PSO-LSSVM对LIBS定量分析精度的提高

针对土壤定量分析受基体效应影响大，LIBS定量分析精度不佳等问题，采用粒子群算法对LSSVM进行优化，提高模型的精确度。选取Pb Ⅰ 405.78 nm和Cr Ⅰ 425.44 nm作为分析谱线进行分析。采集十二个不同浓度样品的特征光谱，每个浓度样品在不同点采集20组数据，将其中17组数据设为训练集，3组数据设为预测集，用LSSVM和PSO-LSSVM两种方法建立定标模型。对比两种模型的拟合相关系数（R2）、训练集均方根误差（RMSEC）和预测集均方根误差(RMSEP)。由于自吸收效应的影响，随着浓度的增加，预测值逐渐低于实际值，LSSVM定标模型的拟合程度较低，无法达到实验要求，模型性能有待提高。利用粒子群算法对LSSVM的模型参数惩罚系数和核函数参数进行优化，得到最佳的参数组合，Pb元素为(8 096.8, 138.865 7)，Cr元素为(4 908.6, 393.563 5)，用最佳的参数组合构建LSSVM的定标模型。相比于LSSVM，PSO-LSSVM定标模型的精确度更高，Pb和Cr元素的R2提高到了0.982 8和0.985 0，拟合效果明显提升。Pb和Cr元素的训练集均方根误差由0.026 0 Wt%和0.027 2 Wt%下降到0.022 4 Wt%和0.019 1 Wt%，预测集均方根误差由0.101 8 Wt%和0.078 8 Wt% 下降到0.045 8 Wt%和0.042 0 Wt%，模型的稳定性进一步提高。说明PSO-LSSVM算法能够更好地降低土壤基体效应和自吸收效应带来的影响，提高分析结果的精确度与稳定性。     

对称向量拟均衡问题有效解的存在性

利用标量化方法建立对称向量拟均衡问题有效解的存在性定理。作为标量化方法的应用，利用这一方法得到向量变分不等式和拟向量变分不等式有效解的存在性定理。     

Semi-concurrent vector fields in Finsler geometry

In the present paper, we give an answer to a question which is closely related to doubly warped product of Finsler metrics: ‘‘For each n, is there an n-dimensional Finsler manifold $(M,F)$, admitting a non-constant smooth function f on M such that $\frac{\partial f}{\partial x^i}\frac{\partial g^{ij}}{\partial y^k}=0$?”. We relate the preceding mentioned condition to different concepts appeared and studied in Finsler geometry. We introduce and investigate the notion of a semi concurrent vector field on a Finsler manifold. We show that some special Finsler manifolds admitting such vector fields turn out to be Riemannian. We prove that Tachibana's characterization of Finsler manifolds admitting a concurrent vector field leads to Riemannian metrics. Various examples for conic Finsler spaces that admit semi-concurrent vector field are presented.     

利用带无标签数据的双支持向量机对恒星光谱分类

恒星光谱分类是天文技术与方法领域一直关注的热点问题之一。随着观测设备持续运行和不断改进，人类获得的光谱数量与日俱增。这些海量光谱为人工处理带来了极大挑战。鉴于此，研究人员开始关注数据挖掘算法，并尝试对这些光谱进行数据挖掘。近年来，神经网络、自组织映射、关联规则等数据挖掘方法广泛应用于恒星光谱分类。在这些方法中，支持向量机(SVM)以其强大的学习能力和高效的分类性能而备受推崇。SVM的基本思想是试图在两类样本之间找到一个最优分类面将两类分开。SVM在求解时，通过将其最优化问题转化为具有(QP)形式的凸问题，进而得到全局最优解。尽管该方法在实际应用中表现优良，但为了进一步提高其分类能力，有的学者提出双支持向量机(TSVM)。该方法通过构造两个非平行的分类面将两类分开，每一类靠近某个分类面，而远离另一个分类面。TSVM的计算效率较之传统SVM提高近4倍，因此，自TSVM提出后便受到研究人员的持续关注，并出现若干改进算法。在恒星光谱分类中，一般分类算法都是根据历史观测光谱来建立分类模型，其中最关键的是对光谱进行人工标注，这项工作极为繁琐，且容易犯错。如何利用已标记的光谱以及部分无标签的光谱来建立分类模型显得尤为重要。因此，提出带无标签数据的双支持向量机(TSVMUD)用以实现对恒星光谱智能分类的目的。该方法首先将光谱分为训练数据集和测试数据集两部分；然后，在训练集上进行学习，得到分类依据；最后利用分类依据对测试集上的光谱进行验证。继承了双支持向量机的优势，更重要的是，在训练集上学习分类模型过程中，不仅考虑有标记的训练样本，也考虑部分未标记的样本。一方面提高了学习效率，另一方面得到更优的分类模型。在SDSS DR8恒星光谱数据集上的比较实验表明，与支持向量机SVM、双支持向量机TSVM以及K近邻(KNN)等传统分类方法相比，带无标签数据的双支持向量机TSVMUD具有更优的分类能力。然而，该方法亦存在一定的局限性，其中一大难题是其无法处理海量光谱数据。该工作将借鉴海量数据随机采样思想，利用大数据处理技术，来对所提方法在大数据环境下的适应性展开进一步研究。     

