Topotactic condensation of layer silicates with ferrierite-type layers forming porous tectosilicates.

Five different hydrous layer silicates (HLSs) containing fer layers (ferrierite-type layers) were obtained by hydrothermal syntheses from mixtures of silicic acid, water and tetraalkylammonium/tetraalkylphosphonium hydroxides. The organic cations had been added as structure directing agents (SDA). A characteristic feature of the structures is the presence of strong to medium strong hydrogen bonds between the terminal silanol/siloxy groups of neighbouring layers. The five-layered silicates differ chemically only with respect to the organic cations. Structurally, they differ with respect to the arrangement of the fer layers relative to each other, which is distinct for every SDA-fer-layer system. RUB-20 (containing tetramethylammonium) and RUB-40 (tetramethylphosphonium) are monoclinic with stacking sequence AAA and shift vectors between successive layers 1a0 + 0b0 + 0.19c0 and 1a0 + 0b0 + 0.24c0, respectively. RUB-36 (diethyldimethylammonium), RUB-38 (methyltriethylammonium) and RUB-48 (trimethylisopropylammonium) are orthorhombic with stacking sequence ABAB and shift vectors 0.5a0 + 0b0± 0.36c0, 0.5a0 + 0b0 + 0.5c0 and 0.5a0 + 0b0± 0.39c0, respectively. Unprecedented among the HLSs, two monoclinic materials are made up of fer layers which possess a significant amount of ordered defects within the layer. The ordered defects involve one particular Si-O-Si bridge which is, to a fraction of ca. 50%, hydrolyzed to form nests of two ≡Si-OH groups. When heated to 500-600 °C in air, the HLSs condense to form framework silicates. Although all layered precursors were moderately to well ordered, the resulting framework structures were of quite different crystallinity. The orthorhombic materials RUB-36, -38 and -48, general formula SDA4Si36O72(OH)4, which possess very strong hydrogen bonds (d[O···O] ≈ 2.4 Å), transform into a fairly or well ordered CDO-type silica zeolite RUB-37. The monoclinic materials RUB-20 and -40, general formula SDA2Si18O36(OH)2OH, possessing medium strong hydrogen bonds (d[O···O] ≈ 2.65 Å) are transformed into poorly ordered framework silicates. Some rules of thumb can be established concerning the successful zeolite synthesis via a topotactic condensation of layered precursors. Favourably, the precursor (i) possesses already a well ordered structure without defects, (ii) contains strong inter-layer hydrogen bonds and does not contain strong intra-layer hydrogen bonds and (iii) contains a suitable cation. The nature of the organic cation (size, geometry, flexibility, thermal stability) plays a key role in the formation of a microporous tectosilicate with well ordered structure. RUB-36 which meets these criteria yields a well ordered condensation product (RUB-37).

Particle self-bunching in the Schwinger effect in spacetime-dependent electric fields.

Nonperturbative electron-positron pair creation (the Schwinger effect) is studied based on the Dirac-Heisenberg-Wigner formalism in 1+1 dimensions. An ab initio calculation of the Schwinger effect in the presence of a simple space- and time-dependent electric field pulse is performed for the first time, allowing for the calculation of the time evolution of observable quantities such as the charge density, the particle number density or the total number of created particles. We predict a new self-bunching effect of charges in phase space due to the spatial and temporal structure of the pulse.

Momentum signatures for Schwinger pair production in short laser pulses with a subcycle structure.

We investigate electron-positron pair production from vacuum for short laser pulses with a subcycle structure, in the nonperturbative regime (Schwinger pair production). We use the nonequilibrium quantum kinetic approach and show that the momentum spectrum of the created electron-positron pairs is extremely sensitive to the subcycle dynamics-depending on the laser frequency omega, the pulse length tau, and the carrier phase varphi-and shows several distinctive new signatures. This observation could not only help in the design of laser pulses to optimize the experimental signature of Schwinger pair production but also ultimately lead to new probes of light pulses at extremely short time scales.

Comparison of the O Kalpha x-ray emission bands in micro- and mesoporous silica materials and in alpha-quartz.

