Characterizing wood polymers in the primary cell wall of Norway spruce (<Emphasis Type="Italic">Picea abies</Emphasis> (L.) Karst.) using dynamic FT-IR spectroscopy

Dynamic Fourier Transform Infra-Red (FT-IR) spectroscopy was used to examine the interactions among cellulose, xyloglucan, pectin, protein and lignin in the outer fibre wall layers of spruce wood tracheids. Knowledge regarding these interactions is fundamental for understanding the fibre separation in a mechanical pulping process. Sheets made from an enriched primary cell wall material were used for studying the viscoelastic response of the polymers. The results indicated that strong interactions exist among lignin, protein, pectin, xyloglucan and cellulose in the primary cell wall. This signified a closely linked network structure of the components on the fibre surface. This ultrastructural arrangement in the primary cell wall and the relatively high content of lignin, pectin and protein in it, means that the primary cell wall is more submissive to selective chemical attacks, when compared to the secondary cell wall. A low ratio of cellulose Iα to cellulose Iβ in the primary cell wall was also found.     

Comparison of different extraction methods for the determination of essential oils and related compounds from aromatic plants and optimization of solid-phase microextraction/gas chromatography

Different extraction methods for the subsequent gas chromatographic determination of the composition of essential oils and related compounds from marjoram (Origanum majorana L.), caraway (Carum carvi L.), sage (Salvia officinalis L.), and thyme (Thymus vulgaris L.) have been compared. The comparison was also discussed with regard to transformation processes of genuine compounds, particularly in terms of expenditure of time. Hydrodistillation is the method of choice for the determination of the essential oil content of plants. For investigating the composition of genuine essential oils and related, aroma-active compounds, hydrodistillation is not very useful, because of discrimination and transformation processes due to high temperatures and acidic conditions. With cold solvent extraction, accelerated solvent extraction, and supercritical fluid extraction, discrimination of high and non-volatile aroma-active components as well as transformation processes can be diminished, but non-aroma-active fats, waxes, or pigments are often extracted, too. As solid-phase microextraction is a solvent-free fully automizable sample preparation technique, this was the most sparing to sensitive components and the most time-saving method for the rapid determination of the aroma compounds composition in marjoram, caraway, sage, and thyme. Finally, solid-phase microextraction could be successfully optimized for the extraction of the aroma components from the plants for their subsequent gas chromatographic determination.     

On the effect of heat on the chemical composition and dimensions of thermally-modified wood

Heat-induced weight loss (WL) and chemical and dimensional changes of small specimens of beech (Fagus sylvatica L.), Scots pine (Pinus sylvestris L.) and Norway spruce (Picea abies L.) wood were examined after thermal modification in the 190-245 °C temperature range. Treated specimens exhibited reductions in their oven-dry weight in line with the severity of the treatment, with the effect of increasing the temperature of exposure being greater than extending the period of treatment. Wood polysaccharides were found to be distinctly more labile than the lignin constituent; the latter increased possibly as a result of repolymerisation reactions trapping some degradation products in the process. Specimens shrank in the transversal plane in a tangential to radial ratio of 2:1 regardless of the treatment regime, while their length increased marginally for WL < 10-12%. It is proposed that the thermal modification leaves the cell wall material in a permanent strained state.     

Influence of different extraction methods on the yield and linalool content of the extracts of Eugenia uniflora L

This work has been developed using a sylvestral fruit tree, native to the Brazilian forest, the Eugenia uniflora L., one of the Mirtaceae family. The main goal of the analytical study was focused on extraction methods themselves. The method development pointed to the Clevenger extraction as the best yield in relation to SFE and Soxhlet. The SFE method presented a good yield but showed a big amount of components in the final extract, demonstrating low selectivity. The essential oil extracted was analyzed by GC/FID showing a large range of polarity and boiling point compounds, where linalool, a widely used compound, was identified. Furthermore, an analytical solid phase extraction method was used to clean it up and obtain separated classes of compounds that were fractionated and studied by GC/FID and GC/MS.     

Effect of the pre-treatment of the samples on the natural substances extraction from Helianthus annuus L. using supercritical carbon dioxide

The extraction of bioactive compounds from sunflowers (Helianthus annuus L.) with supercritical carbon dioxide has been studied. The samples were treated in four different ways and the effects of two factors (pressure and temperature) were investigated at 100, 500 bar and 35, 50 °C. The best yields were obtained using a high temperature and a high pressure (50 °C and 500 bar). The dry samples produced better extraction yields than the moist samples. The bioactivities of the extracts were compared for the samples treated in different ways. The best activity profiles were obtained for the moist samples extracted at 35 °C and 500 bar.     

