Temperature-sensitive behaviour of poly(glycidol)-b-poly(N-isopropylacrylamide) block copolymers

Temperature-sensitive poly(glycidol)-b-poly(N-isopropylacrylamide) block copolymers (PGl₅₅PNIPAAm_y) were synthesised and their aqueous solutions investigated by different methods including differential scanning calorimetry (DSC), UV-VIS spectroscopy as well as dynamic and static light scattering. The cloud point temperature (T _c) depended on the composition of the investigated block copolymers and increased with decreasing length of the PNIPAAm block in PGl₅₅PNIPAAm_y copolymers. In contrast, the enthalpy of phase separation of PNIPAAm segments measured by DSC decreased with decreasing length of the PNIPAAm block in the polymer. These findings can be correlated with the behaviour of homo-PNIPAAm with similar molecular weights indicating that the influence of PGl on the local environment and phase separation of PNIPAAm chains is similar to the influence observed for PNIPAAm chains bearing different low molecular weight end group. Using DLS measurement, it was shown that the aggregation process depended on the PGl/PNIPAAm block ratio. If the PGl/PNIPAAm ratio was low, stable core-shell aggregates were formed. In contrast, the tendency to formation of large unstable, loose aggregates was observed for copolymers with high PGl/PNIPAAm ratio.     

Passively mode-locked high-power Nd:YAG lasers. with multiple laser heads

We discuss power scaling of passively mode-locked lasers using multiple laser heads in the resonator. We experimentally compared two different approaches for the cavity design, both using three side-pumped Nd:YAG laser heads. We obtained a record-high average output power of up to 27 W with close to diffraction-limited beam quality, a pulse duration of 19 ps, a pulse energy of 0.5 7J, and 23 kW peak power. Single-pass second-harmonic generation in a 10-mm-long LBO crystal yields 16.2 W of 532-nm radiation.     

Phenol adsorption on closed carbon nanotubes

We present the results of systematic studies of phenol adsorption on closed commercially available, unmodified carbon nanotubes. Phenol adsorption is determined by the value of tube-specific surface area, the presence of small amount of surface groups influence adsorption only in very small amount. Phenol can be applied as a probe molecule for comparative analysis of tube surface areas. Tube curvature influences adsorption from solution, i.e., we observe increasing adsorption energy (and slower desorption process) with the decrease in tube curvature. This is in full accordance with molecular simulation results.     

Ring-expanded bicyclic β-lactams: a structure-chiroptical properties relationship investigation by experiment and calculations

In the present work, the validity of the helicity rule relating the absolute configuration of the bridgehead carbon atom in bicyclic β-lactams to the sign of the 220 nm band observed in their electronic circular dichroism (ECD) spectra is examined for ring-expanded cephalosporin analogues. To this end, a series of model compounds with a seven-membered ring condensed with the β-lactam unit was synthesized. A key step of their synthesis was either the ring-closing metathesis (RCM) or the free radical cyclization leading to the seven-membered ring with an S, O, or C atom at the 6 position in the bicyclic skeleton. To investigate the scope and limitations of the simple, empirically established helicity rule, a combination of ECD spectroscopy, variable-temperature ECD measurements, X-ray analysis, and time-dependent density functional theory (TD-DFT) calculations was used. A comparison of the experimental ECD spectra with the spectra simulated by TD-DFT calculations gives a reasonable interpretation of the Cotton effects observed in the 240-215 nm spectral range. The results suggest that the helicity rule does not apply to the investigated compounds because of the planarity of their amide chromophore. Thus, these compounds do not constitute an exception to the rule that was established for bi- and polycyclic β-lactams with the nonplanar amide chromophore only.     

Electron-induced phase transition in hydrogen-bonded solid-state 2-pyridone

This paper presents the results of experimental studies of hydrogen-bonded 2-pyridone crystal IR spectra. Spectral studies have demonstrated the existence of two anhydrous solid-state phases of each compound, namely the α and the β phases. Hydrogen bonds in the high-temperature α phase of these crystals have been estimated to be 40% stronger than the hydrogen bonds in the β phase, which are stable at room temperature. The mechanism of the phase transition in the solid-state 2-pyridone is proposed on the basis of the IR spectral data. This was possible by taking into account small changes in the geometry of heterocyclic molecular skeletons, which accompany the electron density redistribution in the hydrogen bonds occurring during the transition. The phase transition is connected with a partial change in the hydrogen bond nature from the N(+)-H···O(-) in the α phase, to the N-H···O hydrogen bonds in the β phase crystals.     

