Mixed Solvent Of Water Research Articles

Broadband Circularly Polarized Luminescent Films Based on the Heterogeneous Assembly of Cellulose Nanocrystals.

Broadband circularly polarized films display promising applications for multiwavelength lasers and "smart" windows in buildings. Herein, broadband films are fabricated through the heterogeneous assembly of cellulose nanocrystals (CNCs) and thermoplastic polyurethane (TPU) particles in mixed solvents of water and DMF. During the heterogeneous assembly process, a portion of the small TPU particles coassembled with CNCs to form chiral nematic structures and another portion of the TPU particles fused together to form large aggregates. These large aggregates are located around the helical structures of CNCs and induce a twisting effect on the helical axis of the chiral nematic phase. Helical axis twisting continuously occurs in various directions, leading to broad-band reflections of the films. Additionally, multicolor and white right-handed circularly polarized luminescent (CPL) films have been attained by integrating three organic dyes into the chiral structures of CNCs. A high dissymmetry factor value of -0.47 was achieved for the white CPL film.

Complex Phase Transitions of Fully Rigid Sphere-Rod Amphiphiles Induced by Solvent Polarity in Dilute Solutions.

We report complex macrophase and microphase transitions of rigid amphiphiles with spherical Keggin molecular clusters as the solvophilic block and rod-like rigid oligofluorene (OF) as the solvophobic block in mixed solvents of water and polar organic solvent. By properly adjusting the solvent polarity, the amphiphiles are found to respond accordingly by self-assembling into multilayered incomplete onion-like structures (10-25 vol % THF), single-layered vesicular structures (60 vol % THF), and an unexpected macrophase separation in the middle (40-50 vol % THF), which is due to the anomalous trends in Keggin solubility as a result of the nature of TBA+ counterions. The rigidity of the OF block prevents the amphiphile from assembling by following the rule of packing parameters; instead, interdigitation among different rods leads to the formation of the solvophobic domain to achieve self-assembly. The incomplete onion structures are controlled by the interdigitation of rigid rods for the number of layers and the electrostatic interaction among Keggin head groups for the interlayer distance. When the degree of interdigitation becomes lower, the self-assembly process shows a trend that can be explained by the traditional rule of packing parameter. This study demonstrates the formation of different self-assembled structures by rigid amphiphiles and their transitions induced by solvent composition. The self-assembly (microphase separation) of rigid amphiphiles in a dilute solution could indeed represent a broad area containing complicated, uncharted rules.

Gold Nanoclusters Whose Photoluminescent Properties are Dynamically Tunable by Modulating the Assembly Pathway Complexity.

Modulating the assembly pathway is an indispensable strategy for optimizing the performance of optical materials. However, implementing this strategy is nontrivial for metal nanocluster building blocks, due to the limited functional modification of nanoclusters and complexity of their emission mechanism. In this report, we demonstrate that a gold nanocluster modified by 4,6-diamino-2-pyrimidinethiol (DPT-AuNCs) self-assembles into two distinct aggregation structures in methanol (MeOH)/water mixed solvent, thus exhibiting pathway complexity. Kinetic studies show that DPT-AuNCs firstly assembles into non-luminescent nanofibers (kinetically controlled), which further transforms into strongly luminescent microflowers (thermodynamically controlled). In-depth analysis of the assembly mechanism reveals that the transformation of aggregation structures involves the disassembly of nanofibers and a subsequent nucleation-growth process. Temperature-dependent photoluminescence (PL) spectroscopy and infrared (IR) measurements reveal that inter-cluster hydrogen bonding bridged by solvent molecules and C-H⋅⋅⋅π interaction are the key factors for emission enhancement. The photoluminescent property of DPT-AuNCs can be controlled by varying the cosolvent in water, enabling DPT-AuNCs to distinguish different kind of alcohols, particularly the isomerism n-propanol (NPA) and isopropanol (IPA). Additionally, the addition of seeds effectively regulate the assembly kinetics of DPT-AuNCs. This study advances our understanding of assembly pathways and improves the luminescent performance of nanoclusters (NCs).

