Halogen bonds, chalcogen bonds, pnictogen bonds, tetrel bonds and other σ-hole interactions: a snapshot of current progress

We report here on the status of research on halo­gen bonds and other σ-hole inter­actions involving p-block elements in Lewis acidic roles, such as chalcogen bonds, pnictogen bonds and tetrel bonds. A brief overview of the available literature in this area is provided via a survey of the many review articles that address this field. Our focus has been to collect together most review articles published since 2013 to provide an easy entry into the extensive literature in this area. A snapshot of current research in the area is provided by an introduction to the virtual special issue com­piled in this journal, com­prising 11 articles and entitled `Halogen, chalcogen, pnictogen and tetrel bonds: structural chemistry and beyond.

Patient-maintained sedation for oral surgery using a target-controlled infusion of propofol - a pilot study

OBJECTIVE: To assess the safety and efficacy of a new patient-maintained propofol system for conscious sedation in dentistry. DESIGN: Prospective clinical trial SETTING: Department of Sedation, Glasgow Dental Hospital and School, 2001 SUBJECTS AND METHODS: Patients scheduled for oral surgery with conscious sedation. Exclusions included ASA IV -V, inability to use the handset, opioid use and severe respiratory disease. INTERVENTIONS: Patients were given intravenous propofol to a level of 1.0 microg/ml (reducing from 1.5 microg/ml) using a target controlled infusion system, they then controlled their sedation level by double-clicking a handset which on each activation increased the propofol concentration by 0.2 microg/ml. MAIN OUTCOME MEASURES: Oxygen saturation, patient satisfaction, and surgeon satisfaction. RESULTS: Twenty patients were recruited, 16 female and four male. Nineteen patients completed sedation and treatment successfully. Mean lowest oxygen saturation was 94%. No patients were over-sedated. All patients successfully used the system to maintain a level of sedation adequate for their comfort. Patient and surgeon satisfaction were consistently high. CONCLUSIONS: Initial experience with this novel system has confirmed safety, patient satisfaction and surgeon satisfaction

Increasing alkyl chain length in a series of layered metal–organic frameworks aids ultrasonic exfoliation to form nanosheets

Metal–organic framework nanosheets (MONs) are attracting increasing attention as a diverse class of two-dimensional materials derived from metal–organic frameworks (MOFs). The principles behind the design of layered MOFs that can readily be exfoliated to form nanosheets, however, remain poorly understood. Here we systematically investigate an isoreticular series of layered MOFs functionalized with alkoxy substituents in order to understand the effect of substituent alkyl chain length on the structure and properties of the resulting nanosheets. A series of 2,5-alkoxybenzene-1,4-dicarboxylate ligands (O2CC6H2(OR)2CO2, R = methyl–pentyl, 1–5, respectively) was used to synthesize copper paddle-wheel MOFs. Rietveld and Pawley fitting of powder diffraction patterns for compounds Cu(3–5)(DMF) showed they adopt an isoreticular series with two-dimensional connectivity in which the interlayer distance increases from 8.68 Å (R = propyl) to 10.03 Å (R = pentyl). Adsorption of CO2 by the MOFs was found to increase from 27.2 to 40.2 cm3 g–1 with increasing chain length, which we attribute to the increasing accessible volume associated with increasing unit-cell volume. Ultrasound was used to exfoliate the layered MOFs to form MONs, with shorter alkyl chains resulting in higher concentrations of exfoliated material in suspension. The average height of MONs was investigated by AFM and found to decrease from 35 ± 26 to 20 ± 12 nm with increasing chain length, with the thinnest MONs observed being only 5 nm, corresponding to five framework layers. These results indicate that careful choice of ligand functionalities can be used to tune nanosheet structure and properties, enabling optimization for a variety of applications

Dorstone Hill: A Neolithic timescape

Studies of early fourth-millennium BC Britain have typically focused on the Early Neolithic sites of Wessex and Orkney; what can the investigation of sites located in areas beyond these core regions add? The authors report on excavations (2011-2019) at Dorstone Hill in Herefordshire, which have revealed a remarkable complex of Early Neolithic monuments: three long barrows constructed on the footprints of three timber buildings that had been deliberately burned, plus a nearby causewayed enclosure. A Bayesian chronological model demonstrates the precocious character of many of the site's elements and strengthens the evidence for the role of tombs and houses/halls in the creation and commemoration of foundational social groups in Neolithic Britain

