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1.
采用循环伏安法处理Ag电极,得到活化的具有表面增强拉曼光谱(SERS)效应的粗糙Ag表面,进一步采用激光拉曼光谱探讨了2-巯基苯并咪唑(MBI)在其表面的自组装分子层的吸附特性。实验表明,在活性Ag表面的MBI自组装分子层能够产生理想的SERS效应,其强度随探针分子MBI浓度的增加先提高后减弱,达到一定浓度时因受其空间位阻等因素的影响,增强效应减弱。MBI在1×10-6 mol·L-1 浓度时增强效果最大。拉曼增强效应随着体系酸度的变化有着明显不同,在强酸性条件下的增强效应明显优于中性和碱性条件。MBI分子存在两种不同的异构体和在不同酸度下存在3种不同的存在形态,并形成动态平衡。pH <2时,MBI分子主要以硫酮式MBI+存在,并以巯基上的S:与活性Ag以配位方式吸附成键,其整个大π键平面垂直地吸附于Ag表面,产生相对较大的SERS信号。pH >2时,由于硫酮式和硫醇式与活性Ag的键合方式和能力不同,硫醇式上的S与Ag以S-Ag共价方式同时双键侧上的N以配位方式协同参与吸附成键,比硫酮式MBI+的单纯配位吸附要强,因而形成了竞争吸附,表现为SERS在pH=2~3.7之间的急剧下降。MBI硫醇式由于以S-Ag、N-Ag键的协同吸附,形成了倾斜侧卧式垂直吸附,而使拉曼增强效应相对减弱。  相似文献   

2.
利用拉曼光谱仪测定L-半胱氨酸(L-Cys)的常规拉曼光谱(NRS)和表面增强拉曼光谱(SERS),发现L-Cys在纳米银棒上有明显的拉曼增强效应,对分子特征峰进行了归属,研究L-Cys在银纳米棒基底表面吸附机理,在固体NRS中在2 576cm~(-1)出处有明显的S—H伸缩振动峰,而SERS中没有出现,实验表明纳米银棒与L-Cys巯基上的S原子形成了Ag—S键,C—O和C—N伸缩振动有明显的增强。在不同pH值条件下,分析了L-Cys的拉曼光谱差异,探讨吸附行为的变化。在pH值为6时,S—H的伸缩振动峰基本消失,形成了稳定的S—Ag键;随着pH值增加趋于碱性时,羧基易失去H原子形成—COO-易与银发生吸附作用且振动峰增强。在pH值为7时,S原子与Ag形成稳定的S—Ag键,C—O和C—N的振动峰也最稳定。选择在pH值为7的条件下,在L-Cys溶液中加入Na+,Mg~(2+)和Cu~(2+)等10种金属盐,发现Al 3+,Cu~(2+),Zn~(2+),Cd~(2+)和Hg~(2+)使L-Cys分子的结构发生了改变,金属离子与L-Cys另一端羧基发生作用,其中Cu~(2+),Zn~(2+),Cd~(2+)和Hg~(2+)随半径增大与S原子的孤电子发生作用越大。探讨了在不同pH值、不同比例和不同浓度下,金属离子与L-Cys作用SERS的变化,随着pH值、比例和浓度的增大,峰的强度有减小趋势。Cu~(2+)与L-Cys作用的SERS信号很弱,Hg~(2+)与L-Cys作用只出现了一个C—O的振动峰,说明Hg~(2+)完全破坏了L-Cys的空间构型。该研究对蛋白质变性等的研究提供了重要参考信息。  相似文献   

