Polymer nanoparticles with a sensitive CO2‐responsive hydrophilic/hydrophobic surface

Poly(methyl methacrylate) (PMMA) nanoparticles with a sensitive CO₂‐responsive hydrophilic/hydrophobic surface that confers controlled dispersion and aggregation in water were prepared by emulsion polymerization at 50 °C under CO₂ bubbling using amphiphilic diblock copolymers of 2‐dimethylaminoethyl methacrylate (DMAEMA) and N‐isopropyl acrylamide (NIPAAm) as an emulsifier. The amphiphilicity of the hydrophobic–hydrophilic diblock copolymer at 50 °C was triggered by CO₂ bubbling in water and enabled the copolymer to serve as an emulsifier. The resulting PMMA nanoparticles were spherical, approximately 100 nm in diameter and exhibited sensitive CO₂/N₂‐responsive dispersion/aggregation in water. Using copolymers with a longer PNIPAAm block length as an emulsifier resulted in smaller particles. A higher concentration of copolymer emulsifier led to particles with a stickier surface. Given its simple preparation and reversible CO₂‐triggered amphiphilic behavior, this newly developed block copolymer emulsifier offers a highly efficient route toward the fabrication of sensitive CO₂‐stimuli responsive polymeric nanoparticle dispersions. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2149–2156     

Temperature‐modulated differential scanning calorimetry studies on the origin of double melting peaks in isothermally melt‐crystallized poly(L‐lactic acid)

In this work, the melting behaviors of nonisothermally and isothermally melt‐crystallized poly(L ‐lactic acid) (PLLA) from the melt were investigated with differential scanning calorimetry (DSC) and temperature‐modulated differential scanning calorimetry (TMDSC). The isothermal melt crystallizations of PLLA at a temperature in the range of 100–110 °C for 120 min or at 110 °C for a time in the range of 10–180 min appeared to exhibit double melting peaks in the DSC heating curves of 10 °C/min. TMDSC analysis revealed that the melting–recrystallization mechanism dominated the formation of the double melting peaks in PLLA samples following melt crystallizations at 110 °C for a shorter time (≤30 min) or at a lower temperature (100, 103, or 105 °C) for 120 min, whereas the double lamellar thickness model dominated the formation of the double melting peaks in those PLLA samples crystallized at a higher temperature (108 or 110 °C) for 120 min or at 110 °C for a longer time (≥45 min). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 466–474, 2007     

Effects of carbon nanotubes on dynamic mechanical property,thermal property,and crystal structure of poly(L‐lactic acid)

Effects of carbon nanotubes (CNT) on the dynamic mechanical property, thermal property, and crystal structure of poly(L ‐lactic acid) (PLLA) were investigated. Dynamic mechanical analysis (DMA) found that CNT via grafting modification with PLLA (CNT‐g‐PLLA) could result in effective reinforcing effects. Tan δ of DMA found that CNT‐g‐PLLA was compatible with the PLLA matrix, giving a single T_g of the composite with a higher CNT‐g‐PLLA loading giving a higher T_g of the composite. Wide angle X‐ray diffraction (WAXD) data demonstrated that CNT could assist the disorder‐to‐order (α′‐to‐α) transition in PLLA crystals but did not lead to a more compact chain packing of the crystal lattice in PLLA composites than in pure PLLA. The equilibrium melting temperature (T) obtained from Hoffman‐Weeks plots were found to increase with increasing CNT‐g‐PLLA content. Small angle X‐ray scattering data revealed that thicknesses of crystal layer and amorphous layer of PLLA both decreased with increasing CNT contents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 145–152, 2010     

On Aerodynamic Forces for Viscous Compressible Flow

The paper is aimed at reviewing and adding some new results to our recent work on a force theory for viscous compressible flows around a finite body. It has been proposed to analyze aerodynamic forces directly in terms of fluid elements of nonzero vorticity and density gradient. Let ρ denote the density, u the velocity, and ω the vorticity. It is demonstrated that for largely separated flows about bluff bodies, there are two major source elements: R _e(x) =−?u ²∇ρ·∇ϕ and V _e(x) =−u×ω·∇ϕ, where ϕ is an acyclic potential, generated by the solid body moving with unit velocity in the negative direction of the force considered. In particular, under mild conditions, the (unique) choice of ϕ enforces that the elements R _e(x) and V _e(x) decay rapidly away from the body. Four kinds of finite body are considered: a circular cylinder, a sphere, a hemi sphere-cylinder, and a delta wing of elliptic section—all in transonic-to-supersonic regimes. From an extensive numerical study carried out for these bodies, it is found that these two elements contribute to 95% or more of the total drag or lift for all the cases under consideration. Moreover, R _e(x) due to density gradient becomes progressively important relative to V _e(x) due to vorticity as the Mach number increases. The present method of force analysis enables effective analysis and assessment of relative importance of aerodynamics forces, contributed from individual flow structures. The analysis could therefore be very much useful in view of the rapid growth in numerical fluid dynamics; detailed (either local or global) flow information is often available. The paper is dedicated to Sir James Lighthill in honor of his great contributions to aeronautics on the occasion of the publication of his collected works. Received 3 January 1997 and accepted 11 April 1997     

