Chemical constituents of the leaves of rabbiteye blueberry (Vaccinium ashei) and characterisation of polymeric proanthocyanidins containing phenylpropanoid units and A-type linkages

Chemical constituents of the leaves of rabbiteye blueberry (Vaccinium ashei READE) were investigated in detail. The major phenolic components were caffeoyl quinic acids, flavonol glycosides, flavan-3-ols and proanthocyanidins. Catechins and proanthocyanidins having additional phenylpropanoid units, such as cinchonains, kandelins and mururins, characterised the polyphenols of this plant. Among them, vaccinin A, an isomer of mururin A, was found to be a new compound, and the structure was characterised by spectroscopic methods. The most abundant polyphenols (11.3% of freeze-dried leaves) were oligomeric proanthocyanidins. Thiol degradation with mercaptoethanol indicated that the polymer was constituted of (+)-catechin and (−)-epicatechin as the terminal units and (−)-epicatechin, procyanidin A-2, and cinchonains Ia and Ib as the extension units. Mass spectral analysis suggested the presence of at least dodecamers with A-type linkages and phenylpropanoid moieties.     

In vitro and in vivo investigations of upconversion and NIR emitting Gd2O3:Er3+,Yb3+ nanostructures for biomedical applications

The use of an “over 1000-nm near-infrared (NIR) in vivo fluorescence bioimaging” system based on lanthanide containing inorganic nanostructures emitting in the visible and NIR range under 980-nm excitation is proposed. It may overcome problems of currently used biomarkers including color fading, phototoxicity and scattering. Gd₂O₃:Er³⁺,Yb³⁺ nanoparticles and nanorods showing upconversion and NIR emission are synthesized and their cytotoxic behavior is investigated by incubation with B-cell hybridomas and macrophages. Surface modification with PEG-b-PAAc provides the necessary chemical durability reducing the release of toxic Gd³⁺ ions. NIR fluorescence microscopy is used to investigate the suitability of the nanostructures as NIR–NIR biomarkers. The in vitro uptake of bare and modified nanostructures by macrophages is investigated by confocal laser scanning microscopy. In vivo investigations revealed nanostructures in liver, lung, kidneys and spleen a few hours after injection into mice, while most of the nanostructures have been removed from the body after 24?h.     

Fabrication of Langmuir-Blodgett films using amphiphilic peptides

To introduce self-organization ability of transmembrane proteins into Langmuir (L) and Langmuir-Blodgett (LB) techniques, we focused on "amphiphilic peptide" (AP) which is composed of two distinct hydrophilic and hydrophobic domains. Three types of APs of different average hydropathies were used to prepare the AP/lipid mixed L and LB films. According to the circular dichroism spectra, the secondary structures of APs were not uniform but were a mixture of alpha-helix, beta-strand and random coil. The fraction of alpha-helix was higher for lower hydropathy AP. The interaction between AP and lipid in the L film and the structure of the LB film were also depended on the APs used.     

Regioselective carbon-carbon bond formation in proteins with palladium catalysis; new protein chemistry by organometallic chemistry

Palladium-catalyzed reactions have contributed to the advancement of many areas of organic chemistry, in particular, the synthesis of organic compounds such as natural products and polymeric materials. In this study, we have used a Mizoroki-Heck reaction for site-specific carbon-carbon bond formation in the Ras protein. This was performed by the following two steps: 1) the His6-fused Ras protein containing 4-iodo-L-phenylalanine at position 32 (iF32-Ras-His) was prepared by genetic engineering and 2) the aryl iodide group on the iF32-Ras-His was coupled with vinylated biotin in the presence of a palladium catalyst. The biotinylation was confirmed by Western blotting and liquid chromatography-mass spectrometry (LC-MS). The regioselectivity of the Mizoroki-Heck reaction was furthermore confirmed by LC-MS/MS analysis. However, in addition to the biotinylated product (bF32-Ras-His), a dehalogenated product (F32-Ras-His) was detected by LC-MS/MS. This dehalogenation resulted from the undesired termination of the Mizoroki-Heck reaction due to steric and electrostatic hindrance around residue 32. The biotinylated Ras showed binding activity for the Ras-binding domain as its downstream target, Raf-1, with no sign of decomposition. This study is the first report of an application of organometallic chemistry in protein chemistry.     

Dramatic effect of dispersed carbon nanotubes on the mechanical and electroconductive properties of polymers derived from ionic liquids

Free-radical polymerization of an imidazolium ion-based ionic liquid bearing a methacrylate group, gelling with single-walled carbon nanotubes (SWNTs), allows fabrication of a mechanically reinforced, electroconductive soft material (bucky plastic). A film sample of this material displays an excellent conductivity of 1 S cm(-1) and a 120-fold enhancement of the Young's modulus at a 7 wt % content of SWNTs. The conductivity is temperature-dependent in the range 5-300 K, suggesting that the conductive process involves carrier hopping. Scanning electron and atomic force micrographs of a bucky plastic film display the presence of crosslinked networks consisting of finely dispersed SWNTs. Such nanotube networks, developed in the polymer matrix, likely suppress slipping of entrapped polymer molecules via a strong interfacial interaction and also facilitate intertubular carrier transport. Although a bucky plastic derived from a vinylimidazolium ion-based ionic liquid monomer shows a comparable conductivity to that of the methacrylate version, the film is brittle irrespective of the presence or absence of SWNTs.     

