Recent strategies toward microfluidic‐based surface‐enhanced Raman spectroscopy

Surface‐enhanced Raman spectroscopy (SERS) is an extremely powerful analytical tool, which not only yields information about the molecular structure of the analyte in the form of characteristic vibrational spectrum but also gives sensitivities approaching those in fluorescence spectroscopy. The SERS measurement on the microfluidic platform provides possibility to manufacture the device with design perfectly fulfilling the needs of the application with minimal sample consumption. This review aims at describing basic strategies for SERS measurement in microfluidic devices published in the last decade and covers current trends in microfluidics with SERS detection in the field of bioanalysis and approaches toward on‐line coupling of liquid‐based separation techniques with SERS detection.     

Combination of liquid‐based column separations with surface‐enhanced Raman spectroscopy

Surface‐enhanced Raman spectroscopy is a constantly developing analytical method providing not only high‐sensitive quantitative but also qualitative information on an analyte. Thus, it is reasonable that it has been tested as a promising detection method in column separations. Although its implementation in analytical separations is not widespread, some surprising results, like enormous signal enhancement and demonstrations of single‐molecule identifications, proved in only a few special examples, indicate the potential of the method. The high detection sensitivity and selectivity would be of paramount importance in trace analyses of biologically relevant molecules in complex matrices. However, the combination of surface‐enhanced Raman spectroscopy with column separation methods brings two principal issues. Interactions of analytes with metal substrates can cause deteriorations of separations and the detection can be affected by background electrolytes or elution agents. Thus, in principle, this review is on the experimental and methodological solutions to these problems. First, theoretical and practical aspects of Raman scattering, and excitation of surface plasmon in colloid suspensions of nanoparticles and on planar nanostructured substrates are briefly explained. Advances in experimental arrangements of on‐line and at‐line couplings with column liquid phase separation methods, including microfluidic devices, are described together with chosen analytical applications.     

A fast and low‐cost spray method for prototyping and depositing surface‐enhanced Raman scattering arrays on microfluidic paper based device

In this study, a fast, low‐cost, and facile spray method was proposed. This method deposits highly sensitive surface‐enhanced Raman scattering (SERS) silver nanoparticles (AgNPs) on the paper‐microfluidic scheme. The procedures for substrate preparation were studied including different strategies to synthesize AgNPs and the optimization of spray cycles. In addition, the morphologies of the different kinds of paper substrates were characterized by SEM and investigated by their SERS signals. The established method was found to be favorable for obtaining good sensitivity and reproducible results. The RSDs of Raman intensity of randomly analyzing 20 spots on the same paper or different filter papers depositing AgNPs are both below 15%. The SERS enhancement factor is approximately 2 × 10⁷. The whole fabrication is very rapid, robust, and does not require specific instruments. Furthermore, the total cost for 1000 pieces of chip is less than $20. These advantages demonstrated the potential for growing SERS applications in the area of environmental monitoring, food safety, and bioanalysis in the future.     

Hydrophobic‐hydrophilic monolithic dual‐phase layer for two‐dimensional thin‐layer chromatography coupled with surface‐enhanced Raman spectroscopy detection

Hydrophobic‐hydrophilic monolithic dual‐phase plates have been prepared by a two‐step polymerization method for two‐dimensional thin‐layer chromatography of low‐molecular‐weight compounds, namely, several dyes. The thin 200 μm poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) layers attached to microscope glass plates were prepared using a UV‐initiated polymerization method within a simple glass mold. After cutting and cleaning the specific area of the layer, the reassembled mold was filled with a polymerization mixture of butyl methacrylate and ethylene dimethacrylate and subsequently irradiated with UV light. During the second polymerization process, the former layer was protected from the UV light with a UV mask. After extracting the porogens and hydrolyzing the poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) area, these two‐dimensional layers were used to separate a mixture of dyes with great difference in their polarity using reversed‐phase chromatography mode within the hydrophobic layer and then hydrophilic interaction chromatography mode along the hydrophilic area. In the latter dimension only the specific spot was developed further. Detection of the separated dyes could be achieved with surface‐enhanced Raman spectroscopy.     

