Microwave-enhanced alkali treatment of Pinus yunnanensis: Physiochemical characterization of the dissolved lignins

Pinus yunnanensis was subjected to water-bath and microwave treatments in 1% NaOH aqueous solutions at 100 °C with various ratios of bath heating time to microwave heating time (0/120, 20/100, 40/80, 60/60, 80/40, 100/20 and 120/0 min). The lignins dissolved in the alkali liquors were separated and purified, and their physicochemical features were comparatively characterized by sugar analysis, GPC, FT-IR, ¹³C and HSQC NMR, as well as thermogravimetric analysis (TGA). The results showed that the lignin fractions extracted with microwave heating (20-120 min) had high molecular weights and polydispersities (M_w 3150-5710 g/mol, M_n 2130-3020 g/mol, M_w/M_n 1.48-2.00) as compared to those prepared without microwave heating (M_w 3080 g/mol, M_n 2080 g/mol, M_w/M_n 1.48). The most striking characteristic of all lignin fractions was the almost absence of associated sugars (0.16-3.25%). The TGA results indicated that the thermal stability of the lignin fraction increased with the increment of the molecular weight. FT-IR and NMR spectra suggested that the lignin fractions showed similar structures which were mainly composed of guaiacyl (G) and minor amounts of p-hydroxyphenyl (H) units. Moreover, HSQC NMR spectrum of a typical lignin fraction (prepared with microwave heating for 120 min) revealed that it contained dominant amounts of β-O-4′ linkages (64.6%) and phenylcoumaran (β-5′) substructures (25.8%) together with small amounts of resinol (β-β′) substructures (6.7%) and coniferyl alcohol end groups (2.9%).     

Physicochemical characterization of hemicelluloses from bamboo (Phyllostachys pubescens Mazel) stem

In this paper, hemicelluloses from bamboo (Phyllostachys pubescens Mazel) stem aged six months were sequentially extracted with hot water, 2% KOH, and 5% NaOH. The water-soluble hemicelluloses H₁, and four alkali-soluble hemicellulosic fractions H₂, H₃, H₄ and H₅ were obtained, achieving a total yield of 59.60% based on the original hemicelluloses. Sugar composition analysis showed that the hemicelluloses were mainly composed of xylose (44.39-72.71%), arabinose (26.36-51.87%), ribose (0.93-2.72%), and uronic acid (0.29-5.27%). The structures of the hemicelluloses were determined to be mainly arabinoxylan, using the FT-IR and NMR techniques. The AFM images of fraction H₃ revealed a distribution of spherical nanoparticles with different sizes, while the fraction H₂ had helix rod and random coil feature. The SEM characterizations indicated that the fraction H₁ displayed spherical particles while the fraction H₃ had mainly flat particles at high magnification. Thermal stability was also analyzed using TG-DTG method and first-order kinetics model.     

Mild peroxyformic acid fractionation of Miscanthus × giganteus bark. Behaviour and structural characterization of lignin

Miscanthus × giganteus bark was subjected to mild fractionation with peroxyformic acid by a two stage process. A factorial experimental design was used to study and quantify the effect of the variables (formic acid concentration (80-90%), hydrogen peroxide concentration (0.2-0.4%), temperature of the first stage (60-80 °C), and treatment time of the second stage (60-120 min)) on the main parameters of fractionation: pulp yield, remaining lignin and total polysaccharides in pulp. The dependence of lignin precipitation rate on hydrogen peroxide concentration in liquor was also studied. Hydrogen peroxide concentrations inferior to 0.5% seems to be suitable to recover high percentages of lignin. The isolated lignin was analysed by 2D-HSQC, ¹³C- and ³¹P NMR spectroscopy, FTIR spectroscopy, size-exclusion chromatography and chemical analysis. The most important chemical modifications taken place in the lignin during the fractionation were identified: β-O-4′ cleavage and hydrolysis of LC-bond structures. The C9-formula was also determined: C₉H_6.81O_2.90(OCH₃)_0.68(COOH)_0.07(OH^Ph)_0.38(OH^Al)_0.33.     

