Function Of Solvent Composition Research Articles

Investigating Solvent-Induced Aggregation in Edge-Functionalized Layered Silicates via All-Atom Molecular Dynamics Simulations.

Molecular dynamics simulations can provide the means to visualize and understand the role of intermolecular interactions in the mechanisms involved in molecular aggregation. Along these lines, simulations can allow the study of how surface chemical modifications can influence nanomaterial assembly at the molecular level. Layered silicate clays have been of significant interest for some time, particularly with regard to their use in organic/inorganic nanocomposites. However, despite numerous reports on the covalent linkage of organic moieties via silanol condensation, the theoretical understanding of these systems has heretofore been limited to noncovalent interactions, specifically ionic interactions at the charged basal surfaces. Herein, a model for edge-functionalized layered aluminosilicate clay, based on the siloxane linkage, is presented. In addition to reproducing experimentally observed degrees of molecular aggregation of clay-linked perylene diimide derivatives with different terminal functional groups as a function of solvent composition, a molecular-level understanding of the role of van der Waals interactions and hydrogen bonding of the different end-groups on the aggregation state in different water/N,N-dimethylformamide mixtures is obtained. The reported model provides a means to simulate organic moieties covalently bound to the layered silicate edge, which will enable future simulations of nanocomposites and organic/inorganic hybrids based on this system.

Validation of a quantitative liquid chromatography/hybrid quadrupole-linear ion trap MS/MS method for carfentanil and caffeine in a live human epidermis model.

Carfentanil, an opioid 10K times more potent than morphine, has no licit clinical use. A powerful CNS depressant, it has been identified increasingly as the cause of overdose death in the United States. Because it is highly lipophilic, the law enforcement and medical communities have been concerned that responding personnel could be percutaneously exposed and that exposure could be enhanced with the use of alcohol-containing hand sanitizers. An LC-MS/MS method was developed to evaluate solvent effects on percutaneous absorption of carfentanil in a live human epidermal model. In this study, a quantitative liquid chromatography/hybrid triple quadrupole-linear ion trap method was developed for carfentanil and for caffeine, a molecule routinely used to monitor epidermal cell culture viability. The method employed reverse-phase liquid chromatography coupled with positive electrospray ionization and multiple reaction monitoring (MRM) to quantify carfentanil and caffeine against calibration curves formulated from authentic standards. Limits of detection (LOD) for the two compounds were determined using 10:1 signal-to-noise requirements for all product ions with relative peak areas within ±20% of those observed for a mid-level calibrator. Precision and accuracy were determined by analyzing positive controls formulated in quintuplicate, by a different analyst, at three concentrations bracketing the method dynamic range. Inter-day precision was evaluated using data collected from three separate days of analyses. Calibration curves for seven formulated replicates of the two compounds met linearity requirements over at least four orders of magnitude concentration range. The accuracy of measured concentration results was within ±20% of the actual, precision across results (%CV) was ≤15%, curve coefficients of determination (r) were ≥0.980 (correlation coefficient r > 0.990), and relative ion ratios of all qualifier ions were within ±20% of those for a mid-level standard. Limits of quantification (LOQs) for carfentanil and caffeine were 230 pg/ml and 12 ng/ml, respectively. Intra-day accuracies (mean concentrations) for carfentanil and caffeine ranged from 90.1% to 100.8% and from 87.1% to 108.9%, respectively; inter-day accuracies ranged from 98.7% to 100.4% and from 97.5% to 101.7%, respectively. Intra-day precision (%CV) over the dynamic range ranged from 1.31 to 8.88 and from 1.49 to 6.72 for carfentanil and caffeine, respectively. Inter-day precision ranged from 4.7 to 9.9 %CV for carfentanil and 7.6-121 %CV for caffeine. The method was used to evaluate the percutaneous absorption kinetics of carfentanil in solution as a function of solvent composition using an in vitro, live human epidermis model. Counterintuitively, as previously reported, the addition of organic solvents to the formulations decreased rather than increased the percutaneous absorption rate of the ultra-potent opioid, carfentanil.

