Abstract  Free-standing, ZnO surface decorated Cu nanoparticles of 1-3 nm size were obtained by sequential co-pyrolysis of [Cu(OCHMeCH2NMe2)2] and ZnEt2 in squalane in the absence of additional surfactants and proved to be highly active quasi homogeneous catalysts for methanol synthesis from CO and H2.

Abstract  We have used a squalane adsorbed C-18 phase as presumably a bulk-like stationary phase to secure a simple partition mechanism for solute retention in reversed phase liquid chromatography, and have evaluated the nondispersive (specific) functional group-solvent interaction separately by measuring the retention data of carefully selected solutes in 60/40, 70/30, and 80/20 (v/v%) methanol/water eluents at 25,30,35,40,45, and 50 degrees C. We have found that the absolute magnitude of the carbonyl group (in acetophenone)-mobile phase specific interaction enthalpy is much greater than that of the hydroxyl group (in phenol)-mobile phase specific interaction enthalpy. If we consider the overall differential solute transfer free energy for a pair of polar and nonpolar solutes of the same size, the entropic contribution is dominant for the BT/phenol pair, and the enthalpic contribution, for the ethylbenzene/acetophenone pair. On the other hand, for a pair of nonpolar solutes, the entropic contribution to the differential free energy of solute transfer is much lower than the enthalpic contribution, and the variation in the differential entropy of solute transfer with respect to mobile phase composition is much smaller than the variation in the differential enthalpy, too.

Abstract  The kinetics of the three-phase methanol synthesis over a commercial Cu-Zn-Al2O3 catalyst were studied in an apolar solvent, squalane and a polar solvent, tetraethylene glycol dimethylether (TEGDME). Experimental conditions were varied as follows: P = 3.0-5.3 MPa, T = 488-533 K and Phi(vG)/w =7.5 x 10(-3)-8 x 10(-3) Nm(3) s(-1) kg(cat)(-1). The nature of the slurry-liquid influences the activation energy and the kinetic rate constant by interaction between adsorbed species and solvent and by competitive adsorption of the solvent on the catalyst surface. The rate of reaction to methanol observed in TEGDME appeared to be about 10 times lower than in squalane. TEGDME reduces the reaction rate, which is a disadvantage for its use as a solvent. (C) 1999 Elsevier Science B.V. All rights reserved.

Abstract  Symmetrical peaks, with sample size independent retention times, are obtained when alkanols are chromatographed in columns packed with alkane stationary phases coated on a deactivated solid obtained by coating Chromosorb W with Carbowax 20M, followed by thermal treatment in inert atmosphere and exhaustive extraction with methanol. Adsorption on the solid support/alkane interface is precluded by this deactivation method, but adsorption on the gas/alkane interface persists as a non-negligible contribution to solute retention. Retention volumes of ten alkanols with three to five carbon atoms were measured at five temperatures within the 30-50 degrees C interval in columns containing between 2 and 12 wt.% of squalane or of n-octadecane on the deactivated support. Partition and adsorption coefficients were obtained from the dependence of retention volumes on wt.% of stationary phase. Alkanols infinite dilution activity coefficients were calculated from partition coefficients; it is demonstrated that important errors are introduced on neglecting adsorption contributions. An indirect proof of consistency between calculated adsorption and partition parameters is given by comparing results obtained with both stationary phases. It is furthermore demonstrated that non-combinatorial contributions to the activity coefficients are independent of the alkane solvent.

Abstract  Chlorine species used as disinfectants in tap water have a deteriorating effect on many materials including polyethylene. There are only very few scientific reports on the effect on polyethylene pipes of water containing chlorine dioxide. Medium-density polyethylene pipes stabilized with hindered phenol and phosphite antioxidants were pressure tested with water containing 4 ppm chlorine dioxide at 90 degrees C and pH = 6.8 as internal medium. The stabilizers were rapidly consumed towards the inner pipe wall; the rate of consumption was four times greater than in chlorinated water (4 ppm, pH = 6.8) at the same temperature. The depletion of stabilizer occurred far into the pipe wall. A supplementary study on a polymer analogue (squalane) containing the same stabilizer package showed that the consumption of the phenolic antioxidant was 2.5 times faster when exposed water containing chlorine dioxide than on exposure to chlorinated water. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that in the surface layer which came into contact with the oxidising medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. Scanning electron microscopy showed that propagation of cracks through the pipe wall was assisted by polymer degradation. (C) 2011 Elsevier Ltd. All rights reserved.

