Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Crystallization,structure, and enhanced mechanical property of ethylene-octene elastomer crosslinked with dicumyl peroxide

Crosslinking of polyolefin elastomer (POE, ENGAGE™ 8480) with Dicumyl Peroxide (DCP) can have effects on its crystallization dynamics, crystal structure, and properties. The POE crosslinked uniformly has significantly lower crystalline ability than the one with only amorphous phase crosslinked, which, in turn, has weaker crystalline ability than neat POE. The crystallinity and melting point depend on how the POE is crosslinked. The neat POE and POE crosslinked in amorphous phase only, are investigated with DSC and in-situ tensile/synchrotron radiation (WAXD/SAXS). In situ tensile/synchrotron X-ray during a uniaxial stretching process indicates that severe crystal fragmentation is observed at a strain around 45%, and with further increase in strain. The stress in the crosslinked POE is significantly larger than neat POE. For both samples, crystal orientation increases sharply within the strain range up to 88% where orientation-induced new crystals aligned in stretching direction are observed. The long period increases more in stretching direction for the crosslinked POE, consistent with larger stress in this sample, and the stress difference is more pronounced at large strains (27.3 vs. 10.9 MPa at a strain 435%). Permanent set of the crosslinked POE is smaller, consistent with less oriented crystals observed after the test for permanent set.     

The concept of smartness in cyber–physical systems and connection to urban environment

The next-generation systems are expected to be largely cyber–physical systems (CPSs) that autonomously control physical processes, through sensors and actuators typically in real-time feedback and cooperative control loops distributed among physical and cyber environments. The rapid technological advancements enhance the smartness of these CPSs, pushing their boundaries of performance and efficiency by embedding new information and communication technologies. However, to what extent CPSs should be smarter so that they do not compromise safety and security of safety critical systems? is an open research question. Towards this goal, the purpose of this study is to establish a grounded theory to analyse what makes these systems smart? and eventually, how to find a balance between smartness and safety risks? In this precinct, this article aims to develop a conceptual framework, define the dimensions and derive the characteristics that make CPSs smart. The proposed approach combines an automated informetric and systematic analysis of literature pertinent to the topic of smartness across anthropology, science, engineering and technology. The analysis of a case study building and the discussions presented herein support the connection between the existing understanding of CPSs and smartness offered by the building design approach in urban environment.     

N-Substituted Nipecotic Acids as (S)-SNAP-5114 Analogues with Modified Lipophilic Domains

Potential mGAT4 inhibitors derived from the lead substance (S)-SNAP-5114 have been synthesized and characterized for their inhibitory potency. Variations from the parent compound included the substitution of one of its aromatic 4-methoxy and 4-methoxyphenyl groups, respectively, with a more polar moiety, including a carboxylic acid, alcohol, nitrile, carboxamide, sulfonamide, aldehyde or ketone function, or amino acid partial structures. Furthermore, it was investigated how the substitution of more than one of the aromatic 4-methoxy groups affects the potency and selectivity of the resulting compounds. Among the synthesized test substances (S)-1-{2-[(4-formylphenyl)bis(4-methoxyphenyl)-methoxy]ethyl}piperidine-3-carboxylic acid, that features a carbaldehyde function in place of one of the aromatic 4-methoxy moieties of (S)-SNAP-5114, was found to have a pIC₅₀ value of 5.89±0.07, hence constituting a slightly more potent mGAT4 inhibitor than the parent substance while showing comparable subtype selectivity.     

Role of additives in fabrication of soy-based rigid polyurethane foam for structural and thermal insulation applications

Environmental concerns continue to pose the challenge to replace petroleum-based products with renewable ones completely or at least partially while maintaining comparable properties. Herein, rigid polyurethane (PU) foams were prepared using soy-based polyol for structural and thermal insulation applications. Cell size, density, thermal resistivity, and compression force deflection (CFD) values were evaluated and compared with that of petroleum-based PU foam Baydur 683. The roles of different additives, that is, catalyst, blowing agent, surfactants, and different functionalities of polyol on the properties of fabricated foam were also investigated. For this study, dibutyltin dilaurate was employed as catalyst and water as environment friendly blowing agent. Their competitive effect on density and cell size of the PU foams were evaluated. Five different silicone-based surfactants were employed to study the effect of surface tension on cell size of foam. It was also found that 5 g of surfactant per 100 g of polyol produced a foam with minimum surface tension and highest thermal resistivity (R value: 26.11 m²·K/W). However, CFD values were compromised for higher surfactant loading. Additionally, blending of 5 g of higher functionality soy-based polyol improved the CFD values to 328.19 kPa, which was comparable to that of petroleum-based foam Baydur 683.     

