Low Molar Mass Research Articles

Simultaneous Optimization of Deacetylation Degree and Molar Mass of Chitosan from Shrimp Waste.

Shrimp waste is a valuable source for chitin extraction and consequently for chitosan preparation. In the process of obtaining chitosan, a determining step is the chitin deacetylation. The main characteristic of chitosan is the degree of deacetylation, which must be as high as possible. The molar mass is another important parameter that defines its utilizations, and according to these, high or low molar masses are required. The present study is an attempt to optimize the deacetylation step to obtain chitosan with a high degree of deacetylation and high or low molar mass. The study was carried out based on experimental data obtained in the frame of a central composite design where three working parameters were considered: NaOH concentration, liquid:solid ratio, and process duration. The regression models defined for the degree of deacetylation (DD) and for the mean molar mass (MM) of chitosan powders were used in the formulation of optimization problems. The objectives considered were simultaneous maximum DD and maximum/minimum MM for the final chitosan samples. For these purposes, multiobjective optimization problems were formulated and solved using genetic algorithms implemented in Matlab®. The multiple optimal solutions represented by trade-offs between the two objectives are presented for each case.

Determination of Molecular Dimensions of Carbohydrate Polymers (Polysaccharides) by Size Exclusion Chromatography (SEC).

Calibrated size exclusion chromatography (SEC) is a useful tool for the analysis of molecular dimensions of polysaccharides. The calibration takes place with a set of narrow distributed dextran standards and peak position technique. Adapted columns systems and dissolving processes enable for the adequate separation of carbohydrate polymers. Plant-extracted fructan (ahomopolymer with low molar mass and excellent water solubility) and mucilage (differently structured, high molar massheteropolysaccarides that includeexisting supramolecular structures, and require a long dissolving time) are presented as examples of the versatility of this technique. Since narrow standards similar to the samples (chemically and structurally) are often unavailable, it must be noted that the obtained molar mass values and distributions by this method are only apparent (relative) values, expressed as dextran equivalents.

Extrinsic pseudocapacitive ultrathin 2D MoS2 nanoflakes clamped on 1D Sb2S3 nanorods: an advanced heterostructured anode for high-energy ammonium ion hybrid capacitors

Nanorods of Sb2S3 serve as a 1D conductive core, and 2D MoS2 nanosheets offer abundant active sites with large interlayer galleries for facial ion movement during the charge–discharge process and improve the electrochemical performance.

Low molar mass cyclic poly(L-lactide)s: separate transesterification reactions of cycles and linear chains in the solid state.

L-Lactide (LA) was polymerized with neat tin(II) 2-ethylhexanoate (SnOct2) in toluene at 115 °C at low concentration with variation of the LA/Cat ratio. Cyclic polylactides (cPLAs) with number average molecular weights (Mn) between 7000 and 17 000 were obtained. MALDI-TOF mass spectrometry also revealed the formation of a few percent of linear chains. Crystalline cPLAs with Mn around 9000 and 14 000 were annealed at 140 °C in the presence of ScOct2 or dibutyl-2-stanna-1,3-dithiolane (DSTL). Simultaneously, crystallites of extended linear chains and crystallites of extended cycles were formed regardless of the catalyst, indicating that transesterification reaction proceeded different for linear chains and for cycles, governed by thermodynamic control. The formation of extended chain crystallites with low dispersity indicates the existence of symproportionation of short and long chains. A complementary experiment was carried out with a PLA ethyl ester composed mainly of linear chains with a small fraction of cycles.

Physically crosslinked polyacrylates by quadruple hydrogen bonding side chains.

Dynamic polymer materials can be obtained by introducing supramolecular interactions between the polymer chains. Here we report on the preparation and mechanical properties of poly(methyl acrylate) (PMA) and poly(n-butyl acrylate) (PBA) funcionalized with ureidopyrimidinone (UPy) in the side chains. In contrast to the traditional UPy with a methyl group, the selected UPy motif contained a branched alkyl side chain, which enhances solubility, compatibility with the polymer matrix and potentially prevents stacking of UPy dimers. Low molar mass PMA and PBA were synthesized via Cu(0)-mediated radical polymerization and allyl bonds were introduced with different degrees of functionalization by stoichiometrically controlled transesterification with allyl alcohol. The allyl esters served as functional handles for UPy attachment via UV-initiated radical thiol-ene coupling. The PMA-UPy materials displayed a more glassy appearance, in contrast to the rubbery PBA-UPy polymer networks, associated to its higher glass transition temperature. The mechanical properties of the resulting hydrogen bonded polymer networks were assessed by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical thermal analysis and tensile testing, followed by rheological analysis of the network dynamics. Furthermore, the effect of associative groups on the linear viscoelastic response is discussed based on a modified sticky Rouse model indicating the absence of significant aggregation or phase separation of the UPY units.

