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81.
Addition of a small amount of polar solvent (i.e., modifier) to CO2 in packed column supercritical fluid chromatography (SFC) has shown major improvements in both polar analyte solubility and interaction of the polar analyte with the stationary phase. Recently, the addition of an ionic component (i.e., additive) to the primary modifier by one of us has been shown to extend even further the application of SFC to polar analytes. In this work, the effect of various ionic additives on the elution of ionic compounds, such as sodium 4-dodecylbenzene sulfonate and sodium 4-octylbenene sulfonate, has been studied. The additives were lithium acetate, ammonium acetate, tetramethylammonium acetate, tetrabutylammonium acetate, and ammonium chloride dissolved in methanol. Three stationary phases with different degrees of deactivation were considered: conventional cyanopropyl, deltabond cyanopropyl, and bare silica. The effect of additive concentration and additive functionality on analyte retention was investigated. Sodium 4-dodecylbenzene sulfonate was successfully eluted using all the additives with good peak shape under isocratic/isobaric/isothermal conditions. Different additives, however, yielded different retention times and in some cases different peak shapes. 相似文献
82.
M.G.?CarvalhoEmail author J.M.R.C.A.?Santos A.A.?Martins M.M.?Figueiredo 《Cellulose (London, England)》2005,12(4):371-383
In this work attention has been focused on the effects of papermaking beating, web forming and sizing operations on the physical/chemical
surface properties of bleached Eucalyptus globulus kraft fibres. Inverse gas chromatography (IGC) was used to determine the dispersive component of surface tension (γsd) as well as the acidic/basic character (according to the Lewis concept) of the solid surfaces (pulp fibres and pulp handsheets).
The results have shown that the main effect of beating is to increase the fibre's Lewis acidic character. Web forming caused
a strong decrease in γsd and significant increments in the adhesion works of both acidic and basic probes, lowering the ratio between the two. Nevertheless,
the surface of handsheets still exhibited a dominant acidic character. The sizing operation did not change the dispersive
component of the surface tension significantly but decreased the difference between the adhesion works of the acidic and basic
probes, rendering the handsheet surface less Lewis acidic and more Lewis basic. Thus, although internal sizing is expected
to strongly influence liquid spreading at the paper surface and liquid penetration of the fibre's network, it is concluded
that beating and web forming lead to important changes in the surface energetic properties of the Eucalyptus globulus kraft fibres. 相似文献
83.
The growth rate of isotactic polypropylene is deduced from microscopic observations during isothermal crystallizations. A change in the growth regime is observed at 138 C and interpreted as a Regime III Regime II transition, according to Hoffman's kinetic theory of polymer crystallization. A Regime II Regime I transition is also theoretically predicted at 155 C, i. e. at a temperature outside the investigated temperature range. The Regime III Regime II transition is related to the positive to negative change in the spherulite birefringence, which is generally attributed to a change in the organization of crystalline lamellae: quadritic arrays of intercrossing lamellae atT
c < 138 C (Regime III) and preferentially radiating lamellae atT
c > 138 C (Regime II). It is suggested that such a morphological change could be interpreted using the concept of non-adjacent re-entry introduced in Hoffman's kinetic theory. This interpretation could also explain the interspherulitic ruptures observed in negative spherulites. 相似文献
84.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献
85.
The interaction energy of a molecule M with a point-like charge q can be partitioned into simpler contributions, two of which can be expressed in terms of the charge distribution M of the sole M. The first term, qV(r), represents the interaction of q with the undistorted charge
M
0
of M while the second q
2
P(r) gives the additional contributions due to the polarization of
M
0
under the influence of the charge q placed at the point r. In this paper we investigate the possibility of getting an inexpensive and sufficiently accurate analytical representation of P(r) over the whole space outside the van der Waals volume of M. 相似文献
86.
Shujun Su 《Journal of Molecular Structure》1998,430(1-3):137-148
The potential energy hypersurface of the ground triplet states of the BNO-BON-NBO system has been investigated using traditional ab initio electronic structure theory. The molecules studied have the molecular formula BON and include three linear and three angular species, and two transition states for the isomerization of an angular N-B-O to an angular B-O-N and a linear B-NO, respectively. All stationary points on the BNO-BON-NBO isomerization potential energy surface have been characterized employing UMP2, UMP4, and Gaussian-2 (G2) theory with the 6-311G(d), 6-311G(2d), and TZ2P basis sets. The isomerization for an angular N-BO to the linear B-NO has a lower energy barrier than that of the former to an angular B-ON. Energetics are presented with G2 energies. Two sets of resonance structures for both bent B-NO (boron nitrosyl) and B-ON (boron isonitrosyl) were proposed and the bonding in the two species was analyzed. For the purpose of comparison, the density functional theory based hybrid methods B3LYP/6-311G(d) and B3LYP/TZ2P have also been applied to both geometry optimization and single-point calculations. It is found that the B3LYP prediction of the nature of the linear B-O is contradictory to that made by all MPn(n = 2 and 4) calculations. The cause for this contradiction is discussed. 相似文献
87.
