N-H center dot center dot center dot pi hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H center dot center dot center dot pi hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr center dot Bz, Pyr center dot Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H center dot center dot center dot pi hydrogen bond to the benzene ring. The pyrrole is tipped by omega(S(0)) = +/- 13 degrees relative to the surface normal of Bz. The N center dot center dot center dot ring distance is 3.13 angstrom. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle omega(S(1)) = +/- 21 degrees. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H center dot center dot center dot pi interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1) <- S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr center dot Bz in the same region exhibits a weak 0(0)(0) band that is red-shifted by 58 cm(-1) relative to that of Bz (38 086 cm(-1)). The origin appears due to symmetry-breaking of the p-electron system of Bz by the asymmetric pyrrole NH center dot center dot center dot pi hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0(0)(0) band. The Bz moiety in Pyr center dot Bz exhibits a 6a(0)(1) band at 0(0)(0) + 518 cm(-1) that is about 20x more intense than the origin band. The symmetry breaking by the NH center dot center dot center dot pi hydrogen bond splits the degeneracy of the v(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by similar to 6 cm(-1). Both the 0(0)(0) and 6(0)(1) bands of Pyr center dot Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration omega', in agreement with the change of the omega tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.

MIAWARA-C, a new ground based water vapor radiometer for measurement campaigns

In this paper a new 22 GHz water vapor spectro-radiometer which has been specifically designed for profile measurement campaigns of the middle atmosphere is presented. The instrument is of a compact design and has a simple set up procedure. It can be operated as a standalone instrument as it maintains its own weather station and a calibration scheme that does not rely on other instruments or the use of liquid nitrogen. The optical system of MIAWARA-C combines a choked gaussian horn antenna with a parabolic mirror which reduces the size of the instrument in comparison with currently existing radiometers. For the data acquisition a correlation receiver is used together with a digital cross correlating spectrometer. The complete backend section, including the computer, is located in the same housing as the instrument. The receiver section is temperature stabilized to minimize gain fluctuations. Calibration of the instrument is achieved through a balancing scheme with the sky used as the cold load and the tropospheric properties are determined by performing regular tipping curves. Since MIAWARA-C is used in measurement campaigns it is important to be able to determine the elevation pointing in a simple manner as this is a crucial parameter in the calibration process. Here we present two different methods; scanning the sky and the Sun. Finally, we report on the first spectra and retrieved water vapor profiles acquired during the Lapbiat campaign at the Finnish Meteorological Institute Arctic Research Centre in Sodankylä, Finland. The performance of MIAWARA-C is validated here by comparison of the presented profiles against the equivalent profiles from the Microwave Limb Sounder on the EOS/Aura satellite.

Global Change and the World's Mountains-Research Needs and Emerging Themes for Sustainable Development A Synthesis From the 2010 Perth II Conference

The conference on Global Change and the World’s Mountains held in Perth, Scotland, in 2010 offered a unique opportunity to analyze the state and progress of mountain research and its contribution to sustainable mountain development, as well as to reflect on required reorientations of research agendas. In this paper we provide the results of a three-step assessment of the research presented by 450 researchers from around the world. First, we determined the state of the art of mountain research and categorized it based on the analytical structure of the Global Land Project (GLP 2005). Second, we identified emerging themes for future research. Finally, we assessed the contribution of mountain research to sustainable development along the lines of the Grand Challenges in Global Sustainability Research (International Council for Science 2010). Analysis revealed that despite the growing recognition of the importance of more integrative research (inter- and transdisciplinary), the research community gathered in Perth still focuses on environmental drivers of change and on interactions within ecological systems. Only a small percentage of current research seeks to enhance understanding of social systems and of interactions between social and ecological systems. From the ecological systems perspective, a greater effort is needed to disentangle and assess different drivers of change and to investigate impacts on the rendering of ecosystem services. From the social systems perspective, significant shortcomings remain in understanding the characteristics, trends, and impacts of human movements to, within, and out of mountain areas as a form of global change. Likewise, sociocultural drivers affecting collective behavior as well as incentive systems devised by policy and decision makers are little understood and require more in-depth investigation. Both the complexity of coupled social– ecological systems and incomplete data sets hinder integrated systems research. Increased understanding of linkages and feedbacks between social and ecological systems will help to identify nonlinearities and thresholds (tipping points) in both system types. This presupposes effective collaboration between ecological and social sciences. Reflections on the Grand Challenges in Sustainability Research put forth by the International Council for Science (2010) reveal the need to intensify research on effective responses and innovations. This will help to achieve sustainable development in mountain regions while maintaining the core competence of mountain research in forecasting and observation.

