PLURONIC x TETRONIC polyols: study of their properties and performance in the destabilization of emulsions formed in the petroleum industry

In this work, a new family of branched poly(ethylene oxide-propylene oxide) (PEO-PPO) block copolymers designed as TETRONIC polyols is evaluated and compared to linear PEO-PPO block copolymers designed as PLURONIC polyols. Additives have been employed as well in order to improve solubility of these materials in aqueous solution. Such additives include the sodium p-toluene sulfonate (NaPTS) hydrotrope and concentrated hydrochloric acid. Solubility tests and aqueous solution surface tension data showed consistent results: the structure of the block PEO-PPO copolymers exerts a huge influence on their solubility in water. The solubility of such copolymers is increased by the presence of the sodium toluene sulfonate (NaPTS) hydrotrope. The presence of HCl caused increased solubility for the copolymer TETRONIC polyol only, the effect being less than that observed for the hydrotrope. It is concluded that as regards emulsion stabilization, TETRONIC copolymer polyols perform better. Correlation between structure and properties leads to the optimization of block PEO-PPO copolymer selection aiming at using these materials for the separation of petroleum industry emulsions.     

Interaction of ZnII Porphyrin with TiO2 Nanoparticles: From Mechanism to Synthesis of Hybrid Nanomaterials

The mechanism of interaction of Zn porphyrin (ZnPP) with TiO₂ surfaces is investigated with a view to optimizing the synthesis of hybrid nanomaterials. The strategy consists of studying the adsorption of ZnPP on TiO₂ flat surfaces by taking advantage of complementary surface characterization techniques. Combining a detailed X‐ray photoelectron spectroscopic analysis with AFM imaging allows ZnPP–surface and ZnPP intermolecular interactions to be discriminated. Probing the adsorption of ZnPP on TiO₂ nanoparticles (NPs) reveals the dominant role of ZnPP‐mediated interactions, which are associated with the formation of ZnPP multilayers and/or with the state of aggregation of NPs. These preliminary investigations provide a guideline to synthesizing a novel ZnPP–TiO₂ hybrid nanomaterial in a one‐step protocol. In this material, ZnPP molecules are presumably involved in the TiO₂ lattice rather than on the NP surface. Furthermore, ZnPP molecules preserve their electronic properties within the TiO₂ NPs, and this makes the ZnPP–TiO₂ hybrid nanomaterial an excellent candidate for nanomedicine and related applications, such as localization of nanoparticles in cells and tissues or in photodynamic therapy.     

Transparent titanium dioxide/block copolymer modified epoxy-based systems in the long scale microphase separation threshold

Microphase separated epoxy-based materials modified with an amphiphilic poly(styrene-block-ethylene oxide) diblock copolymer (PS-b-PEO) with low amount of PEO-block as well as ternary systems modified with this block copolymer and containing via sol–gel in situ synthesized TiO₂ nanoparticles were prepared and characterized. The obtained results indicate that block copolymer had enough amount of PEO-block in order to achieve microphase separated materials for a high range of PS-b-PEO contents, morphologies changing from spherical micelles to long wormlike micelles passing through vesicles upon increasing copolymer amounts. In the case of 20 wt.% inorganic/organic epoxy-based materials, addition of synthesized TiO₂ nanoparticles into PS-b-PEO-(DGEBA/MCDEA) system led to location of the nanoparticles in PEO-block/epoxy-rich confined between two microphase separated PS-block-rich phases. Designed highly transparent multiphase inorganic/organic epoxy-based materials possess interesting specific properties such as high UV shielding efficiency and high water repellence.     

