Linear and nonlinear optical studies of CdS1−x Se x quantum dots

In this contribution we present and discuss our measurements on CdS_1?x Se _x quantum dots in a glass matrix. In linear absorption measurements we find the typical blue shift of the transitions with decreasing crystallite radius due to quantization. The luminescence shows a significant Stokes shift with respect to absorption, which is interpreted in terms of strong exciton-phonon coupling and allows to deduce the Huang-Rhys factor S. Under high excitation we find an additional emission band on the high energy side, which can be attributed to the recombination of an excited two electron-hole pair state to a one electron-hole pair state in agreement with theory. Pump and probe beam experiments give a bleaching but no hole burning. Finally we discuss some open questions especially concerning the high energy structures in the absorption spectrum.     

Control of off-flavor compounds in aluminum can production

Aluminum cans have intermittently been associated with the development of off-flavors in beverages. Certain organic compounds, e.g., aldehydes and ketones, are known to contribute to flavor defects; trans-2-nonenal can be detected at 0.1 μg l^?1 levels by trained tasters. In a recent study, the production process used to form two-piece aluminum cans was examined. Samples of aluminum coil stock, partly formed cans and finished cans were obtained from typical production lins and examined by a flavor panel and by chromatographic and spectroscopic methods in an effort to develop routine techniques for monitoring can production. Capillary-column gas chromatography and, after derivatization with dinitrophenylhydrazone, high-performance liquid chromatography are useful for quantifying off-flavor compounds and precursors in lubricants and other materials used in rolling mills and can-making operations, but are not adaptable to on-line monitoring. Correlations between gas-chromatographic data and flavor panel assessments were good.     

Regio- and Stereoselective Reactions of 17-Phenyl-18,19,20-trinorprostaglandin F(2)(alpha) Isopropyl Ester

Novel prostaglandin F(2)(alpha) derivatives, functionalized at C13 and C14, have been prepared. 17-Phenyl-18,19,20-trinorprostaglandin F(2)(alpha) isopropyl ester [(15S)-1] and its epimer [(15R)-1] were stereoselectively epoxidized, using Sharpless conditions, to produce each of the four diastereomeric epoxides (15S)-2, (15S)-3, (15R)-2, and (15R)-3. Treatment of the four epoxides with LiOH stereospecifically-produced the pentahydroxy substituted analogues 12 and 13. Alternatively, epoxides 2 and 3were allowed to react with thiophenolate ion. The attack of the sulfur nucleophile on the epoxide occurred at either C13 or C14 depending on the stereochemistry of the epoxide and of C15.     

Shear flow experiments in an assembly of gel beads and modelling of bingham behavior

In this paper, we present a rheological study of a compact layer of highly swollen gel beads. The flow regimes of these systems are modelled by an elastic sinusoid moving in a Newtonian fluid. This model predicts a yield stress varying with the square root of the elastic modulus of the gel bead. The slope at the origin (at zero velocity) of the flow curve is expected to depend only on geometrical parameters and on the solvent viscosity. The experimental data are in qualitative agreement with the theoretical predictions.     

Saturated heterocycles. 57. Synthesis of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydro-2H-pyrimido[6,1-a]isoquinolin-2-ones

A large number of 4-substituted-9,10-dialkoxy-1,6,7,11b-tetrahydropyrimido[6,1-a]isoquinolin-2-ones were prepared by the reaction of 1-(ethoxycarbonylmethyl)-6,7-dialkoxy-1,2,3,4-tetrahydroisoquinolines with iminoethers. Reaction of the corresponding isoquinoline-1-acetic acid derivatives with iminoethers led to the formation of N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides. In the hydrolysis of the prepared 4-substituted-pyrimido[6,1-a]isoquinolin-2-ones, the corresponding N-acyl-1,2,3,4-tetrahydroisoquinolin-1-acetamides were obtained. While reduction of the 4-phenyl derivative resulted in the corresponding 1,3,4,6,7,11b-hexahydropyrimidinone. The steric structures of the tetrahydro- and hexahydropyrimido[6,1-a]isoquinolines were determined by nmr spectroscopy.     

Reference electrodes based on conducting polymers

Several attempts to produce conducting polymer based all-solid-state reference electrodes are presented. Open circuit potential of conducting polymers is redox sensitive and Donan equilibrium dependent. Therefore, more sophisticated constructions are necessary. Most promising were bilayers composed of conducting polymers with different ion-exchanger properties.     

