Persistent polarization in polymers. II. Depolarization currents

Depolarization currents were used to study the persistent polarization induced in polystyrene and poly(methyl methacrylate) by cooling with flow under pressure. These studies showed that the charge on electrets made by flow under pressure consists in part of a surface charge which leaks off rapidly in moist air and in part of a charge due to volume polarization which decays more slowly. The volume polymerization produced in poly(methyl methacrylate) by flow under pressure is of the same order as that produced by cooling under a voltage drop, but flow under pressure produces a larger surface charge.     

Mechanistic studies of the photocatalytic oxidation of trichloroethylene with visible-light-driven N-doped TiO2 photocatalysts

Visible-light-driven TiO2 photocatalysts doped with nitrogen have been prepared as powders and thin films in a cylindrical tubular furnace under a stream of ammonia gas. The photocatalysts thus obtained were found to have a band-gap energy of 2.95 eV. Electron spin resonance (ESR) under irradiation with visible light (lambda > or = 430 nm) afforded the increase in intensity in the visible-light region. The concentration of trapped holes was about fourfold higher than that of trapped electrons. Nitrogen-doped TiO2 has been used to investigate mechanistically the photocatalytic oxidation of trichloroethylene (TCE) under irradiation with visible light (lambda > or = 420 nm). Cl and O radicals, which contribute significantly to the generation of dichloroacetyl chloride (DCAC) in the photocatalytic oxidation of TCE under UV irradiation, were found to be deactivated under irradiation with visible light. As the main by-product, only phosgene was detected in the photocatalytic oxidation of TCE under irradiation with visible light. Thus, the reaction mechanism of TCE photooxidation under irradiation with visible light clearly differs markedly from that under UV irradiation. Based on the results of the present study, we propose a new reaction mechanism and adsorbed species for the photocatalytic oxidation of TCE under irradiation with visible light. The energy band for TiO2 by doping with nitrogen may involve an isolated band above the valence band.     

Study of elution behaviour with gradient voltage in CEC using methacrylate monolithic columns

A theoretical study on the retention behaviour and chromatographic performance of neutral solutes using a lauryl methacrylate‐based monolithic column under voltage gradient mode in CEC was carried out. Through a flexible mathematical function based on a modified Gaussian model, the peak shape of compounds was firstly fitted under constant and gradient voltage. Using the peak shape parameters and retention time, the estimation of global chromatographic performance, efficiency and peak capacity under several voltage conditions was performed. The influence of voltage gradient on the separation efficiency is discussed and simple equations are presented to calculate retention and peak widths under voltage gradient conditions. A comparison in terms of chromatographic performance of a test mixture of neutral solutes under constant and gradient voltage modes was also carried out. The experiments carried out under gradient voltage showed better efficiencies (172 000 plates/m) and lower peak widths than those obtained under constant voltage (52 000 plates/m).     

聚合物在压力下的流动诱导结晶

流动诱导聚合物结晶研究很少在压力场下开展,其原因是压力下流动诱导聚合物结晶对实验设备要求较高。然而,实际加工中不仅存在流动场,还有压力场。为此,作者课题组利用自制的装置对压力下流动诱导聚合物结晶开展了系统研究,发现其结晶行为与常压的流动诱导结晶有较大差别。等规聚丙烯(iPP)在压力和剪切场下可形成独特取向球形晶体形态。在短时间内(30min),iPP片晶可快速增厚,形成熔点接近平衡熔点的厚片晶(近180℃),其原因是在压力和流动场协同作用下,片晶增厚活化能快速减小。同时,从研究结果也获得了添加β成核剂的iPP体系在压力和流动场下形成β晶的窗口条件。对聚乳酸(PLA)的研究也发现了相似的片晶快速增厚规律。另外,在压力和流动场下,可直接从PLA熔体中获得可增韧PLA的β晶。研究成果为实际加工中的聚合物形态结构调控提供了理论和实验依据。     

Influence of inherent iron and oxygen concentrations on selenite sorption process using bentonite

The oxygen concentration and inherent Fe in bentonite have a significant influence on the Se(IV) sorption process.In this study,the sorption of selenite on natural bentonite was investigated using a batch experiment method,and the distribution coefficient(K_d)values were obtained in the pH range from 2.0 to 10.0 under oxic/anoxic conditions.The K_d values always reached a maximum value at a pH of 4 under oxic conditions and at a pH of 8 under anoxic conditions;meanwhile,the K_d value under anoxic conditions was larger than the value under oxic conditions,especially in regard to the maximum K_d values.The oxygen conditions have a significant influence on the ratio of redox-sensitive Fe~(2+)/Fe~(3+),which was closely related to the difference in the K_d values under both oxic/anoxic conditions.Ferric selenite and green rust could be responsible for the maximum K_d values under oxic/anoxic conditions.In the leaching experiments,we found that the Fe~(2+) in bentonite could replace Mg~(2+) and Al~(3+) in the octahedral sheet.Spectroscopy methods,such as Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD) and X-ray absorption spectroscopy(XAS) were used to characterize the surface properties of the samples after reaction.Overall,this study shows that the addition of Fe~(2+)-containing materials into backfill/buffer materials under anoxic condition could enhance the sorption of ~(79)Se(IV).     

