Syntheses and comparison of 2,6-di-O-methyl celluloses from natural and synthetic celluloses

2,6-Di-O-methylcellulose was prepared from natural and synthetic celluloses. Natural cellulose was converted to 2,6-di-O-thexyldimethylsilylcellulose, then to 3-mono-O-allyl-2,6-di-O-methylcellulose, and finally into 2,6-di-O-methylcellulose. Alternatively, 2,6 di-O-methylcellulose was synthesized from the synthetic cellulose derivative 3-mono-O-benzyl-2,6-di-O-pivaloylcellulose by depivaloylation and methylation to give 3-mono-O-benzyl-2,6-di-O-methylcellulose, which was debenzylated to yield the dimethyl ether. Both types of 2,6-di-O-methylcellulose are insoluble in water and common organic solvents. The structures of all cellulose derivatives were determined by NMR.     

Glucans of higher plants

This review gives literature information on the glucan polysaccharides of higher plants, excluding glucans of the type of starch and cellulose.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 40 64 75. Translated from Khimiya Prirodnykh Soedinenii, Vol. 33, No. 1, pp. 3–15, January–February, 1997.     

Sensory principles of higher plants

Plants respond to a broad variety of stimuli from the interior of their body and from the outside environment. A revolution in our knowledge of the sensory capabilities of plants took place during the last decade, thanks to the consequent application of the tools of molecular genetics and the focusing of most work, in a world-wide effort, on a single, representative, higher plant: Arabidopsis thaliana. This review concentrates on the complete sensory periphery of higher plants, with focus placed on the principles rather than the details, and such systems that have been functionally identified unambiguously. Higher plants are no less fascinating, no less complex, and no less sensitive than animals, even man, with respect to their sensory capabilities. Plants constantly monitor their environment and their interior situation by using a stunning array of sensory systems, that are mostly different from those of animals or man.     

Synthesis, Raman and Rietveld analysis of thorium diphosphate

We report the synthesis of thorium diphosphate ThP₂O₇ and its study by Raman spectroscopy and Rietveld analysis. This compound has been found to be closely related to the zirconium diphosphate type, with space group Pa-3 and a=8.7601(3) Å. No superstructure was observed. The metastability of ThP₂O₇ appears to stem from the six-fold oxygen environment of Th^IV, a unique case in the structural chemistry of this cation.     

Photoactive protochlorophyllide regeneration in cotyledons and leaves from higher plants

Chlorophyll accumulation during greening implies the continuous transformation of photoactive protochlorophyllide (Pchlide) to chlorophyllide. Since this reaction is a light-dependent step, the study of regeneration of photoactive Pchlide under a continuous illumination is difficult. Therefore this process is best studied on etiolated plants during a period of darkness following the initial photoreduction of photoactive Pchlide. In this study, the regeneration process has been studied using spinach cotyledons, as well as barley and bean leaves, illuminated by a single saturating flash. The regeneration was characterized using 77 K fluorescence emission and excitation spectra and high-performance liquid chromatography. The fluorescence data indicated that the same spectral forms of photoactive Pchlide are regenerated by different pathways: (1) photoactive Pchlide regeneration starts immediately after the photoreduction through the formation of a nonphotoactive Pchlide form, emitting fluorescence at approximately 651 nm. This form is similar to the large aggregate of photoactive Pchlide present before the illumination, but it contains oxidized form of nicotinamide adenine dinucleotide phosphate, instead of the reduced form (NADPH), in the ternary complexes; and (2) after the dislocation of the large aggregates of chlorophyllide-light-dependent NADPH:Pchlide a photooxidoreductase-NADPH ternary complexes, the regeneration occurs at the expense of the several nonphotoactive Pchlide spectral forms present before the illumination.     

