Anticancer activity of organotin compounds. 2. Interaction of diorganotin dihalides with nucleic acid bases and nucleosides; the synthesis of adenine, adenosine and 9-methyladenine adducts

The syntheses of the complexes formulated as SnMe2Cl2(Ad)2 (I), SnMe2Cl2(Ado)2 (II), SnMe2Cl2- (9-MeAd)2 (III) [Ad = adenine, Ado = adenosine, 9-MeAd = 9-methyladenine] as well as the more unexpected SnPhCl2(OH)(Ad)2·3H2O (IV) and SnPhCl3(Ado)2 (V) by reaction of SnMe2Cl2 or SnPh2Cl2 with the appropriate bases in methanol is described. 1H NMR studies suggest that coordination is through the N-7 position of the adenine base.

Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

The vertical cloud structure of the West African monsoon: a 4 year climatology using CloudSat and CALIPSO

The West African summer monsoon (WAM) is an important driver of the global climate and locally provides most of the annual rainfall. A solid climatological knowledge of the complex vertical cloud structure is invaluable to forecasters and modelers to improve the understanding of the WAM. In this paper, 4 years of data from the CloudSat profiling radar and CALIPSO are used to create a composite zonal mean vertical cloud and precipitation structure for the WAM. For the first time, the near-coincident vertical radar and lidar profiles allow for the identification of individual cloud types from optically thin cirrus and shallow cumulus to congestus and deep convection. A clear diurnal signal in zonal mean cloud structure is observed for the WAM, with deep convective activity enhanced at night producing extensive anvil and cirrus, while daytime observations show more shallow cloud and congestus. A layer of altocumulus is frequently observed over the Sahara at night and day, extending southward to the coastline, and the majority of this cloud is shown to contain supercooled liquid in the top. The occurrence of deep convective systems and congestus in relation to the position of the African easterly jet is studied, but only the daytime cumulonimbus distribution indicates some influence of the jet position.

Design of a biomimetic skin for an octopus-inspired robot– Part I: characterising octopus skin

Octopus skin samples were tested under quasi-static and scissor cutting conditions to measure the in-plane material properties and fracture toughness. Samples from all eight arms of one octopus were tested statically to investigate how properties vary from arm to arm. Another nine octopus skins were measured to study the influence of body mass on skin properties. Influence of specimen location on skin mechanical properties was also studied. Material properties of skin, i.e. the Young's modulus, ultimate stress, failure strain and fracture toughness have been plotted against the position of skin along the length of arm or body. Statistical studies were carried out to help analyzing experimental data obtained. Results of this work will be used as guidelines for the design and development of artificial skins for an octopus-inspired robot.

X-ray diffraction study of the influence of temperature on the structural correlations of poly(2-hydroxypropyl ether of bisphenol A)

The X-ray diffraction pattern of glassy poly(2-hydroxypropyl ether of bisphenol A) is studied at room temperature on oriented samples in order to associate its different peaks to different structural correlations. On the other hand, X-ray diffraction patterns have been obtained at different temperatures from Tg − 50 K up to Tg + 50 K for the above-mentioned polymer. Attention has been paid to the evolution with temperature of the position of the wide diffraction maximum corresponding to interchain correlations in the polymer. The temperature evolution of this parameter shows a marked discontinuity just at the glass transition temperature.

The location of executive suites and business centers in the United States: an exploratory analysis

Increasingly, corporate occupiers seek more flexible ways of meeting their accommodation needs. One consequence of this process has been the growth of the executive suite, serviced office or business centre market. This paper, the final report of a research project funded by the Real Estate Research Institute, focuses upon the geographical distribution of business centers offering executive suites within the US. After a brief review of the development of the market, the paper examines the availability of data, provides basic descriptive statistics of the distribution of executive suites by state and by metropolitan statistical area and then attempts to model the distribution using demographic and socio-economic data at MSA level. The distribution reflects employment in key growth sectors and the position of the MSA in the urban hierarchy. An appendix presents a preliminary view of the global distribution of suites.

Access to the countryside of England and Wales: public/private partnership or the privatisation of public rights?

This paper examines the evolution of public rights of access to private land in England and Wales. Since the Eighteenth Century the administration and protection of these rights has been though a form of public/private partnership in which the judiciary, while maintaining the dominance of private property, have safeguarded de facto public access by refusing consistently to punish simple trespass. While this situation has been modified, principally by post-World War II legislation, to allow for some formalisation of access arrangements and consequent compensation to landowners in areas of high recreational pressure and low legal accessibility, recent policy initiatives suggest that the balance of the partnership has now shifted in favour of landowners. In particular, the new access payment schemes, developed by the UK Government in response to the European Commission's Agri-Environment Regulations, locate the landowner as the beneficiary of the partnership, financed by tax revenue and justified on the spurious basis of improved 'access provision'. As such the state, as the former upholder of citizen rights, now assumes the duplicitous position of underwriting private property ownership through the commodification of access, while proclaiming a significant improvement in citizens' access rights.

