Molecular Dynamics Simulation Studies of Zeolite-A. IV. Structure and Dynamics of NH4 + ions in a Rigid Dehydrated Zeolite-A

Abstract

In recent papers [1–3] we reported molecular dynamics simulation studies of ions and water molecules adsorbed in a rigid zeolite-A framework using a simple Lennard-Jones potential plus Coulomb potential with Ewald summation to investigate the structure and dynamics of the adsorbates. In the present paper the same technique is applied to study the local structure and dynamics of NH₄ ⁺ ions in a rigid dehydrated zeolite-A. During the preliminary equilibration, the unstable NH₄(4) type ion (the 12th ion) is pushed down to near a more stable 6-ring position in the α-cage that is already associated with an NH₄(1) type ion (the 1st) in the β-cage, which moves to another 6-ring position in the β-cage that is already associated with an NH₄(2) type ion (the 7th) in the α-cage. Calculated x, y, and z coordinates of some NH₄ ⁺ ions are in good agreement with those obtained from an X-ray diffraction experiment except that no NH₄(4) type ion is found and there are six NH₄(2) type ions instead of 0.5 and 5.5 occupancy. The analyses of calculated interatomic distances and time correlation functions of these ions indicate that the NH₄(1 – 1) and NH₄(3) type ions are associated loosely with only one O (3) atom of the 6-ring and with only one O (1) atom of the 8-ring windows, respectively, while the NH₄(1–2) and NH₄(2) type ions are associated strongly with two or three O (3) atoms of the 6-ring windows in the α- and β-cages, respectively. The analysis of hydrogen bond time correlation functions of these ions indicate that about one, two or three, three, and one hydrogen bond of each NH₄(1–1), NH₄(1–2), NH₄(2) and NH₄(3) type ion is kept for 1.4, 21, 75, and 1.4 ps, respectively, before breakup of the hydrogen bond occurs and significant exchange of O atom hydrogen-bonded to the ion.     

Spectral Estimation by Variable Span Log Periodogram Smoothing: An Application to Annual Lynx Numbers

Spectral estimation is commonly based on smoothing the periodogram or its logarithm. In such a smoothing exercise, it is not entirely sensible to use the same bandwidth for all frequencies, since the smoothness of the underlying spectrum may vary. This note describes the use of a variable span smoother in estimating the log spectrum. An application to annual lynx data is presented.     

Application of Multiple Test Procedures to the Combination of Multivariate and Univariate Tests with Varying Variable Sets

The positive ascertainment of location differences in a multivariate comparison of two or more groups gives rise to the question for the contribution of the single variables or of subsets of variables to the multivariate difference. In this paper two methods are proposed to accomplish the original multivariate test by tests in variable subsets or in single variables using a closed test procedure and Holm's procedure, respectively. Both control the multiple level of the whole procedure.     

A tailed primers protocol to identify the association of eNOS gene variable number of tandem repeats polymorphism with ischemic stroke in Chinese Han population by capillary electrophoresis

Endothelial nitric oxide synthase (eNOS) plays an important role in mediating endothelium-dependent vasodilatation and antithrombotic action and is thus involved in the development of ischemic stroke (IS). Controversial results regarding the association of eNOS gene variable number of tandem repeats (VNTR) polymorphism with IS have been reported by conventional PCR-polyacrylamide gel electrophoresis methods. We aimed to identify any common association of eNOS gene VNTR polymorphism with IS in Chinese Han population by capillary electrophoresis (CE). The VNTR polymorphism of 27 bp within the eNOS intron-4 was determined by CE with specially designed tailed primers in Chinese Han patients with IS (n = 457) and matched elderly controls without IS (n = 457). Significant differences in BMI, WHR, hypertension, diabetes, smoking, TG, HDL, LDL, LDL, and FBG were observed between cases and controls. The distributions of eNOS VNTR polymorphism were not significantly associated with IS after adjustment for cardiovascular risk factors (OR = 1.18, 95% CI: 0.82–1.69). This finding was consistent with the further meta-analysis in Asians. The meta-analysis in Americans demonstrated that 4a/4b + 4a/4a genotype was significantly associated with IS risk with an OR of 1.54 (95% CI, 1.09–2.17) compared with the 4b/4b genotype. Our data suggests that BMI, WHR, hypertension, diabetes, smoking, TG, LDL, and FBG may increase the risk of IS. However, eNOS VNTR polymorphism may be not an independent major contributor for IS in Chinese Han population. The VNTR polymorphism might be associated with IS in Americans based on meta-analysis.     