Targeting the conversion of ceramide to sphingosine 1-phosphate as a novel strategy for cancer therapy

Sphingolipids not only function as structural components of cell membranes but also act as signaling molecules to regulate fundamental cellular responses, such as cell death and differentiation, proliferation and certain types of inflammation. Particularly the cellular balance between ceramide and sphingosine 1-phosphate seems to be crucial for a cell's decision to either undergo apoptosis or proliferate, two events which are implicated in tumor development and growth. Whereas ceramide possesses proapoptotic capacity in many cell types, sphingosine 1-phosphate acts as a counterplayer able to induce cell proliferation and protect cells from undergoing apoptosis. Therefore, tipping the balance in favour of ceramide production, i.e. by inhibiting ceramidase or sphingosine kinase activities has potential to support its proapoptotic action and hence represents a promising rational approach to effective cancer therapy. This review highlights most recent data on the regulation of cellular sphingolipid formation and their potential implication in tumor development, and provides perspectives for their use as targets in molecular intervention therapy.

Saving soils at degradation frontlines: Sustainable land management in drylands

Healthy soils are fundamental to life. They grow the food we eat and the wood we use for shelter and fuel, purify the water we drink, and hold fast to the roots of the natural world we cherish. They are the ground beneath our feet and beneath our homes. But they are under threat, especially from human overuse and climate change. Nowhere is this more evident than in dryland areas, where soil degradation – or desertification – wears away at this essential resource, sometimes with sudden rapidity when a tipping point is crossed. Though it is a challenge, preserving and restoring healthy soils in drylands is possible, and it concerns all of us. Sustainable land management points the way.

Challenges in the participatory assessment of sustainable management practices in dryland ecosystems under regime shifts

Regime shifts, defined as a radical and persistent reconfiguration of an ecosystem following a disturbance, have been acknowledged by scientists as a very important aspect of the dynamic of ecosystems. However, their consideration in land management planning remains marginal and limited to specific processes and systems. Current research focuses on mathematical modeling and statistical analysis of spatio-temporal data for specific environmental variables. These methods do not fulfill the needs of land managers, who are confronted with a multitude of processes and pressure types and require clear and simple strategies to prevent regime shift or to increase the resilience of their environment. The EU-FP7 CASCADE project is looking at regime shifts of dryland ecosystems in southern Europe and specifically focuses on rangeland and forest systems which are prone to various land degradation threats. One of the aims of the project is to evaluate the impact of different management practices on the dynamic of the environment in a participatory manner, including a multi-stakeholder evaluation of the state of the environment and of the management potential. To achieve this objective we have organized several stakeholder meetings and we have compiled a review of management practices using the WOCAT methodology, which enables merging scientific and land users knowledge. We highlight here the main challenges we have encountered in applying the notion of regime shift to real world socio-ecological systems and in translating related concepts such as tipping points, stable states, hysteresis and resilience to land managers, using concrete examples from CASCADE study sites. Secondly, we explore the advantages of including land users’ knowledge in the scientific understanding of regime shifts. Moreover, we discuss useful alternative concepts and lessons learnt that will allow us to build a participatory method for the assessment of resilient management practices in specific socio-ecological systems and to foster adaptive dryland management.

