Molecular Weight Determination Research Articles

Preparation and performance evaluation of a low‐damage fracturing fluid for unconventional reservoirs

AbstractThe characteristics of tight matrix, underdeveloped natural fractures, small pore throat radius, poor pore connectivity, and abundant clay minerals result in a high potential for damage to the tight sandstone reservoirs of the Shaximiao Formation in the Qiulin Block in the Sichuan Basin. In order to reduce the retention damage caused by fracturing fluid to the tight sandstone reservoir, a low damage fracturing fluid system applicable to the target reservoir is developed in this work, and the indoor performance meets the requirements of on‐site fracturing operation. A low‐damage, heat‐resistant, shear‐stable amphiphilic polyacrylamide (PAAD) was prepared by free radical polymerization in aqueous solution using acrylamide, acrylic acid, and methacryloyloyloxyethyl dimethyloctadecyl ammonium bromide (DM18) as the monomers. The amphoteric polyacrylamide was characterized by Fourier infrared spectroscopy, nuclear magnetic resonance spectroscopy (1H NMR), light scattering molecular weight determination, and thermogravimetric analysis. Fracturing fluids were formulated with the amphiphilic hydrophobic associative polymer PAAD as a drag‐reducing agent, the fluorine‐containing and nonionic complex surfactant FD1 as a clean‐up additive, CT10‐4B as a bactericide and CT1‐12 as an emulsion breaker. The fracturing fluid formulation was preferred, and the performance of the fracturing fluid was evaluated in terms of temperature resistance and shear resistance, drag reduction, anti‐expansion, and core damage. The fracturing fluid showed good temperature and shear resistance, with a viscosity retention of 58.4% at 120°C and 170 s−1 shear for 1 h. At a loading of 0.1%, the drag reduction rate reaches 72.3%, the anti‐expansion rate of the gel‐breaking fluid is 86.04%, and the damage rate to the tight sandstone core is 16.25%. The results show that the fracturing fluid has good heat resistance and shear stability, as well as low damage and good resistance reduction and anti‐expansion properties. This work can provide new strategies for designing polymeric fracturing fluids with low damage, good heat resistance and shear stability.

Pharmaceutical Applications and Advances with Zetasizer: An Essential Analytical Tool for Size and Zeta Potential Analysis

: Zetasizer is an advanced device that measures various properties of particles or molecules suspended in a liquid medium. It is extensively used for evaluating the size of nanoparticles, colloids, and biomolecular particles, and for determining particle charge. There are several analytical techniques by which the size, zeta potential, and molecular weight can be determined, like Dynamic Light Scattering (DLS) that measures the size of particles in dispersed systems, which can range from sub-nanometers to several micrometers in diameter. Electrophoretic Light Scattering (ELS) analyzes the mobility and charge of particles, also known as the zeta potential. Static Light Scattering (SLS) determines the molecular weight of particles in a solution. The Zetasizer is part of the Zetasizer Advance range of benchtop systems available for laboratory use. The Zetasizer Ultra model offers unique measurement capabilities, such as Multi-angle Dynamic Light Scattering (MADLS) and particle concentration. These features offer a deeper understanding of samples, making the Zetasizer a vital instrument in numerous scientific and industrial applications. In this review, we have discussed Zetasizer’s principles for the determination of particle size, zeta potential, and molecular weight, along with its qualification and applications in different formulations.

Comparative analysis of electrophoresis and interferometric optical detection method for molecular weight determination of proteins

Analytical detection methods play a pivotal role in scientific research, enabling the identification and quantification of specific analytes in various disciplines. This scientific report aims to compare two very different methodologies for determining the Molecular Mass (MM, also known as Molecular Weight, MW) of proteins: electrophoresis gel and the Interferometric Optical Detection Method (IODM). For this purpose, several proteins with different MM were selected.The electrophoresis technique was employed to validate the structure and MM of different parts or fragments of the Matrix Metallopeptidase 9 antibody (anti-MMP9), antibody against S100 calcium binding protein A6 (anti-S100A6) and Cystatin S4 antibody (anti-CST4) by examining the presence of bands with expected sizes. The IODM was applied to study the above-mentioned proteins (part of the antibodies) together with the protein G, as a reference to correlate the MM and protein sizes with the measured signal.We report the evidence of IODM as a competitive analytical approach for the determination of the MM of proteins for the first time. This innovative method allows for accurate MM determination using minimal sample volumes and concentrations, employing a simple experimental procedure that eliminates the requirement for protein denaturation.

