Polymer Size Research Articles

Hydrothermal–Microwave Processing for Starch Extraction from Mexican Avocado Seeds: Operational Conditions and Characterization

Avocado seeds are an agroindustrial residue widely produced in Mexico that are causing various environmental problems due to their accumulation. The evaluation of avocado residues to recover biopolymers by microwave-assisted extraction (MAE) and the characterization of avocado starch properties were studied in the present work. A central-composite design was used to optimize the MAE process. Moreover, a comparison was performed between MAE non-isothermal mode (NO–ISO) and conventional extraction. Starch optimization by MAE was obtained at 161.09 °C for 56.23 min with an extraction yield of 49.52% ± 0.69%, while with NO–ISO at 161 °C was obtained 45.75% ± 2.18%. Conventional extraction was 39.04% ± 2.22%. Compared with conventional starch, MAE starch showed similar proprieties and molecular spectra. In contrast, MAE starch showed high solubility, low water absorption capacity, a non-granular structure with small particle size (<2 µm) and polydispersity of fragments at different sizes of polymers. Therefore, MAE is a viable technology to extract the starch, and avocado seed can be considered an excellent starch source for the development of novel functional foods, contributing to promoting sustainability across the food chain.

Accelerating polymer simulation by means of tree data-structures and a parsimonious Metropolis algorithm

We show how a Monte Carlo method for generating self-avoiding walks on lattice geometries which employs a binary-tree data-structure can be adapted for hard-sphere polymers with continuous degrees of freedom. Data suggests that the time per Monte Carlo move scales logarithmically with polymer size. Next we generalize the method to Lennard-Jones polymers with untruncated monomer–monomer interaction. To this end we propose a variant of the Metropolis algorithm and demonstrate that in combination with the tree data-structure logarithmic scaling can be preserved. We further show how the replica-exchange method can be adapted for the same purpose.

Rheological analysis of the interplay between the molecular weight and concentration of hyaluronic acid in formulations of supramolecular HA/FmocFF hybrid hydrogels

In this report, we evaluated the interplay between molecular weight and mass ratio of polymer during development of viscoelastic properties in HA/FmocFF hybrid supramolecular hydrogels. Rheology was the main tool to assess this complex relationship and the kinetics of network formation during self-assembly were correlated with inherent material properties. Formation of long-rang elastic interactions, ductility and plastic flow were strongly dependent on both size and concentration of polymer, providing a convenient application window to tune the flow properties of the hybrid hydrogels according to the intended application.

Simulating the Effects of Excluded-Volume Interactions in Polymer Solutions

Excluded-volume interactions are ubiquitous to modeling the average size of polymers in solution. This paper shows how simulations can be used by students to explore the emergence of mathematical scaling relations from excluded-volume interactions. Simulations provide robust visual representations of the system, and can be used to investigate a wide scope of problems and scenarios. The simulations were built with the free VPython coding environment and relatively basic algorithms. The results align with the mathematical theories of Flory and De Gennes and provide access to additional insights that are less obvious in the mathematical treatments. Students with relatively basic programming knowledge were able to extend and modify these models and to examine their alignment with mathematical theories. These examples extend the growing literature on simulation-based approaches for teaching and learning chemistry.

Rheology and fluid loss of a polyacrylamide-based micro-gel particles in a water-based drilling fluid

In this paper, the cross-linked micro-gel polymer between acrylamide (AM) and N, N-Methylenebisacrylamide (MBA) was synthesized by dispersion polymerization. The initiator and crosslinking agent concentration were used to control the particle size of micro-gel polymer. The filtration property and mechanism of micro-gel were investigated comprehensively. The characteristics of micro-gel were checked by means of Fourier transform infrared spectroscopy, thermogravimetry, transmission electron microscopy, and particle size distribution, respectively. The results indicated that the cross-linked micro-gel polymer exhibited several outstanding merits, such as thermal stability (up to 200 °C), filtration control and rheological property. Microstructure analysis and particle size distribution examinations showed that the scale of micro-gel polymer was micro, which is in accord with design. Rheological tests demonstrated that the nonlinear structure of micro-gel polymer showed less impact on the apparent viscosity. The anti-high temperature property of micro-gel polymer was better than poly anioniccellulose (PAC) and asphalt widely applied in drilling fluid for anti-high temperature fluid-loss additive. As a result, the cross-linked micro-gel polymer had great potential to be applied in high temperature water-based mud.

