Synthesis and biodistribution of the 99mTc nitrido complex with 2-(4-nitro-1H-imidazolyl)ethyl dithiocarbamate (NIET)

Sodium and chlorine measurements were made by instrumental neutron activation analysis (INAA) on stratigraphically dated ice core samples from Byrd Station, Antarctica, for the last three centuries. The time period between 1969 and 1989 showed an enhanced impact on the Antarctic ice sheets from oceans in the form of marine aerosols. A disturbed ocean-atmosphere interface due to El Niño Southern Oscillation (ENSO) events seems to be a candidate for this observation in Antarctica.     

THE MICROPARTICLE CONCENTRATION MEASUREMENT AND ITS CLIMATIC IMPLICATIONS IN AN ICE CORE FROM COAST AREA,ANTARCTICA

The microparticle concentration in an ice core from coast area, East Antarctica, has been measured by a Coulter counter and optic counting. It is proposed in the present paper that the microparticle concentrations in different areas are different, especially from the coast to the inland in Antarctica. After its comparison with microparticle concentrations from other cores, it is also proposed that there is a lag between the coldest climate (i. e. 18 ka B. P.) and the highest microparticle concentration.     

Neutron activation analysis of snow and ice in Antarctica

In order minimize the possible contamination during storing and pre-treatment of such pure samples as ice and snow collected in Antarctica, trace elements in experimental tools such as bottles, beakers, tubings and filters were determined by neutron activation analysis. By using well certified tools, ice and snow samples from Antarctica and high mountains in China and in Japan were analyzed. Relative concentrations of volatile elements such as Zn, Cd, As, Sb or Ag to Al or Fe which are major components in the earth crust were found to be 10 to 1000 times higher than in the ordinary soil for the samples from Antarctica and Mt. Naimonanyi in China.     

Interfacial Materials for Anti‐Icing: Beyond Superhydrophobic Surfaces

The design and fabrication of interfacial materials for anti‐icing is of great importance, since undesired ice accumulation leads to serious economic, energy, and safety issues. Substantial progress on interfacial materials for the passive removal of ice has been achieved in the past three years. The present focus review critically summarizes and analyzes recent breakthroughs in interfacial materials for anti‐icing. In particular, we focus on the effect of surface textures on the timely removal of water droplets, the microscopic mechanism of ice formation, and the effect of an interfacial layer's properties on easy shedding of formed ice with a view towards designing high‐performance and durable interfacial materials for anti‐icing beyond superhydrophobic materials.     

Determination of the spallogenic radionuclides26Al and53Mn in Antarctic meteorites with respect to cosmic ray exposure and terrestrial ages

The spallogenic radionuclides²⁶Al (T=7.18·10⁵ a) and⁵³Mn (T=3.8·10⁶ a) were determined in 11 ordinary chondrites and 7 achondrites from Antarctica by nondestructive coincidence counting techniques and radiochemical neutron activation analysis, respectively. The results are discussed with respect to exposure ages, terrestrial residence times and possible genetic relationships of the meteorites investigated. The high terrestrial ages of some specimens (up to 800 000 years) are of importance for the study of the ice flow in Antarctica.     

Studying Ice with Environmental Scanning Electron Microscopy

Scanning electron microscopy (SEM) is a powerful imaging technique able to obtain astonishing images of the micro- and the nano-world. Unfortunately, the technique has been limited to vacuum conditions for many years. In the last decades, the ability to introduce water vapor into the SEM chamber and still collect the electrons by the detector, combined with the temperature control of the sample, has enabled the study of ice at nanoscale. Astounding images of hexagonal ice crystals suddenly became real. Since these first images were produced, several studies have been focusing their interest on using SEM to study ice nucleation, morphology, thaw, etc. In this paper, we want to review the different investigations devoted to this goal that have been conducted in recent years in the literature and the kind of information, beyond images, that was obtained. We focus our attention on studies trying to clarify the mechanisms of ice nucleation and those devoted to the study of ice dynamics. We also discuss these findings to elucidate the present and future of SEM applied to this field.     

