Patterned and controlled polyelectrolyte fractal growth and aggregations

Two-dimensional patterned and controlled polyelectrolyte aggregations (e.g., tree-like ramified structures) created by microcontact printing have been demonstrated and discussed. Polyelectrolyte-micropatterned aggregations on surfaces were controlled by the micropattern size and shape of PDMS stamps. The formation of aggregates was dependent on the ink and surface conditions, and the aggregates consisted of two distinct layers; strongly adsorbed, primary uniform layers and weakly adsorbed, secondary aggregation layers positioned on top of the primary layers. The adsorption of the primary layers was strong enough not to be washed away, while the aggregated secondary layers were easily removed by washing. The aggregation of secondary layers showed typical tree-like ramified structures of fractal growth and aggregation. Directional and confined stamping led to directing and confining the growth of the fractal polyelectrolyte clusters, respectively. The micropatterned primary uniform layers were not removed by extensive washing, and they were identified by selective nickel plating and charged particle selective adsorption in which the surface formed positive and negative micropatterns. These functional and patterned surfaces have great potentials for advanced devices and sensors.     

Quantification of polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB) in the picogram/liter range in water of the river Elbe

Sampling and determination of dissolved and particlebound PCBs and HCB in the river Elbe are described. A new filtration/adsorption unit for sampling of dissolved lipophilic contaminants was developed. The detection limit for dissolved PCBs and HCB was 5 pg/l. The data show that more than 98% of the PCBs and of HCB in the water of the river Elbe are particle-bound.     

Preparation and mechanical properties of thermal energy storage microcapsules

A series of heat energy storage microcapsules was prepared using melamine-formaldehyde resin as the shell material and the mechanical properties of the shell were investigated. A phase change material whose melting point was 24 °C was used as core and the quantity of heat involved in phase transition was 225.5 J/g. Average diameter of the microcapsules varied from 5 to 10 μm, and the globular surface was smooth and compact. The mechanical properties of the shell were evaluated by observing the surface morphological structure change after application of pressure by means of scanning electron microscopy. When the mass ratio of the core and shell material is 3:1, a yield point of about 1.1×10⁵ Pa was found and when the compression was increased beyond this point the microcapsules showed plastic behavior. This has been attributed to the cross-link density and to the high degree of reaction of the shell material. Different yield points subsequently reflected differences in the mechanical behavior. It was also found that the mechanical intensity of double-shell microcapsules was better than that of single shelled ones.     

Spectrum analysis of U-doped LaBr3 single crystals. Part 1: crystal-field analysis

Single crystals of U³⁺:LaBr₃ were grown by the Bridgman-Stockbarger technique. High-resolution polarized absorption spectra of the crystals were recorded at 4.2 K in the 4000-50,000 cm⁻¹ range. Sixty-four experimental crystal-field energy levels of the U³⁺ ion were fitted to a semiempirical Hamiltonian employing free-ion, one-electron crystal-field as well as two-particle correlation crystal-field (CCF) operators with an r.m.s. deviation of 28 cm⁻¹. The performed analysis of the spectra enabled the determination of crystal-field parameters and assignment of the observed 5f³→5f³ transitions. The effects of selected CCF operators on the splitting of some specific U³⁺ multiplets have been investigated and the obtained values of Hamiltonian parameters are discussed and compared with those reported in previous analyses.     

Reaction of methyl 4-nitrobenzenesulfonate with Br- in water-formamide tetradecyltrimethylammonium bromide micellar solutions

Summary The reaction methyl 4-nitrobenzenesulfonate + Br^- was studied in water-formamide tetradecyltrimethylammonium bromide micellar solutions. A pseudophase kinetic model was used to quantitatively rationalize the kinetic micellar effects observed     

The exo-selectivity of the new non-natural chiral auxiliary (+)-(1R,endo)-2-benzonorbornenol in an asymmetric aza-Diels-Alder reaction

The recently reported compound (+)-(1R,endo)-2-benzonorbornenol (2) proved to be an efficient chiral auxiliary in the asymmetric aza-Diels-Alder reaction between cyclopentadiene and the N-benzyl imine of its glyoxylate, which afforded a virtually all-exo mixture of cycloaducts with a 1S:1R diastereomeric ratio of 63:37.     