Abstract  The dynamics of the gas-liquid interfacial reaction of the first electronically excited state of the oxygen atom, O((1)D), with the surface of a liquid hydrocarbon, squalane (C(30)H(62); 2,6,10,15,19,23-hexamethyltetracosane) has been studied experimentally. Translationally hot O((1)D) atoms were generated by 193 nm photolysis of a low pressure (nominally 1 mTorr) of N(2)O a short distance (mean = 6 mm) above a continually refreshed liquid squalane surface. Nascent OH (X(2)Π, v' = 0) reaction products were detected by laser-induced fluorescence (LIF) on the OH A(2)Σ(+)-X(2)Π (1,0) band at the same distance above the surface. The speed distribution of the recoiling OH was characterized by measuring the appearance profiles as a function of photolysis-probe delay for selected rotational levels, N'. The rotational (and, partially, fine-structure) state distributions were also measured by recording LIF excitation spectra at selected photolysis-probe delays. The OH v' = 0 rotational distribution is bimodal and can be empirically decomposed into near thermal (~300 K) and much hotter (~6000 K) Boltzmann-temperature components. There is a strong positive correlation between rotational excitation and translation energy. However, the colder rotational component still represents a significant fraction (~30%) of the fastest products, which have substantially superthermal speeds. We estimate an approximate upper limit of 3% for the quantum yield of OH per O((1)D) atom that collides with the surface. By comparison with established mechanisms for the corresponding reactions in the gas phase, we conclude that the rotationally and translationally hot products are formed via a nonstatistical insertion mechanism. The rotationally cold but translationally hot component is most likely produced by direct abstraction. Secondary collisions at the liquid surface of products of either of the previous two mechanisms are most likely responsible for the rotationally and translationally cold products. We do not think it likely, a priori, that they could be produced in the observed significant yield via a statistical insertion mechanism for a molecule the size of squalane embedded in a surrounding liquid surface.

Abstract  The calculation of retention times, retention indices, and partition constants is a long sought-after goal for theoretical studies in gas chromatography. Although advances in computational chemistry have improved our understanding of molecular interactions, little attention has been focused on chromatography, let alone calculations of retention properties. Configurational-bias Monte Carlo simulations in the Gibbs ensemble have been used to calculate single and multi-component phase diagrams for a variety of hydrocarbon systems. Transferable force fields for linear and branched alkanes have been derived from these simulations. Using calculations for helium/n-heptane/n-pentane systems, it is demonstrated that this approach yields very precise partition constants and free energies of transfer. Thereafter, the partitioning of linear and branched alkane solutes (with five to eight carbon atoms) between a squalane liquid phase and a helium vapor phase is investigated. The Kovats retention indices of the solutes are calculated directly from the partition constants.

Abstract  We demonstrate the first capture and analysis of secondary organic aerosol (SOA) on a droplet suspended in an aerosol optical tweezers (AOT). We examine three initial chemical systems of aqueous NaCl, aqueous glycerol, and squalane at ∼75% relative humidity. For each system we added α-pinene SOA-generated directly in the AOT chamber-to the trapped droplet. The resulting morphology was always observed to be a core of the original droplet phase surrounded by a shell of the added SOA. We also observed a stable emulsion of SOA particles when added to an aqueous NaCl core phase, in addition to the shell of SOA. The persistence of the emulsified SOA particles suspended in the aqueous core suggests that this metastable state may persist for a significant fraction of the aerosol lifecycle for mixed SOA/aqueous particle systems. We conclude that the α-pinene SOA shell creates no major diffusion limitations for water, glycerol, and squalane core phases under humid conditions. These experimental results support the current prompt-partitioning framework used to describe organic aerosol in most atmospheric chemical transport models and highlight the prominence of core-shell morphologies for SOA on a range of core chemical phases.

Abstract  Biodegradability was conducted according to OECD guideline n°301B. Sample biodegradability was equal to 55.9% after 28 days and 66.3% after 36 days.

