Sub-Nominal Resolution Fourier Transform Spectrometry with Chip-Based Combs

Chip-based optical frequency combs address the demand for compact, bright, coherent light sources of equidistant phase-locked lines. Traditionally, the Fourier Transform Spectroscopy (FTS) technique is considered a suboptimal choice for resolving comb lines in chip-based sensing applications due to the requirement of long optical delays, and spectral distortion from the instrumental line shape. Here, a sub-nominal resolution FTS technique is developed that extracts the comb's offset frequency in any spectral region directly from the measured interferogram without resorting to nonlinear $$-to- $$ interferometry. This in turn enables 10's of MHz resolution spectrometry with millimeter optical retardations currently limited by the emission linewidth and phase noise of the used lasers. Low-pressure Doppler-broadened absorption lines probed by widely-tunable chip-scale mid-infrared optical frequen with electrical pumping are fully resolved over a span of tens of nanometers. This versatile technique paves the way for compact, electrostatically-actuated, or even all-on-chip high-fidelity FTS, and can be readily applied to boost the resolution of existing commercial instruments with compact interferometers several hundred times.     

Peroxyoxalate-chemiluminescence of Tinopal CBS as a commercially important optical brightener: Mechanistic study and quantification

The peroxyoxalate-chemiluminescence arising from reaction of bis(2,4,6-trichlorophenyl)oxalate with hydrogen peroxide in the presence of a brightener Tinopal CBS (2,2′-((1,1′-biphenyl)-4,4′-diyldi-2.1-ethenediyl)bisbenzene sulfonic acid, disodium salt) has been studied. The relationship between the chemiluminescence intensity and concentrations of bis(2,4,6-trichlorophenyl)oxalate, sodium salicylate (as catalyst), hydrogen peroxide and Tinopal CBS is reported. The chemiluminescence parameters including intensity at maximum chemiluminescence, time at maximum intensity, total light yield, theoretical maximum level of intensity and pseudo-first-order rate constants for the rise and fall of the chemiluminescence burst (k_r and k_f) were evaluated from computer fitting of the resulting intensity-time plots. The activation parameters E_a, ΔH^‡, ΔS^‡ and ΔG^‡ for the rise and fall steps were evaluated from the temperature dependence of k_r and k_f values. The results were discussed in terms of chemically initiated electron transfer between a reactive intermediate and Tinopal CBS as fluorescence activator. A possible mechanism involving dioxetanone derivatives as intermediates is proposed. Since there is a linear relationship between reciprocal of chemiluminescence intensity and reciprocal of fluorescer concentration, an analytical method based on partial least squares (PLS) regression was proposed for quantitative determination of Tinopal CBS. Satisfactory results were obtained with percent relative prediction error (RPE%) of 2.52 and detection limit of 2.7×10⁻⁵ M.     

Spectrophotometric determination of tranexamic acid in pharmaceutical bulk and dosage forms.

In this study, a simple, fast, accurate and sensitive spectrophotometric method has been developed for the determination of tranexamic acid in bulk and pharmaceutical preparations. The method is based on the reaction of ninhydrin with the primary amino group of tranexamic acid in the basic medium at pH 8.0. The reaction produces a bluish-purple color which absorbs maximally at 565 nm. Beer's law was obeyed in the range of 3-40 microg ml(-1) with molar absorptivity of 5.093 x 10(3) L mol(-1) cm(-1). The effects of various factors such as temperature, heating time, concentration of reagent, color stability and interferences were investigated to optimize the procedure. The results have been validated analytically and statistically. The proposed method has been applied for the determination of tranexamic acid in bulk and pharmaceutical preparations with good results.     

TmDOTA-: a sensitive probe for MR thermometry in vivo.

The lanthanide complex, thulium 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (TmDOTA-), has been investigated as an agent for MR thermometry in vivo. The chemical shifts of the TmDOTA- protons were highly sensitive to temperature at a clinically relevant field strength, yet insensitive to pH and the presence of Ca2+. Given the excellent stability of lanthanide-DOTA complexes and high thermal sensitivity, TmDOTA- is expected to be a good candidate for MR thermometry in vivo.     

