Mass spectrometry in the diagnosis of thyroid disease and in the study of thyroid hormone metabolism

The importance of thyroid hormones in the regulation of development, growth, and energy metabolism is well known. Over the last decades, mass spectrometry has been extensively used to investigate thyroid hormone metabolism and to discover and characterize new molecules involved in thyroid hormones production, such as thyrotropin-releasing hormone. In the earlier period, the quantification methods, usually based on gas chromatography–mass spectrometry, were complicated and time consuming. They were mainly focused on basic research, and were not suitable for clinical diagnostics on a routine basis. The development of the modern mass spectrometers, mainly coupled to liquid chromatography, enabled simpler sample preparation procedures, and the accurate quantification of thyroid hormones, of their precursors, and of their metabolites in biological fluids, tissues, and cells became feasible. Nowadays, molecules of physiological and pathological interest can be assayed also for diagnostic purposes on a routine basis, and mass spectrometry is slowly entering the clinical laboratory. This review takes stock of the advancements in the field of thyroid metabolism that were carried out with mass spectrometry, with special focus on the use of this technique for the quantification of molecules involved in thyroid diseases.     

Redispersible Polymer Powders with High Bio-Based Content from Core–Shell Nanoparticles

Redispersible polymer powders (RDPPs), i.e., additives obtained from core–shell nanoparticles and commercialized in the form of a dry powder, find intensive application in the concrete industry. However, they are mainly produced from fossil resources. Therefore, the development of bio-based RDPPs is important to reduce the carbon footprint of these additives. In this work, two types of core–shell nanoparticles with a high percentage of bio-based content are synthesized and show to be good candidates as RDPPs. In the first case, up to 75% of bio-based content is obtained by combining lauryl acrylate, derived from coconut and palm kernel oil, as main core material, with isobornyl methacrylate, coming from pine resin, exploited to create the outer harder shell. In the second case, a degradable macromonomer obtained by the ring opening polymerization of lactide using 2-hydroxyethyl methacrylate as initiator is used as the core-forming monomer to obtain degradable RDPPs. In both cases, the particles are synthesized with a two-step emulsion polymerization process conducted in one pot and then spray-dried to obtain the RDPPs of interest. The morphology and redispersibility of the powders are characterized. Finally, their use as concrete additives is preliminarily assessed by evaluating their effect on changes in the surface morphologies of concrete specimens.     

Dynamic analyses of information encoding in neural ensembles

Neural spike train decoding algorithms and techniques to compute Shannon mutual information are important methods for analyzing how neural systems represent biological signals. Decoding algorithms are also one of several strategies being used to design controls for brain-machine interfaces. Developing optimal strategies to design decoding algorithms and compute mutual information are therefore important problems in computational neuroscience. We present a general recursive filter decoding algorithm based on a point process model of individual neuron spiking activity and a linear stochastic state-space model of the biological signal. We derive from the algorithm new instantaneous estimates of the entropy, entropy rate, and the mutual information between the signal and the ensemble spiking activity. We assess the accuracy of the algorithm by computing, along with the decoding error, the true coverage probability of the approximate 0.95 confidence regions for the individual signal estimates. We illustrate the new algorithm by reanalyzing the position and ensemble neural spiking activity of CA1 hippocampal neurons from two rats foraging in an open circular environment. We compare the performance of this algorithm with a linear filter constructed by the widely used reverse correlation method. The median decoding error for Animal 1 (2) during 10 minutes of open foraging was 5.9 (5.5) cm, the median entropy was 6.9 (7.0) bits, the median information was 9.4 (9.4) bits, and the true coverage probability for 0.95 confidence regions was 0.67 (0.75) using 34 (32) neurons. These findings improve significantly on our previous results and suggest an integrated approach to dynamically reading neural codes, measuring their properties, and quantifying the accuracy with which encoded information is extracted.     

Online Portable Microcantilever Biosensors for Salmonella enterica Serotype Enteritidis Detection

The micro- and nano-technologies coupled with a deep knowledge of organic/inorganic interfaces guarantee an exceptional sensitivity and specificity of the sensor, while the lab-on-a-chip platform reduces assay times and limits sampling and/or sample preparation, providing compact and portable objects. Therefore, the development of innovative biosensors such as antibody-immobilized microcantilevers can overcome the evident limits of nowadays technologies, such as time consuming, expensiveness, difficult automation, low sensitivity, accuracy, and precision for quantitative methods. The present study proposes two device designs for the detection of food pathogens, exploiting an antibody-immobilized microcantilever biosensors, a novel class of mass detectors. For the first one, we integrated the mechanical sensors on a microfluidic platform (lab-on-a-chip) to perform online analysis, directly in liquid environment. We showed that our portable biosensors could easily detect the presence of pathogenic bacteria such as Salmonella enterica serotype enteritidis in concentration 10⁵ cfu/mL in just 40 min, without any enrichment and/or sample preparation. To increase the mass sensitivity of our analysis, we also fabricated microstructures optimized for vibrating in vacuum environment. Using a dip-and-dry technique, we showed that, in such configuration, the experimental limit of detection is as low as 10³ cfu/mL. Due to the extremely small volumes needed, our biosensors operating in vacuum have the potentiality of detecting the presence or absence of a single cell.     