Contribution from non-ideality and preferential solvation to non-linear solvatochromism in binary mixtures

The knowledge of preferential solvation is of critical importance in description of the solute behavior in mixed solvents. The analysis of solvatochromic shifts as a function of solvent composition is popular in this regard, since it gives molecular information on solute-solvent interactions. However, due to the complexity of the interactions and possible non-ideality of mixed solvents, implementing an efficient approach for interpretation of solvent-solvent interactions is an opening major challenge in modeling solvatochromism to get reliable results on preferential solvation. Here, we proposed a new methodology to treat solvatochromism in solvent mixtures in order to reach a more reliable picture of the local composition around the solute. As the main idea, the effect of solvent-solvent interactions on spectral shift was considered by formulating the non-ideality of solvent in solvation shell of the solute as a function of the local composition by exploiting the results obtained from the analysis of the bulk mixture non-ideality. From that, the non-linear variation in spectral shift can be well separated into contributions from preferential solvation and the local non-ideality. To test this approach, solvatochroimsm of 2-methyl-4-nitroaniline was studied in some mono-solvents and binary mixtures. The spectral properties of 2-methyl-4-nitroaniline and its response to solvent were rationalized by quantum chemical calculation and linear solvation energy relationships analysis in mono-solvents. Then, the observed strong non-linear solvatochromism of 2-methyl-4-nitroaniline in aqueous mixtures of ethanol, DMF and DMSO was treated by the proposed model that provided both physically and statistically more reliable results on preferential solvation and molecular interactions, with respect to the other widely-used solvent exchange models. As an interesting and important result, non-ideality, but not preferential solvation, was responsible for non-linear solvatochromism in aqueous solutions of ethanol and DMF.

Neuroprotective Potential of Tamarillo (Cyphomandra betacea) Epicarp Extracts Obtained by Sustainable Extraction Process.

Tamarillo (Cyphomandra betacea (Cav.) Sendt.), or tree tomato, is a tropical fruit from the Andean region of South America; it is highly rich in vitamins, minerals, and polyphenolic compounds. In this study, extracts from tamarillo epicarp (TE) were obtained by pressurized liquid extraction (PLE), and their in-vitro neuroprotective potential was assessed. A central composite design with response surface methodology was performed to optimize PLE as a function of solvent composition and temperature. Selected response variables were extraction yield, total phenolic content (TPC), total flavonoid content (TFC), total carotenoid content (TCC), antioxidant (ABTS), and anti-inflammatory (LOX) activities, and anti-acetylcholinesterase (AChE) inhibitory capacity. According to the desirability function, the optimal conditions were 100% ethanol and 180°C with a 0.87 desirability value. Next, the anti-butyrylcholinesterase enzyme (BChE), reactive oxygen species (ROS), and reactive nitrogen species (RNS) inhibition as well as cytotoxicity in HK-2, THP-1 monocytes, and SH-5YSY neuroblastoma cell lines were studied for the TE extract obtained under optimized conditions. The optimum TE extract provided the following results: extraction yield (36.25%), TPC (92.09 mg GAE/g extract), TFC (4.4 mg QE/g extract), TCC (107.15 mg CE/g extract), antioxidant capacity (ABTS, IC50 = 6.33 mg/ml extract), LOX (IC50 = 48.3 mg/ml extract), and AChE (IC50 = 97.46 mg/ml extract), and showed no toxicity at concentration up to 120 μg/ml extract for all the tested cell lines. Finally, chemical characterization by liquid chromatography-tandem mass spectrometry (UHPLC-q-TOF-MS/MS) of the optimum TE extract exhibited an important presence of hydroxycinnamic acid derivatives and other phenolic acids as well as quercetin hexoside and rutin, as main metabolites responsible for the observed biological properties. All these results suggested that TE, which represents between 8 and 15% of the total fruit, could become a promising natural by-product with a potential “multitarget” activity against Alzheimer's disease.