Jasmina M. Dimitrić Marković Zoran S. Marković Jelisaveta M. Baranac Marina L. Dašić 《Monatshefte für Chemie / Chemical Monthly》2007,138(12):1225-1232
Summary. The study of delphinidin complexation with trivalent aluminum in acidic aqueous buffered (pH 3.0 and 3.8) and methanolic solutions was performed utilizing electronic absorption spectroscopy and quantum chemical calculations.
In its structure delphinidin possesses several chelating sites in competition towards aluminum(III). Molar ratio plots denoted
the formation of only one aluminum(III):delphinidin complex of stoichiometry of 1:1 in both investigated media. Semiempirical
calculations, performed at the restricted HF AM1 level, enabled the determination of the structural features of free delphinidin and structural modifications caused by
chelation of aluminum(III). Considering the pigment molecular structure and the results of the theoretical calculations it
is possible to equally implicate C3′–C4′ and C4′–C5′ hydroxyl groups as those with the predominant chelating power. 相似文献
88.
Khuloud Takrouri Israel Goldberg Morris Srebnik 《Journal of organometallic chemistry》2005,690(18):4150-4158
The first examples of diborane (4) compounds derived from amine cyanoboranes are described. A series of monobromo derivatives of amine cyanoboranes (A:BHBrCN), and dibromo derivatives (A:BBr2CN), 1-7, were prepared. Lithiation of the monobromo derivative of trimethylamine cyanoborane, using n-BuLi, did not produce the C-lithiated intermediate Li+ [CH2NMe2BHBrCN]−, but instead the B-lithiated intermediate Li+ [Me3NBHCN]−, was obtained. This intermediate, when allowed to react for 16 h, coupled with the un-lithiated trimethylamine monobromocyanoborane (Me3NBHBrCN) and resulted in diborane (4) derivative formation as the 2LiBr complex. The same result was obtained when one equiv of the trimethylamine monobromocyanoborane was added to the reaction mixture 1 h after lithiation. Following the same procedure, novel diborane (4) derivatives of amine cyanoboranes were successfully obtained, 8-11, as their 2LiBr complexes from the monobromo derivatives of the corresponding amine cyanoboranes. Molecular structures of the trimethylamine dibromocyanoborane, 6, and the triethylamine dibromocyanoborane, 7, were determined using X-ray crystallography. 相似文献
89.
本文提出了富烯碳原子簇的石墨层间闭合形成机理,由该机理推出的许多结果与实验事实符合很好。我们认为碳原子簇自由基的快速淬灭及其淬灭速度是富烯碳原子簇形成及其丰度的决定因素。由此得出富烯碳原子簇在给定实验条件下产生的必然性,并预言不同大小的富烯碳原子簇可以通过优化实验条件选择性地合成。 相似文献
90.
为了更好地认识页岩油微观赋存状态及类型,避免实验过程中水钻取样对原油分布的影响,选取吉木萨尔页岩典型含油岩芯,采用全程液氮钻、切、磨制样工序,通过全能谱扫描电子显微镜、二次电子成像及背散射相结合的技术手段,获得微观储层矿物类型和结构、储集空间类型、形貌以及C, O, Si, Al, Ca, K, Na,Mg等元素在微、纳米尺度的分布。依据去除矿物因素后的C元素含量分布,判别原油在微、纳米空间尺度的富集程度。结合矿物岩石组构和储集空间形貌,对微、纳米尺度页岩油原油的赋存状态及分布类型进行直观的定量表征,并基于C元素含量推测微观含油饱和度的相对变化。针对原油与孔喉的配置关系,进行储层微观孔喉结构与原油赋存状态的表征,明确原油赋存类型。总结出研究区4种微观原油赋存类型:白云质溶蚀微米级大孔道中的可动油、砂质粒间微纳米级孔中可动油、砂质粒间孔喉壁吸附的半束缚状态的油膜以及自生黏土矿物晶间孔内束缚油。 相似文献