高光谱成像的土壤剖面水分含量反演及制图

传统土壤水分的获取方法仅可获得离散的土壤水分点位数据，难以获得剖面上精细且连续的水分含量分布图。研究了野外条件下利用近红外高光谱（882～1 709 nm）成像反演剖面土壤水分含量（SMC），并实现精细制图的可行性。研究剖面位于江苏省东台市，我们利用近红外高光谱成像仪对剖面进行了5天原位连续观测，共采集了280个土样用于烘干法测定SMC。原始高光谱图像经数字量化值（DN）校正、黑白校正、拼接、几何校正、剪切和掩膜等一系列预处理后，提取各采样点的平均光谱反射率。提取光谱（Raw）经吸光度[LOG₁₀(1/R)]，Savitzky-Golay平滑（SG）、一阶微分（FD）、二阶微分（SD）、多元散射校正（MSC）和标准正态变量（SNV）转换后，采用偏最小二乘回归（PLSR）和最小二乘支持向量机（LS-SVM）方法建立SMC预测模型，并对比分析不同光谱预处理方法与建模方法组合条件下SMC的预测精度。结果表明，光谱反射率随SMC增加逐渐降低，不同光谱预处理方法的预测精度有所差异，除MSC方法外，同一光谱预处理方法的LS-SVM模型预测精度均高于PLSR模型，并且基于LOG₁₀(1/R)光谱的LS-SVM模型对SMC预测精度最高，其建模集的决定系数（R2_c）和均方根误差（RMSE_c）分别为0.96和0.65%，预测集的决定系数（R2_p）、均方根误差（RMSE_p）和相对分析误差（RPD_p）分别为0.88，1.05%和2.88。利用最优模型进行剖面SMC的高空间分辨率精细制图，通过比较SMC反演图中提取的预测值与实测值关系发现预测精度较高（R2: 0.85～0.95, RMSE: 0.94%～1.02%），且两者在剖面中的变化趋势基本一致，说明SMC反演图不仅能很好地反映出土壤水分在整个剖面中毫米级的含量分布信息，也可反映出同一位置处不同天数间的含量差异。因此，利用近红外高光谱成像结合优化的预测模型，能够实现土壤剖面SMC的定量预测及精细制图，有助于快速、有效监测田间剖面土壤水分状况。     

In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a C −C Stille Coupling

Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent.     

Star-Shaped Ruthenium Complexes as Prototypes of Molecular Gears

The design and synthesis of two families of molecular-gear prototypes is reported, with the aim of assembling them into trains of gears on a surface and ultimately achieving controlled intermolecular gearing motion. These piano-stool ruthenium complexes incorporate a hydrotris(indazolyl)borate moiety as tripodal rotation axle and a pentaarylcyclopentadienyl ligand as star-shaped cogwheel, equipped with five teeth ranging from pseudo-1D aryl groups to large planar 2D paddles. A divergent synthetic approach was followed, starting from a pentakis(p-bromophenyl)cyclopentadienyl ruthenium(II) complex as key precursor or from its iodinated counterpart, obtained by copper-catalyzed aromatic Br/I exchange. Subsequent fivefold cross-coupling reactions with various partners allowed high structural diversity to be reached and yielded molecular-gear prototypes with aryl-, carbazole-, BODIPY- and porphyrin-derived teeth of increasing size and length.     

