Solvent Exchange Procedure Research Articles

Photothermal Activation of Metal-Organic Frameworks Using a UV-Vis Light Source.

Metal-organic frameworks (MOFs) usually require meticulous removal of the solvent molecules to unlock their potential porosity. Herein, we report a novel one-step method for activating MOFs based on the photothermal effect induced by directly irradiating them with a UV-vis lamp. The localized light-to-heat conversion produced in the MOF crystals upon irradiation enables a very fast solvent removal, thereby significantly reducing the activation time to as low as 30 min and suppressing the need for time-consuming solvent-exchange procedures and vacuum conditions. This approach is successful for a broad range of MOFs, including HKUST-1, UiO-66-NH2, ZIF-67, CPO-27-M (M = Zn, Ni, and Mg), Fe-MIL-101-NH2, and IRMOF-3, all of which exhibit absorption bands in the light emission range. In addition, we anticipate that this photothermal activation can also be used to activate covalent organic frameworks (COFs).

Tuning the rheological properties of protein-based oleogels by water addition and heat treatment

Although mostly known for their gelling ability in water, proteins can also be used to structure oil into so-called oleogels. To create these oleogels, protein aggregates (d ∼190 nm) were formed by heat treatment in an aqueous environment and then suspended in oil using a solvent exchange procedure. To control the interactions between colloidal protein aggregates in oil, the effect of the addition of a small amount of water and the application of a heat treatment were investigated. Addition of water was shown to induce clustering of the protein aggregates. The effect of increased particle clustering was observed up to water addition in the amount of 0.5 g water/g protein, above which free water droplets were formed. As a result of water addition, G′ increased dramatically by up to three orders of magnitude. Besides an increase in G′, also an increase in critical strain and yield stress was observed. Moreover, the gels became responsive to temperature when water was added. G’ increased even further upon heating, and regained gel strength upon cooling due to enhanced particle-particle interactions. We propose that these interactions are most likely due to the formation of capillary bridges between the protein aggregates. Addition of water and subsequent heat treatment are thus effective ways to increase the interactions between protein aggregates. This simple approach forms an interesting route to tune the rheological properties of protein oleogels.

Fabrication of Redox-Responsive Degradable Capsule Particles by a Shell-Selective Photoinduced Cross-Linking Approach from Spherical Polymer Particles.

In this study, a fabrication route towards functional capsule particles was successfully developed by means of a self-templating shell-selective cross-linking strategy that enables us to prepare shell-cross-linked hollow polymer particles directly from homogeneous spherical polymer particles. To prepare redox-responsive degradable capsule particles, a newly designed monomer bearing a photoinduced post-cross-linking group (cinnamoyl group) and a redox-environment-responsive cleavable group (disulfide group), N-cinnamoyl-N'-methyacryloylcystamine (MCC), was synthesized. Redox-responsive degradable capsule particles were successfully prepared from homogeneous spherical poly(MCC)-based particles by a self-templating shell-selective photoinduced cross-linking approach. Moreover, the cargo loading capability of the shell-cross-linked hollow particles was confirmed through a solvent exchange procedure using dyes, polymer precursors and anticancer reagents. Furthermore, redox-responsive degradability of the capsule polymer particles was also confirmed by adding a reducing agent for cleavage of the disulfide linkage. We hope that the efficient fabrication route of functional capsule particles directly from spherical polymer particles opens efficient routes for the fabrication of a wide range of capsule particles; in particular, this technique is robust, productive, and facile because neither additional sacrificial template particles nor toxic solvents are required.

Fluorous Phase‐Directed Peptide Assembly Affords Nano‐Peptisomes Capable of Ultrasound‐Triggered Cellular Delivery

AbstractHere, we report the design, synthesis and efficacy of a new class of ultrasound (US)‐sensitive self‐assembled peptide‐based nanoparticle. Peptisomes are prepared via templated assembly of a de novo designed peptide at the interface of fluorinated nanodroplets. Utilizing peptide assembly allows for facile particle synthesis, direct incorporation of bioactive sequences displayed from the particle corona, and the ability to easily encapsulate biologics during particle preparation using a mild solvent exchange procedure. Further, nano‐peptisome size can be precisely controlled by simply modulating the starting peptide and fluorinated solvent concentrations during synthesis. Biomolecular cargo encapsulated within the particle core can be directly delivered to the cytoplasm of cells upon US‐mediated rupture of the carrier. Thus, nano‐peptisomes represent a novel class of US‐activated carriers that can shuttle cell‐impermeable biomacromolecules into cells with spatial and temporal precision.

