Cytidylic acid "a" trihydrate: structure and conformation

Cytidylic acid "a" (cytidine 2'-monophosphate) crystallizes in the triclinic space group P1 with two molecules of cytidine monophosphate (C(9)H(14)O(8)N(3)P) and six molecules of water in the unit cell. X-ray analysis of this crystal shows that in both molecules, the base is in the anti conformation, the ribose ring is C(2')-endo puckered, and the hydroxyl O(5') is gauche-gauche. The two molecules are linked by a short hydrogen bond through the phosphate oxygens.     

C 2H 5N 4- C 6H 3N 3O-7氢键相互作用的理论研究

运用密度泛函理论方法,在B3LYP/6-311++G**水平上对4-氨基-1,2,4-三唑阳离子(AT)和2,4,6-三硝基苯酚阴离子(PA)形成的氢键二聚体进行理论计算研究.计算得到4种稳定结构的氢键复合物及最稳定异构体D1的振动频率、电子吸收光谱与热力学性质.结果表明,氢键复合物中存在较强的N—H…O与C—H…O红移氢键.经过基组重叠误差和零点振动能校正后,D1的氢键相互作用能为-30.71kJ/mol.热力学计算显示,在298.15K和标准状态下,D1气态氢键复合物分子的形成过程是放热、熵减小的非自发过程,但在低温下能自发进行.D1分子的标准摩尔生成焓和标准摩尔生成自由能分别为98.7,474.4kJ/mol.     

Water at hydrophobic surfaces: weak hydrogen bonding and strong orientation effects

Vibrational studies that selectively probe molecular structure at CCl4/H2O and hydrocarbon/H2O interfaces show that the hydrogen bonding between adjacent water molecules at these interfaces is weak, in contrast to generally accepted models of water next to fluid hydrophobic surfaces that suggest strong hydrogen bonding. However, interactions between these water molecules and the organic phase result in substantial orientation of these weakly hydrogen-bonded water molecules in the interfacial region. The results have important implications for understanding water adjacent to hydrophobic surfaces and the penetration of water into hydrophobic phases.     

Boron-Oxygen Polyanion in the Crystal Structure of Tunellite

The crystal structure of tunellite, SrO.3B(2)O(3).4H(2)O, with infinite sheets of composition n[B(6)O(9)(OH)(2)](2-), has cations and water molecules in the spaces within the sheets. Adjacent sheets are held together by hydrogen bonding through the water molecules. The boron-oxygen polyanions provide the first example in hydrated borate crystals of one oxygen linked to three borons.     

Isolating the spectroscopic signature of a hydration shell with the use of clusters: superoxide tetrahydrate

Cluster spectroscopy, aided by ab initio theory, was used to determine the detailed structure of a complete hydration shell around an anion. Infrared spectra of size-selected O(2)-. (H(2)O)(n) (n = 1 to 4) cluster ions were obtained by photoevaporation of an argon nanomatrix. Four water molecules are required to complete the coordination shell. The simple spectrum of the tetrahydrate reveals a structure in which each water molecule is engaged in a single hydrogen bond to one of the four lobes of the pi* orbital of the superoxide, whereas the water molecules bind together in pairs. This illustrates how water networks deform upon accommodating a solute ion to create a distinct supramolecular species.     

Direct Detection of C4H2 Photochemical Products: Possible Routes to Complex Hydrocarbons in Planetary Atmospheres

The photochemistry of diacetylene (C4H2), the largest hydrocarbon to be unambiguously identified in planetary atmospheres, is of considerable importance to understanding the mechanisms by which complex molecules are formed in the solar system. In this work, the primary products of C4H2's ultraviolet photochemistry were determined in a two-laser pump-probe scheme in which the products of C4H2 photoexcitation are detected by vacuum ultraviolet photoionization in a time-of-flight mass spectrometer. Three larger hydrocarbon primary products were observed with good yield in the C4H2* + C4H2 reaction: C6H2, C812, and C8H3. Neither C6H2 nor C8H3 is anticipated by current photochemical models of the atmospheres of Titan, Uranus, Neptune, Pluto, and Triton. The free hydrogen atoms that are released during the formation of the C8H3 and C8H2 products also may partially offset the role of C4H2 in catalysing the recombination of free hydrogen atoms in the planetary atmospheres.     

