SYNTHESIS AND CHARACTERIZATION OF SURFACE-HYPERBRANCHED MAGNETITE NANOPARTICLE FOR BOVINE SERUM ALBUMIN IMMOBILIZATION

A hyperbranched polyamidoamine polymer was synthesized on the surface of magnetite nanoparticles to enhance bovine serum albumin (BSA) immobilization efficiency. The amount of immobilized bovine serum albumin (BSA) on the surface-hyperbranched magnetite nanoparticle was up to 2.5 times as much as that of magnetite nanoparticle modified with only amino silane.     

Trends and challenges of refractometric nanoplasmonic biosensors: A review

Motivated by potential benefits such as sensor miniaturization, multiplexing opportunities and higher sensitivities, refractometric nanoplasmonic biosensing has profiled itself in a short time span as an interesting alternative to conventional Surface Plasmon Resonance (SPR) biosensors. This latter conventional sensing concept has been subjected during the last decades to strong commercialization, thereby strongly leaning on well-developed thin-film surface chemistry protocols. Not surprisingly, the examples found in literature based on this sensing concept are generally characterized by extensive analytical studies of relevant clinical and diagnostic problems. In contrast, the more novel Localized Surface Plasmon Resonance (LSPR) alternative finds itself in a much earlier, and especially, more fundamental stage of development. Driven by new fabrication methodologies to create nanostructured substrates, published work typically focuses on the novelty of the presented material, its optical properties and its use – generally limited to a proof-of-concept – as a label-free biosensing scheme. Given the different stages of development both SPR and LSPR sensors find themselves in, it becomes apparent that providing a comparative analysis of both concepts is not a trivial task. Nevertheless, in this review we make an effort to provide an overview that illustrates the progress booked in both fields during the last five years. First, we discuss the most relevant advances in SPR biosensing, including interesting analytical applications, together with different strategies that assure improvements in performance, throughput and/or integration. Subsequently, the remaining part of this work focuses on the use of nanoplasmonic sensors for real label-free biosensing applications. First, we discuss the motivation that serves as a driving force behind this research topic, together with a brief summary that comprises the main fabrication methodologies used in this field. Next, the sensing performance of LSPR sensors is examined by analyzing different parameters that can be invoked in order to quantitatively assess their overall sensing performance. Two aspects are highlighted that turn out to be especially important when trying to maximize their sensing performance, being (1) the targeted functionalization of the electromagnetic hotspots of the nanostructures, and (2) overcoming inherent negative influence that stem from the presence of a high refractive index substrate that supports the nanostructures. Next, although few in numbers, an overview is given of the most exhaustive and diagnostically relevant LSPR sensing assays that have been recently reported in literature, followed by examples that exploit inherent LSPR characteristics in order to create highly integrated and high-throughput optical biosensors. Finally, we discuss a series of considerations that, in our opinion, should be addressed in order to bring the realization of a stand-alone LSPR biosensor with competitive levels of sensitivity, robustness and integration (when compared to a conventional SPR sensor) much closer to reality.     

Modern mass spectrometry in the characterization and degradation of biodegradable polymers

In the last decades, the solid-waste management related to the extensively growing production of plastic materials, in concert with their durability, have stimulated increasing interest in biodegradable polymers. At present, a variety of biodegradable polymers has already been introduced onto the market and can now be competitive with non biodegradable thermoplastics in different fields (packaging, biomedical, textile, etc.). However, a significant economical effort is still directed in tailoring structural properties in order to further broaden the range of applications without impairing biodegradation. Improving the performance of biodegradable materials requires a good characterization of both physico-chemical and mechanical parameters. Polymer analysis can involve many different features including detailed characterization of chemical structures and compositions as well as average molecular mass determination. It is of outstanding importance in troubleshooting of a polymer manufacturing process and for quality control, especially in biomedical applications. This review describes recent trends in the structural characterization of biodegradable materials by modern mass spectrometry (MS). It provides an overview of the analytical tools used to evaluate their degradation. Several successful applications of MALDI-TOF MS (matrix assisted laser desorption ionization time of flight) and ESI MS (electrospray mass spectrometry) for the determination of the structural architecture of biodegradable macromolecules, including their topology, composition, chemical structure of the end groups have been reported. However, MS methodologies have been recently applied to evaluate the biodegradation of polymeric materials. ESI MS represents the most useful technique for characterizing water-soluble polymers possessing different end group structures, with the advantage of being easily interfaced with solution-based separation techniques such as high-performance liquid chromatography (HPLC).     