Synthesis of 4-Hydroxy 6-Methyl 3-β-Arylpropionyl 2-Pyrones by Selective Catalytic Hydrogenation of 3-Cinnamoyl 4-Hydroxy 6-Methyl 2-Pyrones

We report a simple method for synthesis of 4-hydroxy 6-methyl 3-β-arylpropionyl 2-pyrones 1 from 3-cinnamoyl 4-hydroxy 6-methyl 2-pyrones by selective hydrogenation at ambient temperature under pressure using 10% palladium on carbon as catalyst.     

Reaction of 4-Hydroxy-6-Methyl-3-β-arylpropionyl-2-Pyrones with Phenylhydrazine-Synthesis of a New Pyrazole Series

We report the synthesis of a new pyrazole series by the action of phenylhydrazine on 4-hydroxy-6-methyl-3-β-arylpropionyl-2-pyrones.     

Synthesis of polysiloxane xerogels with fluorine-containing groups in the surface layer and their sorption properties

Hydrolysis and polycondensation reactions of tetraethoxysilane (TEOS) with 3,3,3-trifluoropropyl-trimethoxysilane (TFMS) or 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFES) were used to synthesize xerogels functionalized with fluorine-containing groups. According to transmission electron microscopy, the skeletons of synthesized polysiloxane xerogels have globular structures and consist of agglomerates of particles with fluorinated groups on their surfaces. FTIR spectroscopy showed that primary xerogel particles possess spatial polysiloxane networks, with fluorinated groups along with silanol groups and water in the surface layer. According to thermal analyses, the water content was 3–8 wt.%, and it decreased with increasing length of the fluorinated chain. Thermal destruction of the surface layer starts above 300 °C. The sorbents that were obtained were predominantly mesoporous materials with well-developed porous structures (S_BET = 400–960 m² g⁻¹, V_s = 0.66–0.93 cm³ g⁻¹). The influence of the TEOS/functional silane ratio and the natures of the functional groups on the structural and adsorptive properties were shown. The samples synthesized are organophilic. The affinity for n-hexane increases with increasing length of the fluorine-containing chain (PFES) and the content of fluorinated groups in the surface layer. The hybrid organic–inorganic materials that were obtained can be used for adsorption of hydrocarbons, including oil, from water.     

Sampling procedure and a radio-indicator study of mercury determination in whole blood by using an AMA 254 atomic absorption spectrometer

A sampling procedure appropriate for the determination of mercury in whole blood was tested by using both inactive controls and a ¹⁹⁷Hg mercury radio-indicator. To exclude the influence of the instrumental device (an AMA 254 single-purpose mercury atomic absorption spectrometer) on the determination of mercury in whole blood, the function of the instrument was checked by using rat blood with metabolised ¹⁹⁷Hg. The measurement procedure was found to be free of errors. However, the study showed that the material used for the sampling vessels is a crucial parameter for obtaining accurate analytical results. The stability of solutions and samples was tested towards polyethylene (PE) and polypropylene (PP) vessels. PE displayed a time-dependent increase in the mercury content both in the samples and in the blood control material. The probable cause of this increase was direct contamination from the material of the vessel and/or diffusion of mercury from the environment through the vessel walls related to a strong complexing affinity of the sample matrix. This assumption was confirmed by supplying the vessels with the complexing agent Na₂EDTA (0.05 mol L^–1). Commercial PP vessels for blood sampling (Sarstedt S-Monovette Metall Analytik) did not give rise to statistically significant variations in mercury content in the samples and blood control material over a 30-day period.     

Comparison of photodynamic efficacy of tetraarylporphyrin pegylated or encapsulated in liposomes: In vitro studies

Two photosensitizing systems: (1) tetrakis(4-hydroxyphenyl)porphyrin (p-THPP) encapsulated in sterically stabilized liposomes (SSL) and (2) p-THPP functionalized by covalent attachment of poly(ethylene glycol) (p-THPP–PEG₂₀₀₀) were studied in vitro. The dark and photo cytotoxicity of these systems were evaluated on two cell lines: HCT 116, a human colorectal carcinoma cell line, and DU 145, a prostate cancer cell line and compared with these determined for free p-THPP. It was demonstrated that both encapsulation in liposomes as well as attachment of PEG chain result in pronounced reduction of the dark cytotoxicity of the parent porphyrin. The liposomal formulation showed higher than p-THPP–PEG₂₀₀₀ photocytotoxicity towards both cell lines used in the studies.