A core-satellite self-assembled SERS aptasensor containing a“biological-silent region”Raman tag for the accurate and ultrasensitive detection of histamine

Herein,a novel interference-free surface-enhanced Raman spectroscopy(SERS)strategy based on magnetic nanoparticles(MNPs)and aptamer-driven assemblies was proposed for the ultrasensitive detection of histamine.A core-satellite SERS aptasensor was constructed by combining aptamer-decorated Fe_(3)O_(4)@Au MNPs(as the recognize probe for histamine)and complementary DNA-modified silver nanoparticles carrying 4-mercaptobenzonitrile(4-MBN)(Ag@4-MBN@Ag-c-DNA)as the SERS signal probe for the indirect detection of histamine.Under an applied magnetic field in the absence of histamine,the assembly gave an intense Raman signal at“Raman biological-silent”region due to 4-MBN.In the presence of histamine,the Ag@4-MBN@Ag-c-DNA SERS-tag was released from the Fe_(3)O_(4)@Au MNPs,thus decreasing the SERS signal.Under optimal conditions,an ultra-low limit of detection of 0.65×10^(-3)ng/mL and a linear range 10^(-2)-10^5 ng/mL on the SERS aptasensor were obtained.The histamine content in four food samples were analyzed using the SERS aptasensor,with the results consistent with those determined by high performance liquid chromatography.The present work highlights the merits of indirect strategies for the ultrasensitive and highly selective SERS detection of small biological molecules in complex matrices.

不同变质程度煤中镜质组的元素分布特征:基于Raman和原位微区XRF分析

为明确煤中元素与有机质之间的关系,本文选择山西太原西山煤田6个矿区石炭系—二叠系太原组8号煤层煤样(镜质体最大反射率为1.26%~2.03%)为研究对象,挑选其中的镜煤条带,利用激光共聚焦拉曼光谱仪(Raman)选出镜质组,结合微区X射线荧光光谱仪(μ-XRF)对镜质组中元素含量和分布特征进行分析,试图探讨不同变质程度煤中镜质组的拉曼光谱和元素的耦合关系。研究发现,镜质组中仍然存在着大量的纳米级矿物,在实验操作过程中即使Raman光谱的结果限定了有机组分,但是由于束斑大小的差异,μ-XRF测试时不可避免的受到了煤中纳米级矿物的影响;Al、Si、K、Ti、V、Fe、Co、Ca主要赋存于镜质组中的纳米级矿物中,Ni、Zn、Ga、Ge、Br、S则主要以有机结合态的形式存在。

LiF-ZrF_(4)熔盐体系离子结构的Raman光谱

采用Raman光谱和量子化学计算相结合的方法,研究了803~1 086 K下,ZrF_(4)摩尔分数为10%~60%的LiF-ZrF_(4)熔盐体系的离子结构特征及变化规律.研究结果表明:熔体中含有ZrF_(5)^(-),ZrF_(6)^(2-),ZrF_(7)^(3-)和ZrF_(8)^(4-)四种络合阴离子团,其中以ZrF_(7)^(3-)和ZrF_(8)^(4-)为主,二者摩尔分数之和高达90%~94%,ZrF_(5)^(-)和ZrF_(6)^(2-)含量较少.在熔盐升温初始阶段,熔盐中发生ZrF_(7)^(3-)与ZrF_(6)^(2-)生成ZrF_(8)^(4-)和ZrF_(5)^(-)的反应(ZrF_(7)^(3-)+ZrF_(6)^(2-)→ZrF_(8)^(4-)+ZrF_(5)^(-));到达一定温度后,熔盐中发生ZrF_(8)^(4-)与ZrF_(6)^(2-)生成ZrF_(7)^(3-),ZrF_(5)^(-)和F-的反应(ZrF_(8)^(4-)+ZrF_(6)^(2-)→ZrF_(7)^(3-)+ZrF_(5)^(-)+2F-).随着ZrF_(4)质量分数增加,熔盐中ZrF_(5)^(-)含量增加,ZrF_(6)^(2-),ZrF_(7)^(3-)和ZrF_(8)^(4-)的含量减少.