C NMR Spectroscopy of conventional and microwave heated vital wheat gluten

The mobility of gluten and carbohydrate polymers in vital wheat gluten that was heated by microwave radiation or conventionally at different starch-water ratios was studied. MacRitchie fractions were prepared and evaluated by SDS-PAGE and ¹³C NMR. The major groupings of gluten polymers were present in most MacRitchie fractions. Few differences associated with heating were found in the mobility of amino acid moieties as measured by ¹³C NMR. Mobilities associated with carbohydrates appeared to be affected by starch-water ratios and to a lesser extent by heating method as the fractionation proceeded. Implications for rheological analyses are discussed.     

Brominated compounds from marine sponges of the genus Aplysina and a compilation of their 13C NMR spectral data

Aplysina is the best representative genus of the family Aplysinidae. Halogenated substances are its main class of metabolites. These substances contribute greatly to the chemotaxonomy and characterization of the sponges belonging to this genus. Due to their pharmacological activities, these alkaloids are of special interest. The chemistry of halogenated substances and of the alkaloids has long been extensively studied in terrestrial organisms, while the number of marine organisms studied has just started to increase in the last decades. This review describes 101 halogenated substances from 14 species of Aplysina from different parts of the world. These substances can be divided into the following classes: bromotyramines (A), cavernicolins (B), hydroverongiaquinols (C), bromotyrosineketals (D), bromotyrosine lactone derivatives (E), oxazolidones (F), spiroisoxazolines (G), verongiabenzenoids (H), verongiaquinols (I), and dibromocyclohexadienes (J). A compilation of their (13)C NMR data is also part of the review. For this purpose 138 references were consulted.     

Lipid composition and deposition during grain filling in intact barley (Hordeum vulgare) mutant grains as studied by H HR MAS NMR

Conventional barley has an excellent nutritional value, but a lower content of lipids than oat. Nevertheless, barley lipids deserve a focused interest due to their fatty acid composition and their vitamin E composition. In this study, ¹H HR MAS NMR was used to monitor the deposition of lipids during grain filling of conventional barley, and of two barley endosperm mutants with increased lipid content. The lipids in the mutants are primarily synthesized between days 9 and 13, whereas the lipid biosynthesis in the conventional barley took place ten days later. GC analysis on barley flour lipids showed that the mutants and the control exhibit comparable relative levels of the major fatty acids: C16:0, C18:1 and C18:2 despite the higher content of lipids in the mutants. Differences in the minor fatty acid composition between control and mutants were also observed. The degree of unsaturation was found to be increasing during grain filling for both conventional barley and the two mutants.     

Molecular interactions between cereal soluble dietary fibre polymers and a model bile salt deduced from C NMR titration

Soluble dietary fibres (SDF) such as (1,3:1,4)-beta-d-glucan (βG) and arabinoxylan (AX) have been reported to lower plasma cholesterol levels in the human body, at least in part by preventing bile salts (BS) from being reabsorbed into the enterohepatic circulation. The mechanism(s) by which SDF interact with BS in the digestive tract is not known. This report describes investigations of molecular interactions between a model bile salt (taurochenodeoxycholate – TCDC) micelle with each of βG and AX using ¹³C NMR. In the presence of βG, chemical shift changes were observed for many bile salt resonances, but not βG resonances, without any apparent change in line widths. In contrast, in the presence of AX, no consistent chemical shift changes were observed for either TCDC or AX resonances, but TCDC signal intensities were reduced. This was not due to simple viscosity effects as the viscosity of the βG used was greater than that of the AX. The results suggest two different mechanisms of interaction between cereal non-starch polysaccharides and TCDC micelles: βG interacts directly on a molecular length scale with the micelles, whilst AX changes the local environment, resulting in reduced micellar mobility without direct molecular interaction.     