Insight into Protein-Polymer Conjugate Relaxation Dynamics: The Importance of Polymer Grafting.

The bio and chemical physics of protein-polymer conjugates are related to parameters that characterize each component. With this work, it is intended to feature the dynamical properties of the protein-polymer conjugate myoglobin (Mb)-poly(ethyl ethylene phosphate), in the ps and ns time scales, in order to understand the respective roles of the protein and of the polymer size in the dynamics of the conjugate. Elastic and quasi-elastic neutron scattering is performed on completely hydrogenated samples with variable number of polymer chains covalently attached to the protein. The role of the polymer length in the protein solvation and internal dynamics is investigated using two conjugates formed by polymers of different molecular weight. It is confirmed that the flexibility of the complex increases with the number of grafted polymer chains and that a sharp dynamical transition appears when either grafting density or polymer molecular weight are high. It is shown that protein size is crucial for the polymer structural organization and interaction on the protein surface and it is established that the glass properties of the polymer change upon conjugation. The results give a better insight of the equivalence of the polymer coating and the role of water on the surface of proteins.

Molecular Weight Parameters of Collagen from Different Feedstock and Dynamics of Their Change upon Enzymatic Hydrolysis by Pancreatin

Samples of high-molecular-weight collagen are isolated from the skins of various animals (cod, pig, and chicken) and characterized by molecular weight parameters. It is shown that the values of the molecular weight and polydispersity index of the polymer and particle sizes significantly differ depending on the nature of collagen. The performed studies are of interest for the area of tissue engineering associated with the development and investigation of the properties of scaffolds based on natural biopolymers and for the determination of the interrelation of chemical and biological processes.

Overlap Concentration and the Effect of Macromolecular Crowding on Citrate Synthase Activity

Although it is well-known that the environment of mitochondria is a densely packed network of macromolecules, the kinetics of the essential metabolic enzyme, citrate synthase, has been studied only under dilute conditions. To understand how this crowded environment impacts the behavior of citrate synthase, Michaelis-Menten kinetics were measured spectrophotometrically in the presence of synthetic crowders as a function of size, concentration, and identity. The largest factor contributing to crowding effects was the overlap concentration (c*), the concentration above which polymers begin to interact. The presence of the crowder dextran decreased the maximum rate of the reaction by ∼20% in the dilute regime (<c*) and 40% in the semidilute regime (>c*) regardless of polymer size. The disparate effects observed from different crowding agents of similar size also reveal the importance of transient interactions from crowding.

Densely Grafted Polyelectrolyte Brushes Trigger “Water-in-Salt”-like Scenarios and Ultraconfinement Effect

Summary This paper presents an all-atom molecular dynamics (MD) simulation of highly charged and densely grafted polyelectrolyte (PE) brushes on a flat surface. Simulation findings for the variation of brush height with polymer size and grafting density are explained by the scaling laws for brushes in the non-linear osmotic regime. More importantly, this study establishes the triggering of an ultraconfinement effect by the densely grafted brushes. This effect leads to significant changes in the distribution, structure, and properties as well as a massive mobility reduction of both the counterions and water. Furthermore, the interplay of the ultraconfinement effect and the large counterion-PE electrostatic interactions trigger a “water-in-salt”-like scenario (witnessed in highly concentrated aqueous electrolyte solutions), which is characterized by the counterion-PE-functional group serving as the “salt” with the “salt” overwhelming the water in both mass and volume and affecting the solvation structure of the counterions by replacing the solvation water with the PE-functional group.