The molecular weight ratio of monomethoxypolyethylene glycol (mPEG) to protein determines the immunotolerogenicity of mPEG proteins

Immunotolerogenic activity of monomethoxypolyethylene glycol-(mPEG) conjugated proteins is a beneficial property in proteinpharmaceutics. However, procedures for the preparation of tolerogenicmPEG proteins have not yet been defined. We prepared mPEG proteinswith different mPEG contents using three proteins, hen egg lysozyme,ovalbumin and bovine gamma globulin, and their tolerogenicitiesto antigen-specific T and B cell responses were examined. Wefound the most appropriate ratio of tolerance induction to be1.5–2.0, which is the molecular weight ratio of conjugatedtotal mPEGs to protein. This value may assist in the preparationof tolerogenic mPEG proteins.     

Differentiating the natural and man-made terraces of Lake Van, Eastern Anatolia, utilizing earth science methods

The Fertile Crescent of the Middle East region, embracing Syria, eastern Turkey and Iraq, marks the region where settled agriculture began, and where the landscape has been shaped for millennia by human activities. The lacustrine and fluvial terraces of the Late Pleistocene and Holocene Eras are common geomorphic features in many areas around Lake Van in eastern Turkey, being sustainably used since the Urartian Period (800–400 years bc ). Fluctuations in the water levels of Lake Van have resulted in the development of widely distributed natural terraces around the Lake. The undulating slopes of these terraces have limited their cultivation, however, leading people to reconstruct terraces as a means for utilizing particular production sites, as anthroscapes (this concept is generally confined to situations where marked differences or deviations from the normal, natural landscapes are attributable to effects/shaping by humans). The region exhibits semiarid climatic conditions and a short crop‐growing season, currently being under the threat of land degradation. Recent mismanagement of these lands as a result of increasing population pressures has led to the degradation of both the natural and the man‐made terraces. Thus, there is an urgent need to conserve and understand the indigenous management and soil quality attributes of these man‐made terraces. To this end, this study examined soil profiles and analysed soil samples for their chemical, physical and mineralogical characteristics, in order to determine the human effects of leaching and/or accumulation. These analyses revealed significant differences between the physical, chemical, microbiological and mineralogical properties of the man‐made/reworked terraces and natural terraces under essentially similar parent materials and environment, thereby providing clues as to the sustainable management of these land surfaces in eastern Turkey. The approaches used in this study provide useful evidence for attempting to explain the historical evolution of land use in similar environments elsewhere, as well as the significance of terraces in combating coastal erosion in lake environments.     

Selective adsorption of precious metals from hydrochloric acid solutions using porous carbon prepared from barley straw and rice husk

Porous carbon was prepared by carbonization from agro-waste such as rice husk and barley straw to evaluate the adsorption of precious and base metals from metal solutions. The effects of hydrochloric acid concentration, metal ion concentration, and contact time on adsorption were examined. Rice husk carbon was found to be highly selective for Au(III) and inert to Pt(IV), Pd(II) and other base metals. Barley straw carbon adsorbed these three precious metal ions, but was inert to base metal ions such as Cu(II), Fe(III) and Ni(II). The maximum adsorption capacity of rice husk carbon for Au(III) was 0.76 mol/kg and the maximum adsorption capacity of barley straw carbon for Au(III), Pt(IV) and Pd(II) was 1.47, 0.39 and 0.64 mol/kg, respectively. The effectiveness of recovery of precious metals from industrial solution was also tested and barley straw carbon was found to be highly efficient and selective for the targeted metal ions in the presence of excess of other metal ions. Rice husk and barley straw carbon are thus potential alternatives to commercially available activated carbon as they have high selectivity and are efficient with low production costs.     

Study of the friction error for a high-speed high precision table

Friction is one of the important factors resulting in the contour error of feed servo systems for high-speed, high precision CNC machine tools. A mathematical model of a high speed high precision feed servo table with PID controlling has been established with consideration of friction effects. The friction can be calculated according to the sliding speed and the oil film between the two contact surfaces by using a two-component mixed friction model. The protrusion error occurring at the quadrant boundary in the circular motion is profoundly studied by means of numerical simulation and experiments under different work conditions, and the conclusion that the quadrant protrusion error lags with the rising of the feed rate is obtained. Comparisons between the simulation results and the experimental results demonstrate that with the mathematical model, the dynamics of high speed high precision servo feed systems under PID controlling can be accurately simulated, and the friction error and its characteristics in the course of feeding can be precisely predicted.