Simple thin layer chromatography–ultraviolet spectrophotometric method for quality assessment of binary fixed‐dose‐combinations of lamivudine/tenofovir disoproxil fumarate and lamivudine/zidovudine in tablet formulations

Antiretroviral fixed‐dose‐combination drugs are best assayed with high‐performance liquid chromatography, or liquid chromatography–tandem mass spectrometry. However, most scientists in developing nations have no access to these expensive instruments. A more affordable quantitative technique is the use of ultraviolet–visible spectroscopy—where often the absorption spectra of these antiretrovirals are overlapping; thus complex derivative methodologies are required for quantification. A simple, rapid, and accurate thin layer chromatography–ultraviolet spectrophotometric method for the quantification of binary mixtures of lamivudine, zidovudine, and tenofovir–disoproxil–fumarate in tablet formulations was developed. Lamivudine/tenofovir–disoproxil–fumarate and lamivudine/zidovudine were extracted and separated on glass thin‐layer chromatography plates. Drugs were identified in ultraviolet light at 254 nm and quantified in acidic medium using ultraviolet spectrophotometry. The retardation factors were 0.43, 0.79, and 0.81 for lamivudine, tenofovir–disoproxil–fumarate, and zidovudine, respectively, with corresponding absorption maxima at 270, 260, and 265 nm. Linearity ranged from 1 to 40 µg/mL for all drugs (R = 0.9998–0.9999), while recovery studies were 95.10–102.11% and amount in formulations ranged from 97.99 ± 0.63 to 101.47 ± 2.39%. The paired t‐test (n = 5) indicated no significant difference between the proposed and high‐performance liquid chromatography methods, hence comparable and can be used as an alternative method in routine quality determination of antiretroviral medicines.     

qNMR for profiling the production of fungal secondary metabolites

Analysis of complex mixtures is a common challenge in natural products research. Quantitative nuclear magnetic resonance spectroscopy offers analysis of complex mixtures at early stages and with benefits that are orthogonal to more common methods of quantitation, including ultraviolet absorption spectroscopy and mass spectrometry. Several experiments were conducted to construct a methodology for use in analysis of extracts of fungal cultures. A broadly applicable method was sought for analysis of both pure and complex samples through use of an externally calibrated method. This method has the benefit of not contaminating valuable samples with the calibrant, and it passed scrutiny for line fitting and reproducibility. The method was implemented to measure the yield of griseofulvin and dechlorogriseofulvin from three fungal isolates. An isolate of Xylaria cubensis (coded MSX48662) was found to biosynthesize griseofulvin in the greatest yield, 149 ± 8 mg per fermentation, and was selected for further supply experiments. Copyright © 2016 John Wiley & Sons, Ltd.     

Improved Ionization Energies for the Two Isomers of Phenylpropargyl Radical

The ionization of two resonantly stabilized radicals, namely 1‐phenylpropargyl (1PPR) and 3‐phenylpropargyl (3PPR) are reinvestigated applying vacuum ultraviolet synchrotron radiation and threshold photoelectron spectroscopy. Ionization energies of 7.24±0.02 and 7.25±0.01 eV are obtained for 1 and 3PPR respectively, which compare well with ab initio calculations. The quality of the spectra are significantly improved mostly due to the application of a new high‐photon‐flux grating available at the VUV‐beamline of Swiss Light Source. Resolved vibrational features are assigned according to a Franck–Condon approach.     

Stepped collisional energy MSAll: an analytical approach for optimal MS/MS acquisition of complex mixture with diverse physicochemical properties

The analysis of complex mixtures is becoming increasingly important in various fields, such as nutrition, medicinal plants and metabolomics. The components contained in such complex mixtures are always characterized with diverse physiochemical properties that pose a major challenge during the optimization of various parameters using liquid chromatography‐mass spectrometer (LC‐MS). The parameter ‘CE energy’ that is normally set at a fixed value with a moderate range of CE spread during data‐dependent acquisition (DDA) analysis, a prevalent approach for untargeted identification, often fails to generate sufficient MS/MS fragment ions for untargeted identification of components from complex mixtures. Here we developed a simple and generally applicable acquisition method named stepped MS^All (sMS^All) in this study, aiming to obtain optimal MS/MS spectra for identification of chemically diverse compounds from complex mixtures. sMS^All collects serial MS^All scans acquired at low CE to gradually ramped‐up high CE values in a cycle that conventional DDA scans cannot afford. The resultant MS/MS spectra of each compound were compared and evaluated among serial MS^All scans, and the optimal spectra were used for identification. An untargeted data analysis strategy was then employed to analyze these optimal MS/MS spectra by searching common diagnostic ions and connecting the diagnostic ion families into a network via bridging components. This sMS^All‐based route enables identification of 71 natural products from a herbal preparation, whereas only 53 out of 71 compounds were identified using the classical DDA approach. Therefore, the sMS^All‐based approach is expected to find its wide applications for characterization of vastly diverse compounds with no priori knowledge from various complex mixtures. Copyright © 2016 John Wiley & Sons, Ltd.     

