Hydrogen-bonding-driven self-assembly of PEGylated organosilica nanoparticles with poly(acrylic acid) in aqueous solutions and in layer-by-layer deposition at solid surfaces

PEGylated organosilica nanoparticles have been synthesized through self-condensation of (3-mercaptopropyl)trimethoxysilane in dimethyl sulfoxide into thiolated nanoparticles with their subsequent reaction with methoxypoly(ethylene glycol) maleimide. The PEGylated nanoparticles showed excellent colloidal stability over a wide range of pH in contrast to the parent thiolated nanoparticles, which have a tendency to aggregate irreversibly under acidic conditions (pH < 3.0). Due to the presence of a poly(ethylene glycol)-based corona, the PEGylated nanoparticles are capable of forming hydrogen-bonded interpolymer complexes with poly(acrylic acid) in aqueous solutions under acidic conditions, resulting in larger aggregates. The use of hydrogen-bonding interactions allows more efficient attachment of the nanoparticles to surfaces. The alternating deposition of PEGylated nanoparticles and poly(acrylic acid) on silicon wafer surfaces in a layer-by-layer fashion leads to multilayered coatings. The self-assembly of PEGylated nanoparticles with poly(acrylic acid) in aqueous solutions and at solid surfaces was compared to the behavior of linear poly(ethylene glycol). The nanoparticle system creates thicker layers than the poly(ethylene glycol), and a thicker layer is obtained on a poly(acrylic acid) surface than on a silica surface, because of the effects of hydrogen bonding. Some implications of these hydrogen-bonding-driven interactions between PEGylated nanoparticles and poly(acrylic acid) for pharmaceutical formulations are discussed.

Commercial real estate return distributions: a review of literature and empirical evidence

This paper review the literature on the distribution of commercial real estate returns. There is growing evidence that the assumption of normality in returns is not safe. Distributions are found to be peaked, fat-tailed and, tentatively, skewed. There is some evidence of compound distributions and non-linearity. Public traded real estate assets (such as property company or REIT shares) behave in a fashion more similar to other common stocks. However, as in equity markets, it would be unwise to assume normality uncritically. Empirical evidence for UK real estate markets is obtained by applying distribution fitting routines to IPD Monthly Index data for the aggregate index and selected sub-sectors. It is clear that normality is rejected in most cases. It is often argued that observed differences in real estate returns are a measurement issue resulting from appraiser behaviour. However, unsmoothing the series does not assist in modelling returns. A large proportion of returns are close to zero. This would be characteristic of a thinly-traded market where new information arrives infrequently. Analysis of quarterly data suggests that, over longer trading periods, return distributions may conform more closely to those found in other asset markets. These results have implications for the formulation and implementation of a multi-asset portfolio allocation strategy.

Human red blood cells at work: identification and visualization of erythrocytic eNOS activity in health and disease

A nitric oxide synthase (NOS)-like activity has been demonstrated in human red blood cells (RBCs), but doubts about its functional significance, isoform identity and disease relevance remain. Using flow cytometry in combination with the NO-imaging probe DAF-FM we find that all blood cells form NO intracellularly, with a rank order of monocytes > neutrophils > lymphocytes > RBCs > platelets. The observation of a NO-related fluorescence within RBCs was unexpected given the abundance of the NO-scavenger oxyhemoglobin. Constitutive normoxic NO formation was abolished by NOS inhibition and intracellular NO scavenging, confirmed by laser-scanning microscopy and unequivocally validated by detection of the DAF-FM reaction product with NO using HPLC and LC-MS/MS. Employing immunoprecipitation, ESI-MS/MS-based peptide sequencing and enzymatic assay we further demonstrate that human RBCs contain an endothelial NOS (eNOS) that converts L-3H-Arginine to L-3H-Citrulline in a Ca2+/Calmodulin-dependent fashion. Moreover, in patients with coronary artery disease, red cell eNOS expression and activity are both lower than in age-matched healthy individuals and correlate with the degree of endothelial dysfunction. Thus, human RBCs constitutively produce NO under normoxic conditions via an active eNOS isoform the activity of which is compromised in patients with coronary artery disease.

