Curing theory of A_f-A_g type free radical polymerization (I)──Distribution function and its invariant property

ＴｈｅｔｈｅｏｒｙｏｆｎｏｎｌｉｎｅａｒｐｏｌｙｍｅｒｉｚａｔｉｏｎｗａｓｉｎｉｔｉａｔｅｄｂｙＦｌｏｒｙ[1]ａｎｄＳｔｏｃｋｍａｙｅｒ[2].Ｆｏｒｓｉｍｐｌｉｆｙｉｎｇｔｈｅｅｖａｌｕａｔｉｏｎｏｆａｖｅｒａｇｅｐｏｌｙｍｅｒｑｕａｎｔｉｔｉｅｓ,ｍａｎｙｏｔｈｅｒｓｔａｔｉｓｔｉｃａｌｍｅｔｈｏｄｓｓｕｃｈａｓｔｈｅｐｒｏｂａｂｉｌｉｔｙｏｆｇｅｎｅｒａｔｉｎｇｆｕｎｃｔｉｏｎｍｅｔｈｏｄ[3],ｔｈｅｌａｗｏｆｔｏｔａｌｐｒｏｂａｂｉｌｉｔｙｍｅｔｈｏｄ[4,5]ａｎｄｔｈｅｏｔｈｅｒｍｅｔｈｏｄｓ[6…     

Quantum Instantons with Classical Moduli Spaces

 We introduce a quantum Minkowski space-time based on the quantum group SU(2) _q extended by a degree operator and formulate a quantum version of the anti-self-dual Yang-Mills equation. We construct solutions of the quantum equations using the classical ADHM linear data, and conjecture that, up to gauge transformations, our construction yields all the solutions. We also find a deformation of Penrose's twistor diagram, giving a correspondence between the quantum Minkowski space-time and the classical projective space ℙ³. Received: 10 May 2002 / Accepted: 10 January 2003 Published online: 5 May 2003 Communicated by L. Takhtajan     

Microwave-immobilized polybutadiene stationary phase for reversed-phase high-performance liquid chromatography

Polybutadiene (PBD) has been immobilized on high-performance liquid chromatography (HPLC) silica by microwave radiation at various power levels (52-663 W) and actuation times (3-60 min). Columns prepared from these reversed-phase HPLC materials, as well as from similar non-irradiated materials, were tested with standard sample mixtures and characterized by elemental analysis (%C) and infrared spectroscopy. A microwave irradiation of 20 min at 663 W gives a layer of immobilized PBD that presented good performance. Longer irradiation times give thicker immobilized layers having less favorable chromatographic properties.     

Some new selective stationary phases for RP-HPLC

At the present time, more complex analyses of apolar compounds with similar chemical structures or of polar compounds, especially basic ones, having diverse properties require more selective stationary phases having better stabilities. This paper describes several new stationary phases with directed selectivities that were prepared by immobilizing two different phenyl group-containing siloxanes and a trifluoropropyl-containing siloxane onto chromatographic silica and, in the case of the fluorinated siloxane, onto zirconized silica, using thermal treatment or microware radiation. The chromatographic properties and stabilities of these new phases were determined and several applications were evaluated. The phenyl-containing phases showed excellent characteristics related to the separation of several different types of aromatic compounds while the fluorinated phases, which present a more polar character, revealed selectivity for the separation of positional isomers as well as for a mixture of basic pharmaceuticals. Stability tests indicate that immobilization of the polysiloxanes increases column lifetimes by making the stationary phases less susceptible to dissolution, while the phases immobilized with microwave radiation were somewhat more stable than those immobilized by thermal treatments.     