Drastic high magnetic field effect on suppression of Escherichia coli death

When Escherichia coli B was aerobically grown in a medium containing one-fourth the concentration of the LB medium supplemented with glutamic acid at 43 degrees C under an inhomogeneous 5.2-6.1 T magnetic field, the number of cells in the stationary phase under the high magnetic field was 100,000 times higher than that under a geomagnetic field. The finding that the amount of sigma S factor encoded by the rpoS gene under the high magnetic field was larger than that under the control geomagnetic field indicated that the activity of the rpoS gene was affected by the high magnetic field.     

Reaction of levoglucosenone with Dane’s diene

Cycloaddition of levoglucosenone to 7-methoxy-4-vinyl-1,2-dihydronaphthalene has been studied under different conditions, including heating under atmospheric pressure, in a sealed ampule, and under high pressure, as well as under microwave irradiation and in the presence of various catalysts. The chiral Diels–Alder adduct thus obtained can be used in the synthesis of estrone and its analogs.     

Microwave-assisted enzyme-catalyzed reactions in various solvent systems

The work describes the accelerated enzymatic digestion of several proteins in various solvent systems under microwave irradiation. The tryptic fragments of the proteins were analyzed by matrix-assisted laser desorption/ionization mass spectrometry. Under the influence of rapid microwave heating, these enzymatic reactions can proceed in a solvent such as chloroform, which, under traditional digestion conditions, renders the enzyme inactive. The digestion efficiencies and sequence coverages were increased when the trypsin digestions occurred in acetonitrile-, methanol- and chloroform-containing solutions that were heated under microwave irradiation for 10 min using a commercial microwave applicator. The percentage of the protein digested under microwave irradiation increased with the relative acetonitrile content, but decreased as the methanol content was increased. These observations suggest that acetonitrile does not deactivate the enzyme during the irradiation period; in contrast, methanol does deactivate it. In all cases, the digestion efficiencies under microwave irradiation exceed those under conventional conditions.     

毛竹在氢气中的催化热解研究

本文以分布广、产量大的速生生物质——毛竹为原料,研究其在H2氛围中、不同反应温度下热解所得产物的产率和分布,并与其在N2氛围中热解的结果进行了比较。结果表明,毛竹在H2气氛中热解,比在N2气氛中更有利于液体产物的生成。两种氛围中温度对液体产物影响的趋势不同,在本文条件下,H2气氛中升高温度始终有利于增加液体产率,使生物质有效转化率提高,在H2中毛竹热解生成甲醇、环丙基甲醇、呋喃甲醛等,这在N2中是不易得到的,但液体产物中含量最高的仍是乙酸。     

Effect of Cloud Cover on UVB Exposure Under Tree Canopies: Will Climate Change Affect UVB Exposure?

The effect of cloud cover on the amount of solar UV radiation that reaches pedestrians under tree cover was evaluated with a three-dimensional canopy radiation transport model. The spatial distribution of UVB irradiance at the base of a regular array of spherical tree crowns was modeled under the full range of sky conditions. The spatial mean relative irradiance (I), and erythemal irradiance of the entire below-canopy domain and the spatial mean relative irradiance and erythemal irradiance in the shaded regions of the domain were determined for solar zenith angles from 15° to 60°. The erythemal UV irradiance under skies with 50% or less cloud cover was not remarkably different from that under clear skies. In the shade, the actual irradiance was greater under partly cloudy than under clear skies. The mean ultraviolet protection factor for tree canopies under skies with 50% or less cloud cover was nearly equivalent to that for clear sky days. Regression equations of spatially averaged I_r . as a function of cloud cover fraction, solar zenith angle and canopy cover were used to predict the variation in erythemal irradiance in different land uses across Baltimore, MD.     

