Investigation of the influence of high-risk human papillomavirus on the biochemical composition of cervical cancer cells using vibrational spectroscopy

The main aetiology of cervical cancer is infection with high-risk human papillomavirus (HPV). Cervical cancer is almost 100% curable if detected in the early stages. Thus, information about the presence and levels of HPV in patient samples has high clinical value. As current screening methods, such as the Pap smear test, are highly subjective and in many cases show low sensitivity and specificity, new supportive techniques are desirable to improve the quality of cervical cancer screening. In this study, vibrational spectroscopic techniques (Raman and Fourier Transform Infra Red absorption) have been applied to the investigation of four cervical cancer cell lines: HPV negative C33A, HPV-18 positive HeLa with 20-50 integrated HPV copies per cell, HPV-16 positive SiHa with 1-2 integrated HPV strands per cell and HPV-16 positive CaSki containing 60-600 integrated HPV copies per cell. Results show that vibrational spectroscopic techniques can discriminate between the cell lines and elucidate cellular differences originating from proteins, nucleic acids and lipids. Similarities between C33A and SiHa cells were exhibited in the Raman and infrared spectra and were confirmed by Principal Component Analysis (PCA). Analysis of the biochemical composition of the investigated cells, with the aid of PCA, showed a clear discrimination between the C33A-SiHa group and HeLa and CaSki cell lines indicating the potential of vibrational spectroscopic techniques as a support to current methods for cervical cancer screening.     

On-column derivatization with o-phthaldialdehyde for fast determination of homocysteine in human urine

A new assay for urinary homocysteine is described. The assay relies on an on-column derivatization with o-phthaldialdehyde, using a reversed-phase HPLC column and detection/quantification by fluorescence. The analysis time for reduced and total homocysteine, including sample work-up, was 5 and 13 min, respectively. Quantification limit was 25 nM.     

Two-step scheme for solution of the seismic response of liquid-filled composite cylindrical container

This paper presents the seismic response analysis of a cylindrical container made of laminated composite. The analytical homogenization is used for calculation of the material properties of unidirectional fiber-reinforced composite layer. Constitutive relations for laminate within the classical laminate theory are considered. Effective modulus of elasticity is obtained and put into a calculation of internal forces of the laminated composite cylindrical tank. The seismic analysis of liquid storage facilities has to have different approaches as the analysis of typical structures. Because of an earthquake, the hydrodynamic impulsive and convective pressures are generated in addition to hydrostatic pressure. The solved liquid-filled container made of the laminated composite was situated for the region of Slovak Republic and was analyzed in respect of Eurocode 8 recommendations.     

Zwitterionically modified hydroxypropylcellulose for biomedical applications

Novel polyelectrolytes have been synthesized by grafting sulfobetaine side chains onto hydroxypropylcellulose backbone. Polymers with various degrees of grafting have been obtained. The polymers do not interact with model anionic, cationic and zwitterionic surfactants as found in fluorescence studies using pyrene as a molecular probe. Dynamic light scattering (DLS) studies indicated that in the graft polymer solution two types of polymers are present. The films were formed from the grafted polymers. Using atomic force microscopy (AFM) technique it was found that they are resistant to the adhesion of proteins and can be used for the preparation of antiadhesive surfaces which may find biomedical applications.     

How does the type of counterion influence the polymerization rate and thermal properties of tailored choline-based linear- and star-shaped poly(ionic liquid)s PILs?

The synthesis of tailored [2-(methacryloyloxy)ethyl]-trimethylammonium chloride (ChMA/Cl⁻) and bis(trifluoromethanesulfonate) imide (ChMA/NTf₂⁻)-based ionic homopolymers by sustainable activators generated by electron transfer atom transfer radical polymerization (ATRP) method has been demonstrated. Linear and four-arm star-shaped macromolecules were obtained with the use of two synthetic strategies: (a) direct polymerization of ionic monomers with counterions differing in hydrophilicity (prepolymerization) and (2) modification by ion exchange from Cl⁻ to NTf₂⁻ (postpolymerization) using both classical ATRP initiator and pentaerythritol-based initiator. The effect of counterions on the polymerization kinetics and the physicochemical and thermodynamical properties of resulted poly(ionic liquid)s (PILs) has been investigated. Results showed that polymerizations of ChMA/NTf₂⁻ proceeded with higher rate in comparison to ChMA/Cl⁻ one independently on the predetermined topologies (linear and four-arm star-shaped). From thermodynamical point of view, the glass transition temperature T_g increased with molecular weight M_n for linear- and star-shaped PILs for both types of counterion. In addition, star-shaped polymers of comparable M_n to linear ones were characterized by slightly higher T_g values. The resulting polyelectrolytes, after modification via exchange of Cl⁻ anions to NTf₂⁻ ones were characterized by much higher T_g in comparison to those produced by direct polymerization of ionic monomer, indicating the crucial role of postpolymerization modification on thermodynamical properties of PILs. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2681–2691     

Influence of Freeze-Dried Phenolic-Rich Plant Powders on the Bioactive Compounds Profile,Antioxidant Activity and Aroma of Different Types of Chocolates

