Dynamics of excess electronic charge in aliphatic ionic liquids containing the bis(trifluoromethylsulfonyl)amide anion

In a recent article (J. Am. Chem. Soc. 2011, 133, 20186) we investigated the initial spatial distribution of dry excess electrons in a series of room-temperature ionic liquids (RTILs). Perhaps unexpectedly, we found that in some alkylammonium-based systems the excess negative charge resided on anions and not on the positive cations. Following on these results, in the current paper we describe the time evolution of an excess electronic charge introduced in alkylammonium- and pyrrolidinium-based ionic liquids coupled with the bis(trifluoromethylsulfonyl)amide ([TfN]) anion. We find that on a 50 fs time scale an initially delocalized excess electron localizes on a single [TfN] anion which begins a fragmentation process. Low-energy transitions have a very different physical origin on the several femtoseconds time scale when compared to what occurs on the picosecond time scale. At time zero, these are intraband transitions of the excess electron. However after 40 fs when the excess electronic charge localizes on a single anion, these transitions disappear, and the spectrum is dominated by electron-transfer transitions between the fragments of the doubly charged breaking anion. © 2013 American Chemical Society.

Neutron Scattering of Aromatic and Aliphatic Liquids

Organic solvents, such as cyclohexane, cyclohexene, methylcyclohexane, benzene and toluene, are widely used as both reagents and solvents in industrial processes. Despite the ubiquity of these liquids, the local structures that govern the chemical properties have not been studied extensively. Herein, we report neutron diffraction measurements on liquid cyclohexane, cyclohexene, methylcyclohexane, benzene and toluene at 298 K to obtain a detailed description of the local structure in these compounds. The radial distribution functions of the centres of the molecules, as well as the partial distribution functions for the double bond for cyclohexene and methyl group for methylcyclohexane and toluene have been calculated. Additionally, probability density functions and angular radial distribution functions were extracted to provide a full description of the local structure within the chosen liquids. Structural motifs are discussed and compared for all liquids, referring specifically to the functional group and aromaticity present in the different liquids.

Studies of tetrahedral haloboron cations of pyridines and aliphatic tertiary amines

The preparation of the haloboron cations D2BF2 + and DD'BF 2+, where D=R3N or a pyridine, has been systematically . 19 11 studied uS1ng F and B n.m.r. Both types of amines form numerous difluoroboron cations by heavy halogen displacement from D.BF 2X (X=CI,Br) adducts. Previously, D.BFX2 (X=CI,Br) adducts of aliphatic tertiary amines were unreactive towards cation formation. However, with the more-reactive pyridines, D.BFX 2 adducts formed new monofluoroboron cations D2BFX+ In non-fluorinated D.BX Y3 systems for n -n both pyridines and R3N, haloboron cations of type D2BX2 + and D2BXY+ can be similarly prepared. FAB-MS studies of ionic salts of our haloboron cations resulted in m/z peaks characteristic of D2 BX2 + and its f ragmentation products. These results s upport our n.m.r. solution s t u d ies. Pairwise interaction n . m.r . parameters for tetrahedral boron halide species were def i ned, then used to assist confirmation of our haloboron cations.

The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines

To study the complex formation of group 5 elements (Nb, Ta, Ha, and pseudoanalog Pa) in aqueous HCI solutions of medium and high concentrations the electronic structures of anionic complexes of these elements [MCl_6]^-, [MOCl_4]^-, [M(OH)-2 Cl_4]^-, and [MOCl_5]^2- have been calculated using the relativistic Dirac-Slater Discrete-Variational Method. The charge density distribution analysis has shown that tantalum occupies a specific position in the group and has the highest tendency to form the pure halide complex, [TaCl_6-. This fact along with a high covalency of this complex explains its good extractability into aliphatic amines. Niobium has equal trends to form pure halide [NbCl_6]^- and oxyhalide [NbOCl_5]^2- species at medium and high acid concentrations. Protactinium has a slight preference for the [PaOCl_5]^2- form or for the pure halide complexes with coordination number higher than 6 under these conditions. Element 105 at high HCl concentrations will have a preference to form oxyhalide anionic complex [HaOCl_5]^2- rather than [HaCl_6]^-. For the same sort of anionic oxychloride complexes an estimate has been done of their partition between the organic and aqueous phases in the extraction by aliphatic amines, which shows the following succession of the partition coefficients: P_Nb < P_Ha < P_Pa.

