Differential spectrometry

Toschek and coworkers 345) used a technique called tuned laser differential spectrometry which is based on simultaneous interaction of gas atoms with two different laser beams, one of these being a weak probe beam the tuning of which scans the saturation on the common level of the two transitions induced by the other beam 346) The experiment employed the two He-Ne laser lines at X = 1.15 ju and X = 0.6328 which share the common lower level. 

The data were taken from H. von Halban G. Kortiim, Z. Elektrochem. 40 (1934) 502. Weighed amounts of 2,4-dinitrophenol were dissolved in carbonate-free water, and were compared by differential spectrometry with similarly weighed solutions of the same dye in 5 mM NaOH, in which... 

Table 6.1-1 The total analytical concentration Cof 2,4-dinitrophenol in water, and the resulting concentration [A-] of2,4-dinitrophenolateas measured by differential spectrometry.

Another frequently used technique involves the detection of some physical or chemical change in either biomacromolecule or the ligand upon binding, such as differential spectrometry or changes in biological activities. The fractional saturation, 0, which expresses the fraction of sites in biomacromolecule occupied by ligand, A can be written as... 

Haemoglobin can also be determined after complex formation with inositol hexaphosphate that is quantified by differential spectrometry to avoid the strong absorbance of the protein. 

Allen, H. C. Brauers, T. Finlayson-Pitts, B. J. Illustrating Deviations in the Beer-Lambert Law in an Instrumental Analysis Laboratory Measuring Atmospheric Pollutants by Differential Optical Absorption Spectrometry, /. Chem. 

In many applications in mass spectrometry (MS), the sample to be analyzed is present as a solution in a solvent, such as methanol or acetonitrile, or an aqueous one, as with body fluids. The solution may be an effluent from a liquid chromatography (LC) column. In any case, a solution flows into the front end of a mass spectrometer, but before it can provide a mass spectrum, the bulk of the solvent must be removed without losing the sample (solute). If the solvent is not removed, then its vaporization as it enters the ion source would produce a large increase in pressure and stop the spectrometer from working. At the same time that the solvent is removed, the dissolved sample must be retained so that its mass spectrum can be measured. There are several means of effecting this differentiation between carrier solvent and the solute of interest, and thermospray is just one of them. Plasmaspray is a variant of thermospray in which the basic method of solvent removal is the same, but the number of ions obtained is enhanced (see below). 

A common mistake for beginners in mass spectrometry is to confuse average atomic mass and isotopic mass. For example, the average atomic mass for chlorine is close to 35.45, but this average is of the numbers and masses of Cl and Cl isotopes. This average must be used for instruments that cannot differentiate isotopes (for example, gravimetric balances). Mass spectrometers do differentiate isotopes by mass, so it is important in mass spectrometry that isotopic masses be used... 

Qualitative. The classic method for the quaUtative determination of silver ia solution is precipitation as silver chloride with dilute nitric acid and chloride ion. The silver chloride can be differentiated from lead or mercurous chlorides, which also may precipitate, by the fact that lead chloride is soluble ia hot water but not ia ammonium hydroxide, whereas mercurous chloride turns black ia ammonium hydroxide. Silver chloride dissolves ia ammonium hydroxide because of the formation of soluble silver—ammonia complexes. A number of selective spot tests (24) iaclude reactions with /)-dimethy1amino-henz1idenerhodanine, ceric ammonium nitrate, or bromopyrogaHol red [16574-43-9]. Silver is detected by x-ray fluorescence and arc-emission spectrometry. Two sensitive arc-emission lines for silver occur at 328.1 and 338.3 nm. 

Thermogravimetric analysis has also been used in conjunction with other techniques, such as differential thermal analysis (DTA), gas chromatography, and mass spectrometry, for the study and characterisation of complex materials such as clays, soils and polymers.35... 

The power of mass spectrometry lies in the fact that the mass spectra of many compounds are sufficiently specific to allow their identification with a high degree of confidence, if not with complete certainty. If the analyte of interest is encountered as part of a mixture, however, the mass spectrum obtained will contain ions from all of the compounds present and, particularly if the analyte of interest is a minor component of that mixture, identification with any degree of certainty is made much more difficult, if not impossible. The combination of the separation capability of chromatography to allow pure compounds to be introduced into the mass spectrometer with the identification capability of the mass spectrometer is clearly therefore advantageous, particularly as many compounds with similar or identical retention characteristics have quite different mass spectra and can therefore be differentiated. This extra specificity allows quantitation to be carried out which, with chromatography alone, would not be possible. 

Resolution is a term encountered in many areas of analytical science and refers to the abihty to differentiate between closely related signals. In mass spectrometry, these signals are the m/z ratios of the ions, with the resolution being defined mathematically as follows ... 

Walter, W.D. Leslie, Jr., D.M. (2009). Stable isotope ratio analysi to differentiate temporal diets of a free-ranging herbivore. Rapid Communications in Mass Spectrometry, Vol. 23, pp. 2190-2194. (http //dx.doi.org/10.1002/rcm.4135)... 

