Polymer Size Research Articles

Effects of Viscosity and Refractive Index on the Emission and Diffusion Properties of Alexa Fluor 405 Using Fluorescence Correlation and Lifetime Spectroscopies

Fluorescence Correlation Spectroscopy (FCS) studies of the interaction of polymers or proteins in solution are strongly affected by the viscosity and refractive index of the medium, and the effects are likely to be more significant with the use of short wavelength excitation (e.g., 405 nm diode lasers). Failing to account for these issues can lead to incorrect measurement of average size, conformational changes, and dynamic behaviour of polymers and proteins. Steady-state, time-resolved, and FCS measurements of Alexa 405 in glycerol:water mixtures were performed to determine its suitability for FCS measurements with 405 nm excitation. The effects of the refractive index and viscosity on the diffusion coefficient and photophysical parameters (lifetime and relative quantum yield) of the fluorophore were determined. Alexa 405 lifetime decreased from 3.55 ns in water to 3.25 ns in a 50:50 glycerol:water mixture, while its diffusion coefficient dropped from 333 ± 16 to 44 ± 1 µm2s- 1. Lifetime data collected from micromolar solutions of Alexa 405 did however also suggest that as solvent polarity decreased, aggregates (excimers) were formed as evidenced by the appearance of a rising edge in the decay plots. The interdependence between lifetime, refractive index, and diffusion coefficient could be accurately fitted by a simple polynomial function indicating that the probe is well behaved and predictable in the glycerol:water model system. Overall, Alexa 405 is a most promising and reliable probe for FCS measurement using violet laser diode excitation sources.

DPOLY: Deep Learning of Polymer Phases and Phase Transition

Machine learning (ML) and artificial intelligence (AI) have the remarkable ability to classify, recognize, and characterize complex patterns and trends in large data sets. Here, we adopt a subclass of machine learning methods viz., deep learnings and develop a general-purpose AI tool - dPOLY for analyzing molecular dynamics trajectory and predicting phases and phase transitions in polymers. An unsupervised deep neural network is used within this framework to map a molecular dynamics trajectory undergoing thermophysical treatment such as cooling, heating, drying, or compression to a lower dimension. A supervised deep neural network is subsequently developed based on the lower dimensional data to characterize the phases and phase transition. As a proof of concept, we employ this framework to study coil to globule transition of a model polymer system. We conduct coarse-grained molecular dynamics simulations to collect molecular dynamics trajectories of a single polymer chain over a wide range of temperatures and use dPOLY framework to predict polymer phases. The dPOLY framework accurately predicts the critical temperatures for the coil to globule transition for a wide range of polymer sizes. This method is generic and can be extended to capture various other phase transitions and dynamical crossovers in polymers and other soft materials.

Microplastics alter digestive enzyme activities in the marine bivalve, Mytilus galloprovincialis.

Microplastics are eaten by many invertebrates, particularly filter-feeding organisms like mussels. Since microplastics can be retained in the digestive system for extended periods, there is ample opportunity for them to interact with the functions of digestive enzymes. This study determined how the polymer type, size and concentration of ingested spherical microplastics affects the activities of seven key digestive enzymes in the digestive gland of Mytilus galloprovincialis, a common marine mussel. Polymer type significantly affected the activities of carbohydrase enzymes: polystyrene reduced amylase and xylanase activities, and increased cellulase activity. High concentrations of microplastics (5×104 microplastics L-1) caused a 2.5-fold increase in total protease activity. The activities of laminarinase, lipases and lipolytic esterases were unaffected by the polymer type, size or concentration of microplastics. Microplastics-induced changes to digestive enzyme activities can affect mussels' ability to acquire energy from food and reduce their energy reserves.