Partnership in the provision of recreational access: the reconstruction of the public interest in private land in England and Wales

This paper examines the evolution of public rights of access to private land in England and Wales. Since the Eighteenth Century the administration and protection of these rights has been though a form of public/private partnership in which the judiciary, while maintaining the dominance of private property, have safeguarded de facto public access by refusing consistently to punish simple trespass. While this situation has been modified, principally by post-World War II legislation, to allow for some formalisation of access arrangements and consequent compensation to landowners in areas of high recreational pressure and low legal accessibility, recent policy initiatives suggest that the balance of the partnership has now shifted in favour of landowners. In particular, the new access payment schemes, developed by the UK Government in response to the European Commission's Agri-Environment Regulations, identify the landowner as the beneficiary of the partnership, financed by tax revenue and justified on the spurious basis of improved 'access provision'. As such the State, as the former upholder of citizen rights, now assumes the duplicitous position of underwriting private property ownership through the commodification of access, while proclaiming a significant improvement in citizens' access rights.

Fighting Al-Qaeda in Yemen? Rethinking the nature of the Islamist threat and the effectiveness of US counterterrorism strategy

This paper evaluates the US’ perception of and response to al-Qaeda in the Arabian Peninsula (AQAP) operating in Yemen. It evaluates the empirical evidence on which the present understanding of the group is based, the implications of the socio-political context in which it operates, and the uneasy position of the Yemeni government in the war against terror as it has been affected by US policy from the early 1990s to the present. In the contested Yemeni state, AQAP is competing for political legitimacy and is increasingly dependent on public support. The US’ kill-or-capture response, the “on-off” nature of its support that has made Yemen vulnerable to the influence of al-Qaeda in the past, and the actions of the Yemeni government itself, which depends on the continued existence of the threat to secure financial support vital for political survival, means that none of the measures being taken has the potential to defeat AQAP.

Elevated levels of corticotrophin-releasing factor binding protein in the blood of patients suffering from arthritis and septicaemia and the presence of novel ligands in synovial fluid.

In view of the reported inflammatory effects of corticotrophin-releasing factor (CRF) and the associated regulatory elements in the gene of its binding protein (BP), we postulate that both BP as well as novel BP-ligands other than CRF may be involved in inflammatory disease. We have investigated BP in the blood of patients with arthritis and septicaemia and have attempted to identify CRF and other BP-ligands in synovial fluid. The BP was found to be significantly elevated in the blood of patients with rheumatoid arthritis and septicaemia. There was less BP-ligand and CRF in synovial fluid from patients with rheumatoid arthritis that from those with osteo- or psoriatic arthritis. There was at least 10-fold more BP-ligand than CRF in the fluid of all three groups of patients. A small amount of immunoreactive human (h)CRF, eluting in the expected position of CRF-41, was detected after high-pressure liquid chromatography of arthritic synovial fluid; however, the bulk of material with BP-ligand binding activity eluted earlier, suggesting that synovial fluid contained novel peptides that interacted with the BP. These results would suggest that the BP and its ligands could play an endocrine immunomodulatory role in inflammatory disease.

Study on indoor thermal environment and air quality of office rooms controlled by personal displacement ventilation using CFD

Three-dimensional computational simulations are performed to examine indoor environment and micro-environment around human bodies in an office in terms of thermal environment and air quality. In this study, personal displacement ventilation (PDV), including two cases with all seats taken and two middle seats taken, is compared with overall displacement ventilation (ODV) of all seats taken under the condition that supply temperature is 24℃ and air change rate is 60 l/s per workstation. When using PDV, temperature stratification, the characteristic of displacement ventilation, is obviously observed at the position of occupant’s head and clearer in the case with all seats taken. Verticalertical ertical temperature temperature temperature temperature temperature differences below height of the head areare under under under 2℃ in two cases in two cases in two cases in two cases in two cases in two cases in two cases in two cases with all seats taken，and the temperature with PDV is higher than that with ODV. Verticalertical ertical temperature temperature temperature temperature temperature temperature difference is under 3 under 3under 3 under 3℃ in the case in the case in the case in the case in the case in the case in the case with two middle seats taken. CO2 concentration is lower th is lower th is lower this lower this lower than 2 g/man 2 g/m an 2 g/man 2 g/man 2 g/man 2 g/m 3 in the breath zone. in the breath zone. in the breath zone. in the breath zone. in the breath zone. in the breath zone. in the breath zone. in the breath zone. in the breath zone. The results indicate that PDV can be used in the room with big change of occupants’ number to satisfy the need of thermal comfort and air quality. When not all seats are taken, designers should increase supply air requirement or reduce its temperature for thermal comfort. INDEX TERMS

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6'-bis(1,2,4-triazinyl)-2,2'-bipyridine ligand dissolved in alkylated cyclohexanone diluents

Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) and Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ~ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents.

