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101.
Energetic 2,2‐Dimethyltriazanium Salts: A New Family of Nitrogen‐Rich Hydrazine Derivatives 下载免费PDF全文
Dr. Valérian Forquet Dr. Carlos Miró Sabaté Dr. Guy Jacob Dr. Yann Guelou Dr. Henri Delalu Dr. Chaza Darwich 《化学:亚洲杂志》2015,10(8):1668-1675
Amination of 1,1‐dimethylhydrazine with NH2Cl or hydroxylamine‐O‐sulfonic acid yields 2,2‐dimethyltriazanium (DMTZ) chloride ( 3 ) and sulphate ( 4 ), respectively. The DMTZ cation was paired with the nitrogen‐rich anions 5‐aminotetrazolate ( 5 ), 5‐nitrotetrazolate ( 6 ), 5,5′‐azobistetrazolate ( 7 ), and azide ( 8 ), yielding a new family of energetic salts. The synthesis was carried out by metathesis reactions of salts 3 or 4 and a suitable silver or barium salt. To minimize the risks involved when using heavy metal salts, we used electrodialysis for the synthesis of azide 8 , which avoids the use of highly sensitive species. The DMTZ derivatives were characterized by IR and multinuclear NMR spectroscopy, elemental analysis, and X‐ray diffraction. Thermal stabilities were measured using DSC analysis and their sensitivities towards classical stimuli were determined using standard tests. Lastly, the relationship between hydrogen bonding in the solid state and sensitivity is discussed. 相似文献
102.
Dr. Shrinivas Dumbre Dr. Valérie Pezo Guy Schepers Prof. Vitor B. Pinheiro Prof. Eveline Lescrinier Prof. Philipp Holliger Dr. Philippe Marlière Prof. Piet Herdewijn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5009-5022
The synthesis, base‐pairing properties and in vitro and in vivo characteristics of 5‐methyl‐isocytosine (isoCMe) and isoguanine (isoG) nucleosides, incorporated in an HNA(h) (hexitol nucleic acid)–DNA(d) mosaic backbone, are described. The required h‐isoG phosphoramidite was prepared by a selective deamination as a key step. As demonstrated by Tm measurements the hexitol sugar showed slightly better mismatch discrimination against dT. The d‐isoG base mispairing follows the order T>G>C while the h‐isoG base mispairing follows the order G>C>T. The h‐ and d‐isoCMe bases mainly mispair with G. Enzymatic incorporation experiments show that the hexitol backbone has a variable effect on selectivity. In the enzymatic assays, isoG misincorporates mainly with T, and isoCMe misincorporates mainly with A. Further analysis in vivo confirmed the patterns of base‐pair interpretation for the deoxyribose and hexitol isoCMe/isoG bases in a cellular context, through incorporation of the bases into plasmidic DNA. Results in vivo demonstrated that mispairing and misincorporation was dependent on the backbone scaffold of the base, which indicates rational advances towards orthogonality. 相似文献
103.
EPR Studies of the Binding Properties,Guest Dynamics,and Inner‐Space Dimensions of a Water‐Soluble Resorcinarene Capsule 下载免费PDF全文
Dr. Mehmet Menaf Ayhan Dr. Gilles Casano Dr. Hakim Karoui Prof. Antal Rockenbauer Dr. Valérie Monnier Dr. Micaël Hardy Prof. Paul Tordo Dr. David Bardelang Dr. Olivier Ouari 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16404-16410
Nitroxide free radicals have been used to study the inner space of one of Rebek’s water‐soluble capsules. EPR and 1H NMR spectroscopy, ESI‐MS, and DFT calculations showed a preference for the formation of 1:2 complexes. EPR titrations allowed us to determine binding constants (Ka) in the order of 107 M ?2. EPR spectral‐shape analysis provided information on the guest rotational dynamics within the capsule. The interplay between optimum hydrogen bonding upon capsule formation and steric strain for guest accommodation highlights some degree of flexibility for guest inclusion, particularly at the center of the capsule where the hydrogen bond seam can be barely distorted or slightly disturbed. 相似文献
104.
Frontispiece: EPR Studies of the Binding Properties,Guest Dynamics,and Inner‐Space Dimensions of a Water‐Soluble Resorcinarene Capsule 下载免费PDF全文
105.
S. Valère Bitseki Penda Adélaïde Olivier 《Statistical Inference for Stochastic Processes》2017,20(2):179-210
Bifurcating autoregressive processes, which can be seen as an adaptation of autoregressive processes for a binary tree structure, have been extensively studied during the last decade in a parametric context. In this work we do not specify any a priori form for the two autoregressive functions and we use nonparametric techniques. We investigate both nonasymptotic and asymptotic behaviour of the Nadaraya–Watson type estimators of the autoregressive functions. We build our estimators observing the process on a finite subtree denoted by \(\mathbb {T}_n\), up to the depth n. Estimators achieve the classical rate \(|\mathbb {T}_n|^{-\beta /(2\beta +1)}\) in quadratic loss over Hölder classes of smoothness. We prove almost sure convergence, asymptotic normality giving the bias expression when choosing the optimal bandwidth. Finally, we address the question of asymmetry: we develop an asymptotic test for the equality of the two autoregressive functions which we implement both on simulated and real data. 相似文献
106.
In this experimental work, we investigate the influence of an organic counterion, sodium tosylate, on the rheological properties
of an aqueous solution of CTAB at the concentration of 0.05M. With this system we can clearly see shear thickening for small
salt concentrations C
s
and only shear thinning behavior at higher C
s
characterized by a linear evolution of η=f(γ) in a log-log representation. In these evolutions it is only in a very small domain of concentrations of the salt (near
C
s
=0.035M) that we can observe a nearly constant plateau of the shear stress against shear rate. The values of σ0 (characterizing the stress plateau), G
0 (the plateau modulus) and τR (the relaxation time) obtained by dynamical rheological measurements, allow to compare experimental results obtained to predicted
values of the theory of Cates corresponding to the occurrence of shear induced banding structures.
