Increase of fluorescence anisotropy upon self-assembly in headgroup-labeled surfactants

The change in fluorescence anisotropy upon micellization in headgroup-labeled surfactants is investigated. After eliminating the likelihood of depolarizing RET, anisotropy is shown to increase upon self-assembly due to increased rotational correlation times of the fluorophore. This is shown using two surfactant-fluorophore systems. Anisotropy in NBD-labeled phospholipids is studied both in chloroform (unaggregated) and in water (unilamellar vesicles), while in tryptophan-containing peptide-amphiphiles, the variation of anisotropy with concentration leads to a reasonable measurement of CAC. Anisotropy increase is shown to be largely the product of increased rotational correlation times for the fluorophore, relative to its tau. These results serve as a basis for future work that measures the amount of depolarizing energy transfer, characterizing distances between similar fluorescent headgroups on mixed micelles.     

MAS-NMR studies of lithium aluminum silicate (LAS) glasses and glass-ceramics having different Li2O/Al2O3 ratio

Emergence of phases in lithium aluminum silicate (LAS) glasses of composition (wt%) xLi₂O-71.7SiO₂-(17.7−x)Al₂O₃-4.9K₂O-3.2B₂O₃-2.5P₂O₅ (5.1≤x≤12.6) upon heat treatment were studied. ²⁹Si, ²⁷Al, ³¹P and ¹¹B MAS-NMR were employed for structural characterization of both LAS glasses and glass-ceramics. In glass samples, Al is found in tetrahedral coordination, while P exists mainly in the form of orthophosphate units. B exists as BO₃ and BO₄ units. ²⁷Al NMR spectra show no change with crystallization, ruling out the presence of any Al containing phase. Contrary to X-ray diffraction studies carried out, ¹¹B (high field 18.8 T) and ²⁹Si NMR spectra clearly indicate the unexpected crystallization of a borosilicate phase (Li,K)BSi₂O₆, whose structure is similar to the aluminosilicate virgilite. Also, lithium disilicate (Li₂Si₂O₅), lithium metasilicate (Li₂SiO₃) and quartz (SiO₂) were identified in the ²⁹Si NMR spectra of the glass-ceramics. ³¹P NMR spectra of the glass-ceramics revealed the presence of Li₃PO₄ and a mixed phase (Li,K)₃PO₄ at low alkali concentrations.     

Dual/scram-mode combustion limits of ethylene and surrogate endothermically-cracked hydrocarbon fuels at Mach 8 equivalent high-enthalpy conditions

This paper examines the scram/dual-mode combustion limits of hydrocabon fuels within a Mach 8, scramjet combustor. Flight-equivalent flows were delivered to the axisymmetric, cavity combustor via a reflected shock tunnel. Two scramjet fuels were examined: ethylene and a surrogate mixture representing endothermically cracked n-dodecane. Combustion modes were examined via static pressure sensors and through both chemiluminescence imaging, and planar laser induced fluorescence (PLIF) of the OH combustion radical in the combustor exhaust plume. Ethylene-fuelled experiments developed scram-mode combustion under reduced fuelling conditions, experiencing shock wave dominated flowfields. OH PLIF diagnostics indicated such combustion modes developed a ring-like structure of combustion products, primarily axisymmetrically adjacent to the combustor wall. Increased fuelling anchored combustion downstream of the fuel injector, while further increases instigated dual-mode combustion. In this mode, subsonic combustion regions combine with the supersonic coreflow to permit the transfer of information upstream with substantially increased pressure encountered. Optical diagnostics indicate broadly asymmetric, unsteady combustion features. The surrogate mixture representing endothermically cracked n-dodecane experienced rapid onset from no-combustion (optically confirmed) to fully developed dual-mode combustion at critical fuelling rates. OH PLIF signals and chemiluminescence of this fuel were weaker than comparable ethylene cases, indicating potential differences in combustion pathways.     

Radiation stability study on cerium loaded iron phosphate glasses by ion irradiation method

Journal of Radioanalytical and Nuclear Chemistry - To study radiation stability of iron phosphate glasses, cerium is used as surrogate of actinides. Cerium doped iron phosphate glasses have been...     

