953 resultados para ~(13)C NMR
Resumo:
The Raman spectrum of cyclohexanol has been studied in detail in the liquid state at 30° C. and at about 68° C. and in the solid state at about 13° C. The O-H stretching frequency of cyclohexanol has been found to extend from 3106-3571 cm.-1 in the liquid state at 30° C. and from 3204-3652 cm.-1 at 68° C. The 38 lines recorded in the present investigation have been following frequency shifts: 342, 408, 458, 478, 555, 653, 789, 834, 843, 863, 887, 920, 966, 978, 1024, 1047, 1070, 1139, 1173, 1184, 1210, 1235, 1252, 1301, 1329, 1346, 1362, 1438, 1448, 1464, 2660, 2684, 2710, 2854, 2896, 2925, 2940, 3106 to 3511 (band). Those lines which are italicized are the additional lines observed for the first time. The Raman lines at 966 cm.-1 and 1070 cm.-1 have been assigned to C-OH stretching vibrations of the axial and equatorial isomers. The ratio of the integrated intensity of the 1070 cm.-1 line to the 966 cm.-1 gave the equilibrium constant K as 2·896 at 30° C. and as 2·66 at 68° C. Knowing K, the free energy different Δ F was calculated and it was found to be 0·64 Kcal./mole at 30° C. and 0·66 Kcal./mole at about 68° C. Reasonable assignment has been made for most of the observed Raman lines.
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Counting-rate meters normally used for finding pulse frequencies are sluggish in their response to any rapid change in the pulse repetition frequency (P.R.F.). An instrument is described which measures each pulse interval and provides immediately afterwards an output voltage proportional to the reciprocal of interval duration. A response to a change in the P.R.F. as rapidly as is physically possible is obtained. The instrument has wide application in low level radiation detection and in several other fields especially for rapidly varying counting-rates.
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The galactose-specific lectin from the seeds of Dolichos lablab has been crystallized using the hanging-drop vapour-diffusion technique. The crystals belong to space group P1, with unit-cell parameters a = 73.99, b = 84.13, c = 93.15 angstrom, alpha = 89.92, beta = 76.01, gamma = 76.99 degrees. X-ray diffraction data to a resolution of 3.0 angstrom have been collected under cryoconditions ( 100 K) using a MAR imaging-plate detector system mounted on a rotating-anode X-ray generator. Molecular-replacement calculations carried out using the available structures of legume lectins as search models revealed that the galactose-specific lectin from D. lablab forms a tetramer similar to soybean agglutinin; two such tetramers are present in the asymmetric unit.
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C21H27NO2, Mr=325.5 , orthorhombic,P21212,, a = 7.516 (2), b = 13.430 (2), c =18.047 (2) A, U= 1821.79 A 3, Z = 4, D x =1.186 Mg m -a, 2(Cu Ka) = 1.5418 A, # = 0.56 mm -1, F(000) = 704, T= 293 K, final R = 0.04 for 1892 reflections with I _> 3a(I). Ring A is planar, and rings B and C adopt a chair conformation. Rings D and E are envelopes, with C(14) and C(17) displaced from their respective planes by 0.643 (3) and 0.482 (3)A. The ring system A/B shows quasi-trans fusion, whilst ring systems B/C and C/D are trans fused about C(8)-C(9) and C(13)-C(14) respectively. The D/E junction shows cis fusion.
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C22H31NO2.H2 O, M r = 359" 5, orthorhombic,P2~212 ~, a= 10.032 (1), b= 11.186 (1), C = 17.980 (1)/~,, U= 2017.48/~3, Z = 4, D x = 1.276 Mg m -a, 2(Cu Kct) = 1.5418/~, # = 0.69 mm -~,F(000) = 784, T = 293 K. Final R = 0.05 for 1972 unique reflections with I > 3o(/). Ring A is planar, and rings B and C adopt a chair conformation. Rings D and E are envelopes, with C(14) and C(20) displaced from their respective ring planes by 0-616 (2) and 0.648 (3)/~. The A/B ring junction is quasi-trans,whilst ring systems B/C and C/D are trans fused about the bonds C(8)-C(9) and C(13)-C(14) respectively.The D/E junction shows cis fusion.
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Abstract. C25H44N20 , M r= 388.6, orthorhombic, P21212 I, a = 6.185 (2), b = 18.123 (2), c = 20.852 (2) A, U= 2337.2 A 3, Z = 4, D x = 1.104 Mg m -a, 2(Cu Ka) = 1.5418 A,/~ = 0.47 mm -~, F(000) = 864, T= 293 K. Final R - 0.038 for 1791 reflections with I >_ 3a(I). Rings A and C are in chair conformation. Ring B is in an 8fl,9a-half-chair conformation. Ring D adopts a conformation in between 13fl,14a-half-chair and 13t-envelope. There is a quasitrans fusion of rings A and B, whilst ring systems B/C and C/D are trans fused about the bonds C(8)-C(9)and C(13)-C(14).