Small-scale method for the determination of selected organochlorine pesticides in soil

A small-scale method was developed for the simultaneous determination of gamma-HCH, heptachlor, aldrin, dicofol, mirex, endosulfan I, endosulfan II and endosulfan sulphate in soil. The extraction and clean-up steps were combined into one step by transferring soil samples to chromatographic columns prepacked with neutral alumina. The pesticides elution was processed with n-hexane : dichloromethane (7 : 3) and the concentrated eluate was analysed using gas-liquid chromatography with electron capture detection. Analyses of the "in vitro" fortified samples with the selected pesticides were performed at three different levels. Mean recoveries for aldrin, gamma-HCH and heptachlor, at levels of 2, 10 and 20 ng/g, ranged from 71 to 87%; for dicofol, at levels of 8, 40 and 80 ng/g, ranged from 97 to 103%; for endosulfan I and II, at levels of 5, 25 and 50 ng/g, ranged from 88 to 96%; for mirex, at levels of 6, 30 and 60 ng/g, ranged from 86 to 110%; and for endosulfan sulphate, at levels of 15, 75 and 150 ng/g, ranged from 93 to 104%. The method can be used for rapid determination of these pesticides in soil.     

New generation of sterically protected C18 stationary phases containing embedded urea groups for use in high-performance liquid chromatography

New monofunctional C18 urea stationary phases with sterically protecting dimethyl and diisopropyl groups were prepared by a single step modification process. ProntoSil spherical silica (3 microm) was chemically modified with the monofunctional ethoxysilanes, [(3-octadecylurea)propyl]dimethyl and [(3-octadecylurea)propyl]diisopropyl ethoxysilanes. The phases were characterized by elemental analysis, infrared and solid-state 29Si and 13C NMR spectroscopies. Chromatographic characterizations of the new phases in 50x3.9 mm HPLC columns were performed by the separation of two different test mixtures, containing nonpolar, polar and highly basic compounds.     

Structural Deterioration of Well-Faceted MOFs upon H2S Exposure and Its Effect in the Adsorption Performance

The structural deterioration of archetypical, well-faceted metal–organic frameworks (MOFs) has been evaluated upon exposure to an acidic environment (H₂S). Experimental results show that the structural damage highly depends on the nature of the hybrid network (e.g., softness of the metal ions, hydrophilic properties, among others) and the crystallographic orientation of the exposed facets. Microscopy images show that HKUST-1 with well-defined octahedral (111) facets is completely deteriorated, ZIF-8 with preferentially exposed (110) facets exhibits a large external deterioration with the development of holes or cavities in the mesoporous range, whereas UiO-66-NH₂ with (111) exposed facets, and PCN-250 with (100) facets does not reflect any sign of surface damage. Despite the selectivity in the external deterioration, X-ray diffraction and gas adsorption measurements confirm that indeed all MOFs suffer an important internal deterioration, these effects being more severe for MOFs based on softer cations (e.g., Cu-based HKUST-1 and Fe-based PCN-250). These structural changes have inevitable important effects in the final adsorption performance for CO₂ and CH₄ at low and high pressures.     

Poly(methyloctylsiloxane) immobilized on silica as a sorbent for solid-phase extraction of some pesticides

A laboratory-made sorbent for solid-phase extraction (SPE) was obtained by thermal immobilization of poly(methyloctylsiloxane) (PMOS) onto silica. Cartridges packed with the new sorbent were used for the simultaneous determination of imazethapyr, nicosulfuron, diuron, linuron and chlorimuron-ethyl in water. These pesticides were separated and quantified using high-performance liquid chromatography with diode array detection (HPLC-DAD). The recoveries achieved with the laboratory-made PMOS cartridges were compared with those of some commercially available silica-based and polymer-based cartridges having C18, C8 and NH(2) pendant groups. Method validation using the laboratory-made sorbent was performed for the five pesticides at three fortifications levels (1x, 2x and 10x the limit of quantification of each pesticide). The laboratory-made PMOS cartridge has low cost preparation and showed good recoveries (72-111%) for all pesticides. Repeatability and intermediate precision were lower than 15%. Its performance was similar or even better, in some cases, than those of the commercial cartridges.     

Preparation of a polybutadiene stationary phase immobilized by gamma radiation for reversed-phase high-performance liquid chromatography

Polybutadiene (PBD) has been immobilized on HPLC silica by gamma radiation doses in the range from 5 to 180 kGy. Columns prepared from these reversed-phase materials, as well as from similar non-irradiated materials, were tested with standard sample mixtures and characterized by elemental analysis (% C) and infrared spectroscopy. A low dose of 5 kGy is sufficient to produce a layer of immobilized PBD which functions as an efficient and stable stationary phase. Higher doses give thicker immobilized layers having less favorable chromatographic properties.