A New Polymorphic Form of Maltol: Crystallization and Structure Refinement

AbstractA new polymorph of maltol, a food and intermediate pharmaceutical material, is discovered through solution crystallization process using a mixed solvent of water and ethanol with l‐menthol as an additive. It belongs to monoclinic crystal system with lattice parameters: a = 7.136(8) Å, b = 24.23(3) Å, c = 7.020(8) Å, and β = 106.22(3)°, volume = 1165 (2) Å3 and the refinement factor is R = 6.64%. With single crystal X‐ray diffraction (SCXRD) data as input, the intermolecular interactions between the new polymorph of maltol is investigated through Hirshfeld surface analysis, the higher percentage of overall interaction between the polymorph (H…H) interaction, and the (O…H) interaction contributes more to the generation of new polymorph. The 2D finger print plot depicts the interactions are mainly due to the hydrogen bonds.

Copper complex@Paclitaxel: A new dual-functional fluorescent-responsive composite material and treatment on esophageal cancer cells

Esophageal cancer (EC) is a common and fatal malignant tumor of the digestive tract, characterized by high morbidity and mortality. Despite advances in surgery, radiotherapy, and anti-cancer drugs, the five-year survival rate remains low. Therefore, exploring effective therapeutic agents to inhibit the proliferation and invasion of EC is crucial. In this study, a novel coordination polymer CP1 was synthesized by reacting the bifunctional ligand 2,5-bis(1H-1,2,4-triazol-1-yl)terephthalic acid (H2dttpa) containing carboxylic acid and triazolyl groups with Cu(NO3)2·3H2O in a mixed solvent of water and N,N-dimethylformamide. Structural analysis revealed that CP1 adopts a two-dimensional layered network with a trinodal (3,4,4)-connected topology. Furthermore, CP1 exhibits excellent fluorescent properties due to charge transfer from the ligand to the metal, making it suitable for selective and sensitive fluorescence sensing of Fe3+ with a quenching efficiency of up to 90.5 %. This indicates the potential application of CP1 as a fluorescent sensor for Fe3+ detection. Moreover, paclitaxel was selected as a model drug to form a prodrug (CP1@Paclitaxel) with hydrogen bonding enhancing the interaction between the prodrug and CP1. The photothermal properties of CP1@Paclitaxel were investigated, showing an increase of 13 °C and 25 °C, respectively, in a concentration-dependent manner. The therapeutic activity of the newly synthesized system against EC cancer was evaluated, and its specific mechanism of action was investigated. This design provides a novel approach to address drug delivery issues in EC and offers a flexible strategy for expanding the biomedical applications of metal–organic frameworks (MOFs).

Eco-friendly preparation of polyimide/boron nitride composite films with excellent thermal conductivity and mechanical properties

Polyimide/hexagonal boron nitride (PI/BN) composite films have attracted interest as heat dissipation materials for advanced microelectronic devices. However, conventional preparations of PI/BN composite films employ harmful and expensive high-boiling organic solvents. In this work, thermally conductive PI/BN composite films were, for the first time, prepared using a nontoxic, eco-friendly, and inexpensive aqueous solvent. BN was ultrasonically exfoliated in a mixed solvent of water and tert-butanol to obtain aqueous BN suspensions, in which a poly(amic acid) salt (PAAS) was synthesized. The PAAS/BN suspensions were then drop-casted, and thermally imidized into PI/BN composite films. The PI/BN films exhibited excellent in-plane and out-of-plane thermal conductivities (up to 15.043 W/mK and 1.142 W/mK, respectively), which is attributed to the effective exfoliation and dispersion of BN in the aqueous solvent. Furthermore, these films exhibited high tensile strength, flexibility, and thermal stability.

Dispersibility of γ-MPS-modified silica sol particles in an ethanol–water mixed solvent

The dispersibility of silica sol particles modified by γ-methacryloxy propyl trimethoxyl silane (γ-MPS) in an ethanol–water mixed solvent was investigated. In the modification process, the hydrolysate of γ-MPS condensed to form oligomers, which further formed hydrogen bonds with the hydroxyl groups on the surface of the silica sol particles to cause agglomeration. Increasing the ethanol concentration inhibited the hydrolysis of γ-MPS and the formation of oligomers, thus inhibiting the agglomeration of silica sol particles. When the ethanol concentration was above 74 wt%, the γ-MPS-modified silica sol slurry was transparent and with a TEM image in a single-particle dispersed state. The dispersibility of the silica sol particles was determined by a double electric layer repulsion mechanism before modification and a steric hindrance mechanism by organic molecules grafted on the surface of the particles after modification. The grafting density of γ-MPS on the surface of silica sol particles affected the hydrophobicity of the modified particles, which can be effectively controlled.