Understanding the Effect of Solvent Environment on the Interaction of Hydronium Ion with Biomass Derived Species: A Molecular Dynamics and Metadynamics Investigation.

The addition of aprotic solvents results in higher reactivities and selectivities in many key aqueous phase biomass reactions, including the acid-catalyzed conversion of fructose to 5-hydroxyl methyl furfural (HMF). The addition of certain co-solvents inhibits the formation of humins via preferential solvation of key functional groups and can alter reaction kinetics. An important factor in this context is the relative stability of the hydronium ion (the catalyst) in the vicinity of the biomass moiety as compared to that in bulk, as it could determine its efficacy in the protonation step. Hence, in the present work, molecular dynamics (MD) simulations of HMF (the model product) and fructose (the model reactant) in acidic water and water-DMSO mixtures are performed to analyze their interaction with the hydronium ions. We show that the presence of DMSO favors the interaction of the hydronium ion with fructose, whereas it has a detrimental effect on the interaction of hydronium ion with HMF. Well-tempered metadynamics (WT-MTD) simulations are performed to determine the relative stability of the hydronium ion in the immediate vicinity of fructose and HMF, as compared to that in the bulk solvent phase, as a function of solvent composition. We find that DMSO improves the stabilization of the hydronium ions in the first solvation shell of fructose compared to that in the bulk solvent. On the other hand, hydronium ions become less stable in the immediate vicinity of HMF, as the concentration of DMSO increases.

Revealing and Attenuating the Electrostatic Properties of Tubulin and Its Polymers.

Tubulin is an electrostatically negative protein that forms cylindrical polymers termed microtubules, which are crucial for a variety of intracellular roles. Exploiting the electrostatic behavior of tubulin and microtubules within functional microfluidic and optoelectronic devices is limited due to the lack of understanding of tubulin behavior as a function of solvent composition. This work displays the tunability of tubulin surface charge using dimethyl sulfoxide (DMSO) for the first time. Increasing the DMSO volume fractions leads to the lowering of tubulin's negative surface charge, eventually causing it to become positive in solutions >80% DMSO. As determined by electrophoretic mobility measurements, this change in surface charge is directionally reversible, i.e., permitting control between -1.5 and + 0.2cm2 (Vs)-1 . When usually negative microtubules are exposed to these conditions, the positively charged tubulin forms tubulin sheets and aggregates, as revealed by an electrophoretic transport assay. Fluorescence-based experiments also indicate that tubulin sheets and aggregates colocalize with negatively charged g-C3 N4 sheets while microtubules do not, further verifying the presence of a positive surface charge. This study illustrates that tubulin and its polymers, in addition to being mechanically robust, are also electrically tunable.

Solvent Effects on the Self-Assembly of an Amphiphilic Polypeptide Incorporating α-Helical Hydrophobic Blocks.

The self-assembly of biological molecules is an important pathway to understanding the molecular basis of complex metabolic events. The presence of a cosolvent in an aqueous solution during the self-assembly process can promote the formation of kinetically trapped metastable intermediates. In nature, a category of cosolvents termed osmolytes can work to strengthen the hydrogen-bond network of water such that the native states of certain proteins are favored, thus modulating their function and stability. However, identifying cosolvents that act as osmolytes in biomimetic applications, such as the self-assembly of soft materials, remains challenging. The present work examined the effects of ethanol (EtOH) and acetonitrile (ACN) as cosolvents on the self-assembly of the amphiphilic polypeptide PSar30-(l-Leu-Aib)6 (S30L12), which incorporates α-helical hydrophobic blocks, in aqueous solution. The results provided a direct observation of morphological behavior of S30L12 as a function of solvent composition. Morphological transitions were investigated using transmission electron microscopy, while the packing of peptide molecules was assessed using circular dichroism analyses and evaluations of membrane fluidity. In the EtOH/H2O mixtures, the EtOH strengthened the hydrogen-bond network of the water, thus limiting the hydrophobic hydration of S30L12 assemblies and enhancing hydrophobic interactions between assemblies. In contrast, ACN formed self-associated nanoclusters in water and at the hydrophobic cores of peptide assemblies to stabilize the edges exposed to bulk water and enhance the assembly kinetics. Fourier transform infrared (FT-IR) analysis indicated that both EtOH and ACN can modify the self-assembly of biomaterials in the same manner as osmolyte protectants or denaturants.

