Band 64, Heft 5

A deuterium-palladium electrode was employed as a new indicator electrode for the titration of weak acids in acetonitrile and benzonitrile. The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid in the concentration range from 0.001 M to 0.1 M with a Nernstian slope of 48 mV in acetonitrile. Sodium methylate, potassium hydroxide and tetrabutylammonium hydroxide proved to be very suitable titrating agents for these titrations. The response time was less than 10-11 s and the lifetime of the electrode was limitless. Advantages of the electrode are: long-term stability, fast response, reproducibility, easy preparation and low cost.

Chemical compositions of 16 Artemisia herba-alba oil samples harvested in eight East Moroccan locations were investigated by GC and GC/MS. Chemical variability of the A. herba-alba oils is also discussed using statistical analysis. Detailed analysis of the essential oils led to the identification of 52 components amounting to 80.5–98.6 % of the total oil. The investigated chemical compositions showed significant qualitative and quantitative differences. According to their major components (camphor, chrysanthenone, and α- and β-thujone), three main groups of essential oils were found. This study also found regional specificity of the major components.

TiO2 film was synthesized by means of the chemical bath deposition (CBD) method from TiCl4 as a precursor and surfactant cetyl trimethyl ammonium bromide (CTAB) as a linking and assembling agent of the titanium hydroxide network on a graphite substrate. Ag and Cu were loaded on the TiO2 film by means of electrodeposition at various applied currents. Photoelectrochemical testing on the composite of Ag-TiO2/G and Cu-TiO2/G was used to define the composite for Escherichia coli-contaminated water disinfection. Disinfection efficiency and the rate of disinfection of E. coli-contaminated water with Ag-TiO2/G as a catalyst was higher than that observed for Cu-TiO2/G in all disinfection methods including photocatalysis (PC), electrocatalysis (EC), and photoelectrocatalysis (PEC). The highest rate constant was achieved by the PEC method using Ag-TiO2/G, k was 6.49 × 10−2 CFU mL−1 min−1. Effective disinfection times of 24 h (EDT24) and 48 h (EDT48) were achieved in all methods except the EC method using Cu-TiO2/G.

Direct electrochemistry and electrocatalysis of horseradish peroxidase (HRP) immobilized on a hyaluronic acid (HA)-single walled carbon nanotubes (SCNs) composite film coated glassy carbon electrode (GCE) was studied for the first time. HRP entrapped in the SCNs-HA composite film exhibited a pair of well-defined, quasi-reversible cyclic voltammetric peaks in a 0.1 M phosphate buffer solution (pH 7.0). Formal potential vs. standard calomel electrode (E°′) was −0.232 V, and E°′ was linearly dependent on the solution pH indicating that the electron transfer was proton-coupled. The current is linearly dependent on the scan rate, indicating that the direct electrochemistry of HRP in that case is a surface-controlled electrode process. UV-VIS spectrum suggested HRP retained its original conformation in the SCNs-HA film. Immobilized HRP showed excellent electrocatalysis in the reduction of hydrogen peroxide (H2O2).

The role of phosphate buffer saline solution (PBS) was investigated here as a solvent in the polycondensation synthesis of an injectable agar-carbomer based hydrogel, a promising new material specifically intended for regenerative medicine applications. The effects of PBS, with respect to standard distilled water (DW), were quantitatively assessed. Experiments were performed both from physico-chemical and biological points of view. Titration showed higher stability due to the presence of the buffer solution; ESEM analysis confirmed its distribution along the polymeric fibers and infrared spectroscopy showed the consequent anionic nature of the polymeric network. This electrostatic nature of the matrix was confirmed by mass equilibrium swelling data performed at different pH values of the swelling medium. A very relevant role of the solvent was observed also with respect to cell housing inside such hydrogels: living cell counts showed a high amount of cells surviving the latency period of encapsulation in hydrogel when PBS was applied while only very few survived in a deionized water based gel. Obtained data allowed a novel understanding of the causeeffect cascades of all observed phenomena which suggest the PBS fundamental role both in fine control of hydrogel preparation and in material tuning according to the specific needs of different target tissues; the latter being a feature of primary importance when applying hydrogels as cell carriers in regenerative medicine applications.

