Selectivity in substrate–enzyme complexation studied by surface forces measurement

The selectivity of substrate in substrate–enzyme complexation of heptaprenyl diphosphate synthase was directly investigated using colloidal probe atomic force microscopy (AFM). This enzyme is composed of two dissociable subunits, which exhibits a catalytic activity only when they are associated together in the presence of a cofactor, Mg²⁺, and a substrate, farnesyl diphosphate (FPP). We have recently succeeded to directly demonstrate a specific interaction involved in this enzyme reaction and obtain new insights into the molecular mechanism of the reaction using the approach based on the colloidal probe AFM. The AFM measurement showed the adhesive force between the subunits only in the presence of both Mg²⁺ and FPP. In this study, we studied the substrate selectivity in the complexation by monitoring the adhesive force. The substrates studied are pyrophosphate (PPi), isopentenyl diphosphate (IPP), geranyl diphosphate (GPP), farnesyl monophosphate (FP), and farnesyl geranyl diphosphate (FGPP). No adhesion was observed in the case of PPi, IPP, and GPP. On the other hand, the significant adhesion was observed for phosphate derivatives, which bear prenyl units longer than three. This is in good agreement with the selectivity of the substrates by this enzyme, which catalyzes the condensation reaction of four IPP molecules with FPP to give heptaprenyl (C₃₅) diphosphates. Our study showed a useful methodology for examining the elemental processes of biological reactions.     

Segmented block copolyesters using click chemistry

Copper(I) catalyzed azide‐alkyne 1,3‐Huisgen cycloaddition reaction afforded the synthesis of triazole‐containing polyesters and segmented block copolyesters at moderate temperatures. Triazole‐containing homopolyesters exhibited significantly increased (～40 °C) glass transition temperatures (T_g) relative to high temperature, melt synthesis of polyesters with analogous structures. Quantitative synthesis of azido‐terminated poly(propylene glycol) (PPG) allowed for the preparation of segmented polyesters, which exhibited increased solubility and mechanical ductility relative to triazole‐containing homopolyesters. Differential scanning calorimetry demonstrated a soft segment (SS) T_g near ?60 °C for the segmented polyesters, consistent with microphase separation. Tensile testing revealed Young's moduli ranging from 7 to 133 MPa as a function of hard segment (HS) content, and stress at break values approached 10 MPa for 50 wt % HS segmented click polyesters. Dynamic mechanical analysis demonstrated an increased rubbery plateau modulus with increased HS content, and the T_g's of both the SS and HS did not vary with composition, confirming microphase separation. Atomic force microscopy also indicated microphase separated and semicrystalline morphologies for the segmented click polyesters. This is the first report detailing the preparation of segmented copolyesters using click chemistry for the formation of ductile membranes with excellent thermomechanical response. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Visualization of arborescent architecture of polystyrenes prepared by raft‐based initiator‐monomer polymerization using atomic force microscopy

This article presents the utilization of “molecular amplification” to visualize the molecular architecture of “arborescent” (tree‐like) polystyrenes (arbPSs) using atomic force microscopy (AFM). arbPSs with M_n > 80,000 g/mol were synthesized via initiator‐monomer‐type (inimer) RAFT polymerization of styrene mediated by 4‐vinylbenzyl dithiobenzoate in bulk. These arbPS were then used as macrochain transfer agents for polymerization of vinylbenzyl chloride (VBCl) to give arborescent poly(styrene‐block‐vinylbenzyl chloride) (arbPS‐b‐VBCl). Poly(styryl) diphenylethyl lithium (M_n = 11,000 g/mol) was then grafted onto the VBCl units of the arbPS‐b‐VBCl. The M_n of the amplified arbPSs increased over >10 million g/mol, exceeding the exclusion limit of our size exclusion chromatography equipment. AFM confirmed the proposed branches on branches architecture in the samples, together with lesser branched species. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Improving charge transport in poly(3‐hexylthiophene) transistors via blending with an alkyl‐substituted phenylene–thiophene–thiophene–phenylene molecule

A prototypical semiconducting bicomponent system consisting of a conjugated polymer, that is, poly(3‐hexylthiophene) (P3HT), blended with a small thiophene containing conjugated molecule, that is, an alkyl‐substituted bisphenyl‐bithiophene [phenylene–thiophene–thiophene–phenylene (PTTP)], has been used as an electroactive active layer in field‐effect transistors (FETs). The self‐assembly of this bicomponent system at surfaces has been studied at different length scales, from the nanoscale to the macroscale, and compared with the behavior of monocomponent films of PTTP and P3HT. The correlation between morphology and electric properties of the semiconducting material is explored by fabricating prototypes of FETs varying the relative concentrations of the two‐component blend. The maximum charge carrier mobility value, achieved with a few percent of PTTP component, is not simply due to a uniform dispersion of the molecules in the polymer matrix, but rather to the generation of very long percolation paths, whose composition and electrical properties can be tuned with the PTTP concentration. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Atomic force microscopy characterization of β-casein nanoparticles on mica and graphite

