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151.
G. Glöckner 《Chromatographia》1987,23(7):517-524
Summary Prerequisite of quantitative evaluation in chromatography is equivalence of sample composition and detector signal. This includes
complete retention and proper elution of all sample constituents. In polymer HPLC, complete retention requires a poor starting
eluent, a sufficiently active column, and a low ratio of injection volume to column volume. On small pore columns, insufficient
retention caused the polymer to elute either in the interstitial volume (sample exclusion), together with the sample solvent,
or immediately after the solvent plug.Stat-copoly(styrene/ethyl methacrylate) samples are more difficultly retained thanstat-copoly(styrene/acrylonitrile) specimes. With the former copolymer it could be shown that incomplete retention did not cause
sample demixing. In order to gain complete retention, non-exclusion HPLC of polymers should be performed with columns whose
solvent volume is at least 50 times as large as the injection volume. This consequence is of practical importance in chromatographic
cross-fractionation where rather large volumes of SEC eluate are injected into the apparatus for gradient HPLC. 相似文献
152.
Denote by *
n
the set of all k
*-cycle resonant hexagonal chains with n hexagons. For any B
n
*
n
, let m(B
n
) and i(B
n
) be the numbers of matchings (=the Hosoya index) and the number of independent sets (=the Merrifield–Simmons index) of B
n
, respectively. In this paper, we give a characterization of the k
*-cycle resonant hexagonal chains, and show that for any B
n
*
n
, m(H
n
)m(B
n
) and i(H
n
)i(B
n
), where H
n
is the helicene chain. Moreover, equalities hold only if B
n
=H
n
. 相似文献
153.
Six isomeric C20 alkylthiophenes were synthesized in order to prove the occurrence of such compounds in various deep sea sediments. As expected from the analogy with the corresponding saturated hydrocarbons, 2- and 3-heptadecylthiophene have considerably longer relative retention times than the isomeric isoprenoid compounds, i.e. 2- and 3-(4,8,12-trimethyltridecyl)thiophene and 3- and 4-methyl-2-(3,7,11-trimethyldodecyl)thiophene. Covats retention indices for all compounds were determined by isothermal analysis at 190°C on two different silicone-coated capillary columns. The mass spectra of the monoalkylated thiophenes show a base peak at m/z 98 corresponding to a Mcafferty rearrangement product in the case of the 3-substituted isomers, whereas a simple benzylic cleavage dominates in the mass spectra of 2-alkylthiophenes. 4-Methyl-2-(3,7,11-trimethylodecy)thiophene is an exception from this simple rule because also shows the McLafferty rearrangement as dominant fragmentation. Two of the isoprenoid thiophenes are prominent compounds in various deep sea sediments. 相似文献
154.
Vesselin Dimitrov 《Journal of solid state chemistry》2005,178(3):831-846
A classification of binary oxide glasses has been proposed taking into account the values obtained on their refractive index-based oxide ion polarizability αO2−(n0), optical basicity Λ(n0), metallization criterion M(n0), interaction parameter A(n0), and ion's effective charges as well as O1s and metal binding energies determined by XPS. Four groups of oxide glasses have been established: glasses formed by two glass-forming acidic oxides; glasses formed by glass-forming acidic oxide and modifier's basic oxide; glasses formed by glass-forming acidic and conditional glass-forming basic oxide; glasses formed by two basic oxides. The role of electronic ion polarizability in chemical bonding of oxide glasses has been also estimated. Good agreement has been found with the previous results concerning classification of simple oxides. The results obtained probably provide good basis for prediction of type of bonding in oxide glasses on the basis of refractive index as well as for prediction of new nonlinear optical materials. 相似文献
155.
