Search

This paper reviews and summarises the work that has been conducted and the technology used in exploring and developing the Northern Bowen and Galilee basins in Queensland. It examines the methods operators have used in drilling, completing and testing wells through the varying stages of exploration, appraisal and development in the different parts of the basins. It examines all the work conducted in the Betts Creek Beds and Aramac Coal Measures throughout the Galilee Basin; the Moranbah Coal Measures, Rangal Coal Measures and Fort Cooper Coal Measures in the Moranbah area of the Bowen Basin; the Rangal Coal Measures, Burngrove Formation and Fairhill Formation in the Blackwater area; the conventional and coal seam gas developments in the Rolleston area, including the Bandanna Formation plays near Injune; and the Baralaba Coal Measures in the Moura area. Wells have been completed both open and cased hole with techniques including vertical wells, both with and without hydraulic fracturing and cavitation, as well as a variety of horizontal well designs including surface to inseam wells with vertical intercept wells and multiple lateral sections, chevron wells and both heel and toe intercepts. Operators have also implemented multiple wells on one pad. Throughout the Northern Bowen Basin, horizontal well drilling has been a key technology in commercial development. Generally, activities within the Galilee Basin have not progressed as far as the Bowen Basin, but nevertheless, horizontal wells are also emerging as a key technology.

ABSTRACTThe internationalisation of Higher Education is broadly seen as a positive development. It is a process that is said to contribute to intercultural skills acquisition, which is deemed crucial in today’s globalised society. Yet, research has shown that the benefits of being confronted with other ideas and viewpoints can get lost in translation due to different languages and academic cultures. We set out to explore the impact of the international classroom on study success and argue that there might be an optimum level of internationalisation. Based on a dataset that includes more than 2822 GPA scores for 836 students from four first-year cohorts of an international Bachelor in European Studies, we find strong empirical evidence that students’ study success is lower when there are few (below 3) or many (above 6) different nationalities in the classroom. We find the strongest effects of internationalisation for students who regularly attend class (i.e. 80–90%). Hence, we present strong evidence that internationalisation has a both a negative and a positive impact on students’ study success but students will only experience these beneficial and detrimental effects of learning in an international environment when they attend class.

Automated driving systems, which can take over certain dynamic driving tasks from the driver, are becoming increasingly available in commercial vehicles. One of these automated driving systems widely introduced in commercial vehicles is adaptive cruise control (ACC). This system is designed to maintain certain desired driving speeds and time headways as chosen by drivers and based on the settings available within the system. The properties and actual performance of these systems will affect the traffic flow and its stability. However, the specific properties and their workings are rarely publicly available. Therefore, the main aim of this paper is to test the actual performance of a commercial ACC system under different desired speed and distance gap settings, as well as driving modes in a car-following situation. For this purpose, a pilot field test was conducted in the Netherlands in which two identical commercial vehicles equipped with ACC systems were driven simultaneously. The first vehicle was used to create a pre-specified speed profile by adapting the ACC system settings manually, whereas the second vehicle followed the lead vehicle when the ACC system was engaged to test its actual performance. The main findings indicate that the different system settings affect the car-following indicators, and system response times were found to be comparable to human response times. The eco mode was found to affect some of the car-following indicators, and it does not deteriorate safety below the safety level of driving with short headway setting in drive mode.

AbstractIt is under debate how preferential perfusion of the brain (brain-sparing) in fetal growth restriction (FGR) relates to long-term neurodevelopmental outcome. Epigenetic modification of neurotrophic genes by altered fetal oxygenation may be involved. To explore this theory, we performed a follow-up study of 21 FGR children, in whom we prospectively measured the prenatal cerebroplacental ratio (CPR) with Doppler sonography. At 4 years of age, we tested their neurodevelopmental outcome using the Wechsler Preschool and Primary Scale of Intelligence, the Child Behavior Checklist, and the Behavior Rating Inventory of Executive Function. In addition, we collected their buccal DNA to determine the methylation status at predefined genetic regions within the genes hypoxia-inducible factor-1 alpha (HIF1A), vascular endothelial growth factor A (VEGFA), erythropoietin (EPO), EPO-receptor (EPOR), brain-derived neurotrophic factor (BDNF), and neurotrophic tyrosine kinase, receptor, type 2 (NTRK2) by pyrosequencing. We found that FGR children with fetal brain-sparing (CPR <1, n= 8) demonstrated a trend (0.05 < p< 0.1) toward hypermethylation of HIF1Aand VEGFAat their hypoxia-response element (HRE) compared with FGR children without fetal brain-sparing. Moreover, in cases with fetal brain-sparing, we observed statistically significant hypermethylation at a binding site for cyclic adenosine monophophate response element binding protein (CREB) of BDNFpromoter exon 4 and hypomethylation at an HRE located within the NTRK2promoter (both p<0.05). Hypermethylation of VEGFAwas associated with a poorer Performance Intelligence Quotient, while hypermethylation of BDNFwas associated with better inhibitory self-control (both p<0.05). These results led us to formulate the hypothesis that early oxygen-dependent epigenetic alterations due to hemodynamic alterations in FGR may be associated with altered neurodevelopmental outcome in later life. We recommend further studies to test this hypothesis.

