Intermediate Molar Mass Research Articles

Hyaluronic Acid in the Intestinal Tract: Influence of Structure, Rheology, and Mucoadhesion on the Intestinal Uptake in Rats.

Oral hyaluronic acid (HA) is a ubiquitous biopolymer that has gained attention as a treatment for local or systemic diseases. Here, we prepared and characterized structures of free HA (f-HA) with a high (>105 Da), intermediate (≤105 Da), and low (≤104 Da) average molar mass (MM); nanoparticles crosslinked with adipic dihydrazide (n-HA); and mixed formulations (mixed-HA) containing f-HA and n-HA. MM distribution determined the structure, hydrodynamic diameter, and zeta potential of the f-HAs. Crosslinking changed the physicochemical properties in n-HA. In vitro tack adhesion assays, using mucin tablets or a viable rat intestinal mucosa, showed better mucoadhesion with f-HA (intermediate MM) and mixed-HA (25% n-HA), especially in the jejunum segment. High MM f-HA presented negligible mucoadhesion. n-HA showed the deepest diffusion into the porous of the membranes. In vivo results showed that, except for high MM f-HA, there is an inverse relationship between rheological changes in the intestinal membrane macerates resulting from mucoadhesion and the effective intestinal permeability that led to blood clearance of the structures. We conclude that the n-HA formulations are promising for targeting other tissues, while formulations of f-HA (intermediate MM) and mixed-HA are better for treating dysbiosis.

Time-dependent self-association of spruce galactoglucomannans depends on pH and mechanical shearing

The demand for naturally derived, functional and cost-effective raw materials for various food applications is escalating. Spruce wood is a sustainable and abundant, but underutilized source of novel hydrocolloids—galactoglucomannans (GGM). Pressurized-hot water extracted GGM with an intermediate molar mass are hypothesized to form colloidal solutions. To design superior quality products from GGM, an understanding of their colloidal stability and their potential effect in multiphasic systems is required. The present study addresses the functionality of GGM by characterizing their properties in a bi-phasic system, and for the first time, their time-dependent colloidal stability at different extrinsic conditions— pH, ionic strength and after the application of high-intensity mechanical shearing. Amongst the conditions studied, the colloidal stability of aqueous GGM solution was highly pH dependent. The results showed that an intermediate molar mass polysaccharide like GGM formed inter-/intra molecular assemblies, which grew over time, depending on the composition and processing of the aqueous medium. The molecular dispersion of GGM and their dynamic behavior was also compared to solutions of known food hydrocolloids—gum Arabic and hydroxypropylmethyl cellulose. The observed solution properties explain the hydrocolloid functionality of GGM and contribute to design of colloidal polysaccharide systems in food application.

Environmentally-compatible alkyd paints stabilized by wood hemicelluloses

Wood biorefining currently involves large-scale industrial processes where a notable portion of raw materials, namely hemicelluloses and lignin, are either lost with the process water, degraded, or burnt for energy. Value-added utilization of polymeric hemicelluloses is challenging due to their intermediate molar mass and the presence of other wood components, such as phenolic residues or wood extractives. Oil-in-water (O/W) emulsions represent a diverse and abundant class of applications in which the natural properties of wood hemicelluloses are beneficial. In the current work, we present highly promising new technical alkyd paint emulsion systems stabilized with hardwood glucuronoxylans (GX) and softwood galactoglucomannans (GGM). Samples from three isolation methods and their further fractionation by ethanol precipitation were systematically compared with regard to hemicellulose composition, interfacial activity, and functionality in emulsions. Emulsification of alkyd resins was successful with both GX and GGM obtained by various biorefining strategies. The highest emulsion stability over storage was achieved using crude non-purified GX and GGM fractions, and was correlated with the presence of phenolic compounds and extractives, interfacial activity, and small droplet size. Hardwood GX and softwood GGM are envisioned as natural emulsifiers of alkyd O/W emulsions, which are examples of diverse and abundantly-used technical dispersions. This study can be utilized as a guideline for targeted extraction of hemicelluloses with desired functionality, and as a protocol for developing environmentally-compatible industrial dispersions.

Determination of the speciation and bioavailability of samarium to Chlamydomonas reinhardtii in the presence of natural organic matter.