Abstract  This study presents first results on angle-resolved, inelastic collision dynamics of thermal and hyperthermal molecular beams of NO at gas-liquid interfaces. Specifically, a collimated incident beam of supersonically cooled NO (2Π1/2, J = 0.5) is directed toward a series of low vapor pressure liquid surfaces ([bmim][Tf2N], squalane, and PFPE) at θinc = 45(1)°, with the scattered molecules detected with quantum state resolution over a series of final angles (θs = -60°, -30°, 0°, 30°, 45°, and 60°) via spatially filtered laser induced fluorescence. At low collision energies [Einc = 2.7(9) kcal/mol], the angle-resolved quantum state distributions reveal (i) cos(θs) probabilities for the scattered NO and (ii) electronic/rotational temperatures independent of final angle (θs), in support of a simple physical picture of angle independent sticking coefficients and all incident NO thermally accommodating on the surface. However, the observed electronic/rotational temperatures for NO scattering reveal cooling below the surface temperature (Telec < Trot < TS) for all three liquids, indicating a significant dependence of the sticking coefficient on NO internal quantum state. Angle-resolved scattering at high collision energies [Einc = 20(2) kcal/mol] has also been explored, for which the NO scattering populations reveal angle-dependent dynamical branching between thermal desorption and impulsive scattering (IS) pathways that depend strongly on θs. Characterization of the data in terms of the final angle, rotational state, spin-orbit electronic state, collision energy, and liquid permit new correlations to be revealed and investigated in detail. For example, the IS rotational distributions reveal an enhanced propensity for higher J/spin-orbit excited states scattered into near specular angles and thus hotter rotational/electronic distributions measured in the forward scattering direction. Even more surprisingly, the average NO scattering angle (⟨θs⟩) exhibits a remarkably strong correlation with final angular momentum, N, which implies a linear scaling between net forward scattering propensity and torque delivered to the NO projectile by the gas-liquid interface.

Abstract  Colloidal GaP nanowires (NWs) were synthesized on a large scale by a surfactant-free, self-seeded solution-liquid-solid (SLS) method using triethylgallium and tris(trimethylsilyl)phosphine as precursors and a noncoordinating squalane solvent. Ga nanoscale droplets were generated in situ by thermal decomposition of the Ga precursor and subsequently promoted the NW growth. The GaP NWs were not intentionally doped and showed a positive open-circuit photovoltage based on photoelectrochemical measurements. Purified GaP NWs were used for visible-light-driven water splitting. Upon photodeposition of Pt nanoparticles on the wire surfaces, significantly enhanced hydrogen production was observed. The results indicate that colloidal surfactant-free GaP NWs combined with potent surface electrocatalysts could serve as promising photocathodes for artificial photosynthesis.

Abstract  A photophysical analysis of 10(-4) M solutions of 7-azaindole in hydrocarbon solvents including 2-methylbutane, 3-methylpentane, ethylcyclohexane, decalin, and squalane revealed that the viability of the two-proton phototautomerism in its dimer is clearly medium-dependent. However, in all media studied, a small tunneling contribution in the photoinduced double proton transfer continues to exist at low temperatures.

Abstract  All-trans-octatetraene 3,10-di(tert-butyl)-2,2,11,11-tetramethyl-3,5,7,9-dodecatetraene emits fluorescence in three different regions of the visible spectrum. Thus, it produces an extremely weak emission in the gas phase that can hardly be detected in the condensed phase; such an emission exhibits a negligible Stokes shift with respect to the 1A(g)-->1B(u) absorption transition and can, in principle, be assigned to the 1B(u)-->1A(g) emission for the compound. A second, structureless fluorescence emission, centered in the region of 525 nm, is observed in the gas phase and at somewhat higher wavelengths in the condensed phase [viz., 570 nm in 2-methylbutane (2MB) and 550 nm in squalane (SQ)]. While detectable, this emission increases significantly, with no change in spectral position, as the solution temperature is lowered; also, it is abruptly replaced by a new, strongly blueshifted emission at approximately 490 nm in 2MB and 455 mm in SQ when the viscosity of the medium exceeds a given level. The fact that the two fluorescence emissions considerably depart from the expected behavior for a 1B(u)-->1A(g) emission in an all-trans-polyene, and that one disappears while the other simultaneously appears as the medium becomes more rigid, suggests that the two emissions are produced by two different molecular structures and that the rigidity of the medium switches their production from the originally excited all-trans 1B(u) form. The observed spectral behavior is consistent with a recently proposed model [J. Catalan, Chem. Phys. 335, 69 (2007)] in which the 1B(u) excited state of octatetraene can give two distinct molecular conformers as a result of twisting about different C-C single bonds.

