Influence of Cyclodextrins on the Kinetics of Oxidation of Amino Acids and BSA by Hydrazyl Radicals

The kinetics of oxidation of amino acids (Arg, His, Lys, Phe, Thr and Tyr), a dipeptide (Gly-His), and BSA (bovine serum albumin) by two persistent water soluble free radicals of the hydrazyl type has been studied.The rate decreases in the order Arg>Lys>Tyr>Thr>HisBSAPheGly-His with bothfree radicals. Addition to the reaction mixture of - and -cyclodextrin decreases the oxidation rate, probably due to amino acidencapsulation in the cyclodextrin cavity. -Cyclodextrin protects more efficiently against oxidation than -cyclodextrin.     

The microscopic investigation of structures of moving flux lines by neutron and muon techniques

We have used a variety of microscopic techniques to reveal the structure and motion of flux line arrangements, when the flux lines in low T _c type II superconductors are caused to move by a transport current. Using small-angle neutron scattering by the flux line lattice (FLL), we are able to demonstrate directly the alignment by motion of the nearest-neighbor FLL direction. This tends to be parallel to the direction of flux line motion, as had been suspected from two-dimensional simulations. We also see the destruction of the ordered FLL by plastic flow and the bending of flux lines. Another technique that our collaboration has employed is the direct measurement of flux line motion, using the ultra-high-resolution spectroscopy of the neutron spin-echo technique to observe the energy change of neutrons diffracted by moving flux lines. The muon spin rotation (μSR) technique gives the distribution of values of magnetic field within the FLL. We have recently succeeded in performing μSR measurements while the FLL is moving. Such measurements give complementary information about the local speed and orientation of the FLL motion. We conclude by discussing the possible application of this technique to thin film superconductors.     

Paper-based piezoresistive MEMS sensors

This paper describes the development of MEMS force sensors constructed using paper as the structural material. The working principle on which these paper-based sensors are based is the piezoresistive effect generated by conductive materials patterned on a paper substrate. The device is inexpensive (～$0.04 per device for materials), simple to fabricate, lightweight, and disposable. Paper can be readily folded into three-dimensional structures to increase the stiffness of the sensor while keeping it light in weight. The entire fabrication process can be completed within one hour without expensive cleanroom facilities using simple tools (e.g., a paper cutter and a painting knife). We demonstrated that the paper-based sensor can measure forces with moderate performance (i.e., resolution: 120 μN, measurement range: ±16 mN, and sensitivity: 0.84 mV mN(-1)). We applied this sensor to characterizing the mechanical properties of a soft material. Leveraging the same sensing concept, we also developed a paper-based balance with a measurement range of 15 g, and a resolution of 0.39 g.     

Swellable molecularly imprinted polyN-(N-propyl)acrylamide particles for detection of emerging organic contaminants using surface plasmon resonance spectroscopy

Lightly crosslinked theophylline imprinted polyN-(N-propyl)acrylamide particles (ca. 300 nm in diameter) that are designed to swell and shrink as a function of analyte concentration in aqueous media were spin coated onto a gold surface. The nanospheres responded selectively to the targeted analyte due to molecular imprinting. Chemical sensing was based on changes in the refractive index of the imprinted particles that accompanied swelling due to binding of the targeted analyte, which was detected using surface plasmon resonance (SPR) spectroscopy. Because swelling leads to an increase in the percentage of water in the polymer, the refractive index of the polymer nanospheres decreased as the particles swelled. In the presence of aqueous theophylline at concentrations as low as 10⁻⁶ M, particle swelling is both pronounced and readily detectable. The full scale response of the imprinted particles to template occurs in less than 10 min. Swelling is also reversible and independent of the ionic strength of the solution in contact with the polymer. Replicate precision is less than 10⁻⁴ RI units. By comparison, there is no response to caffeine which is similar in structure to theophylline at concentrations as high as 1 × 10⁻² M. Changes in the refractive index of the imprinted polymer particles, as low as 10⁻⁴ RI units could be readily detected. A unique aspect of the prepared particles is the use of light crosslinking rather than heavy crosslinking. This is a significant development as it indicates that heavy crosslinking is not entirely necessary for selectivity in molecular imprinting with polyacrylamides.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Evaluating the variation of ion energy under different parameter settings in traveling wave ion mobility mass spectrometry

