Deuterated methane observed on saturn

Absorptions for the V(2) band of deuterated methane (CH(3)D) have been observed in the 5-micron spectrum of Saturn, obtained with a Fourier transform spectrometer. Analysis of the band yields a CH(3)D abundance of 2.6 +/- 0.8 centimeter-amagat and a temperature of 175 +/- 30 K for the mean level of spectroscopic line formation. This temperature indicates that a substantial portion of Saturn's flux at 5 microns is due to thermal radiation, and that we are therefore looking fairly deep into its atmosphere, as is the case for the Jupiter 5-micron window. This CH(3)D abundance leads to a deuteriumlhydrogen ratio of about 2 x 10(-5) in Saturn's atmosphere. This ratio is much lower than the terrestrial value but comparable to that determined for Jupiter and may be taken as representative of the deuteriumlhydrogen ratio in the solar system at the time of its formation.     

Large first hyperpolarizabilities in push-pull polyenes by tuning of the bond length alternation and aromaticity

Conjugated organic compounds with 3-phenyl-5-isoxazolone or N,N'-diethylthiobarbituric acid acceptors have large first molecular hyperpolarizabilities (beta) in comparison with compounds with 4-nitrophenyl acceptors. For example, julolidinyl-(CH=CH)(3)-CH=N,N'- diethylthiobarbituric acid, which has 12 atoms between the donor and acceptor, has a beta(0) of 911 x 10(-30) electrostatic units, whereas (CH(3))(2)NC(6)H(4),-(CH=CH)(4)-C(6)H(4)NO(2), with 16 atoms between its donor and acceptor, has a beta(0) of 133 x 10(-30) electrostatic units. The design strategies demonstrated here have resulted in chromophores that when incorporated into poled-polymer electrooptic modulators exhibited significant enhancements in electrooptic coefficients relative to polymers containing the commonly used dye Disperse Red-1. Poled polymer devices based on these or related chromophores may ultimately lead to high-speed electrooptic switching elements with low drive-power requirements, suitable for telecommunications applications.     

Selective bond dissociation and rearrangement with optimally tailored, strong-field laser pulses

We used strong-field laser pulses that were tailored with closed-loop optimal control to govern specified chemical dissociation and reactivity channels in a series of organic molecules. Selective cleavage and rearrangement of chemical bonds having dissociation energies up to approximately 100 kilocalories per mole (about 4 electron volts) are reported for polyatomic molecules, including (CH3)2CO (acetone), CH3COCF3 (trifluoroacetone), and C6H5COCH3 (acetophenone). Control over the formation of CH(3)CO from (CH3)2CO, CF3 (or CH3) from CH3COCF3, and C6H5CH3 (toluene) from C6H5COCH3 was observed with high selectivity. Strong-field control appears to have generic applicability for manipulating molecular reactivity because the tailored intense laser fields (about 10(13) watts per square centimeter) can dynamically Stark shift many excited states into resonance, and consequently, the method is not confined by resonant spectral restrictions found in the perturbative (weak-field) regime.     

Metal oxide chemistry in solution: the early transition metal polyoxoanions

Many of the early transition elements form large polynuclear metal-oxygen anions containing up to 200 atoms or more. Although these polyoxoanions have been investigated for more than a century, detailed studies of structure and reactivity were not possible until the development of modern x-ray crystallographic and nuclear magnetic resonance spectroscopic techniques. Systematic studies of small polyoxoanions in inert, aprotic solvents have clarified many of the principles governing their structure and reactivity, and also have made possible the preparation of entirely new types of covalent derivatives such as CH(2)Mo(4)O(15)H(3-), C(5)H(5)TiMo(5)O(18)(3-), and (OC)(3)Mn(Nb(2)W(4)O(19))(3-). Since most early transition metal polyoxoanions have structures based on close-packed oxygen arrays containing interstitial metal centers, their chemistry offers a rare opportunity to study chemical transformations in detail on well-defined metal oxide surfaces.     