3.
刘江美  刘文涵  滕渊洁  袁荣辉 《发光学报》2015,36(12):1477-1484
采用共沉淀法合成Fe3O4纳米颗粒,再以柠檬酸三钠还原AgNO3获得了具有SERS活性的Fe3O4@Ag磁性纳米复合材料。基于密度泛函理论(DFT)的量子化学计算方法和表面增强拉曼光谱(SERS)技术,从理论计算和实验测定表征探讨了2-噻吩甲酸(2-TCA)在Fe3O4@Ag表面的吸附行为和增强效应。结果表明:理论计算得到的拉曼光谱与实际测得的常规拉曼光谱基本一致,而在DFT理论计算中所键连的Ag原子数越多,与实测值就越接近。溶液的浓度和pH对拉曼增强效果有很大的影响,当溶液的pH=3且浓度为1×10-4 mol·L-1时有最大拉曼增强效应。峰强随2-TCA浓度的增加呈现先增大后减小的趋势,浓度过大会导致大量2-TCA分子吸附聚集在Ag表面形成局部"拥堵",阻碍了激发光尤其是光谱信号的散射通过,从而减弱了拉曼增强效应。pH的变化使溶液中2-TCA分子形态发生改变,结构形态不同,其在Ag表面的吸附方式也不同。中性C4H3SCOOH分子以环上S:形式垂直吸附键合在Ag表面,形成S—Ag配位键而产生SERS光谱。-1价C4H3SCOO-离子以S—Ag配位和O—Ag共价"双键合"侧卧方式共同吸附在Ag表面而产生SERS光谱。在Ag表面,以单独S—Ag配位键吸附或键合的能力比S—Ag配位和O—Ag共价共同吸附方式要弱,但其产生的SERS信号更强,故2-TCA中性分子比2-TCA-离子更有利于SERS的产生。随着pH值的增加,溶液中的2-TCA由中性分子逐渐转化为-1价的C4H3SCOO-离子,因而在pH>3以后,拉曼增强效应逐步减弱。  相似文献   

4.
为探讨胞嘧啶(Cytosine,Cy)在基底银表面的吸附特性和规律,采用表面增强拉曼散射(SERS)光谱对其吸附行为进行分析,并结合量子化学密度泛函理论(DFT)/B3LYP计算方法对Cy分子的常规拉曼光谱(NRS)及Cy与Ag团簇吸附的SERS光谱进行计算,与测定结果进行比对且对其拉曼峰进行系统指认及归属,理论计算结合实测值探讨了Cy在基底Ag上的增强效应和吸附行为。考察了Cy分子在Ag纳米粒子上的不同吸附时间、浓度、pH等条件对SERS光谱的影响及优化,发现pH影响最大,在中性和强碱性条件下的增强效应明显优于酸性。Cy分子存在2种不同的异构体和3种不同的存在形态,并随酸度变化相互转化而达动态平衡。基于Cy在不同pH时的形态分布和相应的SERS变化规律,结合DFT算得的Cy分子中的电荷分布及在银基底表面的吸附机制,详细探讨了酸碱对Cy分子的SRES光谱影响的内因和吸附机理,指出在中性和弱碱性时,是Cy中的N3和O与Ag形成配位吸附;在pH大于11时,N与Ag形成配位吸附,而O与Ag形成共价吸附。  相似文献   

5.
本文获得了草原毛虫核型多角体病毒包涵体外膜蛋白在Ag胶中的表面增强拉曼光谱(SERS)。包涵体通过膜蛋白的COO~-和NH_2基团吸附在Ag表面上,其增强作用具有短程特性。低波数(~230cm~(-1))峰的出现表明包涵体和Ag胶粒子产生了化学吸附。包涵体在不同pH下的SERS谱很不同,说明此时它在Ag表面上的吸附状态有变化。  相似文献   

6.
苯丙氨酸银溶胶表面增强拉曼光谱的研究   总被引:2,自引:1,他引:1  
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514.42nm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。  相似文献   

7.
氨基酸在银胶溶液中的表面增强拉曼效应   总被引:3,自引:2,他引:1  
文章报道了通过制备合适的银胶盐纳米溶液 ,得到的甘氨酸、缬氨酸和赖氨酸在银胶溶液中的表面增强拉曼光谱。低波数 2 38cm-1谱带的出现 ,表明氨基酸分子已与银表面产生明显吸附。在所得SERS图谱中 ,表征C—C基团的 90 0~ 930cm-1谱带、表征NH2 基团的 110 0cm-1左右谱带和表征COO-基团的14 0 0cm-1附近的谱带振动都得到显著加强 ,其原因主要是通过羧基基团及氨基基团与银粒子表面产生吸附 ,增强机制属于化学增强 ,为短程效应。本实验中 ,当银胶溶液 pH值降低时 ,对拉曼散射的增强效果影响不大。  相似文献   

