Detection of trace mercury ions in water with a bovine-serum-albumin-modified Au@SiNWA surface-enhanced-Raman-scattering sensor.

Accurate detection of mercury ions (Hg2+) in water is of great importance for environmental protection. Here, a surface-enhanced Raman scattering (SERS) sensor using bovine-serum-albumin-modified gold-silicon nanowire arrays (Au@SiNWAs) is used to detect the ions. The SiNWAs were grown via chemical etching; the addition of modified gold particles on the surface formed Au@SiNWAs to increase the surface activity. The Raman enhancement factor was as large as ∼2.52 × 105, which was also confirmed with finite-difference time-domain simulations. The detection limit for Hg2+ ions in water was as low as ∼10-12 M, which is much lower than that stipulated by the United States Environmental Protection Agency's maximum residue requirements for drinking water. Furthermore, the SERS intensity was linear with the log of the Hg2+ concentration between 1 pM and 100 nM, with a correlation coefficient of 0.992. There was no significant interference when other metal ions were present, which shows the excellent selectivity of the SERS sensor. Unknown Hg2+ concentrations in water can be readily determined in an accurate and reliable manner, with a relative standard deviation of ∼9.21%.

Facile synthesis of Au nanoparticle-coated Fe3O4 magnetic composite nanospheres and their application in SERS detection of malachite green.

A facile method for synthesizing Au nanoparticle-coated Fe3O4 magnetic composite nanospheres (Fe3O4@Au MCS) via seed-mediated growth and iterative reduction is reported. The nanospheres were then successfully used to detect malachite green (MG) residues in water bodies via surface-enhanced Raman scattering (SERS) technique. Fe3O4@Au MCS has excellent optical properties and superparamagnetism; it can be dispersed into the solution to fully adsorb target molecules and then collected with a magnet to increase the molecular density and the number of SERS hot spots. Magnetic enrichment was superior to conventional detection method. The limit of detection for MG was 10-7 M and the enhancement factor was 1.1 × 105. The logarithm of the SERS intensity of the characteristic peak at 1618 cm-1 exhibited a linear relationship with the logarithm of the MG concentration over the range of 10-3- 10-7 M, with a correlation coefficient of 0.966. The Fe3O4@Au MCS had good uniformity of SERS signals, with a 18.59% relative standard deviation for the SERS intensity. MG detection in aquaculture water conformed with the established quantitative regulations. The SERS spectrum calculated with density function theory for MG adsorbed on Fe3O4@Au MCS was very close to the experimental spectrum, which verified enhancement by the substrate. Overall, Fe3O4@Au MCS enabled ultrasensitive, quantitative SERS detection of MG.

Rapid determination of 1,3-propanediol in fermentation process based on a novel surface-enhanced Raman scattering biosensor.

The production of 1,3-propanediol (1,3-PDO) is an important fermentation process. However, 1,3-PDO could not be distinguished separately and efficiently in fermentations previously because it has a highly similar molecular structure to the feedstock glycerol (GLY) and by-product lactic acid (Lac), which leads to the difficulty of quantification. In this paper, a low-cost and environmentally friendly biosensor based on surface-enhanced Raman scattering (SERS) technique was developed. Using it, the concentration of 1,3-PDO and Lac in a fermentation solution can be determined directly from their respective characteristic peaks in Raman spectroscopy. Moreover, by analyzing the respective contributions of 1,3-PDO, Lac, and GLY to the integrated intensities of the 2920 cm-1 Raman peak common to these three substances, the concentration of GLY could also be quantified. SERS study on various 1,3-PDO:GLY and Lac:GLY molar ratios were conducted to establish the proportional relationships of these compounds by analyzing the relationship between the concentration and the Raman peak intensities. The 1,3-PDO:Lac:GLY with serial concentration gradient was carried out to verify the relationship between the concentration and the Raman peak intensities by the high-performance liquid chromatography (HPLC) with relative deviations <25%. Concentrations of 1,3-PDO and Lac as low as 1 g/L and concentration of GLY as low as 4 g/L were analyzed to determine the limit of detection. Therefore, this new method allows the rapid quantification of 1,3-PDO, Lac and GLY concentrations on a SERS-based biosensor.

