Solvent Exchange Process Research Articles

A novel approach for immobilizing Ag/ZnO nanorods on a glass substrate: Application in solar light-driven degradation of micropollutants in water

One of the main challenges in applying photocatalysts for water treatment is the complex separation and recycling process. In this study, we developed highly stable, porous zinc oxide nanorods (ZnO NRs) immobilized on glass vials using a solvent exchange process (SEP) and hydrothermal calcination. Key parameters, including oleic acid concentration and hydrothermal growth time, were optimized to maximize the active surface area, significantly enhancing photodegradation performance. Under the best conditions, ZnO NRs-coated vials achieved nearly 100% degradation of sulfamethoxazole (SMX) in 10 h of simulated solar irradiation. Depositing silver nanoparticles on the surface of ZnO NRs (Ag/ZnO NRs) further improved performance, reducing degradation time to 4 h and increasing photocatalyst stability. The Ag/ZnO NRs-coated vials, optimized with an Ag precursor concentration of 0.05 M, also demonstrated high degradation rates (>99%) for eight organic micropollutants at environmentally relevant concentrations over multiple reuse cycles and with minimal metal leaching. This study presents an innovative, tunable method for immobilizing photocatalysts on glass substrates, offering high surface area, excellent photocatalytic activity, and mechanical properties, making it highly suitable for water treatment applications.

Fabrication of Hierarchical Nanostructures Featuring Amplified Asymmetry Through Co-Assembly of Liquid Crystalline Block Copolymer and Chiral Amphiphiles.

The widespread presence of hierarchical asymmetric structures in nature has sparked considerable interest because of their unique functionalities. These ingenious structures across multiple scales often emerge from the transfer and amplification of asymmetry from chiral molecules under various synergistic effects. However, constructing artificial chiral asymmetric structures, particularly in developing hierarchical multicomponent structures analogous to those formed in nature through synergistic non-covalent interactions, still presents tremendous challenges. Herein, we propose a co-assembly strategy to fabricate hierarchical chiral mesostructures by combining a liquid crystalline block copolymer (LC-BCP) with a small molecular amphiphile containing chiral alanine or phenylalanine as a linker. Through a classic solvent-exchange process, chiral amphiphiles embedded within LC-BCP finely regulate the LC ordering effect and facilitate transfer and amplification of asymmetry. Consequently, various co-assembled structures with significant hierarchical chirality features are obtained through synergetic effects. Remarkably, subtle alterations to the side groups of amino acids in the amphiphiles effectively adjust the hierarchical morphology transition. Moreover, the covalent bonding sequence of amino acids in the amphiphiles emerges as a critical factor governing the formation of hierarchical nanofibers and multilayered vesicles exhibiting a superhelical sense.

Enhancement of mechanical properties of nanocellulose xerogels using TEMPO-oxidized fibers

We report xerogels prepared from TEMPO-oxidized cellulose nanofiber (Ox-CNF) that have enhanced yield stresses and Young's Modulus (E) up to 15.4 MPa. The xerogels were highly porous (>95 %) and were measured by density determination, SEM, Brunauer-Emmet-Teller (BET) experiments, and microCT analysis. The xerogels had a density of 0.0182 to 0.0471 g/cm3. We report that the solvent exchange process introduces a distribution of pore sizes and leads to enhanced mechanical properties. Mechanical properties were evaluated by monotonic and cyclical uniaxial compression measurements using a flat punch. These highly porous Ox-CNF xerogels have superior mechanical properties to other CNF xerogels and aerogels.

Measurement of ethanol concentration for monitoring the solvent exchange during the alcogel preparation

A crucial and time-consuming stage in aerogel production is the solvent exchange process for alcogel formation. This process involves multiple steps, exposing the hydrogel to ethanol solutions with increasing concentration until the equilibrium in each step. Currently, the determination of contact time between phases (hydrogel and liquid solution) is either arbitrary or based on prior studies. However, considering the unique physicochemical characteristics of each system, as well as the solid-liquid interactions and the liquid diffusion within the matrix, the required time may vary. Monitoring this step can lead to a reduction in the time needed for alcogel production and the optimization of the entire process. The refractive index serves as a tool to assess ethanol concentration in the liquid solution over time, providing immediate information about the status of the solvent exchange. Alongside, differential scanning calorimetry can be employed to evaluate ethanol content in the alcogel (solid phase), confirming the attainment of equilibrium between phases.•This research introduces a technique for monitoring solvent exchange.•Refractive index measurement of the liquid solvent offers immediate concentration information into the status of the solvent exchange.•Differential scanning calorimetry is applicable for measuring the ethanol content within the alcogel and validating refractive index findings.

