Polymer Dissolution Research Articles

MUCO-DIS: a New AFM-Based Nanoscale Dissolution Technique

Mucoadhesion-based drug delivery systems have recently gained interest because of their bio-adhesion capability, which results in enhanced residence time leading to prolonged duration of action with the mucosal surface, potentially improving compliance and convenience. Mucoadhesion testing of these formulations is widely reported; however, this is technically challenging due to the absence of any standard methods and difficulty in conducting mucoadhesion, formulation-mucosal surface interaction, mucosal surface topography and drug release in a single experiment. As these measurements are currently conducted separately, on replicate formulations, results can often be subjective and difficult to correlate. Hence, the aim of the present study was to develop a new AFM-based single-entity ex vivo muco-dissolution (MUCO-DIS) technique to simultaneously evaluate mucoadhesion force, 3D surface topography, polymer dissolution and drug release characteristics. To demonstrate the potential of the current technique, the interactions between model pectin microparticles containing metformin HCl and a range of gastrointestinal mucosal surfaces (gastric, small intestine, large intestine and buccal) were studied. This novel system has not only successfully determined the mucoadhesion force, polymer dissolution and drug release information but has also highlighted the difference in microparticle performance with different mucosal targets. The current work has highlighted the potential of this newly developed MUCO-DIS system and we believe this will be a valuable tool for characterising these popular pharmaceutical formulations. This technique could also provide an opportunity to other scientific fields to evaluate materials, substrate behaviour and their interactions in their hydrated state at nanoscale with real-time chemical and surface mapping.

Enhanced Photoelectrochemical Water Splitting at Hematite Photoanodes by Effect of a NiFe-Oxide co-Catalyst

Tandem photoelectrochemical cells (PECs), made up of a solid electrolyte membrane between two low-cost photoelectrodes, were investigated to produce “green” hydrogen by exploiting renewable solar energy. The assembly of the PEC consisted of an anionic solid polymer electrolyte membrane (gas separator) clamped between an n-type Fe2O3 photoanode and a p-type CuO photocathode. The semiconductors were deposited on fluorine-doped tin oxide (FTO) transparent substrates and the cell was investigated with the hematite surface directly exposed to a solar simulator. Ionomer dispersions obtained from the dissolution of commercial polymers in the appropriate solvents were employed as an ionic interface with the photoelectrodes. Thus, the overall photoelectrochemical water splitting occurred in two membrane-separated compartments, i.e., the oxygen evolution reaction (OER) at the anode and the hydrogen evolution reaction (HER) at the cathode. A cost-effective NiFeOx co-catalyst was deposited on the hematite photoanode surface and investigated as a surface catalytic enhancer in order to improve the OER kinetics, this reaction being the rate-determining step of the entire process. The co-catalyst was compared with other well-known OER electrocatalysts such as La0.6Sr0.4Fe0.8CoO3 (LSFCO) perovskite and IrRuOx. The Ni-Fe oxide was the most promising co-catalyst for the oxygen evolution in the anionic environment in terms of an enhanced PEC photocurrent and efficiency. The materials were physico-chemically characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM).

One-step preparation of porous cellulose/chitosan macro-spheres from ionic liquid-based solutions

Environmentally friendly and easily biodegradable porous adsorbents for water purification based on cellulose and chitosan blends have been prepared by a green technology utilizing room temperature ionic liquids as main solvent component. The dissolution and re-precipitation mechanisms for the two biopolymers and of their mixtures have been studied in detail, targeting to optimize the composition of the casting solutions and make them adequate for preparation of porous polymer spheres by the “dropping cum phase separation” technique. With the increase of the chitosan content in the sample the time required for the polymer dissolution was increasing and the amount of water necessary to destabilize the formed casting solution was decreasing. Further on, the viscosities of the casting solutions had a strong impact on the formation of the porous structure during the non-solvent induced phase separation process. For the blend spheres prepared from 1-butyl-3-methylimidazolium acetate ([Bmim][OAc]) based solutions materials with higher specific surface areas and improved Cu2+ adsorption capacity were obtained at the increase of the chitosan fraction in the polymer blend. For the samples prepared from 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]) based solutions no such a trend has been observed.