Investigations of the use of 4-(5-nonyl)pyridine as a liquid anion exchanger for tetrachloroferrate ions in aqueous chloride media

In an attempt to gain an understanding of factors affecting the extraction of iron(III) by 4-(5-nonyl)pyridine, the equilibria between hydrogen chloride and benzene solutions of 4-(5-nonyl)pyridine have been studied. From acid distribution data and visible absorption spectra of the organic phases, it was concluded that FeCl ₄ ⁻ ion, with a tetrahedral sp³ configuration is the principal iron containing species. The pyridine extraction of macro and trace amounts of the metal has indicated the formation of 1∶1 and 2∶1 complexes respectively. The 2∶1 complexes are assumed to result from association of a 1∶1 complex with a molecule of the pyridine hydrochloride. The salting-out effect increases in the order, LiCl<NaCl<MgCl₂<AlCl₃ and these differences in the effect have been attributed to the different degree of hydration of cations of the salts present and to the ionic radii. The effect of various anions including the reducing agents have been described. Separation factors of several metal ions relative to ferric iron, in 6M HCl, are also reported.     

Poly (vinyl chloride) decomposition in solution

Thermal degradation of PVC in various solvents at 180° has been observed to be in the following order: benzonitrite > nitrobenzene > cyclohexanone > dioctyl phthalate > α-bromonaphthalane > decahydronaphthalene. The effect has been explained on the basis of β-eliminations of E₁-type favoured by polar solvents. An inhibition in PVC degradation has been observed in nitrobenzene containing stationary hydrogen chloride gas. The deceleration in degradation by predissolved HCl has been accounted for as a Mass Law effect.     

A new phthalic acid ester from Ajuga bracteosa

A new phthalic acid ester 1,2-benzenedicarboxylic acid bis(2S-methyl heptyl) ester (1) was isolated from the hexane extract of the whole plant of Ajuga bracteosa. In addition, chloroform and methanol extracts yielded neo-clerodane diterpene ajugarin-I and two iridoid glycosides, reptoside and 8-O-acetyl harpagide. The structures of all the compounds were confirmed by extensive spectroscopic analysis. From the two oily fractions nine and six volatile constituents respectively were identified by GCMS. Linalyl acetate was found to be common in both the oil fractions. This plant is a new source of linalyl acetate, a valuable perfumery compound.     

Material ablation and plasma plume expansion study from Fe and graphite targets in Ar gas atmosphere

Study of expansion dynamics of pulsed-laser ablation plasmas from Fe and graphite targets is presented. A 532 nm Q-switched Nd:YAG laser with fluence of 30 J cm⁻² is used to ablate the Fe and graphite targets in various Ar ambient gas pressures. Plasma ablation parameters for the two target materials are estimated using snow-plow and shock-wave models, which show that the laser beam energy deposited to ablated species remains at 70% for both targets at all ambient pressures. The plume splitting was observed, more prominently, for Fe plasma as it moves faster compared to graphite plasma. The difference in plasma plume fronts’ speeds for different targets was attributed to the significant difference in mass of the ablated plasma for two targets, as estimated from simulation results.     

High Pressure High Temperature Dynamic Rheometry of Sulfonated Polyacrylamide Solutions in Electrolyte Media as Used for Oil Recovery Applications

Sulfonated polyacrylamide (SPAA) solutions were prepared and the effects of pressure, polymer concentration, and water temperature, pH and salinity on their rheological behavior were investigated using a concentric cylinder dynamic rheometer equipped with a high pressure cell. According to the rheological flow curves the shear stress of SPAA solutions increased less than in proportion to their shear rates; that is, a shear thinning effect occurred. For polymer solutions containing 15,000 ppm of SPAA, shear viscosity, and stress were nearly insensitive to pressure. However, the shear viscosity and stress of SPAA solutions were affected by temperature and this effect was more evident at lower pressure. The flow curves indicated the shear viscosity and stress of the samples increased with increasing SPAA concentration and pH of the water, but were decreased with increasing water salinity and temperature.