Classifying dynamical forcing mechanisms using a climatology of extratropical cyclones

A climatology of almost 700 extratropical cyclones is compiled by applying an automated feature tracking algorithm to a database of objectively identified cyclonic features. Cyclones are classified according to the relative contributions to the midlevel vertical motion of the forcing from upper and lower levels averaged over the cyclone intensification period (average U/L ratio) and also by the horizontal separation between their upper-level trough and low-level cyclone (tilt). The frequency distribution of the average U/L ratio of the cyclones contains two significant peaks and a long tail at high U/L ratio. Although discrete categories of cyclones have not been identified, the cyclones comprising the peaks and tail have characteristics that have been shown to be consistent with the type A, B, and C cyclones of the threefold classification scheme. Using the thresholds in average U/L ratio determined from the frequency distribution, type A, B, and C cyclones account for 30\%, 38\%, and 32\% of the total number of cyclones respectively. Cyclones with small average U/L ratio are more likely to be developing cyclones (attain a relative vorticity $\ge 1.2 \times 10^{-4} \mbox{s}^{-1}$) whereas cyclones with large average U/L ratio are more likely to be nondeveloping cyclones (60\% of type A cyclones develop whereas 31\% of type C cyclones develop). Type A cyclogenesis dominates in the development region East of the Rockies and over the gulf stream, type B cyclogenesis dominates in the region off the East coast of the USA, and type C cyclogenesis is more common over the oceans in regions of weaker low-level baroclinicity.

An objective climatology of the dynamical forcing of polar lows in the Nordic seas

A new objective climatology of polar lows in the Nordic (Norwegian and Barents) seas has been derived from a database of diagnostics of objectively identified cyclones spanning the period January 2000 to April 2004. There are two distinct parts to this study: the development of the objective climatology and a characterization of the dynamical forcing of the polar lows identified. Polar lows are an intense subset of polar mesocyclones. Polar mesocyclones are distinguished from other cyclones in the database as those that occur in cold air outbreaks over the open ocean. The difference between the wet-bulb potential temperature at 700 hPa and the sea surface temperature (SST) is found to be an effective discriminator between the atmospheric conditions associated with polar lows and other cyclones in the Nordic seas. A verification study shows that the objective identification method is reliable in the Nordic seas region. After demonstrating success at identifying polar lows using the above method, the dynamical forcing of the polar lows in the Nordic seas is characterized. Diagnostics of the ratio of mid-level vertical motion attributable to quasi-geostrophic forcing from upper and lower levels (U/L ratio) are used to determine the prevalence of a recently proposed category of extratropical cyclogenesis, type C, for which latent heat release is crucial to development. Thirty-one percent of the objectively identified polar low events (36 from 115) exceeded the U/L ratio of 4.0, previously identified as a threshold for type C cyclones. There is a contrast between polar lows to the north and south of the Nordic seas. In the southern Norwegian Sea, the population of polar low events is dominated by type C cyclones. These possess strong convection and weak low-level baroclinicity. Over the Barents and northern Norwegian seas, the well-known cyclogenesis types A and B dominate. These possess stronger low-level baroclinicity and weaker convection.

The spatial distribution and evolution characteristics of North Atlantic cyclones

A climatology of extratropical cyclones is produced using an objective method of identifying cyclones based on gradients of 1-km height wet-bulb potential temperature. Cyclone track and genesis density statistics are analyzed and this method is found to compare well with other cyclone identification methods. The North Atlantic storm track is reproduced along with the major regions of genesis. Cyclones are grouped according to their genesis location and the corresponding lysis regions are identified. Most of the cyclones that cross western Europe originate in the east Atlantic where the baroclinicity and the sea surface temperature gradients are weak compared to the west Atlantic. East Atlantic cyclones also have higher 1-km height relative vorticity and lower mean sea level pressure at their genesis point than west Atlantic cyclones. This is consistent with the hypothesis that they are secondary cyclones developing on the trailing fronts of preexisting “parent” cyclones. The evolution characteristics of composite west and east Atlantic cyclones have been compared. The ratio of their upper- to lower-level forcing indicates that type B cyclones are predominant in both the west and east Atlantic, with strong upper- and lower-level features. Among the remaining cyclones, there is a higher proportion of type C cyclones in the east Atlantic, whereas types A and C are equally frequent in the west Atlantic.

Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

Coriolis perturbations in the infrared spectrum of ethylene

Rotational structure has been resolved and analyzed in two of the infrared‐active perpendicular bands of C2H4 vapor: the Type b fundamental band, ν10, at 826 cm—1, and the Type c fundamental band, ν7, at 949 cm—1. Many of the individual PP and RR branch lines have been observed. The analysis has been confined to values of the quantum number K≥3, for which energy levels ethylene shows no detectable deviations from a symmetric‐top rotational structure. The analysis reveals a Coriolis interaction between ν7 and ν10, and between ν4 and ν10, and values of the Coriolis constants ζ7,10z and ζ4,10y are obtained; these are related to normal coordinate calculations for the appropriate symmetry species, and force constants are derived to fit the observed zeta constants. The band center of ν10 has been revised from the original figure of 810 cm—1 to the new value, 826 cm—1, and the inactive frequency ν4 is estimated to lie at 1023±3 cm—1, in good agreement with the previous estimate of 1027 cm—1. The change in the value of ν10 leads to a suggested change in the value of the Raman‐active fundamental ν6 from 1236 to 1222 cm—1. New combination bands have been observed at 2174 cm—1, assigned as ν3+ν10; and at 2252 cm—1, assigned as ν4+ν6; also rotational structure has been resolved and analyzed in the ν6+ν10 band at 2048 cm—1. The new data obtained for the C2H4 molecule are summarized in Table XII, with all of the other data presently available on the vibrational and rotational constants.

Microwave spectrum of CHD2CN and CHD2NC, and the harmonic force field and rz structure of methyl cyanide and isocyanide

The microwave spectra of CHD2CN and CHD2NC have been measured from 18 to 40 GHz; about 20 type A and 30 type C transitions have been observed for each molecule. These have been fitted to a Hamiltonian using 3 rotational constants, and 5 quartic and 4 sextic distortion constants, in the IrS reduction of Watson [in “Vibrational spectra and structure” Vol. 6 (1977)]; the standard error of the fit is 26 kHz. For methyl cyanide the 5 quartic distortion constants have been used to further refine the recent harmonic force field of Duncan et al. [J. Mol. Spectrosc. 69, 123 (1978)], but the changes are small. Finally, for both molecules, the harmonic force field has been used to determine zero point average moments of inertia Iz from the ground state rotational constants for many isotopic species, and these have been used to determine an rz structure. The results are compared with rs structure calculations.

Coriolis perturbations in the infrared spectrum of diborane

High‐resolution infrared spectra of B2H6 vapor are reported. The sample was prepared from the naturally occurring 11B☒10B isotopic mixture. The rotational structure of the infrared bands has been analysed for Coriolis perturbations due to rotation about the axis of least moment of inertia (the B⋅⋅⋅B axis). The following results have been obtained: (a) interaction between the Type A fundamental ν18 and the inactive fundamental ν5 has been observed, thus confirming the assignment of ν5 at 833 cm—1, giving ∣ ζ5,18Z ∣=0.55±0.05; (b) interaction observed between the Type A combination band (ν10+ν12) at 1283 cm—1 and the inactive combination (ν10+ν7) gives an estimate of the unobserved fundamental ν7 as 850±30 cm—1, and an estimate of ∣ ζ7,12Z ∣=0.6±0.1; (c) the absence of any observed perturbation of the Type C fundamental ν14 at 973 cm—1, suggests, by negative arguments, that either the unobserved fundamental ν9 does not lie in the frequency range 900 to 1100 cm—1, or ∣ ζ9,14Z ∣<0.2. The assignment of the unobserved fundamental vibrations of diborane is discussed in the light of this evidence.

The dynamics of a polar low assessed using potential vorticity inversion

The dynamics of a polar low are examined using a piecewise potential vorticity (PV) inversion method. In previous studies of this and other polar lows, structural evolution has been described in terms of regions of anomalous PV. In this study the relative importance of different PV anomalies and the interactions between them have been quantified using PV diagnostics. The intensification of the polar low occurred in three stages (in contrast to previous studies of polar lows that have only identified two stages). The dynamical characteristics of stages one and two are consistent with the proposed type C cyclogenesis mechanism. A diabatically-generated lower-tropospheric PV anomaly dominated intensification after initial triggering by a positive upper-level PV anomaly. A phase tilt between the upper and lower levels was maintained through retardation of the positive upper-level anomaly by the effects of latent heat release. Stage three was a period of growth dominated by wind-induced surface heat exchange (WISHE), which contributed at least 18% to the amplitude of the mature surface polar low.

