Sandwich-type immunosensors and immunoassays exploiting nanostructure labels: A review

Methods based on sandwich-type immunosensors and immunoassays have been developed for detection of multivalent antigens/analytes with more than one eptiope due to the use of two matched antibodies. High-affinity antibodies and appropriate labels are usually employed for the amplification of detectable signal. Recent research has looked to develop innovative and powerful novel nanoparticle labels, controlling and tailoring their properties in a very predictable manner to meet the requirements of specific applications. This articles reviews recent advances, exploiting nanoparticle labels, in the sandwich-type immunosensors and immunoassays. Routine approaches involve noble metal nanoparticles, carbon nanomaterials, semiconductor nanoparticles, metal oxide nanostructures, and hybrid nanostructures. The enormous signal enhancement associated with the use of nanoparticle labels and with the formation of nanoparticle-antibody-antigen assemblies provides the basis for sensitive detection of disease-related proteins or biomolecules. Techniques commonly rely on the use of biofunctionalized nanoparticles, inorganic-biological hybrid nanoparticles, and signal tag-doped nanoparticles. Rather than being exhaustive, this review focuses on selected examples to illustrate novel concepts and promising applications. Approaches described include the biofunctionalized nanoparticles, inorganic-biological hybrid nanoparticles, and signal tage-doped nanoparticles. Further, promising application in electrochemical, mass-sensitive, optical and multianalyte detection are discussed in detail.     

Analytical application of carbon nanotubes,fullerenes and nanodiamonds in nanomaterials-based chromatographic stationary phases: A review

An overview of the most significative results so far attained in the application of carbon nanotubes, fullerenes and nanodiamonds as chromatographic separation media is presented. In particular, the authors focus on their use in capillary and packed-column gas chromatography, in high performance liquid chromatography and capillary electrochromatography, paying also attention to recently developed stationary phases for fast chromatography and nanochromatography. The performance of the nanomaterials is compared to that of planar and amorphous carbon sorbents and critically discussed in regard to retentive capability and selectivity. A wide part of this review is devoted to the most recent improvements achieved in terms of selectivity by use of functionalized nanotubes and by combination of carbon nanotubes with ionic liquids. Practical aspects of synthetic procedures in preparing novel stationary phases in relationship with their chromatographic behaviour are also commented.     

Applications of in vivo and in vitro solid-phase microextraction techniques in plant analysis: A review

As a very popular sample preparation technique, solid-phase microextraction (SPME) coupled with various analytical instrumentation, has been widely used for the determination of trace levels of different plant compounds, such as volatile organic compounds (VOCs) emitted from the different plant organs, and environmental contaminants in plants. In this review, recent applications of in vitro and in vivo SPME in plant analysis are discussed and summarized according to the different organs of plants, including fruits, flowers, leaves, stems, roots and seeds, and the whole plant as well. Future developments and applications of SPME in plant analysis, especially in vivo sampling approaches, are also prospected.     

Analysis and comparison of Direct Digital Frequency Synthesizers implemented on FPGA

The Direct Digital Frequency Synthesizer (DDFS) is a critical component routinely implemented in communication or signal processing systems.     

Fault-tolerant analysis of TMR design with noise-aware logic

Due to the effect of thermal noise, ground bounce and process variations in nanometer process, the behavior of any logical circuit becomes increasingly probabilistic. In this paper, based on the noise model [5] on the input and output nodes of a probabilistic CMOS (PCMOS) gate, the correctness probabilities of four PCMOS primitive gates, NOT, NAND, NOR and XOR, can be firstly computed. Based on the concept of the probabilistic transfer matrices (PTMs) and the corresponding operations on PTMs for the serial and parallel compositions of the components in a well-formed circuit, the correctness probability of the output in a 3-input PCMOS majority circuit in a triple modular redundancy (TMR) design can be further computed. For a given circuit with smaller error, it is well known that a TMR design has good fault-tolerant characterization and the correctness probability of the original output is converged to 1. Under the use of noise-aware logic in a TMR design, it is obvious that the fault-tolerant characterization of a TMR design is degraded and the correctness probability of the original output is not converged to 1. The experimental results show that the improvement region of the correctness probability of the original output will be narrowed due to the noise effect on the gates in a 3-input PCMOS majority circuit.     

