一种基于代价函数和模糊熵的图像分割方法

提出了一种基于代价函数和模糊熵的图像分割方法.该方法先用代价函数最小化法对退化的图像作预处理,之后,利用模糊熵作进一步的处理.实验结果表明:新方法和一般的阈值分割方法相比,不但分割图像的错分率较小,而且图像的视觉效果也有较大的改善.     

A new type of noncovalent surface–π stacking interaction occurring on peroxide-modified titania nanosheets driven by vertical π-state polarization

Noncovalent π stacking of aromatic molecules is a universal form of noncovalent interactions normally occurring on planar structures (such as aromatic molecules and graphene) based on sp²-hybridized atoms. Here we reveal a new type of noncovalent surface–π stacking unusually occurring between aromatic groups and peroxide-modified titania (PMT) nanosheets, which can drive versatile aromatic adsorptions. We experimentally explore the underlying electronic-level origin by probing the perturbed changes of unoccupied Ti 3d states with near-edge X-ray absorption fine structures (NEXAFS), and find that aromatic groups can vertically attract π electrons in the surface peroxo-Ti states and increase their delocalization regions. Our discovery updates the concept of noncovalent π-stacking interactions by extending the substrates from carbon-based structures to a transition metal oxide, and presents an approach to exploit the surface chemistry of nanomaterials based on noncovalent interactions.

A new type of noncovalent surface–π stacking interaction occurring on a transition metal oxide, titania, is reported, which is different from the traditional forms on sp²-hybridized planar structures like graphene.     

Utilization of Active Ni to Fabricate Pt–Ni Nanoframe/NiAl Layered Double Hydroxide Multifunctional Catalyst through In Situ Precipitation

Integration of different active sites into metallic catalysts, which may impart new properties and functionalities, is desirable yet challenging. Herein, a novel dealloying strategy is demonstrated to decorate nickel–aluminum layered double hydroxide (NiAl–LDH) onto a Pt–Ni alloy surface. The incorporation of chemical etching of Pt–Ni alloy and in situ precipitation of LDH are studied by joint experimental and theoretical efforts. The initial Ni‐rich Pt–Ni octahedra transform by interior erosion into Pt₃Ni nanoframes with enlarged surface areas. Furthermore, owing to the basic active sites of the decorated LDH together with the metallic sites of Pt₃Ni, the resulting Pt–Ni nanoframe/NiAl–LDH composites exhibit excellent catalytic activity and selectivity in the dehydrogenation of benzylamine and hydrogenation of furfural.     

Interaction of Hydrogen with Ceria: Hydroxylation,Reduction, and Hydride Formation on the Surface and in the Bulk

The study reports the first attempt to address the interplay between surface and bulk in hydride formation in ceria (CeO₂) by combining experiment, using surface sensitive and bulk sensitive spectroscopic techniques on the two sample systems, i.e., CeO₂(111) thin films and CeO₂ powders, and theoretical calculations of CeO₂(111) surfaces with oxygen vacancies (O_v) at the surface and in the bulk. We show that, on a stoichiometric CeO₂(111) surface, H₂ dissociates and forms surface hydroxyls (OH). On the pre-reduced CeO_2−x samples, both films and powders, hydroxyls and hydrides (Ce−H) are formed on the surface as well as in the bulk, accompanied by the Ce³⁺ ↔ Ce⁴⁺ redox reaction. As the O_v concentration increases, hydroxyl is destabilized and hydride becomes more stable. Surface hydroxyl is more stable than bulk hydroxyl, whereas bulk hydride is more stable than surface hydride. The surface hydride formation is the kinetically favorable process at relatively low temperatures, and the resulting surface hydride may diffuse into the bulk region and be stabilized therein. At higher temperatures, surface hydroxyls can react to produce water and create additional oxygen vacancies, increasing its concentration, which controls the H₂/CeO₂ interaction. The results demonstrate a large diversity of reaction pathways, which have to be taken into account for better understanding of reactivity of ceria-based catalysts in a hydrogen-rich atmosphere.     

Preferential Co substitution on Ni sites in Ni–Fe oxide arrays enabling large-current-density alkaline oxygen evolution

Developing low-cost and high-activity transition metal oxide electrocatalysts for an efficient oxygen evolution reaction (OER) at a large current density is highly demanded for industrial application and remains a big challenge. Herein, we report vertically aligned cobalt doped Ni–Fe based oxide (Co–NiO/Fe₂O₃) arrays as a robust OER electrocatalyst via a simple method combining hydrothermal reaction with heat treatment. Density functional theory calculation and XRD Rietveld refinement reveal that Co preferentially occupies the Ni sites compared to Fe in the Ni–Fe based oxides. The electronic structures of the Co–NiO/Fe₂O₃ could be further optimized, leading to the improvement of the intrinsic electronic conductivity and d-band center energy level and the decrease in the reaction energy barrier of the rate-determining step for the OER, thus accelerating its OER electrocatalytic activity. The Co–NiO/Fe₂O₃ nanosheet arrays display state-of-the-art OER activities at a large current density for industrial demands among Fe–Co–Ni based oxide electrocatalysts, which only require an ultra-low overpotential of 230 mV at a high current density of 500 mA cm⁻², and exhibit superb durability at 500 mA cm⁻² for at least 300 h without obvious degradation. The Co–NiO/Fe₂O₃ nanosheet arrays also have a small Tafel slope of 33.9 mV dec⁻¹, demonstrating fast reaction kinetics. This work affords a simple and effective method to design and construct transition metal oxide based electrocatalysts for efficient water oxidation.

Co–NiO/Fe₂O₃ nanosheets featuring Co substitution on Ni sites can effectively regulate electronic structures and exhibit high OER activities with low overpotential (η₅₀₀ = 230 mV), small Tafel slope (33.9 mV dec⁻¹) and superb durability for 300 h.     

