Photo-redox induced cationic polymerization of divinyl ethers

The cationic polymerization of diethyleneglycoldivinyl ether was initiated by cationic species originating from the redox reaction between photochemically generated free radicals or excited state photosensitizers and various onium salts. For the oxidation of free radicals, the efficiency of the initiation process depended primarily on the redox potential of the redox couple and hence the reactivity could be altered by choosing an appropriate combination of free radical photoinitiator and onium salt. The electron transfer from excited state photosensitizers to the phenacyletramethylenesulfonium salt showed no correlation between the free energy of the process and the initiation efficiency.     

Genomic responses in rat cerebral cortex after traumatic brain injury

Background  

Traumatic brain injury (TBI) initiates a complex sequence of destructive and neuroprotective cellular responses. The initial mechanical injury is followed by an extended time period of secondary brain damage. Due to the complicated pathological picture a better understanding of the molecular events occurring during this secondary phase of injury is needed. This study was aimed at analysing gene expression patterns following cerebral cortical contusion in rat using high throughput microarray technology with the goal of identifying genes involved in an early and in a more delayed phase of trauma, as genomic responses behind secondary mechanisms likely are time-dependent.     

Molecularly imprinted polymers in capillary electrochromatography: recent developments and future trends

The developments in molecularly imprinted polymer (MIP)-based capillary electrochromatography (CEC) achieved during the past years are reviewed in this article. The MIP is prepared using a templated polymerization reaction and results in a material with a high selectivity towards a predetermined target. The selectivity of the MIP is comparable to that of the biological antibodies, however, the MIP is much more stable and is thus able to withstand extremely harsh conditions in terms of pH, temperature, and organic solvents. The high selectivity and stability of the MIP made it an interesting candidate for application as stationary phase sorbent in chromatography. However, due to slow kinetics the efficiency of the early MIP columns, which were predominantly applied in high-performance liquid chromatography (HPLC), were limited. The use of CEC was thought to improve the efficiency of the MIP-based separation system. The small dimensions of the capillary format employed in CEC have put demands on the polymer systems which have resulted in the development of many different polymer formats. Thus, this need for novel MIP formats for applications in CEC has contributed a lot to the general development of MIP formats as well as to the knowledge in MIP synthesis and characteristics.     

Studies of selenium and selenium dioxide isochromats

The allotropic forms of selenium, hexagonal and amorphous, and selenium dioxide have been studied by the isochromat method. A high vacuum spectrometer provided with bent crystal and water cooled targets was used. It is shown that a shift of the short wave-length limit of the continuous X-ray spectrum occurs for a semiconductor in comparison with a metal. The shift of hexagonal Se is found to be 1.7 ± 0.2 V, amorphous Se 1.5±0.3 V and SeO₂ 1.3 ± 0.2 V. The temperature was held at about 320 °K for the amorphous sample and at 400 °K for the others. The shifts of hexagonal and amorphous Se are in good agreement with the energy band gaps found by other methods. The fine structure near the short wave-length limit is discussed considering the Nijboer theory. Attempts have been made to explain the isochromat structure by comparison withL _I -absorption and characteristic energy loss spectra. The characteristic energy loss values found by the present method, which impliesreappearing intervals in the isochromats, have been compared with the theoretical values of? ω _p , given by the plasma oscillation theory.     

Uniform stability of a class of parabolic difference operators

Conditions on a class of parabolic difference operators are given which are sufficient for maximumnorm stability, uniform in the mesh-widths. This paper is a generalization of a previous result by Hakberg [4].     

Total synthesis of (-)-stemoamide

A stereocontrolled total synthesis of (-)-stemoamide (1) is presented. The synthesis starts from commercially available (S)-pyroglutaminol (4). A chemoselective iodoboration of 5 was used to access key intermediate 3. The beta,gamma-unsaturated azepine derivative 2 was obtained via a Pd(0)-catalyzed sp(2)-sp(3) Negishi cross-coupling using a Reformatsky nucleophile followed by a ring-closing metathesis reaction. The required C8-C9 trans-stereochemistry of 1 was accessed through a stereoselective bromolactonization/1,4-reduction sequence.     