Stoichiometric aryl nitrile formation from amides and aroyl isocyanates using high-valent early transition metal complexes and a catalytic process from the aroyl isocyanates

Reaction of PhCONH₂ with [WCl₆] under reflux in benzene gives a near quantitative yield of [WOCl₄(NCPh)] (1) which can be prepared directly by the reaction of PhCN and [WOCl₄]. PhCONH₂ reacts with [WOCl₄] under reflux in benzene to give [WO₂Cl₂(NCPh)] (2) and with [NbCl₅] under similar conditions to give [NbOCl₃(NCPh)] (3). PhCONH₂ and TiCl₄ give [TiCl₄(NH₂COPh)₂] (4). Reaction of the aroyl isocyanate PhCONCO with [WOCl₄] gave [WOCl₄(NCPh)] (1) and 4-Me₃CPhCONCO and [WOCl₄] gave [WOCl₄(NCPhCMe₃-4)] (5). PhCONCO reacts catalytically with [WOCl₄] or [WOCl₄(NCPh)] to give quantitative yields of PhCN. Similarly, 4-Me₃CPhCONCO and 2-ClCPhCONCO react catalytically with [WOCl₄] to give complete conversion to 4-Me₃CPhCN and 2-ClCPhCN. DFT studies show structures and intermediates in support of a possible catalytic mechanism. This involves initial complexation followed by formation of a metallocycle from the WO bond and the CN bond of the isocyanate. Rearrangement and elimination of CO₂ leads to an amidate complex that undergoes C-O bond scission and O migration to the W atom to give PhCN bound to the WOCl₄ moiety in a cis arrangement. This complex is unstable with respect to dissociation which completes the catalytic cycle. The overall reaction WOCl₄ + PhC(O)NCO → WOCl₄·PhCN + CO₂ is exothermic (ΔH = −20.7 kJ mol⁻¹) and is favoured from free energy considerations (ΔG = −69.3 kJ mol⁻¹).     

Oxidative and hydrolytic DNA cleavage by Cu(II) complexes of salicylidene tyrosine schiff base and 1,10 phenanthroline/bipyridine

Ternary Cu(II) complexes [Cu(II)(saltyr)(B)] (1,2), (saltyr = salicylidene tyrosine, B = 1,10 phenanthroline (1) or 2,2′ bipyridine (2)) were synthesized and characterized by various techniques. The complexes exhibit square pyramidal (CuN₃O₂) geometry. CT-DNA binding studies revealed that the complexes show good binding propensity (K_b = 3.47 × 10⁴ M⁻¹ and 3.01 × 10⁴ M⁻¹ for 1 and 2, respectively). The role of these complexes in the oxidative and hydrolytic DNA cleavage was studied. The catalytic ability of 1 and 2 follows the order: 1 > 2. The rate constants for the hydrolysis of phosphodiester bond were determined as 2.80 h⁻¹ and 2.11 h⁻¹ for 1 and 2, respectively. It amounts to (0.58-0.77) × 10⁸ fold rate enhancement compared to non-catalyzed DNA cleavage, which is significant.     

Recent developments in polymer dynamics investigations of architecturally complex systems

The tube model for linear and branched architectures is nowadays able to predict in high precision the linear viscoelastic relaxation time spectrum. For linear chains, the involved time scales fit to the commonly accessible dynamic scattering techniques. This makes it possible to microscopically investigate the correlation between structures and relaxation processes. In branched systems, however, the hierarchical nature of relaxations limits direct investigation via these microscopic methods as the dynamic processes are prolongated to much longer relaxation times that are no more accessible to usual dynamic scattering methods. A way to overcome this difficulty is offered by the use of static small angle neutron scattering. Here, the combination of annealing and quenching steps after a step deformation provides unique information of the structure at particular times along the relaxation spectrum. This, however, necessitates the availability of architecturally clean and specifically deuterium labelled model polymers due to the sensitivity of the scattering method. Therefore, we outline in this contribution first the current status on the synthesis and analysis of such compounds with relation to neutron scattering. Secondly, we present exemplary neutron scattering results from in situ stress relaxation studies inside the neutron beam on linear and H-shaped branched polymers which were molecularly designed to highlight specific relaxation processes. We discuss the relevance of the tube model parameters in linear and non-linear studies.     

Polyzwitterionic brushes: Extreme lubrication by design

Polymers offer the advantage that they may independently combine desirable supramolecular structure with useful local monomeric properties to yield optimal performance of different tasks. Here we utilise the remarkable lubricating properties both of dense polymer brushes, and of hydration sheaths about charges via the emerging paradigm of hydration lubrication, to design a grafted-from polyzwitterionic brush system, where each of the monomers has a structure similar to the highly-hydrated phosphorylcholine headgroups of phosphatidylcholine lipids. Such polyzwitterions are grown from a macroinitiator coating the substrate (mica) surface using atom transfer radical polymerisation (ATRP) of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC) to form exceptionally robust poly(MPC) brushes. We have characterized these brush layers via X-ray reflectometry, X-ray photoelectron spectroscopy, surface forces measurements and atomic force microscopy. Such brushes, designed to optimise their lubrication properties, are indeed found to provide state of the art boundary lubrication, achieving friction coefficients as low as 0.0004 at pressures up to 75 atmospheres over a wide range of sliding velocities. Such low friction is comparable with that of articular cartilage in healthy mammalian joints, which represents nature’s benchmark for boundary lubrication in living organisms, and suggests that hydration lubrication plays a major role in reducing friction in biological systems.