Many pregnant women experience symptoms of depression, and are often treated with selective serotonin reuptake inhibitor (SSRI) antidepressants, such as fluoxetine. In utero exposure to SSRIs and maternal depressive symptoms is associated with sex-specific effects on the brain and behavior. However, knowledge about the neurobiological mechanisms underlying these sex differences is limited. In addition, most animal research into developmental SSRI exposure neglects the influence of maternal adversity. Therefore, we used a rat model relevant to depression to investigate the molecular effects of perinatal fluoxetine exposure in male and female juvenile offspring. We performed RNA sequencing and targeted DNA methylation analyses on the prefrontal cortex and basolateral amygdala; key regions of the corticolimbic circuit. Perinatal fluoxetine enhanced myelin-related gene expression in the prefrontal cortex, while inhibiting it in the basolateral amygdala. SSRI exposure and maternal adversity interacted to affect expression of genes such as myelin-associated glycoprotein (Mag) and myelin basic protein (Mbp). We speculate that altered myelination reflects altered brain maturation. In addition, these effects are stronger in males than in females, resembling known behavioral outcomes. Finally, Magand Mbpexpression correlated with DNA methylation, highlighting epigenetic regulation as a potential mechanism for developmental fluoxetine-induced changes in myelination.

ABSTRACTEuropean legislation continues to drive down emission limit values, making the emission measurement of narrow stacks of increasing importance. However, the applicable standards (EN ISO 16911–1 and EN 15259) are poorly validated for narrow stacks, and the effect of flow disturbances on the described methods are largely unknown. In this article, measurement errors are investigated in narrow stacks with flow disturbances and swirl, both experimentally and through computational fluid dynamics (CFD) simulations. The results indicate that measurement errors due to misalignment of the flow with typical measuring probes (pitot tubes) are small compared to errors resulting from the positioning of these probes in the measurement plane. Errors up to 15% are reported using the standardized methods, while the measurement error is both smaller and more predictable when using additional measurement points.Implications: Current international standards provide methods to measure emissions from industrial stacks. With increasingly small emission limit values, the accuracy of these measurements is becoming considerably more important. The data from this study can be used to inform revisions of these standards, in particular with respect to flow disturbances in narrow stacks, and can help law- and policy-makers to obtain insight into the uncertainties of emission measurements in these specific situations.

AbstractThe soluble fms-like tyrosine kinase factor 1 (sFlt-1) is a major contributor to antiangiogenesis during preeclampsia. However, little is known about the effects of sFlt-1 on fetal health. In this study we aim to evaluate the effects of the sFlt-1 concentration during pregnancy on fetal liver physiology. We used adenoviral gene delivery in Sprague-Dawley dams (seven females, 10 weeks old) during mid-gestation (gestational day 8) with adenovirus overexpressing sFlt-1, and age-matched controls (six females, 10 weeks old) with empty adenoviral virus in order to quantify the sFlt-1 concentrations in pregnant dams. Dams exposed to adenoviral sFlt-1 delivery were subdivided into a low (n=4) and high sFlt-1 (n=3) group based on host response to the virus. One-way analysis of variance showed that fetuses (five per dam) exposed to high sFlt-1 concentrations in uteroshow fetal growth restriction (1.84±0.043 g high sFlt-1 v.2.32±0.036 g control; mean (M)±s.e.m.; P<0.001), without hypertension or proteinuria in the dams. In continuation, the microarray analysis of the fetal liver of the high sFlt-1 group showed significant enrichment of key genes for fatty acid metabolism and Ppara targets. In addition, using pyrosequencing, we found that the Ppara enrichment in the high sFlt-1 group is accompanied by decreased methylation of its promoter (1.89±0.097 mean % methylation in high sFlt-1 v.2.26±0.095 mean % methylation in control, M±s.e.m., P<0.02). Our data show that high sFlt-1 concentrations during pregnancy have detrimental effects on the fatty acid metabolism genes and the Ppara targets in the fetal liver.

ABSTRACTThis symposium Regional Authority and the Postfunctionalist Theory of Governance engages two recent books on regional governance. The first sets out a measure of regional authority for 81 countries in North America, Europe, Latin America, Asia and the Pacific between 1950 and 2010. The second theorizes how regional governance is shaped by functional and communal pressures. These pressures are detected in many historical episodes of jurisdictional reform. These books seek to pin them down empirically. Community and efficiency appear to have tangible and contrasting effects that explain how jurisdictions are designed, why regional governance has become differentiated and how multilevel governance has deepened over the past several decades. The symposium consists of contributions by Kent Eaton, Jean-Paul Faguet and Imke Harbers followed by a response from the authors: Liesbet Hooghe, Gary Marks, Arjan H. Schakel, Sara Niedzwiecki, Sandra Chapman Osterkatz and Sarah Shair-Rosenfield, Measuring Regional Authority: A Postfunctionalist Theory of Governance, Vol. I. Oxford: Oxford University Press, 2016; and Liesbet Hooghe and Gary Marks, with Arjan H. Schakel, Sara Niedzwiecki, Sandra Chapman Osterkatz and Sarah Shair-Rosenfield, Community, Scale, and Regional Governance: A Postfunctionalist Theory of Governance, Vol. II. Oxford: Oxford University Press, 2016.

