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221.
Margaret C. Gerthoffer Sikai Wu Bo Chen Tao Wang Steven Huss Shalisa M. Oburn Vincent H. Crespi John V. Badding Elizabeth Elacqua 《Chemical science》2020,11(42):11419
Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp3-hybridized nanothreads from sp2-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.Supramolecular synthons are exploited to synthesize –OH functionalized sp3-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal. 相似文献
222.
A simple and efficient preparation of gramicidin S and its analogues is described. It involves solid-phase peptide synthesis and on-resin macrolactamization without side chain protection, affording cyclic products in high yield and high purity. The high specificity of the cyclization reaction was shown to originate in the formation of a pre-organized conformation of the linear biosynthetic precursor of gramicidin S. This facile method will provide convenient access to the analogues of the natural product for functional optimization to counter microbial resistance. 相似文献
223.
Yu JQ Wu HC Ramarao C Spencer JB Ley SV 《Chemical communications (Cambridge, England)》2003,(6):678-679
A robust and recyclable palladium catalyst [Pd0EnCat] has been prepared by ligand exchange of polyurea-encapsulated palladium(II) acetate with formic acid, resulting in deposition of Pd(0) in the support material; Pd0EnCat is shown to be a highly efficient transfer hydrogenation catalyst for chemoselective reduction of a wide range of aryl ketones to benzyl alcohols. 相似文献
224.
Dong-Dong Zhou Jun Wang Pin Chen Yangyong He Jun-Xi Wu Sen Gao Zhihao Zhong Yunfei Du Dingyong Zhong Jie-Peng Zhang 《Chemical science》2021,12(4):1272
Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H3btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N–H⋯N hydrogen bonds. While the H3btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag3(btim)] coordination networks based on double N–Ag–N bonds at 423 K, by virtue of the unconventional metal–acid replacement reaction (Ag reduces H+). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host–guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.A hydrogen-bonded network on a Ag(111) surface can transform into an isostructural Ag(i) coordination network, giving drastically different host–guest recognition behaviours. 相似文献
225.
IMPROVED PROPERTIES OF METALLOCENE-CATALYZED LINEAR LOW-DENSITY POLYETHYLENE/POLYPROPYLENE BLENDS DURING ULTRASONIC EXTRUSION 总被引:1,自引:0,他引:1
Hong Wu Shao-yun Guo 《高分子科学》2007,(4):357-364
Metallocene-catalyzed linear low-density polyethylene/polypropylene (mLLDPE/PP) blends were prepared by ultrasonic extrusion in this work. Their extrusion processing behaviors were estimated by online measured data, such as the die pressure and flow rate. Crystallization and mechanical properties of the blends were also investigated. The results show that the addition of PP improves the processing behaviors of mLLDPE, but has little effect on its mechanical properties. On the other hand, the addition of mLLDPE improves the impact strength of PP, but has little effect on its processing behavior. The processing behaviors and mechanical properties of mLLDPE/PP blends get further improved due to the presence of ultrasonic oscillation during extrusion. Compared with PP-rich blends, the apparent viscosity drop of mLLDPE-rich blends is more sensitive to ultrasonic oscillation. The ultrasonic oscillation affects the crystal nucleation, while barely the other crystalline behaviors of the blends. 相似文献
226.
An efficient Pd‐catalyzed three‐component coupling reaction of allyl carboxylates, norbornenes and diboronates is described, which allows efficient assembly of C(sp3)—C(sp3) and C(sp3)—B bonds in a single process. Moreover, this approach shows advantages of good chemo‐ and regioselectivity, as well as good substrates suitability. 相似文献
227.
笼形聚偕胺肟树脂的研究HX/ACAO树脂吸附贵金属 总被引:3,自引:0,他引:3
氢卤酸、硝酸、硫酸、磷酸和硼酸处理的笼形聚偕胺肟树脂(HX/A-CAO)对Ag+和等贵金属离子的吸附能力按如下顺序:PdCl42-:H3BO3/ACAO>BCAO>H3PO4/ACAO>HI/ACAO>H2SO4/ACAO>HCl/ACAO>HNO3/ACAO>HF/ACAO.IrCl62-:BCAO>H3PO4/ACAO>H3BO3/ACAO>HCl/ACAO>HF/ACAO>HI/ACAO>H2SO4/ACAO≥HNO3/ACAO.PtCl62:BCAO>H3BO3/ACAO>H2SO4/ACAO>HNO3/ACAO>HCl/ACAO>HF/ACAO>H3PO4/ACAO>HI/ACAO.Ag+:BCAO>H3BO3/ACAO>HI/ACAO>H2SO4/ACAO>HF/ACAO>HCl/ACAO>H3PO4/ACAO>HNO3/ACAO.AuCl4-:BCAO>H3BO3>H3PO4/ACAO>HF/ACAO>HCl/A-CAO>H2SO4/ACAO>HI/ACAO>HNO3/A-CAO.研究了H3BO3/ACAO树脂对Ag+和离子的吸附动力学,讨论了吸附机理. 相似文献
228.
The crystal structure of new compound Ba3BPO7 was determined by ab initio method from high-resolution conventional X-ray powder diffraction data. The Rietveld refinement converged to Rp=5.92%, Rwp=8.87%, Rexp=5.00% with the following details: Hexagonal, space group P63mc, a=5.4898 (1) Å, c=14.7551(1) Å, Z=2. The basic unit of the structure is the [BaO10]-[BO3]-[PO4] polar polyhedra-chain composed of Ba1-B-P-O cluster. These chains, running along c-axis, stack in a HCP mode to build the whole structure with triangular prism channels. The channels are parallel to c-axis too, in which Ba2 and Ba3 are located. 相似文献
229.
D.-G. Chen D.-S. Wu H. Zhang Y.-C. Zhang Y.-J. Gong Z.-G. Kan 《Journal of solid state chemistry》2004,177(11):3927-3933
A novel compound Ba2ZnV2O8 has been synthesized in high temperature solution reaction and its crystal structure has been characterized by means of single crystal X-ray diffraction analysis. It crystallizes in monoclinic system and belongs to space group P21/c with a=7.9050(16), b=16.149(3), , β=90.49(3). It builds up from 1-D branchy chains of [ZnV2O84−]∞, and the Ba2+ cations are located in the space among these chains. The IR spectrum, ultraviolet-visible diffuse reflection integral spectrum and fluorescent spectra of this compound have been investigated. The calculated results of energy band structure by the density functional theory method show that the solid-state compound of Ba2ZnV2O8 is an insulator with direct band gap of 3.48 eV. The calculated total and partial density of states indicate that the top valence bands are contributions from the mixings of O-2p, V-3d, and Zn-3d states and low conduction bands mostly originate from unoccupied antibonding states between the V-3d and O-2p states. The V-O bonds are mostly covalence characters and Zn-O bonds are mostly ionic interactions, and the ionic interaction strength is stronger between the Ba-O than between the Zn-O. The refractive index of nx, ny, and nz is estimated to be 1.7453, 1.7469, and 1.7126, respectively, at wavelength of 1060 nm for Ba2ZnV2O8 crystal. 相似文献
230.