Surface-Enhanced Raman Scattering-Active Substrate Prepared with New Plasmon-Activated Water.

Conventionally, reactions in aqueous solutions are prepared using deionized (DI) water, the properties of which are related to inert "bulk water" comprising a tetrahedral hydrogen-bonded network. In this work, we demonstrate the distinguished benefits of using in situ plasmon-activated water (PAW) with reduced hydrogen bonds instead of DI water in electrochemical reactions, which generally are governed by diffusion and kinetic controls. Compared with DI water-based systems, the diffusion coefficient and the electron-transfer rate constant of K3Fe(CN)6 in PAW in situ can be increased by ca. 35 and 15%, respectively. These advantages are responsible for the improved performance of surface-enhanced Raman scattering (SERS). On the basis of PAW in situ, the SERS enhancement of twofold higher intensity of rhodamine 6G and the corresponding low relative standard deviation of 5%, which is comparable to and even better than those based on complicated processes shown in the literature, are encouraging.

Triggering comprehensive enhancement in oxygen evolution reaction by using newly created solvent.

Theoretical calculations indicate that the properties of confined liquid water, or liquid water at surfaces, are dramatically different from those of liquid bulk water. Here we present an experimentally innovative strategy on comprehensively efficient oxygen evolution reaction (OER) utilizing plasmon-induced activated water, creating from hot electron decay at resonantly illuminated Au nanoparticles (NPs). Compared to conventional deionized (DI) water, the created water owns intrinsically reduced hydrogen-bonded structure and a higher chemical potential. The created water takes an advantage in OER because the corresponding activation energy can be effectively reduced by itself. Compared to DI water-based solutions, the OER efficiencies at Pt electrodes increased by 69.3%, 21.1% and 14.5% in created water-based acidic, neutral and alkaline electrolyte solutions, respectively. The created water was also effective for OERs in photoelectrochemically catalytic and in inert systems. In addition, the efficiency of OER increased by 47.5% in created water-based alkaline electrolyte solution prepared in situ on a roughened Au electrode. These results suggest that the created water has emerged as an innovative activator in comprehensively effective OERs.

Direct electron transfer of glucose oxidase and dual hydrogen peroxide and glucose detection based on water-dispersible carbon nanotubes derivative.

A water-dispersible multi-walled carbon nanotubes (MWCNTs) derivative, MWCNTs-1-one-dihydroxypyridine (MWCNTs-Py) was synthesis via Friedel-Crafts chemical acylation. Raman spectra demonstrated the conjugated level of MWCNTs-Py was retained after this chemical modification. MWCNTs-Py showed dual hydrogen peroxide (H2O2) and glucose detections without mutual interference by adjusting pH value. It was sensitive to H2O2 in acidic solution and displayed the high performances of sensitivity, linear range, response time and stability; meanwhile it did not respond to H2O2 in neutral solution. In addition, this positively charged MWCNTs-Py could adsorb glucose oxidase (GOD) by electrostatic attraction. MWCNTs-Py-GOD/GC electrode showed the direct electron transfer (DET) of GOD with a pair of well-defined redox peaks, attesting the bioactivity of GOD was retained due to the non-destroyed immobilization. The high surface coverage of active GOD (3.5×10(-9) mol cm(-2)) resulted in exhibiting a good electrocatalytic activity toward glucose. This glucose sensor showed high sensitivity (68.1 µA mM(-1) cm(-2)) in a linear range from 3 µM to 7 mM in neutral buffer solution. The proposed sensor could distinguish H2O2 and glucose, thus owning high selectivity and reliability.

Quantitative evaluation on activated property-tunable bulk liquid water with reduced hydrogen bonds using deconvoluted Raman spectroscopy.

Interesting properties of water with distinguishable hydrogen-bonding structure on interfacial phase or in confined environment have drawn wide attentions. However, these unique properties of water are only found within the interfacial phase and confined environment, thus, their applications are limited. In addition, quantitative evaluation on these unique properties associating with the enhancement of water's physical and chemical activities represents a notable challenge. Here we report a practicable production of free-standing liquid water at room temperature with weak hydrogen-bonded structure naming Au nanoparticles (NPs)-treated (AuNT) water via treating by plasmon-induced hot electron transfer occurred on resonantly illuminated gold NPs (AuNPs). Compared to well-known untreated bulk water (deionized water), the prepared AuNT water exhibits many distinct activities in generally physical and chemical reactions, such as high solubilities to NaCl and O2. Also, reducing interaction energy within water molecules provides lower overpotential and higher efficiency in electrolytic hydrogen production. In addition, these enhanced catalytic activities of AuNT water are tunable by mixing with deionized water. Also, most of these tunable activities are linearly proportional to its degree of nonhydrogen-bonded structure (DNHBS), which is derived from the O-H stretching in deconvoluted Raman spectrum.