Neutron activation analysis of atmospheric biomonitors from the Azores: A comparative study of lower and higher plants

Summary Within an extensive survey of lower and higher plants in the Azores' Terceira and Santa Maria islands, this study is focused on the evaluation of ectohydric bryophytes and bark from Cryptomeria japonica as an alternative to epiphytic lichens for air-monitoring purposes. Neutron activation analysis (k₀-NAA) has been applied to all field samples for elemental determinations. Judging from the present results, and since the islands embody most features of the whole archipelago, bryophytes do not appear as an option for further campaigns in the Azores, due to scanty supply and relatively poor performance as biomonitors. On the other hand, comparisons of bark with lichens collected at the same sites seem fairly good, and elements are enriched in bark to an even greater extent than in lichens. All things considered - including material availability and ecological concern - bark stands for a sensible choice for biomonitoring in the Azores.     

SEC-MALLS analysis of TEMPO-oxidized celluloses using methylation of carboxyl groups

Two cellouronic acids [sodium (1 → 4)-β-polyglucuronates, CUAs] and one 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized wood cellulose (TOC) became soluble in 8 % lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) after the methylation of C6 carboxyl groups in these samples using trimethylsilyldiazomethane (TMSD). The obtained solutions were diluted to 1 % LiCl/DMAc and subjected to size-exclusion chromatography combined with multi-angle laser-light scattering (SEC-MALLS). Neither depolymerization nor side reactions took place during methylation; this was confirmed by SEC-MALLS and nuclear magnetic resonance analyses, using CUAs as models. The SEC-MALLS analysis of the original wood cellulose and the carboxyl-methylated TOC prepared from it, using 1 % LiCl/N,N-dimethyl-2-imidazolidinone and 1 % LiCl/DMAc, respectively, as eluents, showed that the weight-average degree of polymerization of the original wood cellulose decreased from 3,100 to 2,210 through TEMPO-mediated oxidation. The molecular-mass distributions of the original wood cellulose and the TOC both consisted of one large peak with a small shoulder, indicating that some of the oxidized hemicelluloses remained in the TOC. The combination of methylation of carboxyl groups in polysaccharides using TMSD and subsequent SEC-MALLS analysis using 1 % LiCl/DMAc as an eluent may be applicable not only to TOCs, but also to other polysaccharides with carboxyl groups, for evaluation of their molecular-mass parameters.     

Two-dimensional electrophoretic analysis of nuclear proteins from human tumors

During the last decade several strategies have been developed to identify proteins which could serve as markers in tumor biology. One avenue of great promise to detect such proteins seems to be the separation of prefractionated organelles from tumor cells by high resolution two-dimensional electrophoresis. Using detergent-lysed nuclei from several human tumor cell lines, especially from brain tumors, and two-dimensional electrophoresis, we analyzed the nuclear protein pattern obtained after sequential salt extraction of tumor cell nuclei. In addition to proteins occurring in all tumor cell lines, the pattern of different tumor cell lines exhibits considerable differences when proteins were visualized by silver staining, thus emphasizing the specificity of nuclear proteins with respect to the cell type. Even quantitative variations of the nuclear phosphoproteins 23/4 were detectable, indicating a potential correlation between their synthesis/phosphorylation and the proliferation behavior of tumor cells. The data indicate that nuclear proteins with their distinct heterogeneity and tissue specificity may represent a powerful source in determining tumor-specific proteins. The extent of chromosomal protein heterogeneity may be additionally increased by their covalent modification by nuclear kinases; therefore, tumor-specific nuclear proteins may occur as quantitative and qualitative variations.     

Improved liquid chromatographic method for the analysis of photosynthetic pigments of higher plants

The paper presents an improved reversed-phase LC method for the separation of the pigments from green leaves. A good separation of carotenoids and of their cis- and trans-isomers was achieved, especially for the separation of trans-lutein, zeaxanthin, cis-lutein, which are usually not well separated. No perfect separation of alpha-carotene, beta-carotene and pheophytin a was possible, but conditions for a perfect coelution of pheophytin a with either beta-carotene or alpha-carotene were established. Simultaneous equations allowing the determination of pheophytin a and alpha-carotene or pheophytin a and beta-carotene are also given.     

