Crystal structure and thermoanalytical study of a manganese(II) complex with 1-allylimidazole

The crystal structure of a manganese(II) 1-allylimidazole complex ([Mn(1-AIm)₃(NO₃)₂], where 1-Aim=1-allylimidazole), was characterized by X-ray diffraction (XRD) using SHELX-97. The thermal behaviour of the complex was investigated by thermogravimetry (TG) coupled with an FTIR unit. The complex showed a multi-step decomposition related to the release of the ligand molecules, followed by oxidation. The final residue at 1073 K was found to be manganese(II) oxide. Evolved gas analysis allowed to prove the oxidative decomposition pattern of the examined complex, initially proposed by the percentage mass loss data. Finally, a kinetic analysis of the oxidative decomposition steps was made using the Kissinger equation, while the complex nature of the decomposition kinetics was revealed by the isoconversional Ozawa-Flynn-Wall method.     

Toward [18F]-labeled aryltrifluoroborate radiotracers: in vivo positron emission tomography imaging of stable aryltrifluoroborate clearance in mice

The use of a boronic ester as a captor of aqueous [(18)F]-fluoride has been previously suggested as a means of labeling biomolecules in one step for positron emission tomography (PET) imaging. For this approach to be seriously considered, the [(18)F]-labeled trifluoroborate should be humorally stable such that it neither leaches free [(18)F]-fluoride to the bone nor accumulates therein. Herein, we have synthesized a biotinylated boronic ester that is converted to the corresponding trifluoroborate salt in the presence of aqueous [(18)F]-fluoride. In keeping with its in vitro aqueous kinetic stability at pH 7.5, the trifluoroborate appears to clear in vivo quite rapidly to the bladder as the stable trifluoroborate salt with no detectable leaching of free [(18)F]-fluoride to the bone. When this labeled biotin is preincubated with avidin, the pharmacokinetic clearance of the resulting complex is visibly altered. This work validates initial claims that boronic esters are potentially useful as readily labeled precursors to [(18)F]-PET reagents.     

Enrichment of deuterium oxide at hydrophilic interfaces in aqueous solutions

The structure of water at aqueous interfaces is of the utmost importance in biology, chemistry, and geology. We use neutron reflectivity and quartz crystal microbalance to probe an interface between hydrophilic quartz and bulk liquid solutions of H2O/D2O mixtures. We find that near the interface the neutron scattering length density is larger than in the bulk solution and there is an excess adsorbed mass. We interpret this as showing that there is a region adjacent to the quartz that is enriched in D2O and extends 5-10 nm into the solution. This suggests caution when interpreting results where D2O is substituted for H2O in aqueous interfacial chemistry.     

Glyco-acrylate copolymers for bilayer tethering on benzophenone-modified substrates

Model biological membranes are becoming increasingly important for studying fundamental biophysical phenomena and developing membrane-based devices. To address the anticipated problem of non-physiological interactions between membrane proteins and substrates seen in “solid-supported lipid bilayers” that are formed directly on hydrophilic substrates, we have developed a polymer-tethered lipid bilayer system based on a random copolymer with multiple lipid analogue anchors and a glyco-acrylate backbone. This system is targeted at applications that, most importantly, require stability and robustness since each copolymer has multiple lipid analogues that insert into the bilayer. We have combined this copolymer with a flexible photochemical coupling scheme that covalently attaches the copolymer to the substrate. The Langmuir isotherms of mixed copolymer/free lipid monolayers measured at the air–water interface indicate that the alkyl chains of the copolymer lipid analogues and the free lipids dominate the film behavior. In addition, no significant phase transitions are seen in the isotherms, while hysteresis experiments confirm that no irreversible states are formed during the monolayer compression. Isobaric creep experiments at the air–water interface and AFM experiments of the transferred monolayer are used to guide processing parameters for creating a fluid, homogeneous bilayer. Bilayer homogeneity and fluidity are monitored using fluorescence microscopy. Continuous bilayers with lateral diffusion coefficients of 0.6 μm²/s for both leaflets of the bilayer are observed for a 5% copolymer system.     

