An in situ time-dependent study of the photodimerisation of chloro-derivatives of trans-cinnamic acid using infrared microspectroscopy with a synchrotron radiation source

The photodimerisation of single crystals of substituted cinnamic acid has been monitored continuously by infrared microscopy using a synchrotron source. The beta-form of 2,4-dichloro-trans-cinnamic acid dimerises under ultraviolet irradiation to form the corresponding beta-truxinic acid derivative in a reaction which follows strictly first order kinetics. By contrast the corresponding reactions in single crystals of beta-2-chloro-trans-cinnamic acid and beta-4-chloro-trans-cinnamic acid deviate somewhat from first order kinetics as a result of solid-state effects. In all three cases the reactions proceed smoothly from monomer to dimer with no hint of any reaction intermediate.

Spectral design and verification of HIRDLS filters and antireflection coatings using an integrated system performance approach

The HIRDLS instrument contains 21 spectral channels spanning a wavelength range from 6 to 18mm. For each of these channels the spectral bandwidth and position are isolated by an interference bandpass filter at 301K placed at an intermediate focal plane of the instrument. A second filter cooled to 65K positioned at the same wavelength but designed with a wider bandwidth is placed directly in front of each cooled detector element to reduce stray radiation from internally reflected in-band signals, and to improve the out-of-band blocking. This paper describes the process of determining the spectral requirements for the two bandpass filters and the antireflection coatings used on the lenses and dewar window of the instrument. This process uses a system throughput performance approach taking the instrument spectral specification as a target. It takes into account the spectral characteristics of the transmissive optical materials, the relative spectral response of the detectors, thermal emission from the instrument, and the predicted atmospheric signal to determine the radiance profile for each channel. Using this design approach an optimal design for the filters can be achieved, minimising the number of layers to improve the in-band transmission and to aid manufacture. The use of this design method also permits the instrument spectral performance to be verified using the measured response from manufactured components. The spectral calculations for an example channel are discussed, together with the spreadsheet calculation method. All the contributions made by the spectrally active components to the resulting instrument channel throughput are identified and presented.

The adsorption and stability of sulfur containing amino acids on Cu{531}

The adsorption of L-CySteine and L-methionine amino acids on a chiral Cu{5 3 1} surface was investigated with high resolution X-ray photoelectron spectroscopy (XPS) and carbon K-edge near edge X-ray absorption fine structure (NEXAFS) Spectroscopy using synchrotron radiation. XPS shows that at 300 K L-cysteine adsorbs through two oxygen, a nitrogen and a sulfur atom, in a four point 'quadrangular footprint', whereas L-methionine adsorbs through only two oxygen and a nitrogen atom in a 'triangular footprint'. NEWS was used to clarify the adsorption geometry of both molecules, which suggests a binding orientation to the top layer and second layer atoms in two different orientations associated with adsorption sites on {1 1 0} and {3 1 1} microfacets; of the Cu{5 3 1} surface. (C) 2009 Elsevier B.V. All rights reserved.

One-pot synthesis and characterization of soluble poly(aryl ether-ketone)s having pendant carboxyl groups

Aromatic poly(ether-ketone)s having pendant carboxyl groups have been obtained by direct, one-pot, Friedel-Crafts copolycondensation of 4,4'-diphenoxybenzophenone with a mixture of terephthaloyl chloride (TC) and trimellitic anhydride acid chloride (TAAC), over a wide range of TAAC/TC molar ratios, in the presence of anhydrous aluminum chloride. The syntheses were performed as precipitation-polycondensations, and the polymers were obtained in particulate form. Besides globular particles of polymer, small quantities of elongated, needlelike particles were observed when the mole ratio TAAC/TC was less than 1. Use of X-ray microdiffraction with synchrotron radiation has revealed that the needlelike material consists of a cyclic compound containing 10 phenylene units, i.e., the crystals are of a [2 + 2] macrocyclic dimer. The polymers obtained are soluble in strong acids and in mixtures of methanesulfonic acid or trifluoroacetic acid with chlorinated hydrocarbons. The molecular structures of the polymers were confirmed by H-1 and C-13 NMR spectroscopy. Reaction of TAAC with 4,4'-diphenoxybenzophenone produced mainly meta-orientation of the resulting ketone linkages. The size of the polymer particles, their molecular weights, and the melting behavior of the products obtained depend on the TAAC/TC ratio used. Ortho-keto acid residues, formed during reaction of anhydride groups of TAAC with 4,4'-diphenoxybenzophenone, exhibit ring-chain tautomerism. A carboxyl-containing aromatic polyketone derived from p-terphenyl, and thus having with no ether linkages in the main chain, was prepared by analogous chemistry, and functional derivatives of carboxy-substituted polyketones were also obtained and characterized.

