桉树杂交种与其亲本的近红外光谱判别

研究桉树控制授粉后目标性状的基因作用方式是探索其基因重组规律的重要内容。常规的数量统计分析精度往往不高,而DNA分析的专业要求高,且费时费力。该研究利用近红外光谱(NIRs)研究不同基因型桉树杂交种、亲本及杂交种与亲本间近红外光谱信息的关系,探索NIRs用于桉树杂交种与其亲本判别的可行性和准确性。以控制授粉的桉树亲本及其杂交F1代材料为对象,每种基因型从各自田间试验分别选取10个单株,采集树冠中上部新鲜健康叶片。用手持式近红外仪Phazir Rx(1624)采集桉树杂交种与其亲本叶片的NIRs信息。每单株选10片完全生理成熟的健康叶片,避开叶脉扫描其正面光谱5次,以50条NIRs信息的均值代表单个叶片的NIRs信息,最终每个基因型获得10条NIRs信息。对原始NIRs采用二阶多项式S.G一阶导数预处理。预处理后的NIRs用于多元统计分析,首先对桉树杂交亲本和子代样本进行主成分分析(PCA),直观展示不同基因型的分类情况。然后运用簇类独立软模式(SIMCA)和偏最小二乘判别分析(PLS-DA)两种有监督的判别模式验证NIRs用于桉树杂交种与其亲本树种的分类判别效果。PCA结果显示,不同的亲本间、杂交种间及杂交种与亲本间样本的主因子得分可以清晰地将各基因型分开。SIMCA模式判别分析中,桉树杂交种样本到亲本PCA模型的样本距离显示,待判别样本能够形成单独的聚类,且能直观反映两者的遗传相似。PLS-DA判别结果显示,桉树杂交亲本的PLS模型能通过预测其杂交子代的响应变量将其与亲本准确分开。结果表明,桉树叶片的NIRs信息可以准确地反映桉树杂交子代遗传信息的传递规律,NIRs判别模型可以准确地将各种基因型予以区分。因此,NIRs信息不仅可用于桉树杂交种和纯种的定性判别,还可以分析桉树基因重组过程中加性遗传效应的大小,从而为桉树遗传基础分析及其育种改良研究提供理论支撑。     

TDPAC and first-principles study of electronic and structural properties of a Pd-vacancy complex in undoped germanium

Pd is one of the metals suitable for inducing low-temperature crystallization in Ge. However, it is not clear how residual Pd atoms are integrated into the Ge lattice. Therefore, time-differential γ–γ perturbed angular correlations (TDPAC) technique using the ¹⁰⁰Pd(→¹⁰⁰Rh) nuclear probe produced by recoil implantation has been applied to study the hyperfine interactions of this probe in single-crystalline undoped Ge. A Pd-vacancy complex aligned along the <111> crystallographic direction with a unique interaction frequency of 8.4(5) Mrad/s has been identified. This complex was measured to have a maximum relative fraction of about 76(4)% following annealing at 350 ^°C. Further annealing at higher temperatures reduced this fraction, possibly via dissociation of the complex. Calculations suggest dissociation energy of 1.94(5) eV for the complex. DFT calculations performed in this work are in reasonable good agreement with the experimental values for the electric-field gradient of the defect complex in Ge and Si for comparison. The calculations predict a split-vacancy configuration with the Pd on a bond-centred interstitial site having a nearest-neighbour semi-vacancy on both sides (V-Pd_BI-V) in Ge and Si.     

The mechanism of ethylene polymerization by nickel salicylaldiminato catalysts - Agostic interactions and their kinetic isotope effects

The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (k_H/k_D = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active.     

铁分子Fe2的自旋极化效应

采用密度泛函方法(B3P86)对 Fe_2分子结构进行了优化.计算结果中未观察到自旋污染,基态波函数与高态波函数并未混杂,结果表明,Fe_2中有8个未配对电子,这些电子空间分布不同和自旋平行产生的自旋极化效应,使 Fe_2能量最低.计算结果表明,Fe_2分子的基态是~9∑_g~ ,并非~7Δ_u,进而表明 Fe_2的自旋平行效应比电子自旋配对效应要强.计算得到该分子基态的二阶、三阶和四阶力常数分别为1.4115×10~(-2)aJ/nm~2、-37.1751×10~3aJ/nm~3和 98.7596×10~4aJ/nm~4；光谱数据ω_eχ_e、B_e、α_e分别为0.3522、0.0345、 0.4963×10~(-4)cm~(-1)；离解能为3.5522eV,平衡键长为0.2137nm,振动频率为292.914cm~(-1)；并得到了 Murrel-Sorbie 函数.     