Probing pharmaceutically important amino acids L-isoleucine and L-tyrosine Solubilities: Unraveling the solvation thermodynamics in diverse mixed solvent systems

The study specifically investigates the solubilities of L-isoleucine and L-tyrosine in water-mixed solvent systems (DMF, DMSO, and ACN), exploring the behaviour of amino acids in complex environments. The experimental methods prioritize meticulous solvent purification to ensure reliable results. The work explores solubility data, uncovering temperature-dependent trends and intricate interactions influencing solubility in the chosen mixed solvent systems. The study emphasizes the impact of thermodynamic properties, solvent-solvent interactions, and amino acid structure on solubility patterns. The broader implications highlight the relevance of understanding amino acid behaviour in diverse solvent environments, offering potential applications in cosmetics and pharmaceutical industries. The distinct solubility patterns contribute valuable insights, enhancing on the understanding of the solution stability and interactions of L-isoleucine and L-tyrosine in different solvent systems. In conclusion, work suggests the enhanced utilization of L-isoleucine and L-tyrosine in various industries, driven by a profound understanding of their solubility in mixed solvent systems. The research expands our knowledge of amino acid behaviour, paving the way for advancements in industries relying on protein-based products and technologies.

Crystal growth and characterization of glycine chlorzoxazone nonlinear optical crystal for energy storage capacitor applications

This research presents the synthesis of a glycine chlorzoxazone (GC) organic single crystal through a slow evaporation process using a mixed solvent of water and ethanol at room temperature. The crystal's functional group coordination is examined via fourier-transform infrared (FTIR) spectroscopy. The study delves into the linear optical properties through UV–visible spectroscopy, and thermal analyses provide insights into the material's thermal behavior. Optical nonlinearity is confirmed using the Kurtz-Perry powder technique. The investigation extends to the electrical properties of prepared crystals, incorporating a combination of AC and DC electrical studies. This comprehensive approach enhances our understanding of the multifaceted characteristics of synthesized crystal, positioning it as a promising candidate for different electronic and optical applications.

A new Cd(II) Complex: Fluorescence Performances, Loading with Budesonide-hydrogels on Pediatric Asthma and Molecular Docking.

By applying the phosphonic acid ligand to the solvothermal reaction of nitrobenzylphosphonic acid (H2L) with Cd(NO3)2·4H2O in a mixed solvent of water and DMF, a novel Cd(II)-based coordination polymer, {[Cd(L)(H2O)2](H2O)}n (1), was successfully synthesized in this study. The excellent fluorescence performance of complex 1 was confirmed through fluorescence spectroscopy testing, and the obtained CIE standard coordinates (0.1599, 0.0786) positioned it in the blue fluorescence region. Transparent hyaluronic acid/carboxymethyl chitosan hydrogels were prepared using chemical synthesis, and their internal microstructure was observed. Using budesonide as a drug model, a new budesonide metal gel was prepared, and its therapeutic efficacy in treating pediatric asthma was evaluated. Molecular docking simulations indicated that the Cd complex formed three hydrogen bonding interactions with the target protein through its nitro group, revealing the potential origin of its biological activity.

Solubility of Gallic Acid in Single and Mixed Solvents

Gallic acid, known for its biological activity contributing to human health, including antioxidant, anti-inflammatory, anticancer, and antimutagenic properties, was the focus of this study. The solubility of gallic acid was experimentally measured in pure and mixed solvents of water, ethanol, and acetic acid and predicted using the COSMO-SAC model and the Hansen solubility parameter. The Hansen solubility parameter method predicted a higher solubility of gallic acid in pure water than in pure ethanol, and in a mixed solvent, it predicted the maximum solubility at 80% water content, showing different results from the experimental data trends. However, using the molar volume obtained from COSMO calculations resulted in a tendency that matched the experimental results. The results revealed higher solubility in ethanol compared to water, with the solubility in mixed solvent falling within the range between them. Using the same method, the Hansen solubility parameter obtained was applied to acetic acid/water and acetic acid/ethanol mixtures, and similar trends were observed compared to experimental data. In particular, gallic acid in the acetic acid/water mixture solvent exhibited maximum solubility, and this phenomenon was well-predicted. As the temperature increased, solubility in both pure and mixed solvents also increased. While the COSMO-SAC model effectively captured this trend, the predicted solubility values were slightly lower than the experimental data. The solubility trends depending on solvent types were confirmed by comparing the σ-profiles of each compound. The σ-profile of gallic acid closely resembled that of ethanol, and this result led to higher solubility than water and acetic acid. The maximum solubility in ethanol/water and acetic acid/water mixed solvents could be anticipated when two solvents with significant differences in their σ-profiles are mixed in an appropriate ratio.