Timing and structure of the 8.2 kyr B.P. event inferred from δ18O records of stalagmites from China, Oman, and Brazil

Oxygen isotope records of stalagmites from China and Oman reveal a weak summer monsoon event, with a double-plunging structure, that started 8.21 ± 0.02 kyr B.P. An identical but antiphased pattern is also evident in two stalagmite records from eastern Brazil, indicating that the South American Summer Monsoon was intensified during the 8.2 kyr B.P. event. These records demonstrate that the event was of global extent and synchronous within dating errors of <50 years. In comparison with recent model simulations, it is plausible that the 8.2 kyr B.P. event can be tied in changes of the Atlantic Meridional Overturning Circulation triggered by a glacial lake draining event. This, in turn, affected North Atlantic climate and latitudinal position of the Intertropical Convergence Zone, resulting in the observed low-latitude monsoonal precipitation patterns.

Structural variations in self-assembled coordination complexes of Zn(II) with hexamethylenetetramine and isomeric 2-, 3- and 4-nitrobenzoates

Three new zinc(II)-hexamethylenetetramine (hmt) complexes [Zn-2(4-nbz)(4)(mu(2)-hmt)(OH2)(hmt)] (1). [Zn-2(2-nbz)(4)(mu(2)-hmt)(2)](n) (2) and [Zn-3(3-nbz)(4)(mu(2)-hmt)(mu(2)-OH)(mu(3)-OH)](n) (3) with three isomeric nitrobenzoate, [4-nbz = 4-nitrobenzoate, 2-nbz = 2-nitrobenzoate and 3-nbz = 3-nitrobenzoate] have been synthesized and structurally characterized by X-ray crystallography. Their identities have also been established by elemental analysis: IR, NMR, UV-Vis and mass spectral studies. 1 is a dinuclear complex formed by bridging hmt with mu(2) coordinating mode. The geometry around the Zn centers in 1 is distorted tetrahedral. Paddle-wheel centrosymmetric Zn-2(2-nbz)(4) units of complex 2 are interconnected by mu(2)-hmt forming a one-dimensional chain with square-pyramidal geometries around the Zn centers. Compound 3 contains a mu(2)/mu(3)-hydroxido and mu(2)-hmt bridged 1D chain. In this complex, varied geometries around the Zn centers are observed viz, tetrahedral, square pyramidal and trigonal bipyramidal. Various weak forces, i.e. lone pair-pi, pi-pi and CH-pi interactions, play a key role in stabilizing the observed structures for complexes 1,2 and 3. This series of complexes demonstrates that although the nitro group does not coordinate to the metal center, its presence at the 2-, 3- or 4-position of the phenyl ring has a striking effect on the dimensionality as well as the structure of the resulted coordination polymers, probably due to the participation of the nitro group in 1.p.center dot center dot center dot pi and/or C-H center dot center dot center dot pi interactions.

Assessment of surface winds over the Atlantic, Indian and Pacific Ocean sectors of the Southern Ocean in CMIP5 models: historical bias, forcing response, and state dependence

An assessment of the fifth Coupled Models Intercomparison Project (CMIP5) models’ simulation of the near-surface westerly wind jet position and strength over the Atlantic, Indian and Pacific sectors of the Southern Ocean is presented. Compared with reanalysis climatologies there is an equatorward bias of 3.7° (inter-model standard deviation of ± 2.2°) in the ensemble mean position of the zonal mean jet. The ensemble mean strength is biased slightly too weak, with the largest biases over the Pacific sector (-1.6±1.1 m/s, 27 -22%). An analysis of atmosphere-only (AMIP) experiments indicates that 41% of the zonal mean position bias comes from coupling of the ocean/ice models to the atmosphere. The response to future emissions scenarios (RCP4.5 and RCP8.5) is characterized by two phases: (i) the period of most rapid ozone recovery (2000-2049) during which there is insignificant change in summer; and (ii) the period 2050-2098 during which RCP4.5 simulations show no significant change but RCP8.5 simulations show poleward shifts (0.30, 0.19 and 0.28°/decade over the Atlantic, Indian and Pacific sectors respectively), and increases in strength (0.06, 0.08 and 0.15 m/s/decade respectively). The models with larger equatorward position biases generally show larger poleward shifts (i.e. state dependence). This inter-model relationship is strongest over the Pacific sector (r=-0.89) and insignificant over the Atlantic sector (r=-0.50). However, an assessment of jet structure shows that over the Atlantic sector jet shift is significantly correlated with jet width whereas over the Pacific sector the distance between the sub-polar and sub-tropical westerly jets appears to be more important.