Apollo lunar module engine exhaust products

Organic combustion products generated by the lunar module descent engine, which burns a 1:1 mixture of unsymmetrical dimethylhydrazine fuel and nitrogen tetroxide oxidizer, have been analyzed. The major gaseous combustion products found were ammonia, water, carbon monoxide, nitrous oxide, oxygen, carbon dioxide, and nitric oxide. The minor products were acetylene, hydrogen cyanide, ethylene, formaldehyde, propadiene, ketene, cyanous acid, hydrazoic acid, various methylamines, acetaldehyde, methyl nitrite, formic acid, nitrous acid, butadiyne, nitrilohydrazines, nitromethane, and nitrosohydrazines with other oxidized derivatives of unsymmetrical dimethylhydrazine and hydrazine. The ion intensities of the various species in all mass spectra were estimated as the following concentrations: the gases (NH(3), H(2)O, CO, NO, O(2), CO(2), and NO(2)), 87.7 percent; compounds of C, H, and O, 6.0 percent; and compounds of C, H, and N (with traces of O), 5.8 percent.     

一维链状镍配合物[Ni（C_（14）H_（10）N_2O_2）（Mf）]_n的合成和晶体结构

合成了含水杨醛缩苯甲酰腙的一维链状镍配合物[Ni（C14H10N2O2）（Mf）]n（Mf=C4H9NO,即吗啡啉）,通过元素分析,红外、电子光谱和X-射线单晶衍射进行了表征.晶体属单斜晶系,空间群为P21/c,a=0.9708（4）nm,b=1.4783（7）nm,c=1.2275（4）nm,β=95.728（14）°,V=1.7528（12）nm3,Z=4,Mr=384.07,Dc=1.455 g.cm-3,μ=1.129 mm-1,F（000）=800,R=0.0759,wR=0.2155.中心镍离子与水杨醛缩苯甲酰腙配体提供的2个氧原子与1个氮原子以及1个配位吗啡啉的氮原子配位,形成了N2O2的平面四边形的配位构型.晶体内每个配合物分子通过分子间氢键与相邻另一个配合物分子缔合成一个沿c轴方向的一维链状结构,N…N氢键键长为0.3239（10）nm,N-H…N氢键键角为173.56°.     

Crystal structure of the 1: 1 complex of 5-fluorouracil and 9-ethylhypoxanthine

9-Ethylhypoxanthine and 5-fluorouracil form a 1 : 1 crystalline complex. The structure of this complex has been solved by x-ray diffraction analysis. The molecules crystallize in a monoclinic lattice and form a sheet structure in which pairs of fluorouracil molecules are held together by two hydrogen bonds. The 9-ethylhypoxanthine residues fill up the rest of the molecular sheet by forming single hydrogen bonds with each uracil pair.     

Infrared observations of the saturnian system from voyager 1

During the passage of Voyager 1 through the Saturn system, the infrared instrument acquired spectral and radiometric data on Saturn, the rings, and Titan and other satellites. Infrared spectra of Saturn indicate the presence of H(2), CH(4), NH(3), PH(3), C(2)H(2), C(2)H(6), and possibly C(3)H(4) and C(3)H(8). A hydrogen mole fraction of 0.94 is inferred with an uncertainty of a few percent, implying a depletion of helium in the atmosphere of Saturn relative to that of Jupiter. The atmospheric thermal structure of Saturn shows hemisphere asymmetries that are consistent with a response to the seasonally varying insolation. Extensive small-scale latitudinal structure is also observed. On Titan, positive identifications of infrared spectral features are made for CH(4), C(2)H(2), C(2)H(4), C(2)H(6), and HCN; tentative identifications are made for C(3)H(4) and C(3)H(8). The infrared continuum opacity on Titan appears to be quite small between 500 and 600 cm(-1), implying that the solid surface is a major contributor to the observed emission over this spectral range; between 500 and 200 cm(-1) theopacity increases with decreasing wave number, attaining an optical thickness in excess of 2 at 200 cm(-1). Temperatures near the 1-millibar level are independent of longitude and local time but show a decrease of approximately 20 K between the equator and north pole, which suggests a seasonally dependent cyclostrophic zonal flow in the stratosphere of approximately 100 meters per second. Measurements of the C ring of Saturn yield a temperature of 85 +/- 1 K and an infrared optical depth of 0.09 +/- 0.01. Radiometer observations of sunlight transmitted through the ring system indicate an optical depth of 10(-1.3 +/-0.3) for the Cassini division. A phase integral of 1.02 +/- 0.06 is inferred for Rhea, which agrees with values for other icy bodies in the solar system. Rhea eclipse observations indicate the presence of surface materials with both high and low thermal inertias, the former most likely a blocky component and the latter a frost.     

