环戊二烯基钠和环戊二烯基乙醇的合成和表征

从双环戊二烯裂解制得环戊二烯．再以直接金属化法制得环成二烯基钠（或钾）．研究了裂解和反应条件对产物收率的影响．继而以环戊二烯基钾与环氧乙烷反应制取环戊二烯基乙醇．研究了抑制环戊二烯基发生Ｄｉｅｌｓ—Ａｌｄｅｒ二聚化的措施，提高了收率，并对环成二烯基乙醇的结构和性质进行了系统表征．     

丙烯酸丁酯共聚单元对氯乙烯聚合物热降解过程的影响

本文利用热重和DSC法研究了丙烯酸丁醌（BA）共聚单元对氯乙烯（VC）滞物热降解过程听影响，发现VC－BA共聚物的侧基消除起始温度比PVC降低，而峰值温度和主链裂解温度却提高，侧基上有残存的C＝O基存在，不象PVC侧基消除时伴有主链裂解产物逸出。BA单元的引入，虽降低了侧基的热稳定性，却提高了消除反应及其产物共轭多烯的稳定性，BA对热降解的反应热效应影响不大。     

菜籽油油脚——皂脚复合裂解清洁工艺研究

提出菜籽油油脚－－皂脚“水解－醇解、皂化”复合裂解清洁工艺。脂基裂解率９８％，脂是率９６％，芥酸纯度９５％。由油脂化工热力学、动力学的理论、实践和极差分析、方差分析得到油脚－皂脚脂基裂解率、脂肪酸得率各主要影响因素的重要性顺序、显著性水平和最佳工艺条件。     

超声波法合成三烷基硼及其裂解制备碳化硼

在超声波作用下采用一步合成法分别制备三乙基硼、三丙基硼和三丁基硼;考察超声波作用对合成产物产率的影响,用红外光谱及元素分析表征合成产物的结构;以合成的三乙基硼、三丙基硼和三丁基硼为原料通过热裂解制备纯度较高的碳化硼超硬材料;讨论不同原料和裂解温度对合成产物中C含量的影响.研究结果表明:以三乙基硼为原料在温度为1 400K进行裂解时,其裂解产物中B4C,B2O3和裂解自由碳的含量分别为94.0%,2.2%和3.8%.     

高温煤气中焦油组分的催化裂解研究

选择了铁基、镍基、５Ａ分子筛和矾土４种催化剂，在固定床反应器条件下对焦油组分（以１－甲基萘为模型化合物进行了催化裂解研究，结果表明这４种催化剂对１－甲基萘的裂解都具有很好的催化活性，其中镍基催化剂和５Ａ分子筛的催化性能更好，它们在５５０℃，空速３０００ｈ＾－１的条件下反应１００ｈ，其催化活性未降低。同时还研究了在这两种催化剂条件下温度和空速对转化率的影响，按一级反应线性回归得出两种催化剂在２５０￣     

退役硅橡胶复合绝缘子热降解行为的研究

采用在线热裂解-气质联用（Py-GC-MS）技术对废旧硅橡胶复合绝缘子在不同温度下（300 ℃,400 ℃,500 ℃,600 ℃）的热降解行为进行了研究,并通过质谱中裂解产物的碎片离子信息对其裂解机理进行探究。结果表明：硅橡胶裂解产物为一系列二甲基硅氧烷环体及少量的链状硅氧烷,主要环体为六甲基环三硅氧烷（D₃）、八甲基环四硅氧烷（D₄）及环五硅氧烷直至环九硅氧烷;较高的裂解温度下,大环基本裂解完全,仅剩小环裂解产物。因此用热裂解处理废旧硅橡胶时,温度需要达到500 ℃及以上才会有较好的效果。     

丙烯酸丁酯共聚单元对氯乙烯聚合物热降解过程的影响

本文利用热重和DSC法研究了丙烯酸丁酯(BA)共聚单元对氯乙烯(VC)聚合物热降解过程的影响,发现VC-BA共聚物的侧基消除起始温度比PVC降低,而峰值温度和主链裂解温度却提高,侧基上有残存的C=O基存在,不象PVC侧基消除时伴有主链裂解产物选出。BA单元的引入,虽降低了侧基的热稳定性,却提高了消除反应及其产物共轭多烯的稳定性。B A对热降解的反应热效应影响不大。     