Halocarbons in Aqueous matrices from the Rennick Glacier and the Ross Sea (Antarctica)

Aqueous matrices from Antarctica were analysed for three volatile chlorinated hydrocarbons (VCHCs): tetrachloromethane (CCl₄), trichloroethylene (C₂HCl₃) and tetrachloroethylene (C₂Cl₄). The matrices analysed were snow from Rennick Nèvè and Rennick Glacier sampled during the Italian Expeditions of 1995/96 and 1996/97, respectively, and seawater, pack ice, sea-microlayer, subsuperficial water and freshwater, collected during the Italian Expedition of 1997/98. Extractions from the aqueous matrices were carried out in Antarctica (the laboratories of the Italian Base, Terra Nova Bay). Because of the critical space–time conditions in these laboratories, an extraction procedure was developed, suitable for large volumes of water (10?L), in order to combine the extraction of other classes of organic compounds (polychlorinated biphenyls, polycyclic aromatic hydrocarbons and chlorinated pesticides) with those of our direct interest. The VCHC organic extracts were analysed in Italy by GC-ECD and GC-MS. The analyses confirmed the presence of the three halocarbons in Antarctica in quantities ranging from units to some dozens of nanograms per kilogram. The results were evaluated with respect to the local distribution of these compounds and their diffusion on a global scale.     

Thallium and cadmium in recent snow and firn layers in the Canadian Arctic by atomic fluorescence and absorption spectrometries

Compared to the Antarctic and Greenland, the Canadian Arctic has seen extremely few trace metal studies on snow and ice. Surface, subsurface and depth samples of snow and firns were collected from the Agassiz Ice Cap, Ellesmere Island, Canada using clean room practices. Results for Tl (directly determined by LEAFS) and Cd (determined by GFAAS) are reported. To our knowledge, the thallium depth profile presented here is the first one so far reported for both polar systems, Greenland or other places. Tl concentrations peak in the winter-spring periods, when the Arctic atmosphere is loaded with foreign pollutants and suspended particulates which sometime severely reduce the visibility, creating a phenomenon commonly known as the Arctic haze. These results are in general accordance with the historical Arctic air pollution and acidity/conductivity data on ice cores. Surface concentrations of Tl range from 0.3 to 0.9 pg/g, which is a few times higher than those found in Antarctica. Cadmium shows seasonal characteristics similar to Tl although there is not a definite correlation between the two. However, there could be two predominant origins of metals which were deposited in the snow: Eurasian origin in January–April corresponding to high level metals (main deposition), and a less definite origin in May–December corresponding to low level metals.     

2-Nitrobenzaldehyde as a chemical actinometer for solution and ice photochemistry

2-Nitrobenzaldehyde (2NB) is a convenient, photochemically sensitive, and thermally robust actinometer. Although 2NB has been used in a number of solution and ice experiments in the laboratory, the quantum efficiencies and molar absorptivities of 2NB have not been critically evaluated, especially on ice. Using a series of laboratory and field measurements we have measured the light absorbance and photochemical properties of 2-nitrobenzaldehyde in solution (water and/or acetonitrile) and in/on water ice. Our results show that the molar absorptivities of 2NB are only weakly dependent upon temperature and that the quantum yield is independent of temperature in water; the quantum yield is also independent of wavelength, as shown by past reports. Furthermore, we find that the photochemistry of 2NB in/on water ice is the same as in liquid water. While most studies employing 2NB cite and use a quantum yield of 0.50, based on a review of the literature, and on our new experimental data, we recommend a quantum yield of 0.41 for 2NB photolysis for both solution and water ice.     

Chemical signals of past climate and environment from polar ice cores and firn air

Chemical and isotopic records obtained from polar ice cores have provided some of the most iconic datasets in Earth system science. Here, I discuss how the different records are formed in the ice sheets, emphasising in particular the contrast between chemistry held in the snow/ice phase, and that which is trapped in air bubbles. Air diffusing slowly through the upper firn layers of the ice sheet can also be sampled in large volumes to give more recent historical information on atmospheric composition. The chemical and geophysical issues that have to be solved to interpret ice core data in terms of atmospheric composition and emission changes are also highlighted. Ice cores and firn air have provided particularly strong evidence about recent changes (last few decades to centuries), including otherwise inaccessible data on increases in compounds that are active as greenhouse gases or as agents of stratospheric depletion. On longer timescales (up to 800?000 years in Antarctica), ice cores reveal major changes in biogeochemical cycling, which acted as feedbacks on the very major changes in climate between glacial and interglacial periods.     

