Peculiar sandwich-like π–π interaction regulating the nonplanarity of the model heme crystals

X-ray crystallographic analysis of bis(pyridine N-oxide) complexes of iron(III) porphyrinates has revealed that the two pyridine rings of the axial ligands correctly sandwich the porphyrin ring to induce the deformation of commonly observed S₄ saddled porphyrin ring.     

Supramolecular π–π assembly of a neutral [Cu(salen)] complex via the templating effect of an ionic inorganic complex Na2[Cu(mnt)2] forming a framework type material having well-defined channels

A classical ionic inorganic complex Na₂[Cu(mnt)₂] (mnt²⁻ = maleonitriledithiolate = 1,2-dicyanoethylenedithiolate), that acts as a template in assembling neutral [Cu(salen)] (salen = bis(salicylidene)ethylenediamine) complexes forming a framework type arrangement, is accommodated in the channel formed in the crystal structure of a new type of host–guest compound [Cu(salen)]₄ · Na₂[Cu(mnt)₂] (1). The non-covalent supramolecular interactions among [Cu(salen)] complexes and between [Cu(salen)] and [Cu(mnt)₂]²⁻ complexes in the crystal lattice of 1 result in weak antiferromagnetic coupling.     

Selective and Practical Oxidation of Sulfides to Diastereopure Sulfoxides: A Combined Experimental and Computational Investigation

We describe an effective oxidation of diltiazem (DTZ)‐like molecules (a class of prochiral sulfides with potential pharmacological properties) using m‐chloroperbenzoic acid (MCPBA) as oxidant either in dichloromethane or methanol. An excellent diastereomeric excess of one sulfoxide has been observed “in the absence of any chiral auxiliary”. The stereochemistry of the two diastereomeric sulfoxides has been determined by TDDFT simulations of the experimental electronic circular dichroism (ECD) spectra. A computational DFT study of the reaction mechanism shows that the attack of MCPBA on the two sulfide enantiotopic faces affords two preliminary complexes M1 and M1′. M1 is more stable than M1′ by 3.3 and 3.5 kcal mol⁻¹ in dichloromethane and methanol, respectively, and after equilibration its population must be dominant. Two diastereomeric pathways originate from M1 and M1′ and give two diastereomeric sulfoxides with R and S configurations at the new chiral sulfur, respectively. Since TS (the transition state originating from M1 ) is more stable than TS′ (the energy gap is 0.7 kcal mol⁻¹ in dichloromethane or methanol), following the Curtin–Hammett principle, the favoured path is the pro‐R channel ( M1 → TS→M2 ) affording the (R_c,R_s)‐ 2a′ product species in agreement with the observed diastereoselectivity. The M1 – M1′ and TS – TS′ energy gaps are actually determined by the difference in the hydrogen bond network that features the two species even if the approaching orientation of the two molecules is governed by the interactions between the π systems of oxidant and substrate aromatic rings. The diastereomeric ratio computed on the basis of the energy difference between TS and TS′ (0.7 kcal mol⁻¹) is 63:37, which must be compared to the experimental value 9:1. When we consider free energy differences (2.4 kcal mol⁻¹ in vacuum and 2.9 kcal mol⁻¹ in solution) this theoretical ratio becomes 85:15 and 89:11, respectively, in excellent agreement with the experimental value 9:1.     

Correlation between viscosity and absorption of electromagnetic waves in an aqueous UNCD suspension

A model of ultrananocrystalline diamond (UNCD) particle in an aqueous suspension produced by a stirred-media milling process of detonation nanodiamonds has been suggested for the first time. This model is based on a hypothesis that surface of the single UNCD particle contains partly disconnected sp² hybridized carbon regions. These regions are formed due to the sp³–sp² phase transition on a surface of UNCD particle as result of local heating of that surface during the stirred-media milling process. Unusual high viscosity, UV–Vis absorption, black color in visible region of the UNCD suspension and difficulty of plasmon resonance absorption observation have been explained in the suggested model.

The percolation between the sp² regions has explained small conductivity of UNCD powder and suggests a dependence of the conductivity on conditions of the milling process.

Our model fits well with recent characterization of UNCD powder by NMR and computer simulation.     