Building operational research capacity in the Pacific

Operational research (OR) in public health aims to investigate strategies, interventions, tools or knowledge that can enhance the quality, coverage, effectiveness or performance of health systems. Attention has recently been drawn to the lack of OR capacity in public health programmes throughout the Pacific Islands, despite considerable investment in implementation. This lack of ongoing and critical reflection may prevent health programme staff from understanding why programme objectives are not being fully achieved, and hinder long-term gains in public health. The International Union Against Tuberculosis and Lung Disease (The Union) has been collaborating with Pacific agencies to conduct OR courses based on the training model developed by The Union and Médecins Sans Frontières Brussels-Luxembourg in 2009. The first of these commenced in 2011 in collaboration with the Fiji National University, the Fiji Ministry of Health, the World Health Organization and other partners. The Union and the Secretariat of the Pacific Community organised a second course for participants from other Pacific Island countries and territories in 2012, and an additional course for Fijian participants commenced in 2013. Twelve participants enrolled in each of the three courses. Of the two courses completed by end 2013, 18 of 24 participants completed their OR and submitted papers by the course deadline, and 17 papers have been published to date. This article describes the context, process and outputs of the Pacific courses, as well as innovations, adaptations and challenges

Contrasting reactivity of B–Cl and B–H bonds at [Ni(IMes)2] to form unsupported Ni-boryls

[Ni(IMes)2] reacts with chloroboranes via oxidative addition to form rare unsupported Ni-boryls. In contrast, the oxidative addition of hydridoboranes is not observed and products from competing reaction pathways are identified. Computational studies relate these differences to the mechanism of oxidative addition: B–Cl activation proceeds via nucleophilic displacement of Cl−, while B–H activation would entail high energy concerted bond cleavage

Building operational research capacity in the Pacific

Operational research (OR) in public health aims to investigate strategies, interventions, tools or knowledge that can enhance the quality, coverage, effectiveness or performance of health systems. Attention has recently been drawn to the lack of OR capacity in public health programmes throughout the Pacific Islands, despite considerable investment in implementation. This lack of ongoing and critical reflection may prevent health programme staff from understanding why programme objectives are not being fully achieved, and hinder long-term gains in public health. The International Union Against Tuberculosis and Lung Disease (The Union) has been collaborating with Pacific agencies to conduct OR courses based on the training model developed by The Union and Médecins Sans Frontières Brussels-Luxembourg in 2009. The first of these commenced in 2011 in collaboration with the Fiji National University, the Fiji Ministry of Health, the World Health Organization and other partners. The Union and the Secretariat of the Pacific Community organised a second course for participants from other Pacific Island countries and territories in 2012, and an additional course for Fijian participants commenced in 2013. Twelve participants enrolled in each of the three courses. Of the two courses completed by end 2013, 18 of 24 participants completed their OR and submitted papers by the course deadline, and 17 papers have been published to date. This article describes the context, process and outputs of the Pacific courses, as well as innovations, adaptations and challenges

Antibiotic Review Kit for Hospitals (ARK-Hospital): study protocol for a stepped-wedge cluster-randomised controlled trial.

