琥珀酸脱氢酶的x光光谱研究

使用同步辐射光源,以荧光模式研究了琥珀脱氢酶的X光吸收光谱,表明所含的铁硫蛋白中,铁处于硫的四面体配位中;由氧化态及还原态的铁K边化学位移大小可知每个铁原子得失电子个数,SDHu(A)为0.39,,SDH(I)为0.30,,都比1小得多;表明有配位体容纳电子的作用,也表明有重组活性的SDH(A),具有较强的接受电子能力.文中引用量子化学计算结果对光谱现象予以合理的解释.     

ALKYLATION OF RAT BRAIN NUCLEIC ACIDS BY N-METHYL-N-NITROSOUREA AND METHYL METHANESULPHONATE

Abstract— Alkylation of rat brain nucleic acids in vivo was measured after a single intravenous injection (1 mmol/kg body wt.) of N -[¹⁴C]methyl- N -nitrosourea and [¹⁴C]methyl methanesulphonate. The main product with both compounds was 7-methylguanine, The extents of methylation on this position in DNA and RNA were similar with methylnitrosourea but methyl methanesulphonate produced twice as much 7-methylguanine in DNA as in cytoplasmic RNA. Brain DNA from rats treated with labelled methylnitrosourea contained radioactive O ⁶-methylguanine, accounting for about 12 per cent of the radioactivity present as 7-methylguanine and cytoplasmic RNA contained about half this amount of O ⁶-methylguanine. Neither DNA nor cytoplasmic RNA from methyl methanesulphonatetreated rats contained any detectable O ⁶-methylguanine. Treatment with both compounds resulted in varying small amounts of methylation of other nucleic acid bases including 1-methyladenine, 3-methyladenine and 3-methylcytosine. The possible relevance of alkylation of brain nucleic acids to the induction of brain tumours is discussed.     

AUTORADIOGRAPHIC STUDIES OF NUCLEIC ACIDS AND PROTEINS DURING MEIOSIS IN LILIUM LONGIFLORUM

Taylor , J. Herbert (Columbia U., New York, N. Y.) Autoradiographic studies of nucleic acids and proteins during meiosis in Lilium longiflorum. Amer. Jour. Bot. 46(7): 477–484. Illus. 1959.—A study was made of the incorporation of glycine-C¹⁴, orotic acid-C¹⁴ and cytidine-H³ into nucleic acids and proteins of sporogenous and tapetal cells of lily anthers preceding and during meiosis. Methods for differential extraction of nucleic acids from tissue sections, which had been frozen, dehydrated by alcohol-substitution, and fixed in hot alcohol, were tested by chromatographic analysis of extracts. Both acid and enzyme hydrolysis were shown to be useful for quantitative or, at least, semi-quantitative work. DNA synthesis was shown to occur only during premeiotic interphase in sporogenous cells, but at two intervals in tapetal nuclei, once when the microsporocytes are in zygotene and again during pachytene. Each time the synthetic period was followed by a normal mitosis. Accumulation of RNA in microsporocytes occurred at stages up to late leptotene. After this period, labeled RNA accumulated almost exclusively in their nuclei and at a slower rate than in earlier stages. DNA synthesis, as measured by incorporation of glycine-C¹⁴ and orotic acid-C¹⁴, gave the same results and confirm earlier results with inorganic phosphate-P³². For RNA, glycine-C¹⁴ and orotic acid-C¹⁴ gave different results. When glycine-C¹⁴ was the source of label, incorporation of C¹⁴ in RNA stopped during DNA synthesis in sporogenous cells. Glycine-C¹⁴ was not utilized to a significant extent at any time by tapetal cells for RNA synthesis, but extensively for DNA and protein synthesis. Orotic acid-C¹⁴ was incorporated into RNA of both tapetum and sporogenous cells at various periods in development apparently including the interval of DNA synthesis. Protein synthesis as measured by incorporation of glycine is relatively rapid during premeiotic interphase and leptotene. It continues during the remainder of prophase, but at a much reduced rate. In tapetal cells the rate is rapid in the nuclei during periods of DNA synthesis, but even faster in both cytoplasm and nucleus after divisions are completed and the microsporocytes are in late prophase and division stages. This period of synthesis is perhaps necessary for the postmeiotic functioning of tapetum when it appears to secrete the wall materials for the microspores.     

X-射线纤维衍射在多糖构型分析中应用的研究进展

本文从Ｘ射线纤维衍射法的原理,实验方法及应用实例三个方面对该方法在多糖构型分析中的应用状况进行综述,引用文献２０篇。     

SYNTHESIS OF SELENIUM-DERIVATIZED NUCLEOSIDES AND OLIGONUCLEOTIDES FOR X-RAY CRYSTALLOGRAPHY

We report here the synthesis of nucleoside and oligonucleotide analogs containing selenium, which serves as an anomalous scattering center to enable MAD phase determination in nucleotide X-ray crystallography. We have developed a phase transfer approach to introduce the selenium functionality in A, C, G, T, and U nucleosides at 5′-positions. In the incorporation of the selenium functionality, the leaving groups (bromide, mesyl, and tosyl) were readily displaced by sodium selenide, sodium diselenide, and sodium methyl selenide with yields higher than 90%. Selenium-derivatized oligonucleotides have been synthesized via phosphoramidite chemistry.     