Molecular structure of an unusual organoactinide hydride complex determined solely by neutron diffraction

The structure of an unusual organometallic complex, {Th[(CH(3))(5)C(5)](2) H(micro-H)}(2) . C(6)H(5)CH(3), has been determined from neutron diffraction data, using only the direct-methods program MULTAN. Besides providing accurate metrical information on the first organometallic actinide hydride complex, these results have general and far-reaching implications concerning the complexity and size of crystal structures that can be elucidated solely on the basis of neutron diffraction data.     

Dianion Stabilization by (M(C5(CH3)5)2)+: Theoretical Evidence for a Localized Ring in (DDQ)2-

Organic dianions have been stabilized by (M(C(5)(CH(3))(5))(2))(+), where M is iron or cobalt. This has allowed the structural and spectroscopic characterization of these dianions. The structure of (M(C(5)(CH(3))(5))(2))(2)(+) (DDQ)(2-), where DDQ is 2,3-dichloro-5,6-dicyanobenzoquinone, has been determined by x-ray crystallography. The structure of (DDQ)(2-)is consistent with ab initio molecular orbital calculations that suggest a localizd as opposed to a delocalized (aromatic) ring structure.     

秦岭火地塘林区不同海拔不同林型土壤CO_2、CH_4、N_2O通量研究

二氧化碳(CO_2)、甲烷(CH_4)、氧化亚氮(N_2O)是3种主要的温室气体,温带森林土壤是CO_2、N_2O重要的源,是CH_4重要的汇,以前的研究大部分都关注这3种温室气体在时间上的变化,而很少开展在空间变化上的研究。2014年10月至2015年10月,采用静态箱-气相色谱法对秦岭南坡火地塘林区不同海拔(海拔1 560、1 585、1 963、2 040、2 160m,分别为落叶阔叶林、温性针叶林、温性针叶林、寒温性针叶林、落叶阔叶林)森林土壤CO_2、CH_4和N_2O通量进行了为期1a的监测。结果表明,CO_2全年都为排放,季节波动较大,总体上随海拔增加排放量减少,海拔由低到高(包括3种林型)年排放量依次为:19.12、12.53、11.78、16.95、14.87t·hm^-2;CH_4全年主要为吸收,在非生长季出现排放,季节波动幅度较大,总体上随海拔增加吸收量增加,海拔由低到高年通量依次为:-2.57、-3.60、-5.94、-5.59、-3.92kg·hm^-2;N_2O全年以排放过程为主,存在吸收现象,季节波动幅度不大,海拔对其通量影响不明显,海拔由低到高年排放量依次为:0.23、0.62、0.63、0.60、0.95kg·hm^-2。土壤温度是影响CO_2、N_2O通量的关键因子。5个样地森林土壤CO_2通量与土壤铵态氮含量(20～40cm)显著相关(P<0.05)。高的土壤NH_4^+含量对CH_4的吸收有抑制作用。在冻融交替期,降雨对N_2O的通量有明显影响。海拔由低到高5个样地的GWP(全球增温潜势)分别为:119.13、12.65、11.85、17.02t·hm^-2和15.07t·hm^-2。     

黄瓜雌性系的育种利用

以英国温室黄瓜Saladqueen和Pandex为原始材料选育黄瓜雌性系 ,经 3代选择得到雄花节位率为 5 %的雌性系 ;GA3 和AgNO3 均有诱雄效果 ,从对黄瓜植株生长的影响考虑 ,以 30 0mg/kgAgNO3 为好 ;以从Saladqueen中选育的雌性系为母本、自交系CH为父本配制的杂种一代“山农 1号”具有强雌性、早熟性和高产性。     

Dynamics of Carbonium Ions Solvated by Molecular Hydrogen: CH5+(H2)n (n = 1, 2, 3)

The dynamics of the carbonium ion (CH(5)(+)), a highly reactive intermediate with no equilibrium structure, was studied by measuring the infrared spectra for internally cold CH(5)(+)(H(2))n(n = 1, 2, 3) stored in an ion trap. First-principle molecular dynamics methods were used to directly simulate the internal motion for these ionic complexes. The combined experimental and theoretical efforts substantiated the anticipated scrambling motion in the CH(5)(+) core and revealed the effect of the solvent molecular hydrogen in slowing down the scrambling. The results indicate the feasibility of using solvent molecules to stabilize the floppy CH(5)(+) ion in order to make it amenable to spectroscopic study.     

