Synthesis and cytotoxicity evaluation of a novel justicidin G analogue and its phosphate ester

The novel justicidin G analogue 13 and its phosphate ester 15 were synthesized as potential anticancer agents in several steps starting from commercially available methyl gallate and veratraldehyde. The cytotoxicity of the intermediates was tested against HCT-8, BEL-7402, KETR3, HELA, BGC-823, KB and MCF-7 cell lines by the MTT test, and compound 15 exhibited significant cytotoxicity in HELA and KB cell lines.     

Synthesis and surface activity of novel glucose ester surfactants containing carbohydrate and hydrocarbon chain

A series of glucosyl esters surfactants were synthesized based on glucose molecule by enzymatic catalysis. It could reach the highest esterification yield of 83.4% at the optimal condition, molar ratio of D-glucose and fatty acyl amino acid as 3:2 using 11% (w/w) enzyme catalyst Lipozyme 435 as catalyst in t-butanol at 40°C. The surface activities were studied, such as the critical micelle concentration (CMC), surface tension (γ_cmc), maximum excess concentration (Γ_max), minimum surface area/molecule (A_min), and the adsorption efficiency (pC₂₀); values of these were obtained by surface tension test. The results show that the longer the hydrophobic chain length, the lower the CMC and γ_cmc. The CMCs of novel glucosyl esters were between 4.4 and 1.5 mM. Further, the micellization physiochemical parameters, including Gibbs free energy of micellization (ΔG), standard enthalpy change (ΔH), and standard entropy change (ΔS) were calculated. It was indicated the micellization of glucosyl esters 9–16 was driven by entropy and deduced at different temperature.     

Quantum mechanical studies on the existence of a trigonal bipyramidal phosphorane intermediate in enzymatic phosphate ester hydrolysis

Phosphate ester hydrolysis is a key step in several enzymatic processes, which follow either a dissociative or an associative mechanism. While in the aqueous phase both pathways are favoured to about the same extent, the associative mechanism is relatively rarely observed. In this paper we report on quantum mechanical calculations for three enzymes HIV integrase, β-phosphoglucomutase and dUTPase, and try to find an explanation for the preference of the associative mechanism in a given enzyme. It is reasonable to suppose that the stabilisation of the pentacovalent, trigonal bipyramidal phosphorane moiety by formation of a covalent bond, one or more hydrogen bonds, or by co-ordination of a divalent metal cation with the equatorial oxygen atoms is the key factor. In all three enzymes studied one of the equatorial oxygen atoms is co-ordinated to a magnesium dication, while a second one is involved in a covalent bond. While in HIV integrase the third oxygen atom may only form a weak hydrogen bond with a solvent water molecule, in β-phosphoglucomutase this atom is stabilised by two strong hydrogen bonds with adjacent protein side chains and in dUTPase it is involved in a covalent bond. Contribution to the Fernando Bernardi Memorial Issue.     

Surface activity and thermodynamic of micellization and adsorption for isooctylphenol ethoxylates, phosphate esters and their mixtures with N-diethoxylated perfluorooctanamide

Three nonionic surfactants; p-isooctylphenol ethoxylates p-[i-OPE10], p-[i-OPE15], and p-[i-OPE20], were phosphorylated to produce three anionic phosphate ester surfactants. In addition, N-diethoxylated perfluorooctanamide (N-DEFOA) was also prepared. The surface and thermodynamic properties of the three types of surfactants and mixtures of the fluorocarbon surfactant (FC) with the hydrocarbon surfactants (HC) have been investigated. Surface tension as a function of concentration of the surfactant in aqueous solution was measured at 30, 40, 50 and 60°C, using the spinning drop technique. From these measurements the critical micelle concentration (CMC), the surface tension at the CMC (γ_CMC), the maximum surface excess concentration (Γ_max), the minimum area per molecule at the aqueous solution/air interface (A_min), and the effectiveness of surface tension reduction (π_CMC), were calculated. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic, ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad, ΔS_ad) for these surfactants and their mixtures were also calculated. Structural effects on micellization, adsorption and effectiveness of surface tension reduction are discussed in terms of these parameters. The results show that the FC surfactant and its mixtures with HC surfactants enhance the efficiency in surface tension reduction and adsorption in the mixed monolayer at the aqueous solution/air interface, and also, reduce γ_CMC and the tendency towards micellization.     

Interaction of phosphate ester dispersants with calcined alumina

The interaction of two commercially available phosphate ester dispersants with calcined alumina has been investigated using the techniques of flow calorimetry and electrophoresis. Flow calorimetric experiments have shown that these dispersants chemically interact with the surface of calcined alumina. The electrical charging of alumina particles in an iso-octane solution containing a phosphate ester indicates that an acid-base interaction mechanism is operative in this system.     