Green synthesis of polyimide by using an ethanol solvothermal method for aqueous zinc batteries.

Polyimides (PIs) are welcomed by battery researchers because of their exceptional heat resistance, structural design versatility, and ion-bearing capabilities. However, most of the reported PIs are synthesized by using toxic and hazardous reagents, such as ethylenediamine, p-phenylenediamine, 1-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), etc., which are not conducive to environmentally friendly development. In this paper, we aim at employing green solvents and raw materials to prepare PIs using a facile solvothermal method. The reactants are urea and 1,4,5,8-naphthalene tetracarboxylic acid dianhydride (NTCDA). The solvents include pure water, pure ethanol, or water-ethanol mixed solvent. The volume ratio of ethanol in the mixed solvent is regulated to obtain the optimum synthesis condition. Depending on the proportion of ethanol, the polyimide products are labeled as U-PI-0, U-PI-50, U-PI-100, etc. The polymerization degree and structure of synthesized PIs are characterized by gel permeation chromatography (GPC), X-ray diffraction (XRD), scanning electron microscopy (SEM), etc. The results indicate that U-PIs exhibit diverse morphological features, including small fragmented, strip-like, and sheet-like structures, and have relative molecular weights ranging from 7500 to 83 000. Notably, the sheet-like U-PI-100 possesses the largest specific surface area, reaching up to 4.20 m2 g-1. When employed as an electrode material in aqueous zinc batteries, U-PI-100 demonstrates superior electrochemical performance compared to others. At a charge-discharge rate of 0.05C, the initial charge/discharge capacity of U-PI-100 is measured to be 314.2/443.7 mA h g-1.

Synthesis of novel 2D ZIF-8 single sheet from bulk multilayed ZIF-8 crystal, through facile mixed solutin strategy, with enhanced photocatalytic performance

Zeolitic Imidazole framework (ZIFs) have got an immense interest in many fields, due to its porous and functional structure with a tunable shape. The functional structure of ZIF-8 in 2D shape will combine both the characteristics of MOFs in 2D shape with unique properties. In this work, 2D thin Zeolitic imidazole framework (ZIF-8) has been prepared in a mixed solvent of water and methanol. The precursors of ZIF-8 in mixture solvent leads to a bulk multilayered ZIF-8 structure. Then the bulk layered ZIF-8 was delaminated into single sheets through physical sonication. The ZIF-8 sheets were investigated with different characterization techniques where, the hexagonal thin sheets with thickness around 200 to 250 nm in size, shows high stability with controlled morphological shape. ZIF-8 sheets show excellent performance for MB degradation and 94.05 % of dye has been removed as compared with 3D normal ZIF-8 crystals which only removed 67.7 % of MB dye. Furthermore, the optical and electrochemical performance shows that, the 2D ZIF-8 has better electrochemical values and confirm the effective separation of photo-generated charges, compared with ZIF-8 crystals.

Determination of naproxen in mixtures of water and an organic solvent based on chemiluminescence of reaction mixtures containing europium ions

