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41.
Skeleton Decoration of NHCs by Amino Groups and its Sequential Booster Effect on the Palladium‐Catalyzed Buchwald–Hartwig Amination 下载免费PDF全文
Yin Zhang Dr. Vincent César Golo Storch Dr. Noël Lugan Dr. Guy Lavigne 《Angewandte Chemie (International ed. in English)》2014,53(25):6482-6486
A challenging synthetic modification of PEPPSI‐type palladium pre‐catalysts consisting of a stepwise incorporation of one and two amino groups onto the NHC skeleton was seen to exert a sequential enhancement of the electronic donor properties. This appears to be positively correlated with the catalytic performances of the corresponding complexes in the Buchwald–Hartwig amination. This is illustrated, for example, by the quantitative amination of 4‐chloroanisole by morpholine within 2 h at 25 °C with a 2 mol % catalyst/substrate ratio or by a significant reduction of catalytic loading (down to 0.005 mol %) for the coupling of aryl chlorides with anilines (max TON: 19 600). 相似文献
42.
43.
We perform numerical simulations of hexagonal quantum dots of AlGaN semiconductors. We show that the competition between surface mass diffusion and evaporation rules the morphology of the quantum dots. The system displays three different behaviors: presence of separated islands without a wetting layer, islands dissolving into the wetting layer, or islands that do not evolve. The first behavior is of special interest because its optoelectrical properties are significantly improved in comparison with quantum dots with a wetting layer. 相似文献
44.
Essential oils in combination and their antimicrobial properties 总被引:1,自引:0,他引:1
Essential oils (EOs) have been long recognized for their antibacterial, antifungal, antiviral, insecticidal and antioxidant properties. They are widely used in medicine and the food industry for these purposes. The increased interest in alternative natural substances is driving the research community to find new uses and applications of these substances. EOs and their components show promising activities against many food-borne pathogens and spoilage microorganisms when tested in vitro. In food systems, higher concentrations of EOs are needed to exert similar antibacterial effects as those obtained in in vitro assays. The use of combinations of EOs and their isolated components are thus new approaches to increase the efficacy of EOs in foods, taking advantage of their synergistic and additive effects. The purpose of this review is to provide an overview on the antimicrobial efficacy of these combinations. A survey of the methods used for the determination of the interactions and mechanisms involved in the antimicrobial activities of these combinations are also reported. 相似文献
45.
We study the influence of lateral stress on the stability of thin viscoelastic films. The free surface of a deposited film under stress is shown to undergo an instability initiated by an anisotropic diffusion of the polymer molecules. This instability ultimately results in the formation of holes provided that the initial surface fluctuations are larger than a critical value. The latter is found to decrease when increasing the stress. An increase of the holes number density with the stress is therefore predicted. Most interestingly, the holes number density is also predicted to increase when increasing the molecular weight of the polymers. Additionally, we demonstrate that the friction of the substrate suppresses any spatial coherence between holes on large length scales. These predictions explain recent experimental observations made on thin spin-coated polystyrene films [G. Reiter, Nat. Mater. 4, 754 (2005)10.1038/nmat1484]. 相似文献
46.
Deschamps M Campbell ID 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2006,178(2):206-211
In experiments performed on protonated proteins at high fields, 80% of the NMR spectrometer time is spent waiting for the 1H atoms to recover their polarization after recording the free induction decay. Selective excitation of a fraction of the protons in a large molecule has previously been shown to lead to faster longitudinal relaxation for the selected protons [K. Pervushin, B. Vögeli, A. Eletsky, Longitudinal 1H relaxation optimization in TROSY NMR spectroscopy, J. Am. Chem. Soc. 124 (2002) 12898–12902; P. Schanda, B. Brutscher, Very fast two-dimensional NMR spectroscopy for real-time investigation of dynamic events in proteins on the time scale of seconds, J. Am. Chem. Soc. 127 (2005) 8014–8015; H.S. Attreya, T. Szyperski, G-matrix Fourier transform NMR spectroscopy for complete protein resonance assignment, Proc. Natl. Acad. Sci. USA 101 (2004) 9642–9647]. The pool of non-selected protons acts as a “thermal bath” and spin-diffusion processes (“flip-flop” transitions) channel the excess energy from the excited pool to the non-selected protons in regions of the molecule where other relaxation processes can dissipate the excess energy. We present here a sensitivity enhanced HSQC sequence (COST-HSQC), based on one selective E-BURP pulse, which can be used on protonated 15N enriched proteins (with or without 13C isotopic enrichment). This experiment is compared to a gradient sensitivity enhanced HSQC with a water flip-back pulse (the water flip-back pulse quenches the spin diffusion between 1HN and 1Hα spins). This experiment is shown to have significant advantages in some circumstances. Some observed limitations, namely sample overheating with short recovery delays and complex longitudinal relaxation behaviour are discussed and analysed. 相似文献
47.