Assessment of Noise Exposure of Sawmill Workers in Southwest,Nigeria

Economic wood processing employs the use of industrial machines for cutting, shaping, milling, and sawing timber, thereby leading to the generation of high levels of noise. Published data from empirical studies have categorized noise as an environmental hazard of global significance. Furthermore, noise exposure limits for different industries and all the industrial machines available has not been formally established as it presently exists in developed nations around the world. Therefore, this study assessed the daily exposure of sawmills workers to noise in Southwestern Nigeria. Reconnaissance surveys were first carried out in Osun, Oyo, Ondo, Ekiti, Lagos, and Ogun States to select sawmills that were fully operational and fit for the study. Two fully functional sawmills in two cities of each State were eventually selected for data collection, making a total of 24 sawmills, while the Circular Machines (CM), Planer Machines (PM), and Band-saw Machines (BM) were the machines in each sawmill considered. Two machines each of CM, PM, and BM were considered in each sawmill, making a total of forty-eight (48) machines each of CM, PM, and BM. Sound data were collected between 7 am and 7 pm each day for six days (between Monday and Saturday) using Extech 407732 sound level meter and all stabilized measurements were taken three times at different intervals. The data collected were in three different periods: Machine No-work Period (NP_m), Machine Idle Period (IP_m), and Machine Working Period (WP_m). A two–way Analysis of Variance (ANOVA) was carried out at P < 0.05 to determine whether there is a significant difference in the sound level average before and after the break, for both the idle and working periods of the three machines considered. This was also done to determine whether there is a significant difference between the sound level average of the results collected during idle and working periods of the three machines. Noise Pollution Levels (L_np) ranged from 83.20 dB (PM) to 107.65 (BM) and 93.42 (CM and PM) – 116.00 (BM) respectively, while IP_m also gave the least noise pollution level of 95.79 dB and WP_m gave the highest level of 102.88 dB. The results revealed that all the machines’ L_np values in the working period are more than the 90 dB acceptable limit the recommendation value of 90 dB while 89.6% of CMs, 75% of PMs, and 89.6% of BM had their L_np above 90 dB in the idle period respectively. The minimum and the maximum noise dose levels for IP_m, WP_m and overall are 0.09 (BM) and 2.37 (CM), 0.50 (CM), and 4.77 (PM) and 0.69 (BM) and 6.64 (PM) respectively. The study found out that the fundamental contributing factors to the high noise levels in sawmills are poor machine maintenance, use of old and obsolete machines, poor housekeeping strategy, limited space, workers’ negligence, lack of PPE, and lack of occupational safety training. The study recommends that proper workplace practices such as use of personal protective equipment, new and modern machines, training, and occupational safety programmes be implemented in the considered sawmills.     

基于i PLS的矿井突水激光诱导荧光光谱特征波段筛选

矿井突水一直威胁着煤矿井下施工人员的生命安全，准确且快速识别矿井突水水源类型对于矿井的安全生产起到关键性作用。激光诱导荧光(LIF)光谱技术识别矿井突水水源，有效避免了常规的水化学法需要测定多种化学参数，水源识别时间过长的缺点。提出一种间隔偏最小二乘法(iPLS)与粒子群联合支持向量分类算法(PSO-SVC)相结合的方法，iPLS算法常应用于光谱波段优选和模型的回归分析，PSO-SVC则在机器学习领域有着重要的应用，激光诱导荧光技术具有快速的时间响应、测量精度高等特点，iPLS和PSO-SVC算法运用于光谱图和光谱数据的分析，进而可以对突水水源类型识别分类。首先，用淮南矿区采集到的7种(每种水样30组)共210组荧光光谱数据进行实验，对老空水、灰岩水、灰岩水和老空水不同体积比混合水样的激光诱导荧光光谱图的差异性进行分析。比较了留出法和Kennard-Stone样本划分方法所得到的PSO-SVC模型分类准确率，采用留出法得到的训练集水样(140组)和测试集水样(70组)作为实验样本。其次，用iPLS算法将全光谱波段依次按10～25波段区间进行等分，选取划分区间的RMSECV(交叉验证均方根误差)值小于全光谱波段RMSECV值(阈值)的波段作为特征波段，结合光谱图对比分析了划分10和14个子区间的建模结果，发现通过直接观察得到的特征波段与iPLS算法筛选出的特征波段存在误差。最后，在不进行去噪、降维等预处理条件下，根据iPLS划分不同区间数的评价指标统计数据，选取划分11个区间所筛选出具有561个波长点的410.078～478.424和545.078～674.104 nm特征波段范围数据作为PSO-SVC模型的输入，以iPLS结合PSO-SVC算法筛选出的特征波段与全光谱波段、直接观察得到波段建模准确率相比，训练集与测试集的分类准确率高达100%，PSO寻优到的最佳惩罚系数c为1.367 0，核函数参数g为0.576 2。从实验结果可以看出，利用iPLS进行荧光光谱的特征波段筛选是切实可行的，提取出的特征波段能充分反映出全光谱波段的有效信息，为激光诱导荧光光谱技术用于矿井突水水源精准在线识别的研究提供了理论依据。