Fluorous Phase-Directed Peptide Assembly Affords Nano-Peptisomes Capable of Ultrasound-Triggered Cellular Delivery.

Here, we report the design, synthesis and efficacy of a new class of ultrasound (US)-sensitive self-assembled peptide-based nanoparticle. Peptisomes are prepared via templated assembly of a de novo designed peptide at the interface of fluorinated nanodroplets. Utilizing peptide assembly allows for facile particle synthesis, direct incorporation of bioactive sequences displayed from the particle corona, and the ability to easily encapsulate biologics during particle preparation using a mild solvent exchange procedure. Further, nano-peptisome size can be precisely controlled by simply modulating the starting peptide and fluorinated solvent concentrations during synthesis. Biomolecular cargo encapsulated within the particle core can be directly delivered to the cytoplasm of cells upon US-mediated rupture of the carrier. Thus, nano-peptisomes represent a novel class of US-activated carriers that can shuttle cell-impermeable biomacromolecules into cells with spatial and temporal precision.

Solvent Exchange Leading to Nanobubble Nucleation: A Molecular Dynamics Study.

The solvent exchange procedure has become the most-used protocol to produce surface nanobubbles, while the molecular mechanisms behind the solvent exchange are far from being fully understood. In this paper, we build a simple model and use molecular dynamics simulations to investigate the dynamic characteristics of solvent exchange for producing nanobubbles. We find that at the first stage of solvent exchange, there exists an interface between interchanging solvents of different gas solubility. This interface moves toward the substrate gradually as the exchange process proceeds. Our simulations reveal directed diffusion of gas molecules against the gas concentration gradient, driven by the solubility gradient of the liquid composition across the moving solvent–solvent interface. It is this directed diffusion that causes gas retention and produces a local gas oversaturation much higher near the substrate than far from it. At the second stage of solvent exchange, the high local gas oversaturation leads to bubble nucleation either on the solid surface or in the bulk solution, which is found to depend on the substrate hydrophobicity and the degree of local gas oversaturation. Our findings suggest that solvent exchange could be developed into a standard procedure to produce oversaturation and used to a variety of nucleation applications other than generating nanobubbles.

Preparation and Adsorption Performance of Cellulose-graft-Polycaprolactone/Polycaprolactone Porous Material

Cellulose-graft-polycaprolactone/polycaprolactone (cell-g-PCL/PCL) was formed by grafting cotton linter pulp with caprolactone via ring-opening polymerization catalyzed by Ti(O-n-Bu)4. The cell-g-PCL/PCL and polycaprolactone (PCL) were used to prepare porous materials (PMs) using solvent exchange and freeze-drying procedures. The obtained PMs were characterized by their porosity, tensile strength, and thermal stability via thermal gravimetric analysis and scanning electron microscopy. The preparation conditions of the cell-g-PCL/PCL PM were optimized based on the characterization results. Compared with PCL PM, cell-g-PCL/PCL PM showed higher porosity and better thermal stability. The adsorptivity of cell-g-PCL/PCL PM for the organic pollutant chlorobenzene was greatly improved compared with that of PCL PM. The adsorption processes of both PMs fit well with the Lagergren pseudo-first-order and pseudo-second-order kinetic models. The results of isothermal adsorption simulation indicated that cell-g-PCL/PCL PM and PCL PM fit better with the Langmuir model and Freundlich model, respectively.

Controlling Agglomeration of Protein Aggregates for Structure Formation in Liquid Oil: A Sticky Business

Proteins are known to be effective building blocks when it comes to structure formation in aqueous environments. Recently, we have shown that submicron colloidal protein particles can also be used to provide structure to liquid oil and form so-called oleogels (de VriesA.J. Colloid Interface Sci.2017, 486, 75−83)27693552. To prevent particle agglomeration, a solvent exchange procedure was used to transfer the aggregates from water to the oil phase. The aim of the current paper was to elucidate on the enhanced stability against agglomeration of heat-set whey protein isolate (WPI) aggregates to develop an alternative for the solvent exchange procedure. Protein aggregates were transferred from water to several solvents differing in polarity to investigate the effect on agglomeration and changes in protein composition. We show that after drying protein aggregates by evaporation from solvents with a low polarity (e.g., hexane), the protein powder shows good dispersibility in liquid oil compared to powders dried from solvents with a high polarity. This difference in dispersibility could not be related to changes in protein composition or conformation but was instead related to the reduction of attractive capillary forces between the protein aggregates during drying. Following another route, agglomeration was also prevented by applying high freezing rates prior to freeze-drying. The rheological properties of the oleogels prepared with such freeze-dried protein aggregates were shown to be similar to that of oleogels prepared using a solvent exchange procedure. This Research Article provides valuable insights in how to tune the drying process to control protein agglomeration to allow for subsequent structure formation of proteins in liquid oil.

