Theory of chromatography of linear and cyclic polymers with functional groups

We discuss the chromatographic behavior of linear polymers and rings having specific (functional) adsorption-active groups. Functionalized eight-shaped, daisy-like and theta-shaped macromolecules are considered as well. By using a model of an ideal chain with point-type defects in a slit-like pore we derive equations for the distribution coefficient covering all modes of chromatography of functionalized polymers of any molar mass in both narrow and wide pores. Additionally simple approximate formulae are obtained for a number of important modes of chromatography; chromatograms are simulated for model mixtures of polydisperse non-functional and functional polymers. By using the theory we analyze separation of polymers by molar mass, functionality and topology. Although there is a principal possibility to use adsorption chromatography or size-exclusion chromatography (SEC), we conclude that the liquid chromatography at the critical condition (LCCC) is especially efficient for separation of polydisperse polymers by both functionality and topology. The theory predicts that functionalized linear and cyclic polymers can be separated from each others by LCCC even better than non-functionalized ones. The LCCC behavior of some other types of polymers such as comb-like and semicyclic ones is discussed as well.     

尿素络合法生产重质液体石蜡的工艺研究

以大庆直馏柴油为原料 ,经异丙醇尿素脱蜡制得纯度较高的重质液体石蜡和低凝点脱蜡油。研究了络合反应温度、尿油比、反应时间以及络合物洗涤次数和洗涤油用量对工艺过程的影响 ,并得出了适宜的生产条件     

Characterization of star-shaped poly(l-lactide)s by liquid chromatography at critical conditions

A series of linear and star-shaped poly(l-lactide)s (PLA's) have been prepared by living polymerization of l,l-dilactide (LA) and analyzed by liquid chromatography at critical conditions (LC-CC). For the analysis of the PLA's LC-CC conditions have been used corresponding to silica gel as the stationary phase and a mixture of 1,4-dioxane/n-hexane (56.25/43.75 by vol%) at 50 °C as the mobile phase. At the critical point of adsorption, a series of linear C₄H₉-PLA-OH's having molar masses (M_n) in the range from 2.3×10³ to 7.4×10⁴, prepared by ring-opening polymerization of LA initiated with Sn(OC₄H₉)₂ (THF, 80 °C), showed no dependence of the elution volumes on molar mass. In subsequent experiments, star-shaped PLA's bearing various numbers of PLA-OH arms (R-(PLA-OH)_x) have been prepared in a controlled synthesis starting from various polyols (R-(OH)_x) containing exclusively primary hydroxyl groups: diethyleneglycol (x=2), trimethylolpropane (x=3), di(trimethylolpropane) (x=4), dipentaerithritol (x=6), and poly(3-ethyl-3-hydroxymethyloxetane) (〈x〉=13.4) and LA monomer. As coinitiator/catalyst tin(II) octoate (Sn(Oct)₂) has been used (bulk polymerization, 120 °C). ¹H NMR analysis of the resulting star-shaped polymers revealed that all OH-groups in the polyols started growth of the PLA chains. The series of star-shaped PLA's have been analyzed by LC-CC as well as by two-dimensional (2D) chromatography (i.e. LC-CC versus size exclusion chromatography (SEC)) with regard to possible structural imperfections. It has been shown, that the LC-CC elution volumes of the resulting R-(PLA-OH)_x increase with the number of PLA-OH arms, allowing discrimination of the individual R-(PLA-OH)_x's in their mixture. An exponential increase of the retention volume as a function of the number of arms has been found. Eventually, LC-CC measurements of the elution volumes carried out for acetylated star-shaped PLA's (R(PLA-OOCCH₃)_x) have shown that for the interactions of the R-(PLA-OH)_x macromolecules with the column packing the hydroxyl end-groups are mostly responsible.     