Investigation of Drug–Polymer Miscibility, Molecular Interaction, and Their Effects on the Physical Stabilities and Dissolution Behaviors of Norfloxacin Amorphous Solid Dispersions

This study investigated the drug–polymer miscibility, intermolecular interaction, physical stability, and dissolution performance of amorphous solid dispersions (ASDs) of norfloxacin (NFX) with pol...

Surface dissolution and transesterification of thermoset dimethacrylate polymer by dimethacrylate adhesive resin and organic catalyst-alcohol solution

ObjectivesTo evaluate transesterification based dissolution of dimethacrylate and epoxy polymers, the former containing ester groups. Polymer substrates were treated with an adhesive resin (Stick™ Resin) and an organic catalyst-alcohol solution (ethylene glycol and triazabicyclodecene). The surface was chemically and nanomechanically analyzed with Fourier Transform-Infrared (FTIR) spectroscopy, surface profile peak (Rp) and nanohardness and modulus of elasticity. MethodsA total of 100 specimens each of light-cured dimethacrylate polymer and heat-cured diepoxy polymer were prepared. 20 specimens were randomly selected and used as control group (0s). The remaining specimens were randomly divided into 40 each for treatment with an Stick™ resin and ethylene glycol+triazabicyclodecene. Within each group the 40 specimens were randomly subdivided into 20 each for treatment at 5min and 24h, with 10 specimens for FTIR and nanohardness and modulus of elasticity, and the other 10 for SEM and surface Rp analyses. ResultsDimethacrylate polymer showed a reduction in the nanohardness and modulus of elasticity, Rp values and SEM also showed significant topographical changes after being treated with either Stick™ resin or ethylene glycol+triazabicyclodecene, whereas epoxy resin substrate did not. FTIR analyses affirmed changes in the intensity of ester groups. SignificanceEster group containing dimethacrylate polymer showed a reduction in NMP within 5min of exposure to the treatment agents with softening by solution ethylene glycol+triazabicyclodecene associated to the reduction of ester groups in the polymer structure by transesterification. Epoxy polymer without ester groups was not affected by surface softening with treatment agents. Adhesive resin caused surface swelling.

Evolution of supersaturation from amorphous solid dispersions in water-insoluble polymer carriers: Effects of swelling capacity and interplay between partition and diffusion.

The use of water-insoluble carriers for amorphous solid dispersions (ASDs) has attracted more recent interest as the kinetic solubility profiles (KSP) from these systems can achieve a more sustained level of supersaturation when compared with ASDs based on water-soluble polymers. However, the effect of swelling capacity of water-insoluble carriers on the resulting KSP of ASDs has not been fully explored in terms of their achievable degree and extent of drug supersaturation. Thus, the objective of this study is to compare kinetic solubility profiles of ASDs based on commercially available water-insoluble carriers in order to bridge this knowledge gap and provide fundamental information important to the design of ASDs based on water-insoluble carriers. This was achieved by comparing the KSP from non-sink dissolution studies of ASDs of two model poorly-water soluble drugs, indomethacin (IND) and posaconazole (PCZ) based on commercially available water-insoluble carriers with different equilibrium water swelling such as fully hydrolyzed (physically crosslinked) poly (vinyl alcohol) (PVA), Eudragit RS PO, as well as chemically crosslinked PHEMA hydrogels . Our results show that the higher the swelling capacity of the water-insoluble carrier, the faster the rate of supersaturation generation, and the shorter the sustained supersaturation due to drug precipitation. The interplay of particle size, total dose and the swelling capacity was also shown to be an essential aspect when tailoring the supersaturation generation from water-insoluble polymer-based ASDs. The importance of the swelling feature was confirmed using firstly different polymer carriers (PVA, Eudragit RS PO, and PHEMA) and then polymer samples of identical composition and drug loading but with different swelling capacities (e.g., PVA, physically crosslinked to different degrees). Furthermore, a large drug partitioning value between the polymer carrier and dissolution medium was found to limit the extent of drug release or supersaturation buildup from these ASDs. Finally, the existence of electrostatic polymer-drug interactions realized from our molecular dynamic simulations supports the observed impact of the large partitioning of the model drug IND between the polymer ED RS PO and the dissolution medium, thereby leading to a lower degree of supersaturation generation (or slower drug release) from this ASD.

