Suspension Property of Gemini Surfactant in Seed Coating Agent

Suspension properties of Gemini surfactant, polyethylene glycol diester alpha sulfonated stearic acid disodium salt, on 15% thiram/carbofuran/triadimefon seed coating agent of maize, 17% carbendazim/carbofuran/triadimefon seed coating agent of wheat and 15% carbendazim/thiram/triadimefon seed coating agent of cotton were studied. Under these conditions, Gemini surfactant had a good suspension property by itself and an excellent synergistic effect with some nonionic surfactant such as OP‐10, Tween 80, and AEO‐7. Also, it can be mixed with attapulgite clay to provide a better suspension property than suspension system without attapulgite clay. Its suspending rates on three kinds of seed coating agents mentioned above are, respectively, up to 97%, 95%, and 98% for 90 days. In comparison with traditional surfactant suspending agent of LAS and SDS, Gemini surfactant had less changes in suspending efficiency at high temperatures, and in viscidity in impact tests. In a germination experiment, cotton seeds coated with Gemini surfactant suspending agent have an 88% germination rate for 10 days and a 69% excavation rate, which was higher than those bare seeds, and grow fully.     

Enzyme immobilization to ultra‐fine cellulose fibers via amphiphilic polyethylene glycol spacers

Ultra‐high specific surface cellulose fibers with an average diameter of 500 nm were generated from electrospinning and alkaline hydrolysis of cellulose acetate and used as porous supports for enzyme immobilization. The cellulose fiber surfaces were reacted with polyethylene glycol (PEG) diacylchloride to simultaneously add amphiphilic spacers and reactive end groups for coupling with a lipase enzyme. The quantity of reactive carboxylic acid on the fiber surfaces could be readily controlled by COCl/OH molar ratios and PEG lengths. The highest free acid (COOH) content of 1.0 mmol per gram of cellulose was obtained at 10 COCl/OH ratio with the 600‐Da PEG diacylchloride. Enzyme coupling on such PEG‐attached cellulose was optimal in the presence of a water‐soluble carbodiimide [1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide (EDC)] at a very low EDC/COOH molar ratio of 0.2 under acidic condition and at ambient temperature. Whereas the free lipase retained only 25% of its original activity, the fiber‐bound lipase possessed much superior retention of catalytic activity after exposure to cyclohexane (81%) and toluene (62%) and hexane (34%). The fiber‐bound lipase also exhibited significantly higher catalytic activity at elevated temperatures than the free form, that is, 10 times at 70 °C. The ultra‐fine, fibrous, and porous structures were retained throughout alkaline hydrolysis, activation, coupling, and activity assays. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4289–4299, 2004     

Synthesis of pH‐sensitive surfactants by the terpolymerization of methacrylic acid,methoxy poly(ethylene glycol) methacrylate,and lauryl methacrylate: Initiator effect and reactivity ratio study

For the development of pH‐sensitive surfactants to be used in water‐in‐oil fermentation, the free‐radical terpolymerization of methacrylic acid (MAA), methoxy poly(ethylene glycol) methacrylate (MPEGMA), and lauryl methacrylate (LMA), at a molar ratio of 1.0:0.04:0.76, was studied with two initiators, azobisisobutyronitrile (AIBN) and hydrogen peroxide, at different concentrations. The polymer synthesized with 0.45% AIBN as the initiator was the most promising, giving similar conversions of all three monomers throughout the 10‐h polymerization. The subsequent study on AIBN‐initiated systems indicated that MPEGMA caused an increase‐then‐decrease profile of the MAA conversion with a plateau around an ethylene glycol/MAA ratio of 1–2. This observation was fairly consistent with the well‐known type II template polymerization of poly(ethylene glycol) (PEG)–MAA systems. The reactivity ratios obtained in this study suggested that the polymer synthesized with AIBN as the initiator had a structure of alternating blocks of MAA and LMA, with isolated PEG grafts. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2950–2959, 2004     

Adsorption and elektrokinetic properties of the system: carboxymethylcellulose/manganese oxide/surfactant

The adsorption of carboxymethylcellulose (CMC) in the presence of the surfactants: anionic SDS, nonionic polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether (Triton X-100) and their mixtures SDS/polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether with different molar ratios (1:1; 1:3 and 3:1) from the electrolyte solutions (NaCl, CaCl₂) on the manganese dioxide surface (MnO₂) was studied. In every measured system the increase of CMC adsorption in the presence of surfactants was observed. This increase was the smallest in the presence of SDS, a bit larger in the presence of polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether and the largest when the mixtures of SDS/polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether were used. Among the measured mixtures, the mixture of SDS/polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether with the molar ratio 1:3 caused the largest increase of CMC adsorption amount. These results are a consequence of formation of complexes between the carboxymethylcellulose macromolecules and the surfactant molecules. In order to determine the electrokinetic properties of the system the surface charge density of MnO₂ and the zeta potential measurements were conducted in the presence of the CMC macromolecules and the surfactants. The obtained data showed that the adsorption of CMC or CMC/surfactants complexes on the manganese dioxide surface strongly influences the structure of the electric double layer MnO₂/electrolyte solution.     