X-ray emission spectroscopy (XES) at the O Kalpha threshold has been used to investigate the electronic structure of a microporous pure calcined zeolite with the crystal structure of the MFI-type framework (silicalite), a deboronated MFI zeolite (DB-MFI), a pure mesoporous cubic MCM-48 material, a MCM-48 loaded with copper and zinc oxide nanoparticles (CuZnO-MCM-48), and a crystalline layered silicic acid H-RUB-18. For comparison, the XES O Kalpha spectrum of pure alpha-quartz has also been recorded. In the nonresonant energy regime the XES O Kalpha spectra for all these compounds look very similar indicating that the electronic structure of the micro- and mesoporous silica materials is very similar to that of quartz. In the resonant regime, however, the spectra exhibit significant differences. In all the materials under study, the resonant XES O Kalpha spectra recorded at photon energies close to the positions of the O K edges show Raman-type inelastic peaks with an energy loss of 11 eV, originating from electronic excitations within these insulating materials. The prominent features in the XES O Kalpha spectra of alpha-quartz and H-RUB-18 are analyzed by means of quantum chemical ab initio cluster calculations.

The reduction of copper in porous matrices--the role of electrostatic stabilisation.

The redox properties of Cu(II) species in FAU matrices have been studied by temperature programmed reduction (TPR) in hydrogen and by XAFS analysis of the products obtained after (stationary) reduction treatments at various temperatures. The influence of the matrix polarity was investigated by comparing aluminosilicate FAU (Y zeolite) with siliceous FAU. In addition, the influence of Zn ions on the reduction process was studied. It was found that both the matrix composition and the presence of zinc ions exert a significant influence on the course of the reduction. In Y zeolite, heat treatment which is known to transfer Cu(II) ions to remote sites (SI, SI', SII') affects the reduction process dramatically. Cu(II) is most easily reduced in siliceous FAU, but the reduction proceeds in two clearly separated steps. Between these steps, small Cu(0) nuclei coexist with Cu(I) species, apparently unable to activate hydrogen for the autocatalytic reduction of the remaining Cu ions. The polarity of the matrix causes an upshift of the Cu(II) reduction temperature (in TPR by ca. 80 K for sites in the large cavity, by ca. 105 K for the remote sites), but the reduction of Cu(I) depends strongly on the simultaneous presence of Cu(0) and on its ability to activate hydrogen and induce an autocatalytic reduction mechanism. While Cu(I) species in the large cavities are easily reduced to the metal, tending to segregate from the zeolite lattice, Cu(I) ions in remote sites are strongly stabilized towards further reduction and even traces of Cu metal form only at very high temperatures. In the presence of zinc ions, the Cu metal particles formed were found to be smaller than in zinc-free samples.

Reduction of copper in porous matrixes. Stepwise and autocatalytic reduction routes.

The reduction of Cu(II) oxide species in siliceous matrixes of different porosity (MFI, FAU, MCM-48) and in alumosilicate MFI was studied by temperature-programmed reduction in hydrogen (TPR), by X-ray absorption fine structure (after stationary hydrogen treatments), and by transmission electron microscopy. It was found that the reduction may proceed in one or in two reduction steps. The two-step scheme known for zeolites was observed also for Cu(II) in siliceous microporous matrixes, with similar temperature of Cu(II) reduction onset as for the alumosilicate MFI. Therefore, the two-step scheme cannot be explained by the stabilization of Cu ions by intra-zeolite electrical fields. CuOx clusters in MCM-48 were reduced in a one-step scheme (similar to bulk CuO) at high Cu content (6 wt %) but in a two-step scheme at low Cu content (1 wt %). The two reduction steps observed with most samples cannot be identified with the transitions of all Cu(II) to Cu(I) and of Cu(I) to Cu(0). Instead, Cu(0) nuclei were observed already at low reduction temperatures and were found to coexist with Cu ions over temperature ranges of different extension. This coexistence range was narrow in materials that favor aggregation of the Cu nuclei into particles: Cu-MCM-48 of low Cu content and Cu-ZSM-5. In the latter, metal segregation from the pore system was found to be accompanied by an autocatalytic initiation of the second reduction step. In the siliceous microporous matrixes, the Cu(0) nuclei were observed to coexist with Cu ions over wide temperature ranges (100 K for MFI) at temperatures far above that of Cu reduction in the bulk oxide. These observations suggest that oligomeric Cu metal nuclei which may have been formed, e.g., at the intersections of the MFI channel system, may be unable to activate hydrogen, which would be required for rapid reduction of the coexisting Cu ions.

