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991.
Shuchi Gupta Olga Zhovtiuk Aleksandar Vaneski Yan‐Cheng Lin Wu‐Ching Chou Stephen V. Kershaw Andrey L. Rogach 《Particle & Particle Systems Characterization》2013,30(4):346-354
The energy gap between valence and conduction levels in colloidal semiconductor quantum dots can be tuned via the nanoparticle diameter when this is comparable to or less than the Bohr radius. In materials such as cadmium mercury telluride, which readily forms a single phase ternary alloy, this quantum confinement tuning can also be augmented by compositional tuning, which brings a further degree of freedom in the bandgap engineering. Here it is shown that compositional control of 2.3 nm diameter CdxHg(1?x)Te nanocrystals by exchange of Hg2+ in place of Cd2+ ions can be used to tune their optical properties across a technologically useful range, from 500 nm to almost 1200 nm. Data on composition‐dependent changes in the optical properties are provided, including bandgap, extinction coefficient, emission energy and spectral shape, Stokes shift, quantum efficiency, and radiative lifetimes as the exchange process occurs, which are highly relevant for those seeking to use these technologically important QD materials. 相似文献
992.
Hongkang Wang Yu Wang Stephen V. Kershaw Tak Fu Hung Jun Xu Andrey L. Rogach 《Particle & Particle Systems Characterization》2013,30(4):332-337
Fluorinated Eu‐doped SnO2 nanostructures with tunable morphology (shuttle‐like and ring‐like) are prepared by a hydrothermal method, using NaF as the morphology controlling agent. X‐ray diffraction, field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, X‐ray photoelectron spectroscopy, and energy dispersive spectroscopy are used to characterize their phase, shape, lattice structure, composition, and element distribution. The data suggest that Eu3+ ions are uniformly embedded into SnO2 nanocrystallites either through substitution of Sn4+ ions or through formation of Eu‐F bonds, allowing for high‐level Eu3+ doping. Photoluminescence features such as transition intensity ratios and Stark splitting indicate diverse localization of Eu3+ ions in the SnO2 nanoparticles, either in the crystalline lattice or in the grain boundaries. Due to formation of Eu‐F and Sn‐F bonds, the fluorinated surface of SnO2 nanocrystallites efficiently inhibits the hydroxyl quenching effect, which accounts for their improved photoluminescence intensity. 相似文献
993.
Zhe-Cheng Wei Qiao Wang Li-Jing Min Joanna Bajsa-Hirschel Charles L. Cantrell Liang Han Cheng-Xia Tan Jian-Quan Weng Yu-Xin Li Na-Bo Sun Stephen O. Duke Xing-Hai Liu 《Molecules (Basel, Switzerland)》2023,28(1)
Natural products are a source for pesticide or drug discovery. In order to discover lead compounds with high fungicidal or herbicidal activity, new niacinamide derivatives derived from the natural product niacinamide, containing chiral flexible chains, were designed and synthesized. Their structures were confirmed by 1H NMR, 13C NMR and HRMS analysis. The fungicidal and herbicidal activities of these compounds were tested. The fungicidal activity results demonstrated that the compound (S)-2-(2-chloronicotinamido)propyl-2-methylbenzoate (3i) exhibited good fungicidal activity (92.3% inhibition) against the plant pathogen Botryosphaeria berengriana at 50 μg/mL and with an EC50 of 6.68 ± 0.72 μg/mL, which is the same as the positive control (fluxapyroxad). Compound 3i was not phytotoxic and could therefore be used as a fungicide on crops. Structure-activity relationships (SAR) were studied by molecular docking simulations with the succinate dehydrogenase of the fungal mitochondrial respiratory chain. 相似文献
994.
Dr. Albert C. Rowett Stephen G. Sweeting Dr. David M. Heard Dr. Alastair J. J. Lennox 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(21):e202400570
The haloform reaction from methyl ketones to carboxylic acids is one of the oldest known synthetic organic reactions, which has been used in myriad applications over the decades. The corresponding reaction to produce esters is, however, less developed, as the reaction is generally limited to simple, primary alcohols that are used in solvent-level quantities, thereby restricting the complexity of esters that can be directly formed. Herein, we detail the development of a general ester-forming haloform coupling reaction using one equivalent of alcohol. Mechanistic and kinetic modelling studies demonstrated that the key intermediates are formed under equilibrium, which facilitated the development of conditions that are amenable to secondary alcohols. 相似文献
995.
Non-solvent induced phase separation (NIPS) method was employed to fabricate biodegradable poly(lactic acid) (PLA) nanocomposite membranes. Morphological studies using scanning electron microscopy revealed that all the membranes prepared display asymmetric structures comprising finger-like macropores. The incorporation of modified polyhedral oligomeric silsesquioxane (POSS) particles into the PLA matrix resulted in enhanced crystallinity, mechanical, and thermal properties. Annealing of the membranes was performed to explore the influence of temperature on the morphology and properties. After annealing, membranes become more thin and compact, and drastic enhancement in crystallinity is also observed. Consequently, Young's modulus experiences a significant improvement. The reduction in oil absorption capacity after annealing can be attributed to the higher level of crystallinity, reduced porosity, and smaller pore diameter observed in the annealed membranes. Additionally, the unannealed PLA nanocomposite membranes demonstrated exceptional oil absorption capacity, reaching approximately 88%. It is foreseeable that these PLA/POSS nanocomposite membranes possess the potential to be utilized as effective tools for oil–water separation, offering the advantage of mitigating secondary pollution. 相似文献
996.
