Performance of Φ-Sulfo Fatty Methyl Ester Sulfonate Versus Linear Alkylbenzene Sulfonate,Secondary Alkane Sulfonate and α-Sulfo Fatty Methyl Ester Sulfonate

Sulfoxidation of fatty acid methyl esters with SO_2, O₂ and ultraviolet light of appropriate wavelength, has led to the synthesis of methyl esters sulfonates or sulfoxylates, known as Φ-MES, because of the possible random position of SO₃ group in the alkyl chain. Aqueous solutions based on the sulfoxylated methyl ester of palmitic acid (Φ-MES C16) have been studied and compared to the leading types of surfactants used today: linear alkylbenzene sulfonate (LAS) secondary alkane sulfonate (SAS) and α-sulfo fatty methyl ester sulfonate (α-MES) with regard to solubility, performance and skin compatibility. The experimental results obtained indicate that Φ-MES C16 can be regarded as a potential component of detergent formulations and most likely also of body care products.

Methyl zealactonoate:玉米产生的根寄生杂草发芽刺激物

<正>玉米是根寄生杂草独脚金Striga hermonthica和Striga asiatica的主要寄主,已报道其能产生数种独脚金内酯。在已知的独脚金内酯中,独脚金醇是从玉米根渗出液中分离得到的主要独脚金属杂草种子萌发刺激物。此外,从玉米根渗出液中也发现了sorgomol和5-deoxystrigol。最近,Jamil等人报道通过LC-MS/MS分析检测到玉米根渗出液中的新颖萌发刺激物,暂时     

Adsorption of Methyl Orange on Magnetically Separable Mesoporous Titania Nanocomposite☆

The adsorption of mesoporous Fe3O4–SiO2–TiO2 (MFST), which can be separated easily from solution by a mag-net, for the removal of methyl orange (MO) was investigated. The nitrogen adsorption–desorption...     

Pervaporative Separation of Methanol–Methyl Acetate Mixtures with Commercial PVA Membranes

Pervaporation may successfully be implemented for the separation of azeotropic mixtures which generally requires energy intensive separation procedures. Separation of methanol from methyl acetate by pervaporation is a representative application. In this study the commercial polyvinyl alcohol (PVA)-based membranes PERVAP^TM 4155-30, PERVAP^TM 4155-70, and PERVAP^TM 4155-80 were used to recover methanol from binary methanol–methyl acetate mixtures. The separation performance was investigated for various operating parameters such as feed composition, feed temperature, and permeate pressure and discussed in terms of permeance and selectivity. An empirical model was developed to quantify the effect of membrane swelling on the permeate flux.     

Methyl acetate–methanol mixture separation by extractive distillation: Economic aspects

Methyl acetate is considered low toxicity volatile solvent produced either as a by-product during methanol carbonylation or via acetic acid esterification with methanol. In both cases, pure methyl acetate has to be isolated from the reaction mixture. Simulation of methyl acetate separation from its mixture with methanol by extraction distillation was carried out in ASPEN + software. In total three case studies were assumed using two different extraction solvents and two solvent regeneration strategies. In case A, novel extraction solvent 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid, was considered. Raw material separation was achieved in an extraction distillation column while the solvent regeneration was accomplished in a second distillation column in this case. In case study B, the same extraction solvent was used; however, its regeneration was carried out in a single-effect evaporator. Dimethyl sulfoxide was the second extraction solvent selected. Its use in methyl acetate-methanol separation is presented in case study C. As high purity of dimethyl sulfoxide was required for the methyl acetate-methanol azeotrope breaking, its regeneration was carried out in the second distillation column only. To simulate the ternary methyl acetate–methanol–extraction solvent mixtures separation, vapor–liquid equilibrium was predicted based on the NRTL equation. Further, unknown properties of the considered ionic liquid and variation of these properties with temperature were predicted and introduced into the ASPEN + components properties database. Based on these data, optimum operation parameters of the respective separation equipment were established. In all case studies, the same condition had to be fulfilled, namely minimum methyl acetate content in the distillate from the extraction distillation column of 99.5mol-%. Results of simulations using the respective optimum operation parameters were employed in the economic evaluation of the three separation unit designs studied. It was found that the least energy-demanding design corresponds to the case study B in terms of both capital as well as operation expenses.