Tailoring the Pore Size and Chemistry of Ionic Ultramicroporous Polymers for Trace Sulfur Dioxide Capture with High Capacity and Selectivity

AbstractHere we demonstrate the deep removal of SO2 with high uptake capacity (1.55 mmol g−1) and record SO2/CO2 selectivity (>5000) at ultra‐low pressure of 0.002 bar, using ionic ultramicroporous polymers (IUPs) with high density of basic anions. The successful construction of uniform ultramicropores via polymerizing ionic monomers into IUPs enables the fully exploitation of the selective anionic sites. Notably, the aperture size and surface chemistry of IUPs can be finely tuned by adjusting the branched structure of ionic monomers, which play critical roles in excluding CH4 and N2, as well as reducing the coadsorption of CO2. The swelling property of IUPs with adsorption of SO2 contributed to the high SO2 uptake capacity and high separation selectivity. Systematic investigations including static gas adsorption, dynamic breakthrough experiments, stability tests and modeling studies confirmed the efficient performance of IUPs for trace SO2 capture.

Tailoring the Pore Size and Chemistry of Ionic Ultramicroporous Polymers for Trace Sulfur Dioxide Capture with High Capacity and Selectivity.

Here we demonstrate the deep removal of SO2 with high uptake capacity (1.55 mmol g-1 ) and record SO2 /CO2 selectivity (>5000) at ultra-low pressure of 0.002 bar, using ionic ultramicroporous polymers (IUPs) with high density of basic anions. The successful construction of uniform ultramicropores via polymerizing ionic monomers into IUPs enables the fully exploitation of the selective anionic sites. Notably, the aperture size and surface chemistry of IUPs can be finely tuned by adjusting the branched structure of ionic monomers, which play critical roles in excluding CH4 and N2 , as well as reducing the coadsorption of CO2 . The swelling property of IUPs with adsorption of SO2 contributed to the high SO2 uptake capacity and high separation selectivity. Systematic investigations including static gas adsorption, dynamic breakthrough experiments, stability tests and modeling studies confirmed the efficient performance of IUPs for trace SO2 capture.

Investigation of Ring and Star Polymers in Confined Geometries: Theory and Simulations.

The calculations of the dimensionless layer monomer density profiles for a dilute solution of phantom ideal ring polymer chains and star polymers with arms in a -solvent confined in a slit geometry of two parallel walls with repulsive surfaces and for the mixed case of one repulsive and the other inert surface were performed. Furthermore, taking into account the Derjaguin approximation, the dimensionless layer monomer density profiles for phantom ideal ring polymer chains and star polymers immersed in a solution of big colloidal particles with different adsorbing or repelling properties with respect to polymers were calculated. The density-force relation for the above-mentioned cases was analyzed, and the universal amplitude ratio B was obtained. Taking into account the small sphere expansion allowed obtaining the monomer density profiles for a dilute solution of phantom ideal ring polymers immersed in a solution of small spherical particles, or nano-particles of finite size, which are much smaller than the polymer size and the other characteristic mesoscopic length of the system. We performed molecular dynamics simulations of a dilute solution of linear, ring, and star-shaped polymers with , 300 (360), and 1201 (4 × 300 + 1-star polymer with four arms) beads accordingly. The obtained analytical and numerical results for phantom ring and star polymers are compared with the results for linear polymer chains in confined geometries.

Effect of Different Gamma Dose and Chemical Etching on Pre- and Post-Alpha-Irradiated PM-355 Polymer

This work is based on the effect of different gamma doses with pre- and post-alpha-irradiated PM-355 polymer (polycarbonate of allyl diglycol). The phase crystallinity and structural analysis of the reference and irradiated PM-355 polymer were analyzed using an X-ray diffraction (XRD) study. It is revealed that the irradiation and etching reduce the %crystallinity but increase the crystallite size of the PM-355 polymer. The increase in crystallite size of PM-355 polymer after irradiation is supported by the scanning electron microscopic (SEM) analysis. The etching of the samples results in an increase in its track diameter. The optical band gap energy, measured by ultraviolet-visible (UV-VIS) spectroscopy, shows a decrement trend with the increase of gamma and alpha irradiation doses, and etching for all sets of samples under investigation. The number of carbon atoms per conjugation and per cluster has increased after gamma irradiation and etching. However, the increment is more pronounced for etched samples compared to nonetched ones. This indicates that etching results in a bigger size of cluster. Photoluminescence (PL) for both cases before and after etching has a dominant peak around 430 nm before and after irradiation, and change in peak intensity after irradiation confirmed that particle bombardment induced defects and clusters in the PM-355, which serves as nonradiative centers. The polymer can be used as a detector for gamma irradiation.