Structural characteristics and anti-photoaging effect of Pyracantha fortuneana fruit polysaccharides in vitro and in vivo

Pyracantha fortuneana is a cultivated pant extensively cultivated worldwide for its ornamental value and ecological benefits. In this study, a polysaccharide with anti-photoaging activity was extracted and purified from P. fortuneana fruit (PPFP). The structural constitution of PPFP was elucidated by molecular weight determination, FT-IR, monosaccharide composition analysis, smith degradation, methylation, and NMR spectroscopy. The results revealed that PPFP is a macromolecular polysaccharide with a weight-average molecular weight of 70,895 Da. The PPFP is predominantly characterized by →3,6)-β-Galp-(1→, →5,3)-α-Araf-(1 → and →4,2)-α-Xylp-(1→, →4)-β-Galp-(1 → and →4)-β-GalpA-(1 → glycosidic linkages, with t-α-Araf-(1 → and t-α-Glcp-(1 → terminal units. The anti-photoaging activity and potential mechanism of action of PPFP was investigated in vitro and in vivo. Results showed that PPFP exerted anti-photoaging effect on UVB-damaged HaCaT cells by ameliorating cell apoptosis, regulating the mitochondrial membrane potential and oxidative stress level, alleviating the phosphorylation level of the proteins in MAPK pathways, and repairing the expression of tight junction proteins. Moreover, PPFP enhanced the lifespan and diminished the oxidative stress in UVB-injured Caenorhabditis elegans. Collectively, this study comprehensively elucidates the anti-photodamaging potential of P. fortuneana fruit polysaccharide and offers a novel plant-derived adjuvant therapy for the treating photodamage.

Expression, characterization, and application of human-like recombinant gelatin

Gelatin is a product obtained through partial hydrolysis and thermal denaturation of collagen, belonging to natural biopeptides. With irreplaceable biological functions in the field of biomedical science and tissue engineering, it has been widely applied. The amino acid sequence of recombinant human-like gelatin was constructed through a newly designed hexamer composed of six protein monomer sequences in series, with the minimum repeating unit being the characteristic Gly-X-Y sequence found in type III human collagen α1 chain. The nucleotide sequence was subsequently inserted into the genome of Pichia pastoris to enable soluble secretion expression of recombinant gelatin. At the shake flask fermentation level, the yield of recombinant gelatin is up to 0.057 g/L, and its purity can rise up to 95% through affinity purification. It was confirmed in the molecular weight determination and amino acid analysis that the amino acid composition of the obtained recombinant gelatin is identical to that of the theoretically designed. Furthermore, scanning electron microscopy revealed that the freeze-dried recombinant gelatin hydrogel exhibited a porous structure. After culturing cells continuously within these gelatin microspheres for two days followed by fluorescence staining and observation through confocal laser scanning microscopy, it was observed that cells clustered together within the gelatin matrix, exhibiting three-dimensional growth characteristics while maintaining good viability. This research presents promising prospects for developing recombinant gelatin as a biomedical material.

A Complementary Multitechnique Approach to Assess the Bias in Molecular Weight Determination of Lignin by Derivatization-Free Gel Permeation Chromatography.