Thomas R. Puleo Stephen J. Sujansky Shawn E. Wright Prof. Dr. Jeffrey S. Bandar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(13):4216-4229
Organic superbases are a distinct and increasingly utilized class of Brønsted base that possess properties complementary to common inorganic bases. This Concept article discusses recent applications of commercial organic superbases in modern synthetic methodologies. Examples of the advantages of organic superbases in three areas are highlighted, including the discovery of new base-catalyzed reactions, the optimization of reactions that require stoichiometric Brønsted base, and in high-throughput experimentation technology. 相似文献
997.
Alexandria N. Bone Chelsea N. Widener Duncan H. Moseley Zhiming Liu Zhengguang Lu Dr. Yongqiang Cheng Dr. Luke L. Daemen Dr. Mykhaylo Ozerov Prof. Joshua Telser Prof. Komalavalli Thirunavukkuarasu Dr. Dmitry Smirnov Samuel M. Greer Prof. Stephen Hill Dr. J. Krzystek Dr. Karsten Holldack Azar Aliabadi Dr. Alexander Schnegg Prof. Kim R. Dunbar Prof. Zi-Ling Xue 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(43):11110-11125
Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh3)2X2 ( Co-X ; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X , showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling. 相似文献
998.
999.
Luke Britton Jamie H. Docherty Jan Sklyaruk Jessica Cooney Gary S. Nichol Andrew P. Dominey Stephen P. Thomas 《Chemical science》2022,13(35):10291
C–H functionalisation reactions offer a sustainable method for molecular construction and diversification. These reactions however remain dominated by precious metal catalysis. While significant interest in iron-catalysed C–H activation reactions has emerged, the isolation, characterisation and mechanistic understanding of these processes remain lacking. Herein the iron-catalysed C(sp2)–H bond hydrogen/deuterium exchange reaction using CD3OD is reported for both heterocycles and, for the first time, alkenes (38 examples). Isolation and characterisation, including by single-crystal X-ray diffraction, of the key iron-aryl and iron-alkenyl C–H metallation intermediates provided evidence for a reversible protonation of the active iron hydride catalyst. Good chemoselectivity was observed for both substrate classes. The developed procedure is orthogonal to previous iron-catalysed H/D exchange methods which used C6D6, D2, or D2O as the deuterium source, and uses only bench-stable reagents, including the iron(ii) pre-catalyst. Further, a new mechanism of iron-hydride formation is reported in which β-hydride elimination from an alcohol generates the iron hydride. The ability to produce, isolate and characterise the organometallic products arising from C–H activation presents a basis for future discovery and development.The iron-catalysed C(sp2)–H bond H/D exchange reaction using CD3OD is reported for both heterocycles and alkenes. Characterisation of the key C–H metallation intermediates provided evidence for reversible protonation of the iron hydride catalyst. 相似文献
1000.
Giovanni Bressan Michael Jirasek Palas Roy Harry L. Anderson Stephen R. Meech Ismael A. Heisler 《Chemical science》2022,13(33):9624
In photosynthesis, nature exploits the distinctive electronic properties of chromophores arranged in supramolecular rings for efficient light harvesting. Among synthetic supramolecular cyclic structures, porphyrin nanorings have attracted considerable attention as they have a resemblance to naturally occurring light-harvesting structures but offer the ability to control ring size and the level of disorder. Here, broadband femtosecond transient absorption spectroscopy, with pump pulses in resonance with either the high or the low energy sides of the inhomogeneously broadened absorption spectrum, is used to study the population dynamics and ground and excited state vibrational coherence in large porphyrin nanorings. A series of fully conjugated, alkyne bridged, nanorings constituted of between ten and forty porphyrin units is studied. Pump-wavelength dependent fast spectral evolution is found. A fast rise or decay of the stimulated emission is found when large porphyrin nanorings are excited on, respectively, the high or low energy side of the absorption spectrum. Such dynamics are consistent with the hypothesis of a variation in transition dipole moment across the inhomogeneously broadened ground state ensemble. The observed dynamics indicate the interplay of nanoring conformation and oscillator strength. Oscillatory dynamics on the sub-ps time domain are observed in both pumping conditions. A combined analysis of the excitation wavelength-dependent transient spectra along with the amplitude and phase evolution of the oscillations allows assignment to vibrational wavepackets evolving on either ground or excited states electronic potential energy surfaces. Even though porphyrin nanorings support highly delocalized electronic wavefunctions, with coherence length spanning tens of chromophores, the measured vibrational coherences remain localised on the monomers. The main contributions to the beatings are assigned to two vibrational modes localised on the porphyrin cores: a Zn–N stretching mode and a skeletal methinic/pyrrolic C–C stretching and in-plane bending mode.Pump wavelength-dependent, ultrafast excited state dynamics arising from inhomogeneous broadening and ground and excited state nuclear wavepackets were observed for a series of Zn porphyrin nanorings made of 10 to 40 repeating units. 相似文献