Understanding of Adsorption and Desorption Mechanisms of Anthocyanins and Proanthocyanidins on Heterogeneous and Homogeneous Cation-Exchange Membranes.

The presence of membrane fouling is the main drawback in membrane processes, and it is related to the premature use and high cost for the replacement of membranes. Polyphenols in cranberry juice are associated with ion-exchange membrane fouling, and it results in a loss of these beneficial compounds in the juice when treated by membrane processes such as electrodialysis. In the present work, four heterogeneous or pseudohomogeneous cation-exchange membranes (CSE-fg, MK-40, CEM Type-II, and CJMC-5), different in terms of the polymer matrix (aromatic, aliphatic), exchange capacity, size, and location of meso and macropores, were studied to understand the impact of the membrane structure and physico-chemical properties on adsorption and desorption of phenolic compounds (anthocyanins and proanthocyanidins) from cranberry juice. It appeared from these results that MK-40, CEM Type-II, and CSE-fg were more prone to fouling due to their high ion-exchange capacity, their thickness, and the presence of meso and macropores in their structure. Indeed, electrostatic interactions occurred between fixed groups of membranes and polyphenolic ions. Desorption of the entire membrane and cryogenic grinding with pH adjusted to 10 allowed a better recovery of anthocyanins and proanthocyanidins (PACs), respectively, since hydroxide ions competed with polyphenols and membrane that induced desorption of polyphenols. In the future, this new knowledge will become the basis for a more sensible choice of membranes and for the development of protocols for extending their life cycle.

Effect of the polydispersity on the dispersion of polymers through silicas having different morphologies (fully porous and core-shell particles and monoliths)

The effect of the polydispersity of polystyrenes on the dispersion through silicas having different morphologies (fully porous, core-shell particles and monoliths) was investigated. The heights equivalent to a theoretical plate (HETP) of those columns were measured for a small molecule (toluene) and a series of polystyrenes of different sizes in non-adsorbing conditions. The different contributions to the total HETP including polydispersity were determined experimentally. The longitudinal diffusion and the mass transfer resistance term were obtained from peak parking experiments. The eddy dispersion was obtained from models and experiments. The effect of polydispersity on the HETP values (Hpoly) can thus be calculated from the total HETP by substraction of the other contributions. The results were compared to the Knox model which surestimates the Hpoly values for porous and core-shell particles which is usually explained by an overestimation of the polydispersity index (PDI) given by the manufacturer. The PDI of two polymers (P02, Mw= 690 g.mol−1 and P03, Mw=1380 g.mol−1) was verified by liquid chromatography by separating each fraction of the polymer on the silica columns by using adsorbing conditions which are obtained with a mixture of heptane and THF. The PDI obtained are comparable to the PDI given by the manufacturer meaning that the assumptions made by Knox are not entirely valid. A direct method is proposed in this paper in order to determine Hpoly. In this method the excess of spreading as compared with a polymer with only one size corresponding to the average size is studied assuming the polymer size distribution is gaussian. The Hpoly values obtained by the direct method are comparable to the experimental values.

Molecular crystallization directed by polymer size and overlap under dilute and crowded macromolecular conditions

We demonstrate that dissolved polymers can direct molecular crystallization behavior under dilute and crowded conditions. Larger poly(ethylene glycol)s (PEGs) accelerated caffeine crystal formation in the dilute regime of PEG solutions, which was attributed to the depletion attraction that promoted caffeine cluster aggregation into crystal nuclei. Alternatively, in the semidilute regime, the caffeine crystal formation rate was insensitive to the molecular weight (MW) of PEGs. PEGs with various MWs appeared to induce depletion attraction to a similar extent as the properties of polymer solutions in the semidilute regime described by blobs, which are constant in size at a given polymer concentration irrespective of MW. This study highlights differences between in vitro polymer solutions and crowded intracellular environments composed of folded biomacromolecules and contributes to developing the use of in vitro macromolecular crowding for the control of molecular self-assembly. Dissolved polymers directed molecular crystallization behavior under dilute and crowding conditions. Larger poly(ethylene glycol)s (PEGs) accelerated caffeine crystal formation in the dilute regime of PEG solutions, which was attributed to the depletion attraction that promoted caffeine cluster aggregation into crystal nuclei. In the semidilute regime, the crystal formation rate was insensitive to the molecular weight of PEGs. This observation was consistent with polymer blob properties, which govern depletion attraction and maintain a constant size at a given polymer concentration, irrespective of molecular weight in the semidilute regime.

