecular probe for CXCR4-targeting biological studies.
Shape-Persistent [4+4] Imine Cages with a Truncated Tetrahedral Geometry
Lauer, Jochen C.,Zhang, Wen-Shan,Rominger, Frank,Schr?der, Rasmus R.,Mastalerz, Michael
, p. 1816 - 1820 (2018/01/22)
The synthesis of shape-persistent organic cage compounds is often based on the usage of multiple dynamic covalent bond formation (such as imines) of readily available precursors. By careful choice of the precursors geometry, the geometry and size of the resulting cage can be accurately designed and indeed a number of different geometries and sizes have been realized to date. Despite of this fact, little is known about the precursors conformational rigidity and steric preorganization of reacting functional groups on the outcome of the reaction. Herein, the influence of conformational rigidity in the precursors on the formation of a [4+4] imine cage with truncated tetrahedral geometry is discussed.
Octupolar organometallic Pt(II) NCN-pincer complexes; Synthesis, electronic, photophysical, and NLO properties
Batema, Guido D.,van Walree, Cornelis A.,van Klink, Gerard P.M.,de Mello Donegá, Celso,Meijerink, Andries,Perez-Moreno, Javier,Clays, Koen,van Koten, Gerard
, p. 246 - 252 (2018/02/06)
A series of organometallic octupolar 1,3,5-substituted-2,4,6-styryl-benzene complexes was synthesized by post-modification of parent [PtCl(NCN-CHO-4)], i.e. 1,3,5-tri-R-2,4,6-tris[(4-(PtCl)(3,5-bis[(dimethylamino)methyl]styryl)]benzene (NCN = [C6H2(CH2NMe2)2-2,6]– in which R = OMe, H, Br (1–3). Their synthesis involved a triple Horner-Wadsworth-Emmons reaction of [PtCl(NCN-CHO-4)] with the appropriate tris[(diethoxyphosphoryl)]methyl]benzene derivative. The 195Pt{1H} NMR chemical shift reflects the electronic properties of the π-system to which it is connected. The UV/Vis bands of the octupolar platinum complexes are only slightly red-shifted (by 5–12 nm) with respect to those of corresponding stilbenoid Pt-Cl pincer compounds (i.e., the separate branches), suggesting that there is only a limited electronic interaction between these branches. The fluorescence Stokes shift, quantum yields and lifetimes of 1–3 also are of the same order of magnitude as those of stilbenoid Pt-Cl pincer compounds, indicating that a dipolar excited state is formed, which is localized on one of the three branches. The hyper-Rayleigh scattering technique revealed hyperpolarizabilites βHRS of 430, 870 and 183 × 10?30 esu for 1, 2 and 3, respectively, which are among the highest for transition metal complexes. The highest value was found for the compound lacking a donor or acceptor group at the central core, lending support to the idea that dispersion overwhelms charge transfer in determining the magnitude of the first hyperpolarizability in octupolar compounds.
A Degradable and Recyclable Photothermal Conversion Polymer
Xu, Xiao-Qi,Wang, Zhen,Li, Ruiting,He, Yonglin,Wang, Yapei
supporting information, p. 9769 - 9772 (2018/07/25)
Decomposition and repolymerization of conjugated polymers offer great promise for developing recyclable photothermal conversion materials, which yet remain challenging. Herein, a crosslinked conjugated polymer based on a dynamic covalent bond of Schiff base is developed. This polymer possesses photothermal conversion efficiency as high as 90.4 %. Decomposition of the polymer under specialized conditions is corroborated by various characterizations. The kinetics study is also investigated to understand this degradation process. Furthermore, those decomposed species can be repolymerized back to conjugated polymers which possess the same photothermal conversion efficiency as the pristine polymer. Such a degradable and recyclable photothermal polymer is successfully used as a heat source for photothermal-electrical conversion to generate Seebeck voltage under either near infrared (NIR) irradiation or solar illumination.
Synthetic study and structure of cage-type cyclophane C36H36S6
Takemura, Hiroyuki,Nagaoka, Maiko,Kawasaki, Chihiro,Tokumoto, Kasumi,Tobita, Noriko,Takano, Yuki,Iwanaga, Tetsuo
, p. 1066 - 1070 (2017/03/31)
A cage compound was synthesized in order to investigate the structure and cation-π interactions of the metal ion complex. The multi-step synthesis was achieved starting from trimesic acid triethyl ester. In solution, a completely symmetrical structure that was anticipated by the molecular design was observed by 1H and 13C NMR spectroscopy. However, in the solid state, X-ray crystallographic analysis revealed that the compound had a collapsed structure.
Method for synthetizing 1,3,5-benzenetricarboxaldehyde from trimesic acid
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Paragraph 0020, (2018/01/17)
The invention provides an experiment method for synthetizing 1,3,5-benzenetricarboxaldehyde by using trimesic acid as raw materials. The experiment conditions are improved; the purification process of the 1,3,5-benzenetricarboxaldehyde is optimized; a 1,3,5-benzenetricarboxaldehyde synthetizing method with mild reaction conditions, low production cost and high product yield is obtained.
Photoinduced charge transfer in a conformational switching chlorin dimer-azafulleroid in polar and nonpolar media
Nikkonen, Taru,Muuronen, Mikko,Helaja, Juho,Oliva, Mara Moreno,Kahnt, Axel,Guldi, Dirk M.
supporting information, p. 590 - 600 (2015/08/26)
In the present study, a biomimetic reaction center model, that is, a molecular triad consisting of a chlorin dimer and an azafulleroid, is synthesized and its photophysical properties are studied in comparison with the corresponding molecular dyad, which consists only of a chlorin monomer and an azafulleroid. As evidenced by 1H NMR, UV/Vis, and fluorescence spectroscopy, the chlorin dimer-azafulleroid folds in nonpolar media into a C2-symmetric geometry through hydrogen bonding, resulting in appreciable electronic interactions between the chlorins, whereas in polar media the two chlorins diverge from contact. Femtosecond transient absorption spectroscopy studies reveal longer charge-separated states for the chlorin dimer-azafulleroid; 1.6 ns in toluene, compared with the lifetime of ≈0.9 ns for the corresponding chlorin monomer-azafulleroid in toluene. In polar media, for example, benzonitrile, similar charge-separated states are observed, but the lifetimes are inevitably shorter: 65 and 73 ps for the dimeric and monomeric chlorin-azafulleroids, respectively. Nanosecond transient absorption and singlet oxygen phosphorescence studies corroborate that in toluene, the charge-separated state decays indirectly via the triplet excited state to the ground state, whereas in benzonitrile, direct recombination to the ground state is observed. Complementary DFT studies suggest two energy-minima conformations, that is, a folded chlorin dimer-azafulleroid, which is present in nonpolar media, and another conformation in polar media, in which the two hydrophobic chlorins wrap the azafulleroid. Inspection of the frontier molecular orbitals shows that in the folded conformation, the HOMO on each chlorin is equivalent and is shared owing to partial π-π overlap, resulting in delocalization of the conjugated π electrons, whereas the wrapped conformation lacks this stabilization. As such, the longer charge-separated lifetime for the dimer is rationalized by both the electron donor-acceptor separation distance and the stabilization of the radical cation through delocalization. The chlorin folding seems to change the photophysical properties in a manner similar to that observed in the chlorophyll dimer in natural photosynthetic reaction centers.