The growing interest in lignin valorization in the past decades calls for analytical techniques for lignin characterization, ranging from wet chemistry techniques to highly sophisticated chromatographic and spectroscopic methods. One of the key parameters to consider is the molecular weight profile of lignin, which is routinely determined by size-exclusion chromatography; however, this is by no means straightforward and is prone to being hampered by considerable errors. Our study expands the fundamental understanding of the bias-inducing mechanisms in gel permeation chromatography (GPC), the magnitude of error originating from using polystyrene standards for mass calibration, and an evaluation of the effects of the solvent and type of lignin on the observed bias. The developed partial least-squares (PLS) regression model for lignin-related monomers revealed that lignin is prone to association mainly via hydrogen bonding. This hypothesis was supported by functional group-based analysis of the bias as well as pulse field gradient (pfg) diffusion NMR spectroscopy of model compounds in THF-d8. Furthermore, although the lack of standards hindered drawing conclusions based on functionalities, direct infusion electrospray ionization mass spectrometry indicated that the relative bias decreases considerably for higher molecular weight species. The results from pfg-diffusion NMR spectroscopy on whole lignin samples were comparable when the same solvents were used in both experiments; in addition, the comparison between results obtained by pfg-diffusion NMR in different solvents gives some additional insights into the aggregation.

Synthesis and Characterization of Novel Terpolymers as Viscosity Index Improvers Using Industrial Waste for Iraqi Lubricating Oil

The potential utilization of industrial waste, specifically polyethylene wax, to enhance the efficiency of alkyl acrylate polymers as viscosity index improver (VII) additives in lubricating compositions has been investigated. Four terpolymers (w1, w2, w3, and w4) were synthesized via free radical polymerization, incorporating hexyl acrylate, 1-tetradecene, and industrial waste-sourced polyethylene wax at varying molar ratios. These terpolymers were characterized through gel permeation chromatography (GPC) for molecular weight determination, Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H-NMR) spectroscopy for chemical structure analysis, and thermal gravimetric analysis (TGA) for thermal stability assessment. The study evaluated the efficiency of these terpolymers as viscosity index improvers (VII) in combination with free additives Iraqi lubricating oil (base oil 60). Our results demonstrate the feasibility of significantly enhancing the efficiency of viscosity improvers through the utilization of industrial waste, with improvements proportional to terpolymer concentration. The terpolymer w3, characterized by a balanced molar ratio of 1:1:1, exhibiting the highest degree of efficacy, which gave VI of 206 at 5 wt.% concentration compared with free additive lubricating oil, which gives VI of 98. This study offers promising insights into the sustainable use of industrial waste to improve lubricating compositions.

Real-Time Determination of Molecular Weight: Use of MaDDOSY (Mass Determination Diffusion Ordered Spectroscopy) to Monitor the Progress of Polymerization Reactions.

Knowledge of molecular weight is an integral factor in polymer synthesis, and while many synthetic strategies have been developed to help control this, determination of the final molecular weight is often only measured at the end of the reaction. Herein, we provide a technique for the online determination of polymer molecular weight using a universal, solvent-independent diffusion ordered spectroscopy (DOSY) calibration and evidence its use in a variety of polymerization reactions.

Fulvic acid transdermal patch: Its properties, optimization and release

There is a high demand for the design of fulvic acids (FA) transdermal patches being natural biologically active substances with a wide action. The difficulties in FA transdermal patches creating are due to the peculiarities of FA obtaining with high purity and solubility, the existence of many several polymorphic forms, as well as the problems of their insertion into dosage forms. In this work, we modified the FA isolation as water-soluble polymorph. This operation allowed us to reduce the impurities in the product, to optimize the formulation of the emulsion-based transdermal patches, to provide a quantitative assessment of FA release. Data of IR, 13C NMR, AAS, ICP-AES-spectra, direct and reverse titration of carboxyl groups and phenolic hydroxyls, potentiometry, molecular weight determination by cryoscopy (M.m=740 g/mol), fluorescent analysis, solubility (3.3 mL of water per gram) confirmed the receipt of the desired polymorph. Optimization of the transdermal patches formulations by Response Surface Methodology and release evaluation and kinetics mathematical modeling using a Franz cell showed the preferences of Pluronic Kolliphor p237 as a transcutant. The obtained water-soluble FA can be used as a potential component of transdermal patches with controlled release parameters.
 Keywords: fulvic acid, transdermal patches, pluronics, release

