傅里叶变换红外光谱在胃癌淋巴结转移诊断中的应用研究

观察傅里叶变换红外光谱技术无创、原位、快速诊断胃癌淋巴结转移的可行性。联合使用衰减全反射探头及傅里叶变换红外光谱仪测量新鲜离体胃周淋巴结红外光谱,发现每条光谱在吸收波长3 000～1 000 cm-1之间循序出现13条谱带,依据病理检测结果将淋巴结分为转移组及非转移组,比较两组淋巴结红外光谱的峰位和相对峰强等指标结果,最后进行标准统计学分析。36例胃癌患者,共检测淋巴结720枚,其中转移性淋巴结180枚,未转移540枚;与非转移淋巴结相比,转移淋巴结红外光谱有如下特征：(1)与核酸相关的峰强比I_{1 240}/I_{1 460}(p=0.015)和I_{1 080}/I_{1 460}(p=0.034)显著升高,提示转移淋巴结细胞的核酸含量增多;(2)与蛋白相关的I_{1 640}/I_{1 460}(p=0.001)和I_{1 546}/I_{1 460}(p=0.027)峰强比值升高,表明转移淋巴结组织的蛋白质含量明显升高;(3)与脂类相关的I_{2 855}/I_{1 460}和I_{1 740}/I_{1 460}显著降低(p＜0.001),提示癌组织脂类含量相对减少;(4)I_{1 160}/I_{1 460}(p=0.023)显著降低,表明恶性细胞糖类物质的减少。研究结果显示,傅里叶变换红外光谱分析技术有望成为术中原位、在体和快速诊断胃癌淋巴结转移的新方法。     

不同预处理方法对苯丙酮尿症FTIR/ATR光谱筛查模型的影响

建立苯丙酮尿症的FTIR/ATR光谱筛查模型,比较基线校正、平滑、求导、傅里叶退卷积等光谱预处理方法对模型精度的影响。利用多模型共识偏最小二乘法(cPLS)建立干血片中苯丙氨酸浓度的校正模型,以相关系数(r)、预测均方根误差(RMSEP)、平均相对误差(MRE)和预测准确率(Acc)等指标,考察不同预处理方法对建模效果的影响。结果 一阶微分9点平滑处理方法效果最好。与原始光谱相比,模型的r,RMSEP,MRE和Acc分别从0.822 7,115.8,0.395和94.6改善到0.889 9,102.2,0.286和100。本方法直接快速、 不消耗试剂、 不产生污染,有望成为PKU大人群快速筛查的简便、 绿色新技术。     

质子数Z 分别位于Ru 之上和之下的A~(100~126) 丰中子原子核三轴形变在原子核形状变迁和共存中的重要作用(英文)

