Fullerenes are graphitic cage structures incorporating exactly twelve pentagons. The smallest possible fullerene is thus C20, which consists solely of pentagons. But the extreme curvature and reactivity of this structure have led to doubts about its existence and stability. Although theoretical calculations have identified, besides this cage, a bowl and a monocyclic ring isomer as low-energy members of the C20 cluster family, only ring isomers of C20 have been observed so far. Here we show that the cage-structured fullerene C20 can be produced from its perhydrogenated form (dodecahedrane C20H20) by replacing the hydrogen atoms with relatively weakly bound bromine atoms, followed by gas-phase debromination. For comparison we have also produced the bowl isomer of C20 using the same procedure. We characterize the generated C20 clusters using mass-selective anion photoelectron spectroscopy; the observed electron affinities and vibrational structures of these two C20 isomers differ significantly from each other, as well as from those of the known monocyclic isomer. We expect that these unique C20 species will serve as a benchmark test for further theoretical studies.

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"One-pot" substitution of the twenty hydrogen atoms in pentagonal dodecahedrane (C(20)H(20)) by OH, F, Cl, and Br atoms is explored. Electrophilic insertion of oxygen atoms with DMDO and TFMDO as oxidizing reagents ended, far off the desired C(20)(OH)(20), in complex polyol mixtures (up to C(20)H(10)(OH)(10) decols, a trace of C(20)H(OH)(19)?). Perfluorination was successful in a NaF matrix but (nearly pure) C(20)F(20) could be secured only in very low yield. "Brute-force" photochlorination (heat, light, pressure, time) provided a mixture of hydrogen-free, barely soluble C(20)Cl(16) dienes in high yield and C(20)Cl(20) as a trace component. Upon electron-impact ionization of the C(20)Cl(16) material sequential loss of the chlorine atoms was the major fragmentation pathway furnishing, however, only minor amounts of chlorine-free C(20) (+) ions. "Brute-force" photobrominations delivered an extremely complex mixture of polybromides with C(20)HBr(13) trienes as the highest masses. The MS spectra exhibited exclusive loss of the Br substituents ending in rather intense singly, doubly, and triply charged C(20)H(4-0) (+(2+)(3+)) ions. The insoluble approximately C(20)HBr(13) fraction (C(20)Br(14) trienes as highest masses) obtained along a modified bromination protocol, ultimately allowed the neat mass selection of C(20) (-) ions. The C(20)Cl(16) dienes and C(20)H(0-3)Br(14-12) tri-/tetraenes, in spite of their very high olefinic pyramidalization, proved resistant to oxygen and dimerization (polymerization) but added CH(2)N(2) smoothly. Dehalogenation of the respective cycloaddition products through electron-impact ionization resulted in C(22-24)H(4-8) (+(2+)) ions possibly constituting bis-/tris-/tetrakis-methano-C(20) fullerenes or partly hydrogenated C(22), C(23), and C(24) cages.

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a fast analysis tool employed for the detection of a broad range of analytes. However, MALDI-MS has a reputation of not being suitable for quantitative analysis. Inhomogeneous analyte/matrix co-crystallization, spot-to-spot inhomogeneity, as well as a typically low number of replicates are the main contributing factors. Here, we present a novel MALDI sample target for quantitative MALDI-MS applications, which addresses the limitations mentioned above. The platform is based on the recently developed microarray for mass spectrometry (MAMS) technology and contains parallel lanes of hydrophilic reservoirs. Samples are not pipetted manually but deposited by dragging one or several sample droplets with a metal sliding device along these lanes. Sample is rapidly and automatically aliquoted into the sample spots due to the interplay of hydrophilic/hydrophobic interactions. With a few microliters of sample, it is possible to aliquot up to 40 replicates within seconds, each aliquot containing just 10 nL. The analyte droplet dries immediately and homogeneously, and consumption of the whole spot during MALDI-MS analysis is typically accomplished within few seconds. We evaluated these sample targets with respect to their suitability for use with different samples and matrices. Furthermore, we tested their application for generating calibration curves of standard peptides with α-cyano-4-hdydroxycinnamic acid as a matrix. For angiotensin II and [Glu(1)]-fibrinopeptide B we achieved coefficients of determination (r(2)) greater than 0.99 without the use of internal standards.

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Electron-impact ionization in a time-of-flight mass spectrometer of C(20)H(0-3)Br(14-12) probes-secured from C(20)H(20) dodecahedrane by a "brute-force" bromination protocol-provided bromine-free C(20)H(0-2(3)) anions in amounts that allowed the clean mass-separation of the hydrogen-free C(20) (-) ions and the photoelectron (PE) spectroscopic characterization as C(20) fullerene (electron affinity (EA)=2.25+/-0.03 eV, vibrational progressions of 730+/-70). The extremely strained C(20) fullerene ions surfaced as kinetically rather stable entities (lifetime of at least the total flight time of 0.4 ms); they only very sluggishly expel a C(2) unit. The HOMO and LUMO are suggested to be almost degenerate (DeltaE=0.27 eV). The assignment as a fullerene was corroborated by the PE characterization of the C(20) bowl (EA=2.17+/-0.03 eV, vibrational progression of 2060+/-50 cm(-1)) analogously generated from C(20)H(10) corannulene (C(20)H(1-3)Br(9-8) samples) and comparably stable. Highly resolved low-temperature PE spectra of the known C(20) ring (EA=2.49+/-0.03 eV, vibrational progressions 2022+/-45 and 455+/-30 cm(-1)), obtained from graphite, display an admixture of, most probably, a bicyclic isomer (EA=3.40+/-0.03 eV, vibrational progression 455+/-30 cm(-1)). The C(20) (+(-)) and C(20)H(2) (+(-)) cluster ions generated from polybrominated perylene (C(20)H(0-2)Br(12-10)) have (most probably) retained the planar perylene-type skeleton (sheet, EA=2.47+/-0.03 eV, vibrational progressions of 2089+/-30 and 492+/-30 cm(-1) and EA=2.18+/-0.03 eV, vibrational progressions of 2105+/-30 and 468+/-30 cm(-1)).

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