Oxidation of pentan-2-ol – part II: Experimental and modeling study

The oxidation of pentan-2-ol was investigated at high-pressure in a jet-stirred reactor and in a shock tube. Experiments in the JSR were carried out at 10 atm, between 500 and 1180 K, for five different equivalence ratios of φ = 0.35, 0.5, 1, 2, 4 and 1000 ppm of fuel, at a constant residence time of 0.7 s. Reactant, product and intermediate species mole fractions were quantified using Fourier transform infrared spectrometry (FTIR) and gas chromatography (GC). Ignition delay times were measured for pentan-2-ol/O₂ mixtures in argon in a shock tube at 20 and 40 bar, in a temperature range of 1070–1460 K and for equivalence ratios of φ = 0.5, 1 and 2. Ignition delay times of a stoichiometric mixture were also measured in air at 20 bar. Under these conditions, this alcohol exhibited no low-temperature reactivity in either experimental set-ups. Based on ab initio calculations presented in the companion paper, a detailed kinetic mechanism was developed in order to reproduce the present data and analyze the reaction pathways.     

A note on two-person zero-sum communicating stochastic games

For undiscounted two-person zero-sum communicating stochastic games with finite state and action spaces, a solution procedure is proposed that exploits the communication property, i.e., working with irreducible games over restricted strategy spaces. The proposed procedure gives the value of the communicating game with an arbitrarily small error when the value is independent of the initial state.     

Synthesis of silver(I) and palladium(II) <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene complexes and their use as catalysts for the direct C5 arylation of heteroaromatic compounds

Silver(I) N-heterocyclic carbene complexes were synthesized in good yields by the reactions of 1,3-dialkylperhydrobenzimidazolium salts with silver(I) oxide in dichloromethane. The silver complexes were used as carbene-transfer agents to synthesize palladium(II) N-heterocyclic carbene complexes. All of the complexes were characterized by physicochemical and spectroscopic methods. The new palladium complexes were tested as catalysts in the direct C5 arylation of 2-n-butylfuran, 2-n-butylthiophene and 2-n-propylthiazole with aryl bromides at 130 °C in N,N-dimethylacetamide. The arylation reactions proceeded selectively at the C5 position of the heteroaromatic compounds, and the corresponding coupling products were obtained in moderate to good yields by using 0.5 mol% of the palladium complex.     

5'-Tethered stilbene derivatives as fidelity- and affinity-enhancing modulators of DNA duplex stability

A series of 5'-linked stilbene-DNA conjugates with different substituents in the distal aromatic ring of the stilbene was prepared, and the effect of the modifications on duplex stability was determined via UV-melting curves. A trimethoxystilbene derivative as a 5'-substituent increases duplex melting points by up to 12.2 degrees C per modification. With this alkoxystilbene substituent, terminal mismatches in DNA duplexes lower the melting point by up to 23.4 degrees C over the perfectly matched control, whereas terminal mismatches in unmodified DNA cause melting point depressions of no more than 6.1 degrees C. An aminomethylstilbene substituent linked to an oligopyrrolamide minor groove binder increases the melting point of an all-A/T decamer by up to 32.7 degrees C, thus shifting the melting point into a range typical for duplexes with statistical G/C-content. An affinity- and selectivity-enhancing effect was also observed when the trimethoxystilbene cap was employed on a small DNA microarray. The phosphoramidite of the trimethoxystilbene can be readily employed in automatic DNA synthesis, facilitating the generation of DNA chips with improved fidelity.     

Bioinspired Multi-Layer Biopolymer-Based Dental Implant Coating for Enhanced Osseointegration

The major drawbacks of metal-based implants are weak osseointegration and post-operational infections. These limitations restrict the long-term use of implants that may cause severe tissue damage and replacement of the implant. Recent strategies to enhance the osseointegration process require an elaborate fabrication process and suffer from post-operative complications. To address the current challenges taking inspiration from the extracellular matrix (ECM), the current study is designed to establish enhanced osseointegration with lowered risk of infection. Natural biopolymer pectin, peptide amphiphiles, and enzyme-mimicking fullerene moieties are governed to present an ECM-like environment around the implant surfaces. This multifunctional approach promotes osseointegration via inducing biomineralization and osteoblast differentiation. Application of the biopolymer-based composite to the metal surfaces significantly enhances cellular attachment, supports the mineral deposition, and upregulates osteoblast-specific gene expression. In addition to the osteoinductive properties of the constructed layers, the inherent antimicrobial properties of multilayer coating are also used to prevent infection possibility. The reported biopolymer-artificial enzyme composite demonstrates antimicrobial activity against Escherichia coli and Bacillus subtilis as a multifunctional surface coating.     

