New cerebrosides from the basidiomycete <Emphasis Type="Italic">Cortinarius tenuipes</Emphasis>

Five cerebrosides (1–5), including three new ones named cortenuamide A (1), cortenuamide B (2), and cortenuamide C (3), were isolated from the fruiting bodies of the basid-iomycete Cortinarius tenuipes. The structures of those compounds were elucidated as (4E,8E)-N-d-2′-hydroxytetracosanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (1), (4E,8E)-N-d-2′-hydroxytricosanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8 sphingadienine (2), (4E, 8E)-N-d-2′-hydroxydocosanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (3), (4E, 8E)-N-d-2′-hydroxyoctadecanoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (4), and (4E, 8E)-N-d-2′-hydroxypalmitoyl-1-O-β-d-glycopyranosyl-9-methyl-4,8-sphingadienine (5) by spectral and chemical methods.     

(1S,2R,4S,5S)-angelicoidenol-2-o-β-d-glucopyranoside—A moose deterrent compound in Scots pine (Pinus sylvestris L.)

Hydrophilic extracts of Scots pine (Pinus sylvestris L.) twigs have been investigated for palatability to moose in feeding experiments. The predominant repellent effect was observed from the 2-O--d-glucopyranoside of the monoterpene (1S,2R,4S,5S)-angelicoidenol. Of other isolated and tested substances, only taxifolin-3-O--d-glucopyranoside had a deterring effect. One fraction-containing mainly aliphatic compounds-also had a strong effect, but the effect was lost after further fractionation. Tannin-containing fractions had no effect. Angelicoidenol glucoside has not previously been reported fromP. sylvestris. The results are discussed in view of phenols as defense compounds.     

New Nortriterpenoid and Ceramides From Stems and Leaves of Cultivated <Emphasis Type="Italic">Triumfetta cordifolia</Emphasis> A Rich (Tiliaceae)

To highlight the role of plants in traditional healing, the leaves and the stems of cultivated Triumfetta cordifolia were phytochemically studied yielding a new nor-ursane type (1), a new ceramide (2) and a new piperidinic ceramide derivative (3) named, respectively, 2α,19α-dihydroxy-3-oxo-23-nor-urs-12-en-28-oic acid, (2R)-2-hydroxy-N-[(2S,3S,4R,26E)-1,3,4-trihydroxy-26-triaconten-2-yl] tetradecanamide and (2R,8Z)-2-hydroxy-{(2S,3R,5R,6S)-3,5-dihydroxy-6-[(1E,5Z)-hexadeca-1,5-dienyl]-2-(β-d-glucopyranosyloxy)methyl piperidine-1-yl} tetracos-8-enamide (3). These were obtained together with lupeol (4), stigmasterol (5), 3-O-β-d-glucopyranoside of β-sitosterol (6), tormentic acid (7) from stems and heptadecanoic acid (8), β-carotene (9), oleanolic acid (10), and 24-hydroxytormentic acid (11) from leaves. The structures were determined on the basis of NMR data (¹H-, ¹³C-, 2D-NMR analyses), mass spectrometry and confirmed by chemical transformations as well as comparison of spectral data with those reported in the literature. The FRAP method was used to evaluate the antioxidant activity of fractions collected from flash chromatography and isolated compounds. Among the fractions, four reduced Fe^III-TPTZ to Fe^II-TPTZ while isolated pure compounds showed no activity.     

Preparation and properties of new surfactants containingd-glucosamine as the building block

Three types of new surfactants were prepared by usingN-acetyl-d-glucosamine as a starting material. The first type of surfactant, sodium methyl 4,6-O-alkylidene-2-(carboxyl-atomethylamino)-2-deoxy-d-glucopyranoside, was prepared successively by the following treatments: methyl glucosidation ofN-acetyl-d-glucosamine, transacetalization with an appropriate aldehyde dimethyl acetal, deacetylation, and finally reaction of the resulting methyl-4,6-O-alkylidene-2-amino-2-deoxy-d-glucopyranoside (2-amino precursor) with bromoacetic acid. The reaction of this 2-amino precursor with methyl iodide yielded the second type of surfactant, methyl 4,6-O-alkylidene-2-deoxy-2-(trimethylammonio)-d-glucopyranoside iodide, in excellent yield. The last type of compound, sodium methyl 2-acetamide-4,6-O-alkylidene-3-O-[1-(carboxylato)-ethyl]-2-deoxy-d-glucopyranoside, was synthesized by the reaction of methyl 2-acetamide-4,6-O-alkylidene-2-deoxy-d-glucopyranoside with 2-chloropropionic acid. Concerning the two carboxylate types of surfactants, the compounds containing a C₉ or C₁₁ hydrophobic chain in the alkylidene part showed higher water solubility than the corresponding compounds containing a C₇ hydrophobic chain. Both the micelle-forming property and the ability to lower the surface tension of these carboxylate types of compounds increased with an increase in the length of the hydrophobic chain in the alkylidene part. These compounds can be applied to new acid-decomposable types of cleavable surfactants because they contain an acetal group. The acetal bond of the ammonium type of compound was cleaved more slowly than that of the corresponding carboxylate types of surfactants in 2% aqueous HCI solution. The biodegradabilities of these compounds were also determined.     