A Landau‐Lifshitz‐Gilbert‐Type equation and torsion effects on the dynamics of magnetization 下载免费PDF全文
Based on the non‐relativistic regime of electrons described by a Dirac equation coupled to a torsion pseudo‐vector, we study the dynamics of magnetization and how it may be affected by the presence of this (background) torsion field. The latter describes some anisotropy of the bulk and it may be accounted for in two ways: by means of a minimal coupling in a covariant derivative endowed with spin connection and a gauge magnetic field; in addition, through a non‐minimal interaction term with the spin density. We show, within this framework, that it is possible to attain a version of the Landau‐Lifshitz equation in presence of the torsion background where its effects are included, re‐enforcing that torsion corresponds to a geometric anisotropy with relevant unfolds on the spin coupling mechanism. We also conclude that the torsion terms can open up two important landscapes in the magnetization dynamics: one of them, related with a damping effect; the other, related with the screw dislocation that gives us a global effect like a sharped‐helix damping. The whole effort here is then to pursue an investigation of torsion in connection with the precession dynamics of the magnetization.
48.
Dubois F Meunier S Rabau G Poisson F Guyader G 《The Journal of the Acoustical Society of America》2011,130(5):EL284-EL289
The detection of multicomponent signals for which the components are not equidetectable is precisely investigated as a function of the level difference ΔL(i∕j) between components. The detection thresholds are determined for a seven-tone complex signal with random starting phases masked by white noise. Level differences between the components are examined. A model for non-equidetectable conditions based on the statistical summation model is described. The improvement in detection is calculated from the level difference between components that is related to the thresholds for single components. The model predictions are in accordance with the experimental results. 相似文献
49.
With through space and through bond experiments in two-dimensional NMR we analyze the transformation from the thorium phosphate-hydrogen phosphate hydrate (TPHPH) to the β form of the thorium phosphate diphosphate (β-TPD) in relation with the phosphorus networks. These techniques are complementary: the through space coupling gives an insight on the dipolar phosphorus networks while the through bond coupling is particularly efficient in the detection of the P2O7 groups. With these experiments we show that in a first step, by heating the precursor TPHPH above 250 °C, it transforms into an form of TPD. This transformation is due to the complete condensation of hydrogen phosphate groups HPO4 into P2O7 entities. By heating -TPD above 950 °C it transforms into its well-known β form. The form is characterized by a hygroscopic behavior: some water molecules are present near the P2O7 groups that makes non-equivalent their phosphorus nuclei. PO4 dipolar networks are always present in the form. The main effect of these PO4 and P2O7 units is to give the system a channel structure and the water enters in them. 相似文献
50.
We constrain the possible time variation of the Higgs vacuum expectation value (v) by recent results on the primordial 4He abundance (Y
P
). For that, we use an analytic approach which enables us to take important issues into consideration, that have been ignored
by previous works, like the v-dependence of the relevant cross sections of deuterium production and photodisintegration, including the full Klein–Nishina
cross section. Furthermore, we take a non-equilibrium Ansatz for the freeze-out concentration of neutrons and protons and
incorporate the latest results on the neutron decay. Finally, we approximate the key-parameters of the primordial 4He production (the mean lifetime of the free neutron and the binding energy of the deuteron) by terms of
(where v
0 denotes the present theoretical estimate). Eventually, we derive the relation
and the most stringent limit on a possible time variation of v is given by:
. 相似文献