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  • Articles  (1,248)
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  • Articles  (1,248)
Source
  • Latest Papers from Table of Contents or Articles in Press  (1,248)
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  • Springer  (1,248)
  • American Institute of Physics
  • Blackwell Publishing Ltd
  • Cell Press
  • Oxford University Press
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  • 2010-2014  (694)
  • 2005-2009  (356)
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Year
Journal
Topic
  • 1
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    Micelle-assisted cerium(IV) oxidation of L-sorbose in aqueous sulfuric acid (2007)
    Springer
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    Publication Date: 2007-03-24
    Print ISSN: 0372-820X
    Electronic ISSN: 1435-1536
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 2
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    Capillary theory of free fluid surfaces (2007)
    Springer
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    Publication Date: 2007-03-23
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 3
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    Synthesis and characterization of microencapsulated dicyclopentadiene with melamine–formaldehyde resins (2007)
    Springer
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    Publication Date: 2007-03-02
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 4
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    Studies on rheological behaviour of hydrophobically associating polyacrylamide with strong positive salinity sensitivity (2007)
    Springer
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    Publication Date: 2007-03-20
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 5
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    Obtaining surface tension from contact angle data by the individual representation approach (2007)
    Springer
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    Publication Date: 2007-03-08
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 6
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    Thermal transitions in associating aqueous block copolymers: light scattering, rheology and spectroscopy (2007)
    Springer
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    Publication Date: 2007-02-17
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 7
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    The aggregation of nonionic surfactants in the presence of poly(methacrylic acid) (2007)
    Springer
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    Publication Date: 2007-02-14
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 8
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    New anionic gemini surfactant based on EDTA accessible by convenient synthesis (2007)
    Springer
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    Publication Date: 2007-06-13
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 9
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    Investigation of PEG 6000/Tween 80/Span 80/H2O niosome microstructure (2007)
    Springer
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    Publication Date: 2007-01-19
    Print ISSN: 0372-820X
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    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 10
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    Synthesis of nearly micron-sized particles by soap-free emulsion polymerization of methacrylic monomer using an oil-soluble initiator (2013)
    Springer
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    Publication Date: 2013-09-14
    Description: Methacrylic monomer was used in soap-free emulsion polymerization in order to obtain a stable dispersion containing particles of the polymerized monomer. 2,2′-Azobis(2-methylpropionitrile) (AIBN) or 1,1′-azobis(1-acetoxy-1-phenylethane) (OT AZO -15) were used as the radical initiator. Although particles with a size of about 1.0 μm were obtained when using methyl methacrylate as the monomer and AIBN as the initiator, the particles did not exhibit good dispersion stability. When OT AZO -15, which has phenyl rings, was used as the initiator, the monomer phase solidified instead of forming particles in the aqueous phase. Benzyl methacrylate (BMA) monomer, which contains a phenyl ring, was polymerized using AIBN. Negatively charged particles with a size of 0.90 μm were formed. These particles exhibited good dispersion stability probably because of the pi electrons of the phenyl ring in the BMA monomer. The method in this study allows the synthesis of nearly micron-sized particles without surfactant, organic solvent, and electrolyte.
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  • 11
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    Ionic liquid–water mixtures as solvents for poly( N -vinylimidazole) (2013)
    Springer
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    Publication Date: 2013-09-19
    Description: Ionic liquids extend the Hofmeister series and create a wide range of new possibilities for processes involving salt effects on both soluble and crosslinked systems. This work reports on some mixtures of water with NaCl or an ionic liquid, either 1-ethyl-3-methylimidazolium tosylate or 1-hexyl-3-methylimidazolium chloride, which are better solvents for linear poly( N -vinylimidazole) (L-PVI) than water, i.e., that exhibit a salting-in effect. The intensity of the salt effects was measured on the basis of the polymer solubility, the decrease in polymer–solvent interaction parameter (measured by light scattering), and the increase of coil size (measured through the intrinsic viscosity). It was thus found that the intensity of the salting-in effect of either NaCl or 1-hexyl-3-methylimidazolium chloride on L-PVI is different (larger for the ionic liquid), which denotes that salt effects are not under anion control, and the mechanisms operating in the linear and crosslinked polymers are different. These results are discussed after accounting for the role of ion–polymer interactions.
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  • 12
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    Microrheology of polysaccharide nanogel-integrated system (2013)
    Springer
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    Publication Date: 2013-10-03
    Description: The viscoelastic behavior of a cholesterol-modified pullulan (CHP) nanogel at various concentrations was measured using passive particle-tracking microrheology. Microrheology measures stress–strain relationships in small volumes of material by monitoring the response of probes embedded in the medium. Although microrheology is a useful way to overcome sample volume limitations, the application of the method to CHP nanogel systems has not been reported. The viscoelastic spectra of the CHP nanogels obtained from the microrheological measurements were in good agreement with the bulk rheological measurements for each sample, demonstrating that microrheological measurement is effective in CHP nanogel systems. The gelation behavior of CHP nanogel dispersions containing pullulans of different molecular weights was also investigated by microrheology. CHP nanogels made from 1.0 or 4.0 × 10 5 molecular weight pullulans formed a macrogel at around 3.0 wt%, whereas the CHP nanogel consisting of 0.55 × 10 5 molecular weight pullulan did not form a macrogel. This suggests that the mechanical properties of the system can be controlled by the molecular weight of the pullulan used. These insights into gelation behavior should be useful in predicting the most favorable conditions for developing novel materials.
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  • 13
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    Magnetic and hydrophilic imprinted particles via ATRP at room temperature for selective separation of sulfamethazine (2013)
    Springer
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    Publication Date: 2013-10-03
    Description: In this work, a facile route to prepare hydrophilic molecularly imprinted particles with magnetic susceptibility (MMIPs) was first reported via atom transfer radical precipitation polymerization (ATRPP) in a methanol/water solvent at low temperature (298 K), which can be considered as an environment-friendly system. During the process, 2-hydroxyethyl methacrylate and N , N -methylenebisacrylamide monomers were added to improve the hydrophilicity of the polymers. The obtained materials were characterized in detail by X-ray diffraction, transform infrared spectroscopy, thermogravimetric analysis, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy, and then used for the selective separation of sulfamethazine (SMZ) from aqueous medium. The images showed Fe 3 O 4 nanoparticles that were successfully embedded into the polymer particles with the size ranging from 450 to 650 nm, which exhibited great superparamagnetic susceptivity and high thermal stability. Batch adsorption experiments were performed to determine specific adsorption equilibrium, kinetics, and selective recognition and separation. The effect of the ratio of the double monomers used in the adsorption property was also studied. The equilibrium data of MMIPs toward SMZ was well fitted by the Langmuir isotherm model, and the maximum adsorption capacity estimated was 66.67 μmol g −1 . The adsorption kinetics rapidly achieved equilibrium within 1.0 h and was well described by the pseudo-second-order model. The MMIPs synthesized showed outstanding affinity and selectivity toward SMZ over structurally analogous antibiotics and easily achieved magnetic separation under an external magnetic field. In addition, the adsorption performance of the resulting MMIPs was no obviously decreased at least six repeated cycles.
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  • 14
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    Enhancing the conductivity of isotactic polypropylene/polyethylene/carbon black composites by oscillatory shear (2013)
    Springer
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    Publication Date: 2013-10-05
    Description: The influence of oscillatory shear on the conductivity of the isotactic polypropylene/polyethylene/carbon black composites is studied. It is found that the oscillatory shear under high strain amplitude can enhance the conductivity of the ternary composites with a HDPE/CB concentration in the percolation region. This is related to the fact that the high-strain oscillatory shear can improve the continuity of the conductive HDPE/CB phase in the composites. This finding has not been previously reported, and it may be used in industry to improve the conductivity of the ternary conductive composites with a low filler loading.
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  • 15
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    Micelle-encapsulated multi-wall carbon nanotubes with photosensitive copolymer and its application in the detection of dopamine (2013)
    Springer
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    Publication Date: 2013-09-11
    Description: Photosensitive copolymer P(St- alt -MAn)- co -P(VM- alt -MAn) was synthesized and employed to disperse multi-wall carbon nanotubes (MWCNTs). It was found that copolymer could form micelles in aqueous solution and adsorb onto the surface of MWCNTs to produce micelle-encapsulated MWCNTs (e-MWCNTs) by in situ photo crosslinking after irradiation with ultraviolet light and a stable suspension of e-MWCNTs in aqueous solution was obtained. When deposited onto polyaniline (PANI)-modified glassy carbon electrodes, a thin film of e-MWCNTs composite was obtained and the performance of the e-MWCNTs/PANI electrode toward dopamine was then evaluated. The experimental results suggest that the hybrid film modified electrode exhibits a dramatic electrocatalytic effect on the oxidation of dopamine (DA), as evidenced by a marked enhancement of the current response. A series of CVs was obtained by modified glassy-carbon electrodes with different size of micelles was also researched. The result shows that the peak current increased with the increasing size of micelles. A linear calibration plot was obtained in a wide range of 1.0 × 10 −7 –1.0 × 10 −3  M and the detection limit was 5.0 × 10 −8  M. In addition, the interference from ascorbic acid (AA) was effectively suppressed due to the presence of the negatively charged carboxylate groups of copolymer on the outside of MWCNTs which repels AA anions and provides a transport channel only for DA cations.
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  • 16
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    Greatly accelerated crystallization of poly(lactic acid): cooperative effect of stereocomplex crystallites and polyethylene glycol (2013)
    Springer
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    Publication Date: 2013-09-12
    Description: Stereocomplex crystallite (SC) between enantiomeric poly( l- lactic acid) (PLLA) and poly( d -lactic acid) (PDLA), with largely improved thermal resistance and mechanical properties compared with PLLA and PDLA, is a good nucleating agent for poly(lactic acid) (PLA). The effects of SC and/or polyethylene glycol (PEG) on the crystallization behaviors of PLA were investigated. The non-isothermal and isothermal crystallization kinetics revealed that SC and PEG can separately promote the crystallization rate of PLA by heterogeneous nucleation and increasing crystal growth rate, respectively. However, their promoting effect is limited when used alone, and the modified PLA cannot crystallize completely under a cooling rate of 20 °C/min. When SC and PEG are both present, the crystallization rate of PLA is greatly accelerated, and even under a cooling rate of 40 °C/min, PLA can crystallize completely and get a high crystallinity owing to the excellent balance between simultaneously improved nucleation and crystal growth rate.
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  • 17
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    Phase behavior and solubilization of microemulsion systems containing Gemini imidazoliums and their monomeric analogues (2013)
    Springer
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    Publication Date: 2013-06-07
    Description: The Gemini imidazolium surfactants with a four-methylene spacer group [C n (Bim) 2 -2Br, n  = 12, 14, 16] and their corresponding monomers [C n mimBr, n  = 12, 14, 16] were synthesized and characterized. The phase behavior and solubilization of microemulsion systems containing C n (Bim) 2 -2Br/butan-1-ol/octane/brine as well as microemulsion systems containing C n mimBr/butan-1-ol/octane/brine were studied and compared. The C n (Bim) 2 -2Br-based microemulsion systems have greater solubilization ability than that of the corresponding mono surfactants C n mimBr-based systems. As the carbon chain lengths of the surfactants [C n (Bim) 2 -2Br and C n mimBr] increase, the mass fraction of the alcohol in the interfacial layer A S would decrease, whereas the solubilization ability ( SP* ) would increase. The maximum solubilization ability ( SP* ) of the two microemulsion systems was attained when the oil/water mass ratio ( α ) approaches 0.5. The solubilization ability of both microemulsion systems would increase with increasing NaCl concentrations in aqueous phase. In C n (Bim) 2 -2Br-based microemulsion systems, the alcohol is significantly more soluble in aqueous phase than in the oleic phase. And it was noted that the alcohol is more soluble in C n (Bim) 2 -2Br-based systems than in C n mimBr-based systems in both aqueous and oleic phases.
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  • 18
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    Synthesis of Mg 2 Al-Cl layered double hydroxide nanosheets in a surfactant-free reverse microemulsion (2013)
    Springer
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    Publication Date: 2013-06-08
    Description: The synthesis of Mg 2 Al-Cl layered double hydroxide (LDH) nanosheets in a surfactant-free reverse microemulsion is described. The microemulsion was composed of toluene, isopropanol, and an aqueous solution as the dispersed phase. An aqueous LDH nanosheet dispersion was obtained by a double-microemulsion technique. LDH nanosheets were characterized by X-ray powder diffraction, transmission electron microscopy, scanning electron microscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and thermogravimetric and elemental analyses. The LDH nanosheets consisted of a single brucite layer without any loading of organic molecules. To the best of our knowledge, this is the first report of a naked LDH monolayer aqueous dispersion being directly obtained. The LDH monolayers can be used as building blocks for LDH-based functional materials.