Molar mass determination via linear regression from SEC measurements: The case of polylactide, polycaprolactone and poly(2,2‐dimethylthrimethylene carbonate)

AbstractMolar mass correction coefficients (cc) were determined for calculating the absolute molar masses of polylactide (PLA), polycaprolactone (PCL), and poly(2,2‐dimethyltrimethylene carbonate) (PDTC) in the range of 2,5–190 kg/mol, using calibration based on polystyrene standards (PS). Linear PLAs, PCLs, and PDTCs with a wide range of molar masses were synthesized using tin (II) octoate and diol as a catalyst/initiator system. Size Exclusion Chromatography (SEC) coupled with a Refractive Index detector (SEC‐RI) or a Multi‐Angle Laser Light Scattering detector (SEC‐MALLS) was utilized to determine the relative molar mass or absolute molar mass of the samples under investigation. Additionally, for comparison, the absolute molar mass of low molar mass PLA, PCL, or PDTC was calculated based on end‐group analysis using the 1H NMR method. Correction coefficients were subsequently calculated by comparing the molar mass obtained from SEC‐MALLS and SEC‐RI. The calculated correction coefficients ranged from 0.40 to 0.87 and increased with the rising molar mass of the polymers. The derived equation could be used to evaluate the absolute molar masses from PS standards over a broad range for the analyzed polymers.

Lewis acid ionic liquid catalysed synthesis of bioderived surfactants from β-pinene

Cationic polymerisation of β-pinene (βP) via earth abundant catalysis has been investigated as a route to low molar mass poly(β-pinene) (PBP) for surfactant applications. As a ‘greener’ alternative to the...

Molecular weight-dependent antitumor effects of prunes-derived type I arabinogalactan on human and murine triple wild-type melanomas

The regulation of metastasis-related cellular aspects of two structurally similar AGIs from prunes tea infusion, with different molar masses, was studied in vitro against Triple Wild-Type metastatic melanoma (TWM) from murine and human origin. The higher molar mass AGI (AGI-78KDa) induced TWMs cells death and, in murine cell line, it decreased some metastasis-related cellular processes: invasiveness capacity, cell-extracellular matrix interaction, and colonies sizes. The lower molar mass AGI (AGI-12KDa) did not induce cell death but decreased TWMs proliferation rate and, in murine cell line, it decreased cell adhesion and colonies sizes. Both AGIs alter the clonogenic capacity of human cell line. In spite to understand why we saw so many differences between AGIs effects on murine and human cell lines we performed in silico analysis that demonstrated differential gene expression profiles between them. Complementary network topological predictions suggested that AGIs can modulate multiple pathways in a specie-dependent manner, which explain differential results obtained in vitro between cell lines. Our results pointed to therapeutic potential of AGIs from prunes tea against TWMs and showed that molecular weight of AGIs may influence their antitumor effects.

Bio-based polyester-polyurethane foams: synthesis and degradability by Aspergillus niger and Aspergillus clavatus.

In this article, the degradability by Aspergillus niger and Aspergillus clavatus of three bio-based polyurethane (PU) foams is compared to previous degradability studies involving a Pseudomonas sp. bacterium and similar initial materials (Spontón et al. in Int. Biodet. Biodeg. 85:85-94, 2013, https://doi.org/10.1016/j.ibiod.2013.05.019 ). First, three new polyester-polyurethane foams were prepared from mixtures of castor oil (CO), maleated castor oil (MACO), toluene diisocyanate (TDI), and water. Then, their degradation tests were carried out in an aqueous medium, and employing the two mentioned fungi, after their isolation from the environment. From the degradation tests, the following was observed: (a) the insoluble (and slightly collapsed) foams exhibited free hydroxyl, carboxyl, and amine moieties; and (b) the water soluble (and low molar mass) compounds contained amines, carboxylic acids, and glycerol. The most degraded foam contained the highest amount of MACO, and therefore the highest concentration of hydrolytic bonds. A basic biodegradation mechanism was proposed that involves hydrolysis and oxidation reactions.