多孔聚合物骨架的超声及微波辅助合成

首次采用超声与微波辅助合成方法制得数种高比表面积吸附纤维和树脂新材料。研究表明,1)分别以4,4’-二氯甲基-联苯(CMDP)、1,4-二氯甲基苯(XDC)以及FeCl3为单体和催化剂,采用超声辅助Fridel-Crafts烷基化自聚合反应制得比表面积可达1320m2/g的超高交联多孔吸附树脂新材料;2)以PP-ST-DVB基纤维为基体,分别采用超声或超声-微波辅助Fridel-Crafts后交联反应制得比表面积可达84.25m2/g和83.96m2/g的超高交联吸附纤维新材料。与现有多孔高分子骨架制备方法相比,这种多孔聚合物合成新技术可有效克服液固相接枝聚合反应中受热不均所带来的种种弊病,且具有促进溶解(溶胀)和反应时间大幅缩短的优点。     

In Vivo Metabolism Study of Timosaponin BIII in Rat Using HPLC-QTOF-MS/MS

Timosaponin BIII, as one of the steroid saponins isolated from Anemarrhena asphodeloides Bge., was proved to have many pharmacological activities in recent years and became a natural active compound with good development prospect. In the present study, a simple and rapid method using high-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry was developed for the determination of the structures of timosaponin BIII and its metabolites in rats after administrating intragastrically at 300 mg kg⁻¹. By comparing their changes in molecular masses (ΔM), retention times and spectral patterns with those of the parent compound, nine metabolites were detected and identified in urine, and eight in plasma as well as four in brain. It is also indicated that the deglycosylation and oxidation reactions were the main metabolic pathways in the biotransformation of timosaponin BIII in vivo and the structures of the nine metabolites were identified and proposed to be timosaponin BII(M1), the hydroxylated metabolite of TBII(M2), the hydroxylated metabolites of TBIII(M3 and M4), deglycosylation and monooxygenation product of TBIII(M5), the deglycosylation product of TBII(M6), timosaponin AIII(M8), the isomers of timosaponin AIII(M7 and M9).

     

TiO2晶面依赖的Ir-TiOx相互作用对Ir/TiO2催化剂巴豆醛选择性加氢性能的影响

α,β-不饱和醇是一类重要的精细化学品,主要通过α,β-不饱和醛选择性加氢获得.由于α,β-不饱和醛分子中含有共轭的C=C键和C=O键,且后者键能更大,在热力学和动力学上均不利于C=O键的选择性加氢生成α,β-不饱和醇.因此,提高α,β-不饱和醛中C=O的加氢选择性是催化领域中一项挑战性的课题.巴豆醛属于典型的α,β-不饱和醛,研究其选择性加氢生成巴豆醇具有广泛的代表意义;Ir负载在具有还原性载体(如TiO2)上时,表现出很好的C=O加氢选择性,因此,成为近年来的研究热点.由于暴露不同晶面的TiO2具有不同的形貌和电子结构,因此研究Ir-TiO2相互作用的晶面依赖性及其对巴豆醛选择性加氢反应的影响具有重要意义.本文以分别暴露{101}、{100}和{001}晶面的锐钛矿TiO2纳米晶为载体,制备了负载型Ir/TiO2催化剂,系统研究了催化剂经过不同的预处理过程(在不同温度下H2还原和O2再氧化)后对巴豆醛的气相选择性加氢的性能.利用高分辨透射电镜、原位X射线光电子能谱和原位漫反射红外光谱及氨程序升温脱附等技术研究发现,预处理条件显著改变了Ir-TiOx的相互作用,包括Ir金属的几何、电子性质及催化剂表面酸性.这种相互作用与TiO2的暴露晶面密切相关,从而改变了不同Ir/TiO2催化剂上不同加氢反应行为.研究结果表明,经300℃预还原的Ir/TiO2-{101}催化剂催化性能最好,在80℃下初始反应速率为166.1 μmol g-Ir-1 s-1,巴豆醇的生成转化频率为0.022 s-1.与其他催化剂相比,Ir/TiO2-{101}催化剂表面Ir0浓度最高,表面酸度适中,因此表现出最佳的催化性能.同时Ir-TiOx界面在反应中的协同作用,对H2和巴豆醛分子中C=O键的吸附和活化起到了关键作用.然而当催化剂经过400℃的H2预还原后,由于产生了强的金属-载体相互作用使得TiOx对Ir粒子进行了包裹从而导致Ir-TiOx界面缺失,因而催化剂催化巴豆醛加氢性能降低.本文为理解金属-载体相互作用对巴豆醛选择性加氢反应的影响提供了新的见解,并为设计高性能α,β-不饱和醛选择性加氢催化剂提供了理论依据.     

Multi-reference lens-less Fourier-transform holography with a Greek-ladder sieve array

Lens-less Fourier-transform holography has been actively studied because of its simple optical structure and its single-shot recording.However,a low-contrast interferogram between the reference and object waves limits its signal to noise ratio.Here,multi-reference lens-less Fourier-transform holography with a Greek-ladder sieve array is proposed in the experiment and demonstrated effectively to improve the signal to noise ratio.The key technique in our proposed method is a Greek-ladder sieve array,which acts as not only a wave-front modulator but also a beam splitter.With advantages of the common path,single shot,and no need for a lens,this system has enormous potential in imaging and especially in extreme ultraviolet and soft X-ray holography.     

相依样本情形时的经验似然比置信区间

本文讨论了强平稳φ混合样本的经验似然比置信区间,推广了Ｏｗｅｎ（１９８８,１９９０）在独立同分布情况下的结果,指出了相依情况时经验似然比置信区间的不足并进行了合理的改进。