Protein oleogels from heat-set whey protein aggregates

In this research we use heat-set whey protein aggregates (diameter∼200nm) as novel building blocks for structure formation in liquid oil to form oleogels. To transfer the aggregates to the oil phase, a solvent exchange procedure to sunflower oil was applied using acetone as an intermediate solvent. We found that agglomeration of the aggregates was prevented and the particle size in oil did not change from that in the initial aqueous phase. The small protein aggregates assemble into a space-spanning network, thereby providing solid-like properties to liquid oil. From oscillatory rheology we conclude that the aggregates are highly effective in forming a network. Already at ∼3% we found that G′>G″ and G′ scales with protein concentration as G′∼cp5.3. Applying a fractal gel network theory to the rheological data we deduce that the gels are in the strong link regime with a fractal dimension of 2.2. The results show that protein aggregates, besides their well-known functionality in aqueous solvents, are capable of forming a network in liquid oil. This provides a novel and promising way to design oleogels with tuneable rheological properties, applicable to e.g. foods, pharmaceuticals and/or cosmetics.

Stepwise injection potentiometric determination of caffeine in saliva using single-drop microextraction combined with solvent exchange

A flow potentiometric method for determination of caffeine in saliva is suggested. This task is important for non-invasive assessment of drug metabolizing system activity in hepatocytes. In the current study, stepwise injection analysis (SWIA) was successfully combined with single-drop liquid microextraction (SDLME) and solvent exchange procedure. The method is based on the caffeine SDLME with subsequent solvent evaporation and dissolution of analyte in sulfuric acid followed by potentiometric detection using poly(vinyl chloride) membrane electrode containing potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as electroactive component. SDLME was employed for elimination of interfering matrix effects of saliva and caffeine metabolites such as theophylline, theobromine and paraxanthine. A linear range of 10−5–10−2M was established for caffeine with detection limit at 6×10−6M. The sample throughput was 6 samples h−1. The proposed method was successfully applied to the determination of caffeine in saliva and the analytical results agreed well with the results obtained with reference HPLC method.

Insoluble layer deposition and dilatational rheology at a microscale spherical cap interface.

The dilatational properties of insoluble monolayers are important for understanding the mechanics of biological systems and consumer products, but isolating the dilatational response of an interface is challenging due to the difficulties in separating dilatation from shear and other deformation modes. Oscillations of a microscale bubble radius are useful for generating purely dilatational flows, but the current deposition methods for insoluble layers onto fluid interfaces are not easily scaled down. In this paper, we describe a miscible solvent exchange procedure for generating insoluble layers at an air-water interface pinned at the tip of a capillary tens of micrometers in diameter. We show that the amount of surfactant adsorbed at the interface can be controlled by the initial concentration dissolved in isopropanol (the starting solvent) and the volumetric flow rate of solvent exchange. Surface pressure-area isotherms and dilatational moduli are measured concurrently for three insoluble surfactants: palmitic acid (PA), dimyristoylphosphatidylcholine (DMPC) and dipalmitoylphosphatidylcholine (DPPC). The isotherms measured on the microscale interface compare well with previous experiments performed on a Langmuir trough. However, the magnitudes of the dilatational moduli differ from those measured on either Langmuir trough or pendant drop apparatuses. Several possible reasons for the observed differences are discussed. A comparison of the dilatational modulus with the Gibbs elasticity is used to determine the presence of dilatational extra stresses at the interface. The isotherm and dilatational modulus of the insoluble component of the industrial surfactant Tween 80 are measured using this approach. The methods developed here also open the possibility for future study of the important role of finite size effects on microstructure formation and the resulting interfacial mechanics.

Protein Oleogels from Protein Hydrogels via a Stepwise Solvent Exchange Route.