Smell and Stress Response in the Brain: Review of the Connection between Chemistry and Neuropharmacology

The stress response in the brain is not fully understood, although stress is one of the risk factors for developing mental disorders. On the other hand, the stimulation of the olfactory system can influence stress levels, and a certain smell has been empirically known to have a stress-suppressing effect, indeed. In this review, we first outline what stress is and previous studies on stress-responsive biomarkers (stress markers) in the brain. Subsequently, we confirm the olfactory system and review previous studies on the relationship between smell and stress response by species, such as humans, rats, and mice. Numerous studies demonstrated the stress-suppressing effects of aroma. There are also investigations showing the effects of odor that induce stress in experimental animals. In addition, we introduce recent studies on the effects of aroma of coffee beans and essential oils, such as lavender, cypress, α-pinene, and thyme linalool on the behavior and the expression of stress marker candidates in the brain. The transfer of volatile components into the brain is also discussed while using the results of thyme linalool as an example. These studies may provide a good opportunity to connect chemical research at the molecular level with neuropharmacological approaches in the future.     

Influence of ice and snow covers on the UV exposure of terrestrial microbial communities: dosimetric studies

Bacillus subtilis spore biological dosimeters and electronic dosimeters were used to investigate the exposure of terrestrial microbial communities in micro-habitats covered by snow and ice in Antarctica. The melting of snow covers of between 5- and 15-cm thickness, depending on age and heterogeneity, could increase B. subtilis spore inactivation by up to an order of magnitude, a relative increase twice that caused by a 50% ozone depletion. Within the snow-pack at depths of less than approximately 3 cm snow algae could receive two to three times the DNA-weighted irradiance they would receive on bare ground. At the edge of the snow-pack, warming of low albedo soils resulted in the formation of overhangs that provided transient UV protection to thawed and growing microbial communities on the soils underneath. In shallow aquatic habitats, thin layers of heterogeneous ice of a few millimetres thickness were found to reduce DNA-weighted irradiances by up to 55% compared to full-sky values with equivalent DNA-weighted diffuse attenuation coefficients (K(DNA)) of >200 m(-1). A 2-mm snow-encrusted ice cover on a pond was equivalent to 10 cm of ice on a perennially ice covered lake. Ice covers also had the effect of stabilizing the UV exposure, which was often subject to rapid variations of up to 33% of the mean value caused by wind-rippling of the water surface. These data show that changing ice and snow covers cause relative changes in microbial UV exposure at least as great as those caused by changing ozone column abundance.     

Micrometeorites in Antarctic ice detected by Ir: estimation of 120k year old accretion rate

The accretion rate of micrometeorites (MMs) was estimated from Ir contents in snow around Dome Fuji Station and ice shards obtained during ice core drilling at Dome Fuji Station, Antarctica. The snow and ice shards were melted and filtered from the residues. Although MMs were not found on filters, we tried to detect them from the residues as Ir peaks determined by instrumental neutron activation analysis (INAA). Although Ir is very rare in the earth’s crust, its concentration is high in extraterrestrial matter (e.g., chondrites). Trace amounts of Ir can be easily detected by INAA, because the cross section of Ir is relatively large (e.g., 309 barn). The accretion rates were estimated for 120k year ago, 5k year ago and at present, as (3.2 ± 0.9) × 10² t/year (8.6 ± 0.18) × 10³ t/year and (1.3 ± 0.10) × 10³ t/year, respectively. These estimates were comparable to those of previous studies, however the rate of 120k year ago was approximately an order of magnitudes lower than the others.     

The effect of pressure on the raman spectrum of ice at low temperature

Extensive experimental studies of the Raman spectra of H₂O and D₂O ice in the lattice translational and OH (OD) stretching regions are reported for the first time at 88 K and from 0→6 kbar. An unambiguous transformation from ice I_h to ice IX has been observed, although previous studies suggest that a transition to ice II would have occurred. The ice I_h data are analysed in terms of various coefficients.     

Peptidomics and proteomics based on CE‐MS as a robust tool in clinical application: The past,the present,and the future

Capillary electrophoresis combined with mass spectrometry (CE‐MS) has been used for several years for the investigation of proteins and peptides as biomarkers for diagnosis and prognosis of diseases. In addition, the technology has recently been introduced to support the stratification of patients in clinical trials and in large clinical studies. In this review, we aim at presenting the development of CE‐MS over the last 20 years, by focusing on the clinical potential of proteome and peptidome analysis and highlighting some of the key technical issues and advancements that have been made in this context towards implementation. Based on the reviewed literature, it has become evident that CE‐MS is now an accepted tool in clinical application in several disease areas. Apart from a critical overview on the current state‐of‐the‐art in CE‐MS, we also indicate the expected developments for potential future use.     