Stereoretentive Olefin Metathesis: A New Avenue for the Synthesis of All-cis Poly(p-phenylene vinylene)s and Stereo­defined Polyalkenamers

AbstractOlefin metathesis has tremendously impacted all fields of synthetic chemistry. However, the control of the olefin stereochemistry during this process remains a grand challenge. Recent innovations in catalyst design have permitted control of the stereochemistry of the olefin product. Here, we discuss the development of stereoretentive olefin metathesis, with an emphasis on the synthesis of stereodefined polyalkenamers through ring-opening metathesis polymerization (ROMP). We then present our application of this unique reaction manifold to the preparation of all-cis poly(p-phenylene vinylene)s (PPVs). A dithiolate Ru catalyst was found to deliver perfect cis selectivity for the polymerization of a paracyclophane diene monomer. By using optimized conditions, all-cis PPVs with narrow dispersities and predictable molar masses were obtained by varying the ratio of monomer to catalyst. The high chain fidelity of the stereoretentive ROMP with a paracyclophane diene monomer enabled the preparation of well-defined diblock copolymers with a norbornene co-monomer. Photochemical isomerization of all-cis to all-trans PPVs was effected with both homopolymers and diblock copolymers. This process was shown to be selective for the PPV block, and resulted in changes in optical properties, polymer size, and solubility. Stereoretentive ROMP provides a promising platform for synthesizing polymers with unique properties, including photoresponsive all-cis PPVs with living characteristics.1 Introduction2 Synthetic Applications of Stereoretentive Olefin Metathesis3 Stereocontrol of Polyalkenamers through Stereoretentive ROMP4 Stereoretentive ROMP To Access All-cis Poly(p-phenylene vinylene)s5 Conclusion

Effects of precipitated size of water-soluble amide-containing polymers and pore size of filters on recovery of Pd nanoparticles dispersed in acetone solution including colloidal polymer

ABSTRACT When immobilized Pd nanoparticles (Pd NP) are used for the hydrogenation of nitrile butadiene rubber (NBR), some Pd NP leaks into the reaction medium. This Pd NP is expensive and must be recovered. In this study, Pd NP were recovered from an NBR acetone medium by precipitation with poly N-[2-(dimethylamino)ethyl] methacrylamide (poly(DAEMA)) and filtration. When poly(DAEMA) solution was added to the Pd NP NBR acetone solution, poly(DAEMA) interacted with Pd NP and formed a precipitate by dehydration. The poly(DAEMA) precipitate including trapped Pd NP was completely recovered by filtration through a filter with a pore size of 1 μm. Poly(acrylamide) solutions of different molecular weights were tested for Pd NP recovery, and those with high molecular weights formed large quantities of precipitates, resulting in low recovery percentages. The concentration and molecular weight of the polymer used for the recovery of Pd NP by nanoprecipitation and filtration must be chosen carefully for optimal recovery. Especially, 40 kDa of PAA and 1 μm filter pores were suitable for efficient Pd NP recovery.

The role of mode switching in a population of actin polymers with constraints.