GC/multiple collector-ICPMS method for chlorine stable isotope analysis of chlorinated aliphatic hydrocarbons

Stable isotopic characterization of chlorine in chlorinated aliphatic pollution is potentially very valuable for risk assessment and monitoring remediation or natural attenuation. The approach has been underused because of the complexity of analysis and the time it takes. We have developed a new method that eliminates sample preparation. Gas chromatography produces individually eluted sample peaks for analysis. The He carrier gas is mixed with Ar and introduced directly into the torch of a multicollector ICPMS. The MC-ICPMS is run at a high mass resolution of >= 10 000 to eliminate interference of mass 37 ArH with Cl. The standardization approach is similar to that for continuous flow stable isotope analysis in which sample and reference materials are measured successively. We have measured PCE relative to a laboratory TCE standard mixed with the sample. Solvent samples of 200 nmol to 1.3 mu mol ( 24- 165 mu g of Cl) were measured. The PCE gave the same value relative to the TCE as measured by the conventional method with a precision of 0.12% ( 2 x standard error) but poorer precision for the smaller samples.

Segregated self-assembly and pillaring action of aliphatic dicarboxylic acids in the super structure of Cu-picolinate complexes

Three new supramolecular assemblies of co-crystallized metal complexes and aliphatic dicarboxylic acids, {[Cu(pic)(2)(H2O)(2)](H(2)mal)}(n) (1), {[Cu(pic)(2)(H2O)(2)](H(2)mal)(2)(H2O)(2)}(n) (2) and {[Cu(pic)(2)(MeOH)](H(2)succ)}(n) (3) {Hpic = 2-picolinic acid, H(2)mal = malonic acid and H(2)succ = succinic acid} have been synthesized and characterized by X-ray single-crystal structure determination. The crystal packings of the complexes reveal that supramolecular associations of the monomeric complex units lead to the formation of layers through hydrogen bonding. In all the complexes, the dicarboxylic acid units connect the 2-D layers to act as pillars. The interaction between water molecules and the dicarboxylic acid plays an important role in the overall supramolecular assembly. (C) 2008 Elsevier Ltd. All rights reserved.

Thermally responsive elastomeric supramolecular polymers featuring flexible aliphatic hydrogen-bonding end-groups

The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

Film-forming polymers containing in the main-chain dibenzo crown ethers with aliphatic (C-10-C-16), aliphatic-aromatic, or oxyindole spacers

Novel, linear, soluble, high-molecular-weight, film-forming polymers and copolymers in which main-chain crown ether units alternate with aliphatic (C-10-C-16) units have been obtained for the first time from aromatic electrophilic substitution reactions of crown ethers by aliphatic dicarboxylic acids followed by reduction of the carbonyl groups. The crown ether unit is dibenzo-18-crown-6, dibenzo-21-crown-7, dibenzo-24-crown-8, or dibenzo-30-crown-10; the aliphatic spacer is derived from a dicarboxylic acid (sebacic, 1,12-dodecanedicarboxylic, hexadecanedioic or 1,4-phenylenediacetic acids). The reactions were performed at 35 degrees C in a mixture of methanesulfonic acid (MSA) with phosphorus pentoxide, 12:1 (w/w), (Eaton's reagent). The carbonyl groups in the polyketones obtained were completely reduced to methylene linkages by treatment at room temperature with triethylsilane in a mixture of trifluoroacetic acid and dichloromethane. Polymers containing in the main chain crown ethers alternating with oxyindole fragments were prepared by one-pot condensation of crown ethers with isatin in a medium of Eaton's reagent. A possible reaction mechanism is suggested. According to IR and NMR analyses, the polyacylation reactions lead to the formation of isomeric (syn/anti-substituted) crown ether units in the main chain. The polymers obtained were soluble in the common organic solvents, and flexible transparent films could be cast from the solutions. DSC and X-ray studies of the polymers with "symmetrical" crown ethers reveal the presence of the endotherms corresponding to the supramolecular assemblies.

