On-Surface Carbon Nitride Growth from Polymerization of 2,5,8-Triazido-s-heptazine.

Carbon nitrides have recently come into focus for photo- and thermal catalysis, both as support materials for metal nanoparticles as well as photocatalysts themselves. While many approaches for the synthesis of three-dimensional carbon nitride materials are available, only top-down approaches by exfoliation of powders lead to thin-film flakes of this inherently two-dimensional material. Here, we describe an in situ on-surface synthesis of monolayer 2D carbon nitride films as a first step toward precise combination with other 2D materials. Starting with a single monomer precursor, we show that 2,5,8-triazido-s-heptazine can be evaporated intact, deposited on a single crystalline Au(111) or graphite support, and activated via azide decomposition and subsequent coupling to form a covalent polyheptazine network. We demonstrate that the activation can occur in three pathways, via electrons (X-ray illumination), via photons (UV illumination), and thermally. Our work paves the way to coat materials with extended carbon nitride networks that are, as we show, stable under ambient conditions.

Dissipative Parametric Gain in a GaAs/AlGaAs Superlattice.

Parametric generation of oscillations and waves is a paradigm, which is known to be realized in various physical systems. Unique properties of quantum semiconductor superlattices allow us to investigate high-frequency phenomena induced by the Bragg reflections and negative differential velocity of the miniband electrons. Effects of parametric gain in the superlattices at different strengths of dissipation have been earlier discussed in a number of theoretical works, but their experimental demonstrations are so far absent. Here, we report on the first observation of the dissipative parametric generation in a subcritically doped GaAs/AlGaAs superlattice subjected to a dc bias and a microwave pump. We argue that the dissipative parametric mechanism originates from a periodic variation of the negative differential velocity. It enforces excitation of slow electrostatic waves in the superlattice that provide a significant enhancement of the gain coefficient. This work paves the way for a development of a miniature solid-state parametric generator of GHz-THz frequencies operating at room temperature.

Injury incidence and prevalence in Finnish top-level football - one-season prospective cohort study.

OJECTIVE: To investigate the injury characteristics in Finnish male football players. DESIGN: One-season prospective epidemiological study. Data were collected via injury reports from the medical staff and directly from the players using the Olso Sports Trauma Research Center Health Questionnaire. PARTICIPANTS: The first team squads of Finnish football league (n = 12 teams, 236 players). MAIN OUTCOME MEASUREMENT: Injury incidence. RESULTS: A total of 541 injuries occurred during the exposure of 62 878 hours. Injury incidence per 1000 exposure hours was 8.6 (30.6 in matches and 3.4 in training). A player sustained on average 2.3 (median 2, range 0-13) injuries during the study. Thigh and ankle were the most commonly injured body parts for acute injuries and hip/groin were the most commonly injured body part for overuse injuries. The median absence time for all injuries was 12 (range 0-107) days, 12 (range 0-107) for acute, and 8 (range 0-61) for overuse injuries. Thigh injuries caused the greatest consequences in terms of absence from full participation (median 5 days, range 0-88). CONCLUSION: Lower limb muscle injuries were the most prevalent injuries in the study. Collecting data directly from the players enabled to report more injuries compared to what was reported only by the medical staff.

Walter Reppe Revival - Identification and Genesis of Copper Acetylides Cu2 C2 as Active Species in Ethynylation Reactions.

More than six decades after proposing copper acetylide, Cu2 C2 , as catalytically active species in ethynylation reactions by Walter Reppe, the explosive species have been experimentally identified and investigated during catalysis in detail now. Taking into account specific safety precautions, unequivocal qualitative characterization was achieved by Raman spectroscopy and X-ray powder diffraction of supported copper catalysts Cu/Bi/SiO2 during and after activation and catalysis in comparison to bulk Cu2 C2 materials. Quantification of Cu2 C2 succeeded by thermal analysis and Raman spectroscopy. Its formation in aqueous suspension is studied starting from copper(II) oxide catalysts including dissolution, reduction and precipitation steps. Copper acetylide formation can be correlated with catalytic performance in the ethynylation of formaldehyde to 1,4-butynediol.