Preparation of Chitosan Nanoparticles through a Readily Solvent-Exchange Process for Efficient and Enhanced Gene Delivery.

In view of the excellent prospects of gene therapy and the potential safety and immunogenicity issues challenged by viral vectors, it is of great significance to develop a nonviral vector with low toxicity and low cost. In this work, we report a chitosan nanoparticle (CSNP) to be used as a gene vector prepared through a facile solvent-exchange strategy. Chitosan is first dissolved in ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIM Ac), and then, the solvent is exchanged with water/phosphate-buffered saline (PBS) to remove ionic liquid, forming a final CSNP dispersion after ultrasonication. The prepared CSNP shows a positive surface charge and can condense green fluorescent protein-encoding plasmid (pGFP) at weight ratios (CSNP/pGFP) of 5/1 or higher. Dynamic light scattering size and ζ-potential characterization and gel retardation results confirm the formation of CSNP/pGFP complexes. Compared with plain pGFP, efficient cellular internalization and significantly enhanced green fluorescent protein (GFP) expression are observed by using CSNP as a plasmid vector. Benefitting from the intrinsic biocompatibility, low cost, low immunogenicity, and abundant sources of chitosan, as well as the facile preparation and the efficient gene transfection capacity of CSNP, it is believed that this CSNP could be used as a nonviral gene vector with great clinical translational potentials.

Self-assembly of peptide nanocapsules by a solvent concentration gradient.

Biological systems can create materials with intricate structures and specialized functions. In comparison, precise control of structures in human-made materials has been challenging. Here we report on insect cuticle peptides that spontaneously form nanocapsules through a single-step solvent exchange process, where the concentration gradient resulting from the mixing of water and acetone drives the localization and self-assembly of the peptides into hollow nanocapsules. The underlying driving force is found to be the intrinsic affinity of the peptides for a particular solvent concentration, while the diffusion of water and acetone creates a gradient interface that triggers peptide localization and self-assembly. This gradient-mediated self-assembly offers a transformative pathway towards simple generation of drug delivery systems based on peptide nanocapsules.

Preparation of Antibacterial Biobased Fibers by Triaxial Microfluidic Spinning Technology Using Ionic Liquids as the Solvents.

Bacterial infections have become a serious threat to public health. The utilization of antibacterial textiles offers an effective way to combat bacterial infections at the source, instead of relying solely on antibiotic consumption. Herein, efficient and durable antibacterial fibers based on quercetin and cellulose were prepared by a triaxial microfluidic spinning technology using ionic liquids (ILs) as the solvents. It was indicated that the structure and properties of the antibacterial fibers were affected by the type of IL and the flow rates during the triaxial microfluidic spinning process. Quercetin regenerated from [Emim]Ac underwent structural transformation and obtained an increased water solubility, while quercetin regenerated from [Emim]DEP remained unchanged, which was proven by FI-IR, XRD, and UV analyses. Furthermore, antibacterial fibers regenerated from [Emim]Ac exhibited the highest antibacterial activity of 96.9% against S. aureus, achieved by reducing the inner-to-outer flow rate ratio to 0 and concentrating quercetin at the center of fibers. On the other hand, when [Emim]DEP was used as the solvent, balancing the inner-to-outer flow rate ratio to concentrate quercetin in the middle layer of the fiber was optimal for achieving the best antibacterial activity of 93.3% because it promised both the higher encapsulation efficiency and release rate. Computational fluid dynamics (CFD) mathematically predicted the solvent exchange process during triaxial spinning, explaining the influence of IL types and flow rates on quercetin distribution and encapsulation efficiency. It was indicated that optimizing the distribution of antibacterial agents within the fibers can fully unleash its antibacterial potential while preserving the mechanical properties of the fiber. Therefore, the proposed simple triaxial spinning strategy provides valuable insights into the design of biomedical materials.

