Surfactant-free synthesis of poly (styrene-co-acrylamide) monodisperse nanoparticles using hybrid flow-to-batch chemistry

We have demonstrated a hybrid flow-to-batch process for synthesizing monodisperse poly(styrene-co-acrylamide) nanoparticles via a surfactant-free emulsion radical polymerization. The flow-to-batch synthesized nanoparticles have a smaller average particle size, tighter particle size distribution, higher molecular weight, and lower molecular weight distribution compared to conventionally batch-synthesized nanoparticles. Our results also indicate that the flow-to-batch synthesized nanoparticles have more hydrophilic acrylamide segments on the particle surface than the batch-synthesized nanoparticles. These results demonstrate that a flow synthesis process can improve the quality of nanoparticles due to the efficient mixing and heat transfer in a flow reactor and simplify the scale up of nanoparticle synthesis in a conventional chemistry lab.     

Nonaqueous and Surfactant-Free Synthesis Routes to Metal Oxide Nanoparticles

Nonaqueous sol–gel routes to metal oxide nanoparticles have become a promising alternative to aqueous methods, allowing the controlled synthesis of a variety of metal oxides as highly crystalline products at comparably low temperatures. The use of solvents like benzyl alcohol that also function as surface modifiers makes the addition of surfactants superfluous, resulting in improved product purity. In addition to a short overview of such nonaqueous routes to binary and ternary metal oxides, the facile synthesis of sodium and potassium niobates as well as of sodium tantalate and barium stannate nanoparticles via straightforward, surfactant-free pathways is reported.     

Synthesis of high magnetization hydrophilic magnetite (Fe3O4) nanoparticles in single reaction—Surfactantless polyol process

High magnetization hydrophilic magnetite nanoparticles have been synthesized in two different batches with mean particle sizes of 32.3 and 9.2 nm by inexpensive and surfactant-free facile one-pot modified polyol method. In the synthesis, polyethylene glycol was used as a solvent media and it has been found to play a key role to act as a reducing agent as well as a stabilizer simultaneously. It was shown that the size of the nanoparticles can be effectively controlled by modifying the reaction parameters such as reaction temperature, time and polyol/metal precursor ratio. X-ray diffraction and energy dispersive spectroscopy studies confirm the formation of a pure magnetite phase without the presence of any other phases. Transmission electron microscopy and the Fourier transform infrared spectroscopy results reveal that the particle size and surface adsorption properties are very much dependent on reaction parameters. The magnetic properties of the samples measured by physical property measurement system have shown that the as-synthesized magnetite nanoparticles possess a high magnetization of 85.87 emu/g at 300 K and 91.7 emu/g at 5 K with negligible coercivities. The structural and magnetic characterizations of these polyol coated, hydrophilic, monodisperse, superparamagnetic nanoparticles clearly indicate that they are suitable for biomedical applications.     

Preparation of lamellar magnesium hydroxide nanoparticles via precipitation method

Lamellar magnesium hydroxide (MH) nanoparticles were synthesized via surfactant-free precipitation method using MgCl₂ ·6H₂O and NaOH as raw materials, urea and ethanol as assistant additives. The products were characterized by XRD, TEM, EDS, FTIR and Raman spectroscopy. It is found that the prepared nanoparticles are almost hexagonal lamellas when ethanol is added into the reaction system, which indicates that ethanol is helpful to regulate the morphology of MH nanoparticles. In addition, high-purity MH nanoparticles can be obtained when urea is employed. Both XRD patterns and EDS analysis suggest that the generation of impurities was prevented by adding urea, particularly, under the condition of high concentration raw materials. The possible purification mechanism is due to the coordination interaction of urea with Mg²⁺, which can prevent the impurity from generating.     

