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971.
Nelaka Govinna Ilin Sadeghi Ayse Asatekin Peggy Cebe 《Journal of Polymer Science.Polymer Physics》2019,57(6):312-322
We report the structure and thermal properties of blends comprising poly(vinylidene fluoride) (PVDF) and a random fluorinated copolymer (FCP) of poly(methyl methacrylate)‐random‐1H,1H,2H,2H‐perfluorodecyl methacrylate, promising membrane materials for oil–water separation. The roles of processing method and copolymer content on structure and properties were studied for fibrous membranes and films with varying compositions. Bead‐free, nonwoven fibrous membranes were obtained by electrospinning. Fiber diameters ranged from 0.4 to 1.9 μm, and thinner fibers were obtained for PVDF content >80%. As copolymer content increased, degree of crystallinity and onset of degradation for each blend decreased. Processing conditions have a greater impact on the crystallographic phase of PVDF than copolymer content. Fibers have polar beta phase; solution‐cast films contain gamma and beta phase; and melt crystallized films form alpha phase. Kwei's model was used to model the glass transition temperatures of the blends. Addition of FCP increases hydrophobicity of the electrospun membranes. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 312–322 相似文献
972.
Gakhyun Kim Dr. Ranjan Dutta Dr. Won-Young Cha Dr. Seong-Jin Hong Dr. Juwon Oh Dr. Dikhi Firmansyah Hongil Jo Prof. Dr. Kang Min Ok Prof. Dr. Chang-Hee Lee Prof. Dr. Dongho Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16434-16440
π–π Stacking is omnipresent not only in nature but in a wide variety of practical fields applied to our lives. Because of its importance in a performance of natural and artificial systems, such as light harvesting system and working layer in device, many researchers have put intensive effort into identifying its underlying nature. However, for the case of π–π stacked systems composed of antiaromatic units, the understanding of the fundamental mechanisms is still unclear. Herein, we synthesized a new type of planar β,β’-phenylene-bridged hexaphyrin (1.0.1.0.1.0), referred as naphthorosarin which possesses the 24π-electron conjugated pathway. Especially, the corresponding antiaromatic porphyrinoid shows the unique property to form dimeric species adopting the face-to-face geometry which is unprecedented in cases of known annulated naphthorosarins. In order to elucidate the intriguing properties derived from the stacked dimer, the current study focuses on the experimental support to rationalize the observed π–π interactions between the two subunits. 相似文献
973.
Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty. 相似文献
974.
Prof. Santiago Alvarez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(19):4350-4377
After briefly reviewing the applications of the coordination ability indices proposed earlier for anions and solvents toward transition metals and lanthanides, a new analysis of crystal structures is applied now to a much larger number of coordinating species: anions (including those that are present in ionic solvents), solvents, amino acids, gases, and a sample of neutral ligands. The coordinating ability towards s-block elements is now also considered. The effect of several factors on the coordinating ability will be discussed: (a) the charge of an anion, (b) the chelating nature of anions and solvents, (c) the degree of protonation of oxo-anions, carboxylates and amino carboxylates, and (d) the substitution of hydrogen atoms by methyl groups in NH3, ethylenediamine, benzene, ethylene, pyridine and aldehydes. Hit parades of solvents and anions most commonly used in the areas of transition metal, s-block and lanthanide chemistry are deduced from the statistics of their presence in crystal structures. 相似文献
975.
Tingke Rao Prof. Maria Luisa Saladino Prof. Yuanxing Fang Prof. Xinchen Wang Dr. Cristina Giordano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16676-16682
A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc–gallium oxynitrides and zinc–gallium–indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m2 g−1). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h−1), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H2 evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement. 相似文献
976.
Yan‐Ping Zhang Yue Li Guan‐Cheng Xu Jin‐Yu Li Hua‐Ying Luo Jin‐Yao Li Li Zhang Dian‐Zeng Jia 《应用有机金属化学》2019,33(3)
Two new complexes, namely [Cu6L6] ( 1 ) and [Zn(HL)2] ( 2 ) (H2L = N‐(1‐phenyl‐3‐methyl‐4‐propenylidene‐5‐pyrazolone)‐2‐furancarboxylic acid hydrazide), have been synthesized and characterized. Single crystal X‐ray analysis indicates that complex 1 has a hexanuclear structure and complex 2 exhibits a mononuclear structure. The DNA/bovine serum albumin (BSA) binding properties of complexes 1 and 2 were investigated by absorption spectroscopy and fluorescence quenching. Both complexes could effectively intercalate to DNA with calculated quenching constants of 2.6 × 105 and 1.25 × 105 M?1, respectively. The quenching mechanism of the intrinsic fluorescence of BSA by the complexes was found to be a static one. The cytotoxicities of 1 and 2 were investigated in two human tumor cell lines, human esophageal cancer cells (Eca‐109) and cervical cancer cells (HeLa). Complex 1 exhibits higher antitumor activity than 2 . Furthermore, 1 can inhibit HeLa cells by inducing apoptosis and G0/G1 phase cell cycle arrest. All results demonstrate that 1 and 2 both have DNA/BSA binding capacity and antitumor activity. 相似文献
977.