Reverse atom transfer radical solution polymerization of methyl methacrylate under pulsed microwave irradiation

The reverse atom transfer radical polymerization (RATRP) of methyl methacrylate (MMA) was successfully carried out under pulsed microwave irradiation (PMI) at 69 °C with N,N‐dimethylformamide as a solvent and with azobisisobutyronitrile (AIBN)/CuBr₂/tetramethylethylenediamine as an initiation system. PMI resulted in a significant increase in the polymerization rate of RATRP. A 10.5% conversion for a polymer with a number‐average molecular weight of 34,500 and a polydispersity index of 1.23 was obtained under PMI with a mean power of 4.5 W in only 52 min, but 103 min was needed under a conventional heating process (CH) to reach a 8.3% conversion under identical conditions. At different [MMA]₀/[AIBN]₀ molar ratios, the apparent rate constant of polymerization under PMI was 1.5–2.3 times larger than that under CH. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3823–3834, 2002     

Self-assembly of a dialkylurea gelator in organic solvents in the presence of centrifugal and shearing forces

A novel dialkylurea gelator, 1-methyl-2,4-bis(N(')-octadecaneureido)benzene (designated as MBOB) was synthesized, which can turn some organic solvents into organogels at extremely low concentrations (<2 wt%). The (1)H NMR spectra of MBOB in solution (110 degrees C) and in the gel state (30 degrees C) indicate that intermolecular hydrogen bonding is the driving force for the self-assembly of MBOB. In the process of the self-assembly of MBOB, orientation of MBOB aggregates occurs under the influence of external fields, such as a centrifugal force and shearing force fields. The minimum gelation concentrations of MBOB in organic solvents under a centrifugal force field were significantly higher than those in the absence of a centrifugal force field, indicating a significant effect of the external field on the self-assembly of MBOB. Field emission scanning electron microscopy (FE-SEM) provided evidence for a significantly phase transition of the MBOB aggregates from an amorphous state in the absence of the external field to an oriented state under conditions of a centrifugal or shearing force during the gelation process. A self-assembled structure of MBOB is proposed based upon an X-ray diffraction (XRD) analysis and a molecular simulation. DSC analysis of the organogels indicates that the phase transition temperature increased from 58.5 degrees C in the absence of the external field to 63.3 degrees C under a centrifugal force field and 62.2 degrees C under a shearing force field. The enthalpy of the phase transition decreased from 3.1 J/g in the absence of an external field to 2.6 J/g under a centrifugal force field and 2.7 J/g under a shearing force field.     

Microwave- and ultrasound-assisted Suzuki–Miyaura cross-coupling reactions catalyzed by Pd/PVP

Suzuki–Miyaura reactions using Pd/PVP as a catalyst source were carried out in water–ethanol solution. Under MW, sonication or thermal condition yields were very similar, from moderate to very good, in a variety of examples. However, TOFs were very different, 750/h under MW, 250/h under sonication, and 28/h under thermal conditions. Studies carried out under sonication showed that the whole system after product extraction can be re-used at least twice without any noticeable loss of yield.     

High-intensity ultrasound and microwave, alone or combined, promote Pd/C-catalyzed aryl-aryl couplings

Pd-catalyzed homo- and cross-couplings of boronic acids and aryl halides were successfully carried out both in aqueous media under high-intensity ultrasound (US) and in DME under microwave (MW). Heterogeneous catalysis with Pd/C was employed, avoiding phosphine ligands and phase-transfer catalysts. In a trial series involving 15 different iodo- and bromoaryls and 7 boronic acids, both energy sources drastically reduced reaction times affording biaryls in acceptable to good yields. With palladium(II) acetate as catalyst, electron-deficient aryl chlorides also reacted, affording a few biaryls in acceptable yields. Ullmann-type zinc-mediated homocoupling of iodo- and bromoaryls in the presence of Pd/C under CO₂ atmosphere was achieved in aqueous media under US, though not under MW. Suzuki homo- and cross-couplings were also carried out in a new reactor developed in our laboratory, featuring combined US and MW irradiation, further improving a green synthetic method.     

Free-flow electrophoresis under microgravity: evidence for enhanced resolution of cell separation

A mixture of fixed rabbit, guinea pig and rat erythrocytes, suspended in a relatively conductive solution, was separated by means of continuous free flow electrophoresis (CFFE) under 1 g- and microgram- conditions using a specially designed electrophoretic module. Short duration microgram conditions were realized on board a sounding rocket. Due to the energy input and the associated thermal convection a separation of the three differently charged cell types in distinct peaks was not possible under 1 g-conditions as shown by reference experiments on the ground before launch. In contrast to the poor resolution under 1 g-conditions, clear separation of the cell mixture could be recorded after lift-off of the rocket under microgram-conditions. Repeated measurements demonstrated that the separation profile was completely stable during the entire microgram-phase of about 6 min. Since the CFFE experiment in space was an exact replica of the ground reference experiments, the results demonstrated unambiguously the potential of CFFE for cell separation under microgram-conditions in media of high ionic strength.     

