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Query: EC:2.7.10.2 (
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An analytical technique utilizing a near-field effect (to enhance the incident light energy on the thin tip of an Ag needle) in a laser ablation inductively coupled plasma mass spectrometry (NF-LA-
ICP
-MS) procedure was developed. To produce the thin needles with a tip diameter in the hundreds of nm range a robust needle etching procedure was established. The 'sample-to-tip' distance was controlled via the measurement of a tunnel current between the needle and sample surface. The NF-LA-
ICP
-MS technique thus developed was applied for the analysis of copper isotopic standard reference material NIST
SRM
976 and tungsten-molybdenum alloy NIST
SRM
480 in the nm resolution range. The observed craters ranged from 200 nm to about 2 microm in diameter and were dependent on the needle used as well as on the 'sample-to-tip' distance. The mass spectrometric measurements of (63)Cu(+) ion intensity on NIST
SRM
976 showed that using near-field enhancement in laser ablation allowed a roughly 6-fold increase in the ion intensity of the analyte when the needle was about 100 nm (and below) from the surface, in contrast to when it was far away (e.g. 10 microm) from the sample. The relative standard deviation (RSD) of the (65)Cu(+)/(63)Cu(+) isotopic ratio measurements by NF-LA-
ICP
-MS was 3.9% (n = 9). The detection efficiencies obtained for the compared LA-
ICP
-MS and NF-LA-
ICP
-MS methods were found to be 4.6 x 10(-3) counts per second (cps)/ablated atom and 2.7 x 10(-5) cps/ablated atom, respectively.
...
PMID:Near-field laser ablation inductively coupled plasma mass spectrometry: a novel elemental analytical technique at the nanometer scale. 1905 Dec 33
Environmental archives like peat deposits allow for the reconstruction of both naturally and anthropogenically forced changes in the biogeochemical cycle of Pb as well as the quantification of past and present atmospheric Pb pollution. However, records of atmospheric Pb deposition from pre-industrial times are lacking. In a publication by Weiss et al. [Weiss, D., Shotyk, W., Boyle, E.A., Kramers, J.D., Appleby, P.G., Cheburkin, A.K., Comparative study of the temporal evolution of atmospheric lead deposition in Scotland and eastern Canada using blanket peat bogs. Sci Total Environ 2002;292:7-18]. Pb isotopes data measured by Q-
ICP
-MS and TIMS, concentration and enrichment data was presented for sites in eastern Canada (PeW1) and northwestern Scotland (LL7c), dating to 1586 A.D and 715 A.D., respectively. Here these same cores are re-analysed for Pb isotopes by MC-
ICP
-MS thereby acquiring 204Pb data and improving on the original data in terms of resolution and temporal coverage. Significant differences were found between the Q-
ICP
-MS/TIMS and MC-
ICP
-MS measurements, particularly at PeW1. These discrepancies are attributed to the problematic presence of organic matter during sample preparation and analysis complicated by the heterogeneity of the organic compounds that survived sample preparation steps. The precision and accuracy of Pb isotopes in complex matrices like peat is not always well estimated by industrial standards like NIST-
SRM
981 Pb. Lead pollution histories at each site were constructed using the MC-
ICP
-MS data. The entire LL7c record is likely subject to anthropogenic additions. Contributions from local mining were detected in Medieval times. Later, coal use and mining in Scotland, Wales and England became important. After industrialization (ca. 1885 A.D.) contributions from Broken Hill type ores and hence, leaded petrol, dominate atmospheric Pb signatures right up to modern times. At PeW1 anthropogenic impacts are first distinguishable in the late 17th century with the mining and use of local coal. After industrialization (ca. 1810 A.D.), coal and petrol are the main Pb sources. A comprehensive estimate of the natural atmospheric background 206Pb/207Pb signature in eastern Canadian aerosols is made with a value of approximately 1.19.
...
PMID:Two high resolution terrestrial records of atmospheric Pb deposition from New Brunswick, Canada, and Loch Laxford, Scotland. 1906 75
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of Cu and other essential elements (such as K, Mg, Mn, P, S and B) in the leaves of a Cu-tolerant plant Elsholtzia splendens treated with the enriched (65)Cu isotope tracer (isotope abundance of 89.2%). The leaves (newly formed, fully grown and oldest) were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based
ICP
-MS (ICP-QMS), and the ion intensities of (65)Cu(+), (39)K(+), (24)Mg(+), (55)Mn(+), (31)P(+), (34)S(+) and (11)B(+) were measured by
ICP
-QMS to study the accumulation of Cu and other elements of interest. Standard reference material NIST
SRM
1515 Apple Leaves doped with known concentrations of analytes (from 0.1 to 2000mgL(-1)) was measured together with the samples by LA-
ICP
-MS and was used for the quantification of the analytical data. Notable accumulation of Cu in the newly formed leaves was clearly identified by imaging LA-
ICP
-MS. The increased isotope ratios of (65)Cu/(63)Cu measured by LA-
ICP
-MS demonstrated the path of Cu uptake and accumulation via the petiole and main veins in the leaves. Cu stress-induced accumulation of K, Mg, Mn, P and S in the newly formed leaves was observed, while B was not significantly affected. In the present study, the concentrations of K, Mg, Mn, P and S were not obviously changed in the fully grown leaves after short-term treatment. Along with the treatment, a visible decrease of K and P was found in the oldest leaves, while other elements were not influenced by Cu stress.