Abstract  The exchange of copolymer chains between 1 vol % PS-PEP (poly(styrene-b-ethylene-alt-propylene)) di-block copolymer micelles in squalane (selective for PEP) is investigated using time-resolved small-angle neutron scattering (TR-SANS) as a function of added PEP homopolymer. The solvent squalane, C30H62, is substituted in part or completely with PEP homopolymers that are the same molecular weight as the corona blocks. Polymer solutions/mixtures (1 vol % PS-PEP, plus 2, 7, or 15 vol % PEP in squalane, and 1 vol % PS-PEP in PEP) were separately prepared using normal (h-PS) or deuterated equivalent (d-PS) PS-PEP diblock copolymers. The solvent was contrast matched to a 50/50 mixed h-/d-PS micelle core, so that the scattering intensity decays with the mixing of h- and d-PS-PEP chains undergoing exchange between micelles. The chain exchange rate can therefore be assessed quantitatively. As the concentration of added homopolymer in solution increases above the overlap concentration of PEP chains, the chain exchange rate drops significantly. The results are compared to an earlier study of chain exchange between PS-PEP micelles in a 15% solution in squalane, which was also found to be significantly slower than when the solution is dilute. The primary factor in this slowing down of chain exchange is an increased screening of excluded volume interactions among the corona blocks. The role of increasing micelle aggregation number with PEP concentration is found not to be the dominant effect up to 15% added PEP but may play an increasingly important role in the PEP melt matrix, where no chain exchange could be detected in these experiments.

Abstract  The effect of temperature on the steady-shear viscosity of a soft semi-crystalline crosslinked-polyethylene microparticle suspension in squalane was studied using rotational rheometry. The results show a sharp increase in the viscosity of the system occurring at about 86 degrees C. The magnitude of this spike is dependent on the concentration of the suspension and is reproducible over multiple heating and cooling cycles. This phenomenon has been attributed to the melting of the crystalline regions within the particles, causing them to swell by soaking up squalane. The Mooney equation was used to model the viscosity data based on swelling data obtained from separate experiments. The results showed that the model is inadequate for describing the observed phenomenon, suggesting the possibility of additional interactions existing among the particles. POLYM. ENG. SCI., 48:329-335, 2008. (c) 2007 Society of Plastics Engineers.

Abstract  The kinetics have been studied for two processes whose limiting stage is the diffusion of molecular oxygen: (i) oxidation of radicals after irradiation; and (ii) quenching of phenanthrene phosphorescence. The processes were studied in glassy squalane and poly(methyl methacrylate) matrices. Comparison between the kinetic properties of these processes allowed us to conclude about predominant stabilization of radicals near structural defects of glass. In squalane this manifests itself in anomalously high value of reaction radius for oxidation of radicals and in poly(methyl methacrylate) in quantitative difference in the parameters of distribution in rate constants for processes (i) and (ii).

Abstract  Squalane is an important ingredient in the cosmetic, nutraceutical, and pharmaceutical industries. It has also been used as a model compound for the hydrocracking of crude and microalgae oil. Thus, a series of green heterogeneous metal catalysts were prepared to achieve complete hydrogenation of highly unsaturated squalene into squalane. Surface modification of the clay and metal intercalation simultaneously occurred during wet impregnation. The Pd-nanoparticles-intercalated clay with a dominating Pd(111) facet showed the highest reactivity and selectivity. The catalyst was stable with very low Pd leaching (approximate to 0.03 ppm) and was recyclable without losing any significant catalytic activity.

