467 resultados para 5’S


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Cultivation of the endophytic fungus Penicillium commune, which was isolated from the semi-mangrove plant Hibiscus tiliaceus, afforded one new compound 1-O-(2,4-dihydroxy-6-methylbenzoyl)-glycerol (1) along with thirteen known products, including 1-O-acetylglycerol (2), N-acetyltryptophan (3), 3-indolylacetic acid methyl ester (4), 1-(2,4-dihydroxy-3,5-dimethylphenyl)ethanone (5), 2-(2,5-dihydroxyphenyl)acetic acid (6), (4R,5S)-5-hydroxyhexan-4-olide (7), thymidine (8), uracil (9), thymine (10), ergosterol (11), beta-sitosterol (12), beta-daucosterol (13), and ergosta-7,22-dien-3 beta,5 alpha,6 beta-triol (14). The structures of these compounds were established by detailed NMR spectroscopic analysis, as well as by comparison with literature data or with authentic samples.

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本研究将荧光原位杂交(Fluorescence in situ hybridization, FISH)技术引入中国明对虾和栉孔扇贝这两种重要的海水养殖动物的染色体研究中,建立了相关技术平台,在染色体上定位了部分功能基因,详述如下: 1. 在中国明对虾和栉孔扇贝中建立了FISH平台,利用单色和双色FISH技术在中国明对虾和栉孔扇贝染色体上成功定位了多拷贝基因,发现5S rDNA定位于中国明对虾的一对同源染色体上,栉孔扇贝18S rDNA和组蛋白序列也各自定位于一对同源染色体上,它们均可以作为染色体特异性探针来鉴别染色体。 2. 在栉孔扇贝中发展了BAC-FISH技术,定位了包含热休克蛋白70(HSP70)、丝氨酸蛋白酶(Serine Protease)和脂多糖葡聚糖结合蛋白(LGBP)等免疫相关基因的BAC克隆,发现它们均定位于一对同源染色体的长臂上。利用双色BAC-FISH技术,发现6个包含栉孔扇贝LGBP基因的BAC克隆在间期细胞核上共定位。对栉孔扇贝5个探针进行了同时定位,初步鉴别了栉孔扇贝5条染色体。 3. 在栉孔扇贝热休克蛋白70(HSP70)、丝氨酸蛋白酶(Serine Protease)和脂多糖葡聚糖结合蛋白(LGBP)等免疫相关基因内部发掘了数个潜在的SNP位点,展示了栉孔扇贝SNP位点的丰富性。这些SNP位点可以用于图谱整合。