Hydrogenation of furfural by noble metal-free nickel modified tungsten carbide catalysts.

Nickel-tungsten carbide catalysts convert furfural to high value products in a liquid phase catalytic reaction. The product distribution depends on the solvent and the Ni-W-ratio of the catalyst. In isopropyl alcohol a combination of Ni and W x C enables the opening of the furan ring to yield 1,2-pentanediol. Nickel accelerates the tungsten oxide reduction in the tungsten carbide catalyst synthesis and facilitates the carbon insertion. Nickel modified tungsten carbide is a promising, noble metal-free catalyst system for the upgrading of furfural based renewable resources. Its preparation is facilitated compared to unmodified tungsten carbide catalysts.

The Formation Mechanism Investigations of Nano-Tungsten Carbide Powder.

Formation mechanism of synthesizing nanoparticle tungsten carbide (WC) was studied. WC was synthesized by carbothermal hydrogen reduction (CHR) method under various reaction temperatures for holding different post-treatment time in 20% (v/v) CH4/H2. The phase transformation mechanism of gaining WC was investigated, by combining CHR with X-ray diffraction (XRD) and temperature programmed reduction mass spectroscopy (TPR-MS). The results show that pure phase of WC has been obtained by CHR after isothermal heat treatment for 24 hours at 750 °C and 12 hours at 950 °C, respectively. These results indicated that two key parameters of higher temperature and longer isothermal heat treatment time are necessary for synthesizing pure phase of WC powder. In order to find out the phase transformation mechanism of tungsten trioxide (WO3) to WC, the reduction and carburization process among the temperature range from 600 °C to 1000 °C for holding 3 hours at the final temperature were studied. It was shown that at 600 °C, WO3 was reduced to WO2, and from 600 °C to 750 °C, WO2 was reduced to metallic tungsten (W). Moreover, at the temperature range from 750 °C to 900 °C, the mixture phases of tungsten carbide (WC), metallic tungsten (W), or/and tungsten sub-carbide (W2C) were formed without any oxides species, which indicated that tungsten carbides (WC and W2C) phases appeared because the oxides phase was thoroughly reduced. However, the occurrence of carburization process was still limited due to the presence of oxygen in the solid. Because of the formed CO and CO2 there was not enough activated methane reacting with metallic tungsten, so the phase of WC and W2C were both formed simultaneously, but the reaction of forming WC was the main reaction in the whole carburization process. Moreover, the TPR-MS and XRD results indicated that, WC was formed at lower temperature (750 °C) by the reduced metallic W, which was produced form W2C in the gas mixture for holding a long time, while at a higher temperature (950 °C), WC was formed form W2C with the mixture gas directly.

SOMC grafting of vanadium oxytriisopropoxide (VO(O i Pr)3) on dehydroxylated silica; analysis of surface complexes and thermal restructuring mechanism.

Vanadium oxytriisopropoxide (VO(O i Pr)3), 1, was grafted on highly dehydroxylated silica (SiO2-700: aerosil silica treated at 700 °C under high vacuum) to generate compound 2 following the concepts and methodology of surface organometallic chemistry (SOMC). The resulting compound was analyzed by elemental analysis, FT-IR, 1H, 13C and 51V solid state (SS) NMR, Raman and EPR spectroscopies. The grafting reaction of 1 to generate 2 was found to lead to the formation of a monopodal surface complex [([triple bond, length as m-dash]Si-O-)V(O)(O i Pr)2], 2m, as well as bipodal [([triple bond, length as m-dash]Si-O-)2V(O)(O i Pr)], 2b, formed along with ([triple bond, length as m-dash]Si-O- i Pr) moieties as an effect of the classical rearrangement of 2m with strained siloxane bridges. Upon controlled thermal treatment at 200 °C under high vacuum, 2m and 2b were found to mainly rearrange to tetrahedral VO4 moieties [([triple bond, length as m-dash]Si-O-)3V(O)] (3) with formation of propylene whereas the ([triple bond, length as m-dash]Si-O- i Pr) groups were preserved. The mechanism of the thermal rearrangement of the isopropoxide groups was investigated by a DFT approach revealing the occurrence of a concerted γ-H-transfer and olefin elimination mechanism.