Locking Screws With a Threaded Degradable Polymer Collar Reduce Construct Stiffness Over Time.

The stiffness of locking plates provide increased stability for early fracture healing but may limit late interfragmentary motion (IFM) necessary for secondary bone healing. An ideal plating construct would provide early rigidity and late flexibility to optimize bone healing. A novel screw plate construct utilizing locking screws with a degradable polymer locking mechanism is a dynamic option. Conventional locked plating constructs (group A) were compared with locking screws with a threaded degradable polymer collar before (group B) and after polymer dissolution (group C). Monotonic axial compression, monotonic torsion, cyclic axial load to failure, and IFM at the near and far cortices were tested on synthetic bone models. One-way analysis of variance and post hoc Tukey-Kramer testing demonstrated similar axial stiffness in group A (873 ± 146 N/mm) and B (694 ± 314 N/mm) but significantly less stiffness in group C (379 ± 59 N/mm; F(2,15) = 9.12, P = 0.003). Groups A and B also had similar IFM, but group C had significantly increased IFM at both the near (F(2, 15) = 48.66, P = 2.76E-07) and far (F(2, 15) = 11.78, P = 0.0008) cortices. In cyclic axial load to failure, group A (1593 ± 233 N) and B (1277 ± 141 N) were again similar, but group C was significantly less (912 ± 256 N; F(2, 15) = 15.00, P = 0.0003). All failures were above the 500-N threshold seen in typical weight-bearing restrictions for fracture care. Torsional stiffness demonstrated significant differences between all groups (F(2, 15) = 106.64, P = 1.4E-09). Use of locking plates with a degradable polymer collar show potential for in vitro construct dynamization. Future in vivo studies are warranted to assess performance under combined loading and the effects of decreasing construct stiffness during the course of bony healing.

A Method for Rapid Determination of Polymer Dissolution Time

In view of the limited space of offshore platform and the large amount of polymer injection, the dissolution time method, solution viscosity method, conductivity method, undissolved filtration method and falling ball method are used as the rapid detection methods of polymer dissolution. The results show that the error of conductivity method is the largest, and that of dissolution time method is the second, and both methods are time-consuming. Solution viscosity method and insolubles filtration method have small error, but they are time-consuming, especially for offshore platforms, which makes detection inconvenient. The drop ball method is simple in operation and has a small error, so it is a promising method for rapid determination of polymer dissolution time.

Pullulan-based dissolving microneedle arrays for enhanced transdermal delivery of small and large biomolecules

One specific technological advance in transdermal drug delivery is the development of dissolving microneedles (DMNs), which efficiently deliver therapeutics through a rapid dissolution of polymers after penetration into the skin. However, there is a limited range of water soluble, biodegradable polymers that can be used to manufacture DMN. Here, we report for the first time, the preparation and characterisation of a DMN system from the carbohydrate biopolymer, pullulan (PL). PL gels, of varying concentration, were studied for viscosity, film formation properties, and subsequently, microneedle formation. Model molecules and protein/peptide were loaded into PL DMN and characterised. The stability of model biomolecules, such as FITC-BSA and insulin, following DMN manufacture were assessed using circular dichroism. Ex-vivo porcine skin permeation studies using Franz diffusion cell apparatus for Flu-Na and FITC-BSA loaded PL-DMN were conducted. This study demonstrates that PL DMNs may serve as a promising tool for efficient transdermal drug delivery.

Electrospun Nanofibers With pH-Responsive Coatings for Control of Release Kinetics.