Raman spectra of crystalline double sulphates

Raman spectra of single crystals of K₂M(SO₄)₂ · 6 H₂O where M=Mg, Zn, Ni or Co have been recorded for the first time usingλ 2537 as the exciting radiation. The corresponding five single sulphates have also been studied. Interesting results concerning the substitution of magnesium, zinc, nickel or cobalt in the double sulphate lattice on the sulphate frequencies are observed. The lattice spectra of these double sulphates are analysed group theoretically and discussed in relation to the lattice spectra of the corresponding individual sulphates. Certain new results concerning the Raman spectra of the individual sulphates have also been obtained and in the case of CoSO₄ · 7 H₂O the spectrum has been recorded for the first time.     

Polarisation studies on the Raman spectra of cubic crystals

Polarisation characters of the Raman lines of calcium fluoride (fluorspar) and potassium aluminium sulphate (alum) were investigated under the following conditions. Unpolarised light was incident normally on a face of the crystal making an angle 22.5° with a cubic face and the light scattered transversely along a cubic axis was analysed by a double image prism kept with its principal axes inclined at 45° to the vertical. Under these conditions the depolarisation factors of the Raman lines belonging to the totally symmetric (A), the doubly degenerate (E) and the triply degenerate (F) modes should be respectively =1, >1 and <1. The characteristic Raman line of CaF₂ at 322 cm^?1 exhibited a depolarisation value less than 1, showing thereby that the corresponding mode is a triply degenerate one (F). The Raman lines observed in the spectrum of K-alum were also classified and the results were compared with those given by previous investigators using standard crystal orientations.     

Potentiometric titration in a low volume of solution for rapid assay of uranium: application to quantitative electro-reduction of uranium(VI)

A simple, inexpensive PC based potentiometric titration technique for the assay of uranium using low volumes of sample aliquot (25–100 μL) along with all reagents (total volume of solution being less than 2.5 mL) is presented. The technique involves modification of the well known Davies and Gray Method recommended for assay of uranium(VI) in nuclear materials by introducing an innovative potentiometric titration device with a mini cell developed in-house. After appropriate chemical conditioning the titration is completed within a couple of minutes with display of online titration plot showing the progress of titration. The first derivative plot generated immediately after titration provides information of end point. The main advantage of using this technique is to carry out titration with minimum volumes of sample and reagents generating minimum volume of wastes after titration. The validity of the technique was evaluated using standard certified samples. This technique was applied for assay of uranium in a typical sample collected from fuel reprocessing laboratory. Further, the present technique was deployed in investigating the optimum conditions for efficient in situ production of U(IV). The precision in the estimation of uranium is highly satisfactory (RSD less than 1.0%).     

A Comparative Overview of Glass-Ceramic Characterization by MAS-NMR and XRD

Glass-ceramics are polycrystalline materials formed by controlled crystallization of parent glasses, which can be studied complementarily by XRD and NMR. XRD probes long-range order, while NMR is more element specific and probes the immediate environment around the atoms. These techniques allow considerable insights into the crystalline and amorphous constituents of glass-ceramics. In this article, we highlight some key issues in the characterization of glass-ceramics: phase identification and quantification, and structural characterization of the residual glass. The application of both NMR and XRD techniques are considered in these areas and their advantages and limitations discussed using our recent work and examples from the literature.     

Feasibility studies for the detection of third phase during reprocessing of fast reactor fuel

A conductometric technique for the determination of third phase, a phase formed by splitting of organic phase during malfunction in operation, during reprocessing of fast reactor fuel using a high resolution conductivity monitoring instrument with pulsating sensor developed in-house was tested. Initial studies were carried out in laboratory using uranous salt solutions (U⁴⁺) in various synthetic samples containing different aqueous (A) to organic (O) phase ratios (A/O). Results show that there is appreciable increase in conductivity of third phase solution compared to the other organic phase (~100 to ~300 times higher). Such a large change in conductivity in third phase with respect to the other organic phase can be used as a deciding parameter to give first hand information about the occurrence of third phase.