Dark chocolate and reduced snack consumption in mildly hypertensive adults: an intervention study.

BACKGROUND: Several studies have shown that cocoa and cocoa-containing foods have the potential to lower blood pressure and improve endothelial function. Most of the studies reporting the beneficial effects of dark chocolate on blood pressure have been short (≤ 4 weeks). The aim of the present 8-wks (weeks) study was to assess the effects of regular consumption of dark chocolate during a reduced snack consumption intervention on blood pressure and other cardiovascular risk factors in mildly hypertensive individuals. DESIGN: This was a randomized, controlled, cross-over trial involving 22 adults (8 women, 14 men), aged 33-64 y, BMI 27.7 ± 3.7 kg/m(2) with mild hypertension. During the intervention period (8-wks) the participants reduced the intake of habitual snacks and replaced them with dark chocolate (49 g/day). In the control period, they only reduced the snacks without any added chocolate. Data (blood lipid profile, glucose, insulin, 24 h blood pressure) was collected in the beginning and end of both periods (intervention and control), and some variables also in the run-in and run-out periods (weight, body fat percentage, blood pressure, arterial stiffness index, diet and physical activity). RESULTS: Daily consumption of dark chocolate had no effects on 24 h blood pressure, resting blood pressure (mean ± SD, pre 142 ± 11.5/89 ± 8.4 mmHg vs. post 142 ± 14.2/88 ± 9.4 mmHg in systolic and diastolic blood pressure, respectively) or arterial stiffness (mean ± SD, pre 7.68 ± 0.88 vs. post 7.76 ± 0.89). Weight was reduced by 1.0 ± 2.2 kg during the control (reduced snack only) period, but was unchanged while eating chocolate (p < 0.027 between the treatments). CONCLUSION: The data collected in this study indicates that inclusion of dark chocolate daily in the diet had no significant effects on blood pressure or other cardiovascular risk factors during a reduced snack period. TRIAL REGISTRATION: ClinicalTrials.gov identifier NCT02130141.

Fluoridonitrosyl complexes of technetium(I) and technetium(II). Synthesis, characterization, reactions, and DFT calculations.

A mixture of [Tc(NO)F5](2-) and [Tc(NO)(NH3)4F](+) is formed during the reaction of pertechnetate with acetohydroxamic acid (Haha) in aqueous HF. The blue pentafluoridonitrosyltechnetate(II) has been isolated in crystalline form as potassium and rubidium salts, while the orange-red ammine complex crystallizes as bifluoride or PF6(-) salts. Reactions of [Tc(NO)F5](2-) salts with HCl give the corresponding [Tc(NO)Cl4/5](-/2-) complexes, while reflux in neat pyridine (py) results in the formation of the technetium(I) cation [Tc(NO)(py)4F](+), which can be crystallized as hexafluoridophosphate. The same compound can be synthesized directly from pertechnetate, Haha, HF, and py or by a ligand-exchange procedure starting from [Tc(NO)(NH3)4F](HF2). The technetium(I) cation [Tc(NO)(NH3)4F](+) can be oxidized electrochemically or by the reaction with Ce(SO4)2 to give the corresponding Tc(II) compound [Tc(NO)(NH3)4F](2+). The fluorido ligand in [Tc(NO)(NH3)4F](+) can be replaced by CF3COO(-), leaving the "[Tc(NO)(NH3)4](2+) core" untouched. The experimental results are confirmed by density functional theory calculations on [Tc(NO)F5](2-), [Tc(NO)(py)4F](+), [Tc(NO)(NH3)4F](+), and [Tc(NO)(NH3)4F](2+).

From communicative functions to prosodic forms.

