Ionic liquids as selectors for the enhanced detection of proteins

Herein, we report an approach for protein detection enhanced by ionic liquid (IL) selectors in capillary electrophoresis (CE), with avidin as a model protein. Hydrophilic ILs were added into the running buffer of CE and acted as selectors for sample injection, enriching the positive target and excluding the negative from the capillary. When using 3% (v/v) IL selector, the detection sensitivity of avidin was improved by over one order of magnitude, while the interference from protein adsorption was effectively avoided, even in an uncoated capillary. The electrochemiluminescence method was initially used for IL-based CE with low noise that was independent of the IL concentration, making ILs almost transparent as additives in the electrophoresis buffer.

Capillary electrophoresis and microchip capillary electrophoresis with electrochemical and electrochemiluminescence detection

Recent advances and key strategies in capillary electrophoresis and microchip CE with electrochemical detection (ECD) and electrochemiluminescence (ECL) detection are reviewed. This article consists of four main parts: CE-ECD; microchip CE-ECD; CE-ECL; and microchip CE-ECL. It is expected that ECD and ECL will become powerful tools for CE microchip systems and will lead to the creation of truly disposable devices. The focus is on papers published in the last two years (from 2005 to 2006).

Capillary electrophoresis with boron doped diamond electrode for amperometric detection of low molecular weight biological substrate

The research work in this thesis included the sensitive and selective separation of biological substance by capillary electrophoresis with a boron doped diamond electrode for amperometric detection. Chapter 1 introduced the capillary electrophoresis and electrochemical detection. It included the different modes of capillary electrophoresis, polyelectrolyte multilayers coating for open tubular capillary electrochromatography, different modes of electrochemical detection and carbon based electrodes. Chapter 2 showed the synthesized and electropolymerized N-acetyltyramine with a negatively charged sulfobutylether-β-cyclodextrin on a boron doped diamond (BDD) electrode followed by the electropolymerzation of pyrrole to form a stable and permselective film for selective dopamine detection. For comparison, a glassy carbon (GC) electrode with a combined electropolymerized permselective film of polytyramine and polypyrrole-1-propionic acid was used for selective detection of dopamine. The detection limit of dopamine was improved from 100 nM at a GC electrode to 5 nM at a BDD electrode. Chapter 3 showed field-amplified sample stacking using a fused silica capillary coated with gold nanoparticles embedded in poly(diallyldimethylammonium) chloride, which has been investigated for the electrophoretic separation of indoxyl sulphate, homovanillic acid and vanillylmandelic acid. The detection limit of the three analytes obtained by using a boron doped diamond electrode was around 75 nM, which was significantly below their normal physiological levels in biological fluids. This combined separation and detection scheme was applied to the direct analysis of these analytes and other interfereing chemicals including uric and ascorbic acids in urine samples without off-line sample treatment or preconcentration. Chapter 4 showed the selective detection of Pseudomonas Quinolone Signal, PQS for quorum sensing from its precursor HHQ, using a simply boron doped diamond electrode. Furthermore, by combining poly(diallyldimethylammonium) chloride modified fused silica capillary with a BDD electrode for amperometric detection, PQS was separated from HHQ and other analogues. The detection limit of PQS was as low as 65 nM. Different P. aeruginosa mutant strains were studied. Chapter 5 showed the separation of aminothiols by layer-by-layer coating of silica capillary with a boron doped diamond electrode. The capillary was layer-by-layer coated with the polycation poly(diallyldimethylammonium) chloride and negatively charged silica nanoparticles. All the aminothiols was separated and detected using a BDD electrode in an acidic electrolyte. It was a novel scheme for the separation and detection of glutathione reduced and oxidized forms, which is important for estimated overstressed level in the human system.