Study on structure and molecular dynamics of starch/poly(sodium acrylate)-grafted superabsorbent by <Superscript>13</Superscript>C solid state NMR

The domain-structure of samples containing a series of starch/poly(sodium acrylate)-grafted superabsorbents, pure starch, pure poly(sodium acrylate), and blend of starch/poly(sodium acrylate) has been studied by high-resolution solid-state ¹³C NMR spectroscopy at room temperature. The result shows that the crystallinity of starch decreases greatly in the grafted and blended samples. The values of ¹H spin-lattice relaxation time in rotating frame T _1ρ and ¹H spin-lattice relaxation time T ₁ shows that starch and poly(sodium acrylate) components in both grafted and blended samples have good compatibility in nanometer scale. In the ¹³C cross-polarization/magic-angle-spinning (CP/MAS) spectra, the chemical shift of the carbonyl group of poly(sodium acrylate) depends on the composition of the grafting samples, which indicates that the starch and the poly(sodium acrylate) components of the grafting samples exhibit better compatibility with each other than that of blended samples at molecular level.     

Metabolite fingerprint of “capim dourado” (Syngonanthus nitens), a basis of Brazilian handcrafts

Syngonanthus nitens is a grass-like species, whose flower stems assume a beautiful golden colour when dried, hence their common name “capim dourado”. This plant represents an important source of income for rural communities, especially in Jalapão region, being the scapes used in the craft industry to make, together with buriti palm strips, traditional handcrafts from their coils. Therefore, considering that scapes and not flowerheads are used, we carried out an analytical study to define the metabolite fingerprint of both S. nitens parts, with the aim, on one hand, to identify the molecules responsible for the characteristic golden colour of the capim dourado herb and, on the other hand, to identify the occurrence of interesting constituents in S. nitens flowerheads to increase the value of this part of the plant, considered a waste matter of golden grass handcrafts. Therefore an HPLC-ESI-MSⁿ method, based on high-performance liquid chromatography coupled to electrospray negative ionization multistage ion trap mass spectrometry, was developed to rapidly identify and guide the isolation of the secondary metabolites occurring in flowers and scapes. On the basis of the on-line HPLC-ESI-MSⁿ screening, 17 compounds, including 6 new molecules, were isolated, and their structures were unambiguously elucidated by NMR spectroscopic data.     

Partial purification and characterization of polyphenoloxidase from durum wheat (Triticum durum L.)

A bright yellow color of pasta is an important qualitative trait for the durum wheat industry. Final color is the result of the balance between yellow and brown components in semolina. Polyphenoloxidase (PPO) is implicated as playing a significant role in darkening. This study aimed to characterize PPO activity of durum wheats. PPO was extracted and partially purified by ion-exchange chromatography on a column packed with diethyaminoethyl cellulose (DEAE). This procedure led to 26.33-fold purification with 24.7% recovery. The optimum temperature and pH of PPO were found to be 40 °C and 6.5, respectively. Heat stability of durum wheat PPO decreased as the temperatures increased from 30 to 80 °C. The z-value was calculated as 23.4 °C. It increased to 26.3 and 48.4 °C in the presence of 40% sucrose and 1 M NaCl, respectively. Durum wheat PPO was shown to use several phenolic compounds as substrate. Among the substrates used, the greatest substrate specificity was observed with catechol. Durum wheat PPO was sensitive to inhibitors such as ascorbic acid, cysteine, oxalic acid and citric acid. Ascorbic acid was the most effective inhibitor.     

Moisture sorption isotherms, heat of sorption and properties of sorbed water of raw bamboo (Dendrocalamus longispathus) shoots

Moisture sorption isotherms of raw bamboo shoot were determined by static gravimetric technique based on isopiestic transfer of water vapor at 20, 30 and 35 °C. Inorganic saturated salt solutions in the range of 11.2-97.2% were used to create the required controlled humidity environment in a closed chamber. In the study, the sorption isotherms obtained were of sigmoid shape and of BET II type classification. Out of three sorption models i.e., BET, Caurie and GAB, fitted to the experimental data, Caurie model was found superior in interpreting the moisture sorption characteristics of bamboo shoot at three temperatures. The monolayer moisture content M_m as estimated by the best fitted Caurie's model for the sorption processes were 6.012%, 5.801%, 5.014%, and 5.987%, 5.816%, 4.998% (dry basis) at 20, 30, and 35 °C, respectively. The isosteric heats of sorption for both the adsorption and desorption process of bamboo shoots were found to increase with decrease in moisture content suggesting endothermic reaction at lower moisture content and it approached the value of heat of vaporization of free water at higher moisture content.     