液相色谱分离技术的小型评价装置及其应用

建立了一套液相色谱分离技术的小型评价装置及数据处理方法,该装置由吸附柱、计量泵、定量管、六通切换阀、恒温水浴等组成;数据处理中详细介绍了流出曲线的绘制、应用及分离过程的评价等,最后结合对木糖醇母液的分离过程说明了评价装置的具体用途。     

Liquid chromatography at critical conditions of polyethylene

Olefin copolymers are of increasing scientific interest due to their important application potential. Liquid chromatography can deliver important information, especially on their molecular structure. In particular, liquid chromatography at critical conditions (LCCC) is of interest because, in this chromatographic mode, the elution is molar mass independent for a given repeat unit. LCCC is conducted at conditions where the entropic effect of size exclusion is equal to the enthalpic effect of interaction between the macromolecules and the stationary phase and can be used to separate copolymers as well as some homopolymers containing one single repeat unit but having different end groups. For the first time, critical conditions for linear PE were experimentally identified by using porous graphite (Hypercarb™) as the stationary phase, and either 1-decanol/ortho-dichlorobenzene (ODCB), 1-decanol/1,2,4-trichlorobenzene (TCB), n-decane/ODCB, or n-decane/TCB as the mobile phase at 160 °C. The identified critical conditions for PE using the above approach in the above solvents have been verified to be correct, barring slight deviations, by two different techniques which were previously used to determine critical conditions for polymers soluble at ambient temperature. The critical conditions for polyethylene were applied to separate statistical copolymers of ethylene/1-octene with similar molar mass.     

Fast determination of critical eluent composition for polymers by gradient chromatography

Gradient chromatography was applied in order to calculate the composition at elution for different methacrylates on normal phase columns. In addition the composition at elution was determined for polyethyleneoxide on a reverse phase column. It is shown that high molar mass polymers elute for a given homopolymer irrespective of their molar mass at the same eluent composition, which varies only slightly with gradient slope. In general the composition at elution in gradient chromatography is expected to be slightly lower than the true critical composition. For high molar mass polymers we found this composition to be close to the critical composition determined by isocratic experiments. The difference between the composition at elution and the true critical composition for a variety of polymethacrylates and for polyethyleneglycol was found to be only between 0.2 and 5%. Thus, after estimating the composition at elution, only a small number of additional isocratic experiments is needed to find the exact critical composition.     

Methods to determine solubility parameters of polymers using inverse gas chromatography

Experimental values of the Flory–Huggins parameter, χ, between polymers and solvents, are frequently used to determine the solubility parameters of the polymers. A method using nonlinear curve fitting of RTχ/V was compared to the linear regression method commonly used. It was found that the formulas for the solubility parameter were the same, but the linear method produced a slightly different entropy term. The nonlinear method gave a lower correlation coefficient and wider confidence intervals and was more effective at distinguishing systems than the linear model. The effect of the deviation of probes in the solubility parameter model is discussed. Using probes with low solubility parameters to measure the polymer solubility parameter gave wider confidence intervals. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2894–2902, 2004     

液相色谱法测定苄嘧磺隆可湿性粉剂有效成分含量

应用液相色谱法测定苄嘧磺隆可湿性粉剂有效成分含量,该方法分析速度快,操作简便,出峰时间短.经验证应用液相色谱法测定其加标回收率为100.03,线性回归方程为:Y=0.02+2.136 7X,相关系数:r=0.999 6.     

百菌清、腐霉利复合烟剂的气相色谱分析

采用气相色谱法分析百菌清、腐霉利复合烟剂中百菌清、腐霉剂含量 ,选用SE 30柱 ,以邻苯二甲酸二丁酯为内标物。该方法的标准偏差 :百菌清为 0 18,腐霉利为 0 45 ,变异系数为 3 4% ,2 9% ,百菌清回收率为 99 2 %～ 10 0 1% ,腐霉利回收率为 98 9%～ 99 9%。该方法快速、准确 ,可有效控制产品质量     

A theory of topological separation of linear and star-shaped polymers by two-dimensional chromatography