The smart meter and a smarter consumer: quantifying the benefits of smart meter implementation in the United States

The electric grid in the United States has been suffering from underinvestment for years, and now faces pressing challenges from rising demand and deteriorating infrastructure. High congestion levels in transmission lines are greatly reducing the efficiency of electricity generation and distribution. In this paper, we assess the faults of the current electric grid and quantify the costs of maintaining the current system into the future. While the proposed "smart grid" contains many proposals to upgrade the ailing infrastructure of the electric grid, we argue that smart meter installation in each U.S. household will offer a significant reduction in peak demand on the current system. A smart meter is a device which monitors a household's electricity consumption in real-time, and has the ability to display real-time pricing in each household. We conclude that these devices will provide short-term and long-term benefits to utilities and consumers. The smart meter will enable utilities to closely monitor electricity consumption in real-time, while also allowing households to adjust electricity consumption in response to real-time price adjustments.     

Constructing isothermal curvature line coordinates on surfaces which admit them

Isothermic parameterizations are synonyms of isothermal curvature line parameterizations, for surfaces immersed in Euclidean spaces. We provide a method of constructing isothermic coordinate charts on surfaces which admit them, starting from an arbitrary chart. One of the primary applications of this work consists of numerical algorithms for surface visualization.     

The relationship between mathematical problem-solving skills and self-regulated learning through homework behaviours,motivation, and metacognition

Studies highlight that using appropriate strategies during problem solving is important to improve problem-solving skills and draw attention to the fact that using these skills is an important part of students’ self-regulated learning ability. Studies on this matter view the self-regulated learning ability as key to improving problem-solving skills. The aim of this study is to investigate the relationship between mathematical problem-solving skills and the three dimensions of self-regulated learning (motivation, metacognition, and behaviour), and whether this relationship is of a predictive nature. The sample of this study consists of 323 students from two public secondary schools in Istanbul. In this study, the mathematics homework behaviour scale was administered to measure students’ homework behaviours. For metacognition measurements, the mathematics metacognition skills test for students was administered to measure offline mathematical metacognitive skills, and the metacognitive experience scale was used to measure the online mathematical metacognitive experience. The internal and external motivational scales used in the Programme for International Student Assessment (PISA) test were administered to measure motivation. A hierarchic regression analysis was conducted to determine the relationship between the dependent and independent variables in the study. Based on the findings, a model was formed in which 24% of the total variance in students’ mathematical problem-solving skills is explained by the three sub-dimensions of the self-regulated learning model: internal motivation (13%), willingness to do homework (7%), and post-problem retrospective metacognitive experience (4%).     

Synthesis and photopolymerization of new dental monomers from o‐hydroxyaryl phosphonates

Novel aromatic mono‐ and diphosphonate monomers based on t‐butyl α‐bromomethacrylate were prepared for use in dental composites. The synthesis of the two monomers involved three steps: the reaction of diethyl phosphite with phenol or hydroquinone, the rearrangement of the resulting phosphate derivatives into o‐hydroxyaryl phosphonates with lithium diisopropylamide, and the reaction of o‐hydroxyaryl phosphonates with t‐butyl α‐bromomethacrylate. Then, the selective hydrolysis of the t‐butyl ester groups of the monomers with trifluoroacetic acid gave the other carboxylic acid containing monomers. The photopolymerization behaviors of the synthesized monomers with glycerol dimethacrylate and triethylene glycol dimethacrylate were investigated with photodifferential scanning calorimetry at 40 °C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as the photoinitiator. The hydrolysis of the t‐butyl groups of the monomers increased the reactivity and the rates of polymerization of the monomers. The mixtures of the acid monomers showed rates of polymerizations similar to those of homopolymerizations of triethylene glycol dimethacrylate and glycerol dimethacrylate. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6775–6781, 2006     

Chain Sliding versus β-Sheet Formation upon Shearing Single α-Helical Coiled Coils

Coiled coils (CCs) are key building blocks of biogenic materials and determine their mechanical response to large deformations. Of particular interest is the observation that CC-based materials display a force-induced transition from α-helices to mechanically stronger β-sheets (αβT). Steered molecular dynamics simulations predict that this αβT requires a minimum, pulling speed-dependent CC length. Here, de novo designed CCs with a length between four to seven heptads are utilized to probe if the transition found in natural CCs can be mimicked with synthetic sequences. Using single-molecule force spectroscopy and molecular dynamics simulations, these CCs are mechanically loaded in shear geometry and their rupture forces and structural responses to the applied load are determined. Simulations at the highest pulling speed (0.01 nm ns⁻¹) show the appearance of β-sheet structures for the five- and six-heptad CCs and a concomitant increase in mechanical strength. The αβT is less probable at a lower pulling speed of 0.001 nm ns⁻¹ and is not observed in force spectroscopy experiments. For CCs loaded in shear geometry, the formation of β-sheets competes with interchain sliding. β-sheet formation is only possible in higher-order CC assemblies or in tensile-loading geometries where chain sliding and dissociation are prohibited.