Characterization of Solanum chomatophilum resistance to 2 aphid potato pests, Macrosiphum euphorbiae (Thomas) and Myzus persicae (Sulzer)

The aphids Macrosiphum euphorbiae (Thomas) and Myzus persicae (Sulzer) (Hemiptera: Aphididae) are responsible for yield reduction in potato (Solanum tuberosum) production by direct phloem feeding and by spreading viruses. Breeding resistant traits from Solanum chomatophilum into the potato germplasm provides alternative means to control aphid infestations. Integrated pest management strategy, using plant resistance, benefits from the characterization of the resistance and of its impact on aphid biology. Our objective was to characterize the resistance of S. chomatophilum by assessing the effects of accessions, plant parts on aphid performance, and by assessing the impact of the resistance factors on different aphid developmental stages and on alate morph production. Detailed aphid performance was obtained by measuring fecundity, survival, percentage of nymphs that reached adult moult, and population growth using whole plant and clip cage experimental designs. Accession and plant physiological age, but not aphid developmental stage, influenced all life-history parameters, except for alate morph production which was not induced on the resistant accessions. Plant part influence was independent of plant species and accession. Both experimental designs resulted in congruent resistance levels at the accession level for each of the two aphid species, supporting the use of any of them in S. chomatophilum resistance screening. PI243340 was resistant to both aphid species, while PI365324 and PI310990 were also resistant to M. euphorbiae and M. persicae, respectively.     

Conversion of starch from dry common beans (Phaseolus vulgaris L.) to ethanol

Dry common beans (Phaseolus vulgaris L.) were evaluated for potential conversion of starch to ethanol. Eight varieties of beans with average starch content of 46% (db) were assayed in a laboratory-scaled process based upon the commercial corn dry grind fermentation process. Ethanol yield was 0.43-0.51 g ethanol/g glucose (0.19-0.23 g ethanol/g beans). The average ethanol yield for the eight bean types was 92% of maximum theoretical yield, demonstrating that starch from beans could be efficiently converted to ethanol. Ethanol concentration obtained from 20% (w/w) solids loading was 3.5-4.4% (w/v). The residual fermentation solids contained, on a dry basis, 37.1-43.6% crude protein, 10.8-15.1% acid detergent fiber and 19.1-31.3% neutral detergent fiber.     

Comparative susceptibility of Ostrinia furnacalis, Ostrinia nubilalis and Diatraea saccharalis (Lepidoptera: Crambidae) to Bacillus thuringiensis Cry1 toxins

Transgenic corn hybrids that express toxins from Bacillus thuringiensis (Bt) are highly effective against the European corn borer, Ostrinia nubilalis (Hübner), and the closely related Asian corn borer, Ostrinia furnacalis (Guenée). Since the registration of Bt corn hybrids in the U.S. in 1996, there has been a great deal of information generated on O. nubilalis. However, relatively little information exists for O. furnacalis. To help determine whether the information generated for O. nubilalis can be leveraged for decisions regarding the use of transgenic Bt corn against O. furnacalis, experiments were designed to determine whether the pattern of sensitivity to various Bt Cry1 toxins is similar between the two species. Test insects included laboratory-reared O. furnacalis originating from Malaysia, a Bt-susceptible laboratory colony of O. nubilalis maintained at the University of Nebraska-Lincoln (UNL) and an out-group consisting of the sugarcane borer, Diatraea saccharalis (F.), from Louisiana which represents a different genus from the same family. O. furnacalis and O. nubilalis exhibited a similar pattern of susceptibility to all the Cry1 toxins and were highly susceptible to the range of Bt toxins tested including Cry1Aa, Cry1Ab, Cry1Ac and Cry1F. Both of the Ostrinia species were more tolerant to Cry1Ba compared with D. saccharalis, although sensitivity of O. furnacalis was intermediate and did not differ significantly from that of O. nubilalis and D. saccharalis. D. saccharalis was also susceptible to the range of toxins tested but unlike the two Ostrinia species, was more tolerant to Cry1F and more susceptible to Cry1Ba. These results indicate that both of the Ostrinia corn borer species are similar in sensitivity to the Cry1Aa, Cry1Ab, Cry1Ac, Cry1Ba and Cry1F toxins, thus suggesting shared toxin receptors and mechanisms of toxicity for the two species.     