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本研究应用显带技术和荧光原位杂交(Fluorescence in situ hybridization,FISH)技术,鉴定了牡蛎的染色体;应用FISH方法定位了一系列的重复序列和大分子的P1克隆DNA;制备了染色体特异性探针。应用FISH特异性探针成功地鉴定了长牡蛎的三体10。结果如下:1.分析了G带和C带在美洲牡蛎染色体上的分布。G带在每一条染色体上的带型不同,某些染色体间(如第1对和第4对染色体,第7对和第9对染色体)的带型差别不是很明显。G带型容易受染色体收缩程度的影响。C带型重复性较好,染色体带型较清楚,分布在染色体的端粒区域和着丝粒区域。G带和C带带型能够用来鉴定牡蛎的染色体,但是重复性低和带型差异不显著,并不适合常规的染色体鉴定。2.早期胚胎和担轮幼虫制备的染色体适合于FISH分析。染色体制备方法重复性好,可适用于其它贝类的染色体制备。3.研究了重复序列基因--rDNA的定位:1)18S-5.8S rDNA在研究的五种巨蛎属Crassostrea牡蛎均只有一个位 点。太平洋种(C.gigas,C. ariakensis和C. plicatula)中,杂交信号位于最短的染色体一第10对染色体长臂的端粒区域,在大西洋种(C. virginica和C. rhizophorae)中,同一序列定位在第2对染色体短臂的端粒区域。2)18S-28S rDNA在两种蛤中有两个位点。rDNA探针定位在侏儒蛤(Mulinis Lateralis)的第15对和第19对染色体的端粒区域,同一序列定位在硬壳蛤(Mercenaria mercenaria)的第10对染色体的长臂和第12对染色体短臂的端粒区域。信号强度在两对染色体之间有差异。 3)5s rDNA位于美洲牡蛎的第5对染色体的短臂上靠近着丝粒区域和第6 对染色体的短臂的中间区域。信号强度在两对染色体之间没有显著差异。5S rDNA探针可以作为鉴定和识别第5对和第6对染色体的特异性探针。4.研究了一些重复序列的定位1)两个短的重复序列1G8,1P2均产生很强的荧光信号分布在美洲牡蛎所有的染色体上。在低严谨条件下,这些序列均产生很强的信号散布在所有的染色体上。在高严谨条件下,信号强度大大减弱,但是信号仍散布在所有的染色体上。这些重复序列散布在美洲牡蛎的整个基因组中。2)高度重复序列Cgl70产生的信号分布在长牡蛎的7对染色体的着丝粒区域,没有发现间区信号。在第1对,第2对,第4对和第7对染色体上的荧光信号强且稳定。在第5对,第8对和第10对染色体上的信号相对弱且不稳定。在剩余的染色体上(第3对,第6对和第9对染色体)没有检测到荧光信号。结果表明此卫星序列是一个着丝粒卫星序列。在美洲牡蛎的染色体上没有检测到荧光信号,表明了这个着丝粒卫星序列在这两种牡蛎中的分布存在着显著的差异。3)脊椎动物端粒序列(TTAGGG)n的FISH信号局限在四种双壳贝类(美洲牡蛎,the mangrove oyster,硬壳蛤,侏儒蛤)所有染色体的端粒区域,没有发现间区信号的存在。研究结果与已报道的研究结果表明脊椎动物端粒序列或许存在于所有双壳贝类的染色体末端。双壳贝类是目前研究过的唯一含有脊椎动物端粒序列DNA的无脊椎动物。4)研究了RAPD探针在美洲牡蛎染色体上的定位。大多数RAPD探针产生了多个信号散布在间期细胞核和所有的染色体上。引物OPX-03,OPX-04,OPX—06,OPG-02,OPM—04,OPM-11,0PS-02制备的探针在适宜的条件下产生特异性荧光 信号,分布在牡蛎的特定的染色体上。PCR特异性带产生的探针OPX—06—310和0PG-02—300产生了特异性的荧光信号:OPX—06—310产生的信号位于第5对染色体的短臂的近端粒区域,0PG—02—300探针定位到第3对染色体的短臂上。这两个探针是鉴定美洲牡蛎单条染色体的特异性探针。5.研究了大分子Pl克隆DNA(插入片断为80~100 kb)在美洲牡蛎染色体上的定位。Pl克隆DNA通过切口平移方法标记digoxigenin—11-dUTP用作FISH的探针。Cot-1 DNA作为竞争剂有效地抑制了Pl克隆序列中的重复序列产生的信号。杂交信号用fluorescein标记的anti—digoxigenin抗体来检测,用两层抗体rabbit-anti-sheep抗体和FITC anti—rabbit抗体来扩增信号。9个P1探针成功地定位在特定的染色体上。46—1探针杂交到第1对染色体的长臂靠近着丝粒区域;47-10探针定位到第2对染色体的长臂近端粒区域;Cvpl和48-13两探针定位到第3对染色体上:Cvpl位于短臂的端粒区域,48-13探针位于长臂的近着丝粒区域;48—10探针杂交到第4对染色体的长臂上;48-1探针杂交到第5对染色体长臂的近着丝粒区域;49-11探针位于第7对染色体长臂上;探针49-10和44-11位于第8对染色体长臂上。同时我们成功地将2个P1探针杂交到同一染色体分裂相中,进一步确定了Pl探针在美洲牡蛎染色体 上的定位。6.应用18S-28S rDNA探针成功地鉴定出长牡蛎非整倍体中的三体10。经鉴定AF-35,AF-39和AF-3三体家系属于三体10家系。rDNA探针分布在三条染色体上,即多出的一条染色体为染色体10。相应地在间期细胞核上有三个信号出现。AF-34和AF-36家系不属于三体10家系。rDNA探针分布在两条染色体上,相应地在间期细胞核上有两个信号出现。FISH和染色体特异性探针为非整倍体的鉴定提供了一个快速准确可靠的方法和途径。

