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1.
Flame-heated tubes are widespread in flame-AAS, mainly for the determination of hydride-forming elements. Instead of the introduction of gaseous compounds liquids can also be introduced continuously in such an absorption cell. With the aid of an HPLC pump the liquid is forced through a very fine nozzle, generating an aerosol beam less than 0.5 mm in diameter. This beam travels a distance of 10cm as a "free-flying aerosol jet" into the sample introduction hole of a metal tube furnace placed in the flame. Both introduction of the entire sample and the long residence time lead to a considerable improvement in power of detection. The detection limit for 100 microL samples amounts to 7 microg/L (Pb) and to 0.2 microg/L (Cd), which means an increase in power of detection of between one and two orders of magnitude compared to conventional flame-AAS. The relative standard deviation (100 microL sample volume, N = 10) was found to be 1.3% (signal area) for 600 microg/L Pb and to be 1.5% (signal-area) for 15 microg/L Cd. RSD values from measurements in peak-height amounted to 2.2% (Pb) and to 1.7% (Cd). 相似文献
2.
De la Fuente JR Jullian C Saitz C Neira V Poblete O Sobarzo-Sánchez E 《The Journal of organic chemistry》2005,70(22):8712-8716
[reaction: see text] Photoreduction of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-proton-electron transfer that leads to the N-hydrogen oxoisoaporphine anion. When triethylamine, TEA, was used as the electron donor in anaerobic conditions, 1-diethylaminobutadiene, DEAB, was one of the oxidation products of TEA, among diethylamine and acetaldehyde. DEAB was identified by (1)H NMR and GC-MS experiments by comparison with the authentic 1-diethylaminobutadiene. This is the first report of a butadienyl derivative formed in the dye-sensitized photooxidation of TEA. In addition, isotopic exchange experiments with TEA-d(15) and D(2)O show that the hydrogens at carbon-2 and carbon-4 of the butadienyl moiety are exchangeable. The observed isotopic exchange pattern could be explained by the head-to-tail coupling of an N,N-diethylvinylamine intermediate that exchanges hydrogens at the C-beta via the enammonium ion. 相似文献
3.
Chemical modifiers in arsenic determination in biological materials by tungsten coil electrothermal atomic absorption spectrometry 总被引:2,自引:0,他引:2
Palladium, iridium, and rhodium are evaluated as possible chemical modifiers in the determination of As in digest solutions of biological materials (human hair and clam) by tungsten coil electrothermal atomic absorption spectrophotometry (TCA-AAS). The modifier in solution was applied onto the coil and thermally pre-reduced; the pre-reduction conditions, the amount of modifier, and the thermal program were optimized. Palladium was not satisfactory, whereas Ir and Rh were effective modifiers and rendered better relative sensitivity for As by a factor of 1.4 and 1.9, respectively compared to the case without modifier. Upon optimization of thermal conditions for As in pre-reduced Ir (2.0 µg) and Rh (2.0 µg) modifiers and in the digest solutions of the study matrices, Rh (2.0 µg) was more effective modifier and was selected as such. The mean within-day repeatability was 2.8% in consecutive measurements (25–100 µg L–1) (3 cycles, each of n=6) and confirmed good short-term stability of the absorbance measurements. The mean reproducibility was 4.4% (n=20 in a 3-day period) and the detection limit (3
blank/slope) was 29 pg (n=15). The useful coil lifetime in Rh modifier was extended to 300–400 firings. Validation was by determination of As in the certified reference material (CRM) of Oyster tissue solution with a percentage relative error (E
rel%) of 2% and percentage relative standard deviation (RSD%) of 3% (n=4), and by analytical recovery of As spiked in CRM of human hair [94±8% (n=4)]. The methodology is simple, fast (sample readout frequency 21 h–1), reliable, of low cost, and was applied to the determination of As in hair samples of exposed and unexposed workers. 相似文献
4.
Santhi Latha Pandrangi Prasanthi Chittineedi Sphoorthi Shree Chalumuri Avtar Singh Meena Juan Alejandro Neira Mosquera Sungey Naynee Snchez Llaguno Ramachandra Reddy Pamuru Gooty Jaffer Mohiddin Arifullah Mohammad 《Molecules (Basel, Switzerland)》2022,27(9)
Iron is a crucial element required for the proper functioning of the body. For instance, hemoglobin is the vital component in the blood that delivers oxygen to various parts of the body. The heme protein present in hemoglobin comprises iron in the form of a ferrous state which regulates oxygen delivery. Excess iron in the body is stored as ferritin and would be utilized under iron-deficient conditions. Surprisingly, cancer cells as well as cancer stem cells have elevated ferritin levels suggesting that iron plays a vital role in protecting these cells. However, apart from the cytoprotective role iron also has the potential to induce cell death via ferroptosis which is a non-apoptotic cell death dependent on iron reserves. Apoptosis a caspase-dependent cell death mechanism is effective on cancer cells however little is known about its impact on cancer stem cell death. This paper focuses on the molecular characteristics of apoptosis and ferroptosis and the importance of switching to ferroptosis to target cancer stem cells death thereby preventing cancer relapse. To the best of our knowledge, this is the first review to demonstrate the importance of intracellular iron in regulating the switching of tumor cells and therapy resistant CSCs from apoptosis to ferroptosis. 相似文献
5.