Hydrogen-Water Vapor Mixtures: Control of Hydrothermal Atmospheres by Hydrogen Osmosis

Experiments at 700 degrees C and 800 bars total pressure demonstrate positive deviations from ideality for mixtures of hydrogen and H(2)O gases. The deviations are greater than predicted with Stockmayer's method. The composition of the mixture and the fugacity of hydrogen are controlled by diffusing hydrogen through metallic membranes. The results give the fugacities of both H(2)O and oxygen.     

Parent volatiles in comet 9P/Tempel 1: before and after impact

We quantified eight parent volatiles (H2O, C2H6, HCN, CO, CH3OH, H2CO, C2H2, and CH4) in the Jupiter-family comet Tempel 1 using high-dispersion infrared spectroscopy in the wavelength range 2.8 to 5.0 micrometers. The abundance ratio for ethane was significantly higher after impact, whereas those for methanol and hydrogen cyanide were unchanged. The abundance ratios in the ejecta are similar to those for most Oort cloud comets, but methanol and acetylene are lower in Tempel 1 by a factor of about 2. These results suggest that the volatile ices in Tempel 1 and in most Oort cloud comets originated in a common region of the protoplanetary disk.     

Cytosine to thymine transitions from decay of cytosine-5-3H in bacteriophage S13

Decay of cytosine-5-(3)H incorporated into bacteriophage S13 DNA causes a molectular rearrangement of the cytosine molecutle undergoing the decay. The molecular rearrangement produces a cytosine to thyimine coding change with at efficiency approaching one. Decay of either thymidine-(methyl)-(3)H or cytosine-6-(3)H is less than 1 percent as effective in calusing either cytosine to thymine or thymine to cytosine transitions.     

A synthetic nickel electrocatalyst with a turnover frequency above 100,000 s⁻¹ for H₂ production

Reduction of acids to molecular hydrogen as a means of storing energy is catalyzed by platinum, but its low abundance and high cost are problematic. Precisely controlled delivery of protons is critical in hydrogenase enzymes in nature that catalyze hydrogen (H(2)) production using earth-abundant metals (iron and nickel). Here, we report that a synthetic nickel complex, [Ni(P(Ph)(2)N(Ph))(2)](BF(4))(2), (P(Ph)(2)N(Ph) = 1,3,6-triphenyl-1-aza-3,6-diphosphacycloheptane), catalyzes the production of H(2) using protonated dimethylformamide as the proton source, with turnover frequencies of 33,000 per second (s(-1)) in dry acetonitrile and 106,000 s(-1) in the presence of 1.2 M of water, at a potential of -1.13 volt (versus the ferrocenium/ferrocene couple). The mechanistic implications of these remarkably fast catalysts point to a key role of pendant amines that function as proton relays.     

Water-mediated proton hopping on an iron oxide surface

The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion.     