基于Ru (Z = 44) 丰中子同位素中存在最大三轴形变的理论预言和实验证据,综述了近年来Rh (Z = 45),Pd (Z =46), Ag (Z =47), Cd (Z =48)(质子数Z 位于Ru,Z =44 之上)及Zr (Z =40), Nb (Z =41), Mo (Z =42),Tc (Z =43)(质子数Z 位于Ru,Z =44 之下) 的A~ (100~126) 丰中子同位素中关于三轴形变的形状变迁和形状共存系统性研究的重要进展。252Cf 自发裂变瞬发 射线-- 三重符合、特别是新建立的--- 四重符合数据的系统观测和研究,在Ru, Pd, Cd 和Nb 丰中子同位素中显著扩展或首次观测到了一系列能带,为这个核区原子核形状的研究提供了新的、重要的实验数据。联系此前报道的有关进展,使用PES, TRS, PSM, CCCSM 和SCTAC 理论模型计算拟合新的实验数据,在该核区沿同中素和同位素链,并随自旋和激发能变化各自由度,跟踪原子核形状渐进变化,获得了新的系统性研究成果,显著扩展和深化了人们对原子核形状变迁和形状共存的认知。对于Ru 及其上的Rh (Z = 45), Pd (Z = 46), Ag (Z = 47) 和Cd (Z = 48) 丰中子同位素的研究表明:Rh 丰中子核具有比最大值稍小的三轴形变,γ = 28°,并在103{106Rh 同位素链上鉴别出了手征对称破缺;在三轴形变核112Ru和114Pd(N = 68)中发现了三轴原子核的摆动运动,该摆动运动也可能在114Ru (N = 70)中存在;观察到了从具有最大三轴形变的110,112Ru 中手征破缺到稍小三轴形变的112,114,116Pd 中扰动的手征破缺的过渡;在较软的Ag 核中观察到了丰富的谱学结构,在104,105Ag 中鉴别出了可能的手征对称破缺,在较重的115,117Ag 中提出了趋于三轴形变的软度;具有小形变的Cd核的能级结构被解释为准粒子耦合、准转动和软三轴形变;最近的库伦激发的研究提供了Z = 50, N = 82满壳附近122,124,126Cd 核中出现核集体性的实验和理论证据;上述研究成果展现出从Ru中的最大三轴形变(γ=30°,三轴形变极小增益为0.67 MeV), 经具有大三轴形变的Rh核γ=28°),到Pd核中的稍小、但稳定于中等自旋到高自旋区的三轴形变(γ~41°,三轴形变极小增益为0.32 MeV),再经Ag核中的软度,最后到具有很小形变、但仍出现集体性质、包括软三轴形变的Cd核的过渡。对于Pd核转动带交叉系统性的研究揭示了其第一带交叉(νh_11/2)2 中子转动顺排的上行驱动,和第二带交叉(πg_9/2)2质子转动顺排的下行驱动效应,成功地解释了114Pd 中的三轴摆动运动,并给出了110-118Pd同位素链中理论早已预言、而比早期理论预言更为完整准确的形状渐进变迁和形状共存的图像。根据该核区的系统研究,发现最大三轴形变出现在112Ru,而在相邻的偶Z(Pd)同位素链,三轴形变极小的中心在114Pd, 两者均为N = 68。上述系统性研究沿相邻的Ru和Pd偶Z同位素链,在N =68同中素中鉴别出最大三轴形变,均比理论预言的108Ru 和110Pd 多4个中子。在Z值位于Ru (Z = 44) 之下的Zr (Z = 40), Nb (Z = 41), Mo (Z = 42) and Tc (Z = 43) 丰中子同位素中,Y和Zr核具有很强的轴对称四极形变,而在较重的Zr同位素中出现了自由度;较重的Nb核(A = 104~106) 基态具有中等程度的软三轴形变和强四极形变,随着自旋和激发能的增加,过渡到接近于轴对称的强四极形变;而较轻的Nb核(A≤103) 基态均接近轴对称形状;在Nb同位素链上基态由球形到强四极形变的形状突变发生在100Nb(N = 59),在100-106Nb同位素链中基态的软三轴形变随中子数增加而增加;在Nb核中还观察到关于软三轴形变的形状共存;Mo核具有大的三轴形变,观察到了振动和手征对称破缺;Tc核具有比最大值稍小的三轴形变,γ=26°,并观察到了手征对称破缺。质子数Z从41到48的A~(100~126)丰中子同位素,特别是Pd和Nb 同位素,呈现出关于三轴形变的过渡特征。This paper reviews the systematic investigations and understanding for the shape transitions and coexistence with regard to triaxial deformations in A s 100 to 126 neutron-rich Rh (Z = 45), Pd (Z = 46), Ag (Z = 47), Cd (Z = 48) and Zr (Z = 40), Nb (Z = 41), Mo (Z = 42), Tc (Z = 43) isotopes with Z beyond and below Ru (Z = 44), respectively, in Ru the maximal triaxial deformation having been predicted and deduced. The recent measurements and studies of prompt triple- and four-fold, γ-γ-γ and γ-γ-γ-γ, coincidence data from the spontaneous fission of 252Cf using Gammasphere have yielded considerable expansion and extension or first observation of the bands in Ru, Pd, Cd, and Nb isotopes,which provided important data for the studies of nuclear shapes in this region. Combined with previous investigations, recent systematic studies of the new data well reproduced by PES, TRS, PSM, CCCSM and SCTAC model calculations have traced shape changes along the isotonic and isotopic chains, respectively,and with changing excitations/spins as well, significantly expanding our knowledge of shape transitions/coexistence in nuclei.For the neutron-rich Ru and beyond, Rh, Pd, Ag and Cd isotopes, triaxial deformations γ= 28°,slightly smaller than the maximal value, were deduced in Rh (Z = 45) isotopes, with chiral symmetry breaking proposed in 103-106Rh; onset of wobbling motions were identified in 112Ru and 114Pd (N =68),and probably also in 114Ru (N =70); evolution from chiral symmetry breaking in 110,112Ru with maximal triaxial deformations to disturbed chirality in 112,114,116Pd with less pronounced triaxial deformations was proposed; rich nuclear structure was proposed in soft Ag isotopes with possible chiral doubling structure suggested in 104,105Ag, and softness towards triaxial deformation proposed in heavier 115,117Ag;quasi-particle couplings, quasi-rotations and soft triaxiality were suggested in Cd (Z =48) isotopes with small deformations; onset of collectivity was recently suggested in 122,124,126Cd in the vicinity of Z =50 and N = 82 closed shells by studies of Coulomb excitations; shape evolutions from maximal triaxial deformations in Ru (γ=30°, with triaxial minimum energy gain of 0.67 MeV), through Rh with large triaxial deformations ( γ=28°), to less pronounced triaxiality in Pd (with triaxial minimum energy gain of 0.32 MeV), then soft triaxiality in Ag, and finally to slightly deformed Cd isotopes but with emergence of collectivity and soft triaxiality were proposed. The systematic studies of the band crossings in Pd revealed up-rising drivings of the first band crossings caused by (νh_11/2)2 and down-sloping drivings of the second band crossings by (πg_9/2)2, explained the onset of wobbling motions in 114Pd,and showed a long-sought picture of shape evolution and coexistence in the Pd isotopic chain which is more complete but complex than earlier predictions. Based on the systematic studies in the mass region,maximal triaxial deformation is found to be reached in 112Ru and less-pronounced triaxiality centered at 114Pd, both for N =68, four neutrons more than predicted in earlier theoretical calculations.In the neutron-rich Zr (Z =40), Nb (Z =41), Mo (Z =42) and Tc (Z =43) isotopes with Z just below Ru, large quadrupole deformations of axially symmetric shapes were deduced in Y and Zr isotopes, with emergence of the degree of freedom having been suggested for heavier Zr isotopes; medium triaxial deformations were deduced for the ground states of heavier (A > 104) Nb isotopes, and, with increasing excitations and spins, evolution from medium triaxial deformations with strong quadrupole deformations at ground states to nearly axially-symmetric shapes were deduced; light Nb isotopes (A6103) have near axially-symmetric shapes with strong quadrupole deformations; combining with the identification of onset of strong quadrupole deformation at 100Nb in the Nb isotopic chain, an increase of soft triaxiality with increasing neutron number was proposed in 100-106Nb. Shape coexistence with regard to soft triaxiality is also proposed in Nb isotopes; large triaxial deformations, vibrations and chiral doublets were proposed in Mo isotopes; chiral doubling and large triaxial deformations (γ ~26°) slightly smaller than the maximal triaxiality were suggested in Tc isotopes.The neutron-rich nuclei with Z ranging from 41 through 48 and A ~100 to 126, especially the Pd and Nb isotopes are thus found to be transitional nuclei with regard to triaxiality.     