Room-temperature sensor based on surface-enhanced Raman spectroscopy.

As reported in the literature, several factors, such as scattering cross sections, polarisability and wavelength suitability, contribute to increased SERS enhancement. In general, the advantage of surface-enhanced Raman scattering (SERS)-active Ag nanoparticles (NPs) is their higher SERS enhancement over Au NPs because the molar extinction coefficient of the Ag NPs is the highest of its kind among metals. Nevertheless, the corresponding SERS-active hot spots on Au are of inherently greater stability than on Ag. In this work, innovative temperature sensors based on SERS-active Au and Ag substrates prepared by sonoelectrochemical deposition-dissolution cycles (SEDDCs) are first reported. The SERS intensity of the model probe molecules of Rhodamine 6G (R6G) adsorbed on a SERS-active Ag substrate is monotonically increased from 25 to 50 °C. Moreover, this temperature-dependent intensity is linear with a slope of ca. 430 cps per °C between 25 to 45 °C. In addition, the reversibility and reusability of the developed temperature sensors are evaluated after the R6G-adsorbed sensors are alternately exposed to the temperatures of 25 and 45 °C in a sealed chamber. After every five cycles, the SERS spectra of treated substrates were recorded and compared with those of the as-prepared substrates. Experimental results indicate that SERS enhancement capability is mostly reversible based on 90% intensity of the Raman signal being maintained for the SERS-active Au substrate after 25 cycles (only 15 cycles for the Ag substrate).

Innovative fabrication of a Au nanoparticle-decorated SiO2 mask and its activity on surface-enhanced Raman scattering.

Surface-enhanced Raman scattering (SERS) utilizing the well-defined localized surface plasmon resonance (LSPR) of Ag and Au nanoparticles (NPs) under resonant irradiation has emerged as a promising spectroscopy technique for providing vibrational information on trace molecules. The Raman scattering intensity from molecules close to the surface of these finely divided metals can be significantly enhanced by a factor of more than 10(6). In addition to the high sensitivity, the reproducibility of the SERS signal is also an important parameter for its reliable application. In this work, we report on the innovative and facile fabrication of a Au NP-decorated SiO2 mask coated on indium tin oxide (ITO) glass as a SERS array substrate. First, a highly ordered porous SiO2 mask with pore sizes of 350 nm in diameter and wall thickness of 60 nm was deposited on ITO glass by using spin coating. Then, Au NPs were controllably decorated into the pores of the conductive ITO glass-bottomed SiO2 mask by using sonoelectrochemical deposition-dissolution cycling (SEDDC). Experimental results indicate that the SERS effect of Rhodamine 6G (R6G) observed on this developed substrate increases with an increase in the deposition time of Au NPs in SEDDC. The corresponding optimal enhancement factor (EF) that is obtained is ca. 6.5 × 10(7). Significantly, this system achieves an optimal reproducibility under a medium-length deposition time of Au NPs in SEDDC with a relative standard deviation (RSD) of 12% for measurements of five spots on different areas. The low RSD of the SERS signal and the large EF suggest that the developed array system can serve as an excellent spectroscopy platform for practical applications in analytical chemistry.

Active and stable liquid water innovatively prepared using resonantly illuminated gold nanoparticles.

The properties of confined liquid water, or liquid water in contact with hydrophobic surfaces, are significantly different from those of bulk liquid water. However, all of water's commonly described properties are related to inert "bulk liquid water" which comprises a tetrahedral hydrogen-bonded network. In this work, we report an innovative and facile method for preparing small water clusters (SWCs) with reduced affinity hydrogen bonds by letting bulk water flow through supported Au nanoparticles (NPs) under resonant illumination to give NP-treated (AuNT) water at constant temperature. Utilizing localized surface plasmon resonance on illuminated Au NPs, the strong hydrogen bonds of bulk water can be disordered when water is located at the illuminated Au/water interface. The prepared SWCs are free of Au NPs. The energy efficiency for creating SWCs is ∼17%. The resulting stable AuNT water exhibits distinct properties at room temperature, which are significantly different from the properties of untreated bulk water, examples being their ability to scavenge free hydroxyl and 2,2-diphenyl-1-picrylhydrazyl radicals and to effectively reduce NO release from lipopolysaccharide-induced inflammatory cells.