Identification of an H1N1 subtype of swine influenza virus and serological analysis

To investigate the epizootic of swine influenza virus(SIV), 60 nasal swabs were collected from a clinical cases of pig farm in Tai'an City, Shandong Province of China in April 2017. SIV was isolated by inoculating into 10-day-old Special Pathogen Free embryonated eggs and the whole genome was sequenced. An H1N1 subtype SIV was isolated and designated as A/swine/Shandong/TA04/2017(H1N1). Phylogenetic analysis showed that apart from the polymerase A(PA) fragment belonging to the 2009 pandemic H1N1 branch, seven genome segments belonged to avian-like H1N1 influenza virus lineage. The cleavage site sequence of the hemagglutinin(HA) protein was PSIQSR↓G, which is a typical molecular biological characteristic. Five potential N-glycosylation sites(N14, N26, N277, N484 and N543) were found in the HA gene. To further investigate the epidemiology of SIV in this farm, the 995 serum samples were assessed with EAH1N1 2009 pandemic H1N1 and H3 N2 antigens. The results showed that the total positive rate was 65.43%. The positive rates of single virus infection detected by EAH1N1, 2009 pdmH1N1 and H3 N2 for serum HI(Hemagglutination inhibition) were 48.35, 30.85 and 7.47%, respectively. The results showed that SIV in Shandong Province has been reassorted in some segments and the SIV-positive rate was high on the SIV outbreak farm. These data provide evidence of an epizootic of SIV.     

Free Radicals and Reactive Molecules in Clathrate Cavities

Reactive molecules and free radicals, when located in the cavities of the water clathrate lattice, can be prevented from recombining at temperatures almost up to the decomposition point of the lattice. The active species are produced by selective photochemical dissociation of the guest molecules in the clathrate compounds. Data taken from water clathrates of H(2)S, CH(3)SH, and C(2)H(5)SH suggest that S(2), CH(3)S and C(2)H(5)S can be preserved in this way.     

不同H9N2亚型鸭流感病毒NS1基因克隆和功能进化分析

禽流感病毒（AIV）在高免疫压力情况下会发生变异而逃避免疫系统的监视。其NS1蛋白共有230个氨基酸,其中前73个氨基酸残基以二聚体形式存在,包含了所有RNA的结合活性。NS1的氨基端1—73位是mRNA的结合区,氨基端1—100位是双股RNA依赖性蛋白激酶（PKR）的结合区。PKR抗病毒作用机制如下：病毒侵染宿主细胞时,在宿主干扰素的诱导下,双股RNA与PKR结合,同时真核翻译启动子α亚单位发生磷酸化,导致PKR的激活。激活的PKR能同时抑制宿主细胞和病毒mRNA的翻译,从而最终抑制入侵病毒在细胞中的有效繁殖和扩散。     

Catalytic reduction of dinitrogen to ammonia at a single molybdenum center

Dinitrogen (N2) was reduced to ammonia at room temperature and 1 atmosphere with molybdenum catalysts that contain tetradentate [HIPTN3N]3- triamidoamine ligands (such as [HIPTN3N]Mo(N2), where [HIPTN3N]3- is [(3,5-(2,4,6-i-Pr3C6H2)2C6H3NCH2CH2)3N]3-) in heptane. Slow addition of the proton source [(2,6-lutidinium)(BAr'4), where Ar' is 3,5-(CF3)2C6H3]and reductant (decamethyl chromocene) was critical for achieving high efficiency ( approximately 66% in four turnovers). Numerous x-ray studies, along with isolation and characterization of six proposed intermediates in the catalytic reaction under noncatalytic conditions, suggest that N2 was reduced at a sterically protected, single molybdenum center that cycled from Mo(III) through Mo(VI) states.     

不同碳氮比物料有机肥中腐殖酸含量、 化学组成与结构特征研究

采用重铬酸钾容量法、元素分析、傅立叶变换红外光谱和固体¹³C核磁共振技术对不同碳氮比物料有机肥中腐殖酸含量、化学组成和结构特征进行了初步研究。结果表明,4种不同碳氮比物料配方有机肥中腐殖酸主要为游离腐殖酸,占98%以上;随着碳氮比提高,总腐殖酸和游离腐殖酸含量增加,水溶性腐殖酸降低,但碳氮比25～30:1之间差异很小。4种有机肥腐殖酸主要由C、H、O、N等元素组成;其结构都主要由脂肪碳、含氧脂肪碳、芳香碳和羧基碳、羰基碳等组成。不同碳氮比物料配方有机肥中腐殖酸在官能团上存在差别,20:1有机肥中碳水化合物（或多糖）和羧酸等含氧基团要明显多于其他比例有机肥。