Effect of an inhibitor on high-speed turbulent flames and the transition to detonation

The influence of an inhibitor (CF₃Br or Halon 1301) on the propagation of high-speed turbulent flames, quasi-detonations and the transition to detonation has been investigated for methane-air, propane-air and acetylene-air mixtures. The experiments are carried out in a 13 m tube (15 cm diameter) filled with regularly spaced orifice plates (blockage ratio of 0.39) to ensure rapid flame acceleration. In all cases, the addition of the inhibitor reduces the turbulent flame velocity and extinguishes the flame with sufficient inhibitor concentration (2.7% and 7.5% for methane-air and propane-air, respectively). For acetylene-air mixtures, the quasi-detonation speed is progressively reduced with increasing inhibitor concentration and eventually causes the failure of the quasi-detonation and transition back to a fast turbulent flame. The inhibitor also narrows the propagation limits in all cases. To elucidate the inhibition mechanism, detailed modelling of both the turbulent flame structure as well as the chemical kinetics are required.     

Regulating Molecular Recognition with C‐Shaped Strips Attained by Chirality‐Assisted Synthesis

Chirality‐assisted synthesis (CAS) is a general approach to control the shapes of large molecular strips. CAS is based on enantiomerically pure building blocks that are designed to strictly couple in a single geometric orientation. Fully shape‐persistent structures can thus be created, even in the form of linear chains. With CAS, selective recognition between large host and guest molecules can reliably be designed de novo. To demonstrate this concept, three C‐shaped strips that can embrace a pillar[5]arene macrocycle were synthesized. The pillar[5]arene bound to the strips was a better host for electron‐deficient guests than the free macrocycle. Experimental and computational evidence is provided for these unique cooperative interactions to illustrate how CAS could open the door towards the precise positioning of functional groups for regulated supramolecular recognition and catalysis.     

Effect of substitution of blast-furnace slag by fired drinking water sludge on the properties of pozzolanic cement pastes

Journal of Thermal Analysis and Calorimetry - The effect of fired drinking water sludge (FDWS) as a mineral admixture on the physico-mechanical properties and the fire resistance of pozzolanic...     

Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex

Spirocyclic oxindoles undergo an enantioselective oxygenation reaction (nine examples; e.r. up to 97:3) upon catalysis by a chiral ruthenium porphyrin complex (1 mol %). The catalyst exhibits a lactam ring, which is responsible for substrate association through hydrogen bonds, and an active ruthenium center, which is in a defined spatial relationship to the oxygenation substrate. DFT calculations illustrate the perfect alignment of the active site with the reactive C? H bond and suggest—in line with the kinetic isotope effect—an oxygen rebound mechanism for the reaction.     

Amorphous Silicon: New Insights into an Old Material

Amorphous silicon is synthesized by treating the tetrahalosilanes SiX₄ (X=Cl, F) with molten sodium in high boiling polar and non‐polar solvents such as diglyme or nonane to give a brown or a black solid showing different reactivities towards suitable reagents. With regards to their technical relevance, their stability towards oxygen, air, moisture, chlorine‐containing reaction partners RCl (R=H, Cl, Me) and alcohols is investigated. In particular, reactions with methanol are a versatile tool to deliver important products. Besides tetramethoxysilane formation, methanolysis of silicon releases hydrogen gas under ambient conditions and is thus suitable for a decentralized hydrogen production; competitive insertion into the MeO?H versus the Me?OH bond either yields H‐ and/or methyl‐substituted methoxy functional silanes. Moreover, compounds, such as Me_nSi(OMe)_4?n (n=0–3) are simply accessible in more than 75 % yield from thermolysis of, for example, tetramethoxysilane over molten sodium. Based on our systematic investigations we identified reaction conditions to produce the methoxysilanes Me_nSi(OMe)_4?n in excellent (n=0:100 %) to acceptable yields (n=1:51 %; n=2:27 %); the yield of HSi(OMe)₃ is about 85 %. Thus, the methoxysilanes formed might possibly open the door for future routes to silicon‐based products.     

Further Studies with Ethyl 5‐Amino‐3‐phenyl‐lH‐pyrazole‐4‐carboxylate1

The newly synthesized ethyl 3‐amino‐5‐phenylpyrazole‐4‐carboxylate 1 was diazotized and coupled with β‐naphthol, active methylene reagents 6 , 9 , 12 , 15 , and the active methine 19 to afford the pyrazolo[5,1‐c]triazines 5 , 8 , 11 , 14 , 17 , 18 , and the pyrazolo[5,1‐ c ]‐1,2,4‐triazoles 21 , 22 , and 23 , respectively. Structures are elucidated and mechanisms are discussed.     

Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al(2)O(3)) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.     

Minimising reversion, using seawater and magnesium chloride, caused by the dissolution of tricalcium aluminate hexahydrate

The increase in pH and aluminium concentration after the neutralisation of bauxite refinery residues is commonly known as reversion. This investigation reports the extent of reversion in synthetic supernatant liquor and possible methods to reduce reversion. This work is based on bauxite refinery residues produced from alumina refineries, where reversion is a real life situation in neutralised refinery residues. Tricalcium aluminate hexahydrate, a common phase in bauxite refinery residues, has been found to cause reversion. It has been established that reductions in both pH and aluminium from the seawater neutralisation process are due to the formation of 'Bayer' hydrotalcite Mg(7)Al(2)(OH)(18)(CO(3)(2-),SO(4)(2-))·xH(2)O. This is the primary mechanism involved in the removal of aluminium from solution. Increasing the volume of seawater used for the neutralisation process minimises the extent of reversion for both synthetic supernatant liquor and red mud slurry. The addition of MgCl(2)·6H(2)O also showed a reduction in reversion and confirmed that the decrease in aluminium and hydroxyl ions is due to the formation of Bayer hydrotalcite and not simply a dilution effect.