Synthesis of CdSe–Poly(N‐vinylcarbazole) Nanocomposite by Atom Transfer Radical Polymerization for Potential Optoelectronic Applications

A hybrid inorganic–polymer nanocomposite using CdSe nanocrystals with high electron mobility has been successfully synthesized by atom transfer radical polymerization (ATRP). First the hydroxyl‐coated CdSe nanoparticles (i.e., CdSe–OH) were prepared via a wet chemical route. A polymerization initiator was then prepared for ATRP of N‐vinylcarbazole. FT‐IR, ¹H NMR, and XRD analyses confirmed the successful synthesis of CdSe–poly(N‐vinylcarbazole) (PVK) nanohybrid. UV–Vis spectra and photoluminescence data revealed that grafting of PVK onto the surface of CdSe nanocrystals would reduce the band gap of PVK and cause the red shift of emission peak. TEM and SEM micrographs exhibited CdSe nanoparticles that were well‐coated with PVK polymer.

     

One-step hydrothermal synthesis of feather duster-like NiS@MoS<Subscript>2</Subscript> with hierarchical array structure for the Pt-free dye-sensitized solar cell

Novel feather duster-like nickel sulfide (NiS) @ molybdenum sulfide (MoS₂) with hierarchical array structure is synthesized via a simple one-step hydrothermal method, in which a major structure of rod-like NiS in the center and a secondary structure of MoS₂ nanosheets with a thickness of about 15–55 nm on the surface. The feather duster-like NiS@MoS₂ is employed as the counter electrode (CE) material for the dye-sensitized solar cell (DSSC), which exhibits superior electrocatalytic activity due to its feather duster-like hierarchical array structure can not only support the fast electron transfer and electrolyte diffusion channels, but also can provide high specific surface area (238.19 m² g^?1) with abundant active catalytic sites and large electron injection efficiency from CE to electrolyte. The DSSC based on the NiS@MoS₂ CE achieves a competitive photoelectric conversion efficiency of 8.58%, which is higher than that of the NiS (7.13%), MoS₂ (7.33%), and Pt (8.16%) CEs under the same conditions.

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Graphical abstract Novel feather duster-like NiS@MoS₂ hierarchical structure array with superior electrocatalytic activity was fabricated by a simple one-step hydrothermal method.

     

Crystallization kinetics study of poly(L‐lactic acid)/carbon nanotubes nanocomposites

Effects of carbon nanotubes (CNT) on the isothermal crystallization kinetics of poly(L ‐lactic acid) (PLLA) were quantitatively investigated using the Avrami equation and the secondary nucleation theory of Lauritzen and Hoffman. CNT via grafting modification with PLLA could well disperse in the PLLA matrix and give significantly enhanced crystallization rate and crystallinity of PLLA as analyzed by differential scanning calorimetry and polarized optical microscopy. Analysis of isothermal crystallization kinetics using the Avrami equation demonstrated that CNT significantly enhanced the bulk crystallization of PLLA. Analysis of spherulite growth kinetics using the secondary nucleation theory of Lauritzen and Hoffman found that CNT could expand the temperature range of the crystallization regime III of PLLA. Values of the nucleation constant (K_g) in crystallization regimes III and II of PLLA both increased with increasing CNT contents. The K_g III/K_g II ratios were found to be close to the theoretical value 2 but were not clearly found to depend on the CNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 983–989, 2010     

Trajectory approach to the mode-selected photodissociation of CS2

Through the study of photodissociation events in the CS(2) molecule that originate in various selected vibrational modes, but terminate in the same final predissociation state, we looked for the evidence that photodissociation processes can depend on the initial conditions. Such dependence would not occur within RRKM theory, because of its statistical assumptions. The experimental results were compared with trajectory calculations in normal mode coordinates, in which initial conditions were given in terms of coordinates and momenta. We have found that the photodissociation rate for events originating in the combination nu(1), nu(2) mode is higher than that for events from the pure nu(2) mode, and shows a large variation along the vibrational progression. The experimental observations agree with the trajectory calculations. In addition, the trajectory calculations predict that photodissociation events initiated at small values of the vibrational coordinates result in larger dissociation rates at low excess energy above the dissociation limit, while events from large values of the coordinates result in larger dissociation rates at high excess energies.     

Syntheses of 2,4′-and 3,4′-Bipyridines Via Lithium Halogen Exchange of Bromopyridines and Addition to N-Ethoxycarbonylpyridinium Chloride in the Presence of Cul

2,4′-Bipyridines 4a, 4c, 4d and 3,4′-bipyridines 4b, 4e, 4f, 4g, 4h are obtained in modest yield by the addition of organocuprate reagents derived from bromopyridines 2a-h to N-ethoxycarbonylpyridinium chloride 1 followed by air oxidation.     

A Convenient Synthesis of Halogenated 2-Chloropyridines by Transformation of Halogenated 2-methoxypyridines Under Vilsmeier-Haack Conditions

Several halogenated 2-chloropyddines 2a-2h were conveniently synthesized by transformation of halogenated 2-methoxypyridines 1a-1h under Vilsmeier—Haack conditions in a yield of 50～71%.