This study examines whether or not political representation in the Netherlands is biased toward the rich and higher educated by comparing the political orientations of members of parliament to those of the electorate. The analyses reveal stark differences in the representation of different socio-economic groups. The political views of elected national representatives are far more similar to those of rich, higher educated citizens than to those with less income and education. Moreover, a longitudinal analysis reveals that inequalities in political representation have actually grown in recent years. We also show that the use of measures of ideological self-identification might to lead to highly misleading results regarding the nature of political representation as opposed to the use of issue items. We conclude that, despite a highly proportional electoral system, the views which are represented in the Dutch lower house of parliament contain major distortions of the views of the broader electorate.

•A new performance indicator for CO2utilization is introduced.•Indicator is a proxy for the energy efficiency of CO2utilization options.•Three example case studies highlight the applicability of the indicator.•Indicator enables comparison of CO2utilization options with different functionality.

ABSTRACTThe impact of prenatal smoke exposure (PSE) on DNA methylation has been demonstrated in blood samples from children of smoking mothers, but evidence for sex-dependent smoke-induced effects is limited. As the identified differentially methylated genes can be associated with developmental processes, and insulin-like growth factors (IGFs) play a critical role in prenatal tissue growth, we hypothesized that PSE induces fetal programming of Igf1rand Igf1.Using a mouse model of smoking during pregnancy, we show that PSE alters promoter methylation of Igf1rand Igf1and deregulates their gene expression in lung and liver of fetal (E17.5) and neonatal (D3) mouse offspring. By further comparing female versus male, lung versus liver, or fetal versus neonatal time point, our results demonstrate that CpG site-specific aberrant methylation patterns sex-dependently vary per organ and time point. Moreover, PSE reduces gene expression of Igf1rand Igf1, dependent on organ, sex, and offspring's age. Our results indicate that PSE may be a source of organ-specific rather than general systemic fetal programming. This is exemplified here by gene promoter methylation and mRNA levels of Igf1rand Igf1,together with a sex- and organ-specific naturally established correlation of both parameters that is affected by prenatal smoke exposure. Moreover, the comparison of fetuses with neonates suggests a CpG site-dependent reversibility/persistence of PSE-induced differential methylation patterns.

Automated driving may lead to much higher road capacities, combined with increased road safety, increased driver comfort, and lower costs. Although this vision may hold ground in the long run, first a transitional period will take place in which increasing percentages of vehicles with many levels of automation will drive on the world’s road networks. This transition poses a fundamental scientific challenge. The models used today to simulate and predict vehicular traffic are not valid to predict emergent properties of traffic flows under increasing amounts of vehicle automation. For example, there is no idea of how drivers of nonautomated vehicles will respond to other drivers reading their morning papers behind the steering wheel or the consequences of such interactions on traffic safety and capacity. In this paper, the authors do not propose a new behavioral theory with which the effects of increasing vehicle automation can be predicted. What the authors propose is an advanced open-source simulation framework, OpenTrafficSim, which makes it possible to extend microscopic models incrementally with explanatory mental models, such that new behavioral theories can be tested and shared within the community. Given the societal importance of predicting the effects on safety and efficiency of vehicle automation, the authors sincerely hope this paper will fuel the discussion on how both open-source and closed-source simulation software can be adapted and made ready for the next generation of traffic simulation models that are needed in the coming decades.

•Utilizing CO2into dimethyl ether improves techno-environmental performance.•Climate change potential reduction is limited compared to CO2capture and storage.•Environmental trade-offs of CCU more complex than those of CO2capture and storage.•Techno-environmental analysis improves insights in performance of CO2utilization options.

Automated driving may lead to much higher road capacities, combined with increased road safety, increased driver comfort, and lower costs. Although this vision may hold ground in the long run, first a transitional period will take place in which increasing percentages of vehicles with many levels of automation will drive on the world’s road networks. This transition poses a fundamental scientific challenge. The models used today to simulate and predict vehicular traffic are not valid to predict emergent properties of traffic flows under increasing amounts of vehicle automation. For example, there is no idea of how drivers of nonautomated vehicles will respond to other drivers reading their morning papers behind the steering wheel or the consequences of such interactions on traffic safety and capacity. In this paper, the authors do not propose a new behavioral theory with which the effects of increasing vehicle automation can be predicted. What the authors propose is an advanced open-source simulation framework, OpenTrafficSim, which makes it possible to extend microscopic models incrementally with explanatory mental models, such that new behavioral theories can be tested and shared within the community. Given the societal importance of predicting the effects on safety and efficiency of vehicle automation, the authors sincerely hope this paper will fuel the discussion on how both open-source and closed-source simulation software can be adapted and made ready for the next generation of traffic simulation models that are needed in the coming decades.