As technological interest and environmental emissions of the rare earth elements increase, it is becoming more important to assess their potential environmental impact. Samarium (Sm) is a lanthanide of intermediate molar mass that is used in numerous high-technology applications including wind turbines, solar panels, and electric vehicles. The present study relates the speciation of Sm determined in the presence of natural organic matter (NOM) to its bioavailability to the unicellular green alga Chlamydomonas reinhardtii. The free ion concentration was determined using a cation exchange resin (ion exchange technique) in dynamic mode and compared with thermodynamic modeling. Short-term biouptake experiments were performed in the presence of 4 types of NOM: Suwannee River fulvic acids, Pahokee Peat fulvic acids, Suwannee River humic acids, and a Luther Marsh dissolved organic matter isolate (90-95% humic acids). It was clearly shown that even a small amount of NOM (0.5 mg C L-1 ) resulted in a significant decrease (10 times) in the Sm internalization fluxes. Furthermore, complexation with humic acids (and the corresponding reduction in Sm bioavailability) was stronger than that with fulvic acids. The results showed that the experimentally measured (free) Sm was a better predictor of Sm internalization than either the total concentrations or the free ion concentrations obtained using thermodynamic modeling. Environ Toxicol Chem 2018;37:1623-1631. © 2018 SETAC.

A Simply Synthesized, Tough Polyarylene with Transient Mechanochromic Response

AbstractA simple and high‐yielding route to tough polyarylenes of the type poly(meta,meta,para‐phenylene) (PmmpP) is developed. PmmpP is tough even in its as‐synthesized state which has an intermediate molar mass of Mw≈60 kg mol−1 and exhibits outstanding mechanical properties at further optimized molecular weight of Mw=96 kg mol−1, E=0.9 GPa, ϵ=300 %. Statistical copolymers with para,para‐spiropyran (SP) are mechanochromic, and the toughness allows mechanochromism to be investigated. Strained samples instantaneously lose color upon force release. DFT calculations show this phenomenon to be caused by the PmmpP matrix that allows build‐up of sufficiently large forces to be transduced to SP, and the relatively unstable corresponding merocyanine (MC) form arising from the aromatic co‐monomer. MC units covalently incorporated into PmmpP show a drastically reduced half life time of 3.1 s compared to 4.5 h obtained for SP derivatives with common 6‐nitro substitution.

A Simply Synthesized, Tough Polyarylene with Transient Mechanochromic Response.

A simple and high-yielding route to tough polyarylenes of the type poly(meta,meta,para-phenylene) (PmmpP) is developed. PmmpP is tough even in its as-synthesized state which has an intermediate molar mass of Mw ≈60 kg mol-1 and exhibits outstanding mechanical properties at further optimized molecular weight of Mw =96 kg mol-1 , E=0.9 GPa, ϵ=300 %. Statistical copolymers with para,para-spiropyran (SP) are mechanochromic, and the toughness allows mechanochromism to be investigated. Strained samples instantaneously lose color upon force release. DFT calculations show this phenomenon to be caused by the PmmpP matrix that allows build-up of sufficiently large forces to be transduced to SP, and the relatively unstable corresponding merocyanine (MC) form arising from the aromatic co-monomer. MC units covalently incorporated into PmmpP show a drastically reduced half life time of 3.1 s compared to 4.5 h obtained for SP derivatives with common 6-nitro substitution.

Nanostructured Polyethylene Reactor Blends with Tailored Trimodal Molar Mass Distributions as Melt-Processable All-Polymer Composites

Tailoring trimodal polyethylene (PE) molar mass distributions by means of ethylene polymerization on three-site catalysts, supported on functionalized graphene (FG), enables nanophase separation during polymerization and melt processing, paralleled by PE self-reinforcement. Typically, FG/MAO-supported three-site catalysts combine bis(iminopyridyl)chromium trichloride (CrBIP), producing PE wax having high crystallization rate, and quinolylcyclopentadienylchromium dichloride (CrQCp), forming in situ ultrahigh molecular weight PE (UHMWPE) nanostructures, with bis(iminopyridyl)iron dichloride (FeBIP) or bis(tert-butyl cyclopentadienyl)zirconium (ZrCp), respectively, producing HDPE with variable intermediate molar mass. During injection molding, the formation of shish-kebab fiber-like extended-chain UHMWPE structures, as verified by SEM, AFM, and DSC, account for effective self-reinforcement. Only in the presence of high UHMWPE content, PE wax, usually an unwanted byproduct in HDPE synthesis, functions as a bu...

