利用主成分分析和分层聚类分析法研究氟诺喹酮类药物分子结构活性关系

用密度泛函理论计算了12种具有抗肺炎链球菌的氟诺喹酮类药物分子的分子特性.利用主成分分析和分层聚类分析方法来简化氟诺喹酮类药物数据库的维数.主成分分析法表明,变量 E_(LUMO)、 Q_3、Q_5、Q_A、lgP、MR、VOL、ΔE_(HL)能够有效地对抗肺炎链球菌的氟诺喹酮类药物进行分类.分层聚类方法的结果和主成分分析方法的结果一致.这表明两种方法都能够对新的具有抗肺炎链球菌的氟诺喹酮类药物的分类提供一个可信的规律.利用主成分分析法和分层聚类分析法对其他6个氟诺喹酮类药物分子进行分析,结果都表明有两个药物分子具有较强的抗肺炎链球菌活性.此结果和临床结果相吻合.     

牻牛儿苗科11种中药材红外光谱鉴定及聚类分析

结合傅里叶变换红外光谱技术与聚类分析法,建立牻牛儿苗科11种中药材的快速鉴别方法。采用傅里叶变换红外光谱法鉴别牻牛儿苗科11种中药材;在建立主成分分析模型的基础上,采用SIMCA聚类分析法对三种中药材进行了快速的分类研究。红外光谱结合聚类分析技术对牻牛儿苗科中药材聚类结果较理想,识别率和拒绝率达到98%以上,盲样的预测率达到91%。红外光谱与聚类分析法相结合可以快速、无损识别牻牛儿苗科中药材。     

西洋参中无机元素的主成分分析和聚类分析

采用电感耦合等离子体质谱(ICP/MS)法测定了12个西洋参样品中18种无机元素的含量,建立西洋参无机元素指纹谱,并用SPSS主成分分析法对西洋参中的特征元素进行分析;主成分分析选出五个主因子,得出西洋参的特征元素为Fe,Al,V,Mn,Mg,Sr,Mo,Ca,Cu;聚类分析将12个西洋参样品聚成五大类,表明元素的分布特征与西洋参的品种关系显著;主成分分析法和聚类分析法是西洋参无机元素分析的有效方法.     

基于油液光谱RKPCA的综合传动磨损状态评价

原子发射光谱是分析油液中微小磨损颗粒元素浓度的重要方法。以综合传动全寿命磨损试验不同阶段采集的多个油液样本为研究对象,分别运用基于模糊隶属度的稳健核主成分分析（RKPCA）与传统主成分分析（PCA ）对光谱数据进行主成分提取与对比。在剔除光谱数据中的干扰元素后,计算与比较两种方法的主成分数量与贡献率,并利用RKPCA主成分进行综合传动多摩擦副的分类识别;对光谱数据和RKPCA特征值分别进行模糊C均值聚类,对比两种聚类结果应用在磨损状态评价中的效果。研究表明,由于光谱数据离群值与非线性影响,RKPCA较PCA的主成分数量稍小且累积贡献率高,说明前者能更有效地降低变量维数;通过RKPCA主成分与摩擦副组件的相关性分析可以看出,该方法可以精确的实现综合传动多摩擦副、多磨损部位的分类与识别,进而分类评价不同摩擦副的磨损状态;RKPCA特征值的模糊C均值聚类结果与光谱数据直接聚类结果相比,前者能更精确的定位磨损状态转化的临界点,从而准确评价综合传动整体磨损状态。油液光谱RKPCA分析方法的创新在于将特征值变化规律引入整体磨损状态评价,实现整体评价与关键摩擦副的分类评价相结合。这样不仅有助于综合传动大修期的准确判断,还能给出需维修部件建议。该方法也适用于其他复杂机械系统的磨损监测与评价等相关领域。     

基于油液光谱RKPCA的综合传动磨损状态评价（英文）

原子发射光谱是分析油液中微小磨损颗粒元素浓度的重要方法。以综合传动全寿命磨损试验不同阶段采集的多个油液样本为研究对象,分别运用基于模糊隶属度的稳健核主成分分析(RKPCA)与传统主成分分析(PCA)对光谱数据进行主成分提取与对比。在剔除光谱数据中的干扰元素后,计算与比较两种方法的主成分数量与贡献率,并利用RKPCA主成分进行综合传动多摩擦副的分类识别;对光谱数据和RKPCA特征值分别进行模糊C均值聚类,对比两种聚类结果应用在磨损状态评价中的效果。研究表明,由于光谱数据离群值与非线性影响,RKPCA较PCA的主成分数量稍小且累积贡献率高,说明前者能更有效地降低变量维数;通过RKPCA主成分与摩擦副组件的相关性分析可以看出,该方法可以精确的实现综合传动多摩擦副、多磨损部位的分类与识别,进而分类评价不同摩擦副的磨损状态;RKPCA特征值的模糊C均值聚类结果与光谱数据直接聚类结果相比,前者能更精确的定位磨损状态转化的临界点,从而准确评价综合传动整体磨损状态。油液光谱RKPCA分析方法的创新在于将特征值变化规律引入整体磨损状态评价,实现整体评价与关键摩擦副的分类评价相结合。这样不仅有助于综合传动大修期的准确判断,还能给出需维修部件建议。该方法也适用于其他复杂机械系统的磨损监测与评价等相关领域。     