用长气体靶研究22Na+α共振散射

在日本东京大学CRIB 次级束装置上,用长气体靶开展了22Na+ α共振散射的厚靶实验研究。针对长气体靶实验中的两体运动学重构问题,提出了一套包括构建空间复杂几何关系、计算能量损失以及反应运动学的逐事件分析方法;对22Na+α共振散射的实验数据进行了重构分析,得到了E_c.m. = 4.2 ~ 5.4 MeV 区间22Na( α,α ) 的激发函数,从实验的激发函数中观测到了复合核26Al 5 个较为明显的共振峰。鉴于26Al 共振态的衰变模式比较复杂,本工作发现的26Al新共振态的能级性质有待进一步的理论分析。The 22Na+α resonant scattering is studied via a conventional thick target inverse kinematic method with an extended gas target. A data analysis method is proposed for the two-body reaction kinematic reconstruction, in which the spatial geometry, the reaction kinematics and the energy losses are considered. The experimental data of 22Na+ αresonant scattering have been thus reconstructed, and the excitation function is obtained in the energy interval of Ec.m. =4.2~5.4 MeV. Five resonant states in 26Al are observed in the experimental excitation function. Since several decay modes coexist for the observed 26Al resonant states, multi-channel theoretical analysis is thus needed to reveal their structure and decay features.     