(Invited) Role of Solvent Exchange Dynamics in the Performance of Metal Anode

Designing resilient and high performing batteries is a critical component in decarbonizing our economy. Facilitating the uniform and fully reversible deposition of the metal anode remains a major roadblock in realizing many battery chemistries, including multivalent batteries. The intrinsic electrolyte properties, such as the solvation phenomena of the working cation, have widely known as critical control factor to facilitate the reversible, dendrite-free, and efficient charge transfer at metal anode. However, predominant work in this field is focused on static view of solvation phenomena, such as structure and composition of first sphere solvation shell, although the solvation process is highly dynamic and driven by solvent and/or anion exchange processes driven by thermodynamic and kinetic equilibrium conditions. In this presentation, we will discuss how exchange, conformal, and re-organizational dynamics of electrolyte constituents around divalent metal cations affects the performance metrics of metal anode based batteries, namely (1) the ionic diffusivity and emerging conductivity of the bulk electrolyte; (2) the de/re-solvation processes of metal cations and emergent overpotential; and (3) the SEI evolution and emerging interfacial impedance. Through this study, we aim to generalize the strategies for designing new electrolyte systems for high-performance batteries by recognizing and regulating the critical role of solvation dynamics of working cations.

Solvent exchange assisted 3D printing of low tortuosity thick electrode for high areal energy density and power density supercapacitors

The pursuit of higher energy density for supercapacitors holds enormous practical significance but remains an arduous task. Three-dimensional (3D) thick electrode has emerged as a promising approach for optimizing the utilization of Z-axis space to enhance the energy density of supercapacitors, yet suffering from the limitations of poor mechanical stability and sluggish electron/ion transport. Herein, a solvent exchange assisted 3D printing technique is proposed in this work that allows for the construction of high mass loading, low tortuosity, and high energy and power density supercapacitors. The electrode is composed of carbon nanotubes and cellulose triacetate that are intertwined to create a 3D network uniformly enveloping around the active carbon. This ensures rapid electron transfer and stress release throughout the electrode. Furthermore, the solvent exchange process induces low tortuosity aligned micro-channels, which act as high-speed paths for ion diffusion, overcoming the limitation of sluggish ion transport in 3D thick electrode as the mass loading increases. As a result, the assembled symmetric supercapacitor delivers a superior rate performance (61.3 %, 1–100 mA cm−2) and cycling stability (94 % after 25000 cycles), and presents an impressive areal energy/power density (0.72 mWh∙cm−2/174.4 mW cm−2), outperforming most reported carbon-based electrochemical double-layer capacitors (EDLC) supercapacitors. This work offers an exciting prospect for the fabrication of high-performance energy storage devices with exceptional areal and power energy density, addressing the challenges faced in an energy-fraught era.

Evolutionary Reinforcement of Polymer Networks: A Stepwise-Enhanced Strategy for Ultrarobust Eutectogels.

Gel materials are appealing due to their diverse applications in biomedicine, soft electronics, sensors, and actuators. Nevertheless, the existing synthetic gels are often plagued by feeble network structures and inherent defects associated with solvents, which compromise their mechanical load-bearing capacity and cast persistent doubts about their reliability. Herein, combined with attractive deep eutectic solvent (DES), a stepwise-enhanced strategy is presented to fabricate ultrarobust eutectogels. It focuses on the continuous modulation and optimization of polymer networks through complementary annealing and solvent exchange processes, which drives a progressive increase in both quantity and mass of the interconnected polymer chains at microscopic scale, hence contributing to the evolutionary enhancement of network structure. The resultant eutectogel exhibits superb mechanical properties, including record-breaking strength (31.8MPa), toughness (76.0MJ m-3 ), and Young's modulus (25.6MPa), together with exceptional resistance ability to tear and crack propagation. Moreover, this eutectogel is able to be further programmed through photolithography to in situ create patterned eutectogel for imparting specific functionalities. Enhanced by its broad applicability to various DES combinations, this stepwise-enhanced strategy is poised to serve as a crucial template and methodology for the future development of robust gels.