磷酸酯甜菜碱两性表面活性剂的合成与性能

磷酸酯甜菜碱从皮肤溶出的氨基酸量少,脱脂低,毒性和刺激性低,易降解,是一类性能优良两性表面活性剂[1,2]。它的合成大多以长链卤烷或胺为原料,成本较高。本文以高级脂肪醇、氯乙醇以及二甲胺为原料、P2O5为磷酸化剂,合成了C12H25OCH2CH(OOCCH3)CH2N+(CH3)2CH2CH2OP(O)(O )(OH)磷酸酯甜菜碱。测定了表面张力、泡沫性能、钙皂分散力及增溶能力。1　合成十二烷基缩水甘油醚(Ⅰ)[2]　在500ml三颈烧瓶中加入月桂醇0 2mol,正已烷200ml和四丁基溴化铵0 01mol;在室温和强烈搅拌下加入50%的NaOH水溶液48g,滴加环氧氯丙烷0 4mol后升…     

Synthesis and characterization of new epoxy and cyanate ester resins

New epoxide and cyanate ester resins with an aromatic ester backbone namely 1,3-[di-(4-glycidyloxy diphenyl-2,2^′-propane)]-isophthalate (DGDPI) and 1,4-[di-(4-cyanato diphenyl-2,2^′-propane)]-terephthalate (DCDPT) were synthesized and the intermediates were characterized by IR, 1H-/¹³C-NMR spectroscopic methods. The cured products from DGDPI and DHDPI exhibited higher T_g compared with standard epoxy system. The increase in the T_g may be due to the cyanate ester and rigid aromatic backbones present in the curing system.     

Synthesis of aromatic phosphates via cycloaddition of phosphate dienes

Cycloadditions of phosphate dienes and quinones can be used to generate aromatic phosphates. Diethyl 3-methoxy-1-methylene-2-propenyl phosphate shows reactivity, stability, and regioselectivity comparable to the corresponding silyloxy diene. Because the phosphate ester in the product originates in the diene, cycloadditions with quinones will place this ester regiospecifically in the B-ring and allow facile distinction between the B- and A-ring oxygens of the cycloadduct.     

酶促反应合成糖脂化合物

对糖脂化合物的酶促合成研究进行了总结,其中包括有机相中和无溶剂条件下的糖脂酶促合成。     

新型聚原酸酯共聚物的合成及性能研究

以二聚甘油为原料,经过酯交换及氨基脱保护反应合成了一种两端含氨基的环状原酸酯新单体。该单体与辛二酸/十二烷二酸活性酯缩聚得到两种新的疏水性聚原酸酯共聚物POEAd-1和POEAd-2,其数均分子量分别由凝胶渗透色谱(GPC)测得为1.24×104及1.81×104,分散度(PDI)分别为1.59及1.93。热失重分析法证实POEAd-1和POEAd-2具有较高的热稳定性能,其起始降解温度分别可达198.5℃及202.5℃。溶血试验和MTT细胞毒性试验表明,POEAd-1和POEAd-2均具有良好生物相容性,作为一种潜在的生物医用材料,在药物缓控释领域将具有广阔的应用前景。     

Adsorption of surfactants onto acrylic ester resins with different pore size distribution

In this study, a series of acrylic ester resins with different pore size distribution were prepared successfully by varying the type and the amount of pore-forming agents. In order to inves-tigate the adsorption behavior and mechanism of surfactants on acrylic ester resins, three kinds of surfactants were utilized as adsorbates that were sodium 6-dodecyl benzenesulfonate (6-NaDBS), sodium 1-dodecyl benzene sulfonate (1-NaDBS) and sodium 1-dodecyl sulfonate, respectively. It was observed that the surface area was available in a particular pore size and an appropriate pore size of resins appeared to be more important for the adsorption of surfactants. As compared to commercial acrylic ester resins XAD-7 and HP2MG, 50# and 38# resins exhibited more excellent adsorption properties toward 1-NaDBS and 6-NaDBS. The experimental equilibrium data were fitted to the Langmuir, and double-Langmuir models. Two models provided very good fittings for all resins over the temperature range studied. The investigation indicated that electrostatic attraction and hydrogen bond between resins and surfactants were the main forces and had an obvious effect on adsorption proc-ess.     

谷氨酸二烷基酯的合成及其表面活性研究

合成了谷氨酸二烷基酯类表面活性剂,其链长分别为C_8、C_(10)、C_(12)、C_(14)、C_(16)、C_(18)及C_(18)~(Δ9,10),经IR光谱及~1H NMR谱测定证明了产品的结构,界面张力与表面压的测定结果表明该系列表面活性剂具有较高的表面活性效率。     

Effect of cationic gemini surfactants on the hydrolysis of carboxylate and phosphate esters using hydroxamate ions

The kinetics of the hydrolysis of p-nitrophenyl acetate (PNPA) and p-nitrophenyl diphenyl phosphate (PNPDPP) by hydroxamate ions mediated by gemini surfactants with quaternary ammonium bromide (16-n-16,2Br⁻, n = 3, 4, 6, 12) and pyridinium chloride (12py-n-py12,2Cl⁻, n = 3, 4) head group have been investigated at 27 °C. The gemini surfactant with the pyridinium head group, 12-py-4-py12,2Cl⁻ (tetramethylene-1,4 bis dodecylpyridinium chloride) shows a large rate acceleration effect than that with an ammonium head group, 16-12-16,2Br⁻, relative to those in water. The apparent pK _a of the hydroxamic acids have been determined in the presence of gemini surfactants. Catalytic system N-phenylbenzohydroxamate/12py-4-py12,2Cl⁻ demonstrated over ~1,590-fold and ~255-fold rate enhancement in the hydrolysis of PNPA and PNPDPP, respectively, for the identical reaction performed in buffer aqueous media at 27 °C. The second order rate constant and binding constants for reactions were determined employing pseudophase model for micellar catalysis.     