Ion mobility mass spectrometry (IM-MS) can be used to differentiate and identify isobaric ions. To improve IM-MS resolution, the second generation of traveling wave ion mobility (TWIM) technology was launched. There were reports showing ions were heated up by TWIM. With higher ion energy, it could alter the conformation of larger ions or MS/MS experiments. To monitor the energy exchange relating to the TWIM process, the combined use of thermometer ions with unique molecular structure and theoretical calculations to determine the effective temperature of ions had been explored. In this report, the use of a simple experimental approach to estimate the variation on the ion energy that result from changing a TWIM parameter setting is demonstrated. The approach aims to achieve the same percentage of ion dissociation in a collision cell, which is part of the original instrument and located at the exit of TWIM cell. Similar to the traditional MS/MS experiments, the same level of ion dissociation could be achieved by adjusting the electrical potential that was applied to the collision cell. The higher the ion energy after the TWIM separation, the lower the electrical potential was required to achieve the same level of ion dissociation. Together with the information on the number of electrical charge in the selected ion, the difference in the required electrical potentials could be converted into electron volt of ion energy that resulted from changing the TWIM parameter setting. The results showed ion energy could be changed 1–9 eV when the parameter of TWIM was adjusted.     

Electrophoresis on a polyester thread coupled with an end-channel pencil electrode detector

We present the design and characterization of a low cost, thread-based electrophoretic device with integrated electrochemical detection. The device has an end-channel pencil graphite electrode placement system for performing electrochemical detection on the thread electrophoresis platform with direct sample pipetting onto the thread. We also established the use of methylene blue and neutral red as a pair of reference migration markers for separation techniques coupled with electrochemical detection, as they have different colors for visual analysis and are both electroactive. Importantly, neutral red was also found to migrate at a similar rate to the EOF, indicating that it can be used as a visual identifier of EOF. The utility of our system was demonstrated by electrophoretic separation and electrochemical detection of physiologically relevant concentrations of pyocyanin in a solution containing multiple electroactive compounds. Pyocyanin is a biomarker for the detection of pathogenic Pseudomonas aeruginosa and has a redox potential that is similar to that of methylene blue. The system was able to effectively resolve methylene blue, neutral red, and pyocyanin in less than 7 min of electrophoretic separation. The theoretical limit of detection for pyocyanin was determined to be 559 nM. The electrophoretic mobilities of methylene blue (0.0236 ± 0.0007 mm²/V·s), neutral red (0.0149 ± 0.0007 mm²/V·s), and pyocyanin (0.0107 ± 0.0003 mm²/V·s) were also determined.     

A materials approach to site-isolation of Grubbs catalysts from incompatible solvents and m-chloroperoxybenzoic acid

The development of a method for site-isolation of Grubbs second-generation catalyst from MCPBA is described. In these reactions, Grubbs catalyst was dissolved in a solvent consisting of a mixture (1:1 v/v) of 1-butyl-3-methylimidazolium hexafluorophosphate and methylene chloride and completely encapsulated within a thimble fabricated from polydimethylsiloxane (PDMS). A series of molecules that react by cross metathesis or ring-closing metathesis were added to the interior of the thimble and allowed to react. In the last step, m-chloroperoxybenzoic acid (MCPBA) dissolved in MeOH/H(2)O (1:1 v/v) was added to the exterior of the PDMS thimble. Small organic molecules diffused through the PDMS to react with MCPBA to form epoxides, but the Grubbs catalyst remained encapsulated. This result is important because Grubbs catalyst catalytically decomposes MCPBA at ratios of MCPBA to Grubbs of 3000 to 1. The yields for this two-step cascade sequence ranged from 67 to 83 %. The concept behind this sequence is that small organic molecules have high flux through PDMS but large molecules--such as Grubbs catalyst--and ionic reagents--such as MCPBA--have much lower flux through PDMS. Small molecules can thus react both outside and inside PDMS thimbles, whereas incompatible catalysts and reagents remain site-isolated from each other. This method does not require alteration of structures of the catalysts or reagents, so it may be applied to a wide range of homogeneous catalysts and reagents. To demonstrate further that the catalyst was encapsulated, the Grubbs catalyst was successfully recycled within the cascade sequence.