Recent research has shown that there exists large heterogeneity in car-following behaviour such that different car-following models best describe different drivers' behaviour. A literature review reveals that current approaches to calibrate and compare different models for one driver do not take the complexity of the models into account or are only able to compare a specific set of models. This contribution applies Bayesian techniques to the calibration of car-following models. The Bayesian framework promotes models that fit the data well but punishes models with a high complexity, resulting in a measure called the evidence. This evidence quantifies how probable each model is to be the model that best describes the car-following behaviour of a single driver. It can be computed for any car-following model. When considered over multiple drivers, the evidences can be used to describe the heterogeneity of the driving population. In an experiment seven different car-following models are calibrated and compared using a data set that was collected with a helicopter. The results indicate that multi-leader models better describe the car-following models even if their higher complexity is accounted for, and that for the description of microscopic driving behaviour the reaction time is essential; models without a reaction time perform significantly worse.

Territory is a salient issue in post-communist countries in Europe, yet subnational elections have received surprisingly little attention. This article analyses congruence between national and regional elections in Croatia, the Czech Republic, Hungary, Poland, Romania and the Slovak Republic held between 1993 and 2010. The findings suggest that election incongruence can be partly explained by approaches which work well in the West European context – territorial cleavages, regional authority and the second-order election model – but in order to fully grasp regional election outcomes in post-communist countries one also needs to take into account electoral alliance strategies and party supply change.

A proposed lane change model can be integrated with a car-following model to form a complete microscopic driver model. The model resembles traffic better at a macroscopic level, especially regarding the amount of traffic volume per lane, the traffic speeds in different lanes, and the onset of congestion. In a new approach, lane change incentives are combined for determining a lane change desire. Included incentives are to follow a route, to gain speed, and to keep right. Classification of lane changes is based on behavior that depends on the level of lane change desire. Integration with a car-following model is achieved by influencing car-following behavior for relaxation and synchronization, that is, following vehicles in adjacent lanes. Other improvements of the model are trade-offs between lane change incentives and the use of anticipation speed for the speed gain incentive. Although all these effects are captured, the lane change model has only seven parameters. Loop detector data were used to validate and calibrate the model, and an accurate representation of lane distribution and the onset of congestion was shown.

A proposed lane change model can be integrated with a car-following model to form a complete microscopic driver model. The model resembles traffic better at a macroscopic level, especially regarding the amount of traffic volume per lane, the traffic speeds in different lanes, and the onset of congestion. In a new approach, lane change incentives are combined for determining a lane change desire. Included incentives are to follow a route, to gain speed, and to keep right. Classification of lane changes is based on behavior that depends on the level of lane change desire. Integration with a car-following model is achieved by influencing car-following behavior for relaxation and synchronization, that is, following vehicles in adjacent lanes. Other improvements of the model are trade-offs between lane change incentives and the use of anticipation speed for the speed gain incentive. Although all these effects are captured, the lane change model has only seven parameters. Loop detector data were used to validate and calibrate the model, and an accurate representation of lane distribution and the onset of congestion was shown.

The role of neutrophils as key players in the regulation of innate and adaptive immune responses is increasingly being recognized. We report that human neutrophils establish a network with both natural killer (NK) cells and 6-sulfo LacNAc+ dendritic cells (slanDCs), which ultimately serves to up-regulate NK-derived interferonγ (IFNγ). This network involves direct reciprocal interactions and positive amplification loops mediated by cell-derived cytokines. Accordingly, we show that after lipopolysaccharide + interleukin-2 (IL-2) or IL-15/IL-18 stimulation, neutrophils directly interact with and potentiate the activity of both slanDCs and NK cells. On the one hand, neutrophils augment the release of IL-12p70 by slanDCs via a CD18/ intercellular adhesion molecule-1 (ICAM-1) interaction that stimulates activated NK cells to produce IFNγ. IFNγ further potentiates the interaction between neutrophils and slanDCs and the release of slanDC-derived IL-12p70, thus creating a positive feedback loop. On the other hand, neutrophils directly costimulate NK cells via CD18/ICAM-3, leading to the production of IFNγ. Colocalization of neutrophils, NK cells, and slanDCs, as well as of IL-12p70 and IFNγ, in inflamed tissues of Crohn disease and psoriasis provides strong evidence for a novel cellular and cytokine cooperation within the innate immune system in which neutrophils act as amplifiers of NK cell/slanDC-mediated responses.

The role of neutrophils as key players in the regulation of innate and adaptive immune responses is increasingly being recognized. We report that human neutrophils establish a network with both natural killer (NK) cells and 6-sulfo LacNAc+dendritic cells (slanDCs), which ultimately serves to up-regulate NK-derived interferonγ (IFNγ). This network involves direct reciprocal interactions and positive amplification loops mediated by cell-derived cytokines. Accordingly, we show that after lipopolysaccharide + interleukin-2 (IL-2) or IL-15/IL-18 stimulation, neutrophils directly interact with and potentiate the activity of both slanDCs and NK cells. On the one hand, neutrophils augment the release of IL-12p70 by slanDCs via a CD18/ intercellular adhesion molecule-1 (ICAM-1) interaction that stimulates activated NK cells to produce IFNγ. IFNγ further potentiates the interaction between neutrophils and slanDCs and the release of slanDC-derived IL-12p70, thus creating a positive feedback loop. On the other hand, neutrophils directly costimulate NK cells via CD18/ICAM-3, leading to the production of IFNγ. Colocalization of neutrophils, NK cells, and slanDCs, as well as of IL-12p70 and IFNγ, in inflamed tissues of Crohn disease and psoriasis provides strong evidence for a novel cellular and cytokine cooperation within the innate immune system in which neutrophils act as amplifiers of NK cell/slanDC-mediated responses.