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海藻是海洋生物中的一大类群,由于其特殊的生活环境,能够代谢产生大量结构独特多变和活性特殊多样的代谢产物,是化学和生物活性多样性研究的重要对象之一。我国海域辽阔,海藻资源丰富,为寻找结构新颖、生理活性独特的先导化合物,加强对海藻资源的开发利用,本论文对中国沿海的三种海洋红藻进行了化学成分和生物活性研究,同时对山东青岛海域生物量丰富的一种海洋红藻松节藻进行了动物体内抗糖尿病活性研究。 利用正相硅胶柱色谱、Sephadex LH-20柱色谱以及反相HPLC和重结晶等现代分离手段,对山东青岛沿海的红藻扇形叉枝藻(Gymnogongrus flabelliformis)进行了系统的化学成分研究,从中得到单体化合物26个,通过波谱学方法(IR、MS、NMR等)鉴定了他们的结构,分别为(3R,6R,7E)-(+)-3-O-phenylacetyl- 4,7-megastigmadiene-9-one(1),(3R,7E)-(-)-3-O-phenylacetyl-5,7-megastigmadiene -9-one(2),(3S,6R,7E)-(+)-3-hydroxyl-4,7-megastigmadien-9-one(3),(3S,5R,6S,7E)- (-)-3-hydroxy-5,6-epoxy-7-megastigmene-9-one(4),(3S,5S,6R,7E)-(+)-3-hydroxy- 5,6-epoxy-7-megastigmene-9-one(5),Dehydrovomifoliol(6),(3R)-(-)-4-[(2R,4S)-4- acetoxy-2-hydroxy-2,6,6-trimethylcyclohexylidene]-3-buten-2-one(7),2,3,3′-三溴-4,4′,5,5′-四羟基-1′-乙氧甲基双苯基甲烷(8),2,2′,3,3′-四溴-4,4′,5,5′-四羟基双苯基甲烷(9),3-溴-4,5-二羟基苯甲醛(10),2,3-二溴-4,5-二羟基苯甲基甲醚(11),2,3-二溴-4,5-二羟基苯甲醇(12),N, N-二甲基酪胺(13),4-羟基苯甲酸乙酯(14),4-羟基苯甲基乙醚(15),4-羟基苯乙基乙酯(16),4-羟基苯乙酸甲酯(17),4-羟基苯甲醛(18),豆甾-4-烯-3-酮(19),胆甾-4-烯-3-酮(20),胆甾醇(21),尿嘧啶(22),尿嘧啶核苷(23),腺嘌呤核苷(24),丁二酸(25),5-羟基-4-甲基-5-戊基-2,5-二氢呋喃-2-酮(26)。其中化合物1、2为新化合物,化合物3为新天然产物,所有化合物均为首次从该属海藻中分离得到。