We investigated the use of whey protein isolate (WPI) as oleogelator in liquid oil. First, heat-set WPI hydrogels were prepared varying in microstructure and network density. Then, by applying a stepwise solvent exchange procedure via an intermediate solvent, full replacement of the internal aqueous phase within the protein matrix by sunflower oil was achieved. The solvent exchange procedure was performed by using either acetone or tetrahydrofuran (THF) as intermediate solvent. The oil inside the protein matrix was homogeneously distributed without any noticeable damage to the structure. Analyzing the weight change of the protein gel as a result of the solvent exchange shows that the oil holding capacity depends on the microstructure, the polarity of the intermediate solvent, and the kinetics of the solvent exchange. Depending on the gel microstructure and protein concentration of the preceding hydrogel, the oil content in the oleogels was found to be as high as 91 wt %. Oil holding capacity correlated well with the water holding capacity of the preceding hydrogel, and its Young's modulus (stiffness). It was found that the oleogels, compared to the hydrogels, were much stiffer, as the Young's modulus increased by 2 orders of magnitude and showed a lower strain at fracture. Our novel route of structuring oil by immobilizing liquid oil inside a biodegradable protein gel matrix with tunable mechanical properties could be relevant for developing novel materials, e.g., in pharmaceutical, nutraceutical, and food applications.

Highly stable organic fluorescent nanorods for living-cell imaging

Metal-free, organic-dye-based fluorescent nanorods were fabricated through a simple solvent-exchange procedure. The as-prepared nanorods exhibit low toxicity to living cells and excellent photostability. Furthermore, they are stable in solutions of various pHs and high ionic strength and in solutions with interfering metal ions. Compared with the free DPP-Br molecules in THF, these nanorods exhibit larger Stokes shift, broader absorption spectra, and greatly improved photostability. We successfully demonstrated the application of the nanorods, including their aforementioned beneficial characteristics, as a good fluorescence probe for bio-imaging.

Solvent-assisted lipid bilayer formation on silicon dioxide and gold.

Planar lipid bilayers on solid supports mimic the fundamental structure of biological membranes and can be investigated using a wide range of surface-sensitive techniques. Despite these advantages, planar bilayer fabrication is challenging, and there are no simple universal methods to form such bilayers on diverse material substrates. One of the novel methods recently proposed and proven to form a planar bilayer on silicon dioxide involves lipid deposition in organic solvent and solvent exchange to influence the phase of adsorbed lipids. To scrutinize the specifics of this solvent-assisted lipid bilayer (SALB) formation method and clarify the limits of its applicability, we have developed a simplified, continuous solvent-exchange version to form planar bilayers on silicon dioxide, gold, and alkanethiol-coated gold (in the latter case, a lipid monolayer is formed to yield a hybrid bilayer) and varied the type of organic solvent and rate of solvent exchange. By tracking the SALB formation process with simultaneous quartz crystal microbalance-dissipation (QCM-D) and ellipsometry, it was determined that the acoustic, optical, and hydration masses along with the acoustic and optical thicknesses, measured at the end of the process, are comparable to those observed by employing conventional fabrication methods (e.g., vesicle fusion). As shown by QCM-D measurements, the obtained planar bilayers are highly resistant to protein adsorption, and several, but not all, water-miscible organic solvents could be successfully used in the SALB procedure, with isopropanol yielding particularly high-quality bilayers. In addition, fluorescence recovery after photobleaching (FRAP) measurements demonstrated that the coefficient of lateral lipid diffusion in the fabricated bilayers corresponds to that measured earlier in the planar bilayers formed by vesicle fusion. With increasing rate of solvent exchange, it was also observed that the bilayer became incomplete and a phenomenological model was developed in order to explain this feature. The results obtained allowed us to clarify and discriminate likely steps of the SALB formation process as well as determine the corresponding influence of organic solvent type and flow conditions on these steps. Taken together, the findings demonstrate that the SALB formation method can be adapted to a continuous solvent-exchange procedure that is technically minimal, quick, and efficient to form planar bilayers on solid supports.

Nanobubble formation on a warmer substrate.

The solvent exchange procedure is an often-used protocol to produce surface nanobubbles. In this procedure, the substrate is exposed to a good solvent for gas which is then mixed and rinsed with a poor solvent for gas and the nanobubbles form on the solid-liquid interface. Here we study the effects of temperatures of the substrate and the first solvent on nanobubble formation. Atomic force microscopy with temperature control was used to examine the formation of nanobubbles at temperatures between 37 °C and 54 °C. It was found that the probability of nanobubble formation was larger on substrates at higher temperatures. Moreover, on warmer substrates we found nanobubbles with lateral extensions up to 8 μm. A morphologic analysis shows that all nanobubbles, including giant nanobubbles, have a similar aspect ratio, independent of the substrate temperature, and that this aspect ratio corresponds to a contact angle between 13° and 22° (on the gas side), much smaller than the macroscopic counterparts. We finally discuss the implications of our results for various theories on nanobubble stability.

