Prediction of 195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects?

¹⁹⁵Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO₃)_n(OH)_{6 ? n}]^2?, [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 1–6), and [Pt(NO₃)_{6 ? n ? m}(OH)_m(OH₂)_n]^{?2 + n ? m} formed by dissolution of platinic acid, H₂[Pt(OH)₆], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge‐including atomic orbitals (GIAO)‐PBE0/segmented all‐electron relativistically contracted–zeroth‐order regular approximation (SARC–ZORA)(Pt) ∪ 6–31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second‐order polynomial plots of δ_calcd(¹⁹⁵Pt) versus δ_exptl(¹⁹⁵Pt) chemical shifts and δ_calcd(¹⁹⁵Pt) versus the natural atomic charge Q_Pt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ ¹⁹⁵Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σ^{iso 195}Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ ¹⁹⁵Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter‐ion effects on the ¹⁹⁵Pt NMR chemical shifts of the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? and cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} (n = 0–3) complexes we calculated the ¹⁹⁵Pt NMR chemical shifts of the neutral (PyH)₂[Pt(NO₃)_n(OH)_{6 ? n}] (n = 1–6; PyH = pyridinium cation, C₅H₅NH⁺) and [Pt(NO₃)_n(H₂O)_{6 ? n}](NO₃)_{4 ? n} (n = 0–3) complexes. Counter‐anion effects are very important for the accurate prediction of the ¹⁹⁵Pt NMR chemical shifts of the cationic [Pt(NO₃)_n(OH₂)_{6 ? n}]^{4 ? n} complexes, while counter‐cation effects are less important for the anionic [Pt(NO₃)_n(OH)_{6 ? n}]^2? complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd.     

Network regularised Cox regression and multiplex network models to predict disease comorbidities and survival of cancer

In cancer genomics, gene expression levels provide important molecular signatures for all types of cancer, and this could be very useful for predicting the survival of cancer patients. However, the main challenge of gene expression data analysis is high dimensionality, and microarray is characterised by few number of samples with large number of genes. To overcome this problem, a variety of penalised Cox proportional hazard models have been proposed. We introduce a novel network regularised Cox proportional hazard model and a novel multiplex network model to measure the disease comorbidities and to predict survival of the cancer patient. Our methods are applied to analyse seven microarray cancer gene expression datasets: breast cancer, ovarian cancer, lung cancer, liver cancer, renal cancer and osteosarcoma. Firstly, we applied a principal component analysis to reduce the dimensionality of original gene expression data. Secondly, we applied a network regularised Cox regression model on the reduced gene expression datasets. By using normalised mutual information method and multiplex network model, we predict the comorbidities for the liver cancer based on the integration of diverse set of omics and clinical data, and we find the diseasome associations (disease–gene association) among different cancers based on the identified common significant genes. Finally, we evaluated the precision of the approach with respect to the accuracy of survival prediction using ROC curves. We report that colon cancer, liver cancer and renal cancer share the CXCL5 gene, and breast cancer, ovarian cancer and renal cancer share the CCND2 gene. Our methods are useful to predict survival of the patient and disease comorbidities more accurately and helpful for improvement of the care of patients with comorbidity. Software in Matlab and R is available on our GitHub page: https://github.com/ssnhcom/NetworkRegularisedCox.git.     

Full Bayesian analysis of claims reserving uncertainty

We revisit the gamma–gamma Bayesian chain-ladder (BCL) model for claims reserving in non-life insurance. This claims reserving model is usually used in an empirical Bayesian way using plug-in estimates for the variance parameters. The advantage of this empirical Bayesian framework is that allows us for closed form solutions. The main purpose of this paper is to develop the full Bayesian case also considering prior distributions for the variance parameters and to study the resulting sensitivities.     

A self‐adaptive intelligence gray prediction model with the optimal fractional order accumulating operator and its application

The self‐adaptive intelligence gray predictive model (SAIGM) has an alterable‐flexible model structure, and it can build a dynamic structure to fit different external environments by adjusting the parameter values of SAIGM. However, the order number of the raw SAIGM model is not optimal, which is an integer. For this, a new SAIGM model with the fractional order accumulating operator (SAIGM_FO) was proposed in this paper. Specifically, the final restored expression of SAIGM_FO was deduced in detail, and the parameter estimation method of SAIGM_FO was studied. After that, the Particle Swarm Optimization algorithm was used to optimize the order number of SAIGM_FO, and some steps were provided. Finally, the SAIGM_FO model was applied to simulate China's electricity consumption from 2001 to 2008 and forecast it during 2009 to 2015, and the mean relative simulation and prediction percentage errors of the new model were only 0.860% and 2.661%, in comparison with the ones obtained from the raw SAIGM model, the GM(1, 1) model with the optimal fractional order accumulating operator and the GM(1, 1) model, which were (1.201%, 5.321%), (1.356%, 3.324%), and (2.013%, 23.944%), respectively. The findings showed both the simulation and the prediction performance of the proposed SAIGM_FO model were the best among the 4 models.     

