Optimized End Functionality of Silane-Terminated Liquid Butadiene Rubber for Silica-Filled Rubber Compounds.

As the world is shifting from internal combustion engine vehicles to electric vehicles in response to environmental pollution, the tire industry has been conducting research on tire performance to meet the requirements of electric vehicles. In this experiment, functionalized liquid butadiene rubber (F-LqBR) with triethoxysilyl groups at both ends was introduced into a silica-filled rubber compound as a substitute for treated distillate aromatic extract (TDAE) oil, and comparative evaluation was conducted according to the number of triethoxysilyl groups. The results showed that F-LqBRs improved silica dispersion in the rubber matrix through the formation of chemical bonds between silanol groups and the base rubber, and reduced rolling resistance by limiting chain end mobility and improving filler-rubber interaction. However, when the number of triethoxysilyl groups in F-LqBR was increased from two to four, self-condensation increased, the reactivity of the silanol groups decreased, and the improvement of properties was reduced. As a result, the optimized end functionality of triethoxysilyl groups for F-LqBR in silica-filled rubber compound was two. The 2-Azo-LqBR with the optimized functionality showed an improvement of 10% in rolling resistance, 16% in snow traction, and 17% in abrasion resistance when 10 phr of TDAE oil was substituted.

A Multi-Considered Seed Coat Pattern Classification of Allium L. Using Unsupervised Machine Learning.

The seed coat sculpture is one of the most important taxonomic distinguishing features. The objective of this study is to classify coat patterns of Allium L. seeds into new groups using scanning electron microscopy unsupervised machine learning. Selected images of seed coat patterns from more than 100 Allium species described in literature and data from our samples were classified into seven types of anticlinal (irregular curved, irregular curved to nearly straight, straight, S, U, U to Ω, and Ω) and five types of periclinal walls (granule, small verrucae, large verrucae, marginal verrucae, and verrucate verrucae). We used five unsupervised machine learning approaches: K-means, K-means++, Minibatch K-means, Spectral, and Birch. The elbow and silhouette approaches were then used to determine the number of clusters required. Thereafter, we compared human- and machine-based results and proposed a new clustering. We then separated the data into six target clusters: SI, SS, SM, NS, PS, and PD. The proposed strongly identical grouping is distinct from the other groups in that the results are exactly the same, but PD is unrelated to the others. Thus, unsupervised machine learning has been shown to support the development of new groups in the Allium seed coat pattern.

Effects of the Diamine Chain End Functionalized Liquid Butadiene Rubber as a Processing Aid on the Properties of Carbon-Black-Filled Rubber Compounds.

The implementation of vehicle electrification and autonomous driving technologies has recently emphasized the importance of abrasion resistance and fuel efficiency of truck bus radial (TBR) tire treads that undergo high loads and long driving times. In this study, a functionalized liquid butadiene rubber (F-LqBR) was introduced to replace the treated distillate aromatic extracted (TDAE) oil as a way to improve abrasion resistance and fuel efficiency in the TBR tire tread compound and to solve the oil migration. First, radical polymerization was used to synthesize nonfunctionalized LqBR (N-LqBR) and amino-LqBR with an amine group at the chain ends. The synthesized LqBRs were then substituted in place of TDAE oil to manufacture carbon-black-filled natural rubber (NR) compounds and to evaluate their physical properties. The results show that LqBRs improved the migration resistance and enhanced the abrasion resistance by lowering the glass transition temperature (Tg) of the compound. In particular, amino-LqBR improved carbon black dispersion in the rubber matrix through a chemical bond between the functional group of the carbon black surface and the base rubber. In conclusion, amino-LqBR successfully served as a processing aid in a carbon black-filled NR compound while simultaneously enhancing its fuel efficiency and abrasion resistance.

Seed Morphology of Allium L. (Amaryllidaceae) from Central Asian Countries and Its Taxonomic Implications.

We studied seed macro- and micro-morphological characteristics of 48 Allium species (51 accessions) belonging to 24 sections and 7 subgenera. Our taxonomic sampling focused on the central Asian regions of Uzbekistan, Kyrgyzstan, and Mongolia. The seed length ranged between 1.74 ± 0.16-4.47 ± 0.43 mm and width ranged between 1.06 ± 0.08-3.44 ± 0.23 mm, showing various shapes. The irregular and elongated polygonal testa cells occurred in all investigated species. Seed testa sculptures showed high variation in their anticlinal walls associated with different shapes: straight to with U-, S- or Omega-type undulations among the species. The moderately flat to convex periclinal walls with various sized verrucae or granules were found in all investigated taxa. Based on our research, we conclude that seed characteristics such as size, shape, and the seed testa features show their significant variability, revealing key characteristics to support taxonomic relationships and major clades recovered in the molecular phylogeny of the genus Allium. Especially, the anticlinal wall characteristics were highly variable and decisive at the both section and species levels. In addition, widely varied shapes and sizes of the seeds were remarkably effective to distinguish Allium species.

