Highlights on the Binding of Cobalta-Bis-(Dicarbollide) with Glucose Units

Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C₂B₉H₁₁)₂]⁻, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations.     

Improved Interfacial Bonding Strength and Reliability of Functionalized Graphene Oxide for Cement Reinforcement Applications

Poor bonding strength between nanomaterials and cement composites inevitably lead to the failure of reinforcement. Herein, a novel functionalization method for the fabrication of functionalized graphene oxide (FGO), which is capable of forming highly reliable covalent bonds with cement hydration products, and therefore, suitable for use as an efficient reinforcing agent for cement composites, is discussed. The bonding strength between cement and aggregates was improved more than 21 times with the reinforcement of FGO. The fabricated FGO also demonstrated many important features, including high reliability in cement pastes, good dispersibility, and efficient structural refinement of cement hydration products. With the incorporation of FGO, cement mortar samples demonstrated up to 40 % increased early and ultimate strength. Such results make the fast demolding and manufacture of light constructions become highly possible, and show strong advantages on improving productivity, saving cost, and reducing CO₂ emissions in practical applications.     

On modifying properties of polymeric melts by nanoscopic particles

We study geometric and energetic factors that partake in modifying properties of polymeric melts via inserting well‐dispersed nanoscopic particles (NP). Model systems are cis‐1,4‐polybutadiene melts including a single atomic clusters of size varied in the range 10–150 atoms (3–7 Å in radius; 0.1–1.5% v/v). We modify the interactions between the chains and the particle by tuning attractive van der Waals interactions. Using molecular dynamics, we study equilibrium fluctuations and dynamical properties at the interface. The NPs move in the polymer matrix in two different regimes corresponding to trapped and free diffusion, depending on the NP size. Furthermore, degree of crowding around the NP by the polymer chains is quantified. Effect of NP size and interaction strength both on volume and volumetric fluctuations is manifested in mechanical properties, quantified here by bulk modulus, K. Tuning NP size and nonbonded interactions results in ～15% enhancement in K by addition of a maximum of 1.5% v/v NP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Global persistence of geometrical structures for the Boussinesq equation with no diffusion

Our main aim is to investigate the temperature patch problem for the two-dimensional incompressible Boussinesq system with partial viscosity: the initial temperature is the characteristic function of some simply connected domain with 𝒞^1,𝜀 Hölder regularity. Although recent results ensure that the 𝒞¹ regularity of the patch persists for all time, whether higher order regularity is preserved has remained an open question. In the present paper, we give a positive answer to that issue. We also study the higher dimensional case, after prescribing an additional smallness condition involving critical Lebesgue or weak-Lebesgue norms of the data, so as to get a global-in-time statement. All our results stem from general properties of persistence of geometrical structures (of independent interest), that we establish in the first part of the paper.     

Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Scanning Probe Microscopy beyond Imaging: A General Tool for Quantitative Analysis

A simple, fast and general approach for quantitative analysis of scanning probe microscopy (SPM) images is reported. As a proof of concept it is used to determine with a high degree of precision the value of observables such as 1) the height, 2) the flowing current and 3) the corresponding surface potential (SP) of flat nanostructures such as gold electrodes, organic semiconductor architectures and graphenic sheets. Despite histogram analysis, or frequency count (Fc), being the most common mathematical tool used to analyse SPM images, the analytical approach is still lacking. By using the mathematical relationship between Fc and the collected data, the proposed method allows quantitative information on observable values close to the noise level to be gained. For instance, the thickness of nanostructures deposited on very rough substrates can be quantified, and this makes it possible to distinguish the contribution of an adsorbed nanostructure from that of the underlying substrate. Being non‐numerical, this versatile analytical approach is a useful and general tool for quantitative analysis of the Fc that enables all signals acquired and recorded by an SPM data array to be studied with high precision.     