Formation of crystalline macrocyclic phases during electrophilic precipitation-polycondensation syntheses of poly(arylene ether ketone)s

Elongated crystalline particles formed as by-products during poly(arylene ether ketone) synthesis by electrophilic precipitation-polycondensation of 4,4'-diphenoxybenzophenone with terephthaloyl chloride or isophthaloyl chloride, thought previously to be polymer-whiskers, have now been identified as macrocyclic phases. Single crystal X-ray analysis of the needle-like particles formed in the reaction with terephthaloyl chloride, using the microdiffraction technique with synchrotron radiation, revealed that they consist of a macrocylic compound containing ten phenylene units, i.e. the [2 + 2] cyclic dimer. An analogous structure has also been demonstrated for the corresponding macrocycle derived from the reaction of 4,4-diphenoxybenzophenone with isophthaloyl chloride. Chloroform extraction of the products of the two polycondensations dissolved the macrocyclic material (but not the linear polymer), and analysis of the extracts by MALDI-TOF mass spectrometry demonstrated the presence in both cases of homologous families of macrocyclic products. Higher yields of macrocycles were obtained under pseudo-high dilution conditions, enabling the [2 + 2] cyclodimers from reactions of 4,4'-diphenoxybenzophenone with both terephthaloyl and isophthaloyl chloride to be isolated as pure compounds and fully characterised. (C) 2003 Published by Elsevier Ltd.

Mapping fibre orientation in complex-shaped biological systems with micrometre resolution by scanning X-ray microdiffraction

A fully automated procedure to extract and to image local fibre orientation in biological tissues from scanning X-ray diffraction is presented. The preferred chitin fibre orientation in the flow sensing system of crickets is determined with high spatial resolution by applying synchrotron radiation based X-ray microbeam diffraction in conjunction with advanced sample sectioning using a UV micro-laser. The data analysis is based on an automated detection of azimuthal diffraction maxima after 2D convolution filtering (smoothing) of the 2D diffraction patterns. Under the assumption of crystallographic fibre symmetry around the morphological fibre axis, the evaluation method allows mapping the three-dimensional orientation of the fibre axes in space. The resulting two-dimensional maps of the local fibre orientations - together with the complex shape of the flow sensing system - may be useful for a better understanding of the mechanical optimization of such tissues.

Solvent influences on metastable polymorph lifetimes: real-time interconversions using energy dispersive X-ray diffractometry

Solvent influences on the crystallization of polymorph and hydrate forms of the nootropic drug piracetam (2-oxo-pyrrolidineacetamide) were investigated from water, methanol, 2-propanol, isobutanol, and nitromethane. Crystal growth profiles of piracetam polymorphs were constructed using time-resolved diffraction snapshots collected for each solvent system. Measurements were performed by in situ energy dispersive X-ray diffraction recorded in Station 16.4 at the synchrotron radiation source (SRS) at Daresbury Laboratory, CCLRC UK. Crystallizations from methanol, 2-propanol, isobutanol, and nitromethane progressed in a similar fashion with the initial formation of form I which then converted relatively quickly to form II with form III being generated upon further cooling. However, considerable differences were observed for the polymorphs lifetime and both the rate and temperature of conversion using the different solvents. The thermodynamically unstable form I was kinetically favored in isobutanol and nitromethane where traces of this polymorph were observed below 10 degrees C. In contrast, the transformation of form II and subsequent growth of form III were inhibited in 2-propanol and nitromethane solutions. Aqueous solutions produced hydrate forms of piracetam which are different from the reported monohydrate; this crystallization evolved through successive generation of transient structures which transformed upon exchange of intramolecular water between the liquid and crystalline phases. (c) 2007 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 96:1069-1078, 2007.

The molecular structure and one-pot synthesis of [Li(thf)3·Sn(SiMe3)3]

The molecular structure of [Li(thf)3 · Sn(SiMe3)3], prepared by a new, one-pot synthesis in 44% yield, has been determined by a single crystal X-ray diffraction study using synchrotron radiation and a CCD detector. The +Li(thf)3 and −Sn(SiMe3)3 moieties are joined by a Li–Sn bond, 2.865(5) Å in length. [Li(thf)3 · Sn(SiMe3)3] is isomorphous with its germanium analogue.