Highly sensitive and selective sensing platform based on π–π interaction between tricyclic aromatic hydrocarbons with thionine–graphene composite

We are just beginning to exploit the fascinating potential of thionine, called electrochemical probe that can selectively recognize specific polycyclic aromatic hydrocarbons (PAHs), as tools for the detection of tricyclic aromatic hydrocarbons phenanthrene (PHE) and anthracene (ANT). A novel electrochemical sensing platform by modification of electroactive thionine functionalized graphene onto glass carbon electrode (Th/GRs/GCE) surface was constructed. The immobilized thionine showed a remarkable stability, which may benefit from the π–π stacking force with graphene. Under optimum conditions, the proposed electrochemical sensor exhibited high sensitivity and low detection limit for detecting PHE and ANT. The total amount of PHE and ANT could be quantified in a wide range of 10 pM–0.1 μM with a good linearity (R² = 0.9979) and a low detection limit of 0.1 pM (S/N = 3). Compounds which possess one or two benzene rings or PAHs with more than three rings, such as benzene, naphthalene (NAP), benzo[a]pyrene (BaP) and pyrene (PYR) show little interference on the detection. Consequently, a simple and sensitive electrochemical method was proposed for the determination of PHE and ANT, which was used to determine PHE and ANT in waste water samples. The electrochemical method provides a general tool that complements the commonly used spectroscopic methods and immune method for the detection of PAHs.     

A review on preparative and semi-preparative offgel electrophoresis for multidimensional protein/peptide assessment

Mass spectrometry (MS) techniques are commonly used for protein identification and further analysis of selected protein spots after high resolution 2-D electrophoresis. Complementary gel-free approaches have been developed during the last few years and have shown to be useful tools in modern proteomics. The development and application of various gel-free electrophoresis devices for performing protein fractionation according to the pI differences is therefore a topic of interest. This review describes the current state of isoelectric focusing (IEF) gel-free electrophoresis based on the Agilent offgel 3100 fractionator. The review includes, therefore, (i) an overview on IEF as well as other previous IEF gel-free electrophoresis developments; (ii) offgel fundamentals and future trends; (iii) advantages and disadvantages of current offgel procedures; (iv) requirements of isolated protein pellets for further offgel fractionation; (v) offgel fraction requirements to perform the second dimensional analysis by advance electrophoresis and chromatographic techniques; and (vi) effect of the offgel operating conditions on the stability of metal–protein complexes.     

Rational strategy for characterization of nanoscale particles by asymmetric-flow field flow fractionation: A tutorial

This tutorial proposes a comprehensive and rational measurement strategy that provides specific guidance for the application of asymmetric-flow field flow fractionation (A4F) to the size-dependent separation and characterization of nanoscale particles (NPs) dispersed in aqueous media. A range of fractionation conditions are considered, and challenging applications, including industrially relevant materials (e.g., metal NPs, asymmetric NPs), are utilized in order to validate and illustrate this approach. We demonstrate that optimization is material dependent and that polystyrene NPs, widely used as a reference standard for retention calibration in A4F, in fact represent a class of materials with unique selectivity, recovery and optimal conditions for fractionation; thus use of these standards to calibrate retention for other materials must be validated a posteriori. We discuss the use and relevance of different detection modalities that can potentially yield multi-dimensional and complementary information on NP systems. We illustrate the fractionation of atomically precise nanoclusters, which are the lower limit of the nanoscale regime. Conversely, we address the upper size limit for normal mode elution in A4F. The protocol for A4F fractionation, including the methods described in the present work is proposed as a standardized strategy to realize interlaboratory comparability and to facilitate the selection and validation of material-specific measurement parameters and conditions. It is intended for both novice and advanced users of this measurement technology.     