A simple and sensitive method, based on chemiluminescence of a reaction system containing europium(III) ions, for determination of naproxen in mixed solvents of water and an organic solvent (methanol, ethanol, 1-propanol, 1-butanol and acetonitrile) is proposed. Organic solvents are often used in the preliminary procedures of sample preparation for determination of active ingredients. The method is based on chemiluminescence accompanying naproxen oxidation by Ce(IV) ions in the environment of sulfuric acid, sensitized with europium(III) ions. This environment ensures stable and reproducible conditions of measurements in water and mixed solvents. In such a system a linear relation was observed between the integrated intensity of chemiluminescence in the spectral range λ > 585 nm and naproxen concentration in the range from 6 × 10−8 molL−1 to 6 × 10−6 molL−1, and with the limit of detection of 1.5 × 10−8 molL−1 (0.004 μg/mL). The relation is described by the same linear equation in water and in mixed solvent of water and 0.1–20 % (v/v) of an organic solvent. The method is characterized by high tolerance of the presence of foreign substances, including other nonsteroid anti-inflammatory drugs (NSAIDs). The proposed method has been successfully used for determination of naproxen in pharmaceutical formulations and samples of human urine subjected to preliminary treatment with alcohol or acetonitrile.

Antisolvent Effects of C1–C4 Primary Alcohols on Solid-Liquid Equilibria of Potassium Dihydrogen Phosphate in Aqueous Solutions

The focus of this study was to examine antisolvent effects, which hold significance in particulate processes, such as crystallization and precipitation. In the first section, an experimental investigation revealed that C1–C4 primary alcohols significantly reduced the solubility of potassium dihydrogen phosphate (KDP) in water. The solid–liquid equilibria of KDP solutions were determined using an innovative polythermal method, demonstrating time and labor efficiency compared to the traditional isothermal method while maintaining solubility determination quality. This achievement established an efficient tool for high-throughput solvent screening, a crucial aspect of particulate process development. In addition to the experimental approach, in the second part, the influence of these alcohols on KDP solubility was analyzed using the eNRTL thermodynamics model. The model’s estimated parameters confirmed that the addition of these alcohols induced strong non-ideal behavior in the solutions, altered interactions between solute species and solvent components, and reduced KDP solubility. Under the effects of these alcohols, KDP solubility generally increased with the length of the alkyl chain in the added alcohols, although methanol deviated from this observation. Furthermore, the present work also discussed the limitation of the well-known Bromley’s equation, particularly when applied for KDP in alcohol–water mixed solvents. Consequently, binary and ternary systems consisting of KDP, water, and C1–C4 primary alcohols were successfully modeled using eNRTL. Furthermore, it was determined that the obtained model was insufficient for quaternary systems with a higher alcohol content, particularly when high-order interactions were neglected as in the cases of binary and ternary systems. In short, these investigated alcohols have potential for future applications in the design of particulate processes, with a particular emphasis on antisolvent crystallization.

Treatment activity of the injectable hydrogels loaded with dexamethasone In(iii) complex on glioma by inhibiting the VEGF signaling pathway

Abstract In this work, a novel In(iii) coordination polymer, i.e., {[In(L)(im)(H2O)](H2O)} n (1) was produced from the synthetic reactions in water and dimethylformamide mixed solvents and using methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylic acid (H2L) and imidazole (Him) as the co-ligands, and then successfully loaded with dexamethasone. The injectable hydrogels were prepared from natural polysaccharide hyaluronic acid with good biocompatibility and successfully loaded with In(iii) complex. The suppressive inhibitory effect of hydrogels toward U251 human glioma cell line viability was assessed using the Cell Counting Kit-8 assay kit, and the relatively expressed levels of the vascular endothelial growth factor signaling pathway were determined by real-time RT-PCR.

Visible Light-Accelerated Photoiniferter Polymerization in Ionic Liquid.

The effect of ionic liquids on the reversible addition-fragmentation chain transfer (RAFT) polymerization mediated by a visible-light-induced photoiniferter mechanism was investigated. N,N-Dimethyl acrylamide was polymerized by photoiniferter polymerization in 1-ethyl-3-methylimidazolium ethylsulfate [EMIM][EtSO4] ionic liquid. We observed a considerable increase in the polymerization rate constants in ionic liquids (ILs), as well as in the mixed solvent of water and the IL, compared to those observed with water alone as the solvent. To demonstrate the robustness of the process, block copolymers with varying block ratios were synthesized with precise control over their molecular weight and mass dispersity (Đ). The very high chain-end fidelity provided by the photoiniferter polymerization in IL was described by using MALDI-ToF MS analysis.