Stabilization of natural gas foams using different surfactants at high pressure and high temperature conditions

Natural gas foam can be used for mobility control and channel blocking during natural gas injection for enhanced oil recovery, in which stable foams need to be used at high reservoir temperature, high pressure and high water salinity conditions in field applications. In this study, the performance of methane (CH₄) foams stabilized by different types of surfactants was tested using a high pressure and high temperature foam meter for surfactant screening and selection, including anionic surfactant (sodium dodecyl sulfate), non-anionic surfactant (alkyl polyglycoside), zwitterionic surfactant (dodecyl dimethyl betaine) and cationic surfactant (dodecyl trimethyl ammonium chloride), and the results show that CH₄-SDS foam has much better performance than that of the other three surfactants. The influences of gas types (CH₄, N₂, and CO₂), surfactant concentration, temperature (up to 110°C), pressure (up to 12.0 MPa), and the presence of polymers as foam stabilizer on foam performance was also evaluated using SDS surfactant. The experimental results show that the stability of CH₄ foam is better than that of CO₂ foam, while N₂ foam is the most stable, and CO₂ foam has the largest foam volume, which can be attributed to the strong interactions between CO₂ molecules with H₂O. The foaming ability and foam stability increase with the increase of the SDS concentration up to 1.0 wt% (0.035 mol/L), but a further increase of the surfactant concentration has a negative effect. The high temperature can greatly reduce the stability of CH₄-SDS foam, while the foaming ability and foam stability can be significantly enhanced at high pressure. The addition of a small amount of polyacrylamide as a foam stabilizer can significantly increase the viscosity of the bulk solution and improve the foam stability, and the higher the molecular weight of the polymer, the higher viscosity of the foam liquid film, the better foam performance.     

Novel ceramides and a new glucoceramide from the roots of <Emphasis Type="Italic">Incarvillea arguta</Emphasis>

Novel ceramides, rel-(3S,4S,5S)-3-[(2R)-2-hydroxycosanoyl-hexacosanoylamino]-4-hydroxy-5-[(4Z)-tetradecane-4-ene]-2,3,4,5-tetrahydrofuran (1a-g), and a new glucoceramide, 1-O-β-d-glucopyranosyl-(2S,3S,4R,8E)-2-[(2R)-2-hydroxytetracosanoylamino]-1,3,4-octodecanetriol-8-ene (2) were isolated from the aqueous ethanolic extract of the roots of Incarvillea arguta, together with eight known compounds: β-sitosterol (3), oleanolic acid (4), ursolic acid (5), piperin (6), maslinic acid (7), β-sitosterol 6′-O-acyl-β-d-glucopyranoside (8), 8-epideoxyloganic acid (9), and plantarenaloside (10). Their structures were elucidated on the basis of spectral data including IR, MS, NMR [¹H NMR, ¹³C NMR (distortionless enhancement by polarization transfer), ¹H−¹H COSY, heteronuclear multiplequantum coherence, and heteronuclear multiple-bond coherence correlations]. The relative configurations were established by nuclear Overhauser effect spectroscopy experiments and by comparison of the NMR spectral data and coupling constants with those already reported in the literature.     

Sugar-based cationic surfactants: Synthesis and aggregation of methyl 2-acylamido-6-trimethylammonio-2,6-dideoxy-d-glucopyranoside chlorides

The synthesis of the sugar-based cationic surfactants methyl 2-acylamido-6-trimethylammonio-2,6-dideoxy-d-glucopyranoside chlorides is reported here. Aggregation of these surfactants (predominantly α anomers) in water was studied at 25°C by conductivity measurements. Increasing the chain length of the amido group R decreased the critical micelle concentration (CMC) and the degree of counter-ion dissociation. The dependence of the Gibbs' free energy of micellization and CMC on the length of R is similar to that observed for other ionic surfactants. The free energy of transfer of the head group, i.e., cationic amino sugar moiety, from water to the micelle is more negative than that of other ionic surfactants, including sodium methyl 2-acylamido-2-deoxy-6-O-sulfo-d-glucopyranosides, probably due to a combination of a micellar “medium” effect and intermolecular H-bonding in the micellar pseudophase.     

