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991.
Marcelo L. Pereira Júnior Prof. Luiz A. Ribeiro Júnior Wjefferson H. S. Brandão Acrisio L. Aguiar Douglas S. Galvão José M. de Sousa 《Chemphyschem》2020,21(17):1918-1924
Popgraphene (PopG) is a new 2D planar carbon allotrope which is composed of 5–8–5 carbon rings. PopG is intrinsically metallic and possesses excellent thermal and mechanical stability. In this work, we report a detailed study of the thermal effects on the mechanical properties of PopG membranes using fully-atomistic reactive (ReaxFF) molecular dynamics simulations. Our results showed that PopG presents very distinct fracture mechanisms depending on the temperature and direction of the applied stretching. The main fracture dynamics trends are temperature independent and exhibit an abrupt rupture followed by fast crack propagation. The reason for this anisotropy is due to the fact that y-direction stretching leads to a deformation in the shape of the rings that cause the breaking of bonds in the pentagon-octagon and pentagon-pentagon ring connections, which is not observed for the x-direction. PopG is less stiff than graphene membranes, but the Young's modulus value is only 15 % smaller. 相似文献
992.
Dr. Giovanny Carvalho dos Santos Juan Carlos Roldao Dr. Junqing Shi Dr. Begoña Milián-Medina Prof. Dr. Luiz Carlos da Silva-Filho Dr. Johannes Gierschner 《Chemphyschem》2020,21(16):1797-1804
A combined spectroscopic and TD-DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino- vs. nitro-substituted 2,4-diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset-corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low-lying n-π* and ππ* transitions, which is decisive for the non-/emissive nature of the different compounds. In all, this might provide a valuable tool for computer-aided design of related classes of compounds. 相似文献
993.
Dr. Hiromichi Nakahara Dr. Marie Pierre Krafft Prof. Osamu Shibata 《Chemphyschem》2020,21(17):1966-1970
We found that monolayers of dipalmitoylphosphatidylcholine (DPPC) and semi-fluorinated tetrablock di(F10H16) self-assemble to form a new type of large, complex flower-like patterns on the surface of water and on solid substrates. The hierarchical organization of these unusual self-assemblies was investigated using compression and surface potential isotherms, in situ fluorescence and Brewster angle microscopies, and atomic force microscopy after transfer. 相似文献
994.
Dr. Bence Kutus Jun Zhu Dr. Jian Luo Prof. Dr. Qi-Qiang Wang Dr. Alexandru Lupan Dr. Amr A. A. Attia Prof. Dr. De-Xian Wang Dr. Johannes Hunger 《Chemphyschem》2020,21(17):1957-1965
Tritopic ion-pair receptors can bind bivalent salts in solution; yet, these salts have a tendency to form ion-pairs even in the absence of receptors. The extent to which such receptors can enhance ion pairing has however remained elusive. Here, we study ion pairing of M2+ (Ba2+, Sr2+) and X− (I−, ClO4−) in acetonitrile with and without a dichlorooxacalix[2]arene[2]triazine-related receptor containing a pentaethylene-glycol moiety. We find marked ion association already in receptor-free solutions. When present, most of the MX+ ion-pairs are bound to the receptor and the overall degree of ion association is enhanced due to coordinative, hydrogen-bonding, and anion-π interactions. The receptor shows higher selectivity for iodides but also stabilizes perchlorates, despite the latter are often considered as weakly coordinating anions. Our results show that ion-pair binding is strongly correlated to ion pairing in these solutions, thereby highlighting the importance of taking ion association in organic solvents into account. 相似文献
995.
996.
Mechanically induced C−C bond formation was demonstrated by the laser driven shock wave generated in liquid normal alkanes at room temperature. Gas chromatography mass spectrometry analysis revealed the dehydrogenation condensation between two alkane molecules, for seven normal alkanes from pentane to undecane. Major products were identified to be linear and branched alkane molecules with double the number of carbons, and exactly coincided with the molecules predicted by supposing that a C−C bond was formed between two starting molecules. The production of the alkane molecules showed that the C−C bond formation occurred almost evenly at all the carbon positions. The dependence of the production on the laser pulse energy clearly indicated that the process was attributed to the shock wave. The C−C bond formation observed was not a conventional passive chemical reaction but an unprecedented active reaction. 相似文献
997.
