~1H和~(19)F NMR研究镍系催化丁二烯聚合中醇类对BF_3·OEt_2的增溶作用

<正> 在镍系催化丁二烯聚合中,助催化剂BF_3·OEt_2在加氢汽油中溶解性差,往往形成非均相体系,因而降低了催化剂体系的稳定性和氟的利用率。我们曾研究了A1(i-Bu)_3分别与丙醇、丁醇、戊醇,己醇、辛醇、壬醇、癸醇和十六醇按等摩尔交换,制得A1(i-Bu)_2OR作助催化剂,观察Al/B与催化活性的关系,发现以十六醇为最好,Al/B在0.25—0.95聚合活性较高,超出此限活性迅速下降。为了进一步提高Al/B,采用了向镍催化体系添加醇的方法。聚合实验证实了该法可提高氟的利用率。测定醇-硼体系的~1HNMR,证实了醇-硼分子间形成了氟-氢氢键。     

紫乌定及其类似物~(13)C核磁共振谱的研究

本文报道了十一种紫乌定及其类似物的~(13)C核磁共振谱,有助于此类二萜生物碱的结构测定。     

THE CORRELATION BETWEEN ~(13)C CHEMICAL SHIFTS OF DNA AND INTERSTRAND PURINE-PURINE CLASH

The correlation between ~(13)C chemical shifts of DNA and structure parameters (the mainaxis helix twist angle Ω, base--plane roll angle ρ, main chain torsion angle δ and pro-peller twist angle ω) has been discovered and proved indirectly. The carbons relating tothe structure parameters have been found and interpreted theoretically. Relative variationsin chemical shifts of these carbons obviously reflect purine-purine clash (steric hindrance)and have been compared with sum functions Σ of Calladine--Dickerson rules. It would bepossible to provide the information about conformation of DNA from ~(13)C NMR spectra andto observe the structure parameters of Ω,ρ,δ and ω of DNA in solution.     

POLY(10-UNDECENOIC ACID) AND SOME OF ITS DERIVATIVES

Commercially available 10-undecenoic acid was esterified with 2,5-dimethylphenol. After the supply of ester was properly complexed, it was polymerized in quantities and in high yield to high molcular polymers. The polymeric esters were hydrolyzed with base to the acid salt, which were converted to the acids. Reactions with 1,1′-carbonyldiimidazole gave polyethylene-based polymeric imidazolids.     

C40,Nb@C40^＋,La@C40^＋的从头算研究

用量子化学从头算方法研究了Ｃ４０、Ｎｂ＠Ｃ４０＾＋，Ｌａ＾＠Ｃ４０＾＋的几何构型和电子结构，Ｃ４０最稳定构型具有Ｄ２对称性。Ｌａ和Ｎ原子内含于Ｃ４０笼中，形成金属夹心碳笼Ｎｂ＠Ｃ４０＾＋、Ｌａ＠Ｃ４０＾＋。Ｃ４０结合能大于Ｍ＠Ｃ４０＾＋（Ｍ＝Ｎｂ，Ｌａ）。     

STUDY OF THE MECHANISM OF LOESS COLLAPSE

In this paper, firstly, the amount of collapsible space is statistically determined from the pore-size distributions of loess slices before and after collapse by using a polarizing microscope. Then, the characteristics of the structure and the copulation of loess grains are studied, and the copulations which decrease in strength upon contact with water are discovered. Lastly, by studying the joint action of external causes——a certain load and a certain moisture content——and internal conditions, the mechanism of loess collapse is advanced.     

~(13)C NMR STUDIES ON DYNAMICS OF POLY (n - ALKYL METHACRYLATES)

The dynamics of a series of poly(n-alkyl methacrylates) is investigated by means of ~(13)C spin-lattice relaxation experiments. The results show that the dynamics has the polymer property dependence.     

离子交换分离钨钼及微波诱导树脂再生的研究

本文研究了不同型号的树脂和硫化条件对离子交换分离钨钼的影响。探讨了用D201树脂交换除钼及其树脂再生的机理。实验结果表明：碱性钨酸铵（AT）溶液经硫化转型后,可用阴离子交换柱除去其微量钼;该除钼树脂经微波场辐照诱导-减性食盐水协同再生处理,可基本恢复其除相交换容量。     

~(59)Co-NMR MEDIUM EFFECT, ISOTOPE EFFECT AND CHELATE COMPLEX STEREOISOMERS

The ~(59)Co-NMR spectra of several cobalt (Ⅲ) complexes have been directly recorded bypulsed Fourier transform nuclear magnetic resonance (FT-NMR) technique. The influences ofsolvents, concentration and temperature on ~(59)Co spectra have been investigated. Optical andgeometric isomers of the chelate complexes have been distinguished by ~(59)Co-NMR spectra. ForCo(±pn)_3Cl_3, the resonances of Δ(λλλ) and Δ(δδδ) appeared at the lower field, the δ_(mer) beinggreater than δ_(fac), followed by the peaks of Δ(λλδ) and Δ(δδλ). For Co(en)_3Cl_3-D_n, all the13 isotopic isomers, from D_0 to D_(12), have been resolved in their ~(59)Co spectra. Each H/Dexchange causes ~(59)Co peaks to move upfield 5.4 ppm. The factors affecting the direction andmagnitude of isotopic shift and its additivity have been discussed. Chemical equilibrium isotopiceffect has also been studied.     