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  • 19
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    Controllable synthesis of β-NaYF 4 :Yb,Er nanorods by potassium oleate as ligand (2013)
    Springer
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    Publication Date: 2013-06-13
    Description: By using potassium oleate (KOL) as a part of ligand, nanorods of β-NaYF 4 :Yb,Er were synthesized. The aspect ratio of β-NaYF 4 :Yb,Er nanocrystals was tuned by changing the amount of KOL. We found that potassium from KOL is not only absorbed on the surface of nanocrystals, but also partially substitutes Na element in nanocrystals lattice. Different from the classical shape control mechanism that oleate ions are absorbed on different facets of nanocrystals, the anisotropic growth of β-NaYF 4 :Yb,Er in current work is caused by the doping of K + . The incorporation of K + would not lead to obvious decrease of the upconversion fluorescence intensity. Meanwhile, oleate ions promote the phase transition of nanocrystals from cubic to hexagonal phase, resulting in the simultaneous controllability of the nanocrystals size.
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  • 20
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    Reinforcement of poly(vinyl alcohol) with chiral poly(amide-imide)s nanoparticles containing S-valine under simple ultrasonic irradiation method (2013)
    Springer
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    Publication Date: 2013-06-08
    Description: Nanostructured amino acid containing poly(amide-imide) (PAI) was synthesized from the direct polycondensation reaction of 2–(3,5–diaminophenyl)–benzimidazole and N , N ′–(pyromellitoyl)–bis–phenylalanine diacid under green condition by using tetrabutylammonium bromide as molten ionic liquid. Field emission scanning electron microscopy images show that the average diameter of polymeric nanoparticles with spherical shape was around 20–35 nm. In the next step, these polymeric nanoparticles were used as nano-fillers for reinforcement of poly(vinyl alcohol) (PVA) for the first time. Bionanocomposite of PVA and various compositions of PAI nanoparticles were produced through ultrasound-assisted technique. Fourier transform infrared spectroscopy, x-ray diffraction, field emission scanning electron microscopy, and thermogravimetric analysis were utilized to characterize the obtained hybrid materials, morphology, and properties. Results of thermal properties indicated that the thermal stability is enhanced. The improvement of thermal properties was attributed to the homogeneous and good dispersion of PAI nanoparticles in the PVA matrix and the strong hydrogen bonding between O–H groups of PVA and the carbonyl of amide and imide groups of the used PAI nanoparticles.
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  • 21
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    Controlled radical emulsion polymerization of polystyrene (2013)
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    Publication Date: 2013-06-10
    Description: In this paper, a new water-soluble initiator system, 2-bromopropane/CuSO 4 /sodium ascorbate, was used as the initiator for emulsion polymerization. Radical emulsion polymerization of styrene was successfully carried out at 80 °C by using sodium dodecylbenzenesulfonate as the emulsifier. The 2-bromopropane/CuSO 4 /sodium ascorbate-initiated emulsion polymerization shows the controlled free-radical polymerization features with linear growth of molecular weight. Polystyrene with a relatively high molecular weight and a narrow molecular weight distribution can be synthesized by this method. On the other hand, stable polystyrene latex can be obtained, and the size of the polystyrene latex increased with the increase in monomer conversion.
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  • 22
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    Facile preparation of α-Fe 2 O 3 /carbon and polyhydroxy iron cation/polyaniline hollow particles (2013)
    Springer
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    Publication Date: 2013-04-11
    Description: By virtue of a smartly designed strategy, we successfully prepared the α-Fe 2 O 3 /carbon and electromagnetic polyhydroxy iron cation/polyaniline (PIC/PANi) hollow particles. First, poly(styrene-butyl acrylate)/polyhydroxy iron cation (P(S-BA)/PIC) composite particles were prepared based on electrostatic attraction between the P(S-BA) and PIC. Second, the coating of P(S-BA)/PIC composite particles with PANi was achieved by the “Swelling–Diffusion–Interfacial-Polymerization Method”. Finally, α-Fe 2 O 3 /carbon and PIC/PANi hollow particles were obtained by calcination or solvent extraction of the P(S-BA)/PIC/PANi composite particles, respectively. The whole preparation process was monitored by transmission electron microscope, scanning electron microscope, Fourier transform infrared, and X-ray diffraction. The synthesized α-Fe 2 O 3 /carbon and PIC/PANi hollow particles possessed of a narrow size distribution and well-defined morphology.
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  • 23
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    Frontal polymerization synthesis and characterization of temperature- and pH-sensitive hydrogels (2013)
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    Publication Date: 2013-04-11
    Description: The temperature- and pH-sensitive hydrogels, poly( N -isopropylacrylamide- co -acrylic acid) (P(NIPAM- co -AAc)), were synthesized via frontal polymerization (FP). The reaction components have been varied in order to find their influences on frontal parameters and copolymer features. The results showed that front velocity and front temperature were dependent on the initiator concentration, reactant dilution, and NIPMA/AAc molar ratio. In addition, the morphology and sensitive behavior of the FP hydrogels were mainly affected by monomers’ ratio. Namely, the pore size, swelling abilities, LCST, and response kinetics of copolymer hydrogels obviously increased with the increasing acrylic acid concentration; however, they slightly changed with varying of amounts of initiator and solvent. Finally, in comparison with the hydrogels prepared by conventional batch polymerization, the ones synthesized by frontal polymerization exhibited more homogeneous chain composition and improved microstructure and response ability.
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  • 24
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    Poly(urea)urethanes based on amorphous quaternizable hard segments and a crystalline polyol derived from castor oil (2013)
    Springer
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    Publication Date: 2013-04-11
    Description: A set of poly(urea)urethanes (PUU), with different contents of amorphous hard segment and castor oil-derived crystalline polyol as soft segment, was prepared combining bulk and solution polymerizations. It is shown that both the soft segment crystallinity and hard segment glassy nature control the stiffness of the materials and that phase mixing at intermediate hard segment compositions produces softer materials. Upon yielding, PUU developed large plasticity associated to the nature of soft segments. At longer strains, PUU presented strain-induced crystallization related both to soft segments alignment and crystallization, leading to strong and tough materials, especially with high hard segment content compositions. Despite the hydrophobicity of the soft segments, the PUU with 65 wt% hard segment content was dispersable in water after quaternization with acetic acid. The high amount of urea groups in this quaternized PUU makes one think of these types of polymers as promising water soluble environmentally friendly strong adhesives, coatings, or water soluble polymeric electrolites.
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  • 25
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    Synthesis and electrorheology of rod-like titanium oxide particles prepared via microwave-assisted molten-salt method (2013)
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    Publication Date: 2013-04-11
    Description: The rod-like titanium dioxide (TiO 2 ) particles were synthesized by a simple and rapid microwave-assisted molten-salt method. The X-ray diffraction analysis revealed the phase composition transformation from the anatase phase of original TiO 2 nanomaterial to the rutile phase of high crystallinity. Scanning electron microscopy proved the conversion of originally globular particles of original anatase TiO 2 sized from 200 to 500 nm into rods with a length of 5–10 μm and a diameter between 0.5 and 2 μm. The electrorheological (ER) measurements performed under steady-state flow as a function of the applied electric field strength and particle concentration showed that suspended rutile rod-like TiO 2 particle-based fluid exhibits much higher ER activity than that of original anatase TiO 2 material powder. These observations were clearly demonstrated by viewing their dielectric spectra analyses.
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  • 26
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    Development and micro-gap flow evaluation of electro-rheological nano-suspensions (2013)
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    Publication Date: 2013-04-11
    Description: Electro-rheological (ER) nano-suspensions based on titanium dioxide nano-particles with particle diameter on the order of 100 nm were prepared. Micro-gap flow behavior and microstructure were evaluated for the suspensions with a particle volume fraction of 8.8 vol%. For the nano-suspension based on a silicone oil, the ER effect and flow behavior were found to be stable during the sharing time on the order of 10 2  s. The ER response measured at a given strength of the electric field for the nano-suspension based on a chemically modified silicone oil was effectively induced by the electric field, especially with low strengths, and it was larger than that of the nano-suspension based on the silicone oil but slightly lower than that based on a hydrocarbon oil. Furthermore, the relaxation of the ER response after removal of the electric field was somewhat slow for the nano-suspension based on the hydrocarbon oil, whereas it was fairly well for the nano-suspension based on the modified silicone oil.
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    Yield stress analysis of 1D calcium and titanium precipitate-based giant electrorheological fluids (2013)
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    Publication Date: 2013-04-11
    Description: 1D calcium and titanium composite nanorods synthesized were applied as electrorheological (ER) active materials with extremely high static yield stresses, i.e., giant ER effect. The yield stress of this giant ER fluid was analyzed using a new universal yield stress scaling equation in the form of the modified Bessel functions with two different limiting behaviors in a low and high electric field region. The universal yield stress equation collapsed the yield stress data onto a single curve.
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    The influence of chondroitin sulfate on composite multilamellar liposomes containing chitosan (2013)
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    Publication Date: 2013-04-11
    Description: A composite multilamellar liposome containing chitosan attached to the inside and outside of the membrane as well as an opposite charged polyelectrolyte, chondroitin, adsorbed at the surface was developed. Not only the chitosan/chondroitin ratio but also the concentration of them were varied. The structure and superficial properties of the liposomes were studied through a combination of light scattering, zeta potential, and small-angle X-rays scattering techniques. While the chitosan/chondroitin ratio affected the superficial charge distributions, the concentration of polyelectrolytes affected the structural properties of the liposomes, as the rigidity of the phospholipid layers. The superficial charge of the resultant composite liposome was influenced by the type and concentration of the polyelectrolyte. Information about the charge density could be obtained by the treatment of zeta potential data, and it was used to estimate the amount of chondroitin adsorbed to the liposome surface. Applying the modified Caillé theory to the X-rays scattering curves, information about the internal structure of the liposomes was accessed. The ability to control the properties of composite multilamellar liposomes is an important issue when they have to be applied as a biomaterial device component.
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    In situ synthesis of polystyrene/nano-CdSe core/shell microspheres in aqueous solution at room temperature (2013)
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    Publication Date: 2013-04-11
    Description: Polystyrene/nano-CdSe (PS/CdSe) core/shell microspheres were synthesized via in situ soap-free emulsion polymerization using various functional monomers such as 2-(dimethylamino)ethyl methacrylate, 1-vinylimidazole, 2-vinylpridine, and 4-vinylpridine. They were co-polymerized with styrene monomer and provided the location for coordinating with Cd 2+ ions on the PS particle surfaces. Then, we used an alkaline selenium solution as a selenium source. Reaction of the alkaline selenium solution with the previous emulsion produced nanocrystalline CdSe onto the surface of PS particles at room temperature under atmospheric pressure. The different kinds of functional monomers and the amount of both Cd 2+ ion and functional monomer were playing important roles to obtain stable and uniform morphologies of CdSe particles. Morphological observations were carried out by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Through the SEM and TEM microphotographs, we could confirm the formation of PS/nano-CdSe composite particles. Ultraviolet–visible absorption measurement indicated the quantum dot effect in the resulted PS/nano-CdSe core/shell microspheres.
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    Preparation of hemispherical polyimide particles by inverse emulsion technique from poly(amic acid) ammonium salts (2013)
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    Publication Date: 2013-04-11
    Description: Nonspherical polymer particles have attracted increasing attention recently. In this paper, micron-scale hemispherical polyimide (PI) particles were fabricated using water-soluble poly(amic acid) ammonium salts (PAAS) by a novel inverse emulsion technique. In the process, liquid paraffin was used as a continuous phase, the mixed solution of PAAS and water as a dispersed phase and sorbitan monooleate (Span80) as a surfactant. The research suggested that water as a stabilizing agent played an important role in forming stable emulsion. As the amount of water increased, stability of the emulsion increased gradually and morphology of PI particles transformed from sphere to ellipsoid, and finally to hemisphere. The concentration of PAAS solution and Span80 both affected the shape of particles, which changed from spherical to hemispherical by increasing the PAAS/Span80 concentration. The mechanism of forming hemispherical PI particles was discussed based on interfacial tension and interfacial free energy changes. Via adjusting the composition of the system to change the corresponding interfacial tension, we could get the particles with different morphologies. Furthermore, the change in structure characterized by FT-IR spectroscopy demonstrated that PAAS had been converted to PI after adding the dehydrating agent to the emulsion. And TGA results showed that the obtained PI particles had excellent thermal stability.