The two Caenorhabditis elegans metallothioneins (CeMT-1 and CeMT-2) discriminate between essential zinc and toxic cadmium

The nematode Caenorhabditis elegans expresses two metallothioneins (MTs), CeMT-1 and CeMT-2, that are believed to be key players in the protection against metal toxicity. In this study, both isoforms were expressed in vitro in the presence of either Zn(II) or Cd(II). Metal binding stoichiometries and affinities were determined by ESI-MS and NMR, respectively. Both isoforms had equal zinc binding ability, but differed in their cadmium binding behaviour, with higher affinity found for CeMT-2. In addition, wild-type C. elegans, single MT knockouts and a double MT knockout allele were exposed to zinc (340 μm) or cadmium (25 μm) to investigate effects in vivo. Zinc levels were significantly increased in all knockout strains, but were most pronounced in the CeMT-1 knockout, mtl-1 (tm1770), while cadmium accumulation was highest in the CeMT-2 knockout, mtl-2 (gk125) and the double knockout mtl-1;mtl-2 (zs1). In addition, metal speciation was assessed by X-ray absorption fine-structure spectroscopy. This showed that O-donating, probably phosphate-rich, ligands play a dominant role in maintaining the physiological concentration of zinc, independently of metallothionein status. In contrast, cadmium was shown to coordinate with thiol groups, and the cadmium speciation of the wild-type and the CeMT-2 knockout strain was distinctly different to the CeMT-1 and double knockouts. Taken together, and supported by a simple model calculation, these findings show for the first time that the two MT isoforms have differential affinities towards Cd(II) and Zn(II) at a cellular level, and this is reflected at the protein level. This suggests that the two MT isoforms have distinct in vivo roles.

Baroclinic waves with parameterized effects of moisture interpreted using Rossby wave components

A theoretical framework is developed for the evolution of baroclinic waves with latent heat release parameterized in terms of vertical velocity. Both wave–conditional instability of the second kind (CISK) and large-scale rain approaches are included. The new quasigeostrophic framework covers evolution from general initial conditions on zonal flows with vertical shear, planetary vorticity gradient, a lower boundary, and a tropopause. The formulation is given completely in terms of potential vorticity, enabling the partition of perturbations into Rossby wave components, just as for the dry problem. Both modal and nonmodal development can be understood to a good approximation in terms of propagation and interaction between these components alone. The key change with moisture is that growing normal modes are described in terms of four counterpropagating Rossby wave (CRW) components rather than two. Moist CRWs exist above and below the maximum in latent heating, in addition to the upper- and lower-level CRWs of dry theory. Four classifications of baroclinic development are defined by quantifying the strength of interaction between the four components and identifying the dominant pairs, which range from essentially dry instability to instability in the limit of strong heating far from boundaries, with type-C cyclogenesis and diabatic Rossby waves being intermediate types. General initial conditions must also include passively advected residual PV, as in the dry problem.

Mononuclear palladium and heterodinuclear palladium–ruthenium complexes of semicarbazone ligands: synthesis, characterization, and application in C–C cross-coupling reactions

Reaction of salicylaldehyde semicarbazone (L-1), 2-hydroxyacetophenone semicarbazone (L-2), and 2-hydroxynaphthaldehyde semicarbazone (L-3) with [Pd(PPh3)(2)Cl-2] in ethanol in the presence of a base (NEt3) affords a family of yellow complexes (1a, 1b and 1c, respectively). In these complexes the semicarbazone ligands are coordinated to palladium in a rather unusual tridentate ONN-mode, and a PPh3 also remains coordinated to the metal center. Crystal structures of the 1b and 1c complexes have been determined, and structure of 1a has been optimized by a DFT method. In these complexes two potential donor sites of the coordinated semicarbazone, viz. the hydrazinic nitrogen and carbonylic oxygen, remain unutilized. Further reaction of these palladium complexes (1a, 1b and 1c) with [Ru(PPh3)(2)(CO)(2)Cl-2] yields a family of orange complexes (2a, 2b and 2c, respectively). In these heterodinuclear (Pd-Ru) complexes, the hydrazinic nitrogen (via dissociation of the N-H proton) and the carbonylic oxygen from the palladium-containing fragment bind to the ruthenium center by displacing a chloride and a carbonyl. Crystal structures of 2a and 2c have been determined, and the structure of 2b has been optimized by a DFT method. All the complexes show characteristic H-1 NMR spectra and, intense absorptions in the visible and ultraviolet region. Cyclic voltammetry on all the complexes shows an irreversible oxidation of the coordinated semicarbazone within 0.86-0.93 V vs. SCE, and an irreversible reduction of the same ligand within -0.96 to -1.14 V vs. SCE. Both the mononuclear (1a, 1b and 1c) and heterodinuclear (2a, 2b and 2c) complexes are found to efficiently catalyze Suzuki, Heck and Sonogashira type C-C coupling reactions utilizing a variety of aryl bromides and aryl chlorides. The Pd-Ru complexes (2a, 2b and 2c) are found to be better catalysts than the Pd complexes (1a, 1b and 1c) for Suzuki and Heck coupling reactions.

