Motion of redox molecules in solution monitored by the highly-sensitive EQCM technique

The behavior of redox molecules in solution that was not detected by electrochemical techniques was measured by a highly-sensitive electrochemical quartz crystal microbalance (EQCM) technique that has been improved in this study to obtain a high sensitivity of EQCM measurement in solution. The improved EQCM technique allowed to monitor the motion of a redox molecule, that is an access of the molecule to an electrode surface and repulsion from the surface during redox. An EQCM technique currently in use has measured adsorption of redox molecules on an electrode surface or polymerization on the surface caused by a chemical reaction following redox, which exhibits an enough large mass change response to detect with an EQCM measurement. However, access and repulsion of redox molecule, which is a slight motion of the molecule near on electrode surface, has not been detected and investigated by an EQCM technique, because the mass change response seems to be very small. In this study, the redox behavior of methyl viologen on a bare gold surface, pyridinethiol surface and methylpyridinethiol surface was investigated. Although the three electrodes give the same cyclic voltammogram of methyl viologen, the three are different in QCM response recorded at the same time as the voltammetry. Access/repulsion of methyl viologen within an electrical double layer was monitored by the highly-sensitive EQCM technique.     

Motion of redox molecules in solution monitored by the highly-sensitive EQCM technique

The behavior of redox molecules in solution that was not detected by electrochemical techniques was measured by a highly-sensitive electrochemical quartz crystal microbalance (EQCM) technique that has been improved in this study to obtain a high sensitivity of EQCM measurement in solution. The improved EQCM technique allowed to monitor the motion of a redox molecule, that is an access of the molecule to an electrode surface and repulsion from the surface during redox. An EQCM technique currently in use has measured adsorption of redox molecules on an electrode surface or polymerization on the surface caused by a chemical reaction following redox, which exhibits an enough large mass change response to detect with an EQCM measurement. However, access and repulsion of redox molecule, which is a slight motion of the molecule near on electrode surface, has not been detected and investigated by an EQCM technique, because the mass change response seems to be very small. In this study, the redox behavior of methyl viologen on a bare gold surface, pyridinethiol surface and methylpyridinethiol surface was investigated. Although the three electrodes give the same cyclic voltammogram of methyl viologen, the three are different in QCM response recorded at the same time as the voltammetry. Access/repulsion of methyl viologen within an electrical double layer was monitored by the highly-sensitive EQCM technique.     

Size selective assembly of colloidal particles on a template by directed self-assembly technique

We report a simple and effective approach to organize micron- and submicron-sized particles in a size selective manner. This approach utilizes the template assisted directed self-assembly technique. A topographically patterned photoresist surface is fabricated and used to create an ordered array of colloidal particles from their aqueous suspensions. Assembly of particles on this template is then achieved by using a conventional spin coating technique. Feasibility of this technique to form a large area of patterned particle assemblies has been investigated. To arrange the particles on the template, the physical confinement offered by the surface topography must overcome a joint effect of centrifugal force and the hydrophobic nature of the photoresist surface. This concept has been extended to the size selective sorting of colloidal particles. The capability of this technique for sorting and organizing colloidal particles of a particular diameter from a mixture of microspheres is demonstrated.     

Electrospray ionization and tandem ion trap mass spectrometry for the confirmation of seven beta-lactam antibiotics in bovine milk

The feasibility of a technique to confirm the presence of residues from seven beta-lactam antibiotics in bovine milk has been demonstrated. The technique makes use of electrospray ionization and tandem ion trap mass spectrometry. Residues are first extracted from milk by reversed-phase solid phase extraction. Target analytes are separated by on-line reversed-phase liquid chromatography and ionized in the electrospray interface. The product ion mass spectra are acquired following collision-induced dissociation of protonated molecules. Confirmation is based on comparison of full scan spectra between unknowns and bona fide standards. The feasibility of this technique has been demonstrated for the six beta-lactams currently approved for use in lactating dairy cattle (penicillin G, ampicillin, amoxicillin, cloxacillin, cephapirin and ceftiofur) and a drug not approved for animal use, cefazolin. The technique has been applied to control milk fortified at 5 ng/mL of penicillin G and 10 ng/mL of the other six drugs.     

Enzymatic reaction of the immobilized enzyme on porous silicon studied by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry

Desorption/ionization on silicon mass spectrometry (DIOS-MS) is a matrix-free technique that allows for the direct desorption/ionization of low-molecular-weight compounds with little or no fragmentation of analytes. This technique has a relatively high tolerance for contaminants commonly found in biological samples. DIOS-MS has been applied to determine the activity of immobilized enzymes on the porous silicon surface. Enzyme activities were also monitored with the addition of a competitive inhibitor in the substrate solution. It is demonstrated that this method can be applied to the screening of enzyme inhibitors. Furthermore, a method for peptide mapping analysis by in situ digestion of proteins on the porous silicon surface modified by trypsin, combined with matrix-assisted laser desorption/ionization-time of flight-MS has been developed.     