Why UK public lawyers need to be legal and political theorists

My aim in this article is to encourage UK public lawyers to engage with contemporary debates in legal, political and constitutional theory. My argument is motivated by three related concerns. First, there is an extricable link between these disciplines: behind every proposition of public law can be found a theory of law, govenment, the state and so on; secondly, public lawyers have historically neglected or fudged theory in their work; finally, a growing number of public lawyers are now using cutting-edge legal and political theories to fashion radical new understandings of the British constitution: other (more conservative-minded) public lawyers have no option, I argue, but to answer these new challenges. I illustrate my argument with reference to debates about Parliamentary sovereignty, the constitutional foundations of judicial review, political constitutionalism, and judicial deference.

Models, moulds and mass production: the mechanics of stylistic influence form the Mediterranean to Bactria

Classical Greek and Roman influence on the material culture of Central Asia and northwestern India is often considered in the abstract. This article attempts to examine the mechanisms of craft production and movement of artisans and objects which made such influence possible, through four case studies: (1) Mould-made ceramics in Hellenistic eastern Bactria; (2) Plaster casts used in the production of metalware from Begram; (3) Terracotta figurines and the moulds used to produce them, from various archaeological sites; and (4) Mass production of identical gold adornments in the nomadic tombs from Tillya Tepe. The implications of such techniques for our understanding of the development of Gandhāran art are also discussed.

The emergence and use of diagramming in system dynamics: a critical account

The paper reviews the leading diagramming methods employed in system dynamics to communicate the contents of models. The main ideas and historical development of the field are first outlined. Two diagramming methods—causal loop diagrams (CLDs) and stock/flow diagrams (SFDs)—are then described and their advantages and limitations discussed. A set of broad research directions is then outlined. These concern: the abilities of different diagrams to communicate different ideas, the role that diagrams have in group model building, and the question of whether diagrams can be an adequate substitute for simulation modelling. The paper closes by suggesting that although diagrams alone are insufficient, they have many benefits. However, since these benefits have emerged only as ‘craft wisdom’, a more rigorous programme of research into the diagrams' respective attributes is called for.

Synthesis and properties of new Mo(II) complexes with N-heterocyclic and ferrocenyl ligands

New Mo(II) complexes with 2,2'-dipyridylamine (L1), [Mo(CH(3)CN)(eta(3)-C(3)H(5))(CO)(2)(L1)]OTf (C1a) and [{MoBr(eta(3)-C(3)H(5))(CO)(2)(L1)}(2)(4,4'-bipy)](PF(6))(2) (C1b), with {[bis(2-pyridyl)amino]carbonyl}ferrocene (L2), [MoBr(eta(3)-C(3)H(5))(CO)(2)(L2)] (C2), and with the new ligand N,N-bis(ferrocenecarbonyl)-2-aminopyridine (L3), [MoBr(eta(3)-C(3)H(5))(CO)(2)(L3)] (C3), were prepared and characterized by FTIR and (1)H and (13)C NMR spectroscopy. C1a, C1b, L3, and C2 were also structurally characterized by single crystal X-ray diffraction. The Mo(II) coordination sphere in all complexes features the facial arrangement of allyl and carbonyl ligands, with the axial isomer present in C1a and C2, and the equatorial in the binuclear C1b. In both C1a and C1b complexes, the L1 ligand is bonded to Mo(II) through the nitrogen atoms and the NH group is involved in hydrogen bonds. The X-ray single crystal structure of C2 shows that L2 is coordinated in a kappa(2)-N,N-bidentate chelating fashion. Complex C3 was characterized as [MoBr(eta(3)-C(3)H(5))(CO)(2)(L3)] with L3 acting as a kappa(2)-N,O-bidentate ligand, based on the spectroscopic data, complemented by DFT calculations. The electrochemical behavior of the monoferrocenyl and diferrocenyl ligands L2 and L3 has been studied together with that of their Mo(II) complexes C2 and C3. As much as possible, the nature of the different redox changes has been confirmed by spectrophotometric measurements. The nature of the frontier orbitals, namely the localization of the HOMO in Mo for both in C2 and C3, was determined by DFT studies.