Study of Structural Elucidation, Degradation Kinetics and Antimicrobial Analysis of Copper (II) Sesame-Soap Complexes with Urea and Thiourea Ligand in Non-aqueous Solvents

Abstract: Surfactants have great importance in biological and drug industries and the complexes of metallic soaps with various ligands are used in approximately every region of national economy. Therefore, our keen interest to study of degradation kinetics and biological importance of Cu (II) surfactants in non-aqueous and non-polar solvent benzene. Present research work has been initiated with synthesis, systematic study of structural elucidation, thermal degradation, kinetics and biocidal activities of copper (II) sesame-soap complexes with macrocyclic nitrogen and sulphur containing donar ligands like urea and thiourea. The thermal degradation of copper (II) sesame-soap complexes were carried out for analysis of degradation kinetics and estimation of kinetic and thermodynamic parameters using different methods at heating rate 10oC min-1. Copper (II) sesame-soap complexes of such ligands have also been analysed against Staphylococus aureus. This research work consolidates the synthesis of copper (II) sesame soap-urea and thiourea complexes by conventional methods and the structure of these complexes were assigned according to elemental analysis and molecular weight determinations. IR, NMR and ESR spectral studies have also been done to understand structural aspects. The anti-microbial activities of copper (II) sesame-soap urea and thiourea complexes have been evaluated by testing against Staphylococus aureus. The present research work includes information of thermal analysis using TGA technique to find out their kinetic and thermodynamic parameters by using diverse equations such as Coats-Redfern equation, Horowitz-Metzger equation, Broido equation, Piloyan–Novikova equation. Moreover, the results obtained from anti-microbial screening have been used to analyze the anti-microbial activities of copper (II) sesame-soap urea and thiourea complexes against gram-positive bacteria Staphylococus aureus. These results show that complexes of copper ion co-ordinated with different nitrogen, oxygen and sulphur containing ligands, are very important in the field of pharmaceutical chemistry due to its significant role in the inhibition activity. The study of these complexes concludes that the synthesized complexes were found to possess appreciable bactericidal properties at different concentrations because chelation increases the anti-microbial potency.

Dynamic Non-Covalent Exchange Intrinsic Self-Healing at 20 °C Mechanism of Polyurethane Induced by Interactions among Polycarbonate Soft Segments.

Two polyurethanes (PUs) were similarly synthesized by reacting a cycloaliphatic isocyanate with 1,4-butanediol and two polyols of different nature (polyester, polycarbonate diol) with molecular weights of 1000 Da. Only the PU synthesized with polycarbonate diol polyol (YCD) showed intrinsic self-healing at 20 °C. For assessing the mechanism of intrinsic self-healing of YCD, a structural characterization by molecular weights determination, infrared and X-ray photoelectronic spectroscopies, differential scanning calorimetry, X-ray diffraction, thermal gravimetric analysis, and dynamic mechanical thermal analysis was carried out. The experimental evidence concluded that the self-healing at 20 °C of YCD was due to dynamic non-covalent exchange interactions among the polycarbonate soft segments. Therefore, the chemical nature of the polyol played a key role in developing PUs with intrinsic self-healing at 20 °C.

An accessible technique for molecular weight determination by cryoscopy applicable for coordination compounds

An improved computerized method is proposed for determination of molecular weights by cryoscopy. The use of a precision digital platinum resistance thermometer greatly simplifies the measurement process in comparison with the classic Beckmann apparatus. All component parts of the device are factory-made (interchangeable) details, which are widely used in laboratory practice. A test report is formed with the aid of a computer using Microsoft Excel software. The use of molecular sieves for drying dimethyl sulfoxide (DMSO), as well as experimental procedures specific to organolithium compounds, make it possible to obtain reproducible measurement results for coordination compounds that are prone to oligomerization in solutions. The molecular structure of the bis(acetylacetonato)di(dimethyl sulfoxide)nickel(II) obtained from dimethyl sulfoxide solutions was determined by single crystal X-ray diffraction. P21/c, a = 8.7916(2), b = 12.3061(3), c = 8.7421(2) (Å), β = 99.4460(10)°, Z = 2. The complex [Ni(C5H7O2)2(C2H6OS)2] is mononuclear with a square-bipyramidal environment of the central atom. The coordination polyhedron of the Ni ion is formed by four oxygen atoms of two chelating acetylacetonate anions in the equatorial position and two atoms of dimethyl sulfoxide molecules in axial positions.

