CONVENTIONAL CHEMICAL AND DIRECT ELECTROCHEMICAL SYNTHESIS OF THE CHELATES OF 2-(N-TOSYLAMINE)BENZALDOXIME AND 2-(N-TOSYLAMINE)BENZAL-O-METHYLOXIME

Abstract

The chemical and direct electrochemical syntheses of copper, cobalt, nickel and zinc chelates of 2-[N-tosylamine)benzaldoxime (L¹H₂) and 2-[N-tosylamine)benzal-O-methyloxime (L²H) are reported. On the basis of the elemental analyse IR and EPR spectra and magnetic properties, dimeric structures ML are suggested from L¹H₂ under the conditions of the chemical synthesis, while electrosynthesis leads to the monomeric complexes M(L¹H)₂. Using L²H as a ligand, only the chelates ML² ₂ are formed, regardless of the method of synthesis.

The copper dimers CuL¹ have antiferromagnetic properties, while the chelates M(L¹H)₂ and ML₂ have normal magnetic moments. In agreement with the magnetic properties and literature data on structures of four-coordinate complexes a tetrahedral structure is assigned.     

Template‐Engaged Solid‐State Synthesis of Barium Magnesium Silicate Yolk@Shell Particles and Their High Photoluminescence Efficiency

This study presents a new synthetic method for fabricating yolk@shell‐structured barium magnesium silicate (BMS) particles through a template‐engaged solid‐state reaction. First, as the core template, (BaMg)CO₃ spherical particles were prepared based on the coprecipitation of Ba²⁺ and Mg²⁺. These core particles were then uniformly shelled with silica (SiO₂) by using CTAB as the structure‐directing template to form (BaMg)CO₃@SiO₂ particles with a core@shell structure. The (BaMg)CO₃@SiO₂ particles were then converted to yolk@shell barium magnesium silicate (BMS) particles by an interfacial solid‐state reaction between the (BaMg)CO₃ (core) and the SiO₂ (shell) at 750 °C. During this interfacial solid‐state reaction, Kirkendall diffusion contributed to the formation of yolk@shell BMS particles. Thus, the synthetic temperature for the (BaMg)SiO₄:Eu³⁺ phosphor is significantly reduced from 1200 °C with the conventional method to 750 °C with the proposed method. In addition, the photoluminescence intensity of the yolk@shell (BaMg)SiO₄:Eu³⁺phosphor was found to be 9.8 times higher than that of the conventional (BaMg)SiO₄:Eu³⁺ phosphor. The higher absorption of excitation light by the structure of the yolk@shell phosphor is induced by multiple light‐reflection and ‐scattering events in the interstitial void between the yolk and the shell. When preparing the yolk@shell (BaMg)SiO₄:Eu³⁺ phosphor, a hydrogen environment for the solid‐state reaction results in higher photoluminescence efficiency than nitrogen and air environments. The proposed synthetic method can be easily extended to the synthesis of other yolk@shell multicomponent metal silicates.     

常压下玉米秸秆液化工艺的优化及其生物油分析

随着化石能源的日益短缺，可再生木质生物质资源的利用越来越受到重视，常压液化技术是生物质资源高效利用的主要方式之一。利用单因素方法，探讨液化温度、复配液化剂二甘醇（DEG）与1,2-丙二醇（PG）的混合比、液固比、催化剂磷酸的用量、反应时间等因素对玉米秸秆液化得率的影响，以便优化其液化工艺；然后采用热重分析仪（TGA）、气相色谱-质谱技术（GC-MS）和核磁共振（NMR）技术对此优化条件下所得生物油的挥发降解特性和主要组成成分进行了检测探讨。分析表明，玉米秸秆液化时优化工艺参数为：液化温度170 ℃，液化剂DEG与PG混合比1∶2，液固比5∶1，H₃PO₄用量10%，反应时间45 min；此时玉米秸秆液化得率高至99.50%。TGA结果表明，此条件下所得生物油含有80%以上碳数小于25的化合物，热解后最终残炭量约为15%。GC-MS表明，可以检测出此生物油中含有的39种有机物，其中，醇类有机物的含量最多，酚类有机物的含量次之，它们相对含量依次是70.70%和25.63%，其还含有一定量的有机酸（2.80%）、醚类（0.64%）、酯类（0.10%）和酮类（0.13%）等有机物；其组分十分复杂，高含氧量，稳定性较差。1H-和13C-NMR分析表明，不同化学位移δ与生物油中不同类型的质子和碳原子相对应，明确生物油中不同类型H和C的分布，有利于对其分子结构进行深入探讨。这些研究为非木材生物质高效液化条件的选择及液化产物制备化学品和生物燃油给予理论基础与应用支持，促进了生物质资源的有效转化利用及其生物质基产品的开发。     