Influence of the temperature and type of macromolecule on phase diagrams of aqueous two-phase systems

Phase diagrams for aqueous two-phase systems formed by L64 + Na2SO3 + H2O, F68 + Na2SO3 + H2O, polyethylene glycol 10,000 g·mol–1 (PEG10k) + Na2SO3 + H2O and PEG 35,000 g·mol–1 (PEG35k) + Na2SO3 + H2O were determined experimentally at temperatures of 278.15, 288.15 and 298.15 K, at 0.09 MPa. The binodal curve is not significantly shifted with varying temperature, indicating a small change on the system enthalpy during the phase separation process, but an increase in the temperature promoted an increase in the slope of tie-line. The effectiveness of macromolecules in promoting phase separation occurs in the following order: PEG35k > PEG10k ≈ F68 > L64. An increase in molar mass requires lower concentrations to induce phase separation, due to the decrease of configurational entropy of the solution. When comparing macromolecules with similar molar masses, PEG10k required slightly lower concentrations than F68 to induce phase segregation. Although PEG10k has a higher molar mass, the structure of F68 contains hydrophobic groups (poly(propylene glycol)) that compensate for its lower molar mass, which generates similar phase segregation induction capabilities. Therefore, new aqueous two-phase systems have been characterized by extending the range of systems available for applications.

Adsorption of sodium alginate on calcium carbonate microparticles: Effect of molar mass and composition

Sodium alginate and calcium carbonate are natural materials with a high compositional variability. The molar mass and structural composition of sodium alginate and the crystalline structure of calcium carbonate can affect their interactions in pure water. Herein, we studied the adsorption of sodium alginate onto calcium carbonate microparticles in pure water. The adsorption appears to be driven by electrostatic interactions stabilized by calcium ions at the surface of the particles and in solution due to the dissolution of calcium carbonate in pure water. We found that the adsorption of sodium alginate is favored onto microparticles with more calcite. We also found that the adsorption of sodium alginate polymers with low guluronate content (~ 30%) onto calcium carbonate particles tends to increase for polymers with lower average molar mass and more flexible polymer chains. In contrast, polymers with high guluronate content (~ 65%) tend to adsorb more onto calcite when they present a lower average molar mass polymers as well as a higher proportion of guluronate monomers.

Effects of polycaprolactone viscosity on morphology, mechanical properties, water uptake, and cellular viability in poly(3‐hydroxybutyrate)/polycaprolactone blends for tissue engineering

AbstractIn this study, two polycaprolactones (PCLs) with different molar masses were evaluated regarding their influence on the melt processability, morphology viscoelastic and mechanical properties, water uptake, and fibroblast and pre‐osteoblast viability of poly(3‐hydroxybutyrate)/polycaprolactone (PHB/PCL) blends. PHB/PCL blends were prepared in a mixing chamber following 90/10 and 70/30 ratios and later compression molded. The torque rheometry results show that the blends' processability is influenced by the ratio and molar mass of the PCL used in its obtaining, those being more strongly affected by the PCL with lower molar mass. The results indicate that the polymeric blend was immiscible in any proportion and molar mass of PCL used. The blends showed a sea‐island morphology in which the diameter of the dispersed phase depended on the composition. In general, even though the molar mass of PCL differed, the blends showed similar behaviors. However, a great difference was observed in the fracture mechanism for the blend with PCL of lower molar mass, which did not present the ability to fibrillate before rupture, due to its low mechanical resistance. The blends showed greater water uptake capabilities when compared to the pure polymers due to the diffusion of water through the gaps in between the phases. The blends showed high cell viability when tested in fibroblast cells of the L929 lineage and pre‐osteoblast cells of the MCT3‐E1 lineage, indicating that these materials are promising for application in bone tissue engineering.

Xylan-cellulose core structure of oat water-extractable β-glucan macromolecule: Insight into interactions and organization of the cell wall complex

Water-extractable β-glucan with high molar mass (HM) determines health benefits of oat food. Oat β-glucan was extracted by a standardized in vitro digestion method and co-existing water-extractable polysaccharide (WEP) fraction and its HM-arabinoxylan (HM-AX) subfraction were isolated to identify their highly acid-resistant subunit and investigate molecular interactions between constituent polymers. The WEP and HM-AX samples consisted of arabinoxylans (AXs) (74 and 76 %, respectively), however, cellulose constituted the secondary component (6.6 and 12.8 %, respectively). Multi-detection HPSEC along with specific enzymatic hydrolysis of AXs revealed the presence of the HM-xylan domain (16 and 34 %, respectively) built of numerous single- and multi-component populations with random coil and rod-like conformations, which were embedded in a xylan matrix with spherical conformation and controlled the macromolecular shape. Unlike single-component populations, the multi-component ones were resistant to hydrolytic action of AX-hydrolyzing enzymes and represented the subunits that anchor matrix polysaccharides onto cellulose surface. These results indicate that water-extractable β-glucan macromolecule comprises as integral element a cellulose core with two linking populations, HM-xylan and low molar mass glucomannan, which are surrounded by a feruloylated AX-arabinan-arabinogalactan composite and next laminated by β-glucan matrix. The stiff cellulose-xylan backbone is the basis of HM β-glucan organization, controlled by its cellulose-like segments.

