Chromophore concentration effect on holographic grating formation efficiency in novel azobenzene‐functionalized polymers

Optically active photochromic poly(amideimide)s containing azobenzene side groups in the repeating unit were prepared. The polymers were designed and synthesized specifically for this work in order to evaluate chromophore concentration effect on holographic grating recording. The poly(amideimide)s with mono‐ and bis‐azobenzene moieties were obtained via direct high temperature polycondensation and compared with respect to their ability of diffraction grating formation due to the light‐induced optical anisotropy effects. Holographic gratings were fabricated in polymer films upon exposure to an interference pattern of two polarized Ar⁺ laser beams at 514.5 nm wavelength. Different geometries of laser beams polarization were applied. It should be emphasized that although the azobenzene moieties are rigidly connected to the polymers backbone, some of polymers exhibited the unusually high light diffraction efficiency of around 40%. The created surface relief gratings (SRGs) were successfully observed using the atomic force microscopy (AFM). AFM images show regularly defined and aligned grating structures. It should be stressed that the SRGs with maximum of relief height up to 260 nm in polyimide derivatives with side azobenzene group were observed for the first time. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The Molecular Bases of the Interaction between a Saponin from the Roots of Gypsophila paniculata L. and Model Lipid Membranes

In view of the possible medical applications of saponins, the molecular structure of a GOTCAB saponin from the roots of Gypsophila paniculata L. was determined by NMR. The biological activity of saponins may depend on the interaction with cell membranes. To obtain more insight in the mechanism of membrane-related saponin function, an experimental and theoretical study was conducted. Ternary lipid systems composed of sphingomyelin, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, and cholesterol were used as models of mammalian cell membranes. The membrane–saponin interaction was studied experimentally by monitoring surface pressure in the monomolecular films formed at the air–aqueous subphase interface. The behavior of GOTCAB saponin in a water box and model monolayer systems was characterized by molecular dynamics simulations. The results obtained showed that, in the systems used, cholesterol had a decisive effect on the interaction between GOTCAB and phosphocholine or sphingomyelin as well as on its location within the lipid film.     

Alteration of Ethanol Reward by Prior Mephedrone Exposure: The Role of Age and Matrix Metalloproteinase-9 (MMP-9)

Mephedrone, a synthetic cathinone, is widely abused by adolescents and young adults. The aim of this study was to determine: (i) whether prior mephedrone exposure would alter ethanol reward and (ii) whether age and matrix metalloproteinase-9 (MMP-9) are important in this regard. In our research, male Wistar rats at postnatal day 30 (PND30) received mephedrone at the dose of 10 mg/kg, i.p., 3 times a day for 7 days. To clarify the role of MMP-9 in the mephedrone effects, one mephedrone-treated group received minocycline, as an MMP-9 antagonist. Animals were then assigned to conditioned place preference (CPP) procedure at PND38 (adolescent) or at PND69 (adult). After the CPP test (PND48/79), expression of dopamine D1 receptors (D1R), Cav1.2 (a subtype of L-type calcium channels), and MMP-9 was quantified in the rat ventral striatum (vSTR). The influence of mephedrone administration on the N-methyl-D-aspartate glutamate receptors (NMDAR) subunits (GluN1, GluN2A, and GluN2B) was then assessed in the vSTR of adult rats (only). These results indicate that, in contrast with adolescent rats, adult rats with prior mephedrone administration appear to be more sensitive to the ethanol effect in the CPP test under the drug-free state. The mephedrone effect in adult rats was associated with upregulation of D1R, NMDAR/GluN2B, MMP-9, and Cav1.2 signaling. MMP-9 appears to contribute to these changes in proteins expression because minocycline pretreatment blocked mephedrone-evoked sensitivity to ethanol reward. Thus, our results suggest that prior mephedrone exposure differentially alters ethanol reward in adolescent and adult rats.     