Poor Solvents Improve Yield of Grafting-Through Radical Polymerization of OEO19MA.

Radical polymerization of poly(ethylene glycol) methyl ether methacrylate (OEO19MA, Mn ∼ 950) at an initial monomer concentration of 150 mM was investigated as a function of solvent composition. Conventional and controlled radical polymerizations in anisole at 60 °C converged at approximately the same equilibrium monomer concentration ([M]eq) of ∼38 mM, suggesting that livingness or diminished termination did not affect the thermodynamic parameters of polymerization. Conventional radical polymerizations (RPs) in anisole, dimethylformamide (DMF), toluene, and 1×PBS buffered water were taken to approximately 98% thermal initiator decomposition to determine [M]eq at reaction completion within a broad temperature range. The enthalpy (ΔHp) and entropy (ΔSp°) of polymerization were solvent-dependent. Polymerizations in 1×PBS were the most thermodynamically favorable, followed by those in DMF, toluene, and anisole. -ΔHp and -ΔSp increased with the square of the difference in the Hansen solubility parameters of poly(ethylene glycol) and the solvent. It is proposed that poor solvents favor polymer-polymer interactions over polymer-solvent interactions, which improves the thermodynamic polymerizability.

Characterization of the solvent specific evaporation from a fluoropolymer surface roughened by layered double oxide (LDO) particles

Abstract Solid/ liquid interaction strongly depends, among other things, on the chemical and physical properties of fluids, therefore, there are unexploited analytical possibilities in investigating the surface wetting and evaporation behavior. Strongly hydrophobic rough surface thin films were prepared by spray-coating a fluoropolymer film with incorporated layered double oxide (LDO) microparticles. We studied the evaporation of ethanol–water mixtures from the low energy (8.4 ± 2.6 mJ/m2) composite surfaces by simultaneous high-speed visible imaging, infrared imaging and weight loss monitoring. The wetting behavior changed from Cassie's wetting mode (pure water) to Wenzel's (pure ethanol) as a function of solvent composition. The vaporization process could be divided into three stages described by constant evaporate rates and the heat transfer coefficient between the studied layer and water is KT = 1768 W/(m2K). We have found strong correlations between parameters of the measured evaporation profiles and certain physical properties of the solvents. It is possible to estimate the viscosity, the boiling point, or the surface tension of a studied liquid merely from the total evaporation time. This novel solvent identification method can serve as a new application field for such low energy hybrid surfaces.

Tyrocidine A interactions with saccharides investigated by CD and NMR spectroscopies.

