Charge control in the formation of complexes of phenol with ethylene derivatives containing organoelemental group IVB substituants

The v(OH) frequency shifts of phenol and the v_R resonance components of these shifts in the IR spectra of phenol H-complexes with ethylene derivatives containing various substituents including organosilicon, organogermanium, and organotin groups have been studied. The relationship between v and v_R and the values that characterize the influence of substituents on the effective charges of the double bonded carbon atoms was established; the latter values have been calculated previously usingab initio quantum chemical methods. The effective charges for the compounds with organoelemental substituents have been calculated. It has been elucidated that of the two types of possible interactions, charge controlled and orbital controlled, occurring in the formation of a complex of a hard acid, phenol, with the studied ethylene derivatives, the former is predominant.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1383–1387, August, 1993.     

Deep Multilabel Multilingual Document Learning for Cross-Lingual Document Retrieval

Cross-lingual document retrieval, which aims to take a query in one language to retrieve relevant documents in another, has attracted strong research interest in the last decades. Most studies on this task start with cross-lingual comparisons at the word level and then represent documents via word embeddings, which leads to insufficient structure information. In this work, the cross-lingual comparison at the document level is achieved through the cross-lingual semantic space. Our method, MDL (deep multilabel multilingual document learning), leverages a six-layer fully connected network to project cross-lingual documents into a shared semantic space. The semantic distances can be calculated when the cross-lingual documents are transformed into embeddings in semantic space. The supervision signals are automatically extracted from the data and then used to construct the semantic space via a linear classifier. The ambiguity of manual labels could be avoided and the multilabel supervision signals can be acquired instead of a single label. The representation of the semantic space is enriched by multilabel supervision signals, which improves the discriminative ability of the embeddings. The MDL is easy to extend to other fields since it does not depend on specific data. Furthermore, MDL is more efficient than the models training all languages jointly, since each language is trained individually. Experiments on Wikipedia data showed that the proposed method outperforms the state-of-the-art cross-lingual document retrieval methods.     

Effect of calcination temperature on the structure of vanadium phosphorus oxide materials and their catalytic activity in the decomposition of 2-propanol

The synthesis of vanadyl phosphate by reaction of an alcoholic solution of V₂O₅ and o-H₃PO₄ has been studied. The solids obtained were investigated by various physico-chemical techniques as in situ X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential thermal analysis (DTA) under inert atmosphere. The compounds have been further characterized by infrared and UV–Visible spectroscopies. The isopropanol conversion is carried out to evaluate the catalytic activity of the samples. The isopropanol conversion increases with the reaction temperature from 433 to 503 K for vanadyl phosphorus oxides calcined at a different temperature. However, the conversion attains 100% at 503 K, and the solid calcined at 973 K exhibits high selectivity towards propene (100% at 503 K).     

溶液和熔化状态下分子间的能量传递

通过二维红外光谱研究了GdmSCN/KSCN=1/1,GdmSCN/KS¹³CN=1/1和GdmSCN/KS¹³C¹⁵N=1/1三种混合晶体在熔融和溶液状态下的共振和非共振的分子间振动能量传递的性质. 在这些样品中,给体/受体的能量差越大,能量传递越慢. 而能量传递的快慢与拉曼光谱无关. 非共振能量传递与给体/受体的能量差的关系不能用声子补偿的机理来描述. 相反,它们的关系却可以用退相位机理来定量描述. 在熔融状态下,共振和非共振能量速率与温度的依赖关系也与退相位机理的预测相符合. 这一系列的结果表明只要分子的运动(平动和转动)远远快于非共振能量传递速率,那么退相位机理不仅在溶液中占主导,而且在熔融状态下(纯液体,不含溶剂)也占主导.     

基于多层次特征的跨场景服装检索

针对跨场景服装检索如何提取更有表述力的服装特征问题,提出了一种新的基于高层公共特征约束的相似性度量算法。首先,通过类别空间学习提取不同场景域的类别信息;然后,在场景域空间网络用类别信息约束传统对比损失函数,增大对类间负样本对的惩罚以减轻过拟合;最后,融合类别公共特征和域特定特征并通过类别判断进行辅助检索。分析和实验结果表明,新算法对跨场景服装检索的准确度要优于当前前沿的方法。     

多源异构土地基础数据一体化管理检索方法研究

为了从多源异构的复杂土地基础数据中快速准确地提取用户所需信息,提出了基于元数据的一体化管理检索方法.在元数据信息提取、元数据加权索引、实体同义词扩展检索3个环节中,结合土地领域专业知识和用户实际需求,设计和开发了共享元数据表结构、加权元数据中字段相对重要性和信息熵因子,构建地名实体和专题数据层实体同义词库,并集成到包括中文分词、实体识别、同义词扩展、索引检索和相似度计算的一体化管理检索框架中,解决了多源异构土地基础数据统一管理和精确检索的问题.实践表明,该方法较传统的通用信息检索方法具有更好的适用性和更高的准确率.     

壳聚糖亚胺环钯化合物的合成与表征

用水杨醛接枝改性后的壳聚糖亚胺与Li₂PdCl₄甲醇溶液反应得到壳聚糖环钯化合物。壳聚糖、壳聚糖席夫碱及其钯化合物用红外光谱(IR)、X射线衍射光谱(XRD)、热分析(DTA-TG)、荧光光谱以及X射线光电子能谱(XPS)等分析手段进行了表征分析。根据表征结果提出了席夫碱及壳聚糖亚胺环钯化合物的结构。     

谱峰相对强度比法在碳炔含量测定中应用

碳炔材料是一种不溶不熔高聚物 ,红外谱图是最简易的一种分析测试工具。将 C—H键的振动峰面积与 C C键的振动峰面积相关联 ,用谱峰相对强度比法测定不同制备条件下产生的碳炔材料的相对含量。结果表明 ,两者比值对反应物浓度的变化具有相关性 ,可用作碳炔材料制备中实验条件的优选手段。     

NO分子在钙钛矿表面吸附的红外光谱分析

用柠檬酸络合法合成了LaMnO3、LaCoO3和LaFeO3.NO分子红外光谱表明在上述化合物中存在不同类型的不饱和配位阳离子.对于LaFeO3来说,不饱和配位Fe2 的出现与表面缺陷有关;对于LaCoO3和LaMnO3表面来说,主要是不饱和配位Me3 与氧的配位性更强.     

Combination of LFP‐TRIR spectroscopy and DFT computation as a tool to determine the intermediate during the photooxidation of triarylphosphine

Laser flash photolysis‐time‐resolved infrared spectroscopy (LFP‐TRIR) was performed on an acetonitrile or dichloromethane solution of triarylphosphines, Ar₃P, in air. A transient spectrum consisting of several absorption bands appeared in the region of 1050–1300 cm^?1 on the TRIR on a microsecond timescale, which disappeared on a millisecond timescale. To identify the observed transient intermediate, the IR spectra of possible intermediates of the photoreaction were simulated by theoretical calculations based on density functional theory (DFT). The IR spectrum simulated for the phosphine peroxidic radical cation, Ar₃P⁺OO^?, well predicted the observed IR spectrum, showing that Ar₃P⁺OO^? is formed as a transient intermediate upon the LFP of Ar₃P in air. Copyright © 2014 John Wiley & Sons, Ltd.