Fast-atom-bombardment and tandem mass spectrometry for determining structures of fatty acids as their picolinyl ester derivatives

Picolinyl ester derivatives of common fatty acids can be readily desorbed by fast atom bombardment (FAB) as positive ions and then collisionally activated. Collisionally activated spectra of the (M + H)⁺ ions of the derivatives reveal that structurally informative remote-charge-site fragmentations occur. The presence of substitutents such as double bond, branch points, cyclopropane rings, hydroxy groups, and epoxy rings interrupts the fragmentation process in such a way that the substituent can be identified and its location on the alkyl chain can be determined. This method is also applicable to the picolinyl esters of short-chain fatty acids and to the analysis of mixtures of fatty acid derivatives. The approach is advantageous becasue the epicolinyl ester derivatives are also amenable to gas chromatography/mass spectrometry (GC/MS). Therefore, the FAB-MS/MS approach developed here is complementary to GC/MS.     

Frequency-dependent linear response of superconducting systems

We present a density functional scheme for calculating the frequency-dependent linear response of superconductors. The central result is a set of integral equations determining the linear response of the normal and anomalous densities to external perturbations. Analytic solutions of these integral equations are obtained for homogeneous systems with separable effective interactions. For inhomogeneous superconductors, the formalism leads to a scheme for calculating the critical temperature without explicitly solving the gap equation. © 1995 John Wiley & Sons, Inc.     

Examining the role of surfactant packing in phase transformations of periodic templated silica/surfactant composites

In this work, we examine the role of curvature and surfactant packing in controlling the structure of periodic silica/surfactant composites by driving such materials through a transformation from a hexagonal to a lamellar phase. We focus on how the interplay of desired packing and volume constraints dictates the resulting structures. In general, surfactants expand in a complex way upon heating, and this can cause a change in the optimal packing geometry. However, the presence of a rigid silica framework may prevent surfactants from reaching this preferred volume and/or curvature. Real-time in situ X-ray diffraction is used to monitor the structural evolution of these materials heated under hydrothermal treatments. Because the thermal-driven disorder of the surfactant tails drives the phase transition, we examine four types of composites with varying tail density. Ordinarily, composites consist of surfactants with one 20-carbon tail and one positively charged ammonium headgroup. Tail density is varied by replacing a small amount (0-16%) of these single-tail, single-head surfactants with single-tail, double-head 'gemini' surfactants. A greater head--tail ratio indeed produces different results, causing the phase transition to occur at higher temperatures. Using simple geometric models to gain better understanding of our experimental results, we find that, while both unfavorable curvature and limited volume may exist for the surfactants in these composites, the constrained curvature appears to be the dominant effect in driving structural rearrangement.     

The utilization of classical spin Monte Carlo methods to simulate the magnetic behavior of extended three-dimensional cubic networks incorporating M(II) ions with an S = 5/2 ground state spin

The numerical simulations of the magnetic properties of extended three-dimensional networks containing M(II) ions with an S = 5/2 ground-state spin have been carried out within the framework of the isotropic Heisenberg model. Analytical expressions fitting the numerical simulations for the primitive cubic, diamond, together with (10-3) cubic networks have all been derived. With these empirical formulas in hands, we can now extract the interaction between the magnetic ions from the experimental data for these networks. In the case of the primitive cubic network, these expressions are directly compared with those from the high-temperature expansions of the partition function. A fit of the experimental data for three complexes, namely [(N(CH(3))(4)][Mn(N(3))] 1, [Mn(CN(4))](n)() 2, and [Fe(II)(bipy)(3)][Mn(II)(2)(ox)(3)] 3, has been carried out. The best fits were those obtained using the following parameters, J = -3.5 cm(-)(1), g = 2.01 (1); J = -8.3 cm(-)(1), g = 1.95 (2); and J = -2.0 cm(-)(1), g = 1.95 (3).     

Ion chromatographic determination of nitrate and nitrite in vegetable and fruit baby foods

An ion chromatographic method was developed for the determination of nitrate and nitrite in vegetable and fruit baby foods. The introduction of nitrate or nitrite to food may be natural or artificial as a preservative. Because of the higher pH found in babies' stomachs, nitrate can act as a reservoir for the production of nitrite by nitrate-reducing bacteria that can be harbored in the intestinal tract. This problem does not exist in adults because of the lower pH of the adult stomach. Exposure to nitrite by infants can result in methemoglobinemia (blue baby syndrome). There are also indications that carcinogenic nitrosamines can be formed from nitrates at the higher pH. These gastric conditions disappear at approximately 6 months of age. In this method, nitrate and nitrite were separated on a hydroxide-selective anion exchange column using online electrolytically generated high-purity hydroxide eluant and detected using suppressed conductivity detection. Average recoveries of spiked nitrite residue ranged from 91 to 104% and spiked nitrate residue ranged from 87 to 104%. This method and the AOAC Official Method yield comparable results for samples containing incurred nitrate residue. In addition, this method eliminates the hazardous waste associated with the use of cadmium found in the AOAC Official Method.     

Time-dependent density functional theory: past, present, and future

Time-dependent density functional theory (TDDFT) is presently enjoying enormous popularity in quantum chemistry, as a useful tool for extracting electronic excited state energies. This article discusses how TDDFT is much broader in scope, and yields predictions for many more properties. We discuss some of the challenges involved in making accurate predictions for these properties.     

The Formation of C?C Bonds with the Aid of α-Halogeno Ethers,Sulfides, and Amines

α-Halogeno ethers, sulfides, and amines are reactive compounds which can be used for the formation of new C? C bonds, either as nucleophilic or as electrophilic reagents, or by α-elimination. The use of these compounds in the synthesis of many classes of organic compounds is reviewed.     

Bislactonization of unsaturated diacids using lead tetraacetate

The reaction of lead tetraacetate with unsaturated carboxylic acids (or salts) to from bislactones (γ or δ) can be controlled to produce efficiently $\text{cis}$ addition of two carboxylic oxygens to the double bond, in consonance with an initial plumbolactonization step followed by S_N2 displacement of lead.     

The chemistry of the azanonaborane cluster RNH2---B8H11NHR

The preparation and properties of the R¹R²NH---B₈H₁₁NHR cluster are described. The cluster is stable to aqueous solutions and can be made water-soluble by the introduction of a few hydrophilic groups. This makes the cluster a good candidate as the boron moiety in compounds for boron neutron capture therapy. The chemistry of the cluster preparation, the stability of the cluster, and conditions for reactions of the organic moieties are reviewed. Pyridine derivatives of the cluster show electronic interaction between the cluster and the pyridine.