与DNA形成电子激发态复合物的水溶铜卟啉Cu（NEAE）的共振拉曼研究

本文用４００ｎｍ和４４５ｎｍ脉冲激光激发测量了不同功率条件下的水溶酮卟啉Ｃｕ（ＮＥＡＥ）（４－Ｎ－乙酸酯基－吡啶基铜卟啉）及其与小牛胸腺脱氧核糖核酸（ＤＮＡ）复合物的共振拉曼光谱。结果表明，Ｃｕ（ＮＥＡＥ）与ＤＮＡ形成了电子激发态复合物。首次观察到激发态铜卟啉除拉曼谱带Ⅵ（～１３７０ｃｍ＾－１）和Ⅷ（～１５７０ｃｍ＾－１）外Ⅶ带（～１４７０ｃｍ＾－１）也出现代表激发态复合物形成的额外峰。激发态复合     

非晶PET纤维的分子链段取向分布的研究

用对称透射法,收集在室温下不同拉伸比的非晶聚酯（ＰＥＴ）纤维之二有Ｘ射线散射（ＷＡＸＳ）强度函数Ｉ（κ,α）,采用自编ＭＰＳ９６型全谱分峰程序,将不同方位角α测得的ＷＡＸＳ强度曲线上的４个非晶重叠峰进行分解,获得分子链间原子 射引起的２个峰为：ＫＡ＝０．１４１ｎｍ＾－１,ＫＢ＝０．１７２ｎｍ＾－１;分子链内原子 射引起的２个峰为;ＫＣ＝０．３１１ｎｍ＾－１,ＫＤ＝０．５５５ｎｍ＾－１,详细分析了     

Eu2（DBM）6 4,4‘—BIPY的合成,光谱及铕（Ⅲ）格位

合成了配合物Ｅｕ２（ＤＢＭ）６４，６｀－ＢＩＰＹ，ＩＲ和Ｒａｍａｎ光谱都证实了配合物的生成，７７Ｋ正派激发高分辨激光激发光谱和荧光光谱表明配合物存在＾５Ｄ０能级能量差别为１５ｃｍ＾－１的两种Ｅｕ（Ⅲ）格位，两种Ｅｕ（Ⅲ）离子均不位于对称中心，由＾５Ｄ０→＾７Ｄ０．１，２跃迁荧光光谱峰数判断，两种Ｅｕ（Ⅲ）格位的区域对称性均为Ｃ１或Ｃ２或Ｃ，两种格位Ｅｕ（Ⅲ）离子的发光寿命分别为０．３７ｍｓ和０．３     

四氯合铜酸苯铵盐的结构及其红外与拉曼光谱研究

制备了四氯四铜酸苯铵盐（Ｃ６Ｈ５ＮＨ３）２ＣｕＣｌ４单晶，Ｍｒ＝１８７．２６，由四园衍射数据确定了晶体结构，晶体属单斜晶系，空间群Ｐ２１／ａ，ａ＝０．７１８４（１），ｂ＝０．７４４８（２），ｃ＝１．５０７０（４）ｎｍ，β＝１００．６７（２）°，Ｖ＝０．７９２４ｎｍ＾３，Ｚ＝２，Ｄｘ＝１．６５０ｇｃｍ＾－３，（Ｍｏ，Ｋａ）＝０．０７１０６９ｎｍ，μ＝４．０５６ｍｍ＾－１，Ｆ（０００）＝３８９，Ｒ＝０     

Ba^2＋对卤磷酸盐掺Eu^2＋荧光粉辐照特性的影响

在国家同步辐射实验室的时间分辨光谱站（Ｕ１０Ｂ光束线）研究掺杂Ｅｕ２＋的卤磷酸盐：（Ｃａ，Ｓｒ，Ｂａ）５（ＰＯ４）３ＣｌＥｕ２＋样品和（Ｃａ，Ｓｒ）５（ＰＯ４）３ＣｌＥｕ２＋的真空紫外辐照特性、反射光谱．前者在１８５ｎｍ光的激发下，６０分钟内没有观察到明显的发光强度下降；而后者在１８５ｎｍ光的激发下，１５分钟内就可以观察到其４５０ｎｍ发光的明显变化，从强到弱，直至完全消失．测量了两种样品的反射谱（１００ｎｍ至４００ｎｍ），并根据Ｋ－Ｋ关系计算得出的吸收谱，我们认为：由于Ｂａ２＋的加入，改变了晶格对称性，（Ｏ）－色心的能级发生变化，晶体对１８５ｎｍ附近紫外光的吸收明显降低，从而起到了耐１８５ｎｍ辐照的作用     

