Intensification of ice nucleation observed in ocean ship emissions.

Shipping contributes primary and secondary emission products to the atmospheric aerosol burden that have implications for climate, clouds, and air quality from regional to global scales. In this study we exam the potential impact of ship emissions with regards to ice nucleating particles. Particles that nucleate ice are known to directly affect precipitation and cloud microphysical properties. We have collected and analyzed particles for their ice nucleating capacity from a shipping channel outside a large Scandinavia port. We observe that ship plumes amplify the background levels of ice nucleating particles and discuss the larger scale implications. The measured ice nucleating particles suggest that the observed amplification is most likely important in regions with low levels of background particles. The Arctic, which as the sea ice pack declines is opening to transit and natural resource exploration and exploitation at an ever increasing rate, is highlighted as such a region.

Hot water from cold. The dissociative recombination of water cluster ions.

Dissociative recombination of the Zundel cation D(5)O(2)(+) almost exclusively produces D + 2 D(2)O with a maximum kinetic energy release of 5.1 eV. An imaging technique is used to investigate the distribution of the available reaction energy among these products. Analysis shows that as much as 4 eV can be stored internally by the molecular fragments, with a preference for producing highly excited molecular fragments, and that the deuteron shows a nonrandom distribution of kinetic energies. A possible mechanism and the implications for these observations are addressed.

Can leek interfere with bean plant-bean fly interaction? Test of ecological pest management in mixed cropping.

Effects of volatile odors from leek, Allium porum L., on the behavior of bean fly, Ophiomyia phaseoli (Tryon) (Diptera: Agromyzidae), were tested in laboratory olfactometer bioassays. Aqueous and solvent extracts (dichloromethane and methanol) of leek were repellent to adult flies. Whole leek plants were repellent and prevented attraction to the host plant, beans. Beans that had been exposed to volatiles from living leek plants for 7 d became repellent to the fly. Leek and several other crops were tested in field experiments to identify candidate crops for a mixed cropping system to minimize bean fly attack in beans, Phaseolus vulgaris L. In a wet season field experiment, mixed cropping of bean with leek or three other vegetable crops did not significantly reduce bean fly infestation or infection with Fusarium oxysporum Schltdl. compared with a mono crop, but significantly reduced plant death caused by both agents combined. In two dry season field experiments, mixed cropping of beans with leek significantly reduced adult bean fly settling, emergence, and death of bean plants compared with a mono crop. Bean yield per row was approximately 150% higher for the mixed crop, and economic returns were approximately Sri Lankan Rs. 180,000/ha, higher than for the mono crop. For the mono crop, the farmer had a monetary loss, which would become a small profit only if the costs of family labor are excluded. The study is an example of the first steps toward development of sustainable plant protection in a subsistence system.

Dissociative recombination of water cluster ions with free electrons: cross sections and branching ratios.

Dissociative recombination (DR) of water cluster ions H(+)(H(2)O)(n) (n=4-6) with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, branching ratios have been determined for the dominating product channels and absolute DR cross sections have been measured in the energy range from 0.001 to 0.7 eV. Dissociative recombination is concluded to result in extensive fragmentation for all three cluster ions, and a maximum number of heavy oxygen-containing fragments is produced with a probability close to unity. The branching ratio results agree with earlier DR studies of smaller water cluster ions where the channel nH(2)O+H has been observed to dominate and where energy transfer to internal degrees of freedom has been concluded to be highly efficient. The absolute DR cross sections for H(+)(H(2)O)(n) (n=4-6) decrease monotonically with increasing energy with an energy dependence close to E(-1) in the lower part of the energy range and a faster falloff at higher energies, in agreement with the behavior of other studied heavy ions. The cross section data have been used to calculate DR rate coefficients in the temperature range of 10-2000 K. The results from storage ring experiments with water cluster ions are concluded to partly confirm the earlier results from afterglow experiments. The DR rate coefficients for H(+)(H(2)O)(n) (n=1-6) are in general somewhat lower than reported from afterglow experiments. The rate coefficient tends to increase with increasing cluster size, but not in the monotonic way that has been reported from afterglow experiments. The needs for further experimental studies and for theoretical models that can be used to predict the DR rate of polyatomic ions are discussed.