A rapid method to authenticate vegetable oils through surface-enhanced Raman scattering.

Vegetable oils are essential in our daily diet. Among various vegetable oils, the major difference lies in the composition of fatty acids, including unsaturated fatty acids (USFA) and saturated fatty acids (SFA). USFA include oleic acid (OA), linoleic acid (LA), and α-linolenic acid (ALA), while SFA are mainly palmitic acid (PA). In this study, the most typical and abundant USFA present with PA in vegetable oils were quantified. More importantly, certain proportional relationships between the integrated intensities of peaks centered at 1656 cm(-1) (S1656) in the surface-enhanced Raman scattering spectra of different USFA were confirmed. Therefore, the LA or ALA content could be converted into an equivalent virtual OA content enabling the characterization of the USFA content in vegetable oils using the equivalent total OA content. In combination with the S1656 of pure OA and using peanut, sesame, and soybean oils as examples, the ranges of S1656 corresponding to the National Standards of China were established to allow the rapid authentication of vegetable oils. Gas chromatograph-mass spectrometer analyses verified the accuracy of the method, with relative errors of less than 5%. Moreover, this method can be extended to other detection fields, such as diseases.

Ag@Au core-shell dendrites: a stable, reusable and sensitive surface enhanced Raman scattering substrate.

Surface enhanced Raman scattering (SERS) substrate based on fabricated Ag@Au core-shell dendrite was achieved. Ag dendrites were grown on Si wafer by the hydrothermal corrosion method and Au nanofilm on the surface of Ag dendritic nanostructure was then fabricated by chemical reduction. With the help of sodium borohydride in water, Au surface absorbates such as thiophene, adenine, rhodamine, small anions (Br(-) and I(-)), and a polymer (PVP, poly(N-vinylpyrrolidone)) can be completely and rapidly removed. After four repeatable experiments, the substrate SERS function did not decrease at all, indicating that the Ag@Au dendrite should be of great significance to SERS application because it can save much resource. Six-month-duration stability tests showed that the Ag@Au core-shell dendrite substrate is much more stable than the Ag dendrite substrates. We have also experimented on fast detection of Cd(2+) at 10(-8) M concentration by decorating single-stranded DNA containing adenine and guanine bases on the surface of this Ag@Au dendrite. Finite-difference time-domain simulations were carried out to investigate the influence of Au nanolayer on Ag dendrites, which showed that the local electric fields and enhancement factor are hardly affected when a 4 nm Au nanolayer is coated on Ag dendrite surface.

[Near-infrared quantum cutting downconversion luminescence of Yb3+ ion cooperative energy transferred from YVO4 matrix donor].

The present manuscript researches the near infrared quantum cutting luminescence phenomena of Yb3+ ion in YVO4 crystal matrix The luminescence spectra, excitation spectra and fluorescence lifetimes were measured. It was found that the excitation of YVO4 crystal matrix energy band by 322.0 nm light can result in the effective secondary cooperative energy transfer of Yba+ ion from the YVO4 crystal matrix It results in the intense 985.5 nm 2F(5/2)-->2F(7/2) near infrared quantum cutting luminescence of Yb3+ ion. Meanwhile, the 430.O nm luminescence intensity of YVO4 crystal matrix decreases greatly. From the experimental measurements, it was found that the lifetime of 430.0 nm fluorescence of (A) Yb(1.5) : YVO4 crystal is tauA = 3.785 s and that of (B) YVO4 crystal is tauB=22.72 s. It was found also that the theoretical efficiency up limit of quantum cutting of (A) Yb(1.5) : YVO4 crystal is about eta1.5%=183-3%.