1. Download : Download high-res image (193KB)
2. Download : Download full-size image

     

Formation and tribological properties of two‐component ultrathin ionic liquid films on Si

Several single‐component and two‐component imidazolium ionic liquids (ILs) ultrathin films were formed on Si substrates by a dip‐coating and heat treatment process. The formation and surface properties of the films were analyzed by means of ellipsometric thickness measurement, X‐ray photoelectron spectra and atomic force microscope. The adhesive and nanotribological behaviors of the films were evaluated by a homemade colloidal probe. A ball‐on‐plate tribometer was used to test the microtribological performances of these films. As a result, the two‐component ILs ultrathin film containing 80% solid‐like ILs phase shows more homogenous surface morphologies and optimal micro/nano‐tribological properties as compared to single‐component ILs films, which is ascribed to a synergic effect between the steady solid‐like ILs phase as the backbone and the proper amount of flowable liquid‐like ILs phase. By studying the influence of various solid/liquid ILs ratios on tribological properties of the two‐component ILs films, we might find the way to design ILs films with excellent comprehensive tribological properties. Copyright © 2010 John Wiley & Sons, Ltd.     

Pesticide‐conjugated polyacrylate nanoparticles: novel opportunities for improving the photostability of emamectin benzoate

Emamectin benzoate, a macrocyclic lactone, can be used in low quantities to control arthropod pests, effectively. However, its poor photostability prevents its further use. To delay its photodegradation, novel acrylate‐type polymeric nanoparticles were synthesized and tested as materials for improving pesticide photostability. N‐acylated emamectin benzoate was synthesized via bonding emamectin benzoate to acrylamide. The resulting pesticide, containing the double bond linkage –C=C–N–, was copolymerized with butyl acrylate and methyl methacrylate by the emulsion polymerization method. The refined polymers were characterized by Fourier transform infrared spectroscopy spectroscopy, and result illustrated the pesticide was conjugated to the polymers. Atomic force microscope and dynamic light scattering analyses were also used for determining the average particle diameters of pesticide–polymer conjugates. Photostability tests showed that the nanoparticles obtained exhibited greatly improved photostability. Additionally, the laboratory toxicity tests demonstrated that the insecticidal effects of the novel emamectin benzoate formulation were better than those of the control pesticide formulation (emamectin benzoate EC). Copyright © 2012 John Wiley & Sons, Ltd.     

Cleaning requirements for silica‐coated sensors used in optical waveguide lightmode spectroscopy

Optical waveguide lightmode spectroscopy (OWLS), based on the incoupling of laser light into a waveguide sensor by an optical grating, allows for the in situ measurement of protein adsorption. Few reports have described cleaning methods for the surfaces of such sensors, and in this investigation, we compare common methods for cleaning of silica surfaces in relation to their effectiveness for cleaning silica‐coated waveguide sensors used in OWLS. For this purpose, atomic force microscopy (AFM) analysis of surface morphology and OWLS detection of protein adsorption kinetics were used to evaluate waveguide sensors before and after cleaning. While AFM line scans showed a substantial increase in average waveguide peak‐to‐valley height after RCA cleaning relative to all other methods tested, chemical etching owing to the alkaline component of the rolling circle amplification method rendered the waveguide unusable for detection of protein adsorption with OWLS. A revised method, based on replacement of the alkaline step with immersion in sodium dodecyl sulfate, was not only effective at cleaning OWLS waveguides off‐the‐shelf but also showed excellent protein adsorption reproducibility after ex situ cleaning. Moreover, the revised method showed excellent reproducibility when applied in situ, between repeated adsorption‐elution cycles. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface and Catalytic Properties of K/V Catalysts Coating on Porous Al2O3 Substrate

The morphology of different ratio K/V catalysts supported on porous α‐alumina substrate was investigated by atomic force microscopy (AFM). Changes in the particle size distribution, pore size distribution were analyzed respectively using AFM software. In addition, their catalytic activities and compositions for carbon oxidation were studied by x‐ray diffraction (XRD), differential scanning calorimetry (DSC), and temperature‐programmed reactions (TPR). As a result, with the increase of K concentration, the mean particle size gradually increased and the mean pore size decreased. According to the catalytic activity studies, the catalytic activity of the KVO₃ and K₃V₅O₁₄ phases are more effective than KCl.