Dynamic 19F NMR studies The torsional barrier in pentafluorobenzaldehyde,its conjugate acid and protonated pentafluoroacetophenone

An upper limit of the barrier to internal rotation around the phenyl-carbonyl bond in pentalfluorobenzaldehyde dissolved in a freon mixture has been estimated from low temperature ₁₉F NMR study. Protonation of this compound increases drastically the free energy of activation ΔG≠. Complete lineshape analysis leads to ΔG≠ (273 K) = 60.4 kJ/mol, comparable to the value obtained for protonated benzaldehyde. This result, as well as those obtained by CNDO/2 calculations support the conclusions that protonated pentafluorobenzaldehyde is planar in the ground state. This is not the case for protonated pentafluoroacetophenone in which the lower barrier height when compared to protonated acetophenon has been related to the steric strain and dipole repulsion.     

Fluorimetric determination of lactate with immobilized lactate dehydrogenase

In measuring inter-phase distribution coefficients (k_{$\text{1}\text{11}$})it is often convenient, and sometimes necessary, to obtain all of the analytical data from one phase. A rigorous formula, applicable to both low and high k_{$\text{1}\text{11}$} values has been derived; measurements of the distribution of mercury, methylmercury and ⁶⁷Cu²⁺ between various pairs of phases with this formula gave k_{$\text{1}\text{11}$} values similar to those obtained from other approaches.     

Nonlinear electric response of polyampholytes

The behavior of polyampholytes (PAs) in electric fields is investigated by Monte Carlo simulations. In bulk it is found that the response of the PA depends on the charge sequence. For small repeating units of positive and negative charges the response is linear, while bigger units results in a nonlinear response in both the induced dipole moment and the resulting polymer conformation. This is reflected in how PAs modify colloidal suspensions, and while PAs always decrease the repulsion between charged colloidal particles, some net-neutral PAs can even induce an effective attraction between the colloidal particles.Contribution to the Björn Roos Honorary Issue     

Multivariate NIR spectroscopy models for moisture, ash and calorific content in biofuels using bi-orthogonal partial least squares regression

The multitude of biofuels in use and their widely different characteristics stress the need for improved characterisation of their chemical and physical properties. Industrial use of biofuels further demands rapid characterisation methods suitable for on-line measurements. The single most important property in biofuels is the calorific value. This is influenced by moisture and ash content as well as the chemical composition of the dry biomass. Near infrared (NIR) spectroscopy and bi-orthogonal partial least squares (BPLS) regression were used to model moisture and ash content as well as gross calorific value in ground samples of stem and branches wood. Samples from 16 individual trees of Norway spruce were artificially moistened into five classes (10, 20, 30, 40 and 50%). Three different models for decomposition of the spectral variation into structure and noise were applied. In total 16 BPLS models were used, all of which showed high accuracy in prediction for a test set and they explained 95.4-99.8% of the reference variable variation. The models for moisture content were spanned by the O-H and C-H overtones, i.e. between water and organic matter. The models for ash content appeared to be based on interactions in carbon chains. For calorific value the models was spanned by C-H stretching, by O-H stretching and bending and by combinations of O-H and C-O stretching. Also -C=C- bonds contributed in the prediction of calorific value. This study illustrates the possibility of using the NIR technique in combination with multivariate calibration to predict economically important properties of biofuels and to interpret models. This concept may also be applied for on-line prediction in processes to standardize biofuels or in biofuelled plants for process monitoring.     

Neighboring Group Participation in a Regio- and Stereoselective Chlorination of a Bicyclo[2.2.2]octanone

The zinc chloride-mediated acetylation of the optically active silyl enol ether 2a gave the beta-diketone 3a (48%) together with the regio- and stereoselectively chlorinated compound 4 (27%). The yield of 4 increased to 70% by starting from the O-acetyl derivative 2c. The chlorination most likely occurs via neighboring group participation by the endo acetoxy group.     