Functional and stimuli-responsive nanofibers with an enhanced surface area/volume ratio provide controlled and triggered drug release with higher efficacy. In this study, chemotherapeutic agent Rose Bengal (RB) (4,5,6,7-tetrachloro-2′, 4′,5′,7′-tetraiodofluoresceindisodium)-loaded water-soluble polyvinyl alcohol (PVA) nanofibers were synthesized by using the electrospinning method. A thin layer of poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) p(4VP-co-EGDMA) was deposited on the RB-loaded nanofibers (PVA-RB) via initiated chemical vapor deposition (iCVD), coating the fiber surfaces to provide controllable solubility and pH response to the nanofibers. The uncoated and [p(4VP-co-EGDMA)-PVA] coated PVA-RB nanofiber mats were studied at different pH values to analyze their degradation and drug release profiles. The coated nanofibers demonstrated high stability at neutral and basic pH values for long incubation durations of 72 h, whereas the uncoated nanofibers dissolved in <2 h. The drug release studies showed that the RB release from coated PVA-RB nanofibers was higher at neutral and basic pH values, and proportional to the pH of the solution, whereas the degradation and RB release rates from the uncoated PVA-RB nanofibers were significantly higher and did not depend on the pH of environment. Further analysis of the release kinetics using the Peppas model showed that while polymer swelling and dissolution were the dominant mechanisms for the uncoated nanofibers, for the coated nanofibers, Fickian diffusion was the dominant release mechanism. The biocompatibility and therapeutic efficiency of the coated PVA-RB nanofibers against brain cancer was investigated on glioblastoma multiforme cancer cells (U87MG). The coated PVA nanofibers were observed to be highly biocompatible, and they significantly stimulated the ROS production in cells, increasing apoptosis. These promising results confirmed the therapeutic activity of the coated PVA-RB nanofibers on brain cancer cells, and encouraged their further evaluation as drug carrier structures in brain cancer treatment.

Measurement, correlation and modelling of high-pressure phase equilibrium of PLGA solutions in CO2

Poly (lactic-co-glycolic acid) (PLGA) is a copolymer used as drug carrier in controlled release systems as microparticles or scaffolds. Foamed structures are industrially obtained by injecting gas at temperatures above the melting point of the polymer that may promote PLGA degradation. High temperatures are avoidable in this foaming process if a polymer dissolution is used. Ethyl acetate and ethyl lactate are suitable solvents for the PLGA since the polymer is easily solubilised, is environmentally friendly and highly recommendable for medical purposes. CO2 is proposed as antisolvent because is environmentally benign, non-flammable and non-toxic. The knowledge of the solubility of these solvents in CO2 is essential to find the most appropriate working conditions for the foaming process. In this work, the solubility of ethyl acetate and ethyl lactate in CO2 in the presence of different initial concentrations of PLGA has been studied at 298.15 K and at pressures up to 150 bar using a high-pressure variable volume view cell.

Fabrication of Activated Porous Carbon Using Polymer Decomposition for Electrical Double-Layer Capacitors

Because of their excellent stability and highly specific surface area, carbon based materials have received attention as electrode materials of electrical double-layer capacitors(EDLCs). Biomass based carbon materials have been studied for electrode materials of EDLCs; these materials have low capacitance and high-rate performance. We fabricated tofu based porous activated carbon by polymer dissolution reaction and KOH activation. The activated porous carbon(APC-15), which has an optimum condition of 15 wt%, has a high specific surface area(1,296.1 m2 g−1), an increased average pore diameter(2.3194 nm), and a high mesopore distribution(32.4 %), as well as increased surface functional groups. In addition, APC has a high specific capacitance(195 F g−1) at low current density of 0.1 A g−1 and excellent specific capacitance(164 F g−1) at high current density of 2.0 A g−1. Due to the increased specific surface area, volume ratio of mesopores, and surface functional groups, the specific capacitance and high-rate performance increased. Consequently, the tofu based activated porous carbon can be proposed as an electrode material for high-performance EDLCs.

Polyacrylamide flocculants in phase separation processes of mineral ore salt dispersions

The features of clay-saline (potassium and sodium chlorides) dispersions flocculation using polyacrylamide and its cationic and anionic copolymers are described, including the effect of flocculant concentration, solid concentration in dispersion, method of polymer dissolution in water or saline solution on the sedimentation rate and flocculation density. It is shown that polyacrylamide has the highest flocculating ability towards clay-saline dispersion, and cationic copolymers – the lowest effect. It is shown that in concentrated clay dispersions flocculation starts at lower flocculant dose rate and occurs in a narrow range of polymer concentrations. The sedimentation rate of clay in salt dispersion increases by 15–20% with the introduction of flocculant in two stages, and by 50% times – with consequent dosing of cationic and anionic flocculant. It is also stated that polymer solutions prepared using concentrated salt solutions of potassium and sodium chlorides provide a higher efficiency of clay flocculation in comparison with solutions of polymers prepared in water.

