Mass spectrometry of halo-pyrazolium salts

Eleven halogen substituted 1-methyl-2-phenylpyrazolium bromides or chlorides were investigated by field desorption, field ionization, and electron impact mass spectrometry. Dealkylation was found to be the predominant thermal decomposition. An exchange between covalent and ionic halogen prior to dealkylation was observed and is discussed in detail.     

Dimensions and Lyapunov exponents from exchange rate series

Detecting the presence of deterministic chaos in economic time series is an important problem that may be solved by measuring the largest Lyapunov exponent. In this paper we present estimates of the largest Lyapunov exponent in daily data for the Swedish Krona vs Deutsche Mark, ECU, U.S. Dollar and Yen exchange rates. In order to estimate the dimension of the systems producing these exchange rate series, we also present estimates of the correlation dimension. We found indications of deterministic chaos in all exchange rate series. However, the estimates for the largest Lyapunov exponents are not reliable, except in the Swedish Krona-ECU case, because of the limited number of data points. In the Swedish Krona-ECU case, we found indications of a low-order chaotic dynamical system.     

Two-dimensional spectroscopic imaging for pretreatment evaluation of prostate cancer: comparison with the step-section histology after radical prostatectomy

Purpose

To minimize user and vendor dependence of the spectrum processing of prostate spectra, to measure the ratio of choline (Cho) plus creatine (Cr) to citrate (Cit) in the prostate tissue of normal volunteers and cancer patients, and to compare the results with pathologic findings after radical prostatectomy.

Materials and methods

Four healthy volunteers and 13 patients with prostate cancer were measured. Measurements were performed using two-dimensional magnetic resonance spectroscopic imaging (MRSI) and endorectal coil. A standard vendor's spectrum processing approach has been modified. An original feature of this methodology was the combination of vendor-optimized and user-independent spectrum preprocessing in the scanner and user-independent quantitation in the environment of an MRUI software package. (Cho+Cr)/Cit ratio was used for the classification of prostate tissue. Results were compared with histopathology after radical prostatectomy.

Results

Eight of 13 cancer patients were classified as suspicious or very suspicious for cancer at spectroscopy, three were ambiguous for cancer and two patients were evaluated as false negative. A considerable overlap of metabolite ratios at various Gleason score was found.

Conclusion

The proposed spectrum processing has the potential to improve the accuracy and user independency of the (Cho+Cr)/Cit quantitation. This study confirmed the previous results that a considerable overlap of (Cho+Cr)/Cit ratios exists at various Gleason score levels.     

Enhanced protein adsorption due to charge regulation

When a protein molecule approaches a charged surface, its protonation state can undergo dramatic changes due to the imposed electric potential. This has a large impact on adsorption strengths that may be enhanced by several kT. Using mesoscopic simulation techniques as well as analytical theories, we have investigated this regulation mechanism and demonstrate how it is influenced by salt concentration and solution pH. Using hisactophilin as a test case, we show how the binding to a lipid membrane is governed by small changes in pH and that this is intimately coupled to the charge regulation mechanism.     

Artificial glycosyl phosphorylases

alpha- and beta-Cyclodextrin 6(A),6(D)-diacids (1 and 2), beta-cyclodextrin-6-monoacid (14), beta-cyclodextrin 6(A),6(D)-di-O-sulfate (16) and beta-cyclodextrin-6-heptasulfate (19) were synthesised. Acids 1, 2 and 14 were made from perbenzylated alpha- or beta-cyclodextrin, by diisobutylaluminum hydride (DIBAL)-promoted debenzylation, oxidation and deprotection. Addition of molecular sieves was found to improve the debenzylation reaction. Sulfates 16 and 19 were made by sulfation of the appropriately partially protected derivatives and deprotection. Catalysis of 4-nitrophenyl glycoside cleavage by these cyclodextrin derivatives was studied. Compounds 1, 2 and 16 were found to catalyse the reaction, with the catalysis following Michaelis-Menten kinetics and depending first order on the phosphate concentration. In a phosphate buffer (0.5 M, 59 degrees C, pH 8.0), K(M) varied from 2-10 mM and the k(cat)/k(uncat) ratio from 80-1000 depending on the stereochemistry of the substrate and the catalyst, with 2 being the best catalyst and with the sulfated 16 also displaying catalytic ability. The monoacid 14 and the heptasulfate 19 were not catalytic.     

Numerical Approximation for a White Noise Driven SPDE with Locally Bounded Drift

A numerical scheme for a stochastic partial differential equation of heat equation type is considered where the drift is locally bounded and the dispersion may be state dependent. Uniform convergence in probability is obtained. Roger Pettersson: Partially supported by the EU grant ref. ERBF MRX CT96 0057A.     

Narrowband bulk Bragg grating optical parametric oscillator

A narrowband, pulsed optical parametric oscillator (OPO) whose output coupler is a bulk glass Bragg grating is demonstrated. The OPO is based on periodically poled KTiOPO4 and is pumped by a pulsed, frequency-doubled Nd:YAG laser at 532 nm, generating a signal at 975 nm with a total efficiency of 35%. This novel and compact device shows a spectral bandwidth of 0.16 nm (50 GHz), a decrease by a factor of 20 compared with that when a conventional mirror is used. By using a folded cavity, we demonstrate tunable radiation with a tuning range of 60 nm and maintained spectral bandwidth.     

Quantitative analysis of WC grain shape in sintered WC-Co cemented carbides

The morphology of WC grains is examined by ab initio calculations, and by transmission electron microscopy in a WC-Co cemented carbide. Two compositions are studied to determine the effect of carbon chemical potential on the shape development. The WC grains are found to be truncated triangles, and the grain morphology is adequately reproduced by the ab initio calculations. The energy difference between the two types of grain facets is shown to be due to the formation of stronger bonds with more covalent character between low coordinated W and Co atoms at one type of facet.