Measuring Solvent Exchange in Silica Nanoparticles with Rotor-Based Fluorophore.

Measuring the diffusivity of molecules is the first step toward understanding their dependence and controlling diffusion, but the challenge increases with the decrease of molecular size, particularly for non-fluorescent and non-reactive molecules such as solvents. Here, the capability to monitor the solvent exchange process within the micropores of silica with millisecond time resolution is demonstrated, by simply embedding a rotor-based fluorophore (thioflavin T) in colloidal silica nanoparticles. Basically, the silica provides an extreme case of viscous microenvironment, which is affected by the polarity of the solvents. The fluorescence intensity traces can be well fitted to the Fickian diffusion model, allowing analytical solution of the diffusion process, and revealing the diffusion coefficients. The validation experiments, involving the water-to-ethanol and ethanol-to-water solvent exchange, the comparison of different drying conditions, and the variation in the degree of cross-linking in silica, confirmed the effectiveness and sensitivity of this method for characterizing diffusion in silica micropores. This work focuses on the method development of measuring diffusivity and the high temporal resolution in tracking solvent exchange dynamics over a short distance (within 165nm) opens enormous possibilities for further studies.

A Shape Memory Hydrogel with Excellent Mechanical Properties, Water Retention Capacity, and Tunable Fluorescence for Dual Encryption.

Information encryption platforms with reliable encryption performance, excellent mechanical performance, and high water retention capacity are highly desired. In this study, a tough double-network hydrogel is designed using the first network of a polyion complex containing lanthanide complexes via one-pot polymerization and the second network of a poly (N-hydroxyethyl acrylamide) (PHEAA) obtained by deep eutectic solvent (DES)-assisted introduction and subsequent photopolymerization. In this system, the pH-induced shape memory function and pH-/wavelength-dependent fluorescence allow the use of the prepared hydrogel as a dual-encryption platform. Owing to its high response reversibility, the hydrogel-based platform exhibits both a high security level and the advantages of rewritability, reprogrammability, and reusability. Additionally, the excellent mechanical properties and water retention capacity owing to the solvent exchange process involving the low-volatility solvent DES and the resulting introduction of the second network of PHEAA offer high practical application value for the hydrogel-based dual encryption platform, demonstrating its potential for information security protection.

Solubilization of chitosan in biologically relevant solvents by a low-temperature solvent-exchange method for developing biocompatible chitosan materials

Chitosan has great potential for biomedical applications. However, the intractable solubility of chitosan is a major bottleneck hampering its utilization. In this work, we report a low-temperature solvent-exchange method to solubilize chitosan in biologically relevant solvents (bio-solvents) including water, salines, and cell culture media. Chitosan was firstly dissolved in ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate (EMIM Ac). The chitosan/IL solution was then dialyzed against bio-solvents at 4 °C, during which a solvent exchange process took place. At the end of 24 h dialysis, aqueous chitosan pseudosolutions formed. Low temperature is found to be crucial for efficient solubilization of chitosan during the solvent exchange process. Increasing temperature to 50 °C leads to the formation of solid chitosan hydrogel. Chitosan in the water-based pseudosolution presents as positively charged particles. The pseudosolution shows a high positive zeta potential of about +52.6 mV and good colloidal stability. The water-based pseudosolutions with different amounts of chitosan contents exhibit the rheological features of weak liquid gels. By using these pseudosolutions, the fabrication of various chitosan materials is realized readily. Both chitosan pseudosolution and its downstream products are highly biocompatible. In this strategy, using IL as a solvent-medium and processing a low-temperature solvent exchange are the two key parameters to solubilize chitosan.

Greatly Intensified Guest Exchange Strategy for Highly-Efficient Activation of Metal-Organic Frameworks.