Applications of capillary electrophoresis and mass spectrometry for the analysis of thiosalts

Thiosalt species are unstable, partially oxidized sulfur oxyanions formed in sulfur-rich environments but also during the flotation and milling of sulfidic minerals especially those containing pyrite (FeS₂) and pyrrhotite (Fe₍₁₋ₓ₎S, x = 0 to 0.2). Detecting and quantifying the major thiosalt species such as sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻), trithionate (S₃O₆²⁻), tetrathionate (S₄O₆²⁻) and higher polythionates (SₓO₆²⁻, where 3 ≤ x ≤ 10) in the milling process and in the treated tailings is important to understand how thiosalts are generated and provides insight into potential treatment. As these species are unstable, a fast and reliable analytical technique is required for their analysis. Three capillary zone electrophoresis (CZE) methods using indirect UV-vis detection were developed for the simultaneous separation and determination of five thiosalt anions: SO₄²⁻, S₂O₃²⁻, S₃O₆²⁻, S₄O₆²⁻ and S₅O₆²⁻. Both univariate and multivariate experimental design approaches were used to optimize the most critical factors (background electrolyte (BGE) and instrumental conditions) to achieve fast separation and quantitative analysis of the thiosalt species. The mathematically predicted responses for the multivariate experiments were in good agreement with the experimental results. Limits of detection (LODs) (S/N = 3) for the methods were between 0.09 and 0.34 μg/mL without a sample stacking technique and nearly four-fold increase in LODs with the application of field-amplified sample stacking. As direct analysis of thiosalts by mass spectrometry (MS) is limited by their low m/z values and detection in negative mode electrospray ionization (ESI), which is typically less sensitive than positive ESI, imidazolium-based (IP-L-Imid and IP-T-Imid) and phosphonium-based (IP-T-Phos) tricationic ion-pairing reagents were used to form stable high mass ions non-covalent +1 ion-pairs with these species for ESI-MS analysis and the association constants (Kassoc) determined for these ion-pairs. Kassoc values were between 6.85 × 10² M⁻¹ and 3.56 × 10⁵ M⁻¹ with the linear IP-L-Imid; 1.89 ×10³ M⁻¹ and 1.05 × 10⁵ M⁻¹ with the trigonal IP-T-Imid ion-pairs; and 7.51×10² M⁻¹ and 4.91× 10⁴ M⁻¹ with the trigonal IP-T-Phos ion-pairs. The highest formation constants were obtained for S₃O₆²⁻ and the imidazolium-based linear ion-pairing reagent (IP-L-Imid), whereas the lowest were for IP-L-Imid: SO₄²⁻ ion-pair.

Determination of reserpine in urine by capillary electrophoresis with electrochemiluminescence detection

A fast and sensitive approach to detect reserpine in urine using micellar electrokinetic capillary chromatography with electrochemiluminescence (ECL) of Ru(bpy)(3)(2+) detection is described. Using a 25 mum i.d. capillary as separation column, the ECL detector was coupled to the capillary in the absence of an electric field decoupler. Field-amplified injection was used to minimize the effect of ionic strength in the sample and to achieve high sensitivity. In this way, the sample was analyzed directly without any pretreatment. The method was validated for reserpine in the urine over the range of 1 x 10(-6) - 1 x 10(-4) mol/L with a correlation coefficient of 0.996. The RSD for reserpine at a level of 5 mumol/L was 4.3%. The LOD (S/N = 3) was estimated to be 7.0 x 10(-8) mol/L. The average recoveries for 10 mumol/L reserpine spiked in human urine were 94%.

The use of CE-electrochemiluminescence with ionic liquid for the determination of bioactive constituents in Chinese traditional medicine