New polymer syntheses 16. LC-copolyesters of 3-(4-hydroxyphenyl) propionic acid and 4-hydroxy benzoic acids

The polycondensation of 3-(4-hydroxy phenyl)-propionic acid, 4-Hypp, by means of acetanhydride or acetylchloride was conducted either in the presence or in the absence of a liquid reaction medium. DSC measurements, polarizing microscope, and X-ray diffraction studies indicate poly(4-Hypp) possesses at about 215°C a reversible first order transition between two solid phases. Copolyesters containing various mole ratios of 4-Hypp and 4-hydroxy benzoic acid, 4-Hybe, were prepared by bulk condensation with acetanhydride at 320°C. At 4-Hypp/4-Hybe ratios less than 1.0:1.5 the reaction product was heterogeneous, containing crystals of pure poly(4-Hybe). Neither increasing the reaction time nor the variation of the transesterification catalyst resulted in an entirely homogeneous copolyester. However, for 4-Hypp/4-Hybe ratios greater than 1.0:1.5, ¹³C NMR spectra indicate perfectly random sequences. Also, terpolyesters containing 3-chloro-4-hydroxy- or 3,5-dichloro-4-hydroxy-benzoic acid were heterogeneous with less than 30 mol % 4-Hypp. DSC measurements revealed for all polyesters a glass transition in the range of 55–78°C. Temperature dependent X-ray diffraction studies confirm that the solid phase is a s.c. LC-glss. Correspondingly low heat distortion temperatures were found by thermomechanical analyses. The copolyesters display under the polarizing microscope LC-phase up to temperatures of 450–480°C, where rapid thermal degradation prevents further investigations. In the case of the 4-Hypp/4-Hybe 1:1 copolyester, the LC-phase extends over a temperature range of about 400°C. TGA measurements indicate beginning thermal degradation at temperatures between 350 and 380°C.     

Reaction of polyvinyl alcohol with aluminium isopropoxide

The uncatalyzed and oxalic acid catalyzed modification of polyvinyl alcohol (PVA) with aluminium isopropoxide have been studied for reaction in a suspension of powdered PVA in boiling benzene. Isopropyl alcohol (IPA) formed during the reaction was removed by continuous distillation of an IPA-benzene mixture. The reaction was initially quite fast but slowed up rapidly and practically stopped when only 4–12% of the OH-groups had reacted. Thermogravimetric analysis (TGA) showed that products with 6.8 mole A1/100 mole VA exhibit a significant rise in decomposition temperature from 250 to 285°. The characteristics are attributed to the occurrence of vicinal OH-groups in PVA.     

用双表面活性剂为共模板合成中孔分子筛MCM-48

利用水热法以非离子表面活性剂聚乙二醇辛基苯基醚和阳离子表面活性剂十六烷基三甲基溴化铵为共模板合成了中孔分子筛MCM-48.实验中发现利用较强的范德华力和氢键,聚乙二醇辛基苯基醚可在很大程度上降低合成MCM-48所需阳离子表面活性剂的用量,且利于制备有序性好、骨架聚合度高、稳定性好的MCM-48.通过调节聚乙二醇辛基苯基醚与十六烷基三甲基溴化铵的比例,可得到不同物相结构的分子筛.     

Sulfonation of Liquefied Wood and Suspension Property of Its Product in Seed Coating Agent

For the utilization of product from wood liquefaction by ionic liquid, the liquefied product was sulfonated by chlorosulfonic acid as a sulfonating agent, and the product of wood liquefaction sulfonation (WLS) was obtained. The characterization of WLS is determined using FTIR, and the strong absorption peak of sulfonic group is clear. The suitable reaction conditions are as follows, the mass ratio of chlorosulfonic acid to liquefied wood and formaldehyde to liquefied wood are 0.8:1 and 0.9:1, reaction temperature of sulfonation and condensation are at 85°C and 90°C, reaction time of sulfonation and condensation are for 2.5 and 3.0 hours. When the solution concentration of WLS is 15 g · L^?1, the surface tension is 46.9 mN · m^?1. In the formula of seed coating agent, WLS shows better suspension property and less change of viscosity in impact test than that of conventional surfactants, also, it can generate synergy effects with the other surfactants to make higher suspending rate in binary or ternary mixed system than that in single system.     