通过 MTT 法对部分单体化合物进行了肿瘤细胞毒活性筛选, 结果表明,化合物8、9、10、12对筛选的所有细胞株均有较强细胞毒活性,化合物11对人肺癌细胞株(A549)、人肝癌细胞株(Bel 7402)、人结肠癌细胞株(HCT-8)有一定细胞毒活性。通过研究单体化合物对小鼠腹腔巨噬细胞TNF-分泌的影响,对其进行抗炎活性筛选,结果表明,化合物8、9、11、13、17、23、24、25对小鼠腹腔巨噬细胞TNF-分泌表现出明显的抑制作用。 从采自山东荣成镆铘岛的红藻小珊瑚藻(Corallina pilulifera)的乙酸乙酯萃取物中分离得到16个单体化合物,通过波谱学方法鉴定化合物结构14个(另外2个正在鉴定中),分别为2α-乙氧酰基-2β-羟基-A-降胆甾-5-烯-4-酮(27),胆甾-4-烯-3-酮(28),胆甾醇(29),3β-羟基-胆甾-5,24(28)-二烯-7-酮(30),2α-羟基-胆甾-4-烯-3-酮(31),6α-羟基-胆甾-4-烯-3-酮(32),3β-羟基-胆甾-5-烯-7-酮(33),(E)-phytol epoxide(34),Phytenal(35),3,7,11,15- tetramethyl-hexadec-2-en-1-oll(Phytol)(36),Loloilide(37),(3S,5R,6S,7E)-(-)-3-hydroxy-5,6-epoxy-7- megastigmene-9-one(38),Dehydrovomifoliol(39),4-羟基苯甲醛(40)。其中,化合物 31为新天然产物,化合物27为首次从植物中分离得到,所有化合物均为首次从该种海藻中分离得到。通过 MTT 法对分离得到的单体化合物进行了肿瘤细胞毒活性筛选,化合物27和化合物32对筛选的所有肿瘤细胞株均有细胞毒活性,且化合物27对人胃癌细胞株(BGC-823)、人结肠癌细胞株(HCT-8)和人卵巢癌细胞株(A2780)具有中等强度抑制活性。化合物28、化合物31和化合物33对人肝癌细胞株(Bel 7402)、人结肠癌细胞株(HCT-8)和人卵巢癌细胞株(A2780)有一定细胞毒活性。 从采自广西北海涠洲岛的多管藻Polysiphonia sp.的乙酸乙酯萃取物中分离得到6个单体化合物,通过波谱学方法鉴定化合物结构5个(另外1个仍在鉴定),分别为胆甾醇(41),3,7,11,15-tetramethyl-hexadec-2-en-1-ol(Phytol)(42),3-吲哚甲醛(43),4-羟基苯甲醛(44),4-羟基苯甲酸(45)。 对山东青岛沿海的松节藻 (Rhodomela confervoides) 乙醇提取物进行了初步的体内抗糖尿病活性研究,采用链脲佐菌素诱导的2型糖尿病(STZ-DM)大鼠模型对其进行体内降糖实验,结果发现,松节藻乙醇提取物在糖尿病大鼠体内不仅具有显著的降血糖作用,且呈现良好的量–效关系,而且能够纠正糖尿病引发的物质代谢紊乱,增加体重,提高试验动物的成活率,因此具有良好的应用开发前景。