CE/tris(2,2-bipyridyl) ruthenium(ll) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL), CEECL, with an ionic liquid (IL) detection system was established for the determination of bioactive constituents in Chinese traditional medicine opium poppy which contain large amounts of coexistent substances. A minimal sample pretreatment which involves a one-step extraction approach avoids both sample loss and environmental pollution. As the nearby hydroxyl groups in some alkaloid such as morphine may react with borate to form complexes and IL, as a high-conductivity additive in running buffer, could cause an enhanced field-amplified effect of electrokinetic injection. Running buffer containing 25 mM borax-8 mM 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF(4)) IL (pH 9.18) was used which resulted in significant changes in separation selectivity and obvious enhancement in ECL intensities for those alkaloids with similar structures. Sensitive detection could be achieved when the distance between the Pt working electrode and the outlet of separation capillary was set at 150 mu m and the stainless steel cannula was fixed approximately 1 cm away from the outlet of the capillary. Quantitative analysis of four alkaloids was achieved at a detection voltage of 1.2 V and a separation voltage of 15 kV in less than 7 min.

中国大中型气田天然气成藏物理化学模拟研究

Natural gas pays more important role in the society as clean fuel. Natural gas exploration has been enhanced in recent years in many countries. It also has prospective future in our country through "85" and "95" national research. Many big size gas fields have been discovered in different formations in different basins such as lower and upper Paleozoic in Erdos basin, Tertiary system in Kuche depression in Tarim basin, Triassic system in east of Sichuan basin. Because gas bearing basins had been experienced multiple tectogenesis. The characteristics of natural gases usually in one gas field are that they have multiple source rocks and are multiple maturities and formed in different ages. There has most difficult to research on the gas-rock correlation and mechanism of gas formation. Develop advanced techniques and methods and apply them to solve above problems is necessary. The research is focused on the critical techniques of geochemistry and physical simulation of gas-rock correlation and gas formation. The lists in the following are conclusions through research and lots of experiments. I 8 advanced techniques have been developed or improved about gas-rock correlation and gas migration, accumulation and formation. A series of geochemistry techniques has been developed about analyzing inclusion enclave. They are analyzing gas and liquid composition and biomarker and on-line individual carbon isotope composition in inclusion enclave. These techniques combing the inclusion homogeneous temperature can be applied to study on gas-rock correlation directly and gas migration, filling and formation ages. Technique of on-line determination individual gas carbon isotope composition in kerogen and bitumen thermal pyrolysis is developed. It is applied to determine the source of natural is kerogen thermal degradation or oil pyrolysis. Method of on-line determination individual gas carbon isotope composition in rock thermal simulation has being improved. Based on the "95"former research, on-line determination individual gas carbon isotope composition in different type of maceral and rocks thermal pyrolys is has been determined. The conclusion is that carbon isotope composition of benzene and toluene in homogenous texture kerogen thermal degradation is almost same at different maturity. By comparison, that in mixture type kerogen thermal pyrolysis jumps from step to step with the changes of maturity. This conclusion is a good proof of gas-rock dynamic correlation. 3. Biomarker of rock can be determined directly through research. It solves the problems such as long period preparing sample, light composition losing and sample contamination etc. It can be applied to research the character of source rock and mechanism of source rock expulsion and the path of hydrocarbon migration etc. 4. The process of hydrocarbon dynamic generation in source rock can be seen at every stage applying locating observation and thermal simulation of ESEM. The mechanism of hydrocarbon generation and expulsion in source rock is discussed according to the experiments. This technique is advanced in the world. 5. A sample injection system whose character is higher vacuum, lower leaks and lower blank has been built up to analyze inert gas. He,Ar,Kr and Xe can be determined continuously on one instrument and one injection. This is advanced in domestic. 7. Quality and quantity analysis of benzene ring compounds and phenolic compounds and determination of organic acid and aqueous gas analysis are applied to research the relationship between compounds in formation water and gas formation. This is another new idea to study the gas-rock correlation and gas formation. 8. Inclusion analysis data can be used to calculate the Paleo-fluid density, Paleo-geothermal gradient and Paleo-geopressure gradient and then to calculate the Paleo-fluid potential. It's also a new method to research the direction of hydrocarbon migration and accumulation. 