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    Effect of cosolvent NMP on properties of cationic fluorocarbon emulsifier-free emulsion (2013)
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    Publication Date: 2013-04-11
    Description: Cationic fluorocarbon emulsifier-free emulsion was prepared via a novel method of adding organic cosolvent N -methylpyrrolidone (NMP), which was characteristic of the reaction transferring from solution to emulsion polymerization system. The emulsion stability was analyzed by the coagulation and precipitation ratio. The properties of particles were characterized by dynamic laser light scattering, surface potential particle size analyzer, and transmission electron microscopy, respectively. The latex film surface properties and immersion behaviors were investigated by contact angles. The results showed that, with NMP increasing from 5 to 30 %, the emulsion stability became better. Also, particle sizes decreased from 264.0 to 95.5 nm, and their distribution transformed from multidispersion to monodispersion. Zeta potentials increased gently. Meanwhile, the latex film surface performance was slightly improved, and the more the content of NMP, the less the influence of the cure temperature on surface property. There was less mobility of fluorinated groups in the films with more NMP used. Figure A novel method was to prepare cationic fluorocarbon emulsifier-free emulsion. It was characteristic of the reaction transferred from solution to emulsion reactive polymerization system, of which the cosolvent NMP was used in the first step of the reaction. Its influences on particle properties were obvious. With NMP increasing, the particle sizes decreased, their distribution transformed from multidispersion to monodispersion, and the D decreased from 3.88 to 1.09. Their impact on particle properties also affected latex film surface properties and immersion behaviors.
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    Efficient synthesis of asymmetric particles by sol-gel process (2013)
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    Publication Date: 2013-04-11
    Description: This paper presents a novel and facile method of synthesizing polymer/silica particles with controlled asymmetric morphologies. Our approach is based on the sol–gel process in which cross-linked polystyrene particles (CPS) are adopted as templates and 3-mercaptopropyltriethoxysilane is used as a single silica source. The reaction process causes silane oligomer to preferentially grow on the local surface of CPS, giving rise to polystyrene/thiol-functionalized silica composite particles with a tunable shape. It is found that the morphologies of particles can be easily tailored by changing the ratio of ethanol/water in the reaction medium. In addition, the amount of cross-linker used during the polymerization also plays a key role in the formation of various complex-shaped particles. Controlled geometries of these organic/inorganic composite particles will allow a broad range of potential applications, such as photonic crystals, Pickering emulsifier, sensors, and so on.
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    Improvement of ammonia sensing properties of polypyrrole by nanocomposite with graphitic materials (2013)
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    Publication Date: 2013-04-11
    Description: The more sensitive and rapid ammonia gas sensors were prepared with nanocomposites of polypyrrole (PPy) and graphitic materials such as graphite, graphite oxide (GO), and reduced graphene oxide (RGO). Pyrrole was polymerized uniformly on the surface of graphitic materials by in situ polymerization method. The structures of nanocomposites were studied by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy indicating the well-exfoliated GO and RGO in PPy matrix with favorable interfacial interaction. PPy/RGO nanocomposite showed the highly improved response in detecting ammonia gas mainly due to the effective electron charge transfer between PPy and ammonia and the efficient transfer of electrical resistance variation by the uniformly dispersed conductive RGO in PPy. PPy/RGO nanocomposite gas sensor also showed the excellent reproducibility in ammonia sensing behavior during the recovery process at lower temperature of 373 K.
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    Enhanced crystallization behaviors of poly(ethylene terephthalate) via adding expanded graphite and poly(ethylene glycol) (2013)
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    Publication Date: 2013-04-10
    Description: A compound additive system consisting of expanded graphite (EG) and poly(ethylene glycol) (PEG) was designed to enhance the crystallization of poly(ethylene terephthalate) (PET). In this additive system, EG acted as a heterogeneous nucleating agent to reduce energy barrier for nucleation, while PEG played as plasticizer to improve mobility of PET chains. Simultaneously adding EG and PEG resulted in faster crystallization kinetics than the cases of solely adding EG or PEG in both of non-isothermal and isothermal crystallization processes, indicating a synergistic effect of EG and PEG on enhancing PET crystallization. However, for non-isothermal crystallization process, in which crystallization occurred from a cooling melt, EG played a dominant role. As to isothermal crystallization process where crystallization took place in a super-cooling state, PEG seemed to be more important. Moreover, the chain conformation change among the semi-crystalline PET specimens was ascertained by Fourier transform infrared spectroscopy.
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    Generalizing the polymerization conditions for the production of monodisperse polymeric particles via dispersion polymerization (2013)
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    Publication Date: 2013-04-10
    Description: In this study, the preparation of various methacrylic particles with monodisperse size via dispersion polymerization in polar media was discussed. The effect of various polymerization conditions such as polarity of the medium, monomer, stabilizer, and initiator concentration, polymerization temperature, and initiator type on the size and size distribution of these particles was evaluated. The experimental results showed that, with a decrease in the difference between medium solubility parameter (MSP) and polymer solubility parameter (PSP), stabilizer concentration and with an increase in monomer content size of the particles increased and size distribution of them became broader. The obtained results showed that the particle size and size distribution of various polymers were different functions of initiator concentration. It means that, for the production of monodisperse particles, specific amount of initiator is needed for each type of the polymers. Moreover, it was observed that the size and size distribution of the particles with higher polarity were more sensitive to changing the polarity of the medium, and the size distribution of the particles with lower glass transition temperature ( T g ) is more sensitive to changing the stabilizer concentration which is because of less stability of them. Furthermore, to our surprise, the obtained results showed that, in MSP-PSP of 18.5 MPa 0.5 , size and size distribution of all types of the particles became equivalent.
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    Synthesis and surface properties of self-crosslinking core–shell acrylic copolymer emulsions containing fluorine/silicone in the shell (2013)
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    Publication Date: 2013-09-14
    Description: Stable emulsions of a core–shell acrylic copolymer (non-crosslinkable V0, and crosslinkable V2, V4, V6, and V8, where the numbers indicate the wt% of crosslinking agent based on the total acrylate monomer content) containing butyl acrylate (BA, 45 wt%), glycidyl methacrylate (GMA, 45 wt%), heptadecafluorodecyl methacrylate (PFA, 10 wt%), and various contents of crosslinking agent (vinyltriethoxysilane, VTES) were synthesized using a three-stage seeded emulsion polymerization process with a small amount of surfactant. The average particle size and viscosity of emulsions increased significantly with increasing VTES content. This study examined the effects of the VTES content on the surface/mechanical properties of self-crosslinked copolymer film samples containing a fixed acrylate monomer content to find the optimum VTES content. XPS showed that the film–air surface of the copolymer samples had a higher fluorine/silicone content than the film–dish interface. The tensile strength/modulus, thermal stability, and two Tgs (α and β Tgs) of the film samples increased significantly with increasing VTES content. The contact angle of the film samples increased with increasing VTES content up to approximately 6 wt%, and then decreased slightly. The optimum VTES content was approximately 6 wt% based on the total acrylate monomer content to obtain a high water/oil repellent coating material (V6) with the highest water/methylene iodide-contact angles (118.2°/81.8°) and lowest surface energy (18.4 mN/m).
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    Amphiphilicity and self-assembly behaviors of polystyrene-grafted multi-walled carbon nanotubes in selective solvents (2013)
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    Publication Date: 2013-09-14
    Description: Multi-walled carbon nanotubes (MWCNTs) can self-assemble as cylindrical bundles in some solvents after polystyrene (PS) grafting. In these three-dimensional regular structures, the tubes are oriented and parallel arranged. Every self-assembly structure has an order head and a comparatively loose tail. In order to find out the role that solvent plays, MWCNTs were dispersed in several organic solvents before and after modification. Based on macroscopic stability of suspensions and microscopic state of nanotubes, compatibility between solvents and MWCNTs can be confirmed. According to compatibility difference between tubes and PS, five chosen solvents are divided into three groups: selective solvent, good solvent, and bad solvent. MWCNT-g-PS can self-assemble only in selective solvents. Tetrahydrofuran and benzene are well compatible with PS, but bad with MWCNTs. Driven by the solvent–philic/solvent–phobic interaction, MWCNT-g-PS self-organized regularly as bundles. Because each part of the MWCNT-g-PS is compatible well with 1,2-dichlorobenzene, gathering tendency of the modified tubes have been enervated by their good compatibility and weak amphiphilicity. Grafted or not, nanotubes reveal poor compatibility with methanol and ethanol. Strong incompatibility and limited amphiphilicity make MWCNT-g-PS agglomerate as quickly and irregularly as raw tubes. An adapted hydrophilic/lipophilic balance system is introduced to qualify compatibility and amphiphilicity of MWCNT-g-PS in each solvent. This novel model not only reveals the relationship between solvent and microscopic state of unmodified/modified tubes, but also signifies the decisive role of solvent in self-assembly behaviors of MWCNT-g-PS.
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    Soap-free emulsion polymerization of poly (methyl methacrylate-co-butyl acrylate): effects of anionic comonomers and methanol on the different characteristics of the latexes (2013)
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    Publication Date: 2013-09-14
    Description: Soap-free emulsion polymerization (SFEP) of methyl methacrylate, butyl acrylate was conducted in water/methanol media with sodium salts of four different acidic comonomers, namely styrene sulfonic acid (NaSS), 2-acrylamide-2-methyl-1-propane sulfonic acid (NaAmps), acrylic acid (NaAA), and itaconic acid (Na 2 ita). It was found that the introduction of methanol as co-solvent (35 wt%) to the medium greatly decreases the amount of water-soluble polyelectrolyte in the cases NaAA and Na 2 ita while it does not make difference for NaSS and NaAmps. Having employed the concept of conductance dependency to the ion mobility, the onset concentration in which soluble chains were formed was detected. The addition of sulfonic-based comonomers (NaSS and NaAmps), first decreased particle size and then led to predomination of solution polymerization over SFEP. On the contrary, the incorporation of carboxylic-based comonomers (NaAA and Na 2 ita) led to increase in particle size. Moreover, the particle size results were in good qualitative agreement with the classical Smith–Ewart theory.
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    Photocatalytic performance of silver-modified TiO 2 embedded in poly(ethyl-acrylate-co-methyl metacrylate) matrix (2013)
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    Publication Date: 2013-09-16
    Description: The plasmonic Ag-TiO 2 (with 0.5 wt% Ag) photocatalyst was prepared on P25 TiO 2 surface. The presence of AgNPs on the titania was indicated by the UV–vis spectrum, which showed a plasmonic absorbance band in the visible range ( λ max  = 455 nm). XPS measurements suggested that Ag was in metallic (Ag) and in oxide forms on TiO 2 . Ag-TiO 2 photocatalyst and TiO 2 were embedded in [poly(ethyl acrylate-co-methyl methacrylate; p(EA-co-MMA)] copolymer to attain mechanically stable, photocatalytically active nanocomposite films. The photooxidation of ethanol was slower on the photocatalyst/polymer nanocomposites, but it could be significantly improved by irradiating them with UV light. The photoaging was applied as a post-preparation treatment to improve the photocatalytic activity of the nanocomposite films. Changed surface morphology and the partial destruction of the polymer were supported by AFM and FTIR results. Contact angle measurements were used to determine the surface free energies of the prepared and the photoaged nanocomposite films.
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    Preparation of protein microcapsules with narrow size distribution by sonochemical method (2013)
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    Publication Date: 2013-09-19
    Description: Protein microcapsules with narrow size distribution have been prepared by sonochemical method which is a simple, fast, environmental friendly and cost-effective method. The prepared microcapsules are composed of a water-insoluble core and an outer protein shell. The hydrophobic drugs could be encapsulated into protein microcapsules directly via sonochemical method by dissolving drugs in the nontoxic and edible vegetable oil before ultrasonication, which is a potential solution for drug resistance by hiding cytotoxic drugs in the carrier and allows for the delivery of high doses in relatively small volume. The size and size distribution of protein microcapsules are very important for their practical application. In this paper, the factors affecting the size and size distribution of protein microcapsules are investigated in detail. Moreover, confocal laser scanning microscopy and transmission electron microscopy confirmed that the protein microcapsules with narrow size distribution were obtained.
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    Inclusion complexes of α-cyclodextrins with poly( d , l -lactic acid): structural, characterization, and glass transition dynamics (2013)
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    Publication Date: 2013-12-03
    Description: Poly ( d , l -lactic acid) (PDLLA) was combined with α-CD to form inclusion complexes (ICs) with distinct PDLLA fractions. The structural changes resulting from this coalescence process were analyzed by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance ( 1 H NMR), and X-ray diffraction (XRD). The presence of both components in the ICs was confirmed by FTIR. The encapsulated PDLLA fraction was quantified by 1 H NMR. XRD data evidenced that it was possible to transform the amorphous PDLLA into a well-organized channel-type crystalline structure. DSC showed that the glass transition temperature of the PDLLA fraction in the ICs was higher than in the pure polymer, indicating that the ultra-confinement effect imposed by the ICs organization clearly limits PDLLA molecular dynamics. The confinement effect on the glass transition dynamics was investigated by unconventional dynamic mechanical analysis experiments, which confirmed that ICs segmental mobility is highly restricted when compared with the one of pure PDLLA. Bulk PDLLA presents a typical VFTH behavior while the ICs dynamics shows an Arrhenius trend.
