How Aromatic Fluorination Exchanges the Interaction Role of Pyridine with Carbonyl Compounds: The Formaldehyde Adduct

The rotational spectrum of the weakly bound complex pentafluoropyridine⋅⋅⋅formaldehyde has been investigated using Fourier transform microwave spectroscopy. From the analysis of the rotational parameters of the parent species and of the ¹³C and ¹⁵N isotopologues, the structural arrangement of the adduct has been unambiguously established. The full ring fluorination of pyridine has a dramatic effect on its binding properties: It alters the electron density distribution at the π-cloud of pyridine creating a π-hole and changing its electron donor-acceptor capabilities. In the complex, formaldehyde lies above the aromatic ring with one of the oxygen lone pairs, as conventionally envisaged, pointing toward its centre. This lone pair⋅⋅⋅π-hole interaction, reinforced by a weak C−H⋅⋅⋅N interaction, indicates an exchange of the electron-acceptor roles of both molecules when compared to the pyridine⋅⋅⋅formaldehyde adduct. Tunnelling doublets due to the internal rotation of formaldehyde have also been observed and analysed leading to a discussion on the competition between lone pair⋅⋅⋅π-hole and π⋅⋅⋅π stacking interactions.     

1，1'-二羟基-5，5'-联四唑的镧系金属配合物的合成、表征及热行为

以1,1′-二羟基-5,5′-联四唑(H_2BTO)为配体,镧系金属离子作为金属中心,采用溶剂热法制备了5种金属配合物:[La_2(BTO)_3(H_2O)_8]·2H_2O (1)、[Ce_2(BTO)_3(H_2O)_8]·2H_2O (2)、[Pr_2(BTO)_3(H_2O)_8]·2H_2O (3)、[Sm_2(BTO)_3(H_2O)_8]·2H_2O (4)和[Nd_2(BTO)_3(DMF)_4]·6H_2O (5)。通过单晶X射线衍射和元素分析对5种配合物的结构进行了表征。结果表明,5种配合物均属于单斜晶系,P2_1/n空间群。利用差示扫描量热法研究了配合物1～4的热稳定性,采用Kissinger法和Ozawa法分别计算了其热分解动力学参数。     

Catalytic transfer hydrogenation of biomass-derived furfural to furfuryl alcohol with formic acid as hydrogen donor over CuCs-MCM catalyst

Catalytic transfer hydroge nation(CTH) of furfural(FF) to furfu ryl alcohol(FFA) has received great intere st in recent years.He rein,Cu-Cs bimetallic supported catalyst,CuCs(2)-MCM,was developed for the CTH of FF to FFA using formic as hydrogen donor.CuCs(2)-MCM achieved a 99.6% FFA yield at an optimized reaction conditions of 170℃,1 h.Cu species in CuCs(2)-MCM had dual functions in catalytically decomposing formic acid to generate hydrogen and hydrogenating FF to FFA.The doping of Cs made the size of Cu particles smaller and improved the dispersion of the Cu active sites.Impo rtantly,the Cs species played a favorable role in enhancing the hydrogenation activity as a promoter by adjusting the surface acidity of Cu species to an appropriate level.Correlation analysis showed that surface acidity is the primary factor to affect the catalytic activity of CuCs(2)-MCM.     

High-yield synthesis of a novel water-soluble macrocycle for selective recognition of naphthalene

A novel good water-soluble macrocycle containing two pyridinium moieties was synthesized in high yield.It could form 1:1 complexes with neutral guests containing naphthalene or phenyl units in water.The water-soluble macrocycle can selectively encapsulate naphthalene to form a 1:1 complex over a variety of polycyclic aromatic hydrocarbons.     

A Combined Experimental and Theoretical Study on the Formation of Ag Filaments on β‐Ag2MoO4 Induced by Electron Irradiation

A combined experimental and theoretical study is presented to understand the novel observed nucleation and early evolution of Ag filaments on β‐Ag₂MoO₄ crystals, driven by an accelerated electron beam from an electronic microscope under high vacuum. The growth process, chemical composition, and the element distribution in these filaments are analyzed in depth at the nanoscale level using field‐emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) with energy‐dispersive spectroscopy (EDS) characterization. To complement experimental results, chemical stability, structural and electronic aspects have been studied systematically using first‐principles electronic structure theory within a quantum theory of atoms in molecules (QTAIM) framework. The Ag nucleation and formation on β‐Ag₂MoO₄ are a result of structural and electronic changes of the AgO₄ tetrahedral cluster as a constituent building block of β‐Ag₂MoO₄, consistent with Ag metallic formation. The formation of Ag filament transforms the β‐Ag₂MoO₄ semiconductor from n‐ to p‐type concomitant with the appearance of Ag defects.     

High pressure and thermal pasteurization effects on sweet cherry juice microbiological stability and physicochemical properties

This study evaluated high pressure processing (P1 – 400?MPa/5?min; P2 – 550?MPa/2?min) and thermal pasteurization (TP – 70°C/30?s) effects on sweet cherry juice's microbiological and physicochemical parameters, during four weeks of refrigerated storage. All treatments reduced the microbiological load to undetectable levels not affecting total soluble solids and titratable acidity. The pH increased with all treatments, however, it decreased during storage. Phenols were differently affected: TP increased them by 6%, P1 had no effect while P2 decreased them by 11%. During storage, phenols in control and TP samples decreased by 26% and 20%, P1 samples decreased them by 11% whereas P2 showed no variation. TP had no effect on anthocyanins, while pressure treatments increased them by 8%. Anthocyanins decreased during storage, particularly in the control and P1 (decreasing 41%). All treatments had no effect on antioxidant activity until the 14th day, thereafter high pressure processing samples showed the highest antioxidant activity.     

基于非同步替代光谱定标的地表下垫面影响分析

对760nm附近的氧气吸收带,选用植被、枯萎植被、人工地物、沙地和雪地五种典型地表类型,基于模拟数据进行非同步替代光谱定标方法的误差分析,比较不同地表类型得到的光谱定标准确度,为高光谱成像仪的非同步替代光谱定标提供定标图像选择策略.结果表明:运用两种光谱匹配方法——光谱角度匹配和欧氏距离法得到的定标误差基本一致;730~800nm的地表反射率曲线标准差在0.05nm以内时,定标误差集中在±0.5nm范围内;人工地物类型中个别地物如橄榄绿光泽涂料和植被大面积覆盖的图像数据不适合用于非同步替代光谱定标.     

Efficiency assessment of primary care providers: A conditional nonparametric approach

This paper uses a fully nonparametric approach to estimate efficiency measures for primary care units incorporating the effect of (exogenous) environmental factors. This methodology allows us to account for different types of variables (continuous and discrete) describing the main characteristics of patients served by those providers. In addition, we use an extension of this nonparametric approach to deal with the presence of undesirable outputs in data, represented by the rates of hospitalization for ambulatory care sensitive condition (ACSC). The empirical results show that all the exogenous variables considered have a significant and negative effect on efficiency estimates.