表面活性剂合成中的磺乙基化反应

磺烷基化反应可向分子中间引入强亲水性阴离子磺酸基,是合成阴离子型或两性离子型表面活性剂的重要手段之一。本文详细介绍磺乙基反应在表面活性剂合成中的应用。

磺乙基淀粉的合成与性能

本文采用土豆淀粉。以2-氯乙磺酸钠为醚化剂,在NaOH存在下合成了一种新型的淀粉衍生物——磺乙基淀粉(SES)。借助热重分析和红外光谱研究了SES的热稳定性和化学结构,并就产物在泥浆中的降滤失性能进行了初步评价。

磺乙基化与传统壳聚糖对比研究其对水体中铅有效性降低效应

选用水体中流动性、生物毒性较强的典型重金属铅为目标离子,系统的研究N-(2-磺乙基)壳聚糖以及传统壳聚糖(CTS)对目标离子的吸附固定作用。结果显示,NSEC和CTS均符合朗格缪尔曲线和准二阶动力学模型,且NSEC相比CTS优势明显,其可显著降低水体中Pb^(2+)的浓度(CTS的吸附容量为38.96 mg/g,NSEC吸附容量为99.79mg/g)。不同溶液pH值、不同接触时间以及Pb^(2+)浓度条件下,NSEC相对于CTS吸附性能都具有明显优势。在与不同类型的吸附剂比较中,NSEC对重金属离子铅的吸附有着更为出色的吸附容量。

高取代度羧甲基磺乙基纤维素醚

本发明涉及某些高取代度羧甲基磺乙基纤维素醚（CMSEC）的简化而经济的生产工艺，以及作为纺织品中印花增稠剂的用途。

酵母葡聚糖衍生物对凡纳滨对虾血细胞免疫反应的影响

酵母葡聚糖是水产养殖中使用最广泛的免疫增强剂之一,但其不溶解性不利于其免疫增强作用的发挥。为了增加酵母葡聚糖的溶解性,研究共制备了8种酵母葡聚糖衍生物,即4种不同取代度的羧甲基葡聚糖和磺乙基葡聚糖。将葡聚糖和其8种衍生物分别按照5、25和100μg/mL的浓度分别添加到原代培养凡纳滨对虾血细胞的培养液中。以空白血细胞作为对照。孵育6h、12h和24h后分别取样,测定血细胞的酚氧化酶和呼吸暴发活力。结果表明,在6h时,所有葡聚糖衍生物处理组的酚氧化酶活力均显著高于相同浓度下的未衍生葡聚糖处理组(P<0.05)。而25μg/mL酵母葡聚糖衍生物处理组的呼吸暴发活力显著高于同浓度未经衍生葡聚糖处理组(P<0.05)。在12h时,所有酵母葡聚糖衍生物处理组的酚氧化酶和呼吸暴发活力均显著高于未衍生葡聚糖处理组(P<0.05)。在6h和12h时,同浓度各葡聚糖衍生物处理组的血细胞酚氧化酶和呼吸暴发活力并无显著差异(P>0.05)。研究结果表明,羧甲基葡聚糖和磺乙基葡聚糖均比未衍生葡聚糖具有更强的免疫促进作用,而且这种免疫促进作用在两种衍生物之间没有显著差异;另一方面,酵母葡聚糖衍生物的免疫促进作用与其使用浓度有关,而与其取代度没有明显的关系。

Investigation on specific heat capacity and thermal behavior of sodium hydroxyethyl sulfonate

The thermal decomposition process was studied by the TG–DTA analyzer. The results show that the decomposition process of sodium hydroxyethyl sulfonate consisted of three stages: the mass loss for the first, the second and third stages may be about the groups of CH_3CH_2OH, CH_3CHO and SO_2 volatilized, respectively. The decomposition residuum of three stages was analyzed by FT-IR, and the results of FT-IR agreed with the decomposition process predicted by theoretical weight loss. The specific heat capacity of sodium hydroxyethyl sulfonate was determined by differential scanning calorimetry(DSC). The melting temperature and melting enthalpy were obtained to be 465.41 K and 25.69 kJ·mol^(-1), respectively. The molar specific heat capacity of sodium hydroxyethyl sulfonate was determinated from 310.15 K to 365.15 K and expressed as a function of temperature.

SOLID PHASE SYNTHESIS OF ISOXAZOLINES

The solid-phase synthesis of isoxazolines on 2-polystyrylsulfonamidoethanol resin is reported. 2-Polystyrylsulfonamidoethanol resin 1 was reacted with acryloyl chloride to afford 2-polystyrylsulfonylamidoethyl acrylate resin 2, which was further reacted with brominated aldoximes by [3+2] cycloaddition to give isoxazoline resin 4. Resin 4 was treated with aqueous 6 mol/L HCl solution to obtain isoxazolines in good yield and purity.