Synthesis of magnetic polyphosphazene-Ag composite particles as surface enhanced Raman spectroscopy substrates for the detection of melamine

Magnetic polyphosphazene(MPZS) particles coated by Ag nanoparticles(MPZS-Ag) have been developed as surface enhanced Raman spectroscopy(SERS) substrates for sensitive detection of melamine in aqueous solutions and milk samples.5,5'-Dithiobis-(2-nitrobenzoic acid)(DTNB) was used as model analyte to test the SERS activity of the MPZS-Ag particles.The prepared MPZS-Ag particles possess both magnetic responsiveness and excellent SERS properties.SERS detection of different concentrations of melamine aqueous solutions and spiked milk samples were performed by the MPZS-Ag particles.The limit of detection(LOD) of the melamine in aqueous solutions was 10-7 mol/L(0.0126 mg/L) and 0.6 mg/L in real milk samples using the MPZS-Ag particles as SERS substrates.The LOD of the melamine are much lower than the safety values of Food and Drug Administration and Codex Alimentarius Commission.These results indicate that the MPZS-Ag particles have promising application prospect for SERS analysis in food safety fields.     

Synthesis of magnetic polyphosphazene-Ag composite particles as surface enhanced Raman spectroscopy substrates for the detection of melamine

Preparation process of the MPZS-Ag composite particles based on polyphosphazene and application for the detection of melamine as a novel SERS substrate.     

A review of developments and applications of thin‐film microextraction coupled to surface‐enhanced Raman scattering

Surface‐enhanced Raman scattering (SERS) greatly expands the applications of Raman spectroscopy and is a promising technique for food safety, environmental analysis, and public safety. Thin‐film microextraction (TFME) provides an efficient sample preparation method for SERS to improve its selectivity and detection efficiency. This review comprehensively describes the development and applications of SERS and TFME, including the history, mechanisim, and active substrate of SERS and the theory, device, forms, and practical applications of TFME. The applications of TFME‐SERS in food safety and environment monitoring are discussed, which could improve their advantages. TFME extracts and enriches the target analytes to eliminate the interfering substance, providing a facial way for SERS to analyze the target analytes in complex matrices. The development of TFME‐SERS technology not only expands the application range of TFME, but greatly improves the anti‐interference ability and detection sensitivity of SERS. Thus, the established methods are fast, convenient, and highly sensitive. This technology is potential to be applied in the on‐site and real‐time detection.     

Development of a four-zone carousel process packed with metal ion-imprinted polymer for continuous separation of copper ions from manganese ions,cobalt ions,and the constituent metal ions of the buffer solution used as eluent

A three-zone carousel process, in which Cu(II)-imprinted polymer (Cu-MIP) and a buffer solution were employed as adsorbent and eluent respectively, has been developed previously for continuous separation of Cu²⁺ (product) from Mn²⁺ and Co²⁺ (impurities). Although this process was reported to be successful in the aforementioned separation task, the way of using a buffer solution as eluent made it inevitable that the product stream included the buffer-related metal ions (i.e., the constituent metal ions of the buffer solution) as well as copper ions. For a more perfect recovery of copper ions, it would be necessary to improve the previous carousel process such that it can remove the buffer-related metal ions from copper ions while maintaining the previous function of separating copper ions from the other 2 impure heavy-metal ions. This improvement was made in this study by proposing a four-zone carousel process based on the following strategy: (1) the addition of one more zone for performing the two-step re-equilibration tasks and (2) the use of water as the eluent of the washing step in the separation zone. The operating conditions of such a proposed process were determined on the basis of the data from a series of single-column experiments. Under the determined operating conditions, 3 runs of carousel experiments were carried out. The results of these experiments revealed that the feed-loading time was a key parameter affecting the performance of the proposed process. Consequently, the continuous separation of copper ions from both the impure heavy-metal ions and the buffer-related metal ions could be achieved with a purity of 91.9% and a yield of 92.8% by using the proposed carousel process based on a properly chosen feed-loading time.     

Analysis of forchlorfenuron and thidiazuron in fruits and vegetables by surface‐enhanced Raman spectroscopy after selective solid‐phase extraction with modified β‐cyclodextrin

β‐Cyclodextrin and its derivatives can selectively bind to various organic molecules in its cavity and provide good applications in sample preparation. Surface‐enhanced Raman spectroscopy is a sensitive technique and has received increasing attention in the last decade. Herein, 3,5‐dimethyl phenyl carbamoylated β‐cyclodextrin bonded silica gel was used as a ssorbent in solid‐phase extraction to selectively enrich forchlorfenuron and thidiazuron followed by determination with surface‐enhanced Raman spectroscopy. It showed excellent selectivity for forchlorfenuron and thidiazuron and the adsorption capacities were 40.0 and 30.0 μg/g, respectively. A rapid and sensitive method based on the modified β‐cyclodextrin solid‐phase extraction coupled with surface‐enhanced Raman spectroscopy was developed. The linear ranges were 30.0–300.0 μg/L for forchlorfenuron and thidiazuron at 1005 and 640 cm^?1, respectively. Both of the limits of detection were 15.0 μg/L, which were significantly lower than the maximum permitted by the National Standard. The recoveries of forchlorfenuron and thidiazuron were 78.9–87.9% for the spiked grape, kiwi, cucumber and tomato, with relative standard deviations of 8.1–13.2%. The results show that this method is sensitive, selective, and relatively time saving, and has great potential in the analysis of trace amounts of plant growth regulators in fruits and vegetables.     