Characterization of the global structure of low methoxyl pectin in solution

Low methoxyl citrus pectin (LMP) and amidated low methoxyl pectin (LMAP) were characterized by high performance size exclusion chromatography (HPSEC) with online light scattering (LS), intrinsic viscosity (ηw), differential refractive index (dRI) and ultra-violet (UV) detection, by amino acid analysis (AAA) and by atomic force microscopy (AFM). HPSEC revealed the following: the weight average molar mass (Mw), ranged 103–288 × 103 Da, (ηw), ranged 2.69–4.27 dL/g, radius of gyration (Rgz), was 28.6–49.5 nm and hydrated radius (Rhzv), was 26.3–41.8 nm. The presence of phenylalanine and tyrosine residues as shown by the UV absorbance at 278 nm in the high molar mass range is indicative of protein or fragments associated with LMP derived from citrus fruit. The ρ value (Rgz/Rhzv) as a function of molar mass indicated that high molar mass pectin was more compact in shape than intermediate molar mass pectin. AFM images in this study and earlier studies indicate that high methoxyl pectin (HMP) and LMP form network structures in aqueous solution. Unlike HMP networks, LMP networks do not dissociate when dissolved in water at concentrations that are less than 6.6 μg/mL. Furthermore, AFM images, Mw and ηw values for LMP and LMAP indicate that little or no added sugar is bound.

Evaluation of pH‐sensitive hydrogels to control the permeability anisotropy of oil reservoirs

ABSTRACTIn stratified or fractured oil reservoirs, the oil recovery efficiency tends to be low as the injected fluid flows mainly through the matrix's most permeable regions, leaving behind part of the displaceable oil in the matrix's unswept zones. Given this issue, this study aims to evaluate the potential of applying seven commercial samples, based on poly(acrylic acid), to control the anisotropic permeability profile of reservoirs. To perform this study, first, continuous and oscillatory shear tests were conducted to characterize the hydrogel's rheological and viscoelastic behavior in various subsurface conditions (salinity, temperature, and/or pH value). Second, polymer dispersion elution tests were performed in a porous medium to evaluate the matrix's permeability reduction after treatment with hydrogels. The seven commercial samples were classified as pseudoplastic fluids at pH values ranging from 1 to 10. Under typical reservoir conditions, PAAr 70 (which has intermediate molar mass and intermediate number of crosslinks) was the only sample to behave as a strong gel (G′/G″ > 10). Elution tests confirmed that the PAAr 70 hydrogel gelified inside the consolidated sandstone plugs and reduced the matrix's permeability four‐fold. Therefore, samples based on poly(acrylic acid) with high crosslink density proved to be the most promising for controlling the anisotropic permeability profile of heterogeneous oil reservoirs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40665.

Molar Mass Dependent Growth of Poly(ε-caprolactone) Crystals in Langmuir Films

Poly(epsilon-caprolactone) (PCL) samples with number average molar masses (Mn) ranging from 3.5 to 36 kg.mol-1 exhibit molar mass dependent nucleation and growth of crystals, crystal morphologies, and melting properties at a temperature of 22.5 degrees C in Langmuir films at the air/water (A/W) interface. At surface area per monomer, A, greater than approximately 0.37 nm2.monomer-1, surface pressure, Pi, and surface elasticity exhibit molar mass independent behavior that is consistent with a semidilute PCL monolayer. In this regime, the scaling exponent indicates that the A/W interface is a good solvent for the liquid-expanded PCL monolayers. Pi-A isotherms show molar mass dependent behavior in the vicinity of the collapse transition, i.e., the supersaturated monolayer state, corresponding to the onset of the nucleation of crystals. Molar mass dependent morphological features for PCL crystals and their subsequent crystal melting are studied by in situ Brewster angle microscopy during hysteresis experiments. The competition between lower segmental mobility and a greater degree of undercooling with increasing molar mass produces a maximum average growth rate at intermediate molar mass. This behavior is analogous to spherulitic growth in bulk PCL melts. The plateau regions in the expansion isotherms represent the melting process, where the polymer chains continuously return to the monolayer state. The magnitude of Pi for the plateau during expansion decreases with increasing molar mass, indicating that the melting process is strongly molar mass dependent.