Modulation of the Physicochemical Properties of Donor–Spiro–Acceptor Derivatives through Donor Unit Planarisation: Phenylacridine versus Indoloacridine—New Hosts for Green and Blue Phosphorescent Organic Light‐Emitting Diodes (PhOLEDs)

This work reports a detailed structure–property relationship study of a series of efficient host materials based on the donor–spiro–acceptor (D‐spiro‐A) design for green and sky‐blue phosphorescent organic light‐emitting diodes (PhOLEDs). The electronic and physical effects of the indoloacridine (IA) fragment connected through a spiro bridge to different acceptor units, namely, fluorene, dioxothioxanthene or diazafluorene moiety, have been investigated in depth. The resulting host materials have been easily synthesised through short, efficient, low‐cost, and highly adaptable synthetic routes by using common intermediates. The dyes possess a very high triplet energy (E_T) and tuneable HOMO/LUMO levels, depending on the strength of the donor/acceptor combination. The peculiar electrochemical and optical properties of the IA moiety have been investigated though a fine comparison with their phenylacridine counterparts to study the influence of planarisation. Finally, these molecules have been incorporated as hosts in green and sky‐blue PhOLEDs. For the derivative SIA‐TXO₂ as a host, external quantum efficiencies as high as 23 and 14 % have been obtained for green and sky‐blue PhOLEDs, respectively.     

VIBRATIONAL SPECTRA AND NORMAL COORDINATE ANALYSIS OF 1,2-BIS(2-FORMYLGLYCINEBENZENESULFENYL) ETHANE Pd(II) DICHLORIDE COMPLEX

The normal coordinate analysis of the title complex, 1,2-bis(2-formylglycinebenzenesulfenyl) ethane Pd(II) dichloride has been carried out by using the Urey-Bradley force field. According to the molecular structure determined by x-ray crystallographic analysis, 182 internal coordinates were established and 112 theoretical vibration frequencies agree well with the observed values with the average difference of 2.53 cm^?1 and the maximum deviation of 16.0 cm^?1.     

Indirect Determination of Electronic Transition Frequencies of Coronene,Triphenylene and 1,2,5,6-Dibenzanthracene in the Vapor Phase

Frequencies of absorption band maxima for the first two electronic singlet transitions of coronene, triphenylene and 1,2,5,6-dibenzanthracene in vapor phase were calculated indirectly from solution spectral data. The calculations were based on two different models: the first one was a linear correlation between the solution absorption frequencies in nonpolar solvents and the solvent refractive indices. The accuracy of both methods was checked with anthracene and some of its derivatives: both methods gave a good agreement with the experimental values.     

Radiation background due to radioactive sources in a luminescence dating laboratory

For practical reasons, usually, luminescence dating laboratories contain in the same room (or in adjacent rooms) the equipment and the radioactive sources, as well as the storage cabinet for the samples. It is generally assumed that the absorbed dose due to ambient radioactivity is null or at least negligible in terms of human health (below the dose limit).To test the actual dose rate inside our laboratory room, an investigation combining portable dose rate meter, portable NaI(Tl) gamma spectrometry, and blue-OSL dosimetry using Al₂O₃:C pellets was made. Although our measurements show the presence of X-rays as far as 3 m from the sources, the dose rates are below the safety regulation and does not affect the dating of the sample stored in the same room as the radioactive sources.     

Structural deformation monitored by vibrational properties and orbital modeling in (Pb,Sm)TiO3 systems

Pb_1−xSm_xTiO₃ (PST) powders with x varying from 0 to 0.1 were obtained by the polymeric precursor method, a soft chemical route. The vibrational properties relating tetragonal to pseudo-cubic phase transition were studied by Raman spectroscopy. The results obtained showed that the phase transition is extremely dependent upon the samarium content and presents a diffuse behavior. Monitoring of the oxygen 2p and titanium 3d orbitals was performed by the periodic mechanical quantum method, revealing the changes that occur with the distribution and contribution of the hybrid orbitals due to the samarium influence.