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Background: Primary distal renal tubular acidosis (dRTA) caused by mutations in the genes that codify for the H+ -ATPase pump subunits is a heterogeneous disease with a poor phenotype-genotype correlation. Up to now, large cohorts of dRTA Tunisian patients have not been analyzed, and molecular defects may differ from those described in other ethnicities. We aim to identify molecular defects present in the ATP6V1B1, ATP6V0A4 and SLC4A1 genes in a Tunisian cohort, according to the following algorithm: first, ATP6V1B1 gene analysis in dRTA patients with sensorineural hearing loss (SNHL) or unknown hearing status. Afterwards, ATP6V0A4 gene study in dRTA patients with normal hearing, and in those without any structural mutation in the ATP6V1B1 gene despite presenting SNHL. Finally, analysis of the SLC4A1 gene in those patients with a negative result for the previous studies. Methods: 25 children (19 boys) with dRTA from 20 families of Tunisian origin were studied. DNAs were extracted by the standard phenol/chloroform method. Molecular analysis was performed by PCR amplification and direct sequencing. Results: In the index cases, ATP6V1B1 gene screening resulted in a mutation detection rate of 81.25%, which increased up to 95% after ATP6V0A4 gene analysis. Three ATP6V1B1 mutations were observed: one frameshift mutation (c.1155dupC; p.Ile386fs), in exon 12; a G to C single nucleotide substitution, on the acceptor splicing site (c.175-1G > C; p.?) in intron 2, and one novel missense mutation (c. 1102G > A; p. Glu368Lys), in exon 11. We also report four mutations in the ATP6V0A4 gene: one single nucleotide deletion in exon 13 (c.1221delG; p. Met408Cysfs* 10); the nonsense c.16C > T; p.Arg6*, in exon 3; and the missense changes c.1739 T > C; p.Met580Thr, in exon 17 and c.2035G > T; p.Asp679Tyr, in exon 19. Conclusion: Molecular diagnosis of ATP6V1B1 and ATP6V0A4 genes was performed in a large Tunisian cohort with dRTA. We identified three different ATP6V1B1 and four different ATP6V0A4 mutations in 25 Tunisian children. One of them, c.1102G > A; p.Glu368Lys in the ATP6V1B1 gene, had not previously been described. Among deaf since childhood patients, 75% had the ATP6V1B1 gene c. 1155dupC mutation in homozygosis. Based on the results, we propose a new diagnostic strategy to facilitate the genetic testing in North Africans with dRTA and SNHL.
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One of the greatest challenges in science lies in disentangling causality in complex, coupled systems. This is illustrated no better than in the dynamic interplay between the Earth and life. The early evolution and diversification of animals occurred within a backdrop of global change, yet reconstructing the potential role of the environment in this evolutionary transition is challenging. In the 200 million years from the end-Cryogenian to the Ordovician, enigmatic Ediacaran fauna explored body plans, animals diversified and began to biomineralize, forever changing the ocean's chemical cycles, and the biological community in shallow marine ecosystems transitioned from a microbial one to an animal one.
In the following dissertation, a multi-faceted approach combining macro- and micro-scale analyses is presented that draws on the sedimentology, geochemistry and paleontology of the rocks that span this transition to better constrain the potential environmental changes during this interval.
In Chapter 1, the potential of clumped isotope thermometry in deep time is explored by assessing the importance of burial and diagenesis on the thermometer. Eocene- to Precambrian-aged carbonates from the Sultanate of Oman were analyzed from current burial depths of 350-5850 meters. Two end-member styles of diagenesis independent of burial depth were observed.
Chapters 2, 3 and 4 explore the fallibility of the Ediacaran carbon isotope record and aspects of the sedimentology and geochemistry of the rocks preserving the largest negative carbon isotope excursion on record---the Shuram Excursion. Chapter 2 documents the importance of temperature, fluid composition and mineralogy on the delta 18-O min record and interrogates the bulk trace metal signal. Chapter 3 explores the spatial variability in delta 13-C recorded in the transgressive Johnnie Oolite and finds a north-to-south trend recording the onset of the excursion. Chapter 4 investigates the nature of seafloor precipitation during this excursion and more broadly. We document the potential importance of microbial respiratory reactions on the carbonate chemistry of the sediment-water interface through time.