Effects of ion pairing on the capillary electrophoretic separation and ultraviolet‐absorption detection of quaternary ammonium cations using meso‐octamethylcalix[4]pyrrole as the background electrolyte additive

Five quaternary ammonium cations, including tetramethylammonium, tetraethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium, and 1‐butyl‐3‐methylimidazolium, have been separated by capillary electrophoresis. A direct ultraviolet method has been achieved when tetrabutylammonium fluoride was the background electrolyte and meso‐octamethylcalix[4]pyrrole was the background electrolyte additive. The ultraviolet spectra of meso‐octamethylcalix[4]pyrrole and cation mixtures showed that redshifts can be attributed to the size of cations, and the maximum absorption wavelength shifted from 218 to 230 nm when tetrabutylammonium cation was substituted with tetramethylammonium cation or tetraethylammonium cation. Conductivity measurements were performed to evaluate the ion‐pairing effect of tetrabutylammonium fluoride in a mixture of acetonitrile/ethanol (80:20, v/v), and the ion‐pairing formation constant, K_ip, was calculated (K_ip = 14.8 ± 0.3 L/mol) using the Fuoss extended model. Ion pairing also occurs between cations of the analytes and counterion, a fluoride complex of meso‐octamethylcalix[4]pyrrole. The tetramethylammonium cations associate more strongly with this counterion than the tetraethylammonium cation that contributes to the change of selectivity in capillary electrophoresis separation. The effective mobilities of the cations with trimethyl groups, such as tetramethylammonium cation, benzyltrimethylammonium cation, and hexadecyltrimethylammonium cation, decreased faster than others with the increase of meso‐octamethylcalix[4]pyrrole concentration, highlighting the fact that the ion‐pairing effect played an important role in this method.     

新型全色发光材料NaCaPO4∶Dy3+制备及发光性能

釆用高温固相法制备了NaCaPO4∶Dy3+系列样品, 并在紫外(UV)及真空紫外(VUV)区域研究了系列样品的发光性能. 紫外激发光谱显示在350 nm处有最强的激发峰, 可以有效地吸收紫外光并将其转化为可见光. 真空紫外激发光谱表明, NaCaPO4∶Dy3+能有效地吸收无汞荧光灯的激发源并将其转化为可见光. 系列样品发光均呈现为白色, 这种材料有潜力作为全色显示材料应用于发光二极管(LED)和无汞荧光灯中.     

Production of N3 upon Photolysis of Solid Nitrogen at 3 K with Synchrotron Radiation

The photodissociation of gaseous molecular nitrogen has been investigated intensively, but the corresponding knowledge in a solid phase is lacking. Irradiation of pure solid nitrogen at 3 K with vacuum‐ultraviolet light from a synchrotron produced infrared absorption lines of product l‐N₃ at 1657.8 and 1652.6 cm^?1. The threshold wavelength to generate l‐N₃ was determined to be (143.7±1.8) nm, corresponding to an energy of (8.63±0.11) eV. Quantum‐chemical calculations support the formation of l‐N₃ from the reaction N₂+N₂, possibly through an activated complex l‐N₄ upon photoexcitation with energy above 8.63 eV. The results provide a possible application to an understanding of the nitrogen cycle in astronomical environments.     

Spectroscopy of Dibenzorubicene: Experimental Data for a Search in Interstellar Spectra

We report on the characterization of dibenzo[cde,opq]rubicene (C₃₀H₁₄). The molecule was studied in solution at room temperature with absorption spectroscopy in the visible (vis) and ultraviolet (UV) wavelength ranges, and with emission spectroscopy. The infrared (IR), visible, ultraviolet, and vacuum ultraviolet (VUV) absorption spectra of a thin film were measured also at room temperature. In addition, the UV/vis absorption spectrum was measured at cryogenic temperatures using the matrix isolation spectroscopy technique. The interpretation of spectra was supported by theoretical calculations based on semiempirical and ab initio models, as well as on density functional theory. Finally, the results of the laboratory study were compared with interstellar spectra.     

