Simultaneous Determination of Acetylsalicylic Acid and Caffeine in Pharmaceutical Formulation by First Derivative Synchronous Fluorimetric Method

A sensitive, rapid, and specific assay has been developed for the simultaneous determination of acetylsalicylic acid and caffeine in commercial tablets based on their natural fluorescence. The mixture of these drugs was resolved by first derivative synchronous fluorimetric technique using two scans. At Δλ=106 nm, using first derivative synchronous scanning, only acetylsalicylic acid yields a detectable signal at 316 nm (peak to zero method) which is unaffected by caffeine. At Δλ=30 nm, the signal of caffeine at 288 nm (peak to zero method) is not affected by acetylsalicylic acid. The range of application is between 0.021 and 41.62 μg ml⁻¹ (correlation coefficient, R=0.9995) for acetylsalicylic acid and between 0.4486 and 44.86 μg ml⁻¹ (correlation coefficient, R=0.99786) for caffeine. The recovery range of 98.40–102% for acetylsalicylic acid and 90–100.5% for caffeine from their synthetic mixture was reported. Overall recovery of both compounds about 97–99% for acetylsalicylic acid and 97–98% for caffeine was obtained from real sample analysis. The detection limits are 0.0013 μg ml⁻¹ and 0.0306 μg ml⁻¹ for acetylsalicylic acid and caffeine, respectively. The relative standard deviation (n=10) for 20 μg ml⁻¹ of acetylsalicylic acid is 2.75% and for 2.2 μg ml⁻¹of caffeine is 1.7%.     

Leaky modes and their contributions to the compressional head wave in a borehole excited by a dipole source

A method of studying the contributions of leaky modes to the wave field is presented based on the analysis of the Riemann surface structure of the characteristic function, and the sensitivities of con- tributions to various factors of interest are examimed. Numerical results show that their contributions to the compressional head wave are related to the distributions of complex poles on (-1, -1) and (0, -1) Riemann sheets on the frequency-wavenumber (ω - k) plane. For fast formations, their contributions ar...     

Calculation of conformations and vibrational spectra of a monomeric fragment of the 2,6-carboxymethyl cellulose molecule

A theoretical conformational analysis has been carried out for the side substituents of a fragment of the molecule for 2,6-carboxymethyl cellulose (a water-soluble cellulose ether), and the frequencies and the potential energy distribution of the normal vibrations have been calculated for the most stable conformers of the ether groups of this fragment in the approximation of the molecular mechanics method. It has been shown that the most stable conformers are those that have the conformations gg, t, g⁻, g⁻, g⁻-for the groups of atoms on the bonds C5-C6, C6-O6, C13-O6, C10-C13, C10-O9 and the conformations g⁺g⁻, g⁺, g⁻, g⁻; g⁺g⁻, g⁻, g⁻, g⁻; g⁺g⁻, g⁻, g⁺, t for the groups of atoms on the bonds C2-O2, C11-O2, C7-C11, C7-O8. Comparative analysis of the calculated frequencies and the potential energy distribution of the normal vibrations for 13 of the most stable conformers showed, as in the case of the 2,6-hydroxyethyl cellulose molecule, that the frequencies and modes of the normal vibrations are highly sensitive to conformational transitions in the analyzed spectral region (800–1500 cm⁻¹). The characteristic patterns for the change in the frequencies and modes of the normal vibrations have been established in connection with conformational transitions within both side substituents. The observed conformational lability of the bulky substituents in the cellulose ether molecules and its manifestations in the vibrational spectrum provide a basis for hypothesizing that one of the major mechanisms for the process of their thermal gelation in aqueous solutions is conformational transitions within these substituents. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 5–15, January–February, 2007.     