Polymerization of n-octadecene-1 with catalysts derived from titanium tetrachloride and triethylaluminum

The effects of variation in Al/Ti mole ratio, catalyst concentration, reaction time, and temperature on the yield and some physical properties of polymers of n-octadecene-1 obtained with the use of Ziegler catalyst systems derived from titanium tetrachloride and triethylaluminum have been investigated. Results show many features similar to those obtained by other workers with lower olefins. In general, the yield of polymer shows a distinct maximum at an Al:Ti mole ratio of 2.8:1 and total catalyst concentration (at the stated mole ratio) of 4%, based on monomer; the yield increases sharply with polymerization temperature to a maximum at about 40°C. and with time up to about 12 hr. at 25°C. Polymer intrinsic viscosity also shows a strong dependence on Al:Ti mole ratio and catalyst concentration, increasing between Al:Ti mole ratios of 2.0–3.4, and showing a maximum at catalyst concentration of 3.5% on monomer. Polymer intrinsic viscosity shows a decrease with increasing reaction temperature and an increase with time of polymerization. The polymer densities, melting points, and fraction soluble in hexane (at 25°C.) appear to show much less dependence on the variables under consideration, and no firm conclusions are drawn. An important reaction concurrent with polymerization is the formation of a trans nonterminal isomer of octadecene. This certainly affects the yield (the nonterminal isomer not being polymerizable under the same conditions); the effect of the presence during polymerization of isomerized monomer on the physical characteristics of the polymer is less clear, and further work is proceeding.     

Gemini阳离子表面活性剂的合成及其胶束生成 Gemini阳离子表面活性剂的合成及其胶束生成

Cationic Gemini surfactants, alkanediyl-α,ω-bis(dimethyldodecylammonium bromide) have been synthesized by the following method: firstly dodecyl bromide was prepared by the reaction of dodecanol with bromic acid in the presence of strong sulfuric acid. Dodecylbromide was then reacted with N,N-tetramethyl ethane diamine(or N,N-tetramethyl hexana diamine) to prepare the title-compounds. Micellization of these Gemini surfactants was investigated using conductivity measurement. The results showed that the critical micelle concentration(cmc) of the Gemini surfactants has a much lower value compared with that of the corresponding “ monomer” . For a series of the Geminis with the same length(s) in the spacer chain, the cmc decreased with increasing the carbon number (m) in the alkyl chain. The aggregation number(N) of the micelle also drastically decreased with m. For the same value of m, the cmc varied slightly with s, which indicated that the electrostatic interaction between the ionic-groups of the “ monomer” has been naturally changed duo to a link between the two ionic-groups of the “ monomer” through a spacer. However, N was strongly decreased with s,which may be a reason of steric inhibition coming from the ionic-groups due to a link of spacer. With increasing temperature, micellization of the Gemini surfactants was slightly enhanced.     

Simultaneous separation of nonionic surfactants and polyethylene glycols by reversed phase high performance liquid chromatography

Summary The simultaneous separation of polyethylene glycol and its derivatives such as the lauryl alcohol and lauric acid ethoxylate oligomers was carried out by reversed phase high performance liquid chromatography. Branched fluorinated silica gel columns combined with evaporative light scattering detection were used for the characterization of nonionic surfactants. Lauryl alcohol ethoxylate oligomers were separated at 10°C with an isocratic eluent according to ethoxylate number and the retention time of the oligomers decreases with increasing ethoxylate number. The Van’t Hoff plots of retention factor of lauryl alcohol ethoxylate gave a complex cure, which is anomalous behavior for reversed phase high performance liquid chromatography. The anomalous Van’t Hoff plots were explained by a partial conformational change from polar to less polar conformers with increasing temperature. The most significant features for the analysis of the lauryl alcohol ethoxylate were the use of acetonitrile as mobile phase and operating temperature. The polyethylene glycol was separated according to ethoxylate number and the retention time of oligomers increased with increasing ethoxylate number. The Van’t Hoff plots of retention factor of polyethylene glycol had negative slopes. It was presumed that the polar conformation of the ethylene oxide chain decreased with increasing temperature. The lauryl alcohol ethoxylate and polyethylene glycol were separated simultaneously in gradient elution as a result of the conformational change of the ethylene oxide chain. As a practical example, lauric acid ethoxylate simultaneously separated into free polyethylene glycol, ethoxylate monolaurate and ethoxylate dilaurate in gradient elution.     

