From Glucose Direct to Succinic Acid: an Optimized Recyclable Bi-functional Ru@MNP-MWCNT Catalyst

Ru@MNP-MWCNT catalysts were obtained via functionalization of nanostructured carbon-based carriers (ie, MWCNT) with base molecules (ie, 2-aminophenol and ethylenediamine) followed by the complexation with RuCl₃. These structures demonstrated a highly efficient behavior for the selective wet oxidation of levulinic acid and glucose to succinic acid. However, to ensure an easy recovery and high recyclability the MWCNTs nanotubes were modified by incorporation of super-paramagnetic Fe₃O₄ nanoparticles into porous structure. Besides the catalytic performances the resulted composites showed a good mechanical resistance.     

Influence of microfibrillated cellulose and soft biocomponent on the morphology and thermal properties of thermoplastic polyurethanes

Composite materials from thermoplastic polyurethanes (TPUs) with biodegradable segments and microfibrillated cellulose (MFC) were developed as alternatives to traditional materials used in packaging or biomedical applications. Two TPUs were synthesized by the prepolymer method starting from different soft segments, poly(ε-caprolactone)/poly(butylene adipate) (PUBA) or poly(ε-caprolactone)/poly(ethylene oxide) (PUEO), and isophorone diisocyanate/aliphatic chain extender. Proton nuclear magnetic resonance (¹H NMR) confirmed the structure and Fourier transform infrared spectroscopy (FTIR) along with scanning electron microscopy showed that the soft segments with different hydrophobicity led to a higher phase mixing in PUBA and improved microphase separation in PUEO. MFC was added in the TPUs with different soft segments to increase biocompatibility, strength, and degradation rate. A better thermal stability, a gradual increase of crystallinity and a better dispersion of MFC were noticed in PUEO composites compared to PUBA ones. The crystallinity increased with 78% and 50% in PUBA and PUEO composites with 5 wt% MFC compared to the neat polyurethanes showing the nucleating ability of MFC. In addition, the enhanced storage modulus, with 75% and 25% in PUEO and PUBA composites, highlighted the reinforcing efficiency of MFC. Therefore, the addition of MFC to the already synthesized TPUs allows tailoring the morphology and thermal properties of TPUs for industrial application.     

Automatic validation of phosphopeptide identifications from tandem mass spectra

We developed and compared two approaches for automated validation of phosphopeptide tandem mass spectra identified using database searching algorithms. Phosphopeptide identifications were obtained through SEQUEST searches of a protein database appended with its decoy (reversed sequences). Statistical evaluation and iterative searches were employed to create a high-quality data set of phosphopeptides. Automation of postsearch validation was approached by two different strategies. By using statistical multiple testing, we calculate a p value for each tentative peptide phosphorylation. In a second method, we use a support vector machine (SVM; a machine learning algorithm) binary classifier to predict whether a tentative peptide phosphorylation is true. We show good agreement (85%) between postsearch validation of phosphopeptide/spectrum matches by multiple testing and that from support vector machines. Automatic methods conform very well with manual expert validation in a blinded test. Additionally, the algorithms were tested on the identification of synthetic phosphopeptides. We show that phosphate neutral losses in tandem mass spectra can be used to assess the correctness of phosphopeptide/spectrum matches. An SVM classifier with a radial basis function provided classification accuracy from 95.7% to 96.8% of the positive data set, depending on search algorithm used. Establishing the efficacy of an identification is a necessary step for further postsearch interrogation of the spectra for complete localization of phosphorylation sites. Our current implementation performs validation of phosphoserine/phosphothreonine-containing peptides having one or two phosphorylation sites from data gathered on an ion trap mass spectrometer. The SVM-based algorithm has been implemented in the software package DeBunker. We illustrate the application of the SVM-based software DeBunker on a large phosphorylation data set.     

Antibody covalent immobilization on carbon nanotubes and assessment of antigen binding

Controlling the covalent bonding of antibodies onto functionalized carbon nanotubes is a key step in the design and preparation of nanotube-based conjugates for targeting cancer cells. For this purpose, an anti-MUC1 antibody (Ab) is linked to both multi-walled (MWCNTs) and double-walled carbon nanotubes (DWCNTs) using different synthetic strategies. The presence of the Ab attached to the nanotubes is confirmed by gel electrophoresis and thermogravimetric analysis. Most importantly, molecular recognition of the antigen by surface plasmon resonance is able to determine similar Ab binding capacities for both Ab-DWCNTs and Ab-MWCNTs. These results are very relevant for the design of future receptor-targeting strategies using chemically functionalized carbon nanotubes.     