Investigations on selected gallium and strontium doped lanthanum chromites as electrode materials for HC detection

Perovskite-type mixed oxides with the formula LaCr_1−yGa_yO_3−δ and La_0.95Sr_0.02Cr_1−yGa_yO_3−δ with y=0.1; 0.2; 0.3 were investigated in view of their usability as electrode materials in exhaust gas sensors for hydrocarbon (HC) detection. The electrode materials were characterized regarding their catalytic activity for propylene and propane oxidation and their potentiometric behavior in oxygen containing gaseous mixtures of these combustibles. The potentiometric measurements with propane indicate higher sensitivities of the strontium doped materials than of the materials without strontium. The comparison of these results with those of the catalytic investigations using propane show, that a lower catalytic activity comes along with a higher sensitivity. The electrodes show non-Nernstian behavior. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Kinetics of the initial stage in a first-order phase transformation in thin films

The nucleation and growth of islands of a new phase on the surface of solids has been studied both experimentally and theoretically for the particular case of the transition from the pyrochlore to perovskite phase in a thin film of a lead zirconate-titanate ferroelectric. This transformation was chosen because the new-phase islands have a stable circular shape in this case, a relatively large size (10⁻⁵–10⁻⁴ m) permitting their observation with an optical microscope, and a low growth rate (10⁻⁸–10⁻⁹ m/s). A theoretical analysis of the process, based on the kinetic theory of first-order phase transitions proposed earlier, has been carried out and the behavior in time of all main characteristics of a phase transformation, namely, nucleation rate, concentration of the new-phase islands, their size distribution, and relative overheating, has been calculated. The same characteristics have been measured experimentally, thus permitting one for the first time to make a thorough comparison of the theoretical with experimental data on the kinetics of first-order phase transitions. They have been found to be in a good agreement. Fiz. Tverd. Tela (St. Petersburg) 39, 121–126 (January 1997)     

Self-diffusion of lithium,hydrogen, and oxygen ions in crystalline lithium hydroxide

The self-diffusion coefficients of ions of the three chemical elements forming lithium hydroxide have been determined by the crystal-crystal and crystal-gas isotope exchange method in the temperature range 500–720 K. Crystal samples with different isotope compositions have been grown by the Bridgman method from melts. The melting temperature is 743 ± 2 K. Original methods have been developed for high-precision measurements of the isotope ratios of all three elements, i.e., lithium (⁶Li/⁷Li), hydrogen (H/D), and oxygen (¹⁶O/¹⁸O), and their changes after diffusion annealings with the use of the same sample. The self-diffusion coefficients of lithium and hydrogen ions differ but by a factor of no more than 3–5; however, their values exceed those for oxygen by several orders of magnitude. In particular, at 670 K, they are equal to 6.0 × 10⁻⁹, 3.2 × 10⁻⁹, and 2.0 × 10⁻¹² cm² s⁻¹ for hydrogen, lithium, and oxygen, respectively. In the range 680–720 K, the self-diffusion coefficients of hydrogen and lithium increase sharply with increasing temperature to approximately 10⁻⁶ cm² s⁻¹. A probable mechanism of migration of protons and lithium ions in LiOH and the role played in this process by the oxygen ions with a lower mobility have been discussed.     

Negative ions Ar<Superscript>−</Superscript>, Kr<Superscript>−</Superscript>, and Xe<Superscript>−</Superscript> in superfluid helium

The catalogue of negative ions in superfluid helium has been extended using the example of Ar⁻, Kr⁻, and Xe⁻. Such objects cannot exist in vacuum, since the polarization attraction of an electron to the inert A atom is insufficient for the formation of the bound state A⁻. However, these objects exist in helium as stable or metastable with a very long lifetime. The effect is due to the electron localization in liquid helium. If a mixture of excited A* atoms and electrons is prepared in the gas phase above liquid helium, the reaction A* + e = A*⁻ becomes possible for all atoms of the periodic table. Such charges can be immersed into liquid helium by the electric field. In this case, the radiative decay A*⁻ = A + e allowed in vacuum can be forbidden in liquid. This leads to the formation of the new unique objects A⁻, which can exist in liquid helium but are absent in nature. The size of such charged formations has been determined and is close the radius of a usual electron bubble in helium.     

