A hydrogel readout for autonomous detection of ions in microchannels

Readouts that work autonomously on colorimetric principles were fabricated inside a microchannel by immobilizing dyes in a hydrogel matrix. Two pH-sensitive dyes (congo red and phenolphthalein) were studied. The response time of the readout varied between 20 s for phenolphthalein and 45 s for congo red dyes. The robustness of the dyed gels was tested at different flow rates (0.1, 0.25 and 0.5 mL min(-1)). Combinatorial readouts consisting of gels with the different dyes were fabricated and tested. Based on the limits of human perception, the fabrication methodology and the principles of functioning; general design rules for fabricating a readout device are discussed. The simple and low cost fabrication technique combined with autonomous functioning make the readout appropriate for portable microfluidic systems.     

General approaches in ensemble quantum computing

We have developed methodology for NMR quantum computing focusing on enhancing the efficiency of initialization, of logic gate implementation and of readout. Our general strategy involves the application of rotating frame pulse sequences to prepare pseudopure states and to perform logic operations. We demonstrate experimentally our methodology for both homonuclear and heteronuclear spin ensembles. On model two-spin systems, the initialization time of one of our sequences is three-fourths (in the heteronuclear case) or one-fourth (in the homonuclear case), of the typical pulsed free precession sequences, attaining the same initialization efficiency. We have implemented the logical SWAP operation in homonuclear AMX spin systems using selective isotropic mixing, reducing the duration taken to a third compared to the standard re-focused INEPT-type sequence. We introduce the 1D version for readout of the rotating frame SWAP operation, in an attempt to reduce readout time. We further demonstrate the Hadamard mode of 1D SWAP, which offers 2^N-fold reduction in experiment time for a system with N-working bits, attaining the same sensitivity as the standard 1D version.     

Flow injection analysis for calcium in serum,water and waste waters by spectrophotometry and by ion-selective electrode

The Flow Injection technique is shown to provide fast, reliable and sensitive methods for the determination of calcium in various aqueous as well as serum samples; spectrophotometric or potentiometric detection can be used. At sampling rates of 100–110 samples per hour, with 30-μl sample injections, high reproducibility of measurement and low reagent consumption are achieved in both methods. In the spectrophotometric method, the analytical readout is available within 12 s after sample injection at a total reagent consumption of 0.75 ml per analysis. The potentiometric measurement of the calcium activity in serum is placed on a reliable basis by alternating measurements of serum samples and aqueous standards without incurring any non-reproducible changes in potential between aqueous and serum solutions. This permits the simultaneous determination of pH and pCa, the analytical readout being available within XXX s of sample injection. The good agreement between the results obtained with the Flow Injection method and those attained by atomic absorption and EDTA titrations as well as pCa stat-measurements show that the new methods are potentially suitable for routine analysis.     

Characterization of a new photo-fluorescent film dosimeter for high-radiation dose applications

Characterization studies on one of the first versions of the Sunna fluorescent dosimeter™ have been published by Kovács and McLaughlin. This present study describes testing results of a newer version of the dosimeter (Model γ, batch 0399-20). This dosimeter is a 1-cm×3-cm polymeric film of 0.5 mm thickness that emits a green fluorescence component at intensities almost linear with dose. The manufacturing method (injection molding) allows potential batch sizes on the order of a million while maintaining a signal precision on the order of ±1%. Studies include dose response, dose rate dependence, energy dependence, post-irradiation stability, environmental effects, and variation of response within a batch. Data for both food irradiation and sterilization dose levels were obtained. The results indicate that the green signal (0.3–250 kGy) works well for food irradiation dose levels, especially in refrigerated facilities that maintain tight temperature control. The green signal also works well in sterilization facilities because its irradiation temperature coefficient above room temperature is minimal at sterilization doses. If the user requires readout results in < 22 h after room temperature irradiation, the user can either calibrate for a specific post-irradiation readout time(s) or simply heat the dosimeters in a small laboratory oven to quickly stabilize the signal.     