Samenvatting: Elektronische netwerken in de zorg winnen aan belang. Zorgaanbieders kunnen via uitwisseling van informatie via een elektronisch netwerk de zorgverlening aan hun patiënten kwalitatief beter, efficiënter en veiliger doen verlopen. Ook zorgaanbieders die niet vanaf de oprichting van een netwerk zijn aangesloten, moeten in een later stadium alsnog onder voorwaarden kunnen aansluiten. In de praktijk blijkt deze toetreding niet altijd soepel te verlopen. Zowel de Nederlandse Mededingingsautoriteit (NMa) als de Nederlandse Zorgautoriteit (NZa) heeft aangegeven hoe zorgaanbieders die deelnemen aan een elektronisch netwerk moeten omgaan met zorgaanbieders die wensen toe te treden: het moet transparant zijn hoe een zorgaanbieder tot het netwerk kan toetreden en de voorwaarden voor toetreding moeten redelijk, objectief en niet discriminerend zijn. De regeling die de NZa hier in december 2009 voor heeft vastgesteld, moet ervoor zorgen dat toetreding in de praktijk vergemakkelijkt wordt. Dit artikel schetst de bredere context van deze voorwaarden aan elektronische netwerken en bespreekt wat toetreders van deelnemers aan een netwerk mogen verwachten.

Generating the transient electrophilic tungsten pentacarbonylphenylphosphinidene complex PhPWCO5in the presence of 2,7dimethylocta2,3,5,6tetraene leads to the formation of a 3,4disubstituted phosphole or a complexed phospholene, depending on the reaction conditions. The formation of the phospholene results from the reaction of PhPWCO5with the diallene, while the formation of the phosphole arises from reaction with 3,4diisopropylidenecyclobutene, which is formed in situfrom the isomerization of the conjugated allene.

Scanning probe microscopy is at the verge of revolutionizing microscopy once again. Video‐rate scanning tunneling microscope (STM) and video‐rate atomic force microscope (AFM) technology will enable the direct observation of many dynamic processes that are impossible to observe today, such as atom or molecule diffusion, real time film growth, or catalytic reactions. In this paper we discuss the critical aspects that have to be taken into account when working on increasing the imaging speed of scanning probe microscopes. We highlight the state‐of‐the‐art developments in the control of the piezoelectric scanning elements and describe the latest innovations regarding the design and construction of the whole mechanical loop including new scanner geometries. We identify critical aspects for which no obvious solution exists and aspects where advanced control engineering can help, like piezo non‐linearities, the acceleration limit and the challenging technical requirements for the preamplifiers that are needed for measuring a tunneling current. Finally, we provide an overview of a number of new directions that are being pursued to solve the problems currently encountered in scanning probe technology. Copyright © 2009 John Wiley and Sons Asia Pte Ltd and Chinese Automatic Control Society

1,2‐Addition of transient W(CO)5‐complexed phosphinidenes exoto hexamethyl Dewar benzene affords the novel 3‐phosphatricyclo[3.2.0.02,4]hept‐6‐ene complexes. The fused tricyclic phosphiranes are obtained as both the Zand the thermally less stable Eisomers, the 31P NMR chemical shifts of which differ by about 60 ppm. A computational investigation shows that the phosphorus pyramidalization and the presence of the γ double bond are responsible for this effect. The semiquantitative results contribute to a more systematic understanding of the structural influences on 31P chemical shieldings. The congested double bond of the Zisomer can be epoxidized with m‐chloroperbenzoic acid (MCPBA) to afford a fused tetracyclic P,O bis‐adduct.

Phosphorus-based macrocycles with acetylenic scaffolds have been built from acetylene-substituted phosphane oxides that were formed from diisopropylphosphoramidic dibromide (3) and an acetylenic Grignard reagent. The four- and six-edged macrocycles 15 and 16, in which the iPr2NP(O) units are connected through 1,3-butadiyne rods, were obtained from the monosilylated derivative of iPr2NP(O)(C2H)2 (7) by multiple acetylene coupling reactions under oxidative Hay conditions. Reaction of iPr2NP(O)(Br)2 (3) with lithiated 1,2-diethynylbenzene gave a mixture of cis and trans monocyclic bis(phosphane oxide) 18. An X-ray crystal structure determination of the trans isomer shows the ring structure to adopt a puckered form.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Samenvatting: Sinds de inwerkingtreding van de Wet marktordening gezondheidszorg (Wmg) op 1 oktober 2006 heeft de Nederlandse Zorgautoriteit (NZa) de bevoegdheid om het gedrag van een zorgaanbieder of zorgverzekeraar die over ‘aanmerkelijke marktmacht’ (amm) beschikt te disciplineren door het opleggen van passende verplichtingen. Recent heeft de NZa een consultatiedocument ‘Aanmerkelijke marktmacht (amm) in de zorg’ uitgebracht waarin zij de wijze beschrijft waarop de NZa voornemens is het amm-instrument toe te passen.2 Dit artikel geeft de visie van de NZa weer zoals die in dit consultatiedocument is beschreven. Tot 17 februari 2007 is het voor eenieder mogelijk op dit consultatiedocument te reageren.