Molar-mass distribution of celluloses

The investigation of polymers by gel permeation chromatography has become a standard method for the determination of the molecular weight distribution. In case of cellulose and pulps the samples are mostly carbanilated or nitrated in order to get them soluble in organic solvents. In this context it is important that the derivatives obtained represent the composition of the starting material. High molecular wood pulps were carbanilated and further prepared for chromatographic separation using different methods. For bleached and unbleached pulps, the influence of the refining conditions on the molecular weight distribution and on the percentage of the soluble portion of the derivatives was investigated. It could be shown that low-molecular portions of the cellulose samples were lost applying those refining methods which included precipitation steps. For unbleached pulps, the risk existed that part of the derivatives remained insoluble and formed gel-like particles. For some pulp samples better results could be obtained by elongation of the derivatization time. Some selected pulps were carbanilated and nitrated, and the corresponding results were compared.     

Galactans and galactan-containing polysaccharides of higher plants

Research on the chemical structure and physiological activity of galactan and galactan-containing polysaccharides of higher plants is reviewed. The principal chain in galactan-containing polysaccharides consists of 1–3, 1–4, 1–6, and - and -bonded D-galactopyranoses. The side chains contain separate or bonded chains of galactose, arabinose, glucose, rhamnose, and uronic acids. The relationship of chemical structure and physiological activity of the polysaccharides of higher plants is discussed.S. Yu. Yunusov Institute of the Chemistry of Plant Substances. Academy of Sciences of the Republic of Uzbekistan, Tashkent. fax (99871) 120 64 75. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 185–197, May–June, 2000.     

X-ray analysis of powdered celluloses obtained with the use of Lewis acids

It is established via an X-ray method that the preparation of powdered forms of cellulose under the action of Lewis acids on fibrous hardwood cellulose is accompanied by a change in its crystallographic characteristics. The degrees of crystallinity, the sizes of crystallites, and the periods and monoclinic angles of the unit cells of the obtained powdered celluloses were determined.     

Comprehensive analysis of the substituent distribution in hydroxyethyl celluloses by quantitative MALDI-ToF-MS

Three HECs with a high MS (HEC 1: 1.89, HEC 2: 1.94, HEC 3: 3.03) were analyzed with respect to their substituent distribution and tandem reaction in the glucosyl unit by GLC of the corresponding glucitol acetates, and along the polymer chain by MALDI-ToF-MS after a multi-step sample preparation. For comparison of the experimental data with a random pattern an extended Bernoulli plot was applied to calculate a random distribution for the composition of un-, mono-, di-, tri-, and up to heptasubstituted glucosyl units (c0, c1, c2, ... c7).     

Degrees of polymerization (DP) and DP distribution of cellouronic acids prepared from alkali-treated celluloses and ball-milled native celluloses by TEMPO-mediated oxidation

Various cellulose II samples, ball-milled native celluloses and ball-milled wood saw dust were subjected to 2,2,6,6-tetramethypyperidine-1-oxyl radical (TEMPO)-mediated oxidation to prepare cellouronic acid Na salts (CUAs). The TEMPO-oxidized products obtained were analyzed by ¹³C-NMR and size-exclusion chromatography (SEC). When the cellulose II samples with degrees of polymerization (DP) of 220–680 were used as the starting materials, the CUAs obtained had weight-average DP (DPw) values of only 38–79. Thus, significant depolymerization occurs on cellulose chains during the TEMPO-mediated oxidation. These DP values of CUAs correspond to the cellulose II crystal sizes along the chain direction in the original cellulose II samples, but not necessarily to their leveling-off DP values. CUAs can be obtained also from ball-milled native celluloses in good yields by TEMPO-mediated oxidation, although their DPw values are lower than about 80. On the other hand, CUA with DPw of about 170 was obtained from ball-milled wood saw dust.