Stability-indicating RP-LC method for the determination of vildagliptin and mass spectrometry detection for a main degradation product

A simple, precise and stability-indicating reversed-phase liquid chromatography method was developed and validated for the determination of vildagliptin (VLG) in pharmaceutical dosage form. The chromatographic separation was obtained within 6 min and was linear in the range of 20-80 μg/mL (r(2) = 0.9999). Limit of detection and limit of quantitation were 0.63 and 2.82 μg/mL, respectively. The method was validated in accordance with International Conference on Harmonization acceptance criteria for specificity, linearity, precision, accuracy, robustness and system suitability. Stress studies were carried out and no interference of the degradation products was observed. The excipients did not interfere in the determination of VLG. Furthermore, the main degradation product obtained from the stress studies (thermal, oxidative and alkaline hydrolysis) was evaluated for mass spectrometry and its molecular structure was predicted. The proposed method was successfully applied for the quantitative analysis of VLG in tablet dosage form, which will help to improve quality control and contribute to stability studies of pharmaceutical tablets containing this drug.     

Applied biological and physicochemical activity of isoquinoline alkaloids: oxoisoaporphine and boldine

The aim of this study was to determine the electronic influence of substituent groups and annelated rings such as oxazole-oxazinone on the physicochemical and photoprotection, antioxidant capacity, toxicity and singlet oxygen photosensitization biological properties of isoquinoline alkaloid frameworks. Thus, oxoisoaporphine derivatives 1-5 and 3-azaoxoisoaporphine (6), some of them with phenolic structures, did not present any antioxidant capacity, possibly either by formation of keto-enol tautomerism species or the formation of unstable free radicals. Due to the singlet oxygen quantum yields (F_D) near to unity, and greater photostability than phenalenone, oxoisoaporphines 4-6 may be considered as photosensitizers for singlet oxygen production and can be used as new universal study tools. The biological application as antibacterial agents is an important and possible tool in the study of compounds with low cytotoxicity and high reactivity in antineoplastic chemotherapy. On the other hand, when boldine and its annelated derivatives B1-4 are irradiated, a photoprotector effect is observed (SPF = 2.35), even after 30 minutes of irradiation. They also act as photoprotectors in cell fibroblast cultures. No hemolysis was detected for boldine hydrochloride and its salts without irradiation. In solutions irradiated before incubation (at concentrations over 200 ppm) photoproducts were toxic to the nauplii of Artemia salina.     

Hierarchical self-assembly of polycyclic heteroaromatic stars into snowflake patterns

Seeing stars: The two-dimensional patterns of the polycyclic heteroaromatic star molecules 1 on graphite vary with the side chain length. For n=12, frustrated self-assembly leads to hierarchically organized superstructures: up to 10?molecules form triangular aggregates which pack densely into hexagonal patterns with very large (15.5?nm) lattice constants.     

Incorporation of β-(1,6)-linked glucooligosaccharides (pustulooligosaccharides) into plant cell wall structures

Protein extract of germinating nasturtium (Tropaeolum majus) seeds containing xyloglucan endotransglycosylase (xyloglucan xyloglucosyl transferase, EC 2.4.1.207, abbreviated XET) exhibited the heterotransglycosylating activity with donor/acceptor substrate pair xyloglucan/sulphorhodamine labelled pustulooligosaccharides (XG/PUOS-SR) in a dot blot assay. The heterotransglycosylating activity was confirmed by the substrate-product changes during transglycosylation by HPLC size-exclusion chromatography. Another donor substrate capable of being coupled with PUOS-SR was cellulose, probably owing to its structural similarity to xyloglucan. Surprisingly, microscopic comparison of the incorporation of the labelled xyloglucan nonasaccharide XGO9-SR (specific substrate for XET) and PUOS-SR into the cell wall structures clearly showed differences in their binding to specific cell structures: the primary cell wall and the plasma membrane. These findings indicate the existence in nasturtium of XETs with different localisation, substrate specificity and, probably, function.     

Synthesis,adsorption and adhesive properties of a cationic amphiphilic block copolymer for use as compatibilizer in composites

In this work, the objective was to synthesize a compatibilizer that can electrostatically adsorb onto cellulose fibers, in fiber-based composites, to enhance the interaction between the fibers and non-polar polymer matrices. This physical route to attach the compatibilizer onto and thereby modify a fiber surface is convenient since it can be performed in water under mild conditions. Polystyrene (PS) was used for the high molecular weight, non-polar, block and poly(dimethylamino)ethyl methacrylate (PDMAEMA) was used as the polar block, which was subsequently quaternized to obtain cationic charges. The block copolymer self-assembles in water into cationic micelles and the adsorption to both silicon oxide surfaces and cellulose model surfaces was studied. The micelles spread out on the surface after heat treatment and contact angle measurements showed that the contact angles against water increased significantly after this treatment. AFM force measurements were performed with a PS probe to study the adhesive properties. The adhesion increased with increasing contact time for the treated surfaces, probably due to entanglements between the polystyrene blocks at the treated surface and the probe. This demonstrates that the use of this type of amphiphilic block copolymer is a promising route to improve the compatibility between charged reinforcing materials, such as cellulose-based fibers/fibrils, and hydrophobic matrices in composite materials.     

Characterization of a Transformation Function of a Photochromic Adaptive Filter

Simple, fast and accurate procedure is developed for measuring a Transformation Function (TF) of a Photochromic Adaptive Filter (PAF). Photochromic filters, whose spectral transmittance depends on previous and immediate radiant exposure and other environmental conditions, require special methods of spectro-photometry to determine their properties. This article describes methodology of characterizing the luminous transmittance as a function of light intensity using easy to implement method. Transformation functions of sample filters for different sources of radiation and varied light intensity are evaluated. The measuring system can also be used for fast determination of spatially and spectrally uniform light sources with UV spectral component.     

Classification of iron‐based inks by means of micro‐Raman spectroscopy and multivariate data analysis

In this work, multivariate data analysis methods were applied to the analysis and interpretation of micro‐Raman spectra, collected from a broad set of historical iron‐based ink samples, previously characterised for the content of organic acids (gallic acid, ellagic acid and protocatechuic acid). The proposed method relies on principal component analysis of the noisy spectra typically obtained on original, degraded, organic samples, where fluorescence could affect the Raman signal. The signal components could be distinguished from the noise components and then used to build a linear discriminant analysis (LDA) model, achieving separation of the spectra into three classes. Selection of pure signal factors also improved effectiveness and performances of partial least square regression (PLS) algorithms, allowing quantification of condensed tannic acid residuals. Application of multivariate methods to discriminate signal from noise removes the need for spectral data manipulation (filtering, smoothing and differentiating). The obtained classification method for discrimination of historic inks and the regression method for determination of condensed tannic acid residuals supports the use of Raman analysis of fluorescing organic materials, and may provide information to scholars on ink composition and potentially on its provenance. Copyright © 2013 John Wiley & Sons, Ltd.