9. Equipment of natural gas formation simulation is produced during the research to probe how the physical properties of rock affect the gas migration and accumulation and what efficiency of gas migrate and factors of gas formation and the models of different type of migration are. II study is focused on that if the source rocks of lower Paleozoic generated hydrocarbon and what the source rocks of weathered formation gas pool and the mechanism of gas formation are though many advanced techniques application. There are four conclusions. 1.The maturity of Majiagou formation source rocks is higher in south than that in north. There also have parts of the higher maturity in middle and east. Anomalous thermal pays important role in big size field formation in middle of basin. 2. The amount of gas generation in high-over maturity source rocks in lower Paleozoic is lager than that of most absorption of source rocks. Lower Paleozoic source rocks are effective source rocks. Universal bitumen exists in Ordovician source rocks to prove that Ordovician source rocks had generated hydrocarbon. Bitumen has some attribution to the middle gas pool formation. 3. Comprehensive gas-rock correlation says that natural gases of north, west, south of middle gas field of basin mainly come from lower Paleozoic source rocks. The attribution ratio of lower Paleozoic source rocks is 60%-70%. Natural gases of other areas mainly come from upper Paleozoic. The attribution ratio of upper Paleozoic source rocks is 70%. 4. Paleozoic gases migration phase of Erdos basin are also interesting. The relative abundance of gasoline aromatic is quite low especially toluene that of which is divided by that of methyl-cyclohexane is less than 0.2 in upper Paleozoic gas pool. The migration phase of upper Paleozoic gas may be aqueous phase. By comparison, the relative abundance of gasoline aromatic is higher in lower Paleozoic gas. The distribution character of gasoline gas is similar with that in source rock thermal simulation. The migration phase of it may be free phase. IH Comprehensive gas-rock correlation is also processed in Kuche depression Tarim basin. The mechanism of gas formation is probed and the gas formation model has been built up. Four conclusions list below. 1. Gases in Kuche depression come from Triassic-Jurassic coal-measure source rocks. They are high-over maturity. Comparatively, the highest maturity area is Kelasu, next is Dabei area, Yinan area. 2. Kerogen thermal degradation is main reason of the dry gas in Kuche depression. Small part of dry gas comes from oil pyrolysis. VI 3.The K12 natural gas lays out some of hydro-gas character. Oil dissolved in the gas. Hydro-gas is also a factor making the gas drier and carbon isotope composition heavier. 4. The mechanism and genesis of KL2 gas pool list as below. Overpressure has being existed in Triassic-Jurassic source rocks since Keche period. Natural gases were expulsed by episode style from overpressure source rocks. Hetero-face was main migration style of gas, oil and water at that time. The fluids transferred the pressure of source rocks when they migrated and then separated when they got in reservoir. After that, natural gas migrated up and accumulated and formed with the techno-genesis. Tectonic extrusion made the natural gas overpressure continuously. When the pressure was up to the critical pressure, the C6-C7 composition in natural gas changed. The results were that relative abundance of alkane and aromatic decreased while cycloalkane and isoparaffin increased. There was lots of natural gas filling during every tectonic. The main factors of overpressure of natural gas were tectonic extrusion and fluid transferring pressure of source rocks. Well preservation was also important in the KL2 gas pool formation. The reserves of gas can satisfy the need of pipeline where is from west to east. IV A good idea of natural gas migration and accumulation modeling whose apparent character is real core and formation condition is suggested to model the physical process of gas formation. Following is the modeling results. 1. Modeling results prove that the gas accumulation rule under cap layer and gas fraction on migration path. 2. Natural gas migration as free phase is difficult in dense rock. 3. Natural gases accumulated easily in good physical properties reservoirs where are under the plugging layer. Under the condition of that permeability of rock is more than 1 * 10~(-3)μm~(-1), the more better the physical properties and the more bigger pore of rock, the more easier the gas accumulation in there. On the contrary, natural gas canonly migrate further to accumulate in good physical properties of rock. 4. Natural gas migrate up is different from that down. Under the same situation, the amount of gas migration up is lager than that of gas migration down and the distance of migration up is 3 times as that of migration down. 5. After gas leaks from dense confining layer, the ability of its dynamic plug-back decreased apparently. Gas lost from these arils easily. These confining layer can confine again only after geology condition changes. 6. Water-wetted and capillary-blocking rocks can't block water but gases generally. The result is that water can migrate continuously through blocking rocks but the gases stay under the blocking rocks then form in there. The experiments have proved the formation model of deep basin gas.