盐湖卤水中硼酸盐化学形态及Raman光谱定量分析

我国青藏盐湖以富含硼锂而著称,卤水中硼化学赋存状态随湖水化学类型的不同而发生变化,其中以硫酸盐型盐湖卤水中硼酸盐的存在形式变化最为复杂,卤水蒸发过程一般不以固体盐形式结晶析出,而是以多硼物种形式富集于氯化镁饱和老卤中,表现出严重的过饱和性,对后续锂盐和镁盐的分离提取影响较大。开展盐湖卤水体系中硼酸盐化学形态、分布规律及离子间作用机制等溶液化学研究对盐湖资源高效开发具有重要的意义。相比常规拉曼光谱技术,拉曼积分球基于拉曼散射原理可极大地提高激发光的使用效率和拉曼散射信号,对硼酸盐溶液结构检测具有拉曼响应信号强、检出限低、信噪比高等优点,为盐卤复杂体系硼酸盐化学形态的定量分析奠定了基础。利用拉曼积分球开展了盐湖卤水硼酸盐化学形态研究,阐述了卤水蒸发过程多硼酸根离子的变化规律;同时借助响应曲面法进行实验设计与优化,建立了共存盐类干扰回归模型用于盐湖卤水中单硼物种B(OH)_(3)的准确测定。结果表明,盐湖卤水浓缩过程中硼不断聚合生成多聚度硼酸根离子如B_(3)O_(3)(OH)_(4)^(-)和B_(6)O_(7)(OH)_(7)^(2-)等,硼的化学形态变化规律与碱土金属如MgCl_(2)-MgO-2B_(2)O_(3)-H_(2)O体系中硼物种变化一致,但与碱金属溶液体系物种变化差别较大。回归模型对卤水中正硼酸B(OH)_(3)定量分析的相对误差小于5%,准确度较高;阐明了蒸发浓缩过程中B(OH)_(3)物种分布的变化规律,从定量视角初步阐述了卤水富集过程硼酸根离子间的聚合作用关系,可为后续开展盐卤体系多硼物种分布及作用机制研究提供新思路、新方法。

基于Raman光谱的3,5-二氨基-1,2,4-三唑(DAT)合成反应在线监测与反应机理探究——推荐一个仪器分析综合实验

本实验介绍了一个仪器分析综合性实验——基于Raman光谱的3,5-二氨基-1,2,4-三唑(DAT)合成的在线监测与反应机理探究。该实验是一个科研转化的仪器分析综合实验,内容包括DAT的合成、基于Raman光谱的合成反应过程在线监测以及合成反应机理解析。在实验中,采用化学计量学方法对Raman光谱数据进行处理和分析,以更深入地理解合成反应的机理。通过本实验,可以巩固学生的化学专业知识,提高学生的综合实验操作技能,激发学生对科学研究的兴趣,培养学生的科研探究能力。

基于Raman的复方柳安咖注射液主要成分分析

本文应用拉曼光谱技术对复方柳安咖注射液的主要成分及含量进行了分析。首先测试分析了62个复方柳安咖注射液样品的拉曼光谱,结果表明62个注射液样品的拉曼光谱主要由水杨酸钠、安替比林和咖啡因的水溶液拉曼谱带组成;进一步利用密度泛函理论(DFT)计算了其主要成分的理论拉曼光谱和红外光谱,与实验测定的固体粉末光谱和溶液光谱进行比较分析,进而对复方柳安咖注射液拉曼光谱谱峰的振动模式进行了归属;最后利用水杨酸钠和安替比林浓度梯度溶液拉曼光谱特征峰的峰高和峰面积,分别建立定量分析模型,对62个复方柳安咖注射液样品中主要成分水杨酸钠和安替比林的含量进行预测,并与液相色谱法测试值进行了对比,结果显示预测值与液相色谱法测试值相近,得到了较好的主要成分含量预测结果。研究结果可为复方柳安咖注射液药剂的生产、药品质量的监控、药品光谱分析研究等方面提供参考。

^(13)C NMR、FT-IR、Raman和建模技术对烟煤和无烟煤分子结构的应用研究

【目的】探究高精度煤的结构演化及其机理的定量表征。【方法】通过显微组分鉴定、镜质体反射率、工业品质、元素分析和光谱分析,确定了烟煤(FS1)和无烟煤(ZY1)碳骨架结构、官能团的赋存状态等信息,并通过计算机辅助分子设计建立2个分子结构模型。【结果】结果表明,随着煤化作用的进行,烟煤到无烟煤过程中,亚甲基的损失速率比甲基的损失速率快,芳香性增强,芳香环的脂肪族链变短且支化度较高,含氧官能团逐渐减少,煤结晶程度增强,煤的化学结构趋于成熟稳定,且煤中的脂肪碳减少,芳香碳增加,甲基碳和亚甲基碳含量减少。经过多次尝试确定了芳香炭、脂肪族侧链和氧官能团之间的键合模式,获得最终的分子结构模型:C_(175)H_(162)O_(13)N_(2)(FS1)、C_(190)H_(159)O_(5)N_(3)(ZY1).该模型较好地反映煤的真实结构,模拟的^(13)C NMR光谱与实验光谱具有良好的一致性。上述研究为不同变质程度煤的分子结构演化提供了理论参考,为建立高可信度的分子结构表征提供了方法。

