Determination of optical properties of slices of turbid media by diffuse CW laser light scattering profilometry

In this work we present a method for determining the optical parameters of turbid media, namely its absorption coefficient (μ_a) and its reduced scattering coefficient . It is based on the measurement of CW transmittance profiles and analysis of the experimental data by a theoretical model based on the diffusion approximation (DA) of the radiative transfer equation (RTE). The method developed has been investigated with solid polymer probes but it could be applied for liquid materials as well. Experimental results are presented and compared to those of other authors together with a discussion about the accuracy of measurements. In addition, measurements using integrating spheres as well as Monte Carlo simulations are also presented to validate these results.     

TITAN: an ion trap for accurate mass measurements of ms-half-life nuclides

The introduction of Paul traps, in particular linear radio-frequency quadrupoles in the early 2000s, has revolutionized the use of ion traps for probing the properties of radioactive nuclides. It opened the path to trapping all available nuclides, independent of their chemical properties. We present an overview of direct mass measurements of short-lived nuclides using TITAN, a Penning trap mass spectrometer facility particularly suitable for precision measurements of ms-half-life nuclides.     

Synthetic thermally reversible gel systems. IV

The polymerization kinetics in water of acrylylglycinamide (AG) initiated by K₂S₂O₈ was studied over the temperature range 40.0 to 60.0°C. Monomer concentration was varied from 7.8 × 10^?3 to 31.2 × 10^?3M and catalyst from 1.85 × to 11.10 × 10^?5M. The rate expression is ?d[M]/dt = R_p, = k_1.22[K₂S₂O₈]^0.5[M]^1.22, and the overall empirical rate constant, k_1.22 = 1.14 × 10¹¹e^?15,800/RT 1.^0.72 mole^?0.72 min^?1. To explain the dependence on monomer, a kinetic scheme which includes a bimolecular reaction (k₂) between monomer and initiator is suggested. The simplified expression which describes the initial rate of polymerization is: ?d[M]/dt = R_p, = k₄(2[I]/k₅)^1/2[M](k₁ + k₂[M])^1/2, where k₁, k₂, k₄ and k₅ are rate constants for S₂O₈ = decomposition, a bimolecular reaction between monomer and initiator, propagation, and termination, respectively. Individual bimolecular rate constants are expressed in liter/mole-min. The equation predicts a dependence on monomer concentration between 1.0 and 1.5 with 1.5 being approached a t high monomer concentrations. Plots of R_P²/[M]² versus [M] are linear, as predicted by the postulated reaction route and values for k₂ and k₄/k₅^1/2 were obtained from the slopes and intercepts of these plots. The temperature dependence of the bimolecular monomer-initiator reaction is k₂ = 5.19 × 10²¹e^?36,000/RT. Instead of the usual behavior, the k₄/k₅^1/2 ratio was found to decrease with temperature and the difference of activation energies, (E₄ ? E₅/2), is ?1.50 kcal. The temperature dependence of the propagation to square root of the termination rate constant ratio is k₄/k₅^1/2 = 6.16e^1500/RT. These rather unusual results may be related to the ability of AG polymers in water to form thermally reversible gels; even above the gel melting points, the polymers are considerably aggregated in solution. This would tend to make the bimolecular termination reaction more temperature dependent and also account for the high values (59–69) for the k₄/k₅^1/2 ratios. For similar temperatures, the overall rate constants for AG are approximately four times those for acrylamide.     

From sulfur-amine solutions to metal sulfide nanocrystals: peering into the oleylamine-sulfur black box

In this Article, we present our findings on the formation of metal sulfide nanocrystals from sulfur-alkylamine solutions. By pulsed field gradient diffusion NMR along with the standard toolbox of 1D and 2D NMR, we determined that sulfur-amine solutions used as a sulfur precursor exist as alkylammonium polysulfides at low temperatures. Upon heating to temperatures used in nanocrystal synthesis, the polysulfide ions react with excess amine to generate H(2)S, which combines with the metal precursor to form metal sulfide. Four different reaction pathways were found, each of which produced H(2)S and the byproducts identified in this Article. Thioamides were identified as an intermediate and were shown to exhibit much more rapid kinetics than sulfur-alkylamine solutions at low temperatures in the synthesis of metal sulfide nanocrystals.     

Three-dimensional representation of metastable peaks at high mass resolution

Isobaric daughter ions formed from a common metastable ion have been analysed at high mass resolution. A three-dimensional representation is used to summarize the data for competitive CO and C₂H₄ losses and competitive CHO˙ and C₂H₅˙ losses from metastable molecular ions of cyclohexanone.     

Graphical aids and scanning modes for tandem mass spectrometry

In tandem mass spectrometry, where typically one analyser is used to study the reactions of ions selected by another analyser from a mixture leaving the ion source, the output contains an additional dimension of information compared to that from conventional mass spectrometry. The increase in dimensionality tends to make the results less easy to assimilate and interpret, but the difficulties may be overcome in large measure by presenting the results in an appropriate graphical form. This review deals with the use of graphical representations of three-dimensional data to display the results of experiments in tandem mass spectrometry. Perspective diagrams or contour maps can be used to show the identity of the parent and daughter ions for all of the reactions occurring in a tandem mass spectrometer, including reactions of positive ions, reactions of negative ions and charge inversion reactions. A graphical approach is particularly valuable when double focusing mass spectrometers are used for tandem mass spectrometry, because it can make it much easier to establish the origin of the ions contributing to an observed peak and thus to determine whether interference is occurring. Factors bearing on the choice of a coordinate system are discussed. Relationships characterizing the more important simple and linked scanning modes are listed and the features to which they correspond in two selected coordinate systems are shown. Factors that influence the resolution of neighbouring peaks by sector field tandem mass spectrometers are discussed.     

Titrimetric methods for the microdetermination of halogens in organic compounds by the rapid combustion procedure: The determination of individual halogens

A critical study has been carried out of titrimetric methods suitable for the microdetermination of each of the halogens, chlorine, bromine and iodine, in their possible organic combinations with the elements, oxygen, nitrogen and sulphur, following organic decomposition by the rapid empty tube combustion procedure.     

Tricyclic-isoxazolidine analogues via intramolecular 1,3-dipolar cycloaddition reactions of nitrones

The tricyclic-isoxazolidine analogues tetrahydrothiochromenoisoxazoles, hexahydroisoxazolequinolines and tetrahydroisoxazolepyranopyridines were prepared by an intramolecular 1,3-dipolar cycloaddition reaction of a nitrone with an alkene. For N-alkylated hexahydroisoxazolequinolines, reduction of the reaction time from two days to 40 min was achieved using microwave heating. The cyclization to form tetrahydroisoxazolepyranopyridines only proceeded when the alkene was substituted with an electron withdrawing group.     

Reversible,Photoinduced Activation of P4 by Low‐Coordinate Main Group Compounds

Two unique systems based on low‐coordinate main group elements that activate P₄ are shown to quantitatively release the phosphorus cage upon short exposure to UV light. This reactivity marks the first reversible reactivity of P₄, and the germanium system can be cycled 5 times without appreciable loss in activity. Theoretical calculations reveal that the LUMO is antibonding with respect to the main group element–phosphorus bonds and bonding with respect to reforming the P₄ tetrahedron, providing a rationale for this unprecedented activity, and suggesting that the process is tunable based on the substituents.