Electro‐rheological properties of anhydrous ER suspensions based on phosphoric ester cellulose particles

The electro‐rheological (ER) behaviour of suspensions in silicone oil of phosphoric ester cellulose particles (average particle size 17.77 µm) was investigated at room temperature with electric fields up to 2.5 kV mm⁻¹ with the aim of developing anhydrous ER suspensions applicable over a wide temperature range. Anhydrous ER suspensions dispersing cellulose particles which were treated by phosphoric ester reaction of 2 mol phosphoric acid and 4 mol urea were measured; not only were the electrical characteristics such as dielectric constant, current density and electrical conductivity studied but also the rheological properties on the electric fields and volume fraction of dispersing particles. Anhydrous ER suspensions dispersing phosphoric ester cellulose particles showed very low current density, conductivity and very high performance of ER effect (τ_A/ τ₀ ≈ 1030) on the 2.5 kV mm⁻¹ electric field, and the yield stress (τ_y) had a quadratic dependence on electric fields. © 2000 Society of Chemical Industry     

A study of Cu(I)‐ethylene complexation for olefin–paraffin separation

The current cryogenic distillation technology used for olefin–paraffin separation incurs extensive capital and operating costs. An alternative olefin–paraffin separation process, based on reactive absorption, could yield significant cost reductions. The research efforts described herein explored the structural characteristics of an NMP‐CuCl‐aniline absorption solution with ethylene to aid future development of olefin–paraffin separation systems. Solution IR and ¹H NMR spectroscopy suggested weak and labile Cu(I)‐ethylene and Cu(I)‐aniline coordination, which point to the coexistence of multiple structures in solution. Experiments also revealed solvent‐dependent and temperature‐dependent coordination. The agreement of the collected spectral data with literature implied single ethylene coordination, whereas the Cl^? ion likely remained coordinated with Cu(I). Solvent interference prohibited detailed investigation of IR spectra, but ¹H NMR spectroscopy showed more promise as an analytical technique for the NMP‐CuCl‐aniline‐ethylene system. Finally, a tradeoff appears to exist between ethylene capacity and complex stability, and thus, an optimal ligand must be found that balances these two competing needs. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

An unusual dichromium(II,II) compound bearing di-2-pyridyl ketone oximate ligands and prepared by the ligand-assisted reduction of a trichromium(III,III,III) complex in air

The reaction of the oxide-centred triangular, trichromium(III,III,III) complex [Cr₃O(O₂CCMe₃)₆(H₂O)₃](O₂CCMe₃) with di-2-pyridyl ketone oxime, (py)₂CNOH, in MeCN under aerobic and refluxing conditions yields the pivalate-free, dichromium(II,II) complex [Cr₂{(py)₂CNO}₄] · 2H₂O (1 · 2H₂O). The dinuclear complex can also be prepared by the reaction of [Cr(CO)₆] with (py)₂CNOH in refluxing MeCN/H₂O in air. The two high-spin Cr^II atoms are doubly bridged by two 2.1110 oximate ligands, while a chelating 1.0110 (py)₂CNO⁻ ion completes distorted trigonal bipyramidal coordination at each metal centre. The dimers are stabilized by intramolecular stacking interactions between the terminal (py)₂CNO⁻ ligands, and the structural effects of these interactions are discussed.     

Utilization of spent petrochemical sulfuric acid in the production of wet‐process phosphoric acid

The possibility of the application of spent sulfuric acid from the petrochemical industry in wet‐process phosphoric acid technology was investigated. The effect of organic impurities in sulfuric acid from benzol acidic refining on the solubility of calcium sulfate hydrates is discussed. Solubility isotherms and regression equations for CaSO₄–H₃PO₄–H₂SO₄–H₂O (pure and containing impurities) systems are presented. Phase transition temperatures between dihydrate and hemihydrate calcium sulfate were determined. The difference between pure and polluted sulfuric acid systems observed is negligible over the range of typical wet‐process phosphoric acid technology parameters. It is concluded that the application of spent sulfuric acid from benzol acidic refining does not have a negative influence on the crystallization process of dihydrate calcium sulfate and therefore can be applied in wet‐process phosphoric acid technology. Copyright © 2005 Society of Chemical Industry     