Rapid Open-Air Digital Light 3D Printing of Thermoplastic Polymer.

3D printing has witnessed a new era in which highly complexed customized products become reality. Realizing its ultimate potential requires simultaneous attainment of both printing speed and product versatility. Among various printing techniques, digital light processing (DLP) stands out in its high speed but is limited to intractable light curable thermosets. Thermoplastic polymers, despite their reprocessibility that allows more options for further manipulation, are restricted to intrinsically slow printing methods such as fused deposition modeling. Extending DLP to thermoplastics is highly desirable, but is challenging due to the need to reach rapid liquid-solid separation during the printing process. Here, a successful attempt at DLP printing of thermoplastic polymers is reported, realized by controlling two competing kinetic processes (polymerization and polymer dissolution) simultaneously occurring during printing. With a selected monomer, 4-acryloylmorpholine (ACMO), printing of thermoplastic 3D scaffolds is demonstrated, which can be further converted into various materials/devices utilizing its unique water-soluble characteristic. The ultralow viscosity of ACMO, along with surface oxygen inhibition, allows rapid liquid flow toward high-speed open-air printing. The process simplicity, enabling mechanism, and material versatility broaden the scope of 3D printing in constructing functional 3D devices including reconfigurable antenna, shape-shifting structures, and microfluidics.

Flocculating and Hydrodynamic Properties of Aqueous-Salt Solutions of Acrylamide Polymers

Specific features of flocculation of aqueous-salt (KCl, NaCl) clay dispersions with polyacrylamide and anionic acrylamide copolymers, including the influence exerted by the procedure of polymer dissolution in water or salt solution on the sedimentation rate and density of floccules and on the hydrodynamic properties of the polymers, are described. The use of aqueous-salt solutions of flocculants enhances the flocculating effect. The most effective flocculant for aqueous-salt clay dispersions is polyacrylamide prepared in a salt solution, which is due to higher flexibility of the polymer chain. The results obtained are of practical interest in connection with the possibility of enhancing the efficiency of the flocculation of aqueous-salt clay dispersions in dressing of potassium ores.

Evaluation of proanthocyanidin-crosslinked sericin/alginate blend for ketoprofen extended release

Sericin and alginate blend has shown good results for obtaining sustained release dosage forms. In the case of ketoprofen, it was necessary to resort to the use of the proanthocyanidin (PA) as crosslinking agent in order to achieve this same goal. Thus, various formulations were developed by adding different initial amounts of PA to the sericin and alginate blend with incorporated ketoprofen. The best results for drug loading, entrapment efficiency and release prolongation were obtained for the particle with the lowest amount of PA (0.5%). Mathematical modeling has indicated that different mechanisms may be involved in drug release, especially a complex release mechanism, with polymer dissolution and polymer chain relaxation allowing drug release. Particles characterization confirmed the incorporation of ketoprofen into the sericin, alginate and proanthocyanidin blend. It was verified that there was no interaction between them and there were no major changes in the physicochemical properties of the drug.

Reaction-Diffusion Model for Thermosetting Polymer Dissolution through Exchange Reactions Assisted by Small-Molecule Solvents

Thermosetting polymers involving dynamic bonds or exchange reactions (also known as vitrimers) can be fully dissolved in a solvent utilizing a small-molecule-participated bond-exchange reaction (BE...

Solvation Structure of Poly(benzyl methacrylate) in a Solvate Ionic Liquid: Preferential Solvation of Li-Glyme Complex Cation.