Thin‐layer chromatography combined with surface‐enhanced Raman scattering for rapid detection of benzidine and 4‐aminobiphenyl in migration from food contact materials based on gold nanoparticle doped metal‐organic framework

In this work, a rapid and sensitive thin‐layer chromatography combined with surface‐enhanced Raman spectroscopy method was established for rapid detection of benzidine and 4‐aminobiphenyl in migration from food contact materials based on Au nanoparticle doped metal‐organic framework. Benzidine and 4‐aminobiphenyl were firstly separated by thin‐layer chromatography to solve the limitation of their overlapping Raman peaks. Then the target molecules were monitored by adding AuNPs/MIL‐101(Cr) on the sample spots. Under the optimum conditions, the concentration of benzidine and 4‐aminobiphenyl can be quantitatively measured in the range of 2.0‐20.0 and1.0‐15.0 μg/L, respectively with good linear relationship, and the limits of detection were 0.21 and 0.23 μg/L, respectively. Furthermore, the developed method was applied to analyze benzidine and 4‐aminobiphenyl in migration of different food contact materials. The recoveries of benzidine and 4‐aminobiphenyl for migration of food contact materials, including paper cups, polypropylene food containers, and polyethylene glycol terephthalate bottles, were 80.6‐116.0 and 80.7‐118% with relative standard deviations of 1.1‐9.1 and 3.1‐9.9%, respectively. Surface‐enhanced Raman scattering detection was performed conveniently in the on‐plate mode without additional elution process. The method shows great potential in rapid monitoring of hazardous substances with overlapping characteristic Raman peaks in food contact materials.     

铬酸根离子的SERS检测及磁分离研究

介绍了一种基于表面增强拉曼光谱技术(SERS)的简单快速检测低浓度铬酸根离子的方法. 通过介质中水与铬酸根离子以及修饰在金基底和金纳米粒子表面的羧酸根形成氢键而构建“巯基苯甲酸-金基底/铬酸根-水/巯基苯甲酸-金纳米粒子”三明治结构. 通过检测标记分子的SERS信号判断溶液中是否存在铬酸根离子. 研究表明标记分子的SERS强度与铬酸根离子的浓度有关, 随浓度增加SERS强度呈非线性增强, 在10^－9 mol/L出现转折点. 利用以上三明治结构, 通过引入功能化的Fe₂O₃@Au核壳磁性纳米粒子, 利用外加磁场可富集分离溶液中的铬酸根离子, 经SERS 检测表明10^－5 mol/L的铬酸根离子磁分离后其浓度降低了约4～6个数量级.     

Electrodeposition of dendritic gold/silver nanaoparticles on disposable screen‐printed carbon electrode and its application of 4‐mercaptopyridine in in situ electrochemical surface‐enhanced Raman scattering

Column electrodes pretreated through oxidation–reduction cycles were traditionally used in electrochemical surface‐enhanced Raman scattering (SERS). In this study, a disposable screen‐printed carbon electrode was introduced into in situ electrochemical SERS through the electrodeposition of dendritic gold/silver nanoparticles (Au/AgNPs) onto the surface of the carbon working electrode to induce the SERS enhancement effect on the electrode. Scanning electron microscopy images showed that dendritic Au/AgNPs nanostructures could be fabricated under appropriate electrodeposition conditions and could present a minimum SERS factor of 4.25 × 10⁵. Furthermore, the absorbed behavior of 4‐mercaptopyridine was investigated under different potentials. The adsorption configuration was inferred to transform from ‘vertical’ to ‘lying‐flat’. The proposed new electrode combined with a portable Raman spectrometer could be useful in the identifying products or intermediates during electrochemical synthesis or electrochemical catalysis in in situ electrochemical SERS. Copyright © 2016 John Wiley & Sons, Ltd.     