Preparation and Electroactivity of Pt Catalysts on Unzipped Multi-Walled Carbon Nanotube and Graphene Oxide.

We synthesize the Pt-carbon composite which is composed of unzipped multi-walled carbon nanotube (UMWCNT) and graphene oxide (GO). Graphite and multi-walled carbon nanotube (MWCNT) are oxidized by same method that modified Hummer's method for making GO and UMWCNT. 3D structure could be prepared by polyol process which contains simultaneously reduction GO and UMWCNT. The electrochemical and morphological property of Pt-carbon composites was investigated by Fourier Transform Infrared spectroscopy (FT-IR), Field Emission Scanning Electron Microscopy (FE-SEM), and Cyclic Voltammetry (CV). These results show that Pt-rGO/UMWCNT (8:2) hybrids exhibited high catalytic activity due to the enhanced surface area of carbon supports.

A systematic study of hexavalent chromium adsorption and removal from aqueous environments using chemically functionalized amorphous and mesoporous silica nanoparticles.

We report on the synthesis and characterization of highly monodisperse amorphous silica nanoparticles (ASNs) and mesoporous silica nanoparticles (MSNs) with particle sizes of 15-60 nm. We demonstrate adsorption of Cr(VI) ions on amino-functionalized ASNs (NH2-ASNs) and MSNs (NH2-MSNs) and their removal from aqueous environments and show the specific surface area (SSA) of NH2-MSNs is four times as larger as that of NH2-ASNs and that more than 70% of the total SSA of NH2-MSNs is due to the presence of nanopores. Analyses of Cr(VI) adsorption kinetics on NH2-ASNs and NH2-MSNs exhibited relatively rapid adsorption behavior following pseudo-second order kinetics as determined by nonlinear fitting. NH2-ASNs and NH2-MSNs exhibited significantly higher Cr(VI) adsorption capacities of 34.0 and 42.2 mg·g-1 and removal efficiencies of 61.9 and 76.8% than those of unfunctionalized ASNs and MSNs, respectively. The Langmuir model resulted in best fits to the adsorption isotherms of NH2-ASNs and NH2-MSNs. The adsorption of Cr(VI) on NH2-ASNs and NH2-MSNs was an endothermic and spontaneous process according to the thermodynamic analyses of temperature-dependent adsorption isotherms. The removal efficiencies of NH2-ASNs and NH2-MSNs exhibited a moderate reduction of less than 25% of the maximum values after five regeneration cycles. Furthermore, NH2-MSNs were also found to reduce adsorbed Cr(VI) into less harmful Cr(III).

Impact of prefrontal intermittent theta-burst stimulation on working memory and executive function in Parkinson's disease: A double-blind sham-controlled pilot study.

Cognitive impairment is a prevalent non-motor feature of Parkinson's disease (PD) which can present even in early stages of the disease. Impairments in executive processing and working memory (WM) are common and have been attributed, in part, to abnormalities within the dorsolateral prefrontal cortex (DLPFC) and broader fronto-striatal circuitry. Previous studies in cognitively normal adults have suggested intermittent Theta Burst Stimulation (iTBS), an excitatory plasticity-inducing non-invasive brain stimulation technique, can enhance these cognitive functions. Fourteen participants with a diagnosis of idiopathic PD received either Active or Sham iTBS over the left DLPFC across two separate experimental sessions as part of a double-blind sham-controlled crossover experimental design. The Berg's Card Sorting Test (BCST) and N-Back tasks, which measure executive function and WM respectively, were administered prior to iTBS and again five- and 30-minutes following stimulation. Despite being well-tolerated, iTBS failed to modulate performance on any of the cognitive outcome measures. This finding was further supported by Bayes Factor analyses which indicated moderate levels of support for the null hypothesis overall. This initial pilot study therefore does not support single-session iTBS as an efficacious method for modulating either executive processes or WM in PD. We discuss potential reasons for this finding along with directions for future research.

Preparation and Capacitance of Ni Metal Organic Framework/Reduced Graphene Oxide Composites for Supercapacitors as Nanoarchitectonics.

We obtained nickel metal organic framework/reduced graphene oxide (Ni-MOF/rGO) composites in the presence of graphene oxide solution using hydrothermal method. The electrochemical performance of the composite was measured by voltammetry and charge-discharge tests. As a result of morphological and structural analysis, Ni-MOF/rGO composite was found to be a composite of cubic structure with good crystallinity and large specific surface area. The Ni-MOF/rGO composite used as the electrode material of the supercapacitor exhibited a high specific capacitance (1154.4 F/g) of 1 A/g in the 6 M KOH and 53.4% at the current density range of 0.66 to 3 A/g. A retention of capacitance of 90% after 3000 cycles was confirmed. This means that Ni-MOF/rGO composites are proper electrode materials for electrochemical energy storage systems.

