Ammonium ion mediated resorcarene capsules: ESI-FTICRMS study on gas-phase structure and ammonium ion affinity of tetraethyl resorcarene and its per-methylated derivative

The ammonium ion binding affinities of tetraethyl resorcarene (1) and its per-methylated derivative (2) were studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Ten different ammonium ions were tested as guests for the resorcarenes. A strong tendency for complex formation was observed with all ammonium ions of size and charge distribution suitable for noncovalent interactions with the cavities of the resorcarene hosts 1 and 2. Although differences in ammonium ion affinities were observed between 1 and 2 due to the dissimilar conformations, the overall tendency was that increase in the degree of substitution and the length of carbon chain of the ammonium cation facilitated the complex formation until the sterical hindrance impeded the complexation. Dimeric as well as monomeric ammonium ion complexes were formed with resorcarene 1, but resorcarene 2 was unable to form the dimeric capsules because of the lack of H-bond donor possibilities. The nature of binding of the guest was further investigated with ion-molecule reactions and by determination of the single crystal X-ray structure of host 1 complexed with tetramethyl ammonium bromide.     

A study of a polysulfone membrane for use in an in-situ tunable microdialysis probe during monitoring of starch enzymatic hydrolysates

We report a study made on a 5 kDa molecular weight cut-off (MWCO) polysulfone membrane (SPS 4005) for use in microdialysis sampling of starch enzymatic hydrolysates on-line coupled to column liquid chromatography with integrated pulsed electrochemical detection. Membrane characteristics were evaluated by examining both the membrane and membrane support layer using a scanning electron microscope (SEM). This study was made so as to elucidate the mechanism or mode by which a membrane exposed to different bioprocess conditions is either fouled or destroyed. The correlation of extraction fraction data with SEM was a confirmatory test for the observed change in the membrane characteristics. Examinations were made after keeping the membrane in pure water for 5, 10 and 30 min at room temperature or after perfusing the membrane with pure water continuously at room temperature, 60 and 90°C for 24 h. Extraction fractions were evaluated at these temperatures to see applicability of the SPS 4005 membrane to high temperature bioprocesses. Scanning electron microscopy studies were also made on membranes used for sampling and sample clean-up during on-line monitoring of the hydrolysis of soluble starch (according to Zulkowsky) for 32 h, and the hydrolysis of wheat starch at room temperature, 60 and 90°C for 6 h. Non-specific/directed protein-membrane interactions were evaluated by sampling maltoheptaose with a microdialysis probe fitted with a 10 mm SPS 4005 membrane, before and after treatment with an enzyme solution of Termamyl (endo-1,4-- -glucan glucanohydrolase EC 3.2.1.78).     

Regiospecific photohydroxyalkylation of pentafluoropyridine

Irradiation of 1-hydroxyalkane solutions of pentafluoropyridine in the presence of benzo-phenone resulted in regiospecific substitution at position 4, thus forming 2,3,5,6-tetrafluoro-4-(1-hydroxyalkyl)pyridine.     

Molecular-weight scaling of coexistence curves for monodisperse polymer solutions

The available data for the polymer volume fraction along the coexistence curves for monodisperse solutions of polystyrene in methylcyclohexane are used to derive the exponent z ≈ 0.61 such that the “correct” order parameter is only a function of ?M^Z (M is the polymer's molecular weight while ? is the reduced temperature). It is shown that a knowledge of the “correct” order parameter is unnecessary for a determination of z which is expected to be universal, i.e. independent of the polymer-solvent system.     

Solid-state photodimerization kinetics of alpha-trans-cinnamic acid to alpha-truxillic acid studied via solid-state NMR

The present work focuses on the topochemical photoconversion process in which alpha-trans-cinnamic acid becomes alpha-truxillic acid. This solid-state [2 + 2] cycloaddition reaction has previously been studied with X-ray diffraction, atomic force microscopy, and vibrational spectroscopy. However structural and kinetic details about the reaction are still debated. We present results from (13)C cross-polarization magic angle spinning solid-state NMR experiments that suggest that the Johnson, Mehl, Avrami, and Kolmogorov model of phase transformation kinetics can be applied to this system. The model elucidates parameters of the reaction, such as the nucleation rate, diffusion rate, and dimensionality of the reaction. From our data, it is concluded that this reaction follows one-dimensional growth with a decreasing nucleation rate.     

A method of proving non-unitarity of representations of p-adic groups I

In this paper we exhibit a new method of proving non-unitarity of representations, based on semi simplicity of unitarizable representations. Non-unitarity is proved for a half of all irreducible representations of classical p-adic groups whose infinitesimal character is the same as the infinitesimal character of a generalized Steinberg representation (as defined in Tadić, Am J Math 120:159–210, 1998). Only the Steinberg representation and its Aubert dual are expected to be unitary here. In this way we partially generalize a result of Casselman to the case of classical groups. Our argument is completely different from Casselman’s argument (which is hard to extend to this case). It requires a very limited knowledge of the inducing cuspidal representation.