Biocompatibilty of starch-based films from starch of Andean crops for biomedical applications

In this communication we report the use of starch films as cell substrates. To the best of our knowledge it is the first time that films prepared from native Andean starches are studied as biomaterials. For the present study 3T3 fibroblast cells were seeded in seventeen novel starch based films from different Andean crops. In order to analyze the use of these types of starch as biomedical materials, biocompatibility, viability and cell adhesion studies were performed at the third day of incubation on supplemented DMEM medium. After cultured, films made from starch of “tunta”, “muro-huayro” potato and white carrot showed the highest level of living cells and cell viability. These results indicate that native starches from Andean crops can be used for biomedical applications.     

Three-dimensional dual-morphotype species modeling of activated sludge flocs

An individual-based model, originally developed for a biofilm system, was adapted to simulate three-dimensional formation of activated sludge flocs. The model was extended to two different bacterial morphotypes (floc-forming and filamentous bacteria), allowing spatial development of the floc according to the bacterial morphology, diffusion, reaction, and growth processes. The model needed also extension with a process for attachment of individual cells. Despite being in an early stage of development, the model is already a tool that enables us to obtain useful information about the microfloc environment. The model indicates that filamentous bacterial morphology and substrate microgradients are important aspects in the formation of bacterial structures. In mass transport-limited regimes filamentous bacterial structures prevail, whereas in growth-limited regimes irregular shaped flocs with fingerlike structures are dominant. These modeling results suggest that activated sludge flocs and biofilms might be different manifestations of the same phenomena. The model results support the hypothesis that floc-macrogradients can be the most important parameter for development of bulking sludge. The model suggests that attachment has a very strong effect on floc structure, leading to enhancement of the effect of substrate microgradients.     

Effects of murta (Ugni molinae Turcz) extract on gas and water vapor permeability of carboxymethylcellulose-based edible films

The effect of murta (Ugni molinae Turcz) leaves extract on water vapor permeability (WVP) and gas permeability (GP) of carboxymethylcellulose (CMC)-based films was studied. Two ecotypes of murta leaves “Soloyo Grande” (SG) and “Soloyo Chico” (SC), were analyzed for their composition (HPLC-MS) and SC extract revealed a higher concentration of flavonols than the SG extract. The film forming solution was prepared with 2 g of CMC, 0.4 ml of glycerol and 0.5 ml of sunflower oil in 100 ml of water (Control), 50 ml of water and 50 ml of each exctract (SC50 or SG50) and 100 ml of each extract (SC 100 or SG 100). The addition of murta leaves extract modified the WVP and GP of the films. The WVP decreased significantly (P?0.05) with the incorporation of SG extract in the film but not with the SC extract (P>0.05). The CO₂ and O₂ permeability of the films were influenced by the kind and concentration of murta leaves extract used. The CO₂ permeability, with SG extract was higher than without extract (P?0.05) and with SC extract was not modified. The O₂ permeability with murta leaves extract were lower than without extract. Therefore, it is possible to consider that films with SC acts only as barrier to the oxygen, but with SG the water vapor and gas barrier properties were modified, being more permeable to the CO₂ and acting as barrier to O₂ and water vapor.     

Nanowire‐Intensified Metal‐Enhanced Fluorescence in Hybrid Polymer‐Plasmonic Electrospun Filaments

Hybrid polymer‐plasmonic nanostructures might combine high enhancement of localized fields from metal nanoparticles with light confinement and long‐range transport in subwavelength dielectric structures. Here, the complex behavior of fluorophores coupling to Au nanoparticles within polymer nanowires, which features localized metal‐enhanced fluorescence (MEF) with unique characteristics compared to conventional structures, is reported. The intensification effect when the particle is placed in the organic filaments is remarkably higher with respect to thin films of comparable thickness, thus highlighting a specific, nanowire‐related enhancement of MEF effects. A dependence on the confinement volume in the dielectric nanowire is also indicated, with MEF significantly increasing upon reduction of the wire diameter. These findings are rationalized by finite element simulations, predicting a position‐dependent enhancement of the quantum yield of fluorophores embedded in the fibers. Calculation of the ensemble‐averaged fluorescence enhancement unveils the possibility of strongly enhancing the overall emission intensity for structures with size twice the diameter of the embedded metal particles. These new, hybrid fluorescent systems with localized enhanced emission, and the general nanowire‐enhanced MEF effects associated to them, are highly relevant for developing nanoscale light‐emitting devices with high efficiency and intercoupled through nanofiber networks, highly sensitive optical sensors, and novel laser architectures.