BACKGROUND: To ensure patients continue to get early access to antibiotics at admission, while also safely reducing antibiotic use in hospitals, one needs to target the continued need for antibiotics as more diagnostic information becomes available. UK Department of Health guidance promotes an initiative called 'Start Smart then Focus': early effective antibiotics followed by active 'review and revision' 24-72 h later. However in 2017, < 10% of antibiotic prescriptions were discontinued at review, despite studies suggesting that 20-30% of prescriptions could be stopped safely. METHODS/DESIGN: Antibiotic Review Kit for Hospitals (ARK-Hospital) is a complex 'review and revise' behavioural intervention targeting healthcare professionals involved in antibiotic prescribing or administration in inpatients admitted to acute/general medicine (the largest consumers of non-prophylactic antibiotics in hospitals). The primary study objective is to evaluate whether ARK-Hospital can safely reduce the total antibiotic burden in acute/general medical inpatients by at least 15%. The primary hypotheses are therefore that the introduction of the behavioural intervention will be non-inferior in terms of 30-day mortality post-admission (relative margin 5%) for an acute/general medical inpatient, and superior in terms of defined daily doses of antibiotics per acute/general medical admission (co-primary outcomes). The unit of observation is a hospital organisation, a single hospital or group of hospitals organised with one executive board and governance framework (National Health Service trusts in England; health boards in Northern Ireland, Wales and Scotland). The study comprises a feasibility study in one organisation (phase I), an internal pilot trial in three organisations (phase II) and a cluster (organisation)-randomised stepped-wedge trial (phase III) targeting a minimum of 36 organisations in total. Randomisation will occur over 18 months from November 2017 with a further 12 months follow-up to assess sustainability. The behavioural intervention will be delivered to healthcare professionals involved in antibiotic prescribing or administration in adult inpatients admitted to acute/general medicine. Outcomes will be assessed in adult inpatients admitted to acute/general medicine, collected through routine electronic health records in all patients. DISCUSSION: ARK-Hospital aims to provide a feasible, sustainable and generalisable mechanism for increasing antibiotic stopping in patients who no longer need to receive them at 'review and revise'. TRIAL REGISTRATION: ISRCTN Current Controlled Trials, ISRCTN12674243 . Registered on 10 April 2017

Population and labour force projections for 27 European countries, 2002-052: impact of international migration on population ageing: Projections de population et de population active pour 27 pays européens 2002-052: impact de la migration internationale sur le vieillissement de la population

Population and labour force projections are made for 27 selected European countries for 2002-052, focussing on the impact of international migration on population and labour force dynamics. Starting from single scenarios for fertility, mortality and economic activity, three sets of assumptions are explored regarding migration flows, taking into account probable policy developments in Europe following the enlargement of the EU. In addition to age structures, various support ratio indicators are analysed. The results indicate that plausible immigration cannot offset the negative effects of population and labour force ageing