Tyrocidines are a family of cyclic decapeptides produced by the soil bacterium, Brevibacillus parabrevis. These antibiotic peptides can be used to prevent infections in agriculture and food industry but also to prepare antimicrobial lozenges, creams, and dressings for medical applications. It has been observed that the tyrocidines interact with saccharides such as cellulose from their soil environment, as well as sugars in culture media and glycans in fungal cell walls. Here, we investigated the interactions of tyrocidines with glucose, sucrose, and cellotetraose (as cellulose model) in a quantitative fashion utilising CD and NMR spectroscopy. The CD and NMR spectra of tyrocidine A (TrcA) were analysed as a function of solvent composition, and the spectral properties agree with the formation of oligomeric structures that are governed by β-sheet secondary structures once the acetonitrile content of the solvent is increased. Saccharides seem to also induce TrcA spectral changes reverting those induced by organic solvents. The CD spectral changes of TrcA in the presence of glucose agree with new ordered H-bonding, possibly β-sheet structures. The amides involved in intramolecular H-bonding remained largely unaffected by the environmental changes. In contrast, amides exposed to the exterior and/or involved in TrcA intermolecular association show the largest 1 H chemical shift changes. CD and NMR spectroscopic investigations correlated well with TrcA-glucose interactions characterized by a dissociation constant around 200μM. Interestingly, the association of cellotetraose corresponds closely to the additive effect from four glucose moieties, while a much higher dissociation constant was observed for sucrose. Similar trends to TrcA for binding to the three saccharides were observed for the analogous tyrocidines, tyrocidine B, and tyrocidine C. These results therefore indicate that the tyrocidine interactions with the glucose monosaccharide unit are fairly specific and reversible.

195Pt NMR and Molecular Dynamics Simulation Study of the Solvation of [PtCl6]2- in Water-Methanol and Water-Dimethoxyethane Binary Mixtures.

The experimental 195Pt NMR chemical shift, δ(195Pt), of the [PtCl6]2- anion dissolved in binary mixtures of water and a fully miscible organic solvent is extremely sensitive to the composition of the mixture at room temperature. Significantly nonlinear δ(195Pt) trends as a function of solvent composition are observed in mixtures of water-methanol, or ethylene glycol, 2-methoxyethanol, and 1,2-dimethoxyethane (DME). The extent of the deviation from linearity of the δ(195Pt) trend depends strongly on the nature of the organic component in these solutions, which broadly suggests preferential solvation of the [PtCl6]2- anion by the organic molecule. This simplistic interpretation is based on an accepted view pertaining to monovalent cations in similar binary solvent mixtures. To elucidate these phenomena in detail, classical molecular dynamics computer simulations were performed for [PtCl6]2- in water-methanol and water-DME mixtures using the anionic charge scaling approach to account for the effect of electronic dielectric screening. Our simulations suggest that the simplistic model of preferential solvation of [PtCl6]2- by the organic component as inferred from nonlinear δ(195Pt) trends is not entirely accurate, particularly for water-DME mixtures. The δ(195Pt) trend in these mixtures levels off for high DME mole fractions, which results from apparent preferential location of [PtCl6]2- anions at the borders of water-rich regions or clusters within these inherently micro-heterogeneous mixtures. By contrast in water-methanol mixtures, apparently less pronounced mixed solvent micro-heterogeneity is found, suggesting the experimental δ(195Pt) trend is consistent with a more moderate preferential solvation of [PtCl6]2- anions. This finding underlines the important role of solvent-solvent interactions and micro-heterogeneity in determining the solvation environment of [PtCl6]2- anions in binary solvent mixtures, probed by highly sensitive 195Pt NMR. The notion that preferential solvation of [PtCl6]2- results primarily from competing ion-solvent interactions as generally assumed for monatomic ions, may not be appropriate in general.

New method for predictingn-tetradecane/bitumen mixture density: correlation development

Nowadays, incredible growth of the energy consumption has changed the global attention to the production and utilization of the heavy crude oils such as bitumen resources around the globe. Amongst the bitumen properties, density is an important parameter which improves bitumen recovery efficiency and transportation quality. For easy production of bitumen,n-alkanes are usually injected into the reservoir to reduce its viscosity and density; however, there are few numbers of models focusing on proper estimation/prediction of diluted bitumen mixture density in literature. In present work, a new method was proposed to accurately prognosticate the bitumen/n-tetradecane mixture density as a function of thermodynamic conditions using Gene Expression Programming (GEP) for the first time as a function of solvent composition, pressure and temperature. Consequently, the proposed model here predicts the mixture density with the average Absolute Relative Deviation (AARD%) of 0.3016% andR-squared (R2) of 0.9943. Moreover, it is found out the solvent concentration has the highest impact value on mixture density estimation. In conclusion, results of the present study can be so valuable for field engineers and researchers working on solvent-assisted recovery methods from heavy oil reservoirs.