The preservation and accessibility of pores are prerequisites to the application of metal-organic frameworks (MOFs). Activation is a key step to eliciting rich features of pores, but it needs a repeated solvent-exchange process which is tedious and time/cost-consuming. Herein, a facile strategy for highly-efficient activation of MOFs utilizing rotating packed bedis proposed. With the tremendous enhancement of molecular mixing and mass transfer in high-gravity and strong-shearing surrounding, nine representative MOFs are completely activated within 2h without structural change. Compared with conventional process, this activation displays surprising efficiency by accelerating the diffusion of solvents and redissolution of residual reactants in the pores. The complete activation time can be significantly shortened by over 90%. As a proof-of-concept, the methane storage of as-activated UiO-66 is five times that of as-synthesized UiO-66. This strategy provides a potential platform with industrial worth for the activation of MOF materials with ultra-high efficiency and versatility.

Synergetic Self-Assembly of Liquid Crystalline Block Copolymer with Amphiphiles for Fabrication of Hierarchical Assemblies.

Novel functions and advanced structure, where each single component could not be produced individually, can exhibit from the collective and synergistic behavior of component systems. This synergetic strategy has been successfully demonstrated for co-assembly of polymer-polymer to construct hierarchical nanomaterials. However, differences in the natures of polymer and small molecules impose challenges in the construction of sophisticated co-assemblies with geometrical and compositional control. Herein, a synergetic self-assembly strategy is proposed to prepare organic-organic hybrid colloidal mesostructures by blending a liquid crystalline block copolymer (LC-BCP) with small molecular amphiphiles. Through a classic solvent-exchange process, amphiphiles embedded with LC-BCP realize multi-component nucleation and hierarchical assembly driven by anisotropic interaction from the LC ordering alignment of the core-forming block. 1D nanofibers with a periodic striped structure are formed by further LC component fusion and refinement. In addition, LC ordering effect of LC-BCP can be regulated by selecting appropriate solvents and leads to the formation of vesicular co-micelles. By means of the thermal-responsive behavior of amphiphiles, hexagonal pore arrays are finally generated on the surface of those vesicles.

Donor-acceptor based enhanced electrochemiluminescence of coumarin microcrystals: Mechanism study and sensing application

Simple and efficient strategy to obtain ideal organic electrochemiluminescence (ECL) luminophores still is a central challenge. Here a series of coumarin microcrystals (C545 MCs) as new generation of ECL luminophores were facilely synthesized by a solvent exchange process. Among them, leaf-like C545 MCs with donor-acceptor system display a stable and robust anodic ECL response with triethanolamine (TEOA) as coreactant, which is 9.28 times higher than that of C545 monomer. Combined with its predecessors (coumarin and coumarin 6 H), the effects of donor and acceptor on the ECL properties of C545 were investigated with the help of experiments and theoretical calculation. On the basis of the quenching effect of dopamine (DA) toward the C545 MCs-TEOA ECL system, it was employed to construct a sensitive sensing platform for DA detection. A low limit of detection (0.38 nmol·L−1, S/N = 3) is obtained in a wide linear range (1 nmol·L−1 – 1 mmol·L−1). This work forcefully enriches the design and application of donor-acceptor based coumarin materials in ECL sensing.

Preferential solvation and solvato(fluor)chromism of a green synthesized carbon nanodots in aqueous low molecular weight alcohols

Solvent medium effects on the optical spectra of a carbon nanodot (C-dots) as a solvato(fluor)chromic indicator have been investigated. The molar fluorescence transition energies of C-dots in different aqueous low molecular weight alcohols (C1-C3) were interpreted in terms of the Kamlet, Abboud and Taft equation. Emission results demonstrate that acidity is the most influential feature for the case of lighter methanol and ethanol, whereas the polarizability of the mixed solvent was the dominant factor for the propanol. The preferential solvation of the C-dots under consideration in the mixed water/alcohol solvents has been studied and were analyzed using two different models. In words, solvent exchange process and an excess function model were employed to evaluate the extent of preferential solvation. Correspondingly, both models exploited, confirmed the tendency of C-dots to be preferably solvated by alcohols rather than water. Interestingly, with an increase in the length of the alcohol carbon chain the extent of preferential solvation illustrated a decreasing trend.