Semi-quantitative analysis of the structural evolution of mesophase pitch-based carbon foams by Raman and FTIR spectroscopy

Graphitized carbon foams(GFms)were prepared using mesophase pitch(MP)as a raw material by foaming(450℃),pre-oxidation(320℃),carbonization(1000℃)and graphitization(2800℃).The differences in structure and properties of GFms prepared from different MP precursors pretreated by ball milling or liquid phase extraction were investigated and compared,and semi-quantitative calculations were conducted on the Raman and FTIR spectra of samples at each preparation stage.Semi-quantitat-ive spectroscopic analysis provided detailed information on the structure and chemical composition changes of the MP and GFm de-rived from it.Combined with microscopic observations,the change from precursor to GFm was analyzed.The results showed that ball milling concentrated the distribution of aromatic molecules in the pitch,which contributed to uniform foaming to give a GFm with a uniform pore distribution and good properties.Liquid phase extraction helped remove light components while retaining large aromatics to form graphitic planes with the largest average size during post-treatment to produce a GFm with the highest degree of graphitization and the fewest open pores,giving the best compression resistance(2.47 MPa),the highest thermal conductivity(64.47 W/(m·K))and the lowest electrical resistance(13.02μΩ·m).Characterization combining semi-quantitative spectroscopic ana-lysis with microscopic observations allowed us to control the preparation of the MP-derived GFms.

Real-time model correction using Kalman filter for Raman-controlled cell culture processes

Raman spectroscopy has found extensive use in monitoring and controlling cell culture processes.In this context,the prediction accuracy of Raman-based models is of paramount importance.However,models established with data from manually fed-batch cultures often exhibit poor performance in Raman-controlled cultures.Thus,there is a need for effective methods to rectify these models.The objective of this paper is to investigate the efficacy of Kalman filter(KF)algorithm in correcting Raman-based models during cell culture.Initially,partial least squares(PLS)models for different components were constructed using data from manually fed-batch cultures,and the predictive performance of these models was compared.Subsequently,various correction methods including the PLS-KF-KF method proposed in this study were employed to refine the PLS models.Finally,a case study involving the auto-control of glucose concentration demonstrated the application of optimal model correction method.The results indicated that the original PLS models exhibited differential performance between manually fed-batch cultures and Raman-controlled cultures.For glucose,the root mean square error of prediction(RMSEP)of manually fed-batch culture and Raman-controlled culture was 0.23 and 0.40 g·L^(-1).With the implementation of model correction methods,there was a significant improvement in model performance within Raman-controlled cultures.The RMSEP for glucose from updating-PLS,KF-PLS,and PLS-KF-KF was 0.38,0.36 and 0.17 g·L^(-1),respectively.Notably,the proposed PLS-KF-KF model correction method was found to be more effective and stable,playing a vital role in the automated nutrient feeding of cell cultures.

Shock Raman spectra and structural transformation of powdered TKX-50 by the plate impact experiments combined with real-time Raman detection

As an energetic material of great interest,the work capacity of dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate(TKX-50)has been questioned recently.Although some research groups have explored the reasons for the low working ability of TKX-50,the plane impact experiment on powdered TKX-50 is obviously closer to the practical application,and the conclusions based on this are more guiding.Hence,we performed shock Hugoniot measurements of powdered TKX-50 between 5.65 and 16.29 GPa.The plane impact experiments of powdered TKX-50 were carried out and the shocked Raman spectra were collected.By Raman spectroscopy analysis,a new peak of powdered TKX-50 was found between19.47 GPa and 24.96 GPa,which may be caused by decomposition/phase transition and was related with the low work capacity.

Evolution of molecular structure of TATB under shock loading from transient Raman spectroscopic technique

By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.