On a possible radical-cation mechanism of the biomimetic oxidation of the saturated hydrocarbon 1,3-dimethyladamantane in a Gif-type system containing a Fe2+ salt, picolinic acid, and pyridine

Based on an analysis of the ratio between the final products of the oxidation of 1,3-dimethyladamantane (1,3-DMA) with hydrogen peroxide under new catalytic conditions, an EPR-spectroscopic study of the 1,3-DMA radical cation under model radiation-chemical conditions, and the results of PM3 quantum-chemical calculations, a new mechanism was proposed for the biomimetic oxidation of the saturated hydrocarbon. This mechanism involves the intermediate formation of the 1,3-DMA radical cation, in which a tertiary C-H bond is selectively activated. Next, oxene (oxygen atom) is inserted into this C-H bond to form a tertiary alcohol. It was found that a comparison of the composition of final products in the oxidation of saturated hydrocarbons under conditions of a real chemical experiment with the structure and reactivity of their radical cations under model radiation-chemical conditions can be a methodologically new general technique for the analysis and prediction of the reactivity of saturated hydrocarbons under oxidative conditions.     

Change in broth culture is associated with significant suppression of Escherichia coli death under high magnetic field

When Escherichia coli B was cultivated under an inhomogeneous magnetic field of 5.2-6.1 T, a significant 100,000-fold suppression of cell death was observed [Bioelectrochemistry 53 (2001) 149]. The limited magnetic field exposure for 12 h after logarithmic growth phase was sufficient to observe similar suppressive effects on cell death [Bioelectrochemistry 54 (2001) 101]. These results suggest some possible changes in either the medium or the cells during the magnetic field exposure. When the cell-free filtrate of the broth cultured under the magnetic field for 10 h and the cells of E. coli cultivated under the geomagnetic field for 30 h were mixed, and the mixture was subsequently cultivated under the geomagnetic field, the number of cells observed in the filtrate exposed to the high magnetic field was 20,000 times higher than that in the filtrate exposed to the geomagnetic field. When the cells cultivated under the magnetic field for 10 h and the cell-free filtrate of the broth culture exposed to the geomagnetic field were mixed, only a 50-fold difference in the number of cell between under the magnetic field and under the geomagnetic field was observed. This suggests that the filtrate of the broth culture exposed to the magnetic field is primarily responsible for the cell death suppression. It was also revealed that the small difference in pH of the filtrates of the broth culture between under the magnetic field and under the geomagnetic field was critical for the cell death suppression.     

Fast and mild palladium(II)-catalyzed 1,4-oxidation of 1,3-dienes via activation of molecular oxygen with a designed cobalt(II) porphyrin

The use of a Co(porphyrin)-amide ligand, , in the palladium(II)-catalyzed 1,4-diacetoxylation of conjugated dienes under O2 results in aerobic oxidation. The catalyst was highly active under O2, and the 1,4-diacetoxylation reaction could also be performed under air.     

Interface-Induced Coarsening Process in Polymer Blends

The coarsening process of the droplets in a two-phase polymer blend (PP/EVAc) was studied under two-dimensional and three-dimensional conditions using a phase contrast microscope and computer image analyzer. The results showed that under three-dimensional conditions the growth of the droplet's radius with time follows r(3) approximately t(1.01), corresponding to the evaporation-condensation theory of Lifshitz-Slyozov, r(3) approximately t, while under two-dimensional conditions the growth law is r(3) approximately t(1.31). The growth rate of the droplets under two-dimensional conditions is faster than that under three-dimensional conditions. This difference is caused by an interfacial interaction (wetting effects) between the substrates and polymer blend. The existence of the interface promoted the coarsening process of the polymer blend under two-dimensional conditions. Copyright 2001 Academic Press.     

Photochemistry and phototoxicity of fluocinolone 16,17-acetonide

Fluocinolone 16,17-acetonide is a corticosteroid used topically to treat various inflammatory skin diseases. Its photoreactivity was studied under UV-A and UV-B light in aqueous buffer in the presence of oxygen. This drug is photolabile under UV-B light and, to a lesser extent, under UV-A light, which is absorbed far less. In phosphate buffer, approximately 80% of fluocinolone acetonide decomposes after 5 J/cm2 of UV-B irradiation, whereas under 30 J/cm2 of UV-A light approximately only 20% decomposes. Both the drug and its photoproducts have been evaluated through a battery of in vitro studies and found to cause photohemolysis and induce photodamage to proteins (erythrocyte ghosts, bovine serum albumin) and linoleic acid. In addition, one of the photoproducts (the 17-hydroperoxy derivative) is highly toxic in the dark. Therefore, both loss of therapeutic activity and light-induced adverse effects may be expected when patients expose themselves to sunlight after drug administration. A major mechanism for phototoxicity involves radicals forming from drug breakdown, at least under UV-B, although reactive oxygen species may play a role, particularly under UV-A.