Crystal Structure and Magnetic Properties of Copper(II) and Nickel(II) Binuclear Complexes with Bisacylhydrazones Based on 2,6‐Diformyl‐4‐methylphenol

The series of binuclear Cu(II) and Ni(II) complexes with an asymmetrical exchange fragment based on 2,6‐diformyl‐4‐methylphenol bishydrazone has been synthesized for the first time. The compositions and structures of both ligands and its complexes have been established with the data of IR, ¹H NMR, and extended X‐ray absorption fine structure (EXAFS) spectroscopical studies as well as magnetic measurements. The structure of [Ni₂L₃(μ‐Pz)] · 2CH₃OH (L = triply deprotonated form of bishydrazone, Pz = pyrazol) was confirmed by X‐ray crystallographic analysis. In this complex, the coordination environment of two nickel ions is quite different, one nickel atom is square‐planar and the other is distorted octahedral coordinated. The values of exchange parameter calculated in terms of HDVV theory have been compared with the features of an asymmetrical exchange fragment's electronic and geometrical structure.     

Copper(II) and Cadmium(II) Complexes Based on N,N‐Bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine Ligand: Syntheses,Structures, Magnetic,and Luminescent Properties

The reaction of the aryl‐oxide ligand H₂L [H₂L = N,N‐bis(3, 5‐dimethyl‐2‐hydroxybenzyl)‐N‐(2‐pyridylmethyl)amine] with CuSO₄ · 5H₂O, CuCl₂ · 2H₂O, CuBr₂, CdCl₂ · 2.5H₂O, and Cd(OAc)₂ · 2H₂O, respectively, under hydrothermal conditions gave the complexes [Cu(H₂L¹)₂] · SO₄ · 3CH₃OH ( 1 ), [Cu₂(H₂L²)₂Cl₄] ( 2 ), [Cu₂(H₂L²)₂Br₄] ( 3 ), [Cd₂(HL)₂Cl₂] ( 4 ), and [Cd₂(L)₂(CH₃COOH)₂] · H₂L ( 5 ), where H₂L¹ [H₂L¹ = 2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenol] and H₂L² [H₂L² = 2‐(2, 4‐dimethyl‐6‐((pyridin‐2‐ylmethylamino)methyl)phenoxy)‐4, 6‐dimethylphenol] were derived from the solvothermal in situ metal/ligand reactions. These complexes were characterized by IR spectroscopy, elementary analysis, and X‐ray diffraction. A low‐temperature magnetic susceptibility measurement for the solid sample of 2 revealed antiferromagnetic interactions between two central copper(II) atoms. The emission property studies for complexes 4 and 5 indicated strong luminescence emission.     

IR,Raman, and Surface‐enhanced Raman Spectroscopic Study on Triruthenium Dipyridylamide Diruthenium Nickel Dipyridylamide Family: Metal‐metal Bonding and Structures

We report the infrared, Raman, and surface‐enhanced Raman scattering (SERS) spectra of triruthenium dipyridylamido complexes and of diruthenium mixed nickel metal‐string complexes. From the results of analysis on the vibrational modes, we assigned their vibrational frequencies and structures. The infrared band at 323–326 cm^?1 is assigned to the Ru₃ asymmetric stretching mode for [Ru₃(dpa)₄Cl₂]^0–2+. In these complexes we observed no Raman band corresponding to the Ru₃ symmetric stretching mode although this mode is expected to have substantial Raman intensity. There is no frequency shift in the Ru₃ asymmetric stretching modes for the complexes with varied oxidational states. No splitting in Raman spectra for the pyridyl breathing line indicates similar bonding environment for both pyridyls in dpa^– , thus a delocalized structure in the [Ru₃]^6–8+ unit is proposed. For Ru₃(dpa)₄(CN)₂ complex series, we assign the infrared band at 302 cm^?1 to the Ru₃ asymmetric stretching mode and the weak Raman line at 285 cm^?1 to the Ru₃ symmetric stretching. Coordination to the strong axial ligand CN^– weakens the Ru‐Ru bonding. For the diruthenium nickel complex [Ru₂Ni(dpa)₄Cl₂]^0–1+, the diruthenium stretching mode ν_Ru‐Ru is assigned to the intense band at 327 and 333 cm^?1 in the Raman spectra for the neutral and oxidized forms, respectively. This implies a strong Ru‐Ru metal‐metal bonding.     

Synthesis,Characterization, and Magnetic Properties of Novel Cobalt(II) and Copper(II) Complexes with 5‐(Isonicotinamido)isophthalate Ligand

Two new complexes, {[Co(INAIP) · H₂O] · 2H₂O}_n ( 1 ), and {[Cu(INAIP)] · H₂O}_n ( 2 ) [H₂INAIP = 5‐(isonicotinamido)isophthalic acid] were synthesized under hydrothermal conditions, and characterized by single‐crystal X‐ray structure determination, thermogravimetric analysis, X‐ray powder diffraction, and magnetic studies. In complex 1 both Co^II atoms and INAIP^2– ligands act as four‐connected node, whereas in 2 both Cu^II atoms and INAIP^2– ligands act as three‐connected node.