Differential response of pea (Pisum sativum) to Orobanche crenata, Orobanche foetida and Phelipanche aegyptiaca

Several broomrape species including Orobanche crenata, Orobanche foetida and Phelipanche aegyptiaca are reported to infect various grain and forage legumes in the Mediterranean and West Asia. Pea (Pisum sativum) is severely damaged by O. crenata, but there are no reports on O. foetida or P. aegyptiaca infection. We report here that pea can induce high germination of seeds of O. crenata, O. foetida and P. aegyptiaca but only O. crenata success infecting pea roots and developing further. Some differences in levels of infection by O. crenata were observed among pea accessions what can be exploited in pea resistance breeding programmes. On the contrary, all pea accessions studied were highly resistant to infection by both O. foetida and P. aegyptiaca, preventing any tubercle attachment and development. This makes pea a promising candidate as trap crop for O. foetida and P. aegyptiaca seed bank demise in infested soils.     

Chemical characterization of barks from Picea abies and Pinus sylvestris after fractioning into different particle sizes

The composition of Norway spruce (Picea abies (L.) Karst.) and Scots pine (Pinus sylvestris L.) barks was studied after grinding and fractioning into different particles sizes.Both barks fractionated well and with similar fraction yield profile. The yield of fines was low and the major fractions were larger particles, i.e. 2.4% and 3.1% of particles under 0.425 mm and 66.0% and 50.3% of particles over 2 mm, respectively for spruce and pine bark.The chemical composition of spruce and pine barks, as a mass weighed average of all granulometric fractions was, respectively: ash 3.3 and 4.6%; total extractives 21.6 and 18.8% (hydrophilic extractives were dominant), lignin 27.9 and 33.7% and holocellulose 42.7 and 37.6%. Suberin accounted for 1.3% and 1.6% of spruce and pine bark, respectively. The non-cellulosic monosaccharides showed in both barks predominance of arabinose followed by xylose and mannose.Ash elemental composition showed that N represented about 35% of the total inorganics, Ca 35% and K 17%. Zn, Cu, Ni, Cr and Pb were present in both barks at levels under 1% of the total inorganics. Spruce bark had in average higher contents compared to pine bark, except for Pb and Cr.Size reduction of spruce and pine bark did not apply randomly to the different components and instead resulted into partial separation of the inorganic and organic matter into different size particles. Fine particles concentrated higher amounts of inorganic material and of extractives.     

Processing of Lespedeza stalks by pretreatment with low severity steam and post-treatment with alkaline peroxide

The steam pre-treatment with low severity preserves valuable biomass components, and further delignification with alkaline peroxide could improve hydrolysis. A combination of low severity steam pretreatment and alkaline peroxide post-treatment of Lespedeza stalks was investigated. The post-treatment of steam-pretreated Lespedeza stalks with alkaline peroxide significantly increased the cellulose content and changed the structure of the cellulose-rich fractions. A glucose yield of 503.5 mg g⁻¹ raw material from enzyme hydrolysis was obtained when the steam-pretreated material (184 °C for 4 min) was post-treated with 2% hydrogen peroxide at 60 °C for 24 h with a substrate concentration of 3.3%. Its hydrolysis yield is 88.8%, which is higher than that of samples processed by steam pretreatment alone (63.7%). The samples obtained by post-treatment with alkaline peroxide were found to have a smoother surface and looser structure in scanning electron microscopy images. The isolated lignin preparations had a yield range from 10.9 to 14.7 (% dry matter). The lignin was characterized by thermogravimetric analysis/differential thermal analysis, Fourier transform infrared spectroscopy, and gel permeation chromatography. Alkaline peroxide treatment increased the thermal stability of lignin, and decreased the amounts of all functional groups. Depolymerization and repolymerization occurred during the alkaline peroxide treatment.     