Fibrin matrix for suspension of regenerative cells in an artificial nerve conduit.

Peripheral nerve injury presents with specific problems of neuronal reconstructions, and from a clinical viewpoint a tissue engineering approach would facilitate the process of repair and regeneration. We have previously used artificial nerve conduits made from bioresorbable poly-3-hydroxybutyrate (PHB) in order to refine the ways in which peripheral nerves are repaired and reconnected to the target muscles and skin. The addition of Schwann cells (SC) or differentiated mesenchymal stem cells (dMSC) to the conduits enhances regeneration. In this study, we have used a matrix based on fibrin (Tisseel) to fill optimally the nerve-conduits with cells. In vitro analysis showed that both SC and MSC adhered significantly better to PHB in the presence of fibrin and cells continued to maintain their differentiated state. Cells were more optimally distributed throughout the conduit when seeded in fibrin than by delivery in growth medium alone. Transplantation of the nerve conduits in vivo showed that cells in combination with fibrin matrix significantly increased nerve regeneration distance (using PGP9.5 and S100 distal and proximal immunohistochemistry) when compared with empty PHB conduits. This study shows the beneficial combinatory effect of an optimised matrix, cells and conduit material as a step towards bridging nerve gaps which should ultimately lead to improved functional recovery following nerve injury.

Dissociative recombination of H+(H2O)3 and D+(D2O)3 water cluster ions with electrons: cross sections and branching ratios.

Dissociative recombination (DR) of the water cluster ions H(+)(H(2)O)(3) and D(+)(D(2)O)(3) with electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). For the first time, absolute DR cross sections have been measured for H(+)(H(2)O)(3) in the energy range of 0.001-0.8 eV, and relative cross sections have been measured for D(+)(D(2)O)(3) in the energy range of 0.001-1.0 eV. The DR cross sections for H(+)(H(2)O)(3) are larger than previously observed for H(+)(H(2)O)(n) (n=1,2), which is in agreement with the previously observed trend indicating that the DR rate coefficient increases with size of the water cluster ion. Branching ratios have been determined for the dominating product channels. Dissociative recombination of H(+)(H(2)O)(3) mainly results in the formation of 3H(2)O+H (probability of 0.95+/-0.05) and with a possible minor channel resulting in 2H(2)O+OH+H(2) (0.05+/-0.05). The dominating channels for DR of D(+)(D(2)O)(3) are 3D(2)O+D (0.88+/-0.03) and 2D(2)O+OD+D(2) (0.09+/-0.02). The branching ratios are comparable to earlier DR results for H(+)(H(2)O)(2) and D(+)(D(2)O)(2), which gave 2X(2)O+X (X=H,D) with a probability of over 0.9.

Dissociative recombination of ammonia clusters studied by storage ring experiments.

Dissociative recombination of ammonia cluster ions with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The absolute cross sections for dissociative recombination of H+(NH3)2, H+(NH3)3, D+(ND3)2, and D+(ND3)3 in the collision energy range of 0.001-27 eV are reported, and thermal rate coefficients for the temperature interval from 10 to 1000 K are calculated from the experimental data and compared with earlier results. The fragmentation patterns for the two ions H+(NH3)2 and D+(ND3)2 show no clear isotope effect. Dissociative recombination of X+(NX3)2 (X=H or D) is dominated by the product channels 2NX3+X [0.95+/-0.02 for H+(NH3)2 and 1.00+/-0.02 for D+(ND3)2]. Dissociative recombination of D+(ND3)3 is dominated by the channels yielding three N-containing fragments (0.95+/-0.05).

Dissociative recombination of NH4+ and ND4+ ions: storage ring experiments and ab initio molecular dynamics.

