Comparative study for separation of aquatic humic-type organic constituents by DAX-8, PVP and DEAE sorbing solids and tangential ultrafiltration: elemental composition, size-exclusion chromatography, UV-vis and FT-IR

Aquatic humic-type solutes were separated in parallel from the same fresh water source by four different procedures: non-ionic polymethyl methacrylate (DAX-8) and functional cross-linked polyvinylpyrrolidone (PVP) resins, functional diethylaminoethyl cellulose (DEAE) and tangential ultrafiltration completed with a weakly basic anion exchange resin (IRA-67). The similarity-dissimilarity between the quantities and qualities of the different humic samples is discussed, especially in the light of the original dissolved organic matter (DOM). During the past two decades, a significant progress has occurred in the aquatic humic research due to the so-called hydrophobic-hydrophilic properties possessed by certain non-ionic sorbing solids. As a result of many coincidences, it may be justifiable to examine critically the prevailing isolation techniques of aquatic humic solutes and to try to update their complicated definitions. For that reason, it is reasonable to summarize the leading principles of different isolation techniques in Section 1 of this article. The results of the present study strongly support the applicability of the PVP resin, alone or completed in sequence with a suitable non-ionic sorbing solid, for isolation of aquatic humic-type solutes from both quantitative and qualitative points of view. In certain cases, the DEAE cellulose gives a useful alternative for conventional sorbing solids in the isolation of the bulk of aquatic humic solutes. The base-catalyzed ester hydrolysis of the HM during the chromatographic isolation of the DOM seems to be relative minor.     

Solvent Effects on Acrylate kp in Organic Media?—A Systematic PLP–SEC Study

The Arrhenius parameters of the propagation rate coefficient, k_p, are determined employing high‐frequency pulsed laser polymerization–size exclusion chromatography (PLP–SEC) for the homologous series of five linear alkyl acrylates (i.e., methyl acrylate (MA), butyl acrylate (BA), dodecyl acrylate (DA), stearyl acrylate (SA), and behenyl acrylate (BeA)) in 1 m solution in butyl acetate (BuAc) as well as in toluene. The comparison of the obtained k_p values with the literature known values for bulk demonstrates that no significant solvent influence neither in BuAc nor in toluene on the propagation reaction compared to bulk is detectable. Concomitantly, the k_p values in toluene and in BuAc solution display a similar increase with increasing number of C‐atoms in the ester side chain as was previously reported for the bulk systems. These findings are in clear contrast to earlier studies, which report a decrease of k_p with increasing ester side chain length in toluene. The additional investigation of the longest and shortest ester side chain acrylate (i.e., BeA and MA) over the entire experimentally available concentration range at one temperature (i.e., 50 °C) does not reveal any general concentration dependence and all observed differences in the k_p are within the experimental error.

     

Speciation analysis of aluminium and aluminium fluoride complexes by HPIC-UVVIS

The study presents a new analytical method for speciation analysis in fractionation of aluminium fluoride complexes and free Al³⁺ in soil samples. Aluminium speciation was studied in model solutions and soil extract samples by means of high performance ion chromatography (HPIC) with UV-VIS detection using post-column reaction with tiron for the separation and detection of aluminium fluoride complex and Al³⁺ forms during one analysis. The paper presents particular stages of the chromatographic process optimization involving selecting the appropriate eluent strength, type of elution or concentration and quantity of derivatization reagent. HPIC was performed on a bifunctional analytical column Dionex IonPac CS5A. The use of gradient elution and the eluents A: 1 M NH₄Cl and B: water acidified to pH of eluent phase, enabled full separation of fluoride aluminium forms as AlF₂⁺, AlF₃⁰, AlF₄⁻ (first signal), AlF²⁺ (second signal) and form Al³⁺ in a single analytical procedure. The proposed new method HPIC-UVVIS was applied successfully in the quantitative and qualitative analysis of soil samples.     

体积排阻色谱法测定低分子量肝素抗凝血因子Xa的活性

发展了一种基于体积排阻色谱测定低分子量肝素(LMWH)抗凝血活性的方法。利用肝素与抗凝血酶Ⅲ(ATⅢ)结合后可增强ATⅢ对凝血因子Xa(FXa)抑制作用的原理,通过测定加入LMWH后FXa水解其生色底物产生对硝基苯胺(pNA)这一反应的抑制程度确定LMWH的活性。首先将含有一定浓度LMWH的缓冲溶液与ATⅢ溶液混合,然后依次加入FXa和生色底物,分别孵育一段时间。底物被FXa水解,产生游离的pNA。体积排阻色谱可将小分子产物pNA与其他大分子分离开,因而可以在pNA的最大吸收波长下得到高灵敏度的测定,并且不再受其他成分的干扰。该方法重复性好,灵敏度高,极大地减少了样品的消耗量,降低了成本,并且还可进行各种复杂样品(如血浆)中LMWH抗FXa活性的监测。     

Composition effects on ethylene/propylene copolymers studied by GPC-MALS and GPC-IR