In-situ thermal Raman mapping and stress analysis of CNT/CF/epoxy interfaces

A study of the interfacial behavior and internal thermal stress distribution in fiber-reinforced composites is essential to assess their performance and reliability.CNT/carbon fiber(CF)hybrid fibers were constructed using electrophoretic deposition.The interfacial properties of CF/epoxy and CNT/CF/epoxy composites were statistically investigated and compared using in-situ thermal Raman mapping by dispersing CNTs as a Raman sensing medium(CNT_(R))in a resin.The associated local thermal stress changes can be simulated by capturing the G'band position distribution of CNT_(R) in the epoxy at different temperatures.It was found that the G'band shifted to lower positions with increasing temperature,reaching a maximum difference of 2.43 cm^(−1) at 100℃.The interfacial bonding between CNT/CF and the matrix and the stress distribution and changes during heat treatment(20-100℃)were investig-ated in detail.This work is important for studying thermal stress in fiber-reinforced composites by in-situ thermal Raman mapping technology.

The Fabrication and Detection Performance of High Sensitivity Au-Ag Alloy Nanostar/Paper Flexible Surface Enhanced Raman Spectroscopy Sensors

Au-Ag alloy nanostars based flexible paper surface enhanced Raman spectroscopy sensors were fabricated through simple nanostar coating on regular office paper,and the surface enhanced Raman spectroscopy detection performances were investigated using crystal violet dye analyte.Au-Ag nanostars with sharp tips were synthesized via metal ions reduction method.Transmission electron microscope images,X-Ray diffraction pattern and energy dispersive spectroscopy elemental mapping confirmed the nanostar geometry and Au/Ag components of the nanostructure.UV-Vis-NIR absorption spectrum shows wide local surface plasmon resonance induced optical extinction.In addition,finite-difference time-domain simulation shows much stronger electromagnetic field from nanostars than from sphere nanoparticle.The effect of coating layer on Raman signal intensities was discussed,and optimized 5-layer coating with best Raman signal was obtained.The Au-Ag nanostatrs homogeneously distribute on paper fiber surface.The detection limit is 10-10 M,and the relationship between analyte concentrations and Raman signal intensities shows well linear,for potential quantitative analysis.The calculated enhancement factor is 4.795×10^(6).The flexible paper surface enhanced Raman spectroscopy sensors could be applied for trace chemical and biology molecule detection.

Identifying the effect of photo-generated carriers on the phonons in rutile TiO_(2) through Raman spectroscopy

Investigating lattice vibrations through Raman spectroscopy is a crucial method for studying crystalline materials.Carriers can interact with lattices and influence lattice vibrations;thus,it is feasible to study the effect of photo-generated carriers on phonons by analyzing changes in the Raman spectra of semiconductors.Rutile is one of the predominant crystalline phases of TiO_(2),which is a widely utilized metal oxide semiconductor.In this work,rutile TiO_(2) is coated on a thinned optical fiber to concentrate ultraviolet light energy within the material,thereby enhancing the generation of carriers and amplifying the changes in the Raman spectra.A Raman detection laser with a wavelength of 532 nm is utilized to collect the Raman spectra of rutile TiO_(2) during irradiation.Using this setup,the impact of photo-generated carriers on the phonons corresponding to Raman vibrational modes is researched.The localization and non-radiative recombination of photo-generated carriers contribute to a reduction in both the frequencies and lifetimes of phonons.This work provides a novel approach to researching the effect of carriers on phonons.

Exploring the Cation Regulation Mechanism for Interfacial Water Involved in the Hydrogen Evolution Reaction by In Situ Raman Spectroscopy

Interfacial water molecules are the most important participants in the hydrogen evolution reaction(HER).Hence,understanding the behavior and role that interfacial water plays will ultimately reveal the HER mechanism.Unfortunately,investigating interfacial water is extremely challenging owing to the interference caused by bulk water molecules and complexity of the interfacial environment.Here,the behaviors of interfacial water in different cationic electrolytes on Pd surfaces were investigated by the electrochemistry,in situ core-shell nanostructure enhanced Raman spectroscopy and theoretical simulation techniques.Direct spectral evidence reveals a red shift in the frequency and a decrease in the intensity of interfacial water as the potential is shifted in the positively direction.When comparing the different cation electrolyte systems at a given potential,the frequency of the interfacial water peak increases in the specified order:Li+<Na^(+)<K^(+)<Ca^(2+)<Sr^(2+).The structure of interfacial water was optimized by adjusting the radius,valence,and concentration of cation to form the two-H down structure.This unique interfacial water structure will improve the charge transfer efficiency between the water and electrode further enhancing the HER performance.Therefore,local cation tuning strategies can be used to improve the HER performance by optimizing the interfacial water structure.