An Overlooked Entry Pathway of Microplastics into Agricultural Soils from Application of Sludge-Based Fertilizers.

The widespread application of sewage sludge produced from wastewater treatment plants for agricultural use has been regarded as a primary source of microplastics (MPs) into soils. However, little is known regarding MPs in sludge-based fertilizers and their relevant fate in soils as being applied in agriculture. We comprehensively investigated the abundance, polymer size, type, and morphology of MPs in dewatered sludge, sewage sludge composts, sludge-based fertilizer-amended soils, and earthworms by stereoscopy and micro Fourier transform infrared (μ-FTIR) spectrometry methods. The results clearly showed that the quantity of MPs in soils exhibited a close correlation with the application rate of sludge-based fertilizers. The total abundances of MPs were 545.9 and 87.6 items/kg in soils after annual amendment with 30 (field A) and 15 t/ha (field B) of sludge composts, which is significantly higher than that without compost application (field C, 5.0 items/kg). Correspondingly, MPs were found in earthworms with low quantities of 1.8 and 0.4 items/individual in fields A and B, respectively, while no MP was detected in field C. We speculate that sludge composts may act as a vehicle of MPs into soils and then enter soil biota and in turn influence the spread of MPs in the environment.

Optical model to describe coherent transmittance of polymer dispersed liquid crystal film doped with carbon nanotubes

An optical model has been developed for analyzing the coherent transmittance of a polymer dispersed liquid crystal films doped with carbon nanotubes (CNTs) at uniform normal droplet-polymer interface anchoring. It is based on the Foldy–Twersky and anomalous diffraction approximations, Maxwell-Garnett equations, and the order parameters concept. The model allows one to analyze the electro-optical response of films depending on their thickness, the refractive indices of the liquid crystal (LC) and polymer matrix, size and concentration of the LC droplets, concentration of nanotubes, conductivities of the LC and the polymer. Experimental verification of the model is performed.

Microplastics in Sea Turtles, Marine Mammals and Humans: A One Environmental Health Perspective.

Microplastics are ubiquitous pollutants in the marine environment and a health concern. They are generated directly for commercial purposes or indirectly from the breakdown of larger plastics. Examining a toxicological profile for microplastics is a challenge due to their large variety of physico-chemical properties and toxicological behavior. In addition to their concentration, other parameters such as polymer type, size, shape and color are important to consider in their potential toxicity. Microplastics can adsorb pollutants such as polycyclic aromatic hydrocarbons (PAHs) or metals on their surface and are likely to contain plastic additives that add to their toxicity. The observations of microplastics in seafood increased concern for potential human exposure. Since literature considering microplastics in humans is scarce, using a One Environmental Health approach can help better inform about potential human exposures. Marine mammals and sea turtles are long-lived sentinel species regularly used for biomonitoring the health status of the ocean and share trophic chain and habitat with humans. This review considers the available research regarding microplastic and plastic fiber exposures in humans, marine mammals and turtles. Overall, across the literature, the concentration of microplastics, size, color, shape and polymer types found in GI tract and feces from sea turtles, marine mammals and humans are similar, showing that they might be exposed to the same microplastics profile. Additionally, even if ingestion is a major route of exposure due to contaminated food and water, dermal and inhalation studies in humans have provided data showing that these exposures are also health concerns and more effort on these routes of exposures is needed. In vitro studies looked at a variety of endpoints showing that microplastics can induce immune response, oxidative stress, cytotoxicity, alter membrane integrity and cause differential expression of genes. However, these studies only considered three polymer types and short-term exposures, whereas, due to physiological relevance, prolonged exposures might be more informative.