Silver overlayer-modified surface-enhanced Raman scattering-active gold substrates for potential applications in trace detection of biochemical species.

Because Ag and Au nanoparticles (NPs) possess well-defined localized surface plasmon resonance (LSPR) they are popularly employed in the studies of surface-enhanced Raman scattering (SERS). As shown in the literature and in our previous studies, the advantage of SERS-active Ag NPs is their higher SERS enhancement over Au NPs. On the other hand, the disadvantage of SERS-active Ag NPs compared to Au NPs is their serious decay of SERS enhancement in ambient laboratory air. In this work, we develop a new strategy for preparing highly SERS-active Ag NPs deposited on a roughened Au substrate. This strategy is derived from the modification of electrochemical underpotential deposition (UPD) of metals. The coverage of Ag NPs on the roughened Au substrate can be as high as 0.95. Experimental results indicate that the SERS of Rhodamine 6G (R6G) observed on this developed substrate exhibits a higher intensity by ca. 50-fold of magnitude, as compared with that of R6G observed on the substrate without the deposition of Ag NPs. The limit of detection (LOD) for R6G measured on this substrate is markedly reduced to 2×10(-15)M. Moreover, aging of SERS effect observed on this developed substrate is significantly depressed, as compared with that observed on a generally prepared SERS-active Ag substrate. These aging tests were performed in an atmosphere of 50% relative humidity (RH) and 20% (v/v) O2 at 30°C for 60 day. Also, the developed SERS-active substrate enables it practically applicable in the trace detection of monosodium urate (MSU)-containing solution in gouty arthritis without a further purification process.

Improved stabilities on surface-enhanced Raman scattering-active Ag/Al2O3 films on substrates.

As is shown in the literature, surface-enhanced Raman scattering (SERS)-active Ag films obtained by the salting-out of Ag colloids from solutions with some salts, are popularly used to examine the structure of analytes. SERS-active Ag nanoparticles (NPs) demonstrate more significant SERS effects than Au NPs, however, problems regarding the stabilities of SERS-active Ag NPs remain to be overcome. In this work, Ag/Al(2)O(3) colloids were prepared in 0.1 M HNO(3) solutions containing Al(2)O(3) NPs with higher heat capacity by sonoelectrochemical methods. SERS-active Ag/Al(2)O(3) films deposited on glass slides were prepared by the addition of a saturated NaCl solution in the prepared Ag/Al(2)O(3) colloids-containing solution. In an acceptable sacrifice of Raman intensity by ca. 30% magnitude, the prepared Ag/Al(2)O(3) films markedly improved thermal stability by raising the operation temperature over 100 °C, compared to Ag films. Meanwhile, aging of SERS enhancement capability in an atmosphere of relative humidity (RH) of 50% and 20% (v/v) O(2) at 30 °C is significantly depressed using Ag/Al(2)O(3) films.

Surface-enhanced Raman scattering-active Au/SiO2 nanocomposites prepared using sonoelectrochemical pulse deposition methods.

For improving signals, reproducibility, and stabilities of surface-enhanced Raman scattering (SERS), numerous technologies have recently been reported in the literature. However, the fabrication processes are usually complicated. It is well-known that nanoparticles (NPs) of Au and SiO(2) are SERS active and inactive materials, respectively. In this work, a simple synthesis route based on sonoelectrochemical pulse deposition (SEPD) methods has been developed to synthesize effectively SERS-active Au/SiO(2) nanocomposites (NCs) with an enhancement factor of 5.4 × 10(8). Experimental results indicate that pH value of solution and addition of SiO(2) NPs before and after oxidation-reduction cycles (ORCs) can significantly influence the corresponding SERS activities. Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on the developed Au/SiO(2) NCs exhibits a higher intensity by more than 1 order of magnitude, as compared with that of R6G adsorbed on Au NPs synthesized using the same method. Moreover, this improved SERS activity is successfully verified from the mechanisms of electromagnetic (EM) and chemical (CHEM) enhancements.

Surface-enhanced Raman scattering-active gold nanoparticles modified with a monolayer of silver film.