Study on the rapid deswelling mechanism of comb-type N-isopropylacrylamide gels

The shrinking mechanism of comb-type grafted poly(N-isopropylacrylamide) gel was investigated by fluorescence spectroscopy and small-angle X-ray Scattering (SAXS). The SAXS reveals that the microdomain structure with characteristic dimension of 460 Å is developed in the comb-type grafted poly(N-isopropylacrylamide) gel during the shrinking process. Fluorescence spectroscopy together with SAXS observation suggests that the freely mobile characteristics of the grafted chains are expected to show the rapid dehydration to make tightly packed globules with temperature, followed by the subsequent hydrophobic intermolecular aggregation of the dehydrated graft chains. The dehydrated grafted chains created the hydrophobic cores, which enhance the hydrophobic aggregation of the networks. These aggregations of the NIPA chains contribute to an increase in void volume, which allow the gel having a pathway of water molecules by the phase separation.     

The influence of methanol and ethanol on the efficiency of extraction of lanthanides(III) with 1-(2-pyridylazo)-2-naphthol (PAN) in carbon tetrachloride

The efficiency of extraction of microquantities of Eu(III), Sm(III) and Gd(III) from water—50% (v/v) methanol phase or water—50% (v/v) ethanol phase withPAN solutions in CCl₄ was examined. Separation factors for the following pairs of lanthanides(III) were determined: Eu-Sm, Eu-Gd, Sm-Gd, as well as Eu-Ln, Sm-Ln and Gd-Ln, where:Ln=Tb, Ho, or Lu; their changes with respect to the composition of the polar phase were also estimated.

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Der Einfluß von Methanol und Ethanol auf die Effektivität der Extraktion der Lanthaniden mit Lösungen von 1-(2-pyridylazo)-2-naphthol (PAN) in Tetrachlorkohlenstoff

Zusammenfassung Die Effektivität der Extraktion von Mikromengen Eu(III), Sm(III) und Gd(III) aus der Wasser-Methanol- und Wasser-Ethanol-Phase (50 vol. %), mit Hilfe vonPAN-Lösungen in CCl₄ wurde untersucht. Die Trennfaktoren für nachstehende Lanthaniden(III)-Paare: Eu-Sm, Eu-Gd, Sm-Gd und Eu-Ln, Sm-Ln, Gd-Ln(Ln=Tb, Ho oder Lu) wurden berechnet und ihre Änderungen in der Abhängigkeit von der polaren Phase geschätzt.

     

The investigation of a series of n-hydroxybenzoic acids (n=p, m, o) on a new surface enhanced Raman scattering active substrate

Ag nanoparticles, organized on indium tin oxide (ITO) surface, can act as a new surface enhanced Raman scattering (SERS) active substrate as well as a dry electrode. Compared with the traditional SERS-active substrate, its notable advantage is that the microcosmic changes of the film can be reflected by the SERS spectrum during the investigation of the film's electrical and other macroscopic characteristics. To illuminate the above-mentioned property of this new substrate, a series of n-hydroxybenzoic acids (n-HBA; n=p, m and o) was tested as probe molecules by SERS technique. These SERS spectra indicate that the significant changes of frequencies as well as intensities, respectively, arise from the changes of the adsorption behavior along with the proportional variation of molecules and silver nanoparticles. Excellent SERS signals prove that the silver nanoparticles-coated ITO is a highly SERS-active substrate and can efficiently reflect the microcosmic property of the film, which suggest it has promising potential of being a new technique for further application in the field of thin-film research.     

The outer-sphere association of p-sulfonatothiacalix[4]arene with some Co(III) complexes: the effect on their redox activity in aqueous solutions

The effect of the ion-pairing of Co(III) complexes with p-sulfonatothiacalix[4]arene (STCA) on Fe(II)–Co(III) electron transfer rate was evaluated from the analysis and comparison of kinetic data in double Co(III)–Fe(II) and triple Co(III)–Fe(II)—STCA systems at various concentration conditions. Complexes [Co(en)₃]³⁺(1), [Co(en)₂ox]⁺(2), [Co(dipy)₃]³⁺ (3), [Co(His)₂]⁺(4) and [Fe(CN)₆]⁴⁻ were chosen as Co(III) and Fe(II) compounds. The effect of STCA was found to correlate with the association mode. The outer-sphere association with STCA was found to exhibit the insignificant effect on Fe(II)–Co(III) electron transfer k _et constants for complexes 3 and 4 with bulky and rigid chelate rings, while more sufficient inclusion of flexible ethylendiaminate rings of 1 and 2 into the cavity of STCA results in the unusual increase of k _et.     