In this study, the blueberries (BLUB), raspberries (RASB), blackberries (BLCB), pomegranates pomace (POME) and beetroots (BEET) freeze-dried powders were used as the sources of phenolic compounds to enrich different types of chocolates, substituting a part of the sweetener. It was found that 1% addition of fruit or vegetable powders to chocolates increased the content of total phenolic compounds (flavan-3-ols, phenolic acids and anthocyanins) of enriched dark and milk chocolates compared to the control ones dependent on the powder used. Among the enriched chocolates, the chocolates with the addition of BLUB powder were characterized by the highest total polyphenol content. The highest percentage increase (approximately 80%) in the total polyphenol content was observed in MCH chocolate enriched with BLUB powder. Chocolates incorporated with BLUB, RASB, BLCB and POME powders presented a richer phenolic compound profile than control counterparts. The highest DPPH radical-scavenging capacity was exhibited by the DCH98S chocolate enriched with BEET powder. However, the DCH98ESt chocolates enriched with POME and BEET powders demonstrated the highest FRAP values. An electronic nose analysis confirmed the existence of differences between the profiles of volatile compounds of various types of chocolates enriched with fruit or vegetable powders. Thus, the enrichment of dark and milk chocolates with BLUB, RASB, BLCB, POME and BEET powders seemed to be an interesting approach to enhance bioactivity and to enrich the sensory features of various chocolate types.     

Synthesis and studies on spectroscopic as well as electron donating properties of the two alkoxy benzo[b]thiophenes

Synthesis, characterization, steady state and time resolved, using time correlated single photon counting as well as laser flash photolysis techniques, spectroscopic investigations were made for two alkoxy benzo[b]thiophene molecules: 5-methoxy benzo[b]thiophene (5MBT) and 5-methoxymethyl benzo[b]thiophene (5MMBT). In both non-polar n-heptane (NH) and polar acetonitrile (ACN) solvents and at ambient temperature the electronic absorption spectra of these thiophenes exhibit different band systems whose assignments were made from the measurements of the steady state excitation polarization spectra. Steady state fluorescence spectra of these molecules in the different polarity solvents show the presence of non-specific interactions. From the redox properties of the benzothiophenes, measured by cyclic voltammetry, their electron donating properties were observed in the presence of the well-known electron acceptor 9cyanoanthracene (9CNA). Further, detailed studies by laser flash photolysis techniques show that ion-recombination mechanism predominates after the initial excitation of the acceptor moiety using the third harmonic of Nd:YAG laser. This recombination together with the external heavy atom effect (the donor containing 'sulphur' atom) appears to be responsible for the formation of the triplet of the monomeric acceptor 9CNA. From the steady state experiments it is shown that both in non-polar NH and highly polar ACN the quenching in the fluorescence emission of 9CNA in the presence of the benzothiophene donors is brought about primarily by the external heavy atom effect and in ACN, although the presence of the photoinduced ET reaction is confirmed, this process seems, from the observed bimolecular dynamic quenching rate, kq to be significantly masked by the external heavy atom effect.     

New perspectives about molecular arrangement of primary and permanent dentin

The dentin quality of primary and permanent teeth was inspected by Fourier transformed Raman spectroscopy (FT-Raman); scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS) and hardness test. Middle dentin of crowns were reached by carbide bur abrading providing a uniform smear layer. Phosphoric acid was applied in order to simulate the etching of total etching adhesive systems. The groups were (n = 10): G1 (primary dentin smear layer); G2 (35% phosphoric acid etched primary dentin); G3 (permanent dentin smear layer); G4 (35% phosphoric acid etched permanent dentin). FT-Raman results were subjected to cluster analysis. SEM/EDS were made in order to add the data obtained by FT-Raman. The hardness data were subjected to ANOVA and Tukey test. FT-Raman showed differences among groups, either to organic or inorganic content. For the organic content, primary and permanent dentin became similar after the etching; conversely, the inorganic content showed differences for the two substrates. Hardness test showed no significant differences between primary and permanent dentin, before or after etching, but the etching decreased these values. The mineral content arrangement of primary dentin is different from permanent dentin, independently of the etching. The substrate type did no influence the hardness, but the etching decreased it.     

Biodegradable polycarbonates containing side carboxyl groups—synthesis,properties, and degradation study

The main objective of the presented research was to synthesise biodegradable aliphatic polycarbonates containing reactive carboxyl pendant groups and to examine the influence of the copolymer chain microstructure and composition on the process of their hydrolytic degradation and cytocompatibility. The work describes copolymerization of cyclic trimethylene carbonate derivative containing benzyl‐ester pendant group (benzyl 5‐methyl‐2‐oxo‐1,3‐dioxane‐5‐carboxylate) with trimethylene carbonate. The copolymerization was conducted with the use of zinc (II) and lanthanum (III) acetylacetonates as ring‐opening polymerization coordination initiators. Detailed NMR analysis allowed to define the microstructure of the obtained copolymers, which depended on the composition and type of used initiator. The final tapered chain microstructure of the obtained copolymers was related to huge differences in comonomers reactivity and evidenced low level of transesterification of the main copolymer backbone. Chosen copolymers, with unprotected carbonyl groups, were subjected to in vitro degradation test and cytocompatibility studies. It was found that high concentration of carboxyl groups resulted in copolymers which formed hydrogels and were very prone to hydrolytic degradation; they were also cytotoxic toward osteoblast‐like MG 63 cells. Copolymers with lower content of carboxyl groups were found less susceptible to degradation and cytocompatible with studied cells. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2756–2769