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S1 state is the only significant product of the radiationless decay of the S2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pKs) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0M NaClO4 and a temperature of 298K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. The ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.

Enhanced Chelate Cooperativity in Polar Solvents.

High-throughput UV-vis titrations in combination with chemical double-mutant cycles (DMCs) have been used to study the competition of a polar solvent for formation of intramolecular H-bonds. Twenty-four different zinc porphyrin-pyridine complexes were investigated in mixtures of toluene and phenol. DMCs were used to determine effective molarities (EM) for the formation of intramolecular phenol-amide H-bonds as a function of solvent composition. The values of EM increase by an order of magnitude with increasing concentrations of the more polar solvent, phenol. Phenol solvates the amide groups on the ligands strongly, increasing the steric bulk and destabilizing the complexes. These adverse steric interactions are removed when intramolecular H-bonds are formed and therefore provide an increased driving force for formation of cooperative interactions. The result is that the effects of competitive interactions with polar solvents that reduce binding affinity are attenuated to a significant extent by a corresponding increase in EM in multivalent complexes.

Influence of Solvent on Radical Trap-Assisted Dimerization and Cyclization of Polystyrene Radicals

The extent of dimerization in radical trap-assisted atom transfer radical coupling (RTA-ATRC) was studied as a function of solvent composition, with accelerated rates of coupling observed in solvent mixtures consisting of THF and hydrocarbons compared to either pure solvent. Aggregation of the nitroso radical trap was speculated to be responsible for the trend in coupling rates of RTA-ATRC reactions, with less polar solvents such as hydrocarbons favoring the active, monomeric form. The mixed solvent system of THF and cyclohexane was found to be transferrable to the synthesis of macrocyclic PS by intramolecular RTA-ATRC, with 50/50 (v/v) THF:cyclohexane reaction medium giving higher yields of cyclic product compared to reactions performed in the pure solvents.

Unperturbed dimension, interaction parameters, zeta potential and rheology of sodium alginate in binary solvent mixtures

The intrinsic viscosity [η] of sodium alginate having different molecular weights (high molecular weight (type A), medium molecular weight (type B) and low molecular weight (type C)) is measured at 293–303 K temperature in various mixtures of water (good solvent), acetone (ACE, poor solvent) and water-ethoxy ethanol (EE, poor solvent). The observed result particularly the Huggins constant (K H) values shows a significant variation of cosolvency as a function of solvent composition (ΦACE/ΦEE) and the temperature. Unperturbed dimensions (K θ) under non-theta condition have been calculated using various equations in different water-acetone and water-ethoxy ethanol mixtures. The value of K θ obtained from three different methods of measurements viz., Burchard-Stockmayer and Fixman (BSF), Berry and Inagaki-Suzuki-Kurata (ISK) agree well with each other except in a few compositions of solvents. The molecular extension factor (α n) and actual end-to-end distance (α n K θ) have also been computed herein. Further, the shear thinning nature of the sodium alginate solutions (representative illustration: type A) in water and water-acetone mixed systems has been investigated at increasing strain rate. Results show that the viscous modulus G″ predominates over the elastic modulus G′ and the systems behave as viscoelastic fluids under present conditions. Higher value of G′ in acetone-water mixed solvent system compared to that in pure water undoubtedly indicates enhancement of the elasticity in alginate system in the presence of acetone. Finally, zeta potential measurement demonstrates that the polymeric surface of sodium alginate (representative illustration: type A) is essentially negatively charged and the zeta potential of the polymer is more responsive to the composition of ethoxy ethanol than that of acetone in the aqueous-organic mixed solvents.