Electron conduction across electrode-immobilized neutravidin bound with biotin-labeled ruthenium pentaamine

Voltammetry is reported here of a self-assembled redox-protein conjugate consisting of neutravidin conjugated with a biotin derivative redox probe, Ru(NH3)5(N-[(N-[(4-pyridyl)methyl]biotinamide], immobilized on gold electrodes modified by self-assembled monolayers of mercaptoundecanoic acid. This voltammetry indicates that self-assembly of the conjugate/electrode electronic interface, driven by electrostatic binding between the monolayer and a single redox probe, favors orientation of the conjugate, resulting in electronic accessibility of the remaining three redox probes.     

Animal models for treatment of unresectable liver tumours: a histopathologic and ultra-structural study of cellular toxic changes after electrochemical treatment in rat and dog liver

INTRODUCTION: Electrochemical treatment (EChT) has been taken under serious consideration as being one of several techniques for local treatment of malignancies. The advantage of EChT is the minimal invasive approach and the absence of serious side effects. Macroscopic, histopathological and ultra-structural findings in liver following a four-electrode configuration (dog) and a two-electrode EChT design (dog and rat) were studied. MATERIALS AND METHODS: 30 female Sprague-Dawley rats and four female beagle dogs were studied with EChT using Platinum:Iridium electrodes and the delivered dose was 5, 10 or 90 C (As). After EChT, the animals were euthanized. RESULTS: The distribution of the lesions was predictable, irrespective of dose and electrode configuration. Destruction volumes were found to fit into a logarithmic curve (dose-response). Histopathological examination confirmed a spherical (rat) and cylindrical/ellipsoidal (dog) lesion. The type of necrosis differed due to electrode polarity. Ultra-structural analysis showed distinct features of cell damage depending on the distance from the electrode. Histopathological and ultra-structural examination demonstrated that the liver tissue close to the border of the lesion displayed a normal morphology. CONCLUSIONS: The in vivo dose-planning model is reliable, even in species with larger tissue mass such as dogs. A multi-electrode EChT-design could obtain predictable lesions. The cellular toxicity following EChT is clearly identified and varies with the distance from the electrode and polarity. The distinct border between the lesion and normal tissue suggests that EChT in a clinical setting for the treatment of liver tumours can give a reliable destruction margin.     

NMR spectra of a microcrystalline protein at 30 kHz MAS

Proteins are not always available in amounts desirable for solid-state magic-angle spinning (MAS) nuclear-magnetic resonance (NMR) spectroscopy. To maximize the signal-to-noise ratio achievable with small samples, the filling factor must be optimized by using small-diameter MAS rotors. These rotors have the added benefit of allowing higher radio frequency field amplitudes during polarization transfer steps and during decoupling periods as well as allowing higher spinning frequencies. We demonstrate the advantages of relatively fast MAS (30 kHz using a 2.5 mm rotor) compared to MAS at 12 kHz for the 10.4 kDa model protein Crh with 93 residues and show that the signal-to-noise ratio in two-dimensional correlation spectra can be significantly improved by taking advantage of optimized pulse sequences available with rapid MAS.     

Photoinduced electron transfer in platinum(II) terpyridinyl acetylide complexes connected to a porphyrin unit

A series of six new dyads consisting of a zinc or magnesium porphyrin appended to a platinum terpyridine acetylide complex via a para-phenylene bisacetylene spacer are described. Different substituents on the 4' position of the terpyridinyl ligand were explored (OC7H15, PO3Et2, and H). The ground-state electronic properties of the dyads are studied by electronic absorption spectroscopy and electrochemistry, and they indicate some electronic interactions between the porphyrin subunit and the platinum complex. The photophysical properties of these dyads were investigated by steady-state, time-resolved, and femtosecond transient absorption spectroscopy in N,N-dimethylformamide solution. Excitation of the porphyrin unit leads to a very rapid electron transfer (2-20 ps) to the nearby platinum complex followed by an ultrafast charge recombination, thus preventing any observation of the charge separated state. The variation in the rate of the photoinduced electron transfer in the series of dyads is consistent with Marcus theory. The results underscore the potential of the para-phenylene bisacetylene bridge to mediate a rapid electron transfer over a long donor-acceptor distance.