Anomalous accelerations in spacecraft flybys of the Earth

[EN] The flyby anomaly is a persistent riddle in astrodynamics. Orbital analysis in several flybys of the Earth since the Galileo spacecraft flyby of the Earth in 1990 have shown that the asymptotic post-encounter velocity exhibits a difference with the initial velocity that cannot be attributed to conventional effects. To elucidate its origin, we have developed an orbital program for analyzing the trajectory of the spacecraft in the vicinity of the perigee, including both the Sun and the Moon¿s tidal perturbations and the geopotential zonal, tesseral and sectorial harmonics provided by the EGM96 model. The magnitude and direction of the anomalous acceleration acting upon the spacecraft can be estimated from the orbital determination program by comparing with the trajectories fitted to telemetry data as provided by the mission teams. This acceleration amounts to a fraction of a mm/s2 and decays very fast with altitude. The possibility of some new physics of gravity in the altitude range for spacecraft flybys is discussed.Acedo Rodríguez, L. (2017). Anomalous accelerations in spacecraft flybys of the Earth. Astrophysics and Space Science. 362(12):1-15. doi:10.1007/s10509-017-3205-xS11536212Acedo, L.: Galaxies 3, 113 (2015)Acedo, L.: Mon. Not. R. Astron. Soc. 463(2), 2119 (2016)Acedo, L.: Adv. Space Res. 59(7), 1715 (2017). 1701.06939Acedo, L., Bel, L.: Astron. Nachr. 338(1), 117 (2017). 1602.03669Adler, S.L.: Int. J. Mod. Phys. A 25, 4577 (2010). 0908.2414 . doi: 10.1142/S0217751X10050706Adler, S.L.: In: Proceedings of the Conference in Honour of Murray Gellimann’s 80th Birthday, p. 352 (2011). doi: 10.1142/9789814335614_0032Anderson, J.D., Nieto, M.M.: In: Klioner, S.A., Seidelmann, P.K., Soffel, M.H. (eds.) Relativity in Fundamental Astronomy: Dynamics, Reference Frames, and Data Analysis. IAU Symposium, vol. 261, p. 189 (2010). doi: 10.1017/S1743921309990378Anderson, J.D., Laing, P.A., Lau, E.L., Liu, A.S., Nieto, M.M., Turyshev, S.G.: Phys. Rev. Lett. 81(14), 2858 (1998). gr-qc/0104064 . doi: 10.1103/PhysRevLett.81.2858Anderson, J.D., Laing, P.A., Lau, E.L., Liu, A.S., Nieto, M.M., Turyshev, S.G.: Phys. Rev. D 65(8), 082004 (2002). gr-qc/0104064 . doi: 10.1103/PhysRevD.65.082004Anderson, J.D., Campbell, J.K., Ekelund, J.E., Ellis, J., Jordan, J.F.: Phys. Rev. Lett. 100(9), 091102 (2008). doi: 10.1103/PhysRevLett.100.091102Atchison, J.A., Peck, M.A.: J. Guid. Control Dyn. 33, 1115 (2010). doi: 10.2514/1.47413Bertolami, O., Francisco, F., Gil, P.J.S.: Class. Quantum Gravity 33(12), 125021 (2016). 1507.08457 . doi: 10.1088/0264-9381/33/12/125021Bolton, S.J., Adriani, A., Adumitroaie, V., Allison, M., Anderson, J., Atreya, S., Bloxham, J., Brown, S., Connerney, J.E.P., DeJong, E., Folkner, W., Gautier, D., Grassi, D., Gulkis, S., Guillot, T., Hansen, C., Hubbard, W.B., Iess, L., Ingersoll, A., Janssen, M., Jorgensen, J., Kaspi, Y., Levin, S.M., Li, C., Lunine, J., Miguel, Y., Mura, A., Orton, G., Owen, T., Ravine, M., Smith, E., Steffes, P., Stone, E., Stevenson, D., Thorne, R., Waite, J., Durante, D., Ebert, R.W., Greathouse, T.K., Hue, V., Parisi, M., Szalay, J.R., Wilson, R.: Science 356, 821 (2017). doi: 10.1126/science.aal2108Cahill, R.T.: ArXiv e-prints (2008). 0804.0039Chamberlin, A., Yeomans, D., Giorgini, J., Chodas, P.: Horizons Ephemeris System (2016). http://ssd.jpl.nasa.gov/horizons.cgi . Accessed: 2016-10-27Chao, B.F.: C. R. Géosci. 338, 1123 (2006). doi: 10.1016/j.crte.2006.09.014Coddington, E., Levinson, N.: McGraw-Hill, New York (1955)Debono, I., Smoot, G.F.: Universe 2(4), 23 (2016). doi: 10.3390/universe2040023Desai, S.D.: J. Geophys. Res., Oceans 107(C11), 7 (2002). 