A sonochemical method for synthesis of Fe3O4 nanoparticles and thermal stable PVA-based magnetic nanocomposite

Fe₃O₄ nanoparticles were synthesized via a simple surfactant-free sonochemical reaction. Room temperature synthesis without using inert atmosphere is the novelty of this work. The effect of different parameters on the morphology of the products was investigated. The magnetic properties of the samples were also investigated using an alternating gradient force magnetometer. Fe₃O₄ nanoparticles exhibit a ferromagnetic behavior with a saturation magnetization of 66 emu/g and a coercivity of 39 Oe at room temperature. For preparation magnetic nanocomposite, Fe₃O₄ nanoparticles were added to the polyvinyl alcohol (PVA). Nanoparticles can enhance the thermal stability and flame retardant property of the PVA matrix.     

Self-assembly of gold nanoparticles to silver microspheres as highly efficient 3D SERS substrates

Herein we report a simple, one-pot, surfactant-free synthesis of 3D Ag microspheres (AgMSs) in aqueous phase at room temperature. The 3D AgMSs act as supports to fix the gold nanoparticles (GNPs) in 3D space via the interaction between the carboxyl groups of GNPs and the Ag atoms of AgMSs. The ensemble of AgMSs@GNPs with high surface-enhanced Raman scattering (SERS) activity and sensitivity can be an ideal 3D substrate choice for practical SERS detection applications. The simple self-assembly strategy may be extended to other metallic materials with great potentials in SERS, catalysis, and photoelectronic devices.     

Microwave-assisted synthesis of hybrid colloids for design of conducting films

We report synthesis of colloids with polymer core and inorganic shell consisting of silver nanoparticles (AgNPs) which can be used as building blocks for the preparation of conducting composite films. Polymer colloids based on copolymer of styrene and butyl acrylate with variable film formation temperature and functional surface have been prepared by surfactant-free emulsion polymerization. Polymer particles with average size between 140 nm and 220 nm and narrow size distribution were used as templates for deposition of AgNPs by microwave-assisted reduction of silver precursors in aqueous medium. The loading of the AgNPs on the polymer particle surface has been increased up to 60 wt.-%. Obtained hybrid colloids were used for preparation of composite films. The electrical conductivity of the composite films starts to increase if the AgNPs loading on the polymer particle surface is above 20 wt.-%.     

Facile Synthesis and Catalytic Application of Silver-Deposited Magnetic Nanoparticles

In this work, we have investigated a novel one-step fabrication of Ag-deposited Fe₂O₃ nanoparticles and their application for the catalytic reduction of 4-nitrophenol to 4-aminophenol by NaBH₄. To deposit Ag onto them, Fe₂O₃ particles were dispersed in a reaction mixture consisting of ethanolic AgNO₃ and butylamine, and then the reaction mixture was incubated and shaken for 40 min at 45 °C. With this simple and surfactant-free fabrication of Ag-deposited Fe₂O₃ nanoparticles, we can avoid contamination in the final product, which makes them suitable for further catalytic applications. Since the magnetic particles are readily recovered from the solution phase without centrifugation and/or filtering, the Ag-deposited Fe₂O₃ nanoparticles prepared in this work have been exploited as solid phase catalysts for the reduction of 4-nitrophenol in the presence of NaBH₄. At the end of the reaction, the Ag-deposited Fe₂O₃ catalyst particles still remain active. They can thus be separated from the product, 4-aminophenol, simply using a neodium magnet and can be recycled a number of times.     

Surfactant-free emulsion polymerization of chlorotrifluoroethylene with vinylacetate or vinylidene fluoride

A surfactant-free emulsion process has been developed for the preparation of copolymers of chlorotrifluoroethylene with vinylacetate or vinylidene fluoride. A redox initiator system, consisting of sodium-meta-bisulfite, t-butylhydroperoxide, and ferrous sulfate heptahydrate, has been found to be effective in preparing self-emulsifying fluoropolymers with a monodisperse particle size distribution, having up to 45% polymer solids in water. Over the range studied in this investigation, the particle number and the ultimate particle size is linearly related to the quantity of initially charged redox catalyst. Under conditions of optimal catalyst concentrations, a greater number of particles is produced in the surfactant-free process than that which can be obtained using conventional fluorosurfactants. Particle number is defined at the earliest stage of polymerization and remains constant throughout the polymerization, unless surfactant is postadded to the surfactant-free latex at a very early stage in the polymerization. The aqueous phases of various latices have been purified by ion-exchange and dialysis, enabling the sulfonic acid-terminated fluoropolymer end groups to be quantified. The highest level of bound sulfonic acid is obtained at elevated temperatures. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 2211–2225, 1998     

