A cesium 6S(1/2) --> 8S(1/2) two-photon-transition (TPT)-stabilized 822.5 nm diode laser is reported for the first time to our knowledge. Allan deviation of 4.4 x 10(-13) (60 s) was achieved, and the possible systematic errors were evaluated as smaller than 2 kHz. We demonstrate that the cesium TPT-stabilized diode laser could be a reliable frequency reference at 822.5 nm wavelength.
A systematic study of the negative-ion chemical ionization mass spectra produced by the reaction of F− with a wide variety of organic compounds has been accomplished. A time-of-flight mass spectrometer fitted with a modified high pressure ion source was employed for these experiments. The F− reagent ion was generated from CF3H or NF3, typically at an ion source pressure of 100 μm. In pure NF3, F− is the major ion formed and constitutes more than 90% of the total ion intensity. While F− is also the major primary ion formed in pure CF3H, it undergoes rapid ion-molecule reactions at elevated source pressures, yielding (HF)nF− (n = 1−3) ions, which makes CF3H less suitable as a chemical ionization reagent gas. Among the organic compounds investigated were carboxylic acids, ketones, aldehydes, esters, alcohols, phenols, halides, nitriles, nitrobenzene, ethers, amines and hydrocarbons. An intense (M − 1)− ion was observed in the F− chemical ionization mass spectra of carboxylic acids, ketones, aldehydes and phenols. Alcohols yield only (M + F)− ions upon reaction with F−. A weaker (M + F)− ion was also detected in the F− chemical ionization spectra of carboxylic acids, aldehydes, ketones and nitriles. The F− chemical ionization mass spectra of esters, halides, nitriles, nitrobenzene and ethers are characterized primarily by the ions, RCOO−, X−, CN−, NO2−, and OR−, respectively. In addition, esters show a very weak (M − 1)− ion (except formates). In the F− chemical ionization spectra of some aliphatic alkanes and o-xylene, a very weak (M + F)− ion was observed. Amines and aliphatic alkenes exhibit only insignificant fragment ions under similar conditions, while aromatic hydrocarbons, such as benzene and toluene are not reactive at all with the F− ion. The mechanisms of the various reactions mentioned are discussed, and several experimental complications are noted. In still other studies, the effects of varying several experimental parameters, including source pressure, relative proportions of the reagent and analyte, and other ion source parameters, on the observed chemical ionization mass spectra were also investigated. In a mixture of NF3 and n-butanol, for example, the ratio of the intensities of the ions characteristic of the alcohol to that of the (HF)nF− ion was found to decrease with increasing sample pressure, with increasing NF3 pressure, and with increasing electron energy. No significant effects on the spectra were observed to result from variation of the source repeller field or the source temperature. The addition of argon to the source as a potential moderator did not alter the F− chemical ionization spectrum significantly, but the use of oxygen appears to inhibit formation of the (HF)nF− cluster ion. The advantages of using F− as a chemical ionization reagent are discussed, and comparisons are made with other reagent ions.
Conventional linear ion trap mass analyzers (LIT-MS) provide high ion capacity and show their MS ability; however, the detection of high mass ions is still challenging because LIT-MS with secondary electron detectors (SED) cannot detect high mass ions. To detect high mass ions, we coupled a charge detector (CD) to a rectilinear ion trap mass spectrometer (RIT-MS). Immunoglobulin G ions (m/z ~150,000) are measured successfully with controlled ion kinetic energy. In addition, when mass-to-charge (m/z) ratios of singly charged ions exceed 10 kTh, the detection efficiency of CD is found to be greater than that of SED. The CD can be coupled to LIT-MS to extend the detection mass range and provide the potential to perform MS of high mass ions inside the ion trap. Graphical Abstract ᅟ.
A systematic study of the negative-ion chemical ionization mass spectra produced by the reaction of F(-) with a wide variety of organic compounds has been accomplished. A time-of-flight mass spectrometer fitted with a modified high pressure ion source was employed for these experiments. The F(-) reagent ion was generated from CF(3)H or NF(3), typically at an ion source pressure of 100 mum. In pure NF(3), F(-) is the major ion formed and constitutes more than 90% of the total ion intensity. While F(-) is also the major primary ion formed in pure CF(3)H, it undergoes rapid ion-molecule reactions at elevated source pressures, yielding (HF)(n)F(-) (n = 1-3) ions, which makes CF(3)H less suitable as a chemical ionization reagent gas. Among the organic compounds investigated were carboxylic acids, ketones, aldehydes, esters, alcohols, phenols, halides, nitriles, nitrobenzene, ethers, amines and hydrocarbons. An intense (M - 1)(-) ion was observed in the F(-) chemical ionization mass spectra of carboxylic acids, ketones, aldehydes and phenols. Alcohols yield only (M + F)(-) ions upon reaction with F(-). A weaker (M + F)(-) ion was also detected in the F(-) chemical ionization spectra of carboxylic acids, aldehydes, ketones and nitriles. The F(-) chemical ionization mass spectra of esters, halides, nitriles, nitrobenzene and ethers are characterized primarily by the ions, RCOO(-), X(-), CN(-), NO(2) (-), and OR(-), respectively. In addition, esters show a very weak (M - 1)(-) ion (except formates). In the F(-) chemical ionization spectra of some aliphatic alkanes and o-xylene, a very weak (M + F)(-) ion was observed. Amines and aliphatic alkenes exhibit only insignificant fragment ions under similar conditions, while aromatic hydrocarbons, such as benzene and toluene are not reactive at all with the F(-) ion. The mechanisms of the various reactions mentioned are discussed, and several experimental complications are noted. In still other studies, the effects of varying several experimental parameters, including source pressure, relative proportions of the reagent and analyte, and other ion source parameters, on the observed chemical ionization mass spectra were also investigated. In a mixture of NF(3) and n-butanol, for example, the ratio of the intensities of the ions characteristic of the alcohol to that of the (HF)(n)F(-) ion was found to decrease with increasing sample pressure, with increasing NF(3) pressure, and with increasing electron energy. No significant effects on the spectra were observed to result from variation of the source repeller field or the source temperature. The addition of argon to the source as a potential moderator did not alter the F(-) chemical ionization spectrum significantly, but the use of oxygen appears to inhibit formation of the (HF)(n)F(-) cluster ion. The advantages of using F(-) as a chemical ionization reagent are discussed, and comparisons are made with other reagent ions.
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