A Feeding Stimulant for Manduca sexta from Solanum surattenses

The acceptance of Solanum surattenses as a host plant for the larvae of Manduca sexta was explained by the presence of feeding stimulants in foliage. Bioassay-guided fractionation of plant extracts resulted in the isolation of a highly active compound (1), which was identified as a furostan derivative {26-O-β-d-glucopyranosyl-(25R)-furosta-5-ene-3-β-yl-O-α-l-rhamnopyranosyl-(1″-2′)-O-α-l-rhamnopyranosyl-(1′″-3″)-O-β-d-glucopyranoside}. This compound has the same steroidal core substructure as that in a stimulant (indioside D) previously identified from potato foliage. However, the sugar substituents attached to the core are different.     

New glyceroglycolipid and ceramide from <Emphasis Type="Italic">Premna microphylla</Emphasis>

Iwo new compounds (1,2) were isolated from the ethanolic extract of the leaves of Premna microphylla, together with five known compounds. The structures of compounds 1 and 2 were elucidated as (2S,3S,4R,11E)-2-[(2R)-2-hydroxytetracosanoylamino]-11-octadecene-1,3,4-triol (1) and 1-O(9Z,12Z, 15Z-octadecatrienoyl)-3-O-[β-d-galactopyranosyl-(1→6)-O-β-d-galactopyranosyl-(1→6)-α-d-galactopyranosyl] glycerol (2) by means of spectroscopic and chemical methods.     

Synthesis and characterization of surface-active compounds derived from cholesterol derivatives and glucose

The synthesis and characterization of surface-active compounds based on various steroid derivatives and glucose are presented. The hydrophobic and hydrophilic parts of the compounds were linked via glucosidic bonds. All compounds were found to have very low water solubility and only limited solubility in various organic solvents. The compounds were investigated according to their ability to interact with an anionic surfactant, sodium dodecylsulfate (SDS), in order to induce a decrease in the critical micelle concentration (CMC) of the surfactants. This synergistic effect was pronounced for cholestanol-6-on-β-D-glucopyranoside and for cholestan-3,6-diol-β-D-glucopyranoside. These two compounds lowered the CMC from 8 to 6 and 0.6 mM, respectively, for water solutions of SDS/glucoside with a molar ratio of 92∶8. Furthermore, the ability of the compounds to stabilize lipid membranes, in liposomes, at varying concentrations of Ca²⁺, was studied. The compounds were, as expected, found to induced stabilization similar to that of cholesterol.     

Aggregation arrestant pheromone of the German cockroach,Blattella germanica (L.) (Dictyoptera: Blattellidae): Isolation and structure elucidation of blattellastanoside-A and -B

The aggregation pheromone of the German cockroach,Blattella germanica, consists of attractant and arrestant, which can be detected by olfactometer and choice-chamber assay, respectively. Both were extracted from the frass-contaminated filter paper being used as a shelter. They were separated by solvent partition withn-butanol and water. The arrestant from then-butanol phase was purified by open column chromatography and then successive HPLC isolated two major arrestant components. Spectral evidence from SI-MS, HR-EI-MS, and NMR experiments with pulse techniques provided possible structures as 1-(6-chloro-4,5-epoxy-5-stigmast-3-yl)--d-glucopyranoside and 1-(6-chloro-5-hydroxy-5-stigmast-3-yl)--d-glu-copyranoside, denoted as blattellastanoside-A and blattellastanoside-B, respectively. They represented arrestant activity as median effective doses (ED₅₀) at 0.044 (A) and 3.2 (B) nmol on 1.0 cm² of Whatman No. 1 filter paper.     

Identification of acylated glycoglycerolipids from a cyanobacterium, Synechocystis sp., by tandem mass spectrometry

Acylated glycoglycerolipids were identified in the total lipid extract from cyanobacerium Synechocystis sp. PCC 6803. These compounds have a palmitoyl group esterified to the hydroxyl group at the C-6 position of the terminal glycosyl moiety of digalactosyl monoacylglycerol and digalactosyl diacylglycerol. Their structural elucidation was accomplished by tandem mass spectrometry coupled with fast atom bombardment ionization. Acylated digalactosyl monoacylglycerol has a structure of 1-hydroxy-2-palmitoyl-3-O-[(6-O-palmitoyl)-α-d-galactopyranosyl-(1→6)-β-d-galactopyranosyl]-sn-glycerol. This compound has not been reported previously.     