建立了处理双原子分子-表面相互作用的推广的LEPS势.借助推广的LEPS势,系统研究了一氧化碳分子在铂低指数表面吸附的动力学特性,重现了低指数表面的分子吸附热、吸附几何及本征振动等实验数据;鉴定了某些不合理的文献信息,预测了实验尚未探测到的重要信息:预测到Pt(100)表面四重洞位的C-O伸缩振动频率为1 962.60 cm-1;预测到Pt(110)表面吸附态的C-O及C-Pt键长分别为115.1、147 pm. 相似文献
156.
The main thermodynamic characteristics of the adsorption of haloadamantanes on graphitized thermal carbon black were determined by experimental measurements and by calculations in terms of molecular-statistic theory of adsorption. Using experimental data, the Kovac retention indices were calculated and the optimum conditions for gas-chromatographic separation of haloadamantanes on stationary phases with different polarity were elucidated. The influence of the cage effect in the adamantane unit on the chromatographic properties of haloadamantanes was established. 相似文献
157.
A. Voelkel 《Chromatographia》1987,23(3):195-198
Summary The possibility of evaluation of the parameters representing the dispersive solute-solvent interactions is presented. BN and Bs values can be used to describe the liquid phase polarity and to predict the retention indices of alcohols when the model
polyxyethylene glycol dialkyl ethers and their sulphur analogs are used as stationary phases. The possibility of the first
ionization potentials estimation is also presented. 相似文献
158.
Zusammenfassung In der vorliegenden Arbeit wird eine Methode zur Retentionsindex-Bestimmung beschrieben, die von einem kubischen Zusammenhang zwischen Bruttoretentionszeit-Differenzen der Referenzhomologen und der Kohlenstoffzahl ausgeht. Hieraus ergeben sich direkt die Nettoretentionszeiten. Der Fehler der Totzeitbestimmung entfällt bei dieser Methode. Mit den so gewonnenen Nettoretentionszeiten erhält man über einen kubischen Zusammenhang zwischen 1g ts=f(C) die Retentionsindices. Extrapolationen und Interpolationen sind über 300 Retentionsindexeinheiten mit einem mittleren Fehler von ±0,02 Retentionsindexeinheiten möglich. Das Verfahren bietet sich für eine automatische Berechnung der I-Werte mittels on-line-Datenverarbeitung an.
Cubic calculation of retention indices without determining the dead-time tm
Summary The method for the calculation of retention indices described here is based on a third order relationship between the logarithm of differences of unadjusted retention times of homologues and the carbon number. From this adjusted retention times are directly calculated. A determination of the dead-time is not necessary thus avoiding the errors connected with this factor. A cubic equation for the logarithm of the adjusted retention time lg ts as a function of carbon number Cn is used for the retention index calculation. Extrapolations and interpolations can be done over a range of 300 index units with an average deviation of ±0.02 i.u.. The method offers the possibility of an automated on-line calculation of retention indices by computer merely on the basis of unadjusted retention times.相似文献
159.
采用平衡电负性和相对化学键长对传统距离矩阵进行修正,构建新拓扑指数Nt。结合路径数,建立碳氢化合物、醛、酮和硫醇等化合物在24种极性和非极性色谱柱上的定量结构-色谱保留指数关系(QSRR)模型,23种模型的相关系数大于0.99。模型经留n法交叉检验,显示出良好稳健性和预测能力。模型物理意义明确,表明色谱保留指数可用分子的大小、平衡电负性、支化度和形状等内在结构信息进行有效表征。模型经Needham公式分析,结果显示新指数Nt对保留指数影响最大。借助Hyperchem软件进行对比研究,结果表明拓扑化学法优于量子化学AM1法。 相似文献
160.
Summary The separation of C1–C4 alkyl tert-butyl ethers with the general formula (CH3)3C–O–R (R-alkyl substituent) on fused-silica capillary columns coated with dimethylsilicone and cyanopropylmethylsilicone stationary phases was investigated. Retention indices were determined at two temperatures in order to understand their chromatographic behaviour. The respective standard deviations were 0.3 and 0.5 i.u. 相似文献