Results of the investigation of volatile organic compounds emission during polyethylene extrusion are presented. Two polymers of different processing properties were tested, namely linear low density polyethylene (ExxonMobil) and high density polyethylene (Liten FB 29). Blowing film extrusion in experimental technological line using a single screw extruder as the imported element was done. VOCs were collected on sorbent tubes containing Tenax. Gas chromatography coupled with mass spectrometry (GC/MS) was applied for the identification of volatile degradation products. PE LLD material emits a significantly larger amount of hydrocarbons than PE-HD. Its emission contains mainly C18 and C20 hydrocarbons (alkanes, 1-alkenes, and α,ω-alkadienes). In case of the PE-HD polymer, lower degradation was observed and C18 and C23 hydrocarbons were emitted.

New zinc(II) 4-chloro- and 5-chlorosalicylate complex compounds of the general formula ((4- or 5-Cl)C6H3(2-OH)COO)2Zn · Ln (where L = methyl 3-pyridylcarbamate, phenazone; n = 2, 4) were prepared and characterized by elemental analysis, thermal analysis (TG/DTG, DTA), and IR spectroscopy. During thermal decomposition, mpc, phen, chlorosalicylic acid, chlorophenol, carbon dioxide, and carbon monoxide were released. Volatile products of the thermal decomposition were confirmed by mass spectrometry. The final solid product of the thermal decomposition up to 700°C was zinc oxide or metallic zinc. Antimicrobial activity of the compounds prepared was tested against various strains of bacteria, yeasts and filamentous fungi. The highest antimicrobial effect was determined against the G+ bacteria S. aureus.

Amide and ester conjugates of aceclofenac with polyamidoamine (PAMAM-G0) dendrimer zero generation and dextran (40 kDa) polymeric carrier, respectively, are presented. The prepared conjugates were characterized by UV, TLC, HPLC, IR, and 1H NMR spectroscopy. The average degrees of substitution of amide and ester conjugates were determined and found to be (12.5 ± 0.24) % and (7.5 ± 0.25) %, respectively. The in vitro hydrolysis studies showed that dextran ester conjugate hydrolyzed faster in a phosphate buffer solution of pH 9.0 as compared to PAMAM dendrimer G0 amide conjugate, and followed the first order kinetics. No amount of the drug was regenerated at pH 1.2 in simulated gastric fluid. The dextran conjugate showed short half-life as compared to the PAMAM dendrimer conjugate. Anti-inflammatory and analgesic activities of the dendrimer conjugate were found to be similar to those of the standard drug. Results of chronic ulceroginic activity showed deep ulceration and high ulcer index for aceclofenac, whereas lower ulcer index was found for the PAMAM dendrimer and dextran (40 kDa) conjugates. Experimental data suggest that PAMAM dendrimer and dextran (40 kDa) can be used as carriers for the sustained delivery of aceclofenac along with a remarkable reduction in gastrointestinal toxicity.

Influence of the initiator and additional hydrophobic copolymer on the morphology of thermosensitive poly(N-isopropylacrylamide) (pNIPAM) microspheres, and their presumed application for the stabilization of biologically active molecules were evaluated in this study. Three different types of pNIPAM were synthesized, applying various components: PN1 is a polymer with terminal anionic groups resulting from potassium persulfate initiator; PN2 was synthesized with a 2,2′-azobis(2-methylpropionamidine) dihydrochloride initiator introducing cationic amidine terminal groups; in the PN3 polymer, anionic terminals were implemented, however, increased hydrophobicity was maintained using N-tert-butyl functional groups. Turbidity measurements of the obtained dispersions confirmed specific thermosensitivity of synthesized microspheres in the range of 32–33°C. The polymerization course was proved by infrared spectroscopy and 1H NMR assessments, whereas the size of the synthesized microspheres, expressed as planar area, was evaluated by dynamic light scattering (DLS), scanning electron microscopy (SEM) and optical microscopy (OM). The respective surface patterns of the freeze-dried microspheres were evaluated by SEM. Planar area of the synthesized macromolecules was in the range between 0.41–3.22 μm, depending on the substrates composition and the method applied for the measurements. The assessments performed in the dry stage gave higher values of the diameter and planar area of the observed microspheres. The measured diameter and planar area increased in the following order for the PN3 microspheres: DLS, OM, SEM. In the case of PN1 and PN2, the observed diameters were positioned as: DLS, SEM, OM. These differences were assigned both to varied intramolecular hydrophobic-hydrophilic interactions of the polymer chains and to the environment, i.e. low pressure in the SEM conditions and aqueous solvent in the DLS measurements. The observed gaps in the freeze-dried PN2 polymer resulted in an attempt to evaluate the application of this polymer for mechanical stabilization of certain macromolecules or nanocrystals in the size range between 10 nm and 20 nm.