Solar ultraviolet radiation exposure of infants and small children.

Townsville, in Queensland, Australia, experiences very high levels of ambient solar ultraviolet radiation (UVR) throughout the year and has a predominantly white population which is prone to developing skin cancer. The UVR exposure of 1-year-old and 2 1/2-year-old children raised in Townsville was measured using UVR-sensitive polysulphone film badges. In two separate exposure studies undertaken for 7 days in October 1995 and 5 days in April 1997, exposure at the chest and shoulder for each subject was determined. The chest exposures for the 1-year-olds were significantly higher at weekends than on weekdays, whereas for the 2 1/2-year-old children the shoulder exposures were significantly higher at weekends than on weekdays. The median daily total exposure for 1-year-old infants was 0.4 SED (standard erythemal dose) for the chest and 0.4 SED for the shoulder. The median daily total exposure for 2 1/2-year-olds was 0.6 SED for the chest and 0.9 SED for the shoulder. Although the median daily total exposures were comparatively low, the maximum values for the chest and shoulder were 6.5 SED and 2.4 SED, respectively, for the 1-year-old infants, and 20.6 SED and 8.4 SED, respectively, for the 2 1/2-year-olds. While the 2 1/2-year-old children spent most of their time outside between 9 am and 4 pm, the 1-year-old infants spent more time outside before 9 am and after 4 pm. Exposure increases with age in early childhood. Increased mobility and a greater tendency to play outdoors is likely to account for the higher exposure levels in 2 1/2-year-old children, compared to 1-year-old infants.

Estimation of the annual solar UVR exposure dose of infants and small children in tropical Queensland, Australia.

The solar ultraviolet radiation (UVR) exposure of infants and small children was measured for 1 week using UVR-sensitive polysulfone film attached to the shoulder and chest of the subjects. For the infant study, shoulder and chest badges received similar exposures, while the 2 1/2-year-olds received higher exposures on the shoulder than on the chest. Also, the 2 1/2-year-olds generally received higher exposures than the infants. The median total daily exposures for both groups were 39 and 92 J/m2. The maximum total daily exposures measured were 640 J/m2 (chest) and 240 J/m2 (shoulder) for the infants and 2060 J/m2 (shoulder) and 840 J/m2 (chest) for the 2 1/2 year-olds. Using this exposure data, monthly and annual exposure doses were calculated for both groups and compared to similar data from the UK. The annual exposure dose for infants is 8.4 kJ/m2 or 84 standard erythemal dose (SED) for both shoulder and chest. The annual exposure dose for 2 1/2 year-old children is 39.4 kJ/m2 or 394 SED for the shoulder and 28.8 kJ/m2 or 288 SED for the chest. Apart from the generally higher annual exposure doses experienced by the infants and 2 1/2 year-old children in Townsville, the main difference to the UK is the almost nonexistent drop in monthly exposure doses between summer and winter in Townsville compared to the UK. In the UK, the winter-month exposure dose is only 0.5% of the summer-month dose. However, in Townsville it is around 40%.

The measurement of solar ultraviolet radiation.

High skin cancer rates, stratospheric ozone depletion and increased public interest and concern have resulted in a strong demand for solar ultraviolet radiation measurements and information. The Australian Radiation Laboratory (ARL) has been involved since the mid-1980s in the measurement of solar ultraviolet radiation (UVR) using spectroradiometers (SRM) and a network of broadband detectors at 18 sites in Australia and Antarctica and in Singapore through a collaborative agreement with the Singapore Institute of Science and Forensic Medicine. Measurement locations range from equatorial (Singapore, 1.3 degrees N) through tropical (Darwin, 12.4 degrees S) to polar (Mawson, 67.6 degrees S) and as a result there are many difficulties associated with maintenance and calibration of the network detectors, and transfer of data to ensure an accurate and reliable data collection. Calibration procedures for the various detectors involve the comparison with simultaneous spectral measurements using a portable SRM incorporating a double monochromator, calibrated against traceable standard lamps. Laboratory measurements of cosine response and responsivity are also made. Detectors are intercompared at the Yallambie site for a number of months before installation at another location. As an additional check on the calibrations, computer models of solar UVR at the earth's surface for days with clear sky and known ozone are compared with the UV radiometer measurements.