Analytical quality control: Sampling procedures to detect trace metals in environmental matrices

The problem of contamination during the collection of samples of environmental interest to detect trace metal is discussed. Attention is focused on the leaching of metals from sampling devices used to collect surface and deep seawater. A procedure to test metal release is applied to emphasize the importance of conditioning samplers before use. The procedure for checking the contamination extent and decontamination of firn and ice cores to detect ultratrace elements (particularly Cd and Pb) is presented and applied to some firn cores collected in Antarctica during the 1990–1991 Italian expedition.     

THE COMPARISON OF LANZHOU LOESS PROFILE WITH VOSTOK ICE CORE IN ANTARCTICA OVER THE LAST GLACIATION CYCLE

Loess near Lanzhou in the late Pleistocene is very sensitive to climatic fluctuations. The Beiyuan terrace profile in Linxia City, of which the curve of susceptibility tallies with the trend of isotopic curves of Vostok 2083 m ice core in Antarctica, is 35m thick. There are five layers of paleosols under Malan loess(L_1). Upper three layers (S_(1-a),S(1-b)and S_(1-c) correspond to three warm stages in last interglaciation, Interstadial of Last Glacial (C stage in Antarctic ice core)was clearly recorded in the Beiyuan profile, in which three layers of paleosols and two of loess were formed. The lowest section of the profile belongs to penultimate glaciation, in which fossils of cold-drought-resistant mammal and mollusc have been discovered.     

Biocatalyst CAL-B catalyzed synthesis of modified nucleosides: An overview

Nucleosides are valuable biologically active compounds, which display antitumour and antiviral activities. Various types of bioactive nucleosides are designed to improve their therapeutic efficacy, However this strategy faces the difficult selectivity issues of nucleoside chemistry. Therefore, the goal of this review is to give an idea of the opportunities provided by biocatalyst CAL-B procedures in the preparation of different types of bioactive nucleoside compounds. The function of Candida Antarctica lipase-B (CAL-B) in organic synthesis is reviewed. This enzyme has been found to be a principally efficient and robust lipase catalyzing an unexpected variety of reactions including many different regio- chemo, and diastereo-selective synthesis. Moreover, the structure of Candida Antarctica lipase-B is an example of an enzyme for which its specificity has been predicted based on acylation and deacylation mechanism on substrates.     

Temporal evolution of DMS and DMSP in Antarctic Coastal Sea water

The temporal evolution of concentrations of dimethylsulphide (DMS), its precursor dimethylsulphoniopropionate (DMSP) and chlorophyll a is surveyed weekly in the water column and in a landfast ice core at a coastal station of Gerlache Inlet (Terra Nova Bay, Antarctica) from 27 November 2000 to 14 February 2001. The DMS and DMSP profile concentrations in the water column are similar and show a clear temporal trend, with minimum values (<0.7?nM) at all depths occurring on 27 November 2000 and maximum values (4.8 × 10²?nM for DMS and 1.8 × 10²?nM for DMSP) in surface water on 27 December 2000 for DMS and on 19 December 2000 for DMSP. When the sea-ice cover is present, the temporal evolution of DMSP closely follows that of chlorophyll a in the water column, supporting the idea that DMSP, and therefore DMS, has a phytoplanktonic origin. However, when the ice cover breaks up during the late austral summer, a second phytoplankton bloom occurs, while the DMSP concentration in the sea-water column remains very low. In the ice core, the results show higher concentrations of DMSP than those of the underlying sea water, highlighting the important role of sea ice in the sulphur cycle of the Antarctic ecosystem.     

Adsorption of water on JSC‐1A (simulated moon dust samples)—a surface science study

JSC‐1a (a simulated lunar dust sample) supported on a silica wafer (SiO₂/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x‐ray (EDX) spectroscopy, and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and in addition by collecting isothermal adsorption transients. Blind experiments on the silica support have been performed as well. JSC‐1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg, as characterized in detail in prior studies, for example, at NASA. The particle sizes span the range from a few micrometers up to 100 µm. At small exposures, H₂O TDS is characterized by broad (100–450) K structures; at large exposures, distinct TDS peaks emerge, which are assigned to amorphous solid water (ASW) (145 K) and crystalline ice (CI) (165 K). Water dissociates on JSC‐1a at small exposures but not on the bare silica support. Coadsorption TDS data (alkane–water mixtures) indicate that rather porous condensed ice layers form at large exposures, with the mineral particles acting most likely as nucleation sites. At thermal impact energies, the initial adsorption probability amounts to 0.92 ± 0.05. It is evident that the drop‐and‐dry technique, developed in studies about nanoparticles/tubes, can be extended to obtain samples for surface science studies based on powders consisting of particles with rather large diameters. Copyright © 2008 John Wiley & Sons, Ltd.