The Sensitive Determination of Nucleic Acids Using Fluorescence Enhancement of Eu<Superscript>3+</Superscript>-BenzoylacetoneCetyltrimethylammonium Bromide-Nucleic Acid System

A new quantitative method for micro amounts of nucleic acids in aqueous solution is proposed using Eu³⁺-benzoylacetone (BA) complex as fluorescent probe in the presence of cetyltrimethyl-ammonium bromide (CTMAB). Under the optimum condition, the ratio of the fluorescence intensities with and without nucleic acids is proportional to the concentration of nucleic acid in the range of 1.0 × 10⁻⁹ to 5.0 × 10⁻⁶ g/mL for herring sperm DNA (hsDNA), 3.0 × 10⁻⁹ to 1.0 × 10⁻⁶ g/mL for calf thymus DNA(ctDNA) and 8.0 × 10⁻⁹ to 1.0 × 10⁻⁶ g/mL for yeast RNA (yRNA), and their detection limits are 0.33, 0.21 and 0.99 ng/mL, respectively. Actual sample (DNA of Arabidopsis thaliana) was determined satisfactorily. In addition, the interaction mechanism is also investigated.     

Fluorescence Enhancement of the Silver Nanoparticales – Curcumin - Cetyltrimethylammonium Bromide-nucleic Acids System and its Analytical Application

It is found that silver nanoparticles (AgNPs) can further enhance the fluorescence intensity of curcumin (CU) - cetyltrimethylammonium bromide (CTAB) – nucleic acids and improve its anti-photobleaching activity. Under optimum conditions, the enhanced fluorescence intensity is proportion to the concentration of nucleic acids in the range of 2.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹ for fish sperm DNA (fsDNA), 2.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹ for calf thymus DNA (ctDNA), 1.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹ for yeast RNA (yRNA), and their detection limits (S/N = 3) are 8.0 ng mL⁻¹, 10.5 ng mL⁻¹ and 5.8 ng mL⁻¹, respectively. This method is used for determining the concentration of DNA in actual sample with satisfactory results. The interaction mechanism is also studied.     

Spectrofluorimetric Protocol for Ceftriaxone in Commercial Formulation and Human Plasma After Condensation with Formaldehyde and Ethyl Acetoacetate

A new spectrofluorimetric method has been developed and validated for the quantification of ceftriaxone in bulk powder, pharmaceutical formulations and spiked human plasma. The developed method is reproducible, accurate, sensitive and cost effective. In this method, ceftriaxone was converted into a fluorescent compound by reacting with 0.8 M ethyl acetoacetate and 25% formaldehyde in a buffered medium (pH = 4.2) at 90 °C. The excitation and emission wavelengths of the fluorescent reaction product are 316 nm and 388 nm respectively. Optimization of the experimental conditions affecting the condensation reaction were carefully carried out and the optimum experimental conditions were incorporated in the procedure. The developed method has a broad linear range (0.2–20 μg mL⁻¹) with a correlation coefficient of 0.9992. The limit of detection (LOD) and limit of quantification (LOQ) was found to be 1.94 × 10⁻² μg mL⁻¹ and 6.47 × 10⁻² μg mL⁻¹ respectively. The common excipients and co-administered drugs were investigated for their interferences effect in the assay. The developed method was validated statistically through recovery studies and successfully applied to ceftriaxone determination in bulk powder, pharmaceutical formulations and spiked human plasma samples. The percent recoveries were found to be in the range of 99.04–100.26% for bulk powder, 98.88–99.92% for pharmaceutical formulations and 94.22–98.48% for spiked human plasma. The results were verified by comparing with reference literature HPLC method and were found in good agreement.     