Approach for determination of ATP:ADP molar ratio in mixed solution by surface-enhanced Raman scattering.

The ATP:ADP molar ratio is an important physiological factor. However, in previous literatures, ATP and ADP could not be distinguished by Raman spectroscopy due to the high similarity of molecular structure. To challenge this problem, also considering that the γ phosphate group may interact with adenine group and cause a different variation of the Raman spectrum than that of ADP, a highly sensitive, low-cost, environment protecting, flexible and super-hydrophobic Au nanoparticles/cicada wing (Au/CW) substrate with three-dimension structure was fabricated and employed as an active surface-enhanced Raman scattering (SERS) substrate to detect the ATP:ADP molar ratios. The concentration as low as 10(-8)M for ATP and ADP was analyzed to determine the limit of detection. This SERS study on various ATP:ADP molar ratios demonstrates that ATP:ADP could be distinguished and the quantitative determination of ATP content was achieved. Moreover, a principle was speculated based on the molecular structures of ATP and ADP of the Raman peaks centered at ~685 and ~731cm(-1) to explain the linear relationship between the area ratio and the molar ratio. A new method has been developed for quantitative determination of ATP:ADP molar ratio based on Au/CW substrate by the SERS method.

[Health risk assessment of heavy metals in atmospheric dust of Qingdao City].

Based on the 89 atmospheric dust samples and soil samples that were collected around Qingdao, we tested and analyzed the contents of Cd, Cr, Cu, Hg, Ni, Pb, Zn. Based on these analysis results, the risk of heavy metals in atmospheric dusts to human health were assessed by using the US EPA Health Risk Assessment Model. Analysis showed that the average contents of Cd, Cr, Cu, Hg, Pb, Zn in the atmospheric dust of Shinan, Shibei and Laoshan districts were the highest. Therefore, the air pollution of these districts was more serious than the districts of Licang, Chengyang and Huangdao. Comparing the average contents of heavy metals in atmospheric dust with those in soil, we found that only the content of Hg in atmospheric dust collected from the districts of Shinan, Shibei and Laoshan was lower than that in the corresponding soil. All the contents of other heavy metals in atmospheric dust were higher than those in corresponding soil. As a whole, the heavy metals in atmospheric dust of Qingdao City showed slight difference and were less harmful to human health. However, it was harmful in some samples to human health if the contents of Cr and Pb in atmospheric dusts of Shinan, Laoshan and Chengyang districts were always kept at such high densities. Besides, the accumulation of heavy metals in atmospheric dust through various approaches and categories may obviously increase the risk of damaging human health.

Si/ZnO nanocomb arrays decorated with Ag nanoparticles for highly efficient surface-enhanced Raman scattering.

High-density ZnO nanocombs were first grown on a nanoporous silicon pillar array, and pre-prepared 3D Si/ZnO/Ag nanocomb arrays were employed as substrates for surface-enhanced Raman scattering (SERS). The finite-difference time-domain simulation result shows that two kinds of inter-Ag-NP nanogaps in the geometry create a large number of SERS "hot spots," which contributes to the detection limits for rhodamine-6G as low as 10⁻¹² M and the Raman enhancement factor as large as 109. The linear dependence between the Raman peak intensities and the concentrations of thiram provides a new calibration method for rapid and quantitative detection of trace organic molecules.

Ag@SiO2 core-shell nanoparticles on silicon nanowire arrays as ultrasensitive and ultrastable substrates for surface-enhanced Raman scattering.