Received: 22 July 1997 Accepted: 3 February 1998 相似文献
107.
Maryline Beyler Lucia Flamigni Valérie Heitz Jean‐Pierre Sauvage Barbara Ventura 《Photochemistry and photobiology》2014,90(2):275-286
Multiporphyrinic assemblies were quantitatively formed, in one step, from a gable‐like zinc(II) bis‐porphyrin ZnP2 and free‐base porphyrins bearing pyridyl groups. The different fragments are held together by axial 4′‐N(pyridyl)–Zn interactions. Formation of a macrocycle ZnP2?(4′‐cisDPyP) and a bis‐macrocycle (ZnP2)2?(TPyP) is discussed. The macrocycle and the bis‐macrocycle were crystallized and studied by X‐ray diffraction, which confirmed the excellent complementarity between the various components. Spectrophotometric and spectrofluorimetric titrations and studies reveal high association constants for both multiporphyrinic assemblies due to the almost perfect geometrical match between the interacting units. As expected, energy transfer from the zinc porphyrin component to the free‐base porphyrin quenches the fluorescence of the zinc porphyrin components in both compounds. But while in ZnP2?(4′‐cis DPyP) sensitization of the emission of the free‐base porphyrin was observed, in (ZnP2)2?(TPyP) excitation of the peripheral Zn porphyrin units does not lead to quantitative sensitization of the luminescence of the free‐base porphyrin acceptor. An unusual HOMO–HOMO electron transfer reaction from ZnP2 to the excited TPyP unit was detected and studied. 相似文献
108.
De Vriendt V Miladinovic SM Colaux JL Maseri F Wilkins CL Lucas S 《Langmuir : the ACS journal of surfaces and colloids》2011,27(14):8913-8922
The growth of hydrogenated amorphous carbons (a-C:H) produced by continuous or pulsed discharges of acetylene (C(2)H(2)) in an unbalanced magnetron setup was investigated. At 5 × 10(-3) Torr, only smooth films are obtained, whereas at 5 × 10(-1) Torr using a pulsed discharge some microtextured films are formed if the duty cycle is low. The morphology of these microtextured films consists of nanoparticles, filamentary particles, and particular agglomerates ("microflowers"). This paper presents a study of acetylene gas phase polymerization by mass spectrometry, and a detailed analysis of bulk structure of films by combining three techniques which include IR spectroscopy, Raman spectroscopy, and laser desorption/ionization Fourier transform mass spectrometry (LDI-FTMS). Finally, based on the study of gas phase and film structure, we propose a model for the growth of both smooth and microtextured films. 相似文献
109.
Destribats M Lapeyre V Sellier E Leal-Calderon F Schmitt V Ravaine V 《Langmuir : the ACS journal of surfaces and colloids》2011,27(23):14096-14107
Emulsions were prepared using poly(N-isopropylacrylamide) microgels as thermoresponsive stabilizers. The latter are well-known for their sensitivity to temperature: they are swollen by water below the so-called volume phase transition temperature (VPTT = 33 °C) and shrink when heated above it. Most of the studies reported in the literature reveal that the corresponding emulsions are of the oil-in-water type (O/W) and undergo fast destabilization upon warming above the VPTT. In the present study, whereas O/W emulsions were obtained with a wide panel of oils of variable polarity and were all thermoresponsive, water-in-oil (W/O) emulsions were found only in the presence of fatty alcohols and did not exhibit any thermal sensitivity. To understand the peculiar behavior of emulsions based on fatty alcohols, we investigated the organization of microgels at the oil-water interface and we studied the interactions of pNIPAM microgels with octanol. By combining several microscopy methods and by exploiting the limited coalescence process, we provided evidence that W/O emulsions are stabilized by multilayers of nondeformed microgels located inside the aqueous drops. Such behavior is in contradiction with the empirical Finkle rule stating that the continuous phase of the preferred emulsion is the one in which the stabilizer is preferentially dispersed. The study of microgels in nonemulsified binary water/octanol systems revealed that octanol diffused through the aqueous phase and was incorporated in the microgels. Thus, W/O emulsions were stabilized by microgels whose properties were substantially different from the native ones. In particular, after octanol uptake, they were no longer thermoresponsive, which explained the loss of responsiveness of the corresponding W/O emulsions. Finally, we showed that the incorporation of octanol modified the interfacial properties of the microgels: the higher the octanol uptake before emulsification, the lower the amount of particles in direct contact with the interface. The multilayer arrangement was thus necessary to ensure efficient stabilization against coalescence, as it increased interface cohesiveness. We discussed the origin of this counterexample of the Finkle's rule. 相似文献
110.
Bouchonnet S Kinani S Souissi Y Bourcier S Sablier M Roche P Boireau V Ingrand V 《Rapid communications in mass spectrometry : RCM》2011,25(1):93-103
With the future aim of using gas chromatography coupled with mass spectrometry to characterize the transformation products of ozonated herbicides: metolachlor, acetochlor and alachlor, an interpretation of their electron ionization mass spectra is presented. Fragmentation mechanisms are proposed on the basis of isotopic labelling and multiple-stage mass spectrometry experiments carried out on an ion trap mass spectrometer. We also give examples in order to demonstrate how the elucidation of such fragmentation mechanisms for herbicides may simplify the characterization of their ozonation products. 相似文献