Stereochemical non-rigidity of a metal polyhedron; carbon-13 and platinum-195 fourier transform nuclear magnetic resonance spectra of [Ptn(CO)2n]2- (n = 3, 6, 9, 12 or 15)

Platinum-195 spectra are reported for [Pt_n(CO)_2n]^2- (n = 3, 6, 9, 12 and 15) and carbon-13 spectra are reported for n = 6, 9 and 12 over a range of temperatures. The spectra provide evidence for (a) intramolecular rotation of the Pt₃-triangles about the principal three-fold axis, (b) inter-exchange of Pt₃-triangles, (c) lack of terminal/edge carbonyl exchange within the Pt₃(CO)₃(μ-CO)₃ group. Evidence is also presented for the formation of [Ni₃Pt₃(CO)₁₂]^2- on mixing [Pt₆(CO)₁₂]^2- [Ni₆(CO)₁₂]^2-.     

Analysis of mixtures containing free fatty acids and mono-, di- and triglycerides by high-performance liquid chromatography coupled with evaporative light-scattering detection

Commercial monostearates of glycerol, generally used as antistatic agents for thermoplastic polymers, consist of a complex mixture of mono-, di- and trisubstituted glycerides and the corresponding fatty acids. Thus far, the glycerides and the fatty acids have been analyzed separately by high-performance liquid chromatography (HPLC). In fact, the simultaneous analysis of glycerides and fatty acids requires esterification of the acids in order to avoid overlapping of the chromatographic peaks. This paper describes an HPLC method which allows the direct separation and identification, simultaneously and in a single run, of the variously substituted glycerides, and also the corresponding saturated fatty acids that are found as by-products in commercial glycerol monostearates. The procedure is based on the use of a ternary gradient HPLC instrument equipped with an evaporative light-scattering detector; the stationary phase was a reversed-phase RP-8 end-capped (Merck) column; the mobile phase was two consecutive binary gradients consisting of acetonitile-water plus acetic acid (0.1%, v/v) and acetonitrile-methylene chloride. The method is fast and shows high sensitivity and selectivity, being able to separate also the positional isomers of mono- and digycerides in addition to the mixed di- and triglycerides.     

A theoreticalab initio study of the reaction of formation of 2-fluoroethanol from oxirane and HF

The reaction of ring opening of epoxides under the action of a halogenic acid has been investigated using as model the system C₂H₄O + HF → CH₂OHCH₂F. The physical conditions chosen for the model more directly correspond to the gas phase reaction and under these conditions the preferred mechanism leads to the formation of a halohydrine having the same configuration at the C atom as the reagent. Parallel investigations have been performed on other mechanisms which postulate the preliminary formation of the conjugate acid of the oxirane (C₂H₄OH⁺) and proceed via the well known mechanismsA ₁ orA ₂. In this case the best mechanism corresponds to the so-called “borderlineA ₂” mechanism. This last type of mechanism probably is the dominant one in protic solutions, but by coupling the present calculations with experimental conductometric measurements in anhydrous aprotic media one could consider the first concerted mechanism as a possible candidate also for the reaction in “inert” media. A qualitative analysis of the transition state indicates, in addition, that the propension for the retention path, is probably emphasized by the use of HF as reactant, and that with other acids, like HC1, or even by assuming the presence of dimers like HF·HF, the inversion path could be preferred. The investigations have been done by determining the geometry of the transition state and the reaction coordinate withab initio SCF STO-3G calculations on the whole nuclear configuration space (21 dimensions). These calculations have been supplemented by a few CI calculations on the same basis set and by a few SCF calculations with a larger basis set.     