Novel transient phosphinidene complex Ph−PMo(CO)4PMe3, generated from a 7-phosphanorbornadiene precursor, adds to CC and CC bonds to give Mo(CO)4PMe3-complexed phosphiranes and phosphirenes. The cis-PMe3ligand weakens the interaction between the molybdenum complex and the three-membered ring. Under mild CO pressure the Mo(CO)4PMe3transition metal group detaches from the phosphorus center of the ring structure by selective CO substitution. The resulting byproduct Mo(CO)5PMe3can be reused in the synthesis of the phosphinidene precursor.

Intramolecular phosphinidene addition to the CC bond of Mo‐complexed, seven‐membered phosphorus heterocycles affords three novel [(diphos)Mo(CO)4] complexes (18–20). The three bidentate phosphorus baskets differ in the composition of the seven‐membered ring: one of the phosphorus atoms is flanked by CH2, NCH3, or O. The unsaturated tetrahydrophosphepine precursors are synthesized by either ring‐closing metathesis (C and N derivatives) or by a cyclization sequence (O derivative). The crystal structures of the nitrogen‐ (19) and oxygen‐containing (20) baskets have relatively small P‐Mo‐P angles of 76.240(13)° and 77.626(12)°, respectively, and complex 20has slightly shortened MoP bond lengths.

Novel, highly stable, linear and branched mono‐ and diphospha[n]triangulanes were synthesized in high yields by the CuCl‐catalyzed phosphinidene addition to spirocyclopropanated methylenecyclopropanes and bicyclopropylidenes. The effect of spirofusion on the electronic properties of these esthetically attractive phosphacycles is apparent from X‐ray single crystal structure analyses, which reveals a tightening of the phosphirane ring on additional spirocyclopropanation, and from the NMR features that show deshielded chemical shifts for the ring‐phosphorus and ‐carbon atoms. Steric factors play a role in the addition reaction when the substrate alkene carries a second sphere of spirocyclopropane rings and causes the formation of 2‐phosphabicyclo[3.2.0]heptenes in small amounts. These by‐products most probably result from addition of the [PhP(Cl)W(CO)5]‐Cu‐L (L=alkene or solvent) reagent to the spirocyclopropanated bicyclopropylidene to give an intermediate σ‐complex, which subsequently, facilitated by steric factors, undergoes a cyclopropylcarbinyl to cyclobutyl ring expansion followed by a [1,3]‐sigmatropic shift.

No Abstract

A phosphaspiropentene is the plausible kinetic product from the addition of dichlorocarbene to a phosphatriafulvene, which rearranges to a novel P-substituted triafulvene. The calculated barrier of 18.6 kcal mol^-1 for this process is consistent with the temperature of −40 °C at which this reaction proceeds.

No Abstract

Reaction of the transient phosphinidene complexes R‐PW(CO)5with N‐substituted‐diphenylketenimines leads unexpectedly to the novel 2‐aminophosphindoles, as confirmed by an X‐ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene‐azaphosphirane intermediate was found by using the iron‐complexed phosphinidene iPr2N‐PFe(CO)4, which affords the 2‐aminophosphindole together with the novel methylene‐2,3‐dihydro‐1H‐benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene‐azaphosphirane yields both phosphorus heterocycles by way of a [1,5]‐ or [1,3]‐sigmatropic shift, respectively, followed by a H‐shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents.

The synthesis of highly strained bicyclic phosphirane and phosphirene iron–tetracarbonyl complexes, that is, complexes with 2‐aza‐1‐phosphabicyclo[n.1.0]alkanes and ‐alkenes (n=3–5), is explored by using intramolecular cycloaddition of an in situ generated electrophilic phosphinidene complex, [R(iPr)NPFe(CO)4], to its CC‐ and CC‐containing R substituent. Saturated bicyclic complexes 7 a–cwith n=4–2 are remarkably stable, as illustrated by the X‐ray crystal structure for 7 b(n=3), yet all readily undergo retroaddition to react with phenylacetylene. Shuttling of the phosphinidene iron complex between two equivalent CC groups is demonstrated for a 1‐butene‐substituted 2‐aza‐1‐phosphabicyclo[3.1.0]hexane by selective 1H NMR magnetization transfer from the phosphirane protons to the olefinic protons. Even the more strained unsaturated bicycles 17 a,b(n=4,3) are surprisingly stable as illustrated by the X‐ray crystal structure for 17 a(n=4), but the smaller phosphabicyclo[3.1.0]hex‐5‐ene (17 c, n=2) dimerizes to tricyclic 19with a unique ten‐membered heterocyclic ring; an X‐ray crystal structure is reported. Like their saturated analogues also the bicyclic phosphirenes readily undergo retroaddition as shown by the reaction of their phosphinidene iron moiety with phenylacetylene.