Studies on SDLC (Sodium Dilauraminocystine) and SDMC (Sodium Dimyristaminocystine) Gemini Surfactants

The present work reports the synthesis and evaluation of surface active properties of amino acid-based gemini surfactants, namely, sodium dilauraminocystine (SDLC) and sodium dimyristaminocystine (SDMC) derived from L-cystine and fatty acids. The effect of reaction variables like molar ratio of raw materials and temperature has been studied for the synthesis of these gemini surfactants. In preparation of these gemini surfactants, fatty acids (lauric/myristic) were reacted with thionyl chloride to obtain respective acid chlorides (lauroyl/myristoyl). These acid chlorides were further reacted with L-cystine at different reaction conditions to get amino acid based-gemini surfactants. The study revealed that 1:2.5 molar ratio of reactants, namely, L-cystine and lauroyl/myristoyl chloride and 10–15° reaction temperature resulted in maximum yield of amino acid-based gemini surfactants (SDLC and SDMC). Surface active properties of synthesized gemini surfactants (SDLC and SDMC) were also compared with their corresponding monomeric units, namely, sodium lauroyl cysteine (SLC) and sodium myristoyl cysteine (SMC), respectively. The results demonstrated that gemini surfactants (SDLC and SDMC) had better surface active properties than their corresponding monomeric units. The structures of synthesized amino acid-based gemini surfactants were also confirmed by FTIR, ¹H NMR, ¹³C NMR, and ESI-MS spectral data.     

用聚乙二醇简便合成3-取代-1, 2, 3, 4-四氢吡啶并[3, 2-d]嘧啶-2, 4-二酮

用聚乙二醇作为可溶性聚合物载体和相转移催化剂高效简单的合成了1, 2, 3, 4-四氢吡啶并[3, 2-d]嘧啶类化合物。该合成路线为聚乙二醇与2, 3-吡啶二酸酐反应生成聚乙二醇支载的单酯1,接着1被转化成相应的聚乙二醇支载的酰基叠氮2,2经Curtius重排,与胺加成并同时关环给出目标产物,其总产率为84%-88%。     

Microwave-assisted lipase-catalyzed synthesis of polyethylene glycol stearate in a solvent-free system

Polyethylene glycol stearate, a condensation esterification product of stearic acid and polyethylene glycol 600, was widely applied in the biomedical and healthcare industries. The current work focuses on the enzymatic synthesis of PEG stearate using CALB_ex10000, a commercial Lipase enzyme in solvent-free conditions using microwave irradiation. The influence of various reaction parameters such as temperature, molar ratio of reactants, and enzyme loading was studied to obtain the highest conversion. Maximum conversion of 85% was attained under molar ratio 1:1 (PEG 600 to stearic acid using 0.7% (w/w) enzyme loading at 60 ​°C of temperature in 70 ​min of reaction time. Further, the thermodynamic parameters were analyzed and compared with the conventional and ultrasound-assisted synthesis of PEG stearate. The enzyme was recycled up to 5^th cycle giving more than 35% of the initial activity.     

Accumulation of biopolymers in activated sludge biomass

In this study, activated sludge bacteria from a conventional wastewater treatment process were induced to accumulate polyhydroxyalkanoates (PHAs) under different carbon-nitrogen (C:N) ratios. As the C:N ratio increased from 20 to 140, specific polymer yield increased to a maximum of 0.38 g of polymer/g of dry cell mass while specific growth yield decreased. The highest overall polymer production yield of 0.11 g of polymer/g of carbonaceous substrate consumed was achieved using a C:N ratio of 100. Moreover, the composition of polymer accumulated was dependent on the valeric acid content in the feed. Copolymer poly (3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] was produced in the presence of valeric acid. The 3-hydroxyvalerate (3HV) mole fraction in the copolymer was linearly related tovaleric content in the feed, which reached a maximum of 54% when valeric acid was used as sole carbon source. When the 3HV U in the polymer increased from 0–54 mol%, the melting temperature decreased from 178° to 99°C. Thus, the composition, and hence the mechanical properties, of the copolymer produced from activated sludge can be controlled by adjusting the mole fraction of valeric acid in the feed medium.     