Determination of rare earths in low grade uranium ores and SRM-rock by instrumental neutron activation analysis

An instrumental neutron activation analysis technique has been developed for simultaneous determination of 10 REE in low grade U/Zr ores and other geological materials. The samples were irradiated with reactor neutrons for 2 min to 8 hrs followed by a cooling of 30 min to 3 weeks. The γ-ray activity was measured with a semi-planar Ge(Li) detector. A precision of 5% has been obtained by the repeated analysis of NBS-SRM. The technique is relatively simple and adaptable on the routine basis.     

Analysis of molecular square size and purity via pulsed-field gradient NMR spectroscopy

The size (volume) of a large tetrametallic molecular square, that has resisted characterization by mass spectrometry, has been determined by pulsed-field gradient NMR spectroscopy, a technique that reports on self-diffusion coefficients. These scale inversely with hydrodynamic radii, which in turn scale approximately as the cube of the assembly's mass. The technique has also been used to determine whether NMR spectral complexities observed for the new compound are due to contamination with chemically related assemblies, or instead reflect the intrinsic structural complexities of the compound itself.     

Applications of an optimization technique in submolecular biology

Some applications of an optimization technique due to Levenberg in theoretical submolecular biology are described. This technique has proved a very useful tool for the generation of three-dimensional structures of molecules having cyclic components or other constrained regions. The generated molecular structures provide the starting point for quantum chemical calculations of great value in solving problems of biological interest. The mechanism of transport of alkali metal cations by valinomycin is one such example and this paper describes briefly how various conformations of valinomycin were obtained using the optimization technique. A variant of the same method has been suggested as a new technique for the detection of topographical similarities between apparently dissimilar molecules which are substrates for the same enzyme or receptor site. The technique is illustrated with a comparison of a tricyclic antidepressant with norepinephrine both of which have been postulated to compete for a common receptor site in the “amine pump” of peripheral adrenergic nerve cell membranes. Another area in which the optimization technique has proved useful is in developing an optimum separable localized bond function method designed for rigorous calculations on large saturated molecules. This method is briefly described.     

State-of-the-art in liquid chromatography-mass spectrometry.

Impressive progress has been made in the technology and application of combined liquid chromatography-mass spectrometry (LC-MS) in the past decennium. From a technique, that could only be used by a specialist, it has developed into a routinely applicable technique. LC-MS has become the method-of-choice of analytical support in many stages of drug development within pharmaceutical industries and has found its way into environmental, biochemical and other laboratories. This paper provides a perspective on the current technology, principles and applications of LC-MS.     

Critical review of the atomic spectrometric analysis of arsenic in foods

The literature on the determination of arsenic in foods by atomic spectroscopy involving hydride generation, platform furnace Zeeman and inductively coupled plasma has been critically reviewed. Hydride generation has been largely displaced as a powerful tool by platform furnace Zeeman, using the STPF (stabilized temperature platform furnace) concept for the control of interferences. Inductively coupled plasma with conventional pneumatic nebulization has been little used. An alternative is to employ hydride generation-ICP with extraction of the arsenic in an organic phase. This technique permits proper control of interferences together with an increase in sensitivity. Depending on the contents present in the foodstuff and the technique available, the sample can be solubilized by either wet or dry digestion.     

A numerical technique for predicting microstructure in liquid crystalline polymers

A numerical technique has been developed to model texture in nematic liquid crystals. The technique differentiates between splay, twist and bend distortions and includes splay-splay compensation. The technique is tested by the simulation of the Freedericksz transition and by the determination of minimum energy director fields for specific boundary conditions. To model the bulk, periodic boundary conditions are imposed. The effect of elastic anisotropy on disclination character has been investigated by terminating simulations before all the defects have been annihilated. With a low twist constant, twist disclinations are observed; with a high twist constant, wedge disclinations are observed. With a low twist constant and high splay constant, realistic for polymeric liquid crystals, features observed experimentally are simulated.     

Application of laser plasma confinement and bending effect for direct analysis of powder sample

A new technique involving laser plasma confinement and bending effects has been developed for direct powder spectrochemical analysis by means of a laser ablation method. In this technique, a special powder sample holder has been designed to overcome the blown-off problem suffered by the powder sample and allow the detection of plasma emission to be conducted on the bended shock wave plasma outside the holder, which is practically free from the continuous emission background. The spectra of various powder samples such as CuCl₂, NaCl and ZnS were measured in this experiment. The result shows that this technique offers a promising practical alternative for direct spectrochemical analysis of powder sample of small quantity with extremely low background at reduced surrounding air pressure.     

