Fiber-optic plasmonic probe with nanogap-rich Au nanoislands for on-site surface-enhanced Raman spectroscopy using repeated solid-state dewetting.

We report a fiber-optic plasmonic probe with nanogap-rich gold nanoislands for on-site surface-enhanced Raman spectroscopy (SERS). The plasmonic probe features nanogap-rich Au nanoislands on the top surface of a single multimode fiber. Au nanoislands were monolithically fabricated using repeated solid-state dewetting of thermally evaporated Au thin film. The plasmonic probe shows 7.8 × 106 in SERS enhancement factor and 100 nM in limit-of-detection for crystal violet under both the excitation of laser light and the collection of SERS signals through the optical fiber. The fiber-through measurement also demonstrates the label-free SERS detection of folic acid at micromolar level. The plasmonic probe can provide a tool for on-site and in vivo SERS applications.

Rapid detection of soils contaminated with heavy metals and oils by laser induced breakdown spectroscopy (LIBS).

A laser induced breakdown spectroscopy (LIBS) coupled with the chemometric method was applied to rapidly discriminate between soils contaminated with heavy metals or oils and clean soils. The effects of the water contents and grain sizes of soil samples on LIBS emissions were also investigated. The LIBS emission lines decreased by 59-75% when the water content increased from 1.2% to 7.8%, and soil samples with a grain size of 75 µm displayed higher LIBS emission lines with lower relative standard deviations than those with a 2mm grain size. The water content was found to have a more pronounced effect on the LIBS emission lines than the grain size. Pelletizing and sieving were conducted for all samples collected from abandoned mining areas and military camp to have similar water contents and grain sizes before being analyzed by the LIBS with the chemometric analysis. The data show that three types of soil samples were clearly discerned by using the first three principal components from the spectral data of soil samples. A blind test was conducted with a 100% correction rate for soil samples contaminated with heavy metals and oil residues.

Characterization of non-exhaust coarse and fine particles from on-road driving and laboratory measurements.

We investigated the physical and chemical properties of non-exhaust coarse and fine particles generated by on-road driving and in a laboratory setting using a mobile sampling system. The on-road driving and laboratory measurements performed under constant speed driving revealed that particles produced by tire wear had a size distribution in the range of 2-3 µm, while roadway particles (RWPs) measured behind the front tire during on-road driving largely comprised crustal materials such as road surface wear particles and road dust as well as tire wear particles (TWPs). The mode diameters of particles obtained from on-road driving under cornering conditions were similar to those obtained under constant speed conditions, but with higher concentrations of crustal elements. Under braking conditions, the particulate matter (PM) concentrations of brake wear particles (BWPs) sampled near the brake pad increased significantly and were much higher than the concentration of RWPs during deceleration, indicating that BWPs are one of the main sources of non-exhaust emissions. In addition, BWPs observed from on-road and laboratory measurements had a broader PM size range (1-10 µm) than RWPs. Size-segregated chemical analysis of PM samples indicated that the concentrations of Fe and Ca were highest in the coarse fraction emitted under constant speed and cornering conditions, while Fe, Ba, and Ti were most abundant in the fine fraction emitted during braking events.

Determination of lead in soil at a historical mining and smelting site using laser-induced breakdown spectroscopy.

Laser-induced breakdown spectroscopy (LIBS) was used to determine lead (Pb) concentration in soil and tailing samples collected from a historical mining and smelting area. The Pb emission line at 405.781 nm was found to have the strongest intensity and highest linearity with concentration. It was further normalized by the Al emission line (394.401 nm), and a relationship between the peak area ratio (Pb/Al) and Pb concentration was established to determine Pb concentration of unknown samples. The Pb concentration was the highest at the former smelter site and unremediated mine-tailing areas, indicating that severe Pb contamination is still occurring. The Pb concentration decreased with increasing distance from the two major source areas (smelting and mine-tailing sites), although all samples exceeded the 400 mg/kg standard set by the United States Environmental Protection Agency. The limit of detection (LOD) for Pb was found to be 48 mg/kg, and the Pb concentrations determined by LIBS were in reasonable agreement with concentrations obtained by inductively coupled plasma mass spectroscopy (ICP-MS; within 26%). When Pb concentrations were determined by calibration-free (CF)-LIBS, which does not require standard soil samples and dilution, both LIBS and ICP-MS were also in good agreement, suggesting that the CF-LIBS method can be used to determine Pb concentrations in highly contaminated soil samples. In addition to Pb, other metal emission lines from LIBS spectra were used to classify soil samples among the sites using a principal component analysis (PCA) method, showing a distinct difference in metal distribution between sites that are heavily contaminated by two major sources.

Detection of nutrient elements and contamination by pesticides in spinach and rice samples using laser-induced breakdown spectroscopy (LIBS).

The laser-induced breakdown spectroscopy (LIBS) technique was applied to quantify nutrients (Mg, Ca, Na, and K) in spinach and rice and to discriminate pesticide-contaminated products in a rapid manner. Standard reference materials (spinach leaves and unpolished rice flour) were used to establish a relationship between LIBS intensity and the concentration of each element (Mg, Ca, Na, and K) (i.e., calibration line). The limits of detection (LODs) for Mg, Ca, Na, and K were found to be 29.63, 102.65, 36.36, and 44.46 mg/kg in spinach and 7.54, 1.76, 4.19, and 6.70 mg/kg in unpolished rice, respectively. Concentrations of those nutrient elements present in spinach and unpolished rice from a local market were determined by using the calibration lines and compared with those measured with ICP-OES, showing good agreement. The data also suggested that the LIBS technique with the chemometric method (PLS-DA) could be a great tool to distinguish pesticide-contaminated samples from pesticide-free samples in a rapid manner even though they have similar elemental compositions. Misclassification rates were found to be 0 and 2% for clean spinach and pesticide-contaminated spinach, respectively, by applying the PLS-DA model established from the training set of data to predict the classes of test samples.

Validation of the Patient Health Questionnaire-9 Korean version in the elderly population: the Ansan Geriatric study.

OBJECTIVE: We evaluated the diagnostic validity of the 9-item depression module of the Patient Health Questionnaire-9 (PHQ-9) in elderly Korean patients and suggest an optimal cutoff score to screen for major depressive disorders. METHOD: The PHQ-9 and an elderly health questionnaire were administered to 1060 subjects older than 60 years, chosen using a stratified random sample of the community. The PHQ-9 was measured and compared with the Geriatric Depression Scale, Center for Epidemiological Studies Depression Scale, and Beck Depression Inventory scores. Reliability and validity tests, factor analysis, and receiver operating characteristic curve analysis were performed. RESULTS: The PHQ-9 indicated that 175 subjects had depressive disorders, and 885 subjects were rated as healthy. The PHQ-9 showed significant positive internal consistency (r = 0.88) and test-retest reliability (r = 0.60). The convergent validity with Geriatric Depression Scale and Center for Epidemiological Studies Depression Scale was significantly positive (r = 0.74 and 0.66, respectively). We suggest a score of 5 as the optimal cutoff point when screening for depressive disorders using the PHQ-9. CONCLUSIONS: The Korean version of the PHQ-9 is an appropriate diagnostic tool for depression, and a score of 5 is the optimal cutoff for Korean elderly subjects. Screening for depression in the elderly population using the PHQ-9 would be valuable when medically ill patients show depressive symptoms in a primary health care setting.