Nano-scaled halloysite-supported dicationic ionic liquids as effective additives in the production of low viscosity polyalphaolefin oils by AlCl3 co-initiator

In this research, three nano-scaled halloysite-supported imidazolium based dicationic ionic liquids (ILs) with different electronic features from the second ionic part, namely, 1-methylimidazole (HS-IM), triethanolamine (HS-TEA), and tributylamine (HS-TBA) were prepared. The so called ILs were applied along with AlCl3, when its dose was halved, in the oligomerization of the 1-octene monomer. The microstructure of the synthesized polyalphaolefins (PAOs) was fully characterized using different analytical methods. According to GPC analysis, PAOs synthesized in the presence of ILs contain notably lower molar masses (757–950 g/mol) with mostly lighter fractions, compared to Al-PAO (1820 g/mol) produced using neat AlCl3. Based on the viscosity measurements, the PAOs had outstanding KV100 = 4.5–5.7 cSt and VI = 128–134, which are comparable to the low viscosity commercial counterparts. This achievement presented a proposed much more sustainable and greener polymerization procedure, in which the dose of AlCl3 was halved, compared to the current commercialized technology aided by a hazardous BF3 initiator. Then, to shed light on the origin of this effect in the lowering of the PAOs molar mass produced in the presence of designed dicationic ILs, molecular simulation at the DFT level was considered.

Investigating the Effect of the Crosslinking Factor on the Properties of Hydrogel Materials Containing Tilia platyphyllos Hydrolate.

The use of natural ingredients in recent years has been of great importance in many industries and medicine. In biomedical applications, hydrogel materials also play a significant role. In view of this, the aim of this study was to synthesize and characterize hydrogel materials enriched with broadleaf linden hydrolate. An important aspect was to carry out a series of syntheses with varying types and amounts of crosslinking agents so as to test the possibility of synthesizing materials with controlled properties. The obtained hydrogels were subjected to detailed physicochemical analysis. The results of the tests confirmed the relationship between the selected properties and the type of crosslinking agent used. A crosslinking agent with a lower molar mass (575 g/mol) results in a material with a compact and strongly crosslinked structure, which is characterized by high surface roughness. The use of a crosslinking agent with a molecular weight of 700 g/mol resulted in a material with a looser-packed polymer network capable of absorbing larger amounts of liquids. The work also proved that regardless of the type of crosslinking agent used, the addition of linden hydrolate provides antioxidant properties, which is particularly important in view of the target biomedical application of such materials.

Influence of Rheological and Morphological Characteristics of Polyhydroxybutyrate on Its Meltblown Process Behavior.

Polyhydroxybutyrate (PHB) is a promising biopolymer. However, processing PHB in pure form in thermoplastic processes is limited due to its rapid degradation, very low initial crystallization rate, strong post-crystallization, and its low final stretchability. In this article, we screened commercial PHBs for morphological characteristics, rheological properties, and "performance" in the meltblown process in order to reveal process-relevant properties and overcome the shortcoming of PHB in thermoplastic processes for fiber formation. An evaluation of degradation (extruded (meltblown) material vs. granules) was performed via rheological and SEC analysis. The study revealed large differences in the minimum melt temperature (175 up to 200 °C) and the grade-dependent limitation of accessible throughput on a 500 mm plant. The average fiber diameter could be lowered from around 10 μm to 2.4 μm in median, which are the finest reported values in the literature so far. It was found that the determination of the necessary process temperature can be predicted well from the complex shear viscosity. Different to expectations, it became apparent that a broader initial molar mass distribution (>8) is suitable to overcome the state-of-the art limitations of PHAs in order to stabilize fiber formation, increase the productivity, and obtain better resistance towards thermal degradation in process. Accordingly, longer polymer chain fractions could be more affected by degradation than medium and short polymer chains in the distribution. Further, a low initial narrow distributed molar mass resulted in too brittle fabrics.

Aqueous Organic Batteries Using Proton as Charge Carrier.

