三维荧光与紫外光谱联合表征样品中猝灭剂赋存状态:以胡敏酸与Fe(Ⅲ)相互作用为例

利用三维荧光-紫外光谱表征了荧光猝灭剂的赋存状态,当样品体系中存在Fe(Ⅲ)的情况下,胡敏酸会发生荧光猝灭现象,而其紫外光谱基本不受影响。考察了胡敏酸荧光强度I值(Ex/Em=300 nm/510nm)和紫外吸光度A值(UV300)的变化,I/A比值越小,说明水样中猝灭剂Fe(Ⅲ)浓度越高。当胡敏酸为10,15和20 mg·L~(-1)时,根据Stern-Volmer公式I/I_0=1-f_c×K_c×[c]/(1+K_c×[c])以及拟合函数I/A=f×[k/(CFe~(3+)+c)+b],拟合得到荧光猝灭常数K_c=1.08~1.15,比例系数f_c=1.10~1.14之间,胡敏酸荧光强度值与吸光度比值(I/A)及铁离子浓度(C_(Fe~(3+))相关曲线系数f=0.83~1.19,k=587.19~612.19,c=0.87~0.92,b=-87.09~-46.36,拟合曲线相关性R~2均为0.99。Stern-Volmer公式描述了Fe(Ⅲ)对胡敏酸荧光的猝灭作用,但实际样品测定时难以获得无猝灭剂时的荧光强度I_0。基于荧光强度I_0与紫外吸光度A之间的内在联系,两者比值I/A与Fe(Ⅲ)浓度c的拟合函数亦可以反映Fe(Ⅲ)对胡敏酸荧光的影响。利用拟合公式预测城市污水厂及纳污河流样品的树脂分离富集液中铁离子浓度,与电感耦合等离子体发射光谱仪实际测量值相比,铁离子浓度较高的情况下(铁离子浓度大于0.4 mg·L~(-1)时)预测结果较好,可以判断猝灭剂的存在及相应浓度。     

光谱特征提取对近似矿物光谱差异性影响分析

矿物光谱特征是基于光学遥感数据对矿物进行种类识别及定量反演的理论基础,光谱特征提取是高光谱数据常用的技术手段,但在多光谱数据中较少涉及。近似矿物识别是矿物光谱分类应用中的难点,目前还缺少有效指标来指示近似矿物类别光谱的差异性。光谱特征提取有望提高矿物分类精度,但该处理对近似矿物光谱差异性的影响还缺少相关研究。本文从矿物光谱差异性的原理出发,通过类间和类内光谱角的比值体现不同类别群体差异,并引入样本量因素,提出了类别可分比作为近似矿物光谱差异性的指标。以明矾石和高岭石两种近似矿物为例,对USGS光谱库光谱及Hyperion,ASTER,OLI等传感器的模拟数据进行光谱特征提取处理,通过对比处理前后矿物光谱差异性的变化,分析光谱特征提取对近似矿物光谱差异性的影响。实验结果表明,有效的光谱特征提取可以显著提高近似矿物光谱差异性,并且光谱分辨率越高,近似矿物光谱差异性越大。此外,光谱分辨率及中心波长设置对于包络线去除结果有很大影响,多光谱数据吸收特征提取效果有待进一步提高。该研究为今后近似矿物光谱识别精度的提高奠定了基础,也为未来新型遥感找矿传感器参数设置提供了参考。     

时频域分形维数分析的光谱信号重叠峰解析算法

由于光谱谱线存在自然展宽、多普勒展宽、碰撞展宽等,使混合气体中多种成分的吸收光谱信号出现相邻谱峰重叠现象,给混合气体组成成分的定性或定量检测带来较大的困难。现有的方法在获取先验知识、处理精度、运算效率等方面存在不足。提出基于时频域分形维数分析的光谱信号重叠峰解析算法,结合小波的多尺度观测能力和分形的自相似度的度量能力,识别、定位和解析光谱信号中的重叠峰。首先利用小波对具有重叠谱峰的光谱信号进行光谱频率域和尺度域的分析,然后对该时频域的光谱信号在同一光谱频率下的多尺度数据进行自相似性度量和分形计算。逐频率计算后得到光谱信号在频率域的分形维数曲线。该曲线体现了光谱信号在不同尺度的自相似性,其极值位置与光谱信号的各独立峰的位置具有相关性。依据此特性,结合分形曲线的特征参数,最后利用神经网络解析出对应混合气体成分的混叠在一起的各个独立谱峰。该方法利用小波的多分辨率特性,对信号进行不同尺度的精细度量。分形模型则提高了系统解析复杂信号的能力,对重叠程度高的多谱峰重叠信号也有很强的处理能力。借助人工神经网络,实现了整个算法的自动测量。通过实验结果分析,验证了算法的有效性,并讨论影响算法效果的主要因素。     

Fluorescence and absorption of polystyrene exposed to UV laser radiation

We show that when polystyrene is exposed (for 15–60 sec) to a UV laser light beam (λ = 248 nm), its absorption and luminescent properties change significantly. In the irradiated polymer, optical centers are formed with absorption bands in the 280–460 nm region and fluorescence bands in the 330–520 nm region. We have established the chemical structure of the optical centers for fluorescence of polystyrene. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 54–58, January–February, 2006.     