基于拉曼光谱和多元统计学研究蓝色中性笔油墨

拉曼光谱作为一种无损检验的技术手段,近年来广泛用于文件检验领域中的书写材料种类检验。本实验采集了市面上收集到的28支蓝色中性笔油墨的拉曼光谱图,结合化学计量学中的相似度分析法和主成分分析法对谱图进行了分析,两种分析方法得到的分类结果基本一致,采用两种方法可以将28支蓝色中性笔油墨分为五类。实验结果表明,将拉曼光谱法得到的数据结合化学计量学分析方法进行数据分析,比直接比较谱图得到的分类结果更加客观、准确。     

基于深度聚类的目标细粒度分类方法北大核心CSCD

为提高光电系统对弱小目标的识别和分类能力,降低算法对硬件平台和数据的依赖,提出一种无监督分类方法−基于目标深度特征聚类的细粒度分类方法。该方法通过轮廓、颜色、对比度等浅层特征提取提示目标,经超分辨处理后,利用卷积神经网络对目标的深层特征进行编码,进一步采用基于注意机制的主成分分析方法进行降维生成表征矩阵,最后利用聚类的方式实现目标细粒度分类。实验验证了基于不同神经网络的深度聚类方法在不同数据集上的分类性能,其中采用ResNet-34聚类方法在CIFAR-10测试集上细粒度分类性能达92.71%,结果表明,基于深度聚类的目标细粒度方法能够取得与强监督学习方法相当的目标分类效果。此外,还可以根据不同簇数和聚类等级的选择实现不同细粒度的分类效果。     

红外光谱和聚类分析法无损快速鉴别赤芍

以赤芍的红外指纹图谱作为聚类分析的对象，在建立主成分模型的基础上，采用SIMCA聚类分析法对赤芍进行了快速的分类研究，结果表明，由于野生与野生与栽培赤芍的红外提纹图谱变异度较大，其光谱聚类的结果较理想，盲样检测的正确可达90％，由于不同产地的赤芍的红外指纹图谱异度较小，进行聚类分析后用盲样检测，正确率为75％，对于变异度较小的样品，若要提高识别的置信度，需增加样品的数目和采样的代表性，总之，红外指纹图谱与聚类分析法相结合可以快速鉴别药材的道地性。     

茶叶傅里叶红外光谱的可能模糊K调和均值聚类分析

茶叶的品种不同，其有机化学成分含量往往不同，其功效也是不尽相同的，因此，研究出一种简单、高效、识别率高的茶叶品种鉴别技术方法是十分有必要的。中红外光谱技术是一种快速检测技术，在用中红外光谱仪采集得到的茶叶中红外光谱中含有噪声信号。为了对含噪声茶叶中红外光谱的准确分类以实现茶叶品种分类，将可能模糊C-均值聚类(PFCM)思想应用到K调和均值(KHM)聚类，设计出一种可能模糊K调和均值(PFKHM)聚类算法，计算出PFKHM的模糊隶属度、典型值和聚类中心。可能模糊K调和均值聚类能有效解决K调和均值聚类的噪声敏感性问题。用傅里叶红外光谱分析仪(FTIR-7600型)分别对三种茶叶(优质乐山竹叶青、劣质乐山竹叶青和峨眉山毛峰)进行扫描以获取它们的傅里叶中红外光谱。光谱波数区间是4 001.569～401.121 1 cm-1。先采用主成分分析法(PCA)将光谱数据压缩到20维，再采用线性判别分析(LDA)将光谱数据压缩到两维并提取鉴别特征信息。最后分别用K调和均值聚类和可能模糊K调和均值聚类实现茶叶品种分类。实验结果：当权重指数m=2，q=2和p=2时，KHM具有91.67%的聚类准确率，PFKHM聚类准确率达到94.44%；KHM迭代12次达到收敛，而PFKHM迭代11次就可以达到收敛。采用傅里叶红外光谱技术检测茶叶，用主成分分析和线性判别分析压缩光谱数据，再用可能模糊K调和均值聚类进行品种分类可快速、准确地实现茶叶品种的鉴别。     

