Corrole-fullerene dyads: formation of long-lived charge-separated states in nonpolar solvents

The first example of covalently linked free-base corrole-fullerene dyads is reported. In the newly synthesized dyads, the free-energy calculations performed by employing the redox and singlet excited-state energy in both polar and nonpolar solvents suggested the possibility of electron transfer from the excited singlet state of corrole to the fullerene entity. Accordingly, steady-state and time-resolved emission studies revealed efficient fluorescence quenching of the corrole entity in the dyads. Further studies involving femtosecond laser flash photolysis and nanosecond transient absorption studies confirmed electron transfer to be the quenching mechanism, in which the electron-transfer product, the fullerene anion radical, was able to be spectrally characterized. The rate of charge separation, kCS, was found to be on the order of 10(10)-10(11) s(-1), suggesting an efficient photoinduced electron-transfer process. Interestingly, the rate of charge recombination, kCR, was slower by 5 orders of magnitude in nonpolar solvents, cyclohexane and toluene, resulting in a radical ion-pair lasting for several microseconds. Careful analysis of the kinetic and thermodynamic data using the Marcus approach revealed that this novel feature is due to appropriately positioning the energy level of the charge-separated state below the triplet states of either of the donor and acceptor entities in both polar and nonpolar solvents, a feature that was not evident in donor-acceptor dyads constructed using symmetric tetrapyrroles as electron donors.     

Homoleptic group 12 metal bis(mercaptoimidazolyl)borate complexes M(Bm(R))2 (M = Zn,Cd, Hg)

The sodium salt of the bis(2-mercapto-1-methylimidazolyl)borate anion [Bm(Me)](-) and those of the new bis(2-mercapto-1-alkylimidazolyl)borates [Bm(R)](-) (R = Bz, Bu(t), p-Tol) have been readily obtained from NaBH(4) and the appropriate 2-mercapto-1-alkylimidazoles. To contrast the binding preferences of the group 12 metals in a sulfur-rich environment, the four complete series of homoleptic complexes M[Bm(R)](2) (M = Zn, Cd, Hg), including the first bis(mercaptoimidazolyl)borate derivatives of cadmium and mercury, have been prepared. X-ray diffraction studies of Cd[Bm(Me)](2) and M[Bm(tBu)](2) (M = Zn, Cd, Hg) show the presence of distorted tetrahedral [MS(4)] central cores supplemented by two weak vicinal M.H-B bonds, interactions which appear to be a common feature in the coordination chemistry of Bm(R) ligands. In the case of zinc, it has been found that only in the presence of bulky ligands, as in Zn[Bm(tBu)](2), may an unexpected expansion in the coordination number from four to six be induced. This observation suggests the viability of octahedral intermediates in the processes whereby certain zinc enzymes transfer or exchange metal ions.     

Application of normal-phase high-performance liquid chromatography followed by gas chromatography for analytics of diesel fuel additives

The paper presents the results of investigations on new procedures of determination of selected cleaning additives in diesel fuel. Two procedures: one-step analysis using gas chromatography with flame ionization detection (GC-FID) or mass spectrometry (GC-MS) and a two-step procedure in which normal-phase high-performance liquid chromatography (NP-HPLC) was used for preliminary separation of the additives, were compared. The additive fraction was collected using either simple elution or eluent backflush. Final determinations were performed by GC-FID and GC-MS. The studies revealed that it was impossible to determine the investigated analytes by one-step procedures, i.e. by using solely HPLC or GC. On the other hand, the use of a two-step procedure ensures reproducible results of determinations, and the limits of quantitation are, depending on the method of fraction collection by HPLC, from 1.4–2.2 ppm (GC-MS in SIM mode) to 9.6–24.0 ppm (GC-FID). Precision and accuracy of the developed procedures are compared, and possible determination errors and shortcomings discussed.

Binding of CO, NO, and O2 to heme by density functional and multireference ab initio calculations

Using the CASSCF/CASPT2 approach, along with several DFT methods (PBE0, B3LYP, BP86, OLYP), we have investigated the bonding of CO, NO, and O2 molecules to two model heme systems: an iron(II) porphyrin with and without an axial imidazole ligand. The experimentally available binding energies are best reproduced by the CASPT2 method and with the OLYP functional. The other functionals considered perform much worse, either severely overbinding (BP86) or underbinding (B3LYP, PBE0). Significant discrepancies between the different density functionals are observed, not only for the energetics but sometimes also for structure predictions. This confirms our viewpoint that a balanced treatment of the electronic exchange and correlation is vital to describe the weak metal-ligand bond between heme and CO, NO, or O2. The binding energies DeltaEb were split into two contributions: the so-called spin-pairing energy DeltaE sp and the "inherent" binding energy DeltaEb0, and both contributions were analyzed in terms of method and basis set effects. We have also investigated the spin density distributions resulting from the bonding of the NO molecule (a noninnocent ligand) to heme. Our analysis at the DFT and CASSCF level shows that, while various density functionals predict qualitatively very different spin distributions, the CASSCF spin populations most closely correspond to the results obtained with the pure BP86 or OLYP rather than with the hybrid functionals.     

Quantitative High - Resolution Gas Chromatography and High - Resolution Gas Chromatography/Mass Spectrometry Analyses of Carbonaceous Fine Aerosol Particles

Abstract

Methods have been developed for the quantification of low-microgram levels of the extractable organic matter contained in the atmospheric fine aerosol fraction. Extract quantification is accomplished by computer-assisted high-resolution gas chromatography (HRGC) used in conjunction with a procedural recovery mixture containing perdeuterated compounds of differing polarity and molecular weight. Recovery data for these species indicate that relative volatility rather than functional group classification is the primary factor affecting overall recovery. Routine quality control analysis is performed on a per-sample basis by high-resolution gas chromatography/mass spectrometry (HRGC/MS) for confirmation of the standard components and for identification of procedural contaminants. By the way of illustration, fine aerosol samples have been analyzed from Anaheim. California. The absolute solvent extract yields range from 49 to 346μg of organic carbon, and demonstrate a seasonal variation with winter maximum and summer minimum concentrations.     

Protonated serine octamer cluster: structure elucidation by gas-phase H/D exchange reactions

The H/D exchange kinetics of the protonated serine octamer was investigated by both flow-tube and FT-ICR experiments. The exchange was observed to be bimodal in agreement with previous observations. Quantitative analysis of the experimental results led to site-specific H/D exchange rate constants on the basis of which the structures of both ion populations were deduced. We observe the two separate conformers exchanging 33 hydrogens each-in an independent manner and at different rates. This result was achieved through a probabilistic algorithm that groups together equivalent hydrogen atoms having equal rate constants. The slower exchanging population A is assigned an all-zwitterionic structure. Its faster exchanging counterpart B is assigned an all-neutral structure. Population A was found to be more stable toward collision-induced activation than population B. All of these findings are consistent with previous experimental results, thus comprising a self-consistent picture of the protonated serine octamer and its gas-phase properties.