Abstract  Trans-azobenzene dissolved in different liquid hydrocarbons absorbs fluorescence arising from all acceptors previously used in Fluorescence Detected Magnetic Resonance (FDMR) and Optically Detected ESR (OD ESR) spectroscopy making optical detection impossible. In this report a new acceptor, rubrene, having sufficient quantum yield of fluorescence in the red band 550-620 nm, has been proven successful. OD ESR spectra of the radical-ion pair trans-azobenzene+/rubrene- were detected in liquid squalane (2,6,10,15,19,23-hexamethyl-tetracosane) solution in the temperature range 294-243 K. The experimental isotropic hyperfine splittings of the radical cation of trans-azobenzene (a(N) = 1.4 mT) have been compared with those from MNDO/INDO calculations and with those of earlier work using freon matrix studies.

Abstract  PE microgels were prepared from mechanical fragmentation and from immiscible blends of PS and PE. The surface topology of microgels obtained from mechanical fragmentation was hypothesized to consist of long linear PE chains that are capable of interparticle co-crystallization as suggested by low-strain oscillatory shear experiment results. To investigate this hypothesis, PE microgels with a smooth surface and a PS corona were prepared using immiscible blends of PE and PS, followed by removal of the PS matrix. The rheological response of suspensions of PE microgels with a PS corona in squalane was similar to suspensions of PE microgels with crystallizable surface chains whereby the system would gel and exhibit hysteresis upon a cooling and heating cycle. Suspensions of PE microgels without any surface chains, however, were reversible over multiple cooling and heating cycles. It was determined that the PS corona and the cross-link density of the microgels had an effect (p < 0.01) on the reversibility whereas the microgel concentration in the suspension did not (p = 0.82).

Abstract  Retention data obtained previously at 25 degrees C on a hexadecane capillary column by Zhang et al, and a packed hexadecane column by Abraham et al., both uncorrected for any effects due to interfacial adsorption, were compared with retention data obtained by Poole et al. on a packed squalane column at 120 degrees C, with the latter fully corrected for such effects. It is shown that for most solutes, the capillary and packed column data are equally compatible with the squalene corrected data, but for the solutes dimethyl sulfoxide, dimethylformamide and dimethylacetamide the packed column data are in much better accord with the corrected data than are the capillary column data. It is further shown that both sets of results at 25 degrees C for carboxylic acids are in error, owing to dimerization. Retention volumes on Chromosorb G AW DMCS are reported at 25 and at 93 degrees C. It is shown that at 25 degrees C, there could be some contribution to solute retention from adsorption on the support, but that this is almost impossible at 93 degrees C.

Abstract  The inverse secondary equilibrium isotope effects of Rh(I)-C2H4 and Rh(I)-C2H3D were directly measured using a gas chromatographic column of dicarbonyl-rhodium(I)-3-trifluoroacetyl-1R-camphorate in squalane solution at 283-333 K. Statistical isotope effects were also obtained from a reduced partition function using harmonic vibrational frequencies of RHC-C2H, complexes and normal-mode analysis. The observed isotope effects were in good agreement with those deduced from the reduced partition function. Thermodynamic data of the inverse isotope effect were DELTA(D.H)-DELTA-H = - 469 +/- 12 J mol -1 and DELTA(D.H)DELTA-S = - 0.975 +/- 0.017 J mol -1 K -1, where DELTA(D,H)-DELTA-H = DELTA-H(D) - DELTA-H(H) = the difference of the enthalpy changes of the deuterated and non-deuterated compounds (see refs. 1 and 22) and DELTA(D.H)-DELTA-S = DELTA-S(D) - DELTA-S(H) = the difference of the entropy changes of the deuterated and non-deuterated compounds. The detailed analysis of the force constant most affected, F(C-C) = 8.39 mdyn/angstrom, by metal complexation was closer to that of the carbon-carbon double bond (9.1 mdyn/angstrom) than to that of the carbon-carbon single bond (4.3 mdyn/angstrom).

Abstract  Oxygen diffusion in low temperature squalane glasses was studied by phenanthrene phosphorescence quenching and anthracene fluorescence quenching in geminate pairs (anthracene...O-2). The oxygen mobility can be described by continuous diffusion. Anthracene fluorescence quenching in geminate pairs allow to measure diffusion coefficients till 10(-23) cm(2)/s.