In-Groove Carbon Nanotubes Device for SPME of Aromatic Hydrocarbons

A new solid phase microextraction (SPME) fibre using carbon nanotubes as fibre coating incorporated into a groove of a stainless steel rod is suggested. It is mechanically stable and exhibits relatively high thermal stability (up to 280 °C). The coating showed especially good extraction efficiency for aromatic hydrocarbons. The extraction properties of the fibre to benzene, toluene, ethylbenzene and o-xylene were examined using both direct and headspace SPME modes coupled to gas chromatography-flame ionization detection. The parameters affecting the extraction efficiency (extraction temperature and time, salt addition, desorption temperature and time) were investigated and quality parameters were measured under the optimized conditions. For both headspace and direct SPME the calibration graphs were linear up to 100 mg L⁻¹ (R ² > 0.996) and detection limits ranged from 0.09 to 0.39 μg L⁻¹. The repeatabilities were 5.9–13.3%. The proposed coating was applied for aromatic hydrocarbons determination in petrol station waste waters.     

Array-based capture, distribution, counting and multiplexed assaying of beads on a centrifugal microfluidic platform

We present a novel centrifugal microfluidic platform for the highly efficient manipulation and analysis of particles for applications in bead-based assays. The platform uses an array of geometrical V-cup barriers to trap particles using stopped-flow sedimentation under highly reproducible hydrodynamic conditions. The impact parameters governing the occupancy distribution and capture efficiency of the arrayed traps are investigated. The unique, nearly 100% capture efficiency paired with the capability to establish sharply peaked, single occupancy distributions enables a novel, digital readout mode for color-multiplexed, particle-based assays with low-complexity instrumentation. The presented technology marks an essential step towards a versatile platform for the integration of bead- and cell-based biological assays.     

Low voltage tunable liquid crystal Fibonacci grating

ABSTRACT

In this article, we disclose low voltage tunable liquid crystal Fibonacci gratings (FbG). Photoalignment technique has been used to create two domains of Fibonacci structure using a photomask. Switchable properties of LC are used to tune the diffraction efficiency of different orders by modulating the phase using the electric field. Position of split first orders shows good agreement with the golden ratio characteristic of the FbG. An increase in first-order diffraction efficiency from 3.7% to 6.7% has been achieved with a response time of 5.1 ms. The diffraction almost diminishes at 15 V with a very fast response time of 100 µs, the relaxation time is relatively slower ~26 ms, which is primarily due to higher viscosity. Variation and switching of the intensity of different orders in FbG, by the application of the electric field, can be utilised for selective far-field super-resolution imaging and different photonic applications.     

Fabrication of nanostructured silicon by metal-assisted etching and its effects on matrix-free laser desorption/ionization mass spectrometry

A matrix-free, high sensitivity, nanostructured silicon surface assisted laser desorption/ionization mass spectrometry (LDI-MS) method fabricated by metal-assisted etching was investigated. Effects of key process parameters, such as etching time, substrate resistance and etchant composition, on the nanostructured silicon formation and its LDI-MS efficiency were studied. The results show that the nanostructured silicon pore depth and size increase with etching time, while MS ion intensity increases with etching time to 300 s then decreases until 600 s for both low resistance (0.001–0.02 Ω cm) and high resistance (1–100 Ω cm) silicon substrates. The nanostructured silicon surface morphologies were found to directly affect the LDI-MS signal ion intensity. By characterizing the nanostructured silicon surface roughness using atomic force microscopy (AFM) and sample absorption efficiency using fluorescence microscopy, it was further demonstrated that the nanostructured silicon surface roughness was highly correlated to the LDI-MS performance.     