DYSFUNCTION OF MYOCARDIAL AND VASCULAR TAURINE TRANSPORT IN L-N~ω-NITRO-ARGININE-INDUCED HYPERTENSIVE RATS

Objective.To study the change of taurine transport,and taurine transporter(TAUT)and cysteine sulfinate decarboxylase(CSD)mRNA contents in hypertension and hypertensive cardiomegaly.Methods.Taurine content was determined with a amino acid analyser.Taurine uptakes were deter-mined by( 3 H)-taurine incubation.The content of TAUT and CSD mRNA levels were measured by com-petitive quantitative RT-PCR in myocardial and vascular tissues of L-N ω -nitro-arginine(L-NNA)-in-duced hypertensive rats.Results.After the treatment of rats with L-NNA for28days,myocardial and vascular taurine con-tents decreased by11%and15%(P<0.05),respectively,and plasma taurine level increased by13%(P<0.05).Myocardial and vascular Vmax of taurine uptake reduced by30%and19%(P<0.05),respec-tively.Their Km of taurine uptake increased by36%and17%(P<0.05).Myocardial and vascular TAUT mRNA content decreased by22%and19%(P<0.05),respectively,but CSD mRNA content increased by22%(P<0.05)and30%(P<0.01),respectively.Conclusions.This study suggests that there is a decreased taurine content in myocardial and vascu-lar tissues of L-NNA-induced hypertension rats.The decreased taurine content may result from the de-creased number of TAUT on the cell membrane mainly due to the down-regulation of TAUT gene and TAUT affinity caused by hypertension and hypertensive cardiomegaly.

SYNTHESIS AND PROPERTIES OF SULFHYDRYL CHITOSAN

A new adsorbent for heavy metal ions, sulfhydryl chitosan (S chitosan), was produced by treatment of chitosan with sulhydryl acetic acid in the presence of sulfuric acid as a catalyst. Its structure was confirmed by elemental analysis and FT IR spectra analysis. The adsorption properties of sulfhydryl chitosan for Cu(Ⅱ), Cd(Ⅱ), Pb(Ⅱ), Cr(Ⅲ) and Ni(Ⅱ) were investigated, and the effect of pH value on adsorption, adsorption kinetics, and selective adsorption was examined. It was shown that S chitosan has good adsorption for Pb(Ⅱ), Cu(Ⅱ) and Cd(Ⅱ) like chitosan, is also insoluble in acid solution; has good adsorption kinetic properties for heavy metal ions; and can be used in acid solution. The adsorption capacities of S chitosan can be affected by media acidity. The adsorbed Cu(Ⅱ) Cd(Ⅱ)and Pb(Ⅱ) could be eluted by diluted chlorhydric acid.

Development of efficient solid chiral catalysts with designable linkage for asymmetric transfer hydrogenation of quinoline derivatives

Developing chiral solid catalysts for asymmetric catalysis is desirable for the elimination of homogeneous catalysis flaws but remains an immense challenge.Herein,we report the immobilization of TsDPEN on SBA‐15 with an ionic liquid(IL)linkage via the one‐pot reaction of imidazole‐TsDPEN‐N‐Boc with 3‐(trimethoxysilyl)propyl bromide in the SBA‐15 mesopores.After coordination to Rh,the chiral solid catalysts could efficiently catalyze quinoline transfer hydrogenation,achieving 97%conversion with 93%ee,which was comparable to their homogeneous counterparts.The chiral solid catalyst with the IL linkage afforded much higher turnover frequency than that without the IL linkage(93 h^(–1)vs.33 h^(–1)),attributed to the phase transfer and formate‐enriching ability of the IL linkage.Furthermore,the effect of the pH on the reaction rate of the solid catalyst was investigated,preventing reaction rate retardation during the catalytic process.The tuning of the linkage group is an efficient approach for catalytic activity improvement of immobilized chiral catalysts.

CATALYSIS OF POLYSTYRENE N-HYDROXYL SULFONAMIDE FOR ESTERIFICATION OF BUTANOL WITH ACETIC ANHYDRIDE

Polystyrene N-hydroxyl sulfonamide resin 1 was prepared and used to catalyze the esterification of n-butanol and acetic anhydride. The mechanism of catalytic esterification proved by IR spectra of the resins was found that O-H and N-H of the N-hydroxyl sulfonamide resin reacted with the acetic anhydride respectively to form the active intermediate polystyrene N,O-diacetyl sulfonamate which was cleaved by n-butanol to produce butyl acetate. The catalytic esterification by resin 1 was in good agreement with the kinetic model of 揵i-bi-ping-pong?mechanism.