This is a proposal in favour of proceeding from communicative function to linguistic form, rather than the reverse, for an insightful account of how humans communicate by speech in languages. A functional framework is developed that encompasses argumentation structures, declarative and interrogative functions, and expressive intensification. Such a function orientation can become a powerful tool in comparative prosodic research across the world's languages. The potential of this approach is shown by comparing the prosodic form of Mandarin Chinese data collected in functionally contextualized scenarios with corresponding data from English and German.

The effect of Al-doping on ZnO nanoparticles applied as catalyst support.

A pure ZnO sample and a sample containing 3 mol% Al were prepared by (co)-precipitation as model materials for the oxidic support phase in Cu/ZnO/Al(2)O(3) methanol synthesis catalysts. The samples were characterized with respect to their crystal, defect and micro-structure using various methods (XRD, TEM, XPS, UV-vis spectroscopy, EPR, NMR). It was found that a significant fraction of the Al is incorporated into the ZnO lattice and enhances the defect chemistry of the material. The defect structure, however, was not stable under reducing conditions as applied in catalytic reactions. Al ions migrated towards the surface of the ZnO nanoparticles leading to formation of an Al-rich shell and an Al-depleted core. This process proceeds during the first 10-20 hours on stream and is associated with strong modification of the optical bandgap energy and the EPR signal of donor sites present in ZnO.

The perception of lexical stress in German: effects of segmental duration and vowel quality in different prosodic patterns.

Several decades of research, focusing on English, Dutch and German, have set up a hierarchy of acoustic properties for cueing lexical stress. It attributes the strongest cue to criterial-level f0 change, followed by duration, but low weight to energy and to stressed-vowel spectra. This paper re-examines the established view with new data from German. In the natural productions of the German word pair Kaffee 'coffee' - Café 'locality' (with initial vs. final stress in a North German pronunciation), vowel duration was manipulated in a complementary fashion across the two syllables in five steps, spanning the continuum from initial to final stress on each word. The two base words provided different vowel qualities as the second variable, the intervocalic fricative was varied in two values, long and short, taken from Café and Kaffee, and the generated test words were inserted in a low f0 tail and in a high f0 hat-pattern plateau, which both eliminated f0 change as a cue to lexical stress. The sentence stimuli were judged in two listening experiments by 16 listeners in each as to whether the first or the second syllable of the test word was stressed. The results show highly significant effects of vowel duration, vowel quality and fricative duration. The combined vowel-quality and fricative variable can outweigh vowel duration as a cue to lexical stress. The effect of the prosodic frame is only marginal, especially related to a rhythmic factor. The paper concludes that there is no general hierarchy with a fixed ranking of the variables traditionally adduced to signal lexical stress. Every prosodic embedding of segmental sequences defines the hierarchy afresh.

Suzuki coupling reactions in neat water as the solvent: where in the biphasic reaction mixture do the catalytic reaction steps occur?

Many reports on water-compatible palladium catalysts have appeared in the recent literature. For hydrophobic substrates, mixtures with pure water are biphasic, and it is widely not regarded that the elusive locality of the catalytic process (in water, the organic layer, or at the phase boundary) has an important impact on the mechanism and efficiency of the reaction. In the present work, for the first time systematic variation of reaction parameters has been performed for Suzuki coupling experiments with chloro- and bromoarenes in pure water. The investigations are not only aimed at the factors influencing the catalytic activity, but also at the effects that may occur particularly in water/organic biphasic media, and on the question as to in which of the two liquid phases the reaction takes place. These investigations have revealed that dilution of the base (in the aqueous layer) and the Pd species (in the organic layer) are detrimental to the reaction, and that phase-transfer processes play a major role in the overall mechanism. A series of experiments with variation of parameters like precatalyst hydrophilicity, organic and water phase volume, additives, stirring rate, base concentration, and so forth, indicate that for the systems under study the reaction occurs in the organic layer. The water phase needs to be present to dissolve and provide polar reactants, and re-absorb side products. The results encourage to pay more regard to the question of phase locality of coupling reactions in water in general.

2 µm semiconductor disk laser with a heterodyne linewidth below 10 kHz.

