改进的强相关数据的变量选择方法

针对高维强相关数据的变量选择问题,本文提出了改进的变量选择方法.该方法先利用自适应弹性网方法(Aenet)在原始的强相关数据上建立模型,选出对响应变量起重要作用的群组变量和独立变量;再通过偏最小二乘方法(PLS)对选出的变量作模型估计;最后,将两种方法得到的估计系数做线性组合,并以此系数来建立回归模型.新模型具有精度高、解释性好的优点,数值实验验证了该方法的有效性.     

过渡金属-配体σ键键能在碳-氢键活化中的应用

过渡金属催化的碳-氢(C-H)键活化因其优异的原子经济性及步骤简便性在过去几十年间蓬勃发展,已成为当前构建复杂化合物最常用的策略之一.对该过程中活性中间体的热力学研究有助于加深人们对反应机理的理解,指导新催化剂、新反应的理性设计.然而,近年来该领域的发展颇为缓慢,相应的报道十分零散,缺少系统的归纳和总结.本综述简要梳理了过渡金属-配体σ键键能的研究历程,并举例阐述了这些热力学参数在分析反应可行性、判断反应选择性等方面的应用,旨在推动过渡金属络合物相关的热力学研究的快速发展.     

CDFI鉴别男性乳腺良恶性肿瘤价值及与CXCL1、Gab2、MVD的相关性探究

本研究选取18例男性乳腺恶性肿瘤患者作为研究组,纳入同期41例男性良性乳腺肿瘤及50例健康体检男性分别作为良性对照组和健康对照组,通过对比分析发现,研究组CDFI参数[搏动指数(PI)、阻力指数(RI)、血流速度(PSV)]高于良性对照组和健康对照组(P<0.05);PI、RI、PSV联合诊断男性乳腺恶性肿瘤的AUC高达0.854,具有较高应用价值;研究组患者PI、RI、PSV与CXC型趋化因子配体1(CXCL1)、GRB相关蛋白2(Gab2)、微血管密度(MVD)水平间存在正相关关系(P<0.05)。由此可见,CDFI在鉴别男性乳腺良恶性肿瘤方面具有较高应用价值,且与患者CXCL1、Gab2、MVD表达呈正相关。     

脑胶质瘤磁共振弥散张量成像定量参数与VEGF、MMP-9表达的相关性

本研究旨在分析脑胶质瘤患者的磁共振弥散张量成像(DTI)参数与病变组织血管内皮生长因子(VEGF)和基质金属蛋白酶-9(MMP-9)表达的相关性,以及DTI参数对脑胶质瘤进行分级诊断的价值。根据病理分级将102例脑胶质瘤患者分为低级别组(47例)和高级别组(55例),均行MRI和DTI检查,定量测定表观弥散系数(ADC)、各向异性分数(FA)、相对ADC(rADC)、相对FA(rFA)值及相对轴向扩散系数(rAD)值;用免疫组化法检测VEGF和MMP-9表达情况。结果显示,高级别组患者的rADC、ADC、rAD、FA、rFA均低于低级别组(P<0.05);高级别组患者的VEGF和MMP-9阳性表达均高于低级别组(P<0.05)。rADC、ADC、rAD、FA、rFA与VEGF和MMP-9表达均呈负相关(P<0.05);rADC、ADC、rAD、FA、rFA对脑胶质瘤分级诊断的AUC均具有一定诊断价值(P<0.05)。本研究结果提示DTI定量参数与脑胶质瘤VEGF和MMP-9表达具有相关性,且有助于脑胶质瘤的分级诊断。     

二维超声联合超声造影TIC参数在乳腺导管内病变良/恶性诊断中的应用价值

本研究分析了二维超声(2DUS)联合超声造影(CEUS)时间-强度曲线(TIC)参数在乳腺导管内病变良/恶性鉴别诊断中的应用价值。选取乳腺导管内病变患者81例(共93个病变),均行2DUS及CEUS检查。结果显示,2DUS检出恶性病变17个,良性病变48个,诊断准确度69.89%(65/93)、敏感度53.13%(17/32)、特异度78.69%(48/61),阳性预测值为56.67%(17/30),阴性预测值为76.19%(48/63)。恶性病变达峰时间早于良性病变(P<0.05),峰值强度、曲线上升支斜率、曲线下面积均高于良性病变(P<0.05)。ROC曲线分析结果显示:2DUS联合CEUS-TIC参数鉴别诊断乳腺导管内病变良/恶性的AUC、敏感度、特异度均高于2DUS或CEUS单独检查(P<0.05)。因此可知,对于乳腺导管内病变,2DUS联合CEUS检查可明显提高对良/恶性的鉴别诊断效能。     

Insight into the hydrogen oxidation electrocatalytic performance enhancement on Ni via oxophilic regulation of MoO_2

