Observation of topical catalysis by sphingomyelinase coupled to microspheres

Sphingomyelinase, SMase (EC 3.1.4.12), was coupled onto amino-derivatized acrylate microspheres and was shown to retain its catalytic activity. The immobilized enzyme allows one to carry out topical enzymatic reaction in a controlled manner. Accordingly, these spheres were held with a micropipet and using micromanipulator brought into contact with a giant liposome membrane composed of phosphatidylcholine and sphingomyelin (SOPC/C16:0-SM, 0.75:0.25, molar ratio), representing the substrate for the immobilized enzyme. The macroscopic consequences of the enzyme reaction were visualized using fluorescence microscopy as well as differential interference contrast microscopy. The surface contact of the giant vesicle and immobilized enzyme causes membrane microdomain formation and domain clustering (capping) in the membrane and subsequent shedding of small vesicles from the membrane into the interior of the giant liposome. The method described represents a novel approach to study enzymatic reactions and allows manipulating giant vesicles as well as cultured cells in a spatially controlled manner.     

Thermal and spectroscopic investigation of europium and samarium sulphates hydrates by TG-FTIR and ICP-MS techniques

The investigation of europium(III) sulphate hydrate and samarium(III) sulphate hydrate was performed by thermal analysis (TG-DTG) and simultaneous infrared evolved gas analysis-Fourier transformed infrared (EGA-FTIR) spectroscopy. The TG, DTG and DTA curves were recorded at the 25–1400 °C in the dynamic air atmosphere by TG/DTA analyser. The infrared evolved gas analysis was obtained on the FTIR spectrometer. Eu₂(SO₄)₃·nH₂O (n = 3.97) and Sm₂(SO₄)₃·nH₂O (n = 8.11) were analysed, the dehydration and decomposition steps were investigated and the water content was calculated. The formation of different oxysulphates was studied.

The trace rare earth elements in Eu and Sm sulphates were determined by ICP-MS. The concentration of trace Eu, Sm, La, Gd, Y and Ce ranged from 3.9 × 10⁻⁶ to 1.5 × 10⁻⁴% (m/m).     

Synthesis and Characterization of Optical Sol–Gel Adhesive for Military Protective Polycarbonate Resin

Sol–gel adhesive material for isostatic hotpressing lamination process was synthesized using 3-aminopropyltrimethoxysilane (APTES), 3-glycidyloxypropyltrimethoxysilane (GPTS) and methacryloxypropyltrimethoxysilane (MPTS) as precursors. Reaction dynamics between APTES and GPTS was followed on-line with Raman spectroscopy. The lamination process was optimized by varying hotpressing times and pressures at the constant temperature. Mechanical shear strength properties were found to be excellent for studied composition, 25–30 kg/cm² at its best. One possible application of laminated polycarbonate (PC) structure is a soldier helmet visor. Therefore, the ballistic protection properties were tested by shooting with 1.1 gram standard fragment, and determining the v₅₀ velocity value, which corresponds to 50% perforation. The laminated structure gave 5.7% better protection compared with the solid polycarbonate. The laminated components were found to have high optical transparency at the visible wavelengths as well as high environmental stability.     

Structural Changes of Cellulose Crystallites Induced by Mercerisation in Different Solvent Systems; Determined by Powder X-ray Diffraction Method

The completeness of mercerisation can be evaluated by investigating the changes in the crystalline regions of cellulose from cellulose I (C-I) to cellulose II (C-II) by the X-ray powder diffraction method. Mercerisation experiments in four different solution systems: ethanol/water, acetone, DMSO and xylene, are reported. Also the effect of some additives, external pressure, treatment time and alkalisation temperature were studied. In two-phase solvent systems, structural changes of cellulose crystallites depended primarily on the distribution and solubility of sodium hydroxide in the solvent phases. The sodium hydroxide concentration in the hydrophilic phase must exceed 7–8 w/w-% before complete crystal change from C-I to C-II can occur. The precipitation of sodium hydroxide due to high concentration prevents the successful use of one-phase ethanol/water system in slurry process. On the contrary, the 2-propanol/water/sodium hydroxide system separates into two layers; to the water-rich lower layer and the 2-propanol-rich upper layer, where the sodium hydroxide remains mainly in the water-rich lower layer. This prevents the precipitation of sodium hydroxide and promotes the alkalisation of cellulose. Ammonium chloride and ammonium hydroxide clearly had a positive effect by promoting the crystal changes, however, the urea concentration used in this study was obviously too small. In the advantageous two-phase 2-propanol/water systems, the alkalisation time was only 15 min when the treatment temperature was kept between 0 and 10 °C. Reduced external pressure was found to have a small but still detectable positive effect on cellulose alkalisation while over-pressure prevented crystal changes.     