In-situ grown sweet alyssum flowers-like CoMoO4 for high performance hybrid supercapacitors

Effective optimization of the structure and morphology of the electrode materials of supercapacitors is thought to be a viable option for increasing their energy storage capacity. In this stydy, using a simple hydrothermal/solvothermal method, we synthesized nanostructured CoMoO4 (CMO) with a variety of morphologies, including sweet alyssum flowers, hydrangea flowers and rose petals that were grown directly on the surface of Ni foam. Water and mixed solvents of water plus ethanol, water plus ethylene glycol in 1:1 ratio were used in the CoMoO4 synthesis, and referred to as CMO-W, CMO-W:ET, and CMO-W:EG, respectively. Glucose played a vital role in regulating the morphology in different solvent media. CMO-W alyssum flowers benefit from the synergistic effect of high void space and hierarchical structure, which promotes the adequate exposure of numerous active sites, improves structural stability, and improves the energy storage performance. In view of electrochemical performance, the CMO-W electrode outperformed the other two electrodes, with a superior specific capacity of 1060 C g−1 at 0.5 A g−1 and impressive cycle stability at 5 A g−1, with a retention of 79.5 % after 4000 cycles. A hybrid supercapacitor device was built with CMO-W and activated carbon (AC) as the positive and negative electrodes respectively. This device had a notable long-term stability, with a retention of 80.6 % after 4000 cycles and also shown 68.7 Wh kg−1 of energy density at 824 W kg−1 of power density. Furthermore, two devices connected serially illuminated a red light-emitting diode (LED) for up to 6 min.

2D sheet to 1D rod-like morphology regulated self-assembled ZnCo2O4 microstructures under mixed solvent conditions for battery-type supercapacitors

This study examines the effects of the mixed solvent's characteristics on the nucleation and crystal growth processes and the surface morphologies of zinc cobaltite (ZnCo2O4; ZCO) microstructures. We discovered that the number of interaction sites in ZCO microstructures significantly increases when the solvent changes. This influences the material's high crystallinity, phase purity, morphology, and significantly influences its electrochemical conductivity. One with deionized (DI) water and ethanol mixed solvent and the other with DI water and ethylene glycol (EG) to produce mesoporous ZCO with rod-like and sheet-like microstructures, respectively. The ZCO-R delivered a high specific capacity of 468.5 C g−1 (130.13 mAh g−1) at a current density of 1 A g−1 compared to the ZCO-S (351 C g−1 / 97.5 mAh g−1). Additionally, the ZCO-R microstructures showed good rate performance (82% of its initial capacity) and cyclic stability (90% of capacity retention after 5000 cycles) due to their higher surface area and mesopore features. Hence, utilizing mixed solvent conditions to design morphology-controlled electrode materials is a promising approach to enhancing the electrochemical performance of battery-type supercapacitors.

CsPbBr3 nanocrystals as luminescent probe for in situ detection of chloride and iodide ions in water

All-inorganic cesium lead halide (CsPbX3, X = Cl, Br, I) Perovskite nanocrystals (PNCs) are promising new luminescent nanomaterials. However, PNCs are less stable in ambient environments. The fully encapsulated protective layer greatly improves the stability but limits direct contact with substances in the environment, leading to great challenges for luminescent probe applications. We developed a simple approach that hydrogen-bond cross-linking reinforcement to deal with the challenge. Target ACD-PNCs, which use β-CD (β- cyclodextrin) as the ligand with addition of Arginine, were prepared by adding arginine to an ethanol solution of CsPbBr3 stabilized by β-CD. The ACD-PNCs have a luminescence efficiency of 82% and show good stability in external environments including high temperature, humidity, and ethanol–water mixed solvents. It is worth noting that neither arginine nor cyclodextrin alone could have allowed PNCs to perform so well. More interestingly, the hydrogen-bond network permits the passage of chloride and iodide ions. Through the response of luminescence color upon ion exchange, the ACD-PNCs can detect aqueous Cl− and I− with good selectivity and sensitivity. Under optimum conditions, the LOD and % RSD were determined as 3.2*10−6 M and 5.7% for Cl−, 9.0*10−6 M and 6.7% for I−, respectively. To identify halide ions in samples like sweat, saliva, and kelp, conveniently prepared ACD-PNCs test strips were employed. This work provides insights into the design and development of perovskite probes capable of detection in aqueous solution, and also demonstrates the importance of rapidly forming hydrogen-bonding networks when studying such sensing systems.