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    Colloidal crystallization of spindle-shaped hematite particles coated with polymer brush in deionized aqueous suspension (2013)
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    Publication Date: 2013-12-09
    Description: Colloidal crystallization of highly monodisperse spindle-shaped hematite particles coated with poly(poly(ethylene oxide) methyl ether methacrylate) brush (SHB) was studied by reflection spectroscopy and optical microscopy. SHB suspensions were deionized exhaustively with the mixtures of cation- and anion-exchange resins more than 6 months. The liquid thin film along the vertical cell wall above the horizontal air–liquid interface showed the strong color bands. Furthermore, the reflection spectra composed of many sharp peaks shifted continuously toward shorter wavelengths with time. These observations support the presence of thin film of SHB suspension, where the width is thickened downward by the gravity and the layered liquid further flow downward with time. The rigidities of SHB crystals in the bulk phase estimated from the optical microscopy in the sedimentation equilibrium were 0.007 to 0.7 Pa as SHB concentration increased from 0.006 to 0.35 wt.%. The fluctuation parameter, b -factors of the anisotropic crystals, was from 0.025 to 0.035 and decreased slightly as particle concentration increased. Rigidities and the fluctuation parameters of SHB suspensions support that the elastic properties of the anisotropic-shaped colloidal crystals are close to those of typical crystals of colloidal spheres. Compression of the SHB crystals by the gravity is also suggested in the sedimentation equilibrium state.
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    Preparation of hemispherical particles by cleavage of micrometer-sized, spherical poly(methyl methacrylate)/polystyrene composite particle with Janus structure: effect of molecular weight (2013)
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    Publication Date: 2013-12-14
    Description: Micrometer-sized, hemispherical polymer particles were prepared as a result of cleavage of spherical Janus poly(methyl methacrylate) (PMMA)/polystyrene (PS) composite particle by treating particles with acetone/water solutions. The original PMMA/PS composite particles were prepared by the slow evaporation of toluene from homogeneous PMMA/PS/toluene droplets dispersed in aqueous solution of sodium dodecyl sulfate in advance. Appropriate molecular weights of PMMA and PS were necessary for occurrence of the cleavage of the Janus composite particle, resulting in PMMA and PS hemispherical particles. The cleavage depended on the composition of the acetone/water solution, which was explained by selective solvent absorption into the polymer phases. The results strongly support the cleavage mechanism of Janus composite polymer particles that had been proposed earlier.
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    Crystallization and melting behaviors of polypropylene admixed by graphene and β-phase nucleating agent (2013)
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    Publication Date: 2013-12-14
    Description: In this work, the crystallization and melting behaviors of different polypropylene (PP) materials containing a certain amount of graphene, β-phase nucleating agent (β-NA), and their mixture, respectively, were comparatively investigated. The results showed that graphene exhibited the typical sheet structure in the PP matrix, and the presence of β-NA did not change the dispersion of graphene apparently. Both graphene and β-NA exhibited great nucleating effect for the crystallization of PP. However, the nucleation efficiency of β-NA was much larger than that of graphene. With the simultaneous presence of graphene and β-NA, the crystallization ability of PP matrix was greatly improved, which indicated that there was a synergistic effect between graphene and β-NA in accelerating crystallization of PP matrix. Furthermore, it was proved that the synergistic effect was greatly dependent upon the crystallization conditions. The higher the isothermal crystallization temperature or the bigger the cooling rate, the more apparent the synergistic effect was.
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    Research on association between multi-sticker amphiphilic polymer and water-soluble β-cyclodextrin polymer (2013)
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    Publication Date: 2013-12-09
    Description: The host cyclodextrin polymer-P(AM/A-β-CD/NaA) is prepared by redox free-radical copolymerization. Additionally, the multi-sticker amphiphilic polymer-P(AM/BHAM/NaA) as a guest polymer is synthesized using micellar polymerization. The copolymer structures are characterized by 1 H NMR. Subsequently, all the polymers and inclusion complexes are evaluated in terms of apparent viscosity, optical absorption spectra and rheological property. The results indicate that the inclusion association between the cyclodextrin group (CD) and multi-sticker hydrophobic monomer (BHAM) is in accordance with ternary interaction (CD/BHAM = 2:1). Because of the inclusion association between the host and guest polymers, the solution of inclusion complex has much higher viscoelasticity even under the low amphiphilic polymer concentration. When the molar ratio of CD to BHAM is 1:1, the critical aggregation concentration (CAC) of the inclusion complex solution still remains. Furthermore, above the CAC, two types of associations, inclusion association and inter-molecular hydrophobic association, can occur in the complex solution and these interactions were also verified by fluorescence spectroscopy and atomic force microscopy (AFM). In this paper, the inclusion rule of cyclodextrin polymer with the multi-sticker amphiphilic polymer is discussed, and the rule of the enhanced solution viscosity is further explored.
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    Adsorption characteristics of polyvinyl alcohols on modified zeolites (2013)
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    Publication Date: 2013-12-14
    Description: Adsorption characteristics of two types of polyvinyl alcohols (with different polymerization degrees) on faujasite-type zeolites obtained by SiCl 4 treatment as well as by a combined hydrothermal acid treatment were investigated in an aqueous solution. No adsorption of the polyvinyl alcohol with a polymerization degree of 500 was observed on the SiCl 4 -treated faujasite without secondary pores in the mesopore region, but adsorption did occur (about 0.11 g g −1 ) on the hydrothermal acid-treated faujasite containing secondary pores. On the other hand, the polyvinyl alcohol with a polymerization degree of 2,000 did adsorb on the SiCl 4 -treated faujasite. Scanning electron microscopy measurements confirmed that adsorption occurred on the external surface of the zeolite crystals.
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    Effects of sodium salicylate on the microstructure of a novel zwitterionic gemini surfactant and its rheological responses (2013)
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    Publication Date: 2013-12-14
    Description: Solutions of a novel zwitterionic gemini surfactant, 1,2-bis[ N -ethyl- N -(sodium 2-hydroxyl-3-sulfopropyl)-dodecyl-ammonium] ethane betaine (DBA 2-12 ), in presence of sodium salicylate (NaSal) can form wormlike micelles and thereby show a viscoelasticity. At low molar ratio of NaSal/DBA 2-12 , R  ≤ 0.3, the systems behaved like a Newton fluid. However, as the R increased, the systems exhibited shear-thinning behavior. The zero-shear viscosity η 0 increased dramatically with increasing R and peaked with R  = 0.8 at a value of 18.8 Pa s. This was attributed to the formation of long wormlike micelles (1.6 ∼ 2.9 μm) and network structure confirmed by scanning electron microscopy. Further increase in R beyond 0.8 resulted in a slight decrease in η 0 , which may be caused by the branched micelles formed at high salt concentration. In addition, the tested systems showed a Maxwellian behavior at lower frequencies, but deviated from the Maxwellian mode at higher frequencies.
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    Effective surface immobilization of nanoparticles using bubbles generated by sonication (2013)
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    Publication Date: 2013-12-14
    Description: A nanoscale material represents a promising adsorbent material for water treatment due to its large surface area and its ability to incorporate compounds with specific functions. In this research, the effective immobilization of nanoparticles using an ultrasonic technique and the change of the surface morphology of the substrate by sonication was investigated. The effective surface immobilization of the nano-magnetite powder and an increase in the reactive area with aqueous contaminant were caused by bubbles generated by the sonication method. The effect of the frequency of the ultrasonic wave on the immobilization of the nano-powder was also investigated.
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    On the behavior of an oblate spheroidal hematite particle in a simple shear flow under a uniform magnetic field applied in the flow direction (2013)
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    Publication Date: 2013-12-14
    Description: We discuss the orientational properties of an oblate spheroidal hematite particle and also its influence on the rheological characteristics of a dilute suspension of these magnetic particles, by means of an analytical approach based on the orientational distribution function. A hematite particle with oblate spheroidal shape has an important characteristic; that is, it is magnetized in a direction normal to the particle axis. From the balance of the torques acting on a particle, we have developed the basic equation of the orientational distribution function. This basic equation has been numerically solved in order to investigate the dependence of the orientational distribution on the various factors. If both the magnetic field and the shear flow are weak, the particle does not exhibit specific directional characteristics. If the magnetic field is more dominant, the particle inclines such that the oblate surface is parallel to the magnetic field direction. If the shear flow becomes more dominant, the particle shows a sharper peak of the orientational distribution in the shear flow direction. The viscosity due to the magnetic torque increases and finally converges to a constant value as the magnetic field increases. In a sedimentation process under the gravitational field, the translational diffusion coefficient decreases with increasing magnetic field strength in the present case of the magnetic field direction.
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    Drying dissipative structure of sodium salts of hyaluronic acid (2013)
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    Publication Date: 2013-10-09
    Description: Macroscopic and microscopic patterns during the course of dryness of aqueous solution in sodium salts of hyaluronic acid (NaHLA) were observed on a cover glass, a watch glass, and a Petri glass dish. Dendritic and rod-like microscopic patterns, which are similar to those of sodium salts of carboxymethyl cellulose, were observed for NaHLA especially on a cover glass and a watch glass. The microscopic patterns of NaHLA are supported to be originated from the hexose groups of polysaccharides, though the similar dendritic patterns are also observed for some of polynucleotides, sodium salts of deoxyribonucleic acid, and potassium salts of poly (riboadenylic acid), for example. Macroscopic broad ring size decreased substantially from the initial size of liquid and decreased slightly as polymer concentration decreased. These observations are consistent with existence of the rather strong interpolymer affinitive forces during the course of dryness. In the coexistence of sodium chloride, microscopic dendritic patterns grew large especially on a cover glass and a watch glass, which was so often observed for polysaccharides examined hitherto. Drying patterns are clarified to be formed by the successive and cooperative processes of evaporation, convection, sedimentation, and solidification.
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    Influence of chain structure on crystal polymorphism of poly(lactic acid). Part 1: effect of optical purity of the monomer (2013)
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    Publication Date: 2013-10-09
    Description: The influence of chain structure on crystal polymorphism of poly(lactic acid) (PLA) with high l -lactic acid content (97.8–100 %) is detailed in this contribution. Upon usual processing conditions of PLA, only α and α′ crystals grow, which makes these two polymorphs of major interest for research. The two crystal modifications have similar chain packing, which complicates their quantitative analysis by diffraction methods. The two crystal modifications are instead easily identified by analysis of the crystallization kinetics, which varies not only with temperature, but also with crystal polymorphism. The dependence of the rate of ordering on temperature shows two distinct maxima around 105–110 and 120–125 °C, which are related to growth of α′ and α crystals, respectively. Addition of d -lactic acid co-units leads to a decrease of the overall crystallization rate of PLA, as well as of the rate of spherulite growth ( G ) of both the crystal modifications. The relative crystallization rates of α and α′ forms are highly affected by stereoregularity, especially in the PLA grades that have a high crystallization rate. A high d -lactic acid content results not only in an overall slower crystal growth, but also in a varied temperature range where each of the two crystal modifications prevail, with a shift to lower temperatures of both the maxima of the G vs. temperature plots, indicating that inclusion of d -lactic acid units in the PLA chain affects crystallization rate of both α and α′ crystal modifications.
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    Colloidal stability evolution and completely reversible aggregation of gold nanoparticles functionalized with rationally designed free radical initiators (2013)
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    Publication Date: 2013-10-12
    Description: A series of molecular adsorbates having various chain lengths of terminal poly(ethylene glycol methyl ether) (PEG) moieties, thiol head groups, and intervening free radical initiator moieties was used to functionalize the surface of gold nanoparticles (AuNPs). The bulky PEG groups stabilized the functionalized AuNPs by providing steric hindrance against AuNP aggregation, such aggregation being a major problem in the modification and manipulation of metal nanoparticles. UV–vis spectroscopy was used to evaluate the stability of the adsorbate-functionalized AuNPs as a function of AuNP size (∼15, 40, and 90 nm in diameter) and PEG chain length (Mn 350, 750, and 2,000). The longer PEG chains (Mn 750 and 2,000) afforded stability to AuNPs with smaller gold cores (∼15 and 40 nm in diameter) for up to several days without any marked aggregation. In contrast, the adsorbate-functionalized AuNPs with the largest gold cores (∼90 nm) were noticeably less stable than those with the smaller gold cores. Importantly, the adsorbate-functionalized AuNPs could be isolated in solvent-free “dried” form and readily dispersed in aqueous buffer solution (both acidic and basic) and various organic solvents (protic and aprotic). This isolation–redispersion (i.e., aggregation/deaggregation) process was completely reversible. The chemisorption of the PEG-terminated initiator on the surface of the AuNPs was verified by Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). As a whole, the strategy reported here affords colloidally stable, free radical initiator-functionalized AuNPs and offers a promising general method for encapsulating metal nanoparticles within polymer shells. Figure ᅟ
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    Polymer–polymer complexes of poly( N -isopropylacrylamide) and poly( N , N -diethylacrylamide) with poly(carboxylic acids): a comparative study (2013)
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    Publication Date: 2013-10-12
    Description: In this manuscript, the complexation process between two polyacids, poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA), and two different polyacrylamides, poly( N -isopropylacrylamide) (PNiPAm) and poly( N , N -diethylacrylamide) (PNdEAm), in organic solvents, has been studied. The influence of polymer chemical structure and the effect of polymer–solvent interactions on the complex formation in solution have been analyzed. Specific interactions were studied by Fourier transform infrared (FTIR) spectroscopy, and the composition of the obtained complexes was determined by elemental analysis. The calorimetric study of the interpolymer complexes shows a unique glass transition temperature for all systems except for PNdEAm/PMAA system in which phase separation was observed after thermal treatment.
