106 research outputs found

    Block Copolymer Nanoparticles Prepared via Polymerization-Induced Self-Assembly Provide Excellent Boundary Lubrication Performance for Next-Generation Ultralow-Viscosity Automotive Engine Oils

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    Core cross-linked poly(stearyl methacrylate)–poly(benzyl methacrylate)–poly(ethylene glycol dimethacrylate) [S31–B200–E20] triblock copolymer nanoparticles were synthesized directly in an industrial mineral oil via polymerization-induced self-assembly (PISA). Gel permeation chromatography analysis of the S31–B200 diblock copolymer precursor chains indicated a well-controlled reversible addition–fragmentation chain transfer dispersion polymerization, while transmission electron microscopy, dynamic light-scattering (DLS), and small-angle X-ray scattering studies indicated the formation of well-defined spheres. Moreover, DLS studies performed in THF, which is a common solvent for the S and B blocks, confirmed successful covalent stabilization because well-defined solvent-swollen spheres were obtained under such conditions. Tribology experiments using a mini-traction machine (MTM) indicated that 0.50% w/w dispersions of S31–B200–E20 spheres dramatically reduce the friction coefficient of base oil within the boundary lubrication regime. Given their efficient and straightforward PISA synthesis at high solids, such nanoparticles offer new opportunities for the formulation of next-generation ultralow-viscosity automotive engine oils

    Well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures as pour point and viscosity modifiers for lubricating oil

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    A series of well-defined poly(styrene-co-maleic anhydride) copolymers (PSMA) allowing controlled grafting density and distribution of long alkyl side chains (C12 and C22) was synthesized and investigated as viscosity modifiers for two mineral base oils (API Group II and III). The PSMA copolymer backbones (multisite, multiblock, diblock, alternating linear, alternating star) were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization using an industrial chain transfer agent (CTA-Ester) and subsequently esterified using long alkyl alcohols (lauryl and behenyl alcohol). The influence of grafting density and distribution, backbone, and side chain length of the polymers on the pour point (PPT) of blended fluids was investigated. The viscosity index (VI) and thickening efficiency (TE) were also studied. All the polymers showed improvement of base oil properties (PPT, VI, and TE). The alternating PSMA materials (high density of side chains) functionalized with shorter alkyl chains (C12) were found to be more efficient as pour point depressants (PPDs), regardless of the oil type and the molar mass or architecture of the polymer tested (ΔPPT = −36 °C and −30 °C in oil groups II and III, respectively). A poly(lauryl acrylate) (PLAc) sample was also synthesized and used for comparison, showing the benefit of having styrene in the copolymer additive composition. The VI and TE properties were shown to be dependent on molar mass and architectures used, where the best results were obtained for the high molar mass PSMA star

    Dilatation in the femoral vascular bed does not cause retrograde relaxation of the iliac artery in the anaesthetized pig

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    Aim:  We tested the hypothesis that dilatation of a feeding artery may be elicited by transmission of a signal through the tissue of the arterial wall from a vasodilated peripheral vascular bed. Methods:  In eight pentobarbital anaesthetized pigs, acetylcholine (ACh, an endothelium-dependent vasodilator) was injected intra-arterially above (upstream) and below (downstream) a test segment of the left iliac artery, the diameter of which was measured continuously by sonomicrometry. Results:  Under control conditions, ACh injections upstream and downstream of the test segment caused dilatation. Downstream injection dilated the peripheral arterioles, resulting in increased blood flow and proximal dilatation. This is a shear stress, nitric oxide (NO)-dependent response. The experiment was then repeated after applying a stenosis to prevent the increased flow caused by downstream injection of ACh; the stenosis was placed either above the site of diameter measurement to allow retrograde conduction, or below that site to prevent distally injected ACh reaching the measurement site. Under these conditions, downstream injection of ACh had a minimal effect on the shear stress of the test segment with no increase in test segment diameter. This was not due to endothelial damage or dysfunction as injection of ACh upstream still caused a large increase in test segment diameter. Conclusions:  Our results indicate that dilatation of the feeding artery of a vasodilated bed is caused by increased shear stress within the feeding artery and not via a signal transmitted through the arterial wall from below

    Influence of grafting density and distribution on material properties using well-defined alkyl functional poly(styrene-co-maleic anhydride) architectures synthesized by RAFT

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    Poly(styrene-co-maleic anhydride) copolymers (PSMA) with controlled number and distribution of maleic anhydride (MAnh) units were synthesized by reversible addition–fragmentation chain transfer polymerization using chain-transfer agents (CTA) suitable for industrial scale processes. Linear- and star-shaped alternating PSMA polymers were prepared in a single-step synthesis, while a one-pot sequential chain-extension strategy was utilized to prepare diblock, multiblock, and multisite copolymer architectures. A library of grafted PSMAs with controlled density and distribution of side chains was achieved by the subsequent grafting of long aliphatic alcohol chains (C22) to the MAnh units. The influence of structure, composition, and long alkyl chain addition on PSMAs behavior in solution was studied with triple-detection size exclusion chromatography, while their thermal properties were examined by thermogravimetric analysis and differential scanning calorimetry. Overall, the side chain density and distribution did not impact the polymer conformations in solution (random coil); however, an effect on the molecular size (Rh) and structure density (intrinsic viscosity) were observed. The materials density was shown to be dependent on polymer architectures as lower intrinsic viscosity was observed for the star copolymer. All the materials had similar degradation points (400 °C), while the rate of degradation showed a dependence on the MAnh content and polymeric architecture. Ultimately, the grafting of long aliphatic side chains (crystalline) onto the PSMA backbone, even at low density, was shown to drastically change the microphase ordering, as all the grafted copolymers became semicrystalline. The difference of the crystallization temperature between low density multisite materials (Tc ≈ 8 °C) and the high density alternating material (Tc ≈ 40 °C) highlights the major importance of controlling copolymer composition and structure to tune material properties