COMPARATIVE CONFORMATIONAL ANALYSIS OF NUCLEOSIDES BY NMR,X-RAY,AND SEMI-EMPIRICAL (PM3 VS. AM1) METHODS

The 2′-deoxy-2′-fluoro-β-D-arabinofuranosyl ortho-aza-purine and -pyrimidine nucleosides manifest an unusually rigid sugar N conformation in solution.     

PURIFICATION OF PMPA AMIDATE PRODRUGS BY SMB CHROMATOGRAPHY AND X-RAY CRYSTALLOGRAPHY OF THE DIASTEREOMERICALLY PURE GS-7340

The diastereomers of GS-7171, aryl phosphoramidate derivatives of the anti-HIV nucleotide analog 9-[2-R-(phosphonomethoxy)propyl]adenine (tenofovir, PMPA), were isolated by batch elution chromatography and continuous simulated moving bed chromatography. The absolute configuration of the more pharmacologically active diastereomer, GS-7340, was determined to be (R,S,S) by single crystal x-ray crystallography.     

磷脂分子链构象及相变的拉曼光谱研究

本文报导了几种纯磷脂的固态、分散体或脂质体的激光拉曼光谱特性.在室温条件下固态DMPC、DPPC和DSPC的拉曼光谱表明,它们的分子链的有序性呈现差别.DMPC分子链的有序性远较其它二者为低.研究了DSPC的热致相变,分别观察固态DSPC的Ⅰ_(1100)/Ⅰ_(1064).～温度关系特性曲线和它的分散体的Ⅰ_(2882)/Ⅰ_(2847)～温度关系特性曲线,并发现上述两种关系特性曲线在相变温度之前均出现预相变峰,这可能反映在磷脂分子的相变过程中除trans(?)gauche构象转变外还存在其它构象的变化.DPPC分散体和脂质体的拉曼光谱特性进行比较的结果表明,曲率效应可能是脂质体分子链的有序性不同于分散体的原因.     

付里叶变换红外光谱法研究胰岛素的二级结构

付里叶变换红外光谱法测定了胰岛素的二级结构,讨论了信/噪比、谱解析、曲线拟合和吸收组分的指认对结构测定的影响。测定的胰岛素二级结构与X—光结构分析结果吻合。     

COMPARISON OF NUCLEIC ACIDS IN MAIZE SHOOTS AND PEA EPICOTYLS

A nucleic acid component (x-RNA) has been found in high concentration in maize shoots. It is eluted from a MAK (methylated albumin kieselguhr) column at about the same position as messenger RNA. The amount of x-RNA in pea epicotyls is absent or very low. It is suggested that x-RNA is long-lived messenger RNA and is found in high concentration in monocotyledonous plants, especially in the case of plants of the Gramineae family. Dicotyledonous plants, typically, contain little or no detectable x-RNA as observed by ultraviolet absorbancy. In the case of corn shoots, x-RNA is in highest concentration in the ribosomal fraction (78,500 × g, 70 min). In both maize shoots and pea epicotyls the newly synthesized nucleic acids were confined to the nuclear fraction (10,000 × g, 10 min).     

INTERRELATIONS BETWEEN POLYAMINES AND NUCLEIC ACIDS: CHANGES OF POLYAMINE AND NUCLEIC ACID CONCENTRATIONS IN THE DEVELOPING RAT BRAIN

The rat brain concentrations of protein, RNA, DNA, putrescine, and of the polyamines spermidine and spermine, were studied during development. Putrescine formation is apparently controlled by ornithine decarboxylase. Spermidine and spermine concentrations change in inverse directions to their anabolic enzymes. It has been presumed, therefore, that the low concentrations of the polyamine-synthesizing enzymes in immature brain are compensated for, by high putrescine and S-adenosylmethionine concentrations. In agreement with previous findings for fish brain, the changes in RNA and spermidine concentrations were most closely correlated. The functions of DNA: spermine are directly correlated only during the periods of brain maturation, after cell proliferation has nearly ceased.     

SELECTIVE RETENTION AND FILTRATION OF BRAIN NUCLEIC ACIDS IN AGAROSE GELS

Abstract— Total nucleic acids of rat brain have been separated by agarose gel chromatography at 2 m -NaCl into DNA. transfer RNA plus low molecular weight RNA. and high molecular weight RNA fractions. The DNA fraction contained less than 1 per cent RNA by weight judged by either short-term or long-term labelling with ortho[³²P]phosphate. The high molecular weight RNA fraction contained 28 s and 18 s ribosomal RNAs and a heterogeneous population of 20-60 s RNAs, apparent after short-term labelling and characterized by a high content of nearest-neighbour-labelled uridylic acid. The rapidly sedimenting (>30 s ) portion of these RNAs could be largely separated from ribosomal RNAs by gel filtration using 4% agarose. The ribosomal RNAs could be fully resolved into 28 s and 18 s components by agarose gel chromatography at 0.5 m -0.6 m -NaCl, as shown by analysis of their sedimentation and nucleotide composition.     