The dissociative recombination (DR) process of NH4+ and ND4+ molecular ions with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The absolute cross sections for DR of NH4+ and ND4+ in the collision energy range 0.001-1 eV are reported, and thermal rate coefficients for the temperature interval from 10 to 2000 K are calculated from the experimental data. The absolute cross section for NH4+ agrees well with earlier work and is about a factor of 2 larger than the cross section for ND4+. The dissociative recombination of NH4+ is dominated by the product channels NH3+H (0.85+/-0.04) and NH2+2H (0.13+/-0.01), while the DR of ND4+ mainly results in ND3+D (0.94+/-0.03). Ab initio direct dynamics simulations, based on the assumption that the dissociation dynamics is governed by the neutral ground-state potential energy surface, suggest that the primary product formed in the DR process is NH3+H. The ejection of the H atom is direct and leaves the NH3 molecule highly vibrationally excited. A fraction of the excited ammonia molecules may subsequently undergo secondary fragmentation forming NH2+H. It is concluded that the model results are consistent with gross features of the experimental results, including the sensitivity of the branching ratio for the three-body channel NH2+2H to isotopic exchange.

Quantification of myocardial hypoperfusion with 99m Tc-sestamibi in patients undergoing prolonged coronary artery balloon occlusion.

Percutaneous transluminal coronary angioplasty provides an excellent opportunity to investigate the location and quantity of hypoperfusion during sudden complete occlusion of one of the major coronary arteries. Thirty-five patients referred for elective percutaneous transluminal coronary angioplasty were injected intravenously with 99mTc-sestamibi during balloon inflation. To visualize and quantify the hypoperfused region, a map of perfusion was constructed from that occlusion study and from the control study performed on the following day. Patients were divided into groups according to proximal or distal occlusion within each of the three coronary arteries. The region of myocardium supplied by each coronary artery varied in location and extended outside the typical borders for all arteries, but most prominently for the left circumflex coronary artery. The quantities of hypoperfusion varied within each artery group, but the average hypoperfusion was greater for the left anterior descending coronary artery than for either the right coronary artery or the left circumflex coronary artery. It is concluded that the quantities of hypoperfusion were highly variable within each artery group. Occlusion of the left anterior descending coronary artery was associated with the largest ischaemic region. The area of hypoperfusion extended outside the typical borders, most prominently for the left circumflex coronary artery.

Evaluations of the stability of sheathless electrospray ionization mass spectrometry emitters using electrochemical techniques.

The processes that cause the failure of sheathless electrospray ionization (ESI) emitters, based on different kinds of gold coatings on fused-silica capillaries, are described and explained. The methods chosen for this study include electrochemical methods, ICPMS analysis of the electrolytes used, SEM studies, and electrospray experiments. Generally, the failure occurs by loss of the conductive coating. It is shown that emitters with sputter-coated gold lose their coatings because of mechanical stress caused by the gas evolution accompanying water oxidation or reduction. Emitters with gold coatings on top of adhesion layers of chromium and nickel alloy withstand this mechanical stress and have excellent durability when operating as cathodes. When operating as anodes, the adhesion layer is electrochemically dissolved through the gold film, and the gold film then flakes off. It is shown that the conductive coating behaves as a cathode even in the positive electrospray mode when the magnitude of a superimposed reductive electrophoretic current exceeds that of the oxidative electrospray current. Fairy-dust coatings developed in our laboratory (see Barnidge, D. R.; etal.Anal. Chem. 1999, 71, 4115-4118,) bygluing gold dust onto the emitter, are unaffected by the mechanical stress due to gas evolution. When oxidized, the fairy-dust coatings show an increased surface roughness and decreased conductivities due to the formation of gold oxide. The resistance of this oxide layer is however negligible in comparison with that of the gas phase in ESI. Furthermore, since no flaking and only negligible electrochemical etching of gold was found, practically unlimited emitter lifetimes may be achieved with fairy-dust coatings.

Ice-catalyzed ionization of hydrochloric acid.