含R2dtc配体和V=O基的金属簇红外光谱研究

本文报道两类含Ｒ２ｄｔｃ配体的金属簇的红外光谱特点及某些规律,含Ｒ２ｄｔｃ的立方簇合物在４００－５００ｃｍ＾－１有较宽而弱的吸收,可归结于Ｍ－μ３Ｓ振动。Ｍ－Ｓｄｔｃ在３３０－３８０ｃｍ＾－１,Ｃ－Ｎ振动在１４７０－１５１０ｃｍ＾－１。二甲基ｄｔｃ配体立方的ｖ（Ｃ－Ｎ）与ｖ（Ｃ＝Ｓ）比值他二烷基ｄｔｃ立方烷的相应振动分别蓝移和红移,可归结于甲基超共轭效应所致。「Ｖ２Ｃｕ２Ｓ４（Ｒ２ｄｔｃ）２（ＰｈＳ）２」＾２－和「ＶＣｕ４Ｓ４（Ｒ２ｄｔｃ）ｎ（ＰｈＳ）４－ｎ」＾３－（ｎ＝０,１,２）的Ｍ－μ３Ｓ振动分别出现在４８０和４６５ｃｍ＾－１,可作为区别两类化合物的一个指标。另一类含（Ｒ２ｄｔｃ）２Ｖ２Ｏ２（μ－Ｓ）２单元的金属簇中,Ｖ－Ｏ伸缩频率在８４４－９７０ｃｍ＾－１范围内,（Ｅｔ４Ｎ）「Ｖ２Ｓ２Ｏ３（Ｅｔ２ｄｔｃ     

Eu_2（DBM）_64，4＇－BIPY的合成、光谱及铕（Ⅲ）格位

合成了配合物Ｅｕ２（ＤＢＭ）６４，４＇－ＢＩＰＹ．ＩＲ和Ｒａｍａｎ光谱都证实了配合物的生成．７７Ｋ下激光激发高分辨激发光谱和离光光谱表明配合物存在５Ｄ０能级能量差别为１５ｃｍ－１的两种Ｅｕ（Ⅲ）格位，两种Ｅｕ（Ⅲ）离子均不位于对称中心．由５Ｄ０→７Ｆ０、１、２跃迁荧光光谱峰数判断，两种Ｅｕ（Ⅲ）格位的区域对称性均为Ｃ１或Ｃ２或Ｃ２．两种格位Ｅｕ（Ⅲ）离子的发光寿命分别为０．３７ｍｓ和０．３２ｍｓ．     

NH4Cl作助熔剂合成CaS：Ce的光谱特性及其浓度效应

以ＮＨ４Ｃｌ作助溶剂，碳还原硫酸钙的方法合成了ＣａＳ：Ｃｅ。在紫外光激发下，ＣａＳ：Ｃｅ中存在着Ｃｅ＾３＋的＾２Ｄ－＾２Ｆ５／２（５００ｎｍ）和＾２Ｄ－＾２Ｆ７／２（５５０ｎｍ）跃迁发射，但在蓝色光激发下，只有波峰为５３２ｎｍ半宽度为９２ｎｍ的宽带发射。当Ｃｅ＾３＋的浓度为０．０７５ｍｏｌ％时，＾２Ｄ－＾２Ｆ５／２跃迁发射强度与＾２Ｄ－＾２Ｆ７／２跃迁发射强度相等，而５３２ｎｍ发射猝灭。     