Fourier transform ion cyclotron resonance mass spectral characterization of metal‐humic binding

The interaction between metals and naturally occurring humic substances and the thereby induced issues of bioavailability and hydrogeochemical turnover of metal ions in natural waters have been the subject of intense study for decades. Traditional bulk techniques to investigate metal‐humic binding (e.g. potentiometry and inductively coupled plasma mass spectrometry (ICP‐MS)) can provide quantitative results for the relative abundance and distribution of metal species in humic samples and/or overall binding constants. The shortcoming of these bulk techniques is the absence of structural detail. Ultra‐high‐resolution mass spectrometry, currently the only technique demonstrated to resolve individual humic ions, is not generally employed to provide the missing qualitative information primarily because the identification of metal complexes within the already complex mixtures of humic substances is non‐trivial and time‐consuming to the extent of eliminating any possibility for real‐time manipulation of chelated analytes. Here, it is demonstrated that with tailored selection of the metal ion, it is possible to visually identify large numbers of metal‐humic complexes (～500 for Be²⁺, ～1100 for Mn²⁺, and ～1500 for Cr³⁺) in real‐time as the spectra are being acquired. Metal ions are chosen so that they form primarily even‐m/z complexes with humic ions. These even‐m/z complexes stand out in the spectrum and can readily be characterized based on molecular formulae, which here revealed for example that Suwannee River fulvic acid (SRFA) complexes encompassed primarily highly oxygenated fulvic acids of relatively low double‐bond equivalence. Facile, real‐time identification of even‐m/z metal‐humic complexes additionally allows for the specific selection of metal‐humic complexes for MSⁿ analysis and in‐trap ion‐neutral reactions enabling investigation of metal‐humic complex structure. MS/MS data were collected to demonstrate the potential of the technique as well as highlight some of the remaining challenges. Copyright © 2009 John Wiley & Sons, Ltd.     

新型全色发光材料NaCaPO_4:Dy~(3+)制备及发光性能

釆用高温固相法制备了NaCaPO4∶Dy3+系列样品,并在紫外(UV)及真空紫外(VUV)区域研究了系列样品的发光性能.紫外激发光谱显示在350nm处有最强的激发峰,可以有效地吸收紫外光并将其转化为可见光.真空紫外激发光谱表明,NaCaPO4∶Dy3+能有效地吸收无汞荧光灯的激发源并将其转化为可见光.系列样品发光均呈现为白色,这种材料有潜力作为全色显示材料应用于发光二极管(LED)和无汞荧光灯中.     

Étude de la phényl-2 oxine et de ses chélates: Préparation et propr1étés de la phényl-2 oxine

The authors prepared phenyloxin by three different methods. They obtained a product whose melting point was 59° C and then another form melting at 72° C. Ultraviolet absorption spectra were determined in cyclohexan and in alcohol-watermixtures; from these determiaations, the solubilities of phenyloxin in water and in alcohol-water mixtures of different concentrations were obtained. If ultraviolet absorption spectra are plotted for different pH values (from 1.1 to 13.7) several isobestic points are noted.     

Determination of absolute photoionization cross‐sections of aromatics and aromatic derivatives

The absolute photoionization cross‐sections of aromatics and aromatic derivatives including toluene, ethylbenzene, n‐propylbenzene, o‐xylene, m‐xylene, p‐xylene, 1,3,5‐trimethylbenzene, styrene, phenylacetylene, indene, indane, 1‐methylnaphthalene, benzyl alcohol and benzaldehyde were measured at the photon energy range from ionization thresholds to 11.7 eV. The experiments were performed by tunable synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry. Benzene was chosen as a calibration standard, since its photoionization cross‐section is well known. Binary liquid mixtures of the investigated molecules and benzene were used in the measurements. Photo‐induced fragments from the molecules were also observed, and their photoionization cross‐sections are also presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Photoionization Mass Spectrometry: A Useful Method to Evaluate the Pyrolysis Process of Glycoside Flavor Precursor

The thermal decomposition behavior and the pyrolysis products of benzyl‐2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranoside (BGLU) were studied with synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry at temperatures of 300, 500 and 700 °C at 0.062 Pa. Several pyrolysis products and intermediates were identified by the measurement of photoionization mass spectra at different photon energies. The results indicated that the primary decomposition reaction was the cleavage of O‐glycosidic bond of the glycoside at low temperature, proven by the discoveries of benzyloxy radical (m/z = 107) and glycon radical (m/z = 331) in mass spectra. As pyrolysis temperature increased from 300 to 700 °C, two possible pyrolytic modes were observed. This work reported an application of synchrotron VUV photoionization mass spectrometry in the study of the thermal decomposition of glycoside flavor precursor, which was expected to help understand the thermal decomposition mechanism of this type of compound. The possibility of this glycoside to be used as a flavor precursor in high temperature process was evaluated.     