Objective: The INTERMAP Study is an international cooperative study on the relationship between macro- and micro-nutrient intakes and blood pressure. The present study—ancillary to INTERMAP—is to evaluate validity of the INTERMAP Tables of Food Composition in Japan (ITJ) formulated by modifying the Standard Tables of Food Composition in Japan (STJ), including factoring in changes in weight and nutrient composition of individual foods due to cooking. Methods: With chemical analytical values of 96 meals prepared in two university hospitals in Japan as the “gold standard”, validity of calculated values based on the ITJ was examined for six major components (energy, protein, lipid, carbohydrate, sodium, potassium) by comparison of mean values, correlation, and linear regression analysis. Results: Although both the ITJ-based and STJ-based calculated values for all six components were significantly higher than the analytical values, differences from the analytical values were generally less marked for the ITJ-based values than for the STJ-based values. The STJ-based values were significantly higher than the ITJ-based values for protein and potassium. Analytical values showed slightly stronger correlations with the ITJ-based calculated values (r=0.876 for total energy, r=0.789 for lipid, r=0.832 for potassium) than with the STJ-based calculated values, except for carbohydrates. Conclusions: The ITJ was considered to have greater validity than the STJ. To obtain more accaurate data in nutritional surveys, food composition tables in which changes in nutrient compositions due to cooking methods are taken into consideration should be used.

Reaction of electrophilic phosphinidene complex [MePW(CO)5] with 1,6‐methano‐[10]annulene results in the sole formation of the isomeric CC insertion products 6 c(main) and 6 d(minor). The single‐crystal X‐ray structure of the complexed 1,7‐methano‐3‐phospha[11]annulene (6 c) shows a syn‐W(CO)5group at the exobent phosphorus. The structure displays CC bond alternation without bonding between the bridgehead carbon atoms. Density functional theory calculations indicate 6 cto result from a concerted disrotatory ring opening of an undetected tricyclic exo–synphosphirane intermediate. The endo–antiphosphirane cannot undergo ring expansion, due to the high barrier that is associated with an intramolecular antara–antararetro Diels–Alder reaction. The stabilizing effect of transition‐metal coordination is discussed.

The properties of the 16‐electron phosphinidene complex [CpRIrPR] were investigated experimentally and theoretically. Density functional theory calculations show a preferred bent geometry for the model complex [CpIrPH], in contrast to the linear structure of [CpIrNH]. Dimerization to give [{CpIrPH}2] and ligand addition to afford [Cp(L)IrPH] (L=PH3, CO) were calculated to give compounds that were energetically highly favorable, but which differed from the related imido complexes. Transient 16‐electron phosphinidene complex [Cp*IrPAr] could not be detected experimentally. Dehydrohalogenation of [Cp*IrCl2(PH2Ar)] in CH2Cl2at low temperatures resulted in the novel fused‐ring systems 17(Ar=Mes*) and 20(Ar=Mes), with dimeric [{Cp*IrPAr}2] being the likely intermediate. Intramolecular CH bond activation induced by steric factors is considered to be the driving force for the irreversible formation of 17and 20. ONIOM calculations suggest this arises because of the large steric congestion in [{Cp*IrPAr}2], which forces it toward a more reactive planar structure that is apt to rearrange.

No Abstract

Reaction of an in situ generated phosphinidene complex [PhPW(CO)5] with the aromatic azulene and guaiazulene leads to unexpected 1,4‐adducts of the seven‐membered ring and to CH bond insertion of the five‐membered ring. A DFT analysis suggests that the reaction is initiated by formation of a η1‐complex between the phosphinidene and the five‐membered ring of the aromatic substrate. Four conformations of this complex were identified. Two convert without barrier to the slightly more stable syn‐and anti‐1,2‐adducts. These undergo pericyclic 1,7‐sigmatropic rearrangements with remarkably low barriers to give 1,4‐adducts, with an inverted configuration at the phosphorus center. An X‐ray crystal structure is presented for one of the 1,4‐adducts of guaiazulene. The other two η1‐complexes insert with modest barriers into a CH bond of the five‐membered ring.

No Abstract

No Abstract

No Abstract

The novel phosphinidene complex [Cp*(NHC)Ir&dbond;PMes*] (3; NHC=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) was prepared in high yield from [Cp*(NHC)IrCl2] (2) and [LiPHMes*]·3 THF. It represents the first example of an NHC ligated transition metal phosphinidene complex. The X-ray crystal structure for 3 is also reported. DFT calculations on the N-heterocyclic carbene containing parent complexes [Cp(NHC)Ir&dbond;E] (E=PH, NH, CH2) show that the NHC ligand acts as good σ-donor/weak π-acceptor ligand and forms strong Ir&bond;C(NHC) single bonds. The Ir&dbond;E double bonds result from strong triplet–triplet interactions between [Cp(NHC)Ir] and E.