Improved nitrogen reduction electroactivity by unique MoS_(2)‐SnS_(2) heterogeneous nanoplates supported on poly(zwitterionic liquids)functionalized polypyrrole/graphene oxide

Unique MoS_(2)‐SnS_(2)heterogeneous nanoplates have successfully in‐situ grown on poly(3‐(1‐vinylimidazolium‐3‐yl)propane‐1‐sulfonate)functionalized polypyrrole/graphene oxide(PVIPS/PPy/GO).PVIPS can attract heptamolybdate ion(Mo7O246−)and Sn^(4+)as the precursors by the ion‐exchange,resulting in the simultaneous growth of 1T’‐MoS2 and the berndtite‐2T‐type hexagonal SnS_(2)by the interfacial induced effect of PVIPS.The obtained MoS_(2)‐SnS_(2)/PVIPS/PPy/GO can serve as electrocatalysts,exhibiting good NRR performance by the synergistic effect.The semi‐conducting SnS_(2)would limit the surface electron accessibility for suppressing HER process of 1T’‐MoS_(2),while metallic 1T’‐MoS_(2)might efficiently improve the NRR electroactivity of SnS_(2)by the creation of Mo‐Sn‐Sn trimer catalytic sites.Otherwise,the irreversible crystal phase transition has taken place during the NRR process.Partial 1T’‐MoS_(2)and SnS_(2)have electrochemically reacted with N_(2),and irreversibly converted into Mo^(2)N and SnxNz due to the formation of Mo−N and Sn−N bonding,meanwhile,partial SnS_(2) has been irreversibly evolved into SnS due to the reduction by the power source in the electrochemical system.It would put forward a new design idea for optimizing the preparation method and electrocatalytic activity of transition metal dichalcogenides.

Crystal Structure of Diethyl 1-(p-toluenesulfonamido)-p-chlorophenylmethylphosphonate

The crystal and molecular structure of diethyl l-(p-toluenesulfon-amido ) - p chlofoPhenylmet hylphosphonate has been determined by X- ray d iffractionmethod- The crystal (C18,H23,ClNO5PS) is monoclinic with space group P21/c, a =8. 162(6), b= l8. O64(7), c= l4. 362(4) A, β=96. 29(3)°, V=2lO4. 7 A3, M.=431, 88, Z=4, Dx= l. 364 g/cm3, μ, = 3. 765 cm-1, F(000) = 904, R=0. 047 andRw=0. 0049 for 998 reflections with I>3σ(I). The 1H NMR spetrum of the title com-pound shows that the two ethoxy groups are magnetic nonequivalent, which is in agree-ment with its X-ray analysis result-

Study on the dipeptide vinyl sulfonamide derivatives as proteasome inhibitor

On the basis of the Michael-addition mechanism of classical proteasome inhibitors, six dipeptide vinyl sulfonamide and dipeptide vinyl sulfonate derivatives were designed and synthesized. Moreover, an efficient method for the synthesis of g-amino vinyl sulfonamides, key intermediates to the target molecules, was developed via the Wittig-Horner reaction of peptide aldehyde with Wittig reagents derived from methanesulfonamides.

MULTI-TILLERING DWARF1, a new allele of BRITTLE CULM 12, affects plant height and tiller in rice

Plant height and tillering are crucial factors determining rice plant architecture and influencing rice grain production. In this study, rnulti-tillering dwarf1 （mtdl）, a stable multi-tiller and dwarf mutant, was screened from the ethylmethane sulfonate-treated japonica rice variety Wuyunging7. Compared with the wild type, mtdl mutant exhibited pleiotropic phenotypes, including dwarf- ism, more tillers, brittle culms and delayed heading date. By employing map-based cloning strategy, the gene MTD1 was finally mapped to an approximately 66-kb region on the short arm of chromosome 9. Sequencing results showed that the gene LOCOsO9g02650 （BC12） in mtdl mutant had a single nucleotide substitution （G to A）, which gen- erated a premature translation stop. Over-expressing MTD1/BC12 coding sequ（nce rescued all the phenotypes of mtdl mutants including plant height and tillers, which confirms that BC12 is the mutated gene in mtdl mutant. Quantitative reverse tran,-eription-PCR analysis showed that MTDI/BCI2 could negatively regulate the expression of MONOCULM 1, IDEAL PLANT ARCHITECTURE1 and Tillering and Dwarf 1, and control rice tillering. Remark- ably, a-amylase activity analysis and gibberellic acid （GA） treatment showed that the dwarf phenotype of mtdl mutant was dependent on GA biosynthesis pathway. These results facilitated to further uncover the molecular mechanism of the growth and development in rice.

Pd-catalyzed cross-coupling of polyfluoroarenes with cyclic vinyl triflates

An effective method for Pd-catalyzed cross-coupling between polyfluoroarenes and cyclic vinyl triflates has been developed.This protocol provides a useful and facile access to polyfluoroarylated cyclic alkenes that are difficult to prepare otherwise.The advantages of this method are its high efficiency and operational simplicity.