The Influence of Intermolecular Interactions on Second-Order Susceptibilities of Molecular Crystals: Application to the m-Nitroaniline Crystal

The effects of intermolecular interactions on the second-order susceptibilities (⁽²⁾) of molecular crystals are studied by using a semiempirical quantum–chemical method. These effects are discussed on the basis of the super-molecular approach. The influence of the electrostatic interactions between adjacent unit cells on the tensor components of ⁽²⁾ was modeled by using the technique of cumulative atomic multipole moments (CAMMs).     

The synthesis of fused benzotriazoles based on hexaaminobenzene derivatives

New methods for synthesis of hexaaminobenzene are proposed and, based on this compound, previously unknown preparative procedures for obtaining fused benzotriazoles are developed.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 152–154, January, 1993.     

The effect of polyether ligands on the solution structure of [Li]-α-(phenylthio)benzyllithium in tetrahydrofuran: A H,Li-HOESY NMR study

[⁶Li]-α-(phenylthio)benzyllithium 1-⁶Li was studied in THF/[D₈]THF solution (1:1) in the presence of several acyclic and cyclic polyether ligands by ¹H,⁶Li-HOESY, ¹H and ¹³C NMR spectroscopy. The question whether these ligands are bonded to lithium or not is important for physical–organic investigations as well as for studies of the ground state of (stereoselective) reactions of organolithium compounds in the presence of such ligands. Dimethoxyethane is not bonded to lithium under these conditions. The acyclic ethers diglyme and triglyme coordinate only weakly to the organolithium compound and form contact ion pairs (CIPs) at 25°C. At −80°C, CIPs are in equilibrium with separated ion pairs (SIPs). Very stable complexes of 1-⁶Li are obtained with crown ether ligands. Addition of 12-crown-4 and 15-crown-5, respectively, results in the exclusive formation of SIPs at 25°C and −80°C. With 18-crown-6, a CIP–SIP equilibrium is observed at 25°C which is shifted entirely to the SIP side at −80°C. Graphical analyses of the ¹H and ¹³C NMR spectra of the polyether complexes of 1-⁶Li revealed correlations between the chemical shifts of the para phenyl carbon C-5, the para phenyl proton H-5, the benzylic carbon C-1, and the proton–carbon coupling constant J(C-1,H-1) of 1-Li, which are useful probes for the charge distribution within the carbanionic moiety of 1-⁶Li in the respective complexes, and thus for the ion pair character as a function of the polyether complexation of lithium.     

Assessing the MALDI-TOF MS sample preparation procedure to analyze the influence of thermo-oxidative ageing and thermo-mechanical degradation on poly (Lactide)

Multiple processing by means of successive injection cycles was used to simulate the thermo-mechanical degradation effects on the oligomeric distribution of PLA under mechanical recycling. Likewise, an accelerated thermal ageing over PLA glass transition was performed in order to simulate its service life. MALDI-TOF MS was used for the analysis and the sample preparation procedure was assessed by means of a statistical Design of Experiments (DoE). The quality effects in use for the analysis were signal-to-noise ratio and Resolution. Different matrixes, analyte/matrix proportions and the use of NaTFA as cationization agent were considered. A deep inspection of the statistical results provided a better understanding of the influence of the different factors, individually or in combination, to the signal. The application of DoE for the improvement of the MALDI measurement of PLA stated that the best combination of factors (levels) was the following: matrix (s-DHB), proportion analyte/matrix (1/5 V/V), and no use of cationization agent. Degradation primarily affected the initially predominant cyclic [LA_C]_n and linear H[LA_L]_nOH species, where LA stands for a PLA repeating unit. Intramolecular and intermolecular transesterifications as well as hydrolytic and homolytic reactions took place during the formation and disappearance of oligomeric species. In both degradation mechanisms induced by thermal ageing and thermo-mechanical degradation, the formation of H[LA_L]_nOCH₃ by intermolecular transesterifications was highlighted.     

The products of the photolysis of 2-(4-alkyI(or phenyl)piperazino)-3-amino-1,4-naphthoquinones,their structures and subsequent thermal transformations

Photolysis of 2-(4-alkyI(phenyl)piperazino)-3-amino-1,4-naphthoquinones affords 2-alkyl (phenyl)-1,2,3,4,12,12a-hexahydronaphtho[2,34,5]imidazo[1,2-a]pyrazine-6,11-diols which recyclize at elevated temperatures to yield 1,2,3,4-tetrahydro-13-alkyl(phenyl)-3,1-(iminoethano) benzo[g]quinoxaline-5,10-diols. The latter are oxidated with atmospheric oxygen to the corresponding diones. On the basis of deuterium exchange data a mechanism for the recyclization is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 944–949, May, 1993.