新型酯化反应催化剂在“文献实验”中的尝试与应用

介绍了有机化学实验课中的"文献实验"应用"用固体(超强)酸作催化剂合成脂肪族羧酸酯"的实验方法,其目的在于弥补"验证性实验"乙酸乙酯合成中综合训练的不足,提高实验教学的综合性和创新性。     

Silver-catalyzed C-C bond formation between methane and ethyl diazoacetate in supercritical CO₂

Even in the context of hydrocarbons' general resistance to selective functionalization, methane's volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH(4)) with ethyl diazoacetate (N(2)CHCO(2)Et) to yield ethyl propionate (CH(3)CH(2)CO(2)Et). The use of supercritical carbon dioxide (scCO(2)) as the solvent is key to the reaction's success. Although the catalyst is only sparingly soluble in CH(4)/CO(2) mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.     

Understanding the infrared spectrum of bare CH5+

Protonated methane, CH5+, continues to elude definitive structural assignment, as large-amplitude vibrations and hydrogen scrambling challenge both theory and experiment. Here, the infrared spectrum of bare CH5+ is presented, as detected by reaction with carbon dioxide gas after resonant excitation by the free electron laser at the FELIX facility in the Netherlands. Comparison of the experimental spectrum at approximately 110 kelvin to finite-temperature infrared spectra, calculated by ab initio molecular dynamics, supports fluxionality of bare CH5+ under experimental conditions and provides a dynamical mechanism for exchange of hydrogens between CH3 tripod positions and the three-center bonded H2 moiety, which eventually leads to full hydrogen scrambling. The possibility of artificially freezing out scrambling and internal rotation in the simulations allowed assignment of the infrared spectrum despite this pronounced fluxionality.     

加工番茄叶绿素密度与高光谱数据的相关分析

[目的]分析加工番茄高光谱数据与叶绿素密度的相关关系,为加工番茄生育期生长状况的实时、无损、快速的遥感监测提供理论依据.[方法]通过非成像ASD地物光谱仪获取加工番茄两个品种四个氮素水平冠层关键生育时期的反射光谱,与其相应的冠层叶绿素密度(CH.D)进行逐步回归相关分析.加工番茄冠层CH.D分别在其近红外反射光谱757 nm波段处和红光677 nm波段处的相关系数达最大值(rp757 -CH.D=0.7521**,rp677 -CH.D=-0.8437**,n=44,α=1;);采用这两个波段的反射率分别组成了归一化植被指数(NDVI)和比值植被指数(RVI),建立与加工番茄CH.D的5种线性和非线性的相关模型.[结果]NDⅥ和RVI所构建的加工番茄CH.D的双曲线函数模型的相关性和精度最高,再采用这两个植被指数的双曲线函数模型分别对加工番茄CH.D进行估算,它们的实测CH.D与估测CH.D的相关性均达到极显著检验水平(r实测CH.D-NDVI估测的CH.D -NDVI=0.8041**,r实测CH.D-RVI估测CH.D- RVI=0.8094**,n=44,α=1;),估算精度均为86.6;.[结论]利用高光谱植被指数可以精确提取加工番茄冠层叶绿素密度信息并对其进行遥感估算研究.     

植物根围促生细菌（PGPR）的分离筛选及对黄瓜土传病害的防治

为获取防治黄瓜土传病害的植物根围促生菌(PGPR)并明确其防效,采用促生筛选法与大田小区试验法,对黄瓜根围的促生细菌进行了筛选并对其田间防效进行了研究。结果表明,通过盆栽测定结合平皿初筛,筛选到的三株PGPR菌株,CH1,CH2和CH3都能显著地促进黄瓜生长。此外,离体拮抗试验发现,CH1和CH2对黄瓜枯萎病菌都有拮抗作用,而对瓜果腐霉均无拮抗作用,CH3对两种病原菌都有拮抗作用。盆栽防病效果测定,证实了这三株PGPR对黄瓜枯萎病和猝倒病都有较好的防治效果,田间试验进一步验证了其防效,并且发现PGPR间的亲和与非亲和性组合的促生与防病效果都显著好于单株的。这些试验结果为三株PGPRs的进一步研究和产业化奠定了坚实的基础。     

Simplex optimization of reaction yields

The sequential simplex algorithm, an efficient optimization strategy, rapidly improved reaction yield as a function of time and temperature in the synthesis of pi-C(5)H(5)Mo(CO)(2)CSN(CH(3))(2). The work demonstrates the feasibility and efficiency of the simplex design and suggests its application and usefulness in other syntheses.     