Surface and interfacial properties of PVDF/acrylic copolymer blends before and after UV exposure

Morphological and chemical properties of both the surface and interface of poly(vinylidene fluoride)/poly(methyl methacrylate)-co-poly(ethyl acrylate) (PVDF/PMMA-co-PEA) blend films have been investigated before and after the samples were exposed to ultraviolet (UV) irradiation using a xenon arc lamp at 50 °C and 9% relative humidity (RH) for 7 months. Surface and interfacial morphologies were studied by atomic force microscopy (AFM). Chemical composition information was obtained by confocal Raman microscopy, attenuated total reflection-FTIR spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. Results show an enrichment of the PVDF material at the air surface, while the acrylic copolymer enriches the interface. Blends having greater than 50% mass fraction of PVDF show little change in the surface morphology after UV exposure for 7 months. However, for a lower PVDF content, blends exhibit significant degradation of PMMA-co-PEA copolymer and a much rougher surface after UV exposure. Microstructural changes in the PVDF spherulites are also observed after UV degradation. It is found that the surface and interfacial morphologies are correlated with the chemical properties.     

First-principles study on the origin of optical transitions to be associated with F colour centers for PbWO4 crystals

The electronic structures of PbWO₄ crystals containing F type color centers with the lattice structure optimized are studied within the framework of the fully relativistic self-consistent Direc–Slater theory, using a numerically discrete variational (DV-Xα) method. The calculated results show that F and F⁺ centers have donor energy level in forbidden band. Their optical transition energy are 1.84 eV, 2.21 eV, respectively, which corresponds to the 680 nm, 550 nm absorption bands. It predicts that the 680 nm, 550 nm absorption bands originate form the F and F⁺ centers in PbWO₄ crystals.     

Acoustic characterization and prediction for fan-duct-plenum-room integrations

This paper investigates mutual influence of duct and room acoustics in the whole fan-duct-plenum-room integrations. Applying the parametric design language of finite element software ANSYS (APDL), dimensional and positional influence on system acoustics has been studied. Models with different room dimensions, duct lengths, duct cross-sections, duct locations, duct discharges and duct elbow were constructed, and their characteristics were compared qualitatively. Results show that small rooms, short ducts, large duct cross-sections and bell mouth duct discharges help to increase room sound pressure levels (SPLs); SPLs in ducts and plenums are sensitive to duct dimensions and duct discharge types but insensitive to duct locations and room dimensions; duct elbows have relatively indistinct acoustic influence in each component. Based on the calculation results, a semi-experimental method was proposed for simply and approximately evaluating indoor acoustic spectra of fan-duct-plenum-room integrations, then an example was used to demonstrate the prediction process. Finally, by adopting several ideal models, sound field constitutions, duct and room wall admittances and duct end reflection were explored quantitatively. This study may give a detailed understanding of fan-duct-plenum-room acoustics for researchers, also it might provide a new, simple and approximate prediction method for professionals to evaluate and improve fan-ducted acoustics.     

细菌视紫红质高分辨图象存储中吸收和散射现象的实验研究

本文利用细菌视紫红质变种材料BR_D96N的基态和M态实现了图象的高分辨存储.实验研究了该样品的吸收特性;在此基础上分析了散射光对BR膜图象质量的影响,并通过合理的控制激发光强和激发时间在BR膜样品上得到分辨率为800lp/mm的高分辨图象.     

微波消解-GFAAS法测定蘑菇中的痕量铅

采用微波制样技术，石墨炉原子吸收法测定蘑菇中痕量铅，结果表明，方法的线性范围为0－100μg,检出限为2．6μg,相对标准偏差为3．0％，回收率为98％，该法准确，快速、简便，与常压酸消解法比较，结果基本一致，已用于蘑菇中痕量铅的测定。     

防紫外线伞ATR-OMNI采样器的FTIR分析

本实验使用OMNI采样器，直接对伞面内外进行单反射ATR的分析，快速、简便、不破坏样品，得到分辨率很好的红外图谱，再配合红外谱库的谱图检索，可以分别得到匹配率95％以上的尼龙－6和聚酯型聚氨酯的分析结果。