Effects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method

ABSTRACT: Three-dimensional (3D) TiO2 hierarchical structures with various microstructures have been successfully synthesized via a surfactant-free and single-step solvothermal route, in which hydrochloric acid (HCl), nitric acid (HNO3), and acetic acid (HAc) are employed as the acid medium, respectively. The effects of acid medium on the microstructures and properties of 3D TiO2 hierarchical structure have been studied. The results indicate that 3D dandelion-like microspheres assembled of radial rutile nanorods are obtained in the sample prepared with HCl. Both the fraction of rutile and the diameter of nanorod enhance with the increasing HCl concentration. For the products derived from either HNO3 or HAc, 3D spheres composed of anatase nanoparticles are present. The 3D dandelion-like TiO2 hierarchical structures show low reflectance and efficient light harvesting since this ordered rod geometry offers a light-transfer path for incident light as well as multiple reflective and scattering effects. Moreover, 3D TiO2 with this unique topology shows superior photocatalytic activity despite low surface area, which can be ascribed to the enhanced light harvesting, fast electron transport, and low electron/hole recombination loss.     

Microgel/clay nanohybrids as responsive scavenger systems

Microgel-clay composite particles were prepared by one-step surfactant-free precipitation polymerization. Laponite nanoparticles present in the reaction mixture become encapsulated during the microgel formation process. Microgel-clay composites based on poly(N-vinylcaprolactam-co-acetoacetoxyethyl methacrylate) containing different amount of incorporated clay nanoparticles were synthesized. The clay content was varied from 2 wt% to 18 wt%. The extremely high incorporation efficiency of the clay nanoparticles into microgels was detected. The size of the hybrid microgels was decreased from 700 nm to 100 nm by increase of the clay concentration in the reaction mixture. Obtained hybrid microgels exhibit negative surface charge and excellent colloidal stability. Microgel-clay composite particles display temperature-sensitive behaviour in water. The swelling degree of the hybrid microgels decreases with increase of the clay loading. Microgel-clay composite particles exhibit temperature-controlled uptake of the cationic dye, Methylene blue, and can be used as scavenger systems in aqueous media.     

Supercritical CO2 based processing of amorphous fluoropolymer Teflon-AF: Surfactant-free dispersions and superhydrophobic films

We report the application of a modified RESS process to create and collect in high yield nanoparticles of an amorphous fluoropolymer, Teflon-AF1600. The nanoparticles with diameters ranging from 10 to 100 nm can be synthesized from polymer solutions in supercritical CO₂ at 300 bar and 60 °C. The nanoparticles are collected by formation of dry ice in a liquid nitrogen-cooled trap. Nanoparticles embedded in dry-ice can be dispersed in organic solvents (acetone, ethanol, and n-heptane) creating surfactant-free dispersions. When dispersed in water, the nanoparticles self-assemble at the air–water interface forming a mechanically robust, superhydrophobic film. The film can support large water droplets (up to volume 250 μL) without breaking and is impermeable to water. The films cast from dispersions as well as those lifted-off water surface, are highly porous and superhydrophobic in nature (water contact angle θ_adv = 162°). This work demonstrates the utility of supercritical fluids based processing of fluoropolymers.     