Theoretical studies of the interface between water and Langmuir films of aliphatic alcohols

The interface between water and Langmuir films of long chain aliphatic molecules is investigated using accurate intermolecular potentials. The stabilities of various ice structures which could form at the interface are examined. Antiferroelectric ice is found to be the most stable, but this stability depends crucially on the first layer of water. Ferroelectric structures are found to collapse upon relaxation. Our model was not able to differentiate between the different nucleation properties of C31H63OH and C30H61OH. A better description of the alcohol–water interaction is probably required to account for this difference.

Tuning thermal properties and microphase separation in aliphatic polyester ABA copolymers

Four alkyl substituted β-lactones were investigated as monomers in ring opening polymerisation to produce a family of poly(3-hydroxyalkanoate)s. Homopolymers were synthesised using a robust aluminium salen catalyst, resulting in polymers with low dispersity (Đ < 1.1) and predictable molecular weights. ABA triblock copolymers were prepared using poly(L-lactic acid) as the A block and the aforementioned poly(3-hydroxyalkanoate) as the B block via a sequential addition method. Characterisation of these copolymers determined they were well controlled with low dispersities and predictable molecular weight. DSC analysis determined copolymers prepared from β-butyrolactone or β-valerolactone yielded polymers with tunable and predictable thermal properties. Copolymers prepared from β-heptanolactone yielded a microphase separated material as indicated by SAXS, with two distinct Tgs. The polymers could be readily cast into flexible films and their improved tensile properties were explored.

Synthesis and characterization of hybrids derived from vermiculite chloropropyl and aliphatic diamines

ALVES, Ana Paula de Melo et al. Synthesis and characterization of hybrids derived from vermiculite chloropropyl and aliphatic diamines. Journal of Thermal Analysis and Calorimetry, v.87, n. 3, p.771–774, 2007.

Mortality of Bemisia tabaci biotype B (sternorrhyncha: aleyrodidae) adults by aliphatic and aromatic synthetic sucrose esters

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Durability of adhesives based on different epoxy/aliphatic amine networks

The mechanical and adhesives properties of epoxy formulations based on diglycidyl ether of bisphenol A cured with various aliphatic amines were evaluated in the glass state. Impact tests were used to determine the impact energy. The adhesive properties have been evaluated in terms single lap shear using steel adherends. Its durability in water at ambient temperature (24 degrees C) and at 80 degrees C has also been analyzed. The fracture mechanisms were determined by optical microscopy. It was observed a strong participation of the cohesive fracture mechanisms in all epoxy system studied. The 1-(2-aminoethyl)piperazine epoxy adhesive and piperidine epoxy adhesive presents the best adhesive strength and the largest impact energy. The durability in water causes less damage to piperidine epoxy networks. This behavior appears to be associated with the lower water uptake tendency of homopolymerised resins due to its lower hydroxyl group concentration. (C) 2011 Elsevier Ltd. All rights reserved.

The Cathodic Cleavage of the Nitrobenzoyl Group from Protected Aliphatic Amines in N,N-Dimethylformamide

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

THE CATHODIC CLEAVAGE OF THE NITROBENZENESULFONYL GROUP FROM ALIPHATIC-AMINES IN N,N-DIMETHYLFORMAMIDE

The reduction of benzenesulfonyl derivatives of n-butylamine and N,N-di-n-butylamine with nitro substituents at the 2, 3 and 4 positions of the phenyl ring in N,N-dimethylformamide is reported. The N,N-di-n-butyl-4- and N-n-butyl-2-nitrobenzenesulfonamides are reduced in two cathodic steps. The first one, at about -0.90 V vs. SCE, a reversible one-electron process, gives a stable anion radical. The second reduction step at -1.70 V vs. SCE leads to cleavage of the S-N bond in good yields (> 70%). It is shown that the reduction of the N-n-butyl-3- and N-n-butyl-4-nitrobenzenesulfonamide is different, with three reduction steps. The first reduction step occurs with the formation of an unstable anion radical, which decomposes via N-H bond cleavage. The reduction of this sulfonamide anion occurs at -1.16 V vs. SCE and the third cathodic step arises at -1.70 V vs. SCE when the remaining radical anion is reduced to its dianion. The S-N bond cleavage is rapid but is always a minor process. The mechanisms of the reduction are discussed.