Porous thin film barrier layers from 2,3-dicarboxylic acid cellulose nanofibrils for membrane structures

To fabricate a strong hydrophilic barrier layer for ultrafiltration (UF) membranes, 2,3-dicarboxylic acid cellulose nanofibrils with high anionic surface charge density (1.2mekv/g at pH 7) and a width of 22±4nm were used. A simple vacuum filtration method combined with a solvent exchange procedure resulted in a porous layer with a thickness of ∼0.85μm. The fabricated membranes reached high rejection efficiencies (74–80%) when aqueous dextrans up to 35–45kDa were filtrated to evaluate the molecular weight cut-offs (MWCO). A linear correlation between the barrier layer thickness and the flux rate was observed in all tested cases. Further optimization of the barrier layer thickness can lead to an even more effective structure.

Cellulose nanocrystals as organic nanofillers for transparent polycarbonate films

Cellulose nanocrystals (CNCs) produced by sulfuric acid hydrolysis as organic nanofillers were dispersed into polycarbonate (PC) in organic solution through a solvent exchange procedure, and their influence on the optical, mechanical, and thermal properties of the resulting composite films were studied. It is demonstrated that due to the good dispersion of the nanofillers in the polymeric matrix, the formation of strong hydrogen bonds between carbonyl groups of PC and hydroxyl groups of the CNCs can be achieved, leading to a simultaneous reinforcement effect on mechanical and thermal properties of the composite films. Moreover, it was further found that the existence of nanofillers in the composite efficiently hindered the main thermal degradation pathways of PC involving the chain scission at carbonate linkage and rearrangement of carbonate groups. Compared with neat PC, the composite film with 3 wt% CNCs has an increase of about 30.6 % in tensile strength, 27.3 % in Young’s modulus, and 3.3 % in maximum decomposition temperature, but still remain quite transparent.

Mesostructured Block Copolymer Nanoparticles: Versatile Templates for Hybrid Inorganic/Organic Nanostructures.

We present a versatile strategy to prepare a range of nanostructured poly(styrene)-block-poly(2-vinyl pyridine) copolymer particles with tunable interior morphology and controlled size by a simple solvent exchange procedure. A key feature of this strategy is the use of functional block copolymers incorporating reactive pyridyl moieties which allow the absorption of metal salts and other inorganic precursors to be directed. Upon reduction of the metal salts, well-defined hybrid metal nanoparticle arrays could be prepared, while the use of oxide precursors followed by calcination permits the synthesis of silica and titania particles. In both cases, ordered morphologies templated by the original block copolymer domains were obtained.

Effects of Surfactants on the Formation and the Stability of Interfacial Nanobubbles

Contamination has previously been invoked to explain the flat shape and the long lifetimes of interfacial nanobubbles (INBs). In this study, the effects of surfactants on the formation and the stability of INBs were investigated when surfactants were added to the system before, during, and after the standard solvent exchange procedure (SSEP) for the formation of INBs. The solutions of sodium dodecyl sulfate (SDS) above critical micelle concentration were found to have little effect on the bubble stability. Likewise, cleaning of the substrate with a surfactant solution had little effect. In contrast, addition of a water-insoluble surfactant during the formation dramatically reduced the INBs. Finally, repeated application of SSEP to surfactant-coated substrates progressively rinsed the surfactant off the system. Thus, we found no evidence to support the hypothesis that (1) INBs are stabilized by a layer of insoluble organic contaminant or that (2) SSEP introduces surface-active materials to the system that could stabilize INBs.

Simultaneous improvement of mechanical properties and thermal stability of bacterial polyester by cellulose nanocrystals

Green nanocomposites were prepared by adding well-dispersed cellulose nanocrystals (CNCs) into bacterial polyester poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) matrix. Simultaneous enhancements on the mechanical property and thermal stability of PHBV after reinforcement of CNCs were achieved. Compared to neat PHBV, a 149% improvement in tensile strength and 250% increase in Young's modulus can be obtained for the resulting nanocomposites with 10wt.% CNCs, more importantly, the T0, T5%, Tmax and Tf increased by 51.4, 36.5, 47.1 and 52.9°C, respectively. This was due to a combination of CNCs reinforcement in the polymeric matrix, and especially the formation of strong intermolecular hydrogen bonding interactions through achieving the excellent dispersion of CNCs in the PHBV matrix via the solvent exchange procedure, as a result, the formation of six-membered ring ester during the degradation process of PHBV was clearly suppressed.