Amphiphilic core-shell nanoparticles with dimer fatty acid-based aliphatic polyester core and zwitterionic poly(sulfobetaine) shell for controlled delivery of curcumin

Multifunctional nanocarriers are gaining increasing research interest as polymeric platforms for targeted drug delivery in cancer therapy and diagnosis. In this work, preparation and characterization of surfactant-free polyester nanoparticles (NPs) from a bio-based poly(butylene sebacate-co-butylene dilinoleate)s, poly(butylene sebacate) (PBSE)/poly(butylene dilinoleate) (PBDL), using nanoprecipitation, is reported. The polymeric nanoparticles (sizes narrowly distributed in a range less than 100?nm) were loaded with curcumin (CURC) with an encapsulation efficiency of 98% and drug loading (DL) content of 5–10% wt_drug/wt_polymer. The CURC-loaded nanoparticles were efficiently coated with a novel poly(sulfobetaine)-type zwitterionic polymer synthesized by nitroxide-mediated polymerization and postpolymerization functionalization step. Free and CURC formulated into noncoated and poly(sulfobetaine)-type zwitterionic polymer-coated nanoparticles were further investigated for cytotoxicity and antioxidant activity in a panel of human cell lines and rat liver microsomes, respectively. Formulated into coated NPs, CURC has superior cytotoxic and antioxidant activity versus the free drug and CURC incorporated in noncoated NPs. In addition, cell viability experiments of nonloaded nanoparticles, both coated and noncoated, demonstrated that developed nanoparticles are nontoxic, making them potentially suitable candidates for systemic passive targeting in cancer therapy, namely for treatment of solid tumors exhibiting high tumor accumulation of NPs due to enhanced permeability and retention effect. Polyzwitterion-coated nanoparticles exhibited slower drug release compared with the noncoated ones (half as much after 24?h) presumably due to the presence of the polymer shell around nanoparticles associated with a wider diffusion layer around the particles.     

In Vitro Cytotoxicity of Fluorescent Silica Nanoparticles Hybridized with Aggregation-Induced Emission Luminogens for Living Cell Imaging

Fluorescent silica nanoparticles (FSNPs) can provide high-intensity and photostable fluorescent signals as a probe for biomedical analysis. In this study, FSNPs hybridized with aggregation-induced emission (AIE) luminogens (namely FSNP-SD) were successfully fabricated by a surfactant-free sol-gel method. The FSNP-SD were spherical, monodisperse and uniform in size, with an average diameter of approximately 100 nm, and emitted strong fluorescence at the peak of 490 nm. The FSNP-SD selectively stained the cytoplasmic regions and were distributed in the cytoplasm. Moreover, they can stay inside cells, enabling the tacking of cells over a long period of time. The intracellular vesicles and multinucleated cells were increase gradually with the rise of FSNP-SD concentration. Both cell viability and survival only lost less than 20% when the cells were exposed to the high concentration of 100 μg/mL FSNP-SD. Additionally, the cell apoptosis and intracellular ROS assay indicated that FSNP-SD had no significant toxic effects at the maximum working concentration of 80 μg/mL. This study demonstrated that the FSNP-SD are promising biocompatible fluorescent probes for living cell imaging.     

Sonochemical synthesis of CoFe2O4 nanoparticles and their application in magnetic polystyrene nanocomposites

CoFe₂O₄ (CoFe) nanoparticles were synthesized via a facile surfactant-free sonochemical reaction. For preparation of magnetic polymeric films, CoFe₂O₄ nanoparticles were added to polystyrene (PS). Nanoparticles were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Magnetic properties of the samples were investigated using an alternating gradient force magnetometer (AGFM). CoFe₂O₄ nanoparticles exhibit a ferromagnetic behaviour with a saturation magnetization of 62 emu/g and a coercivity of 640 Oe at room temperature. By preparing magnetic films the coercivity is increased. The coercivity of PS/CoFe₂O₄ (10%) nanocomposites is higher than that obtained for PS/CoFe₂O₄ (30%).     

Attachment of solid particles to air bubbles in surfactant-free aqueous solutions

