New Method for Determination of Excited State Lifetime

The use of optical methods for the detection of plasma waves requires the consideration of propagation properties of waves as well as the excited state lifetimes. In case of known propagation properties of waves the excited state lifetime can be determined from the frequency-dependent decrease of the wave amplitude. The proposed technique represents a new independent method for the determination of excited state lifetimes. This paper deals with first studies on excited state lifetime based on the frequency response of the amplitude of free streaming electron waves in He-dc-discharges. The results demonstrate the correctness of the idea about the decrease of wave signal in consequence of excited state lifetime.     

Taxol Inclusion Complexes with a Cyclodextrin Dimer: Possibilities to Detoxify Chemotherapeutics and to Target Drugs Specifically to Tumors?

The natural drug, paclitaxel (taxol), is highly effectiveas a tumor chemotherapeuticwith a low probability of inducing chemoresistance,but shows severe toxic side effectsat the therapeutic dose. How can this toxicitybe overcome? Here we report the synthesisof cyclodextrin dimers connected at thesecondary face by amide-bonded aliphatic spacers. The spacer length of one of the dimers referred to asdiβCD(2N-A4C5A4) or dimer 7cmatches the distance between the twobenzoic acid residues of paclitaxel. We investigated the physical inclusion of taxol into this dimer using the TNS-label competition method. Affinity constants with the dimer in comparison to free β-cyclodextrin are found to be of the order of 10⁷ l/mole.When included into the cyclodextrin dimer, the drug shows a considerable time delay of incorporation into human tumor cell cultures (OAT SCLC cells) or a total exclusion from the cells. This is the prerequisite to avoid intoxication of other organs of a patient. Possibilities are discussed to detoxify chemotherapeutics and to target their inclusioncomplexes specifically to tumors using specific biological signals.     

Fluorescence imaging of frit effects in capillary separations

The gradient of five dansylated amino acids in a capillary-based separation system commonly used in capillary liquid chromatography (LC) or capillary electrochromatography (CEC) was followed and examined in detail using a detection method based on laser-induced fluorescence imaging. The detection system consisted of an XeCl excimer laser and an image-intensified charge-coupled device (CCD) camera. Fluorescence intensity profiles along the capillary column were displayed and continuously updated on a computer screen. The detector system enabled the separation dynamics in the column to be monitored. The experiments were focused on the course of events, especially at interfaces. The processes occurring at the beginning of the reversed-phase packing material were studied as well as at the transition from stationary phase to the outlet frit and the open tubular area. Striking differences in signal intensity and separation efficiency were revealed depending on where on the column detection was performed. Furthermore, adsorption of the analytes on the frits was observed.     

Renormalization flow of QED

We investigate textbook QED in the framework of the exact renormalization group. In the strong-coupling region, we study the influence of fluctuation-induced photonic and fermionic self-interactions on the nonperturbative running of the gauge coupling. Our findings confirm the triviality hypothesis of complete charge screening if the ultraviolet cutoff is sent to infinity. Though the Landau pole does not belong to the physical coupling domain owing to spontaneous chiral-symmetry-breaking (chiSB), the theory predicts a scale of maximal UV extension of the same order as the Landau pole scale. In addition, we verify that the chiSB phase of the theory which is characterized by a light fermion and a Goldstone boson also has a trivial Yukawa coupling.     

Origins of boat or chair preferences in the Ireland-Claisen rearrangements of cyclohexenyl esters: a theoretical study

The relative energies of the chair and boat transition states of a variety of Ireland-Claisen rearrangements were obtained by B3LYP/6-31G calculations. Theoretical results are in good agreement with experimental data and provide a quantitative analysis of the origins of boat preferences that are observed in some of these reactions.     

Snail‐like Particles from Compartmentalized Microfibers

Electrohydrodynamic cojetting has been employed to synthesize compartmentalized microfibers from thermally responsive hydrogels. The synthesis of the hydrogels as well as their transformation into compartmentalized microcylinders is discussed. After programmable shape‐shifting, snail‐like particles are obtained that undergo functional and structural reconfiguration in response to a change in temperature.

     

Lagrangian avenues of transport in the Earth's mantle

A method of visualizing and characterizing stirring structures of high Rayleigh number geophysical flows whose time dependence is strongly aperiodic is presented. To this end, the system is leaked by defining a smaller region of the flow, so that a particle is considered to be escaped if it enters this region. By means of an ensemble of nonescaped tracers, we are able to characterize stirring and transport processes by visualizing the converging and stretching filamentations (stable and unstable manifolds) in the flow. The method indicates that the present-day Earth's mantle is not well stirred because the time that has passed since the formation of the Earth has not been long enough for the flow of the mantle to generate efficient stirring, and observations reveal indeed the existence of reservoirs of different materials.     

Substituted lithiumtrimethylsiloxysilanides LiSiRR′(OSiMe3) - Investigations of their synthesis, stability and reactivity

The reactions of the trimethylsiloxychlorosilanes (Me₃SiO)RR′SiCl (1a-h: R′ = Ph, 1a: R = H, 1b: R = Me, 1c: R = Et, 1d: R = ⁱPr, 1e: R = ^tBu, 1f: R = Ph, 1g: R = 2,4,6-Me₃C₆H₂ (Mes), 1h: R = 2,4,6-(Me₂CH)₃C₆H₂ (Tip); 1i: R = R′ = Mes) with lithium metal in tetrahydrofuran (THF) at −78 °C and in a mixture of THF/diethyl ether/n-pentane in a volume ratio 4:1:1 at −110 °C lead to mixtures of numerous compounds. Dependent on the substituents silyllithium derivatives (Me₃SiO)RR′SiLi (2b-i), Me₃SiO(RR′Si)₂Li (3a-g), Me₃SiRR′SiLi (4a-h), (LiO)RR′SiLi (12e, 12g-i), trisiloxanes (Me₃SiO)₂SiRR′ (5a-i) and trimethylsiloxydisilanes (6f^∗, 6h^∗, 6i^∗) are formed. All silyllithium compounds were trapped with Me₃SiCl or HMe₂SiCl resulting in the following products: (Me₃SiO)RR′SiSiMe₂R″ (6b-i: R″ = Me, 7c-i: R″ = H), Me₃SiO(RR′Si)₂SiMe₂R″ (8a-g: R″ = Me, 9a-g: R″ = H), Me₃SiRR′SiSiMe₂R″ (10a-h: R″ = Me, 11a-h: R″ = H) and (HMe₂SiO)RR′SiSiMe₂H (13e, 13g-i). The stability of trimethylsiloxysilyllithiums 2 depends on the substituents and on the temperature. (Me₃SiO)Mes₂SiLi (2i) is the most stable compound due to the high steric shielding of the silicon centre. The trimethylsiloxysilyllithiums 2a-g undergo partially self-condensation to afford the corresponding trimethylsiloxydisilanyllithiums Me₃SiO(RR′Si)₂Li (3a-g). (Me₃)Si-O bond cleavage was observed for 2e and 2g-i. The relatively stable trimethylsiloxysilyllithiums 2f, 2g and 2i react with n-butyllithium under nucleophilic butylation to give the n-butyl-substituted silyllithiums ⁿBuRR′SiLi (15g, 15f, 15i), which were trapped with Me₃SiCl. By reaction of 2g and 2i with 2,3-dimethylbuta-1,3-diene the corresponding 1,1-diarylsilacyclopentenes 17g and 17i are obtained.X-ray studies of 17g revealed a folded silacyclopentene ring with the silicon atom located 0.5 Å above the mean plane formed by the four carbon ring atoms.