Copolymer composition and comonomer distribution along the polymer chains are important to determine the properties and the final usefulness of the polymer. There are several ways to study directly or not directly such comonomer distribution because it has a big effect on different kind of properties. GPC-MALS (multi-angle light scattering coupled to size exclusion chromatography), GPC-IR (size exclusion chromatography with an IR detector), CRYSTAF-TREF (crystallization analysis fractionation-temperature rising elution fractionation) or NMR are very common used techniques to obtain such kind of knowledge.In this work several ethylene/propylene copolymers in the whole composition range are characterized using NMR, GPC-IR and GPC-MALS. Average copolymer composition was obtained by ¹³C-NMR and by IR, and a linear correspondence between both results was found. GPC-IR allows to study the percentage of ethylene for each M_w and to check that incorporation of ethylene is done uniformly over the entire range of molecular weights, while the incorporation of propylene presents heterogeneity in the incorporation. GPC-MALS characterization allows the q shape parameter determination and quantification of the effect that the second monomer introduces as impediment to adopt the random coil distribution.     

Effect of the molecular weight and architecture on the size and glass transition of arborescent polyisobutylenes

This article discusses the characterization of arborescent (hyperbranched) polyisobutylenes (arb‐PIBs) by size exclusion chromatography and differential scanning calorimetry, in comparison with linear PIB standards. The radius of gyration (〈r〉^1/2 = R_z), measured from the angle dependence of light scattering of high‐molecular‐weight arb‐PIBs, was significantly larger than the hydrodynamic radius (R_h) from size exclusion chromatography/viscometry, and the R_h values were significantly smaller than R_h of linear PIBs. The glass‐transition temperature of arb‐PIBs having a branch molecular weight higher than the critical entanglement molecular weight was dependent on both the total number‐average molecular weight and BR up to BR ～ 15. A modified Fox–Flory equation is proposed to describe the effect of architecture on the thermal transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1770–1776, 2006     

Determination of engineered nanoparticles on textiles and in textile wastewaters

Textile materials with engineered nanoparticles (ENPs) have excellent properties as they are antibacterial, antimicrobial, water resistant and protective. The textile industry has recognized the importance and the advantages of ENPs, so they comprise one of the fastest developing branches of processing.The most important sources of ENPs released to the environment from textiles are textile-industry wastewaters and waters from large hospital or hotel laundries. In addition, waste textile materials coated with ENPs present a threat to the environment, if such materials are not properly handled and disposed of after use.Currently, the toxicity and the potential harm of ENPs widely applied on textiles are not thoroughly investigated and/or eliminated. Consequently, there is an urgent need to define the most appropriate analytical methods for monitoring ENPs on textiles.This review presents the most important techniques for monitoring ENPs on textile materials and in textile-wastewater samples, from the perspective of protecting the environment and human health.     

Two-dimensional liquid chromatography analysis of synthetic polymers using fast size exclusion chromatography at high column temperature

In recent years, two-dimensional liquid chromatography (2D-LC) has been used increasingly for the analysis of synthetic polymers. A 2D-LC analysis provides richer information than a single chromatography analysis at the cost of longer analysis time. The time required for a comprehensive 2D-LC analysis is essentially proportional to the analysis time of the second dimension separation. Many of 2D-LC analyses of synthetic polymers have employed size exclusion chromatography (SEC) for the second-dimension analysis due to the relatively short analysis time in addition to the wide use in the polymer analysis. Nonetheless, short SEC columns are often used for 2D-LC analyses to reduce the separation time, which inevitably deteriorates the resolution. In this study, we demonstrated that high temperature SEC can be employed as an efficient second-LC in the 2D-LC separation of synthetic polymers. By virtue of high temperature operation (low solvent viscosity and high diffusivity of the polymer molecules), a normal length SEC column can be used at high flow rate with little loss in resolution.     

Towards on-line SEC-GC of pesticide residues? The problem of tailing triglyceride peaks

SEC is used for clean-up of food extracts obtained for analysis of pesticide residues primarily to remove high molecular weight material, among which fat may be present at the largest concentrations. The triglyceride peak, which is usually very large, is eluted before the components of interest. The problem described in this paper deals with the tail of the triglyceride peak: this may intrude into the fraction containing the pesticides and contaminate the GC.     

Fractionation of ethylene/1‐pentene copolymers using a combination of SEC‐FTIR and SEC‐HPer DSC

The short chain branching distribution (SCBD) and thermal properties of ethylene/1‐pentene copolymers were studied using SEC‐FTIR and SEC‐HPer DSC. The copolymers, synthesized with Cp₂ZrCl₂/MAO, were fractionated using size exclusion chromatography (SEC). The infrared analysis of the fractions showed that the copolymers had—on average—higher 1‐pentene concentration in the low molecular weight range. Furthermore, the thermal properties of the SEC deposits of these copolymers on a Germanium disc were studied using high performance differential scanning calorimetry (HPer DSC). Single SEC separations were used to accumulate fractions in the microgram range that were directly analyzed with regard to their thermal properties, thus allowing us to study SCBD as well as thermal behavior simultaneously. When these fractions (with masses ranging from 10–80 μg) were analyzed using HPer DSC, good melting and crystallization temperature distributions were obtained, proving that HPer DSC can be used as a complementary method to SEC‐FTIR. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2956–2965, 2007