一类积分不等式的推广

对一些基本的积分不等式进行了推广，给出了含有n个无关变元的更广泛的非线性积分不等式．利用所得的不等式讨论了某些非线性积分方程解的有界性．     

CONVERGENCE OF CASCADE ALGORITHMS AND SMOOTHNESS OF REFINABLE DISTRIBUTIONS

In this paper, the author at first develops a method to study convergence of the cascade algorithm in a Banach space without stable assumption on the initial (see Theorem 2.1), and then applies the previous result on the convergence to characterizing compactly supported refinable distributions in fractional Sobolev spaces and Holder continuous spaces (see Theorems 3.1, 3.3, and 3.4). Finally the author applies the above characterization to choosing appropriate initial to guarantee the convergence of the cascade algorithm (see Theorem 4.2).     

Smoothing estimation of rate function for recurrent event data with informative censoring

This paper proposes kernel estimation of the occurrence rate function for recurrent event data with informative censoring. An informative censoring model is considered with assumptions made on the joint distribution of the recurrent event process and the censoring time without modeling the censoring distribution. Under the validity of the informative censoring model, we also show that an estimator based on the assumption of independent censoring becomes inappropriate and is generally asymptotically biased. To investigate the asymptotic properties of the proposed estimator, the explicit form of its asymptotic mean squared risk and the asymptotic normality are derived. Meanwhile, the empirical consistent smoothing estimator for the variance function of the estimator is suggested. The performance of the estimators are also studied through Monte Carlo simulations. An epidemiological example of intravenous drug user data is used to show the influence of informative censoring in the estimation of the occurrence rate functions for inpatient cares over time.     

氟代吡啶阳离子的理论研究

利用量子化学密度泛函理论B3LYP方法及 6 31G(d ,p)、6 311G(d ,p)、6 31+G(d ,p)和 6 311+G(d ,p)基组对五氟代吡啶、2 ,6 二氟代吡啶和 2 氟代吡啶分子的阳离子进行了计算研究 .B3LYP构型优化和频率分析计算结果表明这三种氟代吡啶阳离子的结构分别具有C2v、C2v和Cs 对称性 ,电子基态分别为2 A2 、2 A2 和2 A″ .对离子和分子的计算构型做了比较 .利用B3LYP方法和不同的基组对这三种阳离子及其分子进行了自然布居分析计算 .用B3LYP方法对这三种阳离子 (自由基 )中的超精细结构进行了计算 ,对五氟代吡啶、2 ,6 二氟代吡啶和2 氟代吡啶分子的垂直电离势和绝热电离势进行了计算 ,与实验值符合得很好     

Local adsorption sites and bondlength changes in Ni(1 0 0)/H/CO and Ni(1 0 0)/CO

The local adsorption geometry of CO adsorbed in different states on Ni(1 0 0) and on Ni(1 0 0) precovered with atomic hydrogen has been determined by C 1s (and O 1s) scanned-energy mode photoelectron diffraction, using the photoelectron binding energy changes to characterise the different states. The results confirm previous spectroscopic assignments of local atop and bridge sites both with and without coadsorbed hydrogen. The measured Ni–C bondlengths for the Ni(1 0 0)/CO states show an increase of 0.16 ± 0.04 Å in going from atop to bridge sites, while comparison with similar results for Ni(1 1 1)/CO for threefold coordinated adsorption sites show a further lengthening of the bond by 0.05 ± 0.04 Å. These changes in the Ni–CO chemisorption bondlength with bond order (for approximately constant adsorption energy) are consistent with the standard Pauling rules. However, comparison of CO adsorbed in the atop geometry with and without coadsorbed hydrogen shows that the coadsorption increases the Ni–C bondlength by only 0.06 ± 0.04 Å, despite the decrease in adsorption energy of a factor of 2 or more. This result is also reproduced by density functional theory slab calculations. The results of both the experiments and the density functional theory calculations show that CO adsorption onto the Ni(1 0 0)/H surface is accompanied by significant structural modification; the low desorption energy may then be attributed to the energy cost of this restructuring rather than weak local bonding.     

Space time-index plots for probing dynamical nonstationarity

We propose a simple method to efficiently probe dynamical nonstationarity in observed time series. In a space time-index plot, the density distributions as a function of normalized time-index are V-shaped due to nonstationarity. We show that this method is workable for short data sets and typical examples are illustrated.