Preparation and properties of rigid polyimide foams derived from dianhydride and isocyanate

A series of rigid polyimide (PI) foams were synthesized via the reaction of a first solution with a second solution. The first solution was isocyanate‐terminated polyimide prepolymers; the second solution contained deionized water and surfactant. The effect of different water contents and isocyanate index on the structures and properties of rigid PI foams were investigated. The apparent density, hardness, compressive strength, and the 5% weight loss temperatures (T_5%) decreased with the increase of water content. With the increase of isocyanate index, the apparent density and the T_5% values decreased, whereas the glass transition temperatures (T_g) increased and the hardness, compressive strength first increased and then decreased. The rigid PI foams composed of closed‐cells were confirmed by scanning electron microscopy. The maximum compressive strength of rigid PI foams prepared was up to 1.31 MPa. Moreover, excellent thermal stability was presented with the T_5% values were all above 360°C and the residual weights of the foams (R_w) were more than 50% at 800°C. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Investigation and Development of Epoxy Foams

The development of low toxicity rigid epoxy foams as an alternative to polyurethane foams for electronics encapsulation is described. The basic foam components - epoxy resin, hardener, accelerator, blowing agent and surfactant - are blended to form a two part system which is mixed and foamed when required. Each foam component is selected for its contribution to the foaming reaction and the final foam properties. The balance of component miscibility, viscosity, reaction rate and exotherm determine foam quality. Foam properties are affected by (1) density (2) cell structure and (3) the molecular structure of the reactants. Initial foam development utilised epoxy/amine chemistry and produced two foams, Feldex F3 and F4. Subsequently, use of a more reactive polymercaptan hardener improved foam strength and process times, resulting in Feldex F5 and F6 which have been used successfully to prepare quality mouldings and encapsulated electronics. Recently, development has been extended to new areas of application, e.g. high temperature foams. The mechanical, electrical, thermal and chemical properties of the best epoxy foams have been evaluated; selected results are reported. The epoxy foams developed offer low density, high strength, low dielectric constant and loss tangent, high volume resistivity, good thermal insulation, low corrosivity and low toxicity. In addition, epoxy foams soften in acetone, an advantage over their polyurethane counterparts since encapsulated electronics may be retrieved without employing corrosive solvents. (Feldex is a registered trade mark of THORN EMI Electronics.)     

Changes in liquid hold-up in foam and size of foam by perforated plates and contribution to mechanical foam-breaking

Changes in the liquid hold-up, ?, and the diameter of d, of a foam that are induced by perforated plates (PPs) and the contribution of PPs to foam-breaking were studied. A foaming system containing a dilute detergent solution in a column with mechanical agitation fitted with a rotating-disk foam-breaker (MFRD) was used. After the foam passed through the PPs, ? and d decreased and increased, respectively. The use of PPs to achieve a maximum reduction in ? and a maximum increase in d is confirmed. It is also demonstrated that use of PPs contributes not only to improving the foam-breaking performance of the MFRD, but also to power savings.     

Chemical defense in birch. Platyphylloside: A phenol fromBetula pendula inhibiting digestibility

Extracts of Scandinavian birch (Betula pendula Roth) buds and internodes of varying twig diameters have been investigated for their inhibitory effect on ruminant digestibility in vitro. The predominant inhibitory effect was observed in extracts containing the phenol platyphylloside, 5-hydroxy-1,7-bis-(4-hydroxy-phenyl)-3-heptan-one-3-O--d-glucopyranoside. Isolation of the pure compound and incubation with rumen inocula showed that digestibility was negatively related to the concentration. Significant effect was measured below the concentration naturally occurring in birch (0.8% of dry matter). Another isolated compound, the closely related rhododendrin, 4-(4-hydroxyphenyl)-2-butanol-2-O--d-glucopyranoside, did not depress digestibility within the concentrations found in birch. An important phenol of buds, apigenin-4,7-dimethylether, did not have any measurable effect on digestibility, while a nonphenolic fraction of bud extract had a slight inhibitory effect on digestibility. Implications for browsers feeding on birch are briefly discussed.     