...
PMID:Study of essential element accumulation in the leaves of a Cu-tolerant plant Elsholtzia splendens after Cu treatment by imaging laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). 1916 19
Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of nutrient elements (such as K, Mg, Mn, Cu, P, S and B) in the leaves of Elsholtzia splendens. The plant leaves were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based
ICP
-MS (ICP-QMS), and the ion intensities of (39)K(+), (24)Mg(+), (55)Mn(+), (63)Cu(+), (31)P(+), (34)S(+) and (11)B(+) were measured by
ICP
-QMS to study the distribution of the elements of interest. The imaging technique using LA-
ICP
-MS on plant leaves does not require any sample preparation. Carbon ((13)C(+)) was used as an internal standard element to compensate for the difference in the amount of material ablated. Additional experiments were performed in order to study the influence of the water content of the analyzed leaves on the intensity signal of the analyte. For quantification purposes, standard reference material (NIST
SRM
1515 Apple Leaves) was selected and doped with standard solutions of the analytes within the concentration range of 0.1-2000 mg L(-1). The synthetic laboratory standards together with the samples were measured by LA-
ICP
-MS. The shape and structure of the leaves was clearly given by LA-
ICP
-MS imaging of all the elements measured. The elemental distribution varied according to the element, but with a high content in the veins for all the elements investigated. Specifically, Cu was located uniformly in the mesophyll with a slightly higher concentration in the main vein. High ion intensity was measured for S with a high amount of this element in the veins similar to the images of the metals, whereas most of the B was detected at the tip of the leaf. With synthetic laboratory standard calibration, the concentrations of elements in the leaves measured by LA-
ICP
-MS were between 20 microg g(-1) for Cu and 14,000 microg g(-1) for K.
...
PMID:Imaging of nutrient elements in the leaves of Elsholtzia splendens by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). 1917 15
A microwave-assisted double insert multimode vapour-phase digestion method was developed for the digestion of organic samples. The experimental set-up was based on a third generation-type teflon microwave vessel, equipped with an automatic pressure regulating type vessel cover. A borosilicate glass holder insert, containing a smaller quartz sample insert, was fitted inside the vessel. Sulphuric acid was added to the holder insert as a microwave absorbing and temperature transferring liquid, which transferred heat to the sample insert (into which the sample was weighed) and charred the sample material. Oxidation of the sample material was carried out simultaneously with charring using nitric acid vapour, which was generated by the 1:1 (v/v) sulphuric acid-nitric acid mixture located in the bottom of the microwave vessel. This set-up generated high digestion efficiency, without any of the interferences normally associated with direct sulphuric acid usage. The method was used for determining the concentrations of Cd, Cr, Cu, Mn, Mo, Zn and Fe in certified organic reference materials using
ICP
-OES instrumentation. The certified organic reference materials were NRCC DOLT-2 dogfish liver, NIST-
SRM
1577b bovine liver and IRMM VDA cadmium in polyethylene No. 001 and No. 004. The results were in good agreement with the certified values, forepart from Cd. For Cd the results were lower than the certified values due to volatilization losses. Sample materials that could not be digested by an earlier procedure were completely digested during a single-step, 30 min digestion. The tested sample materials included certified reference materials, 3-nitrobenzoic acid (3-NBA) and pike (Esox lucius) muscle. The residual carbon concentrations in the digestion solutions were below the detection limit of the TOC instrument. This type of digestion method is described here for the first time in the literature.
...
PMID:Microwave-assisted double insert vapour-phase digestion of organic samples. 1918 21
The possibilities for universal calibration based on multi-element aqueous standard solutions and graphite laboratory reference materials (graphite standards) for the electrothermal vaporization inductively coupled plasma optical emission spectrometric (ETV
ICP
OES) determination of Al, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, P, Pb, S, Sr, Ti, V, and Zn in plant materials were investigated. A commercially available state-of-the-art ETV device was coupled with an Echelle
ICP
spectrometer equipped with a charge-injection-device (CID) camera for spectral detection. The transition area between transport tube and ETV graphite tube and the gas streams for inner gas, bypass gas, and modifier gas were optimized to achieve best transport efficiencies. The influence of four gaseous modifiers (CCl4, CHCl3, CCl2F2, and C3H8) added to the inner gas was studied. Five reference materials (RM P-Alfalfa, Lucerne; NIES CRM No.9 "Sargasso"; CTA-VTL-2 Virginia Tobacco Leaves; NIST
SRM
1515 Apple Leaves; IAEA-V-10 Hay Powder) were used for method validation. If certified reference materials are not available, calibration against graphite standards or dried aqueous standard solutions is possible. Three carbonization procedures as sample pretreatment for the plant materials were investigated.
...
