Regioselective S-allylation of thiols with cyclic Baylis–Hillman acetates

An efficient and mild S-allylation of thiols with cyclic Baylis–Hillman acetates with no need of a transition-metal-catalyst or an expensive additive is described. Allyl sulfides are prepared in good to excellent yields (60–97%) and a single regioisomer was observed in all cases.absfigure{gsrp809453ab01}     

One-pot synthesis of allyl thioacetate from benzaldehydes and activated alkenes using the Morita–Baylis–Hillman reaction as a key step

An efficient, regioselective and steresoselecitive one-pot protocol for the synthesis of (Z)-S-2-alkoxycarbonyl-3-acylallyl ethanethioates and (E)-S-2-cyano-3-acylallyl ethanethioates from benzaldehydes and activated alkenes (methyl acrylate and acrylonitrile) was developed. Our method consisted of Morita–Baylis–Hillman reaction of benzaldehydes and activated alkenes using DABCO followed by acetylation using acetic anhydride and a catalytic amount of DMAP, and S_N2′ reaction with potassium thioacetate in DMF. The first two reactions proceeded under solvent-free condition.     

Effects of uniaxial stress on alkali–silica reaction induced expansion of concrete

asr affected concrete in real structures is usually subject to loads which affect the macroscopic expansion of the material. An experimental study was undertaken using sensors embedded in reactive and non-reactive samples loaded on modified creep frames. Numerical analysis was used to link micro-structural damage under the load to expansion. We show that load influences the micro-crack propagation, which changes the shape of the expansion curve.     

Effects of strain rate and temperature on compressive strength and fragment size of ZrB2–SiC–graphite composites

The quasi-static (strain rate of 10⁻⁴ s⁻¹) and dynamic compression experiments (strain rate of 200–1500 s⁻¹) of ZrB₂–SiC–graphite composites are conducted at 293 K and 1073 K. The initial compressive strength and Weibull modulus are calculated to handle the discrete quasi-static experimental data. Considering effects of strain rate and temperature, the compressions of ZrB₂–SiC–graphite composites are investigated. The results show that both compressive strength and fragment size are higher at 1073 K than those at room temperature. The compressive strengths increase with increasing strain rate at room temperature and 1073 K, whereas fragment sizes decrease. Moreover, a micromechanical model is utilized to characterize the effect of strain rate on the compressive strength. The predictions of this micromechanical model are good agreement with the experimental results. Meanwhile, the fragment sizes of dynamic compressive specimens are analyzed through analytical approaches.     

The Effects of Nectar–Nicotine on Colony Fitness of Caged Honeybees

Nectar of many bee flowers contains secondary compounds, which are considered toxic for honeybees on repeated exposure. Although many anecdotal reports indicate the toxicity of secondary compounds to bees, only a few studies have tested the extent of toxicity at different honeybee ages, especially at the larval stages. Honeybees encounter nicotine at trace concentrations (between 0.1 and 5 ppm) in floral nectar of a few Nicotiana spp. and in Tilia cordata. Adult honeybee workers tolerate these nicotine concentrations. In controlled nonchoice feeding experiments with caged bees, we investigated the effect of nicotine on hatching success and larval and forager survival. Naturally occurring concentrations of nectar–nicotine did not affect hatching success of larvae or their survival, but the latter was negatively affected by higher concentrations of nicotine (50 ppm). Concentrations of nicotine in fresh honey samples from the hives were 90% lower than the concentrations in the offered experimental sucrose solutions. Our results indicate that honeybees can cope with naturally occurring concentrations of nicotine, without notable mortality, even when consumed in large quantities for more than 3 weeks.     

The effects of solvents on the formation of sol–gel-derived Bi12SiO20 thin films

The sol–gel method was used to synthesize Bi₁₂SiO₂₀ thin films. Two synthesis routes with two different solvents, i.e., 2-ethoxyethanol and acetic acid, were used and compared. Thin films were deposited onto Pt/TiO₂/SiO₂/Si substrates by spin-coating at 3000 rpm and annealed at 700 °C for 1 h. A different coordination of the bismuth ion was observed in the sols prepared with acetic acid (AcOH), and as a result, stable sols were formed with a shorter gelation time t_G = 84 h (c = 0.76 M), when compared with the sols prepared from 2-ethoxyethanol (EtoEtOH) t_G = 580 h (c = 0.76 M). The microstructures of the Bi₁₂SiO₂₀ thin films prepared from sols using EtoEtOH were homogeneous and dense. On the other hand, a porous microstructure was observed for the Bi₁₂SiO₂₀ thin films deposited from the sol in which AcOH was used as the solvent.     