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Adsorption Characteristics and pH‐dependence of Metsulfuron‐Methyl onto Activated Carbons

Abstract

The adsorption characteristics of metsulfuron‐methyl (MM) onto powdered activated carbon (PAC) and granular activated carbon (GAC) were studied at varying solution pHs (4–9) and temperatures (20–40°C). The dependence of pH was observed in aqueous solution with MM. The film mass transfer and intraparticle diffusion coefficients were estimated from concentration decay curves obtained in the batch adsorber. The maximum adsorption capacity decreased with increasing pH and temperature. Among the PAC used, the coconut based PAC had the best adsorption capacity. The adsorption isotherms could be plotted using the Freundlich and Toth models with a reasonable degree of accuracy. The overall adsorption isotherm such as the modified‐Toth model should be applied. The performances of the fixed‐bed GAC system was also simulated by a model developed. The objective of the present study was to investigate the adsorption and pH dependence behavior of MM onto PAC and GAC in order to diminish the environmental risk of MM pollution.     

Zeolite 4A-Incorporated Polymeric Membranes for Pervaporation Separation of Methanol–Methyl Acetate Mixtures

Zeolite 4A-incorporated poly(vinyl alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) membranes were prepared for pervaporation separation of methanol/methyl acetate mixtures. These membranes were characterized by Infrared spectroscopy, X-ray diffraction and Scanning electron microscopy. The results showed that crystallinity of the membrane decreased with the increase of zeolite 4A content. The effect of zeolite loading, feed composition and temperature on the membrane separation performance were discussed in detail. With the increase of zeolite 4A content, permeation flux increased continuously, but separation factor first increased and then decreased. The addition of 2.5 wt% zeolite 4A in the polymer membrane improved the separation factor from 12.9 (for PVA/PVP membrane) to the maximum value of 34.4 for 20 wt% methanol in feed at 45 °C. The separation factor decreased with increasing feed temperature, however, the flux increased with increasing feed temperature. Zeolite 4A-incorporated PVA/PVP membranes provide an effective method for the separation of methanol/methyl acetate azeotropic mixtures.     

Titanium–Silica Catalysts for the Production of Fully Epoxidised Fatty Acid Methyl Esters

Grafted titanium-containing mesoporous silica catalysts were used in the selective epoxidation of C-18 unsaturated fatty acid methyl esters (FAMEs). High yields in mono- and diepoxide derivatives were obtained under acid-free reaction conditions with TBHP as oxidant. Ti-MCM-41 showed the best performance in terms of activity over the three FAMEs. Easy separation of the desired products and recycling of the catalyst were demonstrated.     

Surfactant Synthesis via Lipase Esterification of Methyl α-d-Glucopyranoside with Selected Aliphatic Carboxylic Acids

Lipase‐catalyzed esterification and properties of synthesized carbohydrate esters were investigated. Methyl α‐d ‐glucopyranoside was the acyl group acceptor and different carbon atom chain lengths of aliphatic carboxylic acids (C12, C14 and C16) as the acyl group donors were applied in the esterification. Physico‐chemical studies on the synthesized carbohydrate esters were carried out. It was found that melting point for the methyl 6‐O‐hexadecanoyl‐α‐d ‐glucopyranoside was the highest consecutively followed by methyl 6‐O‐tetradecanoyl‐α‐d ‐glucopyranoside and methyl 6‐O‐dodecanoyl‐α‐d ‐glucopyranoside. Liquid crystal properties of the synthesized carbohydrate ester synthesized were evaluated via optical polarized microscopy. It was found that the liquid crystal textures for mono‐substituted carbohydrate esters were of the smectic phase. In a quaternary system (carbohydrate ester/n‐butanol/n‐hexadecane/water), a maximum 34 % of water (by mass) was contained in the monophasic region of methyl 6‐O‐tetradecanoyl‐α‐d ‐glucopyranoside and a maximum of 52 % water (by mass) was contained in a monophasic methyl 6‐O‐dodecanoyl‐α‐d ‐glucopyranoside. For methyl‐6‐O‐dodecanoyl‐α‐d ‐glucopyranoside, its concentration at aggregation was 5.2 × 10^?4 mM, with minimum air/water surface tension of 26 mN m^?1. The Gibbs energy of micellization was calculated at ?50 kJ mol^?1. The maximum adsorption density of methyl 6‐O‐dodecanoyl‐α‐d ‐glucopyranoside was determined at 4 × 10^?6 mol m^?2 while its minimum area per surfactant molecule at the air/water surface was 47 Ų.     