Low-Temperature Dynamics of the Curie-Weiss Model: Periodic Orbits,Multiple Histories,and Loss of Gibbsianness

We consider the Curie-Weiss model at initial temperature 0<β ⁻¹≤∞ in vanishing external field evolving under a Glauber spin-flip dynamics with temperature 0<β′⁻¹≤∞. We study the limiting conditional probabilities and their continuity properties and discuss their set of points of discontinuity (bad points). We provide a complete analysis of the transition between Gibbsian and non-Gibbsian behavior as a function of time, extending earlier work for the case of independent spin-flip dynamics.     

Production of slow muonic hydrogen isotopes in vacuum

Muonic hydrogen isotopes (μ⁻ p, μ⁻ d, and μ⁻t) are simple quantum mechanical systems ideally suited for studies of numerous fundamental phenomena in electroweak and strong interactions as well as in applied areas such as muon chemistry or muon catalyzed fusion. Emission of muonic hydrogen isotopes into vacuum helps to overcome the limitations which are normally imposed on conventional investigations with gaseous and liquid targets. A proof of principle experiment for this new technique was performed at TRIUMF last year. Negative muons with 30 MeV/c momentum were stopped in a thin film of solid hydrogen and produced very low energy μ⁻d in vacuum. The distribution center of the normal velocity components of emitted μ⁻d atoms was measured to be ∼1 cm/μs. The yield of μ⁻d in vacuum is an increasing function of H₂ film thickness δ up to a value of δ≥1 mm.     

Atmospheric gamma rays in the energy region 40–1000 GeV

A large stack of lead-emulsion sandwich detector assembly was flown over Hyderabad, India. High energy gamma rays at the float altitude were unambiguously identified from the cascades they induced, and their energies reliably determined by improved methods. From an analysis of 163 gamma rays of energy ≳ 30 GeV, it is found that the differential energy spectrum is represented by the power lawJ _r (E)= 129·4E ^{−2·62±0·12} photons m⁻² sr⁻¹sec⁻¹ GeV⁻¹ at an effective atmospheric depth of 14·3 g cm⁻²; this is the first reliable balloon measurement of atmospheric gamma rays in the energy range 40–1000 GeV. After correcting for the gamma rays radiated by the primary cosmic ray electrons, the production spectrum of gamma rays, resulting from the collisions of cosmic ray nuclei with air nuclei, at the top of the atmosphere isP _r (E, 0)=8·2 × 10⁻⁴ E^2.60±0.09 photons g⁻¹sr⁻¹sec⁻¹ GeV⁻¹. The atmospheric propagation of the electromagnetic component due to the cascade process is also derived from the gamma ray production spectrum.     

Spectrofluorimetric Assessment of Doxycycline Hydrochloride in Pharmaceutical Tablets and Serum Sample Based on the Enhancement of the Luminescence Intensity of the Optical Sensor Sm<Superscript>3+</Superscript> Ion

A simple and sensitive spectrofluorimetric method for determination of trace amount of doxycycline hydrochloride (DC) in pharmaceutical tablets and serum samples was developed. In ammonia buffer solution of pH 8.9 the doxycycline hydrochloride can remarkably enhance the luminescence intensity of the Sm³⁺ ion in Sm³⁺- DC complex at λ_ex = 400 nm. The produced luminescence intensity of Sm³⁺- DC complex in DMSO is in proportion to the concentration of DC and used as optical sensor for its determination. The dynamic range for the determination of DC is 1 × 10⁻⁸ – 5 × 10⁻⁶ mol L⁻¹ and in case of quantum yield calculations is 7 × 10⁻⁹ – 5 × 10⁻⁶ mol L⁻¹ with detection limit of 6.5 × 10⁻¹⁰ mol L⁻¹. The enhancement mechanism of the luminescence intensity in the Sm³⁺- DC system has been also discussed. A comparison with other spectrofluorimetric methods for tetracycline derivatives in which Eu³⁺ ion is used instead of Sm³⁺ ion is also studied.     

