Carbon dioxide induced separation of ionic liquids and water

Both hydrophobic and hydrophilic room-temperature ionic liquids can be separated from aqueous solutions with relatively low-pressure gaseous carbon dioxide.     

Turning off phototriggered linkage isomerizations in ruthenium dimethyl sulfoxide complexes

We report on the spectroscopy, electrochemistry, and linkage isomerization in a family of [Ru(tpy)(L2)(dmso)](z)()(+) complexes (tpy is 2,2':6',2' '-terpyridine, dmso is dimethyl sulfoxide, and L2 is a variable ligand: 2,2'-bipyridine (bpy), 2-picolinate (pic), N,N,N',N'-tetramethylethylenediamine (tmen), acetylacetonate (acac), or malonate (mal)). The identity of this bidentate ligand serves to tune the absorption maxima (lambda(max) = 419-502 nm) and the reduction potential (E(1/2) = 1.67 to 0.82 V) of these complexes. Photochemical and electrochemical studies show that S-->O and O-->S linkage isomerization may be triggered through an electron transfer mechanism, resulting in dramatic shifts in both the absorption maxima and the reduction potential (for [Ru(tpy)(pic)(dmso)](+) S-bonded, 421 nm, 1.38 V vs Ag/AgCl; O-bonded, 527 nm, 1.38 V vs Ag/AgCl). Certain of these complexes [Ru(tpy)(acac)(dmso)](+) and [Ru(tpy)(mal)(dmso)] do not undergo isomerization. These results are discussed in the context of electron transfer triggered isomerization.     

Spatially Directed Pyrolysis via Thermally Morphing Surface Adducts

Combustion is often difficult to spatially direct or tune associated kinetics—hence a run-away reaction. Coupling pyrolytic chemical transformation to mass transport and reaction rates (Damköhler number), however, we spatially directed ignition with concomitant switch from combustion to pyrolysis (low oxidant). A ‘surface-then-core’ order in ignition, with concomitant change in burning rate,is therefore established. Herein, alkysilanes grafted onto cellulose fibers are pyrolyzed into non-flammable SiO₂ terminating surface ignition propagation, hence stalling flame propagating. Sustaining high temperatures, however, triggers ignition in the bulk of the fibers but under restricted gas flow (oxidant and/or waste) hence significantly low rate of ignition propagation and pyrolysis compared to open flame (Liñán's equation). This leads to inside-out thermal degradation and, with felicitous choice of conditions, formation of graphitic tubes. Given the temperature dependence, imbibing fibers with an exothermically oxidizing synthon (MnCl₂) or a heat sink (KCl) abets or inhibits pyrolysis leading to tuneable wall thickness. We apply this approach to create magnetic, paramagnetic, or oxide containing carbon fibers. Given the surface sensitivity, we illustrate fabrication of nm- and μm-diameter tubes from appropriately sized fibers.     

Lattice Distortion and H-passivation in Pure Carbon Electrocatalysts for Efficient and Stable Two-electron Oxygen Reduction to H2O2

The exploration of inexpensive and efficient catalysts for oxygen reduction reaction (ORR) is crucial for chemical and energy industries. Carbon materials have been proved promising with different catalysts enabling 2 and 4e⁻ ORR. Nevertheless, their ORR activity and selectivity is still complex and under debate in many cases. Many structures of these active carbon materials are also chemically unstable for practical implementations. Unlike the well-discussed structures, this work presents a strategy to promote efficient and stable 2e⁻ ORR of carbon materials through the synergistic effect of lattice distortion and H-passivation (on the distorted structure). We show how these structures can be formed on carbon cloth, and how the reproducible chemical adsorption can be realized on these structures for efficient and stable H₂O₂ production. The work here gives not only new understandings on the 2e⁻ ORR catalysis, but also the robust catalyst which can be directly used in industry.     

