极低密度聚乙烯与其它聚乙烯的共混

从结构角度，用ＤＳＣ，ＷＡＸＤ，ＳＡＸＳ研究了聚乙烯（ＰＥ）家族中极低密度聚乙烯（ＶＬＤＰＥ）与其它ＰＥ的互容性．ＨＤＰＥ／ＶＬＤＰＥ是共晶互容的，以其大量无规部分“溶解”了ＨＤＰＥ的结晶缺陷部分，提高了ＨＤＰＥ的Ｔｃ，Ｔｍ，Ｘｃ，结晶峰半高宽变窄，晶胞参数随组成而有最低值．ＶＬＤＰＥ与ＬＬＤＰＥ结构极为相似，ＤＳＣ及ＷＡＸＤ证明其共混物是共晶相容体系．ＬＤＰＥ／ＶＬＤＰＥ的结晶度符合按组成的计算值，但晶胞参数ａ，ｂ以及晶粒尺寸增大，ＤＳＣ上有分别相应于两组份的两个Ｔｍ；ＶＬＤＰＥ的Ｔｃ，Ｔｍ峰高之和高于按组份的计算值，ＬＤＰＥ的Ｔｍ，Ｔｃ则低于计算值．认为是正如ＬＬＤＰＥ／ＬＤＰＥ，ＬＤＰＥ向充满整个体积的ＶＬＤＰＥ中不断填入，以ＶＬＤＰＥ为晶核而结晶，形成相分离的不相容体系．     

聚醚醚酮酮的结晶熔融行为

用差示扫描量热法（ＤＳＣ）研究不同热历史聚醚醚酮酮（ＰＥＥＫＫ）的结晶熔融行为。在２２５－３００℃等温热处理样品的ＤＳＣ曲线出现了熔融双峰。低温熔融峰峰温（Ｔｍｌ）较低，Ｔｍｌ与热处理温度Ｔｃ有关；高温熔融峰峰温（Ｔｍ２）较高，Ｔｍ２几乎不受Ｔｃ的影响。研究结果认为，在升温过程中存在结晶的熔融－重结晶过程，熔融双峰归因于结构相同而完整程度不同的ＰＥＥＫＫ结晶的熔融行为。还探讨了升温速度对结晶熔融行     

三(O,O′-二异丙基二硫代磷酸酯)合钴(Ⅲ)和双(O,O′-二乙基二硫代磷酸酯)合镍(Ⅱ)及其吡啶加合物的热行为和热分解反应动力学

用ＴＧ－ＤＴＧ－ＤＳＣ热分析技术研究了三（Ｏ,Ｏ′－二异丙基二硫代磷酸酯）合钴（Ⅲ）、双（Ｏ,Ｏ′－二乙基二硫代磷酸酯）合镍（Ⅱ）及其后者与吡啶或４－甲基吡啶加合物在氮气气氛中的热行为;用传统的微商法（Ａ－Ｂ－Ｓ）和积分法（Ｃ－Ｒ法）以及分别由Ｍａｌｅｋ、Ｄｏｌｌｉｍ ｏｒｅ 提出的两种新型的热分析动力学方法协同处理ＴＧ 数据,获得了四种配合物的热分解反应动力学参数Ｅ和Ａ,确定了反应机理。对它们的热行为和分子结构之间的关系进行了讨论;并试就本文所用的几种数据处理方法作了比较。     

煤焦制备条件对其气化反应性的影响

改变制焦条件（温度、升温速率、保温时间）制备了八个煤焦样品。－７８℃下ＣＯ２物理吸附和２００℃下Ｏ２化学吸附分别测定了它们的总比表面积和活性表面积。用ＸＲＤ测定了它们的碳微晶尺寸。ＴＧ法测定了煤焦与空气在４５０、５００、５５０℃下的等温气化反应活性，并用Ａｒｒｈｅｎｉｕｓ方程和半衰期法分别求得了每个样品的反应活化能Ｅ和指前因子Ａ。结果表明：制焦温度越高，升温速率越慢，保温时间越长，煤焦的反应活性越     