Joncryl chain extender reactivity with polylactide: Effect of d-lactide content, Joncryl type, and processing temperature

In this study, a highly crystallizable and an amorphous polylactide (i.e., cPLA and aPLA) with, respectively, low (0.5 mol. %) and high (12 mol. %) d-lactic acid contents and similar molecular weights were melt compounded with two different multifunctional epoxy-based Joncryl chain extenders (CEs, i.e., ADR 4400 and 4468) at 190 °C. Reactivity of Joncryl grades with aPLA was also explored at melt processing temperatures of 150, 170, and 210 °C. Small amplitude oscillatory shear rheological analysis was conducted to understand the extent of the Joncryl reaction with PLA molecules, and the results were confirmed with molecular weight determination using gel permeation chromatography. Extensional viscosity of the processed samples was also compared to control their strain hardening behavior. Results showed that the Joncryl reaction with cPLA and aPLA differs in terms of preference for chain extension or branching, indicating that molecular regularity affected the interactions with both Joncryl grades during reactive melt processing. Moreover, although the increase in processing temperature accelerated PLA degradation, it noticeably increased the reactivity of both Joncryl grades with aPLA. In all cases, ADR 4468 was more reactive in molecular chain extension/branching due to its higher functionality than ADR 4400. Differential scanning calorimetry results also revealed that the crystallization of cPLA was differently affected by the change in the Joncryl content and type.

Flash extraction of ulvan polysaccharides from marine green macroalga Ulva linza and evaluation of its antioxidant and gut microbiota modulation activities

In this study, flash extraction was used to rapidly extract water-soluble polysaccharides from Ulva linza. The optimal extraction process for the flash extraction was determined by Box–Behnken design with extraction temperature 80 °C, extraction time 117 s, liquid-solid ratio 46:1 (mL/g) and a corresponding yield of 18.5 %. The crude Ulva linza polysaccharides (CULP) were subsequently isolated by chromatography technology to obtain purified Ulva linza polysaccharide (ULP) and characterized by monosaccharide composition and molecular weight determination analysis. Furthermore, the antioxidant bioactivity of ULP was studied and the results revealed that it had a good scavenging effect on DPPH, ABTS and OH, with IC50 values of 149.2 μg/mL, 252.5 μg/mL and 1073 μg/mL, respectively. After in vitro fermentation by human fecal microbiota, the pH value of fermentation culture significantly decreased to 5.06, suggesting that ULP could be hydrolyzed and utilized by gut microbiota. The abundance of beneficial bacteria including Bacteroides, Parabacteroides and Faecalibacterium was improved. Meanwhile, the relative abundance of Prevotella, Blautia and Ruminococcus was decreased, and the low ratio of these organisms might reveal positive effects on maintaining the balance of gut microbial biodiversity. These results suggested that the composition of the human gut microbiota could be modulated by ULP, and ULP might possess the potential to maintain gut homeostasis and improve human intestinal health.

Advancing Molecular Weight Determination of Lignin by Multi-Angle Light Scattering.

Due to the complexity and recalcitrance of lignin, its chemical characterization is a key factor preventing the valorization of this abundant material. Multi-angle light scattering (MALS) is becoming a sought-after technique for absolute molecular weight (MW) determination of polymers and proteins. Lignin is a suitable candidate for MW determination via MALS, yet further investigation is required to confirm its absolute MW values and molecular size. Studies aiming to break down lignin into a variety of renewable products will benefit greatly from a simple and reliable determination method like MALS. Recent pioneering studies, discussed in this review, addressed several key challenges in lignin's MW characterization. Nevertheless, some lignin-specific issues still need to be considered for in-depth characterization. This study explores how MALS instrumentation manages the complexities of determining lignin's MW, e.g., with simultaneous fractionation and fluorescence interference mitigation. Additionally, we rationalize the importance of a more detailed light scattering analysis for lignin characterization, including aspects like the second virial coefficient and radius of gyration.