Asymmetric Synthesis of Bioxindole‐Substituted Hexahydrofuro[2,3‐b]furans via Hydroquinine Anthraquinone‐1,4‐diyl Diether‐Catalyzed Domino Annulation of Acylidenoxindoles/Isatins,Acylidenoxindoles and Allenoates

Hydroquinine anthraquinone‐1,4‐diyl diether [(DHQ)₂AQN]‐catalyzed unprecedented asymmetric domino annulation reactions of acylidenoxindoles/isatins, acylidenoxindoles and allenoates are disclosed in this communication, providing a facile access to hexahydrofuro[2,3‐b]furans containing four contiguous chiral centers in good to excellent yields along with good to excellent ee values and moderate to good dr values. Based on theoretical investigations, a concerted [3+2] ring‐closure process was proposed, in which steric hindrance and π–π stacking interaction between catalyst and substrate subtly co‐control the diastereoselectivity of the reaction.

     

Discovery of α‐Substituted Imidazole‐4‐acetic Acid Analogues as a Novel Class of ρ1 γ‐Aminobutyric Acid Type A Receptor Antagonists with Effect on Retinal Vascular Tone

The ρ‐containing γ‐aminobutyric acid type A receptors (GABA_ARs) play an important role in controlling visual signaling. Therefore, ligands that selectively target these GABA_ARs are of interest. In this study, we demonstrate that the partial GABA_AR agonist imidazole‐4‐acetic acid (IAA) is able to penetrate the blood–brain barrier in vivo; we prepared a series of α‐ and N‐alkylated, as well as bicyclic analogues of IAA to explore the structure–activity relationship of this scaffold focusing on the acetic acid side chain of IAA. The compounds were prepared via IAA from l ‐histidine by an efficient minimal‐step synthesis, and their pharmacological properties were characterized at native rat GABA_ARs in a [³H]muscimol binding assay and at recombinant human α₁β₂γ_2S and ρ₁ GABA_ARs using the FLIPR? membrane potential assay. The (+)‐α‐methyl‐ and α‐cyclopropyl‐substituted IAA analogues ((+)‐ 6 a and 6 c , respectively) were identified as fairly potent antagonists of the ρ₁ GABA_AR that also displayed significant selectivity for this receptor over the α₁β₂γ_2S GABA_AR. Both 6 a and 6 c were shown to inhibit GABA‐induced relaxation of retinal arterioles from porcine eyes.     

A novel lamella 2D Ag(I) coordination polymer of graphite-like structure featuring short interlayer distance

The reaction of Ag₂O with a mixture of benzene-1,3,5-tricarboxylic acid (H₃BTC) and 2-aminopyrazine (APYZ) under the ammoniacal conditions gives rise to a novel metal–organic coordination polymer Ag₆(BTC)₂(APYZ)₆·9H₂O (1). The structure of 1 possesses a high ordered lamella 2D structure with an interesting graphite-like 6³ net which is comprised of Ag₄ and Ag₆ fused hexagonal rings respectively. 1 exhibits photoluminescence maximized at 416 nm upon 330 nm excitation at room temperature, which may be mainly ascribed to ligand-to-ligand charge transfer (LLCT). Semiconducting behavior was also measured at ambient temperature with σ values of 5.56 × 10⁻⁷ S cm⁻¹ based on the π–π stacking and Ag(I)–π interactions.     

A Photochemical Route to Benzo[a]carbazoles via Domino Elimination/Electrocyclization of 2‐Aryl‐3‐(1‐tosylalkyl)indoles

The photochemical synthesis of benzo[a]carbazoles from easily synthesizable 2‐aryl‐3‐(1‐tosylalkyl)indoles is presented. Irradiation of these substrates in polar aprotic solvents (acetone or THF) gives selectively the target products in satisfactory yields. This versatile and efficient procedure promises to be a useful alternative to the multistep strategies reported in the literature.     