树枝状十二酯的合成与结构表征

根据聚酰胺-胺的合成工艺,以乙二胺和丙烯酸十二酯为原料,采用“发散合成法”合成一类新的树枝状化合物;同时采用元素分析、IR和NMR分析手段对合成产品的结构进行表征,结果表明,合成产物的分子结构与理论结构相符.     

Thermal dissociation behavior of copolymers bearing hemiacetal ester moieties and their reactions with epoxides

Copolymers from 1‐propoxyethyl methacrylate and various vinyl monomers such as n‐butyl methacrylate and styrene were synthesized, and the thermal dissociation reaction of the copolymers containing the hemiacetal ester structure was examined. The copolymers, having the ability of thermal dissociation, could control the thermal dissociation temperature because of the bulkiness and flexibility of the vinyl comonomers, the copolymer compositions, and so on. Furthermore, the possibility of control of the initiation in thermally latent addition with epoxides in the case of copolymers was also studied. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3966–3977, 2006     

Surface activity and redox behavior of nonionic surfactants containing an anthraquinone group as the redox-active site

Two new nonionic surfactants, α-anthraquinonyloxyhexyl-ω-hydroxy-oligo(ethylene oxide) (ACPEG) and α-anthraquinonyl-ω-hydroxy-oligo(ethylene oxide) (APEG), were synthesized. The fundamental interfacial behavior of these surfactants at the air/water interface has been investigated by means of surface tensiometry to provide an insight into the relationship between the structure of the hydrophobic moiety and the surfactant properties, with specific emphasis on the anthraquinone linkage. Aggregation numbers of the surfactants have been determined from static light scattering measurements. At a constant hydration of the ethylene oxide chain, the increase in the hydrophobic chain length in ACPEG raises its hydrophobic interaction and results in enhanced aggregation and significant variation in the interfacial and micellization properties compared to APEG. The electrochemical behavior of the surfactants has also been studied in 0.16 M NaCl aqueous solutions and in 0.1 M tetrabutylammonium perchlorate acetonitrile solutions at the interface of a glassy carbon electrode. A difference in the extent of aggregation has a pronounced effect on the cyclic voltammetric behavior of the surfactants in aqueous solution. In organic media, on the other hand, the redox process depends only on the molecular geometry of the monomeric species. A comparison of the electrochemical responses in the two phases has been made to explain the distinctive features of the redox properties of the surfactants. Received: 30 May 1999 Accepted in revised form: 29 June 1999     

吡啶与GCLE碘取代物在不同溶剂中亲核取代反应动力学研究

以7-苯乙酰氨基-3-氯甲基头孢烷烯酸对甲氧基苄酯（GCLE）和吡啶为原料合成头孢他啶中间体7-苯乙酰氨基-3-吡啶甲基头孢-4-羧酸对甲氧苄酯,用高效液相色谱仪监测了吡啶与GCLE碘取代物在二氯甲烷、丙酮、四氢呋喃、乙酸乙酯和DMF混合液中的亲核取代反应,反应的动力学行为可用SN2机理来解释。在一定的溶剂中不同温度的速率常数可用Arrhenius方程很好的关联。根据Arrhenius方程求得了指前因子,进一步讨论了该反应的溶剂效应,得出在不同溶剂中亲核取代反应顺序为：乙酸乙酯-DMF混合液＞二氯甲烷＞四氢呋喃＞丙酮。     

Synthesis of a (β-acetamido-α-acetoxyethyl)boronic ester via azido boronic esters

(Azidomethyl)boronic esters of 1,2-dicyclohexyl-1,2-ethanediol (“DICHED”) and pinanediol have been prepared from the corresponding (bromomethyl)boronic esters. Conversion to (2-azido-1-chloro- or bromoethyl)boronic esters by reaction with a (dihalomethyl)lithium followed. Attempted displacement of halide from DICHED (2-azido-1-haloethyl)boronates with alkoxides failed. Reaction of either pinanediol or DICHED (2-azido-1-chloromethyl)boronate with sodium acetate in acetic acid yielded the 1-acetoxy derivative as a ∼1:1 mixture of diastereomers, indicating probable involvement of an α-boryl carbocation intermediate. Hydrogenation of the pinanediol azido boronic ester over platinum in a solution of hydrogen chloride in dioxane was accompanied by deacetylation to form the impure (2-amino-1-hydroxyethyl)boronic ester hydrochloride. Attempted purification of this material resulted in deboronation to ethanolamine. Acetylation yielded pinanediol (2-acetamido-1-acetoxyethyl)boronate.