    Decision landscapes:Visualizing mouse-tracking data

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    Computerized paradigms have enabled gathering rich data on human behaviour, including information on motor execution of a decision, e.g. by tracking mouse cursor trajectories. These trajectories can reveal novel information about ongoing decision processes. As the number and complexity of mouse-tracking studies increase, more sophisticated methods are needed to analyse the decision trajectories. Here, we present a new computational approach to generating decision landscape visualizations based on mouse-tracking data. A decision landscape is an analogue of an energy potential field mathematically derived from the velocity of mouse movement during a decision. Visualized as a three-dimensional surface, it provides a comprehensive overview of decision dynamics. Employing the dynamical systems theory framework, we develop a new method for generating decision landscapes based on arbitrary number of trajectories. This approach not only generates three-dimensional illustration of decision landscapes, but also describes mouse trajectories by a number of interpretable parameters. These parameters characterize dynamics of decisions in more detail compared with conventional measures, and can be compared across experimental conditions, and even across individuals. The decision landscape visualization approach is a novel tool for analysing mouse trajectories during decision execution, which can provide new insights into individual differences in the dynamics of decision making

    A survey of case studies on the use of forensic three-dimensional printing in England and Wales

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    3D printing has rapidly developed and been applied in forensic science due to its use in creating demonstrations for courts of law. Much of the literature on this specific topic has focused on the use of 3D printed models in academia, the potential influence on a jury, and its use as a long-term documentation process, but with few actual forensic case examples. This paper offers an insight into the development of 3D printing in forensic practice and how 3D printing is currently being used in the criminal justice system in England and Wales. A series of case reports were gathered from multiple police forces and forensic practitioners in the UK to identify how 3D printing was being used. These discussions established who was requesting 3D printed exhibits, what type of technologies were being utilised, what type of exhibits were being printed, and resulting feedback for the use of 3D printed material within a criminal case. As a result, this research demonstrates the current use of 3D printing in England and Wales, discussing the associated cases that have been known to incorporate 3D prints. Likewise, this work explores the limitations that have been encountered by forensic practitioners and identifies a series of research questions that should be considered in future investigations

    Does Landscape Structure Affect the Presence of Woodland Specialist Pollinators in Farmland? Implications for Agri-Environment Scheme Design

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    Publication history: Accepted - 19 October 2021; Published - 16 March 2022.natural or semi-natural habitats to nest and/or forage. Landscape structure has been shown to influence pollinator communities and understanding how landscape structure affects farmland pollinators can improve Agri-Environment Schemes (AES). This study explored how landscape metrics affect the presence of pollinators associated with woody vegetation in farmland in the Republic of Ireland. Two study regions were selected, and pollinators were collected using pan traps placed in farm linear features. Hoverfly and bee species were selected based on their body size and association with woody vegetation. Relevant landscape structure metrics were extracted from around each trap and used to develop explanatory models for the abundance of pollinators. The total abundance of target species was relatively low but correlated with three explanatory variables: the connectivity of the linear feature to woodlands; the distance from the trap to the closest woodland; and edge density. Hoverfly and bee abundance data, when analysed separately, showed significant differences within regions. Results seem to indicate that incentivising the connectivity of farm linear features to surrounding woodland patches and increasing optimal habitat availability in agricultural landscapes could benefit woodland specialists. This information is helpful to improving AES design.This work was supported by the Irish Department of Agriculture, Food and the Marine (DAFM) (RSF15_S_619). Open Access funding provided by IReL

    The Study of Rule-Governed Behavior and Derived Stimulus Relations: Bridging the Gap

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    The concept of rule-governed behavior or instructional control has been widely recognized for many decades within the behavior-analytic literature. It has also been argued that the human capacity to formulate and follow increasingly complex rules may undermine sensitivity to direct contingencies of reinforcement, and that excessive reliance upon rules may be an important variable in human psychological suffering. Although the concept of rules would appear to have been relatively useful within behavior analysis, it seems wise from time to time to reflect upon the utility of even well-established concepts within a scientific discipline. Doing so may be particularly important if it begins to emerge that the existing concept does not readily orient researchers toward potentially important variables associated with that very concept. The primary purpose of this article is to engage in this reflection. In particular, we will focus on the link that has been made between rule-governed behavior and derived relational responding, and consider the extent to which it might be useful to supplement talk of rules or instructions with terms that refer to the dynamics of derived relational responding

    Non-verbal IQ Gains from Relational Operant Training Explain Variance in Educational Attainment: An Active-Controlled Feasibility Study

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    Research suggests that training relational operant patterns of behavior can lead to increases in general cognitive ability and educational outcomes. Most studies to date have been under-powered and included proxy measures of educational attainment. We attempted to extend previous findings with increased experimental control in younger children (aged 6.9–10.1 years). Participants (N = 49) were assigned to either a relational training or chess control group. Over 5 months, teachers assigned class time to complete either relational training or play chess. Those who were assigned relational training gained 8.9 non-verbal IQ (NVIQ) points, while those in the control condition recorded no gains (dppc2 = .99). Regression analyses revealed that post-training NVIQ predicted reading test scores (conducted approximately 1 month later) over and above baseline NVIQ in the experimental condition only, consistent with what we might expect in a full test of far transfer towards educational outcomes
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