以混合模板剂合成TS-1分子筛及其性能研究

以四丁基溴化铵（ＴＢＡＢｒ）＋四乙基氢氧化铵（ＴＥＡＯＨ，ｎ（ＴＢＡ＋）／ｎ（ＴＥＡ＋）＝１）或以四丙基溴化铵（ＴＰＡＢｒ）＋ＴＥＡＯＨ为模板剂，钛酸四丁酯和正硅酸乙酯为原料，于１７０℃水热合成出ＴＳ１分子筛．对合成的ＴＳ１样品进行了ＸＲＤ，ＦＴＩＲ，ＳＥＭ和ＢＥＴ比表面积分析，证实了样品中钛已进入Ｓｉｌｉｃａｌｉｔｅ１骨架．选择戊烷氧化为探针反应，考察了ＴＳ１的催化活性．结果表明以ＴＥＡＯＨ为碱，合成的样品晶粒较大，达到４～１０μｍ，用氨水和ＴＥＡＯＨ调节反应液的碱度，对晶体的生长和形貌的影响各不相同．文中还就ＴＥＡＯＨ引入的作用进行了讨论．     

Cr/MCM-41催化剂上的乙烯聚合行为

以纯硅ＭＣＭ４１为载体，负载Ｐｈｉｌｉｐｓ烯烃聚合催化剂活性组分Ｃｒ．ＸＲＤ及ＴＥＭ表征结果表明，所得到的Ｃｒ／ＭＣＭ４１催化剂具有良好的晶体结构和较理想的长程有序一维孔道．ＦＴＩＲ和Ｒａｍａｎ光谱表征结果表明，Ｃｒ／ＭＣＭ４１上不仅可发生乙烯聚合过程，而且形成的聚乙烯以结晶和无定形两种形态存在．乙烯聚合活性不仅与反应参数有关，而且与Ｃｒ的负载量密切相关．用于乙烯聚合后，Ｃｒ／ＭＣＭ４１催化剂仍保持其特征的晶体结构和一维孔道结构．     

REACTION OF METHANE WITH CARBON DIOXIDE OVER SrNiAl_(11)O_(19)

合成了六铝酸盐ＳｒＮｉＡｌ１１Ｏ１９并用ＸＲＤ、ＵＶＤＲＳ、ＴＧＤＴＡ和ＴＥＭ等技术对其进行了表征。在７５０℃于ＳｒＮｉＡｌ１１Ｏ１９上进行的甲烷与二氧化碳重整反应表明，这类催化剂较Ｎｉ／ＳｒＡｌ１２Ｏ１９具有较大活性和低积碳能力，在催化反应过程中可有效地抑制Ｎｉ颗粒的增大。     

氘代苯乙酮-d8的合成与还原反应

氘代苯乙酮ｄ８及其还原产物氘代α苯乙醇ｄ１０是合成众多氘标记化合物及全氘代化合物的重要中间体．以氘代苯ｄ６和氘代醋酸ｄ４为原料制得氘代苯乙酮ｄ８,经ＬｉＡｌＤ４还原可得氘代α苯乙醇ｄ１０［１］．其缺点是ＬｉＡｌＤ４价格昂贵且不易获得,...     

A NOVEL ALUMINOSILICATE WITH BIMODAL MESOPORE DISTRIBUTION——SYNTHESIS AND CHARACTERIZATION

用十六烷基三甲基氯化铵和四乙基氢氧化铵作混合模板剂直接水热合成出一种新型的硅酸铝材料（ＮＫＦ２）。该材料具有明显的双中孔分布，其中一种中孔分布在约３．８ｎｍ，另一种在２．６ｎｍ。用Ｘ射线衍射、扫描电镜、Ｎ２吸附、红外、热重分析和２７Ａｌ、２９ＳｉＭＡＳＮＭＲ对合成样品进行表征，以弄清固体产物的孔结构和局域原子排布。产物具有无定形的骨架墙和很宽范围的ＳｉＯＳｉ键角。所有Ａｌ原子都在四配体环境中。同时讨论了形成机理。     

(3R,4R)-欧洲榆小蠹聚集信息素的合成

欧洲榆小蠹原产欧洲榆树生长区,美国、加拿大及非洲北部也有分布,其成虫及幼虫蛀食榆树皮,并能传播榆疫病,从而影响榆树生长．Ｐｅａｒｃｅ等分离出其聚集信息素并鉴定其分子结构为（—）４甲基３庚醇（１）［１］,Ｍｏｒｉ等研究结果确定出其天然产物构型为...     