Microwave synthesis of zeolites. 2. Effect of vessel size, precursor volume, and irradiation method

The enhancement of synthesis reactions under microwave heating is dependent on many complex factors. We investigated the importance of several reaction engineering parameters relevant to microwave synthesis. Of interest to this investigation were the reaction vessel size, volume of precursor reacted, microwave power delivery, and microwave cavity design. The syntheses of NaY zeolite and beta-zeolite were carried out under a number of varying conditions to determine the influence of these parameters on the nucleation rate, the crystallization rate, and the particle size and morphology. The rates of NaY and beta-zeolite nucleation and crystallization were more rapid in the multimode CEM MARS-5 oven compared to the more uniform field CEM Discover. The faster synthesis rate in the MARS-5 may be the result of the multimode microwave electric field distribution. Slower rates of NaY and beta-zeolite formation observed in the Discover and a circular waveguide may be the result of a more uniform microwave electric field distribution. Changes in reaction vessel size and precursor volume during the microwave synthesis of beta- and NaY zeolite were found to influence the rate of zeolite formation. These results indicate that reactor geometry needs to be considered in the design of systems used for microwave synthesis. Comparative synthesis reactions were carried out with conventional heating, and microwave heating was shown to be up to over an order of magnitude faster for most of these syntheses.     

High density,high performance optical data storage via volume holography: Viability at last?

The long held promise of using volume holography to deliver high performance optical storage is reviewed. The problems, which limited the development for many years, are accessed. Finally, we describe a series of innovations, which may make the technology viable at last.     

Experimental investigation of the molecular ions of the xylenes

A mass spectrometric method of distinguishing between molecular ions of the three isomeric xylenes (dimethylbenzenes) was sought, in light of recent findigs that photoexcited ions could be distinguished via measurements of kinetic energy release accompanying expulsion of a methyl radical. Provided the molecular ions are formed with low internal energies, reproducible differences were found between relative intensities of collision induced reactions of higher critical energies, than for methyl expulsion. These differences exist both for collision energies in the kilovolt range (double focusing mass spectrometers) and in the range of a few tens of volts (triple quadrupole instrument). Though statistically significant, these differences were small. The mechanism of isomerization and fragmentation was investigated via isotopic labelling studies and measurements of kinetic energy release. Most of the present findings can be rationalized in terms of the most recent version of established mechanisms for reactions of ionized methylbenzenes.     

Two-dimensional infrared (2D IR) spectroscopy. A new tool for interpreting infrared spectra

Two-dimensional infrared (2D IR) spectroscopy is used to study atactic polystyrene. 2D IR is a technique based on time-resolved detection of IR signals in response to an external perturbation, such as mechanical strain. Since different chemical functional groups respond to the applied perturbation at unique and often different rates, characteristic time-dependent variations of the IR-band intensities are observed. Correlation analysis of the dynamic variation of the IR signals yields a new spectrum defined by two independent wave numbers. Peaks located on a 2D IR spectral plane imply interactions and connectivities among chemical functional groups. By spreading convoluted IR bands over two dimensions, the spectral resolution is also greatly enhanced.     

Translational energy release and stereochemistry of steroids. VIII-The mechanism of the elimination of water from metastable ions in epimeric 3-hydroxy steroids of the 5α-series

The mechanism of water elimination from metastable molecular, [M ? CH₃˙]⁺ and [M ? ring D]⁺˙ ions of epimeric 3-hydroxy steroids of the 5α-series has been elucidated. Deuterium labelling, the measurement of the translational energy released during the loss of water, and collision-induced decomposition mass-analysed kinetic energy spectrometry were the techniques used. It was found that the mechanisms of water loss from metastable M⁺˙ and [M ? ring D]⁺˙ ions is different from that from [M ? CH₃˙]⁺ ions.     

Synthesis of some benzimidazole- and benzothiazole-derived ligand systems and their precursory diacids

Procedures are described for the preparation of various bidentate and linear tetradentate benzimidazoles and benzothiazoles incorporating units such as pyridyl and thioether, and for the preparation of certain thioether dicarboxylic acids precursory to them. Condensations of ortho-functinal anilines with carboxylic acids were carried out in polyphosphoric acid or refluxing HCl solution. Syntheses are reported for: [HO₂C(CH₂)2S(CH₂)₂]₂X (X = O, S), 1,9-bis(benzimidazol-2-yl)-2,5,8-trithianonane, 1,11-bis(N-methylbenzimidazol-2-yl)-3,6,9-trithiaundecane, 1,11-bis(2-benzimidazol-2-yl)-6-oxo-3,9-dithiaundecane, 2-(2-pyridyl)benzothiazole, 2,6-bis(benzothiazol-2-yl)pyridine, 2-(2-pyridyl)-N-methylbenzimidazole, 2-(2-pyridylmethyl)benzimidazole and 2-(N-methyl-2-piperidyl)benzimidazole. The compounds were characterized, where appropriate, by their mass, uv and ¹H-nmr spectra.