A two-dimensional X-ray scattering system for in-situ time-resolving studies of polymer structures subjected to controlled deformations

A two-dimensional X-ray scattering system developed around a CCD-based area detector is presented, both in terms of hardware employed and software designed and developed. An essential feature is the integration of hardware and software, detection and sample environment control which enables time-resolving in-situ wide-angle X-ray scattering measurements of global structural and orientational parameters of polymeric systems subjected to a variety of controlled external fields. The development and operation of a number of rheometers purpose-built for the application of such fields are described. Examples of the use of this system in monitoring degrees of shear-induced orientation in liquid-crystalline systems and crystallization of linear polymers subsequent to shear flow are presented.

Preventing carbon contamination of optical devices for X-rays: the effect of oxygen on photon-induced dissociation of CO on platinum

Platinum is one of the most common coatings used to optimize mirror reflectivity in soft X-ray beamlines. Normal operation results in optics contamination by carbon-based molecules present in the residual vacuum of the beamlines. The reflectivity reduction induced by a carbon layer at the mirror surface is a major problem in synchrotron radiation sources. A time-dependent photoelectron spectroscopy study of the chemical reactions which take place at the Pt(111) surface under operating conditions is presented. It is shown that the carbon contamination layer growth can be stopped and reversed by low partial pressures of oxygen for optics operated in intense photon beams at liquidnitrogen temperature. For mirrors operated at room temperature the carbon contamination observed for equivalent partial pressures of CO is reduced and the effects of oxygen are observed on a long time scale.

Speleothems as sensitive recorders of volcanic eruptions - the Bronze Age Minoan eruption recorded in a stalagmite from Turkey

Mounting evidence exists that variations in sulphur content in stalagmites are closely linked to changes in volcanic or anthropogenic atmospheric sulphur. The strong dependency of sulphur on soil pH and ecosystem storage, however, can result in a delay of several years to decades in the registration of volcanic eruptions and anthropogenic emissions by stalagmites. Here we present synchrotron-radiation based trace element analysis performed on a precisely-dated section of a stalagmite from Sofular Cave in Northern Turkey. As this section covers the time interval of the intensively studied Minoan volcanic eruption between 1600 and 1650 BC, we can test whether this vigorous eruption can be traced in a stalagmite. Of all measured trace elements, only bromine shows a clear short-lived peak at 1621±251621±25 BC, whereas sulphur and molybdenum show peaks later at 1617±251617±25 and 1589±251589±25 respectively. We suggest that all trace element peaks are related to the Minoan eruption, whereas the observed phasing of bromine, molybdenum and sulphur is related to differences in their retention rates in the soil above Sofular Cave. For the first time, we can show that bromine appears to be an ideal volcanic tracer in stalagmites, as it is a prominent volatile component in volcanic eruptions, can be easily leached in soils and rapidly transferred from the atmosphere through the soil and bedrock into the cave and stalagmite respectively. Highly resolved oxygen and carbon isotope profiles indicate that the Minoan eruption had no detectable climatic and environmental impact in Northern Turkey.

Kerb and urban increment of highly time-resolved trace elements in PM10, PM2.5 and PM1.0 winter aerosol in London during ClearfLo 2012

Ambient concentrations of trace elements with 2 h time resolution were measured in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 size ranges at kerbside, urban background and rural sites in London during winter 2012. Samples were collected using rotating drum impactors (RDIs) and subsequently analysed with synchrotron radiation-induced X-ray fluorescence spectrometry (SR-XRF). Quantification of kerb and urban increments (defined as kerb-to-urban and urban-to-rural concentration ratios, respectively), and assessment of diurnal and weekly variability provided insight into sources governing urban air quality and the effects of urban micro-environments on human exposure. Traffic-related elements yielded the highest kerb increments, with values in the range of 10.4 to 16.6 for SW winds (3.3–6.9 for NE) observed for elements influenced by brake wear (e.g. Cu, Sb, Ba) and 5.7 to 8.2 for SW (2.6–3.0 for NE) for other traffic-related processes (e.g. Cr, Fe, Zn). Kerb increments for these elements were highest in the PM10–2.5 mass fraction, roughly twice that of the PM1.0–0.3 fraction. These elements also showed the highest urban increments (~ 3.0), although no difference was observed between brake wear and other traffic-related elements. All elements influenced by traffic exhibited higher concentrations during morning and evening rush hours, and on weekdays compared to weekends, with the strongest trends observed at the kerbside site, and additionally enhanced by winds coming directly from the road, consistent with street canyon effects. Elements related to mineral dust (e.g. Al, Si, Ca, Sr) showed significant influences from traffic-induced resuspension, as evidenced by moderate kerb (3.4–5.4 for SW, 1.7–2.3 for NE) and urban (~ 2) increments and increased concentrations during peak traffic flow. Elements related to regional transport showed no significant enhancement at kerb or urban sites, with the exception of PM10–2.5 sea salt (factor of up to 2), which may be influenced by traffic-induced resuspension of sea and/or road salt. Heavy-duty vehicles appeared to have a larger effect than passenger vehicles on the concentrations of all elements influenced by resuspension (including sea salt) and wearing processes. Trace element concentrations in London were influenced by both local and regional sources, with coarse and intermediate fractions dominated by traffic-induced resuspension and wearing processes and fine particles influenced by regional transport.