The Dynamics of Carbon–Nutrient Balance: Effects of Cottonwood Acclimation to Short- and Long-Term Shade on Beetle Feeding Preferences

The carbon–nutrient balance hypothesis (CNBH) predicts that shading should increase leaf palatability to herbivores by decreasing concentrations of carbon (C) -based chemical defenses and increasing nitrogen (N). We measured cottonwood (Populus deltoids) growth, leaf chemistry, and beetle (Plagiodera versicolora) feeding preferences on saplings grown in either continuous high (HH) or low (LL) light, and saplings switched from high to low (HL) or low to high (LH) light for nine days. As expected, based on the CNBH, shading increased total N and decreased total phenol glycoside (C-based secondary metabolites) concentrations in plants from all shade treatments (LL, HL, and LH), relative to HH plants, with plant growth and gross leaf chemistry being affected by initial and final light regime. In contrast, while specific phenol glycoside concentrations were affected by the initial and final light regime, they also showed an initial × final light interaction. Beetles tended to prefer LL to HH plants. Beetles unexpectedly preferred HH to either HL or LH switched plants, most likely because high concentrations of a specific phenol glycoside – salicin – occurred in both switched treatments and inhibited beetle feeding. Plant chemical allocation during light acclimation led to unpredictable changes in specific C-based compounds, even though plant growth and gross chemistry conformed to expectations for shading effects and the CNBH. The response of this herbivore to altered concentrations of a specific compound confounded predictions based on average dynamics of suites of chemicals. Our findings may help explain why relationships between light availability and herbivory in field studies, where light varies on many time scales, can differ from those predicted by the CNBH. Understanding both dynamic plant chemical responses to altered resource availability and controls over allocation to specific compounds would likely enhance future predictability of specific environment-plant-herbivore interactions.     

The Meerwein–Ponndorf–Verley–Oppenauer reaction between 2-hexanol and cyclohexanone on magnesium phosphates

Various magnesium phosphates were tested as catalysts for the vapour-phase Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reaction between 2-hexanol and cyclohexanone. Some of the solids studied are as selective as MgO in this reaction. Others are also active in the dehydration of the alcohols. The activity and selectivity of the catalysts are related to their structure and surface chemical properties. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of electrolyte flow rate and temperature on corrosion and protection of Al–2.5 Mg alloy by (+)-catechin

The effects of flow rate and temperature on the corrosion behaviour of the Al–2.5 Mg alloy in a 3% NaCl solution and the inhibiting efficiency of (+)-catechin on the corrosion of the same alloy have been examined. Measurements were carried out in a flow-through cell, at different flow rates (v ₁ = 0.0029 m s⁻¹, v ₂ = 0.0059 m s⁻¹ and v ₃ = 0.0118 m s⁻¹) and temperatures (20, 30, 40 °C). Electrochemical parameters for the Al–2.5 Mg alloy were determined by polarisation techniques and electrochemical impedance spectroscopy (EIS). Increased flow rate and temperature cause a stronger corrosion attack on the alloy. The addition of (+)-catechin inhibited corrosion at all temperatures and flow rates. The inhibitor efficiency decreased with increase in flow rate and temperature.     

Effects of Ga content and reaction pressure upon the aromatization of propane over H–Ga–Al-bimetallosilicate catalysts

Aromatization of propane has been investigated at 540 °C in a reaction pressure range up to 0.686 MPaG over MFI-type H–Ga–Al-bimetallosilicates having various Ga/(Ga + Al) atomic ratios but a constant Si/(Ga + Al) ratio of 15. Both the propane conversion and the aromatic selectivity increased with increasing the Ga/(Ga + Al) ratio up to 0.25. Further increase in the Ga content decreased the propane conversion, although the aromatic selectivity increased. Of the catalysts examined, the H–Ga–Al-bimetallosilicate sample having the Ga/(Ga + Al) ratio of 0.25 showed the highest performance for propane aromatization. The effect of reaction pressure was investigated using this catalyst. With increasing the reaction pressure, the propane conversion increased, but the aromatic selectivity decreased. The reaction pressure was also found to strongly influence the cracking activity and the deactivation rate of the catalyst. From the analysis of the gaseous products, it was concluded that the aromatization reaction was suppressed under high reaction pressure conditions because of the formation of methane and ethane by protolytic cracking and hydrogen transfer from aromatic precursors to olefinic intermediates.     

The effect of grinding process on mechanical properties and alkali–silica reaction resistance of fly ash incorporated cement mortars

The effect of fineness of fly ash on mechanical properties and alkali–silica reaction resistance of cement mortar mixtures incorporating fly ash has been investigated within the scope of this study. Blaine fineness of fly ash has been increased to 907 m²/kg from its original 290 m²/kg value by a ball mill. Test samples were prepared by replacing cement 20, 40 and 60%, with finer and coarser fly ashes and kept under standard and steam curing conditions until testing. Test results showed that grinding process improved the mechanical properties of all samples significantly. The beneficial effect of grinding fly ash, may increase utilization of this by-product in precast and ready-mix concrete industries. Incorporation of fly ash with different fineness values and ratios also decreased the expansions to harmless levels of cement mortars due to alkali–silica reaction.     