Polyethylene Glycol Size and Protein Stability

Concentrated solutions of synthetic polymers are often used to stabilize proteins, yet there are few systematic studies on the crowding effect of polymer molecular weight. Crowding effects arise from two types of crowder-test protein interactions: hard-core repulsions and soft interactions. Simple hard-core repulsions are only stabilizing, while soft (chemical) interactions can be stabilizing (if repulsive) or destabilizing (if attractive). Most synthetic polymers are assumed to interact with test proteins via hard-core repulsions, but polymers are often not inert. We investigated the temperature dependence of protein stability in polyethylene glycols as a function of polymer size and concentration. We used the 7-kDa metastable N-terminal SH3 domain of Drosophila signal transduction protein drk (SH3) as the test protein. SH3 was fluorine labeled at its single tryptophan enabling observation of the folded and unfolded species using 19F nuclear magnetic resonance spectroscopy. The temperature dependence of the free energy of unfolding (ΔGu°′) was used to obtain the entropy (ΔSu°′) and enthalpy (ΔHu°′) to aid in the separation of hardcore repulsions and soft interactions effects.

Statistics and Dynamics of Polymer Melt in Neutral Diblock Copolymer Single-Crystal Platelets.

Polymer single-crystal (SC) platelets of poly(butylene oxide)-b-poly(lactic acid) (PBO-b-PLLA) of a well-defined shape, size, and grafting density have been fabricated and embedded into PBO melt for the study of the statistics and dynamics of the host polymers. The colloidal liquid-crystalline order of SCs above a threshold concentration of ∼2.2 vol % provides a confining environment for the molten PBO. Meanwhile, the peculiar type-A characteristics of PBO allow us to simultaneously probe the dielectric chain dimensions and the hierarchical dynamics of polymers under confinement. We observe negligible changes to the mean-square end-to-end distance of the polymer melt as well as the chain and segment dynamics, even the interlayer distance approaches the length scale comparable to the size of the host polymers. Our results provide direct evidence of the impacts of neutral walls on both the statistics and the dynamics of confined polymer melts, which can be also enlightening for the field of polymer nanocomposites.

Combinatorial protein–protein interactions on a polymerizing scaffold

Scaffold proteins organize cellular processes by bringing signaling molecules into interaction, sometimes by forming large signalosomes. Several of these scaffolds are known to polymerize. Their assemblies should therefore not be understood as stoichiometric aggregates, but as combinatorial ensembles. We analyze the combinatorial interaction of ligands loaded on polymeric scaffolds, in both a continuum and discrete setting, and compare it with multivalent scaffolds with fixed number of binding sites. The quantity of interest is the abundance of ligand interaction possibilities-the catalytic potential Q-in a configurational mixture. Upon increasing scaffold abundance, scaffolding systems are known to first increase opportunities for ligand interaction and then to shut them down as ligands become isolated on distinct scaffolds. The polymerizing system stands out in that the dependency of Q on protomer concentration switches from being dominated by a first order to a second order term within a range determined by the polymerization affinity. This behavior boosts Q beyond that of any multivalent scaffold system. In addition, the subsequent drop-off is considerably mitigated in that Q decreases with half the power in protomer concentration than for any multivalent scaffold. We explain this behavior in terms of how the concentration profile of the polymer-length distribution adjusts to changes in protomer concentration and affinity. The discrete case turns out to be similar, but the behavior can be exaggerated at small protomer numbers because of a maximal polymer size, analogous to finite-size effects in bond percolation on a lattice.

Creation of Carbazole-Based Fluorescent Porous Polymers for Recognition and Detection of Various Pesticides in Water.