Characterization by Gel Permeation Chromatography of the Molecular Weight of Supramolecular Polymers Generated by Forming Polyrotaxanes through the Introduction of External Stoppers.

Supramolecular polymers find wide applications across diverse domains, and the molecular weight exerts a critical influence on their applicability. Consequently, the measurement of molecular weight for supramolecular polymers assumes paramount significance. Gel Permeation Chromatography (GPC) requiring low-concentration condition is a common characterization employed for molecular weight determination, which is not suitable for supramolecular polymers possessing concentration-independence property. Here, to break this threshold, we synthesized M1 embodying dibenzo-24-crown-8 (DB24C8) moiety as well as dibenzylammonium salt (DBA) group, which was capable of self-assembling into supramolecular polymers terminated with aldehyde groups at its end. Upon the addition of (4- (1,2,2-Triphenylvinyl) phenyl) methylamine (TPE-NH2), supramolecular polymers underwent a transition into polyrotaxanes, for which it was led by the generation of imine bonds. By virtue of GPC, the molecular weight of polyrotaxanes was obtained, then it was available to gain the molecular weight of supramolecular polymers with the help of transformation efficiency.

Phase-dependent polymerization isomerism in the coordination complexes of a flexible bis(β-diketonato) ligand.

First prepared in the late 70s, the pro-ligand 1,3-bis(3,5-dioxo-1-hexyl)benzene (H2bdhb) contains two acetoacetyl terminations linked to a central 1,3-phenylene unit through dimethylene bridges. Since each termination can be either in diketonic or keto-enolic form, in organic solution it exists as a mixture of three spectroscopically resolvable tautomers. In the presence of pyridine, Co2+ and the bdhb2- anion form a crystalline dimeric compound with formula [Co2(bdhb)2(py)4] (2) and a Co⋯Co separation of more than 11 Å. Complex 2 contains two pseudo-octahedrally coordinated and non-interacting high-spin cobalt(II) ions (S = 3/2) displaying a large easy-plane anisotropy (D ∼ 70 cm-1), as consistently indicated by magnetic measurements, X-band EPR spectra, and complete active space self-consistent field/N-electron valence state perturbation theory (CASSCF/NEVPT2) calculations. At cryogenic temperatures (T < 7 K) and in an applied static magnetic field, the compound shows detectably slow magnetic relaxation, which occurs through direct and Raman mechanisms. Combined mass spectrometry, UV-Vis, and 1H/2H NMR data, including an isotopic labelling experiment and a determination of molecular weight by diffusion ordered spectroscopy (DOSY), show that 2 rearranges to monomeric high-spin [Co(bdhb)(py)x] species (x = 0, 1, or 2) in organic solution (CH2Cl2, THF) with concomitant partial dissociation of the py ligands. The X-band EPR spectra in a frozen CH2Cl2/toluene matrix concurrently suggest a significant alteration of the coordination environment upon dissolution. These observations are fairly well reproduced by density functional theory (DFT) and CASSCF/NEVPT2 calculations on the lowest Gibbs free energy conformers of each species, as provided by an extensive conformational search based on meta-dynamics simulations and semiempirical tight-binding methods. After the vanadyl analogue, compound 2 provides the second example of polymerization isomerism in the 1 : 1 adducts of bdhb2- with divalent metal ions.

Quantitation of Active Pharmaceutical Ingredients in Polymeric Drug Products Using Elemental Analysis.