基于函数系数自回归模型的风速时间序列预测

准确预测风电场风速是解决风能对电力系统所造成的安全、稳定运行和电能质量等问题的有效途径之一.风速的难以预测是由于它的高度随机和非线性.基于一种非参数的非线性自回归随机模型来预测风速,模型的自回归系数随模型依赖变量的变化而变化,因而它有灵活的非线性结构.数值实验和比较结果表明了这种函数系数自回归模型在风电场风速预测中的有效性.     

基于模糊灰色新陈代谢FGM(1,1)模型预测及应用探讨

巷道围岩变形是煤矿开采普遍存在的问题,巷道开挖过程中围岩会出现破裂现象.主要探讨模糊灰色系统的深部巷道围岩变形预测模型及应用,通过分析模糊数学理论、灰色理论,给出模糊灰色系统预测新陈代谢模型.     

基于Leslie模型的北京市基础教育学龄人口分城乡预测

以2010年第六次人口普查数据为基点,考虑到已经开放的单独二胎政策以及全面放开的二胎政策等因素,对北京市2020—2030年基础教育学龄人口变动情况分城乡进行预测.研究发现:北京学龄人口总体上呈现先上升后下降趋势;城市学龄人口远远高于农村学龄人口;城市各个阶段学龄人口均出现了先升后降趋势;农村幼儿园学龄人口呈现快速下降趋势,小学、初中学龄人口均呈现了先升后降趋势,农村高中学龄人口呈现了"下降-上升-下降-上升"的反复波动.学龄人口的变化反映了未来教育需求的变动,在未来10-15年,北京市还需要加大教师队伍建设、加强基础设施建设,努力实现城乡教育资源均衡化,最大限度地实现教育公平.     

基于改进免疫遗传算法的近红外光谱变量选择方法

该文在免疫遗传算法（IGA）的基础上,提出一种改进免疫遗传算法（iIGA）用于近红外光谱波长变量的选择。该算法舍去了原算法中固定抗体相似度阈值的思想,取而代之的是抗体相似度阈值自适应,同时引入精英保留策略和贪心算法思想,使得算法朝着正确的方向进行局部性探优。将该算法在玉米的淀粉和蛋白质含量数据集上进行实验测试,建立偏最小二乘（PLS）分析模型,并与IGA、遗传算法（GA）以及全谱方法进行了对比。结果表明,在玉米淀粉含量的预测上,iIGA相较于原IGA算法,预测集均方根误差（RMSEP）从0.312 0降至0.298 0,预测集预测精度提升4.5%;在玉米蛋白质含量的预测上,RMSEP从0.124 4降至0.110 3,预测集预测精度提升11.3%。分别对预测淀粉和蛋白质模型的RMSEP值进行显著性检验,F值分别为165.22和182.05,P值分别为9.5 × 10－23和4.5 × 10－24,P值均小于0.05,因此,iIGA能显著提升模型预测精度。     

Heterocyclic Substitutions Greatly Improve Affinity and Stability of Folic Acid towards FRα. an In Silico Insight

Folate receptor alpha (FRα) is known as a biological marker for many cancers due to its overexpression in cancerous epithelial tissue. The folic acid (FA) binding affinity to the FRα active site provides a basis for designing more specific targets for FRα. Heterocyclic rings have been shown to interact with many receptors and are important to the metabolism and biological processes within the body. Nineteen FA analogs with substitution with various heterocyclic rings were designed to have higher affinity toward FRα. Molecular docking was used to study the binding affinity of designed analogs compared to FA, methotrexate (MTX), and pemetrexed (PTX). Out of 19 FA analogs, analogs with a tetrazole ring (FOL03) and benzothiophene ring (FOL08) showed the most negative binding energy and were able to interact with ASP81 and SER174 through hydrogen bonds and hydrophobic interactions with amino acids of the active site. Hence, 100 ns molecular dynamics (MD) simulations were carried out for FOL03, FOL08 compared to FA, MTX, and PTX. The root mean square deviation (RMSD) and root mean square fluctuation (RMSF) of FOL03 and FOL08 showed an apparent convergence similar to that of FA, and both of them entered the binding pocket (active site) from the pteridine part, while the glutamic part was stuck at the FRα pocket entrance during the MD simulations. Molecular mechanics Poisson-Boltzmann surface accessible (MM-PBSA) and H-bond analysis revealed that FOL03 and FOL08 created more negative free binding and electrostatic energy compared to FA and PTX, and both formed stronger H-bond interactions with ASP81 than FA with excellent H-bond profiles that led them to become bound tightly in the pocket. In addition, pocket volume calculations showed that the volumes of active site for FOL03 and FOL08 inside the FRα pocket were smaller than the FA–FRα system, indicating strong interactions between the protein active site residues with these new FA analogs compared to FA during the MD simulations.