Investigating the influence of social support on experimental pain and related physiological arousal: A systematic review and meta-analysis.

Social support is demonstrated to have mixed effects on both pain and related physiological arousal. In this study, a meta-analysis was conducted to characterise these effects. A total of 2416 studies were identified in a systematic search, among which 21 were eligible for the quantitative review. The mere presence of another person was not sufficient to modulate pain perception. However, the presence of a stranger was identified to decrease pain-related arousal (SMD = -0.31), and the presence of a significant other increased facial expression of pain (SMD = 0.21). We further found verbal support to decrease pain (SMD = -0.69) and arousal (SMD = -0.99), and we demonstrated moderate to large analgesic effects of intimate relationships through touching (SMD = -0.95) and viewing (SMD = -0.60) of a romantic partner. Finally, we presented evidence of publication bias for pain-related arousal but not for behavioural pain outcomes. Together, our findings suggest that the impact of social support on pain is context-dependent with the verbal communication of support and intimate relationships being of particular importance.

Growth of Au and ZnS nanostructures via engineered peptide and M13 bacteriophage templates.

We demonstrate directed nucleation of Au and ZnS patterns on templates comprised of functional peptides and an M13 bacteriophage. We discuss the control over nucleation in terms of the interplay between enhanced ion binding and reduced interfacial energy resulting from the presence of the templates.

Spontaneous and applied potential driven indium recovery on carbon electrode and crystallization using a bioelectrochemical system.

Indium removal and recovery on a carbon electrode under a microbial fuel cell (MFC)-based oxidation/reduction reaction were examined using synthetic wastewater. More than 90% of In3+ ions were removed after continuous operation of the MFC for 14 days with an average current generation of ∼50 µA. During operation, indium particulates formed on the cathode carbon electrode. Scanning electron microscopy equipped with X-ray energy dispersive spectroscopy showed that they were composed of amorphous and crystalline indium hydroxides (In(OH)3 and In(OH)·H2O). When the current flow was reversed to drive the oxidation of the particles to recover the indium from indium hydroxides, a few indium oxide (In2O3) nanocrystals with a rectangular platelet shape formed on the electrode, while the majority of the amorphous and crystalline indium hydroxides re-dissolved into the aqueous environment. Overall, these results demonstrate a feasible route towards the MFC-based recovery of indium with the simultaneous generation of bioelectricity.

The dynamics and energetics of matrix assembly and mineralization.

Formation of biominerals commonly occurs within the context of an organic matrix composed of proteins, polysaccharides, and other macromolecules. Much has been learned about the structure of matrices and the spatial and molecular relationships between matrix and mineral. Only recently has quantitative study of matrix organization and subsequent mineralization been pursued. Here, we review findings from physical studies of matrix assembly in the system of microbial S-layer proteins and of calcium carbonate nucleation on organic templates composed of organothiol self-assembled monolayers on noble metals. Studies on S-layers reveal the importance of multistage assembly pathways and kinetic traps associated with the conformational transformations required to build the basic oligomeric building blocks of the matrix. Experimental investigations of calcium carbonate nucleation on carboxyl-terminated self-assembled monolayers combined with theoretical analyses demonstrate the applicability of classical concepts of nucleation, even when cluster-aggregation pathways are considered, and reveal the underlying energetic and structural source of matrix control over the process. Taken together, these studies highlight the ways in which matrix assembly and mineralization deviate from our classical concepts of crystallization but clearly demonstrate that the concepts of physical chemistry that date back to the days of Gibbs and Ostwald still serve us well in understanding the nucleation and growth of organic matrices and mineral phases.

Direct observation of kinetic traps associated with structural transformations leading to multiple pathways of S-layer assembly.

The concept of a folding funnel with kinetic traps describes folding of individual proteins. Using in situ Atomic Force Microscopy to investigate S-layer assembly on mica, we show this concept is equally valid during self-assembly of proteins into extended matrices. We find the S-layer-on-mica system possesses a kinetic trap associated with conformational differences between a long-lived transient state and the final stable state. Both ordered tetrameric states emerge from clusters of the monomer phase, however, they then track along two different pathways. One leads directly to the final low-energy state and the other to the kinetic trap. Over time, the trapped state transforms into the stable state. By analyzing the time and temperature dependencies of formation and transformation we find that the energy barriers to formation of the two states differ by only 0.7 kT, but once the high-energy state forms, the barrier to transformation to the low-energy state is 25 kT. Thus the transient state exhibits the characteristics of a kinetic trap in a folding funnel.

Multilayered nanofibers from stacks of single-molecular thick nanosheets of hexakis(alkoxy)triphenylenes.