New approach to achieving the potentially high conductivity of polydiacetylene

It is postulated that only the surface layers of the structural formations are doped in single crystals of various polydiacetylenes because of the high packing density of their macromolecules and that this is the reason for the low level of conductivity attained in these conjugated polymers. For the purpose of raising the efficacy of the doping process by increasing the surface-to-volume ratio of the polymer, single crystals of the polydiacetylene poly-1,1,6,6-tetraphenylhexadiinediamine (poly-THD) are ground by various methods. A correlation between the particle size of the ground single crystals and their dc conductivity in the doped state is discovered. A record value of the conductivity (3×10⁻² S/cm) for polydiacetylenes, which is more than two orders of magnitude higher than published values (10⁻³–10⁻⁵ S/cm), is achieved. Fiz. Tverd. Tela (St. Petersburg) 39, 774–777 (April 1997)     

Fluorescence Enhancement Effect for the Determination of Polychlorinated Biphenyls with Bovine Serum Albumin

A sensitive and selective method for the trace determination of 3, 3’, 4, 4’-tetrachlorobiphenyl (PCB77) by using bovine serum albumin (BSA) as a fluorescence probe was introduced. Under optimum conditions, the enhanced fluorescence intensity was proportional to the concentration of polychlorinated biphenyls in the range of 8.9 × 10⁻⁸–5.0 × 10⁻⁶ mol L⁻¹ for PCB77, and 5.0 × 10⁻⁷–5.0 × 10⁻⁶ mol L⁻¹ for 2, 2’, 5, 5’-tetrachlorbiphenyl (PCB52). The detection limits (S/N = 3) of PCB77 and PCB52 were 2.6 × 10⁻⁸ mol L⁻¹ and 2.9 × 10⁻⁷ mol L⁻¹, respectively. Furthermore, the fluorescence enhancement mechanism was discussed in detail. Results indicated that fluorescence enhancement of the system originated from the formation of BSA-PCBs complexes. In addition, PCBs were mainly bound to the tyrosine residues in BSA molecules.     

Variation of radon concentrations in soil and groundwater and its correlation with radon exhalation rate from soil in Budhakedar, Garhwal Himalaya

Radon was measured in soil-gas and groundwater in the Budhakedar area of Tehri Garhwal, India in summer and winter to obtain the seasonal variation and its correlation with radon exhalation rate. The environmental surface gamma dose rate was also measured in the same area. The radon exhalation rate in the soil sample collected from different geological unit of Budhakedar area was measured using plastic track detector (LR-115 type II) technique. The variation in the radon concentration in soil-gas was found to vary from 1098 to 31,776 Bq.m⁻³ with an average of 7456 Bq.m⁻³ in summer season and 3501 to 42883 Bq.m⁻³ with an average of 17148 Bq.m⁻³ in winter season. In groundwater, it was found to vary from 8 to 3047 Bq.l⁻¹ with an average value 510 Bq.l⁻¹ in summer and 26 to 2311 Bq.l⁻¹ with an average value 433 Bq.L⁻¹ in winter. Surface gamma dose rate in the study area varied from 32.4 to 83.6 μR.h⁻¹ with an overall mean of 58.7 μ-R.h⁻¹ in summer and 34.6 to 79.3 μR.h⁻¹ with an average value 58.2 μR.h⁻¹ in winter. Radon exhalation rate from collected soil samples was found to vary from 0.1 × 10⁻⁵ to 5.7 × 10⁻⁵ Bq.kg⁻¹.h⁻¹ with an average of 1.5 × 10⁻⁵ Bq.kg⁻¹.h⁻¹ in summer season and 1.7 × 10⁻⁵ to 9.6 × 10⁻⁵ Bq.kg⁻¹.h⁻¹ with an average of 5.5 × 10⁻⁵ Bq.kg⁻¹.h⁻¹. A weak negative correlation was observed between radon exhalation rate from soil and radon concentration in the soil. Radon exhalation rate from the soil was also not found to be correlated with the gamma dose rate, while it shows a positive correlation with radon concentration in water in summer season. Inter-correlations among various parameters are discussed in detail.      

