Hydroformylation of functional alkenes with heterodonor phosphine rhodium catalysts: substrate or ligand directed regioselectivity?

The catalytic activity and selectivity of heterodonor phosphine rhodium catalysts prepared in situ were tested in the hydroformylation of functional alkenes (ethyl acrylate, methyl methacrylate, styrene, 4-vinyl-1-cyclohexene, dicyclopentadiene and cis-1,2,3,6-tetrahydrophthalic anhydride). Systematic variation of the heterodonor atom in the ortho position of the ligand showed that the heterodonor atom has a significant influence on the activities and selectivities of the reaction. However, the activity seems to depend mainly on the modifying ligand, and the regioselectivity mainly on the substrate (i.e., the structure and functionality of the alkene). Nevertheless, regioselective control is only obtained through synergy between the substrate and the catalyst. Clear regiocontrol was observed in the hydroformylation of ,-unsaturated esters and styrene with an in situ formed o-(thiomethylphenyl)diphenylphosphine rhodium catalyst.     

Preparation and characterization of SO42-/TiO2 and S2O82-/TiO2 catalysts

Nanosized solid superacids SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂, as well as MCM-41-supported SO₄ ²⁻/ZrO₂, were prepared. Their structures, acidities, and catalytic activities were investigated and compared using XRD, N₂ adsorption-desorption, and in situ FTIR-pyridine adsorption, as well as an evaluation reaction with pseudoionone cyclization. The results showed that SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ possess not only nanosized particles with diameters < 7.0 nm, a BET surface greater than 140 cm²/g and relatively regular mesostructures with pores around 4.0 nm, but also a pure anatase phase and strong acidity. Different from the Lewis acid nature of SO₄ ²⁻/ZrO₂/MCM-41, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibit mainly Bronsted acidities. The strongest Bronsted acid sites were produced on SO₄ ²⁻/TiO₂ promoted with H₂SO₄, while Lewis acid sites on S₂O₈ ²⁻/TiO₂ even stronger than those on SO₄ ²⁻/ZrO₂/MCM-41 were generated when persulfate solution was used as sulfating agent. Because of their distinct acid natures, SO₄ ²⁻/TiO₂ and S₂O₈ ²⁻/TiO₂ exhibited catalytic activities for the cyclization of pseudoionone that were much higher than that of SO₄ ²⁻/ZrO₂/MCM-41. It can be concluded that the existence of more Br?nsted acid sites was favorable for proton participation in the cyclization reaction. Translated from Journal of Chemical Engineering of Chinese Universities, 2006, 20(2): 239–244 [译自: 高校化学工程学报]     

Synergistic Sex Pheromone Components of White-Spotted Tussock Moth, Orgyia thyellina

In 1996, the exotic white-spotted tussock moth (WSTM), Orgyia thyellina (Lepidoptera: Lymantriidae), was discovered in Auckland, New Zealand. Because establishment of WSTM would threaten New Zealand's orchard industry and international trade, eradication of WSTM with microbial insecticide was initiated. To monitor and complement eradication of WSTM by capture of male moths in pheromone-baited traps, pheromone components of female WSTM needed to be identified. Coupled gas chromatographic–electroantennographic detection analysis of pheromone gland extract revealed several compounds that elicited responses from male moth antennae. Mass spectra of the two most EAD-active compounds suggested, and comparative GC-MS of authentic standards confirmed, that they were (Z)-6-heneicosen-11-one (Z6–11-one) and (Z)-6-heneicosen-9-one, the latter termed here thyellinone. In field experiments in Japan, Z6–11-one plus thyellinone at a 100:5 ratio attracted WSTM males, whereas either ketone alone failed to attract a single male moth. Addition of further candidate pheromone components did not enhance attractiveness of the binary blend. Through the 1997–1998 summer, 45,000 commercial trap lures baited with 2000 g of Z6–11-one and 100 g of thyellinone were deployed in Auckland towards eradication of the residual WSTM population.Dedicated to my dear mother in honor of her 75th birthday     

一种基于SRT-8算法的SIMD浮点除法器的设计与实现

在科学计算、数字信号处理、通信和图像处理等应用中,除法运算是常用的基本操作之一。基于SRT 8除法算法,设计一个SIMD结构的IEEE 754标准浮点除法器,在同一硬件平台上能够实现双精度浮点除法和两个并行的单精度浮点除法。通过优化SRT 8迭代除法结构,提出商选择和余数加法的并行处理,并采用商数字存储技术降低迭代除法的计算延时,提高频率。同时,采用复用策略减少硬件资源开销,节省面积。实验表明,在40nm工艺下,本设计综合cell面积为18601.9681 μm2,运行频率可达2.5GHz,相对传统的SRT 8实现关键延迟减少了23.81%。     

