硫脲掺杂金刚石的高温高压合成及FT-IR光谱研究

利用温度梯度法,在6.5 GPa、1 300～1 350℃的高温高压极端物理条件下,通过在FeNiCo-C合成体系中添加硫脲(CH4N2S)成功合成了金刚石,所合成的晶体呈现出黄色且具有六-八面体形貌.利用扫描电镜(SEM)对所合成金刚石的表面形貌进行了表征,测试结果表明,随着合成体系中CH4N2S添加量的逐渐增加,所合成金刚石的表面变得逐渐粗糙.借助傅里叶红外(FT-IR)光谱对金刚石样品内部的氮、氢缺陷以及化学键结构进行了测试分析,结果表明,金刚石中的氢元素以-CH3,-CH2-,C-H形式存在,而其内部的氮杂质以C心、A心形式存在.此外,在3 300～3 600 cm-1观察到NH的吸收带.     

触媒组分对高温高压金刚石大单晶生长及裂纹缺陷的影响

本文利用六面顶压机,在5.6 GPa, 1250—1450℃的高压高温条件下,分别选用FeNiCo和NiMnCo触媒合金开展了金刚石大单晶的生长实验,系统地考察了触媒组分对金刚石单晶裂纹缺陷的影响.首先,通过对两种组分触媒晶体生长实验对比发现,金刚石大单晶裂纹缺陷出现的概率与触媒组分相关联.同NiMnCo触媒相比, FeNiCo触媒生长的金刚石单晶更容易出现生长裂纹.我们认为,这与FeNiCo触媒黏度高、流动性差、碳素输运能力差、生长中晶体比表面积大,进而导致其对生长条件稳定性的要求较高有关.其次,两种触媒极限增重速度和生长时间的关系曲线表明,相同生长时间条件下, NiMnCo触媒生长金刚石单晶的极限增重速度相对较大.再次,扫描电子显微镜测试结果表明,裂纹缺陷的出现与否同晶体表面平整度的高低无必然联系,表面平整度高的金刚石单晶内部也可能存在裂纹缺陷.最后,经对金刚石单晶傅里叶微区红外测试结果进行分析,得出了氮杂质含量的高低与金刚石单晶裂纹缺陷的出现与否无内在关联性的研究结论.     

AFFINITY LABELLING OF E.coil LEUCYL-tRNA SYNTHETASE WITH 3''''-OXIDIZED tRNA~(Leu)

The E.coli leucyl-tRNA synthetase (E. C. 6. 1. 1. 4) was specifically labelled with 3'-oxidized tRNA~(Leu) (tRNA_(ox)~(Leu)).The procedure involves a Schiff's base formation and its subsequent reduction by sodium cyanoborohydride. Stoichiometric inactivation of aminoacylation was achieved with the incorporation of 1 mol of tRNA_(ox)~_(Leu) per mol LeuRS.On the other hand, the amino acid activation activity of LeuRS-tRNA_(ox) complex was partially inhibited. After extensive digestion of the complex by pancreatic ribonuclease, the amino acid activation activity was fully recovered, while the aminoacylation activity was not restored at all.The results suggest that the active sites responsible for the activities of LeuRS correlate with each other as well as differ from each other.     

大肠杆菌亮氨酰tRNA合成酶巯基的修饰及标记肽的顺序测定

E. coli LeuRS分别被DTNB,NEM,IAA修饰后,丧失氨基酸活化和氨酰化活性,这两种活性基本上平行地下降,DTNB,NEM和IAA的二级反应常数分别为1700,150和0.46mol/L~(-1)min~(-1),化学计量显示LeuRS的一个巯基是活性必需的,底物Leu和Leu-AMP对该巯基的修饰有明显的保护作用,表明这一活性巯基处于LeuRS的氨基酸活化区域,经过[~(14)C]NEM标记LeuRS巯基,胰蛋白酶完全酶解,HPLC分离标记肽段及顺序测定,表明[~(14)C]NEM主要的标记位点是~(179)Cys~*-Asp-Thr-Lys~(182),这一结果提供了氮基酸活化区域位于LeuRS N瑞区的证据。     

3′-末端氧化的tRNA~(Leu)对大肠杆菌亮氨酰-tRNA合成酶的亲和标记

本文用3′-末端氧化的tRNA~(Leu)(tRNA_(ox)~(Leu))专一地标记了大肠杆菌亮氨酰-tRNA合成酶(LeuRS)。合成酶标记上等摩尔tRNA_(ox)~(Leu)后,氨酰化活力完全丧失,同时氨基酸活化活力也失去80％。这样失活反应是通过tRNA_(ox)~(Leu)的3′-末端羰基与亮氨酰-tRNA合成酶活性中心或其附近的赖氨酸残基的ε-氨基形成Schiff碱实现的。Schiff碱经硼氢氰化钠还原后稳定。酶与tRNA_(ox)~(Leu)的共价复合物经牛胰核糖核酸酶充分水解后,其活化氨基酸的活力及动力学常数基本恢复到原来水平,而氨基酰化活力未恢复。表明了该合成酶的两种活性中心相互关联又有区别。     