(Table T1) Permeability, electrical resistivity and density of ODP Hole 193-1188A and Site 193-1189 minicores, PACMANUS field

Magmatic fluids, heat fluxes, and fluid/rock interactions associated with hydrothermal systems along spreading centers and convergent margins have a significant impact on the genesis of major sulfide deposits and biological communities. Circulation of hydrothermal fluids is one of the most fundamental processes associated with localized mineralization and is controlled by inherent porous and permeable properties of the ocean crust. Heat from magmatic intrusions drives circulation of seawater through permeable portions of the oceanic crust and upper mantle, discharging at the seafloor as both focused high-temperature (250°-400°C) fluids and diffuse lower-temperature (<250°C) fluids. This complex interaction between the circulating hydrothermal fluids and the oceanic basement greatly influences the physical properties and the composition of the crust (Thompson, 1983; Jacobson, 1992, doi:10.1029/91RG02811; Johnson and Semyan, 1994, doi:10.1029/93JB00717). During Ocean Drilling Program (ODP) Leg 193, 13 holes were drilled in the PACMANUS hydrothermal system (Binns, Barriga, Miller, et al., 2002, doi:10.2973/odp.proc.ir.193.2002). The hydrothermal system consists of isolated hydrothermal deposits lined along the main crest of the Pual Ridge, a 500- to 700-m-high felsic neovolcanic ridge in the eastern Manus Basin. The principal drilling targets were the Snowcap (Site 1188) and Roman Ruins (Site 1189) active hydrothermal fields. Samples from these two sites were used for a series of permeability, electrical resistivity, and X-ray computed tomography measurements.

Malnutrition and pressure ulcer risk in adults in Australian health care facilities

Aims To determine the effect of nutritional status on the presence and severity of pressure ulcers in statewide? public healthcare facilities, in Queensland, Australia. Research Methods A multicentre, cross sectional audit of nutritional status of a convenience sample of subjects was carried out as part of a large audit of pressure ulcers in a sample of state based public healthcare facilities in 2002 and 2003. Dietitians in 20 hospitals and six residential aged care facilities conducted single day nutritional status audits of 2208 acute and 839 aged care subjects using the Subjective Global Assessment. The effect of nutritional status on the presence, highest stage and number of pressure ulcers was determined by logistic regression in a model controlling for age, gender, medical specialty and facility location. The potential clustering effect of facility was accounted for in the model using an analysis of correlated data approach. Results Subjects with malnutrition had an adjusted odds risk of 2.6 (95% CI 1.8-3.5, p<0.001) of having a pressure ulcer in acute facilities and 2.0 (95% CI 1.5-2.7, p<0.001) for residential aged care facilities. There was also increased odds risk of having a pressure ulcer, having a higher stage pressure ulcer and a higher number of pressure ulcers with increased severity of malnutrition. Conclusion Malnutrition was associated with at least twice the odds risk of having a pressure ulcer of in public healthcare facilities in Queensland. Action must be taken to identify, prevent and treat malnutrition, especially in patients at risk of pressure ulcer.

Pressure and temperature dependence of the electrical resistivity of bulk Al23 Te77 glass

Electrical resistivity of bulk amorphous Al23T77 samples has been studied as a function of pressure (up to 80 kbar) and temperature (down to 77 K). At atmospheric pressure the temperature dependence of resistivity obeys the relation = π0 exp(δE/RT) with two activation energies. In the temperature range 300 K T > 234 K the activation energy is 0.58 eV and for 234 >T 185 K the value is δE = 0.30 ev. The activation energy has been measured as a function of pressure. The electrical resistivity decreases exponentially with the increase of pressure and at 70 kbar pressure the electrical behaviour of the sample shows a metallic nature with a positive temperature coefficient. The high pressure phase of the sample is found to be a crystalline hexagonal phase.