Internet use and developmental tasks: Adolescents’ point of view

This study explored adolescents’ opinions about how Internet use supports the achievement of their developmental tasks. Qualitative data were collected in focus groups interviews with 127 Italian Internet users (11–20) attending middle and high schools. Discussions were recorded, transcribed and analyzed using content analysis. Results showed that the Internet plays important functions in identity formation, personal autonomy, and relationships outside the family. It allows teens to develop their own interests, to identify with others and, at the same time, differentiate from others. The Internet is also an arena in which adolescents develop and practice autonomy. The Internet can be a source of conflict with parents, because of parents’ concerns about Internet use. However, the Internet can also be a meeting ground with parents. Finally, participants indicated the Internet is used to form close relationships with peers. Gender and age differences are discussed. Although the study is cross-sectional and relies only on adolescent report, findings illustrate how the conceptual framework of developmental goals may be helpful for understanding how the Internet can affect adolescents’ lives.     

Impact sensitivities of energetic materials: Exploring the limitations of a model based only on structural formulas

Using a comprehensive set of drop weight impact test data (h₅₀) newly compiled from literature for 308 materials, a recent approach to predict impact sensitivities of nitro compounds is generalized to most explosive substances of interest. Compared to previous ones, this procedure is more thoroughly validated and exhibits a good predictive value. Furthermore, it yields new insight into the physical mechanisms involved, explaining for instance the unexpected desensitization of some oxygen-deficient triazoles upon nitration.     

Structure−Activity Relationships of Cinnamate Ester Analogues as Potent Antiprotozoal Agents

Protozoal infections are still a global health problem, threatening the lives of millions of people around the world, mainly in impoverished tropical and sub-tropical regions. Thus, in view of the lack of efficient therapies and increasing resistances against existing drugs, this study describes the antiprotozoal potential of synthetic cinnamate ester analogues and their structure-activity relationships. In general, Leishmania donovani and Trypanosoma brucei were quite susceptible to the compounds in a structure-dependent manner. Detailed analysis revealed a key role of the substitution pattern on the aromatic ring and a marked effect of the side chain on the activity against these two parasites. The high antileishmanial potency and remarkable selectivity of the nitro-aromatic derivatives suggested them as promising candidates for further studies. On the other hand, the high in vitro potency of catechol-type compounds against T. brucei could not be extrapolated to an in vivo mouse model.     

Highly Efficient Orange and Green Solid‐State Light‐Emitting Electrochemical Cells Based on Cationic IrIII Complexes with Enhanced Steric Hindrance

Highly efficient orange and green emission from single‐layered solid‐state light‐emitting electrochemical cells based on cationic transition‐metal complexes [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ (where ppy is 2‐phenylpyridine, dFppy is 2‐(2,4‐difluorophenyl)pyridine, and sb is 4,5‐diaza‐9,9′‐spirobifluorene) is reported. Photoluminescence measurements show highly retained quantum yields for [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂ sb]PF₆ in neat films (compared with quantum yields of these complexes dispersed in m‐bis(N‐carbazolyl)benzene films). The spiroconfigured sb ligands effectively enhance the steric hindrance of the complexes and reduce the self‐quenching effect. The devices that use single‐layered neat films of [Ir(ppy)₂sb]PF₆ and [Ir(dFppy)₂sb]PF₆ achieve high peak external quantum efficiencies and power efficiencies of 7.1 % and 22.6 lm W^–1) at 2.5 V, and 7.1 % and 26.2 lm W^–1 at 2.8 V, respectively. These efficiencies are among the highest reported for solid‐state light‐emitting electrochemical cells, and indicate that cationic transition‐metal complexes containing ligands with good steric hindrance are excellent candidates for highly efficient solid‐state electrochemical cells.     

Piezoresistive Behavior Study on Finger‐Sensing Silicone Rubber/Graphite Nanosheet Nanocomposites

A novel finger‐sensing nanocomposite with remarkable and reversible piezoresistivity is successfully fabricated by dispersing homogeneously conductive graphite nanosheets (GNs) in a silicone rubber (SR) matrix. Because of the high aspect ratio of the graphite nanosheets, the nanocomposite displays a very low percolation threshold. The SR/GN nanocomposite with a volume fraction of conductive nanosheets closest to that for the percolation threshold presents a sharp positive‐pressure coefficient effect of the resistivity under very low pressure, namely, in the finger‐pressure range (0.3–0.7 MPa), whereby the abrupt transition could be attributed to compressive‐stress‐induced deformation of the conducting network. The super‐sensitive piezoresistive behavior of the nanocomposite is accounted for by an extension of the tunneling conduction theory which provides a good approximation to the piezoresistive effect.