Symmetrically substituted hexakis(alkoxy)triphenylene (HAT) derivatives were assembled into single molecular thick 2D nanosheets, which stacked further to give multilayered nanofibers through a convenient solution process. Detailed information on molecular arrangement was unraveled by various imaging techniques and diffraction studies.

Self-catalyzed growth of S layers via an amorphous-to-crystalline transition limited by folding kinetics.

The importance of nonclassical, multistage crystallization pathways is increasingly evident from theoretical studies on colloidal systems and experimental investigations of proteins and biomineral phases. Although theoretical predictions suggest that proteins follow these pathways as a result of fluctuations that create unstable dense-liquid states, microscopic studies indicate these states are long-lived. Using in situ atomic force microscopy to follow 2D assembly of S-layer proteins on supported lipid bilayers, we have obtained a molecular-scale picture of multistage protein crystallization that reveals the importance of conformational transformations in directing the pathway of assembly. We find that monomers with an extended conformation first form a mobile adsorbed phase, from which they condense into amorphous clusters. These clusters undergo a phase transition through S-layer folding into crystalline clusters composed of compact tetramers. Growth then proceeds by formation of new tetramers exclusively at cluster edges, implying tetramer formation is autocatalytic. Analysis of the growth kinetics leads to a quantitative model in which tetramer creation is rate limiting. However, the estimated barrier is much smaller than expected for folding of isolated S-layer proteins, suggesting an energetic rationale for this multistage pathway.

Scanning probe-based fabrication of 3D nanostructures via affinity templates, functional RNA, and meniscus-mediated surface remodeling.

Developing generic platforms to organize discrete molecular elements and nanostructures into deterministic patterns on surfaces is one of the central challenges in the field of nanotechnology. Here we review three applications of the atomic force microscope (AFM) that address this challenge. In the first, we use two-step nanografting to create patterns of self-assembled monolayers (SAMs) to drive the organization of virus particles that have been either genetically or chemically modified to bind to the SAMs. Virus-SAM chemistries are described that provide irreversible and reversible binding, respectively. In the second, we use similar SAM patterns as affinity templates that have been designed to covalently bind oligonucleotides engineered to bind to the SAMs and selected for their ability to mediate the subsequent growth of metallic nanocrystals. In the final application, the liquid meniscus that condenses at the AFM tip-substrate contact is used as a physical tool to both modulate the surface topography of a water soluble substrate and guide the hierarchical assembly of Au nanoparticles into nanowires. All three approaches can be generalized to meet the requirements of a wide variety of materials systems and thereby provide a potential route toward development of a generic platform for molecular and materials organization.

Physical controls on directed virus assembly at nanoscale chemical templates.

Viruses are attractive building blocks for nanoscale heterostructures, but little is understood about the physical principles governing their directed assembly. In situ force microscopy was used to investigate organization of Cowpea Mosaic Virus engineered to bind specifically and reversibly at nanoscale chemical templates with sub-30 nm features. Morphological evolution and assembly kinetics were measured as virus flux and inter-viral potential were varied. The resulting morphologies were similar to those of atomic-scale epitaxial systems, but the underlying thermodynamics was analogous to that of colloidal systems in confined geometries. The 1D templates biased the location of initial cluster formation, introduced asymmetric sticking probabilities, and drove 1D and 2D condensation at sub-critical volume fractions. The growth kinetics followed a t(1/2) law controlled by the slow diffusion of viruses. The ability of poly(ethylene glycol) (PEG) to induce the lateral expansion of virus clusters away from the 1D templates suggests a significant role for weak interactions.

Hybrid organic-inorganic, rod-shaped nanoresistors and diodes.

The electrical properties of template-synthesized three- and four-component rodlike nanostructures consisting of metal and conducting polymer domains have been studied. These structures behave like nanometer-scale resistors and diodes, depending upon their compositions and spatial distribution of the different compositional blocks. In the two-component systems, the conducting polymer block dictates the electrical properties of the nanostructure, and the metal blocks act as leads to facilitate the connection with microscopic circuits. In the three-component systems, the metal blocks provide an additional design flexibility, allowing one to prepare Schottky junctions.

Self-assembly of mesoscopic metal-polymer amphiphiles.

The assembly properties of two- and three-component rod-like building blocks consisting of gold and polymer block domains have been investigated. These structures behave like mesoscopic amphiphiles and form a series of single-layer superstructures consisting of bundles, tubes, and sheets depending upon the compositional periodicity. Unlike molecular systems, the template used to initially synthesize them plays a critical role in the assembly process by prealigning them in a manner that facilitates their assembly by optimizing the correct collisional orientation upon dissolution of the template. Tubular structures with tailorable diameters can be assembled in a predictable manner on the basis of an estimate of the hybrid rod packing parameters.