Topology influences the size of macromolecules, but polymers are usually distributed with respect to molar mass, which also results in the size distribution within a polymeric sample. Due to this fact size-exclusion chromatography (SEC) is not able to separate even moderately polydisperse polymers by topology; the same is also true for the adsorption chromatography (AC). The full separation by molar mass and topology is not possible by any single mode of chromatography. These problems can be solved by means of two-dimensional chromatography which combines SEC and AC mechanisms. A theory of interactive chromatography of linear and star-shaped ideal-chain polymers is used to analyze two-dimensional chromatographic separation of polydisperse linear and star polymers. Basing on this theory, we simulate 2D-chromatograms for model mixtures of polydisperse linear and star-shaped polymers of equal average molar mass, and demonstrate that 2D-separation of such polymers by topology is possible. A possibility to separate symmetric and very asymmetric stars by 2D-chromatography is predicted. The influence of the molar-mass heterogeneity, pore size and adsorption interaction parameter on the 2D chromatographic pattern is analysed, and the conditions for a good separation of linear and star polymers are formulated. The theoretical results are in a qualitative agreement with the experimental data, which have been reported previously by Gerber and Radke.     

Theory of adsorption of macromolecules in cylindrical pores and at surfaces of cylindrical shape

A rigorous theory of adsorption of a Gaussian chain of infinite length into cylindrically shaped pores and onto cylindrical surfaces of arbitrary diameter, D, has been developed for any energy of interaction ??. The change in the conformational free energy of a chain arriving inside the pores from an unrestricted volume is proportional to $\text{(D1)}{}^{\mathrm{?2}}$ ($\text{D1}$ is the effective pore width) over the entire molecular-sieve range (?? < ??_c). In the exclusion range (?? < 0), when the interaction of chain units with the adsorbent exhibits repulsive type forces, $\text{D1}$ is approximately equal to D. As the adsorption forces of attraction increase (0 < ?? < ??_c) the value of $\text{D1}$ increases and becomes infinite at the critical point. This makes it possible to use a single adsorbent for effective chromatographic separation of polymers over a wide range of molecular weights. In the adsorption range, where ?? > ??_c, the conformational free energy of the chain is virtually independent of the width and shape of the pores and is determined mainly by the value of ??. At the critical point, ?? = ??_c, the probability of the arrival of a polymer chain in the pore is independent of both the width and shape of the pore and is determined only by the ratio of geometrical volumes of the free volume to the pore volume. For cylindrical pores, a weak dependence of ??_c on D is observed only for narrow pores. This dependence virtually disappears on passing to adsorbents with wide pores. Consideration of the adsorption of the macromolecule on the outer surface of the cylinder showed that at any finite value of the diameter of the cylinder, D, adsorption occurs as an ‘infinite-order’ phase transition. The maximum value of the specific heat

$\text{(C}{}_{\mathrm{p}}\text{max}\text{k}\text{=}\text{25}\text{3}\text{=?}{}^2{}_{\mathrm{c}}$

does not depend on D. The degree of bonding of the macromolecule to the adsorbent increases with decreasing curvature of the surface, rapidly attaining values characteristic of chain adsorption on a plane.     

Measurement of intraparticle diffusion in reversed phase liquid chromatography

The intraparticle diffusion coefficient was measured using a method based on the fitting of a set of experimental chromatographic profiles to the lumped pore diffusion model. For this purpose, both the analytical solution of the model in the Laplace domain and a numerical method were used. There was an excellent agreement between the results given by the two methods. These results are compared to those obtained by moment analysis of the same set of chromatographic profiles and by the determination of the intraparticle diffusion coefficient from the second central moment of these bands. Nearly identical results were obtained with these two independent methods. The values of the intraparticle diffusion coefficient, D_e, for rubrene in pure methanol was found to be by the modeling method and by the moment analysis method. These values increase with increasing water concentration, to 1.10×10⁻⁶ and , respectively, in a methanol/water solution and to 1.63×10⁻⁶ and , respectively, in a solution.These results confirm the validity and the consistency of the lumped pore model and the moment analysis theory. They show that both approaches describe correctly the mass transfer kinetics in the particles of packing material during the chromatographic process. Systematic determinations of the intraparticle diffusion coefficient can now be undertaken and the influence of various experimental parameters on this important property of packing materials can be investigated.     

