Two novel subphthalocyanines substituted axially with a BODIPY or distyryl BODIPY moiety have been synthesized. Both systems exhibit a highly efficient photoinduced energy transfer process, either from the excited BODIPY to the subphthalocyanine core (for the former) or from the excited subphthalocyanine to the distyryl BODIPY unit (for the latter).

Peptides adducted with different divalent Group IIB metal ions (Zn 2+ , Cd 2+ , and Hg 2+ ) were found to give very different ECD mass spectra. ECD of Zn 2+ adducted peptides gave series of c-/z-type fragment ions with and without metal ions. ECD of Cd 2+ and Hg 2+ adducted model peptides gave mostly a-type fragment ions with M +• and fragment ions corresponding to losses of neutral side chain from M +• . No detectable a-ions could be observed in ECD spectra of Zn 2+ adducted peptides. We rationalized the present findings by invoking both proton-electron recombination and metal-ion reduction processes. . The relative population of these precursor ions depends largely on the acidity of the metal-ion peptide complexes. Peptides adducted with divalent metal-ions of small ionic radii (i.e., Zn 2+ ) would form predominantly species (b) and (c); whereas peptides adducted with metal ions of larger ionic radii (i.e., Hg 2+ ) would adopt predominantly species (a). Species (b) and (c) are believed to be essential for proton-electron recombination process to give c-/z-type fragments via the labile ketylamino radical intermediates. Species (c) is particularly important for the formation of non-metalated c-/z-type fragments. Without any mobile protons, species (a) are believed to undergo metal ion reduction and subsequently induce spontaneous electron transfer from the peptide moiety to the charge-reduced metal ions. Depending on the exothermicity of the electron transfer reaction, the peptide radical cations might be formed with substantial internal energy and might undergo further dissociation to give structural related fragment ions.

yielded abundant metalated a-/y-type fragment ions; whereas ECD of Cu 2+ adducted peptides generated predominantly metalated b-/y-type fragment ions. From the present experimental results, it was postulated that electronic configuration of metal ions is an important factor in determining the ECD behavior of the metalated peptides. Due presumably to the stability of the electronic configuration, metal ions with fully-filled (i.e., Zn 2+ ) and half filled (i.e., Mn 2+ ) d-orbitals might not capture the incoming electron. Dissociation of the metal ions adducted peptides would proceed through the usual ECD channel(s) via "hot-hydrogen" or "superbase" intermediates, to form series of c-/z• -fragments. For other transition metal ions studied, reduction of the metal ions might occur preferentially. The energy liberated by the metal ion reduction would provide enough internal energy to generate the "slow-heating" type of fragment ions, i.e., metalated a-/yfragments and metalated b-/y-fragments.

Many aromatic compounds (e.g., polycyclic aromatic hydrocarbons (PAHs)) found in atmospheric aerosols are toxic and exist in both unsubstituted and substituted forms. Previous studies have mainly concentrated on investigating unsubstituted PAHs, leaving the substituted compounds largely uncharacterized. This study focuses on detection of both unsubstituted and substituted aromatics in ambient aerosol samples using ultrahigh-resolution mass spectrometry. Aerosol samples collected from roadside, urban, and suburban sites in Hong Kong were characterized by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) coupled with atmospheric pressure photoionization (APPI) or electrospray ionization (ESI). In the APPI+ mode, 166 aromatic CH formulas (i.e., formulas containing C and H only and with a double bond equivalent (DBE) of 4 or higher) were determined through molecular formula calculations based on an accurate m/z determination. Among the determined aromatic CH formulas, 141 are possible alkylated monocyclic aromatic hydrocarbon (MAH) or PAH formulas, and account for ≥ 45% of the total intensity by aromatic CH+ formulas. Both APPI+ and ESI+ are effective in detecting nitroaromatics (i.e., CHON formulas and DBE ≥ 5). The two ionization modes provide complementary formula coverage, with formulas determined by APPI+ extending to higher DBE and those by ESI+ covering higher carbon numbers. Alkylated nitrobenzene compounds are the most abundant among nitroaromatics, and they, together with alkylated nitro-PAHs, account for > 80% of the total intensity of aromatic CHON+ formulas, indicating the importance of these compounds in real aerosol samples. Aromatic CHN+ and CHO+ formulas are also determined, confirming the atmospheric presence of some previously reported O- and N-containing aromatic compounds and revealing new possible formulas. The determination of aromatic organic formulas in this study provides useful guidance for future quantitative analysis of hazardous aromatic compounds. Future work is needed to determine the abundance and to study the toxicity of alkylated MAHs and PAHs outside the 16 US EPA priority PAH compounds. Graphical abstract.