As shown in the literature, electrochemical underpotential deposition (UPD) offers the ability to deposit up to a monolayer of one metal onto a more noble metal with a flat surface. In this work, we develop an electrochemical pathway to prepare more surface-enhanced Raman scattering (SERS)-active substrates with Ag UPD-modified Au nanoparticles (NPs) by using sonoelectrochemical deposition-dissolution cycles (SEDDCs). Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on these Ag UPD-modified Au NPs exhibits a higher intensity by ca. 12-fold magnitude, as compared with that of R6G adsorbed on unmodified Au NPs. The prepared SERS-active substrate demonstrates a large Raman scattering enhancement for R6G with a detection limit of 2 × 10(-14) M and an enhancement factor of 5.0 × 10(8). Also, the strategy proposed in this work to improve the SERS effects by using UPD Ag based on SEDDCs has an effect on the smaller probe molecules of 2,2'-bipyridine (BPy).

Size-controllable synthesis of surface-enhanced Raman scattering-active gold nanoparticles coated on TiO2.

As shown in the literature, gold nanoparticles (NPs) were popularly used in the fields of catalyst and surface-enhanced Raman scattering (SERS). In this work, size-controllable Au NPs coated on TiO(2) are synthesized by adjusting the pH of solutions based on sonoelectrochemical methods. The size-controlled Au NPs on TiO(2), ranging from 2 to 80 nm in diameter, can be obtained by varying the pH of solutions from 3 to 7 and placing the sample for 3 h before sonoelectrochemical reductions. The optimal particle sizes of Au NPs on TiO(2) to obtain the strongest SERS effects under an irradiation of 785 nm for probe molecules of adsorbed Rhodamine 6G (R6G) and deposited polypyrrole (PPy) are all ca. 60 nm.

Using a photochemical method and chitosan to prepare surface-enhanced Raman scattering-active silver nanoparticles.

In this paper, we report a new strategy for the preparation of surface-enhanced Raman scattering (SERS)-active silver nanoparticles (Ag NPs), using a photochemical method and the presence of chitosan (Ch). First, Ag substrates were subjected to electrochemical oxidation/reduction cycles (ORCs) in deoxygenated aqueous solutions containing 0.1 M HNO(3) and 1 g L(-1) Ch (pH 6.9, adjusted by adding 1 M NaOH), resulting in Ag(+)-Ch complexes. These substrates were then irradiated with UV light at various wavelengths to yield the SERS-active Ag NPs. A stronger SERS effect was observed on the SERS-active Ag NPs prepared by using UV irradiation at 310 nm. The pH of the solution and the presence of Ch during the preparation process both affected the resulting SERS activities.

New pathway to prepare gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering.

As shown in the literature, additional energies are necessary for the reduction of positively charged noble metal ions to prepare metal nanoparticles (NPs). In this work, we report a new green pathway to prepare Au NPs in neutral 0.1M NaCl aqueous solutions from bulk Au substrates without addition of any stabilizer and reductant just via aid of natural chitosan (Ch) at room temperature. Au- and Ch-containing complexes in aqueous solution were electrochemically prepared. The role of Ch is just an intermediate to perform electron transfer with Au NPs. The stability of these prepared Au NPs is well maintained by Au NPs themselves with slightly positively charged Au remained on the surface of Au NPs. The particle size of prepared spherical Au (111) NPs is ca. 15 nm in diameter. Moreover, increasing the pH of preparation solutions can be contributive to preparing concentrated Au NPs in solutions. The prepared Au NPs are surface-enhanced Raman scattering (SERS)-active for probe molecules of Rhodamine 6G. They also demonstrate significantly catalytic activity for decomposition of acetaldehyde in rice wine.

Surface-enhanced Raman scattering-active silver nanostructures with two domains.

Generally, a controllable and reproduced surface roughness for surface-enhanced Raman scattering (SERS) studies can be generated through control of the electrochemical oxidation-reduction cycles (ORC) procedure. In this work, we propose a new sonoelectrochemical approach to prepare SERS-active substrates with two domain-Ag nanostructures. The method is based on a strategy of deposition-dissolution cycles (DDCs) by using a cathodic overpotential and an anodic overpotential from open circuit potential (OCP) in turn under sonication. The prepared SERS-active substrate demonstrates large Raman scattering enhancement for adsorbed Rhodamine 6G (R6G) with an enhancement factor of 2.3×10(8) and a limit of detection of 2×10(-13)M. The improved SERS performances can be successfully explained from the viewpoints of electromagnetic (EM) and chemical (CHEM) enhancements.

A new strategy to prepare surface-enhanced Raman scattering-active substrates by electrochemical pulse deposition of gold nanoparticles.

In this communication, we develop a simple pathway to prepare SERS-active substrates with Au nanoparticles (NPs) by an electrochemical strategy of deposition-dissolution cycles (DDCs). The prepared SERS-active substrates demonstrate large Raman scattering enhancement for Rhodamine 6G (R6G) with a detection limit of 2 × 10(-12) M and an enhancement factor of 5.8 × 10(7).