L. H. Tagle J. F. Neira F. R. Diaz R. S. Ramirez 《Journal of polymer science. Part A, Polymer chemistry》1975,13(12):2827-2833
Novel polyamide-imides were prepared from 3′,4′-dicarboxy-4″-chloroformyl terephthaloylphenone anhydride and various aromatic and aliphatic diamines. The polymers were characterized by viscosity, infrared spectra, TGA, DSC, and elemental analysis. The thermal stability of the films was comparable to that of polyamide-imides previously reported. 相似文献
6.
A multivariate calibration method was applied to improve the accuracy of the determination of cadmium in the presence of potassium by total reflection X-ray fluorescence (TXRF). Due to TXRF's relatively low resolution, a particular interference caused by potassium at line Kα 3.31 keV as interference can compromise the cadmium determination at line Lα 3.13 keV, respectively. The method is based on the hypothesis that the application of a multivariate calibration method, for example, partial least squares, could reduce variations due to interference and, consequently, improve the selectivity and accuracy in Cd determination. In this work, this strategy was evaluated on the X-ray fluorescence emission signals between 2.50 and 3.90 keV for a set of 26 different synthetic calibration mixtures and eight different mixtures for external calibration. Based on a certified reference material (Clay 2—CRM051) with high potassium levels, a significant improvement of accuracy for cadmium determination was observed, overcoming the problems associated with spectral interferences by potassium. 相似文献
7.
Daniela Mennickent Rosario del Pilar Castillo Juan Araya José Yamil Neira 《X射线光谱测定》2022,51(2):142-150
The high sensitivity Compton and Rayleigh X-ray scattering signals can be used to gain valuable information on the chemical composition of various matrices, by exploiting the ratio of those signals as a function of the effective atomic number (Zeff). Neither total reflection X-ray fluorescence (TXRF) nor the effect of the experimental setup, including sample preparation, X-ray excitation source selection, and band deconvolution procedure, has been assessed in this kind of approach. Here, a Compton/Rayleigh ratio and Zeff-based TXRF method was set up and tested as an analytical tool for milk samples differentiation. The method was developed using a 90° scattering angle and assessed using different X-ray excitation sources: a molybdenum tube (Mo Kα 17.5 KeV) and a tungsten tube (W Lα 8.5 KeV and W-Brems 35 KeV). The evaluation of independent Compton and Rayleigh signals was performed by non-Gaussian and Gaussian curve resolution methods, and both height and area-based calculations were evaluated. Different sample preparation conditions were assessed. By using 11 standard materials, a calibration curve for Compton/Rayleigh ratio versus Zeff was established. The method was tested to determine the Zeff of milk samples, which enabled its use as a parameter to differentiate them. Good precisions were obtained with the Mo excitation source and the area-based calculations, which allowed to differentiate undiluted milk samples by species, treatment, and fat content according to their Compton/Rayleigh ratio. This simple and rapid method has the potential to be used for the differentiation of various types of samples, including liquids, solids, and aerosols. 相似文献
8.
Nuhanović Mirza Smječanin Narcisa Mulahusić Neira Sulejmanović Jasmina 《Journal of Radioanalytical and Nuclear Chemistry》2021,328(2):617-626
Journal of Radioanalytical and Nuclear Chemistry - Modified pomegranate peel was utilized as a sorbent for the biosorption of uranium(VI) from the aqueous solution. The biosorbent was characterized... 相似文献
9.
V. V. Gruzinskii M. A. Senyuk Neira Buéno Oscar Leon L. Sh. Afanasiadi 《Journal of Applied Spectroscopy》1991,54(4):373-376
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 4, pp. 600–604, April, 1991. 相似文献
10.
De la Fuente JR Neira V Saitz C Jullian C Sobarzo-Sanchez E 《The journal of physical chemistry. A》2005,109(26):5897-5904
Photoreduction by amines of oxoisoaporphine dyes occurs via a stepwise mechanism of electron-proton-electron transfer that leads to the metastable N-hydrogen oxoisoaporphine anion. During photoreduction that occurs from the triplet manifold of the oxoisoaporphine, a radical ion A(-)(*), a neutral-hydrogenated radical A-NH(*), and the metastable ion A-NH(-) of the oxoisoaporphine are formed. We present time-resolved spectroscopic data and quantum mechanical semiempirical PM3 and ZINDO/S results for the transient species formed during the flash photolysis of oxoisoaporphines in the presence of amines. These calculations reproduce adequately the experimental spectra of the triplet-triplet absorption near 450 nm, and that of neutral hydrogenated radical of the studied oxoisoaporphines centered at 390 nm. A transient absorption observed near 490 nm, for all of the studied systems, was explained by considering the formation of radical ion pair between the radical anion of the oxoisoaporphine, A(-)(*), and the radical cation of the amine, whose ZINDO/S calculated spectra generate the strongest transition near the experimentally observed absorption maximum at 490 nm, supporting the formation of a radical ion pair complex as the first step of the photoreduction. 相似文献