8.
在银电极表面形成一层C60薄膜,分别在乙腈溶液和水溶液中进行表面增强拉曼光谱(SERS)研究并将两者进行比较,从而消除了溶液中的C60干扰表面吸附C60的SERS谱图的可能性.研究结果表明,C60分子对称性的降低导致SERS谱峰发生了分裂;表面电磁场的作用使得光谱选律在SERS效应中被拓宽,产生了新的拉曼谱峰.该结果与团簇吸附在粗糙银电极表面的C60分子的研究结果相似.与之不同的是在乙腈溶液和水溶液中的SERS谱图的低波数区内分别在348和311 cm-1左右出现一个新峰,经过分析可认为该峰与C60-金属基底的相互作用有关.  相似文献   

9.
依据DFT理论的B3LYP方法下,在6-31G(d,p)(C,H,N,S,Cl)/Lanl2dz(Ag)基组,计算得到噻虫啉及其银配合物的稳定结构和表面增强拉曼光谱(SERS)。并进一步探究SERS与Ag4银簇吸附的位置,分子分别以单端(吡啶氮/氰基)和双端(吡啶氮和氰基)与Ag4银簇吸附。通过比较,TPD在双端吸附银簇下比单端(吡啶氮/氰基)吸附下的SERS(频率)更符合实验值。  相似文献   

10.
采用共沉淀法合成了Fe_3O_4磁性纳米颗粒,进一步以柠檬酸三钠还原法制备出了具有SERS活性的Fe_3O_4/Ag磁性包覆修饰材料,用紫外可见吸收光谱、能谱及透射电镜对结构与形貌进行表征,发现所制备的Fe_3O_4/Ag纳米材料粒径约为30~60nm,形貌规整接近球形,经测试Fe_3O_4/Ag材料很容易被磁铁收集,能够满足分散萃取再收集的需要。根据密度泛函理论(DFT)对杀线威(Oxamyl)、Oxamyl-Ag和OxamylAg4进行了理论结构优化计算,得到了杀线威的理论拉曼光谱和与Ag表面增强拉曼光谱及其谱峰的归属,结合表面增强拉曼光谱(SERS)测定,研究了杀线威在Fe_3O_4/Ag表面的吸附行为和增强效应,测算得到杀线威在Fe_3O_4/Ag表面上的增强因子为2.08×105。研究表明:理论计算的杀线威拉曼光谱与测定的拉曼光谱具有较好的一致性,DFT理论计算中发现研究分子与活性Ag原子作用越多,与实测值常规拉曼NRS越接近;杀线威以双键侧N原子和S原子与Fe_3O_4/Ag表面吸附作用为主;双键侧N优先与Ag吸附成键后,整个分子靠近Ag表面,最终使得双键侧N原子与S原子共同吸附在Ag表面;Fe_3O_4/Ag磁性纳米复合材料具有显著的富集吸附和拉曼增强作用;可利用其作为拉曼基底,以实现SERS光谱法对杀线威农残的快速分析检测。  相似文献   

11.
Two-dimensional scanning of a 0.6328 mum guided-light beam has been realized using noncolinear acousto-optic (AO) coplanar Bragg diffraction together with colinear AO guided-mode to substrate radiation-mode conversion in a Z-cut Xpropagation LiNbO3 proton-exchanged (PE) waveguide. The two surface acoustic (SAW) waves utilized are at the center frequencies of 500 and 200 MHz, propagating in the Y and X axes, respectively. Two-dimensional scanning of approximately 720 resolvable light beam spots, namely, 18 40 (horizontal vertical) scanning, has been demonstrated using a light beam of 1.0 mm aperture. The total number of resolvable beam spots can be greatly increased from 720 by simply utilizing SAW transducers of larger bandwidth and a light beam of greater aperture. It should also be possible to significantly increase the diffraction efficiency from 3 % by optimizing the parameters of the PE waveguide and the SAWs.  相似文献   

12.
A simple technique of pulse compression, based on the linear chirp compensation of self-phase modulation (SPM) spectra in dispersion shifted fibers, is demonstrated. The optimization procedure is carried out, for a short span of a single-mode fiber, using a parabolic law, which describes the behavior of the squared output pulse width versus the pump peak power in the case of Gaussian pulses. The experimental results give a minimum pulse duration of 233 fs, which is in good agreement with the model. Shorter and coherent pulses, down to 90 fs, have been obtained by inserting an interference filter at the optical output.  相似文献   