液相色谱法测定氯嘧磺隆·乙草胺乳油有效成分

应用液相色谱法测定氯嘧磺隆·乙草胺乳油有效成分的质量分数,此方法分析速度快,操作简便,能有效分离2种组分.经验证应用液相色谱法测定乙草胺加标回收率为100.01％,氯嘧磺隆加标回收率为99.83％;乙草胺线性回归方程为:Y=0.005 4+0.768 4X,氯嘧磺隆线性回归方程为y=0.010 8+0.423 6 X;...     

Characterization of branched polymers by size exclusion chromatography coupled with multiangle light scattering detector. I. Size exclusion chromatography elution behavior of branched polymers

The elution behavior of branched macromolecules during their separation by size exclusion chromatography (SEC) was studied. The elution behavior of branched polymers was investigated using samples of randomly branched polystyrene and star branched poly(benzyl methacrylate) of different levels of branching by means of a SEC chromatograph coupled with a multiangle light scattering detector. Abnormal SEC elution behavior was found to be typical for highly branched polymers. After a normal elution at small elution volumes the molar mass and root mean square radius of the eluting molecules increased with increasing elution volume. Several SEC experiments were carried out to find explanation for this effect and SEC separation was compared with the separation by thermal field flow fractionation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1588–1594, 2001     

Supramolecular approach for synthesis and functionalization of cyclic macromolecules

This report highlights our recent findings concerning the synthesis of cyclic polymers based on supramolecular chemistry as well as the stereochemical recognition of helices by a cyclic macromolecule consisting of helical peptides and porphyrins. The first part will focus on an electrostatic self-assembly and covalent fixation strategy for the efficient synthesis of cyclic polymers. It has been shown that a unimeric polymer assembly is formed exclusively from the linear polymer precursor having cyclic ammonium salt end groups carrying dicarboxylate counter ions. An effective synthesis of cyclic polymers has been achieved by the subsequent covalent transformation of the ammonium salt groups. The process has been extended to the synthesis of cyclic macromonomers, which produced a unique polymer network having both covalent and mechanical linkages. The second part will focus on the stereochemical recognition of helices by a cyclic host. α-Aminoisobutyric acid (Aib) peptide-based cyclic hosts having metalloporphyrin units have been synthesized for guest binding and chiroptical sensing. By using these cavities, biologically important “peptide bundling” has been realized through complexation of helical peptide guests, where the three helical chains, two of which are from the host and one from the guest, are harmonized stereochemically in a confined cavity, leading to intense chiroptical outputs in the absorption bands of the metalloporphyrin units. The selective peptide bundling events based on helical senses of the host/guest molecules has also been achieved with a chiral conformational matching.     

Grafting of hyperbranched polymers: From unusual complex polymer topologies to multivalent surface functionalization

In this feature article, the grafting of hyperbranched polymers to different substrates is reviewed. Both grafting onto macromolecules with different topologies (homogeneous grafting) and the resulting complex polymer architectures containing highly branched segments as well as their applications are discussed. In the second part grafting of hyperbranched polymers on surfaces, i.e., planar surfaces and spherical particles (heterogeneous grafting), with respect to specific applications, such as bio-repellent surfaces or soluble carbon nanotubes is described. In all cases, the one-step synthesis and the resulting highly branched topology of the hyperbranched building blocks is beneficial for the convenient introduction of a large number of functional groups to the substrates. These multifunctional hybrid materials open interesting options for applications, e.g., for highly functional nanoparticles or nanocomposites.     