3186. doi: 10.1029/2001JC001224Dickey, J.O., Bender, P.L., Faller, J.E., Newhall, X.X., Ricklefs, R.L., Ries, J.G., Shelus, P.J., Veillet, C., Whipple, A.L., Wiant, J.R., Williams, J.G., Yoder, C.F.: Science 265, 482 (1994). doi: 10.1126/science.265.5171.482Dyson, F.W., Eddington, A.S., Davidson, C.: Philos. Trans. R. Soc. Lond., Ser. A 220, 291 (1920). doi: 10.1098/rsta.1920.0009Everitt, C.W.F., et al.: Phys. Rev. Lett. 221101(106) (2011)Feng, J.L., Fornal, B., Galon, I., Gardner, S., Smolinsky, J., Tait, T.M.P., Tanedo, P.: Phys. Rev. Lett. 117, 071803 (2016). 1604.07411 . doi: 10.1103/PhysRevLett.117.071803Folkner, W.M., Williams, J.G., Boggs, D.H., Park, R.S., Kuchynka, P.: IPN Prog. Rep. 42(196) (2014)Fornberg, B.: Math. Comput. 51(184), 699 (1988). doi: 10.1090/S0025-5718-1988-0935077-0Franklin, A., Fischback, E.: The Rise and Fall of the Fifth Force. Discovery, Pursuit, and Justification in Modern Physics, second edition. Springer, New York (2016)Giorgini, J.D.: Personal communication (2015)Hackmann, E., Laemmerzahl, C.: In: 38th COSPAR Scientific Assembly. COSPAR Meeting, vol. 38, p. 3 (2010)Hafele, J.C.: ArXiv e-prints (2009). 0904.0383ICGEM: International Center for Global Gravity Field Models. http://icgem.gfz-potsdam.de/tom_longtimeIERS: In: Petit, G., Luzum, B. (eds.) IERS Conventions (2010), p. 1. Verlag des Bundesamts für Kartographie und Geodäsie, Frankfurt am Main (2010)Iess, L., Asmar, S.: Int. J. Mod. Phys. D 16, 2117 (2007). doi: 10.1142/S0218271807011449Iess, L., Asmar, S., Tortora, P.: Acta Astronaut. 65, 666 (2009). doi: 10.1016/j.actaastro.2009.01.049Iess, L., Di Benedetto, M., James, M., Mercolino, M., Simone, L., Tortora, P.: Acta Astronaut. 94, 699 (2014). doi: 10.1016/j.actaastro.2013.06.011Iorio, L.: Sch. Res. Exch. (2009). 0811.3924 . doi: 10.3814/2009/807695Iorio, L.: Astron. J. 142, 68 (2011a). 1102.4572 . doi: 10.1088/0004-6256/142/3/68Iorio, L.: Mon. Not. R. Astron. Soc. 415, 1266 (2011b). 1102.0212Iorio, L.: Europhys. Lett. (2011c). 1105.4145 . doi: 10.1209/0295-5075/96/30001Iorio, L.: Adv. Space Res. 54(11), 2441 (2014a). 1311.4218 . doi: 10.1016/j.asr.2014.06.035Iorio, L.: Galaxies 2, 259 (2014b). 1404.6537 . doi: 10.3390/galaxies2020259Iorio, L.: Universe 1(1), 38 (2015a). doi: 10.3390/universe1010038Iorio, L.: Int. J. Mod. Phys. D 24, 1530015 (2015b). 1412.7673Iorio, L., Giudice, G.: New Astron. 11, 600 (2006). gr-qc/0601055Iorio, L., Lichtenegger, H.I.M., Ruggiero, M.L., Corda, C.: Astrophys. Space Sci. 331, 351 (2011). 1009.3225 . doi: 10.1007/s10509-010-0489-5Jouannic, B., Noomen, R., van den IJSel, J.A.A.: In: Proceedings of the 25th International Symposium on Space Flight Dynamics ISSFD, Munich, Germany (2015)Kennefick, D.: Phys. Today 62, 37 (2009). doi: 10.1063/1.3099578King-Hele, D.: Satellite Orbits in an Atmosphere. Theory and Applications. Blackie and Son Ltd., Glasgow (1987)Lämmerzahl, C., Preuss, O., Dittus, H.: In: Dittus, H., Lammerzahl, C., Turyshev, S.G. (eds.) Lasers, Clocks and Drag-Free Control: Exploration of Relativistic Gravity in Space. Astrophysics and Space Science Library, vol. 349, p. 75 (2008). doi: 10.1007/978-3-540-34377-6_3Le Verrier, U.: C. R. Hebd. Acad. Sci. 49, 379 (1859)Lemoine, F.G.E.A.: NASA/TP-1998-206861 (1998)Lewis, R.A.: In: Robertson, G.A. (ed.) American Institute of Physics Conference Series. American Institute of Physics Conference Series, vol. 1103, p. 226 (2009). doi: 10.1063/1.3115499Longair, M.: Philos. Trans. R. Soc., Math. Phys. Eng. Sci. (2015). doi: 10.1098/rsta.2014.0287McCulloch, M.E.: Mon. Not. R. Astron. Soc. 389, 57 (2008). 