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排序方式: 共有439条查询结果,搜索用时 15 毫秒
41.
Formaldehyde (HCHO) is a species involved in numerous key atmospheric chemistry processes that can significantly impact the oxidative capacity of the atmosphere. Since gaseous HCHO is soluble in water, the water droplets of clouds and the ice crystals of snow exchange HCHO with the gas phase and the partitioning of HCHO between the air, water, and ice phases must be known to understand its chemistry. This study proposes thermodynamic formulations for the partitioning of HCHO between the gas phase and the ice and liquid water phases. A reanalysis of existing data on the vapor-liquid equilibrium has shown the inadequacy of the Henry's law formulation, and we instead propose the following equation to predict the mole fraction of HCHO in liquid water at equilibrium, X(HCHO,liq), as a function of the partial pressure P(HCHO) (Pa) and temperature T (K): X(HCHO,liq) = 1.700 × 10(-15)?e((8014/T))(P(HCHO))(1.105). Given the paucity of data on the gas-ice equilibrium, the solubility of HCHO and the diffusion coefficient (D(HCHO)) in ice were measured by exposing large single ice crystals to low P(HCHO). Our recommended value for D(HCHO) over the temperature range 243-266 K is D(HCHO) = 6 × 10(-12) cm(2) s(-1). The solubility of HCHO in ice follows the relationship X(HCHO,ice) = 9.898 × 10(-13)?e((4072/T))(P(HCHO))(0.803). Extrapolation of these data yields the P(HCHO) versus 1/T phase diagram for the H(2)O-HCHO system. The comparison of our results to existing data on the partitioning of HCHO between the snow and the atmosphere in the high arctic highlights the interplay between thermodynamic equilibrium and kinetics processes in natural systems. 相似文献
42.
Héla Habli Leila Mejrissi Houcine Ghalla Saud Jamil Yaghmour Brahim Oujia Florent Xavier Gadéa 《Molecular physics》2013,111(10):1568-1582
A wide adiabatic study has been performed for numerous electronic states of CaLi+ molecular ion. The adiabatic potential energy curves and their spectroscopic constants (Re, De, ωe and Te) have been calculated using an ab initio approach including a nonempirical pseudo-potential for the Ca and Li cores with the core polarisation potentials operator through full configuration interaction (FCI). Thereafter, the energies of vibrational levels and their spacing for all these states have been reported. In addition, the electric dipole moment curves have been investigated for the (1-19) Σ, (1-12) Π and (1-8) Δ electric states. Moreover it lets us check the extreme transition dipole moments (TDM). These behaviours of TDM are more accustomed to estimate the radiative lifetimes for all vibrational levels in 21Σ+ and 31Σ+ states. Also, the bound-bound and the bound-free contribution have been calculated precisely and by employing a Franck–Condon (FC) approximation. 相似文献
43.
Florent Balacheff 《Geometriae Dedicata》2006,121(1):61-71
We study the systolic area (defined as the ratio of the area over the square of the systole) of the 2-sphere endowed with
a smooth Riemannian metric as a function of this metric. This function, bounded from below by a positive constant over the
space of metrics, admits the standard metric g
0 as a critical point, although it does not achieve the conjectured global minimum: we show that for each tangent direction
to the space of metrics at g
0, there exists a variation by metrics corresponding to this direction along which the systolic area can only increase.
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Water-soluble polymers containing a few hydrophobic anchors are known to bind onto lipid vesicles and are used as stabilizers of liposome-based formulas. In contrast, polymers with high hydrophobicity destabilize the lipid bilayers. With macromolecules of intermediate hydrophobic/hydrophilic balance, a gradual sweep of the stabilization-destabilization capacity can be achieved and is considered as promising triggered systems for drug release, although the mechanism of permeabilization and membrane breakage using polymers is essentially conjectural to date. As a model system, we used short octyl-modified poly(acrylic acid)s (MW 8000 g/mol) sensitive to pH, temperature, and ionic strength in conjunction with small unilamellar vesicles mainly comprised of DPPC or egg-PC. Kinetics of vesicle fragmentation was followed using static and dynamic light scattering. Polymer adsorption was studied by nonradiative energy transfer between pyrene-labeled lipids and a naphthalene-modified polymer. The permeability of the vesicles was characterized by calcein leakage experiments. The key findings were (i) the lack of coupling between the density of bound polymer and the rate of disruption and (ii) the qualitative difference depending on whether the polymer contains or not isopropyl side groups. Point i relates to the increase of the rate of polymer adsorption with increasing bulk polymer concentration, while the breakage is essentially unaffected. Point ii relates to the stabilization of large membrane fragments (Stokes radius ca. 40 nm) in the presence of a polymer with no isopropyl side groups, while micelle-like assemblies (Stokes radius 8 nm) containing the lipids are obtained with an isopropyl-containing polymer of similar hydrophobicity. Both polymers display similar efficiency at disrupting small vesicles. The mechanism of polymer-induced disruption appears to differ markedly from the disruption steps now recognized for conventional (molecular) surfactant and is discussed on the basis of data obtained with different membrane fluidity, polymer structure, concentration, and hydrophilicity. 相似文献
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Fernando Ruiperez Cecile Danilo Florent Real Jean‐Pierre Flament Valerie Vallet Ulf Wahlgren 《ChemInform》2009,40(19):no-no
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option. 相似文献
49.
An identifying code of a (di)graph G is a dominating subset C of the vertices of G such that all distinct vertices of G have distinct (in)neighbourhoods within C. In this paper, we classify all finite digraphs which only admit their whole vertex set as an identifying code. We also classify all such infinite oriented graphs. Furthermore, by relating this concept to a well-known theorem of Bondy on set systems, we classify the extremal cases for this theorem. 相似文献
50.
Mathilde Pantin Florent Bodinier Jordan Saillour Yassine M. Youssouf Fabien Boeda Morwenna S.M. Pearson-Long Philippe Bertus 《Tetrahedron》2019,75(33):4657-4662
A convenient access to 2-hydroxycyclopentenones was designed from acylcyanohydrins, by using titanacyclopropane complexes as nucleophilic partners and an intramolecular aldol condensation in basic conditions. The development of a one-pot procedure allows a step- and atom-economic process, and the use of Grignard reagents other than ethylmagnesium bromide provided valuable 3,4-disubstituted 2-hydroxycyclopentenones. The utility of the hydroxy group was illustrated by further functionalization of the α-position using palladium-mediated cross-coupling reactions. 相似文献