Synthesis and characterization of elastomeric polyurea foam

Polymeric foams are ubiquitous in impact mitigation for civilian and military applications; the performance in such loading scenarios can be elucidated through quasi-static and dynamic mechanical testing. The present study reports on the complex microstructure of newly synthesized polyurea foams exhibiting a hierarchical structure consisting of large perforated semi-closed spherical cells with a mean diameter of 370 ± 162 μm surrounded by smaller closed, spherical cells with size distribution of 69 ± 18 μm. The stress–strain curves were used to calculate the basic mechanical properties and to predict the dynamic behavior of the foams. Nonlinear regression and finite element analyses were used to calibrate the Ogden hyperfoam model to explicate the hyperelastic behavior. The performance of the polyurea foam was found to outperform a benchmark foam in nearly all the elastic and energy absorbing properties. For example, one variation of the newly synthesized foam stored nearly doubled the energy of the benchmark foam while being 12% lighter. Low-density polyurea foam was found to decelerate an incoming impact mass with a minimum G-level that was nearly one third lower than the higher density polyurea and benchmark foams. In all, the behavior of the foam is dependent on the parameters of the fabrication process. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48839.     

碳氢/有机硅/低碳醇三元系泡沫及抑制煤自燃的效果分析

泡沫灭火剂是常用的火灾扑救方法之一,但常规泡沫灭火剂存在半衰期短,析液、聚并迅速而影响灭火效能的问题,基于火灾化学和活性剂技术,提出碳氢表面活性剂SDS、有机硅表面活性剂LS-99和低碳醇的三元系泡沫体系,并系统探究碳氢/有机硅/低碳醇的复配配比。通过表面张力、发泡高度、稳泡系数的大量测试,发现LS-99的临界胶束浓度为0.0083%。LS-99和SDS二元系在降低表面张力、提升发泡高度和稳泡系数方面具有良好的协同增效作用。在此基础上引入适量浓度的能够延缓泡沫析液、聚并的异丁醇,设计出了性能优良的碳氢/有机硅/低碳醇泡沫灭火剂。LS-99、SDS和异丁醇的质量分数为0.1%时,测试结果表明SDS/LS-99/醇三元系泡沫的发泡倍数可达52.5倍,25%析液时间可达210 s,300 s时的稳泡系数高达0.958,半衰期远超常规泡沫。煤自燃的灭火抑制实验表明,SDS/LS-99/醇三元系泡沫作用下,煤自燃各反应阶段的活化能相较于空气氛围均增大,反应难度增强;最大失重速率下降,反应剧烈程度减弱。初期吸热阶段的吸热量为78.3 J/g,大于空气氛围下煤氧复合的吸热量,吸热增幅高达2.16倍。放热阶段的放热量为1765.4 J/g,相较于空气氛围放热降幅达到15.15%,表明SDS/LS-99/醇三元系泡沫对煤自燃具有良好的灭火效果。     

Preparation of some linseed esters of methyla-d-glucopyranoside using the methoxycarbonyl blocking group

The three possible methoxycarbonyl derivatives of methyl 4,6-O-benzylidene-a-d-glucopyranoside have been prepared. The methoxycarbonyl at the C₂ position in the 2,3-di-O-methoxycarbonyl derivative is removed selectively in anhydrous ammonia. The ability of the methoxycarbonyl group to block selectively the C₂ hydroxyl in methyl glucoside has been utilized to synthesize some mono-, di-, and tri-linseed esters of methyl glucoside. The use of this new blocking group has permitted the first synthesis of some unsaturated esters of methyl glucoside. Presented in part at AOCS meeting in Minneapolis, Minn., 1963. A laboratory of the No. Utiliz. Res. Dev. Div., ARS, USDA.     

The effects of anionic and cationic surfactants on the hydrolysis of sodium barbital

Alkaline hydrolysis reactions of sodium barbital in micelles of sodium dodecyl sulfate (the anionic surfactant SDS), micelles of cetyl trimethylammonium bromide (the cationic surfactant CTAB), and mixed micelles of surfactant/n-C₅H₁₁OH/H₂O were studied by ultraviolet-visible spectrometry. The reaction rate and the activation energy of the hydrolysis of sodium barbital were calculated. The results showed that the rate of sodium barbital hydrolysis decreased with an increase in CTAB content, whereas it increased in the presence of SDS and n-C₅H₁₁OH. The different effects of CTAB and SDS on the hydrolysis of sodium barbital may be related to their interaction with sodium barbital.