An observing system simulation experiment for climate monitoring with GNSS radio occulation data: setup and testbed study

The long-term stability, high accuracy, all-weather capability, high vertical resolution, and global coverage of Global Navigation Satellite System (GNSS) radio occultation (RO) suggests it as a promising tool for global monitoring of atmospheric temperature change. With the aim to investigate and quantify how well a GNSS RO observing system is able to detect climate trends, we are currently performing an (climate) observing system simulation experiment over the 25-year period 2001 to 2025, which involves quasi-realistic modeling of the neutral atmosphere and the ionosphere. We carried out two climate simulations with the general circulation model MAECHAM5 (Middle Atmosphere European Centre/Hamburg Model Version 5) of the MPI-M Hamburg, covering the period 2001–2025: One control run with natural variability only and one run also including anthropogenic forcings due to greenhouse gases, sulfate aerosols, and tropospheric ozone. On the basis of this, we perform quasi-realistic simulations of RO observables for a small GNSS receiver constellation (six satellites), state-of-the-art data processing for atmospheric profiles retrieval, and a statistical analysis of temperature trends in both the “observed” climatology and the “true” climatology. Here we describe the setup of the experiment and results from a test bed study conducted to obtain a basic set of realistic estimates of observational errors (instrument- and retrieval processing-related errors) and sampling errors (due to spatial-temporal undersampling). The test bed results, obtained for a typical summer season and compared to the climatic 2001–2025 trends from the MAECHAM5 simulation including anthropogenic forcing, were found encouraging for performing the full 25-year experiment. They indicated that observational and sampling errors (both contributing about 0.2 K) are consistent with recent estimates of these errors from real RO data and that they should be sufficiently small for monitoring expected temperature trends in the global atmosphere over the next 10 to 20 years in most regions of the upper troposphere and lower stratosphere (UTLS). Inspection of the MAECHAM5 trends in different RO-accessible atmospheric parameters (microwave refractivity and pressure/geopotential height in addition to temperature) indicates complementary climate change sensitivity in different regions of the UTLS so that optimized climate monitoring shall combine information from all climatic key variables retrievable from GNSS RO data.

Assessment of the consistency of near-infrared water vapor line intensities using high-spectral-resolution ground-based Fourier transform measurements of solar radiation

Calculations of the absorption of solar radiation by atmospheric gases, and water vapor in particular, are dependent on the quality of databases of spectral line parameters. There has been increasing scrutiny of databases such as HITRAN in recent years, but this has mostly been performed on a band-by-band basis. We report nine high-spectral-resolution (0.03 cm(-1)) measurements of the solar radiation reaching the surface in southern England over the wave number range 2000 to 12,500 cm(-1) (0.8 to 5 mm) that allow a unique assessment of the consistency of the spectral line databases over this entire spectral region. The data are assessed in terms of the modeled water vapor column that is required to bring calculations and observations into agreement; for an entirely consistent database, this water vapor column should be constant with frequency. For the HITRAN01 database, the spread in water vapor column is about 11%, with distinct shifts between different spectral regions. The HITRAN04 database is in significantly better agreement (about 5% spread) in the completely updated 3000 to 8000 cm(-1) spectral region, but inconsistencies between individual spectral regions remain: for example, in the 8000 to 9500 cm(-1) spectral region, the results indicate an 18% (+/- 1%) underestimate in line intensities with respect to the 3000 to 8000 cm(-1) region. These measurements also indicate the impact of isotopic fractionation of water vapor in the 2500 to 2900 cm(-1) range, where HDO lines dominate over the lines of the most abundant isotope of H2O.