Benefiting from the merits of low cost, non-flammability and high operational safety, aqueous rechargeable batteries have emerged as promising candidates for large-scale energy storage applications. Among various metal-ion/non-metallic charge carriers, proton (H+ ) as a charge carrier possesses numerous unique properties such as a fast proton diffusion dynamics, a low molar mass and a small hydrated ion radius, which endow aqueous proton batteries (APBs) with a salient rate capability, a long-term life span and an excellent low-temperature electrochemical performance. In addition, redox-active organic molecules, with the advantages of structural diversity, rich proton-storage sites and abundant resources, are considered as attractive electrode materials for APBs. However, as far as application is concerned, the charge storage and transport mechanisms of organic electrodes in APBs is still in infancy. Therefore, finding suitable electrode materials and uncovering the H+ storage mechanisms are significant for the applications of organic materials in APBs. Herein, the latest research progresses on organic materials such as small molecules and polymers for APBs are reviewed. Furthermore, a comprehensive summary and evaluation of APBs employing organic electrodes as anode and/or cathode is provided, especially on their low-temperature and high-power performances, along with systematic discussions for guiding the rational design and the construction of APBs based on organic electrodes. This article is protected by copyright. All rights reserved.

Material Characterization of Polypropylene and Polystyrene Regarding Molecular Degradation Behavior.

During the processing of thermoplastics, polymers are subjected to high stress. As a result of this stress, the polymer chains break, leading to a lower molar mass. This further leads to a lower viscosity of the plastic melt and, eventually, to poorer mechanical properties of the manufactured plastic product. Especially in the context of recycling plastics, this poses a challenge to process technology and product properties. This work aims is to provide a prediction of the material degradation under known stress, so that, for example, a process design that is gentle on the material can be carried out. In order to be able to predict material degradation under a load, a test stand for defined material degradation was designed. The test stand allows for material damaging under a defined temperature, shear rate and residence time. At the same time, the test stand can be used to measure the viscosity, which is used to describe the degradation behavior, since the viscosity correlates with the molar mass. The measured decrease in viscosity under stress can be used to predict material damage under the influencing variables of temperature, shear rate and residence time by means of a test plan and a suitable mathematical description of the measured data. The mathematical description can thus be integrated into simulation environments for plastics processing, so that a simulation of the material degradation can be carried out, if necessary also taking the viscosity reduction into account.

Chlorella sp. MBFJNU-17 as an emerging source of starch: Changes in starch structures during heterotrophic cultivation

Chlorella sp. MBFJNU-17 rich in starch and protein could be obtained by modulating the glucose and urea content during its cultivation. Whether MBFJNU-17 was a potential source of starch with adjustable structures was still unclear. In this study, MBFJNU-17 cells with different starch content were collected by regulating glucose (3–15 g/L) and urea content (0–4 g/L) during heterotrophic cultivation. Cells cultured with high glucose content (15 g/L) and low urea content (0 g/L) had a high starch content. Moreover, the starches produced by these cells displayed a larger molar mass and a higher proportion of ordered structures. On the other hand, cells cultured with limited glucose content (3 g/L) and sufficient urea content (0 g/L) showed lower starch content, along with lower molar mass and a reduced amount of ordered structures. Starch granules derived from cells with higher glucose culture conditions demonstrated lower digestibility. Findings suggested that MBFJNU-17 cells with adjustable starch structures and digestibility could be obtained by modulating heterotrophic cultivation conditions.

Gel characteristics of low-acetyl spruce galactoglucomannans

Galactoglucomannans (GGM) recovered from abundant forest industry side-streams has been widely recognized as a renewable hydrocolloid. The low molar mass and presence of O-acetyl side-groups results in low viscous dispersions and weak intermolecular interactions that make GGM unsuitable for hydrogel formation, unless forcefully chemically derivatized and/or crosslinked with other polymers. Here we present the characterization of hydrogels prepared from GGM after tailoring the degree of acetylation by alkaline treatment during its recovery. Specifically, we investigated gel characteristics of low-acetyl GGM dispersions prepared at varied solid concentrations (5, 10 and 15 %) and pH (4, 7 and 10), and then subjected to ultrasonication. The results indicated that low-acetyl GGM dispersions formed gels (G′ > G″) at all other studied solid concentration and pH level combinations except 5 % and pH 4. High pH levels, leading to further removal of acetyl groups, and high solid concentration facilitated the gel formation. GGM hydrogels were weak gels with strong shear-thinning behavior and thixotropic properties, and high hardness and water holding capacity; which were enhanced with increased pH and solid concentration, and prolonged storage time. Our study showed the possibility to utilize low-acetyl GGM as mildly processed gelling or thickening agents, and renewable materials for bio-based hydrogels.