Structural characterization of flavonoid glycosides from leaves of wheat (Triticum aestivum L.) using LC/MS/MS profiling of the target compounds

The aim of this study was to present integrated mass spectrometric methods for the structural characterization and identification of flavonoid glycoconjugates. During the liquid chromatography/mass spectrometry analyses, TriVersa NanoMate chip‐based system with nanoelectrospray ionization and fraction collection was combined to a quadrupole time‐of‐flight mass spectrometer. In the extract samples prepared from green leaves of wheat plantlets, 41 flavonoid derivatives were recognized. Part of the target natural products had the full structure being characterized after the registration of mass spectra, where m/z values for protonated [M + H]⁺ and deprotonated molecules [M ? H]^? were annotated. MS² and pseudo‐MS³ experiments were performed for [M + H]⁺ or [M ? H]^? and aglycone ions (Y₀^+/?‐type), respectively. It should be underlined that pseudo‐MS³ mass spectra were registered for aglycone product ions in the mass spectra of O‐glycosides present in the extract samples. In many cases, only tentative structural identification of aglycones was possible, mainly because of the presence of numerous C‐monoglycoside or C‐diglycoside in the samples. Acylation of the sugar moiety and/or methylation of the aglycone in the flavonoid glycosides under study was observed. The existence of isobaric and/or isomeric compounds was demonstrated in the extract studied. The collision‐induced dissociation mass spectra registered for C,O‐diglycosides and C,C‐diglycosides did not permit to draw complete structural conclusions about the compounds studied. For the investigated class of natural products, unambiguous classification of sugar moieties linked to the aglycones from the recorded mass spectra was not possible. Registration of the positive and negative ion mass spectra did not lead to the precise conclusion about the glycosylation position at C‐6 or C‐8, and O‐4′ or O‐7 atoms. It was possible, on the basis of the collected MS² spectra, to differentiate between O‐glycosides and C‐glycosides present in the samples analyzed. Copyright © 2013 John Wiley & Sons, Ltd.     

X‐ray photoelectron spectroscopic chemical state quantification of mixed nickel metal,oxide and hydroxide systems

Quantitative chemical state X‐ray photoelectron spectroscopic analysis of mixed nickel metal, oxide, hydroxide and oxyhydroxide systems is challenging due to the complexity of the Ni 2p peak shapes resulting from multiplet splitting, shake‐up and plasmon loss structures. Quantification of mixed nickel chemical states and the qualitative determination of low concentrations of Ni(III) species are demonstrated via an approach based on standard spectra from quality reference samples (Ni, NiO, Ni(OH)₂, NiOOH), subtraction of these spectra, and data analysis that integrates information from the Ni 2p spectrum and the O 1s spectra. Quantification of a commercial nickel powder and a thin nickel oxide film grown at 1‐Torr O₂ and 300 °C for 20 min is demonstrated. The effect of uncertain relative sensitivity factors (e.g. Ni 2.67 ± 0.54) is discussed, as is the depth of measurement for thin film analysis based on calculated inelastic mean free paths. Copyright © 2009 John Wiley & Sons, Ltd.     

Multi‐component analysis: blind extraction of pure components mass spectra using sparse component analysis

The paper presents sparse component analysis (SCA)‐based blind decomposition of the mixtures of mass spectra into pure components, wherein the number of mixtures is less than number of pure components. Standard solutions of the related blind source separation (BSS) problem that are published in the open literature require the number of mixtures to be greater than or equal to the unknown number of pure components. Specifically, we have demonstrated experimentally the capability of the SCA to blindly extract five pure components mass spectra from two mixtures only. Two approaches to SCA are tested: the first one based on ?₁ norm minimization implemented through linear programming and the second one implemented through multilayer hierarchical alternating least square nonnegative matrix factorization with sparseness constraints imposed on pure components spectra. In contrast to many existing blind decomposition methods no a priori information about the number of pure components is required. It is estimated from the mixtures using robust data clustering algorithm together with pure components concentration matrix. Proposed methodology can be implemented as a part of software packages used for the analysis of mass spectra and identification of chemical compounds. Copyright © 2009 John Wiley & Sons, Ltd.     