不同产地双色牛肝菌FTIR光谱鉴别研究

同一种蕈菌子实体,由于外观形貌相似,凭传统外观形貌特征难以鉴别产地来源。应用傅里叶变换红外光谱(FTIR)法测定了云南省5个不同地区58个野生双色牛肝菌子实体样品的红外光谱。借助于红外光谱具有的指纹特性,利用SPSS 13.0统计软件对1 350~750 cm-1范围光谱数据进行主成分分析(PCA),根据前三个主成分累积贡献率已达到88.87%以及主成分载荷分析,表明前三个主成分能够反映样品在该段光谱的主要信息。对前三个主成分作投影显示并进行比较,发现以主成分1和主成分2作二维线形投影,对不同产地的双色牛肝菌有较好的聚类和鉴别作用,所有样品被划分为5个区域,98.3%的样品被正确归类。研究结果提示,傅里叶变换红外光谱结合主成分分析方法可以快速、方便地对不同产地的同一种野生双色牛肝菌进行鉴别分类。     

Synthesis and Characterization of Triphenylethylene Derivatives with Aggregation-Induced Emission Characteristics

New aggregation-induced emission (AIE) compounds derived from triphenylethylene were synthesized. The thermal, photophysical, electrochemical and aggregation-induced emissive properties were investigated. All the compounds had strong blue light emission capability and good thermal stability. Their maximum fluorescence emission wavelengths were between 443 to 461 nm in solid states, while their glass transition temperatures ranged from 86 to 129 °C. The decomposition temperatures of the synthesized compounds were in the range of 432–534 °C. The synthesized compounds possessed aggregation-induced emission properties, namely exhibited enhanced fluorescence emission in aggregated states. The highest occupied molecular orbital (HOMO) energy levels estimated from the oxidation potentials were between 5.61 and 5.66 eV and the lowest unoccupied molecular orbital/highest occupied molecular orbital (LUMO/HOMO) energy gap values were found to be in the range of 3.18–3.22 eV. The compounds 4-(4-(2,2-bis(4-(naphthalen-1-yl)phenyl)vinyl)phenyl) dibenzothiophene [(BN)₂Bt] and 4-(4-(2,2-di(biphenyl-4-yl)vinyl)phenyl) dibenzothiophene [(BB)₂Bt] exhibited vibronic fine-structure photoluminescence spectra when the water fraction was less than 70%.     

The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 1 M hydrochloric acid

Corrosion inhibition by some new triazole derivatives on mild steel in 1 M hydrochloric acid solutions has been investigated by weight loss test, electrochemical measurement, scanning electronic microscope analysis and quantum chemical calculations. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds following the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were calculated.     

Studies of Luminescence Performance on Carbazole Donor and Quinoline Acceptor Based Conjugated Polymer

We report on the synthesis of conjugated polymer (CV-QP) containing carbazole (donor) and quinoline (acceptor) using Wittig methodology. The structural, optical and thermal properties of the polymer were investigated by FT-IR, NMR, GPC, UV, PL, cyclic voltammetry, atomic force microscopy (AFM) and thermogravimetric analysis (TGA). The polymer exhibits thermal stability upto 200 °C and shows good solubility in common organic solvents. The polymer has optical absorption band in a thin film at 360 nm and emission band formed at 473 nm. The optical energy band gap was found to be 2.69 eV as calculated from the onset absorption edge. Fluorescence quenching of the polymer CV-QP was found by using DMA (electron donor) and DMTP (electron acceptor). AFM image indicated that triangular shaped particles were observed and the particle size was found as 1.1 μm. The electrochemical studies of CV-QP reveal that, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the CV-QP are 6.35 and 3.70 eV, which indicated that the polymers are expected to provide charge transporting properties for the development of polymer light-emitting diodes (PLEDs).     

Scaled Quantum Chemical Studies of the Molecular Structure and Vibrational Spectra of Minoxidil

The Fourier transform Raman and Fourier transform infrared spectra for minoxidil have been recorded in the region 4000—100 cm^?1 and 4000—450 cm^?1, respectively. The structural and spectroscopy data of the molecule in the ground state were calculated by using density functional theory methods with 6-311G (d, p) basis set. A detailed vibrational analysis of the title compound has been done using normal coordinate analysis following the scaled quantum mechanical force field methodology. The calculated molecular geometry parameters and scaled vibrational wavenumbers are well compared with the experimental data. The electronic properties, such as excitation energies, absorption wavelength, highest occupied molecular orbital (HOMO), and lowest unoccupied molecular orbital (LUMO) energies were performed by time-dependent density functional theory approach, and the results are in good agreement with experimental absorption spectrum. The charge delocalizations of these molecules have been analyzed using natural bond orbital analysis. The molecule orbital contributions are studied by density of energy states. Fukui functions, local softness, and electrophilicity indices for selected atomic sites of the title compound are determined. Finally, the thermal behaviors of the compound have been calculated by different temperature.     