Blends of Poly(ε-caprolactone) and Intermediate Molar Mass Polystyrene as Langmuir Films at the Air/Water Interface

Poly(epsilon-caprolactone)/polystyrene (PCL/PS) blends, where nonamphiphilic PS is glassy in the bulk state at the experimental temperature of 22.5 degrees C, are immiscible as Langmuir films at the air/water (A/W) interface. Surface pressure-area per monomer isotherm analyses indicate that the surface concentration of amphiphilic PCL is the only factor influencing the surface pressure below the collapse transition. For PS-rich blends, Brewster angle microscopy (BAM) studies at the A/W interface and atomic force microscopy studies on Langmuir-Schaefer films reveal that PS nanoparticle aggregates formed at very low surface pressures can form networks upon further compression. The morphologies seen in PS-rich blends (networklike rings) are consistent with a recent study of a nonamphiphilic polyhedral oligomeric silsesquioxane (POSS), octaisobutyl-POSS, blended with amphiphilic poly(dimethylsiloxane), suggesting that the nonamphiphilic PS aggregates at the A/W interface produce domains with dipole densities that differ from that of pure PCL. In all composition regimes, the amphiphilic PCL phase tends to spread and form a continuous surface layer at the A/W interface, while simultaneously improving the dispersion of nonamphiphilic PS domains. During film expansion, BAM images show a gradual change in the surface morphology from highly continuous networklike structures (PS-rich blends) to broken ringlike structures (intermediate composition) to small discontinuous aggregates (PCL-rich blends). This study provides valuable information on the morphological evolution of semicrystalline PCL-based polymer blends confined in a "two-dimensional" geometry at the A/W interface and fundamental insight into the influence of microstructure (domain size, phase-separated structures, crystalline morphology, etc.) on the interfacial properties of blends as Langmuir films.

Efficiency of the activated carbon filtration in the natural organic matter removal

The removal and transformation of natural organic matter were monitored in the different stages of the drinking water treatment train. Several methods to measure the quantity and quality of organic matter were used. The full-scale treatment sequence consisted of coagulation, flocculation, clarification by flotation, disinfection with chlorine dioxide, activated carbon filtration and post-chlorination. High-performance size-exclusion chromatography separation was used to determine the changes in the humic substances content during the purification process; in addition, a UV absorbance at wavelength 254 nm and total organic carbon amount were measured. A special aim was to study the performance and the capacity of the activated carbon filtration in the natural organic matter removal. Four of the activated carbon filters were monitored over the period of 1 year. Depending on the regeneration of the activated carbon filters, filtration was effective to a degree but did not significantly remove the smallest molar mass organic matter fraction. Activated carbon filtration was most effective in the removal of intermediate molar mass compounds (range 1000–4000 g/mol). Regeneration of the carbon improved the removal capacity considerably, but efficiency was returned to a normal level after few months.

Comparison of the Effiency of Aluminium and Ferric Sulphate in the Removal of Natural Organic Matter During Drinking Water Treatment Process

The removal of natural organic matter by coagulation in the drinking water treatment train was studied for a period of two years. In the middle of the study, the coagulation/flotation process was modified by replacing the aluminium sulphate by ferric sulphate. At the same time, the filtration unit was enhanced by adding a sand filter unit before the activated carbon filtration and by changing new carbons on to the activated carbon filters. A special aim was to compare the efficiency of the aluminium and ferric coagulants in the organic matter removal by several methods, including high-performance size-exclusion chromatography. A comparison of quantity and characteristics of organic matter in treated water before and after treatment process modification provided an insight into process performance. Approximately 95% of high molar mass organic substances were removed in the process with both coagulation agents. The greatest difference between the coagulants occurred in the removal of organic matter having molar masses of 1000-4000 g mol−1. These intermediate molar mass organic compounds were removed 25 % more efficiently with iron-based coagulant than with aluminium-based. Low molar mass material was poorly removed regardless of the coagulant. On average, only 10 % of this fraction was removed. According to different measuring techniques used in the study, the ferric sulphate coagulation was 10 % more efficient in the overall organic matter removal compared to the aluminium sulphate coagulation. Turbidity removal was more efficient with aluminium than with ferric sulphate. Turbidity even increased during winter in ferric sulphate coagulation. However, turbidity was effectively removed in filtrations.

