Hinrich Grothe

Ice structures, patterns, and processes: A view across the icefields

European Science Foundation workshop Euroice 2008 held in Granada, Spain from 1–4 October 2008; Spanish national project, Hielocris, financed by the Consejo Superior de Investigaciones Cientificas; funding from FWF, Austria (No. P23027); MINCINN, Spain (No. FIS2010-16455, No. PR2010-0012, and No. FIS2010-22322-528C02-02); and SNSF, Switzerland (No. 200021121857)

Identification of ice nucleation active sites on feldspar dust particles.

Mineral dusts originating from Earth’s crust are known to be important atmospheric ice nuclei. In agreement with earlier studies, feldspar was found as the most active of the tested natural mineral dusts. Here we investigated in closer detail the reasons for its activity and the difference in the activity of the different feldspars. Conclusions are drawn from scanning electron microscopy, X-ray powder diffraction, infrared spectroscopy, and oil-immersion freezing experiments. K-feldspar showed by far the highest ice nucleation activity. Finally, we give a potential explanation of this effect, finding alkali-metal ions having different hydration shells and thus an influence on the ice nucleation activity of feldspar surfaces.

Self-assembly at Air/Water Interfaces and Carbohydrate Binding Properties of the Small Secreted Protein EPL1 from the fungus Trichoderma atroviride

Background: EPL1 belongs to the cerato-platanin protein family found exclusively in fungi and associated with fungus-host interactions. Results: EPL1 self-assembles at air/water interfaces, increases the polarity of surfaces and solutions, and binds to chitin. Conclusion: The reported properties for EPL1 show that cerato-platanin proteins are clearly different from hydrophobins. Significance: This study reports several novel properties for cerato-platanin proteins. The protein EPL1 from the fungus Trichoderma atroviride belongs to the cerato-platanin protein family. These proteins occur only in filamentous fungi and are associated with the induction of defense responses in plants and allergic reactions in humans. However, fungi with other lifestyles also express cerato-platanin proteins, and the primary function of this protein family has not yet been elucidated. In this study, we investigated the biochemical properties of the cerato-platanin protein EPL1 from T. atroviride. Our results showed that EPL1 readily self-assembles at air/water interfaces and forms protein layers that can be redissolved in water. These properties are reminiscent of hydrophobins, which are amphiphilic fungal proteins that accumulate at interfaces. Atomic force microscopy imaging showed that EPL1 assembles into irregular meshwork-like substructures. Furthermore, surface activity measurements with EPL1 revealed that, in contrast to hydrophobins, EPL1 increases the polarity of aqueous solutions and surfaces. In addition, EPL1 was found to bind to various forms of polymeric chitin. The T. atroviride genome contains three epl genes. epl1 was predominantly expressed during hyphal growth, whereas epl2 was mainly expressed during spore formation, suggesting that the respective proteins are involved in different biological processes. For epl3, no gene expression was detected under most growth conditions. Single and double gene knock-out strains of epl1 and epl2 did not reveal a detectable phenotype, showing that these proteins are not essential for fungal growth and development despite their abundant expression.

Spectroscopic Observation of Matrix-Isolated Carbonic Acid Trapped from the Gas Phase**

) is of fundamental importance, forexample,forregulationofbloodpH,intheacidificationoftheoceans, and in the dissolution of carbonates. This six-atommolecule commonly found in carbonated drinks in submicro-molar concentrations has so far eluded most attempts atisolation and direct detection. Despite the widespread beliefthat it is a highly instable molecule, the pure solid could beprepared previously,

Chlorine oxide radicals ClOx (x = 1-4) studied by matrix isolation spectroscopy.

Low pressure flash thermolysis of different precursor molecules containing-ClO, -ClO3 or -OClO3 yield, when highly diluted in Ne or O2 and subsequent quenching of the products in a matrix at 5 or 15 K, ClOx (x = 1, 3, 4) radicals, respectively. If Ne or O2 gas is directed over solid ClO2 at -120 degrees C and the resulting gas mixtures are immediately deposited as a matrix, a high fraction of (OClO)2 is trapped. This enables recording of IR and UV spectra of weakly bonded (OClO)2 dimers and detailed studying of their photochemistry. For Ne or O2 matrix isolated ClO radicals the vibrational wavenumbers and electronic transitions are only slightly affected compared with the gas phase. In this study strong evidence is found for long lived ClO in the electronically excited 2 [symbol: see text] 1/2 state. A comprehensive IR study of Ne matrix isolated ClO3 (fundamentals at 1081, 905, 567, 476 cm-1) yield i) a reliable force field; ii) a OClO bond angle of alpha e = 113.8 +/- 1 degrees and iii) a ClO bond length of 148.5 +/- 2 pm in agreement with predicted data from quantum chemical calculations. The UV/Vis spectrum of ClO3 isolated in a Ne matrix (lambda max at 32,100 and 23,150 cm-1) agrees well with the photoelectron spectrum of ClO3- and theoretical predictions. The origin of the structured high energy absorption is at 22,696 cm-1 and three fundamentals (794, 498, 280 cm-1) are detected in the C2E state. By photolysis of ClO3 with visible light the complex ClO.O2 with ClO in the 2 [symbol: see text] 1/2 state is formed. In an extended spectroscopic study of the elusive ClO4 radical, isolated in a Ne or O2 matrix, three additional IR bands, a complete UV spectrum and a strong interaction with O2 are found. This leads to the conclusion that ClO4 exhibits C2v or Cs symmetry with a shallow potential minimum and forms with O2 the previously unknown peroxy radical O3ClO-O2. All these results are discussed in the context of recent developments in the chemistry and spectroscopy of the important and interesting ClOx (x = 1-4) family of radicals.