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Seven new cadinane sesquiterpenes, (-)-(1R,6S,7S,10R)-1-hydroxycadinan-3-en-5-one (1), (+)-(1R,5S,6R,7S, 10R)-cadinan-3-ene-1,5-diol (2), (+)-(1R,5R,6R,7S,10R)-cadinan-3-ene-1,5-diol (3), (+)-(1R,5S,6R,7S,10R)-cadinan-4(11)-ene-1,5-diol (4), (+)-(1R,5R,6R,7R,10R)-cadinan-4(11)-ene-1,5,12-triol (5), (-)-(1R,4R,5S,6R,7S, 10R)-cadinan-1,4,5-triol (6), and (-)-(1R,6R,7S,10R)-11-oxocadinan-4-en-1-ol (7), together with nine known compounds were isolated from the brown alga Dictyopteris divaricata. The structures of the new natural products, as well as their absolute configuration, were established by means of spectroscopic data including IR, HRMS, 1D and 2D NMR, single-crystal X-ray diffraction, and CD. All compounds were inactive against several human cancer cell lines including lung adenocarcinoma (A549), stomach cancer (BGC-823), breast cancer (MCF-7), hepatoma (Bel7402), and colon cancer (HCT-8) cell lines.

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Five minor sesquiterpenes (1-5) with two novel carbon skeletons, together with a minor new oplopane sesquiterpene ( 6), have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR, and CD, their structures including absolute configurations were assigned as (+)-(1R, 5S, 6S, 9R)3- acetyl-1-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0] non-3-ene ( 1), (+)-(1R, 3S, 4S, 5R, 6S, 9R)-3-acetyl-1,4-dihydroxy-6- isopropyl-9-methylbicyclo[4.3.0] nonane (2), (+)-(1R, 3R, 4R, 5R, 6S, 9R)-3-acetyl-1,4-dihydroxy-6-isopropyl-9-methylbicyclo[ ;4.3.0] nonane ( 3), (+)-(1S, 2R, 6S, 9R)-1-hydroxy-2-(1-hydroxyethyl)-6-isopropyl-9-methylbicyclo[4.3.0] non-4-en-3-one (4), (-)-( 5S, 6R, 9S)-2-acetyl-5-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0] non-1-en-3-one ( 5), and (-)-( 1S, 6S, 9R)- 4-acetyl- 1-hydroxy-6-isopropyl-9-methylbicyclo[ 4.3.0] non-4-en-3-one ( 6). Biogenetically, the carbon skeletons of 1-6 may be derived from the co-occurring cadinane skeleton by different ring contraction rearrangements. Compounds 1-6 were inactive (IC50 > 10 mu g/mL) against several human cancer cell lines.

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Three bisnorsesquiterpenes (1-3) with novel carbon skeletons and a norsesquiterpene (4) have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR techniques, single-crystal X-ray diffraction, and CD, their structures including absolute configurations were proposed as (+)-1R,6S,9R)-1-hydroxyl-6-isopropyl-9-methylbicyclo[4.3.0]non-4-en3-one (1), (-)-(1S,6S,9R)-1-hydroxyl-6-isopropyl-9-methylbicyclo[4.3.0] non-4-en-3-one (2), (+)-(5S,6R,9S)5-hydroxyl-6-isopropyl-9-methylbicyclo [4.3.01 non-1-en-3-one (3), and (-)-(1R,7S,10R)-1-hydroxy-1lnorcadinan-5-en-4-one (4). Biogenetically, the carbon skeleton of 1-3 may be derived from the co-occurring cadinane skeleton by ring contraction and loss of two carbon units, and compound 4 from the oxidation of cadinane derivatives. Compounds 1-4 were inactive (IC50 > 10 mu g/mL) against several human cancer cell lines including lung adenocarcinoma (A549), stomach cancer (BGC-823), breast cancer (MCF-7), hepatoma (Bel7402), and colon cancer (HCT-8) cell lines.

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Karyotype and chromosomal localization of major (18-5.8-28S) and minor (5S) ribosomal RNA genes were studied in two species of Pectinidae, zhikong (Chlamys farreri) and bay (Argopecten irradians irradians) scallops. using fluorescence in situ hybridization (FISH). C. farreri had a haploid number of 19 with a karyotype of 3m + 4sm + 7sm-st + 4st + 1st-t, and A. i. irradians had a haploid number of 16 with a karyotype of 5st + 11t. In C. farreri, the major and minor rRNA genes had one locus each and were mapped to the same chromosome-Chromosome 5. In A. i. irradians, the major rRNA genes had two loci, located on Chromosomes 4 and 8, and the 5S rRNA gene was found at a third chromosome-Chromosome 10. Results of this and other studies indicate that karyotype of A. i. irradians (n = 16, 21 arms) is secondary and derived from an ancestral karyotype similar to that of C. farreri (n = 19, 38 arms) through considerable chromosomal loss and rearrangements. The ability to tolerate significant chromosomal loss suggests that the modal karyotype of Pectinidae and possibly other bivalves with a haploid number of 19 is likely tetraploid; i.e., at least one genome duplication has occurred during the evolution of Bivalvia.