This paper presents a mechanism to explain the attachment of solid particles to air bubbles in surfactant-free aqueous solutions where both solids and air bubbles have the same sign of zeta potential via investigating the mechanical properties of micro air bubbles and the adsorption of hydroxide on air bubble surfaces.Particle-bubble attachment was measured in a Hallimond tube. The results indicate that purified quartz particles attached to air bubbles in surfactant-free deionised water, and the attachment increased with the pH of the aqueous solutions. The mechanical properties of micro air bubbles in aqueous solutions were measured using a novel micromanipulation technique. It was found that the micro air bubbles were pseudo-elastic and spherical in the solutions. The rigidity of the air bubbles decreased with increasing pH of the solutions. When a moving particle with a certain kinetic energy collided with an air bubble in a surfactant-free aqueous solution, the deformation of the air bubble varied with pH of the solution. In an alkaline solution, the micro air bubble was much softer and the deformation was larger than that in an acidic solution. The larger deformation of the softer air bubble resulted in a large contact area between the solid particle and the air bubble, therefore increasing the attachment, and reducing the rebound.The attachment of purified quartz particles to air bubbles in surfactant-free aqueous solutions was possibly due to hydrogen bond formation. The OH⁻ ions on air bubble surfaces formed hydrogen bonds with silicon and oxygen atoms in ≡Si-O-Si≡ or with the adsorbed OH group on quartz surfaces.     

聚苯乙烯磺酸钠掺杂正渗透膜的制备及其性能

通过两步无皂乳液聚合法,改变第二步对苯乙烯磺酸钠的加入量,制备表面携带磺酸根基团量不同的纳米粒子（PSS）,并将其应用于正渗透（FO）膜的制备。采用红外光谱仪（FTIR）和光电子能谱仪（XPS）表征粒子组成,通过扫描电子显微镜（SEM）表征膜的表面和断面形貌,测定膜孔隙率和亲水性,考察表面磺酸根量不同的聚合物粒子对膜结构性能的影响。结果表明,PSS的引入能提高膜的孔隙率,改善膜的亲水性,且随着粒子表面携带的磺酸根基团量增多,膜的孔隙率与亲水性也随之提高。这是因为PSS粒子可以支撑内部孔道,且表面携带的亲水基团-SO3Na可以提高膜的亲水性,影响活性层的形成。所制备的FO膜性能也得到相应改善,水通量达到了61.1L/(m²·h),为纯聚砜膜的2.8倍,盐截留率达到93.2%,J_s/J_v值仅为0.31g/L,性能得到极大提升。     

New developments in the nonaqueous and/or non-hydrolytic sol-gel synthesis of inorganic nanoparticles

The development of nonaqueous and surfactant-free sol-gel routes to metal oxides has become a very active area within the broad field of nanoparticle research, opening up great opportunities to access a wide variety of binary, ternary and doped metal oxide nanoparticles with high crystallinity and well-defined particle morphologies — important parameters towards their application in electrochemistry, (photo)catalysis or gas sensing. Extension to other classes of inorganic nanomaterials such as nitrides and sulfides and energy optimization of the processes by using dielectric heating represents two promising research directions. Remaining future challenges are not only the development of rational synthesis strategies, nanoparticle processing, assembly and patterning into functional and integrated structures, but also the optimization of the synthesis protocol with respect to energy efficiency and waste management. This review aims at giving both an overview of the current state of research as well as a discussion of the perspectives in the area of nonaqueous and/or non-hydrolytic sol-gel technology for the synthesis, processing and application of inorganic nanomaterials.     

Coalescence enhanced synthesis of nanoparticles to control size,morphology and crystalline phase at high concentrations

Size, morphology, and crystalline phase of nanoparticles determine the properties of nanostructured materials. Therefore, the mastery of controlling properties ultimately requires the control of size, morphology, and phase of nanoparticles. From various aerosol methods, highly pure nanoparticles can be produced; however, agglomeration has been considered as almost unavoidable when nanoparticles are generated at high concentrations that are necessary for a practical application. Efforts to control agglomeration have had only limited success. Here we report that the enhancement of coalescence of nanoparticles using laser beam irradiation on aggregates formed in flames can be a solution for this problem and successfully controls the size, morphology, and crystalline phase of high concentration nanoparticles of silica and titania. We demonstrate this principle by not only synthesizing smaller and unagglomerated nanoparticles, but also generating them in high concentrations. In addition, we show that the present method is capable of even controlling the crystalline phase of titania nanoparticles. Surprisingly, stable rutile titania particles have been transformed into metastable anatase and the weight percent of each phase could be controlled.