Effect of interacting nanoparticles on the ordered morphology of block copolymer/nanoparticle mixtures

We investigated the effect of hard additives, that is, magnetic nanoparticles (NPs) and metal NPs, on the ordered morphology of block copolymers by varying the NP concentration. To characterize the structural changes of a block copolymer associated with different NP loadings, small-angle X-ray scattering and transmission electron microscopy were performed. Monodisperse maghemite (γ-Fe₂O₃) NPs (7 nm in diameter) and silver (Ag) NPs (6 nm in diameter) with surfaces modified with oleic acids were synthesized, and a cylinder-forming poly(styrene-block-isoprene) diblock copolymer was used as a structure-directing matrix for the NPs. As the NP concentration increased, domains of NP aggregates were observed for both magnetic and metal NPs. In the case of mixtures of cylinder-forming poly(styrene-block-isoprene) and Ag NPs with weak particle–particle interactions, random aggregates of Ag NPs were observed, and the ordered morphology of the block copolymer lost its long-range order with an increase in the NP concentration. However, regular, latticelike aggregates obtained with γ-Fe₂O₃ NPs, because of the strong interparticle interactions, induced an intriguing morphological transformation from hexagonal cylinders to body-centered-cubic spheres via undulated cylinders, whereas the neat block copolymer did not show such a morphological transition over a wide range of temperatures. The interplay between magnetic NPs and the block copolymer was also tested with magnetic NPs of different sizes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3571–3579, 2006     

Responsive polymer/gold nanoparticle composite thin films fabricated by solvent-induced self-assembly and spin-coating

Self-assembled poly(4-vinylpyridine)-grafted gold (Au) nanoparticles (NPs) and polystyrene-b-poly(4-vinylpyridine) block copolymers were fabricated by the introduction of a selective solvent to a common solution. The assembled mixtures were spin-coated onto solid substrates to fabricate composite gold/polymer thin films composed of copolymer-hybridized Au NPs and independent copolymer micelles. The obtained composite Au thin films had variable localized surface plasmon resonance (LSPR) bands and microscopic morphologies upon vapor annealing with selective solvents because the adsorption and dissolving of solvent molecules into the films could rearrange the copolymer block. The hybrid nanostructured Au thin films may have potential in vapor sensing and organic assays.     

Synthesis of highly dispersed,block copolymer‐grafted TiO2 nanoparticles within neat block copolymer films

The objective of the study is to formulate exclusive block copolymer (BCP) nanocomposites by dispersing bcp end‐grafted nanoparticles (bcp‐g‐nps) of PMMA‐b‐PS‐g‐TiO₂ within PS‐b‐PMMA matrix. PMMA‐b‐PS‐g‐TiO₂ is synthesized using a “grafting‐to” approach and characterized by XPS and TGA to establish that the copolymer chains were bonded to NPs. Good dispersion of bcp‐g‐nps in PMMA and PS‐PMMA bcp films is observed, in contrast to poor dispersion in PS films. In PS‐PMMA films, the compatible and identical bcp nature of the end‐grafted polymer, and large NP size caused it to span across entire PS‐PMMA domains. Poor and good dispersion in PS and PMMA matrices, respectively, can be rationalized by the fact that NPs interactions are driven by the PMMA at the outer corona of the bcp‐g‐nps. Developing bcp‐g‐nps as a strategic route to preparation of highly dispersed high permittivity NPs like titanium dioxide (TiO₂) in bcp matrix can have important ramifications for energy storage devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 468–478     

Oxidation Responsive PEGylated Polyamino Acid Bearing Thioether Pendants for Enhanced Anticancer Drug Delivery

Reactive oxygen species (ROS) in biological tissues are in a state of dynamic balance. However, many diseases such as cancer and inflammation, are accompanied by a long-term increase in ROS. This situation inspires researchers to use ROS-sensitive nanocarriers for a site-specific release of cargo in pathological areas. Polyamino acid materials with good biodegradability, biocompatibility, and regular secondary structure are widely used in the biomedical field. Herein, a new oxidation responsive PEGylated polyamino acid is synthesised for anticancer drug delivery by ring-opening polymerisation of N-carboxyanhydrides bearing thioether pendants. The obtained block copolymer mPEG-b-PMLG self-assembles into spherical nanoparticles (NPs) in water with diameter ≈68.3 nm. NMR measurement demonstrated that the hydrophobic thioether pendants in the NPs can be selectively oxidised to hydrophilic sulfoxide groups by H₂O₂, which will lead to the disassociation of NPs. In vitro drug release results indicated that the encapsulated Nile red is selectively released in the trigger of 10 mM H₂O₂ in PBS. Finally, anticancer drug doxorubicin (DOX) is encapsulated to the NPs, and the obtained NPs/DOX exhibits an improved antitumor efficacy in 4T1 tumour-bearing mice and lower cardiotoxicity than free DOX. These results indicates that the mPEG-b-PMLG NPs are promising for anticancer drug delivery.     