Characterization of sulfated beta-cyclodextrins and determination of enantiomeric purity of (1 R,2S)-ephedrine by capillary zone electrophoresis

Matrix-assisted laser-desorption ionization time-of-flight (MALDI-TOF) mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy were employed to characterize two different sulfated beta-cyclodextrins (HS-beta-CD). It was found that the HS-beta-CDs have broad heterogeneity in terms of sulfation degree. The average sulfate contents were in the range of 6 to 8 per CD molecule. Furthermore the sugar moieties of both HS-beta-CDs were sulfated either at position 6 or at positions 2 and 6, but not at position 3. Enantiomeric separation by capillary zone electrophoresis (CZE) using the HS-beta-CDs as chiral selectors showed that these CDs exhibited similar chiral selectivity and resolution of the ephedrine enantiomers. One of the CDs was employed for the enantiomeric purity evaluation of (1R,2S)-ephedrine (or (-)-ephedrine) by capillary zone electrophoresis. Quantification was done by comparison between the corrected peak areas of the minor enantiomer and (-)-ephedrine.     

Photoinduced electron transfer between a carotenoid and TiO2 nanoparticle

The dynamics of photoinduced electron injection and recombination between all-trans-8'-apo-beta-caroten-8'-oic acid (ACOA) and a TiO(2) colloidal nanoparticle have been studied by means of transient absorption spectroscopy. We observed an ultrafast ( approximately 360 fs) electron injection from the initially excited S(2) state of ACOA into the TiO(2) conduction band with a quantum yield of approximately 40%. As a result, the ACOA(*)(+) radical cation was formed, as demonstrated by its intense absorption band centered at 840 nm. Because of the competing S(2)-S(1) internal conversion, approximately 60% of the S(2)-state population relaxes to the S(1) state. Although the S(1) state is thermodynamically favorable to donate electrons to the TiO(2), no evidence was found for electron injection from the ACOA S(1) state, most likely as a result of a complicated electronic nature of the S(1) state, which decays with a approximately 18 ps time constant to the ground state. The charge recombination between the injected electrons and the ACOA(*)(+) was found to be a highly nonexponential process extending from picoseconds to microseconds. Besides the usual pathway of charge recombination forming the ACOA ground state, about half of the ACOA(*)(+) recombines via the ACOA triplet state, which was monitored by its absorption band at 530 nm. This second channel of recombination proceeds on the nanosecond time scale, and the formed triplet state decays to the ground state with a lifetime of approximately 7.3 micros. By examination of the process of photoinduced electron transfer in a carotenoid-semiconductor system, the results provide an insight into the photophysical properties of carotenoids, as well as evidence that the interfacial electron injection occurs from the initially populated excited state prior to electronic and nuclear relaxation of the carotenoid molecule.     

Normal and friction forces between mucin and mucin-chitosan layers in absence and presence of SDS

Employing the colloidal probe AFM technique we have investigated normal and friction forces between flat mica surfaces and silica particles coated with mucin and combined mucin-chitosan layers in presence and absence of anionic surfactant, SDS, in 30 mM NaCl solution. We have shown that the normal interactions between mucin coated mica and silica surfaces are dominated by long-range steric repulsion on both compression and decompression. Friction forces between such mucin layers are characterized by a low effective friction coefficient, mu(eff)=0.03+/-0.02, which is lower than the value of 0.13+/-0.02 observed when chitosan layers were adsorbed. Forces between combined mucin-chitosan layers have also been measured. Adsorption of chitosan on mucin results in considerable compaction of the layer, and development of attractive forces detectable on separation. Friction between mucin-chitosan layers in 30 mM NaCl solution is high, with mu(eff) approximately 0.4. Adsorption of additional mucin to this layer results in no improvement with respect to lubrication as compared to the mucin-chitosan layer, and mu(eff) approximately 0.4 is observed. We argue that the layers containing both mucin and chitosan are not strictly layered but rather strongly entangled. As a result attractive interactions between oppositely charged moieties of sialic acid residues from mucin and amine groups from chitosan residing on the opposing surfaces contribute to the increased friction. The effects of SDS on normal and friction forces between combined mucin-chitosan layers were also investigated. The relation between surface interactions and friction properties is discussed.     

The number of solutions of some equations in finite groups and a new proof of Itô's theorem

We compute the number of solutions to some equations in finite groups and use these computations to give a new proof of Itô's theorem on the degrees of the irreducible characters.