Stochastic molecular descriptors for polymers. 4. Study of complex mixtures with topological indices of mass spectra spiral and star networks: The blood proteome case

The Quantitative Structure-Property Relationships (QSPRs) based on Graph or Network Theory are important for predicting the properties of polymeric systems. In the three previous papers of this series (Polymer 45 (2004) 3845-3853; Polymer 46 (2005) 2791-2798; and Polymer 46 (2005) 6461-6473) we focused on the uses of molecular graph parameters called topological indices (TIs) to link the structure of polymers with their biological properties. However, there has been little effort to extend these TIs to the study of complex mixtures of artificial polymers or biopolymers such as nucleic acids and proteins. In this sense, Blood Proteome (BP) is one of the most important and complex mixtures containing protein polymers. For instance, outcomes obtained by Mass Spectrometry (MS) analysis of BP are very useful for the early detection of diseases and drug-induced toxicities. Here, we use two Spiral and Star Network representations of the MS outcomes and defined a new type of TIs. The new TIs introduced here are the spectral moments (π_k) of the stochastic matrix associated to the Spiral graph and describe non-linear relationships between the different regions of the MS characteristic of BP. We used the MARCH-INSIDE approach to calculate the π_k(SN) of different BP samples and S2SNet to determine several Star graph TIs. In the second step, we develop the corresponding Quantitative Proteome-Property Relationship (QPPR) models using the Linear Discriminant Analysis (LDA). QPPRs are the analogues of QSPRs in the case of complex biopolymer mixtures. Specifically, the new QPPRs derived here may be used to detect drug-induced cardiac toxicities from BP samples. Different Machine Learning classification algorithms were used to fit the QPPRs based on π_k(SN), showing J48 decision tree classifier to have the best performance. These results suggest that the present approach captures important features of the complex biopolymers mixtures and opens new opportunities to the application of the idea supporting classic QSPRs in polymer sciences.     

Methods to determine solubility parameters of polymers at high temperature using inverse gas chromatography

Experimental values of Flory–Huggins parameters, χ, between polymers and probes, are frequently used to determine the solubility parameters of the polymers by the method of DiPaola–Baranyi and Guillet. The solubility parameters of probes were usually estimated by using heat of vaporization. When χ is measured at a temperature near the critical temperature of the probes and used to determine the solubility parameter of polymers, the departure of enthalpy of the probe vapor from the ideal gas state should be considered. This study discussed the method to make the correction and its effect on the determination solubility parameter of polymers. Without correction in the vapor phase enthalpy, the solubility parameters of the probes and polymer tend to be underestimated and the error increases when the critical temperature is approaching. Analytical expressions for the effect of correction on the solubility parameter of probes and parameters of polymers were derived. By use of probes with a range of solubility parameters on both sides of the solubility parameter of polymers, the correlation between parameters of polymers was shown to be reduced. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1547–1555, 2004     

Thermodynamics and mass transfer kinetics of phenol in reversed phase liquid chromatography

The thermodynamics and the mass transfer kinetics of the chromatographic system made of phenol, in a water-acetonitrile mobile phase, on a C18 RPLC column, were studied in the temperature range from 21 to and the interstitial velocity range of 0.021 to 1.27 cm/s. The equilibrium isotherm was accurately approximated by a multilayer model assuming lateral interactions between adsorbed molecules. The parameters of the kinetics of the phenol mass transfer in this column were measured by the method of moments. These data were analyzed using the available models and correlations. It was proven that the parameters of the mass transfer kinetics measured under linear conditions could be successfully used for the prediction of the concentration profiles obtained under overloaded conditions.     

色谱技术与色谱试剂现状评述

在分析测试领域,用色谱分析的方法和应用越来越广泛,在今天对高质量产品的测定已涉及食品、医药、环保、生化和石油化工等等。色谱技术的发展和变化试剂有着很大的影响,尤其是从事生产制造、经营管理和分析使用者来说,了解色谱技术的发展和现状,来对待色谱试剂的新认识,有助于分析测试的正确性和可靠性的进一步提高。