在He和Ne的流动余辉中POCl3的解离动力学

本文利用流动余辉技术研究了亚稳态原子Ｈｅ（２＾３ｓ）和Ｎｅ（＾３ｐ０．２）与ＰＯＣｌ３分子的传能反应，获得了激发态碎片ＰＯ（Ａ）和ＰＯ（Ｂ）的发射光谱，测定了Ｈｅ（２＾３ｓ）与ＰＯＣｌ３反应中ＰＯ（Ａ）和ＰＯ（Ｂ）的形成速率常数，其数值分别为：ＫＰＯ（Ａ）＝３．６８×１０＾－１１ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１Ｓ＾－１和ＫＰＯ（Ｂ）＝９．４０×１０＾－１１ｃｍ＾３·ｍｏｌｅｃｕｌｅ＾－１·Ｓ＾－１     

析相光度法测定铜（Ⅱ）的研究

本文研究了Ｃｕ－ＰＥＧ－ＤＤＴＣ（铜试剂）（ＮＨ４）２ＳＯ４体系的析相光度法并应用于测定Ｃｕ。最宜酸度为３．６－９．０（ＮａＡｃ－ＨＡｃ，ＮＨ４Ｃｌ－ＮＨ３．Ｈ２Ｏ）缓冲溶液，其络合物的最大吸收位于４５０ｎｍ，表观摩尔吸光系数为９．０５×１０＾３Ｌ．ｍｏｌ＾－１．ｃｍ＾－１，Ｃｕ浓度在０－３０μｇ／Ｌ范围内服从比耳定律，铜与ＤＤＴＣ形成组成为１：２的稳定络合物。该方法用于铝合金中铜的测定，获得了满     

KCl和HCl对结晶紫分子NIR-SERS作用机制的比较研究

本文研究了ＫＣｌ与ＨＣｌ对结晶紫分子近红外表面增强拉曼光谱（ＮＩＲ－ＳＥＲＳ）的影响。表明在以离子作为其ＳＥＲＳ信号的额外增强剂的过程中，更多地注意到对分子结构的选择性对于获得理想的ＳＥＲＳ结构非常必要。     

以PAA为模板制备SERS基底及对三聚氰胺的检测

采用热蒸镀的方法直接在多孔氧化铝(porous anodic alumina,PAA)模板上蒸镀几微米的银膜,然后在HCl溶液中溶解掉模板,得到表面具有纳米尺度规则结构的银膜作为表面增强拉曼散射(surface-en-hanced Raman spectra,SERS)基底,并在该基底上测量了吡啶溶液(0.01 mol.L-1)的增强拉曼光谱,发现平均增强因子大于105。与直接在载玻片上蒸镀的银膜相比,具有纳米尺度规则结构银膜的增强效果提高了30倍。改变激发光功率测量吡啶的拉曼光谱,和普通拉曼散射一样,增强拉曼光谱的峰值强度随激发光强度线性变化,并在该基底上测量了三聚氰胺的拉曼光谱,发现在1 mW的激发功率下对于三聚氰胺的检出限为2.5 mg.L-1。     

噻菌灵农药的表面增强拉曼光谱分析

利用表面增强拉曼光谱技术(SERS)分析噻菌灵农药的拉曼特征峰。采用微波法制备银溶胶表面增强基底,利用激光显微共焦拉曼光谱仪分别采集514.5和785 nm激发波长下的噻菌灵农药拉曼光谱,解析不同激发波长下的拉曼特征峰并进行比较。结果表明：不同激发波长下噻菌灵的拉曼峰强度和拉曼频移差异较大,514.5 nm激发波长下的782和1 012 cm-1最强,是C—H变形振动较强特征峰,而785 nm激发波长下的1 284,1 450和1 592 cm-1最强,是环振动和CN伸缩振动较强特征峰。对比分析各个激发波长下噻菌灵的SERS谱图,找到了噻菌灵农药的5个较强特征拉曼峰：782,1 012,1 284,1 450和1 592 cm-1。这些特征峰可作为食品及农产品中噻菌灵农药残留定性定量判别的依据。     

