Thermodynamic properties of alkali halides. III. Volumes and heat capacities of transfer from H2O to D2O at 25°C

The volumetric specific heats and densities of alkali fluorides, alkali bromides, and soduum halides were measured in D₂O at 25°C in the concentration range 0.05 to 1 aquamolal. The results can be combined with data in H₂O to give the corresponding standard and excess transfer functions from H₂O to D₂O. The volumes and heat capacities of transfer are both negative but, contrary to the hydration functions, show little dependence on ionic size and sign. Also, while heats, entropies, and volumes of transfer are usually small compared with the hydration functions, the heat capacity of transfer is of comparable magnitude. These observations, when interpreted with the Frank and Wen model, suggest that the total number of water molecules in the hydration cosphere is approximately constant for all alkali halides and that heat capacities are more sensitive to structural interactions than volumes and enthalpies. The sign of the excess transfer functions is consistent with the presence of structural ion-ion interactions, but no systematic trend with ionic size can be detected in view of the large experimental uncertainty.     

Nonlinear polarization evolution of ultrashort pulses in microstructure fiber

We present experimental and numerical results for nonlinear polarization evolution of femtosecond pulses during propagation in microstructure fiber. Numerical modeling shows that fiber dispersion permits a long interaction length between the components polarized along the two principal axes, thereby enhancing the effective nonlinear polarization evolution in microstructure fiber.     

Study of the 58Ni(τ, α)57Ni reaction at 25 MeV

The ⁵⁸Ni(τ, α)⁵⁷Ni reaction has been studied at 25 MeV incident energy. Angular distributions have been measured from 5° to 50° with a split-pole spectrometer up to 13.5 MeV excitation energy. A local zero-range DWBA analysis has been carried out, allowing l-assignments for about eighty levels, most of them previously unknown. An isospin-dependent potential has been used in the calculation of the neutron form factor for both T_<and T_> states, and the C²S values deduced using this procedure are compared to those obtained with the usual separation energy method. Analog states of eleven ⁵⁷Co levels have been identified and the eventuality for isospin mixing in ⁵⁷Ni has been discussed. A sum rule analysis has been carried out and energy centroids of hole states have been determined. About 60% of the $\text{1}\text{d}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{and}\text{2}\text{s}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{T}{}_{\mathrm{<}}$ strengths and the full $\text{1}\text{d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{1}\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ hole strengths are observed. It is shown that the two excess neutrons in the ⁵⁸Ni ground state mainly populate the $\text{2}\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{, 1}\text{f}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{and}\text{2}\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ orbitals, whereas the occupancy number of the $\text{1}\text{g}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ subshell is found to be smaller than 0.1%. Some non-pickup angular distributions have also been observed and a CRC analysis assuming two-step processes in the (τ, α) reaction and weak-coupling wave functions for final states has been attempted. Assignments of J^π values are proposed for four ⁵⁷Ni levels, based on this analysis.     

Excess heat capacities of binary mixtures of tetrachloromethane with some aromatic liquids at 298.15 K

A Picker flow calorimeter was used to obtain excess heat capacities at 298.15 K for mixtures of tetrachloromethane + toluene, + each of the three xylenes, + ethylbenzene, + mesitylene, and + chlorobenzene. The excess heat capacities are positive in all cases, with the exception of tetrachloromethane + mesitylene. Comparison of the results with values calculated from a “regular associated solution” model supports the view that complex formation occurs in these mixtures.     

Synthesis of a phosphorano-stabilized U(IV)-carbene via one-electron oxidation of a U(III)-ylide adduct

Addition of the Wittig reagent Ph(3)P═CH(2) to the U(III) tris(amide) U(NR(2))(3) (R = SiMe(3)) generates a mixture of products from which the U(IV) complex U═CHPPh(3)(NR(2))(3) (2) can be obtained. Complex 2 features a short U═C bond and represents a rare example of a uranium carbene. In solution, 2 exists in equilibrium with the U(IV) metallacycle U(CH(2)SiMe(2)NR)(NR(2))(2) and free Ph(3)P═CH(2). Measurement of this equilibrium as a function of temperature provides ΔH(rxn) = 11 kcal/mol and ΔS(rxn) = 31 eu. Additionally, the electronic structure of the U═C bond was investigated using DFT analysis.     

Synthesis, molecular and electronic structure of U(V)(O)[N(SiMe3)2]3

Addition of 1 equiv of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to U(NR(2))(3) in hexanes affords U(O)(NR(2))(3) (2), which can be isolated in 73% yield. Complex 2 is a rare example of a terminal U(V) oxo complex. In contrast, addition of 1 equiv of Me(3)NO to U(NR(2))(3) (R = SiMe(3)) in pentane generates the U(IV) bridging oxo [(NR(2))(3)U](2)(μ-O) (3) in moderate yields. Also formed in this reaction, in low yield, is the U(IV) iodide complex U(I)(NR(2))(3) (4). The iodide ligand in 4 likely originates from residual NaI, present in the U(NR(2))(3) starting material. Complex 4 can be generated rationally by addition of 0.5 equiv of I(2) to a hexane solution of U(NR(2))(3), where it can be isolated in moderate yield as a tan crystalline solid. The solid-state molecular structures and magnetic susceptibilities of 2, 3, and 4 have been measured. In addition, the electronic structures of 2 and 3 have been investigated by density functional theory (DFT) methods.     