We demonstrate a 2 µm semiconductor disk laser emitting in a single longitudinal mode with a linewidth in the <10 kHz range. A heterodyne detection scheme was used for precise linewidth measurements. In these experiments, the output beams of two identical laser cavities were superposed in order to generate a beat note signal on a photodiode. In the absence of active frequency stabilization, a linewidth of 45 kHz was measured at an output power of 100 mW. When using a frequency stabilization consisting of a feedback loop with a Fabry-Perot interferometer as wavelength reference, the linewidth could be further reduced to 9 kHz.

Communicative functions integrate segments in prosodies and prosodies in segments.

This paper takes a new look at the traditionally established divide between sounds and prosodies, viewing it as a useful heuristics in language descriptions that focus on the segmental make- up of words. It pleads for a new approach that bridges this reified compartmentalization of speech in a more global communicative perspective. Data are presented from a German perception experiment in the framework of the Semantic Differential that shows interdependence of f0 contours and the spectral characteristics of a following fricative segment, for the expression of semantic functions along the scales questioning - asserting, excited - calm, forceful - not forceful, contrary - agreeable. The results lead to the conclusion that segments shape prosodies and are shaped by them in varying ways in the coding of semantic functions. This implies that the analysis of sentence prosodies needs to integrate the manifestation of segments, just as the analysis of segments needs to consider their prosodic embedding. In communicative interaction, speakers set broad prosodic time windows of varying sizes, and listeners respond to them. So, future phonetic research needs to concentrate on speech analysis in such windows.

On the role of articulatory prosodies in German message decoding.

A theoretical framework for speech reduction is outlined in which 'coarticulation' and 'articulatory control' operate on sequences of 'opening-closing gestures' in linguistic and communicative settings, leading to suprasegmental properties - 'articulatory prosodies' - in the acoustic output. In linking this gestalt perspective in speech production to the role of phonetic detail in speech understanding, this paper reports on perception experiments that test listeners' reactions to varying extension of an 'articulatory prosody of palatality' in message identification. The point of departure for the experimental design was the German utterance ich kann Ihnen das ja mal sagen 'I can mention this to you' from the Kiel Corpus of Spontaneous Speech, which contains the palatalized stretch [k̟(h)ε̈n(j)n(j)əs] for the sequence of function words /kan i.n(kə)n das/ kann Ihnen das. The utterance also makes sense without the personal pronoun Ihnen. Systematic experimental variation has shown that the extent of palatality has a highly significant influence on the decoding of Ihnen and that the effect of nasal consonant duration depends on the extension of palatality. These results are discussed in a plea to base future speech perception research on a paradigm that makes the traditional segment-prosody divide more permeable, and moves away from the generally practised phoneme orientation.

Copper(II) complexes incorporating poly/perfluorinated alkoxyaluminate-type weakly coordinating anions: syntheses, characterization and catalytic application in stereoselective olefin aziridination.

The synthesis and characterization of a series of cationic copper(II) complexes of the type [Cu(NCR)(6)][Al(OC(CF(3))(2)R')(4)](2) (R = CH(3), Ph; R' = CF(3), Ph, PhCH(3)), incorporating poly/perfluoronated alkoxyaluminates as weakly coordinating anions (WCAs) is presented. Aziridination of various olefins, such as the unreactive olefins e.g. ethylhex-2-enoate and 1-decene, with N-tosyliminophenyliodinane catalyzed by [Cu(NCR)(6)][Al(OC(CF(3))(2)R')(4)](2) affords very good yields (up to 96%) and high TOFs (up to 5000 h(-1)) under mild conditions. Using disubstituted olefins as substrates, high stereoselectivities are obtained at room temperature. The to date highest cis : trans ratio (98 : 2) of the obtained aziridines is achieved for cis-stilbene in good yield (85%) as well as promising TOF (> 2000 h(-1)). The investigation of the solvent effect on yield and selectivity reveals that for certain oleophilic substrates (1-decene), less polar solvents, such as dichloromethane are a better choice than acetonitrile, which is commonly considered as the best solvent for olefin aziridination. Accordingly, a mechanism involving a paramagnetic copper nitrene intermediate with both concerted and stepwise pathways is proposed.