The elusive S2 state, the S1/S2 splitting, and the excimer states of the benzene dimer

We observe the weak S 0 → S 2 transitions of the T-shaped benzene dimers (Bz)2 and (Bz-d 6)2 about 250 cm−1 and 220 cm−1 above their respective S 0 → S 1 electronic origins using two-color resonant two-photon ionization spectroscopy. Spin-component scaled (SCS) second-order approximate coupled-cluster (CC2) calculations predict that for the tipped T-shaped geometry, the S 0 → S 2 electronic oscillator strength f el (S 2) is ∼10 times smaller than f el (S 1) and the S 2 state lies ∼240 cm−1 above S 1, in excellent agreement with experiment. The S 0 → S 1 (ππ ∗) transition is mainly localized on the “stem” benzene, with a minor stem → cap charge-transfer contribution; the S 0 → S 2 transition is mainly localized on the “cap” benzene. The orbitals, electronic oscillator strengths f el (S 1) and f el (S 2), and transition frequencies depend strongly on the tipping angle ω between the two Bz moieties. The SCS-CC2 calculated S 1 and S 2 excitation energies at different T-shaped, stacked-parallel and parallel-displaced stationary points of the (Bz)2 ground-state surface allow to construct approximate S 1 and S 2 potential energy surfaces and reveal their relation to the “excimer” states at the stacked-parallel geometry. The f el (S 1) and f el (S 2) transition dipole moments at the C 2v -symmetric T-shape, parallel-displaced and stacked-parallel geometries are either zero or ∼10 times smaller than at the tipped T-shaped geometry. This unusual property of the S 0 → S 1 and S 0 → S 2 transition-dipole moment surfaces of (Bz)2 restricts its observation by electronic spectroscopy to the tipped and tilted T-shaped geometries; the other ground-state geometries are impossible or extremely difficult to observe. The S 0 → S 1/S 2 spectra of (Bz)2 are compared to those of imidazole ⋅ (Bz)2, which has a rigid triangular structure with a tilted (Bz)2 subunit. The S 0 → S 1/ S 2 transitions of imidazole-(benzene)2 lie at similar energies as those of (Bz)2, confirming our assignment of the (Bz)2 S 0 → S 2 transition.

Influence of unilateral maxillary first molar extraction treatment on second and third molar inclination in Class II subdivision patients.

OBJECTIVE To assess the maxillary second molar (M2) and third molar (M3) inclination following orthodontic treatment of Class II subdivision malocclusion with unilateral maxillary first molar (M1) extraction. MATERIALS AND METHODS Panoramic radiographs of 21 Class II subdivision adolescents (eight boys, 13 girls; mean age, 12.8 years; standard deviation, 1.7 years) before treatment, after treatment with extraction of one maxillary first molar and Begg appliances and after at least 1.8 years in retention were retrospectively collected from a private practice. M2 and M3 inclination angles (M2/ITP, M2/IOP, M3/ITP, M3/IOP), constructed by intertuberosity (ITP) and interorbital planes (IOP), were calculated for the extracted and nonextracted segments. Random effects regression analysis was performed to evaluate the effect on the molar angulation of extraction, time, and gender after adjusting for baseline measurements. RESULTS Time and extraction status were significant predictors for M2 angulation. M2/ITP and M2/IOP decreased by 4.04 (95% confidence interval [CI]: -6.93, 1.16; P  =  .001) and 3.67 (95% CI: -6.76, -0.58; P  =  .020) in the extraction group compared to the nonextraction group after adjusting for time and gender. The adjusted analysis showed that extraction was the only predictor for M3 angulation that reached statistical significance. M3 mesial inclination increased by 7.38° (95% CI: -11.2, -3.54; P < .001) and 7.33° (95% CI: -11.48, -3.19; P  =  .001). CONCLUSIONS M2 and M3 uprighting significantly improved in the extraction side after orthodontic treatment with unilateral maxillary M1 extraction. There was a significant increase in mesial tipping of maxillary second molar crowns over time.