新型8极9槽永磁同步电机静态场的分析

针对采用分布式绕组的缺点,提出一种采用集中式绕组的新型8极9槽永磁同步电机,并在此基础上改变磁钢的参数,对电机的结构进行优化。     

基于多时序特征和卷积神经网络的农作物分类

近年来,以卷积神经网络为主的深度学习模型在各种遥感应用中都显示出巨大的潜力。以加州帝国郡为研究区,以Landsat 8 OLI年内时序遥感影像计算时序植被指数NDVI、EVI、RVI以及TVI,组合后输入到构建的一维卷积神经网络 模型,以实现作物的高精度精细分类。为了验证卷积模型的优越性,另搭建了基于递归神经网络及其变体的深度学习模型。结果表明：①引入其他时序特征后,能够有效地提高卷积神经网络的分类精度。NDVI+EVI+TVI+RVI组合特征总体精度和Kappa系数最高,分别是89.667 4%和0.856 0,对比NDVI时序特征总体精度和Kappa系数提高了近4%和0.6。②在与其他深度学习模型的对比中,一维卷积神经网络分类精度最高,能够从时序数据中较为准确捕捉作物时序特征信息,尽管递归神经网络被广泛应用于序列数据的研究,但分类结果要略差于卷积神经网络。实验表明在NDVI的基础上引入其他植被指数辅助,能够有效地提高分类精度。基于一维卷积神经网络的深度学习框架为长时间序列分类任务提供了一种有效且高效的方法。     

日晒牢度的色度学评价方法研究

传统的牢度测试方法一直是人工目测色差,受到环境、光源、工作人员的视力、辨色经验等因素的限制。随着电脑测色配色技术的迅速发展,研究证明使用仪器代替人眼来评价颜色之间的差异是完全可行的。在5级标准的牢度评价中,有关牢度等级和色度值变化规律已经逐步成熟,但8级评价体系的日晒牢度人工评定等级与色度值变化关系还未见报道。为客观评价日晒牢度,通过测定大量已人工评级的日晒试样的色度值,根据所得的色差值,建立了日晒牢度人工评级和计算机测色的色差值关系表。为了检验所建立的色差值与牢度级别的关系表,测定日晒牢度标准色样中各牢度级别对应的色差值,结果表明,在标准色样中,牢度级别对应的色差值基本符合所建立的关系表。这为日晒牢度的色差值评定提供了参考。     

钎焊温度对SiC/YG8接头微观组织的影响

在保温时间为5min、钎焊温度为940~990℃条件下,采用CuMnNi钎料钎焊SiC陶瓷与YG8硬质合金.利用金相显微镜、扫描电镜和能谱仪对接头的微观组织进行分析,研究钎焊温度对接头微观组织的影响.结果表明:在靠近SiC一侧生成一层带状反应层,主要由Cu基固溶体、硅化物、碳和碳化物组成;焊缝主要由基底Cu基固溶体以及Mn、Si、Co、Cu、Ni元素形成的化合物组成.随着钎焊温度的增加,焊缝的宽度减少,焊缝中心的Cu基固溶体基底减少,而化合物相增多.     

Ti4+ modified MgZrNb2O8 microwave dielectric ceramics with an ultra-high quality factor

Ti⁴⁺-modified MgZrNb₂O₈ (MgZr_1-xTi_xNb₂O₈, x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were synthesized using the traditional solid-state reaction method. Pure MgZr_1–xTi_xNb₂O₈ was detected without any secondary phase via the X-ray diffraction patterns. According to the sintering behavior and the surface morphology results, the introduction of Ti⁴⁺ reduced the sintering temperature and promoted the grain growth. The correlations between the dielectric properties and the crystal structure were analyzed through the Rietveld refinement and Raman spectroscopy. The slight shifts of the Raman peaks, corresponding to different vibration modes, were induced by the substitution of Ti⁴⁺ for Zr⁴⁺ and related to the improved quality factor. In general, the sample of MgZr_0.9Ti_0.1Nb₂O₈ sintered at 1320°C for 4 h exhibited promising microwave dielectric properties with an ultra-high Q × f value of 130 123 GHz (at 7.308 GHz, 20°C), which is potential for 5G communication applications.     

Mechanochemically synthesized ZIF-8 nanoparticles blended into 6FDA-TrMPD membranes for C3H6/C3H8 separation

The mixed matrix membranes (MMMs) consisting zeolitic-imidazolate framework-8 (ZIF-8) nanoparticles in a polymer have been of considerable interest in separation applications. The fillers used are mostly synthesized using the solvothermal method. In this study, the ZIF-8 nanoparticles were synthesized using a solvent-less and salt-free mechanochemical method and were added to 6FDA-TrMPD polyimide to prepare MMMs. The single gas permeation of C₃H₆ and C₃H₈ through the MMMs was investigated. The C₃H₆ permeability and C₃H₆/C₃H₈ ideal selectivity of a 20 wt% mechano-synthesized ZIF-8/6FDA-TrMPD MMM were 70% and 32% higher than those of the neat polymer membrane at 0.1 MPa and 308 K, respectively. The C₃H₆/C₃H₈ separation performance of the mechano-synthesized ZIF-8 MMM was similar to that of the conventional solvothermal-synthesized ZIF-8 MMM. This separation performance was in good agreement with the Maxwell model. Temperature and pressure dependence analyses confirmed that the mechano-synthesized ZIF-8 nanoparticles acted as molecular sieves in the MMMs for the C₃H₆ and C₃H₈ permeation.