生物碱基的反相离子对色谱分离及茶叶中咖啡因测定的研究

报道了在ＹＷＧＣ１８柱上，以甲醇＋水（７．５＋９２．５）、含５ｍｍｏｌ／ＬｐＨ５．０磷酸盐缓冲溶液、１０ｍｍｏｌ／ＬＴＢＡ·Ｂｒ作流动相，同时分离尿嘧啶、９Ｎ二羟丙基腺嘌呤、腺嘌呤、可可碱、尿嘧啶丙酸、９Ｎ二羟丙基茶碱和咖啡因，并用于茶叶中咖啡因的测定，检出限为μｇ／Ｌ级，标准加入回收率为９５．３％～１０５．０％。     

吲哚-3-丙酸稀土二元配合物的合成表征和生物活性

合成了１５种稀土二元配合物．其组成为ＲＥ（ＩＰＡ）３（ＲＥ＝Ｌａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ、Ｙ;ＩＰＡ＝吲哚３丙酸根）．通过化学分析、红外光谱、１ＨＮＭＲ谱、Ｘ射线粉末衍射和热谱等方法对新合成二元配合物的结构及性质进行了研究,并探讨了Ｌａ（ＩＰＡ）３·Ｈ２Ｏ对小麦幼苗根部生长的作用     

合成CFC-12替代物HFC-134a的CrF_3/AlF_3催化剂的研究 Ⅵ.合成氟代烃的多功能催化剂

合成ＣＦＣ１２替代物ＨＦＣ１３４ａ的ＣｒＦ３／ＡｌＦ３催化剂的研究Ⅵ．合成氟代烃的多功能催化剂吕剑石磊王振宇李惠黎（西安近代化学研究所，西安７１００６５）彭少逸（中国科学院山西煤炭化学研究所，太原０３０００１）关键词氟化铬，氟化铝，氟化物催化剂...     

合成CFC-12替代物HFC-134a用CrF_3/AlF_3催化剂的研究 Ⅳ.AlF3基催化剂的制备及性能

本文探讨了γＡｌＦ３的热稳定性和酸性以及活性组分Ｃｒ３＋含量与活性的关系．考察了研制的ＡｌＦ３基催化剂的活性、稳定性及再生性，并对催化剂反应前后的结构进行比较．结果表明，催化剂的强酸中心是ＨＣＦＣ１３３ａ氟化生成ＨＦＣ１３４ａ的活性中心，催化剂晶格的氟离子参与了氟氯交换反应．ＡｌＦ３基催化剂具有高的活性和稳定性，在３５０℃，经２４００ｈ连续运行后，催化剂的晶相结构及比表面积未发生明显的变化．催化剂有较高的热稳定性，在４００℃反应８００ｈ催化剂仍具有一定的活性（３０％）．催化剂结炭失活可在３５０℃通空气或空气与ＨＦ的混合气进行再生     

合成聚芳酯树状分子的新方法

以３，５－二羟基 苯甲酸为起始原料，经甲醇酯化保护羧基，与苯甲酰氯反应，得到３，５－二苯甲酰氧基苯甲酸甲酯用ＡｌＣｌ３．ＮａＩ去掉保护基甲基，以高收率得到３，５－二苯甲酰氧基苯甲酸。其结构均是由ＩＲ，＾１ＨＮＭＲ，ＥＡ等方法证实。     

N-去甲万古霉素的亲和吸附

通过交联聚丙烯酸甲酯与乙醇胺反应,形成聚(N-羟乙基丙烯酰胺)树脂,在酸催化作用下与环氧氯丙烷反应,形成含有α-羟基氯乙基的树脂.含α-羟基氯乙基的树脂与D-丙氨酸、L-丙氨酸或甘氨酸反应,分别得到含有这3种氨基酸的吸附剂.这3种吸附剂吸附N-去甲万古霉素的结果表明,含D-丙氨酸的吸附剂的吸附量最大,含甘氨酸的吸附剂的吸附量次之,而含L-丙氨酸的吸附剂不吸附N-去万古霉素.说明前两种吸附剂对N-去甲万古霉素存在亲和吸附作用.含D-丙氨酸吸附剂的最佳吸附pH值为5.8,当吸附液中的盐(NaCl)浓度增加时,吸附量降低.用0.4mol/LNa₂CO₃/CH₃CN(摩尔比7∶3,pH=9.5)作为洗脱剂可完全脱附被吸附的N-去甲万古霉素.     

Partitioning and adsorption in gas-liquid-solid chromatography: Models of temporal moments for retention and variance

Summary The resolution of gaseous chemical species in gasliquid-solid chromatography is influenced by absorption (partitioning) in the liquid and adsorption at the liquid-solid interface. We consider fundamental mass transfer models with adsorption and partitioning effects for solid chromatographic supports covered with thin films of stationary liquid. The dynamic models, based on mass-balance partial-differential equations, include the significant phenomena: convection, axial dispersion, gas-liquid mass transfer, intraparticle diffusion, and liquid-solid adsorption. Expressions for retention time and band variance (first and second temporal moments) are presented and evaluated for four distinct models: (1) capillary tube with inner surface covered with a uniform-thickness liquid film, (2) column of nonporous spheres covered with a uniform-thickness liquid film, (3) porous spherical particles with intraparticle pores covered with a uniform-thickness liquid film, (4) porous spherical particles with intraparticle pores completely filled with liquid.     