Advance in the Polymerization Strategy for the Synthesis of β-Peptides and β-Peptoids

Peptide mimics, possessing excellent biocompatibility and protease stability, have attracted broad attention and research in the biomedical field. β-Peptides and β-peptoids, as two types of vital peptide mimics, have demonstrated great potential in the field of foldamers, antimicrobials and protein binding, etc. Currently, the main synthetic strategies for β-peptides and β-peptoids include solid-phase synthesis and polymerization. Among them, polymerization in one-pot can minimize the repeated separation and purification used in solid-phase synthesis, and has the advantages of high efficiency and low cost, and can synthesize β-peptides and β-peptoids with high molecular weight. This review summarizes the polymerization methods for β-peptides and β-peptoids. Moreover, future developments of the polymerization method for the synthesis of β-peptides and β-peptoids will be discussed.     

Preparation of long-chain β-enaminones and β-diketones from long-chain 3,5-disubstituted isoxazole compounds

A series of long-chain compounds containing the β-enaminone functionality were prepared in yields ranging from 71 to 88% from their corresponding long-chain 3,5-disubstituted isoxazole precursors utilizing a Raney nickel-catalyzed reductive ring-opening procedure. These newly prepared multifunctional compounds were subsequently hydrolyzed under mild acidic conditions (pH 4–5) to give their corresponding long-chain β-diketones in yields ranging from 79 to 98%. Both the β-enaminone and β-diketone functionalized compounds were characterized by NMR, IR spectroscopy, GC-MS, and m.p. The mass spectra for these two classes of compounds, derived by utilizing electron impact ionization, gave distinctive McLafferty rearrangement fragmentation ions that clearly established the newly introduced functionality to reside at the C-2 and C-4 positions of the lipid’s alkyl chain. ¹H NMR spectra of the pure β-diketone compounds were complex owing to the keto enol tautomerism displayed by the β-diketone moiety. In solution the β-diketone compounds were shown to exist mainly in the enolic tautomeric form. Long-chain β-diketone compounds are known to be relatively common constituents of some plant waxes, and the overall procedure starting from soybean methyl esters provides a complementary approach to prepare these types of compounds.     

Carnivore Attractant or Plant Elicitor? Multifunctional Roles of Methyl Salicylate Lures in Tomato Defense

Synthetic plant volatile lures attract natural enemies, but may have non-target effects due to the multifunctional nature of volatile signals. For example, methyl salicylate (MeSA) is used to attract predators, yet also serves as a signaling hormone involved in plant pathogen defense. We investigated the consequences of deploying MeSA lures to attract predators for tomato (Solanum lycopersicum) defense against herbivores. To understand the spatial distribution of the lure’s effect, we exposed tomatoes in the field to MeSA along a linear distance gradient and induced defenses by simulating feeding by hornworm caterpillars in a fully crossed factorial design (+/? MeSA, +/? herbivory). Subsequently, we analyzed activity of several defensive proteins (protease inhibitors, polyphenol oxidase, peroxidase), development of hornworm larvae (Manduca sexta), growth of fungal pathogens (Cladosporium and Alternaria), and attractiveness to herbivores and predators. Overall, MeSA-exposed plants were more resistant to both insects and pathogens. Secondary pathogen infection was reduced by 25% in MeSA exposed plants, possibly due to elevated polyphenol oxidase activity. Interestingly, we found that lures affected plant pathogen defenses equivalently across all distances (up to 4 m away) indicating that horizontal diffusion of a synthetic volatile may be greater than previously assumed. While thrips avoided colonizing hornworm– damaged tomato plants, this induced resistance was not observed upon pre-exposure to MeSA, suggesting that MeSA suppresses the repellant effect induced by herbivory. Thus, using MeSA lures in biological control may inadvertently protect crops from pathogens, but has mixed effects on plant resistance to insect herbivores.     

Formation of Toxic α,β-Unsaturated 4-Hydroxy-Aldehydes in Thermally Oxidized Fatty Acid Methyl Esters

To investigate the heat induced formation of α,β-unsaturated 4-hydroxy-aldehydes (4-hydroxy-2-trans-hexenal (HHE), 4-hydroxy-2-trans-octenal (HOE), 4-hydroxy-2-trans-nonenal (HNE) and 4-hydroxy-2-trans-decenal (HDE)) fatty acid methyl esters (FAMEs) of stearic, oleic, linoleic and linolenic acids were heated separately at 185°C for 0 to 6 hrs. The formation of 2,4-decadienal, a suspected intermediate in HNE formation, was also measured in these FAMEs. As expected methyl stearate (MS) and methyl oleate (MO) did not produce any of the α,β-unsaturated 4-hydroxy-aldehydes as a consequence of thermally induced lipid peroxidation. The formation of HHE was detected in both methyl linoleate (ML) and methyl linolenate (MLN), with concentration higher in MLN than in ML. The maximum HHE concentration was 3.99 μg HHE/g ML after 2 h and 50.78 μg HHE/g MLN after 4 h of heat treatment. HOE was detected in both ML and MLN, and the maximum concentration was 102.50 μg HOE/g ML after 6 h and 90.56 μg HOE/g MLN after 2 h of heating. HNE was found only in ML and its highest concentration was 84.82 μg HNE/g ML after 3 h of heating. HDE was not detected in any of the four heat treated FAMEs. 2,4-Decadienal was not found to be an intermediate in the formation of HNE in thermally induced oxidation of FAMEs.     