Spectrofluorimetric Assessment of Chlorzoxazone and Ibuprofen in Pharmaceutical Formulations by using Eu-Tetracycline HCl Optical Sensor Doped in Sol–Gel Matrix

A novel, simple, sensitive and selective spectrofluorimetric method was developed for the determination of trace amounts of chlorzoxazone and Ibuprofen in pharmaceutical tablets using optical sensor Eu-Tetracycline HCl doped in sol–gel matrix. The chlorzoxazone or Ibuprofen can remarkably enhance the luminescence intensity of Eu-Tetracycline HCl complex doped in a sol–gel matrix in dimethylformamide (DMF) at pH 9.7 and 6.3, respectively, λ_ex = 400 nm. The enhancing of luminescence intensity peak of Eu-Tetracycline HCl complex at 617 nm is proportional to the concentration of chlorzoxazone or Ibuprofen a result that suggested profitable application as a simple optical sensor for chlorzoxazone or Ibuprofen assessment. The dynamic ranges found for the determination of chlorzoxazone and Ibuprofen concentration are 5 × 10⁻⁹–1 × 10⁻⁴ and 1 × 10⁻⁸–7 × 10⁻⁵ mol L⁻¹, and the limit of detection (LOD) and quantitation limit of detection (LOQ) are 3.1 × 10⁻¹⁰ , 9.6 × 10⁻¹⁰ and 5.6 × 10⁻¹⁰, 1.7 × 10⁻⁹ mol L⁻¹, respectively.     

Magnetic properties and large cryogenic low-field magnetocaloric effect of HoCo<Subscript>2</Subscript> nanoparticles without core/shell structure

The HoCo₂ nanoparticles are found to be stable in air without any shell protection. The HoCo₂ nanoparticles display superparamagnetic properties between their blocking temperature of 40 K and Curie temperature of 78 K. The magnetic-entropy change increases with decreasing temperature at a certain magnetic-field change, which is ascribed to the competition between the Zeeman energy and thermal-agitation energy at low temperatures. A large magnetic-entropy change of 19.4 J kg⁻¹ K⁻¹ was found at 7.5 K in an applied-field change from 1 to 7 T, while 6.1 J kg⁻¹ K⁻¹ was achieved in a low field change of 1 T. HoCo₂ nanoparticles are useful for application of magnetic refrigeration at low temperatures.     

LSP spectral changes correlating with SERS activation and quenching for R6G on immobilized Ag nanoparticles

In terms of chemical enhancement in Surface Enhanced Raman Scattering (SERS), we investigated the effect of halide and other anions to rhodamine 6G (R6G) adsorbed Ag particles that were immobilized on the substrates. The residual species on chemically prepared Ag particles such as citrate or a-carbon were thoroughly substituted by various anions, e.g., Cl⁻, Br⁻, I⁻, SCN⁻, CN⁻, or S₂O₃ ²⁻ anions, whose adsorption features are elucidated by the formation constants for AgX₂ ^(m−1)−, here X denotes the above anions. In particular, Cl⁻, Br⁻, or SCN⁻ ions activated SERS of R6G via intrinsic electronic interaction with Ag, whereas CN⁻, S₂O₃ ²⁻, or I⁻ anions quenched it due to their exclusive adsorption onto the Ag surfaces. We found that the activation process with the anions commonly yields a marked blue-shift of the coupled plasmon peak from ca. 650–700 to 500–550 nm in elastic scattering. It is rationalized by slight increase of the gap size between adjacent Ag nanoparticles by only ca. 1 nm based on theoretical simulations. This is probably caused by slight dissolution, oxidative etching, of the particles according to large formation constants of the complexes. Consequently, partly remaining negative charges on the Ag surface, and a slight increase in the gap size, providing huge electric field, facilitated R6G cations to adsorb on the nanoparticles, especially at the junction.