氧空位缺陷对PbTiO_3铁电薄膜漏电流的调控

基于非平衡格林函数及密度泛函理论第一性原理计算方法,计算了Fe, Al, V和Cu四种阳离子掺杂对氧空位缺陷引起的PbTiO_3铁电薄膜漏电流的调控.研究表明:Fe和Al离子掺杂将会增大由其中氧空位缺陷导致的铁电薄膜的漏电流,而Cu和V离子掺杂对该漏电流的大小具有明显抑制作用.这是因为Cu和V掺杂对氧空位缺陷有明显的钉扎作用.相比于半径更大的Cu离子,由于V的离子半径更小,且更接近于PbTiO_3铁电薄膜中Ti的离子半径,可以预言V离子更可能被掺杂进入薄膜,从而抑制氧空位缺陷引起的漏电流.研究结果对铁电薄膜器件的电学性能控制和优化有一定的理论指导意义.     

硼硫协同掺杂金刚石的高压合成与电学性能研究

FeNiMnCo-C体系中,在压力6.5 GPa、温度1280—1300℃的极端物理条件下,采用温度梯度法成功合成了硼(B)、硫(S)协同掺杂金刚石大单晶.通过傅里叶红外光谱测试对高温高压所制备金刚石中的杂质进行了表征.借助霍尔效应对典型金刚石样品的电输运性能进行了测试,测试结果表明:硼硫协同掺杂有利于提高p型金刚石的电导率,而且硼硫在合成体系中的添加比例可以决定金刚石的p, n特性.此外,第一性原理计算结果表明,合成体系中不同比例的硼硫协同掺杂对金刚石的p, n特性以及电导率有着直接的影响,计算结果与实验测试结果相吻合.     

ARGINYL-tRNA SYNTHETASE FROM Escherichia coli AFFINITY LABELING WITH 3''''-OXIDIZED tRNA~(Arg)

The covalent modification of E. coli arginyl-tRNA synthetase by the 2',3'-dialdehydederivative of tRNA~(Arg) (tRNA_(ox)~(Arg)) resulted in the complete inactivation of the ATP-PPi ex-change and aminoacylation activities of the enzyme. Sodium dodecyl sulfate polyacrylamide gelelectrophoresis of the ArgRS-tRNA_(ox)~(Arg) covalent complexes indicated that two bands simulta-neously appeared on the gel parallel with inactivation corresponding to different higher mo-lecular weights. This result was different from that of the other aminoacyl-tRNA synthetaselabeling systems as previously reported. Upon the ribonuclease treatment of the modifiedArgRS, less than 15% of both the initial ATP-PPi exchange and aminocylation activities wererecovered. During the whole process of labeling and RNase treatment, the two activities ofthe enzyme were closely associated.     

CHEMICAL MODIFICATION OF SULFHYDRYL GROUPS OF E.coli LEUCYL-tRNA SYNTHE-TASE AND SEQUENCING OF [~(14)C]NEM-LABELED PEPTIDES

The chemical modification of the sulfhydryl groups of E. coli Leucyl--tRNA synthetase(LeuRS) by DTNB, NEM and IAA resulted in a time-dependent loss of both amino-acid acti-vation and aminoacylation activities in parallel. The second-order reaction constants of DTNB,NEM and IAA were 1700, 150 and 0.46 mol/L~(-1) min~(-1) respectively. Chemical stoichiometryshowed that only one sulfhydryl group of LeuRS was essential for both activities. Substratesleucine and Leu-AMP protected the active sulfhydryl group from modification, suggestingthat the modified sulfhydryl group is located in or near the active site region responsiblefor amino-acid activation. [~(14)C]NEM--labeled LeuRS was subjected to tryptic digestion, andpeptides were separated and sequenced. 179 Cys~*-Asp-Thr-Leu182 was identified as the major[~(14)C]NEM-labeled site in LeuRS. This result is consistent with the previous observationthat the region for Leu--AMP formation was located at the N--terminal part of LeuRS.     

B,N协同掺杂金刚石电子结构和光学性质的第一性原理研究

基于金刚石的稳定结构, 在实验研究的基础上, 本文采用基于周期性密度泛函理论计算了B/N单掺杂、共掺杂金刚石的晶体结构, 并就掺杂方式和掺杂后形成能进行了对比研究, 得到了B/N双掺杂的最稳定结构. 在此基础上, 进一步计算了N单掺杂及B/N共掺杂最稳定结构的吸收光谱、电子结构和态密度. 通过与实验结果对比可以看出, 较N单掺杂, B/N共掺杂的吸收光谱发生明显红移, 与实验符合较好. 计算结果表明: N原子单掺杂优先于B原子; 由于原子间的协同作用, B/N近邻共掺杂体系的形成能最低, 为掺杂的最可能结构.