Selective Extraction of Mercury(II) by 1‐Naphthylthiourea–Methyl Isobutyl Ketone System

Abstract

Selective extraction of Mercury(II) using 1‐naphthylthiourea–methyl isobutyl ketone (ANTU‐MIBK) system from hydrochloric acid solutions (0.1–10 M) has been studied. Influence of foreign ions, acid and ligand concentrations has been investigated. Addition of ANTU in MIBK enhanced, extraction capacity of MIBK to several times. Low effect of foreign ions and high separation factors for a number of metal ions determined at 0.5 M hydrochloric acid concentration evaluated the proposed method efficient and selective. The experimental data obtained from application of the method for extraction of mercury from a synthetic aqueous solution reveal that more than 99% mercury can be separated from cadmium, zinc and selenium in a single step with five minutes equilibration.     

MgO-SBA-15 Supported Pd-Pb Catalysts for Oxidative Esterification of Methacrolein with Methanol to Methyl Methacrylate☆

Novel MgO–SBA-15 supported catalysts were prepared for oxidative esterification of methacrolein (MAL) with methanol to methyl methacrylate (MMA). The MgO–SBA-15 supports were synthesized with different...     

A novel bridged organocobaloxime/ β-cyclodextrin inclusion complex produced by a β-cyclodextrin induced reaction

A cobalt-to-oxime carbon bridged organocobaloxime/β-cyclodextrin inclusion complex has been formed in a β-cyclodextrin induced reaction, which was confirmed by X-ray structure analysis and FAB-MS.     

UV photopolymerized hydrogels with β-cyclodextrin moieties

Hydrophilic hydrogels based on poly(ethylene glycol)–poly(propylene glycol)–poly(ethylene glycol) block copolymers have potential applications in drug delivery, tissue engineering and other biomedical devices due to their excellent biocompatibility and environmental sensitivity. However, they also exhibit some shortcomings in terms of swelling and mechanical properties as well as affinity for water-insoluble or hydrophobic drug molecules. To address these limitations, new polymeric hydrogels with β-cyclodextrin moieties were prepared by UV photo-polymerization of maleic anhydride-substituted β-CD (MAH-CD) and the block copolymer macromer from Pluronic F68 and poly(ɛ-caprolactone). Their swelling and dynamic rheological properties were investigated with respect to the effects of feed compositions. It was found that the swelling ratio, storage modulus and loss modulus of the resulting hydrogel increased with the increase of MAH-CD amount. Incorporation of MAH-CD resulted in strong viscoelastic system with dominating elastic behavior.     

Phosphorus Acids as Highly Efficient Promoters for the Palladium-Phenanthroline Catalyzed Carbonylation of Nitrobenzene to Methyl Phenylcarbamate†

A new family of promoters, based on phosphorus acids, is reported for the catalytic carbonylation of nitrobenzene to methyl phenylcarbamate by palladium-phenanthroline complexes. With the new promoters, unprecedented reaction rates (TOF up to 6000/h) and catalyst stability (TON up to 10⁵) could be reached. The best promoter is phosphoric acid, which is also very cheap, nontoxic and easily separable from the reaction products.     

Polymerization of β-propiolactone via nickel-chelate complexes

Summary The polymerization of -propiolactone, initiated by nickel propionate-tributylphosphine was studied in toluene at 35°C. Monomer and initiator consumptions were followed by ¹H NMR spectroscopy. The spectra were recorded at regular intervals and show that: (1) The phosphorus-chelated nickel complex is destroyed; (2) the resulting nickel carboxylate creates a new complex with the lactone. (3) The length of this transfer period depends on the initial monomer concentration. (4) The activated lactone leads to the formation of a zwitterion with consumption of tributylphosphine. (5) The zwitterion reacts with complexed lactone to give a -substituted carboxylate.