Ag nanoparticles (NPs) coated with silica nanolayers were decorated onto a large-scale and uniform silicon nanowire array (SiNWA) by simple chemical etching and metal reduction processes. The three-dimensional Ag/SiNWAs thus formed are employed as a substrate for surface-enhanced Raman scattering (SERS), and a detection limit for rhodamine 6G as low as 10(-16) M and a Raman enhancement factor as large as 10(14) were obtained. Simulation results show that two kinds of inter-Ag-NP nanogaps in three-dimensional geometry create a huge number of SERS 'hot spots' where electromagnetic fields are substantially amplified, contributing to the higher SERS sensitivity and lower detection limit. The excellent SERS stability of Ag/SiNWAs is attributed to the presence of the SiO2 nanolayer around Ag NPs that prevented the Ag NP surface from being oxidized. The calibration of the Raman peak intensities of rhodamine 6G and thiram allowed their quantitative detection. Our finding is a significant advance in developing SERS substrates for the fast and quantitative detection of trace organic molecules.

Electroluminescence from ZnO-nanofilm/Si-micropillar heterostructure arrays.

ZnO-nanofilm/Si-micropillar p-n nanoheterostructure arrays were prepared by growing n-type ZnO onto a p-type nanoporous Si pillar array. Its current-voltage characteristics of nanoheterostructure showed good rectifying behavior with onset voltage of ~1.5 V, forward current density of ~28.7 mA/cm(2) at 2.5 V, leakage current density of ~0.15 mA/cm(2) and rectifying ratio of ~121 at ± 2.5 V. The electron transport across nanohetreostructure obeys the trap-charge-limit current model. Moreover, strong white light electroluminescence from ZnO-nanofilm/Si-micropillar light-emitting diode (LED) has been achieved, which could open up possibilities to build new ZnO/Si-based highly efficient solid-state lighting devices.

[The changing process of population probability and fluorescence intensity in ErP5O14 noncrystalline from 0 second to stabilization].

The results of numerical simulation were compared respectively with and without considering the improved coefficient for the energy transfer process in ErP5O14 noncrystalline under 521.8, 450.0, 405.5 and 378.5 nm lights excitation. The results showed that it is essential to take the coefficient into calculation where energy transfer plays a key role. The relative fluorescence intensity ratios of 4I13/2-->4I15/2 to 4I11/2-->4I15/2 under 523.8, 450.0 and 378.5 nm lights excitation were 2.11, 2.82 and 2.99 times larger than that under 979.3 nm light excitation respectively. There are obviously effective near-infrared (NIR) quantum cutting of 4I13/2-->4I15/2 transition. The result indicates that ErP5O14 noncrystalline has potential application in the enhancement of conversion efficiency of germanium solar cells.

[Study of surface enhanced Raman scattering of trace trinitrotoluene based on silver colloid nanoparticles].

Trinitrotoluene (TNT), a representative nitroexplosive, attracts more and more attentions because of the urgent demand for trace analysis of explosives in recent years. The present study investigated the experiment condition of the surface enhanced Raman scattering (SERS) of 10(-6) mol x L(-1) TNT solution, especially the influence of NaCl and basic hydrolysis. The results indicate that SERS spectra of TNT can not be obtained when preparing the SERS samples without NaCl, and it was also shown that the intensity of Raman peaks has a relationship with the concentration of NaCl. With the increase in the concentration of NaCl, the intensity of Raman peak at 1 392 cm(-1) has a maximum value. This report explained the reason why NaCl can affect the intensity of SERS theoretically. It was also shown that the SERS spectrum of TNT treated with basic hydrolysis is more intense than that without basic hydrolysis.

[Infrared multiphoton quantum cutting phenomena of rare earth materials].

Infrared quantum cutting of rare earth ion is an international hot research field. It is significant for the enhancement of solar cell efficiency and for the reduction of solar cell price. The present paper summarizes the research significance of infrared quantum cutting of rare earth ion. Based on the summarization of general principle and loss mechanism of solar cell, the possible method to enhance the solar cell efficiency by infrared quantum cutting is analyzed. Meanwhile, the present paper summarizes the infrared quantum cutting phenomena of Er3+ ion single-doped material. There is intense 4I13/2 --> 4I15/2 infrared quantum cutting luminescence of Er3+ ion when the 2H11/2 energy level is excited. The intense {2H11/2 --> 4I9/2, 4I15/2 --> 4I13/2} cross energy transfer is the main reason for the result in the high quantum cutting efficiency when the 2H11/2 energy level is excited.

