Grosjean E, Green P G, Grosjean D
DGA, Inc., Suite 205, 4526 Telephone Road, Ventura, California 93003, and Department of Environmental Engineering Science, Environmental Analysis Center, California Institute of Technology, Pasadena, California 91125.
Anal Chem. 1999 May 1;71(9):1851-61. doi: 10.1021/ac981022v.
The (2,4-dinitrophenyl)hydrazones of carbonyls are separated by liquid chromatography and detected by ultraviolet spectroscopy (diode array detector) and by atmospheric pressure negative chemical ionization mass spectrometry. Results are presented for 78 carbonyls including 18 1-alkanals (from formaldehyde to octadecanal), 16 other saturated aliphatic carbonyls (5 C(4)-C(7) aldehydes and 11 C(3)-C(9) ketones), 16 unsaturated aliphatic carbonyls (9 C(3)-C(11) aldehydes and 7 C(4)-C(9) ketones), 13 aromatic carbonyls (including hydroxy- and/or methoxy-substituted compounds), 10 C(2)-C(10) aliphatic dicarbonyls, 3 aliphatic carbonyl esters, and 2 other carbonyls. Isomers were observed for α,β-unsaturated ketones and saturated carbonyls that bear other oxygen-containing substituents, e.g. methoxyacetone, 2-furaldehyde, and the 3 carbonyl esters. For all but two of the carbonyls studied, the base peak in the negative APCI mass spectrum was the M - 1 ion (NO(2))(2)C(6)H(3)NN [Formula: see text] CR(1)R(2) (R(1) = H for aldehydes), where M is the molecular mass of the carbonyl (2,4-dinitrophenyl)hydrazone derivative. The dicarbonyls 2,4-pentanedione and succinic dialdehyde reacted with DNPH to yield predominantly other products. Concentrations measured by ultraviolet spectroscopy (peak area) and by mass spectrometry (abundance of M - 1 ion) were in good agreement. Applications described include the measurement of 34 C(1)-C(18) carbonyls at levels of 0.015-14 parts per billion (ppb) in urban air and the identification of carbonyls at ppb concentrations as reaction products in laboratory studies of the atmospheric oxidation of unsaturated organic compounds.
羰基的（2,4 - 二硝基苯基）腙通过液相色谱进行分离，并通过紫外光谱法（二极管阵列检测器）以及大气压负化学电离质谱法进行检测。文中给出了78种羰基化合物的检测结果，包括18种直链醛（从甲醛到十八醛）、16种其他饱和脂肪族羰基化合物（5种C(4)-C(7)醛和11种C(3)-C(9)酮）、16种不饱和脂肪族羰基化合物（9种C(3)-C(11)醛和7种C(4)-C(9)酮）、13种芳香族羰基化合物（包括羟基和/或甲氧基取代的化合物）、10种C(2)-C(10)脂肪族二羰基化合物、3种脂肪族羰基酯以及2种其他羰基化合物。对于α,β - 不饱和酮和带有其他含氧取代基的饱和羰基化合物（如甲氧基丙酮、2 - 呋喃甲醛和3种羰基酯），观察到了异构体。在所研究的除两种羰基化合物之外的所有化合物中，大气压负离子化学电离质谱中的基峰是M - 1离子(NO(2))(2)C(6)H(3)NN [化学式：见正文] CR(1)R(2)（醛的R(1) = H），其中M是羰基（2,4 - 二硝基苯基）腙衍生物的分子量。二羰基化合物2,4 - 戊二酮和琥珀醛与2,4 - 二硝基苯肼反应主要生成其他产物。通过紫外光谱法（峰面积）和质谱法（M - 1离子丰度）测得的浓度结果吻合良好。所描述的应用包括测定城市空气中浓度为0.015 - 14十亿分之一（ppb）的34种C(1)-C(18)羰基化合物，以及在不饱和有机化合物大气氧化的实验室研究中鉴定ppb浓度下作为反应产物的羰基化合物。