Cyclometalated iridium(III) complex of 6‐hydroxydipyrido[3,2‐a:2′,3′‐c]phenazine: synthesis,and acid–base and avid DNA binding properties

A new cyclometalated Ir(III) complex [Ir(ppy)₂(hdppz)]PF₆ (Hppy = 2‐phenylpyridine and hdppz = 6‐hydroxydipyrido[3,2‐a:2′,3′‐c]phenazine) was synthesized and characterized. The pH effects on the UV–vis absorption spectra were studied and ground‐state acid ionization constant pK_a values of the complex were derived. The calf thymus DNA (ct‐DNA) binding properties of the complex were investigated with UV‐vis absorption spectrophotometric titrations, DNA competitive binding with ethidium bromide, DNA melting experiments, viscosity measurements and density functional theory (DFT) calculations. The complex was demonstrated to act as a ct‐DNA intercalator with a large DNA binding constant value of (6.06 ± 0.32) × 10⁶ M ⁻¹ in 50 mM NaCl. The avid DNA binding affinity observed was rationalized by the DFT calculations. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis and deconvolution of dimethylnaphthalene isomers using gas chromatography vacuum ultraviolet spectroscopy and theoretical computations

An issue with most gas chromatographic detectors is their inability to deconvolve coeluting isomers. Dimethylnaphthalenes are a class of compounds that can be particularly difficult to speciate by gas chromatography – mass spectrometry analysis, because of their significant coelution and similar mass spectra. As an alternative, a vacuum ultraviolet spectroscopic detector paired with gas chromatography was used to study the systematic deconvolution of mixtures of coeluting isomers of dimethylnaphthalenes. Various ratio combinations of 75:25; 50:50; 25:75; 20:80; 10:90; 5:95; and 1:99 were prepared to test the accuracy, precision, and sensitivity of the detector for distinguishing overlapping isomers that had distinct, but very similar absorption spectra. It was found that, under reasonable injection conditions, all of the pairwise overlapping isomers tested could be deconvoluted up to nearly two orders of magnitude (up to 99:1) in relative abundance. These experimental deconvolution values were in agreement with theoretical covariance calculations performed for two of the dimethylnaphthalene isomers. Covariance calculations estimated high picogram detection limits for a minor isomer coeluting with low to mid-nanogram quantity of a more abundant isomer. Further characterization of the analytes was performed using density functional theory computations to compare theory with experimental measurements. Additionally, gas chromatography – vacuum ultraviolet spectroscopy was shown to be able to speciate dimethylnaphthalenes in jet and diesel fuel samples.     

Comparative study of ink photoinitiators in food packages using gas chromatography with vacuum ultraviolet detection and gas chromatography with mass spectrometry

This work focused on the development and validation of the analytical procedure using gas chromatography equipped with vacuum‐ultraviolet detection for the specific and sensitive determination of nine photoinitiators in food packages. Subsequently, a comparison of the combination of vacuum ultraviolet spectroscopy with gas chromatography and a developed gas chromatography with mass spectrometry method was performed. The vacuum‐ultraviolet spectra of all tested photoinitiators were collected and found to be highly distinct, even for isomers. Under the optimal conditions, the limits of detection for nine photoinitiators ranged from 1 to 5 mg/L using vacuum ultraviolet detection and from 0.15 to 0.5 mg/L using mass spectrometric detection. Both techniques were successfully applied for screening of photoinitiators in seven kinds of food packages and the obtained data showed good agreement (the relative difference was between 3 and 18%). The variability in concentrations found in triplicate samples was assessed to be below 18%. Predominantly benzophenone was found in all analysed samples in the range of 0.31–4.23 mg/kg. It appears to be preferably selected by food packaging manufacturers. This study proposes a new simple and sensitive technique used for analysis of photoinitiators that could be a good alternative to gas chromatography with mass spectrometry.     

Vacuum ultraviolet laser‐induced fluorescence kinetic study of the reactions of Cl atoms with fluoroalkenes (CxF2x+1CHCH2, x = 1,2,4, 6, and 8) at low pressures

Pulsed laser photolysis/vacuum ultraviolet laser‐induced fluorescence techniques were used to measure rate coefficients for Cl atom reactions with a series of fluoroalkenes (C_xF_2x+1CH?CH₂, x = 1,2,4,6,8) in 6–10 Torr of CF₄ diluent at 295 ± 2 K. Rate coefficients (units of 10^?11 cm³ molecule^?1s^?1) of 4.49 ± 0.64, 6.58 ± 0.59, 8.91 ± 0.58, 9.27 ± 0.64, and 9.00 ± 0.87 were determined for C_xF_2x+1CH?CH₂ with x = 1,2,4,6, and 8, respectively. In 6–10 Torr of CF₄ diluent, the kinetics of the title reactions are at, or near, the high‐pressure limit for x = 4, 6, and 8, approximately 30% below the high‐pressure limit for x = 2, and approximately 50% below the high‐pressure limit for x = 1. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 328–332, 2007