0806.4159 . doi: 10.1111/j.1745-3933.2008.00523.xMoe, M.M., Wallace, S.D., Moe, K.: In: Washington DC American Geophysical Union Geophysical Monograph Series, vol. 87, p. 349 (1995). doi: 10.1029/GM087p0349Murphy, E.M.: Phys. Rev. Lett. 83, 1890 (1998). doi: 10.1103/PhysRevLett.83.1890Naval Observatory: Dept. of the Navy, USA (2009)Newcomb, S.: Tables of the Four Inner Planets. Government Printing Office, Washington (1895)Nyambuya, G.G.: ArXiv e-prints (2008). 0803.1370Nyambuya, G.G.: New Astron. 57, 22 (2017). doi: 10.1016/j.newast.2017.06.001Páramos, J., Hechenblaikner, G.: Adv. Space Res. 79–80(7), 76 (2013). 1210.7333v1Peskin, M.E., Schroeder, D.V.: An Introduction to Quantum Field Theory. Westview Press, Perseus Books Group, London (1995)Pinheiro, M.J.: Phys. Lett. A 378, 3007 (2014). 1404.1101Pinheiro, M.J.: Mon. Not. R. Astron. Soc. 461(4), 3948 (2016)Renzetti, G.: Cent. Eur. J. Phys. 11, 531 (2013). doi: 10.2478/s11534-013-0189-1Rievers, B., Lämmerzahl, C.: Ann. Phys. 523, 439 (2011). 1104.3985 . doi: 10.1002/andp.201100081Roseveare, N.T.: Mercury’s Perihelion, from Le Verrier to Einstein. Clarendon Press, Wotton-under-Edge (1982)Rubincam, D.P.: Icarus 148, 2 (2000). doi: 10.1006/icar.2000.6485Standish, E.M.: In: Macias, A., Lämmerzahl, C., Camacho, A. (eds.) Recent Developments in Gravitation and Cosmology. American Institute of Physics Conference Series, vol. 977, p. 254 (2008). doi: 10.1063/1.2902789Standish, E.M.: In: Klioner, S.A., Seidelmann, P.K., Soffel, M.H. (eds.) Relativity in Fundamental Astronomy: Dynamics, Reference Frames, and Data Analysis. IAU Symposium, vol. 261, p. 179 (2010). doi: 10.1017/S1743921309990354Thompson, P.F., Abrahamson, M., Ardalan, S., Bordi, J.: In: 24th AAS/AIAA Space Flight Mechanics Meeting, Santa Fe, New Mexico, January 26–30, 2014 (2014). http://hdl.handle.net/2014/45519Turyshev, S.G., Toth, V.T.: Living Rev. Relativ. (2010). 1001.3686 . doi: 10.12942/lrr-2010-4Turyshev, S.G., Toth, V.T., Kinsella, G., Lee, S.-C., Lok, S.M., Ellis, J.: Phys. Rev. Lett. 108(24), 241101 (2012). 1204.2507 . doi: 10.1103/PhysRevLett.108.241101Varieschi, G.U.: Gen. Relativ. Gravit. 46, 1741 (2014). 1401.6503 . doi: 10.1007/s10714-014-1741-zWilhelm, K., Dwivedi, B.N.: Astrophys. Space Sci. 358, 18 (2015). doi: 10.1007/s10509-015-2413-5Will, C.M.: Living Rev. Relativ. 3(9) (2006)Will, C.M.: Class. Quantum Gravity (2015). doi: 10.1098/rsta.2014.0287Will, C.M.: In: Peron, R., Colpi, M., Gorini, V., Moschella, U. (eds.) Gravity: Where Do We Stand? Astrophysics and Space Science Library, vol. 349, p. 9 (2016). doi: 10.1007/978-3-319-20224-2_2Williams, J.G., Boggs, D.H.: Celest. Mech. Dyn. Astron. 126, 89 (2016). doi: 10.1007/s10569-016-9702-3Williams, J.G., Dickey, J.O.: In: Noomen, R., Klosko, S., Noll, C., Pearlman, M. (eds.) Proceedings of 13th International Workshop on Laser Ranging, p. 75 (2003). http://cddisa.gsfc.nasa.gov/lw13/lw_proceedings.htmlWilliams, J.G., Newhall, X.X., Dickey, J.O.: Phys. Rev. D 53, 6730 (1996). doi: 10.1103/PhysRevD.53.6730Williams, J.G., Turyshev, S.G., Boggs, D.H.: Phys. Rev. Lett. 93(26), 261101 (2004). gr-qc/0411113 . doi: 10.1103/PhysRevLett.93.261101Williams, J.G., Turyshev, S.G., Boggs, D.H.: Planet. Sci. 3, 2 (2014). doi: 10.1186/s13535-014-0002-5Williams, J.G., Boggs, D.H., Yoder, C.F., Ratcliff, J.T., Dickey, J.O.: J. Geophys. Res. 106, 27933 (2001). doi: 10.1029/2000JE001396Wolfram, S.: The Mathematica Book, fifth edition. Wolfram Media, Champaign (2003