Effect of bromine substituent on optical properties of aryl compounds

Substituents significantly affect optical properties of organic compounds. In this study, a series of organic compounds were synthesized. Ultraviolet‐visible and cyclic voltammetry spectra were determined. The relationships between the number of π electron in an aryl ring and the redshift (and molecular orbital energy levels) were studied. To investigate mechanisms of the bromine substituent effects, theoretical calculations were carried out. Ultraviolet‐visible spectra of bromine‐containing compounds exhibit obvious redshifts (0.04‐0.17 eV) of the maximal absorption wavelengths and enhanced absorbance (11%‐57%) compared with corresponding reference compounds. The lowest unoccupied and highest occupied molecular orbital energy levels of compounds containing bromine substituents are 0.05 to 0.60 and 0.02 to 0.40 eV lower than that of corresponding reference compounds. On the whole, the redshifts and the reduced molecular orbital energy levels caused by bromine substituent decrease with the increase in the number of π electron in an aryl ring. The effects would be attributed to strong p‐π conjugation between p electron in the bromine substituent and π electrons in aryl rings. Therefore, this paper suggests a useful way for tuning optical absorption and molecular orbital energy levels of aryl compounds.     

Theoretical studies on nitrogen‐rich furoxan‐based heterocyclic derivatives

The density functional theory method was used to study the heats of formation (HOFs), energetic properties, electronic structure of a series of 4,4″‐dinitro(3,3′:4′,3′′)tris([1,2,5]oxadiazole)‐2′‐oxide (3,4‐bis[4′‐nitrofurazan‐3′‐yl]furoxan) derivatives. The results show that the substitution of the nitro group is very useful for improving their HOFs and detonation performances. The HOFs of the title compounds are all positive and larger than those of 1,3,5‐trinitro‐1,3,5‐triazinane and 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane. The analysis of oxygen balance shows that the studied compounds need the oxygen in the explosive. Compound A1 has larger detonation velocity and detonation pressure than those of 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane and can be regarded as a potential candidate for high‐energy compounds because of the moderate heat of detonation, high density, and high N. In addition, the energy gaps between the highest occupied molecular orbital and lowest unoccupied molecular orbital of the studied compounds are further investigated.     

Influence of donor and acceptor groups on the S-T energy gap for thermally activated delayed fluorescence emitters

Molecules composed of different donors and acceptors are theoretically designed as potential thermally activated delayed fluorescence emitters, and their singlet–triplet (S-T) energy gap is studied using the optimal Hartree–Fork method. It is found that the S-T energy gap is in reverse proportional to the electron-donating ability. Stronger electron-donating ability of donors will induce smaller highest occupied molecular orbital–lowest unoccupied molecular orbital overlap and also a smaller S-T energy gap. Based on our calculation results, three molecules are proposed to have great potential to be used as thermally activated delayed fluorescence emitters in organic light-emitting diodes.     

AunCu ( n =1-3)二元合金小团簇结构和稳定性的密度泛函研究

采用密度泛函理论(DFT) B3LYP 在SDD基组水平上对AunCu(n =1-3)二元合金小团簇各种可能的构型进行几何优化,预测了各团簇的稳定结构. 并对基态结构进行了研究,计算了平均结合能、最高占据轨道能级和最低空轨道能级以及两者间的能隙.结果表明掺杂Cu原子后使得AunCu(n =1-3)团簇的化学性质更稳定.     

Au_nCu(n=1～3)二元合金小团簇结构和稳定性的密度泛函研究

采用密度泛函理论(DFT)B3LYP在SDD基组水平上对Au_nCu(n=1～3)二元合金小团簇各种可能的构型进行几何优化,预测了各团簇的稳定结构.并对基态结构进行了研究,计算了平均结合能、最高占据轨道能级和最低空轨道能级以及两者间的能隙.结果表明掺杂Cu原子后使得Au_nCu(n=1～3)团簇的化学性质更稳定.     

Ab initio study for structure, electric properties and light emission of linear-trans-quinacridone

The structure, electric properties and emission rate of linear-trans-quinacridone are investigated within the density functional theory (DFT) calculations. We find the structure of the molecule to be planar with an energy gap of 3.06 eV. The emission lifetime from the lowest unoccupied molecular orbital (LUMO) to the highest occupied molecular orbital (HOMO) of this material is found to be 24 ns, which is in good agreement with experimental results.