Thermal properties of several chlorinated phenols and derivatives were studied by differential thermal analysis and mass spectrometry and in bulk reactions. Conditions which might facilitate the formation of stable dioxins were emphasized. No two chlorinated phenols behaved alike. For a given compound the decomposition temperature and rate as well as the product distribution varied considerably with reaction conditions. The phenols themselves seem to pyro-lyze under equilibrium conditions slowly above 250°C. For their alkali salts the onset of decomposition is sharp and around 350°C. The reaction itself is exothermic. Preliminary results indicate that heavy ions such as cupric ion may decrease the decomposition temperature. 

A differential vapour-pressure technique has been used to determine the molecular weights of phosphonic and phosphinic acids in 95% ethanol. Cryoscopic and n.m.r. studies have been made on solutions of phosphinic acids in sulphuric acid and oleum. Mass spectrometry has indicated the ready formation of phosphinylium ions after electron bombardment of phosphonic and phosphinic acids and their derivatives. However, the cryoscopic results in sulphuric acid indicated that reaction did not proceed beyond protonation, and the n.m.r. study on oleum solutions suggested that sulphonation occurred. 

Mazzuca, P. et al.. Mass spectrometry in the study of anthocyanins and their derivatives differentiation of Vitis vinifera and hybrid grapes by liquid chromatogra-phy/electrospray ionization mass spectrometry and tandem mass spectrometry, J. Mass Spectrom., 40, 83, 2005. 

Breithaupt, D.E., Wirt, U., and Bamedi, A., Differentiation between lutein monoester regioisomers and detection of lutein diesters from marigold flowers (Tagetes erecta L.) and several fruits by liquid chromatography-mass spectrometry, J. Agric. Food Chem. 50, 66, 2002. 

In conclusion, synthetic dyes can be determined in solid foods and in nonalcoholic beverages and from their concentrated formulas by spectrometric methods or by several separation techniques such as TEC, HPLC, HPLC coupled with diode array or UV-Vis spectrometry, MECK, MEECK, voltammetry, and CE. ° Many analytical approaches have been used for simultaneous determinations of synthetic food additives thin layer chromatography, " " derivative spectrophotometry, adsorptive voltammetry, differential pulse polarography, and flow-through sensors for the specific determination of Sunset Yellow and its Sudan 1 subsidiary in food, " but they are generally suitable only for analyzing few-component mixtures. 

In situ analysis of the reaction products can also be carried out by mass spectrometry, using the differential electrochemical mass spectrometry (DBMS) technique.This technique permits the detection of gaseous products since they are produced and captured through a porous electrode. It has been confirmed that carbon dioxide is the main reaction product. With this technique, it is also possible to determine the production of CO2... 

The chemical compositions of the isolated Au SR clusters were investigated by mass spectrometry [15,16,18, 22,32-35]. TEM was used to confirm that the species detected by the mass spectrometer represents the clusters in the sample. Figure 3a is a schematic representation of the top view of the mass spectrometer, which consists of five stages of differentially pumped vacuum chambers. The apparatus accommodates two t5 pes of ion sources, electrospray ionization (ESI) and laser-desorption ionization (EDI), and a time-of-flight (TOE) mass spectrometer with a reflectron. Details of the apparatus and the measurement protocols are described below. 

The most significant differences (i.e. independence) in the analytical methods are provided in the final chromatographic separation and detection step using GC/ MS and LC-FL. GC and reversed-phase LG provide significantly different separation mechanisms for PAHs and thus provide the independence required in the separation. The use of mass spectrometry (MS) for the GC detection and fluorescence spectroscopy for the LG detection provide further independence in the methods, e.g. MS can not differentiate among PAH isomers whereas fluorescence spectroscopy often can. For the GC/MS analyses the 5% phenyl methylpolysiloxane phase has been a commonly used phase for the separation of PAHs however, several important PAH isomers are not completely resolved on this phase, i.e. chrysene and triphenylene, benzo[b]fluoranthene and benzofjjfluoranthene, and diben-z[o,h]anthracene and dibenz[a,c]anthracene. To achieve separation of these isomers, GC/MS analyses were also performed using two other phases with different selectivity, a 50% phenyl methylpolysiloxane phase and a smectic liquid crystalline phase. 

Jusys Z, Behm RJ. 2001. Methanol oxidation on a carbon-supported Pt fuel cell catalyst—A kinetic and mechanistic study by differential electrochemical mass spectrometry. J Phys ChemB 105 10874-10883. 

Heinen M, Jusys Z, Behm RJ. 2009. Reaction pathways analysis and reaction intermediate detection via simultaneous differential electrochemical mass spectrometry (DBMS) and attenuated total reflection Bourier transform infrared spectroscopy (ATR-BTIRS). In Vielstich W, Gasteiger HA, Yokokawa H, eds. Handbook of Buel Cells. Volume 5 Advances in Electrocatalysis. Chichester John Wiley Sons, Ltd., in press. 

Jambunathan K, Jayataman S, HiUier AC. 2004. A multielectrode electrochemical and scanning differential electrochemical mass spectrometry study of methanol oxidation on electrodepos-ited PORUy. Langmuir 20 1856 1863. 

JusysZ. 1994. H/D substitution effect on formaldehyde oxidation rate at a copper anode in alkaline medium studied by differential electrochemical mass spectrometry. J Electroanal Chem 375 257-262. 

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