Incorporation of titanium dioxide particles into polymer matrix using block copolymer micelles for fabrication of high refractive and transparent organic–inorganic hybrid materials

We report a novel strategy for incorporation of titanium dioxide (TiO₂) particles into poly(methyl methacrylate) (PMMA) to exploit high refractive and transparent organic–inorganic hybrid materials. Formation of TiO₂ particles of around 20 nm was conducted within hydrophilic core of block copolymer micelles of poly(methyl methacrylate‐block‐acrylic acid) (PMMA‐b‐PAA) in toluene via sol–gel process from titanium isopropoxide and hydrochloric acid. Subsequently, incorporation of TiO₂ particles into PMMA matrix was carried out by casting toluene solution of TiO₂ precursor‐loaded copolymer micelles, prepared from PMMA₃₅₀‐b‐PAA₉₃ and the precursor of mole ratio Ti⁴⁺/carboxyl 4.0, and PMMA. Hybrid films of TiO₂/PMMA exhibited high transparency to achieve transmission over 87% at 500 nm at 30 wt % of TiO₂ content. The refractive index of resulting hybrid films at 633 nm linearly increased with TiO₂ content to attain 1.579 at 30 wt % TiO₂, which was 0.1 higher than that of PMMA. Cross‐sectional transmission electron microscope images of TiO₂/PMMA hybrid films showed existence of TiO₂ clusters less than 100 nm, which were probably formed by aggregation or agglutination of TiO₂ particles during a drying process. It was also observed that decomposition temperature of the hybrid films elevated with increasing TiO₂ content. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Coassembly of Metal and Titanium Dioxide Nanocrystals Directed by Monolayered Block Copolymer Inverse Micelles for Enhanced Photocatalytic Performance

Functional nanostructures of self‐assembled block copolymers (BCPs) incorporated with various inorganic nanomaterials have received considerable attention on account of their many potential applications. Here we demonstrate the two‐dimensional self‐assembly of anisotropic titanium dioxide (TiO₂) nanocrystals (NCs) and metal nanoparticles (NPs) directed by monolayered poly(styrene)‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) copolymer inverse micelles. The independent position‐selective assembly of TiO₂ NCs and silver nanoparticles (AgNPs) preferentially in the intermicelle corona regions and the core of micelles, respectively, for instance, was accomplished by spin‐coating a mixture solution of PS‐b‐P4VP and ex situ synthesized TiO₂ NCs, followed by the reduction of Ag salts coordinated in the cores of micelles into AgNPs. Hydrophobic TiO₂ NCs with a diameter and length of approximately 3 nm and 20–30 nm, respectively, were preferentially sequestered in the intermicelle nonpolar PS corona regions energetically favorable with the minimum entropic packing penalty. Subsequent high‐temperature annealing at 550 °C not only effectively removed the block copolymer but also transformed the TiO₂ NCs into connected nanoparticles, thus leading to a two‐dimensionally ordered TiO₂ network in which AgNPs were also self‐organized. The enhanced photocatalytic activity of the AgNP‐decorated TiO₂ networks by approximately 27 and 44 % over that of Ag‐free TiO₂ networks and randomly deposited TiO₂ nanoparticles, respectively, was confirmed by the UV degradation property of methylene blue.     