Determination of Na(2)O from sodium aluminate NaAlO(2)

The aim of the work was to find a suitable method and conditions for determining Na(2)O wt.% from NaAlO(2). Problems were encountered while titrating NaAlO(2) with hydrochloric acid. The problematic area was the pH range 4-10 where aluminum precipitates as hydroxides. The different species of the aluminate solution were determined using potentiometric and complexometric titrations. The equivalent point of the potentiometric titration was detected using Gran's plotting method. Precipitation of aluminum hydroxides did not interfere with titrations, because in potentiometric titrations the pH value was over 10 and in complexometric titrations the pH was 4. The results were accurate and determinations were easy to carry out. Sodium was also determined by DCP-AES.     

An unexpected allomer of chlorophyll: 13(S)-hydroxy-10-methoxychlorophyll b

The allomerization of chlorophyll b in methanol produced 13²(S)-hydroxy-10-methoxychlorophyll b in a yield of ca. 8%. The formation of this allomer was totally unexpected, as 10-substituted chlorophylls have never been reported before. The structure of the new chlorophyll b derivative was determined on the basis of UV/Vis, FAB-MS, ¹H NMR and 2D ROESY NMR spectra. This letter focuses on the NMR analysis.     

Properties and reactions of 1,3-oxathianes—II: Mass spectra of 1,3-oxathiane and its alkyl derivatives

The mass spectral fragmentation patterns of 1,3-oxathiane and several of its alkyl derivatives have been recorded. Of the nine possible modes of ring cleavage yielding fragments containing two to four atoms, only six modes were actually observed and, moreover, two of them clearly predominated. The modes of fragmentation of 1,3-oxathianes differ from those of 1,3-dioxanes, but resemble closely those observed for 1,3-oxathiolanes when the different ring sizes are taken into account.     

Electronic structure of the enolate anion of chlorophyll b

The enolate anion of chlorophyll b (Chl b) has been synthesized under deoxygenated conditions and its electronic structure characterized for the first time by ¹H NMR and electronic absorption spectroscopy. The formation of the enolate anion caused a marked perturbation to the 18 π-electron [18]diazaannulene aromatic pathway of Chl b. This perturbation appeared as noticeable upfield shifts, exceeding 1 ppm, for the meso-CH protons of the Chl b enolate anion. Nevertheless, the enolate anion remained diatropic, maintaining aromaticity in its delocalized macrocycle.     

A comparative study of solvent extraction of total petroleum hydrocarbons in soil

Three non-specific methods for the extraction of total petroleum hydrocarbons (TPH) from soil into organic solvent were compared. The techniques used for sample preparation were Soxhlet extraction, closed-vessel microwave-assisted extraction, and CEN shake extraction. The total concentrations of extracted compounds in the boiling point range of C10–C40 were determined by gas chromatography with flame ionization detection. The best recovery (99%) and repeatability (±3%) from standard oil mixtures were obtained with microwave-assisted extraction. However, the different extraction methods exhibited different behaviour when spiked soil samples were extracted. The best repeatability was obtained with CEN shake extraction (±6%) but the repeatability values for Soxhlet and microwave-assisted methods were quite high (>20%). However, the larger uncertainties of the latter extraction methods does not necessarily limit the applicability of these methods to the determination of petroleum hydrocarbons in soil, as in the assessment of soil contamination the expanded uncertainty of the result is usually not limited by analytical uncertainty, but rather by the uncertainty of the primary sampling stage. However, distinctive variation found in the chromatographic profiles illustrates that discretion should be obeyed when chromatograms obtained after application of different extraction methods on petroleum contaminated samples are to be used in the fingerprinting or age dating studies. Otherwise, misleading conclusions concerning the age of spillage could be drawn.     

Evidence of substituent-induced electronic interplay. Effect of the remote aromatic ring substituent of phenyl benzoates on the sensitivity of the carbonyl unit to electronic effects of phenyl or benzoyl ring substituents

Carbonyl carbon (13)C NMR chemical shifts delta(C)(C[double bond]O) measured in this work for a wide set of substituted phenyl benzoates p-Y-C(6)H(4)CO(2)C(6)H(4)-p-X (X = NO(2), CN, Cl, Br, H, Me, or MeO; Y = NO(2), Cl, H, Me, MeO, or NMe(2) ) have been used as a tool to study substituent effects on the carbonyl unit. The goal of the work was to study the cross-interaction between X and Y in that respect. Both the phenyl substituents X and the benzoyl substituents Y have a reverse effect on delta(C)(C[double bond]O). Electron-withdrawing substituents cause shielding while electron-donating ones have an opposite influence, with both inductive and resonance effects being significant. The presence of cross-interaction between X and Y could be clearly verified. Electronic effects of the remote aromatic ring substituents systematically modify the sensitivity of the C[double bond]O group to the electronic effects of the phenyl or benzoyl ring substituents. Electron-withdrawing substituents in one ring decrease the sensitivity of delta(C)(C[double bond]O) to the substitution of another ring, while electron-donating substituents inversely affect the sensitivity. It is suggested that the results can be explained by substituent-sensitive balance of the contributions of different resonance structures (electron delocalization, Scheme 1).