MSCs as Tumor-Specific Vectors for the Delivery of Anticancer Agents—A Potential Therapeutic Strategy in Cancer Diseases: Perspectives for Quinazoline Derivatives

Mesenchymal stem cells (MSCs) are considered to be a powerful tool in the treatment of various diseases. Scientists are particularly interested in the possibility of using MSCs in cancer therapy. The research carried out so far has shown that MSCs possess both potential pro-oncogenic and anti-oncogenic properties. It has been confirmed that MSCs can regulate tumor cell growth through a paracrine mechanism, and molecules secreted by MSCs can promote or block a variety of signaling pathways. These findings may be crucial in the development of new MSC-based cell therapeutic strategies. The abilities of MSCs such as tumor tropism, deep migration and immune evasion have evoked considerable interest in their use as tumor-specific vectors for small-molecule anticancer agents. Studies have shown that MSCs can be successfully loaded with chemotherapeutic drugs such as gemcitabine and paclitaxel, and can release them at the site of primary and metastatic neoplasms. The inhibitory effect of MSCs loaded with anti-cancer agents on the proliferation of cancer cells has also been observed. However, not all known chemotherapeutic agents can be used in this approach, mainly due to their cytotoxicity towards MSCs and insufficient loading and release capacity. Quinazoline derivatives appear to be an attractive choice for this therapeutic solution due to their biological and pharmacological properties. There are several quinazolines that have been approved for clinical use as anticancer drugs by the US Food and Drug Administration (FDA). It gives hope that the synthesis of new quinazoline derivatives and the development of methods of their application may contribute to the establishment of highly effective therapies for oncological patients. However, a deeper understanding of interactions between MSCs and tumor cells, and the exploration of the possibilities of using quinazoline derivatives in MSC-based therapy is necessary to achieve this goal. The aim of this review is to discuss the prospects for using MSC-based cell therapy in cancer treatment and the potential use of quinazolines in this procedure.     

Effect of negative pressure on melting behavior of spherulites in thin films of several crystalline polymers

The melting behavior of spherulites in thin films of isotactic polypropylene, poly(ethylene oxide), poly(methylene oxide), and poly(ethylene adipate) crystallized isothermally at various temperatures has been studied by polarized light microscopy. The local increase of melting temperature in regions surrounding cavities and multiple boundary points, dependent on the crystallization temperature, was observed in all studied polymers. In pockets of occluded melt an arising negative pressure lowers an equilibrium melting temperature; hence, decreases an undercooling, which results in the increase of lamellae thickness and their melting temperature. The elevation of melting temperature and the negative pressure buildup depend on the polymer and the crystallization temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1380–1385, 1999     

The Effect of Conjugation with Octaarginine,a Cell-Penetrating Peptide on Antifungal Activity of Imidazoacridinone Derivative

Acridine cell-penetrating peptide conjugates are an extremely important family of compounds in antitumor chemotherapy. These conjugates are not so widely analysed in antimicrobial therapy, although bioactive peptides could be used as nanocarriers to smuggle antimicrobial compounds. An octaarginine conjugate of an imidazoacridinone derivative (Compound 1-R8) synthetized by us exhibited high antifungal activity against reference and fluconazole-resistant clinical strains (MICs ≤ 4 μg mL⁻¹). Our results clearly demonstrate the qualitative difference in accumulation of the mother compound and Compound 1-R8 conjugate into fungal cells. Only the latter was transported and accumulated effectively. Microscopic and flow cytometry analysis provide some evidence that the killing activity of Compound 1-R8 may be associated with a change in the permeability of the fungal cell membrane. The conjugate exhibited low cytotoxicity against human embryonic kidney (HEK-293) and human liver (HEPG2) cancer cell lines. Nevertheless, the selectivity index value of the conjugate for human pathogenic strains remained favourable and no hemolytic activity was observed. The inhibitory effect of the analysed compound on yeast topoisomerase II activity suggested its molecular target. In summary, conjugation with R8 effectively increased imidazoacridinone derivative ability to enter the fungal cell and achieve a concentration inside the cell that resulted in a high antifungal effect.     