The development of sensitive, fast, and portable methods for detecting the residual toxic pesticides is essentially important because of the increasing concerns for public health and safety. For this purpose, three fluorescent porous organic polymers containing pendant N-benzyl carbazole, N-benzyl dibromo-carbazole, and N-benzyl dimethoxy-carbazole groups were synthesized via a one-step polymerization reaction. The resultant polymers emit bright cyan, blue, and green light under the ultraviolet lamp, respectively, with the Brunauer-Emmett-Teller area up to 858 m2 g-1 and tunable pore sizes in the range of 0.5-36 nm. Six pesticides including trifluralin, isopropalin, glyphosate, fenitrothion, imidacloprid, and cyfluothrin are selected as the analytes to investigate the recognition and detection ability of polymers in terms of the different photo-physical properties of polymers, chemical structure of organic pesticides as well as the pore sizes of polymers, and molecular sizes of pesticides. It is interesting to find that, even though in water medium, the measured fluorescent quenching Stern-Volmer coefficient for trifluralin still reaches 26,040 L mol-1 and is nearly unchanged under both acidic or basic service conditions. Moreover, the test paper prepared from the polymer exhibits a rapid fluorescent response when contacting the aqueous trifluralin dispersion liquid, and the sensitivity remains stable after recycling use for twelve times.

Mechanical degradation of polyacrylamide at ultra high deformation rates during hydraulic fracturing

Degradation of drag reducer polyacrylamide under high volume hydraulic fracturing (HVHF) conditions alters its polymer size, distribution and chemical composition, potentially affecting the toxicity and treatability of the resulting wastewater.

Reduction-responsive molecularly imprinted nanogels for drug delivery applications.

Degradable molecularly imprinted polymers (MIPs) with affinity for S-propranolol were prepared by the copolymerization of methacrylic acid as functional monomer and a disulfide-containing cross-linker, bis(2-methacryloyloxyethyl)disulfide (DSDMA), using bulk polymerization or high dilution polymerization for nanogels synthesis. The specificity and the selectivity of DSDMA-based molecularly imprinted polymers toward S-propranolol were studied in batch binding experiments, and their binding properties were compared to a traditional ethylene glycol dimethacrylate (EDMA)-based MIP. Nanosized MIPs prepared with DSDMA as crosslinker could be degraded into lower molecular weight linear polymers by cleaving the disulfide bonds and thus reversing cross-linking using different reducing agents (NaBH4, DTT, GSH). Turbidity, viscosity, polymer size and IR-spectra were measured to study the polymer degradation. The loss of specific recognition and binding capacity of S-propranolol was also observed after MIP degradation. This phenomenon was applied to modulate the release properties of the MIP. In presence of GSH at its intracellular concentration, the S-propranolol release was higher, showing that these materials could potentially be applied as intracellular controlled drug delivery system.

Luminescent spherical particles of lanthanide-based infinite coordination polymers with tailorable sizes

The influence of three different synthetic routes on the size and morphology of luminescent lanthanide-based infinite coordination polymers was investigated.

One polymer composition, various morphologies: the decisive influence of conditions on the polymerization-induced self-assembly (PISA) of N-acryloyl thiomorpholine.

Polymerization-induced self-assembly (PISA) represents a powerful technique for the preparation of nanostructures comprising various morphologies. Herein, we demonstrate that the recently introduced monomer N-acryloylthiomorpholine (NAT) features a unique self-assembly behaviour during an aqueous PISA. The one-pot, aqueous RAFT dispersion polymerization starting from short poly(N-acryloylmorpholine) (PNAM) enables access to all common solution morphologies including spheres, worms, vesicles and lamellae, at very low molar masses (< 8 kDa). Moreover, all these structures can be obtained for the same polymer composition and size by the variation of the polymerization temperature and concentration of the monomer. This exceptional self-assembly behavior is associated with the combination of a high glass transition temperature, excellent water solubility of the monomer, and the early onset of aggregation during the polymerization, which stabilizes the morphology at different stages. This PISA system opens up new opportunities to reproducibly create versatile, functional nanostructures and enables an independent evaluation of morphology-property relationships, as it is exemplarily shown for the oxidative degradation of spherical and wormlike micelles, as well as vesicles.