Large-aperture focusing of high-energy x rays with a rolled polyimide film

We describe a point-focusing x-ray lens made of a rolled polyimide film with etched prisms. The resulting lens is a cylinder with a large number of prisms forming an internal conic structure. The method allows for the manufacturing of lenses with large apertures and short focal lengths, for energies up to at least 100?keV. In order to evaluate the concept, we have hand-rolled a few lenses and evaluated them at a synchrotron source. The measured performance of the prototype is promising, and deviations from the theoretical limits are quantitatively explained.     

Surface complexes of monomethyl phosphate stabilized by hydrogen bonding on goethite (α-FeOOH) nanoparticles

Typically, a significant fraction of phosphorus in soils is composed of organic phosphates, and this fraction thus plays an important role in the global phosphorus cycle. Here we have studied adsorption of monomethyl phosphate (MMP) to goethite (α-FeOOH) as a model system in order to better understand the mechanisms behind adsorption of organic phosphates to soil minerals, and how adsorption affects the stability of these molecules. The adsorption reactions and stability of MMP on goethite were studied at room temperature as a function of pH, time and total concentration of MMP by means of quantitative batch experiments, potentiometry and infrared spectroscopy. MMP was found to be stable at the water-goethite interface within the pH region 3-9 and over extended periods of time, as well as in solution. The infrared spectra indicated that MMP formed three predominating pH-dependent surface complexes on goethite, and that these interacted monodentately with surface Fe. The complexes differed in hydrogen bonding interactions via the auxiliary oxygens of the phosphate group. The presented surface complexation model was based on the collective spectroscopic and macroscopic results, using the Basic Stern approach to describe the interfacial region. The model consisted of three monodentate inner sphere surface complexes where the MMP complexes were stabilized by hydrogen bonding to a neighboring surface site. The three complexes, which had equal proton content and thus could be defined as surface isomers, were distinguished by the distribution of charge over the 0-plane and β-plane. In the high pH-range, MMP acted as a hydrogen bond acceptor whereas it was a hydrogen bond donor at low pH.     

Quantitative adsorption and local structures of gallium(III) at the water-alpha-FeOOH interface

The adsorption of Ga(III) at the water-alpha-FeOOH (goethite) interface has been investigated by means of quantitative adsorption experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. Under the conditions studied, pH range 3-11 and surface coverages of 0.9-3.2 micromol/m2, Ga(III) was found to adsorb strongly to alpha-FeOOH, and the surface species were more resistant toward hydrolysis and formation of soluble Ga(OH)4- than either solid gallium hydroxides or soluble polynuclear complexes. The EXAFS measurements revealed the presence of octahedral Ga(III) complexes at the water-alpha-FeOOH interface, with practically no structural variations as a function of pH or total gallium concentration. Analysis of the first coordination shell required an anharmonic model indicating a distorted geometry of the GaO6 octahedra, with mean Ga-O distances at 1.96-1.98 angstroms. A method based on the continuous Cauchy wavelet transforms (CCWT) was used to identify backscattering atoms in the higher coordination shells. This analysis indicated predominately Fe backscattering, and the quantitative data fitting resulted in three Ga-Fe paths at 3.05, 3.2, and 3.55 angstroms, which correspond to two edge-sharing and one corner-sharing linkage, respectively. The collective results from EXAFS spectroscopy showed that Ga(III) adsorbs to Fe equivalent sites at the surface alpha-FeOOH as an extension of the rows of Fe octahedra in the bulk structure. This interpretation was further corroborated by a Ga-Fe-Fe multiple scattering path at 6.13 angstroms. The quantitative adsorption and proton data were modeled using a surface complexation formalism based on a 1 pK(a) constant capacitance model. In agreement with the EXAFS results, the model obtained included one predominating surface complex with the stoichiometry [triple bond]FeOGa(OH)2(-0.5) and the stability constant log beta(intr.) = -2.55 +/- 0.04 ([triple bond]FeOH(-0.5) + Ga3+ + 2H2O <--> [triple bond]FeOGa(OH)2(-0.5) + 3H+).