表面等离子体子共振传感器用于研究不同材质包裹的磁性纳米粒子性质

利用自行设计组装的以白色发光二极管为光源的表面等离子体子共振传感器实验装置, 检测了不同材质包裹的磁性纳米粒子连接靶向DNA与生物素化DNA探针的结合程度. 结果表明, 与聚苯乙烯磁性微球连接的靶向DNA相比, Fe3O4@SiO2核壳式纳米微球连接的靶向DNA与生物素化的DNA探针结合速率较快, 且其相对标准偏差较小.     

Synthesis of branched copolysilanes from trichlorosilanes

Soluble polymers and copolymers have been prepared from monosubstituted trichlorosilanes via thermal reductive coupling with sodium in toluene. Phenyltrichlorosilane has been copolymerized with methylphenyl dichlorosilane, with n-hexyltrichlorosilane, with tetrachlorosilane and with tetrakis(chlorodimethylsilyl)silane. n-Hexyltrichlorosilane has been copolymerized with methylphenyldichlorosilane, with phenyltrichlorosilane and with silicon tetrachloride. Soluble polymers and copolymers with molecular weight in the range ≈ 2,000 to ≈ 10⁶ have been obtained. The absorption and emission spectra of the resulting polymers are strongly affected by the presence of trisilyl- and tetrasilylsubstituted silicon atoms. © 1995 John Wiley & Sons, Inc.     

Synthesis and copolymerization of new phosphorus‐containing acrylates

Two phosphorus‐containing acrylate monomers were synthesized from the reaction of ethyl α‐chloromethyl acrylate and t‐butyl α‐bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57–60 °C with 2,2′‐azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60 °C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame‐retardant materials. Additionally, α‐(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus‐containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorous‐containing acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus‐containing polymers with desirable properties could be obtained. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2207–2217, 2003     

稀土奥贝蠕铁制取工艺及其性能的研究

稀土奥贝蠕铁可用含稀土的蠕化剂及等温淬火工艺稳定地制取,藉助高温扫描电子显微镜,观察并研究了稀土蠕铁奥氏体化过程及稀土奥贝蠕铁随温度升高时组织的变化。用带有加热装置的万能材料试验等土奥贝蠕铁的各种性能进行了系统测定了如抗拉强度、延伸率、冲吉韧性、热膨胀系数及伸长百分率,结果表明,稀土奥贝蠕铁在室温和高温下均有良好的性能。     

分子动力学模拟研究纳米碳管中甲醇-水混合溶液的结构与输运性质

利用分子动力学模拟方法,对比考察了平衡条件、外压作用、梯度电场作用下,摩尔比为1:1的甲醇-水混合溶液在纳米碳管(CNT)中的静态结构以及输运行为.研究发现:在平衡体系与外压作用下,纳米碳管内甲醇与水呈现出明显的不混溶现象,甲醇主要分布于管壁附近,水分子主要分布于纳米碳管轴心附近;而在梯度电场作用下,纳米碳管由疏水性向亲水性转变,更多的水分子分布于管壁,导致纳米碳管内甲醇-水的不混溶现象消失.另一方面,在外压作用下,纳米碳管内甲醇与水呈现单向移动;而在梯度电场下,甲醇与水呈现快速的双向移动,其流通量较相应外压作用体系高出近一个数量级,但由于双向的流通量大小相近,导致净流通量与外压作用下的净流通量差异不大.     

Selection of anion exchangers for detoxification of dilute-acid hydrolysates from spruce

Six anion-exchange resins with different properties were compared with respect to detoxification of a dilute-acid hydrolysate of spruce prior to ethanolic fermentation with Saccharomyces cerevisiae. The six resins encompassed strong and weak functional groups as well as styrene-, phenol-, and acrylic-based matrices. In an analytical experimental series, fractions from columns packed with the different resins were analyzed regarding pH, glucose, furfural, hydroxymethylfurfural, phenolic compounds, levulinic acid, acetic acid, formic acid, and sulfate. An initial adsorption of glucose occurred in the strong alkaline environment and led to glucose accumulation at a later stage. Acetic and levulinic acid passed through the column before formic acid, whereas sulfate had the strongest affinity. In a preparative experimental series, one fraction from each of six columns packed with the different resins was collected for assay of the fermentability and analysis of glucose, mannose, and fermentation inhibitors. The fractions collected from strong anion-exchange resins with styrene-based matrices displayed the best fermentability: a sevenfold enhancement of ethanol productivity compared with untreated hydrolysate. Fractions from a strong anion exchanger with acrylic-based matrix and a weak exchanger with phenol-based resin displayed an intermediate improvement in fermentability, a four- to fivefold increase in ethanol productivity. The fractions from two weak exchangers with styrene- and acrylic-based matrices displayed a twofold increase in ethanol productivity. Phenolic compounds were more efficiently removed by resins with styrene-and phenol-based matrices than by resins with acrylic-based matrices.     

芳香硝基化合物还原制备芳胺的研究进展

综述了芳香硝基化合物还原制备芳胺的方法及近年的研究进展.其方法主要包括催化氢化法、CO/H2O还原法、金属还原法、硫化碱还原法、金属氢化物还原法、电化学还原法和光化学还原法.其中催化氢化法中的氢气还原法和水合肼还原法符合绿色化学的理念,并且反应收率高,选择性好,具有很高的应用价值.