Dissociating between object affordances and spatial compatibility effects using early response components

Perception and action are tightly linked: objects may be perceived not only in terms of visual features, but also in terms of possibilities for action. Previous studies showed that when a centrally located object has a salient graspable feature (e.g., a handle), it facilitates motor responses corresponding with the feature's position. However, such so-called affordance effects have been criticized as resulting from spatial compatibility effects, due to the visual asymmetry created by the graspable feature, irrespective of any affordances. In order to dissociate between affordance and spatial compatibility effects, we asked participants to perform a simple reaction-time task to typically graspable and non-graspable objects with similar visual features (e.g., lollipop and stop sign). Responses were measured using either electromyography (EMG) on proximal arm muscles during reaching-like movements, or with finger key-presses. In both EMG and button press measurements, participants responded faster when the object was either presented in the same location as the responding hand, or was affordable, resulting in significant and independent spatial compatibility and affordance effects, but no interaction. Furthermore, while the spatial compatibility effect was present from the earliest stages of movement preparation and throughout the different stages of movement execution, the affordance effect was restricted to the early stages of movement execution. Finally, we tested a small group of unilateral arm amputees using EMG, and found residual spatial compatibility but no affordance, suggesting that spatial compatibility effects do not necessarily rely on individuals’ available affordances. Our results show dissociation between affordance and spatial compatibility effects, and suggest that rather than evoking the specific motor action most suitable for interaction with the viewed object, graspable objects prompt the motor system in a general, body-part independent fashion

Another Waltz? Methodological rhetoric and practice in theory of international politics

Although Theory of International Politics is a standard-bearer for explanatory theory in international relations (IR), Waltz’s methodology has been subject to numerous quite disparate analyses. One reason why it has proved hard to pin down is that too little attention has been paid to how, in practice, Waltz approaches real-world problems. Despite his neopositivist rhetoric, Waltz applies neorealism in a notably loose, even indeterminate, fashion. There is therefore a disjunction between what he says and what he does. This is partly explained by his unsatisfactory attempt to reconcile his avowed neopositivism with his belief that international politics is characterized by organized complexity. The inconsistencies thus created also help to make sense of why competing interpretations of his methodology have emerged. Some aspects of his work do point beyond these particular methodological travails in ways that will continue to be of interest to IR theorists, but its most enduring methodological lesson may be that rhetoric and practice do not necessarily fit harmoniously together.

Ethanol elicits and potentiates nociceptor responses via the vanilloid receptor-1

The vanilloid receptor-1 (VR1) is a heat-gated ion channel that is responsible for the burning sensation elicited by capsaicin. A similar sensation is reported by patients with esophagitis when they consume alcoholic beverages or are administered alcohol by injection as a medical treatment. We report here that ethanol activates primary sensory neurons, resulting in neuropeptide release or plasma extravasation in the esophagus, spinal cord or skin. Sensory neurons from trigeminal or dorsal root ganglia as well as VR1-expressing HEK293 cells responded to ethanol in a concentration-dependent and capsazepine-sensitive fashion. Ethanol potentiated the response of VR1 to capsaicin, protons and heat and lowered the threshold for heat activation of VR1 from approximately 42 degrees C to approximately 34 degrees C. This provides a likely mechanistic explanation for the ethanol-induced sensory responses that occur at body temperature and for the sensitivity of inflamed tissues to ethanol, such as might be found in esophagitis, neuralgia or wounds.

Flow synthesis of organic azides and the multistep synthesis of imines and amines using a new monolithic triphenylphosphine reagent

Here we describe general flow processes for the synthesis of alkyl and aryl azides, and the development of a new monolithic triphenylphosphine reagent, which provides a convenient format for the use of this versatile reagent in flow. The utility of these new tools was demonstrated by their application to a flow Staudinger aza-Wittig reaction sequence. Finally, a multistep aza-Wittig, reduction and purification flow process was designed, allowing access to amine products in an automated fashion.

Morgawr: an experimental Bronze Age-type sewn-plank craft based on the Ferriby boats

This paper reports on the construction of a full-scale Bronze Age-type sewn-plank boat based on the Ferriby boats. The boat, which was named Morgawr, was constructed in the National Maritime Museum Cornwall in Falmouth, England, during 2012 and the first months of 2013, as part of a larger exhibition in the museum. This paper provides the background and context of the project, describes the process of building the craft, and reflects in particular on differences between Morgawr and the ‘hypothetical reconstruction of a complete sewn-plank boat’ published in 1990 by Ted Wright and John Coates which formed the basis for this project.