Advantages and limitations of the synchrotron based transmission X-ray microscopy in the study of the clay aggregate structure in aqueous suspensions

This paper reports new application of new transmission X-ray microscopy powered by a synchrotron source for the study of aqueous based clay suspensions. This paper delineates the advantages and limitations of this method. The tested transmission X-ray microscopy (TXM) technique has shown good agreement with the cryo-stage SEM technique. The spacial resolution of this TXM technique is 60 nm and clay particles with diameter below 500 nm are clearly visible and their pseudohexagonal symmetry is recognizable in detail. It is clearly demonstrated the methodology of implementing TXM to study aqueous based clay suspensions that are close to approximately 60 nm tomographic resolution. The technique enables us to study discrete structure of clay suspensions in water and within aggregates. This has never been previously possible. Larger crystals, more compact aggregates and less colloidal fraction present in kaolinite from Georgia has impact on faster settling and gelling in denser suspension than for Birdwood kaolinite in which colloidal particles create gel-like networking in less dense aqueous suspension.     

Diagnosis of congenital adrenal hyperplasia by rapid determination of 17alpha-hydroxyprogesterone in dried blood spots by gas chromatography/mass spectrometry following microwave-assisted silylation

17alpha-Hydroxyprogesterone (17OHP) is considered to be the biomarker of congential adrenal hyperplasia (CAH). Screening for CAH in newborns by measuring levels of the biomarker of 17OHP has become routine. In the work, a rapid, simple and sensitive technique was developed for the diagnosis of neonatal CAH by the quantitative analysis of 17OHP in neonatal blood spots. The technique was based on microwave-assisted silylation (MAS) followed by gas chromatography/mass spectrometry (GC/MS). In the method, fast derivatization of 17OHP with N,O-bis(trimethylsilyl)trifluoroacetamide was performed by using microwave irradiation, and the trimethylsilyl derivative thus formed was analyzed by GC/MS. The results of the experiment indicate that MAS followed by GC/MS analysis is a rapid, simple and sensitive method for the determination of 17OHP in blood samples. The proposed technique has been shown to have potential as a powerful tool for the rapid diagnosis of neonatal CAH.     

Controlled Positioning of Nanoparticles on Graphene by Noninvasive AFM Lithography

Atomic force microscopy is shown to be an excellent lithographic technique to directly deposit nanoparticles on graphene by capillary transport without any previous functionalization of neither the nanoparticles nor the graphene surface while preserving its integrity and conductivity properties. Moreover this technique allows for (sub)micrometric control on the positioning thanks to a new three-step protocol that has been designed with this aim. With this methodology the exact target coordinates are registered by scanning the tip over the predetermined area previous to its coating with the ink and deposition. As a proof-of-concept, this strategy has successfully allowed the controlled deposition of few nanoparticles on 1 μm(2) preselected sites of a graphene surface with high accuracy.     

The oxidation-state dependent structural conformation and supramolecular function of a redox-active [2]rotaxane in solution

A new NMR technique, namely paramagnetic suppression spectroscopy (PASSY), has been used to study the oxidation-state dependent structural conformation and supramolecular function of redox-active rotaxanes and catenanes in solution and at the surfaces of nanoparticles. Specifically, this technique has been used to study the structural conformation and supramolecular function in solution of a redox-active [2]rotaxane and the corresponding radical cation formed by a one-electron reduction. The findings of this and related studies provide important insights into the design of nanoscale devices based on rotaxanes and catenanes.     

Studies of TSD of polyethylene electrets by a differential technique

The determination of charge storage and charge decay processes in polyethylene electrets by means of TSD techniques alone seems to be limited by deficiencies in resolving power and reproducibility. Therefore, in the present work, we describe a new differential technique which cancels the effects of parasitic currents and improves the reproducibility of the measurements. The dependence of the shape of thermograms on experimental poling conditions has been studied. The comparison of discharge currents from the differential technique and from the usual one has also been found to be an interesting means of investigating the charge decay processes.     

流动注射-固相萃取-分光光度法检测半导体工业用水中痕量硅

硅酸盐在酸性介质中与钼酸铵反应生成硅钼黄,硅钼黄还原为硅钼蓝后,可被HLB小柱定量萃取.在此基础上,建立了流动注射-固相萃取-分光光度(FI-SPE-Vis)测定水中痕量硅酸盐的新方法.反应生成的硅钼蓝经HLB小柱萃取后,用水清洗去除杂质,NaOH溶液洗脱,分光光度法检测.实验对各参数进行了优化,优化后的参数为:洗脱剂浓度0.01 mol/L;试样上柱流速28.0 mL/min;洗脱流速3.5 mL/min;反应温度45 ℃;硅钼黄与硅钼蓝反应时间均为5 min;钼酸铵混合溶液、草酸溶液、抗坏血酸溶液的用量分别为3.5,3.5和1.75 mL.本方法具有良好的重现性和灵敏度,测定含硅9.33 μg/L的硅酸盐水样7次,RSD值为1.8%;选取不同的试样富集时间,可将定量分析的线性范围扩展为0.47～117 μg/L;检出限0.18 μg/L;回收率为96.8%～105%.可满足特殊工业用水中痕量硅检测的需要.