Scalar transport and nucleation in quasi-two-dimensional starting jets and puffs

We experimentally investigate the early-stage scalar mixing and transport with solvent exchange in a quasi-two-dimensional (quasi-2D) jet. We inject an ethanol/oil mixture upward into quiescent water, forming quasi-2D turbulent buoyant jets and triggering the ouzo effect with initial Reynolds numbers, Re0=420,840, and 1680. We study two different modes of fluid supply: continuous injection to study a starting jet and finite volume injection to study a puff. While both modes start with the jet stage, the puff exhibits different characteristics in transport, entrainment, mixing, and nucleation, due to the lack of continuous fluid supply. We also inject a dyed ethanol solution as a passive scalar reference case, such that the effect of nucleation for the ethanol/oil mixture can be disentangled.For the starting jets, the total nucleated mass from the ouzo mixture seems very similar to that of the passive scalar total mass, indicating a primary nucleation site slightly above the virtual origin above the injection needle, supplying the mass flux like the passive scalar injection. With continuous mixing above the primary nucleation site, the mildly increasing nucleation rate suggests the occurrence of secondary nucleation throughout the entire ouzo jet.For the puffs, we show that the puff with the smallest Re0 propagates the fastest and its entrainment lasts the longest. We attribute the superior performance to the buoyancy effect, which transforms a turbulent puff into a turbulent thermal, and has been proven to have stronger entrainment. Although the entrainment and nucleation reduce drastically when the injection stops, the mild mixing still leads to non-zero nucleation rates and the reduced decay of the mean puff concentrations for the ouzo mixture.Adapting the theoretical framework established in Landel et al. (2012b) for quasi-2D turbulent jets and puffs, we successfully model the transport of the horizontally-integrated concentrations for the passive scalar. The fitted advection and dispersion coefficients are then used to model the transport of the ouzo mixture, from which the spatial–temporal evolution of the nucleation rate can be extracted. The spatial distribution of the nucleation rate sheds new light on the solvent exchange process in transient turbulent jet flows.

Biorenewable Polymer-Based Light-Absorbing Porous Hydrogel for Efficient Solar Steam Desalination.

An efficient interfacial heating system composed of a light-absorbing material and a hydrophilic porous support is developed through eco-friendly and energy-effective fabrication processes. Lignin nanoparticles (NPs) and cellulose nanofibers (CNFs) are harnessed as biorenewable light absorbers and hydrophilic supports, respectively. Lignin NPs are prepared using a solvent exchange process of the fractionated lignin with organic solvents to improve its π-π stacking and light-absorbing property for efficient photothermal conversion. Then, the lignin NPs are mixed with CNFs and lyophilized to obtain a light-absorbing porous hydrogel (LAPH), and the resulting LAPHs are covalently cross-linked and hybridized with Au NPs through a seed-mediated growth to further enhance their mechanical stability, hydrophilicity, and photothermal conversion properties. The resulting LAPHs exhibit an outstanding and prolonged performance as a solar steam generator such as high salt and pH tolerance, evaporation rate (3.17 kg m-2 h-1), and solar steam generation efficiency (83.4%) under 1 sun irradiation.

PVDF/Clay Spheres Obtained through Phase Inversion for Cu Ion Removal.

In this study, spheres of poly (vinylidene fluoride)/clay were synthesized using an easy dripping method (also known as phase inversion). The spheres were characterized by scanning electron microscopy, X-ray diffraction, and thermal analysis. Finally, application tests were carried out using commercial cachaça, a popular alcoholic beverage in Brazil. The SEM images revealed that during the solvent exchange process for sphere formation, PVDF tends to form a three-layered structure with a low-porosity intermediate layer. However, the inclusion of clay was observed to reduce this layer and also widen the pores in the surface layer. The results of the batch adsorption tests showed that the composite with 30% clay content in relation to the mass of PVDF was the most effective among those tested, with the removal of 32.4% and 46.8% of the total copper present in the aqueous and ethanolic media, respectively. The adsorption of copper from cachaça in columns containing cut spheres resulted in adsorption indexes above 50% for samples with different copper concentrations. Such removal indices fit the samples within the current Brazilian legislation. Adsorption isotherm tests indicate that the data fit better to the BET model.