High pressure clamp for electrical measurements up to 8 GPa and temperature down to 77 K

A compact clamp-type high pressure cell for carrying out electrical conductivity measurements on small solid samples of size 1 mm or less at pressures upto 8 GPa (i.e., 80 kbar) and for use down to 77 K has been designed and fabricated. The pressure generated in the sample region has been calibrated at room temperature against the polymorphic phase transitions of Bismuth and Ytterbium. The pressure relaxation of the clamp at low temperatures has been estimated by monitoring the electrical conductivity behavior of lead. Review of Scientific Instruments is copyrighted by The American Institute of Physics.

An experimental study of suddenly expanded rectangular jet flow field

Flow through a rectangular Passage which is expanded suddenly into another rectangular duct of larger Cross-sectional area has been studied experimentally with stagnation Pressures from 3.5 atmospheres to 1.25 atmospheres. The length to height ratio of the enlarged duct varied from 5.769 to 1.923 and three models with length to height ratios 5.769, 3.846, and 1.923 were studied. The influence of stagnation Pressures and length to height ratio of the enlarged duct on base pressure and flow field mean pressures in the enlarged duct is discussed. The results of the present investigation indicate that the oscillatory nature of the mean pressure flow field in the enlarged portion with rectangular cross-section is appreciably different from that for circular cross-section at similar flow conditions.

Backward switching phenomenon from field forced ferroelectric to antiferroelectric phases in antiferroelectric PbZrO3 thin films

Antiferroelectric materials (example: lead zirconate and modified lead zirconate stannate), in which a field-induced ferroelectric phase transition is feasible due to a small free energy difference between the ferroelectric and the antiferroelectric phases, are proven to be very good candidates for applications involving actuation and high charge storage devices. The property of reverse switching from the field-induced ferroelectric to antiferroelectric phases is studied as a function of temperature, applied electric field, and sample thickness in antiferroelectric lead zirconate thin films deposited by pulsed excimer laser ablation. The maximum released charge density was 22 μC/cm2 from a stored charge density of 36 μC/cm2 in a 0.55 μ thick lead zirconate thin film. This indicated that more than 60% of the stored charge could be released in less than 7 ns at room temperature for a field of 200 kV/cm. The content of net released charge was found to increase with increasing field strength, whereas with increasing temperature the released charge was found to decrease. Thickness-dependent studies on lead zirconate thin films showed that size effects relating to extrinsic and intrinsic pinning mechanisms controlled the released and induced charges through the intrinsic switching time. These results proved that antiferroelectric PZ thin films could be utilized in high-speed charge decoupling capacitors in microelectronics applications.

Room temperature electrical spin injection into GaAs by an oxide spin injector

Spin injection, manipulation and detection are the integral parts of spintronics devices and have attracted tremendous attention in the last decade. It is necessary to judiciously choose the right combination of materials to have compatibility with the existing semiconductor technology. Conventional metallic magnets were the first choice for injecting spins into semiconductors in the past. So far there is no success in using a magnetic oxide material for spin injection, which is very important for the development of oxide based spintronics devices. Here we demonstrate the electrical spin injection from an oxide magnetic material Fe3O4, into GaAs with the help of tunnel barrier MgO at room temperature using 3-terminal Hanle measurement technique. A spin relaxation time tau similar to 0.9 ns for n-GaAs at 300 K is observed along with expected temperature dependence of t. Spin injection using Fe3O4/MgO system is further established by injecting spins into p-GaAs and a tau of similar to 0.32 ns is obtained at 300 K. Enhancement of spin injection efficiency is seen with barrier thickness. In the field of spin injection and detection, our work using an oxide magnetic material establishes a good platform for the development of room temperature oxide based spintronics devices.