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    Electrostatic repulsion between two parallel plates covered with polyelectrolyte brush layers. Effects of interdigitation (2013)
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    Publication Date: 2013-10-14
    Description: A three-stage model is presented for the electrostatic repulsion between two parallel plates covered with polyelectrolyte brushes (i.e., plate-like soft particles) in an electrolyte solution. This is an extension of a previous theory (Ohshima, Colloid Polym Sci 277: 535, 1999 ), which assumes that when the two brushes come into contact, they are squeezed against each other but they do not interdigitate. The present theory covers the case where interdigitation between brushes occurs and proceeds until full interdigitation occurs. Then, compression of the polyelectrolyte brushes starts. That is, in the present model, the interaction process consists of three stages, i.e., interaction before contact of the polyelectrolyte brushes (stage 1), interdigitation (stage 2), and compression (stage 3). It is found that for highly charged polyelectrolyte brushes, the repulsive force between the two plates becomes almost constant independent of the plate separation during interdigitation.
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    Effect of cetyltrimethylammonium bromide addition on the emulsions stabilized by montmorillonite (2013)
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    Publication Date: 2013-10-16
    Description: The wettability of montmorillonite could be in situ modified by cationic surfactant cetyltrimethylammonium bromide (CTAB). The type and stability of emulsions prepared from montmorillonite with different concentrations of cationic surfactant were investigated, and a double phase inversion of emulsions was observed. The adsorption of CTAB on montmorillonite particles was studied by surface tension and zeta potential measurements, and the variation of the wettability of particles with the concentration of CTAB was characterized by the contact angle measurements. The adsorption of particles at the surface of emulsion droplets was observed by laser-induced confocal scanning microscopy. At low surfactant concentrations, the adsorption of CTAB on montmorillonite increased the hydrophobicity of the particles, and the stability of oil-in-water emulsions was enhanced. With the increase of the CTAB concentration, montmorillonite particles changed from hydrophilic to hydrophobic, and water-in-oil emulsions were obtained. However, at higher surfactant concentrations, the emulsions inverts to O/W again because montmorillonite particles were reconverted into hydrophilic due to the formation of CTAB bilayer on the surface of montmorillonite.
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    Polyampholyte-tuned lyotrop lamellar liquid crystalline systems (2013)
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    Publication Date: 2013-10-17
    Description: The influence of a polyampholyte, i.e., poly( N , N ′-diallyl- N , N ′-dimethyl-altmaleamic carboxylate) (PalH), on the lamellar liquid crystalline (LC) system sodium dodecyl sulfate (SDS)/decanol/water was investigated by means of microdifferential scanning calorimetry, small-angle X-ray diffraction (SAXS), and cryo-scanning electron microscopy. After incorporating PalH into the lamellar liquid crystalline system, SAXS measurements show that three different LC phases exist: i.e., a swelling, slightly swelling, and non-swelling one. At pH 4, the positively charged polymer with an extended conformation can directly adsorb at the anionic head groups of the surfactant and more compact vesicles are formed at room temperature. At pH 9, the electrostatic interactions between the polyampholyte (in a more coiled conformation) and the sulfate head groups of the SDS are leveled off and incompact vesicles are formed at room temperature. That means in presence of the polyampholyte the morphology of the LC phase, i.e., the supramolecular vesicle structure, can be tuned by varying the pH and/or the temperature. Figure pH-dependent tuning of the morphology of the lamellar phase
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    Light-responsive drug carrier vesicles assembled by cinnamic acid-based peptide (2013)
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    Publication Date: 2013-10-17
    Description: A novel cinnamic acid-based dipeptide is designed and prepared from cinnamic acid and glycylglycine. In aqueous solution, the molecules can self-assemble into vesicular structures, which were characterized in detail by transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. Aromatic stacking and intermolecular hydrogen bonding interactions are regarded as the driving force in the formation of the stable supramolecular structure. Subsequently, the stimuli-responsive property of the vesicles to UV irradiation was also studied. The vesicles were also found to be able to efficiently carry hydrophobic drugs. We believe that this study may provide more references in the fields of body-friendly smart materials with the hope of in vivo applications.
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    Associative and segregative phase behaviour in mixtures of poly( N - tert -butylacrylamide) and poly( N , N -diethylacrylamide) with poly(4-vi (2013)
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    Publication Date: 2013-10-17
    Description: Interpolymer complexation behaviour between poly(4-vinylphenol) (PVPh), as proton donor, and polyacrylamide derivatives, poly( N - tert -butylacrylamide) and poly( N , N -diethylacrylamide) (PNdEAm), as proton acceptor polymers, with both hydrogen bonding and hydrophobic properties, have been studied. Most mixtures studied in this work resulted in coprecipitation, that is, an associative phase separation. However, for the system PNdEAm/PVPh in aprotic solvents, tetrahydrofuran, acetone and 1,4-dioxane, either an associative (coprecipitation) or a segregative (precipitation of one polymer in presence of the other) behaviour is observed depending on concentration.
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    Giant vesicles prepared by nitroxide-mediated photo-controlled/living radical polymerization-induced self-assembly (2013)
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    Publication Date: 2013-10-17
    Description: Giant vesicles with several-micrometer diameters were prepared by self-assembly induced by the nitroxide-mediated photo-controlled/living radical polymerization. The random block copolymerization of methyl methacrylate (MMA) and methacrylic acid (MAA) were performed using poly(methacrylic acid) (PMAA) as the prepolymer in an aqueous methanol solution to produce a PMAA- block -poly(MMA- random -MAA) random block copolymer (PMAA- b -P(MMA- r -MAA)). PMAA 195 - b -P(MMA 0.817 - r -MAA 0.183 ) 224 formed spherical vesicles with a 4.74 μm diameter and 0.108 μm wall thickness. A differential scanning calorimetry analysis demonstrated that the vesicles had a bilayer structure consisting of a hydrophilic PMAA surface and hydrophobic P(MMA- r -MAA) interface. The wet vesicles before air-drying were flexible and easily transformed by stress, whereas the dry vesicles were fragile and cracked. The vesicles in the solution were dissociated into much smaller vesicles by increasing the temperature. They were also transformed by a further temperature increase into hollow fibers and finally into membranes retaining the bilayer structure.
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    Inclusional association as studied by the drying dissipative structure. Part 3. Drying pattern of aqueous mixtures of β-cyclodextrin and n -alkyltrimethylammonium bromide (2013)
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    Publication Date: 2013-10-17
    Description: Macroscopic and microscopic drying patterns were observed on a cover glass and a watch glass during the course of dryness of aqueous mixtures of β-cyclodextrin (βCD) with n -alkyltrimethylammonium bromide (alkyl: n -decyl, n -dodecyl, n -tetradecyl, and n -hexadecyl). Macroscopic patterns of the broad rings and the spoke lines appeared. The inclusional association constants of βCD with the cationic surfactants were determined from the bent points in the curves of the drying broad-ring size vs. surfactant concentration when a finite amount of cyclodextrin presents. The short and thick rod - like microscopic drying patterns were observed for the inclusional complexes.
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    Sonochemical activation calcium sulfate whisker with enhanced beta-nucleating ability for isotactic polypropylene (2013)
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    Publication Date: 2013-10-17
    Description: The crystalline morphology, structure, and the β-nucleating ability of ultrasound-activated calcium sulfate whisker (CSW)-filled isotactic polypropylene were investigated via X-ray diffraction (XRD), polar light microscopy (PLM), and differential scanning calorimetry (DSC). The XRD results revealed that ultrasound treated CSW (UCSW) could improve the β-nucleated ability, and resulted in enhancing the content of β-crystal form. The ultrasonic time was conducive to the improvement of the contents of β-crystal and reached the maximum value at ultrasonic 120 min. PLM and DSC results verified the enhanced nucleating ability of UCSW supported as β-nucleating agent. The scanning electron microscopy, energy dispersive spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy indicated the surface of CSW treated by ultrasound had been changed. The activity of the calcium ion was improved and the sulfuric acid layer appeared on the whisker surface had a significant effect on the iPP β-heterogeneous nucleation, and resulted in enhancing the content of β-crystal form.
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    Multicompartment micelles from silicone-based triphilic block copolymers (2013)
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    Publication Date: 2013-10-17
    Description: An amphiphilic linear ternary block copolymer was synthesised in three consecutive steps via reversible addition–fragmentation chain transfer polymerisation. Oligo(ethylene glycol) monomethyl ether acrylate was engaged as a hydrophilic building block, while benzyl acrylate and 3-tris(trimethylsiloxy)silyl propyl acrylate served as hydrophobic building blocks. The resulting “triphilic” copolymer consists thus of a hydrophilic (A) and two mutually incompatible “soft” hydrophobic blocks, namely, a lipophilic (B) and a silicone-based (C) block, with all blocks having glass transition temperatures well below 0 °C. The triphilic copolymer self-assembles into spherical multicompartment micellar aggregates in aqueous solution, where the two hydrophobic blocks undergo local phase separation into various ultrastructures as evidenced by cryogenic transmission electron microscopy. Thus, a silicone-based polymer block can replace the hitherto typically employed fluorocarbon-based hydrophobic blocks in triphilic block copolymers for inducing multicompartmentalisation.
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    One-step synthesis of silica hollow particles in a W/O inverse emulsion (2013)
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    Publication Date: 2013-10-17
    Description: Porous silica hollow particles have been fabricated by a one-step approach in water in oil (W/O) inverse emulsion. Ammonia water droplets stabilized by alkyl-phenol polyoxyethylene ether (TX-4) in tetraethoxysilane (TEOS)/cyclohexane solution act as soft templates for constructing the silica hollow particles. The formation mechanism is discussed in detail from the equilibrium between the diffusion and reactions of TEOS and its products (hydrolysates and polycondensates) on the W/O interface. The structure and morphology of the resultant silica hollow particles are well controlled by changing the parameters involving the concentration of TX-4, TEOS, and ammonia. The synthesized products have been characterized using transmission electron microscopy, scanning electron microscopy, solid state NMR, and nitrogen adsorption–desorption measurements.
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    Ni–Zn ferrite-loaded superparamagnetic amorphous carbon nanotubes through a facile route (2013)
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    Publication Date: 2013-10-17
    Description: Partial filling of mixed ferrite (Ni 0.5 Zn 0.5 Fe 2 O 4 ; NZFO) nanoparticles into the amorphous carbon nanotubes (aCNTs) cavity is achieved by simple mixing of the aqueous dispersions of the two (aCNTs and NZFO) at room temperature. The process of incorporation of the nanoparticles into the aCNT cavity is solely mediated by the capillary action of the liquid. NZFO nanoparticles were homogeneously dispersed in the aqueous solution but after mixing they are sparsely distributed into the aCNT channel as a result of the capillary action. The encapsulation of the nanoparticles into the aCNTs amorphous shield was established by means of X-ray diffraction, transmission electron microscopy, Fourier transformed infrared spectroscopy, and Raman spectroscopic analysis. Such entrapment of the nanoparticles causes the composite nanotubes superparamagnetic in nature with blocking temperature ( T B ) at 15 K. However, compared to the powder NZFO nanoparticles, T B appears more sharply and at relatively lower temperature. Low filling density and the spatial confinement of the nanoparticles lessen the inter-particle interactions and the polydispersity within the NZFO nanoparticles which are manifested in their altered magnetic behavior.
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    Temperature effect on the surface phase transitions of monolayer films of C 12 E 1 at air/water interface (2013)
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    Publication Date: 2013-10-17
    Description: The temperature-dependent conformational states of a monolayer film of ethylene glycol monododecyl ether (C 12 E 1 ) at the air/water interface have been investigated using ellipsometry, surface tension, external reflection–absorption FTIR spectroscopy and two-dimensional infrared (2DIR) correlation analysis. The ellipticity coefficients and the entropy associated with C 12 E 1 adsorption changed almost discontinuously at certain temperatures, which manifested the interfacial phase transitions. The phase transition and coexistence of two phases were further clarified using 2DIR correlation analysis with temperature perturbation. The asynchronous correlation maps revealed that both bands of asymmetric and symmetric C–H stretching vibration in one-dimensional IR were split into two components, which confirmed the coexistence of two phases at the interface.