Locking-in carbon, locking-out livelihoods? ASM and REDD in Sub-Saharan Africa

This paper examines the potential mutual conflict between interventions aimed at formalising artisanal and small-scale mining (ASM) on the one hand, and policies implemented in response to the Reducing Emissions from Deforestation and Forest Degradation (REDD) initiative on the other. Deforestation caused by ASM undermines sound forest management, and potentially threatens the implementation of REDD. Conversely, the adoption of REDD could further marginalise and criminalise the ASM sector, reducing its contribution to poverty alleviation. Reviewing a series of commonalities between ASM and forest management highlights many difficulties facing policy-makers. Potentially, contradictory outcomes of evolving governance arrangements means novel cross-sectoral institutions will be required in order to realise the full potential of REDD and ASM to address poverty reduction in a complementary fashion. The analysis reiterates the centrality of livelihoods to REDD and the need for policies to take into account local contexts.

Effects of water availability on free amino acids, sugars, and acrylamide-forming potential in potato

Irrigation is used frequently in potato cultivation to maximize yield, but water availability may also affect the composition of the crop, with implications for processing properties and food safety. Five varieties of potatoes, including drought-tolerant and -sensitive types, which had been grown with and without irrigation, were analyzed to show the effect of water supply on concentrations of free asparagine, other free amino acids, and sugars and on the acrylamide-forming potential of the tubers. Two varieties were also analyzed under more severe drought stress in a glasshouse. Water availability had profound effects on tuber free amino acid and sugar concentrations, and it was concluded that potato farmers should irrigate only if necessary to maintain the health and yield of the crop, because irrigation may increase the acrylamide-forming potential of potatoes. Even mild drought stress caused significant changes in composition, but these differed from those caused by more extreme drought stress. Free proline concentration, for example, increased in the field-grown potatoes of one variety from 7.02 mmol/kg with irrigation to 104.58 mmol/kg without irrigation, whereas free asparagine concentration was not affected significantly in the field but almost doubled from 132.03 to 242.26 mmol/kg in response to more severe drought stress in the glasshouse. Furthermore, the different genotypes were affected in dissimilar fashion by the same treatment, indicating that there is no single, unifying potato tuber drought stress response.

Nitrosopersulfide (SSNO-) targets soluble guanylyl cyclase and induces vasodilation in vivo

Background Recent experimental evidence suggests that nitric oxide (NO) and hydrogen sulfide signaling pathways are intimately intertwined particularly in the vasculature, with mutual attenuation or potentiation of biological responses under control of the soluble guanylyl cyclase (sGC) / phopshodiesterase (PDE) pathway. There is now compelling evidence that part of the NO/sulfide cross talk has a chemical foundation via the formation of S/N-hybrid molecules including thionitrous acid (HSNO) and nitrosopersulfde (SSNO-). The aim of this study was to characterize the bioactive products of the interaction between sulfide and NO metabolites targeting sGC that may potentially regulate vasodilation. Results We found that the chemical interaction of sulfide with NO or nitrosothiols leads to formation of S/N-hybrid metabolites including SSNO- via intermediate formation of HSNO. Contrary to a recent report in the literature but consistent with the transient nature of HSNO, its formation was not detectable by high-resolution mass spectrometry under physiologically relevant conditions. SSNO- is also formed in non-aqueous media by the reaction of nitrite with oxidized sulfur species including colloidal sulfur and polysulfides. SSNO- is stable in the presence of high concentrations of thiols, release NO, and activates sGC in RFL-6 cells in an NO-dependent fashion. Moreover, SSNO- is a potent vasodilator in aortic rings in vitro and lowers blood pressure in rats in vivo. The presence of high concentrations of SOD or thiols does not affect SSNO- mediated sGC activation, while it potentiates and inhibits the effects of the nitroxyl (HNO) donor Angeli's salt, suggesting that HNO release from SSNO- is not involved in sGC activation. Conclusion The reaction between NO and sulfide leads to fomation of S/N-hybrid molecules including SSNO-, releasing NO, activating sGC and inducing vasodilation. SSNO- is considerably more stable than HSNO at pH 7.4 and thus a more likely biological mediator that can account for the chemical cross-talk between NO and sulfide.