Hot Branching Dynamics in a Light‐Harvesting Iron Carbene Complex Revealed by Ultrafast X‐ray Emission Spectroscopy

Iron N‐heterocyclic carbene (NHC) complexes have received a great deal of attention recently because of their growing potential as light sensitizers or photocatalysts. We present a sub‐ps X‐ray spectroscopy study of an Fe^IINHC complex that identifies and quantifies the states involved in the deactivation cascade after light absorption. Excited molecules relax back to the ground state along two pathways: After population of a hot ³MLCT state, from the initially excited ¹MLCT state, 30 % of the molecules undergo ultrafast (150 fs) relaxation to the ³MC state, in competition with vibrational relaxation and cooling to the relaxed ³MLCT state. The relaxed ³MLCT state then decays much more slowly (7.6 ps) to the ³MC state. The ³MC state is rapidly (2.2 ps) deactivated to the ground state. The ⁵MC state is not involved in the deactivation pathway. The ultrafast partial deactivation of the ³MLCT state constitutes a loss channel from the point of view of photochemical efficiency and highlights the necessity to screen transition‐metal complexes for similar ultrafast decays to optimize photochemical performance.     

Carboxymethylated nanofibrillated cellulose: rheological studies

The rheological properties of carboxymethylated nanofibrillated cellulose (NFC), investigated with controlled shear rate- and oscillatory measurements, are reported for the first time. It was shown that the rheological properties of the studied system are similar to those reported for other NFC systems. The carboxymethylated NFC systems showed among other things high elasticity and a shear thinning behaviour when subjected to increasing shear rates. Further, the shear viscosity and storage modulus of the system displayed power-law relations with respect to the dry content of the NFC suspension. The exponential values, 2 and 2.4 respectively, were found to be in good agreement with both theoretical predictions and published experimental work. Furthermore, it was found that the pulp consistency at which NFC is produced affects the properties of the system. The rheological studies imply that there exists a critical pulp concentration below which the efficiency of the delamination process diminishes; the same adverse effect is also observed when the critical concentration is significantly exceeded due to a lower energy input during delamination.     

A discussion of the problem of determining multiple lifetimes from picosecond absorption recovery data as encountered in two carbocyanine dyes

Absorption recovery kinetics data on the picosecond time-scale of a high signalto-noise ratio can be obtained by using continuously operating synchronously modelocked dye lasers. We show that such data make it possible to determine multiple exponential decays with small differences in rate constants. We also show that an absolute prerequisite to accomplish this is that the measurements are performed at a number of different wavelengths, and that the decays are monitored in a time interval corresponding to several lifetimes. These considerations are demonstrated by measurements on two carbocyanine dyes, DQOCI and pinacyanol, respectively.     

High spin collective excitations in 101Ru

The energy level structure of ¹⁰¹Ru was studied using the reactions ¹⁰⁰Mo(α, 3n)¹⁰¹Ru and ¹⁰⁰Mo(³He, 2n)¹⁰¹Ru. Excitation functions, γγ coincidences and γ-ray angular distributions were measured. Three ΔI = 2 cascades proceeding to a $\text{5}\text{2}{}^{\mathrm{+}}$, $\text{7}\text{2}{}^{\mathrm{+}}$ and $\text{11}\text{2}{}^{\mathrm{?}}$ state were observed. A decay scheme is presented showing energies up to 5849 keV and spins up to $\text{35}\text{2}$. The bands are discussed within the framework of the Nilsson model with Coriolis coupling in which the recoil effect has been properly introduced.     

Ultrafast terahertz photoconductivity of bulk heterojunction materials reveals high carrier mobility up to nanosecond time scale

The few-picosecond (ps) decay of terahertz (THz) photoconductivity typically observed for conjugated polymer:fullerene blends (at excitation fluencies ~10(15) photons/cm(2) per pulse) is shown to be a result of charge pair annihilation for two polymer:PCBM blends. At a factor of 100 lower excitation density, the THz decay is in the hundreds of ps time scale, implying that very high carrier mobility (~0.1 cm(2) V(-1) s(-1)) prevails for long time after charge formation, of importance for free charge formation in organic solar cells.     

Synthesis and electron transfer studies of ruthenium-terpyridine-based dyads attached to nanostructured TiO2

A series of bis(terpyridine)RuII complexes have been prepared, where one of the terpyridines is functionalized in the 4'-position by a phosphonic or carboxylic acid group for attachment to TiO2. The other is functionalized, also in the 4'-position, by a potential electron donor. In complexes 1a, 3a, and 4a,b, this donor is tyrosine or hydrogen-bonded tyrosine, while in 2a it is carotenoic amide. The synthesis and photophysical properties of the complexes are discussed. On irradiation with visible light, the formation of a long-lived charge-separated state was anticipated, via primary electron ejection into the TiO2, followed by secondary electron transfer from the donor to the photogenerated RuIII. However, such a charge-separated state could be observed with certainty only with complex 2a. To explain the result, quantum chemical calculations were performed on the different types of complexes.     

Method development for identification of ketobemidone metabolites in microdialysate samples by coupled-column capillary liquid chromatography-tandem mass spectrometry

Methodologies for identification of ketobemidone metabolites in microdialysate samples utilizing coupled-column capillary liquid chromatography-electrospray quadrupole time-of-flight tandem mass spectrometry are presented. Two different methods were developed to efficiently analyze the metabolites norketobemidone, ketobemidone N-oxide and hydroxyketobemidone, respectively. Both methods include on-line desalting and trapping of the analytes on micro-solid-phase extraction columns with different retention mechanisms. Norketobemidone and ketobemidone N-oxide were trapped on a C18 column and then eluted by back-flush followed by isocratic separation on a fluorinated reversed-phase type silica gel column (Fluofix). Retention equations are proposed for the chromatographic observations made on the Fluofix column. Hydroxyketobemidone was trapped on a phenylboronic acid column by complex formation at basic pH and then eluted at acidic pH directly into to the mass spectrometer. Oxidation of hydroxyketobemidone to its corresponding quinone was also observed. The methods were successfully used to analyze synthetic ketobemidone metabolites in dilute low-volume microdialysis samples.