Electrochemically prepared surface-enhanced Raman scattering-active silver substrates with improved stabilities.

In this work, SiO2 nanoparticles-modified surface-enhanced Raman scattering (SERS)-active silver substrates were prepared by electrochemical oxidation-reduction cycles (ORC) methods in 0.1 N HCl aqueous solutions containing 1 mM SiO2 nanoparticles to improve their thermal stabilities and anti-aging abilities in SERS performances. Then these SERS-active substrates were further modified with different contents of SiO2 nanoparticles to improve their corresponding SERS performances. Experimental results indicate that the operation temperature can be significantly raised from 125 to 175°C based on this modified SERS-active Ag substrate. Also, the aging in SERS intensity is also depressed on this modified Ag substrate due to the contribution of SiO2 nanoparticles. Moreover, the SERS enhancement capability on this modified Ag substrate is gradually raised from 25°C to a maximum at 55°C and monotonically decreased from 55 to 60°C. This is a 10°C delay as compared with the similar phenomenon observed on the unmodified Ag substrate.

Simple strategy to improve surface-enhanced Raman scattering based on electrochemically prepared roughened silver substrates.

We develop an easy and effective pathway to improve surface-enhanced Raman scattering (SERS) effects of probe molecules of Rhodamine 6G (R6G) adsorbed on electrochemically prepared roughened Ag substrates. In general SERS studies, SERS-active metal substrates are first prepared. Then probe molecules are adsorbed on them to evaluate the relative SERS effects. In this study, we employ electrochemical oxidation-reduction cycle (ORC) treatments in 0.1 M KCl solutions containing probe molecules of 2 x 10(-5) M R6G to prepare R6G-adsorbed SERS-active Ag substrates for one step. Encouragingly, based on this strategy, the SERS intensity of adsorbed R6G can be increased by 1 order of magnitude, as compared with that of R6G adsorbed on a roughened Ag substrate beforehand, which was generally shown in the literature. Moreover, this improved SERS effect based on this strategy is also effective for 2 x 10(-9) M probe molecules, which is at a level of single molecule detection based on Ag colloids. It is also effective for probe molecules of ClO(4)(-) with low Raman cross section and for other electrochemically prepared SERS-active substrates of Au. Further analyses indicate that the increase in SERS activity in this new method is most likely due to the incorporation of more chloride ions into the substrate.

Direct evidence of chemical effect of surface-enhanced Raman scattering observed on electrochemically prepared rough gold substrates.

In this study, polypyrrole (PPy) films were electrochemically deposited on gold substrates roughened by an electrochemical triangular-wave oxidation-reduction cycles (ORC) in an aqueous solution containing 0.1N KCl. Then the substrates were heated from 25 to 50 degrees C and the corresponding SERS performances of PPy were observed in situ. The results indicate that the SERS enhancement capabilities of substrates are gradually raised from 25 degrees C to a maximum at 40 degrees C and monotonically decreased from 40 to 50 degrees C. These SERS enhancement capabilities ascribed to the charge transfers from PPy to Au, which are responsible for the chemical effects of SERS mechanisms, are successfully observed via SERS and high resolution X-ray photoelectron spectroscopy (HRXPS) analyses. The variation in content of the oxidized PPy peak of the double peaks in the range of 1000-1150cm(-1) in SERS spectrum obtained on an Au substrate at different temperatures is consistent with its corresponding variation in the SERS intensity of PPy. The variation in content of the oxidized nitrogen of PPy deposited on an Au substrate at different temperatures revealed from an HRXPS analysis also confirms this consistence.

Temperature effect of electrochemically roughened gold substrates on polymerization electrocatalysis of polypyrrole.

In this work, electrochemical methods were used to prepare complexes with Au and Cl species on bulk Au substrates. Then the electrochemically roughened Au substrates were further heat-treated at different temperatures. The effect of temperatures used in heat treatments between 25 and 100 degrees C on electrocatalytical polymerization of polypyrrole (PPy) formed on the prepared gold substrates was first investigated. The result indicates that the optimally electrocatalytical capability of the heat-treated Au substrate for PPy polymerization is at 75 degrees C. Moreover, the autopolymerized PPy on the roughened Au substrate treated at 75 degrees C demonstrates the highest oxidation level and oxidation degree of 0.32 and 0.50, respectively. Primary results indicate that complexes with positively charged Au act as oxidants, and perchlorate and chloride ions act as dopants for the oxidation-polymerization of PPy.