A novel route to α,ω-telechelic poly(-caprolactone) diols, precursors of biodegradable polyurethanes, using catalysis by decamolybdate anion

A new convenient route for the synthesis of poly(-caprolactone) (PCL) with α,ω-telechelic diols' end-groups is presented. Synthesis of α,ω-telechelic PCL diols (HOPCLOH) was achieved by ring-opening polymerization (ROP) of -caprolactone (CL) catalyzed with ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] and using diethylene glycol (DEG) as initiator. Obtained HOPCLOH was characterized by ¹H and ¹³C NMR, FT-IR, GPC and MALDI-TOF. Comparative studies demonstrate that ammonium decamolybdate (NH₄)₈[Mo₁₀O₃₄] is better catalyst than Sn-octanoate (SnOct₂) toward CL polymerization in presence of DEG, under the conditions tested. A biodegradable poly(ester-urethane-urea) derivative was efficiently prepared from synthesized HOPCLOH. Obtained polymer shows minor differences with respect to the properties recorded for a poly(ester-urethane-urea) obtained from commercial HOPCLOH.     

Self-assembly through hydrogen-bonding and C–Hπ interactions in metal complexes of N-functionalised glycine

The complex [Ni(L1)₂(py)₂]. toluene (L1 is N-phthaloylglycinato and py is pyridine) was prepared from solid state reaction whereas co-crystals having composition 2[Ni(L1)₂(py)₃(H₂O)] · [Ni(L1)₂(py)₂(H₂O)₂] · 2py · 2H₂O was obtained from solution state reaction.     

Performance of Kenics static mixer over a wide range of Reynolds number

The present study deals with the numerical simulation of flow patterns and mixing behaviour in Kenics static mixer over a wide range of Reynolds number. Three different sets of Kenics mixer (aspect ratio = 1.5) comprised of 3, 9 and 25 elements each have been characterized. The Reynolds number was varied in the range of 1 to 25,000 (i.e., from laminar to turbulent flow regime). The numerical approach takes into account the aspects of the fluid flow at higher Reynolds number values including circumferential velocity profiles at different cross-sections within the Kenics mixer, which were neglected in previous studies. It was observed that cross-sectional mixing in the turbulent flow regime takes place up to 30% of each element length at element-to-element transition; beyond that velocity profiles were uniform. The experiments were also carried out to measure the circumferential and axial velocity profiles and pressure drop in three different Kenics Mixers using air as fluid. The pressure drop per unit element (ΔP/η) was found to be independent of the number of Kenics mixing elements used in the system. The total pressure drop across Kenics mixer obtained by CFD simulations were compared with the experimental pressure drop values and correlations available in the literature. The numerical results were found in good agreement with the experimental as well as the results reported in the literature. A new pressure drop correlation in the Kenics static mixer has been developed.     

Active-oxygen species on non-reducible rare-earth-oxide-based catalysts in oxidative coupling of methane

From supplementary in situ Raman spectroscopic studies of active-oxygen species on non-reducible rare-earth-oxide-based catalysts in the oxidative coupling of methane (OCM) and structural adaptability considerations, further support has been obtained for our proposal that there may be an active and elusive precursor (of O₂ ^– and O₂ ^2– adspecies), most probably O₃ ^2– formed from reversible redox coupling of an O₂ adspecies at an anionic vacancy with a neighboring O^2– in the surface lattice. This active precursor may initiate H abstraction from CH₄ and be itself converted to OH^–+O₂ ^–, or it may abstract an electron from the oxide lattice and be converted to O₂ ^2–+O^–. The prospect of developing this type of OCM catalysts is discussed.     

A review on the mechanical and electrical properties of graphite and modified graphite reinforced polymer composites

Carbon materials particularly in the form of sparkling diamonds have held mankind spellbound for centuries, and in its other forms, like coal and coke continue to serve mankind as a fuel material, like carbon black, carbon fibers, carbon nanofibers and carbon nanotubes meet requirements of reinforcing filler in several applications. All these various forms of carbon are possible because of the element's unique hybridization ability. Graphene (a single two-dimensional layer of carbon atoms bonded together in the hexagonal graphite lattice), the basic building block of graphite, is at the epicenter of present-day materials research because of its high values of Young's modulus, fracture strength, thermal conductivity, specific surface area and fascinating transport phenomena leading to its use in multifarious applications like energy storage materials, liquid crystal devices, mechanical resonators and polymer composites. In this review, we focus on graphite and describe its various modifications for use as modified fillers in polymer matrices for creating polymer-carbon nanocomposites.