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Our study deals with the high resolution body wave tomography in North china and adjacent areas(30°N-43°N,100°E-130°E), where earthquakes occurred many times in history and has a very complicated geological structure. 6870 events recorded at 273 digital seismic stations from CDSN during 1996-2002 and stations settled by Seislab of IGCAS in Bohai Bay area, including 1382 local earthquakes and 5488 teleseismic earthquakes are used in this study. In the data we used, the average number of received stations is greater than 5, the error of picking up direct arrival time is 0.1-0.5s. Before the inversion, we use Checkerboard method to confirm the reliability of result of Local events; use Restoring Resolution Test to confirm the reliability of result of teleseismic events. We also analyzed the effect of different parameters in the inversion. Based the analysis above, the model used in this paper is divided into small blocks with a dimension of 0.33°in the latitude and longitude directions and 5km、15km、30km in depth, and initial velocity model. Using pseudobending method to calculate the ray traveling path, LSQR algorithm to inverse, finally, we got the body velocity images below 25km and above 480km in this area using Joint- inversion with local events and teleseismic events. We made the conclusion at last: (1)at top zone of the south of Sichuan Basin , there exits low velocity anomalies, below 40km is the high velocity zone extend to 300km; (2) Above the 40km of Ordos block exits low velocity zone, while below 40km until 240km, the high velocity anomalies are interlaced by low velocity anomalies. Below 300km, the anomalies are unclear any more; (3) On the whole, the velocity structure below 400km on the mantle transition zone of Eastern China area shows its changes from low velocity to high velocity.

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Using thermosetting epoxy based conductive adhesive films for the flip chip interconnect possess a great deal of attractions to the electronics manufacturing industries due to the ever increasing demands for miniaturized electronic products. Adhesive manufacturers have taken many attempts over the last decade to produce a number of types of adhesives and the coupled anisotropic conductive-nonconductive adhesive film is one of them. The successful formation of the flip chip interconnection using this particular type of adhesive depends on, among factors, how the physical properties of the adhesive changes during the bonding process. Experimental measurements of the temperature in the adhesive have revealed that the temperature becomes very close to the required maximum bonding temperature within the first 1s of the bonding time. The higher the bonding temperature the faster the ramp up of temperature is. A dynamic mechanical analysis (DMA) has been carried out to investigate the nature of the changes of the physical properties of the coupled anisotropic conductive-nonconductive adhesive film for a range of bonding parameters. Adhesive samples that are pre-cured at 170, 190 and 210°C for 3, 5 and 10s have been analyzed using a DMA instrument. The results have revealed that the glass transition temperature of this type of adhesive increases with the increase in the bonding time for the bonding temperatures that have been used in this work. For the curing time of 3 and 5s, the maximum glass transition temperature increases with the increase in the bonding temperature, but for the curing time of 10s the maximum glass transition temperature has been observed in the sample which is cured at 190°C. Based on these results it has been concluded that the optimal bonding temperature and time for this kind of adhesive are 190°C and 10s, respectively.

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The seasonal variations in distribution and abundance of the common zooplankton species in the Bristol Channel and Severn Estuary were related to the salinity regimes observed over the period November 1973 to February 1975. The dominant constituents in all regions were the calanoid copepods, which reached maximum densities in July: approximately 100 times their winter levels. Four zooplankton assemblages were recognised using an objective classification program which computed similarity coefficients and used group-average sorting. The assemblages existed along the salinity gradient observed from the Severn Estuary to the Celtic Sea. The assemblages were classified as true estuarine, estuarine and marine, euryhaline marine and stenohaline marine and were characterized by the copepods Eurytemora affinis (Poppe) (<30‰S), Acartia bifilosa var. inermis (rose) (27 to 33.5‰S), Centropages hamatus (Lilljeborg) (31 to 35‰S) and Calanus helgolandicus (Claus) (>33‰S), respectively.