Surface‐enhanced Raman scattering study of the red dye laccaic acid

FT‐Raman and surface‐enhanced Raman scattering (SERS) spectroscopy were applied to the study of lac dye, a highly fluorescent anthraquinone red dye. The SERS spectra were obtained at different pH values, on Ag nanoparticles prepared by chemical reduction with citrate and hydroxylamine, and at several excitation wavelengths, in order to find the best experimental conditions for the detection of the lac dye. The lower detection limit was achieved using nanoparticles prepared by reduction with hydroxylamine, excitation at 514.5 nm, and slightly acidic pH conditions, thus exploiting a combination of factors including lower electrostatic repulsion between dye and nanoparticles and resonance Raman enhancement. A comparison between the adsorption of laccaic acid (LA) and carminic acid (CA), another anthraquinone red dye, was also done, based on the SERS spectra of both dyes. Copyright © 2007 John Wiley & Sons, Ltd.     

SERS signal response and SERS/SERDS spectra of fluoranthene in water on naturally grown Ag nanoparticle ensembles

We present experimental results of the time‐dependent Raman signal response of fluoranthene adsorbed on a naturally grown Ag nanoparticle ensemble, which serves as surface enhanced Raman scattering (SERS) substrate. In addition, SERS characteristics such as the concentration‐dependent calibration curves and the limit of detection (LOD) for fluoranthene in distilled water will be shown. The SERS substrate was prepared by Volmer–Weber growth under ultrahigh vacuum condition and exhibits a plasmon resonance wavelength at 491 nm. For the measurement of SERS signal response and SERS/shifted excitation Raman difference spectroscopy spectra of fluoranthene in water, experimental Raman setup containing a microsystem light source with two emission wavelengths (487.61 nm and 487.91 nm) was used. We experimentally demonstrate that the maximum SERS intensity is achieved 9 min after changing the analyte concentration from 0 nmol/l to 600 nmol/l. This response time is explained by a time‐dependent adsorption of the probe molecules onto the nanoparticles. The LOD for fluoranthene in water was evaluated applying shifted excitation Raman difference spectroscopy (SERDS) at different molecule concentrations. For SERDS, two emission wavelengths of a prototype microsystem light source have been used for Raman excitation. The experimental results reveal that the LOD for the probe molecules is very low. Experimentally, we have detected a fluoranthene concentration of only 4 nmol/l, which is very close to our estimated LOD of 2 nmol/l. Thus, the presented Raman setup, with a SERS substrate, whose plasmon resonance coincides with the excitation wavelength for SERS measurements, is well suited for in‐situ trace detection of pollutant chemicals in water. Copyright © 2013 John Wiley & Sons, Ltd.     

苯丙氨酸银溶胶表面增强拉曼光谱的研究

研究了银溶胶与L-苯丙氨酸溶液体系的表面增强拉曼光谱(SERS),增强效果明显,L-苯丙氨酸在银溶胶中的SERS光谱与苯丙氨酸固体常规拉曼光谱相比,主要峰位置基本一致,但某些峰发生了频移,相对强度也发生了一定变化。探讨了三种不同的激发光源对SERS光谱强度的影响。用不同光源测定,其SERS光谱图中各峰位置基本不变,但峰强度有明显变化。在实际工作中应根据需要选择合适的光源,一般情况下以514.42 nm为佳。不同浓度的苯丙氨酸在银溶胶中产生的表面增强拉曼光谱有明显的差别,浓度太大或太小都不利于SERS光谱的产生,溶液浓度在1×10-3mol·L-1时SERS最强,增强效果最好。体系的pH对增强效应亦有较大的影响,在pH为8时增强效应最强,这是pH对银溶胶的凝聚状态和苯丙氨酸分子存在状态综合影响的结果。     

A facile method for the synthesis of large‐size Ag nanoparticles as efficient SERS substrates