Formation and phase distribution of nitric acid hydrates in the mole fraction range xHNO3 < 0.25: A combined XRD and IR study

Liquid binary nitric acid/water aerosols (x < 0.25) were shock- frozen (quenched) into X-ray amorphous solids at 35 K. Careful thermal treatment in the temperature interval 35 K < T < 255 K provided the equilibrium phases ice and β-nitric acid trihydrate (β-NAT) as well as the non-equilibrium phases α-NAT, α-nitric acid dihydrate (α-NAD), and nitric acid pentahydrate (NAP, ?). The stability conditions with respect to temperature and composition were determined by X-ray diffraction (XRD) and infrared spectroscopy. In the case of α-NAT they significantly depend on the simultaneous presence of ice such that they overlap with the respective stratospheric conditions.

The crystallization kinetics and morphology of nitric acid trihydrate

Crystallization kinetics of stable and metastable nitric acid trihydrate (NAT) were investigated by time dependent X-ray powder diffraction (XRD) measurements. Kinetic conversion curves were evaluated adopting the Avrami model. The growth and morphology of the respective crystallites were monitored in situ on the cryo-stage of an environmental scanning electron microscope (ESEM) under a partial pressure of nitrogen gas (0.3 Torr, 40 Pa). The results show a close relationship between the presence of ice in the sample and the crystallization mechanism of NAT, which results in different shapes and sizes of NAT crystal particles.

Matrix isolation studies of carbonic acid--the vapor phase above the β-polymorph.

Twenty years ago two different polymorphs of carbonic acid, α- and β-H2CO3, were isolated as thin, crystalline films. They were characterized by infrared and, of late, by Raman spectroscopy. Determination of the crystal structure of these two polymorphs, using cryopowder and thin film X-ray diffraction techniques, has failed so far. Recently, we succeeded in sublimating α-H2CO3 and trapping the vapor phase in a noble gas matrix, which was analyzed by infrared spectroscopy. In the same way we have now investigated the β-polymorph. Unlike α-H2CO3, β-H2CO3 was regarded to decompose upon sublimation. Still, we have succeeded in isolation of undecomposed carbonic acid in the matrix and recondensation after removal of the matrix here. This possibility of sublimation and recondensation cycles of β-H2CO3 adds a new aspect to the chemistry of carbonic acid in astrophysical environments, especially because there is a direct way of β-H2CO3 formation in space, but none for α-H2CO3. Assignments of the FTIR spectra of the isolated molecules unambiguously reveal two different carbonic acid monomer conformers (C2v and Cs). In contrast to the earlier study on α-H2CO3, we do not find evidence for centrosymmetric (C2h) carbonic acid dimers here. This suggests that two monomers are entropically favored at the sublimation temperature of 250 K for β-H2CO3, whereas they are not at the sublimation temperature of 210 K for α-H2CO3.

Towards a microstructural model of bitumen ageing behaviour

When it comes to describe the mechanical behaviour of hot mix asphalt (HMA), the change of the mechanical properties over time due to environmental impacts known as ageing has to be considered. Hardening and embrittlement of bitumen lead to a reduced resistance against cryogenic cracks and premature formation of fatigue cracks in bituminous layers. Within this work, the microstructure of bitumen is investigated by conducting static shear creep tests on artificially composed bitumen with asphaltene contents varying between 0 vol-% and 26.71 vol-% as well as on a paving grade bitumen 70/100. Both are considered in unaged and laboratory-aged (rolling thin-film oven test + pressure ageing vessel) conditions to be able to identify and describe ageing effects. While the properties of the considered material phases of bitumen (identical to saturates, aromatics, resins and asphaltenes (SARA) fractions) seem to remain unaffected, an increase of the asphaltene content due to ageing can be observed. A micromechanical model is proposed that allows a prediction of the consequences of these microstructural changes on the mechanical behaviour of bitumen. Atomic force microscopy and environmental scanning electron microscopy images confirm a composition consisting of a micelle-like structure in a contiguous matrix, a structural representative volume element concept based on SARA fractions is suggested, extending an existing multiscale model for HMA. A very good accordance between model predictions and experimental results indicates the models ability to reproduce as well as to describe the effects related to ageing.

Infrared spectra and ab initio calculations of matrix isolated dimethyl sulfone and its water complex

The infrared spectrum of (CH3)2SO2 (dimethyl sulfone) trapped in several rare gas matrices is reported. Results are compared to previous gas phase and solid state spectra. In water-containing matrices, bands attributed to the ((CH3)2SO2)*(H2O) molecular complex are identified. Spectral results are discussed with reference to the bonding scheme suggested by theoretical ab initio calculations. The similarities to the previously recorded (H2SO4)*(H2O) mode frequencies shed light on the bonding scheme of both. The complex formation between H2O and dimethyl sulfone was studied by ab initio B3LYP computations using the aug-cc-pVTZ basis sets. The calculations show the existence of a stable 1∶1 complex of Cs symmetry, ΔfH = −21 kJ mol−1, with a single O⋯H bond of one water hydrogen bonded to one oxygen of the sulfone.