Combined chemical and phase equilibrium for the hydration of ethylene to ethanol calculated by means of the Peng-Robinson-Stryjek-Vera equation of state and the Wong-Sandler mixing rules

Due to the economics of the ethylene market and the subsidized production of fermentation-based ethanol in some countries, use of the ethylene hydration process to make ethanol has been steadily declining. The economics of this process might improve by combining the reaction and separation in a reactive distillation column, whose conceptual design requires a study of the combined chemical and phase equilibrium (CPE) of the reacting system. In this work, the Peng-Robinson-Stryjek-Vera equation of state was combined with the UNIQUAC activity coefficient model through the Wong-Sandler (WS) mixing rules in order to correlate the available experimental data for the vapor-liquid equilibria (VLE) of the ethylene-water, ethylene-ethanol, and ethanol-water binary systems at 200 °C. The interaction energies of the UNIQUAC model and the binary interaction coefficient of the WS mixing rules were used as the fitting parameters. From the optimum values of these parameters, both the VLE and the combined CPE of the ethylene-water-ethanol ternary system were predicted at 200 °C and various pressures. At this temperature, the catalytic activity of a H-pentasil zeolite has already been reported to exhibit a maximum for ethylene hydration, and also the experimentally measured two-phase region of the ternary system is sufficiently wide. By means of the reactive flash method, the chemical equilibrium compositions of the liquid and vapor phases were determined for several pressures, and the equilibrium conversion and the vapor fraction were calculated as functions of the ethylene to water feed mole ratio. It turns out that the vapor-liquid mixed-phase hydration of ethylene achieves equilibrium conversions much higher than those computed for a vapor-phase reaction that would hypothetically occur at the same conditions of pressure and feed mole ratio. It was found that the reactive phase diagram of the ternary system exhibits a critical point at 200 °C and 155 atm.     

Binuclear zinc(II) complexes with the anti-inflammatory compounds salicylaldehyde semicarbazone and salicylaldehyde-4-chlorobenzoyl hydrazone (H2LASSBio-1064)

Complexes [Zn₂(HL¹)₂(CH₃COO)₂] (1) and [Zn₂(L²)₂] (2) were synthesized with salicylaldehyde semicarbazone (H₂L¹) and salicylaldehyde-4-chlorobenzoyl hydrazone (H₂LASSBio-1064, H₂L²), respectively. The crystal structure of (1) was determined. Upon recrystallization of previously prepared [Zn₂(HL²)₂(Cl)₂] (3) in 1:9 DMSO:acetone crystals of [Zn₂(L²)₂(H₂O)₂]·[Zn₂(L²)₂(DMSO)₄] (3a) were obtained. The crystal structure of 3a was also determined. All crystal structures revealed the presence of phenoxo-bridged binuclear zinc(II) complexes.     

Noisy colored point set matching

We propose a process for determining approximated matches, in terms of the bottleneck distance, under color preserving rigid motions, between two colored point sets A,B∈R², |A|≤|B|. We solve the matching problem by generating all representative motions that bring A close to a subset B^′ of set B and then using a graph matching algorithm. We also present an approximate matching algorithm with improved computational time. In order to get better running times for both algorithms we present a lossless filtering preprocessing step. By using it, we determine some candidate zones which are regions that contain a subset S of B such that A may match one or more subsets B^′ of S. Then, we solve the matching problem between A and every candidate zone. Experimental results using both synthetic and real data are reported to prove the effectiveness of the proposed approach.