盐胁迫下钾吸收途径的抑制对小麦叶片K~+、Na~+含量的影响

为研究盐胁迫下小麦维持钾、钠平衡的生理机制,以耐盐小麦沧麦6005和盐敏感小麦矮抗58为材料,利用TEA、NEM、Ba(NO_3)_2三种药物分别抑制钾离子通道、钾载体及非选择性阳离子通道,测定正常及盐胁迫下小麦叶片K~+、Na~+含量,比较耐盐性不同的小麦品种在K~+、Na~+吸收中的差异。结果显示,盐胁迫下,沧麦6005和矮抗58叶片K~+含量下降,Na~+含量增加;沧麦6005叶片Na~+含量低于矮抗58,K~+/Na~+比值高于矮抗58。正常条件下,NEM、TEA处理均可降低沧麦6005和矮抗58叶片K~+含量,NEM处理较TEA处理效果更为明显;TEA处理显著降低了盐胁迫下矮抗58叶片K~+含量,而NEM处理则明显降低了盐胁迫下沧麦6005的叶片K~+含量;TEA、NEM、Ba(NO_3)_2处理降低了盐胁迫下矮抗58叶片Na~+含量,仅NEM处理降低了沧麦6005叶片Na~+含量。综上所述,正常条件下,钾载体是小麦K~+吸收的主要方式;盐胁迫下,耐盐品种和盐敏感品种K~+吸收途径不同,耐盐品种的NSCCs和钾离子通道具有更强的"拒钠"能力。     

Screening and quantification of an antiseptic alkylamide, spilanthol from in vitro cell and tissue cultures of Spilanthes acmella Murr.

The study revealed, for the first time, accumulation of spilanthol, an antiseptic alkylamide, in in vitro cultures of Spilanthes acmella Murr., a medicinal plant of immense commercial value. To achieve this, in vitro shoots were regenerated via direct organogenesis from leaf-disc explants of Spilanthes. Shoots were induced in the presence of N⁶-benzylaminopurine (BAP) alone or in combination with either α-naphthalene acetic acid (NAA) or Indole-3-acetic acid (IAA) in Murashige and Skoog medium. The best treatment for shoot regeneration was MS + BAP (5.0 μM) + IAA (5.0 μM), which promoted adventitious shoot proliferation in >82% cultures with an average of 5.3 shoots per explant. Regenerated shoots rooted spontaneously with a frequency of 100% on half strength MS medium (major salts reduced to half strength) containing 50 g l⁻¹ sucrose. The plantlets were acclimatized successfully with 90% survival rate. Additionally, ploidy stability of the regenerated plants was assessed by flow cytometry which showed that all investigated plants had the similar ploidy as that of the mother plant. For spilanthol identification, peaks eluted from HPLC were analyzed by mass spectrometry with its characteristic fragmentation pattern. For quantification studies, calibration curve was generated, which revealed a higher amount of spilanthol content (3294.36 ± 12.4 μg/g DW) in the leaves of in vitro plants compare to those of in vivo plants (2703.66 ± 9.6 μg/g DW of spilanthol). An efficient multiplication frequency, ploidy stability and enhanced spilanthol accumulation ensure the efficacy of the protocol developed for this industrially important medicinal plant.     

Characterization of biodiesel and bio-oil from Sterculia striata (chicha) oil

This work describes the mechanical and solvent extraction of Sterculia striata seed oil. It was determined that the seeds contain up to 41% in oil, which has an unusual composition. Indeed, up to 50% of the fatty acid contain cyclopropenoid ring. The oil was used as raw material to produce bio-oil and biodiesel and their physical-chemical properties were evaluated. Some of the studied physical-chemical properties of the S. striata biodiesel are in acceptable range for use as biodiesel in diesel engines, showing a promising economic exploitation of this raw material in semi-arid regions. It was also observed that the cyclopropenoid ring remains after transesterification and is decomposed during pyrolysis.