傅里叶变换红外光谱结合化学计量学鉴别预包装纯菠萝汁中外源糖

为了快速、准确鉴别预包装纯菠萝汁是否掺有外源性糖,采用傅里叶变换衰减全反射中红外光谱技术采集900～1 500 cm-1范围内不同批次的预包装纯菠萝汁样品和掺入甜菜糖浆、大米糖浆、木薯糖浆的菠萝汁掺假样品的中红外光谱共计234例,以线性判别分析和支持向量机分析为掺假鉴别模型的建模方法,比较了全波段谱图与通过主成分载荷系数分析选取特征波长图谱的两种掺假鉴别模型。研究表明,全波段图谱的线性判别分析和支持向量机分类模型对验证集的判断正确率均高于88%;选取8个特征波长之后,线性判别分析模型验证集判断正确率提高至96.15%,支持向量机模型验证集判断正确率提高至94.87%,且模型输入变量由312个减少到8个。利用傅里叶变换衰减全反射中红外光谱技术结合化学计量学方法选取特征波长后建立的模型可以较好的应用于预包装纯菠萝汁外源糖的鉴别。     

三级烯酰胺的串联Heck反应——一种反式2,5-二芳基-3-吡咯啉化合物新颖的合成方法

3-吡咯啉化合物不仅是重要的有机合成中间体, 而且其骨架结构广泛存在于具有生物活性的化合物中. 利用五元环三级烯酰胺的串联Heck反应, 实现了反式2,5-双取代-3-吡咯啉化合物简便、快捷的合成. 该方法首次将环状烯酰胺的α-芳基化反应和双键异构化进行了有效的结合, 为2,5-双取代-3-吡咯啉化合物的合成提供了一种全新的合成方法. 得到的3-吡咯啉产物可分别经氧化反应和还原反应方便地转化成吡咯或吡咯烷化合物.     

锗硅烯与CH3OH加成反应机理及区域选择性

采用密度泛函理论方法,在B3LYP/6-311++G(d, p)水平,研究了几种锗硅烯与CH₃OH的加成反应的微观机理和势能剖面,分析了锗硅烯中Si=Ge双键的极性对加成反应区域选择性的影响.研究结果表明,锗硅烯可分别与CH₃OH的单聚体或二聚体发生加成反应.所有加成反应均从初始亲核或亲电复合物的形成开始.母体锗硅烯H₂Si=GeH₂与CH₃OH二聚体的加成反应比其与CH₃OH单聚体的相应反应在动力学上更容易些,但在其它锗硅烯与CH₃OH的反应中情况则相反.用Ph或SiMe₃基团取代H₂Si=GeH₂中的H原子在动力学上使反应变得不利且SiMe₃基团的影响更显著.加成反应的区域选择性与锗硅烯中Si=Ge双键的极性以及Si-O(Ge-H)和Ge-O (Si-H)键的相对强弱都有关.     

Research on the cyclostationary nearfield acoustic holography based on boundary element method

Cyclostationary sound field is a special kind of nonstationary sound field, in which the pressure signal is modulated seriously and sidebands exist in its spectrum. The reconstructed sound field can＇t figure the cyclostationary features in conventional Nearfield Acoustic Holography （NAH） procedure. On the basis of planar cyclostationary NAH, the cyclostationary NAH based on boundary element method is proposed which can be utilized to analyze radiators with complicated surface. Replacing the Fourier＇s transform with the second-order cyclic statistics, the Cyclic Spectral Density （CSD） functions is used as the reconstructed physical quantity in the proposed NAH technique, instead of the spectrum or power spectral density of pressure signal. By virtue of the demodulation ability of CSD function, the reconstructed CSD can effectively express the information of modulating and carrier wave respectively. The simulation and experiment illustrate that the validity and accuracy of this cyclostationary NAH technique satisfy the request of engineering.     

大气污染物垂直廓线扫描差分吸收光谱方法研究

差分光学吸收光谱法(DOAS)已经成为测量大气痕量气体含量的常用方法,该方法灵敏度高,可同时监测多种大气痕量气体.提出了应用差分吸收光谱方法监测大气痕量气体垂直分布,结合放置数套角反射器的近地层高塔,研制出扫描长光程差分吸收光谱(扫描LP-DOAS)系统.应用此系统于2007年夏季对北京城市重要大气污染物NO2的垂直分布进行了外场监测,准确获得了NO2沿各光路的积分浓度,确定了系统在各光路的检测限和系统总的测量误差.基于垂直廓线模型,成功反演了NO2的垂直廓线和垂直梯度.研究结果表明扫描LP-DOAS技术监测城市大气近地层痕量气体垂直分布的可行性.     

低温下Co(OH)_2晶体的光谱研究

采用点电荷模型,以平均共价因子N作为拟合参量和用Bkq作为晶场参量,运用完全对角化方法对Co(OH):晶体在90K时的吸收光谱进行了理论计算,并首次对其光谱进行了识别.同时讨论了温度对能级和配体键长的影响,从而认识到能级随温度的升高而按一定比例下降的变化关系.