Synthesis and Characterization of Some Amino Acid Derived Schiff Bases Bearing Nonionic Species as Corrosion Inhibitors for Carbon Steel in 2N HCl

A novel series of nonionic amino acid Schiff-Bases were synthesized and characterized using different spectroscopic tools to elucidate their chemical structures. The surface and thermodynamic properties of these compounds were studied using classical measurements including surface and interfacial tension and emulsification tendency. The surface parameters of these compounds including surface tension, critical micelle concentration (CMC), effectiveness (π_cmc), efficiency (Pc₂₀), maximum surface excess (Γ_max), and minimum surface area (A_min) showed their good surface activity. Their thermodynamic parameters of adsorption and micellization including free energy change of micellization and adsorption showed their tendency toward adsorption at the interfaces and also micelle formation at lower concentrations. The synthesized compounds were also evaluated as corrosion inhibitors for carbon steel at different doses (400, 200, 100, 50, and 25 ppm) in 2 N HCl using gravimetric technique (weight loss). The results showed that these inhibitors are characterized by very high corrosion inhibition efficiency ranged between 99.93% and 97.98% and low corrosion rates varied between 0.09 mpy and 0.17 mpy for higher doses (400 ppm). The efficiency of inhibition was decreased by increasing the exposure time. The most efficient corrosion inhibitor of the synthesized compounds was the inhibitor which contains polyethylene oxide chain length of 23 EO units and alkyl chain length of 12 methylene groups. The effect of the hydrophobic and hydrophilic chain length in the inhibitor molecules was discussed and rationalized with their inhibition efficiency. The tendency of these inhibitors toward complexation with the transition metals was also discussed in order to explain their higher efficiency.     

Peroxidyme‐Amplified Radical Chain Reaction (PARCR): Visible Detection of a Catalytic Reporter

Peroxidyme Amplified Radical Chain Reaction (PARCR), a novel enzyme‐free system that achieves exponential amplification of a visible signal, is presented. Typical enzyme‐free amplification systems that produce a visible readout suffer from long reaction times, low sensitivity, and narrow dynamic range. PARCR employs photocatalyzed nonlinear signal generation, enabling unprecedented one‐pot, naked‐eye detection of a catalytic reporter from 1 μm down to 100 pm . In this reaction, hemin‐binding peroxidase‐mimicking DNAzymes (“peroxidymes”) mediate the NADH‐driven oxidation of a colorless, nonfluorescent phenoxazine dye (Amplex Red) to a brightly colored, strongly fluorescent product (resorufin); illumination with green light initiates multiple radical‐forming positive‐feedback loops, rapidly producing visible levels of resorufin. Collectively, these results demonstrate the potential of PARCR as an easy‐to‐use readout for a range of detection schemes, including aptamer labels, hybridization assays, and nucleic acid amplification.     

Tuning the Fluorescence Through Reorientation of the Axle in Calix[6]arene-Based Pseudorotaxanes

This work describes a calix[6]arene-based wheel that binds, in non-polar media, a stilbazolium salt to yield a mixture of pseudorotaxane orientational isomers. The isomer's abundance ratio evolves with time and can be reversibly tuned by adjusting the temperature. The spectroscopic properties, and notably the emission spectrum, of the bound guest depend on its orientation inside the non-palindromic wheel, suggesting such a system as a switch with spectroscopic readout.     

Influence of soluble polymer polyvinylpyrrolidone on separation of small peptides and amino acids by microchip-based capillary electrophoresis

In microchip-based capillary electrophoresis, the resolution and separation efficiency of small peptides and amino acids can be noticeably improved by adding a low molecular weight (30,000) soluble polymer additive, polyvinypyrrolidone in the separation medium. Several separation conditions such as injection time and electrophoretic buffer have been investigated and optimized. Using an electro-stacking scheme, the resolution and separation efficiency of small peptides and amino acids can be enhanced significantly. Under the optimal conditions, the separation of fluorescein isothiocyanate Isomer I-labeled small peptides and amino acids was successfully achieved within 100 s.     