Ionization of hydrochloric acid (HCl) on stratospheric ice particles is believed to be a key step in the depletion of stratospheric ozone. Ab initio calculations based on a model HCl-water cluster show that HCl ionization on ice surfaces is a barrierless process. Since this mechanism is rapid and produces chloride anions that are exposed to ambient stratospheric chlorine reservoir molecules, it is likely to be important for stratospheric chemistry. It complements a previously suggested mechanism where HCl forms part of the ice lattice before ionizing. The mechanism proposed here is also consistent with experimentally observed ionization of HCl on ice at low temperatures and under vacuum, where the HCl is not expected to be encapsulated in the ice lattice.

Response of the ladybird parasitoid Dinocampus coccinellae to toxic alkaloids from the seven-spot ladybird, Coccinella septempunctata.

Electrophysiological and behavioral responses of the ladybird parasitoid Dinocampus coccinellae to volatiles from the seven-spot ladybird, Coccinella septempunctata, were investigated to identify semiochemicals involved in host location. Coupled gas chromatography-electroantennography (GC-EAG) with D. coccinellae located a small peak of prominent activity in an extract of volatiles from adult C. septempunctata. The active compound was identified by coupled GC-mass spectrometry and by comparison with an authentic sample as the free-base alkaloid precoccinelline, which forms part of the toxic defense of this ladybird. Behavioral studies in an olfactometer showed that D. coccinellae was significantly attracted to the volatile extract and also to the alkaloid. Myrrhine, a stereoisomer of precoccinelline found in low amounts in C. septempunctata and in other ladybird species, was shown to be electrophysiologically active and significantly attractive. Perception of ladybird alkaloids by D. coccinellae is a rare example of toxicants acting as aerially transmitted cues for interactions between the third and fourth trophic levels.

The absence of high-frequency QRS changes in the presence of standard electrocardiographic QRS changes of old myocardial infarction.

BACKGROUND: This study compares the high-frequency QRS components (HF-QRS) in patients with and without standard electrocardiogram (ECG) changes indicative of old myocardial infarction (MI). Previous studies have indicated that patients with an old MI differ in their HF-QRS compared with healthy subjects. The HF-QRS has been reported to be decreased during acute coronary occlusion and increased after reperfusion. However, there is controversy about the appearance of HF-QRS after the acute phase of MI. METHODS: A total of 154 patients were included, 57 with and 97 without QRS changes of old MI on the standard ECG. The patients with old MI were divided into subgroups on the basis of the MI location indicated by the standard ECG. Signal-averaged ECGs from the 12 standard leads were recorded. The root-mean-square values of the HF-QRS were determined within two frequency bands: 150 to 250 Hz and 80 to 300 Hz. RESULTS: There was a large interindividual variation in HF-QRS in patients without MI as well as in those with different MI locations. There were no significant differences between the groups in the summed HF-QRS of all 12 leads or in the pattern of lead distribution of the HF-QRS. Not even the patients with the greatest QRS changes of old MI could be differentiated from those without any changes of old MI on the standard ECG. The results were the same in both analyzed frequency bands. CONCLUSIONS: This study shows, contrary to previous studies, that analysis of HF-QRS cannot differentiate between patients with and without old MI.

LcrV is a channel size-determining component of the Yop effector translocon of Yersinia.

Delivery of Yop effector proteins by pathogenic Yersinia across the eukaryotic cell membrane requires LcrV, YopB and YopD. These proteins were also required for channel formation in infected erythrocytes and, using different osmolytes, the contact-dependent haemolysis assay was used to study channel size. Channels associated with LcrV were around 3 nm, whereas the homologous PcrV protein of Pseudomonas aeruginosa induced channels of around 2 nm in diameter. In lipid bilayer membranes, purified LcrV and PcrV induced a stepwise conductance increase of 3 nS and 1 nS, respectively, in 1 M KCl. The regions important for channel size were localized to amino acids 127-195 of LcrV and to amino acids 106-173 of PcrV. The size of the channel correlated with the ability to translocate Yop effectors into host cells. We suggest that LcrV is a size-determining structural component of the Yop translocon.