Equilibrium Topology and Partial Inversion of Janus Drops: A Numerical Analysis

The equilibrium topology of an aqueous Janus emulsion of two oils, O1 and O2, with water, W, [(O1+O2)/W], is numerically evaluated with the following realistic interfacial tensions (γ): γ_O2/W=5 mN m⁻¹, γ_O1/O2=1 mN m⁻¹, and γ_O1/W varies within the range 4–5 mN m⁻¹, which is the limiting range for stable Janus drop topology. The relative significance of the two independently pivotal factors for the topology is evaluated, that is, the local equilibrium at the line of contact between the three liquids and the volume fraction of the two dispersed liquids within the drop. The results reveal a dominant effect of the local equilibrium on the fraction of the O2 drop surface that is covered by O1. In contrast, for a constant volume of O2, the impact of the interfacial tension balance on the limit of the coverage is modest for an infinite volume of O1. Interestingly, when the O1 volume exceeds this value, an emulsion inversion occurs, and the O1 portion of the (O1+O2)/W topology becomes a continuous phase, generating a (W+O2)/O1 Janus configuration.     

Chlorine‐Enhanced Surface Mobility of Au(100)

Motivated by experimental studies of two‐dimensional Ostwald ripening on Au(100) electrodes in chlorine‐containing electrolytes, we have studied diffusion processes using density functional theory. We find that chlorine has a propensity to temporary form AuCl complexes, which diffuse significantly faster than gold adatoms. With and without chlorine, the lowest activation energy is found for the exchange mechanism. Chlorine furthermore reduces the activation energy for the detachment from kink sites. Kinetic Monte Carlo simulations were performed on the basis of extensive density functional theory calculations. The island‐decay rate obtained from these Monte Carlo simulations, as well as the decay rate obtained from the theoretical activation energies and frequency factors when inserted into analytical solutions for Ostwald ripening, are in agreement with experimental island‐decay rates in chlorine‐containing electrolytes.     

Temperature-Dependent Surface-Enrichment Effects of Imidazolium-Based Ionic Liquids

We present the first systematic study of the influence of temperature on the degree of surface enrichment of 1-alkyl-3-methylimidazolium-based ionic liquids (ILs). Using angle-resolved X-ray photoelectron spectroscopy, we demonstrate that the degree of surface enrichment strongly decreases with increasing temperature for all the studied ILs. For ILs with the same cation, but different anions, [C₈C₁Im]Br, [C₈C₁Im][TfO] and [C₈C₁Im][Tf₂N], no significant differences of the temperature-induced partial loss of surface enrichment are found. Measurements for [C₄C₁Im][TfO], [C₈C₁Im][TfO] and [C₁₈C₁Im][TfO] indicate a small effect of the chain length. For [C₁₈C₁Im][TfO], a continuous decrease of alkyl surface enrichment is found with increasing temperature, with no abrupt changes at the phase-transition temperature from the smectic A to the isotropic phase, indicating that the surface enrichment is not affected by this phase transition.     

Ion‐Transfer Electrochemistry of Rat Amylin at the Water–Organogel Microinterface Array and Its Selective Detection in a Protein Mixture

The behavior of proteins and polypeptides at electrified aqueous–organic interfaces is of benefit in label‐free detection strategies. In this work, rat amylin (or islet amyloid polypeptide) was studied at the interface formed between aqueous liquid and gelled organic phases. Amylin is a polypeptide that is co‐secreted with insulin from islet beta‐cells and is implicated in fibril formation. In this study, rat amylin was used, which does not undergo aggregation. The polypeptide underwent an interfacial transfer process, from water to the gelled organic phase, under applied potential stimulation. Cyclic voltammetry revealed steady‐state forward and peak‐shaped reverse voltammograms, which were consistent with diffusion‐controlled water‐to‐organic transfer and thin‐film stripping or desorptive back‐transfer. The diffusion‐controlled forward current was greater when amylin was present in an acidic aqueous phase than when it was present in an aqueous phase at physiological pH; this reflects the greater charge on the polypeptide under acidic conditions. The amylin transfer current was concentration dependent over the range 2–10 μM , at both acidic and physiological pH. At physiological pH, amylin was selectively detected in the presence of a protein mixture, which illustrated the bioanalytical possibilities for this electrochemical behavior.