In Situ Raman Monitoring of Trace Antibiotics in Different Harsh Water Environments

In situ surface-enhanced Raman scattering(SERS)is a widely used operando analytical technique,while facing numerous complex factors in applications under aqueous environment,such as low detection sensitivity,poor anti-interference capability,etc.,resulting in unreliable detectability.To address these issues,herein a new hydrophobic SERS strategy has been attempted.By comprehensively designing and researching a SERS-active structure of superhydrophobic ZnO/Ag nanowires,we demonstrate that hydrophobicity can not only draw analytes from water onto substrate,but also adjust"hottest spot"from the bottom of the nanowires to the top.As a result,the structure can simultaneously concentrate the dispersed molecules in water and the enhanced electric field in structure into a same zone,while perfecting its own anti-interference ability.The underwater in situ analytical enhancement factor of this platform is as high as 1.67×10^(11),and the operando limited of detection for metronidazole(MNZ)reaches to 10^(-9)M.Most importantly,we also successfully generalized this structure to various real in situ detection scenarios,including on-site detection of MNZ in corrosive urine,real-time warning of wrong dose of MNZ during intravenous therapy,in situ monitoring of MNZ in flowing wastewater with particulate interference,etc.,demonstrating the great application potential of this hydrophobic platform.This work realizes a synergistic promotion for in situ SERS performance under aqueous environment,and also provides a novel view for improving other in situ analytical techniques.

Facile electrochemical surface-alloying and etching of Au wires to enable high-performance substrates for surface enhanced Raman scattering

Surface-enhanced Raman Spectroscopy(SERS)is a nondestructive technique for rapid detection of analytes even at the single-molecule level.However,highly sensitive and reliable SERS substrates are mostly fabricated with complex nanofabrication techniques,greatly restricting their practical applications.A convenient electrochemical method for transforming the surface of commercial gold wires/foils into silver-alloyed nanostructures is demonstrated in this report.Au substrates are treated with repetitive anodic and cathodic bias in an electrolyte of thiourea,in a one-pot one-step manner.X-rays absorption fine structure(XAFS)spectroscopy confirms that the AuAg alloy is induced at the surface.The unique AuAg alloyed surface nanostructures are particularly advantageous when served as SERS substrates,enabling a remarkably sensitive detection of Rhodamine B(a detection limit of 10^(-14)M,and uniform strong response throughout the substrates at 10^(-12)M).

Investigation on Binding between Cations and Amides using UV Raman Spectroscopy

The interaction of proteins with salt ions plays an important role in life activities.We used butyramide as a model molecule to investigate the interaction of protein backbones with cations.The experiment was performed in an aqueous solution of metal chloride using UV Raman spectroscopy.It was found that well-hydrated metal cations(Ca^(2+),Mg^(2+))tend to bind to C=O in the amide bond,resulting in redistribution of the amide I band peaks.Specifically,the peak intensity ratio of 1655 cm^(-1)to 1610 cm^(-1)increases significantly with increasing concentrations.However,this phenomenon is not obviously observed in NaCl solution.Furthermore,we studied the effect of salt ions on the water structures.The addition of Ca^(2+)and Mg^(2+)is beneficial to the enhancement of the water signal at the 3400 cm^(-1)position,while the Na^(+)at the same concentration is not obvious.The results have shown that the interaction between cations and amides satisfies the following order:Ca^(2+)>Mg^(2+)>Na^(+),which conforms to the Hofmeister series.

Rapid and real-time analysis of multi-component dissolved gas in seawater by Raman spectroscopy combined with continuous gas-liquid separator

Rapid and sensitive detection of dissolved gases in seawater is quite essential for the investigation of the global carbon cycle.Large quantities of in situ optical detection techniques showed restricted measurement efficiency,owing to the single gas sensor without the identification ability of multiple gases.In this work,a novel gas-liquid Raman detection method of monitoring the multi-component dissolved gases was proposed based on a continuous gas-liquid separator under a large difference of partial pressure.The limit of detection(LOD)of the gas Raman spectrometer could arrive at about 14 μl·L^(-1)for N_(2)gas.Moreover,based on the continuous gas-liquid separation process,the detection time of the dissolved gases could be largely decreased to about 200 s compared with that of the traditional detection method(30 min).Effect of equilibrium time on gas-liquid separation process indicated that the extracted efficiency and decay time of these dissolved gases was CO_(2)>O_(2)>N_(2).In addition,the analysis of the relationship between equilibrium time and flow speed indicated that the decay time decreased with the increase of the flow speed.The validation and application of the developed system presented its great potential for studying the components and spatiotemporal distribution of dissolved gases in seawater.

In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.