The chemical-enzymatic preparation and resolution of β-naphthyl alcohol

通过化学-酶相耦合的方法,成功制备出e.e.值>99%的S-β-萘乙醇,使其光学纯度达到了制备R-2-萘乙胺的要求。研究中以β-萘乙酮为原料,经硼氢化钠还原得到外消旋的β-萘乙醇。经过酶催化动力学拆分,β-萘乙醇中R型底物100%全转化为酯,S构型底物型被保留,这样体系中S构型底物的e.e.值达到近100%。本文还考察了若干因素对酶催化动力学拆分过程的影响,并最终确定了酶催化动力学拆分β-萘乙醇制备S-β-萘乙醇的最适条件：反应温度45 ℃,溶液为甲苯,底物浓度为100 mmol/L。     

The high temperature reaction of ammonia with carbon and SiC–C ceramics

This contribution aimed at developing a treatment under ammonia in order to eliminate free carbon from the surface of SiC-based fine ceramics like fibers or coatings. The reaction of NH₃ with graphitic and non-graphitic carbon was first investigated through kinetic measurements, in situ gas phase analysis and physicochemical investigations of the solid. The carbon etching rate is controlled by heterogeneous reactions involving active sites arising from bulk structural defects and the formation of HCN. A selection of SiC-based fibers and coatings with various carbon contents and (micro)structures was treated in ammonia in favorable conditions. The analyses of the tested SiC–C specimens revealed a reduction of the free carbon content and, simultaneously, a nitridation of the initial Si–C–(O) continuum over a reaction layer. The growth rate, composition and the volume change of this layer vary with the initial microstructure. The ammonia treatment is able to restore the adhesion of carbon-contaminated surfaces.     

Development of a filtered reaction rate model for reactive gas–solid flows based on fine-grid simulations

The filtered reaction rate for the coarse-grid simulations of reactive gas–solid flows can be obtained via a correction to its microscopic reaction rate. The correction term is defined as the mesoscale effectiveness factor η_Δ , which is the ratio of the reaction rate obtained from the fine-grid simulations to that obtained from the coarse-grid simulations. The considered reaction is an isothermal, solid-catalyzed surface reaction with a power law reaction rate model. The simulation results show that the mean η_Δ is almost invariant with the reaction orders at the same Damköhler number. A closure correlation for the mean η_Δ is formulated. However, the standard deviation of η_Δ is found to be quite large. A presumed probability density function model is proposed to capture the fluctuating properties of η_Δ . The predictability of the closure correlations are evaluated via performing the filtered two fluid model simulations in circulating fluidized beds of ozone decomposition.     

Alkali–silica reaction: Current understanding of the reaction mechanisms and the knowledge gaps

Alkali–silica reaction (ASR) is a major concrete durability problem, resulting in significant maintenance and reconstruction costs to concrete infrastructures all over the world. Despite decades of study, the underlying chemical and physical reaction mechanisms remain poorly understood, especially at molecular to micro-scale levels, and this has resulted in the inability to efficiently assess the risk, predict the service life, and mitigate deterioration in ASR-susceptible structures. This paper intends to summarize the current state of understanding and the existing knowledge gaps with respect to reaction mechanisms and the roles of aggregate properties (e.g., composition, mineralogy, size, and surface characteristics), pore solution composition (e.g., pH, alkalis, calcium, aluminum), and exposure conditions (e.g., temperature, humidity) on the rate and magnitude of ASR. In addition, the current state of computer modeling as an alternative or supplement to physical testing for prediction of ASR performance is discussed.     

Effects of Ca-, Mg- and Si-doping on microstructures of alumina–zirconia composites

The aim of this work was to obtain zirconia toughened alumina composites with different microstructures, using a simple process (powder mixing and natural sintering). Adjusting the amount of zirconia directly controls the size and localization of zirconia grains and the size of the alumina grains. Doping the composite with CaO, MgO and SiO₂ allows further control of the microstructures. The influence of the thermal treatments is also investigated. The composites exhibit different structures (nano/nano-, micro/nano- and micro-composites) with zirconia and alumina grains as small as 100 and 200 nm, respectively, and with the proportion of intragranular zirconia grains varying between 0% and 90%. Zirconia plays a major role on grain size distributions as compared to CaO and MgO, whose role is almost negligible. The use of SiO₂ leads to micro/nano composites with intragranular zirconia particles. The influence of these different additions is related to adjustments of the grain boundaries mobility.     

The effect of stator geometry on the flow pattern and energy dissipation rate in a rotor–stator mixer

The effect of stator geometry on the flow pattern and energy dissipation rate in a batch rotor–stator mixer has been investigated using sliding mesh method with standard k–? turbulence model. It has been found that for the stators with narrow openings (small width-to-depth ratio) the liquid at certain distance from stator rotated in the opposite direction to the rotor rotation. This opposite rotation was induced by the strong circulation flows behind the jets. The predicted power numbers for the stators with circular and square openings were about 10% lower than experimental data and the power number for stator with slot openings was about 20% lower. The simulation results showed that the power number was proportional to the total flowrate. For all stators, about 50–60% of energy supplied by the rotor dissipated in the rotor swept region and approximately 25% in the jet region. The fraction of energy dissipated in the hole region was 12–15% for stators with narrow opening and only 8% for stator with wide opening. The order of magnitude of energy dissipation rate in each region (rotor swept region, holes and jets) was practically the same for all stators; however, the distribution of energy dissipation rate in the hole was more uniform in stator with narrow openings.