Dr. Luis Martín-Gomis Sairaman Seetharaman David Herrero Prof. Dr. Paul A. Karr Prof. Dr. Fernando Fernández-Lázaro Prof. Dr. Francis D'Souza Prof. Dr. Ángela Sastre-Santos 《Chemphyschem》2020,21(20):2254-2262
The effect of donor-acceptor distance in controlling the rate of electron transfer in axially linked silicon phthalocyanine-C60 dyads has been investigated. For this, two C60-SiPc-C60 dyads, 1 and 2 , varying in their donor-acceptor distance, have been newly synthesized and characterized. In the case of C60-SiPc-C60 1 where the SiPc and C60 are separated by a phenyl spacer, faster electron transfer was observed with kcs equal to 2.7×109 s−1 in benzonitrile. However, in the case of C60-SiPc-C60 2 , where SiPc and C60 are separated by a biphenyl spacer, a slower electron transfer rate constant, kcs=9.1×108 s−1, was recorded. The addition of an extra phenyl spacer in 2 increased the donor-acceptor distance by ∼4.3 Å, and consequently, slowed down the electron transfer rate constant by a factor of ∼3.7. The charge separated state lasted over 3 ns, monitoring time window of our femtosecond transient spectrometer. Complimentary nanosecond transient absorption studies revealed formation of 3SiPc* as the end product and suggested the final lifetime of the charge separated state to be in the 3–20 ns range. Energy level diagrams established to comprehend these mechanistic details indicated that the comparatively high-energy SiPc.+-C60.− charge separated states (1.57 eV) populated the low-lying 3SiPc* (1.26 eV) prior returning to the ground state. 相似文献
998.
Dr. Anthony Roucou Dr. Manuel Goubet Prof. Isabelle Kleiner Dr. Sabath Bteich Prof. Arnaud Cuisset 《Chemphyschem》2020,21(22):2523-2538
Rotational spectra of ortho-nitrotoluene (2-NT) and para-nitrotoluene (4-NT) have been recorded at low and room temperatures using a supersonic jet Fourier Transform microwave (MW) spectrometer and a millimeter-wave frequency multiplier chain, respectively. Supported by quantum chemistry calculations, the spectral analysis of pure rotation lines in the vibrational ground state has allowed to characterise the rotational energy, the hyperfine structure due to the 14N nucleus and the internal rotation splittings arising from the methyl group. For 2-NT, an anisotropic internal rotation of coupled −CH3 and −NO2 torsional motions was identified by quantum chemistry calculations and discussed from the results of the MW analysis. The study of the internal rotation splittings in the spectra of three NT isomers allowed to characterise the internal rotation potentials of the methyl group and to compare them with other mono-substituted toluene derivatives in order to study the isomeric influence on the internal rotation barrier. 相似文献
999.
Shefali Saxena Sanjana Panchagnula Dr. M. Eugenia Sanz Dr. Cristóbal Pérez Dr. Luca Evangelisti Prof. Brooks H. Pate 《Chemphyschem》2020,21(23):2579-2584
1,4-Naphthoquinone (1,4-NQ) is an important product of naphthalene oxidation, and it appears as a motif in many biologically active compounds. We have investigated the structure of 1,4-NQ using chirped-pulse Fourier transform microwave spectroscopy and quantum chemistry calculations. The rotational spectra of the parent species, and its 13C and 18O isotopologues were observed in natural abundance, and their spectroscopic parameters were obtained. This allowed the determination of the substitution rs, mass-weighted rm and semi-experimental reSE structures of 1,4-NQ. The obtained structural parameters show that the quinone moiety mainly changes the structure of the benzene ring where it is inserted, modifying the C−C bonds to having predominantly single or double bond character. Furthermore, the molecular electrostatic surface potential reveals that the quinone ring becomes electron deficient while the benzene ring remains a nucleophile. The most electrophilic areas are the hydrogens attached to the double bond in the quinone ring. Knowledge of the nucleophilic and electrophilic areas in 1,4-NQ will help understanding its behaviour interacting with other molecules and guide modifications to tune its properties. 相似文献
1000.
Dr. Carles Acosta-Silva Prof. Joan Bertran Prof. Vicenç Branchadell Prof. Antoni Oliva 《Chemphyschem》2020,21(22):2594-2604
The effect of solvent reaction fields and oriented electric fields on the Kemp elimination reaction between methylamine or imidazole and 5-nitrobenzisoxazole has been theoretically studied. The Kemp reaction is the most widely used for the design of new enzymes. Our results, using the SMD continuous model for solvents, are in quite good agreement with the experimental fact that the rate of the analogous reaction with butylamine is one order of magnitude smaller in water than in acetonitrile. In the case of external electric fields, our results show that they can increase or decrease the energy barrier depending on the magnitude and orientation of the field. A duly oriented electric field may have a notable catalytic effect on the reaction. So, external electric fields and reaction fields due to the medium can contribute to the design of new enzymes. Several factors that must be taken into account to increase the catalytic effect are discussed. 相似文献