Phase separation behavior and fluorescence properties of poly(N-isopropylacrylamide) with chalcone side groups in mixed solvents

The phase separation behavior and fluorescence properties of linear PNIPAM with chalcone side groups (PNIPAM-C) in water-cononsolvent systems were studied as a function of solvent composition (x) and temperature. It was found that PNIPAM-C exhibited a single lower critical solution temperature (LCST) in water–methanol, water–acetone, and water–tetrahydrofuran; the addition of organic solvents initially decreased the phase separation temperature and a further addition increased it rapidly. The minimum LCST was −8 °C for the mole fraction of methanol xmethanol ≈ 0.31, 17 °C for xacetone ≈ 0.14, and −2 °C for xtetrahydrofuran ≈ 0.13. However, in water–ethanol solution, a simultaneous LCST and upper critical solution temperature (UCST) existed for lower and higher ethanol concentrations, respectively, and the phase separation temperature decreased drastically with increasing ethanol concentrations. Furthermore, the solvent composition-sensitive and temperature-sensitive fluorescence properties of PNIPAM-C were investigated. The results showed that the fluorescence emission wavelength (λmax) underwent a blue shift and the intensity increased with the addition of a small amount of organic solvent. With further addition of organic solvent, λmax and intensity were almost not changed. However, when the content of organic solvent exceeded a critical value, such as xmethanol > 0.17, λmax blueshifted and the intensity increased with the increase of organic solvent. At low content of organic solvent, λmax decreased greatly and the intensity increased rapidly as the temperature was raised from 20 °C to 50 °C because phase separation occurred when the temperature was elevated.

Predicting the solution morphology of a sulfonated pentablock copolymer in binary solvent mixtures

ABSTRACTThe solution morphologies of a midblock‐sulfonated pentablock copolymer in miscible polar/nonpolar solvent blends were characterized as a function of solvent composition and polymer concentration using small angle X‐ray scattering. Three distinct solution morphologies are observed upon changing the composition of the solvent blend. At low weight fractions of polar solvent, spherical, sulfonated‐core micelles are observed, while spherical, sulfonated‐corona (inverted) micelles are observed at high weight fractions of polar solvent. Polymer solution scattering is observed at intermediate concentrations of polar solvent. Additionally, the characteristic dimensions of the sulfonated‐core micelles were found to change strongly upon variation of the solvent blend composition, indicating that these solutions—and correspondingly the morphology and properties of polymer membranes into which they are cast—can be tuned through simple variations in the solvent blend chemistry. We demonstrate that the solution morphologies and the characteristic micelle dimensions of these complex pentablock copolymer/binary solvent blends can be reliably predicted by considering the relative interactions of each polymer block and the solvent blend using the Hansen solubility parameters. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 254–262

Unperturbed dimensions and interaction parameters of poly(vinyl alcohol)s in water–acetone and water–tetrahydrofuran mixtures

The intrinsic viscosities [η] of poly(vinyl alcohol)s (PVAs, which are biocompatible polymers)—with different (high, medium, and low) molecular weights were measured at 293–303 K in water (good solvent)–acetone (ACE, poor solvent) and water–tetrahydrofuran (THF, poor solvent) mixtures. The results observed, particularly the values of the Huggins constant (KH), indicated that the solvency of each PVA varied as a function of solvent composition (ΦACE/ΦTHF) and temperature. The unperturbed dimensions (Kθ) of the PVAs under nontheta conditions in a variety of water–acetone and water–tetrahydrofuran solutions were also calculated using various equations. The values of Kθ obtained via three different equations, i.e., those of Burchard–Stockmayer–Fixman (BSF), Berry, and Inagaki–Suzuki–Kurata (ISK), agreed well except for a few solvent compositions. The molecular extension factor (αn) and actual end-to-end distance (αnKθ) of each PVA were also computed.