Application of factorial designs and simplex optimisation in the development of flow injection-hydride generation-graphite furnace atomic absorption spectrometry (FI-HG-GFAAS) procedures as demonstrated for the determination of trace levels of germanium

The optimisation of a volume-based FI-HG-GFAAS procedure is described for the trace determination of Ge, comprising in situ collection of the generated germane in the graphite furnace. The response function is the peak area readout (A × s). Based on a preliminary study, where factorial designs were used to identify significant factors and interactions, the procedure was optimised using both simplex and OVAT (one variable at a time) methods. The characteristics and merits of these methods are discussed. Under optimal experimental conditions, using a sample volume of 100 μL, Ge was determined at a sampling frequency of 22 h^–1. The sensitivity, in terms of the characteristic mass, m₀, was 26 pg/0.0044 A × s, with a detection limit of 0.21 μgL^–1 (3σ). The precision (relative standard deviation) was 2.0% (n = 10) at the 1 μgL^–1 level. Received: 12 September 1996 / Revised: 6 December 1996 / Accepted: 16 December 1996     

Rapid determination of corticosteroids in pharmaceuticals by flow injection analysis

The proposed method is based on the reduction of blue tetrazolium by the steroid in an alkaline medium to form a highly colored formazan. The effects of reagent concentration, temperature, flow rate, and manifold design on the reaction are discussed for a typical steroid, methylprednisolone acetate. Analytical readout is obtained within 30 s after sample introduction and up to 100 samples/h can be processed with baseline resolution between peaks. Typical relative standard deviations of 0.5% are obtained with 10-μ1 injection volumes. Results obtained by flow injection analysis are similar to those obtained with the AutoAnalyzer technique.     

Low‐Level Laser Therapy and Sodium Diclofenac in Acute Inflammatory Response Induced by Skeletal Muscle Trauma: Effects in Muscle Morphology and mRNA Gene Expression of Inflammatory Markers

Pharmacological therapy is widely used in the treatment of muscle injuries. On the other hand, low‐level laser therapy (LLLT) arises as a promising nonpharmacological treatment. The aim of this study was to analyze the effects of sodium diclofenac (topical application) and LLLT on morphological aspects and gene expression of biochemical inflammatory markers. We performed a single trauma in tibialis anterior muscle of rats. After 1 h, animals were treated with sodium diclofenac (11.6 mg g^‐1 of solution) or LLLT (810 nm; continuous mode; 100 mW; 3.57 W cm^?2; 1, 3 or 9 J; 10, 30 or 90 s). Histological analysis and quantification of gene expression (real‐time polymerase chain reaction—RT‐PCR) of cyclooxygenase 1 and 2 (COX‐1 and COX‐2) and tumor necrosis factor‐alpha (TNF‐α) were performed at 6, 12 and 24 h after trauma. LLLT with all doses improved morphological aspects of muscle tissue, showing better results than injury and diclofenac groups. All LLLT doses also decreased (P < 0.05) COX‐2 compared to injury group at all time points, and to diclofenac group at 24 h after trauma. In addition, LLLT decreased (P < 0.05) TNF‐α compared both to injury and diclofenac groups at all time points. LLLT mainly with dose of 9 J is better than topical application of diclofenac in acute inflammation after muscle trauma.     

Comparative study of effect of low and medium dose rate of γ irradiation on microporous polysulfone membrane using spectroscopic and imaging techniques

The effect of low (LDR) and medium dose rate (MDR) of γ irradiation at low doses (0-100 kGy) on the structural and chemical changes of microporous polysulfone (PSf) membrane has been studied using UV-vis, FTIR, SEM and dead-end filtration techniques. PSf membrane was cast by phase inversion method. Irradiation was done at room temperature in air media. The doses chosen were 0-100 kGy for LDR and 0-50 kGy for MDR; they were below and above sterilization dose. Analysis of UV-vis and IR spectra and SEM images obtained suggested that chain scissions and crosslink had occurred simultaneously in the irradiated membranes in both cases. This radio-oxidation effects observed start at a very low dose i.e. 1.66 kGy and increase with increase in dose. It is supported by the flux values obtained; it is increased with increase in dose. The results indicate that a very low dose γ irradiation was able to change the physicochemical characteristics of microporous PSf membrane which depend on dose rate of exposure.     