Comparison of the oxidative stability of chemically and enzymatically interesterified fats

A mixture of low erucic acid rapeseed (LEAR) oil and tallow (6:4, w/w) was used for enzymatic interesterification using Lipozyme IM – a sn-1,3-specific lipase of Rhizomucor miehei, or for chemical interesterification using sodium methoxide. The starting mixture and the products of interesterification were separated by column chromatography into pure triacylglycerols (TAGs) and a non-TAG fraction containing free fatty acids, mono- and diacylglycerols. Subsequently, the starting mixture, the products of chemical and enzymatic interesterification and the pure triacylglycerols were oxidized and their oxidative stability was examined by means of DSC. The investigation showed that the pure triacylglycerols isolated from the product of enzymatic interesterification have a comparable oxidative stability to that of the TAGs prepared from the starting mixture. In contrast, the TAGs obtained from the products of chemical interesterification had inferior oxidative stability. The presence of non-TAG fraction in the interesterification products lowers their resistance to oxidation. The starting mixture had the highest oxidative stability.     

Influence of the Type of Amino Acid on the Permeability and Properties of Ibuprofenates of Isopropyl Amino Acid Esters

Modifications of (RS)-2-[4-(2-methylpropyl)phenyl] propanoic acid with amino acid isopropyl esters were synthesised using different methods via a common intermediate. The main reaction was the esterification of the carboxyl group of amino acids with isopropanol and chlorination of the amino group of the amino acid, followed by an exchange or neutralisation reaction and protonation. All of the proposed methods were very efficient, and the compounds obtained have great potential to be more effective drugs with increased skin permeability compared with ibuprofen. In addition, it was shown how the introduction of a modification in the form of an ion pair affects the properties of the obtained compound.     

Involvement of the MetO/Msr System in Two Acer Species That Display Contrasting Characteristics during Germination

The levels of methionine sulfoxide (MetO) and the abundances of methionine sulfoxide reductases (Msrs) were reported as important for the desiccation tolerance of Acer seeds. To determine whether the MetO/Msrs system is related to reactive oxygen species (ROS) and involved in the regulation of germination in orthodox and recalcitrant seeds, Norway maple and sycamore were investigated. Changes in water content, MetO content, the abundance of MsrB1 and MsrB2 in relation to ROS content and the activity of reductases depending on nicotinamide adenine dinucleotides were monitored. Acer seeds differed in germination speed—substantially higher in sycamore—hydration dynamics, levels of hydrogen peroxide, superoxide anion radicals (O₂^•−) and hydroxyl radicals (•OH), which exhibited peaks at different stages of germination. The MetO level dynamically changed, particularly in sycamore embryonic axes, where it was positively correlated with the levels of O₂^•− and the abundance of MsrB1 and negatively with the levels of •OH and the abundance of MsrB2. The MsrB2 abundance increased upon sycamore germination; in contrast, it markedly decreased in Norway maple. We propose that the ROS–MetO–Msr redox system, allowing balanced Met redox homeostasis, participates in the germination process in sycamore, which is characterized by a much higher speed compared to Norway maple.     

Formation of Phospholipid Association Colloids in Rapeseed Oil and Their Effect on Lipid Autoxidation in the Presence of Sinapic and Ferulic Acid

This study describes the formation of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPC) association colloids (reverse micelles) in rapeseed oil and interactions of sinapic and ferulic acids with these structures. Furthermore, the process of oil autoxidation in the presence of DOPC is characterized and the antioxidant efficiency of phenolic acids in the oil containing reverse micelles is determined. Formation of DOPC reverse micelles above the phospholipid critical micelle concentration (51.13 µmol kg^–1) is observed. The fluorescence probe emission parameters confirm the interactions of sinapic and ferulic acids with reverse micelles and changes of their structure (reduced rigidity) as a result of phenolic acid incorporation. In the analyzed rapeseed oil, an evident prooxidative effect of DOPC reverse micelles is found, as their presence accelerates decomposition of hydroperoxides to hexanal. The antioxidant effect of sinapic acid is strongly influenced by the presence of DOPC reverse micelles. Ferulic acid shows a concentration‐dependent antioxidant effect in relation to the formation of hexanal. Practical Applications: Understanding the influence of sinapic and ferulic acids on the structure of association colloids and rapeseed oil autoxidation in the presence of reverse micelles should facilitate extension of shelf life and reduce oil quality deterioration during storage. This knowledge may also be used to optimize industrial oil refining to provide the desired amount of amphiphilic minor components and native antioxidants. Thus, developed refining using mild conditions or even minimizing the degree of refining is attractive in view of greater retention of health‐promoting compounds in vegetable oil, reduction of processing costs, and increased sustainability of the oil‐refining process.