Exploring platinum-group-metal(PGM)free electrocatalysts for hydrogen oxidation reaction(HOR)in alkaline media is essential to the progress of anion exchange membrane fuel cells(AEMFCs).In this work,a Ni/MoO₂ heterostructure catalyst with comparable HOR activity in alkaline electrolyte with PGM catalyst was prepared by a simple hydrothermal-reduction method.Remarkably,the Ni/MoO₂ presents a mass kinetic current density of 38.5 mA mgNi^-1 at the overpotential of 50 mV,which is higher than that of the best PGM free HOR catalyst reported by far.Moreover,the HOR performance of Ni/MoO₂ under 100 ppm CO shows negligible fading,together with the superior durability,render it significant potential for application in AEMFCs.A particular mechanistic study indicates that the excellent HOR performance is ascribed to the accelerated Volmer step by the incorporation of MoO₂.The function of MoO₂ was further confirmed by CO striping experiment on Pt/C-MoO₂ that MoO₂ can facilitated OH adsorption thus accelerate the HOR process.On account of the high performance and low cost,the Ni/MoO₂ electrocatalyst encourages the establishment of high performance PGM free catalyst and shows significant potential for application in AEMFCs.     

Enhancing interfacial stability in solid-state lithium batteries with polymer/garnet solid electrolyte and composite cathode framework

The solid-state lithium battery is considered as an ideal next-generation energy storage device owing to its high safety,high energy density and low cost.However,the poor ionic conductivity of solid electrolyte and low interfacial stability has hindered the application of solid-state lithium battery.Here,a flexible polymer/garnet solid electrolyte is prepared with poly(ethylene oxide),poly(vinylidene fluoride),Li6.75La3 Zr1.75Ta0.25O12,lithium bis(trifluoromethanesulfonyl)imide and oxalate,which exhibits an ionic conductivity of 2.0 ×10^-4 S cm^-1 at 55℃,improved mechanical property,wide electrochemical window(4.8 V vs.Li/Li+),enhanced thermal stabilities.Tiny acidic OX was introduced to inhibit the alkalinity reactions between Li6.75La3 Zr1.75Ta0.25O12 and poly(vinylidene fluoride).In order to improve the interfacial stability between cathode and electrolyte,an Al2 O3@LiNi0.5Co0.2Mn0.3O2 based composite cathode framework is also fabricated with poly(ethylene oxide) polymer and lithium salt as additives.The solid-state lithium battery assembled with polymer/garnet solid electrolyte and composite cathode framework demonstrates a high initial discharge capacity of 150.6 mAh g^-1 and good capacity retention of 86.7% after 80 cycles at 0.2 C and 55℃,which provides a promising choice for achieving the stable electrode/electrolyte interfacial contact in solid-state lithium batteries.     

Insights into the adsorption/desorption of CO_2 and CO on single-atom Fe-nitrogen-graphene catalyst under electrochemical environment

Single-atom metal-nitrogen-graphene(M-N-Gra) catalysts are promising materials for electrocatalytic CO₂ reduction reaction(CO₂ RR). However, theoretical explorations on such systems were greatly hindered because of the complexity in modeling solid/liquid interface and electrochemical environment. In the current work, we investigated two crucial processes in CO₂ RR, i.e. adsorption and desorption of CO₂ and CO at Fe-N₄ center, with an explicit aqueous model. We used the ab initio molecular dynamics simulations associated with free energy sampling methods and electrode potential analysis to estimate the energetics under electrochemical environment, and found significant difference in aqueous solution compared with the same process in vacuum. The effect of applied electrode potential on the adsorption structures,charge transfer and free energies of both CO₂ and CO on Fe-N-Gra was thoroughly discussed. These findings bring insights in fundamental understandings of the CO₂ RR process under realistic conditions, and facilitate future design of efficient M-N-Gra-based CO_2 RR catalysts.     

Conversion of CO_2 and H_2 into propane over InZrO_x and SSZ-13 composite catalyst

Direct converting carbon dioxide into hydrocarbon fuels and value-added chemicals would offer a very attractive approach for efficient utilization of CO₂ as a carbon resource.Although,olefins,aromatics and gasoline have been successfully synthesized by CO₂ hydrogenation,highly selective conversion of CO₂ and H₂ into C₂₊hydrocarbon is still challenging due to a high C-C coupling barrier and inhibiting the production of other long-chain hydrocarbons.Here,we report a composite catalyst made of InZrO_x and SSZ-13 molecular sieve(InZrO_x+SSZ-13),which exhibits 74.5% propane selectivity at 623 K.The 8-MR micropores and the higher strength of the acid for SSZ-13 benefit the formation of propane.Compared with pure InO_x and m-ZrO₂ the composite oxide InZrO_x containing more oxygen vacancies,exhibits to be more readily reduced by H₂ and easier to adsorb and desorb CO₂ within the reaction temperature.All those could be beneficial to the activation and conversion of H₂ and CO₂.The catalytic performance of InZrO_x+SSZ-13 in CO₂ hydrogenation provides a potential for production of propane.