Stopped flow and merging zones — a new approach to enzymatic assay by flow injection analysis

Four alternative flow injection methods based on the concept of merging zones have been developed for the assay of glucose in serum with glucose dehydrogenase. Special attention has been paid to the dispersion and synchronization of the merging zones and to methods of measuring the blank value of serum. The optimal procedure, based on rate measurements, allows the assay of glucose to be done at a rate of 100 determinations per hour, with the analytical readout available 30 s after sample injection. The assay requires less than one unit of enzyme per sample.     

LC/MS/MS identification of some folic acid degradation products after E-beam irradiation

Folates belong to the B vitamin group based on the parental compound folic acid (FA). They are involved in important biochemical processes like DNA synthesis and repair. FA is composed of a pteridine ring, p-aminobenzoic acid and glutamate moieties. The human metabolism is not able to synthesize folates and therefore obtain them from diet. FA, a synthetic vitamin, is used as a food fortificant because of its low price, relative stability and increased bioavailability compared to natural folate forms. FA is known to be a sensitive compound easily degradable in aqueous solution by ultraviolet and visible light towards various by-products. Irradiation is a process for preservation of foods that uses accelerated electrons, gamma rays or X-rays. Irradiation is proposed for the treatment of various food products, eliminating or reducing pathogens and insects, increasing the storage time and replacing chemical fumigants. This study concerns the identification of degradation products of FA after E-beam irradiation. FA aqueous solutions were irradiated with a Van de Graaff electrons beam accelerator (2 MeV, 100 μA current, 20 cm scan width, dose rate about 2 kGy/s). Applied doses were between 0 (control) and 10.0 kGy. Absorbed doses were monitored with FWT 60.00 radiochromic dosimeters.     

Very fast electrophoretic separation on commercial instruments using a combination of two capillaries with different internal diameters

A capillary formed by connecting a 9.7 cm‐long separation capillary with id 25 μm with an auxiliary 22.9 cm‐long capillary with id 100 μm (coupled capillary) was tested for electrophoretic separation at high electric field intensities. The coupled capillary was placed in the cassette of a standard electrophoresis apparatus. It was used in the short‐end injection mode for separation of a mixture of dopamine, noradrenaline, and adrenaline in a BGE of 20 mM citric acid/NaOH, pH 3.2. An intensity of 2.7 kV/cm was attained in the separation part of the capillary at a separation voltage of 30 kV, which is 2.9 times more than maximum intensity value attainable in a capillary with the same length with uniform id. At these high electric field intensities, the migration times of the tested neurotransmitters had values of 12.3–13.3 s and the attained separation efficiency was between 2350 and 2760 plates/s. It is thus demonstrated that an effective separation instrument ‐ a coupled capillary ‐ can be used for very rapid separation in combination with standard, commercially available instrumentation.     

Parallel analysis of stimulants in saliva and urine by gas chromatography/mass spectrometry: perspectives for "in competition" anti-doping analysis

Stimulants are banned by the World Anti-Doping Agency (WADA) if used “in competition”. Being the analysis of stimulants presently carried out on urine samples only, it might be useful, for a better interpretation of analytical data, to discriminate between an early intake of the substance and an administration specifically aimed to improve the sport performance. The purpose of the study was to investigate the differences, in terms of excretion/disappearance of drugs, between urine and oral fluid, a sample that can reflect plasmatic concentrations.Oral fluid and urine samples were collected following oral administration of the following stimulants: modafinil (100 mg), selegiline (10 mg), crotetamide/cropropamide (50 mg each), pentetrazol (100 mg), ephedrine (12 mg), sibutramine (10 mg), mate de coca (a dose containing about 3 mg of cocaine); analysis of drugs/metabolites was carried out by gas chromatography/mass spectrometry (GC/MS) in both body fluids.Our results show that both the absolute concentrations and their variation as a function of time, in urine and in oral fluid, are generally markedly different, being the drugs eliminated from urine much more slowly than from oral fluid. Our results also suggest that the analysis of oral fluid could be used to successfully complement the data obtained from urine for “in competition” anti-doping tests; in all those cases in which the metabolite(s) concentration of a substance in urine is very low and the parent compound is not detected, it is indeed impossible, relying on urinary data only, to discriminate between recent administrations of small doses and remote administrations of higher doses.