~(13)C-NMR对油脂的定量测定

本工作用外加驰豫试剂及反转门控去偶方式对菜籽油和“营养”油进行了~(13)C-NMR谱的定量测定。在归属各峰基础上,认为该两油脂都以甘油酯形式存在。提出了①多烯类结合脂肪酸占烯类总量的摩尔分数P;②烯碳数与饱和碳数之比R;③包括同种油脂及不同油脂间的油脂分子各类功能团的相对含量的测定计算表达式。     

~(29)Si MAS-NMR STUDIES ON DEALUMINATION OF MORDENITE

A series of different H-mordenites from acid leaching and steam calcination have beenmeasured with ~(29)Si NMR. Through analysis of these solid-state ~(29)Si NMR spectra, theresults related to dealumination process of mordenite are obtained. It is shown that mor-denite is combined by four kinds of non-equivalent Si (or Al) via oxygen bridges. The deal-umination order is T(1), T(2), T(4) and T(3). The dealuminated amount in the non-equivalentsites during different dealumination processes has also been discussed in detail.     

~(13)C-NMR STUDY OF ETHYLENE-1-OCTENE COPOLYMERS

A ~(13)C-NMR method is presented for a quantitative determination of the respective monomercomposition and sequence distributions in ethylene-1-octene copolymers prepared with supportedtitanium/magnesium catalyst. On the basis of the sequence distributions, the ethylene-1-octenecopolymerization mechanism was studied. It was found that the observed sequence distributions inethylene-1-octene copolymers are satisfactorily predicted by the two-site model M/M,in whichthe copolymerization proceeds according to first-order Markovian statistics at the two differentsites.     

THE TYPES OF LOESS PORES IN CHINA AND THEIR RELATIONSHIP WITH COLLAPSIBILITY

This paper presents chiefly a classification of the loess pores in the Loess Platcau according to their origin and size and deals with the characteristics of different sorts of pores and their distributional regularities in regions and loess layers of various ages. The relationship between various pores and collapsibility is also discussed in the paper. We come tto a conclusion that the supporting openings are one of the important factors causing the subsidence on wetting because of their looseness and unstability.     

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.     

STUDY ON THE SEQUENCE STRUCTURE OF BUTADIENE-STYRENE RUBBER BY ~(13)C-NMR METHOD V.CALCULATION METHOD OF DIAD COMPOSITION

The calculating equations which could be used to obtain diad composition from the peakintensities of carbon spectra were derived. The result of the microstructure calculated from thediad compositions was in good agreement with that obtained through IR or ~1H-NMR measurement.     

DMS AND ~(13)C NMR STUDIES ON THE COMPATIBILITY AND DYNAMICS OF LATEX BIDIRECTIONAL IPNS AND LATEX IPN OF PVAc/PBA

The compatibility and dynamics of latex bidirectional/nterpenetrating polymer networks (LBIPNs) and latex IPN(LIPN) of poly(vinyl acetate)(PVAc) and poly (butyl acrylate )(PBA) are investigated by means of dynamic mechanical spectroscopy (DMS) and nuclear magnetic resonance (NMR) techniques. The results of DMS show that the compatibility of the LBIPNs is much better than that of the corresponding LIPN and depends to, a large extent on the distribution of PVAc both in the core and in the shell. The results of NMR measurements indicate that the rotational correlation times of the side- groups of PBA in the LBIPN are longer than those in the LIPN. The relation between the ~(13)C linewidths of PBA and temperature is also discussed.     

[~(188)Re(CO)_3(H_2O)_3]~+前体及标记药盒的制备

~(186,188)Re具有优良的核素性质,是放射性治疗药物的首选核素之一~([1]).~(186,188)Re广泛用于有机小分子化合物,单抗(McAb)、单抗片段(Fab)、受体配基和生物小分子肽,以达到靶向治疗的目的~([2-3]).铼的化学性质与锝极其相似,在标记前以~(188)ReO_4~-形式存在,在标记药物中呈低价态.制备时常规方法是将七价铼通过亚锡法还原到五价~([4-5]).     

~(13)C代谢通量分析

代谢通量分析(metabolic flux analysis,MFA)是通过确定代谢网络中代谢流分布来表征细胞代谢状态的强有力的工具。鉴于计量学代谢通量分析在处理复杂代谢网络时表现出的局限性,发展了以13C标记实验为基础的13C MFA。本文介绍了13C MFA的原理与方法,总结和评述了13C MFA在实验与数据分析方面的最新进展以及MFA在功能基因组研究中的重要地位,同时对代谢通量分析的发展前景进行了展望。     

离子色谱法测定铬酸酐中的微量F~-、SO_4~(2-)、Cl~-

建立了离子色谱法测定铬酸酐中微量F~-、SO_4~(2-)和Cl~-的方法。以水合联氨作还原剂,将铬酸酐溶液中的CrO_4~(2-)还原为Cr~(3+),以沉淀的方式除去,采用离子色谱法测定溶液中的微量F~-、SO_4~(2-)和Cl~-,其测量不确定度分别为6％、6％和5％。方法简便,测量结果准确、可靠。