The Hybrids of Polystyrene-block-Poly(ethylene Oxide) Micelles and Sodium Dodecyl Sulfate in Aqueous Solutions: Interaction with Rh Ions and Rh Nanoparticle Formation

The interaction of amphiphilic block copolymer, polystyrene-block-poly(ethylene oxide) (PS-b-PEO), with anionic surfactant, sodium dodecyl sulfate (SDS), in aqueous media has been studied by sedimentation in ultracentrifuge. Three well-defined populations of hybrid aggregates corresponding to micelles, micellar clusters, and supermicellar aggregates were detected in the PS-b-PEO/SDS aqueous solutions at various rotation rates. Parameters of all the micellar aggregates were characterized depending on the SDS loading. An increase in the SDS loading was found to result in an increase in block copolymer/surfactant micelle size and weight at the SDS concentration of 0.8x10(-3) mol/L and in a slight decrease of both parameters at critical micelle concentration and at higher concentration. This decrease was caused by incorporation of SDS molecules in block copolymer micelles followed by charging the PS core and repulsion between similar charges. Using dichlorotetrapyridine rhodium(III)chloride hexahydrate ([Rh(Py)(4)Cl(2)]Clx6H(2)O), ion exchange of surfactant counterions in the hybrid PS-b-PEO/SDS system for Rh cations was carried out, which allowed saturating the micellar structures with Rh species. Subsequent reduction of the Rh-containing hybrid solutions with NaBH(4) resulted in the formation of Rh nanoparticles with a diameter of 2-3 nm mainly located in the block copolymer micellar aggregates. Copyright 2000 Academic Press.     

On the Formation of TiO<Subscript>2</Subscript> Nanoparticles Via Submerged Arc Discharge Technique: Synthesis,Characterization and Photocatalytic Properties

We report a simple and inexpensive synthesis route of TiO₂ nanoparticles using electrical arc discharge between titanium electrodes in oxygen bubbled deionized (DI) water followed by heat treatment. The resulting nanoparticles were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD patterns demonstrate formation of TiO₂ phase in oxygen bubbled water after heat treatment and dominance of rutile to anatase phase. The size and morphology of TiO₂ nanoparticles were studied using different arc currents as a crucial parameter in properties of final product. Microscopic studies reveal nanosize spherical particles. DLS results indicate that at 20 A arc current, the size of the particles is about 37 nm and increases to 59 nm by increasing the arc current up to 40 A. Photodegradation of Rhodamine B (Rh. B) as a standard pollution shows that heat treated samples in oxygen bubbled water for 2 h at 500 °C, have more photocatalytic activity due to enhancement in crystallinity.     

Synthesis of Mesoporous TiO2/SiO2 Hybrid Films as an Efficient Photocatalyst by Polymeric Micelle Assembly

Thermally stable mesoporous TiO₂/SiO₂ hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle‐assembly method. A triblock copolymer, poly(styrene‐b‐2‐vinyl pyridine‐b‐ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO₂/SiO₂ hybrid films with different compositions can be synthesized. The presence of amorphous SiO₂ phase effectively retards the growth of anatase TiO₂ crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO₂/SiO₂ hybrid films are of very high quality, without any cracks or voids. The addition of SiO₂ phase to mesoporous TiO₂ films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO₂ film without SiO₂ phase.     

Photoinduced Electron Transfer in Perylene‐TiO2 Nanoassemblies

The photosensitization effect of three perylene dye derivatives on titanium dioxide nanoparticles (TiO₂ NPs) has been investigated. The dyes used, 1,7‐dibromoperylene‐3,4,9,10‐tetracarboxy dianhydride (1), 1,7‐dipyrrolidinylperylene‐3,4,9,10‐tetracarboxy dianhydride (2) and 1,7‐bis(4‐tert‐butylphenyloxy)perylene‐3,4,9,10‐tetracarboxy dianhydride (3) have in common bisanhydride groups that convert into TiO₂ binding groups upon hydrolysis. The different substituents on the bay position of the dyes enable tuning of their redox properties to yield significantly different driving forces for photoinduced electron transfer (P_eT). Recently developed TiO₂ NPs having a small average size and a narrow distribution (4 ± 1 nm) are used in this work to prepare the dye‐TiO₂ systems under study. Whereas successful sensitization was obtained with 1 and 2 as evidenced by steady‐state spectral shifts and transient absorption results, no evidence for the attachment of 3 to TiO₂ was observed. The comparison of the rates of P_eT (k_PeT) for 1‐ and 2‐TiO₂ systems studied in this work with those obtained for previously reported analogous systems, having TiO₂ NPs covered by a surfactant layer (Hernandez et al. [2012] J. Phys. Chem. B., 117, 4568–4581), indicates that k_PeT for the former systems is slower than that for the later. These results are interpreted in terms of the different energy values of the conduction band edge in each system.     