Reactions with α-substituted cinnamonitriles. A novel synthesis of hexa-substituted pyridines

Whereas acetoacetanilide (II) reacted with α-cyano- and α-benzoylcinnamonitrile derivatives Ia-e to give hexa-substituted pyridines III and V, it reacted with α-carboxamido- and α-thiocarboxamidocinnammonitrile derivatives If-h to afford penta-substituted pyridines VI. One mole of acetonedicarboxylic acid dianilide (VII) reacted with two moles of each of α-cyano- and α-thiocarboxamidocinnamonitriles Ia,b,f,g to yield the dipyridyl ketones VIII and IX, respectively. On the other hand, α-benzoyl- and α-ethoxycarbonylcinnamonitriles Ic,d,i,j reacted with VII in equimolecular ratio to give the pyran derivaties X and XI, respectively. Several schemes were proposed to illustrate reactions steps. The structures of the synthesized compounds were proved by chemical and spectral methods.     

Salt Effects on the Aqueous Two-Phase System of Gemini(12-3-12, 2Br<Superscript>−</Superscript>)/SDS/PEG

The effect of added salts (NaCl, KCl and NaBr) on the aqueous two-phase system (ATPS) formed in mixtures of Gemini(12-3-12, 2Br⁻)/sodium dodecyl sulfate/polyethylene glycol has been investigated. Phase diagrams of the aqueous systems containing Gemini(12-3-12, 2Br⁻), sodium dodecyl sulfate (SDS), polyethylene glycol(PEG) and a salt have been determined experimentally at 313.15 K. The results indicate that the addition of salts not only induces the appearance of ATPS-A (in which anionic surfactant is in excess), shortens the phase separation time, enlarges the regions of ATPS-C (in which cationic surfactant is in excess), and decreases the minimum concentration required for forming an ATPS, but also alters the matching between anionic and cationic surfactants. Extractive experiments also showed that these salts notably enhance the extraction ability of ATPS; the Gemini-rich phase exhibits prominent cohesive action with xylenol orange, regardless of whether or not it is the upper phase or the lower phase.     

风化煤的化学降解

在Ｍｎ－Ｍｏ催化剂存在下用ＨＮＯ３氧化对风化煤进行了化学降解研究。考察一降解条件，氧化产物收率及组成性质，结果表明，与原煤相比，氧解产物中极性功能团大量增加，极性溶剂中抽提率显著提高。     

Synthesis and surface-active property of bis-quaternary ammonium-sodium sulfate Gemini surfactant

N,N-dimethyldodecylamine, hydrochloride and epichlorohydrin (molar ration is 2:1:1) were used to synthesize bis-quaternary ammonium Gemini surfactant with a hydroxyl in its spacer group by the one-pot method. This hydroxyl was sulfonated by chlorosulfonic acid and then neutralized to bis-quaternary ammonium-sodium sulfate zwitterionic Gemini surfactant. The yield of the final product was 78%, and the melting point was 231–233°C. Its structure was characterized by IR, ¹H-NMR, MS, and elemental analyses. The critical micelle concentration (cmc) and surface tension of the novel zwitterionic Gemini surfactant in aqueous solution at 15°C are 7.2×10⁻⁵ mol/L and 34.5 mN/m, respectively. __________ Translated from Journal of Wuhan University (Natural Science Edision), 2005, 51(6) (in Chinese)     

5,12-Diacylated-5,6,11,12-tetrahydrodibenzo[b,f][1,4]-diazocines and related compounds

Both N,N′ -(o-phenylene)diformamide (1) and N,N′ -(4-chloro-1,2-phenylene)diformamide (30) reacted with α,α-dibromo-o-xylene (2) in DMF at 95–100° to give 5,6,11,12-tetrahydrodibenzo-[b,f][1,4]diazocine-5,12-dicarboxaldehyde (3a) and the corresponding 2-chloro derivative (3b). With potassium hydroxide in ethylene glycol at 110°, 3a and 3b were selectively saponified to the 5-carboxaldehyde derivatives (4) and either 21a or 22a. Reacylation of the latter led to a series of 5,12-unsymmetrically diacylated derivatives, 5–18. Additionally, 4 was subjected (a) to a basecatalyzed addition to acrylonitrile to give the 12-cyanoethyl derivative (19) and (b) alkylation with α-bromotoluene to give the 12-benzyl compound (20). Saponification of both carboxaldehyde groups in 3a,b required potassium hydroxide in ethylene glycol at 135° and gave the N,N′ -unsubstituted heterocycles (23 and 24) ; these were subsequently reacted with several aldehydes to yield the 5,12-methano derivatives (25–29) .