微波耦合铁基催化剂辅助废塑料裂解脱氢研究

塑料裂解脱氢可以实现废塑料的高值化利用。与传统塑料热解相比，微波催化可以在较短时间内实现更高的H₂产率和转化率。对比研究了不同结构的Fe基催化剂在微波场下对塑料脱氢产率的影响，探讨了催化剂组成与塑料脱氢活性之间的作用机制。结果表明，Al₂O₃负载型Fe催化剂和Fe-Al复合氧化物均可以获得较高的H₂产率，并促进碳纳米管的生成，后者的H₂产率可达46 mmol/g。通过X 射线衍射和穆斯堡尔谱的表征分析，发现催化剂的微波吸收性能、催化剂中铁的形态和分散度是决定塑料在微波场下裂解脱氢性能的重要因素。此外，采用SiC管反应器屏蔽微波电磁场，研究了微波对塑料裂解脱氢反应的影响。在相同的温度条件下，SiC管反应器中的塑料裂解脱氢性能显著下降，证明微波电磁场对塑料裂解脱氢反应具有促进作用。     

裂解气相色谱质谱法研究Lyocell纤维裂解作用

加热裂解Lyocell纤维,采用气相色谱质谱联用仪研究裂解过程.750℃时,鉴定了其中59种裂解产物,主要的裂解产物为二氧化碳、醛、酮、酸和酯类、呋喃类杂环化合物和糖类化合物等.1,6-脱水-β-D-吡喃葡萄糖(左旋葡聚糖)是Lyocell纤维的重要裂解产物.Lyocell纤维裂解过程中,发生侧基消去水反应,转糖苷作用引起链剪切作用,逆醛醇缩合反应的链剪切作用.经过分子重排,次级反应等形成了各种裂解产物.     

利用电喷雾离子阱质谱研究seselinone和rumphiin的裂解行为

在正离子模式下,利用电喷雾离子阱质谱检测seselinone和rumphiin这两种化学结构比较相似的木脂素类化合物的质谱数据,分析了它们的裂解行为以及化学结构与裂解行为之间的关系.研究结果表明,seselinone存在两种主要的裂解方式,即四氢呋喃环上的取代基断裂和脱氢裂解后生成呋喃型正离子,以及四氢呋喃环上单键断裂...     

Research progresses of artificial nucleic acid cleavage agents

Artificial nucleic acid cleavage agents have attracted close attention because they play important roles in biochemistry and molecular biology. According to the cleavage mechanism of nucleic acid, they are divided into three types, namely free radical, phosphodiester bond hydrolysis and elimination cleavage agents. In this review, a series of cleavage agents, including the site- and sequence-specific ones, are illustrated, and some suggestions for the future researches in this field are also put forward.     

Al66Fe9Ti25合金解理能的经验电子理论分析

用经验电子理论计算了Ｌ１２结构Ａｌ６６Ｆｅ９Ｔｉ２５合金的键结构、键能和主要解理面的解理能．结果表明，解理能低是室温脆性解理的主要原因之一．提出了韧化Ｌ１２型Ａｌ３Ｔｉ金属间化合物的可能途径．     

C－Mn焊缝裂纹试样低温解理断裂机理

在系列低温下，对Ｃ－Ｍｎ焊缝进行了裂纹张开位移（ＣＯＤ）试验，测量了力学性能和断口微观参数，对疲劳裂纹前端形核并长大的微孔和解理微裂改进行了观察。根据实验结果对Ｃ－Ｍｎ焊缝ＣＯＤ试样的低温解理断裂机理进行了分析，发现在低温区，Ｃ－Ｍｎ焊缝的解理断裂临界事件随温度升高发生由起裂控制，第二相、夹杂物尺寸微裂纹扩展控制和铁素体晶粒尺寸微裂纹扩展控制的转变，并对发生这种转变的微观机制进行了分析。     

Single-site enzymatic cleavage of yeast genomic DNA mediated by triple helix formation.

Physical mapping of chromosomes would be facilitated by methods of breaking large DNA into manageable fragments, or cutting uniquely at genetic markers of interest. Key issues in the design of sequence-specific DNA cleaving reagents are the specificity of binding, the generalizability of the recognition motif, and the cleavage yield. Oligonucleotide-directed triple helix formation is a generalizable motif for specific binding to sequences longer than 12 base pairs within DNA of high complexity. Studies with plasmid DNA show that triple helix formation can limit the operational specificity of restriction enzymes to endonuclease recognition sequences that overlap oligonucleotide-binding sites. Triple helix formation, followed by methylase protection, triple helix-disruption, and restriction endonuclease digestion produces near quantitative cleavage at the single overlapping triple helix-endonuclease site. As a demonstration that this technique may be applicable to the orchestrated cleavage of large genomic DNA, we report the near quantitative single-site enzymatic cleavage of the Saccharomyces cerevisiae genome mediated by triple helix formation. The 340-kilobase yeast chromosome III was cut uniquely at an overlapping homopurine-EcoRI target site 27 base pairs long to produce two expected cleavage products of 110 and 230 kilobases. No cleavage of any other chromosome was detected. The potential generalizability of this technique, which is capable of near quantitative cleavage at a single site in at least 14 megabase pairs of DNA, could enable selected regions of chromosomal DNA to be isolated without extensive screening of genomic libraries.     

