Synthesis of raspberry‐like organic–inorganic hybrid nanocapsules via pickering miniemulsion polymerization: Colloidal stability and morphology

Raspberry‐like hybrid nanocapsules with a hydrophobic liquid core were successfully prepared via the copolymerization of styrene, divinylbenzene (DVB), and 4‐vinyl pyridine (4‐VP) in Pickering‐stabilized miniemulsions by using silica particles as the sole emulsifier and hexadecane (HD) as liquid template. When compared with conventional Pickering miniemulsions and Pickering suspensions, the colloidal stability of the current systems is much more sensitive to the variation of reaction parameters such as pH, size, amount of silica particles, and content of 4‐VP. The systems without coagulum were only obtained in a narrow pH range at around 9.5 and by using 12 nm silica particles as emulsifier. The formation of well‐defined raspberry‐like capsules was confirmed by transmission electron microscopy (TEM) and high‐resolution scanning electron microscopy (HRSEM). The stable attachment of silica particles on the surface of hybrid particles was verified by centrifugation and subsequent characterizations, such as Fourier transform infrared spectroscopy, TEM, and HRSEM. The influence of pH and weight content of HD, DVB, and 4‐VP on the particle morphology was extensively investigated. Interestingly, the particle morphology strongly depends on the particle size. When compared with the organic surface‐active surfactant, the formation of capsule morphology could be promoted by the application of silica particles taking advantage of their surface inactivity. The formation mechanisms of capsules/solid particles are discussed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Observation of the Debye-Waller factor in a colloidal single crystal

Bragg diffraction spot intensities of a colloidal single crystal were found to exhibit a DebyeWaller factor-like decay. The Lindemann parameter and the mean-square displacement after infinite times of the colloidal particles could be obtained.     

Preparation of dually, pH- and thermo-responsive nanocapsules in inverse miniemulsion

pH- and thermo-sensitive nanocapsules were successfully synthesized via inverse miniemulsion copolymerization of N-isopropyl acrylamide (NIPAM), N,N'-methylene bisacrylamide (MBA), and a functional monomer, 4-vinyl pyridine (4-VP). The size and size distribution of nanocapsules were measured by dynamic light scattering (DLS). The particle morphology was observed by transmission electron microscopy (TEM). The final morphology of particles was strongly influenced by the hydrophobicity of functional monomers. The use of a hydrophilic functional monomer, acrylic acid, led to the formation of solid particles, while the use of the more hydrophobic functional monomer, 4-VP, resulted in the formation of nanocapsules. The particle morphology, size, and size distribution were investigated in terms of the content of 4-VP, MBA, and the type and content of surfactant. The pH- and thermo-sensitivities were characterized by measuring the size variation with the change of temperature and pH. The organic-inorganic nanocapsules were prepared by coating a layer of silica particles on the surface of the sensitive nanocapsules.     

Formation of sulfur surface species on a commercial NO<Subscript>x</Subscript>-storage reduction catalyst

The influence of SO₂ exposure under lean (oxidizing) and rich (reducing) reaction conditions on the storage and oxidation/reduction function of a commercial NO_x storage-reduction catalyst was investigated by temperature-programmed uptake experiments and high temperature XRD. Both the storage capacity and the oxidation/reduction function of the catalyst were deactivated by SO₂ exposure under lean and rich reaction conditions. The deactivation of the storage component, i.e. the loss of the NO_x storage capacity, resulted mainly from the formation of Ba-sulfates accumulating in the bulk phase, which have a high thermal stability (>800°C) and, therefore, cannot be removed under the typical operation conditions of a NSR catalyst. For the oxidation function only a temporarily deactivation during lean reaction conditions was observed. Besides the formation of SO^2- ₄ species on the storage component at the beginning of the SO₂ exposure under rich conditions, an adsorption of SO₂ on the noble metal component was observed resulting in the formation of sulfur deposits. The oxidation of these sulfur species with a subsequent spillover of SO^2- ₄ species to the storage component during lean conditions could accelerate the deactivation of the storage capacity.     

Charge-assisted hydrogen bond-directed self-assembly of an amphiphilic zwitterionic quinonemonoimine at the liquid-solid interface

Charge-assisted hydrogen bond-directed self-assembly of a zwitterionic quinonemonoimine was investigated at the liquid/solid interface using scanning tunnelling microscopy. Factors governing morphology, chirality and multilayer formation are discussed, presenting an important foundation for understanding the properties of a large family of related molecules with interesting potential in supramolecular design.     

Cole-Cole Analysis of the Superspin Glass System Co 80 Fe 20 /Al 2 O 3

Ac susceptibility measurements were performed on discontinuous magnetic multilayers [Co 80 Fe 20 ( t )/Al 2 O 3 (3 nm)] 10 , t = 0.9 and 1.0 nm, by Superconducting Quantum Interference Device (SQUID) magnetometry. The CoFe forms nearly spherical ferromagnetic single-domain nanoparticles in the diamagnetic Al 2 O 3 matrix. Due to dipolar interactions and random distribution of anisotropy axes the system exhibits a spin-glass phase. We measured the ac susceptibility as a function of temperature 20 h T h 100 K at different dc fields and as a function of frequency 0.01 h f h 1000 Hz. The spectral data were successfully analyzed by use of the phenomenological Cole-Cole model, giving a power-law temperature dependence of the characteristic relaxation time c and a high value for the polydispersivity exponent, f , 0.8, typical of spin glass systems.     

Fine-tuning of relative metal-metal distances within highly ordered chiral 2D nanopatterns

The two-dimensional nanopatterning of a series of neutral alkoxy/alkyl-functionalised bis(salicylaldehydato)/bis(aldiminato)copper(II) and -palladium(II) complexes at a liquid/solid (highly oriented pyrolytic graphite, HOPG) interface has been studied by scanning tunnelling microscopy (STM). The relative metal-metal distances were tuned stepwise in two dimensions by ligand design. Exchange of the carbonyl O-atom for NH or N-alkyl units effects different intermolecular interactions such as weak hydrogen bonds and steric effects that determine, together with the van der Waals forces between the alkyl chains, the relative arrangements of the complexes. Further variation of the length and position of the alkoxy side chains as well as the exchange of CuII for PdII affords an absolute fine-tuning of the surface structures. Highly resolved STM images of the resultant highly ordered adlayers allow us to establish detailed models of the molecular 2D arrays and to classify them into three basic chiral pattern types. Homochirality within the individual domains is induced by the highly regular deposition of the prochiral complexes from the same enantiotopic face. In the case of the C12 O-substituted bis(salicylaldiminato) (NH) Cu(II) complex Cu5, a secondary structure occurs as a racemic mixture of two chiral surface species deposited in a distinct alternating order.