We report the solvation structure of a lower critical solution temperature (LCST)-type thermoresponsive polymer in a solvate ionic liquid (SIL, i.e., an ionic liquid comprising solvate ions) to elucidate the predominant interaction for the dissolution of the thermoresponsive polymer in SIL at low temperatures. The solvation structure of poly(benzyl methacrylate) (PBnMA) and a model compound of its monomer in a typical glyme-based SIL, [Li(G4)][TFSA] (G4: tetraglyme; TFSA: bis(trifluoromethanesulfonyl)amide), have been investigated using high-energy X-ray total scattering and all-atom molecular dynamics simulations. In the model compound/SIL system, the intermolecular components extracted from the total G( r)s revealed that the ester moiety of BnMA is preferentially solvated by Li cations through a cation-dipole interaction, which induces slight desolvation of the G4 molecules, and the aromatic ring of BnMA is secondarily solvated by the [Li(G4)] cation complex through a cation-π interaction with maintaining the complex structure. In contrast, TFSA anions are attracted only by the [Li(G4)] cation. These interactions result in the formation of a solvation layer of SILs around the aromatic ring, which plays a key role in the negative entropy and enthalpy of mixing. Meanwhile, in the polymer solution, the coordination number of the Li cation around the ester moiety significantly decreased. This could be ascribed to the steric effect of the bulky side chains, preventing the approach of the [Li(G4)] cation complex to the ester moiety located near the main chain. These solvation structures lead to small absolute values of negative entropy and enthalpy of mixing, which together are key factors to understand the LCST-type phase behavior in the IL system.

A new redox-active conjugated polymer containing anthraquinone pendants as anode material for aqueous all-organic hybrid-flow battery

Organic redox polymers have attracted extensive research interest due to tunable redox potential and high theoretical capacity. However, sluggish redox kinetics, poor electronic conductivity and low electrochemical stability derived from dissolution of polymers into the electrolyte and/or unexpected side reactions limit their use in batteries and electrochemical capacitors. To overcome these drawbacks, a conjugated redox polymer (Poly(N-anthraquinoyl pyrrole, PAQPy) with electronically conductive polypyrrole backbone and redox-active anthraquinone pendants was synthesized and then utilized as active anode materials for aqueous all-organic hybrid-flow batteries. The PAQPy shows highly reversible redox reaction at −0.2 V vs SHE with good stability in weakly acidic aqueous electrolytes. It is also found that when PAQPy is combined with graphene nanosheets through π-π stacking interactions, their redox capacity can be dramatically increased due to substantial weakening of hydrogen bonding interaction of anthraquinone groups. An aqueous all-organic hybrid-flow battery employing the PAQPy/Graphene composite (PAQPy/G) as the anode and 4-NH2-TEMPO as the flowing catholyte, respectively, displays a discharge capacity of ca. 62.2 mAh g−1 at the current density of 0.2 A g−1, a peak power density of 1.41 W g−1 at 100% SOC and a round-trip energy efficiency of around 74.5% during 100 charge-discharge cycles.

Integrated Polymer Dissolution and Solution Blow Spinning Coupled with Solvent Recovery for Expanded Polystyrene Recycling

With increasing buoyant plastic wastes entering into oceans and food chains, the disposal and recycling of waste expanded polystyrene (WPS) has become an imminent environmental problem. In this work, a recycling scheme for waste WPS is proposed that combines the polymer dissolution recycling approach with the solution blow spinning (SBS) technique that facilitates the high-volume bulk WPS transportation and the value-addition of WPS to nanofibers. Solvent selection is critical for an economical and environmentally favorable implementation of this recycling scheme at large scale. Here, the effect of three solvents with distinct volatility, viz. ethyl acetate, toluene, and N, N- dimethylformamide (DMF) have been studied on the fiber formation and the ease of the solvent recovery, in order to ascertain the practicability of using these solvents for the recycling process. The fiber formation is experimentally demonstrated for the WPS-solvent systems using the SBS process. It is found that the fiber morphology varies for the different WPS-solvent systems. A solvent recovery scheme to recover the solvent from the air-solvent mixture (leaving SBS) is evaluated using ASPEN Plus simulation. The % solvent recovery is determined as a function of the required energy input for different process parameters including compressor pressure and air to polymer solution feed ratio. The simulation studies show that a lower feed air to polymer solution ratio and higher compressor pressure are required to obtain > 70% solvent recovery for high volatility solvents (ethyl acetate and toluene) with lower energy input and optimal operating condenser temperature (~ 0 °C). Conversely, significant solvent losses occur in the SBS process with a lower volatility solvent (DMF), leading to a lower solvent recovery for the whole process. The % DMF recovery can be improved upon by using higher feed air to polymer solution ratio although at a higher energy penalty.