DTPA－Eu~（3＋）螯合物在核酸杂交分析中的应用

报道了靶ＤＮＡ／生物素化λＤＮＡ探针／亲合素／Ｂｉｏ－ＢＳＡ（ＴＧ）－ＤＴＰＡ－Ｅｕ~（３＋）体系在核酸杂交分析中的应用。亲合素做为连结杂交体与Ｂｉｏ－ＢＳＡ－ＤＴＰＡ－Ｅｕ~（３＋）或Ｂｉｏ－ＴＧ－ＤＴＰＡ－Ｅｕ~（３＋）的桥，生物素和ＤＴＰＡ－Ｅｕ~（３＋）均标记在载体蛋白（ＢＳＡ，ＴＧ）上。优化了分析条件，比较了己二胺、乙二胺转胺化探针及载体蛋白对杂交分析的影响。方法灵敏度高（１ｐｇ／ｗｅｌｌ靶λＤＮＡ），重现性较好（ＲＳＤ＝５．７％，ｎ＝６）。     

重油加氢脱硫NiMo/V-Al_2O_3催化剂的失活研究

收集了工业上用于重油加氢脱硫的 Ｎｉ Ｍ ｏ／γ Ａｌ２ Ｏ３ 失活催化剂, 用超声波萃取, 超临界流体萃取（ Ｓ Ｆ Ｅ）等方法对其进行了处理, 用热重（ Ｔ Ｇ）、差热分析（ Ｄ Ｔ Ａ）、程序升温氧化质谱（ Ｔ Ｐ Ｏ Ｍ Ｓ）、扫描电镜能谱仪（ Ｓ Ｅ Ｍ  Ｅ Ｄ Ｓ）、 Ｘ 射线衍射仪（ Ｘ Ｒ Ｄ）、程序升温还原（ Ｔ Ｐ Ｒ）等方法对处理前后的催化剂进行了表征, 探讨了导致催化剂失活的主要原因． 结果表明, 积炭, 金属沉积是催化剂失活的主要原因, 经去除沉积的金属和烧炭后, 失活重油加氢催化剂的活性状态可得到恢复, 同时失活催化剂从工业反应器中的卸出方式也会对催化剂的性质产生影响．     

HYDROLYTIC CLEAVAGE OF ACMET-GLY PROMOTED BY CIS-[Pd(MET)(D_2O)_2](NO_3)_2

ＨＹＤＲＯＬＹＴＩＣＣＬＥＡＶＡＧＥＯＦＡＣＭＥＴ－ＧＬＹＰＲＯＭＯＴＥＤＢＹＣＩＳ－［Ｐｄ（ＭＥＴ）（Ｄ２Ｏ）２］（ＮＯ３）２￥ＸｉａｏＨｕａＣＨＥＮ；ＬｏｎｇＧｅｎＺＨＵ；Ｎ．Ｍ．Ｋｏｓｔｉｃ（ＣｏｏｒｄｉｎａｔｉｏｎＣｈｅｍｉｓｔｒｙＩｎｓｔｉ...     

HDEHP萃取Ga（Ⅲ）的动力学

用生长液滴法研究了ＨＤＥＨＰ在盐酸介质中萃取Ｇａ（Ⅲ）的动力学，结果表明，萃取反应速率取决于发生在界面区域内两步连续反应Ｇａ３＋＋Ａｉ－＝ＧａＡｉ２＋ＧａＡｉ２＋＋Ａｉ－＝ＧａＡ２＋ｉ研究了阴离子表面活性剂ＳＤＳ、ＡＢＳ对ＨＤＥＨＰ萃取Ｇａ（Ⅲ）的影响，二者均不改变ＨＤＥＨＰ萃取Ｇａ（Ⅲ）的分配比，但使其正向萃取初始速率降低，原因是表面活性剂与萃取剂在界面上发生了竞争吸附；其次是表面活性剂的加入导致了界面膜上分子排列更致密和界面膜增厚，产生了更大的传质阻力。     

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．     

STATE OF WATER SORBED ON ION EXCHANGERS

ＳＴＡＴＥＯＦＷＡＴＥＲＳＯＲＢＥＤＯＮＩＯＮＥＸＣＨＡＮＧＥＲＳＶｅｎｋａｔａｒａｍａｎｉＢ．（ＣｈｅｍｉｓｔｒｙＤｉｖｉｓｉｏｎＢｈａｂｈａＡｔｏｍｉｃＲｅｓｅａｃｈＣｅｎｔｒｅＴｏｍｂａｙ，Ｂｏｍｂａｙ４０００８５Ｉｎｄｉａ）Ａｂｓｔｒａｃｔ：...     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.