Changes in high-frequency QRS components are more sensitive than ST-segment deviation for detecting acute coronary artery occlusion.

OBJECTIVES: This study describes changes in high-frequency QRS components (HF-QRS) during percutaneous transluminal coronary angioplasty (PTCA) and compares the ability of these changes in HF-QRS and ST-segment deviation in the standard 12-lead electrocardiogram (ECG) to detect acute coronary artery occlusion. BACKGROUND: Previous studies have shown decreased HF-QRS in the frequency range of 150-250 Hz during acute myocardial ischemia. It would be important to know whether the high-frequency analysis could add information to that available from the ST segments in the standard ECG. METHODS: The study population consisted of 52 patients undergoing prolonged balloon occlusion during PTCA. Signal-averaged electrocardiograms (SAECG) were recorded prior to and during the balloon inflation. The HF-QRS were determined within a bandwidth of 150-250 Hz in the preinflation and inflation SAECGs. The ST-segment deviation during inflation was determined in the standard frequency range. RESULTS: The sensitivity for detecting acute coronary artery occlusion was 88% using the high-frequency method. In 71% of the patients there was ST elevation during inflation. If both ST elevation and depression were considered, the sensitivity was 79%. The sensitivity was significantly higher using the high-frequency method, p<0.002, compared with the assessment of ST elevation. CONCLUSIONS: Acute coronary artery occlusion is detected with higher sensitivity using high-frequency QRS analysis compared with conventional assessment of ST segments. This result suggests that analysis of HF-QRS could provide an adjunctive tool with high sensitivity for detecting acute myocardial ischemia.

Host choice and host leaving in Rhopalosiphum padi (Hemiptera: aphididae) emigrants and repellency of aphid colonies on the winter host.

Host choice and winter-host leaving in emigrants of bird cherry-oat aphid, Rhopalosiphum padi (Linnaeus), were investigated in the laboratory. In settling choice tests, emigrants collected from the winter host, Prunus padus, preferred this plant over a summer host, oats. Emigrants which had left P. padus for up to 24 h did not express a preference as a group, and those which had left for 24-48 h preferred oats. Eighty seven percent of emigrants caged as fourth-instar nymphs on P. padus leaves abandoned the host by the second day of adult life, and apparently did not subsequently return to the leaf. In an olfactometer, P. padus leaves which had supported spring generations of R. padi were repellent to emigrants. Volatiles were entrained from uninfested and R. padi-infested P. padus using cut twigs in the laboratory as well as intact twigs on a tree in the field. Entrainment extracts from uninfested P. padus had no effect on emigrants in the olfactometer, whereas those from twigs infested with nymphal emigrants were repellent. The study indicates that in R. padi, host-alternation is driven by behavioural changes which occur in individuals as well as between morphs.

Normal-phase high-performance liquid chromatography of tocopherols and tocotrienols. Comparison of different chromatographic columns.

Natural vitamin E is composed of eight different vitamers (alpha-, beta-, gamma- and delta-tocopherols and alpha-, beta-, gamma- and delta-tocotrienols). As these eight vitamers have different antioxidant and biological activities, it is necessary to have quantitative data on each substance separately. The aim of this study was to find universal HPLC columns for the separation of all eight components and to test if a few columns of the same material (different batches) will give reproducible results. Normal-phase HPLC separations of vitamin E compounds in a prepared mixture (containing oat extracts, palm oil and tocopherol standards) were tried on six silica, three amino and one diol columns. As shown by calculations of retention factors (k), separation factors (alpha), numbers of theoretical plates (N) and resolutions (Rs), the best separations were obtained on three silica columns and two amino columns using 4 or 5% dioxane in hexane as the mobile phase as well as on a diol column using 4% tert.-butyl methyl ether in hexane as the mobile phase.