We consider the nonlinear problem of inhomogeneous Allen–Cahn equation where Ω is a bounded domain in with smooth boundary, ? is a small positive parameter, ν denotes the unit outward normal of ?Ω, V is a positive smooth function on . Let Γ be a curve intersecting orthogonally with ?Ω at exactly two points and dividing Ω into two parts. Moreover, Γ satisfies stationary and non-degenerate conditions with respect to the functional . We can prove that there exists a solution such that: as , approaches +1 in one part of Ω, while tends to ?1 in the other part, except a small neighborhood of Γ. 相似文献
978.
979.
Carsten Lenczyk Dr. Dipak Kumar Roy Bijoy Ghosh Johannes Schwarzmann Prof. Ashwini K. Phukan Prof. Dr. Holger Braunschweig 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8585-8589
A series of bis(σ)-borane complexes of Group 6 transition metals were prepared by direct dihydroborane coordination to the metal center. Reaction of [M(CO)3(PCy3)2] and two dihydroboranes [DurBH2] and [(Me3Si)2NBH2] (Dur=2,3,5,6-Me4C6H) yielded bis(σ)-borane complexes fac-[M(CO)3(PCy3){η2-(H2BR)}] (R=Dur; 1 : M=Cr, 2 : M=W; R=N(SiMe3)2; 3 : M=Cr, 4 : M=W). In the case of molybdenum, we have isolated an arene complex ( 5 ) with [DurBH2] in which the Dur group acts as a η6-bound ligand, and with [(Me3Si)2NBH2] a similar bis(σ)-borane complex was isolated, cis,trans-[Mo(CO)2(PCy3)2{η2-(H2BN(SiMe3)2}] ( 6 ), with a different pattern of auxiliary ligands. The complexes were investigated by multinuclear NMR spectroscopy, mass spectrometry, X-ray diffraction analysis, and computational methods. Quantum theory of atoms in molecules (QTAIM) calculations demonstrated that the borane complexes may be described as pure bis(σ)-borane complexes rather than elongated or stretched examples given that the calculations do not show the presence of a ring-critical point (RCP) at the ring formed by the interactions of the B−H with metal center. 相似文献
980.
Yinwu Li Jiahao Liu Dr. Xiao Huang Prof. Dr. Ling-Bo Qu Prof. Dr. Cunyuan Zhao Prof. Dr. Robert Langer Prof. Dr. Zhuofeng Ke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(60):13785-13798
As a new type of bifunctional catalyst, the Lewis acid transition-metal (LA-TM) catalysts have been widely applied for hydrogen activation. This study presents a mechanistic framework to understand the LA-TM-catalyzed H2 activation through DFT studies. The mer(trans)-homolytic cleavage, the fac(cis)-homolytic cleavage, the synergetic heterolytic cleavage, and the dissociative heterolytic cleavage should be taken as general mechanisms for the field of LA-TM catalysis. Four typical LA-TM catalysts, the Z-type κ4-L3B-Rh complex tri(azaindolyl)borane-Rh, the X-type κ3-L2B-Co complex bis-phosphino-boryl (PBP)-Co, the η2-BC-type κ3-L2B-Pd complex diphosphine-borane (DPB)-Pd, and the Z-type κ2-LB-Pt complex (boryl)iminomethane (BIM)-Pt are selected as representative models to systematically illustrate their mechanistic features and explore the influencing factors on mechanistic variations. Our results indicate that the tri(azaindolyl)borane-Rh catalyst favors the synergetic heterolytic mechanism; the PBP-Co catalyst prefers the mer(trans)-homolytic mechanism; the DPB-Pd catalyst operates through the fac(cis)-homolytic mechanism, whereas the BIM-Pt catalyst tends to undergo the dissociative heterolytic mechanism. The mechanistic variations are determined by the coordination geometry, the LA-TM bonding nature, the electronic structure of the TM center, and the flexibility or steric effect of the LA ligands. The presented mechanistic framework should provide helpful guidelines for LA-TM catalyst design and reaction developments. 相似文献