A cancer cell turn-on protein-CuSMn nanoparticle as the sensor of breast cancer cell and CH3O-PEG-phosphatide

A cancer activated protein-inorganic nanoparticle was used as breast cancer cell turn-on fluorescence sensor and NIR activated attenuator.     

Hierarchical nanoparticle/block copolymer surface features via synergistic self-assembly at the air-water interface

This work demonstrates the first example of the controlled organization of semiconducting nanoparticles (NPs) using amphiphilic block copolymer self-assembly at the air-water interface. Preferential interactions between polystyrene-functionalized NPs and the polystyrene block of an amphiphilic polystyrene-b-poly(ethylene oxide) block copolymer result in synergistic self-assembly at the air-water interface, forming a range of highly stable one-dimensional NP/polymer surface features, including branched nanowires, nanocables up to 100 microm in length, and nanowires with nanoring connectors. This strategy offers new routes to hierarchical hybrid assemblies with potential photonics applications because the nanoscale organization of NPs is coupled to features with dimensions that are commensurate with optical wavelengths.     

Two-step on-particle ionization/enrichment via a washing- and separation-free approach: multifunctional TiO2 nanoparticles as desalting, accelerating, and affinity probes for microwave-assisted tryptic digestion of phosphoproteins in ESI-MS and MALDI-MS: comparison with microscale TiO2

We introduce a simplified sample preparation method using bare TiO₂ nanoparticles (NPs) to serve as multifunctional nanoprobes (desalting, accelerating, and affinity probes) for effective enrichment of phosphopeptides from microwave-assisted tryptic digestion of phosphoproteins (α-casein, β-casein and milk) in Electrospray Ionization Mass Spectrometry (ESI-MS) and Matrix Assisted Laser Desorption Ionization Mass Spectrometry (MALDI-MS). The results demonstrate that TiO₂ NPs can effectively enrich and accelerate the digestion reactions of phosphoproteins in aqueous solutions and also from complex real samples. After the microwave experiments, we directly injected the resulting solutions into the ESI-MS and MALDI-MS systems for analysis, and excellent sensitivity was achieved without the need for any washing procedure or separation process. The reasons are attributed to the high binding affinity and selectivity of TiO₂ NPs toward phosphopeptides. Thus, phosphopeptides can be adsorbed onto the TiO₂ NP surface. The digested or partially digested phosphoproteins can be concentrated onto the TiO₂ NP surface. This results in the effective or complete digestion of phosphoproteins in a short period of time (45 s). In addition, high sensitivity and sequence coverage of phosphopeptide can be obtained using TiO₂ NPs as microwave absorbers and affinity probes in MALDI-MS and ESI-MS. This is due to the photocatalytic nature of the TiO₂ NPs because the absorption of microwave radiation that can accelerate the activation of trypsin for efficient digestion of phosphoproteins and enhances the ionization of phosphopeptides. The lowest concentrations detected for ESI-MS and MALDI-MS were 0.1 μM and 10 fmol, respectively, for α-casein. Comparing the two-step approach of TiO₂ NPs with microscale TiO₂ particles, the microscale TiO₂ particles shows no effect on the microwave-assisted tryptic digestion of phosphoproteins. The current approach offers multiple advantages, such as great simplicity, high sensitivity and selectivity, straightforward and separation/washing-free technique for phosphorpeptide enrichment analysis.     