Formation of fluorinated nonionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

A structurally related series of fluorinated nonionic oxyethylene glycol surfactants of the type C(m)F(2m+1)(CH(2))(n)O[(CH(2)CH(2)O)(p)H], denoted C(m.n)E(p) (where m=4, 6, or 7, m=1 or 2, and p=4 or 6) were synthesized and their surface behavior in aqueous solution was characterized. The ability of these surfactants to form water-in-hydrofluorocarbon (HFC) propellant 134a microemulsions suitable for use in the aerosolized delivery of water-soluble drugs has been investigated. Phase studies showed that, regardless of the composition used, clear one-phase systems could not be prepared if a fluorinated nonionic surfactant was used alone, or in combination with a short or medium fluorocarbon alcohol cosurfactant. Clear one-phase systems could, however, be prepared if a short-chain hydrocarbon alcohol, such as ethanol, n-propanol, or n-pentanol, was used as cosurfactant, with the extent of the one-phase region increasing with decreased chain length of the alcohol cosurfactant. Light-scattering studies on a number of the hydrocarbon-alcoholcontaining systems in the propellant-rich part of the phase diagram showed that only systems prepared with C(4.2)E(6) and propanol contained microemulsion droplets (all other systems investigated were considered to be cosolvent systems).

Effect of breadmaking process on In Vitro gut microbiota parameters in irritable bowel syndrome

A variety of foods have been implicated in symptoms of patients with Irritable Bowel Syndrome (IBS) but wheat products are most frequently cited by patients as a trigger. Our aim was to investigate the effects of breads, which were fermented for different lengths of time, on the colonic microbiota using in vitro batch culture experiments. A set of in vitro anaerobic culture systems were run over a period of 24 h using faeces from 3 different IBS donors (Rome Criteria–mainly constipated) and 3 healthy donors. Changes in gut microbiota during a time course were identified by fluorescence in situ hybridisation (FISH), whilst the small -molecular weight metabolomic profile was determined by NMR analysis. Gas production was separately investigated in non pH-controlled, 36 h batch culture experiments. Numbers of bifidobacteria were higher in healthy subjects compared to IBS donors. In addition, the healthy donors showed a significant increase in bifidobacteria (P<0.005) after 8 h of fermentation of a bread produced using a sourdough process (type C) compared to breads produced with commercial yeasted dough (type B) and no time fermentation (Chorleywood Breadmaking process) (type A). A significant decrease of δ-Proteobacteria and most Gemmatimonadetes species was observed after 24 h fermentation of type C bread in both IBS and healthy donors. In general, IBS donors showed higher rates of gas production compared to healthy donors. Rates of gas production for type A and conventional long fermentation (type B) breads were almost identical in IBS and healthy donors. Sourdough bread produced significantly lower cumulative gas after 15 h fermentation as compared to type A and B breads in IBS donors but not in the healthy controls. In conclusion, breads fermented by the traditional long fermentation and sourdough are less likely to lead to IBS symptoms compared to bread made using the Chorleywood Breadmaking Process.

Diversity in a honey bee pathogen: first report of a third master variant of the Deformed Wing Virus quasispecies

Treatment of emerging RNA viruses is hampered by the high mutation and replication rates that enable these viruses to operate as a quasispecies. Declining honey bee populations have been attributed to the ectoparasitic mite Varroa destructor and its affiliation with Deformed Wing Virus (DWV). In the current study we use next-generation sequencing to investigate the DWV quasispecies in an apiary known to suffer from overwintering colony losses. We show that the DWV species complex is made up of three master variants. Our results indicate that a new DWV Type C variant is distinct from the previously described types A and B, but together they form a distinct clade compared with other members of the Iflaviridae. The molecular clock estimation predicts that Type C diverged from the other variants ~319 years ago. The discovery of a new master variant of DWV has important implications for the positive identification of the true pathogen within global honey bee populations.

Syk-Dependent Cytokine Induction by Dectin-1 Reveals a Novel Pattern Recognition Pathway for C Type Lectins

Pattern-recognition receptors (PRRs) detect molecular signatures of microbes and initiate immune responses to infection. Prototypical PRRs such as Toll-like receptors (TLRs) signal via a conserved pathway to induce innate response genes. In contrast, the signaling pathways engaged by other classes of putative PRRs remain ill defined. Here, we demonstrate that the β-glucan receptor Dectin-1, a yeast binding C type lectin known to synergize with TLR2 to induce TNFα and IL-12, can also promote synthesis of IL-2 and IL-10 through phosphorylation of the membrane proximal tyrosine in the cytoplasmic domain and recruitment of Syk kinase. syk−/− dendritic cells (DCs) do not make IL-10 or IL-2 upon yeast stimulation but produce IL-12, indicating that the Dectin-1/Syk and Dectin-1/TLR2 pathways can operate independently. These results identify a novel signaling pathway involved in pattern recognition by C type lectins and suggest a potential role for Syk kinase in regulation of innate immunity.