In this paper, we introduce a stochastic model for the dynamics of actin polymers and their interactions with other proteins in the cellular envelop. Each polymer elongates and shortens, and can switch between several modes depending on whether it is bound to accessory proteins that modulate its behaviour as, for example, elongation-promoting factors. Our main aim is to understand the dynamics of a large population of polymers, assuming that the only limiting quantity is the total amount of monomers, set to be constant to some large N. We first focus on the evolution of a very long polymer, of size [Formula: see text], with a rapid switch between modes (compared to the timescale over which the macroscopic fluctuations in the polymer size appear). Letting N tend to infinity, we obtain a fluid limit in which the effect of the switching appears only through the fraction of time spent in each mode at equilibrium. We show in particular that, in our situation where the number of monomers is limiting, a rapid binding-unbinding dynamics may lead to an increased elongation rate compared to the case where the polymer is trapped in any of the modes. Next, we consider a large population of polymers and complexes, represented by a random measure on some appropriate type space. We show that as N tends to infinity, the stochastic system converges to a deterministic limit in which the switching appears as a flow between two categories of polymers. We exhibit some numerical examples in which the limiting behaviour of a single polymer differs from that of a population of competing (shorter) polymers for equivalent model parameters. Taken together, our results demonstrate that under conditions where the total number of monomers is limiting, the study of a single polymer is not sufficient to understand the behaviour of an ensemble of competing polymers.

Beyond the Rule of 5: Impact of PEGylation with Various Polymer Sizes on Pharmacokinetic Properties, Structure-Properties Relationships of mPEGylated Small Agonists of TGR5 Receptor.

PEGylation of therapeutic agents is known to improve the pharmacokinetic behavior of macromolecular drugs and nanoparticles. In this work, we performed the conjugation of polyethylene glycols (220-5000 Da) to a series of non-steroidal small agonists of the bile acids receptor TGR5. A suitable anchoring position on the agonist was identified to retain full agonistic potency with the conjugates. We describe herein an extensive structure-properties relationships study allowing us to finely describe the non-linear effects of the PEG length on the physicochemical as well as the in vitro and in vivo pharmacokinetic properties of these compounds. When appending a PEG of suitable length to the TGR5 pharmacophore, we were able to identify either systemic or gut lumen-restricted TGR5 agonists.

Refining multi-photon polymerization feature size by optimizing solvent content in SU-8 photoresist

An investigation of the impact of solvent content on polymerization feature size in multi-photon polymerization is presented. The negative tone, epoxy photoresist SU-8 is employed, and variety pre-baking time is set to obtain different solvent content. A convenient method, exposure under long-focal length and single pulse, is suggested to evaluate the impact of solvent. By measuring the polymer size under microscope, it shows that the polymerized diameters are reduced by ~40% due to only 4% loss of the solvent content. The inhibition of the mobility of photon-induced H+ cations due to the less solvent is considered to be responsible for the refinement of polymer feature size. It is because that the mobility of photon-induced H+ cation from high to low concentration area is restricted by reducing the solvent. The adjusting solvent content shows its potential to refine the feature size of MPP without influencing the degree of polymerization.

Conformation of Myoglobin-Poly(Ethyl Ethylene Phosphate) Conjugates Probed by SANS: Correlation with Polymer Grafting Density and Interaction.

One can take advantage of the influence of a polymer conjugated with a protein to control the thermal stability and the deployment of the protein. Here, the structural properties are reported of the protein-polymer conjugate myoglobin (Mb)-poly(ethyl ethylene phosphate) (PEEP) in the native and unfolded conformations, in order to understand the respective roles of the protein and of the polymer size in the stability of the conjugate. The effect is also investigated of the grafting density of the linear biodegradable polyphosphoesters covalently attached to the protein. It is observed that, while the conjugation process at room temperature does not modify the secondary and tertiary structure of the Mb, the unfolding process, as a function of temperature, depends on the grafting density. Small angle neutron scattering reveals that, at room temperature, conjugation does not alter the size of the native protein and that the thickness of the polymer shell around the protein increases as a function of grafting density and of polymer molecular weight. The denatured form of all conjugates is described by an unfolded chain and a correlation length due to the presence of local stiffness.

Equilibrium organization, conformation, and dynamics of two polymers under box-like confinement.