Polymeric prodrugs have gained significant popularity as a strategy to enhance the bioavailability and improve the pharmacokinetic properties of active pharmaceutical ingredients (API). Since the amount of the API in a polymeric prodrug product directly impacts both safety and efficacy, there is a pressing need for robust and accurate analytical methods to quantify the API in these formulations. Presently, drug quantification methods include reversed-phase high-performance liquid chromatography (RP-HPLC) and size exclusion chromatography (SEC)-based molecular weight determination. Even though these methods are highly precise and reproducible, a deep understanding of chromatography is required for complex method development, including optimization of the elution profile and selecting the appropriate column and mobile phase. In this chapter, we introduce the automated elemental analyzer for drug quantification, which is simple to use and does not require special method development.

Evaluation of multi-solvent size exclusion chromatography columns packed with sub-2 μm particles for the characterization of synthetic polymers

With the recent development of small particle stationary-phases and dedicated instrumentation, the combination of size-exclusion chromatography (SEC) with ultra-high performance liquid chromatography (UHPLC) technology has been realized. It opened up a new polymer analysis technique called UHP-SEC. Although high resolution and fast analysis can be achieved, the multi-solvent suitability for a given column was limited to either organic or aqueous eluents. In this work, the capability of novel SEC columns (AdvanceBio SEC columns) packed with 1.9 μm particles for the characterization of synthetic polymers in organic solvents as well as the multi-solvent compatibility for organic and aqueous eluents have been demonstrated. About six times faster separation for both polystyrene (PS) and polyethylene glycol (PEG) with good peak shape and repeatability were achieved in comparison with standard SEC columns at comparable resolution. Especially for PEG, in contrast to other SEC columns, this column could provide close-to-accurate determination of molecular weights with tetrahydrofuran (THF) as mobile phase. Good reproducibility was obtained after switching several times from water to THF and vice versa with RSD% in retention times less than 0.5 %. Different samples such as polyols, isocyanates and additives can also be analyzed for molecular weight and distribution or composition determination. Volume overload, especially with injection volumes higher than 10 µL needs to be considered. This new column offers a powerful choice for oligomer and polymer analysis with both aqueous and organic mobile phase. Ultimately, hyphenating SEC columns to various detectors can enable more information regarding chemical composition, molecular weight, concentration, and structure.

High molecular weight bimodal polyethylene elastomers using N,N'-nickel catalysts appended with methoxy and trifluoromethoxy functionality

Polyolefinic materials displaying bimodal molecular weight distributions are of interest since they can potentially provide mechanical toughness from the high molecular weight component without losing processability on account of the low molecular weight component. With this in mind, a series of nickel(II) complexes, [1-[2,6-{(4-MeOC6H4)2CH}2–4-(F3CO)C6H2N]-2-(ArN)C2C10H6]NiBr2 (Ar = 2,4-Me2C6H3Ni1, 2,6-Et2C6H3Ni2, 2,6-iPr2C6H3Ni3, 2,4,6-Me3C6H2, Ni4, 2,6-Et2-4-MeC6H2Ni5, 2,6-Me2C6H3Ni6) have been synthesized and have shown, following treatment with MMAO or Et2AlCl, excellent activity for the polymerization of ethylene (up to 19.87 × 106 g (PE) mol−1 for Ni4/Et2AlCl) generating high molecular weight branched polyethylene. More importantly, the elastomeric material produced using Et2AlCl as activator displays bimodal characteristics as well as low crystallinity and a medium to high branching density. By contrast, the material prepared using MMAO was more unimodal and showed higher crystallinity and lower branching density. Stress–strain and stress–strain recovery tests performed on the bimodal PE’s revealed a range of tensile properties with a sample prepared using Ni5/Et2AlCl combining both high tensile strength and high fracture strength (σ = 20.3 MPa, ε = 892.0 %). Conversely, a PE sample prepared using Ni4/Et2AlCl showed the highest elastic recovery with a stress relaxation (SR) value of 67.6 %. Besides branching analysis, molecular weight determinations and mechanical tests on the polymers, all nickel complexes and precursor 1,2-bis(arylimino)acenaphthenes, have been characterized by a combination of spectroscopic techniques, elemental analysis and in the cases of Ni1(OH2) and Ni4 by single crystal X-ray diffraction. A theory is also proposed to explain the observed bimodality.