Enhancement of the natural organic matter removal from drinking water by nanofiltration

Finnish surface waters are abundant in natural organic matter. Natural organic matter can be removed from drinking water in a water treatment process by coagulation and filtration. The standard treatment operations are not able to remove the smallest molar mass fraction of organic matter and the intermediate molar mass matter is only partly removed. The removal of residual natural organic matter from drinking water by nanofiltration was evalueted in this study. Three different nanofiltration membranes were compared in filtering six pre‐treated surface waters. The total organic carbon content of the feed waters varied from 2.0 to 4.2 mg 1‐1. Other water quality parameters measured were conductivity, alkalinity, hardness, UV‐absorbance, SUVA, E2/E3 value and molecular size distribution by high‐performance size‐exclusion chromatography. The natural organic matter removal efficiencies of the membranes were good and varied between 100% and 49%, and between 85% and 47% according to molecular size distribution and total organic carbon measurements, respectively. Removal of different molecular size fractions varied from 100% to 56%, 100% to 54% and 88% to 19%, regarding high molar mass, intermediate molar mass and low molar mass organic matter, respectively. The Desal‐5 DL membrane produced the highest natural organic matter removals.

Molar mass selectivity in the adsorption of polyacrylates on calcite

Aqueous solutions of polyacrylates, with a wide molar mass distribution, have been equilibrated with aqueous dispersions of calcium carbonate particles. In mixtures with excess polyacrylates, it is found that only a fraction of the original collection of macromolecules adsorbs on the mineral surfaces. The adsorbed macromolecules have been recovered, and their molar mass distribution has been measured using size exclusion chromatography (SEC). It is found that a narrow fraction with intermediate molar mass is preferentially adsorbed. This selection results from a kinetic process where these macromolecules are the first to bind to the surface. Smaller macromolecules do not bind at all and larger ones could bind, but are repelled by the macromolecules that arrived first at the surface.

Influence of poly(acrylic acid) molar mass on the fracture properties of glass polyalkenoate cements based on waste gasifier slags

The failure behaviour of glass polyalkenoate cements was investigated using a linear elastic fracture mechanics (LEFM) approach. Cements were based on Drayton gasifier slag and four poly(acrylic acid)s with number average molar masses ranging from 3.03 × 103 to 6.44 × 104. Cement properties were studied at time intervals of one, seven and twenty eight days. Compressive and flexural strengths of the cements increased with increasing molar mass of the poly(acrylic acid)s and time. The Young's modulii increased with time and were independent of poly(acrylic acid) molar mass. Fracture toughness increased with increasing molar mass of the poly(acrylic acid)s. Fracture toughness increases over an ageing time of one week and subsequently decreased over one month. Toughness increased with poly(acrylic acid) molar mass, these increases being most pronounced at higher molar mass. The toughness values decreased with time for the higher molar mass cements, which is consistent with increased crosslinking of the poly(acrylic acid) chains and reducing molecular flow at the crack tip. Plastic zone size increased with poly(acrylic acid) molar mass and decreased with time for lower molar mass cements, remained constant for intermediate molar mass cements and increased with high molar mass cements.

Poly(ethylene glycol): Protein-repulsive or albumin-compatible?

In the literature, many papers deal with the behavior of proteins in aqueous media in the presence of poly(ethylene glycol) (PEG) molecules or poly(ethylene oxide) (PEO) segments, physically adsorbed onto, or covalently attached to, macromolecules or to solid surfaces. In particular, it is well known that PEO segments make foreign materials stealthy, i.e. they are much less detected by the immune system either through humoral reactions or, at the cell level, through opsonins. Revisiting the literature led us to challenge the largely accepted opinion that the decreased recognition of PEO segment-bearing foreign macromolecules and particles by the mononuclear phagocyte system is primarily the consequence of the repulsion of all blood proteins by PEG segments through the excluded volume effect. This challenge is based on the finding that albumin and PEG are compatible in phosphate-buffered saline at room temperature and at concentrations comparable to those measured by others on the surface of PEO segment-bearing species, whereas fibrinogen and PEG phase-separated and were incompatible despite the much lower concentration of the latter protein. According to literature and to these observations, it is proposed that the stealth effect induced by PEO segments is primarily due to the compatibility between PEO segments of intermediate molar mass and albumin, thus rendering PEO-bearing macromolecules or surfaces to look like native albumin. Under such conditions, the hospitality offered by PEG macromolecules or PEO segments to albumin, the dominant plasma protein, results in a 'chameleon' effect that prevents the activation of other PEG-compatible or-incompatible plasma proteins or cells involved in foreign body recognition and elimination. PEG with molar masses >8000 did not accommodate albumin in agreement with the excluded volume phenomenon.