Motivated by recent nanofluidics experiments, we use Brownian dynamics and Monte Carlo simulations to study the conformation, organization and dynamics of two polymer chains confined to a single box-like cavity. The polymers are modeled as flexible bead-spring chains, and the box has a square cross-section of side length L and a height that is small enough to compress the polymers in that dimension. For sufficiently large L, the system behaviour approaches that of an isolated polymer in a slit. However, the combined effects of crowding and confinement on the polymer organization, conformation and equilibrium dynamics become significant when where is the transverse radius of gyration for a slit geometry. In this regime, the centre-of-mass probability distribution in the transverse plane exhibits a depletion zone near the centre of the cavity (except at very small L) and a 4-fold symmetry with quasi-discrete positions. Reduction in polymer size with decreasing L arises principally from confinement rather than inter-polymer crowding. By contrast, polymer diffusion and internal motion are strongly affected by inter-polymer crowding. The two polymers tend to occupy opposite positions relative to the box centre, about which they diffuse relatively freely. Qualitatively, this static and dynamical behaviour differs significantly from that previously observed for confinement of two polymers to a narrow channel. The simulation results for a suitably chosen box width are qualitatively consistent with results from a recent experimental study of two λ-DNA chains confined to a nanofluidic cavity.

Living supramolecular polymerization of an AIE-active Ir(iii) complex with irregular emission

The aggregation mechanism of an AIE-active Ir(iii) complex 1 with irregular emission has been studied. The living supramolecular polymerization of 1 has been successfully performed and the sizes of supramolecular polymers can be controlled.

Transport of UDP-rhamnose by URGT2, URGT4, and URGT6 modulates rhamnogalacturonan-I length.

Rhamnogalacturonan-I biosynthesis occurs in the lumen of the Golgi apparatus, a compartment where UDP-Rhamnose and UDP-Galacturonic Acid are the main substrates for synthesis of the backbone polymer of pectin. Recent studies showed that UDP-Rha is transported from the cytosol into the Golgi apparatus by a family of six UDP-rhamnose/UDP-galactose transporters (URGT1-6). In this study, analysis of adherent and soluble mucilage (SM) of Arabidopsis thaliana seeds revealed distinct roles of URGT2, URGT4, and URGT6 in mucilage biosynthesis. Characterization of SM polymer size showed shorter chains in the urgt2 urgt4 and urgt2 urgt4 urgt6 mutants, suggesting that URGT2 and URGT4 are mainly involved in Rhamnogalacturonan-I (RG-I) elongation. Meanwhile, mutants in urgt6 exhibited changes only in adherent mucilage (AM). Surprisingly, the estimated number of RG-I polymer chains present in urgt2 urgt4 and urgt2 urgt4 urgt6 mutants was higher than in wild-type. Interestingly, the increased number of shorter RG-I chains was accompanied by an increased amount of xylan. In the urgt mutants, expression analysis of other genes involved in mucilage biosynthesis showed some compensation. Studies of mutants of transcription factors regulating mucilage formation indicated that URGT2, URGT4, and URGT6 are likely part of a gene network controlled by these regulators and involved in RG-I synthesis. These results suggest that URGT2, URGT4, and URGT6 play different roles in the biosynthesis of mucilage, and the lack of all three affects the production of shorter RG-I polymers and longer xylan domains.

Mechanochemical Regulation of Cell Adhesion by Incorporation of Synthetic Polymers to Plasma Membranes.

Chemical control of cell-cell interactions using synthetic materials is useful for a wide range of biomedical applications. Herein, we report a method to regulate cell adhesion and dispersion by introducing repulsive forces to live cell membranes. To induce repulsion, we tethered amphiphilic polymers, such as cholesterol-modified poly(ethylene glycol) (PEG-CLS), to cell membranes. We found that the repulsive forces introduced by these tethered polymers induced cell detachment from a substrate and allowed cell dispersion in a suspension, modulated the speed of cell migration, and improved the separation of cells from tissues. Our analyses showed that coating the cells with tethered polymers most likely generated two distinct repulsive forces, lateral tension and steric repulsion, on the surface, which were tuned by altering the polymer size and density. We modeled how these two forces are generated in kinetically distinctive manners to explain the various responses of cells to the coating. Collectively, our observations demonstrate mechanochemical regulation of cell adhesion and dispersion by simply adding polymers to cells without genetic manipulation or chemical synthesis in the cells, which may contribute to the optimization of chemical coating strategies to regulate various types of cell-cell interacting systems.