Synthesis of inorganic fullerene-like molecules

The reaction of [Cp*Fe(eta5-P5)] with Cu(I)Cl in solvent mixtures of CH2Cl2/CH3CN leads to the formation of entirely inorganic fullerene-like molecules of the formula [[Cp*Fe(eta5:eta1:eta1:eta1:eta1:eta1-P5)]12[CuCl]10[Cu2Cl3]5[Cu(CH3CN)2]5] (1) possessing 90 inorganic core atoms. This compound represents a structural motif similar to that of C60: cyclo-P5 rings of [Cp*Fe(eta5-P5)] molecules are surrounded by six-membered P4Cu2 rings that result from the coordination of each of the phosphorus lone pairs to CuCl metal centers, which are further coordinated by P atoms of other cyclo-P5 rings. Thus, five- and six-membered rings alternate in a manner comparable to that observed in the fullerene molecules. The so-formed half shells are joined by [Cu2Cl3]- as well as by [Cu(CH3CN)2]+ units. The spherical body has an inside diameter of 1.25 nanometers and an outside diameter of 2.13 nanometers, which is about three times as large as that of C60.     

A Molecular Ferromagnet with a Curie Temperature of 6.2 Kelvin: [Mn(C5(CH3)5)2]+[TCNQ]-

The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.     

DNA sequences mediating class switching in alpha-immunoglobulins

Immunoglobulin class switching involves specific DNA rearrangements of the gene segments coding for heavy chain constant regions (CH) during B lymphocyte differentiation. In two different cases of C mu to C alpha switching examined here (T15 and M603) and one taken from the literature (MC101), three different sites on the 5' side of C mu and three different sites on the 5' side of C alpha are joined together in the process of CH switching. The sequences surrounding the three germ-line C alpha sites of recombination are highly conserved blocks of 30 nucleotides that may serve as recognition sequences for CH switching to the C alpha gene. This putative recognition sequence is repeated 17 times in approximately 1400 nucleotides of the germ-line Calpha 5' flanking sequence. The lack of homology between this C alpha sequence and sequences reported for the C gamma 1 and C gamma 2b switch sites suggests that heavy chain switching is mediated by class-specific recognition sequences and, presumably, class-specific regulatory mechanisms. In addition, it appears that in one example (MC101) CH switching progressed from C mu to C alpha to C gamma 1. This switching pathway may present difficulties for the simple deletional model of CH switching.     

Radical reactions of c60

Photochemically generated benzyl radicals react with C(60) producing radical and nonradical adducts Rn C(60) (R = C(6)H(5)CH(2)) with n = 1 to at least 15. The radical adducts with n = 3 and 5 are stable above 50 degrees C and have been identified by electron spin resonance (ESR) spectroscopy as the allylic R(3)C(60)(.) (3) and cyclopentadienyl R(5)C(60)(.) (5) radicals. The unpaired electrons are highly localized on the C(60) surface. The extraordinary stability of these radicals can be attributed to the steric protection of the surface radical sites by the surrounding benzyl substituents. Photochemically generated methyl radicals also add readily to C(60). Mass spectrometric analyses show the formation of (CH(3))nC(60) with n = 1 to at least 34.     

黔花4号小麦及其衍生品系抗白粉病性的遗传特性

黔花４号小麦对白粉菌４１１菌株的抗性遗传研究表明，以感病品种１４２６为杂交亲本时，其抗白粉性受１对显性基因控制，而以感亲绵阳１５号或友谊麦杂交时，其抗性表现则受２对显笥基因控制。在黔花４号×１４２６的高代衍生品系中，ＣＨ２４８和ＣＨ２６４品系为１对显性基因控制抗性，而ＣＨ３３和ＣＨ２７０则为２对基因控制。本文还讨论了不同遗传背景下和同一组合不同品系间所携基因不同的可能原因。