Spontaneous Formation of Microgroove Arrays on the Surface of p‐Type Porous Silicon Induced by a Turing Instability in Electrochemical Dissolution

Self‐organization plays an imperative role in recent materials science. Highly tunable, periodic structures based on dynamic self‐organization at micrometer scales have proven difficult to design, but are desired for the further development of micropatterning. In the present study, we report a microgroove array that spontaneously forms on a p‐type silicon surface during its electrodissolution. Our detailed experimental results suggest that the instability can be classified as Turing instability. The characteristic scale of the Turing‐type pattern is small compared to self‐organized patterns caused by the Turing instabilities reported so far. The mechanism for the miniaturization of self‐organized patterns is strongly related to the semiconducting property of silicon electrodes as well as the dynamics of their surface chemistry.     

Controlled Formation of Polymer Nanocapsules with High Diffusion‐Barrier Properties and Prediction of Encapsulation Efficiency

Polymer nanocapsules with high diffusion‐barrier performance were designed following simple thermodynamic considerations. Hindered diffusion of the enclosed material leads to high encapsulation efficiencies (EEs), which was demonstrated based on the encapsulation of highly volatile compounds of different chemical natures. Low interactions between core and shell materials are key factors to achieve phase separation and a high diffusion barrier of the resulting polymeric shell. These interactions can be characterized and quantified using the Hansen solubility parameters. A systematic study of our copolymer system revealed a linear relationship between the Hansen parameter for hydrogen bonding (δ_h) and encapsulation efficiencies which enables the prediction of encapsulated amounts for any material. Furthermore EEs of poorly encapsulated materials can be increased by mixing them with a mediator compound to give lower overall δ_h values.     

Electron Transfer in Peptides: On the Formation of Silver Nanoparticles

Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag⁺ ions bound by peptides with histidine as the Ag⁺‐binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100 nm Ag@AgCl/peptide nanocomposites which are cleaved into 15 nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time‐resolved UV/Vis spectra which exhibit an isosbestic point.     

Conjugated Polymer Nanoparticle‐Triplet Emitter Hybrids in Aqueous Dispersion: Fabrication and Fluorescence Quenching Behavior

Conjugated polymer nanoparticles based on poly[9,9‐bis(2‐ethylhexyl)fluorene] and poly[N‐(2,4,6‐trimethylphenyl)‐N,N‐diphenylamine)‐4,4′‐diyl] are fabricated using anionic surfactant sodium dodecylsulphate in water by miniemulsion technique. Average diameters of polyfluorene and polytriarylamine nanoparticles range from 70 to 100 and 100 to 140 nm, respectively. The surface of the nanoparticles is decorated with triplet emitting dye, tris(2,2′‐bipyridyl)ruthenium(II) chloride. Intriguing photophysics of aqueous dispersions of these hybrid nanoparticles is investigated. Nearly 50% quenching of fluorescence is observed in the case of dye‐coated polyfluorene nanoparticles; excitation energy transfer is found to be the dominant quenching mechanism. On the other hand, nearly complete quenching of emission is noticed in polytriarylamine nanoparticle‐dye hybrids. It is proposed that the excited state electron transfer from the electron‐rich polytriarylamine donor polymer to Ru complex leads to the complete quenching of emission of polytriarylamine nanoparticles. The current study offers promising avenues for developing aqueous solution processed‐electroluminescent devices involving a conjugated polymer nanoparticle host and Ru or Ir‐based triplet emitting dye as the guest.

     

Insight into Signal Response of Protein Ions in Native ESI-MS from the Analysis of Model Mixtures of Covalently Linked Protein Oligomers

Native ESI-MS is increasingly used for quantitative analysis of biomolecular interactions. In such analyses, peak intensity ratios measured in mass spectra are treated as abundance ratios of the respective molecules in solution. While signal intensities of similar-size analytes, such as a protein and its complex with a small molecule, can be directly compared, significant distortions of the peak ratio due to unequal signal response of analytes impede the application of this approach for large oligomeric biomolecular complexes. We use a model system based on concatenated maltose binding protein units (MBPn, n = 1, 2, 3) to systematically study the behavior of protein mixtures in ESI-MS. The MBP concatamers differ from each other only by their mass while the chemical composition and other properties remain identical. We used native ESI-MS to analyze model mixtures of MBP oligomers, including equimolar mixtures of two proteins, as well as binary mixtures containing different fractions of the individual components. Pronounced deviation from a linear dependence of the signal intensity with concentration was observed for all binary mixtures investigated. While equimolar mixtures showed linear signal dependence at low concentrations, distinct ion suppression was observed above 20 μM. We systematically studied factors that are most often used in the literature to explain the origin of suppression effects. Implications of this effect for quantifying protein–protein binding affinity by native ESI-MS are discussed in general and demonstrated for an example of an anti-MBP antibody with its ligand, MBP.

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Low-frequency dilatational wave propagation through unsaturated porous media containing two immiscible fluids

An analytical theory is presented for the low-frequency behavior of dilatational waves propagating through a homogeneous elastic porous medium containing two immiscible fluids. The theory is based on the Berryman–Thigpen–Chin (BTC) model, in which capillary pressure effects are neglected. We show that the BTC model equations in the frequency domain can be transformed, at sufficiently low frequencies, into a dissipative wave equation (telegraph equation) and a propagating wave equation in the time domain. These partial differential equations describe two independent modes of dilatational wave motion that are analogous to the Biot fast and slow compressional waves in a single-fluid system. The equations can be solved analytically under a variety of initial and boundary conditions. The stipulation of “low frequency” underlying the derivation of our equations in the time domain is shown to require that the excitation frequency of wave motions be much smaller than a critical frequency. This frequency is shown to be the inverse of an intrinsic time scale that depends on an effective kinematic shear viscosity of the interstitial fluids and the intrinsic permeability of the porous medium. Numerical calculations indicate that the critical frequency in both unconsolidated and consolidated materials containing water and a nonaqueous phase liquid ranges typically from kHz to MHz. Thus engineering problems involving the dynamic response of an unsaturated porous medium to low excitation frequencies (e.g., seismic wave stimulation) should be accurately modeled by our equations after suitable initial and boundary conditions are imposed.     

Periodic solutions to some problems of n-body type

We prove the existence of at least one T-periodic solution to a dynamical system of the type $$ - m_i \ddot u_i = \sum\limits_{j = 1,j \ne i}^n {\triangledown V_{ij} (u_i - u_j ,{\text{ }}t)}$$ (1) where the potentials V _ij are T-periodic in t and singular at the origin, u _i ε R ^k i=1, ..., n, and k≧3. We also provide estimates on the H ¹ norm of this solution. The proofs are based on a variant of the Ljusternik-Schnirelman method. The results here generalize to the n-body problem some results obtained by Bahri & Rabinowitz on the 3-body problem in [6].