Facile Phenylphosphinidene Transfer Reactions from Carbene–Phosphinidene Zinc Complexes

Phosphinidenes [R-P] are convenient P₁ building blocks for the synthesis of a plethora of organophosphorus compounds. Thus far, transition-metal-complexed phosphinidenes have been used for their singlet ground-state reactivity to promote selective addition and insertion reactions. One disadvantage of this approach is that after transfer of the P₁ moiety to the substrate, a challenging demetallation step is required to provide the free phosphine. We report a simple method that enables the Lewis acid promoted transfer of phenylphosphinidene, [PhP], from NHC=PPh adducts (NHC=N-heterocyclic carbene) to various substrates to produce directly uncoordinated phosphorus heterocycles that are difficult to obtain otherwise.     

Mechanically Initiated Bulk‐Scale Free‐Radical Polymerization

Mechanical initiation of polymerization offers the chance to generate polymers in new environments using an energy source with unique capabilities. Recently, a renewed interest in mechanically controlled polymerization has yielded many techniques for controlled radical polymerization by ultrasound. However, other types of polymerizations induced by mechanical activation are rare, especially for generating high‐molecular‐weight polymers. Herein is an example of using piezoelectric ZnO nanoparticles to generate free‐radical species that initiate chain‐growth polymerization and polymer crosslinking. The fast generation of high amounts of reactive radicals enable the formation of polymer/gel by ultrasound activation. This chemistry can be used to harness mechanical energy for constructive purposes in polymeric materials and for controlled polymerizations for bulk‐scale reactions.     

Thermodynamic study of the three isomers of bromo and iodobenzoic acids. Part II

Using our technique of combustion of small amount of a substance, we determined by calorimetry the standard molar enthalpy of formation in the condensed state and atT=298.15 K of the three isomers of bromo and iodobenzoic acids. Associating to these values their standard molar enthalpies of sublimation previously measured, it was possible to determine their standard molar enthalpies of formation in the gaseous state and atT=298.15 K. The experimental values of the thermodynamic properties _f H _m ^o (cr, 298.15 K), _f H _m ^o (cr, 298.15 K), _sub H _m ^o (298.15 K), and _f H _m ^o (g, 298.15 K) are given for the two series. From the experimental value of the standard molar enthalpy of atomization, it was possible to determine an enthalpy value for the C_b-Br and C_b-I bonds. The experimental and theoretical values of the resonance energy of bromo and iodobenzoic acids are compatible. The relative stability of some monosubstituted derivatives of benzoic acid studied in our laboratory is also discussed.Part I is concerned with Ref. 22 (for bromobenzoic acids) and with Ref. 23 (for iodobenzoic acids).     

Photochemically-induced fluorescence determination of sulfonylurea herbicides using micellar media

An analytical method based on the use of UV irradiation to produce fluorescent derivatives from four non-fluorescent sulfonylurea herbicides, including chlorsulfuron, metsulfuron methyl, 3-rimsulfuron and sulfometuron methyl is described. Their photochemically-induced fluorescence (PIF) properties in several solvents (water, dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), acetonitrile, methanol, ethanol, propan-2-ol and their binary mixtures with water) and micellar solutions of sodium dodecyl sulfate (SDS), and cetyltrimethylammonium chloride (CTAC) are reported. Physicochemical variable influencing the sensitivity of the method have been optimized. A PIF method is developed for the determination of the four herbicides under study. Micellar media are found to provide the best analytical figures of merits. Linear dynamic ranges are established over about two orders of magnitude. The limit of detection (LOD) range from 0.2 to 6 ng ml(-1) according to the compound, with relative standard deviation (RSD) between 1.2 and 3.9%. Examples of applications to the analysis of these herbicides in spiked river water samples are given. The mean recoveries range from 80 to 104%.     

Development of the Vinylogous Pictet–Spengler Cyclization and Total Synthesis of (±)‐Lundurine A

A novel vinylogous Pictet–Spengler cyclization has been developed for the generation of indole‐annulated medium‐sized rings. The method enables the synthesis of tetrahydroazocinoindoles with a fully substituted carbon center, a prevalent structural motif in many biologically active alkaloids. The strategy has been applied to the total synthesis of (±)‐lundurine A.