Fixed and random effects selection in linear and logistic models

We address the problem of selecting which variables should be included in the fixed and random components of logistic mixed effects models for correlated data. A fully Bayesian variable selection is implemented using a stochastic search Gibbs sampler to estimate the exact model-averaged posterior distribution. This approach automatically identifies subsets of predictors having nonzero fixed effect coefficients or nonzero random effects variance, while allowing uncertainty in the model selection process. Default priors are proposed for the variance components and an efficient parameter expansion Gibbs sampler is developed for posterior computation. The approach is illustrated using simulated data and an epidemiologic example.     

Mg2+ Induced Fluorescence Change in Relation to Thylakoid Surface Electric Charge in Two Varieties of Soybean Chloroplasts

The effects of Mg2+ concentration on chlorophyll a light-in-duced variable fluorescence and eleetrophoretie velocity of chloroplasts obtained from two varieties of soybean (Ji-Pei No. 1 and Feng-Shou Yellow) were recorded. The light induced variable fluorescence yield and the eleetrophoretie mobility of two kinds of ehloroplasts in the suspending medium containing low level of salt differs from each other. But, the fluorescence yield of chloroplast membranes from two varieties of soybean is relative to that of eleetrophoretic mobility. The pattern of kinetic change of Mg2+ induced variable fluorescence intensity is similar to that of eleetrophoretie mobility. The optimum concentrations of Mg2+ required for the effect on chlorophyll fluorescence and the electrophoretie velocity change are also similar These results indicate that Mg2+ induced excitation energy distribution change between the two photosystems is intimately related to Mg2+-indueed alteration of thylakoil membrane surface eleetrostat.ie property. The possible role of earboxyl group of proteins on Mg2+ induced effects has been discussed in this paper.     

松嫩退化草地芦苇不同叶位叶片营养元素代谢特征

对松嫩草地不同退化程度样地的芦苇(Phragmites australis)各叶位叶片的生长及营养元素代谢特征进行分析, 以探讨土壤盐碱化对芦苇叶片营养元素代谢的影响及其适应机制。结果表明: 松嫩草地土壤中Na ⁺含量、全盐含量、pH值是衡量土壤盐碱化程度的主要决定因子, 从典型草地到重度退化草地, 土壤盐碱化程度逐级加剧。芦苇具有一定程度的耐盐碱性, 植株高度和地上部分生物量随土壤盐分增加而降低。检测出10种营养元素: K、Na、Ca、Mg、Fe、Cu、Zn、Mn、P、B, 主成分分析结果显示全部样本均处于95%的置信区间内。方差分析结果表明, 芦苇不同叶位叶片对营养元素的富集能力有所差异。K、P含量随叶位降低而减少; 而Na、Ca、Mg呈现相反分布规律。Fe、Cu集中分布在功能叶和老叶中; Mn只大量聚集在老叶中; 而Zn集中分布在幼叶中。表明土壤盐碱化对老叶营养元素的影响大于幼叶, Na在老叶中的大量积累保护了幼叶免于或者减轻离子的毒害。功能叶和老叶中Ca、Mg、Fe、Cu的积累有利于保障芦苇正常的光合作用。盐碱胁迫下幼叶仍维持较高K、P含量, 这不仅为幼叶的生长提供所需营养, 同时提高了其抗逆性, 这可能是芦苇的生理响应策略。     

云南草寇花序内不同部位的性分配

两性花植物花序内的性分配常存在差异,资源竞争、结构效应、交配环境(雌雄异熟、传粉者定向访花行为等)或授粉不均匀等几种假说可以解释这种现象。为验证上述假说,该研究以云南草寇两种表型(雄先熟型和雌先熟型)为材料,分析了其花序内不同部位(基部、中部和顶部)的每花花粉数、胚珠数、花粉/胚珠比、结实率和结籽率,花序内传粉者的定向访花行为,以及人工辅助授粉和去花处理对结实率和结籽率的影响。结果表明:两种表型花序内每花花粉数不随部位而变化,每花胚珠数、结实率和结籽率由基部到顶部依次降低,每花花粉/胚珠比由基部到顶部依次增加,表明顶部花存在偏雄的性分配。人工辅助授粉后,结实率、结籽率仍由基部到顶部依次降低,表明授粉不均匀假说不能解释云南草寇花序内不同部位结实率、结籽率的差异。去除基部和中部花后,顶部花人工辅助授粉条件下的结实率、结籽率与基部花人工辅助授粉条件下的结实率、结籽率无差异,表明云南草寇花序内不同部位结实率、结籽率的差异主要由资源竞争引起。雌先熟表型每花花粉数、花粉/胚珠比高于雄先熟表型,表明两种表型存在性分配差异。传粉者主要先访问云南草寇基部的花,然后向顶部移动。云南草寇花序内顶部偏雄的性分配可能是由资源竞争和传粉者定向访花造成的。