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排序方式: 共有6001条查询结果,搜索用时 46 毫秒
1.
Gary W. Breton Lauren A. Hahn Kenneth L. Martin 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(9):1208-1212
Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C25H30N4O4, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl3). A tentative reaction pathway for its dissociation based on 1H NMR spectral evidence is provided. 相似文献
2.
Gabrielle A. Leith Allison M. Rice Brandon J. Yarbrough Anna A. Berseneva Richard T. Ly Charles N. Buck III Dr. Denis Chusov Amy J. Brandt Prof. Dr. Donna A. Chen Benjamin W. Lamm Prof. Dr. Morgan Stefik Kenneth S. Stephenson Dr. Mark D. Smith Prof. Dr. Aaron K. Vannucci Dr. Perry J. Pellechia Prof. Dr. Sophya Garashchuk Prof. Dr. Natalia B. Shustova 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6056-6062
The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials. 相似文献
3.
Kamila B. Muchowska Dominic J. Pascoe Stefan Borsley Ivan V. Smolyar Ioulia K. Mati Catherine Adam Gary S. Nichol Kenneth B. Ling Scott L. Cockroft 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14710-14716
Interactions between carbonyl groups are prevalent in protein structures. Earlier investigations identified dominant electrostatic dipolar interactions, while others implicated lone pair n→π* orbital delocalisation. Here these observations are reconciled. A combined experimental and computational approach confirmed the dominance of electrostatic interactions in a new series of synthetic molecular balances, while also highlighting the distance-dependent observation of inductive polarisation manifested by n→π* orbital delocalisation. Computational fiSAPT energy decomposition and natural bonding orbital analyses correlated with experimental data to reveal the contexts in which short-range inductive polarisation augment electrostatic dipolar interactions. Thus, we provide a framework for reconciling the context dependency of the dominance of electrostatic interactions and the occurrence of n→π* orbital delocalisation in C=O⋅⋅⋅C=O interactions. 相似文献
4.
Shaobo Cheng Vidushi Sharma Altug S. Poyraz Lijun Wu Xing Li Amy C. Marschilok Esther S. Takeuchi Kenneth J. Takeuchi Marivi Fernndez-Serra Yimei Zhu 《Chemical science》2020,11(19):4991
Tunneled metal oxides such as α-Mn8O16 (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K+ ions (which act as structure-stabilizing dopants) and H2O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K+-doped α-Mn8O16 (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H2O displaces K+ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K2+ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li+/Na+ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies.Water displaces potassium ions and initiates the formation of a homonuclear dimer ion (K2+) in the tunnels of hollandite. 相似文献
5.
6.
Dr. Mick Hornum Julie Stendevad Dr. Pawan K. Sharma Dr. Pawan Kumar Rasmus B. Nielsen Dr. Michael Petersen Dr. Poul Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7387-7395
Nucleotides that contain two nucleobases (double-headed nucleotides) have the potential to condense the information of two separate nucleotides into one. This presupposes that both bases must successfully pair with a cognate strand. Here, double-headed nucleotides that feature cytosine, guanine, thymine, adenine, hypoxanthine, and diaminopurine linked to the C2′-position of an arabinose scaffold were developed and examined in full detail. These monomeric units were efficiently prepared by convergent synthesis and incorporated into DNA oligonucleotides by means of the automated phosphoramidite method. Their pairing efficiency was assessed by UV-based melting-temperature analysis in several contexts and extensive molecular dynamics studies. Altogether, the results show that these double-headed nucleotides have a well-defined structure and invariably behave as functional dinucleotide mimics in DNA duplexes. 相似文献
7.
Fourier transform infrared (FTIR) smog chamber techniques were used to investigate the atmospheric chemistry of the isotopologues of methane. Relative rate measurements were performed to determine the kinetics of the reaction of the isotopologues of methane with OH radicals in cm3 molecule−1 s−1 units: k(CH3D + OH) = (5.19 ± 0.90) × 10−15, k(CH2D2 + OH) = (4.11 ± 0.74) × 10−15, k(CHD3 + OH) = (2.14 ± 0.43) × 10−15, and k(CD4 + OH) = (1.17 ± 0.19) × 10−15 in 700 Torr of air diluent at 296 ± 2 K. Using the determined OH rate coefficients, the atmospheric lifetimes for CH4–xDx (x = 1–4) were estimated to be 6.1, 7.7, 14.8, and 27.0 years, respectively. The results are discussed in relation to previous measurements of these rate coefficients. 相似文献
8.
9.
A Savitzky–Golay filtering for smoothing and peak search written in Python is presented in this paper alongside its applications in the list-mode digital data acquisition dual gamma–gamma coincidence bismuth germanate (BGO) detector. The study has demonstrated that the software provides a reliable and effective way to quantify trace amounts of 22Na and 7Be in aerosol samples collected at Resolute Bay, Canada with a critical limit of 3 mBq and 5 Bq respectively for a 20 h counting interval, which are believed to be the inherent limitations of the dual-BGO system.
相似文献10.
Controlling effective interactions and spatial dispersion of nanoparticles in multiblock copolymer melts 下载免费PDF全文
Debapriya Banerjee Kenneth S. Schweizer 《Journal of Polymer Science.Polymer Physics》2015,53(16):1098-1111
The microscopic Polymer Reference Interaction Site Model theory is employed to study, for the first time, the effective interactions, spatial organization, and miscibility of dilute spherical nanoparticles in non‐microphase separating, chemically heterogeneous, compositionally symmetric AB multiblock copolymer melts of varying monomer sequence or architecture. The dependence of nanoparticle wettability on copolymer sequence and chemistry results in interparticle potentials‐of‐mean force that are qualitatively different from homopolymers. An important prediction is the ability to improve nanoparticle dispersion via judicious choice of block length and monomer adsorption‐strengths which control both local surface segregation and chain connectivity induced packing constraints and frustration. The degree of dispersion also depends strongly on nanoparticle diameter relative to the block contour length. Small particles in copolymers with longer block lengths experience a more homopolymer‐like environment which renders them relatively insensitive to copolymer chemical heterogeneity and hinders dispersion. Larger particles (sufficiently larger than the monomer diameter) in copolymers of relatively short block lengths provide better dispersion than either a homopolymer or random copolymer. The theory also predicts a novel widening of the miscibility window for large particles upon increasing the overall molecular weight of copolymers composed of relatively long blocks. The influence of a positive chi‐parameter in the pure copolymer melt is briefly studied. Quantitative application to fullerenes in specific copolymers of experimental interest is performed, and miscibility predictions are made. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1098–1111 相似文献