A group of novel 2-ferrocenyl quinoline derivatives was designed and their photophysical properties were thoroughly studied. UV-VIS and steady-state fluorescence spectra show that these compounds gain energy in the ultra-violet region and give red emissions in different organic solvents. More importantly, two transparent hybrid thick films composed of 2-ferrocenyl quinoline and poly[1-(methoxycarbonyl)-1-methylethylene] (poly(methyl 2-methylpropenoate, (poly(methyl methacrylate), PMMA), or poly[2-hydroxyethyl 2-methylprop-2-enoate] (poly(2-hydroxyethyl methacrylate), PHEMA) matrix were successfully prepared. Both films showed red emissions of ferrocenyl quinoline chromophore and the ideal composition of luminescent species is 10−6 M PMMA and 10−5 M PHEMA, respectively. SEM graph exhibited ferrocenyl quinoline molecules dispersed very homogenously within the above polymer hosts.

An acryloyl end-capped four-arm star-shaped poly(ethylene glycol)-branched-oligo(l-lactide) (4A-PEG-PLA) macromer was firstly prepared. A novel kind of hydrogels was synthesized via the Michael-type addition reaction between (2S,3S)-1,4-bis-sulfanylbutane-2,3-diol (dithiothreitol) and this macromer. Gelation time was determined visually as the time when the precursor solution did not flow on inverting the vials. Hydrogel structure was characterized by FTIR analysis, swelling and degradation tests. It was found that colorless and transparent hydrogels were quickly generated in situ. The gelation time, swelling and degradation behaviors of this kind of hydrogels could be adjusted by changing the concentration of the macromer solution in PBS buffer (pH 7.4). This novel hydrogel is expected to be used as a biomedical material.

MW ArF laser irradiation of gaseous cis-dichloroethene results in fast decomposition of this compound and in deposition of solid ultrafine Cl- and H-containing carbonaceous powder which is of interest due to its sub-microscopic structure and possible reactive modification of the C-Cl bonds. The product was characterized by electron microscopy, and FTIR and Raman spectra and it was revealed that HCl, H2, and C/H fragments are lost and graphitic features are adopted upon heating to 700°C.

Full details of the asymmetric total synthesis of erythro-8-O-4′-neolignan, machilin C, and its analogue perseal A are reported. The synthesis was involved in the Sharpless dihydroxylation reaction that occurred with excellent asymmetric induction, and the Mitsunobu reaction which occurred with inversion of the absolute configuration from the threo to the erythro isomer. The synthesis was achieved from simple vanillin in eight to twelve steps.

Dibenzobarrelene (I) was used as a starting compound for the synthesis of some new 3a,4,9,9a-tetrahydro-4,9-[1,2]benzeno-1H-benzo[f]isoindole-1,3(2H)-diones, N-substituted with: 4-toluenesulfonyloxy, III; butoxy, IV; 3-bromopropoxy, V; 3-(4-phenylpiperazin-1-yl)propoxy, VI; 3-chloro-3-oxopropyl, VIII; 3-(4-phenylpiperazin-1-yl)-3-oxopropyl, IXa; 3-(4-methylpiperazin-1-yl)-3-oxopropyl, IXb; 3-oxo-3-(piperidin-1-yl)propyl, X; 3-morpholino-3-oxopropyl, XI; 3-phenylamino-3-oxopropyl, XII; 2-acetylaminoethyl, XIV; 2-aminoethyl, XV, and 2-acetoxyethyl, XVI. Newly synthesized compounds were characterized by IR, 1H and 13C NMR, and mass spectral data. Selected products were tested for antimicrobial activity.

This study focuses on the preparation, single crystal X-ray diffraction, characterization, and optical properties of some anthraquinone-based dyes. The anthraquinone-based antimicrobial dye N-{2-[(9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-2-oxoethyl}-N,N-dimethylbutan-1-aminium chloride monohydrate (III) was obtained from 1-aminoanthraquinone (I) via 2-chloro-N-(9,10-dioxo-9,10-dihydroanthracen-1-yl)acetamide (II) using known preparation and characterization methods. Single crystal X-ray diffraction analysis of III revealed a monoclinic system, space group P21/n, Z = 4. Photoluminescence properties of anthraquinone dyes I–III were also investigated. These dyes gave an intense emission (λmax = 341 nm) upon the irradiation by UV light and showed photoluminescence quantum yields of 73 %, 66 %, and 61 % with long excited-state lifetimes of 6.87 ns, 6.14 ns, and 5.69 ns, respectively. These anthraquinone dyes are of interest as an organic light emitting material for electroluminescent devices.