Graphene Devices: Structured Graphene Devices for Mass Transport (Small 6/2011)

The reversible atomic‐mass transport along graphene devices has been achieved. The motion of Al and Au in the form of atoms or clusters is driven by applying an electric field between the metal electrodes that contact the graphene sheet. It is shown that Al moves in the direction of the applied electric field whereas Au tends to diffuse in all directions. The control of the motion of Al is further demonstrated by achieving a 90° turn, using a graphene device patterned in a crossroads configuration. The controlled motion of Al is attributed to the charge transfer from Al onto the graphene so that the Al is effectively charged and can be accelerated by the applied electric field. To get further insight into the actuation mechanism, theoretical simulations of individual Al and Au impurities on a perfect graphene sheet were performed. The direct (electrostatic) force was found to be ～1 pN and dominant over the wind force. These findings hold promise for practical use in future mass transport in complex circuits.     

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium‐based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high‐strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low‐voltage regime (from 0.1 to 5 V), with long‐term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm^?2), high electrochemical capacitance (≈mF g^?1), and minimal mechanical stress at the polymer/metal composite interface upon deformation.     

Functionalized carbon nanotubes are non-cytotoxic and preserve the functionality of primary immune cells

Carbon nanotubes are emerging as innovative tools in nanobiotechnology. However, their toxic effects on environment and health have become an issue of strong concern. In the present study, we address the impact of functionalized carbon nanotubes (f-CNTs) on cells of the immune system. We have prepared two types of f-CNTs, following the 1,3-dipolar cycloaddition reaction (f-CNTs 1 and 2) and the oxidation/amidation treatment (f-CNTs 3 and 4), respectively. We have found that both types of f-CNTs are uptaken by B and T lymphocytes as well as macrophages in vitro, without affecting cell viability. Subsequently, the functionality of the different cells was analyzed carefully. We discovered that f-CNT 1, which is highly water soluble, did not influence the functional activity of immunoregulatory cells. f-CNT 3, which instead possesses reduced solubility and forms mainly stable water suspensions, preserved lymphocytes' functionality while provoking secretion of proinflammatory cytokines by macrophages.     

Microscopic and spectroscopic characterization of paintbrush-like single-walled carbon nanotubes

Understanding and controlling the chemical reactivity of carbon nanotubes (CNTs) is a fundamental requisite to prepare novel nanoscopic structures with practical uses in materials applications. Here, we present a comprehensive microscopic and spectroscopic characterization of carbon nanotubes which have been chemically modified. Specifically, scanning tunneling microscopy (STM) investigations of short-oxidized single-walled carbon nanotubes (SWNTs) functionalized with aliphatic chains via amide reaction reveal the presence of bright lumps both on the sidewalls and at the tips. The functionalization pattern is consistent with the oxidation reaction which mainly occurs at the nanotube tips. Thermogravimetric analysis (TGA), steady-state electronic absorption (UV-vis-NIR), and Raman spectroscopic studies confirm the STM observations.     

Fast and air stable near-infrared organic detector based on squaraine dyes

In search for an organic material suitable for the detection of near-infrared electromagnetic radiation and at the same time capable of air stable operation of related devices, so to address the many applications envisaged with this technology (remote control, chemical/biological sensing, optical communication, spectroscopic and medical instruments), we explore the performance of a blend of hydrazone end-capped symmetric squaraines and phenyl C₆₁ butyric acid methyl ester. We succeed in developing air stable solution-processed devices with external quantum efficiency in the NIR as high as 3.5% and response times of few hundreds of nanoseconds. Essential to these achievements has been a detailed characterization of the devices performed by correlating the optoelectronic performances to the morphology of the layers (extracted from AFM measurements) and to the charge carrier mobility (extracted from transistor structures), enabling their optimization at the chemical level, by tailoring the squaraine substitution pattern, and at the device level, by tuning the blend composition. We show that a good balance between holes and electrons mobility is essential for high EQE and fast response speed, and that a smooth morphology is mandatory to achieve long term air stability and operability with no need for encapsulation.     

Performance evaluation of wavelet-based distributed video coding schemes

In this paper we propose and compare different distributed video coding (DVC) schemes based on the use of the wavelet transform, which naturally allows for spatial and other forms of scalability. In particular, we propose a hybrid encoder which utilizes channel codes, and evaluate its performance in the absence of a feedback channel. The proposed scheme uses statistical models for the estimation of the required bitrate at the encoder. We also propose a scheme that is based on a modulo reduction procedure and does not use channel codes at the receiver/transmitter. These schemes are compared with more conventional coders that do not or only partially exploit the distributed coding paradigm. Experimental results show that the considered schemes have good performance when compared with similar asymmetric video compression schemes, and that DVC can be an interesting option in appropriate scenarios.