Silver nanoparticles (Ag NPs) enjoy a reputation as an ultrasensitive substrate for surface‐enhanced Raman spectroscopy (SERS). However, large‐scale synthesis of Ag NPs in a controlled manner is a challenging task for a long period of time. Here, we reported a simple seed‐mediated method to synthesize Ag NPs with controllable sizes from 50 to 300 nm, which were characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. SERS spectra of Rhodamine 6G (R6G) from the as‐prepared Ag NPs substrates indicate that the enhancement capability of Ag NPs varies with different excitation wavelengths. The Ag NPs with average sizes of ~150, ~175, and ~225 nm show the highest SERS activities for 532, 633, and 785‐nm excitation, respectively. Significantly, 150‐nm Ag NPs exhibit an enhancement factor exceeding 10⁸ for pyridine (Py) molecules in electrochemical SERS (EC‐SERS) measurements. Furthermore, finite‐difference time‐domain (FDTD) calculation is employed to explain the size‐dependent SERS activity. Finally, the potential of the as‐prepared SERS substrates is demonstrated with the detection of malachite green. Copyright © 2016 John Wiley & Sons, Ltd.     

高密度激发下ZnTe晶体中与自由激子有关的发射

在77—300K温度范围内,用N2分子激光器的3371Å谱线激发未故意掺杂的p型ZnTe晶体,得到了与自由激子有关的发射。发现随着激发密度的增加,其发光光谱的峰值位置红移而谱带的半宽度展宽,这些结果可以用Ex—e和Ex—Ex的相互作用来解释。     

Influence of surface plasmon resonance wavelength on SERS activity of naturally grown silver nanoparticle ensemble

We present experimental results to quantify and optimize the surface‐enhanced Raman scattering (SERS) activity of naturally grown silver nanoparticles. Ag nanoparticle ensembles with mean equivalent radii ranging from 10.6 to 20.3 nm were prepared under ultrahigh vacuum conditions by Volmer–Weber growth on quartz plates. A tuning of the localized surface plasmon polariton resonance wavelength from 453 to 548 nm was performed by varying the morphology of the silver nanoparticles. The dependence of the SERS activity on the plasmon resonance wavelength was investigated with a Raman set‐up containing a microsystem light source with an emission line at 488 nm. Shifted excitation Raman difference spectroscopy was applied to remove the fluorescence‐based background from the SERS spectra of pyrene in water using two slightly different emission wavelengths (487.61 and 487.91 nm) of the microsystem light source. We demonstrate that the Raman activities for all SERS substrates are available in the nanomolar range in a water sample. However, the Raman activity crucially depends on the plasmon resonance wavelength of the nanoparticle ensembles. Although for an on‐resonance ensemble the limit of detection for pyrene in water is very low and was estimated to be 2 nmol/L, it increases rapidly to several tens of nanomol for slightly off‐resonance ensembles. Hence, the highest SERS activity was obtained with a nanoparticle ensemble exhibiting a plasmon resonance wavelength at 491 nm, which almost coincides with the excitation wavelengths. Copyright © 2012 John Wiley & Sons, Ltd.     

Large-scale plasmonic-SERS templates by successive growth steps

This work presents the fabrication of large-scale tunable-plasmonic surface-enhanced Raman scattering (SERS) templates and investigates their Raman enhancement. Substrates for SERS were prepared by deposition of gold nanoparticles on a glass slide followed by their growth. A plasmon shift was observed upon growing due to the formation of elongated nanoparticles and their mutual coupling. The changes in particle size, shape and interparticle distances were indicated by SEM measurements. Surface-enhanced Raman spectra of Nile blue A at a very low concentration on top of a blocking layer were measured. The overall Raman enhancement is correlated with the number of growth steps. For excitation at 532 nm four growth steps lead to maximum enhancement. Better overlap of excitation laser and the plasmon resonances upon growing increased the enhancement until four steps while further growing decreased the enhancement. At longer wavelengths excitation (633 and 785 nm) the enhancement further increased beyond the fourth growth step. This enhancement is caused by the plasmon excitation of narrower gap sizes. The proposed procedure for the SERS substrates is simple, allows covering large surface areas and plasmon band tuning from 530 nm to the near infrared in order to increase overall Raman enhancement.