Preferential sorption, equilibrium swelling degree, and volume of the swollen membrane in systems low-density polyethylene + hexane + aromatic compound (benzene, methylbenzene, or ethylbenzene) were studied using gravimetric and dilatometric methods at the temperature of 25 °C. Aromatic compounds are preferentially sorbed in low-density polyethylene compared to hexane. Experimental volume changes of the membrane were found to be noticeably different from those calculated on the basis of mass sorption data under the assumption of additivity. This difference points to the existence of the interactions between the polymer and the surrounding liquid mixture. The volume swelling degree curves are close to each other in the whole concentration range of the binary liquid mixture (hexane + aromatics) suggesting that the attractive forces between the polymer chains are the deciding factor limiting the volume expansion of the membrane in all three systems to the same extent.

Poly(γ-benzyl l-glutamate)-graft-poly(ethylene glycol) (PBLG-graft-PEG) copolymer was synthesized by the ester exchange reaction of PBLG homopolymer with mPEG. Aggregation behavior of the PBLG-graft-PEG copolymer in mixtures of ethanol and chloroform was investigated by transmission electron microscopy (TEM), dynamic light scattering (DLS), and viscometry. Effects of the polymer solution concentration, grafting degree, test temperature, and chloroform content on the morphology, average particle diameter, and critical micelle concentration (CMC) of the micelles formed by the PBLG-graft-PEG copolymer in the mixed solvents were mainly studied. It was revealed that the PBLG-graft-PEG copolymer can self-assemble into polymeric micelles with a core-shell structure in various shapes depending on the preparation conditions.

Utilization of biomass from forest or agricultural crops for the production of energy or chemical products provides environmental advantages. Leaves of the knotweeds Fallopia japonica, Fallopia sachalinensis, and Fallopia × bohemica are rich sources of phenolics and polysaccharides. In view of their potential utilization before the disposal of these invasive plants, their gross composition was investigated. The content of extractives was the highest in F. sachalinensis. Extractive-free leaves of all species showed similar chemical composition. The content of ash, protein, lignin, uronic acids, and α-cellulose in the leaves of F. sachalinensis, F. × bohemica, and F. japonica was 63.3 %, 64.1 %, and 63.4 %, respectively. The rest comprised hemicelluloses and neutral carbohydrate components of pectic polysaccharides. Sequential extraction of F. sachalinensis with water, EDTA, DMSO, 1 % NaOH, and 5 % NaOH yielded fractions accounting together for 27.6 % of polysaccharides. Pectic polysaccharides predominated in the first three fractions, whereas the hemicellulose components — xylan and xyloglucan, prevailed in the two alkaline fractions. The polysaccharides displayed significant radical scavenging activities in the 1,1-diphenyl-2-picrylhydrazyl free radical assay thus indicating their potential application as novel natural antioxidants.

A new synthesis method of 3-(nitromethylene)indolin-2-one analogues is described, using the Henry reaction of isatin and N-substituted isatins with nitromethane followed by dehydration of the nitroaldol adduct with mesyl chloride. The use of diethylamine (rather than DBU) as the base catalyst in a solvent-free Henry reaction gave the nitroaldol adduct in sufficient purity as to allow its direct dehydration to nitroalkene. Overall yields for this two-step synthesis are satisfactory (typically 50–77 % after chromatographic purification). 3-(Nitromethylene)indolin-2-one analogues are valued protective agents against H2O2-induced apoptosis using PC12 cells, and for their cytotoxicity against the A549 and P388 lung cancer cell lines. One compound, (E)-1-benzyl-3-(nitromethylene)indolin-2-one (VIII), exhibited potent activity in the latter assay.

An efficient ligand-free cross-coupling reaction of 2-chloro-3-(chloromethyl)benzo[h]quinoline with N-heterocycles such as piperidin-4-one, 4(3H)-pyrimidone, and ethyl 6-chloro-1,2-dihydro-2-oxo-4-phenylquinoline-3-carboxylate using a catalytic amount of ZnO nanorods as a recyclable catalyst and KOH as the base in DMSO under reflux at 110°C is reported.