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    Wetting behavior of pulmonary surfactant aqueous solutions (2013)
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    Publication Date: 2013-10-17
    Description: The wetting properties of pulmonary surfactant aqueous solutions with respect to solid surfaces with different degree of hydrophobicity have been studied. The contact angles θ of drops from a pulmonary surfactant solution onto SiO 2 -glass surfaces have been measured as a function of their degree of hydrophobicity θ w . The completely hydrophilic SiO 2 -glass surface is essentially hydrophobized by the animal-derived pulmonary surfactant Curosurf . The hydrophobization depends on the surfactant concentration—the contact angles increase with increasing the Curosurf concentration C s in the low concentration range, but they remain almost constant in a wide range of C s 〉90 μg/ml. Additions like NaCl and bovine serum albumin influence the θ -values. The contact angles θ naturally increase with increasing θ w but this dependence is not linear—the curve steepens at larger θ w values. The thickness h of the wetting thin liquid films from Curosurf aqueous solutions depends on the hydrophobicity θ w of the solid surface and the h ( θ w ) curves always pass a minimum. The h -values, as well as the h ( θ w ) curve, are mainly determined by the steric and hydrophobic disjoining pressures, which depend on the orientations and conformations of the molecules adsorbed on the solid surface from the very complicated multi-component aqueous solutions.
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    Preparation and properties of fluorinated carboxylic acid/silica nanocomposite-encapsulated low molecular weight compounds (2013)
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    Publication Date: 2013-10-07
    Description: Perfluoro-2-methyl-3-oxahexanoic acid/silica nanocomposites [R F -CO 2 H/SiO 2 ] were prepared by the sol–gel reaction of tetraethoxysilane in the presence of silica nanoparticles and the corresponding fluorinated carboxylic acid under alkaline conditions. R F -CO 2 H/SiO 2 nanocomposites were found to exhibit no weight loss in proportion to the contents of fluorinated carboxylic acid in the composites even after calcination at 800 °C. The modified glass surface treated with the R F -CO 2 H/SiO 2 nanocomposites was shown to give a good oleophobicity with superhydrophilicity imparted by fluorinated carboxylic acid in the composites. R F -CO 2 H/SiO 2 nanocomposites were also applied to the encapsulation of a variety of low molecular weight aromatic and aliphatic compounds such as bisphenol AF [BPAF], bisphenol A [BPA], 4,4′-biphenol [BPOH], octafluoro-4,4′-biphenol [FBPOH], 4,4′-bis(triethoxysilyl)-1,1′-biphenyl [BTSBP], 3-(trihydroxysilyl)propane-1-sulfonic acid [THSP], α-cyclodextrin (α-CD), β-cyclodextrin (β-CD), and γ-cyclodextrin (γ-CD). Encapsulated aromatic compounds possessing acidic hydroxyl groups such as BPAF, BPA, and FBPOH in the R F -COOH/SiO 2 nanocomposites were found to exhibit no weight loss corresponding to the contents of aromatic compounds in the composites even after calcination at 800 °C. On the other hand, encapsulated aromatic compounds possessing no acidic hydroxyl groups such as BTSBP and aliphatic compounds (THSP, α-, β-, and γ-CD) gave a clear weight loss corresponding to the contents of these compounds in the composites after calcination. In addition, the fluorinated silica nanocomposite-encapsulated these compounds were applied to the surface modification of glass to exhibit a good oleophobicity with superhydrophilicity imparted by fluorinated carboxylic acid on the surface. Figure ᅟ
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    Optimization of parameters in preparation of PCM microcapsules based on melamine formaldehyde through dispersion polymerization (2013)
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    Publication Date: 2013-10-06
    Description: Microencapsulated phase change materials have attracted special attention due to their wide applications in saving and releasing energy. Here, microencapsulation of hexadecane (HD) in melamine formaldehyde shell was carried out through in situ dispersion polymerization in the aqueous media. Some important parameters such as stabilizer type and amount, surfactant amount, homogenization conditions as the critical affective factors on final particle size, morphology, and thermal resistance of the microcapsules were investigated extensively. The obtained microcapsules were concurrently analyzed by SEM, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) techniques. SEM images showed that the best stabilization was achieved by polyvinyl alcohol. Also, particle size, as an indication of surface area for heat transfer properties, showed a decrement by increasing stabilizer amount, surfactant amount, and homogenization speed. The amount of entrapped HD and efficiencies of microencapsulation were determined by DSC, and the reason for observing such changes were discussed in detail. Thermal stability of the microcapsules as an important property for their performance was investigated, too. The results illustrated that an improved thermal stability would be obtained by an efficient stabilization in the emulsification step. Also the highest thermal stability up to 388 °C was reached at homogenization speed of 6,000 rpm. Finally, the optimized conditions for desirable encapsulation were proposed in such systems.
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    A new approach to decoupling of bacterial adhesion energies measured by AFM into specific and nonspecific components (2013)
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    Publication Date: 2013-10-06
    Description: A new method to decoupling of bacterial interactions measured by atomic force microscopy (AFM) into specific and nonspecific components is proposed. The new method is based on computing the areas under the approach and retraction curves. To test the efficacy of the new method, AFM was used to probe the repulsion and adhesion energies present between Listeria monocytogenes cells cultured at five pH values (5, 6, 7, 8, and 9) and silicon nitride (Si 3 N 4 ). Overall adhesion energy was then decoupled into its specific and nonspecific components using the new method as well as using Poisson statistical approach. Poisson statistical method represents the most commonly used approach to decouple bacterial interactions into their components. For all pH conditions investigated, specific energies dominated the adhesion, and a transition in adhesion and repulsion energies for cells cultured at pH 7 was observed. When compared, the differences in the specific and nonspecific energies obtained using Poisson analysis and the new method were on average 2.2 % and 6.7 %, respectively. The relatively close energies obtained using the two approaches demonstrate the efficacy of the new method as an alternative way to decouple adhesion energies into their specific and nonspecific components.
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    Investigation of the factors affecting the carbohydrate–lectin interaction by ITC and QCM-D (2013)
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    Publication Date: 2013-10-09
    Description: Although the carbohydrate–lectin interactions have been intensively investigated, there is little report concerning the factors that affect the carbohydrate–lectin interaction. The interactions between concanavalin A (Con A) and glycopolymers, namely poly(2-(methacrylamido)-glucopyranose) and poly(2-methacrylamido-2-deoxy-glucitol) containing pyranose ring form and open form of glucosamine, respectively, have been investigated by a combination of isothermal titration calorimetry and quartz crystal microbalance-dissipation. Our results show that not only the pyranose ring form of glucosamine but also the open form can bind to Con A. Moreover, we investigate the influence of temperature on the carbohydrate–lectin interaction. As the temperature increases, the carbohydrate–lectin interaction is enhanced.
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    Synthesis and properties of multifunctional poly(amic acid) with oligoaniline and fluorene groups (2013)
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    Publication Date: 2013-10-17
    Description: A novel multifunctional poly(amic acid) bearing oligoaniline, fluorene groups (PAAOF) has been prepared through the one-step synthetic route. The structure of PAAOF was confirmed via nuclear magnetic resonance (NMR), Fourier-transform infrared spectra (FTIR), and gel permeation chromatography (GPC). Moreover, the electrochemical measurement results revealed that PAAOF material have an expected electrochemical activity, and good electrochromic properties with high contrast value and satisfactory coloration efficiency. The photophysical properties of the as-synthesized PAAOF at various oxidation states were studied. The results indicated that the fluorescence of PAAOF could be tuned by modulating the oxidation states of oligoaniline segments. In the fluorescence tuning, the fluorene groups are fluorophore, and the oligoaniline segments are used as regulatory unit. Figure A novel multifunctional poly(amic acid) containing oligoaniline and fluorene groups was synthesized. This material shows reversible electroactivity and excellent electrochromic properties. Interesting photophysical properties of the as-synthesized PAAOF at various oxidation states were found and studied in detail
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    Simple analytic solution of the rate equations for the early-stage aggregation kinetics of colloidal particles (2013)
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    Publication Date: 2013-10-14
    Description: The potential energy of the interaction between two approaching colloidal particles obtained by the DLVO theory can exhibit a maximum, a primary minimum, and a secondary minimum on the potential curve of the interparticle interaction energy. Behrens and Borkovec (J Colloid Interface Sci 225: 460, 2000) considered a set of coupled nonlinear differential rate equations for the early-stage aggregation kinetics of colloidal particles by taking into account the influence of the secondary minimum and derived an approximate solution to the rate equations as well as their exact numerical solutions. In the present article, an improved simple analytic solution is derived for these rate equations. The obtained solution, which involves two distinct (fast and slow) exponentially decay constants, is found to be in excellent agreement with numerical solutions to the rate equations with negligible errors.
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    Crystal phases, structure, and orientation in isotactic polypropylene after isothermal crystallization under oscillatory shear as a function of nucleation agent (2013)
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    Publication Date: 2013-12-03
    Description: 2D wide-angle X-ray diffraction (2D-WAXD) measurement was performed to investigate the effects of both oscillatory shear and the nucleating agent on the crystalline structure distribution and orientation of isotactic polypropylene (iPP). 1,3:2,4-bis(p-methylbenzylidene) sorbitol (MDBS) and 1,3:2,4-di(3,4-dimethylbenzylidene) sorbitol (DMDBS) can induce α-PP and β-PP simultaneously. The presence of MDBS (or DMDBS) and oscillatory strain (oscillatory frequency is fixed) exhibits a synergistic interaction on increasing the content of β-crystals of iPP. Under the oscillatory shear field at the fixed oscillatory strain, the β-crystal content and the orientation of iPP with and without MDBS (or DMDBS) change slightly with the increase of the oscillatory frequency. Comparing with MDBS (or DMDBS) nucleated iPP crystallization under shear field, the periodically changed flow direction of the oscillatory shear field leads to the shorter α-row nuclei, weaker orientation but more β-crystals of the nucleated iPP.
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    Nonlinear effects on electrokinetics of a highly charged porous sphere (2013)
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    Publication Date: 2013-12-11
    Description: The motivation of the present study is to provide a correct estimate of the electrophoretic mobility of a charged porous particle for wide-range electrokinetic parameters, such as particle charge density, permeability, and Debye length. Based on the Nernst–Planck equation, which takes into account the external electric field and fluid convection on ion transport, we have estimated the mobility of the particle by establishing a force balance. We have validated our results with the linear model due to Hermans and Fujita ( K Nederl Akad Wet Proc Ser B 58:182–187, 1955 ) and the computed solution based on perturbation of the Poisson–Boltzmann model as obtained by Hsu and Lee ( J Colloid Interface Sci 390:85–95, 2013 ). For the case of thin double layer, our computed results agree with the linear model even for large values of charge density of the particle. The linear model overpredicts our computed solution for mobility when the thick Debye layer is considered. However, a large discrepancy of the present model from the results based on the perturbation of the Boltzmann model is observed for all the cases considered. We have analyzed the double-layer polarization and counterion condensation through the distribution of counterions, net charge density, and the effective charge density of the particle.
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    Generation of nanocomposites based on polystyrene-grafted CdSe nanoparticles by grafting through and block copolymer (2013)
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    Publication Date: 2013-07-31
    Description: Continuing with our previous work, in which CdSe nanoparticles were functionalized with polystyrene (PS) brushes (CdSe-PS) by the grafting through method, nanocomposites were prepared by adding them to a poly(styrene- b -butadiene- b -styrene) (SBS) triblock copolymer. After characterizing CdSe-PS nanoparticles obtained at different polymerization times of 3, 5, and 8 h by means of thermogravimetric analysis and gel permeation chromatography, CdSe-PS nanoparticles obtained after 5 h of polymerization (CdSe-PS(5h)) were chosen as the most adequate for the generation of nanocomposites. Atomic force microscopy (AFM) was used for morphological characterization of SBS/CdSe-PS(5h) nanocomposites. AFM images showed a good dispersion of the nanoparticles in the block copolymer, with the placement of the nanoparticles in the PS domains due to the improved affinity obtained by their functionalization with PS brushes.
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    Underwater saturation resistance and electrolytic functionality for superhydrophobic nanocomposites (2013)
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    Publication Date: 2013-07-31
    Description: In the current study, water immersion saturation characterization and saturation resistance are investigated for various superhydrophobic polymer nanocomposite coatings. Two different diagnostic methods are used to characterize superhydrophobic performance longevity under continuous water contact: optical reflectivity (associated with captured air layer) and static contact angle (measured immediately after an immersion period). The results indicate that retention of optical reflectivity and superhydrophobicity vary significantly among coatings, and that superhydrophobicity can be lost within a few minutes whereas optical reflectivity can be maintained for hours. Novel electrolytic reactions on electroconductive polymeric nanocomposites can extend superhydrophobic duration by 400 %.