Multifunctional PES fabrics modified with colloidal Ag and TiO2 nanoparticles

This study is aimed to highlight the possibility of engineering the multifunctional textile nanocomposite material based on the polyester (PES) fabric modified with colloidal Ag and TiO₂ nanoparticles (NPs). The effects of concentration of NPs as well as the order of Ag and TiO₂ NPs loading on antimicrobial, UV protective, and photocatalytic properties of PES fabrics were examined. The antimicrobial activity of differently modified PES fabrics was tested against Gram‐negative bacterium Escherichia coli, Gram‐positive bacterium Staphylococcus aureus, and fungus Candida albicans. The concentration of Ag colloid and the order of Ag and TiO₂ NPs loading considerably affected the antimicrobial efficiency of PES fabrics. The fabrics provided maximum UV protection upon surface modification with Ag and TiO₂ NPs. Ag NPs enhanced Ag NPs enhanced the photodegradation activity of TiO₂ NPs and total photodegradation of methylene blue was achieved after 24 hr of UV illumination. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of heat treatment on electrochromic properties of TiO<Subscript>2</Subscript> thin films

Electrochromic titanium oxide (TiO₂) films were deposited on ITO/glass substrates by chemical solution deposition (CSD). The stock solutions were spin-coated onto substrates and then heated at various temperatures (200–500 °C) in various oxygen concentrations (0–80%) for 10 min. The effects of the processing parameters on the electrochromic properties of TiO₂ films were investigated. X-ray diffraction measurements demonstrated that the amorphous TiO₂ films were crystallized to form anatase films above 400 °C. The electrochromic properties and transmittance of TiO₂ films were measured in 1 M LiClO₄–propylene carbonate (PC) non-aqueous electrolyte. An amorphous 350 nm-thick TiO₂ film that was heated at 300°C in 60% ambient oxygen exhibited the maximum transmittance variation (ΔT%), 14.2%, between the bleached state and the colored state, with a ΔOD of 0.087, Q of 10.9 mC/cm², η of 7.98 cm²/C and x in Li _x ClO₄ of 0.076 at a wavelength (λ) of 550 nm.     

Interaction of sodium and potassium ions with PEO-PPO copolymer investigated by FTIR,Raman and NMR

Many papers have reported that salt ions can exert a great influence on the self-assembly behavior of PEO-PPO copolymers in the aqueous solution. Whereas the mechanism through which salt ions influence the self-assembly behavior of PEO-PPO copolymers is unclear and the dispute is mainly focused on whether the salt ions have a direct interaction with PEO-PPO copolymers. In this paper, the interaction of sodium and potassium ions with PEO-PPO copolymer was investigated by using FTIR, Raman and ²³Na NMR spectroscopy. Experimental results reveal that direct interactions between salt cations and PEO-PPO macromolecular chains indeed occur in appropriate conditions. The present work highlights the role of cations in the self-assembly process of PEO-PPO copolymer.     

Synthesis of mesoporous TiO2 with colloidal gas aphrons,colloidal liquid aphrons,and colloidal emulsion aphrons for dye-sensitized solar cells

High surface area mesoporous titanium dioxide (TiO₂) particles have been prepared by three different kinds of colloidal aphrons: colloidal gas aphrons, colloidal liquid aphrons, and colloidal emulsion aphrons (CEAs). The precipitate of amorphous TiO₂ was prepared by hydrolysis, condensation, and polycondensation reaction of the precursor. The reaction took place under the effect of coulombic repulsion and electrostatic layers of multilayer surfactant molecules. TiO₂ particles with various sizes were prepared with different molar ratio of titanium ion to surfactants, which were sodium lauryl sulfate (SDS), cetyltrimetyhlammonium bromide, triblock copolymer Pluronic P123, and triblock copolymer Pluronic F127. The synthesized samples were characterized by X-ray diffraction, Brunauer-Emmett-Teller analysis, N₂ adsorption/desorption, and transmission electron microscopy. The mesoporous TiO₂ prepared by CEAs method showed a high specific surface area of 224 m²/g with the total pore volume of 0.7751 cm³/g by using SDS as the membrane phase surfactant due to electrostatic attraction favors of anionic surfactant. The solar conversion efficiency of the cell made from TiO₂ increases with the combination of increased surface area and total pore volume for higher amount of dye wetting and loading.