Modeling deoxyribose radicals by neutralization-reionization mass spectrometry. Part 1. Preparation,dissociations, and energetics of 2-hydroxyoxolan-2-yl radical,neutral isomers,and cations

Collisional neutralization of several isomeric C(4)H(7)O(2) cations is used to generate radicals that share some structural features with transient species that are thought to be produced by radiolysis of 2-deoxyribose. The title 2-hydroxyoxolan-2-yl radical (1) undergoes nearly complete dissociation when produced by femtosecond electron transfer from thermal organic electron donors dimethyl disulfide and N,N-dimethylaniline in the gas phase. Product analysis, isotope labeling ((2)H and (18)O), and potential energy surface mapping by ab initio calculations at the G2(MP2) and B3-PMP2 levels of theory and in combination with Rice-Ramsperger-Kassel-Marcus (RRKM) kinetic calculations are used to assign the major and some minor pathways for 1 dissociations. The major (approximately 90%) pathway is initiated by cleavage of the ring C-5[bond]O bond in 1 and proceeds to form ethylene and *CH(2)COOH as main products, whereas loss of a hydrogen atom forms 4-hexenoic acid as a minor product. Loss of the OH hydrogen atom forming butyrolactone (2, approximately 9%) and cleavage of the C-3[bond]C-4 bonds (<1%) in 1 are other minor pathways. The major source of excitation in 1 is by Franck-Condon effects that cause substantial differences between the adiabatic and vertical ionization of 1 (5.40 and 6.89 eV, respectively) and vertical recombination in the precursor ion 1(+) (4.46 eV). (+)NR(+) mass spectra distinguish radical 1 from isomeric radicals 2-oxo-(1H)oxolanium (3), 1,3-dioxan-2-yl (9), and 1,3-dioxan-4-yl (10) that were generated separately from their corresponding ion precursors.     

Determination of bismuth, indium and lead in geological samples by electrothermal AAS Part 2. Comparative study of palladium and molybdenum containing chemical modifiers*

A comparative and systematic study has been carried out of the effects of palladium and molybdenum containing chemical modifiers, such as Pd + Rh, Pd + Pt, Pd + Ru, Pd + Rh + Pt, Pd + Rh + Ru, Mo + Pd, Mo + Rh, Mo + Ru and Mo + Pt and additionally tartaric acid (TA) as a reducing agent together with mixed modifiers for the thermal stabilization of Bi, In and Pb in a Zeeman electrothermal atomic absorption spectrometer (ETAAS). The effect of the mass ratios of the mixed modifier components on the maximum pretreatment temperature for the analytes has been determined. The modifier mixtures of Pd + Rh + Pt, Mo + Pd + TA and Mo + Pt + TA were found to be especially powerful for the determination of Bi, In and Pb. These mixed modifiers could increase the ashing temperatures of the analytes up to 1250–1400° C. They were applied to the determination of Bi and Pb in dissolved geological reference samples and accuracy and precision of the method were thereby enhanced. The percent relative error was decreased from 20.0 to 0.4 for Bi and from 10.5 to 0.3 for Pb, depending on the sample type. Received: 9 May 1997 / Revised: 19 August 1997 / Accepted: 20 August 1997     

Complexation of well-controlled low-molecular weight polyelectrolytes with antisense oligonucleotides

The influences of polymer-related properties such as molecular weight, charge density, counter ion, and hydrophilic block on the complexation of polyelectrolytes and a fluorescein-labeled oligonucleotide (ON) were investigated. A series of well-defined and well-controlled 2-(N,N-dimethylamino)ethyl methacrylate (DMAEMA) polymers and block copolymers were prepared using living anionic and radical polymerization methods. Fluorescence measurement was used to reveal the effects of polymer molecular weight, charge density, and counter ion type on the complexation. PolyDMAEMA samples having double molecular weights of the chosen oligonucleotide gave the optimal complexation performance. Kinetic studies showed that high-molecular weight/high-charge density polymer samples produced very stable complexes. The fully charged polyDMAEMA displayed the strongest binding with the ON. These complexes were therefore less sensitive to the changes in the environment. PolyDMAEMA–DMSQ samples had slightly higher complexation ability than polyDMAEMA–MCQ (DMSQ: dimethylsulfate quat; MCQ: methylchloride quat). Both poly(DMAEMA-b-HEMA) and poly(DMAEMA–MCQ-b-PEG) block copolymers showed good complexation ability and steric stability [HEMA: 2-hydroxyethyl methacrylate; PEG: poly(ethylene glycol)]. PEG, but not HEMA block, enhanced the effectiveness of polyDMAEMA–MCQ binding with the ON.     

Copper(I) hexafluoroantimonate - an example of a compound with Cu in a solely fluorine environment

Yellow-orange single crystals of CuSbF₆, were prepared by reacting Cu wire (∼10 mmol) with SbF₅ (∼3 mmol) in liquid anhydrous hydrogen fluoride (aHF) and by reduction of Cu(SbF₆)₂ with Cu metal in aHF. CuSbF₆ crystallizes rhombohedral at 296 K with the LiSbF₆ structure type, with a = 530.4(4) pm, c = 1453(1) pm and Z = 3, space group R (no. 148). The structure is dominated by isolated layers of regular [SbF₆]⁻ octahedra and Cu⁺ cations.An attempt to prepare CuF by reaction between CuSbF₆ and CsF in aHF at ∼190 K failed. Instead of CuF, a mixture of Cu and CuF₂ was obtained.