Ultrasensitive monitoring of ribozyme cleavage product using molecular-beacon-ligation system

This paper reports a new approach to detect ribozyme cleavage product based on the molecular-beacon-ligation system. The molecular beacon, designed in such a way that one-half of its loop is complementary to ribozyme cleavage product, is used to monitor ligation process of RNA/DNA com-plex in a homogeneous solution and to convert directly cleavage product information into fluorescence signal. The method need not label ribozyme and ribozyme substrate, which is fast, simple and ultra-sensitive for detection of cleavage product. Detection limit of the assay is 0.05 nmol/L. The cleavage product of hammerhead ribozyme against hepatitis C virus RNA (HCV-RNA) was detected perfectly based on this assay. Owing to its ultrasensitivity, excellent specificity, convenience and fidelity, this method might hold out great promise in ribozyme reaction and ribozyme gene therapy.     

Domains specifying thrombin-receptor interaction.

Platelet activation by the coagulation protease thrombin is central to arterial thrombosis, a major cause of morbidity and mortality. We recently isolated a complementary DNA encoding the platelet thrombin receptor. The extracellular amino-terminal extension of this seven transmembrane domain receptor contains the putative thrombin cleavage site LDPR/S which is critical for receptor activation. By replacing this cleavage site with the cleavage site for enterokinase, we have created a functional enterokinase receptor. This result demonstrates that all information necessary for receptor activation is provided by receptor proteolysis. Nanomolar enterokinase concentrations are required to activate this new receptor, in contrast to the picomolar thrombin concentrations that activate wild-type thrombin receptor. We identified a receptor domain critical for thrombin's remarkable potency at its receptor. This domain resembles the carboxyl tail of the leech anticoagulant hirudin and functions by binding to thrombin's anion-binding exosite. Our studies thus define a model for thrombin-receptor interaction. The utility of this model was demonstrated by the design of novel thrombin inhibitors based on receptor peptides.     

软钢及转变态材料中的解理断裂

本文通过力学性能试验、微观观察和理论分析,揭示了碳化物开裂机制也在细晶粒铁素体材料的解理断裂过程中起作用,在上贝氏体钢中,解理断裂的破面单元尺寸是板条束尺寸的3～4倍;还发现在零下196℃下解理断裂应力与屈服应力之间存在良好的线性关系。     

Crystal structure of a hairpin ribozyme-inhibitor complex with implications for catalysis

The hairpin ribozyme catalyses sequence-specific cleavage of RNA. The active site of this natural RNA results from the docking of two irregular helices: stems A and B. One strand of stem A harbours the scissile bond. The 2.4 A resolution structure of a hairpin ribozyme-inhibitor complex reveals that the ribozyme aligns the 2'-OH nucleophile and the 5'-oxo leaving group by twisting apart the nucleotides that flank the scissile phosphate. The base of the nucleotide preceding the cleavage site is stacked within stem A; the next nucleotide, a conserved guanine, is extruded from stem A and accommodated by a highly complementary pocket in the minor groove of stem B. Metal ions are absent from the active site. The bases of four conserved purines are positioned potentially to serve as acid-base catalysts. This is the first structure determination of a fully assembled ribozyme active site that catalyses a phosphodiester cleavage without recourse to metal ions.     

E. coli recA protein-directed cleavage of phage lambda repressor requires polynucleotide

The recA protein mediates both genetic recombination and several cellular responses to DNA damage, including the induction of temperate bacteriophage. Indication of phage lambda results from proteolytic cleavage of lambda repressor directed by recA protein. We show here that this cleavage reaction requires both polynucleotide and ATP. We suggest that a stoichiometric complex of recA protein and DNA is active both to destroy repressors by proteolytic cleavage and to initiate pairing of this DNA to its homologous sequence in a DNA duplex ('strand invasion').