Chapter 5 investigates the latest Precambrian sedimentary record in carbonates from the Sultanate of Oman, including how delta 13-C and delta 34-S CAS vary across depositional and depth gradients. A new model for the correlation of the Buah and Ara formations across Oman is presented. Isotopic results indicate delta 13-C varies with relative eustatic change and delta 34-S CAS may vary in absolute magnitude across Oman.
Chapter 6 investigates the secular rise in delta 18-Omin in the early Paleozoic by using clumped isotope geochemistry on calcitic and phosphatic fossils from the Cambrian and Ordovician. Results do not indicate extreme delta 18-O seawater depletion and instead suggest warmer equatorial temperatures across the early Paleozoic.
A balloon measurement of the isotopic composition of galactic cosmic ray boron, carbon, and nitrogen
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The isotopic compositions of galactic cosmic ray boron, carbon, and nitrogen have been measured at energies near 300 MeV amu-1, using a balloon-borne instrument at an atmospheric depth of ~5 g cm-2. The calibrations of the detectors comprising the instrument are described. The saturation properties of the cesium iodide scintilla tors used for measurement of particle energy are studied in the context of analyzing the data for mass. The achieved rms mass resolution varies from ~ 0.3 amu at boron to ~ 0.5 amu at nitrogen, consistent with a theoretical analysis of the contributing factors. Corrected for detector interactions and the effects of the residual atmosphere, the results are ^(10)B/B = 0.33^(+0.17)_(-0.11), ^(13)C/C = 0.06^(+0.13)_(-0.01), and ^(15)N/N = 0.42 (+0.19)_(-0.17). A model of galactic propagation and solar modulation is described. Assuming a cosmic ray source composition of solar-like isotopic abundances, the model predicts abundances near earth consistent with the measurements.
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在中国北方大部分地区,水分始终是影响植物生长和分布的最主要限制性因子之一,植物在其生长期经常遭受水分胁迫。不仅如此,随着大气同温层中臭氧浓度的减少,过量的有害紫外辐射(主要是UV-B,280nm-320nm)将穿透大气层达到地球表面。随着全球变化的加剧,这些地区的植物将不可避免地受UV-B和水分胁迫的共同作用。 本实验是在北京东灵山暖温带森林生态系统中,选择常见灌丛土庄绣线菊(Spiraea pubescens),建立UV-B控制实验。连续三个生长季每天增补9.4kJ•m-2的辐射剂量,模拟臭氧衰减17%时近地表面UV-B辐射的增强。本实验的目的是观测在野外环境下,长时间人工增强UV-B辐射对土庄绣线菊水分生理、氮素利用以及形态特征的影响。具体对以下指标进行测定:叶片的气孔导度、碳同位素比率(δ13 C)、叶含水量、叶面积、水分利用效率(WUE)、叶全氮含量、叶氮素再吸收率。 实验结果表明,增强UV-B辐射显著减少了土庄绣线菊的叶面积(50.1%),提高了叶片全氮含量(102%),处理植株的氮素再吸收率比对照植株高出50.9%。同时,UV-B辐射还在一定程度上(尽管统计显示不显著)降低了气孔导度(16.1%)、胞间CO2浓度与大气CO2浓度之比(Ci/Ca) (4.0%)、提高了碳同位素比率(δ13 C)(20.5‰)、叶含水量(3.1%)及比叶重(SLW)(5.2%),从而导致水分利用效率(WUE)的增加(4.1%),植物的抗旱能力增强。值得注意的是,深层土壤(30-40cm)含水量变化会影响气孔导度、δ13 C、WUE对紫外辐射的响应程度:在土壤干旱的季节(6月和9月),气孔导度、δ13 C、WUE这些指标处理和对照的差异很小,但是当土壤水分充足时(7月和8月),处理和对照的差异就较为显著。另外,随着实验处理时间的延长UV-B的效应变得不显著。相关分析表明,UV-B辐射降低了土壤含水量(30-40cm)与土庄绣线菊叶含水量、δ13 C、Ci/Ca、气孔导度的相关系数,增强了WUE与土壤含水量的相关性,这也许是由于UV-B辐射增强了WUE对土壤水分变化的敏感性。本研究的结果表明UV-B辐射对土庄绣线菊的形态和生长有显著的影响,但对主要水分生理指标影响不显著。
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利用现代分子生物学和基因工程技术手段,克隆青蒿素生成途径的关键酶基因,研究关键酶基因对青蒿素生物合成的调控规律,是打破青蒿素生物合成的限速步骤,大幅度提高青蒿素含量,最终达到利用植物生物技术工业化生产青蒿素的目的必须解决的关键问题。本论文基于此目的,开展了青蒿素生物合成相关基因的分子克隆工作。 用RACE方法从青蒿高产株系001中克隆了一个新的1886bp的全长倍半萜合酶cDNA。克隆的倍半萜合酶氨基酸序列与烟草马兜铃烯合酶、莨菪岩兰螺旋二烯合酶、棉花杜松烯合酶的一致性分别为39%,38%和41%;与青蒿柏木脑合酶、紫穗槐二烯合酶和一个推测的倍半萜合酶克隆cASC125的一致性为50%,48%和59%。cDNA编码区序列被克隆进原核表达载体pET-30a,并在大肠杆菌BL21(DE3)中诱导表达,但过量表达的蛋白主要是以不溶性蛋白形式存在。RT-PCR分析表明此基因在茎、叶和花中表达,在根中没有表达。 用RT/PCR方法从青蒿高产株系001中克隆了amorpha-4, 11-diene合酶cDNA。将该cDNA插入原核表达载体pET3d并在大肠杆菌BL21(DE3)中过量表达。Southern blot分析表明AMS基因在青蒿基因组中至少有3个拷贝。AMS基因组DNA有一个复杂的结构,包含有7个外显子和6个内含子。RT/PCR分析表明AMS基因在叶片、茎和花中表达,而在根中没有表达。 用RACE方法首次从青蒿中克隆了一个1539 bp全长鲨烯合酶cDNA。青蒿鲨烯合酶氨基酸序列与拟南芥、烟草、人类、酵母鲨烯合酶的一致性分别为70%、77%、44%、39%。青蒿鲨烯合酶基因组DNA有一个复杂的结构,包括14个外显子和13个内含子。全长的或C末端截短的鲨烯合酶cDNA被克隆进原核表达载体pET30a并在大肠杆菌BL21(DE3)中诱导表达。但在含有全长的鲨烯合酶cDNA的大肠杆菌中并没有观察到预期大小的鲨烯合酶表达,而C末端截短30个疏水氨基酸的鲨烯合酶可在大肠杆菌中过量表达。