PMID:Calibration possibilities and modifier use in ETV ICP OES determination of trace and minor elements in plant materials. 1946 19
A slurry sampling inductively coupled plasma mass spectrometry (ICP-MS) method has been developed for the determination of As, Cd, and Hg in cereals using flow injection chemical vapor generation (VG) as the sample introduction system. A slurry containing 6% m/v flour, 0.7% m/v thiourea, 0.4 microg mL(-1) Co(II), and 2.5% v/v HCl was injected into a VG-
ICP
-MS system for the determination of As, Cd, and Hg without dissolution and mineralization. Because the sensitivities of the elements studied in the slurry and that of aqueous solution were quite different, a standard addition method and an isotope dilution method were used for the determination of As, Cd, and Hg in selected cereal samples. The influences of vapor generation conditions and slurry preparation on the ion signals were reported. The effectiveness of the vapor generation sample introduction technique in alleviating various spectral interferences in
ICP
-MS analysis has been demonstrated. This method has been applied for the determination of As, Cd, and Hg in NIST
SRM
1567a Wheat Flour reference material, NIST
SRM
1568a Rice Flour reference material, and cereal samples obtained from local market. The As, Cd, and Hg analysis results of the reference materials agreed with the certified values. The method detection limits estimated from standard addition curves were about 0.10, 0.16, and 0.07 ng g(-1) for As, Cd, and Hg, respectively, in the original cereal samples.
...
PMID:Slurry sampling flow injection chemical vapor generation inductively coupled plasma mass spectrometry for the determination of As, Cd, and Hg in cereals. 1960 66
A flow injection analysis (FIA) method using on-line separation and preconcentration with a novel metal scavenger beads, QuadraSil TA, has been developed for the
ICP
-OES determination of traces of palladium. QuadraSil TA contains diethylenetriamine as a functional group on spherical silica beads and shows the highest selectivity for Pd(II) at pH 1 (0.1 mol l(-1) hydrochloric acid) solution. An aliquot of the sample solution prepared as 0.1 mol l(-1) in hydrochloric acid was passed through the QuadraSil TA column. After washing the column with the carrier solution, the Pd(II) retained on the column was eluted with 0.05 mol l(-1) thiourea solution and the eluate was directly introduced into an
ICP
-OES. The proposed method was successfully applied to the determination of traces of palladium in JSd-2 stream sediment certified reference material [0.019+/-0.001 microg g(-1) (n=3); provisional value: 0.0212 microg g(-1)] and
SRM
2556 used auto catalyst certified reference material [315+/-4 microg g(-1) (n=4); certified value: 326 microg g(-1)]. The detection limit (3 sigma) of 0.28 ng ml(-1) was obtained for 5 ml of sample solution. The sample through puts for 5 ml and 100 microl of the sample solutions were 10 and 15 h(-1), respectively.
...
PMID:Determination of traces of palladium in stream sediment and auto catalyst by FI-ICP-OES using on-line separation and preconcentration with QuadraSil TA. 1961 7
Simultaneous and multi-elemental method was optimized to determine 35 elements in 274 coarse and fine aerosol samples by using HR-
ICP
-MS. The procedures were validated. Measurement uncertainties of all elements including sampling uncertainties were calculated by applying bottom-up approach. The average recoveries obtained for each element ranged between 79% and 129% using NIST
SRM
1648, urban dust. The calculated uncertainties of the analytical methods were between 2.9% and 18% for both sample types. The major contributions to the uncertainty budget come from the calibration curves, repeatability and volume of air.
...
PMID:Uncertainty of high resolution inductively coupled plasma mass spectrometry based aerosol measurements. 1963 63
The quantitative determination of chemical elements in organic or biological samples is an important analytical problem. Normally the elements to be determined in the organic matrix must be transformed into a simple inorganic form. A digestion method by heating on a block digestor has been developed for the determination of Al, As, Ba, Ca, Cd, Co, Cu, Fe, Mg, Mn, V and Zn in Oyster tissue by
ICP
OES. A simplex centroid statistical mixture design has been used to study the effects of changing HNO(3), HCl and H(2)O(2) reagent proportions on the digestion of these samples. Response surface and principal component analyses show that the species Ca, Cd, Cu, Fe, Mg, Mn and Zn have very similar analytical tendencies under this experiment. By means of mixture modeling maximum recoveries for these ions were predicted using 19%, 18% and 63% of the HCl, HNO(3) and H(2)O(2) pseudocomponent mixtures, respectively. This corresponds to 21.4%, 30.8% and 47.8% of the HCl, HNO(3) and H(2)O(2) commercial solutions. Furthermore the As, Co and V ions present large recoveries for these mixtures as well. The Al and Ba ion recoveries are seen to be independent of the mixture proportions. The analysis of Oyster tissue reference material (
SRM
1566b - NIST) under optimized conditions at the selected wavelengths resulted in ion recoveries between 90% and 100%.
...
PMID:Statistical mixture design development of digestion methods for Oyster tissue using inductively coupled plasma optical emission spectrometry for the determination of metallic ions. 1983 20
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