A host-guest optical sensor for aliphatic amines based on lipophilic cyclodextrin

A host-guest optical sensor for the determination of aliphatic amines as exemplified by octylamine is proposed. It is based on the reversible fluorescence enhancement of heptakis(2,6-di-O-isobutyl)-β-cyclodextrin(DOB-β-CD) hosting tetraphenylporphyrin (TPP) immobilized in poly(vinyl chloride) (PVC) membrane by aliphatic amine extracted from aqueous phase into membrane phase. The optimum membrane contained 1.15 wt % TPP, 6.15 wt % DOB-β-CD as sensing reagent and other membrane materials. The fluorescence enhancement of the membrane resulted from the formation of a stable three-component complex among DOB-β-CD, TPP, and aliphatic amines. With the optimum conditions described, the fluorescence response of the sensor to octylamine shows a good correlation with the theoretically derived equation in the range 1.0 × 10^–6 to 8.0 × 10^–4 mol/L. The response characteristics including reversibility, response time, reproducibility and lifetime and selectivity of this optical device are also discussed in detail. This sensor has also been applied for the determination of octylamine in water samples containing interferents with satisfactory recovery.     

Signal enhancement in laser diode thermal desorption‐triple quadrupole mass spectrometry analysis using microwell surface coatings

Laser‐diode thermal desorption (LDTD) is an ionization source usually coupled to triple quadrupole mass spectrometry (QqQMS) and specifically designed for laboratories requiring high‐throughput analysis. It has been observed that surface coatings on LDTD microwell plates can improve the sensitivity of the analysis of small polar molecules. The objective of the present study is to understand and quantify the effect of microwell surface coatings on signal intensity of small organic molecules of clinical, environmental, and forensic interest. Experiments showed that the peak areas of diclofenac, chloramphenicol, salicylic acid, and 11‐nor‐9‐carboxy‐Δ⁹‐tetrahydrocannabinol obtained by LDTD‐QqQMS increased by up to 3 orders of magnitude when using microwells coated with ethylenediaminetetraacetic acid (EDTA). Tests with different chelating agents and polytetrafluoroethylene as microwell surface coatings showed that nitrilotriacetic acid gave significantly higher peak areas for five out of the nine compounds that showed signal enhancement using chelating agents as coatings. Scanning electron microscopy studies of EDTA‐coated and uncoated microwells showed that analytes deposited in the former formed more uniform and thinner films than in the latter. The enhancement effect of surface coatings in LDTD‐QqQMS was explained mainly by the formation of homogenous and thinner layers of nanocrystals of analytes that are easier to desorb thermally than the layers formed when the analytes dry in direct contact with the bare stainless‐steel surface. Chemisorption of some analytes to the stainless‐steel surface of the microwell plate appeared to be a minor factor. Surface coatings widen the number of compounds analyzable by LDTD‐QqQMS and can also improve sensitivity and limits of detection.     

Investigation of the quantitative properties of the quadrupole orthogonal acceleration time-of-flight mass spectrometer with electrospray ionisation using 3,4-methylenedioxymethamphetamine

This paper describes the investigation of the potential of a quadrupole orthogonal acceleration time-of-flight mass spectrometer (Q-TOF) equipped with an atmospheric pressure ionisation interface for quantitative measurements of small molecules separated by reversed phase liquid chromatography. To this end, the detection limits and linear dynamic range in particular were studied in an LC/MS/MS experiment using 3,4-methylenedioxymethamphetamine standards and 3,4-methylenedioxyethylamphetamine for internal standardisation. In a second phase, the experiment was repeated with real biological extracts (whole blood, serum, and vitreous humour). A calibration for 3,4-methylenedioxymethamphetamine and its metabolite 3,4-methylenedioxyamphetamine was prepared in each of these matrices again using 3,4-methylenedioxyethylamphetamine as internal standard. The resulting quantitative data were compared with those obtained by liquid chromatography with fluorescence detection for the same extracts. The Q-TOF results revealed excellent sensitivity and a linear dynamic range of nearly four decades (2-10 000 pg on-column, r(2) = 0.9998, 1/x weighting). Furthermore, all the calibration curves prepared in biological material were superimposable, LC/MS/MS and LC-fluorescence, and the quantitative results for actual samples compared very favourably. It was concluded that the Q-TOF achieves a linear dynamic range for quantitative LC/MS/MS work exceeding that of fluorescence detection and at much better absolute sensitivity. Copyright 1999 John Wiley & Sons, Ltd.     

Single-particle and core-excited states in 49Sc: (I). The 48Ca(3He,d)49Sc reaction

The ⁴⁸Ca(³He, d)⁴⁹Sc reaction has been studied at 25 MeV incident energy. Angular distributions have been measured from 5° to 40° using a split-pole spectrometer, for about 160 levels located up to 18 MeV excitation energy. A local zero-range DWBA analysis has been carried out, using Gamow functions as form factors in the case of unbound states; l-assignments and spectroscopic factors are obtained for a large number of levels, most of them previously unknown. The summed experimental spectroscopic strengths for the T_<, l = 1 and l = 3 levels are in good agreement with the shell-model sum-rule limits for 1f-2p proton states, and their energy centroids have been determined. The $\text{lg}{}_{\mathrm{<mtext>9</mtext><mtext>2</mtext>}}$ strength in ⁴⁹Sc is strongly fragmented: about 27% of the T_< strength is carried by twenty-three levels located between 6.5 and 13.5 MeV. Spectroscopic factors for analog states are compared with those from previous (p, p), (³He, dp) and (d, p) experiments.