[Comparisons of spectral properties of CsI:T1 crystals with various Tl(+)-doped concentrations].

Absorption Spectra and Photoluminescence (PL) spectra of CsI: T1 crystals with various T1+-concentrations were measured for absorption and luminescent research in CsI: T1. Their UV absorption spectra contained three peaks at 297, 273 and 247 nm. The experiments were demonstrated that the peaks in the high T(1+)-concentration CsI: T1 crystals are broader than ones in the low T(1+)-concentration crystals and their absorption A-peak shift by 20 nm, but their PL with UV excitations are similar. It was suggested that lattice distortions in the high T1+-concentration CsI: T1 lead to the changes in absorption or fluorescence excitation peaks, but no changes in the fluorescence band widths and locations at room temperature.

[Spectroscopic properties of Pr3+ doped transparent oxyfluoride vitroceramics].

In the present paper, the room-temperature absorption spectrum of Pr+ -doped transparent oxyfluoride vitroceramics (Pr(0.2):FOV) was studied systematically. The optical characterisation of Pr(0.2):FOV was performed. The standard and modified Judd-Ofelt theories were used to determine the J-O intensity parameters. The problems with standard Judd-Ofelt theorie for Pr3+ were discussed. Based on the intensity parameters, some predicted optical parameters, such as the spontaneous radiative transition probabilities, radiative lifetimes, branching ratios and integrated emission cross section were calculated. And the application of Pr:FOV was analyzed. Especially there are large oscillator strength and large integrated emission cross section in the transitions of (3)P0-->(3)H4, (3)P1-->(3)H5 and (3)P0-->(3)H6, (3)P0-->(3)F2. So, they are more worthy of attention. The obtained spectroscopic results show the potential application of the Pr3+ -doped oxyfluoride vitroceramics for solid-state lasers.

[Optical parameters of Er3+ in Er3+ : YVO4].

In the present paper the authors firstly measured the absorption spectra of Er3+ in the sample Er3+ : YVO4 (0.5%), then calculated the intensity parameters are calculated by using the Judd-Ofelt theory. After that the authors dealed with some predicted spectroscopic parameters, such as the oscillator strength, spontaneous radiative transition rate, branching ratio and integrated emission cross section. And Er : YVO4 crystal application value has been analyzed with the optical parameters. Especially there are large oscillator strengths and large integrated emission cross sections in the transitions of 4 I1/2 --> 4 I15/2, 2 H11/2 --> 4I15/2, 4S3/2 --> 4 I15/2, and 4F9/2 --> 4 I15/2. So, they are more worth of attention. Moreover, by comparing the Er-doped yttrium vanadate crystal and other Er-doped crystal optical properties, the authors can see the advantages of YVO4 as laser crystal. Finally, the authors discussed the splitting of the energy levels of Er3+ in the crystal YVO4 based on the group theory.

[Study of reference material for excitation spectrum wavelength calibration of fluorescence spectrophotometer].

A reference material used for wavelength calibration of fluorescence spectrophotometer was found. The holmium doped oxide reference material GBW(E) 130112 is a kind of standard reference material for absorption spectrophotometer. It can emit 547.7 nm fluorescence when excited by xenon lamp light. The excitation spectrum of 547.7 nm fluorescence was measured. It was found that the measured peaks of excitation spectrum are positioned at 333.56, 360.43 and 418.39 nm, respectively, which are coincident with the true values 333.8, 360.9 and 418.5 nm of reference material certification. It was illustrated that the holmium doped oxide reference material GBW(E)130112 could be used as reference material for the excitation wavelength calibration of the fluorescence spectrophotometer. Its property could be enhanced very much if high luminescent efficiency material is selected as rare earth ion doped matrix, and the purity is enhanced to reduce the cross relaxation.