13.
Results of a study of the effect of γ-radiation on the spectral luminescence properties of cadmium tungstate crystals doped with silver, bismuth, and molybdenum cations are presented. Spectral characteristics of the nondnnnoped crystals are briefly described. Absorption and photo and X-ray luminescence spectra of the crystals taken before and after exposure to γ-radiation (5.5·104 Gy) are compared. It is found that the spectral characteristics of the crystals doped with silver, bismuth, and molybdenum cations do not change markedly after the exposure. The relation between the type of impurity-induced defects, individual characteristics of the impurity cations, and the character of the effect of γ-radiation on the spectral luminescence properties of impure crystals is analyzed (preliminarily). Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 1, pp. 55–60, January–February, 1997.  相似文献   

14.
The Shanghai Synchrotron Radiation Facility(SSRF)booster ring,a full energy injector for the storage ring,is deigned to accelerate the electron beam energy from 150MeV to 3.5GeV that demands high extraction efficiency at the extraction energy with low beam loss rate when electrons are ramping.Closed orbit distortion(COD)caused by bending magnet field uniformity errors which affects the machine performance harmfully could be effectively reduced by bending magnet location sorting.Considering the affections of random errors in measurement,both ideal sorting and realistic sorting are studied based on measured bending magnet field uniformity errors and one reasonable combination of bending magnets which can reduce the horizontal COD by a factor of 5is given as the final installation sequence of the booster bending magnets in this paper.  相似文献   

15.
16.
A review of schemes for multiple access in fiber optic networks shows that a hybrid of wavelength and code division multiple access (WCDMA) combines the best features of both. In particular, the hybrid scheme retains the large information carrying capacity of wavelength division multiple access (WDMA) and flexibility of code division multiple access (CDMA). In this paper WDMA, optical CDMA (OCDMA), and WCDMA networks are discussed. In OCDMA networks, concept of incoherent and coherent coding including inverse decoding and matched filter is introduced. The delay performance of both WDMA and WCDMA networks, under the simple suboptimum access protocols based on cyclic search, is computed. It has been shown quantitatively that tuning delay significantly affects the delay performance of both WDMA and WCDMA networks. Futhermore, delay performance of WCDMA networks is always better than the WDMA networks for the same tuning delay, load, and number of users.  相似文献   

17.
A transient suppression method for piezoelectric ceramic transducer is presented. By adding some special pedestal pulses to the original transmitted signal, the transient effects in the output of the transducer can be just precisely transmission by use of a narrowband transducer. canceled, thereby achieving the broadband The experimental results show that the transient responses of the sinusoid pulses and coded signals are suppressed successfully and the acoustic waveforms radiated into the surrounding water are improved significantly.  相似文献   

18.
We experimentally demonstrate amplitude squeezed soliton utilizing intensity-dependent self-phase modulation in an asymmetric Sagnac interferometer.The system.whose components are connected via ferrule connector/physical connection(FC/PC)fiber connectors,constitutes all-fiber configuration to generate squeezed soliton.Soliton amplitude reduction measured by homodyne detection is near 4.0 dB below the shot-noise level.Optimal squeezing fields in both simple and compact all-fiber configuration are obtained.  相似文献   

19.
The(2 1)-dimensional nonlinear Schr(o)dinger(NLS)equation with spatially inhomogeneous nonlinearities is investigated,which describes propagation of light in(2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities.New types of optical modes and nonlinear effects in optical media are presented numerically.The results reveal that the regular split of beam can be obtained in (2 1)-dimensional nonlinear optical media with inhomogeneous nonlinearities,by adjusting the guiding parameter.Furthermore,the stability of beam regular split is discussed numerically,and the results reveal that the beam regular split is stable to the finite initial perturbations.  相似文献   

20.
In the real-world application of face recognition system, owing to the difficulties of collecting samples or storage space of systems, only one sample image per person is stored in the system, which is so-called one sample per person problem. Moreover, pose and illumination have impact on recognition performance. We propose a novel pose and illumination robust algorithm for face recognition with a single training image per person to solve the above limitations. Experimental results show that the proposed algorithm is an efficient and practical approach for face recognition.  相似文献   

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