SYNTHESIS AND EVALUATION OF PROLYL CARBAMATE NUCLEIC ACIDS (PrCNA)

Carbamate linked prolyl nucleic acids are obtained in high yield and purity under mild conditions in solution and solid phase. p-Nitrophenylchloroformate is used as the activating reagent for alcohol. Homooligomers of PrCNA do not bind to DNA. The introduction of this modification in PNA sequences destabilizes the triplxes, inspite of enhancement in the base stacking.     

SYNTHETIC STUDIES TO IMPROVE THE DEUTERIUM LABELLING IN NUCLEOSIDES FOR FACILITATING STRUCTURAL STUDIES OF LARGE RNAS BY HIGH-FIELD NMR SPECTROSCOPY

Synthetic studies to prepare ribonucleosides deuterated at C2′ and the application of the developed procedures for the synthesis of ² H ₅ -ribonucleosides from 1,2-O-isopropylidene-3-O-benzyl-ribofuranose-3,4,5,5′- ² H ₄ have been reported.     

STRUCTURAL UNITS OF STARCH DETERMINED BY X-RAY CRYSTAL STRUCTURE METHOD

A few brief statements summarizing the foregoing conclusions may make a picture of the structure of the starch grain somewhat clearer. 1. The presence of lines on the negatives indicates a regular arrangement of the planes of atoms. 2. The lines are in close agreement with lines which would be produced by a lattice of the tetragonal system, the elementary cell of which is a square prism with the dimensions 5.94 x 5.94 x 5.05 Å.u. 3. The unit of the lattice occupies a space equal to the volume of the starch group, C₆H₁₀O₅. 4. The large number of atoms in the unit makes it highly probable that principal planes and secondary planes of atoms occur for every reflecting position. 5. The effect of the secondary upon the principal planes may readily account for the differences in the density of the lines produced on the negatives. 6. From theoretical considerations, reflections, such as those obtained, would occur if starch grains were built up of concentric layers of units. 7. Two other factors which might affect the density of the lines are thermal agitation and the curvature of the concentric layers. 8. A model of the starch group was constructed to scale based on the accepted sizes of the atoms involved and upon rather meager chemical evidence. The model apparently fulfills the requirements necessary to produce reflections such as were obtained. 9. The model fits the elementary cell loosely enough to suggest a low density and to allow for considerable thermal movement. At the same time, parts of it approach the faces of the cell closely enough to make cohesion seem possible. 10. The model makes clearer the basis for the assumption that reflection from certain positions would be stronger than from others. If the interpretation of the data is correct and if the assumptions made are sound, then the starch grain is built up of units arranged in concentric layers, and the units are groups of atoms, each containing 6 carbon, 10 hydrogen, and 5 oxygen atoms. Such a structure is certainly not an amorphous structure, and on the other hand it is not crystalline in the common sense of the term. Parts of the grain, it is true, act as crystals in that for certain distances the layers of units are in planes, but taken as a whole the layers are curved. As to the validity of the conclusions, those pertaining to the type of lattice and to the size of the unit may be accepted as sound in our present knowledge of x-rays and crystal structure; those, however, pertaining to the nature and the spherical arrangement of the units, while they seem convincing, need the support of further investigation into the various structures deposited by living protoplasm. In conclusion, the assumption that the units form a sort of spherical space lattice, gives a picture of the starch grain which leads us to ponder over the nature of the activity in protoplasm when it is depositing solid substances. Starch, cellulose, and pectic bodies are about the only solid deposits made directly by the living substance of plants, and all three have the same proportional formula, C₆H₁₀O₅. Investigations, as yet incomplete, indicate that cellulose also consists of a regular arrangement of C₆H₁₀O₅ groups, each acting as a unit, but the spacing (6.14 x 6.14 x 5.55) is slightly different from that of starch. Pectin has not been studied. Protoplasm may be thought of as being composed of molecules of many different sizes, polypeptides, or even proteins forming the larger, and amino-acids the smaller, if water and electrolytes are ignored. The smaller molecules, such as those of the amino-acid, leucine, are approximately equal in size to the C₆H₁₀O₅ group of starch. That being the case, what can be the state of affairs at the interface when the starch particles are being deposited? Is it probable that protoplasm is homogeneous to the extent of being able to deposit these particles at 6 Å.u. intervals? From quite another view-point a clear picture of the units of structure and their arrangement in cellulose should give a new point of attack on the many problems connected with osmosis. And from still a different view-point, it might lead perhaps, to a solution of problems connected with swelling. Another line of thought is suggested by the uniformity of the groups in the starch grain. Since the C₆H₁₀O₅ group occurs as an individual unit, one is inclined to suspect that it is really the molecule. Generally the starch molecule is considered to be very large, to be composed of several dozens of such groups, and to have a molecular weight of 7,000 or much more. No one figure, however, seems satisfactory to the different authorities. There is already at hand considerable evidence which will be assembled in a later paper favoring the single group, C₆H₁₀O₅, as the molecule. Finally, problems in polarized light may receive more satisfactory explanations through a clearer notion of the molecular structure of the carbohydrates.