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Phylogeography has provided a new approach to the analysis of the postglacial history of a wide range of taxa but, to date, little is known about the effect of glacial periods on the marine biota of Europe. We have utilized a combination of nuclear, plastid and mitochondrial genetic markers to study the biogeographic history of the red seaweed Palmaria palmata in the North Atlantic. Analysis of the nuclear rDNA operon (ITS1-5.8S-ITS2), the plastid 16S-trnI-trnA-23S-5S, rbcL-rbcS and rpl12-rps31-rpl9 regions and the mitochondrial cox2–3 spacer has revealed the existence of a previously unidentified marine refugium in the English Channel, along with possible secondary refugia off the southwest coast of Ireland and in northeast North America and/or Iceland. Coalescent and mismatch analyses date the expansion of European populations from approximately 128 000 bp and suggest a continued period of exponential growth since then. Consequently, we postulate that the penultimate (Saale) glacial maximum was the main event in shaping the biogeographic history of European P. palmata populations which persisted throughout the last (Weichselian) glacial maximum (c. 20 000 bp) in the Hurd Deep, an enigmatic trench in the English Channel.

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Single- and multiphoton detachment rates have been calculated for K- using the R-matrix Floquet approach. Single-photon detachment rates, obtained at a laser field peak intensity of 10(9) W cm(-2), are discussed and compared with other theoretical work. Two-photon detachment rates at the same intensity have also been obtained, and similarities with results from earlier calculations for Li- and Na- are discussed. Three-photon rates are also presented at this laser intensity, and are compared and contrasted with those arising in the single-photon case, since both involve resonance structure with P-1(o) symmetry. The influence of resonances such as the 5s(2) S-1(e) doubly excited state and excitations of the residual atom are also considered.

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A high-resolution crystal structure is reported for d(TpA)*, the intramolecular thymine–adenine photoadduct that is produced by direct ultraviolet excitation of the dinucleoside monophosphate d(TpA). It confirms the presence of a central 1,3-diazacyclooctatriene ring linking the remnants of the T and A bases, as previously deduced from heteronuclear NMR measurements by Zhao et al. (The structure of d(TpA)*, the major photoproduct of thymidylyl-(3'-5')-deoxyadenosine. Nucleic Acids Res., 1996, 24, 1554–1560). Within the crystal, the d(TpA)* molecules exist as zwitterions with a protonated amidine fragment of the eight-membered ring neutralizing the charge of the internucleotide phosphate monoanion. The absolute configuration at the original thymine C5 and C6 atoms is determined as 5S,6R. This is consistent with d(TpA)* arising by valence isomerization of a precursor cyclobutane photoproduct with cis–syn stereochemistry that is generated by [2 + 2] photoaddition of the thymine 5,6-double bond across the C6 and C5 positions of adenine. This mode of photoaddition should be favoured by the stacked conformation of adjacent T and A bases in B-form DNA. It is probable that the primary photoreaction is mechanistically analogous to pyrimidine dimerization despite having a much lower quantum yield.

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We present results of wavepacket simulations for multiphoton ionization in argon. A single active electron model is applied to estimate the single-electron ionization rates and photoelectron energy distributions for lambda = 390 nm light with intensities up to I = 2 x 10(14) W cm(-2). The multiphoton ionization rates are compared with R-matrix Floquet calculations and found to be in very good agreement. The photoelectron energy distribution is used to study the nature of ionization at the higher intensities. Our results are consistent with recent calculations and experiments which show the imprint of the tunnelling process in the multiphoton regime. For few-cycle intense pulses, we find that the strong modulation of intensity and increased bandwidth leads to dynamic mixing of the 3d and 5s resonances.