UV protection by clothing: an intercomparison of measurements and methods.

In an attempt to reduce the incidence of skin cancer, cancer foundations have run educational campaigns which encourage the general population to limit their solar UVR exposures. An important part of these campaigns, in particular in Australia, but also more recently in Europe and the U.S., has been the adoption of protective measures such as sunscreens, hats, sunglasses and clothing. The protective properties of fabrics and clothing against ultraviolet radiation (UVR) have been known for some time, but recently there has been considerable interest in quantifying the degree of protection. This has been generated, in part, by the requirements for occupational protection for outdoor workers as well as the provision of UVR protection for the recreational market. The quantification of UVR protection has been laboratory based using in vitro test methods. Development of a standard test method has become an important part of the testing process, and this paper presents results from an intercomparison involving five independent testing laboratories. Agreement is good, in particular for samples with protection factors below 50. Technical difficulties and sources of errors associated with the measurements are discussed.

Ultraviolet radiation protection factors for clothing.

There has been considerable interest and activity in Australia during recent years in providing ultraviolet radiation protection for the public and the work force. Many requests from the public and manufacturers have been received by the Australian Radiation Laboratory for the quantification of the protection provided by different articles of clothing. The laboratory has been making spectral measurements of the ultraviolet radiation transmission of materials and fabrics for a number of years and, to this date, have tested and rated > 2,000 samples. The laboratory test methods for making spectral transmission measurements of both dry and wet fabric samples are described along with the radiometric test methods to determine ultraviolet radiation transmission. A scheme to designate the amount of ultraviolet radiation protection of materials using ultraviolet protection factors is outlined and used to compare the results obtained by different test methods. Some typical measurement results are also summarized and presented.

Bilirubin phototherapy and potential UVR hazards.

Bilirubin phototherapy is a treatment often used in hospitals to alleviate neonatal jaundice in newborn babies. Phototherapy utilizes blue light and although the phototherapy units emit predominantly in this region, emissions from the adjacent ultraviolet region present a possible hazard if the exposure is of sufficient duration. A study of the levels of ultraviolet radiation (UVR) to which patients and staff involved with phototherapy are subjected was therefore undertaken.

Artificial suntanning: spectral irradiance and hazard evaluation of ultraviolet sources.

High incidences of skin damage and skin cancer amongst Australians have resulted in numerous campaigns to encourage people to protect themselves against solar ultraviolet radiation (UVR). The detrimental effects of UV-B radiation have been known for some time but recently there has been concern over the effects of UV-A radiation which had been thought of as relatively harmless. The proliferation of solaria, which incorporate UV-A sources, prompted the issuing of an Australian standard dealing with technical and non-technical aspects of the artificial suntanning industry. The purpose of this study was to measure the irradiance and spectral distribution of the emission from sunbeds and other UVR sources used for tanning, to evaluate the hazard potential and also the compliance with the standard. It was found that the majority of the UV-A lamps evaluated met the requirements of the standard. The UV-B lamps and portable sunlamps are potentially hazardous and their use should be discouraged. In general, the survey of solaria highlighted the need for further education of the public and especially the users and operators of solaria, on the hazards of UVR and of protective measures required for its safe use.

Indications of the occurrence of inflammatory reactions in the clinical improvement phase in multiple sclerosis patients.

In patients with multiple sclerosis (MS) the spontaneous burst activity (BA) of peripheral blood mononuclear cells was related to the clinical course of the disease. In five patients clinical improvement was found while the BA was significantly increased (more than 300% of the controls). During the appearance of new or deteriorating signs and in the period without clinical changes, the BA was not at all or not markedly increased. In two patients without clinical improvement the BA did not reach levels above 300% of the controls. Our findings suggest that inflammatory reactions represented by the BA occur in the phase of clinical improvement. Since burst-stimulating activity was found in the serum of MS patients, cytokines produced by activated immuno-competent cells are assumed to cause the increased BA. A possible role of prednisone and ACTH on the BA of peripheral mononuclear leucocytes is discussed.