New roles for cis-jasmone as an insect semiochemical and in plant defense.

cis-jasmone, or (Z)-jasmone, is well known as a component of plant volatiles, and its release can be induced by damage, for example during insect herbivory. Using the olfactory system of the lettuce aphid to investigate volatiles from plants avoided by this insect, (Z)-jasmone was found to be electrophysiologically active and also to be repellent in laboratory choice tests. In field studies, repellency from traps was demonstrated for the damson-hop aphid, and with cereal aphids numbers were reduced in plots of winter wheat treated with (Z)-jasmone. In contrast, attractant activity was found in laboratory and wind tunnel tests for insects acting antagonistically to aphids, namely the seven-spot ladybird and an aphid parasitoid. When applied in the vapor phase to intact bean plants, (Z)-jasmone induced the production of volatile compounds, including the monoterpene (E)-beta-ocimene, which affect plant defense, for example by stimulating the activity of parasitic insects. These plants were more attractive to the aphid parasitoid in the wind tunnel when tested 48 h after exposure to (Z)-jasmone had ceased. This possible signaling role of (Z)-jasmone is qualitatively different from that of the biosynthetically related methyl jasmonate and gives a long-lasting effect after removal of the stimulus. Differential display was used to compare mRNA populations in bean leaves exposed to the vapor of (Z)-jasmone and methyl jasmonate. One differentially displayed fragment was cloned and shown by Northern blotting to be up-regulated in leaf tissue by (Z)-jasmone. This sequence was identified by homology as being derived from a gene encoding an alpha-tubulin isoform.

Spatial, individual, and temporal variation of the high-frequency QRS amplitudes in the 12 standard electrocardiographic leads.

BACKGROUND: Analysis of high-frequency QRS amplitudes (HF-QRS) may provide an additional diagnostic tool in patients with heart disease, but the basic properties of these waveforms have not been sufficiently investigated. This study describes the spatial, individual, and temporal variation at rest of HF-QRS recorded with the 12 standard electrocardiographic leads in patients with ischemic heart disease. METHODS AND RESULTS: Two consecutive electrocardiographic recordings from 67 patients were signal averaged and analyzed within a bandwidth of 150 to 250 Hz. The HF-QRS values were expressed as root mean square values. There was a spatial variation in HF-QRS among the 12 leads, with higher amplitudes in V(2) through V(4), II, aVF, and III. The individual variation among the patients was large for all leads. The sum of the HF-QRS for all 12 leads in each patient ranged from 20 to 75 microV (mean 36 +/- 11 microV). The mean of the temporal variation in HF-QRS for all 12 leads between the 2 recordings was only 0.10 +/- 0. 09 microV. CONCLUSIONS: Because of the large individual variation, analysis of HF-QRS is probably most applicable in monitoring situations when it is possible to track changes in a patient over time. The temporal variation in HF-QRS at rest is small, both in patients with and those without prior myocardial infarction.

The influence of lipophilicity on binding of boronated DNA-intercalating compounds in human glioma spheroids.

Five boronated DNA-intercalating compounds [5-ortho-carboranyl phenanthridinium (5-o-CP), 5-para-carboranyl phenanthridinium (5-p-CP), 6-para-carboranyl phenanthridinium, water-soluble boronated phenanthridinium and water-soluble boronated acridine (WSA1)], primarily developed for boron neutron capture therapy (BNCT), were analysed regarding their binding in cultured human malignant glioma spheroids. Comparisons were made with the corresponding DNA intercalators ethidium bromide and acridine orange. Octanol/phosphate buffered saline-water coefficients were determined for all compounds, and it was found that the most lipophilic (5-o-CP and 5-p-CP) were most toxic and accumulated high amounts of boron in monolayer cells. These compounds bound primarily in the outermost part of spheroids with poor penetration into the inner region, even after 2 days of continuous exposure. On the other hand, the most hydrophilic compound (WSA1) showed lower toxicity and lower boron accumulation in monolayer cells, and rapid binding in the inner region of spheroids. A reasonable explanation for this observation is that the lipophilic compounds interact mainly with lipophilic parts of the cells, like cellular membranes, and therefore rapidly binds to cells, preventing penetration and binding to cells in the deeper region of the spheroids. The possibility of using these compounds for BNCT are discussed.