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    High performance of interpenetrating polymer network hydrogels induced by frontal polymerization (2013)
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    Publication Date: 2013-07-31
    Description: We report the rapid synthesis of hydrogels with interpenetrating polymer networks (IPNs) by frontal polymerization (FP). Appropriate amounts of diacetone acrylamide (DAAM), N -methylolacrylamide (NMA), thermoplastic polyurethane (TPU), N , N ′-methylenebisacrylamide (MBAA), and ammonium persulfate (APS)/ N , N , N ′, N ′-tetramethylethylenediamine (TMEDA) were mixed together at ambient temperature. FP was initiated by transitorily heating the upper side of the reactants, and poly(DAAM- co -NMA)/TPU IPN hydrogels were obtained within minutes. The preparation parameters were thoroughly investigated. Moreover, we investigated the morphology, swelling capacity, chemical structure and the mechanical properties of poly(DAAM- co -NMA)/TPU IPN hydrogels, along with those of poly(DAAM- co -NMA) hydrogels without IPN structure for comparison. Interestingly, the mechanical strength of poly(DAAM- co -NMA)/TPU IPN hydrogels is notably improved in comparison with that of poly(DAAM- co -NMA) hydrogels. The results indicate that the IPN structure endows hydrogels with high mechanical strength, and FP can be applied as an alternative means for synthesis of IPN hydrogels with additional advantages of speed and efficiency.
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    Acidic ionic liquids catalyst in homo and graft polymerization of ε-caprolactone (2013)
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    Publication Date: 2013-07-31
    Description: Biodegradable polycaprolactone was prepared by ring-opening polymerization in presence of ionic liquids as efficient, inexpensive, nontoxic, and easily handled acid catalysts. The resulting polymer exhibited good yield and inherent viscosity between 0.10 and 0.18 dL/g. The chemical structure of obtained polymer was verified by the 1 H-NMR and Fourier transform infrared spectroscopy (FT-IR) spectra. In continuation, the obtained polymer was applied to improve quality level and mechanical properties and also to reduce the hydrophilic properties of the starch, so the ring-opening polymerization of ε-caprolactone was investigated in the presence of starch hydroxyl groups as initiator and ionic liquid as catalyst. The obtained starch-grafted-polycaprolactone was verified by 1 H-NMR, FT-IR spectra, and field emission scanning electron microscopy analysis.
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    Stability, rheological, magnetorheological and volumetric characterizations of polymer based magnetic nanofluids (2013)
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    Publication Date: 2013-07-31
    Description: The Fe 3 O 4 nanoparticles and Fe 3 O 4 nanoparticles coated with oleic acid have been dispersed in base fluid of poly(ethylene glycol) (PEG). Stability and particle size distribution of these nanofluids have been studied by result analysis of UV–Vis spectroscopy, zeta potential and dynamic light scattering. Blue shift of UV–Vis spectra has been related to quantum effects such as band gap enlargement with particle size decreasing and also to effect of oleic acid on the ultraviolet wavelength. Flow behavior and suspension structure of Fe 3 O 4 nanoparticles dispersed in PEG have been determined by rheological properties. Viscosity values of Fe 3 O 4 -PEG nanofluid as a function of temperature have also been investigated. The chain-like structure of Fe 3 O 4 nanoparticles coated with oleic acid in base fluid of PEG has been verified by measuring the magnetorheological properties. The effect of temperature on magnetorheological properties of Fe 3 O 4 nanoparticles coated with oleic acid has also been investigated in base fluid of PEG. The volumetric properties of Fe 3 O 4 -PEG and Fe 3 O 4 coated with oleic acid–PEG nanofluids and PEG–oleic acid solution have also been measured at different temperatures to specify the suspension structure and also interactions of Fe 3 O 4 , PEG and oleic acid molecules.
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    Coating sulfonated polystyrene microspheres with highly dense gold nanoparticle shell for SERS application (2013)
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    Publication Date: 2013-07-31
    Description: The fabrication of highly dense gold nanoparticles (NPs)-coated sulfonated polystyrene (PS) microspheres and their application in surface-enhanced Raman spectroscopy (SERS) were reported. After the preparation of PS microsphere using dispersion polymerization and subsequent sulfonation, [Ag(NH 3 ) 2 ] + ions were adsorbed on the surfaces of the sulfonated PS microspheres and then reduced to silver nanoseeds for further growth of gold NPs shell by seeded growth approach. Reaction conditions such as the concentration of the growth solution and growth time were adjusted to achieve nonspherical gold NPs-coated PS microspheres with different coverage degree. The application of the as-prepared spiky gold NPs-coated PS microsphere hybrid composite in SERS was finally investigated by using 4-aminothiophenol as probe molecules. The results showed that as-prepared gold NPs-coated PS microspheres could be used as functional hybrid materials to exhibit excellent enhancement ability in SERS. Figure High dense gold nanoparticle shell coated sulfonated polystyrene microspheres for SERS application
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    PE-CPE blends and their graphene oxide nanocomposites with reduced low temperature brittleness (2013)
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    Publication Date: 2013-07-31
    Description: The low-temperature flexibility of polyethylene (PE)–chlorinated polyethylene (CPE) blends and their composites with a small amount of graphene oxide filler was studied. Quantitative height variation in the AFM images, rheological as well as fracture analyses were employed to gain insights into the generation of flexibility in the matrix phase. The semi-crystalline CPE (CPE25) polymer did not induce viscoelastic behavior at temperatures lower than the glass transition temperature of PE, whereas the amorphous CPE (CPE35) had completely different behavior. The samples with CPE35 could not be sufficiently hardened even at −180 °C and remained too soft for cryosectioning. Therefore, compression, which results in a 30–60 % reduction in length along the cutting direction with no change in the dimension perpendicular to it, was very prominent for both thin section and block face of the sample. The composites had even higher degree of compression due to additional effect of weak filler matrix interactions and as a consequence, the topographical variations led to filler pull out during sectioning. It was also confirmed using the rheological analysis that composites (and blends with 10 % CPE35 content) had phase immiscibility as CPE phase was suspected to concentrate near the graphene oxide phase leading to generation of chlorine-rich phases. The addition of graphene oxide did not lead to reduced flexibility and the composites also retained the modulus similar to pure polymer. The mechanical fracture of the samples also confirmed the flexibility of the CPE containing blends and composites as these samples were still flexible at −195 °C.
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    Iron oxide/MCM-41 mesoporous nanocomposites and their magnetorheology (2013)
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    Publication Date: 2013-07-31
    Description: Mesoporous nanocomposite materials of magnetic iron oxide-containing MCM-41 (IO/MCM-41) were prepared by simple thermal oxidation of Fe-containing MCM-41 initially prepared by a direct synthesis route using Fe 3+ salt. The magnetic saturation of the fabricated nanocomposite materials was measured using a vibrating sample magnetometer, while surface morphology and inner framework of the composite materials were studied using a field emission scanning electron microscope and a transmission electron microscope to confirm their mesoporous nanocomposite formation. The fabricated magnetic materials were then adopted as a magnetorheological (MR) fluid, where the IO/MCM-41 magnetic nanocomposites were dispersed in a nonmagnetic medium oil in addition to as an additive for carbonyl iron-based MR fluid. Their MR properties of flow curve along with yield stress and viscoelastic properties under applied magnetic fields were investigated using a rotational rheometer.
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    Some experiments on complex spontaneous emulsification in the system water–benzene–ethanol (2013)
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    Description: The system water–benzene–ethanol was used to illustrate the complexity of spontaneous emulsification, when water-poor emulsions are brought in contact with water. In the first case, an O/W emulsion located close to the plait point in the system was used. The aqueous phase in the emulsion was incompatible with water, and a strong spontaneous emulsification to an O/W between the two liquids took place in the water layer close to the interface between layers. In the second case, a W/O emulsion, also close to the plait point, was brought in contact with water. Now, the spontaneous emulsification between the water and the oil phase of the original emulsion to an O/W emulsion also took place in the water layer forming a distinct emulsion layer beneath the interface.
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    Drying dissipative structure of similar sized aggregates (1.5 μm in diameter) of nano-sized diamond particles (4 nm in diameter) (2013)
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    Publication Date: 2013-07-31
    Description: Macroscopic and microscopic drying patterns were observed on a cover glass, a watch glass, and a Petri glass dish during the course of dryness of aqueous suspensions of similar sized aggregates of diamonds (CD1), which formed from the deionization of the pre-particles of diamond 4 nm in diameter. Two kinds of macroscopic patterns, i.e., outer and inner broad rings, and spoke lines were formed. Cooperative drying processes of the convection, sedimentation, and solidification were clarified. Microscopic drying patterns showing the formation of very large dendritic aggregates from the CD1 particles were observed only when the excess amount of sodium chloride higher than 2 mM coexisted in the initial suspensions before dryness and further initial CD1 concentration is lower than 0.17 wt%.
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    Salting-in effect of ionic liquids on poly( N -vinylimidazole) hydrogels (2013)
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    Publication Date: 2013-07-31
    Description: This work attempts to study the interaction of two ionic liquids (1-ethyl-3-methylimidazolium tosylate and 1-hexyl-3-methylimidazolium chloride) with chemically crosslinked poly( N -vinylimidazole) in aqueous media, and to compare it with that of NaCl, a typical salting-out electrolyte. The three salts show a salting-in effect whose intensity was measured on the basis of the decrease of the polymer–solvent interaction parameter and the increase of swelling with increasing ionic strength. It was thus found that the salting-in effect is the same for the two salts with the same anion (chloride), while the intensity of the salting-in effect exerted by the tosylate ionic liquid is larger. The coefficient of selective sorption, which expresses the salt excess inside the swollen gel with respect to the external solution was determined by comparing the initial and equilibrium compositions of the immersion bath. These results are discussed in terms of the hydrophobic character of the ions involved.
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    Ag/DNQ-novolac-based nanocomposite films for controllable UV lithography morphological patterning (2013)
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    Publication Date: 2013-07-04
    Description: In this study, the detailed characterisation of silver (Ag) nanoparticles/polymer nanocomposite chemical structure and morphology of grating has been carried out. Scanning electron microscopy measurements show spherical shape of Ag nanoparticles (40–80 nm in diameter) prepared in chloroform by reduction of silver nitrate. In the positive photoresist based on 2-diazo-2 H -naphthalen-1-one (DNQ)–novolac, Ag nanoparticles were deposited from organic colloidal solution. The content of nanoparticles in the polymer matrix was varied by increasing the concentration of Ag colloidal solution. Grating was formed by contact lithography. The quantification of Ag nanoparticles and chemical analysis of Ag/DNQ-novolac-based nanocomposite was performed by means of energy dispersive X-ray analyzer and SEM/EDS. In order to study the effect of Ag nanoparticles on the DNQ-novolac-based nanocomposite structure, investigations with Fourier transform infrared spectroscopy were conducted. Ag nanoparticles cause changes associated with substituent-sensitive out-of-plane C–H bending vibrations of aromatic ring. Ag/DNQ-novolac-based nanocomposite film surface morphology and grating topography imaging were performed using atomic force microscopy. Added Ag nanoparticles change the geometrical parameters of the gratings. The split of corrugations was achieved in Ag/DNQ-novolac-patterned films. Their morphology can be tailored by altering the content of Ag nanoparticles.
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    Thermodynamic studies on thin liquid films. V. General formulation for spherical films (2013)
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    Publication Date: 2013-07-04
    Description: Thermodynamic equations were derived for adsorption at interfaces of spherical films and interaction between interfaces in a film. The dependence of film tension on capillary pressure between external and film-forming phases gave thermodynamic film thickness and the one on pressure difference across the film the distance between the surface of tension for the film and the innermost dividing surface. Curvature dependence of film tension was numerically evaluated by using one of the derived equations.
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    Ellipsometric investigations of Fe 3+ -doped polyvinyl alcohol films (2013)
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    Publication Date: 2013-07-07
    Description: In this work, we study the inclusion mechanism of Fe 3+ ions in a polyvinyl alcohol (PVA) matrix. Thin films of pure and FeCl 3 -doped PVA on silicon substrates, prepared by the spin-coating method, are investigated using spectroscopic ellipsometry (SE) and Fourier transform infrared (FT-IR) spectroscopy. SE measurements of PVA and Fe 3+ -doped thin films are carried out at an incidence angle of 75° over the wavelength range of 0.24–1.1 μm. An optical model is used to obtain the refractive index ( n ) and the extinction coefficient ( k ). The gap energy E g is afterwards evaluated. The Fe 3+ doping is found to affect strongly the optical parameters of the polymer films. In fact, an increase in the refractive index with doping is observed, resulting from the intermolecular hydrogen bonding between Fe 3+ ions with the adjacent OH group of PVA. The increase of the thin films' absorption with doping is estimated by the k spectral profile analysis. The gap energy is then calculated and shows an important decrease with the Fe 3+ filling, more pronounced for low doped samples. Such a behavior is confirmed by FT-IR analysis.