The novel phosphinidene complex [Cp*(NHC)IrPMes*] (3; NHC=1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) was prepared in high yield from [Cp*(NHC)IrCl2] (2) and [LiPHMes*]⋅3 THF. It represents the first example of an NHC ligated transition metal phosphinidene complex. The X‐ray crystal structure for 3is also reported. DFT calculations on the N‐heterocyclic carbene containing parent complexes [Cp(NHC)IrE] (E=PH, NH, CH2) show that the NHC ligand acts as good σ‐donor/weak π‐acceptor ligand and forms strong IrC(NHC) single bonds. The IrE double bonds result from strong triplet–triplet interactions between [Cp(NHC)Ir] and E.

Novel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η6‐Ar)(L)MPMes*] (Ar=benzene, p‐cymene; L=PR3, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η6‐Ar)MX2(PH2Mes*)] complexes in the presence of a stabilizing ligand. Xray crystal structures are reported for [(η6‐C6H6)(PPh3)RuPMes*] (9) and [(η6‐pCy)(PPh3)OsPMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new Pspiroannulated Ru2P2‐ring structure 16. Dehydrohalogenation in the presence of but‐2‐yne gave a novel phosphaallyl complex [(η6‐Ar)Ru(η3‐R2PC(Me)CHMe)] 26, for which an Xray crystal structure is reported. The mechanism by which 16and 26are obtained is presumed to involve the intermediate formation of the 16‐electron (η6‐benzene)RuPMes* phosphinidene complex.

Novel, very stable ruthenium and osmium containing terminal phosphinidene complexes [(η⁶-Ar)(L)M&dbond;PMes*] (Ar=benzene, p-cymene; L=PR3, CO, and RNC) have been prepared by dehydrohalogenation of novel [(η⁶-Ar)MX2(PH2Mes*)] complexes in the presence of a stabilizing ligand. Xray crystal structures are reported for [(η⁶-C6H6)(PPh3)Ru&dbond;PMes*] (9) and [(η⁶-pCy)(PPh3)Os&dbond;PMes*] (4). Dehydrohalogenation in the absence of a stabilizing ligand resulted in the new Pspiroannulated Ru2P2-ring structure 16. Dehydrohalogenation in the presence of but-2-yne gave a novel phosphaallyl complex [(η⁶-Ar)Ru(η³-R2PC(Me)CHMe)] 26, for which an Xray crystal structure is reported. The mechanism by which 16 and 26 are obtained is presumed to involve the intermediate formation of the 16-electron (η⁶-benzene)Ru&dbond;PMes* phosphinidene complex.

Novel terminal rhodium- and cobalt-complexed phosphinidenes, Cp*(PR3)Rh&dbd;PAr (3−5) and Cp(PPh3)Co&dbd;PAr (8), were obtained by dehydrohalogenation of the primary phosphine complexes Cp*RhCl2(PH2Ar) (2) and CpCoI2(PH2Ar) (7) in the presence of a phosphine. X-ray crystal structures are reported for Cp*(PPh3)Rh&dbd;PMes* (3) and Cp(PPh3)Co&dbd;PMes* (8). A comparative reactivity study and a computational survey were performed on the Co-, Rh-, and Ir-containing phosphinidene complexes. All react with organic dihalides to form phosphaalkenes, with the rhodium congener being far more reactive than the iridium and cobalt complexes. Density functional theory calculations give geometrical parameters and ³¹P NMR chemical shifts in good agreement with experimental data. The rhodium congeners exhibit the most pronounced charge separation of the Rh&dbd;P bond, which may explain its higher reactivity. The M−L bond is strong in all Cp(L)M&dbd;PH (M = Co, Rh, Ir) complexes and inhibits reactivity at the metal center. Comparisons with the Zr-containing complex Cp2(PH3)Zr−PH are made.

Superfluid phase transitions are discussed from a geometrical perspective as envisaged by Onsager. The approach focuses on vortex loops which close to the critical temperature form a fuctuating vortex tangle. As the transition is approached, vortex lines proliferate and thereby disorder the superfluid state, so that the system reverts to the normal state. It is shown in detail that loop proliferation can be described in exactly the same way as cluster percolation. Picturing vortex loops as worldlines of bosons, with one of the spatial coordinates interpreted as the time coordinate, a quantitative description of vortex loops can be given. Applying a rotation (to superfluids) or a magnetic field (to superconductors), which suppresses the formation of vortex loops and instead can lead to open vortex lines along the field direction, is shown to be equivalent to taking the nonrelativistic limit. The nonrelativistic theory is the one often used to study vortex lattice melting and to describe the resulting entangled vortex liquid.

Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)Ir&dbd;PR, are readily synthesized by (a) the reaction of Cp*(L)IrCl2 (2, L = PPh3) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH2R)IrCl2 (5, R = Mes*, Is, Mes) with in situ capturing of transient Cp*Ir&tbd1;PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Ir&tbd1;PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh3)Ir&dbd;PMes* (3) and Cp*(CO)Ir&dbd;PMes* (15). The more congested 3 has an E configuration for its Ir&dbd;P bond, whereas 15 is obtained in its Z form. The ³¹P NMR chemical shifts and ²JPP coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.