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在细菌视紫红质构象模拟的基础上提出了一个视黄醛顺反异构模型。该模型中视黄醛的C~(13)—C~(14)与Lys—216的C~(δ)—C~(ε) 处于一直线上, 这样, 顺反异构只涉及视黄醛C~(15)和Lys—216的N~(ζ)绕此直线为轴的旋转。理论计算表明, 这是一种空间障碍最小的模型, 并能通过Asp—96和Asp—212传递质子。图3表2参10
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This paper reports on seasonal changes in stable carbon and nitrogen isotope ratios of seston and muscle tissue of silver carp and bighead carp during 2004 and 2005, focusing primarily on the carbon sources and trophic relationships among phytoplankton, zooplankton and silver carp and bighead carp in a large fish pen of Meiliang Bay (Lake Taihu, China). delta C-13 showed a minimal value in March 2005 and a maximal value in August 2005 in seston both inside and outside the pen, whereas delta N-15 of seston showed the minimum in winter and the maximum during algal blooms. A positive correlation between delta C-13 of silver carp and that of seston suggested that temporal variation Of delta C-13 in seston was preserved in fish via the food chain. The differences of delta C-13 among seston, zooplankton and muscle tissue of silver carp and bighead carp ranged only 0.2-1.7%, indicating that plankton production was the primary food source of filter-feeding fishes. According to a mass balance model, we estimated that the contributions of zooplankton to the diets of silver carp and bighead carp were 45.7% and 54.3%, respectively, based on the delta N-15 values of zooplankton and planktivorous fishes. (C) 2007 Elsevier B.V. All rights reserved
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In Gonghu Bay of Lake Taihu, tissue of five mussel species showed delta C-13 values similar to or slightly below that of pelagic suspended particulate organic matter (SPOM). This indicated that mussels in this area either fed non-selectively and so reflected available carbon in the pelagic habitat or selected for phytoplankton. The situation was the same for Anodonta woodiana woodiana and Cristaria plicata in Meiliang Bay; however, for the remaining three species, Hyriopsis cumingii, Arconaia lanceolata, and Lamprotula rochechouarti, tissue had intermediate delta C-13 values, falling between those for pelagic SPOM and benthic sediment organic matter (SOM), suggesting a possible preferential selection of phytoplankton from the pelagic SPOM but more likely reflecting local differences in pelagic SPOM and benthic SOM composition and available organic carbon sources. The mixing model showed that pelagic SPOM accounted for over 98% of carbon incorporated by all mussels in Gonghu Bay and two mussels in Meiliang Bay, suggesting the dietary importance of pelagic food sources for mussels. Less than 50% of the assimilation in H. cumingii, A. lanceolata, and L. rochechouarti came from the pelagic carbon sources in Meiliang Bay, which suggested that these species consumed a mix of benthic and pelagic derived carbon sources.