Structure and molecular conformation of tussah silk fibroin films: Effect of heat treatment

Structural changes of tussah (Antheraea pernyi) silk fibroin films induced by heat treatment were studied as a function of the treatment temperature in the range 200–250°C. The DSC curve of tussah films with α-helix molecular conformation displayed characteristic endo and exo peaks at 216 and 226°C, respectively. These peaks first weakened and then completely disappeared after heating at 230°C. Accordingly, the TMA thermal shrinkage at 206°C disappeared when the films were heated at 230°C. The onset of weight loss was monitored at 210°C by means of TG measurements. X-ray diffraction profiles gradually changed from α-helix to β-sheet crystalline structure as the treatment temperature increased from 200 to 250°C. On raising the heating temperature above 200°C, the intensity of IR and Raman bands characteristic of β-sheet conformation increased in the whole ranges of amide and skeletal modes. The sample treated at 200°C showed a spectral pattern intermediate between α-helix and β-sheet molecular conformation. The IR marker band for random coil structure, still detectable at 200°C, disappeared at higher treatment temperatures. Spectral changes attributable to the onset of thermal degradation appeared at 230°C. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 841–847, 1997     

Immunotoxicity of butyltins in tunicates

This study was designed to investigate the effects of butyltins on yeast phagocytosis in vitro by haemocytes of the colonial ascidian Botryllus schlosseri. This species has been reported to be very sensitive to organotins. Results show that, in analogy to reports on mammalian leukocyte re-activity, butyltins exert inhibitory effects on phagocytosis in a concentration-dependent manner, mainly by influencing cellular calcium homeostasis by interacting with the calcium pump. As the immunosuppressant activity of organotins described in mammals and teleosteans also occurs in an invertebrate marine species, the latter may assume a role as a sensitive biosensor of butyltins as immunotoxins in aqueous ecosystems.     

A note on stable flow-equivalent aggregation in closed networks

We introduce the Conditional Mean Value Analysis (CMVA) algorithm, an exact solution method for product-form load-dependent closed queueing networks that provides a numerically stable solution of models where the load-dependent Mean Value Analysis (MVA) is numerically unstable. Similarly to the MVA algorithm for constant-rate queues, CMVA performs operations in terms of mean quantities only, i.e., queue-lengths, throughput, response times. Numerical stability derives from a new version of the MVA arrival theorem for load-dependent models which is expressed in terms of mean queue-lengths instead of marginal probabilities. The formula is obtained by the analysis of the conditional state spaces which describe network equilibrium as seen by jobs during their residence times at queues. We also provide a generalization of CMVA to multiclass models that preserves the numerical stability property.     

Structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SA) blend films

The structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SF) blend films were analyzed by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, x-ray diffractometry, and scanning (SEM) and transmission (TEM) electron microscopy. DSC curves of PVA/SF blend films showed a major endothermic peak at 220°C, along with a peak at 280°C. These endotherms were assigned to the thermal decomposition of the ordered PVA elements and to the thermal degradation of silk fibroin, respectively. The PVA/SF blends behaved in a manner intermediate to the pure components, as suggested by both contraction expansion and sample weight retention properties recorded by TMA and TGA measurements. The IR absorption spectra of the blends were identified as purely a composite of the absorption bands characteristic of both PVA and SF pure polymers. The X-ray diffraction patterns of PVA/SF blends showed overlapping spacing due to PVA and SF. A dispersed phase formed by spherical particles of 3–7 μm diameter was observed by SEM and TEM. All these findings suggest that PVA and SF are incompatible. © 1994 John Wiley & Sons, Inc.     

Quantum interference of electrons in a ring: tuning of the geometrical phase

We calculate the oscillations of the dc conductance across a mesoscopic ring, simultaneously tuned by applied magnetic and electric fields orthogonal to the ring. The oscillations depend on the Aharonov-Bohm flux and of the spin-orbit coupling. They result from mixing of the dynamical phase, including the Zeeman spin splitting, and of geometric phases. By changing the applied fields, the geometric phase contribution to the conductance oscillations can be tuned from the adiabatic (Berry) to the nonadiabatic (Ahronov-Anandan) regime. To model a realistic device, we also include nonzero backscattering at the connection between ring and contacts, and a random phase for electron wave function, accounting for dephasing effects.