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  • 89
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    The relationship between nanosilica dispersion degree and the tensile properties of polyurethane nanocomposites (2013)
    Springer
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    Publication Date: 2013-07-11
    Description: The tensile properties and structure of silica-based polyurethane (PU) nanocomposites were parametrically studied as a function of silica type and weight concentration, polyol OH number, and mixing methods. The variation of the silica functionalization groups (from silanols to silazanes) had a relevant effect on dispersion. An elevated interparticle distance of the silica agglomerates improved substantially the tensile strength (from 44.3 to 82.8 MPa) and strain to failure (from 3.0 to 7.95) while maintaining elastic modulus (from 2.08 to 2.31 GPa) with respect to the neat PU matrix. Polyol’s with different OH numbers have shown to dramatically modify the silica dispersion degree by the modification of the stability of the colloidal dispersion. An increase of its value deteriorated dispersion and the tensile properties of the nanocomposites. The effect of three dispersion methods (ultrasonic dispersion, high shear mixing, and tip sonication) has shown to have a relative effect on the reduction of agglomerate size and the interparticle distance. High power sonication methods were more effective in reducing agglomerate size in contrast to shear methods. Classical theories of colloidal dispersion (Derjaguin, Landau, Verwey, and Overbeek) have been able to explain the correlation between the silica aggregation state and the final tensile properties of the nanocomposite.
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    One-step fabrication of ZIF-8/polymer composite spheres by a phase inversion method for gas adsorption (2013)
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    Publication Date: 2013-07-14
    Description: This paper reports a phase inversion method for the preparation of macroporous polysulfone (PS) composite spheres through a single orifice spinneret. Surfactant F127 was pre-added in the polymer solution as a surface pore-forming agent, and different amount of zeolitic imidazolate framework-8 (ZIF-8) particles were incorporated to form the ZIF-8/polysulfone (ZIF-8/PS)-composite spheres. ZIF-8 and polymer acted as the adsorbent and binder in the final composite spheres, respectively. The fabrication conditions, such as the types of the surfactant, the amount of the surfactant, and ZIF-8 added in the polymer solution, were investigated. Nitrogen and carbon dioxide sorption analysis indicated the ZIF-8/PS composite spheres had similar properties as the pure ZIF-8 particles, and the active sites of ZIF-8 in the polymer composites were well exposed. The composite spheres exhibited advantages of easy handling and recycling over ZIF-8 particles, and this phase inversion method can be extended to prepare other polymer composite spheres.
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  • 91
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    Preparation and properties of 3-aminopropyltriethoxysilane functionalized graphene/polyurethane nanocomposite coatings (2013)
    Springer
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    Publication Date: 2013-07-17
    Description: Silicone-modified graphene was successfully synthesized by treating graphene oxide with 3-aminopropyltriethoxysilane (AMEO) and then reduced by hydrazine hydrate. Subsequently, the AMEO-functionalized graphene was incorporated into polyurethane (PU) matrix to prepare AMEO-functionalized graphene/PU nanocomposite coatings. The functionalized graphene could disperse homogenously by means of a covalent connection with PU. AMEO-functionalized graphene (AFG)-reinforced PU nanocomposite coatings showed more excellent mechanical and thermal properties than those of pure PU. A 227 % increase in tensile strength and a 71.7 % improvement of elongation at break were obtained by addition 0.2 wt% of AFG. Meanwhile, thermogravimetric analysis reveals that thermal degradation temperature was enhanced almost 50 °C higher than that of neat PU, and differential scanning calorimetry analysis demonstrates that glass transition temperature decreased by around 9 °C. The thermal conductivity of AFG/PU nanocomposite coatings also increased by 40 % at low AFG loadings of 0.2 wt%.
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  • 92
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    Synthesis and self-assembly behaviors of well-defined poly(lauryl methacrylate)- block -poly[ N -(2-methacryloylxyethyl)pyrrolidone] copolymers (2013)
    Springer
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    Publication Date: 2013-07-02
    Description: A series of structurally controllable poly(lauryl methacrylate)- b -poly[ N -(2-methacryloylxyethyl)pyrrolidone], PLMA- b -PNMP, diblock copolymers were synthesized by reversible addition–fragmentation chain transfer polymerization. The self-assembly behaviors of PLMA- b -PNMP in a selective solvent, tetrahydrofuran (THF), were studied by employing static light scattering, dynamic light scattering, and transmission electron microscopy in detail. The relationships between the aggregation parameters, such as critical micelle concentration and the aggregation number ( N agg ), and the molecular structure were established. It was found that spherical micelles can be formed once the solvophobic block length of poly[ N -(2-methacryloylxyethyl)pyrrolidone] is larger than 215. Moreover, extremely small and monodisperse gold nanoparticles (〈2 nm) were synthesized by employing PLMA- b -PNMP diblock copolymers in THF.
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  • 93
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    Multistimuli-responsive hydrogels of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) containing graphene (2013)
    Springer
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    Publication Date: 2013-07-06
    Description: Nanocomposite hydrogels of poly(2-acrylamido-2-methyl-1-propanesulfonic acid) containing graphene were prepared by radical polymerization. Their swelling properties in response to ionic strength and electrical stimuli were assessed. Graphene was obtained through an easy and convenient method lately developed by our research group, which consists in the exfoliation of graphite by sonicating it in a proper solvent medium. It was found that the graphene content influences the swelling properties of hydrogels; in particular, those containing graphene swell more than the filler-free ones; graphene content influences also the swelling ratio variation between the swollen and deswollen states.
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  • 94
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    Chemically modified polyaniline nanocomposites by poly(2-acrylamido-2-methyl-1-propanesulfonicacid)/graphene nanoplatelet (2013)
    Springer
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    Publication Date: 2013-07-11
    Description: New conducting polyaniline (PANI) nanocomposites that were chemically modified by poly(2-acrylamido-2-methyl-1-propanesulfonicacid) (PMP) and graphene nanoplatelets (GNPs) were prepared via in situ deposition. PMP was first synthesized using GNPs, and aniline hydrochloride monomer was then polymerized in the presence of PMP-GNPs. The nanopolymer composites were characterized, and its structural morphology was analyzed via transmission electron microscopy and scanning electron microscopy. Fourier transformation infrared spectroscopy results indicate a strong interaction between PANI, PMP, and GNPs. To understand the conduction behavior of the composites, temperature-dependent DC electrical conductivity was measured between 295 K and 503 K, and the mechanism of transport properties of the new composites was analyzed by Mott’s variable range of hopping model. The PANI/PMP-GNP showed higher conductivity than pure PANI polymer. The high electrical conductivity of the nanocomposites may be useful in fabricating multifunctional materials in bulk for future technological applications.
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    A simple strategy for detecting synthetic polymers on solid surfaces using liquid crystal (2013)
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    Publication Date: 2013-07-11
    Description: In this study, we developed a liquid crystal (LC)-based detection method for polymer films synthesized on solid surfaces. A dark to bright transition in the optical appearance of nematic 4-cyano-4′-pentylbiphenyl (5CB) was observed after transferring a poly(methyl methacrylate) (PMMA) film onto a glass substrate functionalized with n -octyltrichlorosilane (OTS). This phenomenon indicates an orientational transition of 5CB from a homeotropic to a planar-random state. The optical response of 5CB was then evaluated directly through polymerization reactions on the OTS-functionalized glass substrate. Polymer films of PMMA, poly(glycidyl methacrylate) (PGMA), and poly(dimethylsiloxane) (PDMS) were synthesized on OTS surfaces covered with their reaction mixtures. All polymer films displayed bright signals of 5CB, which corresponded to the planar-random orientation of LCs. However, no change in orientation was observed for the control experiments. We confirmed the formation of polymer films on the OTS surface using atomic force microscopy. Overall, our results suggest that LCs can be used to construct optical monitoring systems for the product of polymerization reactions. Figure ᅟ
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    Poly(ε-caprolactone) and cellulose ester hybrid nanoparticles via miniemulsion polymerization (2013)
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    Publication Date: 2013-06-08
    Description: Two types of hybrid acrylic nanoparticles based on biodegradable and biocompatible polymers, cellulose ester and poly(ε-caprolactone), were produced via miniemulsification through high-pressure homogenization. An efficient emulsification procedure was first devised to yield high-solids-content polymer–monomer waterborne miniemulsions, and the fundamental parameters governing the stability of these composite miniemulsions were assessed. In addition, strategies to control the droplet size were investigated upon varying several experimental parameters such as the interfacial tension between the organic and the aqueous phase, the organic phase viscosity and the nature/concentration of surfactant. A series of thermally initiated polymerizations were then performed to produce nanosized hybrid particles.
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    Poly(N-isopropylacrylamide-co-N-t-butylacrylamide)-block-poly(ethylene glycol)-block-poly(N-isopropylacrylamide-co-N-t-butylacrylamide) triblock copolymers: synthesis and thermogelation properties of aqueous solutions (2013)
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    Publication Date: 2013-06-13
    Description: Novel triblock copolymers with PEG middle blocks of 1–10 kDa and poly(N-isopropylacrylamide-co-t-butylacrylamide) statistical copolymer side arms with DP n  ≈ 88 and different compositions, were synthesized by SET-LRP. The thermogelation properties of their aqueous solutions depended on both hydrophobic monomer content of the side blocks and molecular weight (MW) of the poly(ethylene glycol) (PEG) middle block, as proven by dynamic rheometry, DSC, and tube inversion method measurements. At constant PEG chain length, increasing TBAM proportions led to a gelation process occurring at progressively lower temperatures, as well as to a lower stability of the forming hydrogels in the case of shorter-PEG-chain block copolymers. By employing longer PEG blocks (M PEG ≥6,000 Da), stable hydrogels with the gelation temperature below 37 °C could be obtained. For a constant composition of the copolyacrylamide blocks, the dependence of the phase transition temperature (T ph ) on M PEG displayed a different shape at different polymer solution concentrations, because of the stronger variation of T ph with polymer concentration as M PEG increased. Also, the viscoelastic properties of the hydrogels resulting from 20 wt.% polymer aqueous solutions at 37 °C were stronger affected by the MW of the PEG middle block than by the hydrophobic character of the thermosensitive side blocks.
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    Fabrication of polymeric micelles with core–shell–corona structure for applications in controlled drug release (2013)
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    Publication Date: 2013-04-10
    Description: Thermo-responsive polymeric micelles of poly (ethylene glycol)- b -poly(2-hydroxyethyl methacrylate- g -lactide)- b -poly( N -isopropylacrylamide) (PEG-P(HEMA-PLA)-PNIPAM) with core–shell–corona structure were fabricated for applications in controlled drug release. The graft copolymer of PEG-P(HEMA-PLA)-PNIPAM was self-assembled into core–shell micelles with a densely PLA core and mixed PEG/PNIPAM shells at 25 °C in aqueous media. By increasing the temperature above the lower critical solution temperature of PNIPAM, these core–shell micelles could be converted into core–shell–corona micelles because of the collapse of PNIPAM block on the PLA core as the inner shell and the soluble PEG block stretching outside as the outer corona. Anticancer drug doxorubicin (DOX) was loaded in the polymeric micelles as a model drug. Compared with polymeric micelles formed by liner PEG- b -PLA- b -PNIPAM triblock copolymer, these polymeric micelles exhibited higher loading capacity, and release of DOX from the polymeric micelles with core–shell–corona structure was well-controlled.
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    A new approach to visualizing the carbon black/natural rubber interaction layer in carbon black-filled natural rubber vulcanizates and to elucidating the dependence of mechanical properties on quantitative parameters (2013)
    Springer
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    Publication Date: 2013-04-10
    Description: The viscoelastic behavior of carbon black (CB)-filled natural rubber (NR) vulcanizates is explained for the first time by applying a two-phase mixing law, excluding the CB phase, to the volume fraction of the CB/NR interaction layer (CNIL). For CB loadings of 20 phr or less, the CNIL of local CB aggregates induces the reinforcement effect of a series mechanical model of the mixing law. In contrast, for CB loadings of 30 phr or more, the CNIL that forms the CB network (CBN) generates the reinforcement effect of a parallel mechanical model of the mixing law. Therefore, the model of the mixing law presumably changes from a series mechanical model before CBN formation to a parallel one after the network forms. Additionally, employing this fraction, a transition caused by CBN formation was investigated.
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    Synthesis and characterization of polystyrene chains on the surface of silica nanoparticles: comparison of SANS, SAXS, and DLS results (2013)
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    Publication Date: 2013-04-10
    Description: An extensive characterization of well-defined polystyrene (PS)-grafted silica nanoparticles is reported. Bare SiO 2 particles (diameter 50 nm) were functionalized with a suitable initiator for the surface-initiated anionic polymerization of styrene. Both grafted and free PS chains were characterized and compared by size-exclusion chromatography (SEC). PS-grafted particles were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), small-angle x-ray scattering (SAXS), small-angle neutron scattering (SANS), and dynamic light scattering (DLS). The thickness of the grafted PS chains was obtained by SANS and DLS and scaled with $M_{\mathrm {w}}^{0.6}$ displaying similar behavior with free PS chains in the same solvent used, tetrahydrofuran (THF). Grafting densities obtained from SANS data and TGA were found to be small, and the thickness of the grafted PS chains determined by SANS was found to be similar to $2R_{\mathrm {g}}$ of free PS chains in THF. Both results are consistent with a “coil-like” conformation of the grafted PS chains.
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